Carbon blacks and compositions containing them
Abstract
New classes of carbon blacks which may be broadly characterized as having an Iodine adsorption number (I2No.) of 50-112 milligrams/gram (mg/g) and a primary particle size measured in accordance with the procedures in ASTM Test Procedure D3849-89 (hereinafter denoted as "primary particle size") of less than or equal to 25 nanometers (nm). Certain of the carbon blacks of the present invention may be further characterized as having a CDBP (dibutyl absorption value of the crushed carbon black) of less than or equal to 102 cubic centimeters DBP per 100 grams of carbon black (cc/100g). The present invention provides carbon blacks having I2No. of 65-95 mg/g and a primary particle size of less than or equal to 20 nm. Also disclosed and claimed are carbon blacks having an I2No. of 100-112 mg/g and a primary particle size of less than or equal to 20 nm. The present invention further provides carbon blacks having an I2No. of 65-112 mg/g; a primary particle size of less than or equal to 20 nanometers (nm); and a CDBP (dibutyl absorption value of the crushed carbon black) of less than or equal to 102 cubic centimeters DBP per 100 grams of carbon black (cc/100g). In addition, carbon blacks having an I2No. of 50-70 milligrams/gram (mg/g) and a primary particle size of less than or equal to 25 nm, are disclosed and claimed. The present invention also provides carbon blacks having an I2No. of 50-85 mg/g; a primary particle size of less than or equal to 25 nm; and a CDBP of less than or equal to 96 cc/100g. The carbon blacks are particularly well suited for use in the production of polymer compositions. Also described and claimed are polymer compositions incorporating the new carbon blacks.

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Expired 22 January 2017, 9.7 years ago.
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35 claims: 7 independent, 28 dependent
- 1Patent claims Zastrzeżenia patentowe 1. The polymer composition, characterized in that it contains from 0.5 to 300 parts by weight of carbon black per 100 parts by weight of polymer, the carbon black having an iodine number of 65 to 95 mg / g and an original particle size below or equal to 20 nm. 1. Kompozycja polimerowa, znamienna tym, że zawiera od 0,5 do 300 części wagowych sadzy na 100 części wagowych polimeru, przy czym sadza jest o liczbie jodowej od 65 do 95 mg/g i o pierwotnej wielkości cząstek poniżej lub równej 20 nm.
- 4Composition according to claim A composition as claimed in any one of claims 1 to 2, comprising carbon black with a primary particle size less than or equal to 19 nm. 4. Kompozycja według zastrz. 1 albo 2, albo 3, znamienna tym, że zawiera sadzę o pierwotnej wielkości cząstek poniżej lub równej 19 nm.
- 8The polymer composition, characterized in that it contains from 0.5 to 300 parts by weight of carbon black per 100 parts by weight of polymer, the carbon black having an iodine number of 100 to 112 mg / g and an original particle size below or equal to 20 nm. 8. Kompozycja polimerowa, znamienna tym, że zawiera od 0,5 do 300 części wagowych sadzy na 100 części wagowych polimeru, przy czym sadza jest o liczbie jodowej od 100 do 112 mg/g i o pierwotnej wielkości cząstek poniżej lub równej 20 nm.
- 13The polymer composition, characterized in that it contains from 0.5 to 300 parts by weight of carbon black per 100 parts by weight of polymer, the carbon black having an iodine number of 65 to 112 mg / g;with a primary particle size less than or equal to 20 nm;and with a CDBP value below or equal to 102 cm3/ 100 g. 13. Kompozycja polimerowa, znamienna tym, że zawiera od 0,5 do 300 części wagowych sadzy na 100 części wagowych polimeru, przy czym sadza jest o liczbie jodowej od 65 do 112 mg/g;o pierwotneji wielkości cząstek poniżej lub równej 20 nm;i o wartości CDBP poniżej lub równej 102 cm3/100 g.
- 22The polymer composition, characterized in that it contains from 0.5 to 300 parts by weight of carbon black per 100 parts by weight of polymer, the carbon black having an iodine number of 50 to 70 mg / g and an original particle size below or equal to 25 nm. 22. Kompozycja polimerowa, znamienna tym, że zawiera od 0,5 do 300 części wagowych sadzy na 100 części wagowych polimeru, przy czym sadza jest o liczbie jodowej od 50 do 70 mg/g i o pierwotnej wielkości cząstek poniżej lub równej 25 nm.
- 28The polymer composition, characterized in that it contains from 0.5 to 300 parts by weight of carbon black per 100 parts by weight of polymer, the carbon black having an iodine number of 50 to 85 mg / g;with an original particle size less than or equal to 25 nm;and with a CDBP value of less than or equal to 96 cm 7100 g. 28. Kompozycja polimerowa, znamienna tym, że zawiera od 0,5 do 300 części wagowych sadzy na 100 części wagowych polimeru, przy czym sadza jest o liczbie jodowej od 50 do 85 mg/g;o pierwotnej wielkości cząstek poniżej lub równej 25 nm;i o wartości CDBP poniżej lub równej 96 cm 7100 g.
Independent claims7
873 paragraphs in 5 sections, as filed
The present invention relates to a polymer composition (natural rubbers, synthetic rubbers, elastomers, plastomers and / or their mixtures or mixtures) which contains carbon black.
Carbon black is generally produced in furnace reactors by pyrolysis of a hydrocarbon feed with hot flue gas to produce combustion products containing granular soot.
Carbon blacks can be used as pigments, fillers and / or as reinforcing agents in polymer compositions. The term "polymer" as used herein refers to natural rubber, synthetic rubber, elastomer, plastomer and / or mixtures or mixtures thereof.
Carbon black can also be used to impart electrical conductivity and protect against degradation under ultraviolet (UV) light polymer compositions. Carbon black, for example, is generally used to limit the degradation of UV-treated polymer compositions. This UV radiation occurs as a component of natural sunlight. It is generally accepted that the degree of protection against UV degradation is improved when using soot with reduced particle size, e.g. below 25 nanometers (nm). It is generally believed that there are other benefits associated with the use of carbon black with a particle size below 20 nm.
Carbon black is introduced into the polymer composition using various mixing techniques. In the case of carbon black with good UV protection properties, it is generally preferred to use soot that gives the lowest possible viscosity and thus improves processability
188 285 carbon black polymer mixtures. Another desirable feature of carbon black in such applications is the ability to increase the relative carbon black content of the carbon black-polymer mixture within reasonable limits. To reduce the tendency of the polymer composition to absorb moisture, it is desirable to use soot that provides as low a moisture absorption (CMA) as possible. CMA indicates the moisture absorption capacity of carbon black when preparing a given polymer composition.
Thus, it would be beneficial to produce new carbon blacks that give the compositions better viscosity or processability properties for the polymer compositions containing them.
It would also be beneficial to produce new carbon blacks that give better moisture absorption properties to the polymer compositions containing them.
In addition, new polymer compositions that have better viscosity and / or processability properties and give less moisture absorption to the compositions would be preferred.
These and other advantages are obtained by using carbon black in the polymer composition of the invention.
The present invention relates to a polymer composition characterized in that it contains from 0.5 to 300 parts by weight of carbon black per 100 parts by weight of polymer, the carbon black having an iodine number of 65 to 95 mg / g and an original particle size below or equal to 20 nm.
Preferably the composition according to the invention contains carbon black with an iodine value of 73 to 94 mg / g.
Preferably the composition according to the invention contains carbon black with an iodine value of 85 to 93 mg / g.
Preferably, the composition of the invention contains carbon blacks with a primary particle size less than or equal to 19 nm.
Preferably the composition according to the invention contains from 0.5 to 100 parts by weight of carbon black per 100 parts by weight of polymer.
Preferably the composition of the invention contains from 0.5 to 80 parts by weight of carbon black per 100 parts by weight of polymer.
Preferably the composition according to the invention contains polyethylene as the polymer.
Preferably, the composition of the invention contains from 0.5 to 300 parts by weight of carbon black per 100 parts by weight of polymer, the carbon black having an iodine number of 100 to 112 mg / g and an original particle size below or equal to 20 nm.
Preferably, the composition of the invention contains carbon black with a primary particle size less than or equal to 19 nm.
Preferably the composition according to the invention contains from 0.5 to 100 parts by weight of carbon black per 100 parts by weight of polymer.
Preferably the composition of the invention contains from 0.5 to 80 parts by weight of carbon black per 100 parts by weight of polymer.
Preferably the composition according to the invention contains polyethylene as the polymer.
The present invention relates to a polymer composition characterized in that it contains from 0.5 to 300 parts by weight of carbon black per 100 parts by weight of polymer, the carbon black having an iodine number of 65 to 112 mg / g; with a primary particle size less than or equal to 20 nm; and with a CDBP value below or equal to 102 cm<sup>3</sup>/ 100 g.
Preferably the composition according to the invention contains carbon blacks with a CDBP value of 70-100 cm3 / 100 g.
Preferably the composition according to the invention contains carbon blacks with a CDBP value of 80-95 cm3 / 100 g.
Preferably, the composition of the invention contains carbon black with a primary particle size less than or equal to 19 nm.
Preferably the composition of the invention contains carbon black with an iodine value of 73 to 104 mg / g.
Preferably the composition according to the invention contains carbon blacks with an iodine number of 75 to 99 mg / g.
Preferably the composition according to the invention contains from 0.5 to 100 parts by weight of carbon black per 100 parts by weight of polymer.
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Preferably the composition of the invention contains from 0.5 to 80 parts by weight of carbon black per 100 parts by weight of polymer.
Preferably the composition according to the invention contains polyethylene as the polymer.
Preferably, the composition of the invention contains from 0.5 to 300 parts by weight of carbon black per 100 parts by weight of polymer, the carbon black having an iodine number of 50 to 70 mg / g and an original particle size less than or equal to 25 nm.
Preferably, the composition of the invention contains carbon black with a primary particle size of more than 20 nm to 25 nm.
Preferably the composition according to the invention contains carbon black with an iodine value of 55 to 65 mg / g.
Preferably the composition according to the invention contains from 0.5 to 100 parts by weight of carbon black per 100 parts by weight of polymer.
Preferably the composition of the invention contains from 0.5 to 80 parts by weight of carbon black per 100 parts by weight of polymer.
Preferably the composition according to the invention contains polyethylene as the polymer.
Preferably, the composition of the invention contains from 0.5 to 300 parts by weight of carbon black per 100 parts by weight of polymer, the carbon black having an iodine number of 50 to 85 mg / g; with an original particle size less than or equal to 25 nm; and with a CDBP value below or equal to 96 cm<sup>3</sup>/ 100 g.
Preferably the composition according to the invention contains carbon black with an iodine number of 55 to 80 mg / g.
Preferably the composition according to the invention contains carbon black with an iodine number of 60 to 78 mg / g.
Preferably, the composition of the invention contains carbon black with a primary particle size of more than 20 nm to 25 nm.
Preferably the composition according to the invention contains carbon blacks with a CDBP value of 50-96 cm<sup>3</sup>/ 100 g.
Preferably the composition according to the invention contains from 0.5 to 100 parts by weight of carbon black per 100 parts by weight of polymer.
Preferably the composition of the invention contains from 0.5 to 80 parts by weight of carbon black per 100 parts by weight of polymer.
Preferably the composition according to the invention contains polyethylene as the polymer.
The new classes of carbon black used in the composition of the invention can be characterized as carbon blacks with an iodine absorption number (iodine number) of 50 to 112 milligrams / gram (mg / g) and with a primary particle size determined according to ASTM Test Procedure D38-4<sup><</sup>9-89 (referred to herein as the "primary particle size") below or equal to 25 nm. The carbon blacks used in the composition of the invention may further be characterized as carbon black with a CDBP value (i.e., the absorption value of dibutyl phthalate by ground carbon black) below or equal to 102 cm3 DBP per 100 g of carbon black (cm3 / 100 g) measured in accordance with ASTM Test Procedure D3493-86 .
The present invention relates to carbon black containing polymer compositions. The term "polymer" as used herein generally refers to natural rubber, synthetic rubber, elastomer, plastomer and / or mixtures or mixtures thereof.
Oven carbon blacks can be made by any method known in the art. The carbon blacks used in the composition of the invention are produced in a carbon black reactor having a first (combustion) zone, a transition zone, and a reaction zone in which:
- the carbon black raw material is injected into the hot exhaust gas stream;
- the obtained mixture of hot flue gas and raw material is introduced into the reaction zone; and
- the pyrolysis of the carbon black raw material is stopped by quenching the mixture after carbon black formation, with a primary combustion level above 300%, preferably at least 550%, more preferably from 650 to 1200%. The total level of combustion in the carbon black process is at least 22%, preferably from 22% to 35%, more preferably from 25 to 28%. The residence time for the carbon black reaction in the carbon black process is from
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0.55 s to 9.9 s, more preferably 1.06 s to 8.01 s. The method of producing carbon black will be described in more detail below.
The polymer compositions of the invention contain natural rubbers, synthetic rubbers, elastomers, plastomers and / or mixtures or mixtures thereof. The amount of carbon black used in the polymer compositions of the invention is any amount sufficient to provide the desired results for the intended end use of the polymer compositions, these amounts being those commonly used and known in the art. In general, amounts of carbon black produced may be used in the range of 0.5 to 300 parts by weight per 100 parts by weight of polymer. However, it is preferred to use amounts of carbon black in the range of 0.5 to 100 parts by weight of carbon black per 100 parts by weight of polymer, and particularly preferably in the range of 0.5 to 80 parts by weight of carbon black per 100 parts by weight of polymer.
Polymers suitable for use in the composition of the invention are: natural rubber, for example polyisoprene and polybutadiene and their derivatives such as chlorinated rubber; copolymers containing from about 10 to about 70% by weight styrene and from about 90 to about 30% by weight butadiene, such as a copolymer of 19 parts styrene and 81 parts of butadiene, a copolymer of 30 parts styrene and 70 parts of butadiene, a copolymer of 43 parts styrene and 57 parts of butadiene and a copolymer of 50 parts styrene and 50 parts butadiene; polymers and copolymers of conjugated dienes such as polybutadiene, polyisoprene, polychloroprene and the like and copolymers of such conjugated dienes with a copolymerizable with them a monomer containing ethylene groups such as styrene, methylstyrene, chlorostyrene, acrylonitrile, 2-vinylpyridine, vinylpyridine, 5-ethyl-2-vinylpyridine, 2-methyl-5-vinylpyridine, alkyl acrylates, vinyl ketone, methyl isopropenyl ketone, methyl vinyl ether, α-methylene carboxylic acids and their esters and amides such as acrylic acid and dialkylacrylic acid amide; copolymers of ethylene and higher α-olefm such as propylene, 1-butene and 1-pentene are also suitable for use in the composition of the invention; ethylene / propylene copolymers in which the ethylene content is in the range of 20 to 90% by weight are particularly preferred, and ethylene / propylene copolymers containing an additional third monomer such as dicyclopentadiene, 1,4-hexadiene and methylene norbomen. The ethylene-containing polymer is preferably an ethylene / propylene copolymer or an ethylene / propylene terpolymer.
The ethylene-containing polymer is more preferably an ethylene / propylene / diene monomer (EPDM) copolymer. The ethylene-containing polymer is also preferably a polymer containing from 0.5 to 98% by weight of ethylene monomer.
Other preferred polymer compositions are polyolefins such as polypropylene and polyethylene.
The following polymers are also suitable:
a) propylene homopolymers, ethylene homopolymers, ethylene copolymers and graft polymers in which monomers such as butene, hexene, propene, octene, vinyl acetate, acrylic acid, methacrylic acid, acrylic esters, Ci-C8 alkyl esters, comonomers -Alkyl methacrylic acid, maleic anhydride, maleic anhydride half ester and carbon monoxide;
b) elastomers such as natural rubber, polybutadiene, polyisoprene, random or block styrene-butadiene rubber (SBR), polychloroprene, acrylonitrile / butadiene copolymer, ethylene / propylene copolymers and ethylene / propylene / diene monomer (EPDM) copolymers;
c) styrene homopolymers and copolymers such as linear and branched styrene / butadiene / styrene polymer, acrylonitrile / butadiene / styrene (ABS) copolymer and styrene-acrylonitrile copolymer;
d) thermoplastic polymers such as polyethylene terephthalate (PET), poly butylene terephthalate (PBT), polycarbonates, polyamides, polyvinylchlorides (PVC), acetals; and
e) thermosetting plastics such as polyurethanes, epoxies and polyesters.
An advantage of the carbon black used in the composition of the invention is that the carbon blacks give low viscosity to the compositions into which they are incorporated.
Another advantage of carbon black is that these soot give a low CMA value (moisture absorption by the mix) to the compositions into which they are incorporated.
Another advantage of carbon black is that these carbon blacks can be incorporated into polymer compositions in significant amounts.
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Still another advantage of carbon black is that they give low viscosity to polymer compositions.
Another advantage of carbon black is that the polymer compositions have a low CMA (moisture absorption by the blend) value.
Yet another advantage of the polymer compositions of the invention is that these polymer compositions may contain significant amounts of carbon black.
Other advantages of the invention will be apparent from the more detailed description of the present invention.
Figure 1 is a cross-sectional view of a portion of one type of furnace reactor that can be used to make carbon black.
Figure 2 is a cross-sectional view of a portion of another type of furnace reactor that can be used to make carbon black.
Figure 3 is a sample histogram showing the weight fraction of aggregates in the carbon black sample relative to the Stokes diameter in a given sample.
Figure 4 is a graph showing the effect of carbon black content on the melt flow index of carbon black containing polymer compositions, including data on polymer compositions containing control carbon black, as described in the examples of the description.
Figure 5 is a graph showing the effect of the carbon black content on apparent viscosity, at a shear rate of 100 s' of carbon black containing polymer compositions, including data on carbon black containing polymer compositions as described in the examples of the description.
The present invention relates to carbon black containing polymer compositions.
In one embodiment, the invention relates to a polymer composition comprising carbon black with an iodine number of 65 to 95 mg / g, preferably with an iodine number of 73 to 94 mg / g, more preferably with an iodine number of 85 to 93 mg / g; and with a primary particle size less than or equal to 20 nm, preferably less than or equal to 19 nm. More specifically, the invention relates to polymer compositions comprising the following carbon blacks:
(la) carbon black with an iodine value of 65 to 95 mg / g and an original particle size below or equal to 20 nm;
2a) carbon black with an iodine value of 73 to 94 mg / g and an original particle size below or equal to 20 nm;
3a) carbon black with an iodine value of 85 to 93 mg / g and an original particle size below or equal to 20 nm;
4a) carbon black with an iodine value of 65 to 95 mg / g and an original particle size below or equal to 19 nm;
5a) carbon black with an iodine value of 73 to 94 mg / g and an original particle size below or equal to 19 nm; and
6a) carbon black with an iodine value of 85 to 93 mg / g and an original particle size below or equal to 19 nm.
In another embodiment, the invention relates to a polymer composition comprising carbon blacks with an iodine number of 100 to 112 mg / g and an original particle size below or equal to 20 nm, preferably below or equal to 19 nm. More specifically, the invention relates to polymer compositions comprising the following carbon blacks:
(lb) carbon black with an iodine value of 100 to 112 mg / g and an original particle size below or equal to 20 nm; and
2b) carbon black with an iodine value of 100 to 112 mg / g and an original particle size below or equal to 19 nm.
In yet another embodiment, the invention relates to a polymer composition comprising carbon black with an iodine number of 65 to 112 mg / g, preferably with an iodine number of 73 to 104 mg / g, more preferably with an iodine number of 75 to 99 mg / g; with an original particle size less than or equal to 20 nm, preferably less than or equal to 19 nm and a CDBP value less than or equal to 102 cm<sup>3</sup>/ 100 g, preferably from 70 to 100 cm<sup>3</sup>/ 100 g, more preferably 80 to 95 cm<sup>3</sup>/ 100 g. More specifically, the invention relates to polymer compositions comprising the following carbon blacks:
(lc) carbon black with an iodine value of 65 to 112 mg / g; with a primary particle size less than or equal to 20 nm; and with a CDBP value below or equal to 102 cm3 / 100.g;
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2c) carbon black with an iodine value of 65 to 112 mg / g; with a primary particle size less than or equal to 20 nm; and with a CDBP value of 70 to 100 cm<sup>3</sup>/ 100 g;
3c) carbon black with an iodine value of 65 to 112 mg / g; with a primary particle size less than or equal to 20 nm; and with a CDBP value of 80 to 95 cmi / 100 g;
4c) carbon black with an iodine value of 65 to 112 mg / g; with an original particle size less than or equal to 19 nm; and a CDBP-H value below or equal to 102 cm<sup>3</sup>/ 100 g;
5c) carbon black with an iodine value of 65 to 112 mg / g; with a primary particle size less than or equal to 20 nm; and with a CDBP value of 70 to 100 cm3 / 100 g;
6c) carbon black with an iodine value of 65 to 112 mg / g: with a primary particle size below or equal to 19 nm; and with a CDBP value of 80 to 95 cm3 / 100 g;
7c) carbon black with an iodine value of 73 to 104 mg / g; with a primary particle size less than or equal to 20 nm; and with a CDBP value of less than or equal to 102 cm3 / 100 g;
8c) carbon black with an iodine value of 73 to 104 mg / g; with a primary particle size less than or equal to 20 nm; and with a CDBP value of 70 to 100 cm3 / 100 g;
9c) carbon black with an iodine value of 73 to 104 mg / g: with a primary particle size below or equal to 20 nm; and with a CDBP value of 80 to 95 cm / 100 g;
10c) carbon black with an iodine value of 73 to 104 mg / g; with an original particle size less than or equal to 19 nm; and with a CDBP value of less than or equal to 102 cm3 / 100 g;
11c) carbon black with an iodine value of 73 to 104g / g; with an original particle size less than or equal to 19 nm; and with a CDBP value of 70 to 100 cm<sup>3</sup>/ 100 g;
12c) carbon black with an iodine value of 73 to 104 mg / g; with an original particle size less than or equal to 19 nm; and for CDBP values from 80 to 95 cm3 / 100 g;
13c) carbon black with an iodine value of 75 to 99 mg / g; with a primary particle size less than or equal to 20 nm; and with a CDBP value of less than or equal to 102 cm3 / 100 g;
14c) carbon black with an iodine value of 75 to 99 mg / g; with an initial particle size less than or equal to 20 nm; and with a CDBP value of 70 to 100 cm3 / 100 g;
15c) carbon black with an iodine value of 75 to 99 mg / g: with a primary particle size below or equal to 20 nm; and with a CDBP value of 80 to 95 cm<sup>3</sup>/ 100 g;
16c) carbon black with an iodine value of 75 to 99 mg / g; with an original particle size less than or equal to 19 nm; and with a CDBP value of less than or equal to 102 cm3 / 100 g;
17c) carbon black with an iodine value of 75 to 99 mg / g; with an original particle size less than or equal to 19 nm; and with a CDBP value of 70 to 100 cm3 / 100 g; and
18c) carbon black with an iodine value of 75 to 99 mg / g: with a primary particle size below or equal to 19 nm; and with a CDBP value of 80 to 95 cm<sup>3</sup>/ W0 g.
In yet another embodiment, the invention relates to a polymer composition comprising carbon black with an iodine value of 50 to 70 mg / g and an original particle size below or equal to 25 nm. Preferably, the invention relates to polymer compositions containing carbon blacks with an iodine number of 55 to 65 mg / g and / or an original particle size from above 20 nm to 25 nm. More specifically, the invention relates to polymer compositions comprising the following carbon blacks:
1d) carbon black with an iodine value of 50 to 70 mg / g and an original particle size below or equal to 25 nm;
2d) carbon black with an iodine value of 50 to 70 mg / g and an original particle size below or equal to 25 nm;
(3d) carbon black with an iodine value of 55 to 65 mg / g and an original particle size below or equal to 25 nm; and
4d) carbon black with an iodine value of 55 to 65 mg / g and an original particle size from 20 to 25 nm. .
In yet another embodiment, the invention relates to a polymer composition comprising carbon black with an iodine value of 50 to 85 mg / g; with an original particle size less than or equal to 25 nm; and with a CDBP value less than or equal to 96 cm3 / 100 g. Preferably, the invention relates to polymer compositions containing carbon blacks with an iodine value of 55 to 80 mg / g; with an original particle size from above 20 nm to 25 nm; and / or with a CDBP value of 50 to 96 cm3 / 100 g. More preferably, the invention relates to polymer compositions containing carbon blacks with an iodine value of 60 to 78 mg / g; with primary particle size from above 20 nm
188 285 to 25 nm; and / or with a CDBP value from 50 to 96 cm3 / 100 g. More particularly, the invention relates to polymer compositions comprising the following carbon blacks:
1e) soot with an iodine value of 50 to 85 mg / g; with an original particle size less than or equal to 25 nm; and with a CDBP value below or equal to 96 cm3 / 100 g;
2e) carbon black with an iodine value of 55 to 80 mg / g; with an original particle size less than or equal to 25 nm; and with a CDBP value below or equal to 96 cm3 / 100 g;
3e) carbon black with an iodine value of 60 to 78 mg / g; with an original particle size less than or equal to 25 nm; and with a CDBP value below or equal to 96 cm3 / 100 g;
4e) carbon black with an iodine value of 50 to 85 mg / g; with an original particle size less than or equal to 25 nm; and with a CDBP value of 50 to 96 cm3 / 100 g;
5e) carbon black with an iodine value of 55 to 80 mg / g: with a primary particle size below or equal to 25 nm; and with a CDBP value of 50 to 96 cm3 / 100 g;
6e) carbon black with an iodine value of 60 to 78 mg / g; with an original particle size less than or equal to 25 nm; and with a CDBP value of 50 to 96 cm<sup>3</sup>/ 100 g;
7e) carbon black with an iodine value of 50 to 85 mg / g; with an original particle size from above 20 to 25 nm; and with a CDBP value below or equal to 96 cm<sup>3</sup>/ 100 g;
8e) carbon black with an iodine value of 55 to 80 mg / g; with an original particle size from above 20 to 25 nm; and with a CDBP value below or equal to 96 cm<sup>3</sup>/ 100 g;
9e) carbon black with an iodine value of 60 to 78 mg / g; with an original particle size from above 20 nm to 25 nm; and with a CDBP value below or equal to 96 cm<sup>3</sup>/ 100 g;
10e) carbon black with an iodine value of 50 to 85 mg / g; with an original particle size of more than 20 to 25 runes; and with a CDBP value of 50 to 96 cm<sup>3</sup>/ 100 g;
11e) carbon black with an iodine value of 55 to 80 mg / g; with an original particle size from above 20 nm to 25 nm; and with a CDBP value of 50 to 96 cm3 / 100 g; and
12e) carbon black with an iodine value of 60 to 78 mg / g; with an original particle size from above 20 to 25 nm; and with a CDBP value of 50 to 96 cm3 / 100 g.
The carbon blacks used in the composition of the invention may be prepared by any method, but preferably are prepared as described below. However, it is assumed that although the carbon black production method is described below with reference to one type of carbon black reactor, this method can also be carried out with other types of carbon black reactor.
In particular, carbon blacks can be produced in a modular, also referred to as "step" carbon black reactor. A section of a typical modular carbon black reactor that can be used to make carbon black is shown in Figure 1. Other details of a typical modular carbon black reactor can be found, for example, in US Patent No. 3,922,335, which is incorporated by reference herein. of this description as a reference.
Referring to Fig. 1, carbon black can be produced in a carbon black reactor 2 having a combustion zone 10 that has a zone of convergent diameter 11, transition zone 12 and reaction zone 18. End of reaction zone, 18 nearest transition zone 12 has zone or zones 17A and 17B with limited diameter. The diameter of the combustion zone 10 to the point where the zone of convergent diameter 11 begins is shown as D-1; diameter of zone 12 as D-2; zone diameter 17A as D-3A; zone diameter 17B as D-3A; and the diameter of zone 18 as D-4. The length of the combustion zone 10 to the point where the zone with a converging diameter of 11 begins is shown as L-1; the length of the zone of convergent diameter 11 is shown as L-2, the length of the transition zone 12 is shown as L-3; zone length 17A with limited diameter is shown as L-4A; and the length of zone 17B of limited diameter is shown as L-4B.
To produce the carbon black used in the composition of the invention, hot flue gases are generated in the combustion zone 10 by reacting liquid or gaseous fuel with a suitable oxidant, such as air, oxygen, air-oxygen mixtures and the like. Fuels suitable for use in reaction with the oxidant stream in combustion zone 10 to generate hot flue gases may include any flammable stream in the form of gas, vapor or liquid such as natural gas, hydrogen, carbon monoxide, methane, acetylene, alcohols or kerosene. However, it is generally preferred to use fuels with a high carbon content, in particular hydrocarbons. Ratio
188 285 the amount of air to the amount of natural gas used to make the carbon black is at least 30: 1, preferably from 45: 1 to 100: 1. To facilitate the generation of hot flue gases, the oxidant stream may be heated.
For the production of carbon black, a primary combustion level above 300%, preferably at least 550%, is used in the production process. For the production of carbon black, the primary combustion level is more preferably used in a carbon black process from 650 to 1200%.
As discussed herein, primary combustion means the ratio of the amount of oxidant, such as air, used in the first stage of the multistage process to the theoretical amount of oxidant needed to completely burn the hydrocarbon from the first stage to carbon dioxide and water. For convenience, the original level of combustion is expressed as a percentage.
the amount of oxidant needed to completely burn the hydrocarbon from the first stage to carbon dioxide and water is referred to herein as the "ratio of air to combustion gas" and is expressed as the ratio of the theoretical volume of oxidant to volume of gas in the first stage. The amounts of oxidant and hydrocarbon from the first stage are given in any compatible unit system.
The original level of combustion can be determined by the following formula:
Primary combustion level,% = (measured air velocity) x 100 (measured air velocity) x (air to combustion gas ratio) in which:
"Measured air velocity" = the volumetric flow rate of air introduced into the combustion zone of the reactor, measured under normal temperature and pressure conditions; "Measured gas velocity" = volumetric flow rate of gas introduced into the combustion zone of the reactor, measured under normal temperature and pressure conditions, with "measured air velocity", "measured gas velocity" and "air to gas ratio" being given to each other in a system compatible units.
The term "normal temperature and pressure conditions" as used herein refers to a temperature of 0 ° C and a pressure of 101.3 kilopascals (kPa) when describing air or gas, and the term "normal temperature and pressure conditions" refers to a temperature of 2613 ° C and a pressure of 101, 3 kPa when describing the oil or raw material.
The stream of hot flue gas flows with current from zones 10 and 13 to zones 12, 17A, 17B and then to 18. The direction of flow of hot flue gases is indicated by an arrow in Fig. 1. Carbon black raw material 30 is introduced at point 32 in zone 12 This raw material can be introduced either through a probe 15 having a tip 34, or preferably radially inward through a series of holes arranged in the wall of zone 12 at point 32, or at both points. Suitable carbon black hydrocarbon feedstocks that readily escape under reaction conditions are unsaturated hydrocarbons such as acetylene; olefins such as ethylene, propylene, butylene; aromatic hydrocarbons such as benzene, toluene and xylene; certain saturated hydrocarbons; and volatile hydrocarbons such as kerosene, naphthalenes, terpenes, ethylene pitches, aromatic cycle raw materials and the like.
The distance from point 32 with the current to the beginning of zone 17A with a limited diameter in the reaction zone is shown as Fl. In some examples herein, carbon black feed 30 is injected radially inward through a series of holes at point 32 of zone 12, the resulting streams penetrating into the internal regions of the hot flue gas stream and thereby rapidly decomposing to form new soot.
In the other examples provided herein, the carbon black raw material 30 is injected outwardly in a substantially radial direction with a current through a series of holes at the end 34 of probe 15, the resulting streams entering the outer regions of the hot flue gas stream and thereby decomposing rapidly raw material on saga. The distance from the end of probe 15 to the beginning of zone 17A is shown as F-2.
For the production of carbon black, the total level of combustion in the carbon black process is preferably at least 22%, more preferably from 22% to 35%, and most preferably from 25 to 28%.
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As mentioned herein and as known to those skilled in the art, total combustion means the ratio of the total amount of oxidant, such as air, used in the carbon black process to the amount of oxidant needed to completely burn the hydrocarbon present in the total amount of hydrocarbon used in the carbon black production process. coal and water. The total combustion level is usually expressed as a percentage.
For convenience, the amount of oxidant needed to completely burn the carbon black raw material to water dioxide and water is referred to herein as the "air to oil burn ratio" and is expressed as the ratio of the theoretical amount of oxidant to the volume of the carbon black raw material. The amounts of oxidant and carbon black raw material may be given in any compatible unit system.
The total combustion level can be determined by the following formula:
, ". . , ". (measured air speed) x 100
Total combustion level,% = -; --— -------- (measured gas rate) x (air to gas ratio) + + (measured air speed) x (air to gas ratio) in which:
"Measured air velocity" = the volumetric flow rate of air introduced into the combustion zone of the reactor, measured under normal temperature and pressure conditions; "Measured gas rate" = the volumetric flow rate of gas introduced into the combustion zone of the reactor, measured under normal temperature and pressure conditions; "Measured oil speed" = the volumetric flow rate of oil introduced into the reactor, measured under normal temperature and pressure conditions;
wherein "measured air velocity", "measured gas velocity", "measured oil velocity", "air to combustion gas ratio" and "air to combustion oil ratio" are given in a system of mutually compatible units.
A mixture of the soot-giving raw material and hot flue gas flows with current through zones 12, 17A, 17B and to zone 18. Quenching device 40, located at point 42 injecting quenching fluid 50, which in the examples given in the description is water, is used to stop pyrolysis soot-producing raw material during the production of new soot. Point 42 can be marked by any method known in the art for selecting the position of the quenching device to stop pyrolysis.
One way to determine the position of a quenching device to stop pyrolysis is to determine the point where the acceptable toluene extract content for new carbon black is reached. The content of toluene extract can be measured according to ASTM Test Procedure D1618-83, "Determination of soot content of substances extracted with toluene".
In a preferred embodiment of the carbon black production method, the location of the quenching device is determined in such a way that the nominal residence time for the carbon black reaction in the reactor is from 0.55 s to 9.9 s, preferably from 1.06 s to 8.01 s. The nominal residence time in the reactor is defined as the time nominally required for the passage of the oxidant through the reactor from the injection site of the raw material giving soot to the quenching site, if the oxidant was not changed during any method at any stage in the stage reactor, the volumetric flow rate of the oxidant being determined in normal temperature and pressure conditions.
After quenching the mixture of hot flue gases and the soot-producing raw material, the hot gases flow with current to any conventional cooling and separating devices in which carbon black is recovered. Separation of soot from the gas stream is easily accomplished using a conventional device, such as a precipitation device, cyclone separator or bag filter. This separation may be followed by tabletting, for example using a wet tablet press.
Figure 2 is a cross-sectional view of another configuration of the carbon black reactor that can be used to make carbon black and which was used to make the carbon black provided in the examples herein. The reactor 2 shown in Fig. 2 is substantially identical to reactor 12
188 285 rem in Fig. 1 and reference numbers in Fig. 2 are used in the same way as in Fig. 1, with the following exceptions.
In the reactor shown in Figure 2, the reaction zone further includes zones 18A, 18B and 18C. Zone 18A is located next to zone 17B. Zone 18b is located next to zone 18A and is offset by the angle C1 as shown in Figure 2. Zone 18C is located next to zone 18B. The diameter of zone 18A is shown as D-4A; zone diameter 18B as D-4B and zone diameter 18C as D-4C. Zone 18A length is shown as L-5A; the length of each section of zone 18B in a direction parallel to the horizontal is either designated L-5B or L-5C as shown in Fig. 2.
The polymer compositions of the invention contain polymer and carbon black.
Thus, in one embodiment of the invention, the invention relates to polymer compositions comprising polymer and carbon black with an iodine number of 65 to 95 mg / g, preferably with an iodine number of 73 to 94 mg / g, more preferably with an iodine number of 85 to 93 mg / g ; and with a primary particle size less than or equal to 20 nm, preferably less than or equal to 19 nm. More particularly, the invention relates to the following polymer compositions:
la) a polymer composition comprising polymer and carbon black with an iodine value of 65 to 95 mg / g and an original particle size less than or equal to 20 nm;
2a) a polymer composition comprising a polymer and carbon black with an iodine value of 73 to mg / g and an original particle size less than or equal to 20 nm;
3a) a polymer composition comprising a polymer and carbon black with an iodine number of 85 to mg / g and an original particle size less than or equal to 20 nm;
4a) a polymer composition comprising polymer and carbon black with an iodine value of 65 to mg / g and an original particle size less than or equal to 19 nm;
5a) a polymer composition comprising polymer and carbon black with an iodine value of 73 to mg / g and an original particle size less than or equal to 19 nm; and
6a) a polymer composition comprising polymer and carbon black with an iodine value of 85 to 93 mg / g and an original particle size below or equal to 19 nm.
In another embodiment, the invention relates to a polymer composition comprising a polymer and carbon black with an iodine value of 100 to 112 mg / g and an original particle size below or equal to 20 nm, preferably below or equal to 19 nm. More specifically, the invention relates to the following polymer compositions:
lb) a polymer composition comprising a polymer and carbon black with an iodine value of 100 to 112 mg / g and an original particle size less than or equal to 20 nm; and
2b) a polymer composition comprising polymer and carbon black with an iodine value of 100 to 112 mg / g and an original particle size below or equal to 19 nm.
In yet another embodiment, the invention relates to a polymer composition comprising a polymer and carbon black having an iodine value of 65 to 112 mg / g, preferably an iodine number of 73 to 104 mg / g, more preferably an iodine number of 75 to 99 mg / g; with a primary particle size less than or equal to 20 nm, preferably less than or equal to 19 nm, and a CDBP value less than or equal to 102 cm3 / 100 g, preferably 70 to 100 cm3 / 100 g, more preferably 80 to 95 cm3 / 100 g. More specifically, the invention relates to the following polymer compositions:
lc) a polymer composition comprising polymer and carbon black with an iodine value of 65 to 112 mg / g; with a primary particle size less than or equal to 20 nm; and with a CDBP value below or equal to 102 cmr / 100 g;
2c) a polymer composition comprising polymer and carbon black with an iodine value of 65 to 112 mg / g; with a primary particle size less than or equal to 20 nm; and with a CDBP value of 70 to 100 cm<sup>3</sup>/ 100 g;
3c) a polymer composition comprising polymer and carbon black with an iodine value of 65 to 112 mg / g; with a primary particle size less than or equal to 20 nm; and with a CDBP value of 80 to cm<sup>3</sup>/ 100 g;
4c) a polymer composition comprising polymer and carbon black with an iodine value of 65 to 112 mg / g; with an original particle size less than or equal to 19 nm; and with a CDBP value below or equal to 102 cmr / 100 g;
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5c) a polymer composition comprising polymer and carbon black with an iodine value of 65 to 112 mg / g; with a primary particle size less than or equal to 20 nm; and with a CDBP value of 70 to 100 cm3 / 100 g;
6c) a polymer composition comprising polymer and carbon black with an iodine value of 65 to 112 mg / g; with an original particle size less than or equal to 19 nm; and with a CDBP value of 80 to 95 cm3 / 100 g;
7c) a polymer composition comprising polymer and carbon black with an iodine value of 73 to 104 mg / g; with an original particle size less than or equal to 20 mu; and with a CDBP value below or equal to 102 cm<sup>3</sup>/ 100 g;
8c) a polymer composition comprising polymer and carbon black with an iodine value of 73 to 104 mg / g; with a primary particle size less than or equal to 20 nm; and with a CDBP value of 70 to 100 cm<sup>3</sup>/ 100 g;
9c) a polymer composition comprising polymer and carbon black with an iodine value of 73 to 104 mg / g; with a primary particle size less than or equal to 20 nm; and with a CDBP value of 80 to 95 cm<sup>3</sup>/ 100 g;
10c) a polymer composition comprising polymer and carbon black with an iodine value of 73 to 104 mg / g; with an original particle size less than or equal to 19 nm; and with a CDBP value less than or equal to 102 cm'7100 g;
11c) a polymer composition comprising polymer and carbon black with an iodine value of 73 to 104g / g; with an original particle size less than or equal to 19 nm; and with a CDBP value of 70 to 100 cm<sup>5</sup>/ 100 g;
12c) a polymer composition comprising polymer and carbon black with an iodine value of 73 to 104 mg / g; with an original particle size less than or equal to 19 nm; and with a CDBP value of 80 to 95 cm<sup>3</sup>/ 100 g;
13c) a polymer composition comprising polymer and carbon black with an iodine number of 75 to 99 mg / g; with a primary particle size less than or equal to 20 nm; and with a CDBP value below or equal to 102 cmi / 100 g;
14c) a polymer composition comprising a polymer and carbon black with an iodine number of 75 to 99 mg / g; with a primary particle size less than or equal to 20 nm; and with a CDBP value of 70 to 100 cm3 / 100 g;
15c) a polymer composition comprising a polymer and carbon black with an iodine number of 75 to 99 mg / g; with a primary particle size less than or equal to 20 nm; and with a CDBP value of 80 to 95 cm<sup>3</sup>/ 100 g;
16c) a polymer composition comprising polymer and carbon black with an iodine value of 75 to 99 mg / g; with an original particle size less than or equal to 19 nm; and with a CDBP value less than or equal to 102 cm / / 100 g;
17c) a polymer composition comprising a polymer and carbon black with an iodine number of 75 to 99 mg / g; with an original particle size less than or equal to 19 nm; and with a CDBP value of 70 to 100 f cm3 / 100 g; and
18c) a polymer composition comprising polymer and carbon black with an iodine value of 75 to 99 mg / g; with an original particle size less than or equal to 19 nm; and with a CDBP value of 80 to 95 cm<sup>3</sup>/ 100 g.
In yet another embodiment, the invention relates to new polymer compositions comprising polymer and carbon black with an iodine number of 50 to 70 mg / g and an original particle size below or equal to 25 nm. Preferably they contain carbon blacks with an iodine number of 55 to 65 mg / g and / or with a primary particle size above 20 nm to 25 nm. More particularly, the invention relates to the following polymer compositions:
1d) a polymer composition comprising carbon black with an iodine value of 50 to 70 mg / g and an original particle size less than or equal to 25 nm;
2d) a polymer composition comprising carbon black with an iodine value of 50 to 70 mg / g and an original particle size less than or equal to 25 nm;
3d) a polymer composition comprising carbon black with an iodine value of 55 to 65 mg / g and an original particle size less than or equal to 25 nm; and
4d) a polymer composition comprising carbon black with an iodine value of 55 to 65 mg / g and an original particle size of greater than 20 to 25 nm.
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In yet another embodiment, the invention relates to new polymer compositions comprising polymer and carbon black with an iodine value of 50 to 85 mg / g; with an original particle size less than or equal to 25 nm; and with a CDBP value less than or equal to 96 cm3 / 100 g. Preferably carbon black with an iodine number of 55 to 80 mg / g is used; with an original particle size from above 20 nm to 25 nm; and / or with a CDBP value of 50 to 96 cm3 / 100 g. More preferably, carbon black with an iodine value of 60 to 78 mg / g is used; with an original particle size from above 20 nm to 25 nm; and / or with a CDBP value of 50 to 96 cm3 / 100 g. More particularly, the invention relates to the following polymer compositions:
le) a polymer composition comprising carbon black with an iodine value of 50 to 85 mg / g; with an original particle size less than or equal to 25 nm; and with a CDBP value below or equal to 96 cm3 / 100 g;
2e) a polymer composition comprising carbon black with an iodine value of 55 to 80 mg / g; with an original particle size less than or equal to 25 nm; and with a CDBP value below or equal to 96 cm3 / 100 g;
3e) a polymer composition comprising carbon black with an iodine number of 60 to 78 mg / g; with an original particle size less than or equal to 25 nm; and with a CDBP value below or equal to 96 cm3 / 100 g;
4e) a polymer composition comprising carbon black with an iodine value of 50 to 85 mg / g; with an original particle size less than or equal to 25 nm; and with a CDBP value of 50 to 96 cm3 / 100 g;
5e) a polymer composition comprising carbon black with an iodine value of 55 to 80 mg / g; with an original particle size less than or equal to 25 nm; and with a CDBP value of 50 to 96 cm3 / 100 g;
6e) a polymer composition comprising carbon black with an iodine value of 60 to 78 mg / g; with an original particle size less than or equal to 25 nm; and with a CDBP value of 50 to 96 cm<sup>3</sup>/ 100 g;
7e) a polymer composition comprising carbon black with an iodine value of 50 to 85 mg / g; with an original particle size from above 20 to 25 nm; and with a CDBE value below or equal to 96 cm3 / 100 g;
8e) a polymer composition comprising carbon black with an iodine value of 55 to 80 mg / g; with an original particle size from above 20 to 25 nm; and with a CDBP value below or equal to 96 cm<sup>3</sup>/ 100 g;
9e) a polymer composition comprising carbon black with an iodine value of 60 to 78 mg / g; with an original particle size from above 20 nm to 25 nm; and with a CDBP value below or equal to 96 cm3 / 100 g;
10e) a polymer composition comprising carbon black with an iodine value of 50 to 85 mg / g; with an original particle size from above 20 to 25 nm; and with a CDBP value of 50 to 96 cm<sup>3</sup>/ 100 g;
Ile) a polymer composition comprising carbon black with an iodine value of 55 to 80 mg / g; with an original particle size from above 20 to 25 mm; and with a CDBP value of 50 to 96 cm<sup>3</sup>/ 100 g; and
12e) a polymer composition comprising carbon black with an iodine value of 60 to 78 mg / g; with an original particle size from above 20 to 25 nm; and with a CDBP value of 50 to 96 cm3 / 100 g.
While any amount of carbon black may be used in the polymer compositions of the invention to achieve end use, amounts of carbon black in the range of from about 0.5 to about 300 parts by weight for every 100 parts by weight of polymer may generally be used. However, it is preferred to use an amount of carbon black in the range of about 0.5 to about 100 parts by weight per 100 parts by weight of polymer, and it is particularly preferred to use a carbon black in the range of about 0.5 to 80 parts by weight per 100 parts by weight of polymer.
The polymer compositions may also contain other commonly used additives such as hardeners, hydrocarbon oils, accelerators, collagens, antioxidants and the like.
The term "polymer" as used herein refers to natural rubber, synthetic rubber, elastomer, plastomer and / or mixtures or mixtures thereof. Examples of polymers suitable for use in the polymer compositions of the invention are listed above.
The polymer compositions of the invention can be prepared by methods known in the art used to prepare mixtures of polymers with granular components.
The following test methods were used to determine and assess the analytical properties of carbon black and the properties of the carbon black polymer compositions of the invention.
The adsorption range of CTAB (cetyltrimethylammonium bromide) by carbon blacks was determined according to ASTM Test Procedure D3765-85.
Iodine number was determined according to ASTM Test Procedure D1510.
The staining strength ("staining") of the carbon black was determined according to ASTM Test Procedure D3265.
Adsorption of DBP (dibutyl phthalate) by carbon black tablets was determined according to ASTM Test Procedure D2414.
Adsorption of CDBP (dibutyl phthalate) by crushed carbon black tablets was determined according to ASTM Test Procedure D3493-86.
The amount of toluene extract from carbon black was determined using a Spectronic 20 spectrophotometer from Milton Roy, Rochester, New York, according to ASTM Test Procedure D1618.
Soot particle size was determined according to ASTM Test Procedure D3849-89.
The Dmode, Dst and AD50 values of the carbon black were determined based on the Stokes diameter histogram of the carbon black aggregates in the respective carbon black samples as a function of the relative frequency of their occurrence in this sample, as shown in Fig. 3. The histogram is performed for the so-called Stokes diameter of the carbon black aggregates as a function of the relative frequency their occurrence in a given sample.
For examples 1 to 14 and for examples 26 to 33, the data used to generate the histogram was determined using a disk centrifuge, such as a centrifuge manufactured by Joyce Loeble Co., Ltd. of Tyne and Wear, UK. The following procedure is a modification of the method described in the Joyce Loeble disc centrifuge manual, designated DCF 4.008, published on February 1, 1985, which is incorporated herein by reference; this method was used to obtain data.
The procedure is as follows. 10 mg of the carbon black sample was weighed into a weighing vessel, then it was introduced into a 50 cm3 solution consisting of 10% anhydrous ethanol and 90% distilled water and containing 0.05% surfactant NONIDET P-40 (NONIDET P-40 is a trademark of the agent Shell Chemical Co.).
The resulting suspension is dispersed by means of ultrasonic energy within 15 minutes using a Sonifier Model No. At 385, Heat Systems Ultrasonics Inc., Farmingdale, New York.
Before the disk centrifuge is working, the following data is entered into the computer, which records data from the disk centrifuge:
1. Soot specific gravity, taken as 1.86 g / cm3;
2. The volume of carbon black solution dispersed in a solution of water and ethanol; in this case it is 0.5 cm3;
3. The volume of fluid in the centrifuge; in this case it is 10 cm3 of water;
4. The fluid viscosity in the centrifuge, which in this case is taken as equal to 9.33 x 10<sup>4</sup> Pa -s at 23 ° C;
5. The fluid density in the centrifuge, which in this case is 0.9975 g / cm3 at 23 ° C;
6. Platter speed, which in this case is 8000 revolutions per minute;
7. The download interval, which in this case is 1 s.
The disc centrifuge works at a speed of 8000 revolutions per minute, with the strobe running. 10 cm3 of distilled water is injected into the rotating plate as a centrifugal fluid. The turbidity level is set to 0; 10 cm are injected as buffer liquid<sup>3 </sup>solution consisting of 10% anhydrous ethanol and 90% distilled water. The shear and spin plate spin up buttons are then activated to create a smooth concentration gradient between the centrifugal fluid and the buffering liquid and the gradient is visually observed. When the gradient becomes smooth so that you can no longer see the difference16
188 285 of the boundary between the two fluids, 0.5 cm3 of dispersed carbon black in an aqueous ethanol solution is injected into the centrifuge plate and data collection is immediately started. When there is flow, the work is interrupted. The plate rotates within 20 minutes of injecting the carbon black dispersed in an aqueous alcoholic solution. After 20 minutes of centrifugation, the centrifuge plate is stopped, the centrifugal fluid temperature is measured and the mean value of the centrifugal fluid temperature measured at the beginning of work and at the end of work is entered into a computer which records data from the disk centrifuge. These data are analyzed using the standard Stokes equation and presented using the following definitions.
Soot aggregate - a separate, rigid colloidal whole, which is the smallest dispersible unit; it consists of highly coagulated particles.
Stokes diameter - the diameter of the sphere that sediments in a viscous medium in a centrifuge or in a gravitational field according to the Stokes equation. A non-spherical object, such as a soot aggregate, can also be represented by the Stokes diameter if viewed as a smooth, rigid sphere with the same density and sedimentation rate as this object. The Stokes diameter is usually expressed in nanometers.
Fashion (given as Dmode) - Stokes diameter at the peak point (point A in Figure 3 in the description) of the Stokes diameter distribution curve.
Median Stokes diameter - (given as Dst) - a point on the Stokes diameter distribution curve at which 50% by weight of the sample is either larger or smaller (point H in Figure 3 herein). It therefore represents the median value of the assay. A non-spherical object, such as a soot aggregate, can also be represented by the Stokes diameter if viewed as a smooth, rigid sphere with the same density and sedimentation rate as this object.
AD50 - the width of the mass distribution graph measured at the point corresponding to half the maximum of the fashion, which is a measure of the width of the aggregate size distribution. It was determined as follows. As shown in Figure 3, line B is taken from peak A of the histogram in a direction parallel to the Y axis to the X axis and ending at that axis at point C of the histogram. The center point F of the resulting line B is determined and the line G passes through its center point F parallel to the X axis. The G line intersects the histogram distribution curve at two points D and E. The absolute value of the Stokes diameter difference of the soot aggregates at points D and E is the AD50 value.
In Examples 15 to 25, a Model BI-DCP disc centrifuge from Brookhaven Instruments Corp., 750 Blue Point Road, Holtsville, NY 11742, USA was used to generate the histograms described above. The following procedure was used.
mg of carbon black sample was weighed into a weighing dish, then introduced into 25 cm3 solution consisting of 10% anhydrous ethanol and 90% distilled water and containing 0.025% surfactant NONIDET P-40 (NONiDET P-40 is a trademark of surfactant Shell Chemical Co.). The resulting suspension is dispersed by means of ultrasonic energy within 10 minutes using a Sonifier Model No. XL 2015 from Heat Systems Ultrasonics Inc., Farmingdale, New York.
Before the disk centrifuge is working, the following data is entered into the computer, which records data from the disk centrifuge:
1. Soot specific gravity, taken as 1.86 g / cm3;
2. The volume of carbon black solution dispersed in a solution of water and ethanol; in this case it is 0.2 cm3;
3. The volume of fluid in the centrifuge; in this case it is 10 cm3 of water;
4. The fluid viscosity in the centrifuge, which in this case is taken as equal to 9.33 x 10<sup>4</sup> Pa -s at 23 ° C;
5. The fluid density in the centrifuge, which in this case is 0.998 g / cm<sup>3</sup> at a temperature of 23 ° C;
6. The platter speed, which in this case is 4000 rpm;
7. The download interval, which in this case is 1 s.
The disk centrifuge operates at a speed of 4000 rpm, with a strobe running. Inject 10 cm3 of the distilled water and sucrose mixture in which 1 cm3 of sucrose is used per 9 cm3 of water in a rotating plate as a centrifugal fluid. The turbidity level is set to 0; as a buffer liquid, 10 cm of a solution consisting of 10% anhydrous ethanol and 90% distilled water are injected. Next
188 285, the shear and spin-spin buttons are actuated to produce a smooth concentration gradient between the centrifugal fluid and the buffering liquid, and the gradient is visually observed. When the gradient becomes smooth so that you can no longer see the distinguishable border between the two liquids, a 0.2 cm centrifuge plate is injected<sup>3</sup> dispersed soot in a water-ethanolic solution and immediately starts collecting data. When there is flow, the work is interrupted. The plate spins for such a time as is required to return the detector response to the baseline after injection of the carbon black dispersed in the aqueous ethanol solution. After the centrifugation time, the centrifuge plate stops, measures the temperature of the centrifugal fluid and enters the average value of the temperature of the centrifugal fluid measured at the beginning of work and at the end of work to a computer that records data from the disk centrifuge.
Apparent viscosity and melt flow index measurements were made on polymer compositions prepared by incorporating carbon black samples into linear low density polyethylene (LLDPE) at 35% by mass of carbon black in the polymer mixture, except for those cases where other carbon black contents are given below. The following procedure was used to prepare a mixture of carbon black and a polymer containing 35% by mass of carbon black in the mixture. This procedure was also used when contents other than 35% by mass of carbon black were required, but only the relative amounts of carbon black and polymer were changed to the desired carbon black contents in the mixture.
Both 420.7 g of carbon black and 781.4 g of linear low density polyethylene (LLDPE) defined as DFDA7510 for carbon black of examples 1 to 14 and as gRSN7510 for carbon black of examples 26 to 33 were fed into a Banbury laboratory mixer Farrel with a mixing chamber of 1100 cm<sup>3</sup>. DFDA7510 and gRSN7510 polyethylenes are Union Carbide products. The initial temperature of the mixing step was 48.9 ° C and mixing was carried out for 3 minutes: the first 30 s at 77 rpm, the next 45 s at 116 rpm, and the remaining time at 155 rpm. After mixing, the product was formed on a two-roller mixer at 82.2 ° C with 0.0095 m thick boards. The panels were then cut into strips and passed through a belt granulator, turning them into cubes 0.0095 m long. The product was screened to select pieces of uniform shape for the next test.
Apparent viscosity was measured at 190 ° C using the ASTM D3835-93A procedure. For the carbonaceous polymer compositions of Examples 1 to 14, a Gottert Capillary Rheometer Model 1501 capillary rheometer with a 30 mm capillary and 1 mm diameter was used for these measurements. In the case of polymer compositions containing carbon blacks from Examples 26 to 33, a Monsanto Processability Tester apparatus with a 20 mm capillary and 1 mm diameter was used in these measurements.
In order to prepare samples for the measurement of the absorption coefficient (COA) ("COA" from "coefficient of absorption"), the above mixture of soot with LLDPE containing 35% by mass of soot was introduced into the Banbury mixer with such an additional amount of LLDPE to obtain a final mixture containing 2.5 % mass soot. The mixture from this step was then used for COA measurements. COA was measured using the ASTM D3349-86 procedure.
The melt flow index was measured according to the ASTM Test Procedure D1238-90 procedure, using a temperature of 190 ° C for the polymer compositions containing carbon blacks of examples 1 to 14 and a temperature of 230 ° C for the polymer compositions containing carbon black of examples 26 to 33 and load 21.5 kg in the following conditions:
<td>Flow range, g / 10 min</td><td>Proposed sample weight in the cylinder, g</td><td>Measurement period, min</td><td>Factor for obtaining the speed in g / l 0 min</td>
<td>> 1.0 to 3.5</td><td> 3,0-5,0</td><td> 3,00</td><td> 3,33</td>
<td>> 3.5 to 10</td><td> 5,0-8,0</td><td> 1,00</td><td> 10,00</td>
g = grams, min = minutes
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The correct mass of the carbon black polymer composition was weighed, introduced into a cylinder of a Keyness Model 2051 extrusion plastometer or equivalent and compacted. A piston loaded with 1100 g was introduced into the cylinder, the load was heated for 6 minutes at the test temperature. After the heating was completed, the weight applied during heating was removed from the piston and replaced with the weight used during the test of 21.5 g, obtaining the results given in Table 4. When the notch on the piston was hidden in the cylinder, the stamped part at the bottom of the die hole was cut off with a sharp spatula or knife and the measuring period started. At the end of the measurement period, the extrusion at the bottom of the die bore was cut off and weighed. This mass was recorded and replaced with the melt flow index measurement result, multiplied by the appropriate factor from the table above.
Mix moisture absorption (CMA) was measured on a mixture of carbon black and polymer prepared in a Brabender Plasticorder at 100 ° C, using 35.75 g of the above LLDPE polymer and 19.25 g of carbon black. After reaching the desired temperature, the rotors were turned on at a speed of 60 rpm and weighed amounts of polymer and soot were charged through the hopper over 30 s. A weight of 10,000 kg was applied to the piston of the hopper, causing the contents to melt. After melting, the load and funnel were removed. The rotor speed was set at 60 rpm, the Brabender piston was lowered and mixed for 5 minutes. After this time, the mix was removed and passed through a two-roller mixer twice. The resulting CMA plates were ground into smaller pieces using a belt granulator.
The CMA test was performed on the above carbon black and polymer mixture using the following procedure. The tested mix, after grinding it on a belt granulator, as mentioned in the previous paragraph, was sieved through sieves with a mesh size of 4.699 mm and 1.651 mm and the fraction -4, +10 was left for testing. The Wiley Mili machine with a 4 mm screen, model # 3 or equivalent was switched on and about 25 g of screened mix was introduced. The granulated mix was collected and stored in a sealed, labeled jar. The clean, dry weighing bottle and its lid were weighed on an Ainsworth Model 10 or equivalent analytical balance and the weight recorded to the fourth decimal place. 2.0 ± 0.1 g of the granulated mix was placed in this weighing bottle. The weighing bottle with the lid ajar was placed in a vacuum dryer, its door closed and the dryer and vacuum turned on. A temperature of 60 ° C was set and the pressure was reduced to 33.9 kPa. The sample was left in the dryer for at least 2 hours and a maximum of 16 hours. The Blue M Model FR-251B-1 or equivalent humidity chamber was set at 26.7 ° C and 83% relative humidity. After drying the sample, the vacuum was turned off, the vacuum was released, the door was quickly opened and the lid was placed on the weighing vessel without directly touching the lid with his hands; for this purpose gloves or pliers were used. The weighing bottle was then placed in a humidity chamber. If more than one weighing cell was used at the same time, a distance of at least 50 mm was left between the chamber walls and each weighing cell, each weighing cell being at least 12.7 mm from another weighing cell. The vessel was uncovered and the lid was left ajar. The chamber internal door was closed tightly. Then the outer door was also closed. The cell was left in a humidity chamber for 7 days at the above temperature and relative humidity.
After the specified residence time in the humidity chamber, the door was opened and the vessel closed tightly with a lid. The vessel was placed back into the desiccant containing plastic container; only gloves or forceps were used when handling the dish. Each covered dish was weighed on an analytical balance. cMa was calculated based on the weight increase of the sample.
The properties and advantages of the carbon black and polymer compositions of the invention are further illustrated in the following examples.
Examples 1-33
In the reactor generally described herein and shown in Figs. 1 or 2 (as set out below), 33 carbon blacks were made using the reactor conditions and geometry given in Table 2. The carbon blacks produced in Examples 3-10 are furnace carbon black, and the carbon black made in Examples 1 and 2 are
188 285 reference cages. The carbon blacks produced in Examples 12-14 are also furnace carbon black, and the carbon black produced in Example 11 is comparative carbon black. The carbon blacks produced in Examples 15-25 are reference carbon blacks. The carbon blacks produced in Examples 26-29 are furnace carbon blacks, and the carbon black produced in Examples 30-33 are suitable reference carbon blacks.
The fuel used in the combustion reaction was natural gas. Typical properties of the type of liquid raw material used in Examples 1-14 are given in Table 1. The properties of the liquid raw material used in Examples 15-33 are given in Table 1A.
Table 1 Examples 1-14
<td>Hydrogen (% by weight)</td><td> 7,2</td>
<td>Coal (% by weight)</td><td> 91,6</td>
<td>H / C ratio</td><td> 0,94</td>
<td>Specific gravity API 15.6 / 15.6 ° C</td><td> -2,7</td>
<td>BMCI (Viscosity - specific gravity)</td><td> 143</td>
<td>Air to oil ratio (m<sup>3</sup> air / m<sup>3</sup> oil)</td><td> 10900,4</td>
<td>Specific weight</td><td> 1,10</td>
Table 1A Examples 15-33
<td>Properties marked for examples</td><td> 15-25</td><td> 26,30</td><td> 27-29, 31-33</td>
<td>Hydrogen (% by weight)</td><td> 7,2</td><td> 7,0</td><td> 7,1</td>
<td>Coal (% by weight)</td><td> 91,5</td><td> 91,1</td><td> 91,4</td>
<td>H / C ratio</td><td> 0,94</td><td> 0,91</td><td> 0,93</td>
<td>Specific gravity API 15.6 / 15.6 ° C</td><td>NM</td><td> -3,1</td><td> -2,9</td>
<td>BMCI (Viscosity - specific gravity)</td><td>NM</td><td> 137</td><td> 136</td>
<td>Air-to-oil ratio (m3 air / m3 oil)</td><td> 11126,9</td><td> 10999,5</td><td> 11070,3</td>
<td>Specific weight</td><td> 1,105</td><td> 1,102</td><td> 1,10</td>
NM means that this property has not been determined
The operating conditions and geometry of the reactor used in each of the examples are given in Table 2 below. In examples 16-18, each hole used to inject the raw material was equipped with shielding inserts. In examples 19 and 20, the raw material was injected into the process essentially axially in the direction of flow through a pressurized oil spray tip, 0.00229 m in diameter, protruding from the end 34 of probe 15, retracted about 0.02 m from the center of the second stage of the process. The spray tip was a Monarch spray tip F-94-120-45, manufactured by Monarch Manufacturing (Philadelphia, PA, United States of America).
188 285
Table 2
<td>Example</td><td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td>
<td>Figure</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td>
<td>D-1, township</td><td> 0/51</td><td> 0,51</td><td> 0,51</td><td> 0,51</td><td> 0,51</td>
<td>D-2, town</td><td> 0,31</td><td> 0,31</td><td> 0,31</td><td> 0,31</td><td> 0,31</td>
<td>D-3A, township</td><td> 0,46</td><td> 0,46</td><td> 0,46</td><td> 0,46</td><td> 0,46</td>
<td>D-3B, m</td><td> 0,46</td><td> 0,46</td><td> 0,46</td><td> 0,46</td><td> 0,46</td>
<td>D-4, township</td><td> 1/14</td><td> 1,14</td><td> 1,14</td><td> 1,14</td><td> 1,14</td>
<td>D- 4A, town</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>D-4B, township</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>D-4C, m</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>L-1, m</td><td> 0,30</td><td> 0,30</td><td> 0,30</td><td> 0,30</td><td> 0,30</td>
<td>L-2, m</td><td> 0,74</td><td> 0,74</td><td> 0,74</td><td> 0/74</td><td> 0,74</td>
<td>L-3, m</td><td> 0,30</td><td> 0,30</td><td> 0,30</td><td> 0,30</td><td> 0,30</td>
<td>L-4A, m</td><td> 0,23</td><td> 0,23</td><td> 0,23</td><td> 0,23</td><td> 0,23</td>
<td>L-4B, m</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td>
<td>L-5A, m</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>L-5B, m</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>L-5C, m</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>F-1, m</td><td> 0,15</td><td> 0,15</td><td> 0,15</td><td> 0,15</td><td> 0,15</td>
<td>F-2, m</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>Q, m</td><td> 4,57</td><td> 4,57</td><td> 4,57</td><td> 4,57</td><td> 4,57</td>
<td>Ω deg.</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
m is a meter; nr is the number; deg. means degrees; Tip (s) 32.34 means points 32 or 34 in Figures 1 and 2, cm means centimeter, Comb means burning, kPa means kilopascals; SCMS stands for normal cubic meters per second (0 ° C, 101.3 kPa); K + means potassium; g means grams; Temp. is the temperature; s means seconds; Q is the reaction interruption point; E (x) means power (10<sup>x</sup>); NA means not applicable
Table 2 (continued)
<td>Example</td><td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td>
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td>
<td>Figure</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td>
<td>Oil injection tips 33 (No. x dimension, cm)</td><td>12x0,198</td><td>12x0,198</td><td>12x0,211</td><td>12x0,211</td><td>12x0,211</td>
<td>Oil speed, m3 / s</td><td>1.27-03</td><td>l, 27E-03</td><td>1.28-03</td><td>l, 38E-03</td><td>1.36-03</td>
<td>Oil preheat temperature, ° C</td><td> 205</td><td> 205</td><td> 205</td><td> 205</td><td> 205</td>
<td>Oil pressure, kPa</td><td> 1741</td><td> 1834</td><td> 1535</td><td> 1762</td><td> 1721</td>
<td>Combustion air, m3 / s</td><td> 4,019</td><td> 4,019</td><td> 4,019</td><td> 4,019</td><td> 4,019</td>
188 285 table continues
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td>
<td>Combustion air, preheat temperature, ° C</td><td> 649</td><td> 649</td><td> 649</td><td> 649</td><td> 649</td>
<td>Natural gas, m3 / s</td><td> 0,060</td><td> 0,060</td><td> 0,042</td><td> 0,060</td><td> 0,060</td>
<td>Air to fuel oil ratio</td><td> 9,7</td><td> 9,7</td><td> 9,7</td><td> 9,7</td><td> 9,7</td>
<td>Air / gas m3 / s / m3 / s</td><td> 67,5</td><td> 67,5</td><td> 96,4</td><td> 67,5</td><td> 67,5</td>
<td>Primary combustion level,%</td><td> 696</td><td> 696</td><td> 994</td><td> 696</td><td> 696</td>
<td>Total combustion level,%</td><td> 27,9</td><td> 27,9</td><td> 27,9</td><td> 25,7</td><td> 26,0</td>
<td>K<sup>+</sup>, g K<sup>+</sup>/ m<sup>3</sup> oil</td><td> 11,04</td><td> 8,35</td><td> 10,91</td><td> 11,12</td><td> 10,25</td>
<td>Residence time, p</td><td> 1,06</td><td> 1,06</td><td> 1,06</td><td> 1,06</td><td> 1,06</td>
<td>Temperature in Q, ° C</td><td> 705</td><td> 745</td><td> 709</td><td> 714</td><td> 719</td>
<td>Pressure at the interruption point, kPa</td><td> 735</td><td> 708</td><td> 708</td><td> 694</td><td> 708</td>
m is a meter; nr is the number; deg. means degrees; Tip (s) 32.34 means points 32 or 34 in Figures 1 and 2, cm means centimeter, Comb means burning, kPa means kilopascals; K + means potassium; g means grams; Temp. is the temperature; s means seconds; Q is the reaction interruption point; E (x) is the power of (10 *); NA means not applicable
Table 2 (continued)
<td>Example</td><td> 6</td><td> 7</td><td> 8</td><td> 9</td><td> 10</td>
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td>
<td>Figure</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td>
<td>D-1, township</td><td> 0,51</td><td> 0,51</td><td> 0,51</td><td> 0,51</td><td> 0,51</td>
<td>D-2, town</td><td> 0,31</td><td> 0,31</td><td> 0,31</td><td> 0,31</td><td> 0,31</td>
<td>D-3A, township</td><td> 0,46</td><td> 0,46</td><td> 0,46</td><td> 0,46</td><td> 0,46</td>
<td>D-3B, m</td><td> 0,46</td><td> 0,46</td><td> 0,46</td><td> 0,46</td><td> 0,46</td>
<td>D-4, township</td><td> 1,14</td><td> 1,14</td><td> 1,14</td><td> 1,14</td><td> 1,14</td>
<td>D-4A, township</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>D-4B, township</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>D-4C, m</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>L-1, m</td><td> 0,30</td><td> 0,30</td><td> 0,30</td><td> 0,30</td><td> 0,30</td>
<td>L-2, m</td><td> 0,74</td><td> 0,74</td><td> 0,74</td><td> 0,74</td><td> 0,74</td>
<td>L-3, m</td><td> 0,30</td><td> 0,30</td><td> 0,30</td><td> 0,30</td><td> 0,30</td>
<td>L-4A, m</td><td> 0,23</td><td> 0,23</td><td> 0,23</td><td> 0,23</td><td> 0,23</td>
<td>L-4B, m</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td>
<td>L-5A, m</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>L-5B, m</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
188 285 table continues
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td>
<td>L-5C, m</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>F-1, m</td><td> 0,15</td><td> 0,15</td><td> 0,15</td><td> 0,15</td><td> 0,15</td>
<td>F-2, m</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>Q, m</td><td> 24,38</td><td> 24,38</td><td> 13,72</td><td> 13,72</td><td> 4,57</td>
<td>Ω deg</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
Table 2 (continued)
<td>Example</td><td> 6</td><td> 7</td><td> 8</td><td> 9</td><td> 10</td>
<td>Figure</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td>
<td>Oil injection tips 33 (No. x dimension, cm)</td><td>12x0,211</td><td>12x0,218</td><td>12x0,211</td><td>12x0,218</td><td>12x0,218</td>
<td>Oil speed, m3 / s</td><td>l, 36E-03</td><td>1.38-03</td><td>l, 36E-03</td><td>1.38-03</td><td>1.38-03</td>
<td>Oil preheat temperature, ° C</td><td> 205</td><td> 205</td><td> 205</td><td> 205</td><td> 205</td>
<td>Oil pressure, kPa</td><td> 1714</td><td> 1445</td><td> 1707</td><td> 1452</td><td> 1452</td>
<td>Combustion air, m3 / s</td><td> 4,019</td><td> 4,019</td><td> 4,019</td><td> 4,019</td><td> 4,019</td>
<td>Combustion air, preheat temperature, ° C</td><td> 649</td><td> 649</td><td> 649</td><td> 649</td><td> 649</td>
<td>Natural gas, m3 / s</td><td> 0,060</td><td> 0,042</td><td> 0,060</td><td> 0,042</td><td> 0,042</td>
<td>Air-to- oil ratio</td><td> 9,7</td><td> 9,7</td><td> 9,7</td><td> 9,7</td><td> 9,7</td>
<td>Air / gas m<sup>3</sup>/ S / m 3 / s</td><td> 67,5</td><td> 96,4</td><td> 67,5</td><td> 96,4</td><td> 96,4</td>
<td>Primary combustion level,%</td><td> 696</td><td> 694</td><td> 996</td><td> 694</td><td> 694</td>
<td>Total combustion level,%</td><td> 26,0</td><td> 26,0</td><td> 26,0</td><td> 26,0</td><td> 26,0</td>
<td>K +, g K<sup>+</sup>/ m<sup>3</sup> oil</td><td> 10,25</td><td> 9,01</td><td> 6,84</td><td> 6,76</td><td> 6,76</td>
<td>Residence time, p</td><td> 5,85</td><td> 5,85</td><td> 3,27</td><td> 3,27</td><td> 1,06</td>
<td>Temperature in Q, ° C</td><td> 730</td><td> 742</td><td> 742</td><td> 747</td><td> 745</td>
<td>Air to fuel oil ratio</td><td> 9,7</td><td> 9,7</td><td> 9,7</td><td> 9,7</td><td> 9,7</td>
<td>Pressure at the interruption point, kPa</td><td> 722</td><td> 749</td><td> 694</td><td> 673</td><td> 708</td>
Table 2 (continued)
<td>Example</td><td> 11</td><td> 12</td><td> 13</td><td> 14</td>
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td>
<td>Figure</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td>
<td>D-1, township</td><td> 0,51</td><td> 0,51</td><td> 0,51</td><td> 0,51</td>
<td>D-2, town</td><td> 0,31</td><td> 0,31</td><td> 0,31</td><td> 0,31</td>
<td>D-3A, township</td><td> 0,46</td><td> 0,46</td><td> 0,46</td><td> 0,46</td>
<td>D-3B, m</td><td> 0,46</td><td> 0,46</td><td> 0,46</td><td> 0,46</td>
188 285 table continues
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td>
<td>D-4, township</td><td> 1,14</td><td> 1,14</td><td> 1,14</td><td> 1,14</td>
<td>D-4A, township</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>D-4B, township</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>D-4C, m</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>L-1, m</td><td> 0,30</td><td> 0,30</td><td> 0,30</td><td> 0,30</td>
<td>L-2, m</td><td> 0,74</td><td> 0,74</td><td> 0,74</td><td> 0,74</td>
<td>L-3, m</td><td> 0,30</td><td> 0,30</td><td> 0,30</td><td> 0,30</td>
<td>L-4A, m</td><td> 0,23</td><td> 0,23</td><td> 0,23</td><td> 0,23</td>
<td>L-4B, m</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td>
<td>L-5A, m</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>L-5B, m</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>L-5C, m</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>F-1, m</td><td> 0,15</td><td> 0,15</td><td> 0,15</td><td> 0,15</td>
<td>F-2, m</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>Q, m</td><td> 24,38</td><td> 24,38</td><td> 13,72</td><td> 13,72</td>
<td>Ω deg</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
Table 2 (continued)
<td>Example</td><td> 11</td><td> 12</td><td> 13</td><td> 14</td>
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td>
<td>Figure</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td>
<td>Oil injection tips 33 (No. x dimension, cm)</td><td>12x0,198</td><td>12x0,218</td><td>12x0,218</td><td>12x0,218</td>
<td>Oil speed, m3 / s</td><td>1.28-03</td><td>l, 32E-03</td><td>1.31-03</td><td>1.32-03</td>
<td>Oil preheat temperature, ° C</td><td> 205</td><td> 205</td><td> 205</td><td> 205</td>
<td>Oil pressure, kPa</td><td> 1686</td><td> 1293</td><td> 1287</td><td> 1293</td>
<td>Combustion air, m<sup>3</sup>/ s</td><td> 4,019</td><td> 4,019</td><td> 4,019</td><td> 4,019</td>
<td>Combustion air, preheat temperature, ° C</td><td> 649</td><td> 649</td><td> 649</td><td> 649</td>
<td>Natural gas, m3 / s</td><td> 0,060</td><td> 0,042</td><td> 0,045</td><td> 0,042</td>
<td>Air to fuel oil ratio</td><td> 9,7</td><td> 9,7</td><td> 9,7</td><td> 9,7</td>
<td>Air / gas m3 / s / m3 / s</td><td> 67,5</td><td> 96,4</td><td> 88,5</td><td> 96,4</td>
<td>Primary combustion level,%</td><td> 696</td><td> 694</td><td> 913</td><td> 994</td>
<td>Total combustion level,%</td><td> 27,6</td><td> 27,1</td><td> 27,2</td><td> 27,1</td>
188 285 table continues
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td>
<td>K +, g K<sup>+</sup>/ m3 oil</td><td> 10,67</td><td> 6,58</td><td> 6,87</td><td> 6,58</td>
<td>Residence time, p</td><td> 3,27</td><td> 6,58</td><td> 5,85</td><td> 4,37</td>
<td>Temperature in Q, ° C</td><td> 816</td><td> 816</td><td> 805</td><td> 813</td>
<td>Pressure at the interruption point, kPa</td><td> 749</td><td> 701</td><td> 735</td><td> 728</td>
Table 2 (continued)
<td>Example</td><td> 15</td><td> 16</td><td> 17</td><td> 18</td><td> 19</td>
<td>Figure</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td>
<td>D-1, township</td><td> 0,13</td><td> 0,13</td><td> 0,13</td><td> 0,13</td><td> 0,13</td>
<td>D-2, town</td><td> 0,25</td><td> 0,25</td><td> 0,25</td><td> 0,25</td><td> 0,25</td>
<td>D-3A, township</td><td> 0,69</td><td> 0,69</td><td> 0,69</td><td> 0,69</td><td> 0,69</td>
<td>D-3B, m</td><td>ON</td><td> 0,69</td><td> 0,69</td><td> 0,69</td><td> 0,69</td>
<td>D-4, township</td><td> 0,91</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>D-4A, township</td><td> 0,86</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>D-4B, township</td><td> 0,91</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>D-4C, m</td><td> 0,61</td><td> 0,61</td><td> 0,61</td><td> 0,61</td><td> 0,61</td>
<td>L-1, m</td><td> 0,30</td><td> 0,30</td><td> 0,30</td><td> 0,30</td><td> 0,30</td>
<td>L-2, m</td><td> 0,22</td><td> 0,22</td><td> 0,22</td><td> 0,22</td><td> 0,22</td>
<td>L-3, m</td><td> 0,25</td><td> 0,25</td><td> 0,25</td><td> 0,25</td><td> 0,25</td>
<td>L-4A, m</td><td> 0,09</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td>
<td>L-4B, m</td><td> 4,80</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>L-5A, m</td><td> 0,15</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>L-5B, m</td><td> 0,46</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>L-5C, m</td><td> 0,11</td><td> 0,11</td><td> 0,11</td><td> 0,11</td><td> 0,11</td>
<td>F-1, m</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>F-2, m</td><td> 7,71</td><td> 8,02</td><td> 8,02</td><td> 8,02</td><td> 8,02</td>
<td>Q, m</td><td> 31,5</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>Ω deg</td><td> 0,13</td><td> 0,13</td><td> 0,13</td><td> 0,13</td><td> 0,13</td>
188 285
Table 2 (continued)
<td>Example</td><td> 15</td><td> 16</td><td> 17</td><td> 18</td><td> 19</td>
<td>Figure</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td>
<td>Oil injection tips 33 (No. x dimension, cm)</td><td>12x0,206</td><td>12x0,079</td><td>12x0,079</td><td>12 x 0.079</td><td>12x0,229 (Tip 34)</td>
<td>Oil speed, m3 / s</td><td>1.36-04</td><td>l, 29E-04</td><td>1.38-04</td><td>l, 48E-04</td><td>1.34-04</td>
<td>Oil preheat temperature, ° C</td><td> 127</td><td> 129</td><td> 125</td><td> 126</td><td> 130</td>
<td>Oil pressure, kPa</td><td> 253</td><td> 3402</td><td> 3836</td><td> 4394</td><td> 1604</td>
<td>Combustion air, m3 / s</td><td> 0,447</td><td> 0,447</td><td> 0,447</td><td> 0,447</td><td> 0,447</td>
<td>Combustion air, preheat temperature, ° C</td><td> 482</td><td> 482</td><td> 482</td><td> 482</td><td> 482</td>
<td>Natural gas, m<sup>3</sup>/ s</td><td> 0,014</td><td> 0,011</td><td> 0,011</td><td> 0,012</td><td> 0,011</td>
<td>Air to fuel oil ratio</td><td> 9,68</td><td> 9,68</td><td> 9,68</td><td> 9,68</td><td> 9,68</td>
<td>Air / gas m3 / s / m<sup>3</sup>/ s</td><td> 31,9</td><td> 39,2</td><td> 39,2</td><td> 38,5</td><td> 39,0</td>
<td>Primary combustion level,%</td><td> 330</td><td> 405</td><td> 405</td><td> 397</td><td> 402</td>
<td>Total combustion level,%</td><td> 27,2</td><td> 28,7</td><td> 27,2</td><td> 25,4</td><td> 27,9</td>
<td>K +, g K + / m3 oil</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td>
<td>Residence time, p</td><td> 10,39</td><td> 6,31</td><td> 6,31</td><td> 6,31</td><td> 6,31</td>
<td>Temperature in Q, ° C</td><td> 732</td><td> 732</td><td> 732</td><td> 732</td><td> 732</td>
<td>Pressure at the interruption point, kPa</td><td> 542</td><td> 704</td><td> 715</td><td> 722</td><td> 784</td>
Table 2 (continued)
<td>Example</td><td> 20</td><td> 21</td><td> 22</td><td> 23</td><td> 24</td>
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td>
<td>Figure</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td>
<td>D-1, township</td><td> 0,18</td><td> 0,18</td><td> 0,18</td><td> 0,18</td><td> 0,18</td>
<td>D-2, town</td><td> 0,13</td><td> 0,13</td><td> 0,13</td><td> 0,13</td><td> 0,13</td>
<td>D-3A, township</td><td> 0,25</td><td> 0,25</td><td> 0,25</td><td> 0,25</td><td> 0,27</td>
<td>D-3B, m</td><td> 0,69</td><td> 0,69</td><td> 0,69</td><td> 0,69</td><td> 0,27</td>
<td>D-4, township</td><td> 0,69</td><td> 0,69</td><td> 0,69</td><td> 0,69</td><td> 0,69</td>
<td>D-4A, township</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>D-4B, township</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>D-4C, m</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>L-1, m</td><td> 0,61</td><td> 0,61</td><td> 0,61</td><td> 0,61</td><td> 0,61</td>
<td>L-2, m</td><td> 0,30</td><td> 0,30</td><td> 0,30</td><td> 0,30</td><td> 0,30</td>
188 285 table continues
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td>
<td>L-3, m</td><td> 0,22</td><td> 0,22</td><td> 0,22</td><td> 0,22</td><td> 0,22</td>
<td>L-4A, m</td><td> 0,25</td><td> 0,25</td><td> 0,25</td><td> 0,25</td><td> 1,60</td>
<td>L-4B, m</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td>
<td>L-5A, m</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>L-5B, m</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>L-5C, m</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>F-1, m</td><td> 0,11</td><td> 0,11</td><td> 0,11</td><td> 0,11</td><td> 0,11</td>
<td>F-2, m</td><td> 0,13</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>Q, m</td><td> 8,02</td><td> 8,02</td><td> 8,02</td><td> 8,02</td><td> 1,77</td>
<td>Ω deg</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
Table 2 (continued)
<td>Example</td><td> 20</td><td> 21</td><td> 22</td><td> 23</td><td> 24</td>
<td>Figure</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td>
<td>Oil injection tips 33 (No. x dimension, cm)</td><td>12x0,229 (Tip 34)</td><td>12x0,206</td><td>12x0,206</td><td>12x0,206</td><td>12x0,140</td>
<td>Oil speed, m<sup>3</sup>/ s</td><td>l, 40E-04</td><td>l, 90E-04</td><td>1.77-04</td><td>l, 86E-04</td><td>2.08-04</td>
<td>Oil preheat temperature, ° C</td><td> 128</td><td> 127</td><td> 131</td><td> 131</td><td> 129</td>
<td>Oil pressure, kPa</td><td> 1769</td><td> 349</td><td> 3298</td><td> 342</td><td> 1583</td>
<td>Combustion air, m<sup>3</sup>/ s</td><td> 0,447</td><td> 0,633</td><td> 0,633</td><td> 0,633</td><td> 0,744</td>
<td>Combustion air, preheat temperature, ° C</td><td> 482</td><td> 482</td><td> 482</td><td> 482</td><td> 482</td>
<td>Natural gas, m3 / s</td><td> 0,012</td><td> 0,016</td><td> 0,016</td><td> 0,01</td><td> 0,022</td>
<td>Air to fuel oil ratio</td><td> 9,68</td><td> 9,68</td><td> 9,68</td><td> 9,68</td><td> 9,68</td>
<td>Air / gas m3 / s / m3 / s</td><td> 38,2</td><td> 38,5</td><td> 38,5</td><td> 68,0</td><td> 34,7</td>
<td>Primary combustion level,%</td><td> 395</td><td> 397</td><td> 397</td><td> 702</td><td> 359</td>
<td>Total combustion level,%</td><td> 26,7</td><td> 27,8</td><td> 29,8</td><td> 29,3</td><td> 29,4</td>
<td>K + g K<sup>+</sup>/ m3 oil</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 2,96</td>
<td>Residence time, p</td><td> 6,31</td><td> 4,45</td><td> 4,45</td><td> 4,45</td><td> 0,14</td>
<td>Temperature in Q, ° C</td><td> 732</td><td> 732</td><td> 732</td><td> 732</td><td> 732</td>
<td>Pressure at the interruption point, kPa</td><td> 749</td><td> 391</td><td> 405</td><td> 411</td><td> 804</td>
188 285
Table 2 (continued)
<td>Example</td><td> 25</td><td> 26</td><td> 27</td><td> 28</td><td> 29</td>
<td>Figure</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 2</td>
<td>D-1, township</td><td> 0,18</td><td> 0,18</td><td> 0,18</td><td> 0,18</td><td> 0,18</td>
<td>D-2, town</td><td> 0,13</td><td> 0,16</td><td> 0,16</td><td> 0,16</td><td> 0,16</td>
<td>D-3A, township</td><td> 0,27</td><td> 0,19</td><td> 0,19</td><td> 0,19</td><td> 0,19</td>
<td>D-3B, m</td><td> 0,27</td><td> 0,19</td><td> 0,19</td><td> 0,19</td><td> 0,69</td>
<td>D-4, township</td><td> 0,34</td><td> 0,69</td><td> 0,69</td><td> 0,69</td><td>ON</td>
<td>D-4A, township</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td><td> 0,91</td>
<td>D-4B, township</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td><td> 0,86</td>
<td>D-4C, m</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td><td> 0,91</td>
<td>L-1, m</td><td> 0,61</td><td> 0,61</td><td> 0,61</td><td> 0,61</td><td> 0,61</td>
<td>L-2, m</td><td> 0,30</td><td> 0,30</td><td> 0,30</td><td> 0,30</td><td> 0,30</td>
<td>L-3, m</td><td> 0,22</td><td> 0,22</td><td> 0,22</td><td> 0,22</td><td> 0,22</td>
<td>L-4A, m</td><td> 1,60</td><td> 0,13</td><td> 0,13</td><td> 0,13</td><td> 0,13</td>
<td>L-4B, m</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 3,54</td>
<td>L-5A, m</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td><td> 1,60</td>
<td>L-5B, m</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td><td> 0,15</td>
<td>L-5C, m</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td><td> 0,46</td>
<td>F-1, m</td><td> 0,11</td><td> 0,11</td><td> 0,11</td><td> 0,11</td><td> 0,11</td>
<td>F-2, m</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>Q, m</td><td> 3,05</td><td> 3,29</td><td> 3,29</td><td> 3,29</td><td> 9,30</td>
<td>Ω deg</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td><td> 31,5</td>
Table 2 (continued)
<td>Example</td><td> 25</td><td> 26</td><td> 27</td><td> 28</td><td> 29</td>
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td>
<td>Figure</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 2</td>
<td>Oil injection tips 33 (No. x dimension, cm)</td><td>1 x 0.118</td><td>9x0,140</td><td>9x0,140</td><td>9x0140</td><td>9x0140</td>
<td>Oil speed, m<sup>3</sup>/ s</td><td>2.00E-04</td><td>l, 98E-04</td><td>1.98-04</td><td>l, 98E-04</td><td>l, 98E-04</td>
<td>Oil preheat temperature, ° C</td><td> 114</td><td> 136</td><td> 144</td><td> 161</td><td> 163</td>
<td>Oil pressure, kPa</td><td> 2334</td><td> 384</td><td> 384</td><td> 377</td><td> 384</td>
<td>Combustion air, m3 / s</td><td> 0,744</td><td> 0,595</td><td> 0,595</td><td> 0,595</td><td> 0,595</td>
188 285 table continues
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td>
<td>Combustion air, preheat temperature, ° C</td><td> 482</td><td> 482</td><td> 482</td><td> 482</td><td> 482</td>
<td>Natural gas, mTs</td><td> 0,0041</td><td> 0,009</td><td> 0,009</td><td> 0,009</td><td> 0,009</td>
<td>Air to fuel oil ratio</td><td> 9,68</td><td> 9,64</td><td> 9,31</td><td> 9,61</td><td> 9,64</td>
<td>Air / gas m3 / s / m3 / s</td><td> 18,1</td><td> 67,8</td><td> 67,2</td><td> 67,2</td><td> 67,8</td>
<td>Primary combustion level,%</td><td> 187</td><td> 703</td><td> 722</td><td> 700</td><td> 703</td>
<td>Total combustion level,%</td><td> 28,4</td><td> 26,4</td><td> 26,2</td><td> 26,2</td><td> 26,2</td>
<td>K +, g K + / m<sup>3</sup> oil</td><td> 0</td><td> 1,35</td><td> 186,24</td><td> 187,13</td><td> 187,13</td>
<td>Residence time, p</td><td> 0,29</td><td> 1,86</td><td> 1,86</td><td> 1,86</td><td> 8,01</td>
<td>Temperature in Q, ° C</td><td> 732</td><td> 732</td><td> 732</td><td> 732</td><td> 732</td>
<td>Pressure at the interruption point, kPa</td><td> 708</td><td> 425</td><td> 446</td><td> 460</td><td> 329</td>
Table 2 (continued)
<td>Example</td><td> 30</td><td> 31</td><td> 32</td><td> 33</td>
<td>Figure</td><td> 2</td><td> 1</td><td> 2</td><td> 1</td>
<td>D-1, township</td><td> 0,18</td><td> 0,18</td><td> 0,18</td><td> 0,18</td>
<td>D-2, town</td><td> 0,16</td><td> 0,16</td><td> 0,16</td><td> 0,16</td>
<td>D-3A, township</td><td> 0,19</td><td> 0,19</td><td> 0,19</td><td> 0,19</td>
<td>D-3B, m</td><td> 0,69</td><td> 0,19</td><td> 0,69</td><td> 0,19</td>
<td>D-4, township</td><td>ON</td><td> 0,69</td><td>ON</td><td> 0,69</td>
<td>D-4A, township</td><td> 0,91</td><td>ON</td><td> 0,91</td><td>ON</td>
<td>D-4B, township</td><td> 0,86</td><td>ON</td><td> 0,86</td><td>ON</td>
<td>D-4C, m</td><td> 0,91</td><td>ON</td><td> 0,91</td><td>ON</td>
<td>L-1, m</td><td> 0,61</td><td> 0,61</td><td> 0,61</td><td> 0,61</td>
<td>L-2, m</td><td> 0,30</td><td> 0,30</td><td> 0,30</td><td> 0,30</td>
<td>L-3, m</td><td> 0,22</td><td> 0,22</td><td> 0,22</td><td> 0,22</td>
<td>L-4A, m</td><td> 0,13</td><td> 0,13</td><td> 0,13</td><td> 0,13</td>
<td>L-4B, m</td><td> 3,54</td><td> 0</td><td> 3,54</td><td> 0</td>
<td>L-5A, m</td><td> 1,60</td><td>ON</td><td> 1,60</td><td>ON</td>
<td>L-5B, m</td><td> 0,15</td><td>ON</td><td> 0,15</td><td>ON</td>
<td>L-5C, m</td><td> 0,46</td><td>ON</td><td> 0,46</td><td>ON</td>
<td>F-1, m</td><td> 0,11</td><td> 0,11</td><td> 0,11</td><td> 0,11</td>
<td>F-2, m</td><td>ON</td><td>ON</td><td>ON</td><td>ON</td>
<td>Q, m</td><td> 9,30</td><td> 3,29</td><td> 9,30</td><td> 3,29</td>
<td>Ω deg</td><td> 31,5</td><td>ON</td><td> 31,5</td><td>ON</td>
188 285
Table 2 (continued)
<td>Example</td><td> 30</td><td> 31</td><td> 32</td><td> 33</td>
<td>Figure</td><td> 2</td><td> 1</td><td> 2</td><td> 1</td>
<td>Oil injection tips 33 (No. x dimension, cm)</td><td>9 x 0.097</td><td>9 x 0.097</td><td>9 x 0.097</td><td>9 x 0.097</td>
<td>Oil speed, m<sup>3</sup>/ s</td><td>1.69-04</td><td>l, 70E-04</td><td>1.70-04</td><td>1.70-04</td>
<td>Oil preheat temperature, ° C</td><td> 155</td><td> 161</td><td> 159</td><td> 176</td>
<td>Oil pressure, kPa</td><td> 942</td><td> 963</td><td> 908</td><td> 921</td>
<td>Combustion air, m<sup>3</sup>/ s</td><td> 0,595</td><td> 0,595</td><td> 0,595</td><td> 0,595</td>
<td>Combustion air, preheat temperature, ° C</td><td> 482</td><td> 482</td><td> 482</td><td> 482</td>
<td>Natural gas, m3 / s</td><td> 0,042</td><td> 0,042</td><td> 0,042</td><td> 0,039</td>
<td>Air to fuel oil ratio</td><td> 9,35</td><td> 9,35</td><td> 9,32</td><td> 10,30</td>
<td>Air / gas m3 / s / m3 / s</td><td> 14,0</td><td> 14,1</td><td> 14,0</td><td> 15,1</td>
<td>Primary combustion level,%</td><td> 150</td><td> 151</td><td> 150</td><td> 146</td>
<td>Total combustion level,%</td><td> 26,3</td><td> 26,2</td><td> 26,1</td><td> 26,0</td>
<td>K + g K + / m3 oil</td><td> 188,75</td><td> 188,53</td><td> 188,16</td><td> 188,16</td>
<td>Residence time, p</td><td> 8,01</td><td> 1,86</td><td> 8,01</td><td> 1,86</td>
<td>Temperature in Q, ° C</td><td> 732</td><td> 732</td><td> 732</td><td> 732</td>
<td>Pressure at the interruption point, kPa</td><td> 363</td><td> 501</td><td> 370</td><td> 487</td>
The analytical properties of the carbon black produced in Examples 1-33 were analyzed as before. The results are given in Table 3.
Table 3
<td>Example</td><td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td>
<td>Iodine number J2, mg / g</td><td> 120,9</td><td> 117,0</td><td> 104,2</td><td> 89,5</td><td> 91,5</td>
<td>CTAB, m<sup>2</sup>/ g</td><td> 108,9</td><td> 105,8</td><td> 98,2</td><td> 87,0</td><td> 88,5</td>
<td>Tol, Extrakt,%</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td>
<td>Coloring,%</td><td> 109,4</td><td> 106,4</td><td> 104,4</td><td> 99,8</td><td> 99,5</td>
<td>DBP, cm3 / 100 g</td><td> 103,9</td><td> 107,1</td><td> 101,2</td><td> 101,4</td><td> 102,3</td>
<td>CDBP cm3 / 100 g</td><td> 91,8</td><td> 90,7</td><td> 89,0</td><td> 88,9</td><td> 87,9</td>
<td>Dmodn nm</td><td> 112</td><td> 117</td><td> 118</td><td> 128</td><td> 123</td>
<td>D<sub>st</sub>, nm</td><td> 110</td><td> 116</td><td> 116</td><td> 127</td><td> 122</td>
<td>ADj0, nm</td><td> 96</td><td> 101</td><td> 102</td><td> 103</td><td> 101</td>
<td>Particle size, nm</td><td> 14,67</td><td> 14,99</td><td> 16,34</td><td> 18,45</td><td> 17,92</td>
Tol Extrakt means the level of toluene extract
188 285
Table 3 (continued)
<td>Example</td><td> 6</td><td> 7</td><td> 8</td><td> 9</td><td> 10</td>
<td>Iodine number J2, mg / g</td><td> 98,7</td><td> 85,9</td><td> 96,1</td><td> 85,4</td><td> 72,9</td>
<td>CTAB, m2 / g</td><td> 88,7</td><td> 78,8</td><td> 87,1</td><td> 79,3</td><td> 79,2</td>
<td>Tol, Extrakt,%</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td>
<td>Coloring,%</td><td> 99,1</td><td> 91,6</td><td> 96,6</td><td> 90,3</td><td> 93,6</td>
<td>DBP, cm3 / 100 g</td><td> 100,6</td><td> 101,7</td><td> 106,0</td><td> 110,0</td><td> 111,1</td>
<td>CDBP cm3 / 100 g</td><td> 85,6</td><td> 85,7</td><td> 88,6</td><td> 89,9</td><td> 92,2</td>
<td>Dmode, nm</td><td> 127</td><td> 136</td><td> 125</td><td> 138</td><td> 129</td>
<td>D<sub>s</sub>t, nm</td><td> 125</td><td> 137</td><td> 125</td><td> 143</td><td> 130</td>
<td>AD50, nm</td><td> 102</td><td> 110</td><td> 100</td><td> 116</td><td> 107</td>
<td>Particle size, nm</td><td> 17,48</td><td> 19,24</td><td> 16,70</td><td> 17,52</td><td> 18,412</td>
Table 3 (continued)
<td>Example</td><td> 11</td><td> 12</td><td> 13</td><td> 14</td>
<td>Iodine number J2, mg / g</td><td> 125,7</td><td> 85,8</td><td> 90,5</td><td> 89,2</td>
<td>CTAB, m2 / g</td><td> 98,6</td><td> 77,0</td><td> 76,3</td><td> 75,7</td>
<td>Tol, Extrakt,%</td><td> 100</td><td> 100</td><td> 100</td><td> 100</td>
<td>Coloring,%</td><td> 105,0</td><td> 88,7</td><td> 91,1</td><td> 90,4</td>
<td>DBP, cm3 / 100 g</td><td> 106,0</td><td> 101,0</td><td> 101,1</td><td> 103,7</td>
<td>CDBP cm3 / 100 g</td><td> 89,8</td><td> 84,9</td><td> 85,7</td><td> 85,5</td>
<td>Dmode, nm</td><td>NM</td><td>NM</td><td>NM</td><td>NM</td>
<td>Ds, nm</td><td>NM</td><td>NM</td><td>NM</td><td>NM</td>
<td>AD50, nm</td><td>NM</td><td>NM</td><td>NM</td><td>NM</td>
<td>Particle size, nm</td><td> 15,07</td><td> 19,64</td><td> 18,99</td><td> 16,74</td>
NM means "not determined"
Table 3 (continued)
<td>Example</td><td> 15</td><td> 16</td><td> 17</td><td> 18</td>
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td>
<td>Iodine number J2, mg / g</td><td> 77,2</td><td> 96,0</td><td> 80,3</td><td> 63,6</td>
<td>CTAB, m<sup>2</sup>/ g</td><td> 69,6</td><td> 83,2</td><td> 72,2</td><td> 59,9</td>
<td>Tol, Extrakt,%</td><td> 100</td><td> 73</td><td> 100</td><td> 100</td>
<td>Coloring,%</td><td> 86,1</td><td> 92,5</td><td> 84,2</td><td> 74,7</td>
<td>DBP, cm3 / 100 g</td><td> 158,6</td><td> 161,5</td><td> 163,3</td><td> 162,1</td>
188 285 table continues
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td>
<td>CDBP cm3 / 100g</td><td> 99,8</td><td> 107,1</td><td> 102,1</td><td> 99,3</td>
<td>D<sub>can</sub>de, nm</td><td> 122</td><td> 125</td><td> 134</td><td> 135</td>
<td>D<sub>s</sub>"Nm</td><td> 135</td><td> 132</td><td> 146</td><td> 166</td>
<td>AD50, nm</td><td> 101</td><td> 95</td><td> 106</td><td> 130</td>
<td>Particle size, nm</td><td> 29,70</td><td> 16,74</td><td> 23,32</td><td> 33,55</td>
Table 3 (continued)
<td>Example</td><td> 19</td><td> 20</td><td> 21</td><td> 22</td>
<td>Iodine number J<sub>2</sub>, mg / g</td><td> 71,3</td><td> 62,5</td><td> 71,2</td><td> 96,2</td>
<td>CTAB, m<sup>2</sup>/ g</td><td> 63,5</td><td> 54,8</td><td> 63,5</td><td> 83,6</td>
<td>Tol, Extrakt,%</td><td> 100</td><td> 100</td><td> 95</td><td> 72</td>
<td>Coloring,%</td><td> 74,1</td><td> 69,6</td><td> 80,0</td><td> 92,2</td>
<td>DBP, cm3 / 100 g</td><td> 153,3</td><td> 149,9</td><td> 150,5</td><td> 154,2</td>
<td>CDBP cm3 / 100 g</td><td> 97,5</td><td> 96,1</td><td> 98,8</td><td> 102,8</td>
<td>D<sub>m</sub>from, nm</td><td> 146</td><td> 152</td><td> 119</td><td> 107</td>
<td>D<sub>s</sub>t, nm</td><td> 177</td><td> 194</td><td> 158</td><td> 135</td>
<td>AD50, nm</td><td> 151</td><td> 173</td><td> 138</td><td> 116</td>
<td>Particle size, nm</td><td> 22,66</td><td> 29,91</td><td> 32,60</td><td> 20,23</td>
Table 3 (continued)
<td>Example</td><td> 23</td><td> 24</td><td> 25</td>
<td>Iodine number J2, mg / g</td><td> 95,4</td><td> 97,7</td><td> 86,1</td>
<td>CTAB, m2 / g</td><td> 85,0</td><td> 100,9</td><td> 85,4</td>
<td>Tol, Extrakt,%</td><td> 100</td><td> 66</td><td> 93</td>
<td>Coloring,%</td><td> 90,5</td><td> 110,0</td><td> 105,1</td>
<td>DBP, cm3 / 100 g</td><td> 159,0</td><td> 127,7</td><td> 140,4</td>
<td>CDBP cm<sup>3</sup>/ 100g</td><td> 109,7</td><td> 103,2</td><td> 102,0</td>
<td>Dmode, nm</td><td> 126</td><td> 98</td><td> 109</td>
<td>D<sub>s</sub>t, nm</td><td> 132</td><td> 99</td><td> 108</td>
<td>AD50, nm</td><td> 97</td><td> 69</td><td> 71</td>
<td>Particle size, nm</td><td> 21,55</td><td> 19,00</td><td> 25,11</td>
188 285
Table 3 (continued)
<td>Example</td><td> 26</td><td> 27</td><td> 28</td><td> 29</td>
<td>Iodine number J2, mg / g</td><td> 58,6</td><td> 69,8</td><td> 71,5</td><td> 80,6</td>
<td>CTAB, m2 / g</td><td> 63,7</td><td> 75,4</td><td> 76,7</td><td> 79,7</td>
<td>Tol, Extrakt,%</td><td> 82</td><td> 97</td><td> 90</td><td> 100</td>
<td>Coloring,%</td><td> 79,4</td><td> 106,5</td><td> 105,3</td><td> 104,8</td>
<td>DBP, cm3 / 100 g</td><td> 128,5</td><td> 59,4</td><td> 56,8</td><td> 52,2</td>
<td>CDBP cm3 / 100 g</td><td> 100,5</td><td> 57,8</td><td> 56,6</td><td> 52,8</td>
<td>Dmode, nm</td><td> 173</td><td> 109</td><td> 105</td><td> 104</td>
<td>D<sub>st</sub>, nm</td><td> 174</td><td> 112</td><td> 112</td><td> 110</td>
<td>AD50, nm</td><td> 126</td><td> 108</td><td> 105</td><td> 104</td>
<td>Particle size, nm</td><td> 22,66</td><td> 29,91</td><td> 32,60</td><td> 20,23</td>
Table 3 (continued)
<td>Example</td><td> 30</td><td> 31</td><td> 32</td><td> 33</td>
<td>Iodine number J2, mg / g</td><td> 100,0</td><td> 88,4</td><td> 103,2</td><td> 88,9</td>
<td>CTAB, m2 / g</td><td> 90,3</td><td> 83,3</td><td> 91,0</td><td> 87,7</td>
<td>Tol, Extrakt,%</td><td> 100</td><td> 98</td><td> 100</td><td> 100</td>
<td>Coloring,%</td><td> 112,8</td><td> 113,0</td><td> 116,1</td><td> 111,7</td>
<td>DBP, cm3 / 100 g</td><td> 77,0</td><td> 75,3</td><td> 67,7</td><td> 68,8</td>
<td>CDBP cm3 / 100 g</td><td> 72,6</td><td> 71,2</td><td> 66,7</td><td> 68,0</td>
<td>Dmode ^ nm</td><td> 91</td><td> 91</td><td> 85</td><td> 88</td>
<td>D<sub>st</sub>, nm</td><td> 92</td><td> 94</td><td> 87</td><td> 91</td>
<td>AD50, nm</td><td> 66</td><td> 67</td><td> 61</td><td> 64</td>
<td>Particle size, nm</td><td> 23,50</td><td> 24,75</td><td> 22,22</td><td> 22,95</td>
Examples 34-35
These examples illustrate the efficacy and benefits of carbon blacks and polymer compositions of the invention.
Polymer compositions A, B, C, D, E, F, G, H, I, J, K, L, M and N were prepared to assess apparent viscosity, melt index and absorption coefficient of the carbon black polymer compositions from Examples 1- 14. Polymer compositions O, P, Q, R, S, T, U and V were prepared to assess the apparent viscosity and melt index of the polymer compositions containing carbon blacks of examples 26-33.
Each of the carbon blacks produced in Examples 1-14 and 26-33 was incorporated into the polymer composition in an amount of 35% carbon black based on the weight of the polymer composition. AN polymer compositions were prepared using the carbon blacks prepared in Examples 1-14. The polymer compositions C, D, E, F, G, E, I and J were the polymer compositions of the invention containing oven carbon blacks, and the polymer compositions A and B were suitable comparative compositions. The polymer compositions L, M and N were also polymer compositions according to the invention containing oven carbon black, and composition K was a comparative composition. OV polymer compositions were prepared using carbon blacks prepared in 188 285 examples 26-33. The polymer compositions O, P, Q and R were the polymer compositions of the invention containing oven carbon black, and the polymer compositions S, T, V and U, respectively, were comparative compositions. Polymer AV compositions were prepared as follows.
420.7 g of carbon black and 781.4 g of low density polyethylene (LLDPE) identified as DFDA7510 for the carbon black examples 1 to 14 (AN polymer compositions) and GRSN7510 were charged to a Banbury Farrel laboratory mixer with a 1100 cm3 mixing chamber. for the carbon black examples 26-33 (OV polymer compositions). DFDA7510 polyethylene and GRSN7510 polyethylene are manufactured and sold by Union Carbide. The initial temperature in the mixing step was 49 ° C and mixing was carried out for 3 minutes: during the first 30 seconds at 77 rpm, the next 45 seconds at 116 rpm and the rest of the time at 155 rpm. After mixing, the product was laminated on a double-roll mill at 82 ° C into 0.0095 m thick panels. The panels were then cut into strips and passed through a cutter, transforming them into cubes 0.0095 m long. The product was screened to ensure that only pieces of uniform size are used for further testing.
The properties of the polymer compositions were evaluated as described above and the results are given in Table 4. As described above, evaluation of some properties of the polymer compositions was carried out with a carbon black load of less than 35%, which was achieved using an additional amount of LLDPE.
Table 4
<td>Example No.</td><td> 34</td><td> 35</td><td> 36</td><td> 37</td><td> 38</td>
<td>Polymer composition</td><td>AND</td><td>B</td><td>C</td><td>D</td><td>E</td>
<td>Soot</td><td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td>
<td>Apparent viscosity, Pa · s, at shear rate:</td><td colspan="5"></td>
<td>100 s'1</td><td> 2331</td><td> 2342</td><td> 2246</td><td> 2211</td><td> 2257</td>
<td>300 p<sup>1</sup></td><td> 1122</td><td> 1130</td><td> 1083</td><td> 1098</td><td> 1068</td>
<td>600 s'1</td><td> 688</td><td> 696</td><td> 668</td><td> 679</td><td> 679</td>
<td>1000 s'1</td><td> 471</td><td> 478</td><td> 457</td><td> 466</td><td> 466</td>
<td>Melt flow rate, g / 10 minutes</td><td> 3,12</td><td> 3,17</td><td> 3,40</td><td> 4,18</td><td> 4,29</td>
<td>COA, k Abs Unit / m</td><td> 451,4</td><td> 467,7</td><td> 442,4</td><td> 420,7</td><td> 408,4</td>
Carbon black means the carbon black of Example No.;
Pa · s means pass-second;
s'1 means "nanosecond";
g means "gram";
k Abs Unit / m stands for absorbance units per meter, in thousands.
Table 4 (continued)
<td>Example No.</td><td> 39</td><td> 40</td><td> 41</td><td> 42</td><td> 43</td>
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td>
<td>Polymer composition</td><td>F</td><td>G</td><td>H</td><td>AND</td><td>J</td>
<td>Soot</td><td> 6</td><td> 7</td><td> 8</td><td> 9</td><td> 10</td>
<td>Apparent viscosity, Pa · s, at shear rate:</td><td colspan="5"></td>
<td>100 s'1</td><td></td><td></td><td></td><td></td><td></td>
<td>300 s'1</td><td> 2194</td><td> 2160</td><td> 2246</td><td> 2240</td><td> 2539</td>
188 285 table continues
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td><td> 6</td>
<td>600 s</td><td> 1070</td><td> 1064</td><td> 1098</td><td> 1104</td><td> 1136</td>
<td>1000 p<sup>1</sup></td><td> 457</td><td> 455</td><td> 467</td><td> 473</td><td> 471</td>
<td>Melt flow rate, g / 10 minutes</td><td> 6,58</td><td> 7,83</td><td> 5,49</td><td> 7,56</td><td> 3,83</td>
<td>COA, k Abs Unit / m</td><td> 451,4</td><td> 467,7</td><td> 442,4</td><td> 420,7</td><td> 408,4</td>
Table 4 (continued)
<td>Example No.</td><td> 44</td><td> 45</td><td> 46</td><td> 47</td>
<td>Polymer composition</td><td>K</td><td>L</td><td>M</td><td>N</td>
<td>Soot</td><td> 11</td><td> 12</td><td> 13</td><td> 14</td>
<td>Apparent viscosity, Pa · s, at shear rate:</td><td colspan="4"></td>
<td>100 s 1</td><td> 2160</td><td> 1996</td><td> 2006</td><td> 2023</td>
<td>300 s-1</td><td> 1058</td><td> 988</td><td> 1001</td><td> 1009</td>
<td>600 p<sup>1</sup></td><td> 656</td><td> 622</td><td> 628</td><td> 633</td>
<td>1000 s-1</td><td> 451</td><td> 429</td><td> 433</td><td> 436</td>
<td>Melt flow rate, g / 10 minutes</td><td>NM</td><td>NM</td><td>NM</td><td>NM</td>
<td>COA, k Abs Unit / m</td><td> 427</td><td> 377</td><td> 386</td><td> 370</td>
NM means "not determined"
Table 4 (continued)
<td>Example No.</td><td> 48</td><td> 49</td><td> 50</td><td> 51</td>
<td>Polymer composition</td><td>ABOUT</td><td>P</td><td>Q</td><td>R</td>
<td>Soot</td><td> 26</td><td> 27</td><td> 28</td><td> 29</td>
<td>Apparent viscosity, Pa · s, at shear rate:</td><td colspan="4"></td>
<td>100 s-1</td><td> 2795</td><td> 2087</td><td> 2201</td><td> 2087</td>
<td>300 p<sup>1</sup></td><td> 1357</td><td> 1001</td><td> 1047</td><td> 998</td>
<td>600 s<sup>1</sup></td><td> 834</td><td> 618</td><td> 647</td><td> 615</td>
<td>1000 s-1</td><td> 546</td><td> 427</td><td> 429</td><td> 409</td>
<td>Melt flow rate, g / 10 minutes</td><td> 10,80</td><td> 15,90</td><td> 12,56</td><td> 24,54</td>
<td>COA, k Abs Unit / m</td><td>NM</td><td>NM</td><td>NM</td><td>NM</td>
NM means "not determined"
Table 4 (continued)
<td>Example No.</td><td> 52</td><td> 53</td><td> 54</td><td> 55</td>
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td>
<td>Polymer composition</td><td>S</td><td>T</td><td>AT</td><td>V</td>
<td>Soot</td><td> 30</td><td> 31</td><td> 32</td><td> 33</td>
188 285 table continues
<td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td>
<td>Apparent viscosity, Pa · s, at shear rate:</td><td colspan="4"></td>
<td>100 s'<sup>1</sup></td><td> 2236</td><td> 2253</td><td> 2236</td><td> 2279</td>
<td>300 s'</td><td> 1073</td><td> 1078</td><td> 1073</td><td> 1090</td>
<td>600 s'1</td><td> 660</td><td> 663</td><td> 666</td><td> 677</td>
<td>1000 s'1</td><td> 455</td><td> 459</td><td> 451</td><td> 459</td>
<td>Melt flow rate, g / 10 minutes</td><td> 11,00</td><td> 8,10</td><td> 11,30</td><td> 6,97</td>
<td>COA, k Abs Unit / m</td><td>NM</td><td>NM</td><td>NM</td><td>NM</td>
NM means "not determined"
The method for producing carbon black containing polymer compositions requires one or more operations to handle a mixture of carbon black and molten polymer. The viscosity of this mixture of carbon black and molten polymer is an important property in determining the ease of processing the composition. Lower viscosity improves the processing capacity of this mixture of carbon black and molten polymer and is therefore a particularly important and useful property of such compositions. The data presented in the table clearly show that the polymer compositions C, D, E, F, G and H according to the invention, containing carbon blacks, show a lower apparent viscosity at the given shear rates, compared to the corresponding comparative polymer compositions A and B. The data presented in Table 4 also indicate that the L, M and N polymer compositions according to the invention, containing carbon blacks, show a lower apparent viscosity at the given shear rates, compared to the corresponding comparative polymer composition K. The polymer compositions I and J according to the invention show a viscosity at shear rates given comparable to the corresponding comparative polymer compositions A and B. It is believed that the viscosities exhibited by polymer compositions I and J are related to the fact that carbon blacks 9 and 10 used in polymer compositions I and J, respectively, have a higher level of structure (as indicated by DBP values) than comparative carbon blacks 1 and 2 used in polymer compositions A and B, respectively.
A higher melt flow index is another indication of the improved processing properties of compositions containing a mixture of carbon black and molten polymer and is therefore also a particularly desirable property when it comes to improved throughput. The data presented in Table 4 clearly indicate that the carbon black polymer compositions C, D, E, F, G and H of the invention show higher melt flow rates compared to the corresponding comparative polymer compositions A and B. The data presented in table 4 clearly indicate also that the carbon black L, M and N polymer compositions of the invention show higher melt flow rates compared to the corresponding comparative polymer composition K.
Table 4 also provides data on apparent viscosity and melt flow index for the polymer compositions containing carbon blacks of examples 26 to 33.
As shown in Table 4, the polymer compositions P, Q and R, containing the carbon blacks of examples 21, 28 and 29, have lower viscosity and higher melt flow rates compared to the corresponding comparative compositions T, V and U, containing the carbon black of examples 31, 33 and 32. The data in Table 4 indicate that the carbon black polymer composition of Example 26 exhibits a higher viscosity and approximately equivalent melt flow index compared to the polymer composition comprising the example of Example 30. It is believed that this is due to the much higher carbon black structure of Example 26, in a manufacturing process that uses a significantly different rate of reagent addition to the structure compared to the carbon black of Example 30.
The absorption coefficient of the carbon black containing polymer composition is considered as an indication of the extent to which such composition will tolerate UV exposure with minimal degradation of physical properties. Data presented in table 4
188 285 indicate that the polymer compositions C, D, E, F, G, H and J of the invention, containing carbon black, have absorption coefficients comparable to the absorption coefficients of comparative polymer compositions A and B. The data in Table 4 also indicate that the polymer compositions L, M and N according to the invention, containing carbon blacks, have absorption coefficients comparable to the absorption coefficient of the comparative polymer composition K.
Examples 56-77
The efficacy and advantages of the carbon blacks and polymer compositions of the invention are also illustrated in these examples.
Polymer compositions AA, BB, CC, DD, EE, FF, GG, HFI, II, JJ, KK, LL, mM, NN, 00, PP, Qq, RR were prepared. SS, TT, UU and vV to evaluate the moisture absorption (CMA) of polymer compositions containing kiln carbon blacks compared to polymer compositions containing comparative carbon blacks. Each of the carbon blacks produced in Examples 1-14 and 26-33 were incorporated into the polymer composition. The polymer compositions CC, DD, EE, FF, GQ HH, II and JJ were the polymer compositions according to the invention containing the furnace carbon blacks of examples 3-10, and the polymer compositions AA and BB were suitable comparative compositions containing carbon blacks of examples 1 and 2. The LL, MM and NN polymer compositions were also the polymer compositions of the invention containing the furnace carbon blacks of Examples 12, 13 and 14, and the KK polymer composition was a suitable comparative composition containing the example of Example 10. The polymer compositions 00, PP, qQ and RR were the polymer compositions of the invention containing the furnace carbon blacks of examples 26-29, and the polymer compositions SS, TT, VV and UU, respectively, were comparative compositions containing carbon blacks of examples 30-33.
AA-W polymer compositions were prepared as follows.
The polymer compositions were prepared in a Brabender plasticizer at 100 ° C using 35.75 g LLDPE, identified as DFDA7510 for the carbon black examples 1 to 14 and GRSN7510 for the carbon black examples 26-33 and 19.25 g carbon black. DFDA7510 polyethylene and GRSN7510 polyethylene are manufactured and sold by Union Carbide. When the desired temperature is reached, the rotor speed is set to 60 rpm and within 30 seconds the weighed amounts of polymer and soot are charged through the loading chute. The chute piston weighs 10,000 kg, moving the ingredients to melt. The load and piston were removed after the ingredients had melted. The rotor speed was set at 60 rpm, the piston was lowered and the mix was stirred for 5 minutes. After this time, the mix was removed and passed through a double-roller mill twice. The resulting boards were cut into smaller pieces for CMA testing.
Polymer compositions were evaluated for CMA using the procedures described herein. The results are given in Table 5.
Table 5
<td>Example No.</td><td> 56</td><td> 57</td><td> 58</td><td> 59</td><td> 60</td>
<td>Polymer composition</td><td>AA</td><td>BB</td><td>CC</td><td>DD</td><td>EE</td>
<td>Soot</td><td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td>
<td>MOTH, %</td><td> 0,477</td><td> 0,475</td><td> 0,416</td><td> 0,437</td><td> 0,415</td>
Soot means soot from Example No.
Table 5 (continued)
<td>Example No.</td><td> 61</td><td> 62</td><td> 63</td><td> 64</td><td> 65</td>
<td>Polymer composition</td><td>FF</td><td>GG</td><td>HH</td><td>II</td><td>JJ</td>
<td>Soot</td><td> 6</td><td> 7</td><td> 8</td><td> 9</td><td> 10</td>
<td>MOTH, %</td><td> 0,374</td><td> 0,292</td><td> 0,374</td><td> 0,276</td><td> 0,382</td>
188 285
Table 5 (continued)
<td>Example No.</td><td> 66</td><td> 67</td><td> 68</td><td> 69</td>
<td>Polymer composition</td><td>KK</td><td>LL</td><td>MM</td><td>NN</td>
<td>Soot</td><td> 11</td><td> 12</td><td> 12</td><td> 14</td>
<td>MOTH, %</td><td> 0,465</td><td> 0,243</td><td> 0,288</td><td> 0,265</td>
Table 5 (continued)
<td>Example No.</td><td> 70</td><td> 71</td><td> 72</td><td> 73</td>
<td>Polymer composition</td><td>OO</td><td>PP</td><td>QQ</td><td>RR</td>
<td>Soot</td><td> 26</td><td> 27</td><td> 28</td><td> 29</td>
<td>MOTH, %</td><td> 0,258</td><td> 0,080</td><td> 0,085</td><td> 0,308</td>
Table 5 (continued)
<td>Example No.</td><td> 74</td><td> 75</td><td> 76</td><td> 77</td>
<td>Polymer composition</td><td>SS</td><td>TT</td><td>UU</td><td>IN</td>
<td>Soot</td><td> 30</td><td> 31</td><td> 32</td><td> 33</td>
<td>MOTH, %</td><td> 0,513</td><td> 0,385</td><td> 0,485</td><td> 0,086</td>
As indicated previously, the moisture absorption of the carbon black containing polymer composition (CMa) blend is a particularly important property of such compositions. The data presented in Table 5 clearly indicate that the carbon black CC, DD, EE, FF, GG, HH, II, JJ, LL, MM and NN polymer compositions according to the invention show a lower CMA value compared to the corresponding AA comparative polymer compositions , BB and KK.
Table 5 also gives CMA values for the carbon black polymer compositions from Examples 26 to 33. For this group of examples, when comparing the polymer compositions 00, PP, QQ and RR containing carbon black, with the respective comparative compositions (SS, TT polymer compositions W and UU), it can be seen that the polymer compositions of the invention show CMA values that are either lower or comparable to the CMA values of the respective comparative compositions.
Examples 78 and 79.
The efficacy and advantages of the carbon blacks and polymer compositions of the invention are further illustrated by the polymer compositions described in Examples 78 and 79.
The polymer compositions W and X according to the invention were prepared by introducing the carbon black produced in Example 7, with a mass loading of the polymer composition greater than 35% carbon black. The polymer used was LLDPE, identified as DFDA7510 and manufactured and sold by Union Carbide. Table 6 provides the actual weight applied and the properties of the polymer compositions determined as previously described.
188 285
Table 6
<td>Example No.</td><td> 78</td><td> 79</td>
<td>Polymer composition</td><td>IN</td><td>X</td>
<td>Soot</td><td> 7</td><td> 7</td>
<td>The weight load soot, in%, of the polymer composition</td><td> 38</td><td> 40</td>
<td>Apparent viscosity, Pa · s, at shear rate:</td><td colspan="2"></td>
<td>100 p<sup>1</sup></td><td> 2445</td><td> 2707</td>
<td>300 s-1</td><td> 1193</td><td> 1303</td>
<td>600 s'1</td><td> 729</td><td> 784</td>
<td>1000 s_</td><td> 486</td><td> 517</td>
<td>Melt flow rate, g / 10 minutes</td><td> 5,30</td><td> 2,98</td>
For any two polymer compositions differing in carbon black weight load, another mechanism for comparing the processing properties of polymer compositions is to compare melt flow indexes of each polymer composition or, alternatively, the viscosity of each polymer composition subjected to equal shear loading. A polymer composition exhibiting a lower viscosity or higher melt flow rate will usually be easier to process.
By extending this argument to any two series of polymer compositions, each made from different carbon blacks, and so that the compositions in the individual series contain carbon blacks at different weight loads, but are comparable in other respects, these series allow higher carbon weight loads for a given melt flow index or viscosities at constant shear rates will be considered to have improved processing properties.
The results shown in Figures 4 and 5 indicate that furnace carbon blacks show improved processing properties when incorporated into polymer compositions for the following reasons.
Figure 4 shows melt flow indexes of the polymer compositions G, W and X of the invention containing the carbon blacks produced in Example 7 under increased soot loading.
Figure 4 also shows melt flow indexes of comparative polymer compositions A and B. As stated above, the higher melt flow index is shown in Figure 4, and also melt flow indexes of the more easily processed polymer composition.
Thus, Figure 4 clearly indicates that the polymer compositions G, W and X of the invention contain carbon blacks in a weight load that is excess of the load achieved when carbon black is introduced into each of the respective polymer compositions A and B, although they still exhibit substantially such alone or higher melt flow rate.
In a similar manner, Fig. 5 shows apparent viscosities at a shear rate of 100 s<sup>4 </sup>polymer compositions G, W and X according to the invention containing kiln carbon blacks, produced in Example 7 with increasing carbon black weight loads.
Figure 5 also shows apparent viscosities at a shear rate of 100 s<sup>4</sup> comparative polymer compositions A and B.
Thus, Fig. 5 clearly indicates that the polymer compositions G, W and X of the invention contain carbon blacks in a weight load that is an excess of the load achieved when carbon black is introduced into each of the respective polymer compositions A and B, although they still show equivalent or lower apparent viscosity.
It will be clear to the skilled person that furnace carbon blacks can be used at higher loads than those normally used. However, the use of carbon black at such higher loads will not substantially reduce the moisture absorption capacity of the mix
188 285 due to the degree to which the moisture absorption capacity of the mix is improved by kiln carbon blacks.
It should be clearly understood that the embodiments of the invention described herein are merely an illustration thereof and are not intended to limit the scope of the invention.
<img file="PL188285B1_D0001.tif" />
188 285 people
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Stokes diameter, nm with X axis melt flow index, g / 10 mi
FIG. 3
<img file="PL188285B1_D0002.tif" />
Soot content in the polymer composition% by weight of soot
FIG. 4
188 285
Apparent viscosity at a shear rate of 100 s Pa.
<img file="PL188285B1_D0003.tif" />
% by weight of carbon black
FIG. 5
188 285
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UP Department of Publications. Circulation of 50 copies Price PLN 6.00.
Contents5
10 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7 Sheet 8 Sheet 9 Sheet 10
57 members in 30 offices
Priority claims8
| Document | Office | Kind | Date |
|---|---|---|---|
| 59503796 | United States of America | A | |
| 59503796 | United States of America | A | |
| 9700682 | United States of America | W | |
| 9700682 | United States of America | W | |
| 96595037 | – | – | – |
| 97US9700682 | – | – | – |
| US19960595037 | – | – | – |
| WO1997US00682 | – | – | – |
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1 legal event, as the office reported them to INPADOC
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Numbers
- Publication, DOCDB
- 188285
- Publication, EPODOC
- PL188285B
- Application
- 97322554
- Application, DOCDB
- 32255497
- Application, EPODOC
- PL19970322554
Titles2
- English
- CARBON BLACKS AND COMPOSITIONS CONTAINING THEM
- Polish
- Kompozycja polimerowa
Classification
- CPC, 7
- C08K3/04
- C09C1/50
- B29B7/90
- B29B7/7495
- C01P2004/64
- C01P2006/19
- C08K2201/011
- IPC, 5
- C08K3 04
- C08L23 00
- C08L101 00
- C09C1 48
- C09C1 50