Masterbatch composition comprising a matrix having a polysiloxane dispersed therein and a method for the preparation thereof
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47 claims: 7 independent, 40 dependent
- 1REIVINDICAÇÕES 1. Composição de mistura-mãe, caracterizada pelo fato de compreender uma matriz contendo um polisiloxano disperso na mesma.
- 2Composição de mistura-mãe, caracterizada pelo fato de que compreende uma matriz contendo um polisiloxano com organo titanato combinado, disperso na mesma.
- 3Composição de mistura-mãe, caracterizada pelo fato de que compreende uma matriz de resina termoplãstica contendo dispersa, na mesma um polisiloxano que contêm uma unidade, repetitiva da fórmula:V~ --O-ÉRÍ-Si--Z n, - v J x em que R é um radical hidrocarboneto, cada V é hidrogênio, um radical hidrocarboneto ou um grupo hidrolizãvel, Z é um grupo hidrolizãvel, n é um numero inteiro que tem o valor de um até 18 inclusive e x ê um número inteiro que tem valor de pelo menos 2.
- 4Composição de mistura-mãe de acordo com a reivindicação 3, caracterizada pelo fato de que R na unidade repetitiva do polisiloxano é um radical alquileno que tem de um atê 18 ãtomos de carbono inclusive.
- 5Composição de mistura-mãe, de acordo com a reivindicação 3, caracterizada pelo fato de que R na unidade repetitiva do polisiloxano é -CH 2 -CH 2 -.
- 6Composição de mistura-mãe, de acordo com a reivindicação 3, caracterizada pelo fato de que R na unidade repetitiva do polisiloxano ê -CH 2 -CH 2 - CH 2 -.
- 7Composição de mistura-mãe, de acordo com a reivindicação 3, caracterizada pelo fato de que cada V na unidade repetitiva do polisiloxano ê metõxi.
- 8Comp*osição de mistura-mãe, de acordo com a reivindicação 3, caracterizada pelo fato de que cada V na unidade repetitiva ê 2-metoxietõxi.
- 9Composição de mistura-mãe, de acordo com a reivindicação 3, caracte r:'iz ada pelo fato de que o polisiloxano ê derivado de acetooxietiltrimetõxi silano.
- 10Composição de mistura-mãe, de acordo com a reivindicação 3, caracterizada pelo fato de que o polisiloxano ê derivado de acetooxipropiltrimetõxi silano.
- 11Composição de mistura-mãe, de acordo -3··· ·· ·. ,· „ • · · · · β* «Ο · · · · « α • · · Β « ΟΒΒ • · · Β « « ···· « »··« Β. β · Β. * · · • · · • •Ο com a reivindicação 3, caracterizada pelo fato de que o polisiloxano ê derivado de gama-metacriloxipropiltris-(2-metoxietõxi) silano.
- 12Composição de mistura-mãe, de acordo com reivindicação 3, caracterizada pelo fato de que o polietileno ê a matriz de resina termoplãstica.
- 13Composição de mistura-mãe v de acordo com a reivindicação 3, caracterizada pelo fato de que um copolímero de etileno-acrilato de butila que tem teor de acrilato de butila combinado de cerca de 2,5 por cento em peso ê a matriz de resina termpplãstica.
- 14Composição de mistura-mãe, de acordo com a reivindicação 3, caracterizada pelo fato de que um copolímero de etileno-acrilato de etila que tem teor de acrilato de etila combinado de cerca de 2,5 por cento em peso ê a matriz de resina termoplãstica.
- 15Composição de mistura-mãe, de acordo com a reivindicação 3, caracterizada pelo fato de que um terpolímero de etileno-propileno e um monômero dieno é a matriz de resina termoplãstica.
- 16Composição de mistura-mãe, de acordo com a reivindicação 3, caracterizado pelo fato de que um copolímero de etíleno-propileno ê a matriz de resina termoplãstica. -4···· ·· • a · a a ·· • a o · aaaa aa ia aa a a a a «a • a aaa • a · aaa a · a •aaa aa a aaaa aa aa a a a a a a a · a • aaa a a a a a aa aaaa
- 17Composição âe mistura-mãe, âe acorâo com a reivindicação 3, caracterizada pelo fato de conter um organo titanato.
- 18Composição de mistura-mãe, de acordo com a reivindicação 17, caracterizada pelo fato de gue o organo titanato é o titanato de tetraisopropila.
- 19Composição de mistura-mãe, de acordo com a reivindicação 3, caracterizada pelo fato de conter um organo titanato e um catalisador de condensação para silanol carboxilato metálico .
- 20Composição de mistura-mãe, de acorâo com a reivindicação 19, caracterizada pelo fato de gue o organo titanato ê o titanato de tetraisopropila e o carboxilato metálico é o dilaurato de dibutilestanho.
- 21Processo para preparar uma composição de mistura-mae, caracterizado pelo fato de compreender a mistura de uma matriz com um silano monomêrico e um catalisador de condensação para silano resultando em gue o silano monomêrico condensa em um polisiloxano gue ê disperso através da matriz.
- 22Processo, de acordo com a reivindicação 21, caracterizado pelo fato de gue o silano tem a fórmula:θ R^C-O-êRh-Si—Z Ui V -5···· ·· ·· • · Β Β Β Β β • ΒΒ Β Β • Β Β Β ΒΒβΒ 411 ΒΒ WBB* , Βββ Β ΒΒΒΒ Β Β β Β Β ΒΒΒΒ em que R é um radical hidrocarboneto, R^ ê um radical hidrocarboneto, cada V e hidrogênio, um radical hidrocarboneto ou um grupo hidrolizãvel, Z e um grupo hidrolizãvel e n ê um numero inteiro que tem valor de 1 atê 18 inclusive.
- 23Processo, de acordo com a reivindicação 22, caracterizado pelo fato de que o catalisador é um organo titanato.
- 24Processo, de acorâo com a reivindicação 23, caracterizado pelo fato de que o organo titanato ê o titanato de tetraisopropila.
- 25Processo, de acordo com a reivindicação 22, caracterizado pelo fato de que o silano é o acetooxietiltrimetõxi silano.
- 26Processo, de acorâo com a reivindicação 22, carac* terizãdo pelo fato de que o silano ê o acetooxipropiltrimetõxi.silano.
- 27Processo, de acordo com a reivindicação 22, caracterizado pelo fato de que o silano ê o gama-metacriloxipropil-tris-(2-metõxietõxi) silano.
- 28Composição de mistura-mãe, caracterizado pelo fato de ser produzida de acorâo com o processo âa reivindicação 21.
- 29Processo para produzir um copolímero alquileno-acrilato de alquila modificado com silano, curável com ãgua, caracterizado pelo fato de compreender a reação de uma mistura que con*·«« · ΒΒ ·· · -6« β·Β I · · · • Β Β • Β ·· ΒΒΟΒ *ι«ι ΒΒ ΒΒ • β · · · • · · Β Β Β ··· Β • Β · Β ΒΒ ΒΒΒ» V —O— (R)-Si η ι V têm um copolímero alquileno-acrilato de alquila, um organo titanato e um polisiloxano, disperso em uma matriz, que tem a unidade repetitiva:—Z x em que R ê um radical hidrocarboneto, cada V é hidrogênio, um radical hidrocarboneto ou um grupo hidrolizãvel e Z é um grupo hidrolizãvel, n ê um numero inteiro que tem valor de 1 até 18 inclusive, Z é um grupo hidrolizãvel e x é um número inteiro que tem valor de pelo menos 2.
- 30Processo, de acordo com a reivindicação 29, caracterizado pelo fato de ser realizado a uma temperatura de cerca de 80°C atê cerca de 300°C.
- 31Processo, de acordo com a reivindicação 29, caracterizado pelo fato de ser realizado a uma temperatura de cerca de 150°C atê cerca de 230°C.
- 32Processo, de acordo com a reivindicação 29, caracterizado pelo fato de que o organo titanato tem a fórmula:Ti(OR 2 ) 4 2 ~ em cada R ê hidrogênio ou um radical hidrocarboneto.
- 33Processo, de acordo com a reivindicação 32, caracterizado pelo fato de que cada 2 - R e um radical alquila que tem de 1 ate 18 átomos de -7···· «· • ·« · • · · • a «P·. ·· ·· · • α fl * · * · • · ···« ·· • ···· • · β··β « · • · · • · · · a ··· · • · · • ·· ··«* carbono inclusive.
- 34Processo, de acordo com a reivindicação 29, caracterizado pelò fato de que o copolímero e um copolímero de etileno-acrilato de etila.
- 35Processo, de acordo com a reivindicação 29, caracterizado pelo fato de que R-na unidade repetitiva do silano ê um radical alquileno que tem de 1 atê 18 ãtomos de carbono inclusive.
- 36Processo, de acorâo com a reivindicação 29, caracterizado pelo fato de que R na unidade repetitiva do silano ê
- 37Processo, de acorâo com a reivindicação 29, caracterizado pelo fato de que R na unidade repetitiva do silano é -CH^-CH^-CH^-.
- 38Processo, de acordo com a reivindicação 29, caracterizado pelo fato de que cada V na unidade repetitiva do silano ê metoxi.
- 39Processo, de acordo com a reivindicação 29, caracterizado pelo fato de que o organo titanato ê o titanato de tetraisopropila ou o titanato de tetrabutila.
- 40Processo, de acordo com a reivindicação 29, caracterizado pelo fato âe que o organo titanato estã presente em uma proporção de cerca de 0,001 até cerca de 25 por cento em peso em relação ao peso do polisiloxano.
- 41Processo, de acordo com a reivindica• 0 00 0· 00 0 0000 « 00 • · 00 0« 00 00 00 0 • · »000· «00 0 0 « 0' 0 * 0000 « 000 0 «•00000 00 -8- ···· ................ çao 29, caracterizado pelo fato de que o polisiloxano estã presente em uma proporção de cerca de 0,5 atê cerca de 10 por cento em peso em relação ao peso do copolímero.
- 42Processo, de aoordo com a reivindicação 29, caracterizado pelo fato de que o polisiloxano contêm organo titanato combinado.
- 43Processo, de acordo com a reivindicação 29, caracterizado pelo fato de que a mistura contêm um catalisador de condensação para silanol carbokilato metãlico.
- 44Processo, de acordo com a reivindicação 43, caracterizado pelo fato de que o carboxilato metãlico ê o dilaurato de dibutilestanho.
- 45Processo, de acordo com a reivindicação 29, caracterizado pelo fato de que o polisiloxano ê derivado do acetooxietiltrimetõxi silano.
- 46Processo, de acordo com a reivindicação 29, caracterizado pelo fato de que o polisiloxano é derivado do acetooxipropiltrimetõxi silano.
- 47Processo, de acordo com a reivindicação 29, caracterizado pelo fato de que o polisiloxano é derivado de gama-metacriloxipropil-tris-(2-metoxietõxi) s ilano. ΒΒΒΒ ΒΒ ΒΒ Β. . * Ο · Β 1 . Β Β · · • ·· ΒΒΒΒ 5 · · · · ·'— ΒΒΒ Β Β · . ΒΒΒΒ ΒΒ «ΒΒΒ ΒΒ · « ···· ·· ·· BB BB B • B BBBB
Independent claims47
415 paragraphs in 48 sections, as filed
(54) Composition of the mother mixture and process for its preparation; and process to produce an alkylene-alkyl acrylate copolymer
Depositor:
(71) Union Carbide Corporation. (US)
Attorney:
(74) Daniel & Co.
Unfolding:
Inventor:
(72) Miohael John Keogh ββββ ΒΒ ΒΒΒ • Β ·· · • Β Β · · • β · · · β β ΒBBB BBBB BBBB ΒΒ.
ΒΒΒΒ Β «
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04.33 - MATCHING ORDERS
Countries
ARGENTINA .AUSTRALTA.
BELGIUM
CANADA
FRANCE
ITALY
OAPAO
NETHERLANDS
SPAIN
SWEDEN
SWITZERLAND
UNITED KINGDOM
REP. GERMANY FEDERAL
Comments
The dates and numbers of the orders are not yet known.
U-5J.355
<img file="BR8204792A_D0001.tif" />
Descriptive Report of the Invention Patent COMPOSITION OF THE MOTHER MIXTURE AND PROCESS FOR ITS PREPARATION? AND PROCESS TO PRODUCE AN ALKYLENE-ALKYL ACRYLATE COPOLYMER.
The present invention relates to a relatively moisture-stable masterbatch composition consisting of a matrix with a polysiloxane dispersed in it, and a process for preparing it by mixing a monomeric silane and a condensation catalyst. silane in a matrix, resulting in the monomeric silane condensing into a polysiloxane that is dispersed through the matrix. The resulting composition can be mixed with alkylene-alkyl acrylate copolymers, in the presence of an organic titanate, to produce curable compositions<sup>11</sup> with water, consisting of water-curable alkylene-acrylate copolymers modified with silane, which are useful as extruded around wires and cables, providing protective coatings on them, such as insulation and liners.
Fundamentals of the Invention
Alkylene-alkyl acrylate copolymers ··· ·· frfr fra fr fr ··· ·· ·· ··· ·· ·· frfr ·· «· fr • ·· fr · fr fr · ·· frfr fr · * fr ··· fr frfr <sub>O</sub> fr · · e · fr fr —2 ™ ···· ·· α ·· ® ·· · · ·· modified with silane are particularly suitable for use in commercial applications as these polymers and compositions based thereon can be cured by a simple treatment with water, in contrast to the more conventional cure using peroxide, in cross-linked products with high density of retidulation. As a consequence, silane-modified alkylene-acrylate copolymers and compositions based on these polymers are especially useful in extrusion applications, being capable of extrusion under a wide latitude of processing conditions, such as temperatures well beyond the maximum processing equipment used to extrude peroxide-containing compositions.
The production of silane-modified alkylene-acrylate copolymers is carried out, conveniently by mixing a polysiloxane with an alkylene-alkyl acrylate copolymer, in the presence of an organic titanate, as described in detail in Applicant No. 9 of the applicant's co-applicant. 192,319 of September 30, 1980, the description of which is incorporated into this report as a reference, with the result that the polysiloxane reacts with the alkylene-alkyl acrylate copolymer producing a silicon-modified alkali-acrylate polymer cci25 water-curable When carrying out this reaction, care must be taken to protect the polysiloxane from moisture. The
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• · β · ·· β · «· • ·
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polysiloxanes hydrolyze quickly, in contact with moisture, and condense into gelled products that, for practical purposes, are useless. In addition to the water sensitivity problem, it is difficult in some cases to mix the polysiloxane-alkyl acrylate reaction mixtures, particularly when the reaction mixtures are highly loaded with additives. Therefore, additional time and / or steps may be required in order to homogenize the reaction mixtures, which is necessary in order to carry out a substantially complete reaction between the polysiloxane and the alkylene-acrylate copolymer.
Detailed Description of the Invention
The present invention provides moisture-resistant mother mix compositions consisting of a matrix having a polyisoxoxane dispersed therein, produced by mixing a monomeric silane and a condensation catalyst for silane in a matrix with the consequence that the monomeric silane condenses into a polysiloxane that is dispersed through the matrix. The resulting stock mixture composition is resistant to moisture and could be used to produce water-curable silane modified alkylene-acrylate copolymers by mixing the desired proportion of the stock mixture, which contains a known proportion of polysiloxane, with a copolymer. alkylene-alkyl acrylate in the presence of a titanate organo,
-4 • • 44 lll «44 *» 4
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4
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4 4 4
444 44 Β
44*4 44 44
4 4 4
4 4 '444 4
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44 4444
The moisture-resistant mother mixture compositions of the present invention comprise a matrix which has a polysiloxane dispersed therein, isolated or reacted with the matrix. A particularly desirable masterbatch composition is one that contains a polysiloxane that has an organic titanate combined with it.
Illustrative of materials that can be used as matrices are thermoplastic resins such as ethylene polymers that include homopolymers and ethylene copolymers. Ethylene copolymers contain at least about 10 weight percent ethylene and up to about 90 weight percent propylene and / or up to about 70 weight percent of other organic compounds that are polymerizable with ethylene. Examples of these compounds are butene-1, pentene-1, isoprene, butadiene, bicycloheptadiene, bicycloheptene, styrene and the like as well as alkyl acrylates, defined below. exemplified by ethyl acrylate and also vinyl compounds such as vinyl acetate and the like.
Other suitable thermoplastic resins include chlorinated resins such as chlorinated polyethylene, chlorine waxes, styrene-butadiene rubbers, styrene-isoprene rubbers, nitrile-butadiene rubbers, silicone rubbers and oils, natural rubber, chlorosulfonated polyethylene, polypropylenes, ethylene terpolymers *
-propylene-diene, polychloroprene and the like. Others
ΟΒ · β · «« · ao a aa • *
-5 • aa «aaaa · aaa * ··> · aaa aaaa aa ·· aa aaaa aa aa ·· • Β · aaa suitable matrix materials are paraffinic oils, ester plasticizers such as dioctyl phthalate, nonyl phthalate & the like.
As a rule, any solid or liquid or mixtures thereof which have a degree of compatibility with polysiloxane and the copolymer · alkylene-alkyl acrylate and do not interfere negatively with *
the reaction between the polysiloxane and the alkylene-alkyl acrylate copolymer can be used as matrices according to the present invention.
Polysiloxanes, which can be mixed directly with matrices or formed in ~ situ as described subsequently, contain repetitive units of the formula:
Formula I
V
I «R * r — si <sup>n</sup> I
V where R is a divalent hydrocarbon radical that has a maximum of 18 carbon atoms; each V, which can be the same or different, and hydrogen, a monovalent hydrocarbon radical with a maximum of 18 carbon atoms, or a hydrolyzable group; Z is a hydrolyzable group; n is an integer with a value of up to 18 inclusive and ex is an integer with a value of at least 2, usually 2 to 1000, preferably 5 to 25 inclusive.
Illustrative of suitable hydrocarbon radicals for R are alkylene radicals that have a
-6 ·· ·· ·· II.
• 00 * 4 ·· a »•« · 0 »0 0 0 <·« 0 · «« ··> 00 00 0
0000 00 0000 00 0
000 00 00 • 0 0 0 Λ
0 0 0
00 0 0
0 0
00 0000 to 1Õ inclusive carbon atoms, preferably one to 6 inclusive carbon atoms, such as methylene, ethylene, propylene, butylene, hexylene and the like; alkoxy radicals having up to 16 inclusive carbon atoms, preferably one up to 6 inclusive carbon atoms such as methyloxymethyl, methyloxyethyl, methyloxypropyl, ethyloxymethyl, ethyloxyethyl, ethyloxypropyl, propyloxypropyl, propyloxypropyl, propyloxyhexyl and the like.
As stated, each V can be hydrogen, a hydrocarbon radical or a hydrolyzable group. Illustrative of suitable hydrocarbon radicals are alkyl radicals having from up to 18 carbon atoms including, preferably up to 6 carbon atoms including such as methyl, ethyl, n-propyl, isopropyl, n-butyl, n-hexyl and the like; alkoxy radicals having up to 18 inclusive carbon atoms, preferably up to 8 inclusive carbon atoms, such as methoxy, ethoxy, propoxy, hexoxy, dodecyloxy, methoxyethoxy and the like; aryl radicals that have 6 to 8 carbon atoms including such as phenyl, methylphenyl, ethylphenyl and the like? cycloaliphatic radicals having from 5 to 8 carbon atoms including cyclopentyl, cyclohexyl, cyclohexyloxy and the like.
Z, as stated earlier, is a hydrolyzable group among which alkoxy radicals can be noted as previously described for R? ra-7-
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<td></td><td> • ·</td><td colspan="2"> • ··«·</td>
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·· oxyaryl cozn oxyphenyl and similar; oxyaliphatic radicals such as oxyhexyl and the like; halogens such as chlorine and the like and other hydrolyzable groups as further described in US patent 3,408,420 to JB Wiggill, patented October 29, 1968.
Polysiloxanes that have repetitive units included within the scope of Formula I can be prepared as described in US patent no. 3,193,567 from Gerd
Rossmy, patented on July 6, 1965, or condensing silane included in the scope of Formula IX in the presence of a catalyst * with an organo titanate - or a metallic carboxylate.
OV
Formula II R<sup>1</sup>-C — O— (Rr- Si — Z η,
V where it is a monovalent hydrocarbon radical that has a maximum of 18 carbon atoms, such as an alkyl radical that has from up to 18 carbon atoms including, preferably from one to four carbon atoms including such as methyl, ethyl, n-propyl, isopropyl, n-butyl and the like; al20 kilene radicals having two to 18 carbon atoms, preferably two to 4 carbon atoms including ethylene, propylene, isopropenyl and the like; aryl radicals that have six to ten carbon atoms including phenyl, benzyl and similar. Another 25 'variables are as previously defined.
-8 Examples of suitable silanes that fall within the scope of Formula II are as follows:
···· ·· ·· · «· · · ·« · · · • 999 • · · β · ···· · · • · · I «* · ο · · ···· ·· • · · · Β · ·· · ι ch<sub>3</sub>-co-ch<sub>2</sub>ch<sub>2</sub>si4och<sub>3</sub>)<sub>3</sub> acetooxyethyltrimethoxy silane
O
CH<sub>3</sub>-CO-CH<sub>2</sub>CH<sub>2</sub>Si {OCH<sub>2</sub>CH<sub>3</sub>)<sub>3 </sub>acetooxyethyltriethoxy silane
CH<sub>3</sub>-CO-CH<sub>2</sub>CH<sub>2</sub>Si ^ OC<sub>2</sub>H<sub>4</sub>CH<sub>3</sub>)<sub>3</sub> acetooxyethyl-tri s- (2-methoxyethoxy) silane <sup>CH</sup>3
CH<sub>2</sub>= CCO- (CH<sub>2</sub>-> y-SÍ- (OCH<sub>3</sub>) <sub>3</sub>
Beta-methamethyloxyethyltrimethoxysilane <sup>CH</sup>3 <sup>CH</sup>2<sup>=</sup>’<sup>3</sup><sup>Ç</sup><sup>O</sup>‘<sup>fCH</sup>2^3<sup>Si, tOCH</sup>2<sup>CH</sup>3<sup>)</sup> 3 0 gamma-methacryloxypropyltriethoxysilane
CH. <sup>1</sup> 3
CH<sub>3</sub>-CO '(CH<sub>2</sub>^ SÍ-OCH<sub>3</sub>
CH.
acetooxyethyldimethylmethoxy silane?<sup>3 </sup>CH<sub>3</sub>-CO-êCH ^ Si-OCH<sub>3</sub>
CH, acetooxyethylmethyldimethoxysilane ···· ·· · ·· · ....
• · · · · · · . .
<sup>B</sup> ·· · · aa · · * * · · aaaaaa • · · «·. · · · · Aa aaaa aa a · »
-9·« « ?<sup>H</sup>3
CH<sub>2</sub>= CCO-4CH ^ SiáOCH<sub>3</sub>) <sub>3 </sub>Gamma-methacryloxypropyltrimethoxy silane
O
CHg-CO-êCHj ^ Si-êOQ ^) <sub>3 </sub>acetooxypropyltrimethoxy silane
CH<sub>3</sub>-CO «CH ^ SÍ <OCH<sub>2</sub>CH<sub>3</sub>) <sub>3 </sub>acetooxypropyltriethoxy silane ch<sub>3</sub> ch<sub>2</sub>= c-ç-o4ch ^ si {oc<sub>2</sub>H<sub>4</sub>och<sub>3</sub>) <sub>3</sub>
Gamma-methacryloxypropyl-tris- (2-methoxyethoxy) silane
Among the catalysts suitable for condensing monomeric silanes into polysiloxanes, metallic carboxylates such as dibutyltin dilaurate, standard acetate, stannous octoate, lead naphthate, zinc octoate, iron 2-ethyl hexoate and the like can be mentioned. The conditions employed for the production of polysiloxanes, reaction temperatures, proportion of materials and the like, using metallic carboxylates as catalysts are the same as those described later with respect to the use of organic titanates, which can also be used to condense monomeric silanes into polysiloxanes.
Illustrative of organo titanates that are. include within the scope of Formula III:
Formula III Ti (OR<sup>2</sup>)<sub>4</sub> • · · · " • " · · • "The
-10 • * aa ·· ·· aaaa «a in which each R, which can be the same or different, is hydrogen or a monovalent hydrocarbon radical having from one to 18 carbon atoms including, preferably from up to 14 atoms of including carbon, provided that at least one R is a hydrocarbon radical.
Exemplary hydrocarbon radicals suitable for R are alkyl radicals such as methyl, ethyl, n-propyl, isopropyl, butyl, octyl, lauryl, myristyl, stearyl and the like; cycloaliphatic radicals such as cyclopentyl, cyclohexyl and the like; aryl radicals such as phenyl, methylphenyl, chlorophenyl and the like; alkaryl radicals such as benzyl and the like.
Particularly convenient titans that fall within the scope of Formula III are those in which each R is alkyl having up to 18 carbon atoms, give preference to up to 14 carbon atoms, exemplified by tetrabutyl titanate, tetraisopropyl and the like.
Organo titanates that fall within the scope of Formula III are known compounds and can be conveniently prepared as described in US Patent No. 2,984,641 to Leon E. Wolinsky patented May 16, 1961.
Other suitable organo titanates are chelates of titanium organo such as tetraoctylene glycol titanium, triethanol amine titanate, titanium acetyl acetonate, titanium lactate and the like.
At least a catalytic proportion of or- 11 V ·
<img file="BR8204792A_D0006.tif" />
titanate gano is used to produce the polysiloxanes, i.e., a proportion sufficient to catalyze the condensation of raonomeric silanes into polysiloxanes. As a base, the proportion of organo titanate used is in the range of about 0.001 to about 25 weight percent relative to the weight of the monomeric silane. It is preferable to use about 0.5 to about 5 weight percent of titanate organo with respect to the weight of monomeric silane.
The temperature at which the reaction is carried out can be varied over a wide range, for example from about 9 ° C to about 250 ° C. A temperature in the range of about 70 ° C to about 130 ° C is preferred. Likewise, the reaction can be carried out using a suitable solvent, illustrated by hydrocarbon solvents such as toluene, xylene, cumene, decaline, dodecane, chlorobenzene and the like.
The condensation of a monomeric silane in the presence of a catalyst can be carried out under atmospheric, subatmospheric or superatmospheric pressure.
It is preferable to carry out the last stages of the reaction under subatmospheric pressure to allow for easier removal of volatile by-products. Also, the reaction is preferably carried out under the atmosphere of an inert gas such as nitrogen or argon to avoid gel formation due to sensitivity product with water.
The repetitive unit control, Formula
I • I a · ··· tl
-12···· ·· · • · · ·.
• · • · · » » « • · · · · · . ·· ·
<img file="BR8204792A_D0007.tif" />
I, of the polysiloxane can be accomplished by introducing a blocker to the end, such as, for example, a monomeric or polymeric ester in the reaction mixture, at the beginning of the reaction or at any convenient point in the reaction process. ' number of repetitive units of the polysiloxane is equal to the molar ratio of the monomeric silane to the end blocker as exemplified by the following simplified reaction scheme in which the silane is represented as acetooxyethyltrimethoxy silane and the high boiling ester is represented as methyl benzoate.
O
CH <sub>3</sub>“CO ^ CH ^ jS i-êOCH <sub>3</sub>) <sub>3</sub> +
<img file="BR8204792A_D0008.tif" />
mol '~ 0.1 mol
CH_ ι JO t
O
CH.
OCH<sub>3</sub> + o
CH ^ -C-OCH<sub>3</sub>
Suitable end blockers have the general formula:
3
R -COR
II o
where each region can be the same or different, is a hydrocarbon radical as defined for R.
1-5 · ·· ···
-13»··» ·· • · · • ·· ··· ·· • «· «· • ·
9 »999 99 • · β
999 *
<img file="BR8204792A_D0009.tif" />
Ο termination of the reaction and evidenced by the cessation of the evolution of volatiles and the weight / volume of volatiles collected compared to the theoretical weight / volume. Alternatively, the reaction can be run to a desired viscosity level and the reagents cooled to stop the reaction.
Polysiloxanes have a viscosity of about 0.5 poise to about 150 poise, preferably about 1 to about 20 poise as determined by a Gardner-Holt bubble viscometer at 25 ° C.
Preferred polysiloxanes, for the purposes of the present invention, contain repetitive units that fall within the scope of Formula I, have the viscosity indicated above, and are produced using an organo titanate catalyst. Titanium is believed to combine with polosiloxane to produce organo titanate modified polysiloxanes.
Polysiloxanes can be mixed with the desired matrix, when the matrix is solid, and suitably dispersed therein by mixing them in a Brabender mixer at a temperature between the melting point of the matrix and about 250 ° C, preferably at a temperature from about 110 ° C to about 170 ° C.
The mixing is preferably carried out under constant torque until a homogenized product is obtained.
In cases where the matrix is liquid, the liquid and the polysiloxane are mixed in a Hensk mixer «·« ·
-14»*·« ·· • · · * • ·
<img file="BR8204792A_D0010.tif" />
• · · · * β ···· ·· «« ιι • n «a * • · k ·» k · · · 'kkkk kkkkk chel at a temperature of about 110 ° C to about 170 ° C.
It is preferable to produce the polysiloxane in situ by mixing a monomeric silane and catalyst with the matrix and condensing the silane into a polysiloxane under the conditions described above. With respect to this preparation process, the proportion of polysiloxane dispersed in the matrix, on a calculated basis, is equal to the weight of starting material (monomeric silane plus end blocker) minus the weight of the collected volatiles.
The alkylene-alkyl acrylate copolymers with which the polysiloxanes (in the form of a mother mixture composition) are reacted to form the silane modified copolymers are known copolymers produced by reacting an alkene with an alkyl acrylate.
Suitable alkenes are ethylene, propylene, butene-1, isobutylene, pentene-1, 2-methylbutene-1, 3-methylbutene-1, hexane, heptene-1, octene-1, and the like as well as mixtures thereof.
The alkylene fraction of the alkylene-alkyl acrylate copolymers usually contains from 2 to 18 inclusive carbon atoms, preferably from 2 to 3 inclusive carbon atoms.
Suitable alkyl acrylate monomers that are copolymerized with the alkenes fall within the scope of the following formula:
<img file="BR8204792A_D0011.tif" />
Formula IV
I
<img file="BR8204792A_D0012.tif" />
- 5 where R is hydrogen or methyl and R is alkyl which has up to 3 carbon atoms including. Illustrative compounds understood by this formula are: methyl acrylate, ethyl acrylate, t-butyl acrylate, methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl acrylate and the like as well as mixtures thereof.
Alkylene acrylate copolymers as a rule have density (ASTM D-1505 with conditioning as in ASTM D-147-72) from about 0.92 to about 0.94 and fluidity index [ASTM D-1238 in
<img file="BR8204792A_D0013.tif" />
0.5 to about 500 decigrams per minute and contain about 5 to about 50 weight percent of combined alkyl acrylate.
For the purposes of the present invention, the preferred copolymer is an ethylene-ethyl acrylate copolymer, which is usually about. five to about 50 weight percent of combined ethyl acrylate, preferably having about 5 to about 30 weight percent of combined ethyl acrylate.
The production of silane-modified copolymer of an alkylene-alkyl acrylate is carried out, by reacting a polysiloxane, as described, ··· · «· · · • · •«
<img file="BR8204792A_D0014.tif" />
-16·«« ··· <sup>1</sup> · •
Ο · • · «« «• · fca • · · • · • * • Β ···.
with a copolymer - an alkylene alkyl acrylate in the presence of an organo titanate catalyst.
In cases where the polysiloxane contains combined organo titanate, additional organic titanate catalyst may not be necessary, especially when at least about 0.5 weight percent organo titanate, relative to the weight of the monomeric silane, has been used in preparation of polysiloxane.
The proportion of titanium 10 catalyst added to the reaction mixture is a catalytic proportion, sufficient to catalyze the reaction between the polysiloxane and the copolymer. A preferred ratio is from about 0.001 to about 50 weight percent, most preferably about 0.1 to about 25 weight percent relative to the weight of the polysiloxane.
The proportion of polysiloxane used can vary from about 0.05 to about 10 and preferably about 0.3 to about 5 weight percent with respect to the weight of the copolymer.
The temperature at which this reaction is carried out is not critical and can conveniently vary from about 80 ° C. about 300 ° C and preferably from about 150 ° C to about 230 ° C.
The reaction can be carried out at pressure up to 25 spherical, suhatriiospherical or superatmospheric, although atmospheric pressure is preferred. Likewise, the reaction can be carried out in the presence of solvents, previously described.
«000 >0 · 0 9 9
0 • ·
0 0 • 000 •000 00
-17• 000 ·0 0000 «
0 0 0 0.-0 0 000 0
0
0000
Ο completion of the reaction is evidenced by the measurement of viscosity that does not show additional variation.
The recovery of the copolymer modified with 5 silane and carried out by allowing the contents of the bottle to cool and discharging to a suitable container for storage, preferably under an inert gas atmosphere.
The reaction can be carried out in any suitable apparatus, preferably an apparatus in which the copolymer is subjected to mechanical work such as a Brabènder mixer, a Banbury mixer or an extruder. Polysiloxane (mother mixture) can be added to the molten copolymer and the organo titanate, if necessary, added later. Alternatively, the titanate organo, if necessary, can be added to the copolymer prior to the addition of the polysiloxane (mother mixture). Likewise, organo titanate and polysiloxane (mother mixture) can be pre-mixed and added to the melted polymer.
The reaction between the alkylene-alkyl acrylate copolymer and the polysiloxane can be described by the following equation:
O <sup>1 11</sup> 5
-CCOR<sup>3</sup> ι
-Ç
V + - + - 0 {R} —Siri,
V segment of the combined organo titanate alkyl alkylene acrylate copolymer or added
VI · 0 · {Κ ·) - · —Si ~ n
I
-Ç
V
-18 ···· * • 9 · · * «C • aaa aaaa aa« ao a • va «t * a * aaaaa aaa aaaa ia aaaa aa aa« aaaaaa<sup>J</sup> aaa aaa aaaaa aa it · * where the variables are as previously defined and the unit containing silicon is present in a proportion of at least about 0.05 weight percent, usually about 0.1 to about 10 weight percent and preferably about 0.3 to about 5 weight percent relative to the total weight of the modified copolymer.
Curing or crosslinking of the silane-modified alkylene-acrylate copolymer is carried out by exposing the copolymer to moisture. The humidity present in the atmosphere is usually sufficient to allow curing to take place over a period of 48 hours.
The curing speed, in a matter of 30 minutes, can be accelerated by exposure to an artificially moistened atmosphere or by immersion in water, and by heating at high temperatures or by exposure to steam.
As a rule, curing is carried out at temperatures in the range of about 23 ° C to about 100 ° C, preferably about 70 ° C to about 100 ° C.
In addition, crosslinking can be carried out in the presence of a condensation catalyst for silanol. A unique feature of the present invention is that the crosslinking reaction can be carried out at significant speeds in the absence of a condensation catalyst for silanol. The organo-titanate catalyst or remaining catalytic residues-19-
<td>••O</td><td> ··</td><td> ·</td><td></td><td></td>
<td>• Q</td><td> • ·</td><td> • ·</td><td> • «</td><td> 9</td>
<td> •</td><td> ··</td><td> •</td><td> • .</td><td> •</td>
<td></td><td> ·</td><td> •</td><td>• V</td><td> • 1</td>
<td></td><td> • ·</td><td>The</td><td> « ·</td><td></td>
<td> ····</td><td> ··</td><td> ···</td><td>•ç</td><td></td>
·· »· ο
«I • ο ··
V · · · · 0 · cents in the production of silane-modified copolymers also catalyze the cross-linking reaction.
Alternatively, a wide variety of materials which function as condensation catalysts for silanol and which are known in the art can be employed in the crosslinking process. Such materials include metallic carboxylates described above, organic bases such as ethylamine, hexylamine, dibutylamine, piperidine and the like and acids such as mineral acids, fatty acids and the like.
To the silane-modified copolymers of the present invention, various <sub>(</sub>additives, in proportions known in the art such as fillers among which carbon black, clay, talc, talc coated with a fatty acid metal salt having 8 to 20 carbon atoms, calcium silicate, carbonate calcium, silica, aluminum hydroxide and the like. Other additives include silanes such as vinyl tris -. (2-methoxy) silane and other similar hydrophobic materials.
Silane-modified copolymers can become flame retardants by adding halogen-containing flame retardants to them, such as decabromodiphenyl oxide, ethylene (bis-tetrabromophthalimide), chlorinated polyethylene, poly (vinyl chloride) and halogenated, isolated paraffinic waxes or in mixture with inorganic compounds such as antimony oxide and / or oxides, carbonates, hydro%
-20 alkaline earth metal oxides and sulphates. Among these compounds of alkaline earth metals, calcium oxides, calcium carbonate, calcium hydroxide, calcium sulfate, magnesium oxide, magnesium carbonate, magnesium hydroxide and magnesium sulfate can be noted. Other additives such as smoke eliminators illustrated by zinc borate, molybdenum oxide and similare can also be used.
The following examples further illustrate the present invention and are in no way intended to limit the scope thereof.
Example 1
Part A of this example illustrates the preparation in an ethylene polymer matrix, of a polyoxyloxane in which the ethylene polymer serves as a reactive matrix and as an end blocker for the · polysiloxane.
The production of polysiloxane can be described by the following idealized reaction scheme in which the organo silane monomer was acetooxyethyltrimethoxy silane. *
O
CHy— CO ÍCHj ^ Si (OCH<sub>3</sub>) <sub>3</sub> r och ~
I 3 —O-CHI ^ Si — i; 4-titanate organoO + CH ^ C-OCHg
0CII<sub>3</sub> x = 8-9
Forty grams of ethylacrylate, which had methyl acetate, an ethylene copolymer, fluidity index of 2 ··· · 9 «
-21- ..............
and which contained 2.5 weight percent combined ethyl acrylate, were loaded into a Brabender mixer, which had been preheated to a temperature of 120 ° C, and melted in it for 2 minutes.
At the end of the 2 minute period, 20.8 grams of acetooxyethyltrimethoxy silane and 0.43 ml of tetratisopropyl titanate were added to Brabender.
The contents of Brabender were mixed and allowed to react for one hour, under a flow of argon gasses, while the temperature was kept below 135 ° C. During the one hour period, methyl acetate, the volatile generated (boiling point of 57 ° C) was allowed to volatilize under the flow of argon gas. The end of the reaction was evidenced by the cessation of the evolution of volatiles.
Calculations:
Total volatiles recovered - 7.3 grams
13.5 grams of polysiloxane reacted in 40 grams of ethylene-ethyl acrylate copolymer.
The mother mixture composition was discharged, pressed into sheets, 0.254 cm (o, l) thick, cut into small pieces and stored under argon gels in a polyethylene bag. Visual inspection of slides indicated uniform distribution of polysiloxane in the resin matrix. The blades were uniformly opaque in appearance and were not marbled.
Part B
A 40 gram capacity Brabender mixer was preheated to a temperature of 160 ° C ·· ·
<img file="BR8204792A_D0015.tif" />
and loaded with 38 grams of an ethyleneacrylate ethyl copolymer, which had a fidelity index of 1.6 and which contained 15 weight percent combined ethyl acrylate, 5.35 grams of the mother mixture from
Part A and 0.5 cm of a 4 to 1 mixture, by volume, of tetraisopropyl titanate and dibutyl tin dilaurate. The content of Brabender was mixed for 30 minutes at a temperature of 160 ° C to 165 ° C, resulting in the production of a water-curable ethylene-ethyl acrylate copolymer.
The samples were used to prepare test plates, which had dimensions of 7.62 cm (3} by 20.32 cm (8) by 0.317 cm (0.125) in a press, under the following conditions:
Pressure 350 Kg / cm<sup>2</sup> (5000 psi)
Temperature 130 ° C
Time cycle 5 minutes
The plates were immersed in water, which was at a temperature of 90 ° C, for two hours in order to ensure curing in cross-linked products. The plates were then removed from the water, dried and placed in a vacuum oven, which was at a temperature of 50 ° C, for one hour to remove the residual water.
The plates were then subjected to the following tests:
Cure on the Monsanto Rheometer (Kg / cm) (Described in detail in the US patent. Ηθ 4,018,852 of April 19, 1977) 225,46 • ·
-23Extractable in Decal (%) ASTM D-2765
Deformation (%)
ASTM D-621
- - 2 Tensile Strength (Kg / cm) ASTM D-412
B to BB • ·· ·> o ·
B Be Basea • BB · B «• aa bi« .aaa ·· a
25,9 • · • ·'
33,6*
92,4**
Lengthened (%)
ASTM D-412 180 ** * average of two values ** average of three values
The tests reported subsequently were performed using the same test procedures *. The reported test results were based on average values as indicated in Example 1.
<sup>5</sup> Example 2
In order to demonstrate the moisture resistance of the mother mix compositions of the present invention, a sample of the mother mix composition of Example 1, Part A, was placed on an open aluminum plate and allowed to remain under ambient conditions. After 20 hours, the sample was used to repeat Example 1, Part B.
Plates were then prepared, which were cured<sup>11</sup> as described in Example 1 and subjected to the tests described below:
Aged mother mix (hours) *
Monsanto rheometer (cm / Kg)
212.60. i
II ·· ·· ..
• ·· a ι • · »·« · »· ... D« · ·· «
-24 Deformation (%) 25
Tensile Strength 95.9 Kg / cm
Elongation (%) 210
The data in Examples 1 and 2 indicate that the activity of the stock mixture is not negatively affected by being exposed to moisture in the atmosphere.
A sample of 5.35 grams of acetooxyethyl * trimethoxy silane was also placed on an open aluminum plate and left to stand under ambient conditions for 20 hours. Silane, originally a liquid, gelled into a cross-linked product that had no additional reactive activity.
Example 3
Part A
A three liter bottle of capacity was loaded with 2140 grams (10.29 moles) of acetooxyethyltrimethoxy silane, 154 grams (1.03 moles) of ethyl benzoate (end blocker) and the contents of the bottle were brought to a temperature of 85 ° C. To this mixture, 21 grams of tetraisopropyl thi tannate were then added. The solution, maintained under an argon gas atmosphere, was kept under agitation while being heated for 5 hours and three quarters at a temperature of 94-125 ° C. During this time, 752 grams of volatiles were collected in an acetone-dry ice trap. This constituted 98.8 percent of the theoretical proportion of methyl acetate in relation to 100 percent conversion. The product poly-25 '·· ·· • · · * 9 a »·· t · · · · · · ·» ♦ «· ····« B ata * * · ••• a · * β * a • »oaa ·«
B a
B BB
BB siloxane recovered, 1543 grams, was 99.3 percent of the theoretical yield. The viscosity of the product was 1.4 poise. An equation for the preparation of the polysiloxane can be written as follows:
ch<sub>3</sub>-co «ch<sub>2</sub>)<sub>2</sub>yes (och<sub>3</sub>)<sub>3</sub> +
O
^.£_<sub>0</sub>_ç<sub>2</sub>H<sub>5 +</sub> organo. titanate 0
CH<sub>5</sub>C-OCH<sub>3</sub> O<sup>0CH</sup>3
O4CHj} -5fS ± -
OCHoc<sub>2</sub>H<sub>5</sub> + x = 10
Part B
A Brabender mixer for preheating to a temperature of 160 ° C grams was loaded with 30 grams of polyethylene which had a melt index of 1.90, 10 grams of the polysiloxane of Example 3A
O and 0.2 cm of tetraisopropyl titanate. The contents of Brabender were mixed until a constant torque was maintained in the Plasticord recorder. The mother mix was unloaded from Brabender, pressed into sheets, cut into small pieces, and stored - under argon gels in a polyethylene bag.
Part C
Example 3B was repeated using instead of polyethylene, an ethylene-ethyl acrylate copolymeter that had a melt index of 2 and that contained 20 weight percent combined ethyl acrylate.
·· * «» · ··· · - * · · · · «··· · ·· · rt rt ···« · —2o— ···· ·· ···· ·· · · · # ····
The stock mix compositions from Farte B and Part C were used, instead of the stock mix composition of Example 1, to produce silane modified copolymers using the materials and procedures of Example IB with the exception of ge 0, 2 grams of polymerized 1,2-dihydro-2,3,4-trimethylquinoline was added to Brabender.
Plates of each composition were prepared and cured as described in Example 1B. The tests carried out and their results are set out below.
COPOLYMERS MODIFIED WITH SILANO. USING:
MOTHER MIX B MOTHER MIX
Monsanto Rheometer
<td>(cm / kg)</td><td> 246,1</td><td> 215,4</td>
<td>Deformation (%)</td><td> 24,3</td><td> 24,2</td>
<td>Decalable Extractables (%)</td><td> 22,6</td><td> 21,5</td>
<td>Tensile Strength</td><td></td><td></td>
<td>(Kg / cm<sup>2</sup>)</td><td> 27,5</td><td> 91,7</td>
<td>Stretching (%)</td><td> 183</td><td> 150</td>
Example 4
This example illustrates the moisture resistance of the stock mix compositions of the present invention.
Samples of the mother mixture compositions of Examples 3B and .3C were placed on open aluminum plates and left in homes under ambient conditions. After the indicated time, 5.35 grams of each sample were used instead of the mixing composition ·· · f ·
-27 ·· • · • · a · • a • ·· ««
4
of Example 1 to repeat Example 1, part B.
Plates were then prepared, cured as described in Example 1 and subjected to tests
Monsanto rheometer (cm / kg) Deformation (%)
Decal Extralvels (%) Tensile Strength (kg / cm) Elongation (%)
Retained rheometer (%) of original (Example 3)
COPOLYMERS '; ETHYLENE-ETHYLENE ACRYLATE
MODIFIED WITH SILANO PREPARED USING
MEDIUM MIXTURE:
EXAMPLE 3B EXAMPLE 3C
<td rowspan="2">Aged 20 hours</td><td rowspan="2">Aged 100 hours</td><td colspan="2">Aged Aged</td>
<td>20 hours</td><td>100 hours</td>
<td> 240,6</td><td> 240,6</td><td> *233,8</td><td> 195,8</td>
<td> 30,2</td><td> 27,3</td><td> 29,0</td><td> 33</td>
<td> 30,6</td><td> 22,6</td><td> 22,1</td><td> 23,4</td>
<td> 84</td><td> 88,2</td><td> 88,2</td><td> 91</td>
<td> 177</td><td> 183</td><td> 140</td><td> 200</td>
<td> 98</td><td> 98</td><td> 106</td><td> 91</td>
I
K »
<img file="BR8204792A_D0016.tif" />
• β · ft · «« ··
<img file="BR8204792A_D0017.tif" />
• ·
<img file="BR8204792A_D0018.tif" />
«• ft» ··· «·
-29 »· · · · · · · · · · · · ·> * · · · · · · · · · · · · · · ··· · · ··· · ··· 1 * · «• · · · · • ·. · · • «» · · · · ··· ···
Example 5
This example illustrates that the stock mix compositions of the present invention can be used in highly charged systems to produce water-curable silane-modified alkylene-acrylate copolymers.
A composition with a high charge content was. prepared, with the forhiulation indicated below, in a Brabender mixer that had been preheated to a temperature of 120 ° C. After a five minute mixing period, the Brabender contents were discharged, hot, flattened in a press and allowed to cool. FORMULATION 1
Ethyl acrylate-ethylene copolymer containing 15% by weight of combined ethyl acrylate Fluidity index 1.6 56
Talc Coated with Zinc Stearate 21.9
Antimonium oxide 2.55
Calcium Carbonate 2.55
Ethylene (Bis-tetrabromophthalimide) (Flame Retardant Additive) 16,3 l, 2-Dihydro-2,3,4-trimethyl quinoline Polymerized (Antioxidant) 0,5
Vinyl tris (2-methoxy) 0.2 silane
Fifty-three gram samples of this composition, referred to as Formulation I, were used in the preparation of al-30 »4« ·· alkylene acrylate copolymers a. ·· ι • · · * * · ·. a * · * a · a • · · · a ·
*. · «Β
· • a a. · «Aa ·« · · · · · · · · · • aaa aa »· ** silane modified kilos as described in Example 1B, using the following global reagents:
AB
Formulation X
Composition of Mother Misturge Example 3C
Composition of Mother Mixture Example 3B
Catalyst - Pre-mixed solution of 4 parts by volume of Tetraisopropyl Titanate and 1 part by volume of Dibutyltin Dilaurate
Were the plates then prepared, cured as described in Example 1 and subjected to the tests described below?
grams 53 grams
3.75 grams --- 3.75 grams
0.35 cm '
0.35 cm '
AB
Monsanto rheometer (cm / kg) 223.8 (40 / lb) 173.4 (31 / .lb)
Decalable Extractables (%) 21.2 22.9
Deformation (%) 31.2 30.2 * ~ 2
Tensile strength (Kg / cm) 111.3 (1590 psi) 120.4 (1720 psi)
Elongation (%) 103 140
Example 6
This example illustrates the successful use of masterbatch compositions containing varying proportions of polysilanes to produce alkylene-acrylate-modified copolymers modified with. silane.
The reaction mixtures had the following formulations:
Α
Β
C grams 38 grams
Ethylene-ethyl acrylate copolymer Fluidity index of '1.6. Which contained 15% by weight of combined ethyl acrylate
Formulation I
Described in Example 5
I
1,2-Dihydro-2,3,4-trimethyl Quinoline
Polymerized
I
Mother mix I
Polyethylene matrix containing 4.0% by weight of the polysiloxane of Example 3, relative to the weight of polyethylene
Mother Mix II
Polyethylene matrix containing 14.3% by weight of the Polysiloxane of Example 3, relative to the weight of Polyethylene
Catalyst - Tetraisopropyl titanate mixture - Dibutyltin dilaurate
Described in Example 5 grams
0.2 grams 0.2 grams -
2.68 grams - 3.1 grams
10.7 grams
3 3
0.5 cm 0.5 cm 0.3 cm ι
GJ
H
I
<img file="BR8204792A_D0019.tif" />
··· «· β«
<img file="BR8204792A_D0020.tif" />
·· »• · —32— ββββ ΒΒ • · β Β. · • ·· • · • ΒΒΒ • ΒΒΒΒ β · ΒΒ «Β Β
ΒΒΒ
ΒΒΒ «ΒΒΒ« Β Β «« Β
ΒΒ ΒΒΒΒ
Stock mixtures X and II were prepared as described in Example 3B. The mixtures were reacted in the manner described in Example 1, the resulting reaction products plated as described in
Example 1 and subjected to the Monsanto Rheometer test, as initially prepared and after aging under ambient conditions for the indicated periods of time.
MODIFIED ETHYLENE-ETHYL ACRYLATE COPOLYMERS
ÇOM SILANO FROM COMPOSITIONS OF?
<td>Monsanto rheometer (cm / Kg)</td><td>THE</td><td>B</td><td>ç</td>
<td>Initial</td><td> 263,0</td><td> 246,1</td><td> 279,7</td>
<td>Aged 20 hours</td><td> 237,8</td><td> ----</td><td> 346,9</td>
<td>Aged 7 days</td><td> 170,6</td><td> 195,8</td><td> 223,8</td>
<td>Compositions of</td><td colspan="2">mother mix, whose</td><td>formula-</td>
<td>tions are established</td><td>in the Table</td><td>1, were</td><td>mixture-</td>
in a Brabender mixer at a temperature of <125 ° C, under an argon gas atmosphere.
TABLE 1
Polyethylene with Flow Rate 1.3 Low Pressure Polyethylene with Flow Rate of 0.8 and Density of 0.920 Ethylene-Propylene-Mònômero y Dieno Nordel 2722 (Commercialized by EX DuPont Co.
Polymerized 1,2-Dihydro-2,3,4-Trimethyl Quinoline r
GJ
Lü
Polysiloxane (Described in Example 3) Time to homogenize (minutes)
<td>EXAMPLE 7</td><td>EXAMPLE 8</td><td>EXAMPLE 9</td>
<td>30 grams</td><td> --</td><td> —</td>
<td> —</td><td>32 grams</td><td> —</td>
<td> —</td><td></td><td>32 grams</td>
<td>0.1 gram</td><td>0.1 gram</td><td>0.1 gram</td>
<td>10 grams</td><td>8 grams</td><td>8 grams</td>
<td> 48</td><td> 21</td><td> 42</td>
4 «• * · ae« ·
<img file="BR8204792A_D0021.tif" />
4
4 • 4«
4444 aa aaaa 4 a »·· · <β ··· * · ·«
<img file="BR8204792A_D0022.tif" />
· ·· ο »·· · * • · fr t> ·« ··· · · · ···· · ··· · ·· «··· ·· ···· ·· ν ·« · · · ··
-34 Stock mixtures of Examples 7-9 were used to prepare reaction mixtures, the formulations of which are set out in Table II below. The reaction mixtures were reacted to form modified ethylene-ethyl acrylate copolymers, from which plates were formed, cured with water and tested as described in Example 1.
Ethylene-ethyl acrylate copolymer containing 15% by weight of ethyl acrylate <sup>1 </sup>Fluidity index 1.6
Mother mixture Example 7
Mother mix from Example 8
Mother mixture from Example 9
Catalyst: Tetraisopropyl Titanate Dibutyltin Dilaurate Described in Example 5
Polymerized 1,2-Dihydro-2,3,4-Trimethyl Quinoline
TABLE II
COPOLYMERS ;. ETHYLENE-ETHYLENE ACRYLATE
MODIFIED WITH SILANO FROM COMPOSITIONS OF:
EXAMPLE 7 EXAMPLE 8 EXAMPLE 9 grams 5.35 grams
6.7 grams ι grams
ω in
I
6.7 grams
0.3 cm '
0.3 cm 0.3 cm *
0.2 grams 0.2 grams 0.2 grams • · • · ··· a · · · ii atai ·· ·
Monsanto Reometer (cm / Kg) Tensile Strength (Kg / cm) Elongation (%)
Decalable Extractables (%)
<td> 181,8</td><td> 95,1</td><td> 111,9</td>
<td> 87,5</td><td> 122,5</td><td> 78,4</td>
<td> 293</td><td> 513</td><td> 407</td>
<td> 27,8</td><td> 42,3</td><td> 38,1</td>
I ω
σ »
I · · · · · · · · ··· * · · · · · · · · · · · · · · · · · · · · · · · · · · · ···
<img file="BR8204792A_D0023.tif" />
<img file="BR8204792A_D0024.tif" />
·· ····
-37 · * ·*·· ·· ··
It should also be noted that when producing polysiloxanes, in situ or separately, mixtures of silanes can be used.
Similar results are achieved using the following as monomeric silanes, in the preparation of polysiloxanes in situ, as follows:
gamma-methacryloxypropyl-tris {-2-methoxyethoxy) silane acryloxypropyltrimethoxy silane
<img file="BR8204792A_D0025.tif" />
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Contents48
107 members in 23 offices
Priority claims1
| Document | Office | Kind | Date |
|---|---|---|---|
| 29478481 | United States of America | A |
Members107
| Document | Office | Kind | |
|---|---|---|---|
| ES479103A1 | Spain | A1 | |
| DK131579A | Denmark | A | |
| NO791064L | Norway | L | |
| EP0004752A2 | European Patent Office (EPO) | A2 | |
| AU4565379A | Australia | A | |
| EP0004752A3 | European Patent Office (EPO) | A3 | |
| BR7901936A | Brazil | A | |
| JPS54154491A | Japan | A | |
| ZA791416B | South Africa | B | |
| NZ190052A | New Zealand | A | |
| AR222995A1 | Argentina | A1 | |
| ATA238579A | Austria | A | |
| US4291136A | United States of America | A | |
| IL63927A0 | Israel | A0 | |
| IL63927D0 | Israel | D0 | |
| IT8220240A0 | Italy | A0 | |
| IT8220240D0 | Italy | D0 | |
| US4321263A | United States of America | A | |
| DK430381A | Denmark | A | |
| FI813049L | Finland | L | |
| NO813288L | Norway | L | |
| EP0049155A2 | European Patent Office (EPO) | A2 | |
| AU7574681A | Australia | A | |
| US4328323A | United States of America | A | |
| AT366704B | Austria | B | |
| CA1124438A | Canada | A | |
| BR8106256A | Brazil | A | |
| ES505873A0 | Spain | A0 | |
| ES8205828A1 | Spain | A1 | |
| JPS57126804A | Japan | A | |
| US4343917A | United States of America | A | |
| ZA816715B | South Africa | B | |
| US4353997A | United States of America | A | |
| AU525628B2 | Australia | B2 | |
| PL233254A1 | Poland | A1 | |
| EP0049155A3 | European Patent Office (EPO) | A3 | |
| US4369289A | United States of America | A | |
| AU8742882A | Australia | A | |
| EP0073027A2 | European Patent Office (EPO) | A2 | |
| JPS5865724A | Japan | A | |
| ES510639A0 | Spain | A0 | |
| ES8306381A1 | Spain | A1 | |
| AR229176A1 | Argentina | A1 | |
| BR8204792AThis record | Brazil | A | |
| US4404349A | United States of America | A | |
| WO8303353A1 | World Intellectual Property Organization (WIPO) | A1 | |
| ES8400129A1 | Spain | A1 | |
| AU8282682A | Australia | A | |
| DK498383A | Denmark | A | |
| DK498383D0 | Denmark | D0 | |
| KR830007737A | Republic of Korea | A | |
| AU8319982A | Australia | A | |
| EP0093806A1 | European Patent Office (EPO) | A1 | |
| NO834266L | Norway | L | |
| ES510650A0 | Spain | A0 | |
| ES8400875A1 | Spain | A1 | |
| EP0004752B1 | European Patent Office (EPO) | B1 | |
| EP0073027A3 | European Patent Office (EPO) | A3 | |
| US4434272A | United States of America | A | |
| DE2966569D1 | Germany | D1 | |
| JPS59500417A | Japan | A | |
| US4440907A | United States of America | A | |
| EP0104167A1 | European Patent Office (EPO) | A1 | |
| ZA835593B | South Africa | B | |
| US4446279A | United States of America | A | |
| EP0107211A2 | European Patent Office (EPO) | A2 | |
| PL129360B1 | Poland | B1 | |
| CS713181A2 | Czechoslovakia (until 1993) | A2 | |
| GR75020B | Greece | B | |
| NZ200489A | New Zealand | A | |
| JPS59159850A | Japan | A | |
| EP0120115A1 | European Patent Office (EPO) | A1 | |
| CA1176782A | Canada | A | |
| JPS6035027A | Japan | A | |
| IN155681B | India | B | |
| CA1185384A | Canada | A | |
| JPS6069139A | Japan | A | |
| CA1186437A | Canada | A | |
| EP0104167A4 | European Patent Office (EPO) | A4 | |
| JPS6030325B2 | Japan | B2 | |
| EP0107211A3 | European Patent Office (EPO) | A3 | |
| JPS6050824B2 | Japan | B2 | |
| US4552941A | United States of America | A | |
| CA1197645A | Canada | A | |
| AU549650B2 | Australia | B2 | |
| EP0049155B1 | European Patent Office (EPO) | B1 | |
| US4575535A | United States of America | A | |
| DE3173770D1 | Germany | D1 | |
| AU551220B2 | Australia | B2 | |
| AU551430B2 | Australia | B2 | |
| KR860001033B1 | Republic of Korea | B1 | |
| JPS6148523B2 | Japan | B2 | |
| AU556915B2 | Australia | B2 | |
| IT1150693B | Italy | B | |
| JPS6214172B2 | Japan | B2 | |
| EP0073027B1 | European Patent Office (EPO) | B1 | |
| DE3276240D1 | Germany | D1 | |
| EP0120115B1 | European Patent Office (EPO) | B1 | |
| AT32089T | Austria | T | |
| ATE32089T1 | Austria | T1 |
Numbers
- Application
- 8204792
Titles2
- Portuguese
- COMPOSICAO DE MISTURA-MAE E PROCESSO PARA SUA PREPARACAO E PROCESSO PARA PRODUZIR UM COPOLIMERO ALQUILENO-ACRILATO DE ALQUILA
- English
- MAINTENANCE MIXTURE COMPOSITION AND PROCESS FOR ITS PREPARATION AND PROCESS TO PRODUCE AN ALKYLENE-ALKYL ACRYLATE COPOLIMER
Classification
- CPC, 7
- H01B3/46
- C08F8/42
- C08G77/60
- C08G81/024
- C08L23/025
- C08L83/16
- H01B3/44
- IPC, 15
- C08G77 00
- C08F8 42
- C08G77 06
- C08G77 42
- C08G77 60
- C08G81 00
- C08G81 02
- C08J3 22
- C08L23 02
- C08L83 00
- C08L83 02
- C08L83 04
- C08L83 16
- H01B3 44
- H01B3 46