CN1103341C - Organosilicon modified acrylate latex with core-shell structure and its preparing process - Google Patents
Organosilicon modified acrylate latex with core-shell structure and its preparing process Download PDFInfo
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- CN1103341C CN1103341C CN99119980A CN99119980A CN1103341C CN 1103341 C CN1103341 C CN 1103341C CN 99119980 A CN99119980 A CN 99119980A CN 99119980 A CN99119980 A CN 99119980A CN 1103341 C CN1103341 C CN 1103341C
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Abstract
The present invention belongs to the technical field of chemical industry, particularly to organosilicon modified acrylic latex with a core-shell structure and a preparing method thereof. Acrylic latex is obtained by the method that vinyl alkoxy silane monomers are used as a modifying agent and is copolymerized with monomers of alkyl methacrylate, acrylic acid octadecy l phosphite, acrylic acid hydroxyalkyl ester, alkenyl aromatic compound, etc. in a seed emulsion polymerization mode. The stability of products is high; the products can be stored more than one year; the hardness, the tensile strength, the water resisting performance, the adhesive force and the scrab resisting performance of a coating film, can be remarkably improved; the products can be widely used as exterior wall coating, waterproof coating, glass decorating coating, etc.
Description
The invention belongs to chemical technology field, relate to a kind of modification acrylate latex and preparation method thereof.
Acrylate latex has many outstanding advantages, and photostabilization, weathering resistance, resistance to acids and bases and erosion resistance as excellence are widely used at aspects such as coating, tackiness agents.But, wish it is carried out modification because acrylate latex has shortcomings such as poor water resistance and low temperature become fragile easily, high temperature becomes sticky easily.If adopt high temperature resistant, surface energy low and the organosilicon function monomer of water-tolerant carries out modification to acrylate latex, then organic silicone modified acrylate coating material can improve the hardness of filming, tensile strength, ventilation property, wear resistance, sticking power, anti-stickly put forth effort, water tolerance, solvent resistance and scrub resistance.According to foreign literature, organic silicon-acrylate paint coatings ultraviolet resistance irradiation can reach more than 2000 hours, require much larger than common coating 250 hours.
At present, acrylate is being carried out in the research of modification with the organosilicon function monomer, usually adopt mechanical blending or means such as grafting copolymerization process, segment copolymerization method and interact network method, as US4491650, day disclosure special permission communique [putting down] 02127458, EP297505 etc., but these methods all are solvent polymerization method basically.Along with requirement on environmental protection improves day by day, various countries are strict day by day to the regulation of VOC quantity discharged, and therefore, the research and development water-borne coatings has become coating researchist's goal in research.The emulsion polymerization modification acrylate mainly is to utilize the organosilane monomer contain vinyl-functional or performed polymer and acrylic ester monomer to carry out emulsion copolymerization.Because the existence of water in the letex polymerization, the hydrolysis-condensation reaction of alkoxyl group can take place, it forms with the addition reaction of vinyl-functional and competes.And addition reaction than hydrolysis-condensation reaction slowly many, therefore to the selection of comonomer difficulty relatively.The general emulsion polymerization synthetic organic silicon-acrylate latex stability that adopts is bad, and the organosilicon addition is little, is not easy and other monomer copolymerization.
The objective of the invention is to propose organosilicon-modified acrylate latex of a kind of synthetic easily, good stability and preparation method thereof.
The acrylate latex that the present invention proposes is a kind of organosilicon-modified acrylate latex with nucleocapsid structure.It adopts emulsion polymerization to prepare.
Among the present invention, the consisting of of acrylate: (1) contains C
1～C
10Alkyl acrylate; (2) contain C
1～C
10Alkyl methacrylate; (3) contain C
2～C
10Acrylic acid hydroxy alkyl ester; (4) contain C
3～C
6The thiazolinyl carboxylic acid; (5) contain C
4～C
15The vinylformic acid cross-linking monomer; (6) contain the aromatics of vinyl.
The present invention uses and contains C
7～C
18Vinyl alkoxy silane as organosilicon modifier.
The present invention uses and contains C
2～C
12Alkyl sulfhydryl or hydrosulphonyl silane as chain-transfer agent.
The present invention uses negatively charged ion and nonionic compound emulsifier.
The present invention uses redox initiator.
The present invention uses carbonate, supercarbonate, phosphoric acid salt or the hydrosulfate of basic metal, alkaline-earth metal or ammonium as the pH regulator agent.
The present invention specifically describes as follows:
In the present invention, consisting of of acrylate: (1) contains C
1～C
10Alkyl acrylate, consumption is the 30-50% (weight percent of monomer total amount, following monomer is together), as ethyl propenoate, propyl acrylate, butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, ethyl acrylate, vinylformic acid-2-ethylamino ester, vinyl acrylate etc.(2) contain C
1～C
10Alkyl methacrylate, consumption is the 20-40% of monomer total amount, as Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester, methacrylic acid-2-methyl ester, dimethylaminoethyl methacrylate, n octyl methacrylate etc.(3) contain C
2～C
10Acrylic acid hydroxy alkyl ester, consumption is the 10-20% of monomer total amount, as 2-Hydroxy ethyl acrylate, vinylformic acid-3-hydroxy propyl ester, vinylformic acid-2-hydroxyl butyl ester, vinylformic acid-4-hydroxyl butyl ester, vinylformic acid-5-hydroxyl pentyl ester, the vinylformic acid-own ester of 6-hydroxyl, vinylformic acid hydroxyl phenolic ester, methacrylic acid-2,3-dihydroxyl propyl ester etc.(4) contain C
3～C
6The thiazolinyl carboxylic acid, consumption is the 2-10% of monomer total amount, as vinylformic acid, methacrylic acid, alpha-cyano-β phenylacrylic acid etc.(5) contain C
4～C
15The vinylformic acid cross-linking monomer, consumption is the 0.5-3% of monomer total amount.(6) contain the aromatics of vinyl, consumption is the 10-60% of monomer total amount, as vinylbenzene, alpha-methyl styrene, amino-benzene ethene, 2-chlorostyrene, 3-t-butyl styrene, 3, and 4-dimethyl styrene, 4-phenetole ethene etc.
The present invention's redox initiator, preparation earlier has the latex seed of stone, again with after the pre-emulsification of soft shell monomer, adopts continuous dripping method in 2-4 hour pre-emulsion to be added drop-wise in the latex seed, reaction finishes, and can obtain having the organosilicon-modified acrylate latex of stone soft shell structure.Concrete steps are as follows:
1. prepare the latex seed
Composition and usage ratio by the aforesaid propylene acid esters take by weighing each component.The reactor of thermometer, well heater, agitator, filling tube and constant current tubing is equipped with in employing.Elder generation is with vinyl aromatic compounds, water and the corresponding emulsifying agent of 10%～20% alkyl acrylate, thiazolinyl carboxylic acid, 30%-100%, high-speed stirring 5-20 minute, when slowly being warming up to temperature and being 45 ℃-65 ℃, add initiator, behind the several minutes, faint blue light appears in emulsion, restir 5-10 minute, promptly forms stone latex seed.
2. prepare organic-silicon-modified nucleocapsid cinnamic acrylic ester emulsion
Remaining alkyl acrylate, alkyl methacrylate, acrylic acid hydroxy alkyl ester, vinyl aromatic compounds, vinylformic acid cross-linking monomer, organosilicon function monomer, chain-transfer agent, water and emulsifying agent etc. were stirred at a high speed 20-30 minute, make it fully emulsified, obtain monomer pre-emulsion.In 2-4 hour that emulsification is good monomer pre-emulsion, initiator are added drop-wise in the reactor continuously, react with the latex seed, temperature of reaction remains on 50 ℃-65 ℃, after reaction finishes, be incubated 1-2 hour, can obtain the organosilicon-modified acrylate latex of nucleocapsid structure, the latex solid content is 45%-50%.
In the present invention, the organosilicon modifier of use is for containing C
7～C
18Vinyl alkoxy silane, consumption is the 3-20% of monomer total amount.Chain-transfer agent is C
2～C
12Alkyl sulfhydryl or hydrosulphonyl silane, consumption is the 2-5% of monomer total amount, as mercaptoethanol, 2-mercaprol, butanethiol, lauryl mercaptan etc.Compound emulsifying agent employing anion surfactant and nonionogenic tenside are composite, consumption is the 7-20% of monomer total amount, as sodium lauryl sulphate-sorbitan trioleate, Sodium dodecylbenzene sulfonate-polyoxyethylene sorbitan monooleate, Succinic Acid diethyl ester sodium sulfonate-polyoxyethylene sorbitol acid anhydride laurate etc.Initiator is a redox initiator, and consumption is the 1-6% of monomer total amount, as hydrogen peroxide-iron protochloride, Potassium Persulphate-iron protochloride, Potassium Persulphate-sodium bisulfite, hyperis-iron protochloride etc.The pH regulator agent is carbonate, supercarbonate, phosphoric acid salt or the hydrosulfate of basic metal, alkaline-earth metal or ammonium, and consumption is the 0.2-1% of monomer total amount, as sodium bicarbonate, yellow soda ash, potassiumphosphate, sal enixum etc.
The present invention adopts emulsion polymerization to prepare nucleocapsid structure organosilicon-modified acrylate latex, compares with the preparation method of existing organosilicon-modified acrylate, can obtain narrow diameter distribution, nontoxic, do not fire, stable latex.The exterior coating that makes with it can replace mechanical commixed type and solvent borne organosilicon-modified acrylate exterior coating.
Adopt the organosilicon-modified acrylate latex of the present invention's preparation, have the following advantages:
1. the latex of the present invention's preparation is stone soft shell structure, both can reduce the second-order transition temperature of latex, reduces raw materials cost, can improve the mechanical property of filming again, increases the weathering resistance of filming.
2. the organosilicon function monomer that uses among the present invention is water miscible, is very easy to carry out copolymerization with other monomer, can hydrolysis before the copolymerization, and therefore the latex of preparation can be stablized storage more than 1 year.
3. the present invention adds the vinylformic acid cross-linking monomer in emulsion polymerization process, can improve the degree of crosslinking and the sticking power of latex, and need not add and after catalyzer can make organosilicon and other monomer copolymerization hydrolytic crosslinking take place, reduce emulsifying agent and catalyst consumption, increase the water tolerance of latex.
4. this method technology is simple, is easy to control, all can produce stable organosilicon-modified acrylate latex in certain temperature range.
5. this process using emulsion polymerisation process; solvent for use is a water, and the latex of preparation is nontoxic, do not fire, and has both helped environment protection; can reduce production costs again, the exterior coating that makes with it can replace mechanical commixed type and solvent borne organosilicon-modified acrylate exterior coating.
The organosilicon-modified acrylate latex of the present invention preparation than the non-silylation acrylate latex of the following preparation of similarity condition have much better water tolerance, scrub resistance, anti-stickly put forth effort, degree of crosslinking, sticking power, hardness and tensile strength.Can be used as high-grade exterior coating, waterproof paint, glass decoration coating etc.
Latex performance to the present invention's preparation can characterize with the following method: the particle diameter of organosilicon-modified acrylate latex adopts Coulter LS230 particle size analyzer to measure, being coated with film dynamic performance tests with the Instron electronic tension tester, the method that the latex degree of crosslinking was weighed by reflux in 24 hours is measured, adopt GB/T9286-88 cross cross-hatching measure sticking power (wherein 0 grade best, 5 grades the poorest), the test of anti-MEK (methyl ethyl ketone) solvent scouring number of times is to use by the saturated non-woven paper of MEK to come and go the scouring film coated surface, the scouring number of times that record is filmed and just frayed, the pencil hardness of filming is measured by ASTM D-3364.
Embodiment:
Example 1: set of monomers becomes butyl acrylate, 3,4-dimethyl styrene, the vinylformic acid-own ester of 6-hydroxyl, methacrylic acid, contains C
7～C
12Vinyl alkoxy silane, latex component prescription is as follows:
| Form | Weight percent (%) | |
| 1 | Emulsifying agent | 2 |
| 2 | Water | 45 |
| 3 | Methacrylic acid | 1 |
| 4 | Butyl acrylate | 20 |
| 5 | 3, the 4-dimethyl styrene | 20 |
| 6 | Vinylformic acid-own the ester of 6-hydroxyl | 5 |
| 7 | Vinylic organosiloxane | 1 |
| 8 | Potassium Persulphate-ferrous salt | 0.5 |
| 9 | Lauryl mercaptan | 2 |
| 10 | Sodium bicarbonate | 0.2 |
| Latex solid content (%) | 50 | |
With 1 part of emulsifying agent, 13 parts of water, 1 part of methacrylic acid, 3 parts of butyl acrylates, 8 part 3, the 4-dimethyl styrene, 2 parts of own esters of vinylformic acid-6-hydroxyl add in the reactor, stirred 20 minutes, temperature of reaction kettle is heated to 50 ℃, drip initiator, continue to be stirred to latex and faint blue light occurs, after 5 minutes, begin to drip good pre-emulsion of pre-emulsification (residual monomers and 30 parts water high-speed stirring 20 minutes) and initiator, in 3 hours pre-emulsion and initiator are all dripped, continue insulation 1.5 hours, add the pH to 9 that latex is regulated in the pH regulator agent, cold filtration promptly gets organosilicon-modified acrylate latex.
Example 2: set of monomers becomes butyl methacrylate, vinylformic acid-2-ethylamino ester, vinylformic acid hydroxy butyl ester, vinylformic acid, contains C
7～C
12Vinyl alkoxy silane, contain C
4～C
12The vinylformic acid cross-linking monomer, latex formulations is as follows:
| Form | Weight percent (%) | |
| 1 | Emulsifying agent | 4 |
| 2 | Water | 50 |
| 3 | Vinylformic acid | 1 |
| 4 | Vinylformic acid-2-ethylamino ester | 14 |
| 5 | Butyl methacrylate | 16 |
| 6 | The vinylformic acid hydroxy butyl ester | 4 |
| 7 | The vinylformic acid cross-linking monomer | 1 |
| 8 | Vinylic organosiloxane | 3 |
| 9 | Potassium Persulphate-ferrous salt | 0.6 |
| 10 | Mercaptoethanol | 1 |
| 11 | Sal enixum | 0.1 |
| Latex solid content (%) | 47 | |
1 part of emulsifying agent, 13 parts of water, 1 part of vinylformic acid-2-ethylamino ester, 8 parts of butyl methacrylate are added in the reactor, stirred 10 minutes, temperature of reaction kettle is heated to 55 ℃, drip initiator, continue to be stirred to latex and faint blue light occurs, after 5 minutes, begin to drip good pre-emulsion of pre-emulsification (residual monomers and 37 parts water high-speed stirring 30 minutes) and initiator, 2.5 in hour pre-emulsion and initiator are all dripped, continue insulation 2 hours, add the pH regulator agent and regulate the pH to 8 of latex, cold filtration promptly gets organosilicon-modified acrylate latex.
Example 3: set of monomers becomes methacrylic acid-2-methyl ester, ethyl propenoate, Propylene glycol monoacrylate, methacrylic acid, vinylbenzene, contains C
7～C
12Vinyl alkoxy silane, contain C
4～C
12The vinylformic acid cross-linking monomer, latex formulations is as follows:
| Form | Weight percent (%) | |
| 1 | Emulsifying agent | 3 |
| 2 | Water | 50 |
| 3 | Methacrylic acid | 2 |
| 4 | Ethyl propenoate | 10 |
| 5 | Methacrylic acid-2-methyl ester | 16 |
| 6 | Propylene glycol monoacrylate | 5 |
| 7 | Vinylbenzene | 5 |
| 8 | The vinylformic acid cross-linking monomer | 1.5 |
| 9 | Vinylic organosiloxane | 6 |
| 10 | Ammonium persulphate-ferrous salt | 0.6 |
| 11 | Mercaptoethanol | 1 |
| 12 | Yellow soda ash | 0.1 |
| Latex solid content (%) | 45 | |
With 1 part of emulsifying agent, 15 parts of water, 1 part of methacrylic acid, 2 parts of ethyl propenoates, 6 parts of methacrylic acid-2-methyl ester, 1 part of vinylbenzene and 1 part of Propylene glycol monoacrylate add in the reactor, stirred 30 minutes, temperature of reaction kettle is heated to 65 ℃, drip initiator, continue to be stirred to latex and faint blue light occurs, after 15 minutes, begin to drip good pre-emulsion of pre-emulsification (residual monomers and 35 parts water high-speed stirring 20 minutes) and initiator, in 3 hours pre-emulsion and initiator are all dripped, continue insulation 1 hour, add the pH regulator agent and regulate the pH to 7.5 of latex, cold filtration promptly gets organosilicon-modified acrylate latex.
The performance characterization of example 1-3 is as follows:
| Non-silylation latex | Example 1 | Example 2 | Example 3 | |
| Latex particle size (μ m) | 0.114 | 0.116 | 0.118 | 0.113 |
| The latex particle size distribution (plastisied dispersion, %) | 42.2 | 12.5 | 11.7 | 11.2 |
| The latex package stability | Still stable more than 1 year | Still stable more than 1 year | Still stable more than 1 year | |
| Film adhesive/level | 5 | 0 | 0 | 0 |
| Water-resistance property of coating | There is water to film and whitens immediately, film and to peel off | Film after 5 hours and slightly whiten, film not | Film after 15 hours and slightly whiten, film not | Film after 20 hours and slightly whiten, be coated with |
| Can peel off | Can peel off | Film can not peel off | ||
| Anti-stick the putting forth effort of filming | Sticking hand | Tack-free | Tack-free | Tack-free |
| The tensile strength of filming (Mpa) | 1.01 | 1.75 | 2.03 | 2.59 |
| Degree of crosslinking (%) | 20.5 | 70.2 | 83.6 | 92.8 |
| Pencil hardness | 2B | HB | H | 2H |
| Anti-MEK cleans number of times | 30 | ＞200 | ＞300 | ＞300 |
Under same test conditions, the organosilicon modified acrylate latex with core-shell structure of the present invention preparation than the non-silylation acrylate latex of the following preparation of similarity condition have much better water tolerance, scrub resistance, anti-stickly put forth effort, degree of crosslinking, sticking power, hardness and tensile strength.
Claims (10)
1. an organosilicon modified acrylate latex with core-shell structure is prepared by emulsion polymerization, it is characterized in that the monomer component of acrylate is:
(1) contains C
1～C
10Alkyl acrylate, consumption is the 30-50% of monomer total amount;
(2) contain C
1～C
10Alkyl methacrylate, consumption is the 20-40% of monomer total amount;
(3) contain C
2～C
10Acrylic acid hydroxy alkyl ester, consumption is the 10-20% of monomer total amount;
(4) contain C
3～C
6The thiazolinyl carboxylic acid, consumption is the 2-10% of monomer total amount;
(5) contain C
4～C
15The vinylformic acid cross-linking monomer, consumption is the 0.5-3% of monomer total amount;
(6) contain the vinyl aromatic compounds of vinyl, consumption is the 10-60% of monomer total amount;
2. organosilicon acrylate latex with core-shell structure according to claim 1 is characterized in that the aforesaid propylene acid alkyl ester is a kind of of ethyl propenoate, propyl acrylate, butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, ethyl acrylate, vinylformic acid-2-ethylamino ester, vinyl acrylate.
3. organosilicon acrylate latex with core-shell structure according to claim 1 is characterized in that above-mentioned alkyl methacrylate is a kind of of Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester, methacrylic acid-2-methyl ester, dimethylaminoethyl methacrylate, n octyl methacrylate.
4. organosilicon acrylate latex with core-shell structure according to claim 1, it is characterized in that aforesaid propylene acid hydroxy alkyl ester is 2-Hydroxy ethyl acrylate, vinylformic acid-3-hydroxy propyl ester, vinylformic acid-2-hydroxyl butyl ester, vinylformic acid-4-hydroxyl butyl ester, vinylformic acid-5-hydroxyl pentyl ester, the vinylformic acid-own ester of 6-hydroxyl, vinylformic acid hydroxyl phenolic ester, methacrylic acid-2,3-dihydroxyl propyl ester a kind of.
5. organosilicon acrylate latex with core-shell structure according to claim 1 is characterized in that above-mentioned thiazolinyl carboxylic acid is a kind of of vinylformic acid, methacrylic acid, alpha-cyano-β phenylacrylic acid.
6. organosilicon acrylate latex with core-shell structure according to claim 1, it is characterized in that above-mentioned vinyl aromatic compounds is vinylbenzene, alpha-methyl styrene, amino-benzene ethene, 2-chlorostyrene, 3-t-butyl styrene, 3,4-dimethyl styrene, 4-phenetole ethene a kind of.
7. method for preparing according to the organosilicon modified acrylate latex with core-shell structure of claim 1, composition and usage ratio by acrylate take by weighing each component, thermometer is equipped with in employing, well heater, agitator, the reactor of filling tube and constant current tubing, it is characterized in that: (1) is earlier with 10%～20% alkyl acrylate, the thiazolinyl carboxylic acid, the vinyl aromatic compounds of 30%-100%, water and emulsifying agent, high-speed stirring 5-20 minute, be warming up to 45 ℃-65 ℃, add initiator, after several minutes, faint blue light appears in emulsion, restir 5-10 minute, form stone latex seed; (2) with remaining alkyl acrylate, alkyl methacrylate, acrylic acid hydroxy alkyl ester, vinyl aromatic compounds, vinylformic acid cross-linking monomer, organosilicon function monomer, chain-transfer agent, water and emulsifying agent high-speed stirring 20-30 minute, make it fully emulsified, obtain monomer pre-emulsion; Be added drop-wise to continuously in 2-4 hour in the reactor, with the reaction of latex seed, temperature of reaction remains on 50 ℃-65 ℃, and reaction finishes, and is incubated 1-2 hour and gets final product.
8. the preparation method of acrylate latex according to claim 7 is characterized in that chain-transfer agent is C
2～C
12Alkyl sulfhydryl or hydrosulphonyl silane, consumption is the 2-5% of monomer total amount.
9. the preparation method of acrylate latex according to claim 7 is characterized in that emulsifying agent is anion surfactant and nonionogenic tenside, and consumption is the 7-20% of monomer total amount.
10. the preparation method of acrylate latex according to claim 7 is characterized in that initiator is a redox initiator, and consumption is the 1-6% of monomer total amount.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1217361A (en) * | 1997-11-13 | 1999-05-26 | 中国石油化工总公司 | Organosilicon modified propenoic acid emulsion paint |
| CN1217360A (en) * | 1997-11-13 | 1999-05-26 | 中国石油化工总公司 | Process for preparing organosilicon modified propenoic acid emulsion paint |
-
1999
- 1999-11-09 CN CN99119980A patent/CN1103341C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1217361A (en) * | 1997-11-13 | 1999-05-26 | 中国石油化工总公司 | Organosilicon modified propenoic acid emulsion paint |
| CN1217360A (en) * | 1997-11-13 | 1999-05-26 | 中国石油化工总公司 | Process for preparing organosilicon modified propenoic acid emulsion paint |
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