CN107141394A - A kind of styrene-acrylic emulsion of zero VOC content and preparation method thereof - Google Patents
A kind of styrene-acrylic emulsion of zero VOC content and preparation method thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
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- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
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- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
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- C09D125/14—Copolymers of styrene with unsaturated esters
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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Abstract
The invention discloses a kind of styrene-acrylic emulsion of zero VOC content, in parts by mass, including following components, 80 130 parts of water, 5 20 parts of emulsifying agent, 20 50 parts of styrene, 20 50 parts of butyl acrylate, 0.5 5 parts of acrylic acid, 15 parts of cross-linking monomer, 0.2 1 parts of persulfate, 0.1 1 parts of oxidant, 0.2 1 parts of reducing agent.The net taste of styrene-acrylic emulsion environmental protection of the zero VOC content of the present invention, VOC content is extremely low.
Description
Technical field
The present invention relates to a kind of styrene-acrylic emulsion, specifically a kind of styrene-acrylic emulsion of zero VOC content and preparation method thereof,
Belong to building coating technical field.
Background technology
With the improvement of living standards, people increasingly increase for the demand of the net taste of environmental protection of living environment, it is Chinese《Room
Interior trim finishing material nuisance content》Regulation：VOC content palpus≤200g/L in wall finiss；Environmental label certification standard
It is required that the VOC content after wall finiss water removal wants≤80g/L；The standard of developed country is then more harsh, wall finiss in such as EU criteria
VOC content palpus≤75g/L.
And the most of VOC contents of styrene-acrylic emulsion commonly used on the market at present are higher, building coating is made into use, its VOC
Content is generally higher than the VOC content standard (80g/L) after the water removal of the wall finiss of environmental label certification requirement, to the indoor ring of inhabitation
Border is polluted, and smell greatly and not environmentally, has a strong impact on the healthy of occupant.In addition, current overwhelming majority building emulsions
Production cycle it is universal longer, energy consumption is big, production efficiency is relatively low etc., and part has stability between complex operation, batch
Low phenomenon.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of net taste of environmental protection, the phenylpropyl alcohol of zero VOC content
Emulsion.
Another goal of the invention of the present invention is the extremely short-period preparation method for providing a kind of above-mentioned emulsion.
What the goal of the invention of the present invention was realized in：A kind of styrene-acrylic emulsion of zero VOC content, in parts by mass, bag
Include following components, 80-130 parts of water, 5-20 parts of emulsifying agent, 20-50 parts of styrene, 20-50 parts of butyl acrylate, acrylic acid 0.5-
5 parts, 1-5 parts of cross-linking monomer, 0.2-1 parts of persulfate, 0.1-1 parts of oxidant, 0.2-1 parts of reducing agent.
The emulsifying agent is sodium p styrene sulfonate, ethoxylated alkyl sulfate, sulfosuccinic acid ethoxy ethanol list
One kind or mentioned component in ester disodium salt are mixed with arbitrary proportion.
The cross-linking monomer is vinyltrimethoxy silane, trimethylol-propane trimethacrylate, metering system
One kind or mentioned component in allyl propionate are mixed with arbitrary proportion.
The persulfate is one kind or mentioned component in ammonium persulfate, potassium peroxydisulfate and sodium peroxydisulfate with arbitrary proportion
Mixing.
The oxidant is hydrogen peroxide.
The reducing agent is ascorbic acid.
Present invention also offers a kind of preparation method of the styrene-acrylic emulsion of above-mentioned zero VOC content, comprise the following steps：
A) under normal temperature and pressure, 2-10 parts of emulsifying agent and 10-20 parts of water are mixed in emulsion tank, dissolving is sufficiently stirred for
Afterwards, the styrene of formula ratio, butyl acrylate, acrylic acid, cross-linking monomer and uniform stirring 15-30 minute are sequentially added, it is obtained
Pre-emulsion is standby；
B) reactor bottom add 40-50 parts water and residual emulsifier, be warming up to 80-95 DEG C, treat temperature stabilization
Afterwards, pre-emulsion disposably is made as seed to reactor in 10-15 parts of step a) of input, will after stirring 0.5-1 minutes
0.1-0.5 parts of persulfate initiator is added after fully being dissolved with 2-10 parts of water to be reacted, and seed fully reacts 10-30 points
Clock；
C) remaining persulfate initiator is completely dissolved with 5-15 parts of water, by 0.1-0.3 parts of reducing agent residue water
It is completely dissolved, it is standby；
D) after the completion of above-mentioned steps b), at 80-95 DEG C, by remaining pre-emulsion in step a) and the mistake prepared in step c)
Dropwise reaction 80-120min, i.e. completion polymerize simultaneously for the persulfate initiator aqueous solution and reducing agent aqueous solution；
E) after the completion of above-mentioned steps d), 70-90 DEG C is cooled the temperature to, then by 0.05-0.3 parts of oxidants and 0.05-0.4
The reducing agent of part is fed directly in reactor respectively；
F) after the completion of above-mentioned steps e), 60-80 DEG C is cooled to, while remaining oxidant and remaining reducing agent is added dropwise,
20-30min is added dropwise, 5-15 minutes are incubated after dripping off, then cools 40-55 DEG C and uses in caustic soda with pH value to 7-8, filtering is produced
The styrene-acrylic emulsion of zero VOC content.
The present invention has advantages below：
1st, the styrene-acrylic emulsion of zero VOC content of the invention, the monomer reactivity ratio of selection is close, beneficial to abundant reaction, subtracts
Lack residual monomer content, and the emulsion of design, without extra addition coalescents, can further subtract in room temperature (25 DEG C) film forming
Few emulsion VOC content.
2nd, the styrene-acrylic emulsion of zero VOC content of the invention, by taking kind of a reaction to provide good reacting environment, and passes through
Higher temperature coordinates redox system polymerization, and reaction is fully and reaction efficiency is high, so as to further reduce residual monomer content.
3rd, the present invention is used after exclusive post-processing technology, pre-emulsification completion of dropping, and directly cooling is post-processed, with biography
The technique post-processed again after the insulation of system is compared, and can be migrated into the residual monomer for having neither part nor lot in reaction inside latex particle
Before, i.e., residual monomer is also present in aqueous phase or when emulsion particle surface, quickly produced by redox free radical make it is residual
Remaining monomer fully reacts again, and residual monomer content in system is greatly lowered, meanwhile, drip off the uninsulated technique of pre-emulsion
Also the production cycle is substantially reduced, energy consumption is reduced.
4th, reductant-oxidant itself VOC content used in post processing of the invention is extremely low, it is ensured that extremely low remnants are single
Body content, also ensure that the extremely low VOC content of system.
5th, technique, and exclusive, quick post-processing technology are added dropwise by redox, are significantly shorter than reaction time
The styrene-acrylic emulsion of common process production, and due to short production cycle, technique is simple, stability is high between product batches.
6th, the method for testing of VOC content in the use internal mark method determination emulsion that group's offer is provided is surveyed according to China, peace is used
Prompt human relations gas chromatograph for determination, VOC content≤1 (g/L) of polymer emulsion of the invention, well below Taken authentication standard,
It is zero VOC truly.
Embodiment
The styrene-acrylic emulsion of the zero VOC content of the present invention, in parts by mass, including following components, 80-130 parts of water, emulsification
5-20 parts of agent, 20-50 parts of styrene, 20-50 parts of butyl acrylate, 0.5-5 parts of acrylic acid, 1-5 parts of cross-linking monomer, persulfate
0.2-1 parts, 0.1-1 parts of oxidant, 0.2-1 parts of reducing agent.
The present invention is using sodium p styrene sulfonate, ethoxylated alkyl sulfate, sulfosuccinic acid ethoxy ethanol monoesters
One kind or mentioned component in disodium salt are mixed as emulsifying agent using arbitrary proportion, cloudy non-integral sulfosuccinic acid ethyoxyl second
The reactive monomer emulsifying agent sodium p styrene sulfonate of alcohol monoester disodium salt emulsifying agent collocation and ethoxylated alkyl sulfate,
Outstanding emulsification, dispersibility can assign emulsion thinner particle diameter, narrower particle diameter distribution and good stability.
The present invention is using vinyltrimethoxy silane, trimethylol-propane trimethacrylate, methacrylic acid alkene
One kind or mentioned component in propyl ester are mixed as cross-linking monomer using arbitrary proportion, due to have in above-mentioned cross-linker molecules chain compared with
Many active groups, occur substantial amounts of cross-linking reaction in reaction system with styrene, butyl acrylate or acrylic acid, form net
Shape structure, improves the intensity of strand, imparts the outstanding water-fast and scrub performance of emulsion.
The persulfate of the present invention uses one kind or mentioned component in ammonium persulfate, potassium peroxydisulfate and sodium peroxydisulfate to appoint
Meaning ratio is mixed as initiator, because said components are aqueous persulfate, and beneficial to the progress of reaction, chemical reaction is completed
It can assign emulsion excellent water resistance afterwards.
The oxidant that the present invention is used is hydrogen peroxide, is used with ascorbic acid collocation, reaction rate is fast, and efficiency high is right
Residual monomer eliminates ability by force, and catabolite is water and oxygen, complete Diamond Search.
The reducing agent that the present invention is used is ascorbic acid, is used with hydrogen peroxide collocation, reaction rate is fast, efficiency high, to residual
Remaining monomer eliminates ability by force, and smell itself is low, low VOC.
The preparation method of the zero VOC content styrene-acrylic emulsion of the present invention, comprises the following steps：
A) under normal temperature and pressure, 2-10 parts of emulsifying agent and 10-20 parts of water are mixed in emulsion tank, dissolving is sufficiently stirred for
Afterwards, the styrene of formula ratio, butyl acrylate, acrylic acid, cross-linking monomer and uniform stirring 15-30 minute are sequentially added, it is obtained
Pre-emulsion is standby；
B) reactor bottom add 40-50 parts water and residual emulsifier, be warming up to 80-95 DEG C, treat temperature stabilization
Afterwards, pre-emulsion disposably is made as seed to reactor in 10-15 parts of step a) of input, will after stirring 0.5-1 minutes
0.1-0.5 parts of persulfate initiator is added after fully being dissolved with 2-10 parts of water to be reacted, and seed fully reacts 10-30 points
Clock；
C) remaining persulfate initiator is completely dissolved with 5-15 parts of water, by 0.1-0.3 parts of reducing agent residue water
It is completely dissolved, it is standby；
D) after the completion of above-mentioned steps b), at 80-95 DEG C, by remaining pre-emulsion in step a) and the mistake prepared in step c)
Dropwise reaction 80-120min, i.e. completion polymerize simultaneously for the persulfate initiator aqueous solution and reducing agent aqueous solution；
E) after the completion of above-mentioned steps d), 70-90 DEG C is cooled the temperature to, then by 0.05-0.3 parts of oxidants and 0.05-0.4
The reducing agent of part is fed directly in reactor respectively；
F) after the completion of above-mentioned steps e), 60-80 DEG C is cooled to, while remaining oxidant and remaining reducing agent is added dropwise,
20-30min is added dropwise, 5-15 minutes are incubated after dripping off, then cools 40-55 DEG C and uses in caustic soda with pH value to 7-8, filtering is produced
The styrene-acrylic emulsion of zero VOC content.
The method of testing of VOC content in the use internal mark method determination emulsion that group's offer is provided is surveyed by China, it is prompt using peace
Human relations gas chromatograph for determination, equal energy≤1 (g/L) of actual measurement VOC content of polymer emulsion of the invention, well below environmental mark
Valuation Standard.
It is described in detail with reference to a pair of each embodiments of table, but does not therefore limit the invention to the implementation
In the range of example：
Embodiment 1
The styrene-acrylic emulsion of the zero VOC content of the present invention, is not included by mass fraction point counting：80 parts of water, 5 parts of emulsifying agent,
20 parts of styrene, 20 parts of butyl acrylate, 0.5 part of acrylic acid, 1 part of cross-linking monomer, 0.2 part of persulfate, 0.1 part of oxidant,
0.2 part of reducing agent.
The emulsifying agent is sodium p styrene sulfonate.
The cross-linking monomer is vinyltrimethoxy silane.
The persulfate is ammonium persulfate.
The oxidant is hydrogen peroxide.
The reducing agent is ascorbic acid.
The preparation method of the zero VOC content styrene-acrylic emulsion of the present invention, comprises the following steps：
A) under normal temperature and pressure, 2 parts of emulsifying agent and 10 parts of water is mixed in emulsion tank, are sufficiently stirred for after dissolving, according to
It is secondary to add the styrene of formula ratio, butyl acrylate, acrylic acid, cross-linking monomer and uniform stirring 15 minutes, pre-emulsion is made
It is standby；
B) 40 parts of water and residual emulsifier is added in the bottom of reactor, 95 DEG C are warming up to, after after temperature stabilization, once
Property input 10 parts of step a) in pre-emulsion is made as seed to reactor, after stirring 0.5 minute, by 0.1 part of persulfuric acid
Salt initiators are added after fully being dissolved with 2 parts of water to be reacted, and seed fully reacts 10 minutes；
C) remaining persulfate initiator is completely dissolved with 5 parts of water, 0.1 part of reducing agent is completely molten with remaining water
Solution, it is standby；
D) after the completion of above-mentioned steps b), at 95 DEG C, by remaining pre-emulsion in step a) and the over cure prepared in step c)
Dropwise reaction 80min, i.e. completion polymerize simultaneously for hydrochlorate initiator solution and reducing agent aqueous solution；
E) after the completion of above-mentioned steps d), 90 DEG C are cooled the temperature to, then by 0.05 part of oxidant and 0.05 part of reducing agent
It is fed directly to respectively in reactor；
F) after the completion of above-mentioned steps e), 70 DEG C are cooled to, while remaining oxidant and remaining reducing agent is added dropwise, is added dropwise
20min, 5 minutes are incubated after dripping off, and then 40 DEG C of cooling is used in caustic soda and pH value is to 7, and filtering produces the benzene of zero VOC content
Acrylic emulsion.
The method of testing of VOC content in the use internal mark method determination emulsion that group's offer is provided is surveyed by China, it is prompt using peace
Human relations gas chromatograph for determination, equal energy≤1 (g/L) of actual measurement VOC content of polymer emulsion of the invention, well below environmental mark
Valuation Standard.
Embodiment 2
The styrene-acrylic emulsion of the zero VOC content of the present invention, is not included by mass fraction point counting：90 parts of water, 8 parts of emulsifying agent,
25 parts of styrene, 30 parts of butyl acrylate, 2 parts of acrylic acid, 2 parts of cross-linking monomer, 0.3 part of persulfate, 0.2 part of oxidant, also
Former 0.4 part of agent.
The emulsifying agent is ethoxylated alkyl sulfate.
The cross-linking monomer is trimethylol-propane trimethacrylate.
The persulfate is potassium peroxydisulfate.
The oxidant is hydrogen peroxide.
The reducing agent is ascorbic acid.
The preparation method of the zero VOC content styrene-acrylic emulsion of the present invention, comprises the following steps：
A) under normal temperature and pressure, 3 parts of emulsifying agent and 12 parts of water is mixed in emulsion tank, are sufficiently stirred for after dissolving, according to
It is secondary to add the styrene of formula ratio, butyl acrylate, acrylic acid, cross-linking monomer and uniform stirring 16 minutes, pre-emulsion is made
It is standby；
B) 42 parts of water and residual emulsifier is added in the bottom of reactor, 90 DEG C are warming up to, after after temperature stabilization, once
Property input 12 parts of step a) in pre-emulsion is made as seed to reactor, after stirring 0.5 minute, by 0.15 part of persulfuric acid
Salt initiators are added after fully being dissolved with 5 parts of water to be reacted, and seed fully reacts 15 minutes；
C) remaining persulfate initiator is completely dissolved with 8 parts of water, 0.15 part of reducing agent is completely molten with remaining water
Solution, it is standby；
D) after the completion of above-mentioned steps b), at 90 DEG C, by remaining pre-emulsion in step a) and the over cure prepared in step c)
Dropwise reaction 90min, i.e. completion polymerize simultaneously for hydrochlorate initiator solution and reducing agent aqueous solution；
E) after the completion of above-mentioned steps d), 85 DEG C are cooled the temperature to, then by 0.1 part of oxidant and 0.1 part of reducing agent point
It is not fed directly in reactor；
F) after the completion of above-mentioned steps e), 65 DEG C are cooled to, while remaining oxidant and remaining reducing agent is added dropwise, is added dropwise
23min, 8 minutes are incubated after dripping off, and then 45 DEG C of cooling is used in caustic soda and pH value is to 7.2, and filtering produces zero VOC content
Styrene-acrylic emulsion.
The method of testing of VOC content in the use internal mark method determination emulsion that group's offer is provided is surveyed by China, it is prompt using peace
Human relations gas chromatograph for determination, equal energy≤1 (g/L) of actual measurement VOC content of polymer emulsion of the invention, well below environmental mark
Valuation Standard.
Embodiment 3
The styrene-acrylic emulsion of the zero VOC content of the present invention, is not included by mass fraction point counting：100 parts of water, emulsifying agent 11
Part, 30 parts of styrene, 40 parts of butyl acrylate, 3 parts of acrylic acid, 3 parts of cross-linking monomer, 0.4 part of persulfate, 0.4 part of oxidant,
0.6 part of reducing agent.
The emulsifying agent is sulfosuccinic acid ethoxy ethanol monoester disodium salt.
The cross-linking monomer is allyl methacrylate.
The persulfate is sodium peroxydisulfate.
The oxidant is hydrogen peroxide.
The reducing agent is ascorbic acid.
The preparation method of the zero VOC content styrene-acrylic emulsion of the present invention, comprises the following steps：
A) under normal temperature and pressure, 5 parts of emulsifying agent and 15 parts of water is mixed in emulsion tank, are sufficiently stirred for after dissolving, according to
It is secondary to add the styrene of formula ratio, butyl acrylate, acrylic acid, cross-linking monomer and uniform stirring 20 minutes, pre-emulsion is made
It is standby；
B) 45 parts of water and residual emulsifier is added in the bottom of reactor, 85 DEG C are warming up to, after after temperature stabilization, once
Property input 13 parts of step a) in pre-emulsion is made as seed to reactor, after stirring 0.5 minute, by 0.3 part of persulfuric acid
Salt initiators are added after fully being dissolved with 8 parts of water to be reacted, and seed fully reacts 20 minutes；
C) remaining persulfate initiator is completely dissolved with 10 parts of water, 0.2 part of reducing agent is completely molten with remaining water
Solution, it is standby；
D) after the completion of above-mentioned steps b), at 85 DEG C, by remaining pre-emulsion in step a) and the over cure prepared in step c)
Dropwise reaction 100min, i.e. completion polymerize simultaneously for hydrochlorate initiator solution and reducing agent aqueous solution；
E) after the completion of above-mentioned steps d), 80 DEG C are cooled the temperature to, then by 0.15 part of oxidant and 0.2 part of reducing agent point
It is not fed directly in reactor；
F) after the completion of above-mentioned steps e), 70 DEG C are cooled to, while remaining oxidant and remaining reducing agent is added dropwise, is added dropwise
25min, 10 minutes are incubated after dripping off, and then 45 DEG C of cooling is used in caustic soda and pH value is to 7.5, and filtering produces zero VOC content
Styrene-acrylic emulsion.
The method of testing of VOC content in the use internal mark method determination emulsion that group's offer is provided is surveyed by China, it is prompt using peace
Human relations gas chromatograph for determination, equal energy≤1 (g/L) of actual measurement VOC content of polymer emulsion of the invention, well below environmental mark
Valuation Standard.
Embodiment 4
The styrene-acrylic emulsion of the zero VOC content of the present invention, is not included by mass fraction point counting：120 parts of water, emulsifying agent 12
Part, 40 parts of styrene, 45 parts of butyl acrylate, 4 parts of acrylic acid, 4 parts of cross-linking monomer, 0.7 part of persulfate, 0.6 part of oxidant,
0.8 part of reducing agent.
The emulsifying agent is 3 parts of sodium p styrene sulfonate, 7 parts of ethoxylated alkyl sulfate, sulfosuccinic acid ethyoxyl
2 parts of ethanol monoester disodium salt.
The cross-linking monomer is 1 part of vinyltrimethoxy silane, 2 parts of trimethylol-propane trimethacrylate, first
1 part of base allyl acrylate.
The persulfate is 0.1 part of 0.2 part of ammonium persulfate, 0.4 part of potassium peroxydisulfate and sodium peroxydisulfate.
The oxidant is hydrogen peroxide.
The reducing agent is ascorbic acid.
The preparation method of the zero VOC content styrene-acrylic emulsion of the present invention, comprises the following steps：
A) under normal temperature and pressure, 8 parts of emulsifying agent and 17 parts of water is mixed in emulsion tank, are sufficiently stirred for after dissolving, according to
It is secondary to add the styrene of formula ratio, butyl acrylate, acrylic acid, cross-linking monomer and uniform stirring 25 minutes, pre-emulsion is made
It is standby；
B) 45 parts of water and residual emulsifier is added in the bottom of reactor, 85 DEG C are warming up to, after after temperature stabilization, once
Property input 15 parts of step a) in pre-emulsion is made as seed to reactor, after stirring 1 minute, by 0.4 part of persulfate
Initiator is added after fully being dissolved with 10 parts of water to be reacted, and seed fully reacts 25 minutes；
C) remaining persulfate initiator is completely dissolved with 15 parts of water, 0.25 part of reducing agent is completely molten with remaining water
Solution, it is standby；
D) after the completion of above-mentioned steps b), at 85 DEG C, by remaining pre-emulsion in step a) and the over cure prepared in step c)
Dropwise reaction 110min, i.e. completion polymerize simultaneously for hydrochlorate initiator solution and reducing agent aqueous solution；
E) after the completion of above-mentioned steps d), 80 DEG C are cooled the temperature to, then by 0.25 part of oxidant and 0.3 part of reducing agent point
It is not fed directly in reactor；
F) after the completion of above-mentioned steps e), 70 DEG C are cooled to, while remaining oxidant and remaining reducing agent is added dropwise, is added dropwise
25min, 12 minutes are incubated after dripping off, and then 50 DEG C of cooling is used in caustic soda and pH value is to 7.8, and filtering produces zero VOC content
Styrene-acrylic emulsion.
The method of testing of VOC content in the use internal mark method determination emulsion that group's offer is provided is surveyed by China, it is prompt using peace
Human relations gas chromatograph for determination, equal energy≤1 (g/L) of actual measurement VOC content of polymer emulsion of the invention, well below environmental mark
Valuation Standard.
Embodiment 5
The styrene-acrylic emulsion of the zero VOC content of the present invention, is not included by mass fraction point counting：130 parts of water, emulsifying agent 20
Part, 50 parts of styrene, 50 parts of butyl acrylate, 5 parts of acrylic acid, 5 parts of cross-linking monomer, 1 part of persulfate, 1 part of oxidant, reduction
1 part of agent.
The emulsifying agent is 12 parts of sodium p styrene sulfonate, 8 parts of sulfosuccinic acid ethoxy ethanol monoester disodium salt.
The cross-linking monomer is 3 parts of vinyltrimethoxy silane, 2 parts of allyl methacrylate.
The persulfate is 0.5 part of 0.5 part of potassium peroxydisulfate and sodium peroxydisulfate.
The oxidant is hydrogen peroxide.
The reducing agent is ascorbic acid.
The preparation method of the zero VOC content styrene-acrylic emulsion of the present invention, comprises the following steps：
A) under normal temperature and pressure, 10 parts of emulsifying agent and 20 parts of water is mixed in emulsion tank, are sufficiently stirred for after dissolving, according to
It is secondary to add the styrene of formula ratio, butyl acrylate, acrylic acid, cross-linking monomer and uniform stirring 30 minutes, pre-emulsion is made
It is standby；
B) 50 parts of water and residual emulsifier is added in the bottom of reactor, 80 DEG C are warming up to, after after temperature stabilization, once
Property input 15 parts of step a) in pre-emulsion is made as seed to reactor, after stirring 1 minute, by 0.5 part of persulfate
Initiator is added after fully being dissolved with 10 parts of water to be reacted, and seed fully reacts 30 minutes；
C) remaining persulfate initiator is completely dissolved with 15 parts of water, 0.3 part of reducing agent is completely molten with remaining water
Solution, it is standby；
D) after the completion of above-mentioned steps b), at 80 DEG C, by remaining pre-emulsion in step a) and the over cure prepared in step c)
Dropwise reaction 120min, i.e. completion polymerize simultaneously for hydrochlorate initiator solution and reducing agent aqueous solution；
E) after the completion of above-mentioned steps d), 75 DEG C are cooled the temperature to, then by 0.3 part of oxidant and 0.4 part of reducing agent point
It is not fed directly in reactor；
F) after the completion of above-mentioned steps e), 60 DEG C are cooled to, while remaining oxidant and remaining reducing agent is added dropwise, is added dropwise
30min, 15 minutes are incubated after dripping off, and then 55 DEG C of cooling is used in caustic soda and pH value is to 8, and filtering produces zero VOC content
Styrene-acrylic emulsion.
The method of testing of VOC content in the use internal mark method determination emulsion that group's offer is provided is surveyed by China, it is prompt using peace
Human relations gas chromatograph for determination, equal energy≤1 (g/L) of actual measurement VOC content of polymer emulsion of the invention, well below environmental mark
Valuation Standard.
Table one (ingredient units are mass fraction)
Claims (7)
1. a kind of styrene-acrylic emulsion of zero VOC content, it is characterised in that：In parts by mass, including following components, water 80-130
Part, 5-20 parts of emulsifying agent, 20-50 parts of styrene, 20-50 parts of butyl acrylate, 0.5-5 parts of acrylic acid, 1-5 parts of cross-linking monomer,
0.2-1 parts of persulfate, 0.1-1 parts of oxidant, 0.2-1 parts of reducing agent.
2. the styrene-acrylic emulsion of zero VOC content according to claim 1, it is characterised in that：The emulsifying agent is to styrene
Sodium sulfonate, ethoxylated alkyl sulfate, one kind in sulfosuccinic acid ethoxy ethanol monoester disodium salt or mentioned component with
Arbitrary proportion is mixed.
3. the styrene-acrylic emulsion of zero VOC content according to claim 1, it is characterised in that：The cross-linking monomer is vinyl
One kind or mentioned component in trimethoxy silane, trimethylol-propane trimethacrylate, allyl methacrylate with
Arbitrary proportion is mixed.
4. the styrene-acrylic emulsion of zero VOC content according to claim 1, it is characterised in that：The persulfate is persulfuric acid
One kind or mentioned component in ammonium, potassium peroxydisulfate and sodium peroxydisulfate are mixed with arbitrary proportion.
5. the styrene-acrylic emulsion of zero VOC content according to claim 1, it is characterised in that：The oxidant is hydrogen peroxide.
6. the styrene-acrylic emulsion of zero VOC content according to claim 1, it is characterised in that：The reducing agent is ascorbic acid.
7. a kind of preparation method of the styrene-acrylic emulsion of zero VOC content as claimed in claim 1, it is characterised in that：It is described to prepare
Method comprises the following steps：
A) under normal temperature and pressure, 2-10 parts of emulsifying agent and 10-20 parts of water is mixed in emulsion tank, are sufficiently stirred for after dissolving,
Sequentially add the styrene of formula ratio, butyl acrylate, acrylic acid, cross-linking monomer and uniform stirring 15-30 minute, obtained pre- breast
Change liquid standby；
B) 40-50 parts of water and residual emulsifier is added in the bottom of reactor, 80-95 DEG C is warming up to, after after temperature stabilization, one
Secondary property, which is put into 10-15 parts of step a), is made pre-emulsion as seed to reactor, after stirring 0.5-1 minutes, by 0.1-0.5
The persulfate initiator of part is added after fully being dissolved with 2-10 parts of water to be reacted, and seed fully reacts 10-30 minutes；
C) remaining persulfate initiator is completely dissolved with 5-15 parts of water, 0.1-0.3 parts of reducing agent is complete with remaining water
Dissolving, it is standby；
D) after the completion of above-mentioned steps b), at 80-95 DEG C, by remaining pre-emulsion in step a) and the persulfuric acid prepared in step c)
Dropwise reaction 80-120min, i.e. completion polymerize simultaneously for the salt initiators aqueous solution and reducing agent aqueous solution；
E) after the completion of above-mentioned steps d), 70-90 DEG C is cooled the temperature to, then by 0.05-0.3 parts of oxidants and 0.05-0.4 parts
Reducing agent is fed directly in reactor respectively；
F) after the completion of above-mentioned steps e), 60-80 DEG C is cooled to, while remaining oxidant and remaining reducing agent is added dropwise, is added dropwise
20-30min, 5-15 minutes are incubated after dripping off, and then 40-55 DEG C of cooling is used in caustic soda and pH value is to 7-8, and filtering produces ultralow
The styrene-acrylic emulsion of VOC content.
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