Aqueous emulsion polymer associative thickeners
Abstract
POLYMER IN WATER EMULSION, WATER COMPOSITION, DRY POLYMERIC COMPOSITION, AND PROCESSES TO PROVIDE A POLYMER IN WATER EMULSION, TO PROVIDE DRY POLYMERIC COMIPOSITION, TO THICKEN OR MODIFY THE WATER REOLOGY OF A COMIPORIUM. An aqueous emulsion polymer suitable for use in aqueous thickening compositions including with copolymerized units: from 8% to 25% by weight based on the weight of the polymer, from monomer containing acid, from 2% to 30% by weight based on weight of polymer, ester of (meth) acrylic acid of the formula: H ~ 2 ~ C = C (R) -C (O) - (CH ~ 2 ~ - CH ~ 2 ~ O) nR ^ 0 ^, where R is H or CH ~ 3 ~, n is 2 to 100 , and R ^ 0 ^ is a group containing from 4 to 36 carbon atoms, and from 35% to 90% by weight based on the weight of the polymer, (C1-C4) alkyl (acrylate); polymer is formed by a polymerization process by free radical live, alternatively in the presence of a compound containing the group -C (5) -S-, is provided. An aqueous composition including the polymer in aqueous emulsion and a polymeric coating including the polymer are also provided as are certain related processes.
Term
Projected expiry 11 June 2028.
- Priority
- Filed
- Granted
- Today
- Projected expiry
9 claims: 6 independent, 3 dependent
- 1REIVINDICAÇÕES 1. Polímero em emulsão aquosa, caracterizado pelo fato de que compreende como unidades copolimerizadas:de 8% a 25% em peso com base no peso do polímero, de monômero contendo ácido, de 2% a 30% em peso com base no peso do polímero, de éster do ácido (met)acrílico da fórmula: H 2 C=C(R)-C(O)-(CH 2 -CH 2 O) n -R°, em que R é H ou CH 3 , n é de 2 a 100, e R° é um grupo que contém de 4 a 36 átomos de carbono, e de 35% a 90% em peso com base no peso do polímero, de (met)acrilato de alquila (C1-C4);em que dito polímero é formado por um processo de polimerização por radical livre vivo.
- 2Polímero em emulsão aquosa, caracterizado pelo fato de que compreende como unidades copolimerizadas:de 8% a 25% em peso com base no peso do polímero, de monômero contendo ácido, de 2% a 30% em peso com base no peso do polímero, de éster do ácido (met)acrílico da fórmula: H 2 C=C(R)-C(O)-(CH 2 -CH 2 O) n -R°, em que R é H ou CH 3 , n é de 2 a 100, e R° é um grupo que contém de 4 a 36 átomos de carbono, e de 35% a 90% em peso com base no peso do polímero, de (met)acrilato de alquila (C1-C4);em que o dito polímero é formado na presença de um composto que compreende o grupo -C(=S)-S-.
- 3Composição aquosa, caracterizada pelo fato de que compreende o polímero em emulsão aquosa como definido na reivindicação 1 ou reivindicação 2.
- 4Composição polimérica seca, caracterizada pelo fato de que compreende um polímero e o polímero em emulsão aquosa como definido na reivindicação 1 ou reivindicação 2.
- 5Processo para fornecer um polímero em emulsão aquosa, caracterizado pelo fato de que compreende formar um polímero em emulsão aquosa compreendendo como unidades copolimerizadas:de 8% a 25% em peso com base no peso do polímero, do monômero contendo ácido, de 2% a 30% em peso com base no peso do polímero, de éster do ácido (met)acrílico da fórmula: H 2 C=C(R)-C(O)-(CH2-CH 2 O) n -R°, em que R é H ou CH3, n é de 2 a 100, e R° é um grupo que contém de 4 a 36 átomos de carbono, e de 35% a 90% em peso com base no peso do polímero, de (met)acrilato de alquila (C r C 4 );por um processo de polimerização por radical livre vivo.
- 6Processo para fornecer um polímero em emulsão aquosa, caracterizado pelo fato de que compreende formar um polímero em emulsão aquosa compreendendo como unidade copolimerizadas:de 8% a 25% em peso com base no peso do polímero, de monômero contendo ácido, de 2% a 30% em peso com base no peso do polímero, de éster do ácido (met)acrílico da fórmula: H 2 C=C(R)-C(O)-(CH 2 -CH 2 O) n -R°, em que R é H ou CH 3 , n é de 2 a 100, e R° é um grupo que contém de 4 a 36 átomos de carbono, e de 35% a 90% em peso com base no peso do polímero, de (met)acrilato de alquila (C1-C4);na presença de um composto que compreende o grupo -C(=S)-S-.
- 7Processo para fornecer a composição polimérica seca como definida na reivindicação 4, caracterizado pelo fato de que compreende:a) formar uma composição que compreende um meio aquoso e um polímero;b) misturar com esta de 0,1% a 10% em peso com base no peso total do dito polímero, do polímero em emulsão aquosa como definido na reivindicação 1 ou da reivindicação 2;5 c) aplicar a dita mistura ao substrato;e d) secar, ou deixar secar a dita mistura.
- 8Processo para engrossar ou modificar a reologia de uma composição aquosa, caracterizado pelo fato de que compreende:misturar com esta o polímero em emulsão aquosa como definido na reivindicação 1 ou da 10 reivindicação 2;e fornecer a mistura com um pH de 7 ou maior.
- 9Processo para formar um agente de RAFT, caracterizado pelo fato de que compreende:a) fornecer um agente de RAFT de ácido carboxílico funcional e 15 b) contactar o dito agente de RAFT com um grupo hidrofóbico de éter glicidílico funcional, o dito grupo hidrofóbico compreendendo de 4 a 36 átomos de carbono.
Independent claims9
230 paragraphs, as filed
(54) Title: WATER EMULSION POLYMER, WATER COMPOSITION, DRY POLYMERIC COMPOSITION, AND PROCESSES TO PROVIDE A WATER EMULSION POLYMER, TO PROVIDE DRY POLYMERIC COMPOSITION, TO THICKEN OR MODIFY A WATER COMPOSITION REOLOGY TO FORM A WATER COMPOSITION DE RAFT (30) Unionist Priority: 11/06/2007 US60 / 934038 (73) Owner (s): Rohm And Haas Company (72) Inventor (s): Antony Keith Van Dyk, Thomas Glenn Madle (57) Summary: polymer in aqueous emulsion, WATER COMPOSITION, DRY POLYMERIC COMPOSITION, AND, PROCESSES TO PROVIDE A WATER EMULSION POLYMER, TO PROVIDE DRY POLYMERIC COMIPOSITION, TO THICKEN OR MODIFY THE WATER COMIPOSITION RHEOLOGY AND TO FORM A RAFT AGENT. An aqueous emulsion polymer suitable for use in aqueous thickening compositions including with copolymerized units: from 8% to 25% by weight based on the weight of the polymer, from acid-containing monomer, from 2% to 30% by weight based on weight of polymer, ester of (meth) acrylic acid of the formula: H<sub>2</sub>C = C (R) -C (O) - (CH<sub>2</sub>- CH<sub>2</sub>O) nR °, where R is H or CH<sub>3</sub>, n is 2 to 100, and R ° is a group containing 4 to 36 carbon atoms, and 35% to 90% by weight based on the weight of the polymer, alkyl (C) acrylate (C, -Ç<sub>4</sub>); wherein the polymer is formed by a live free radical polymerization process, alternatively in the presence of a compound containing the -C (= S) -S- group, is provided. An aqueous composition including the polymer in aqueous emulsion and a polymeric coating including the polymer are also provided as are certain related processes.
ΡΙ0803024-3 “WATER EMULSION POLYMER, WATER COMPOSITION, DRY POLYMERIC COMPOSITION, AND PROCESSES TO PROVIDE A WATER EMULSION POLYMER, TO PROVIDE DRY POLYMERIC COMPOSITION, TO THICKEN OR
MODIFY THE REOLOGY OF A WATER COMPOSITION AND TO FORM A RAFT AGENT ”
This invention relates to aqueous compositions and processes that include certain aqueous emulsion polymers, particularly those that are effective as associative thickeners for aqueous systems. More particularly, this invention relates to an aqueous emulsion polymer which includes, as copolymerized units: from 8% to 25% by weight, based on the weight of the polymer, acid-containing monomer, from 2% to 30% by weight, with based on polymer weight, (meth) acrylic acid ester of the formula: H<sub>2</sub>C = C (R) C (O) -O- (CH<sub>2</sub>-Ch<sub>2</sub> O)<sub>n</sub>R °, where R is H or CH<sub>3</sub>, n is 2 to 100 and R ° is a group containing 4 to 36 carbon atoms and 35% to 90% by weight, based on the weight of the polymer, (C1-C4) alkyl (acrylate); in which the polymer is formed by an active free radical polymerization process or, alternatively, in which the polymer is formed in the presence of a compound that includes the -C (= S) -S- group. An aqueous composition that includes the aqueous emulsion polymer and a dry polymeric composition that includes the polymer are also provided. In addition, the present invention relates to processes by which the aqueous emulsion polymer, the dry polymeric composition and a RAFT agent are provided. The dry polymeric composition of this invention is particularly useful as a film, coating, sealant or filler having properties of water resistance greater than a corresponding composition which includes previously disclosed higher acid content thickeners.
The present invention relates to an aqueous emulsion polymer formed by "polymerization" by a "controlled" or "active" radical that leads to polymers, especially aqueous emulsion polymers that are telehelic, gradients and block that are insoluble in water, but which take become soluble or swellable in water when the pH rises above about 7.
US Patent Application Publication No. 2006/0039939 5 discloses thiocarbonate compounds that are used as rheology modifiers or associative thickeners for systems, which include aqueous systems. The thiocarbonate compounds include at least one hydrophilic group containing the repeating unit preferably derived from (meth) acrylic acid or (meth) acrylamide or the like and at least one hydrophobic group. However, disclosed thickeners include relatively high hydrophilic monomeric levels, such as relatively high levels of acidic gmpo that can have an adverse effect on systems that incorporate thickeners.
In a first aspect of the present invention, an aqueous emulsion polymer is provided which comprises, as copolymerized units:
from 8% to 25% by weight, based on the weight of the polymer, acid-containing monomer, from 2% to 30% by weight, based on the weight of the polymer, (meth) acrylic acid ester of the formula: H<sub>2</sub>C = C (R) -C (O) -O- (CH2-CH2 O)<sub>n</sub>-R °, where R is H or CH<sub>3</sub>, n is 2 to 100 and R ° is a group containing 4 to 36 carbon atoms and 35% to 90% by weight, based on the weight of the polymer, (C1-C4) alkyl (acrylate);
wherein said polymer is formed by an active free radical polymerization process.
In a second aspect of the present invention, an aqueous emulsion polymer is provided which comprises, as copolymerized units:
from 8% to 25% by weight, based on the weight of the polymer, acid-containing monomer, from 2% to 30% by weight, based on the weight of the polymer, (meth) acrylic acid ester of the formula: H2C = C ( R) -C (O) -O- (CH2CH2 O)<sub>n</sub>-R ° 'where R is H or CH<sub>3</sub>, n is 2 to 100 and R ° is a group containing 4 to 36 carbon atoms and 35% to 90% by weight, based on the weight of the polymer, (C1-C4) alkyl (acrylate);
wherein said polymer is formed in the presence of a compound comprising the group -C (= S) -S-.
In a third aspect of the present invention, an aqueous composition is provided which comprises the aqueous emulsion polymer of the first and second aspects of the present invention.
In a fourth aspect of the present invention, there is provided a dry polymeric composition comprising a polymer and the aqueous emulsion polymer of the first or second aspect of the present invention.
Processes for supplying the aqueous emulsion polymers, the dry polymeric composition and a RAFT agent are also provided.
In an embodiment of the present invention, an aqueous emulsion polymer is provided, which includes, as copolymerized units:
from 8% to 25% by weight, preferably from 10% to 20%, based on the weight of the polymer, monomer containing acid, from 2% to 30% by weight, based on the weight of the polymer, acid ester (met) acrylic formula: H2C = C (R) -C (O) -0- (CE [2-CH2 O)<sub>n</sub>-R °, where R is H or CH<sub>3</sub>, preferably CH<sub>3</sub>; n is 2 to 100, preferably 2 to 60, more preferably 2 to 40 and alternatively 2 to 10 and R ° is a group containing 4 to 36 carbon atoms, preferably 4 to 24 carbon atoms and more preferably 12 to 18 carbon atoms or having an average of 12 to 18 or more carbon atoms, alternatively alkyl, aryl, or polyaryl unsubstituted or substituted and 35% to 90% by weight, based on the weight of the polymer, (meth) (C1-C4) alkyl acrylate, preferably ethyl acrylate;
in which the polymer is formed by an active free radical polymerization process or, alternatively, in which the polymer is formed in the presence of a compound that includes the -C (= S) -S- group.
The use of the term (met) followed by another term, such as (met) acrylate or (met) acrylamide, as used throughout the disclosure, refers to both acrylates or acrylamides and methacrylates and methacrylamides, respectively.
The aqueous emulsion polymer can also include, as copolymerized units, independently from 0% to 10% by weight, based on the weight of the polymer, ethylenically unsaturated hydrophobic monomer having less than 0.1% w / w water solubility at 25 ° C such as, for example, lauryl acrylate; from 0% to 40% by weight, based on the weight of the polymer, ethylenically unsaturated monomer having solubility in water of 0.1% to 20% w / w at 25 ° C, such as, for example, N-vinyl pyrrolidone and 0% to 10% by weight, based on the weight of the polymer, polyethylene unsaturated monomer, such as, for example, allyl (meth) acrylate, diallyl phthalate, 1,4-butylene glycol di (meth) acrylate, di 1,2-ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate and divinyl benzene.
The aqueous emulsion polymer includes, as copolymerized units: from 8% to 25% by weight, preferably from 10% to 20% by weight, based on the weight of the polymer, acid-containing monomer. Acid monomers include carboxylic acid monomers, such as, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, monomethyl itaconate, monomethyl fumarate, monobutyl fumarate and maleic anhydride and acid monomers containing sulfur and phosphorus and mixtures thereof, preferably (meth) acrylic acid.
The aqueous emulsion polymer includes, as copolymerized units, from 2% to 30% by weight, based on the weight of the polymer, (meth) acrylic acid ester of the formula: H<sub>2</sub>C = C (R) -C (O) -O- (CH<sub>2</sub>-Ch<sub>2</sub> O)<sub>n</sub>-R °. R ° is a group containing from 4 to 36 carbon atoms which can be alkyl, aralkyl, polyaryl, such as tristyryl phenol or the residue of a polycyclic hydrocarbyl compound, such as lanolin or cholesterol. Alkyl groups include lauryl, tridecyl, myristyl, pentadecyl, cetyl, palmitile, stearyl and eicosyl. Mixtures can also be used, such as alkyl groups resulting from the ethoxylation of mixtures of lauryl, stearyl, cetyl and palmitic alcohols. aralkyl groups include alkylphenyl groups, such as octylphenyl and nonylphenyl.
The aqueous emulsion polymer is preferably a telekelic, gradient or block aqueous emulsion polymer, by telekelic is meant a final functional polymer where the functionality is a hydrophobic group (hydrophobic with respect to a polymer main chain composition which is typically a composition, such as MAA and EA) that consists of at least one such hydrophobic group at each end. The final functionality may consist of a block containing one, two or more hydrophobic groups at each end of the polymer. A final feature can also consist of a gradient where hydrophobic groups are concentrated near the ends of the polymer.
The polymer in the aqueous emulsion polymer is a water-insoluble polymer. By water-insoluble polymer it is understood here that the polymer obtained by centrifuging a sample of the aqueous emulsion polymer at a pH of 4, has at least 1% w / w of water solubility at 25 ° C at a pH of 3. However, the aqueous emulsion polymer is a material soluble in alkyl, or swellable in alkyl or thickenable in alkyl by which it is understood that the addition of a base to the aqueous emulsion copolymer (in an amount to at least partially neutralize the copolymer) it will dissolve the copolymer and simultaneously cause the polymer to swell and thereby thicken the composition.
The average particle diameter of the aqueous emulsion particle polymer is typically 40 nanometers to 400 nanometers, as measured by a Brookhaven Model BI-90 Particle Sizer supplied by Brookhaven Instrument Corp., Holtsville, NY. The numerical average molecular weight of the aqueous emulsion polymer is typically 10,000 to 500,000, as determined by GPC measurement.
The aqueous emulsion polymer is formed by controlled or active radical polymerization, alternatively, the polymer is formed in the presence of a compound that includes the -C (= S) -S- group. By free radical polymerization active here is meant a process that manufactures block polymers and controlled, preferably, polymers that include at least two blocks of composition that differ in hydrophobicity as can be determined by the Hansch parameter calculated for each block and, thus, it excludes the case of uncontrolled or poorly controlled polymerization. Active free radical polymerization includes processes of ATRP (Atom Transfer Radical Polymerization), NMP (Nitroxide Mediated Polymerization) and RAFT (Reversible Addition-Fragmentation Chain Transfer) that are disclosed in the art. The term, RAFT agent is most closely associated with thiocarbonylthio compounds (which includes dithioesters, trithiocarbonates, xanthates, dixantogen disulfides and others). The RAFT agent tables are listed in The Chemistry of Radical Polymerization Moad and Solomon, Elsevier, 2006, pages 508 to 514. In a more general sense, the term RAFT agent is any compound that mediates the polymerization of RAFT and includes agents of macromonomer RAFT. In certain preferred embodiments, a RAFT agent macromonomer or thiocarbonylthio compound is used, such as, for example, a macromonomer or compound containing -X — C (= S) -S- where X is S, O, N or C e is unsubstituted or substituted, plus dibenzyl trithiocarbonate (DBTTC) or ethyl Oditiocarbamate (Xanthate A).
Conventional free radical polymerization proceeds by the development by propagation of macro-radicals. Those macro-radicals, which have a very short life, irreversibly recombine through connection or discouragement. When polymerization occurs in the presence of several comonomers, the variation in the composition of the mixture is neglected considering the life of the macro-radical, so that the chains have a random chain formation from the monomeric units and not a block chain formation . A process for the preparation of copolymers in the presence of a stable free radical from the nitroxide family is described in US Patent No. 6,255,402. Stable nitroxide-mediated radicals were used for the production of controlled block copolymers, as described in US Patent No. 6,255,448 and US Patent Application No. 2002/0040117. A process for preparing block copolymers in the presence of a RAFT agent (RAFT agent, RAFT agent macromonomer, thiocarbonylthio, xanthate or dixantate compound) is described in US Patent No. 3862975 and 6380335, WO 98/01478, WO 98 / 58974, WO 99/31144, WO 99/35177, WO 03/055919 and WO 2006/037161.
The emulsion polymerization techniques used for the preparation of the aqueous emulsion polymer are well known in the art, such as, for example, as disclosed in US Patent No. 4,325,856; 4,654,397 and 4,814,373. Conventional surfactants can be used, such as, for example, anionic and / or non-ionic emulsifiers such as, for example, alkali metal or alkyl ammonium sulfates, alkyl sulfonic acids, fatty acids and ethoxylated alkyl phenols. The amount of surfactant used is usually 0.1% to 6% by weight, based on the weight of the total monomer. Thermal, redox or UV initiation processes can be used. Conventional free radical initiators can be used in addition to the agents required to provide an active polymerization reaction, such as, for example, hydrogen peroxide, t-butyl hydroperoxide, t-amyl hydroperoxide, alkyl or ammonium persulfates and azo initiators, such as 4,4'-azobis (4-cyanopentanoic acid) and 2,2'azobisisobutyronitrile (AIBN), typically at a level of 0.01% to 3.0% by weight, based on the weight of the total monomer. Redox systems using the same initiators linked with a suitable reducer, such as, for example, sodium formaldehyde sulfoxylate, sodium hydrosulfite, isoascorbic acid, hydroxylamine sulfate and sodium bisulfite can be used at similar levels, optionally in combination with ions metallic, such as, for example, iron and copper, optionally still including complexing agents for the metal. Chain transfer agents, such as mercaptans, can be used to decrease the molecular weight of polymers. The monomer mixture can be added pure or as an emulsion in water. The monomer mixture can be added in a single addition or in multiple additions or continuously over the period using a uniform composition or variant. The process can use a preformed seed emulsion polymer, such as, for example, by adding 5% (based on the total monomer) of a 50 nm preformed seed to the boiler. Techniques for reducing the residual monomer, such as, for example, subjecting the reaction mixture to vapor removal, storage times and additional radical sources can be used. Processes that produce polymodal particle size distributions, such as those disclosed in US Patent No. 4,384,056 and 4,539,361, for example, can be used.
The aqueous emulsion polymer is preferably made according to the process. A RAFT agent with optional surfactant and / or methyl beta cyclodextrin (CD in this) and optional seed latex particles are preferably added to the water in a reaction boiler. Initially, about 2 to about 20 hydrophobic monomers (hydrophobic monomers here, are selected from: (meth) acrylic acid esters of the formula: H<sub>2</sub>C = C (R) -C (O) -O- (CH<sub>2</sub>-Ch<sub>2</sub> O)<sub>n</sub>-R ° 'where R is H or CH<sub>3</sub>, n is 2 to 100 and R ° is a group containing 4 to 36 carbon atoms; ethylenically unsaturated hydrophobic monomer having less than 0.1% w / w solubility in water at 25 ° C; and preferably mixtures of these) are inserted into each RAFT agent with optional monomers, such as
MAA and EA. Mono or bifunctional RAFT agents can be used. In one embodiment, the difunctional RAFT agents, such as, preferably, DBTTC are used, about 10 hydrophobic monomers are inserted on each side of the DBTTC RAFT agent, preferably at least two hydrophobic monomers, such as an acid ester (met ) acrylic of formula: H<sub>2</sub>C = C (R) -C (O) -O- (CH2-CH2 O)<sub>n</sub>-R °, where R is H or CH<sub>3</sub> n is 2 to 100 and R ° is a group containing 4 to 36 carbon atoms are inserted on each side. Other monomers, such as MAA and EA can be optionally included. Combinations of hydrophobic monomers can be used. Monomers, which include hydrophobic monomers, can be added as a dose in a batch polymerization process or added over a period of time, such as 20 minutes. Monomers, which include hydrophobic monomers, can be added neat or as a monomeric emulsion with surfactant and water or a solution with CD and water. Optionally, this first stage polymerization can be carried out under load and subsequently added to the water in a reaction boiler. Subsequently EA, MAA and optional co-monomers, such as N-vinyl pyrrolidone and optional hydrophobic monomer and optional polyethylene unsaturated monomers, such as diallyl phthalate are added, preferably, as a monomeric emulsion with surfactant and water and polymerized for the production of the composition as described above. The pH of the boiler water can be adjusted with H<sub>3</sub>POWDER<sub>4</sub> or similar to below about 3 to improve the incorporation of MAA or another acidic monomer. The same or different and combinations of the same or different, the hydrophobic monomer can be incorporated. Monomer feeds can be constant or differential and pulses and gradients and monomer stages can be used with or without storage periods.
The aqueous composition of the invention includes an aqueous medium, the continuous phase of the aqueous composition excluding any soluble polymer being predominantly water; optionally, the medium can include various soluble materials, such as, for example, alcohols and alcohol esters. In certain embodiments, the aqueous medium can be supplied wholly or in part with the polymer, such as, for example, the aqueous emulsion polymer which can supply both the polymer and an aqueous medium. The aqueous composition of the invention can include a polymer, in addition to the aqueous emulsion polymer, which can be soluble, swellable or dispersed in the aqueous composition. The polymer can be thermoplastic, self-crosslinking or thermosetting through the action of an external crosslinker. Preferably the polymer is a dispersed polymer prepared by emulsion polymerization.
Inorganic particles, such as, for example, pigments and extenders, can be included in the aqueous composition at a level of 0 to 95% by volume based on the total dry volume of the aqueous composition and organic particles. Typically, the aqueous composition of this invention has a solid level in the range of 20 to 50 volume% based on the volume of the aqueous composition. The pH of the aqueous composition is typically in the range of 6 to 11 and preferably in the range of 7 to 10. A suitable viscosity range for the aqueous composition is 50 to 130 Kreb units (KU), preferably 70 to 120 KU and more preferably 90 to 110 KU.
Inorganic particles include: pigments and fillers, such as metallic oxides, such as zinc oxide, calcium oxide, cerium oxide, tin oxide, antimony oxide, zirconium oxide, chromium oxide, cadmium pigments, such as such as cadmium yellow, cadmium red and cadmium cinnabar; bismuth pigments, such as bismuth vanadate and bismuth molybdate vanadate; mixed metal oxide pigments, such as cobalt titanate green and other mixed metal oxide pigments; chromate and molybdate pigments, such as chromium yellow, molybdate red and molybdate orange; oversea pigments; cobalt oxide pigments; antimony nickel titanates; chromium lead; blue iron pigments; carbon black and metallic effect pigments, such as aluminum, copper, copper oxide, bronze, stainless steel, nickel, zinc and brass; lead oxide, aluminum oxide, silicon oxide, titanium dioxide; zinc sulfide, lithopone, calcium carbonate, calcium sulfate, barium sulfate, mica, clay, calcined clay, feldspar, nepheline syenite, wollastonite, diatomaceous earth, alumina silicates, magnesium silicates and talc. Titanium dioxide includes treated and surface coated grades (containing, for example, silica and alumina) useful in coating applications.
In one embodiment, the organic particles can have a particle size that is from 10 nm to 100 gm, preferably from 50 nm to 50 gm. Examples of desired organic particles with a particle size less than 100 gm include zinc oxide, silicon oxide, titanium oxide and iron oxide. In another embodiment, the inorganic particles can have a particle size that is from 100 nm to 100 mm. Examples of desired inorganic particles and fillers with a particle size less than 100 mm include rock, basalt, granite, shale, limestone, clay, calcium oxide, sand, silicon oxide, hydraulic cements and non-hydraulic cements that include gypsum and optional colored pigments that include titanium dioxide and iron oxide.
The aqueous composition can optionally contain particles of organic pigment. Suitable organic pigments include plastic pigments, such as solid drop pigments and microsphere pigments containing voids or vesicles. Examples of solid drop pigments include drops of polystyrene and polyvinyl chloride. Examples of microsphere pigments, which include polymeric particles containing one or more vacuums, include opaque polymers Ropaque ™ and polymeric particles with vesicles, as disclosed in US Patent No. 4,427,835; 4,920,160; 4,594,363; 4,469,825; 4,468,498; 4,880,842; 4,985,064;
5,157,084; 5,041,464; 5,036,109; 5,409,776 and 5,510,422.
The aqueous composition may optionally contain certain other particles of organic or inorganic pigment. The coloring particles provide color to the pigmented polymeric composition and coatings prepared from the pigmented polymeric composition. Dye particles include colored pigments, black pigments, metallic effect pigments and luminescent pigments, such as fluorescent pigments and phosphorescent pigments. Examples of colors for the pigmented polymeric composition include black, magenta, yellow and cyan as well as combinations of these colors, such as orange, blue, red, pink, green and brown. Other colors suitable for the pigmented polymeric composition include fluorescent colors; metallic colors, such as silver, gold, bronze and copper and teen pigments. These colors are obtained using one or more different types of coloring particles.
The coloring particles include particles. inorganic dyes and organic coloring particles. Typically, the coloring particles have average particle diameters in the range of 10 nanometers (nm) to 50 microns, preferably in the range of 20 nm to 5 microns and more preferably, in the range of 40 nm to 2 microns.
Suitable organic coloring particles include, for example, azo pigments, monoazo pigments, diazo pigments, azo pigment lakes, β-naphthol pigments, naphthol AS pigments, benzimidazolone pigments, diazo condensation pigments, metal complex pigments, isoindolinone and isoindoline pigments, polycyclic pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments and perinone pigments, thio-indigo pigments, anthrapyrimidone pigments, flavantrone pigments, ananthrone pigments, dioxazine pigments, triarylcarbonium pigments, quinophthalone pigments and diketopyrrole pyrrole pigments.
Examples of organic coloring particles and r particles
Suitable inorganic dyes include: Color index Pigment yellow 1, 2, 3, 5, 6, 10, 12, 13, 14, 16, 17, 62, 65, 73, 74, 75, 81, 83, 87 , 90, 93, 94, 95, 97, 98, 99, 199, 101, 104, 106, 108, 109, 110, 111, 113, 114, 116,
117, 120, 121, 123, 124, 126, 127, 128, 129, 130, 133, 136, 138, 139, 147,
148, 150, 151, 152, 153, 155, 165, 166, 167, 168, 169, 170, 171, 172, 173,
174, 175, 176, 177, 179, 180, 181, 182, 183, 184, 185, 187, 188, 190, 192, r '
193 and 194; Color Index Pigment Orange 1, 2, 5, 6, 13, 15, 16, 17, 17: 1, 19, 22, 24, 31, 34, 36, 38, 40, 43, 44, 46, 48 , 49, 51, 60, 61, 62, 64, 65, 66, 67, 68 and 69; Color Index Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 21, 22, 23, 31 , 32, 38, 48: 1, 48: 2, 48: 3, 49: 1, 49: 2, 49: 3, 50; 1, 51, 52: 1, 52: 2, 53: 1, 57: 1 , 60: 1, 63: 1, 66, 67, 68, 81, 95, 112, 114, 119, 122, 136, 144, 146, 147, 148, 149, 150, 151, 164, 166, 168, 169 , 170, 171, 172, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190,
192, 194, 200, 202, 204, 206, 207, 210, 211, 212, 213, 214, 216, 220, 222,
237, 238, 239, 240, 242, 243, 245, 247, 248, 251, 252, 253, 254, 255, 256,
258, 261 and 264; Color index Pigment Violet: 1, 2, 3, 5: 1, 13, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44 and 50; Color index Pigment Blue 1, 2, 9, 10, 14, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 15, 16, 18, 19, 24: 1, 25 , 56, 60, 61, 62, 63, 64 and 66; Color index Pigment Green 1, 2, 4, 7, 8, 10, 36 and 45; Color Index Pigment Black 6, 7, 10, 11 and 28 and Color Index Pigment Brown 1, 5, 22, 23, 25, 38, 41 and 42.
A process for thickening or modifying the rheology of an aqueous composition includes mixing with it the aqueous emulsion polymer of the invention and providing the mixture with a pH of 7 or greater, that is, adjusting or maintaining the pH of the mixture at a pH 7 or greater.
The aqueous composition of this invention can find use in adhesives and sealants, concrete, mortars, plasters, plaster, plaster, EIFS (Exterior Insulation Finishing System) and mortars, agricultural and pharmaceutical compositions, treatments for porous substrates such as leather, fabrics , non-woven or woven, wood and others or as an aqueous coating composition. Aqueous compositions which include inorganic particles and optionally organic particles are prepared by techniques which are well known in the art of coatings. First, inorganic particles are typically well dispersed in the presence of an organic polymer dispersant and optionally the aqueous emulsion polymer of the present invention (which includes optional additives, such as surfactants, defoamers, biocides, mildicides, colorants, co-thickeners, auxiliaries and flow, sliding aids, odor masks, solvents, co-solvents and coalescents) in an aqueous medium under high cut, as produced by a COWLES ™ mixer. Then, in some embodiments, an organic pigment and independently, an emulsion polymer can be added under low shear agitation along with other coating adjuvants as desired. The aqueous composition may contain, in addition to the associative thickener with aqueous emulsion polymer of this invention, conventional coating adjuvants, such as, for example, emulsifiers, coalescing agents (coalescents), plasticizers, antifreeze, curing agents, buffers, neutralizers, thickeners, rheology modifiers other than those of the invention, wetting agents, wetting agents, biocides, mildicides, plasticizers, anti-foaming agents, UV absorbers, fluorescent brighteners, light or heat stabilizers, chelating agents, dispersants, colorants, waxes, water repellents and anti-oxidants.
Methods of applying conventional coatings, such as, for example, brushing, revolutions, dipping, smoothing, dispersing, scraping, spraying methods, such as, for example, atomized spraying with air, spray assisted air, spraying without air, electrostatic spray, low pressure spray of high volume and airless spray assisted by air, electrodeposition can be used for the application of the aqueous composition of this invention. Additionally, for some systems, other application techniques can be used for applying the aqueous coating composition, such as printing devices with jet and piezo ink, thermal ink jet, etc., engraving roller, etc., spray gun caulking, roller coatings, curtain coatings and knife-air coating. The aqueous coating composition can be advantageously applied to substrates, such as, for example, plastic, wood, metal, prepared surfaces, previously painted surfaces, painted surfaces exposed to the weather, glass, textiles, paper, non-woven, composite and cementitious substrates . Drying an aqueous composition of this invention that provides a dry polymeric composition such as, for example, a film, coating, sealant or filler compound is typically left to proceed under ambient conditions, such as, for example, at 0 ° C at 35 ° C but can be accelerated with higher temperatures or low humidity.
In an embodiment of the present invention a process for forming a RAFT is provided, including; a) providing a carboxylic acid functional RAFT agent and b) contacting said RAFT agent with a hydrophobic functional group of glycidyl ether, the hydrophobic group comprising from 4 to 36 carbon atoms.
Experimental method
Procedure for identifying aqueous emulsion polymers of the invention.
100g of Rhoplex ™ AC-261 is weighed in a suitable container. Then a solution or dispersion of 0.6 g of the test polymer in 4.4 g of water is added with stirring. The pH is adjusted with the NH4OH solution to pH 9.0. Mixing is continued in a Hauschild SpeedMixer ™ DAC 150 FVZ for 2 minutes to ensure homogeneity. A Brookfield DV-I + viscometer with a number of 3 threads at 100 rpm is used to measure the viscosity of the sample at 25 ° C.
A 25g portion of this expressed composition is removed and mixed with 1.25g of Polystep ™ B7 surfactant solution (30% in water) in a Hauschild SpeedMixer ™ DAC 150 FVZ for 2 minutes. The sample is adjusted to 25 ° C and this viscosity is measured at 100 rpm. Viscosities without and with surfactant are compared. The major difference between the as-is viscosity and the suppressed surfactant viscosity is used as a measure of the associative thickness powder of the thickener. The aqueous emulsion polymer of the present invention is observed to have viscosities of 20 to more than 1000 times greater than its suppressed viscosity of surfactant which is used in this to mean that the hydrophobic associative groups have been incorporated into the final chain.
The following examples are presented to illustrate the purpose.
Abbreviations used EA ethyl acrylate
MAA methacrylic acid
Lauryl acrylate LA
Sodium Lauryl Sulfate SLS
1-Dodecanethiol n-DDM
NaPS sodium persulfate
Deionized water DI water
EXAMPLE 1. Preparation of the aqueous emulsion polymer.
<td>Internship</td><td></td><td>g</td>
<td>THE</td><td>DI water</td><td> 907,3</td>
<td></td><td>AvailableTMFES 32 (30%)</td><td> 17,2</td>
<td></td><td>AND THE</td><td> 33,6</td>
<td></td><td>IVIAA</td><td> 7,46</td>
<td></td><td>C18-E020-MA</td><td> 26,11</td>
<td></td><td>RAFT agent</td><td> 1,52</td>
<td></td><td>NaPS</td><td> 1,0</td>
<td></td><td>hold for 30 minutes</td><td></td>
<td></td><td>add monomer B emulsion for 90 minutes</td><td></td>
<td>B</td><td>DI water</td><td> 275,1</td>
<td></td><td>AvailableTM FES32 (30%)</td><td> 17,2</td>
<td></td><td>AND THE</td><td> 316,4</td>
<td></td><td>MAA</td><td> 61,9</td>
<td></td><td>C12-E023-MA</td><td> 34,4</td>
<td></td><td>hold for 30 minutes</td><td></td>
<td></td><td>29% final solids.</td><td></td>
Disponil ™ FES32 manufactured by Cognis Corp. it is described as sodium lauryl ether sulfate.
Add DI water and surfactant to the reaction boiler and start the stirrer. Heat the boiler to 80 ° C. Dissolve the RAFT agent (such as dibenzyl trithiocarbonate (DBTTC)) in the monomer mixture then add the monomer mixture alone with the NaPS initiator and heat the boiler to 85 ° C and keep for 30 minutes. Add the EA, MAA, and C12-E023-MA monomer emulsion for 1 to 5 hours and then hold for 30 minutes after feeding is completed.
EXAMPLE 2. Preparation of aqueous emulsion polymer.
<td>Internship</td><td></td><td>g</td>
<td>THE</td><td>DI water</td><td> 706,3</td>
<td></td><td>SLS (28%)</td><td> 17,2</td>
<td></td><td>CD 50%</td><td> 200</td>
<td></td><td>AND THE</td><td> 33,6</td>
<td></td><td>MAA</td><td> 7,46</td>
<td></td><td>C18-E020MA</td><td> 26,11</td>
<td></td><td>RAFT agent</td><td> 1,52</td>
<td></td><td>NaPS</td><td> 1,0</td>
<td></td><td>hold for 30 minutes</td><td></td>
<td></td><td>add monomer B emulsion for 120 minutes</td><td></td>
<td>B</td><td>DI water</td><td> 275,2</td>
<td></td><td>SLS (28%)</td><td> 17,2</td>
<td></td><td>AND THE</td><td> 316,4</td>
<td></td><td>MAA</td><td> 61,9</td>
<td></td><td>C12-E023-MA</td><td> 34,4</td>
<td></td><td>hold for 30 minutes</td><td></td>
<td></td><td>35% final solids</td><td></td>
Example 2 is based on Example 1 with the addition of heptaquis (2,6-di-O-methyl) -b-cyclodextrin, CavasolT<sup>M</sup> W7 M TL by Wacker Chemie (CD). Cyclodextrin can optionally be added in a third stage.
EXAMPLE 3. Preparation of aqueous emulsion polymer
<td>Internship</td><td></td><td>g</td>
<td>THE</td><td>DI water</td><td> 906,3</td>
<td></td><td>H3PO4 (85%) to adjust to pH <3.0</td><td> 1,0</td>
<td></td><td>SLS (28%)</td><td> 27,4</td>
<td></td><td>AND THE</td><td> 65,0</td>
<td></td><td>MAA</td><td> 3,0</td>
<td></td><td>OVER THERE</td><td> 5,2</td>
<td></td><td>RAFT agent</td><td> 1,52</td>
<td></td><td>NaPS</td><td> 1,0</td>
<td></td><td>Hold for 30 minutes</td><td></td>
<td></td><td>add monomer B emulsion for 120 minutes</td><td></td>
<td>B</td><td>DI water</td><td> 275,2</td>
<td></td><td>SLS (28%)</td><td> 17,2</td>
<td></td><td>AND THE</td><td> 316,4</td>
<td></td><td>MAA</td><td> 68,5</td>
<td></td><td>C12-E023-MA</td><td> 34,4</td>
<td></td><td>Hold for 30 minutes</td><td></td>
<td></td><td>29% final solids</td><td></td>
Example 3 is based on Example 1 with hydrophobic lauryl acrylate monomer in stage A in place of monomer 08E020-MA.
EXAMPLE 4. Preparation of aqueous emulsion polymer
<td></td><td></td><td>g</td>
<td>THE</td><td>DI water</td><td> 976,3</td>
<td></td><td>SLS (28%)</td><td> 17,2</td>
<td></td><td>AND THE</td><td> 33,6</td>
<td></td><td>MAA</td><td> 7,46</td>
<td></td><td>C18-E020'MA</td><td> 26,11</td>
<td></td><td>RAFT agent</td><td> 1,52</td>
<td></td><td>NaPS</td><td> 1,0</td>
<td></td><td>Hold for 30 minutes</td><td></td>
<td>B</td><td>H3PO4 (85%) to adjust to pH <3.0</td><td> 1,0</td>
<td></td><td>add the following monomer emulsion for 2 hours</td><td></td>
<td>Ç</td><td>DI water</td><td> 70</td>
<td></td><td>SLS (28%)</td><td> 10</td>
<td></td><td>AND THE</td><td> 158</td>
<td></td><td>MAA</td><td> 30,8</td>
<td></td><td>C12-E023-MA</td><td> 22</td>
<td></td><td>Hold for 30 minutes</td><td></td>
<td></td><td>21% final solids</td><td></td>
Example 4 provides an alkaline telekelic expandable emulsion thickener with numerical average molecular weight, Mn, at about 20,000.
<td>internship</td><td></td><td>g</td>
<td>THE</td><td>DI water</td><td> 906,3</td>
<td></td><td>SLS (28%)</td><td> 17,2</td>
<td></td><td>AND THE</td><td> 33,6</td>
<td></td><td>MAA</td><td> 7,46</td>
<td></td><td>C18-E020-MA</td><td> 26,11</td>
<td></td><td>RAFT agent</td><td> 1,52</td>
<td></td><td>NaPS</td><td> 0,6</td>
<td></td><td>Add the following monomer emulsion for 4 hours</td><td></td>
<td>B</td><td>DI water</td><td> 275,2</td>
<td></td><td>SLS (28%)</td><td> 17,2</td>
<td></td><td>AND THE</td><td> 316,4</td>
<td></td><td>MAA</td><td> 61,9</td>
<td></td><td>hold for 120 minutes</td><td></td>
<td></td><td>28% final solids.</td><td></td>
Example 5 uses a lower level of NaPS initiator.
EXAMPLE 6. Preparation of aqueous emulsion polymer
<td>Internship</td><td></td><td></td>
<td>THE</td><td>Water Dl</td><td> 1007,3</td>
<td></td><td>SLS (28%)</td><td> 17,2</td>
<td></td><td>AND THE</td><td> 33,6</td>
<td></td><td>MAA</td><td> 7,46</td>
<td></td><td>SipomerTM SEM-25</td><td> 26,11</td>
<td></td><td>RAFT agent</td><td> 1,52</td>
<td></td><td>NaPS</td><td> 1,0</td>
<td></td><td>Hold for 30 minutes</td><td></td>
<td></td><td>add the following monomer emulsion for 120 minutes</td><td></td>
<td>B</td><td>Water Dl</td><td> 175,1</td>
<td></td><td>SLS (28%)</td><td> 17,2</td>
<td></td><td>AND THE</td><td> 316,4</td>
<td></td><td>1VIAA</td><td> 61,9</td>
<td></td><td>C12-E023-MA</td><td> 34,4</td>
<td></td><td>Hold for 60 minutes</td><td></td>
<td></td><td>29% final solids</td><td></td>
Example 6 uses an alternative hydrophobic monomer in
Stage A
COMPARATIVE EXAMPLE A. Preparation of aqueous emulsion polymer
<td>Internship</td><td></td><td>g</td>
<td>THE</td><td>Water Dl</td><td> 976,3</td>
<td></td><td>SLS (28%)</td><td> 17,2</td>
<td></td><td>AND THE</td><td> 33,6</td>
<td></td><td>MAA</td><td> 7,46</td>
<td></td><td>Cl 8- E020-MA</td><td> 26,11</td>
<td></td><td>RAFT agent</td><td> 1,52</td>
<td></td><td>NaPS</td><td> 0,14</td>
<td></td><td>Hold for 30 minutes</td><td></td>
<td></td><td>Add the following monomer emulsion for 4 hours</td><td></td>
<td>Ç</td><td>Water Dl</td><td> 70</td>
<td></td><td>SLS (28%)</td><td> 10</td>
<td></td><td>AND THE</td><td> 158</td>
<td></td><td>MAA</td><td> 30,8</td>
<td></td><td>Hold for 120 minutes</td><td></td>
<td></td><td>20% final solids</td><td></td>
Comparative example A uses a primer level, NaPS, at about 10% by weight of the RAFT agent as explained in US Patent Application Publication No. 20060039939 and 20060223936. This example has poor conversion, that is, less than about 80% of the monomer is incorporated.
COMPARATIVE EXAMPLE B. Preparation of aqueous emulsion polymer
<td></td><td></td><td>s</td>
<td>THE</td><td>DI water</td><td> 906,3</td>
<td></td><td>SLS (28%)</td><td> 17,2</td>
<td></td><td>AND THE</td><td> 33,6</td>
<td></td><td>MAA</td><td> 7,46</td>
<td></td><td>RAFT Agent 2</td><td> 2,8</td>
<td></td><td>AIBN</td><td> 0,14</td>
<td></td><td>Hold for 30 minutes</td><td></td>
<td></td><td>Add the following monomer emulsion for 4 hours</td><td></td>
<td>Ç</td><td>DI water</td><td> 70</td>
<td></td><td>SLS (28%)</td><td> 10</td>
<td></td><td>AND THE</td><td> 158</td>
<td></td><td>MAA</td><td> 30,8</td>
<td></td><td>Hold for 120 minutes</td><td></td>
<td></td><td>20% final solids.</td><td></td>
RAFT Agent 2
<img file="BRPI0803024A2_D0001.tif" />
Brij 58 Diester of s, s'-bis- (2-methyl-2-carboxymethyl) tritiocarbonate
Comparative example B was made according to the explanations of US Patent Application Publication No. 20060039939. The method disclosed in this includes the esterification of alcohols with carboxylic RAFT agents that result in a low yield of RAFT diester agent and significant degradation of the RAFT agent during the esterification process. In the synthesis described above, very deficient reaction kinetics were observed with low conversion, that is, under about 60% and excessive EA reflux. The polymer was isolated from the non-reactive monomer and found to be a deficient thickener compared to the thickeners of this invention. The thickener dependence on a simple telephonic hydrophobic bonded by an ester group has been observed to cause loss of viscosity over time, presumably like the hydrolyzed ester group, in aqueous coating compositions having a pH of about 9.
EXAMPLE 7. Preparation of aqueous emulsion polymer Example 7 is prepared as comparative example B except that the present example uses a carboxylic acid containing RAFT agent which is reacted with glycidyl ether functionally in a hydrophobe significantly under milder conditions, at lower temperature and with the much higher yield of agent 3 RAFT di-ester, to provide a telekelic alkaline expandable polymer thickener.
RAFT Agent 3
<img file="BRPI0803024A2_D0002.tif" />
HAGE 16 Diester of s, s'-bis- (2-methyl-2-carboxymethyl) tritiocarbonate
EXAMPLE 8. Evaluation of the aqueous emulsion polymer, the aqueous compositions that include, and the dry coatings that include.
The low viscosity aqueous emulsion polymers of
Examples 1 to 6 are swellable with alkali and produce high viscosity compositions and then the pH is raised above about 7. The aqueous alkaline swellable emulsion polymer is an effective thickener for paints, coatings and aqueous compositions that require rheology control .
The associative aqueous emulsion polymer thickeners of Examples 1 to 6 are used in an aqueous coating composition and produce responses of a thickness comparable to the HASE thickeners known as described in US Patent No. 4,421,902, with much improved early bubble formation. and water resistance properties. The thickness response is more effective than that of thickeners, such as comparative example A, disclosed in US Patent Application Publication
Ν °. 20060039939.
An aqueous coating composition that includes the associative thickener of Examples 1 to 6 and comparative example A and B are used to melt a film of 3 mil (25.4 pm) in alkyd compound
6 months old. The film is allowed to dry at 25 ° C and 50% RH for 2 hours.
Then a 1 x 1 square of gauze is applied and soaked with DI water. Films that include each of Examples 1 to 6 do not bubble or slide after soaking for 60 minutes. The films of comparative examples A and B form bubbles in about 5 minutes. Films that include each of Examples 1 to 6 had increased brightness, measured at 60 and 20 degrees, than films that include comparative examples A or B. films that include each of Examples 1 to 6 had better flow and leveling and resistance to curvature comparable to films that include comparative examples A or B.
11 members in 8 offices
Priority claims1
| Document | Office | Kind | Date |
|---|---|---|---|
| 93403807 | United States of America | P |
Members11
| Document | Office | Kind | |
|---|---|---|---|
| US2008306218A1 | United States of America | A1 | |
| KR20080108913A | Republic of Korea | A | |
| CN101323655A | China | A | |
| EP2003152A1 | European Patent Office (EPO) | A1 | |
| AU2008202275A1 | Australia | A1 | |
| JP2009001776A | Japan | A | |
| BRPI0803024A2This record | Brazil | A2 | |
| KR20110007074A | Republic of Korea | A | |
| EP2003152B1 | European Patent Office (EPO) | B1 | |
| DE602008005520D1 | Germany | D1 | |
| JP2011246719A | Japan | A |
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| Patent lapsed as no evidence of payment of the annual fee has been furnished to inpi [chapter 8.11 patent gazette]LapsedREFERENTE AO DESPACHO 8.6 PUBLICADO NA RPI 2258 DE 15/04/2014.B08K | B08K | |
| Application dismissed because of non-payment of annual fees [chapter 8.6 patent gazette]REFERENTE A 6A ANUIDADE.B08F | B08F | |
| Publication of a patent application or of a certificate of addition of invention [chapter 3.1 patent gazette]B03A | B03A | |
| Technical and formal requirements: other requirements [chapter 6.7 patent gazette]SOLICITA-SE A REGULARIZACAO DA PROCURACAO, UMA VEZ QUE BASEADO NO ARTIGO 216 1O DA LPI, O DOCUMENTO DE PROCURACAO DEVE SER APRESENTADO EM SUA FORMA AUTENTICADA; OU SEGUNDO O PARECER DA PROCURADORIA NO 074/93, DEVE CONSTAR UMA DECLARACAO DE VERACIDADE, A QUAL DEVE SER ASSINADA POR UMA PESSOA DEVIDAMENTE AUTORIZADA A REPRESENTAR O INTERESSADO, DEVENDO A MESMA CONSTAR NO INSTRUMENTO DE PROCURACAO, OU NO SEU SUBSTABELECIMENTO.B06G | B06G | |
| Technical and formal requirements: other requirements [chapter 6.7 patent gazette]SOLICITA-SE A REGULARIZACAO DA PROCURACAO, UMA VEZ QUE BASEADO NO ARTIGO 216 � 1O DA LPI, O DOCUMENTO DE PROCURACAO DEVE SER APRESENTADO EM SUA FORMA AUTENTICADA; OU SEGUNDO O PARECER DA PROCURADORIA NO 074/93, DEVE CONSTAR UMA DECLARACAO DE VERACIDADE, A QUAL DEVE SER ASSINADA POR UMA PESSOA DEVIDAMENTE AUTORIZADA A REPRESENTAR O INTERESSADO, DEVENDO A MESMA CONSTAR NO INSTRUMENTO DE PROCURACAO, OU NO SEU SUBSTABELECIMENTO.B06G | B06G |
Numbers
- Application
- 8030243
Titles2
- Portuguese
- polìmero em emulsão aquosa, composição aquosa, composição polimérica seca, e, processos para fornecer um polìmero em emulsão aquosa, para fornecer a composição polimérica seca, para engrossar ou modificar a reologia de uma composição aquosa e para formar um agente de raft
- English
- aqueous emulsion polymer, aqueous composition, dry polymeric composition, and processes for providing an aqueous emulsion polymer, to provide dry polymeric composition, to thicken or modify the rheology of an aqueous composition and to form a raft agent
Classification
- CPC, 14
- C08F220/12
- C08F220/00
- C08F2/38
- C08F4/00
- C08F293/005
- C08L33/02
- C08L33/08
- C08L33/10
- C08L53/00
- C09D7/43
- C08F220/18
- C08F220/1802
- C08L33/04
- C08L33/12
- IPC, 4
- C08F2 00
- C08F2 38
- C08F2 44
- C08F20 00