CN103304727B - A kind of hud typed elastic emulsion, coating and preparation method thereof containing this kind of emulsion - Google Patents
A kind of hud typed elastic emulsion, coating and preparation method thereof containing this kind of emulsion Download PDFInfo
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Abstract
The present invention relates to a kind of hud typed elastic emulsion, containing the coating and preparation method thereof of this kind of emulsion, it is for core with poly-(BA-St), take polymethylmethacrylate as poly-(BA-St)/polymethylmethacrylate nucleocapsid structure aqueous polymer emulsion of shell, by butyl acrylate, vinylbenzene, sodium lauryl sulphate, OP-10, ethylene glycol dimethacrylate, propyl methacrylate and deionized water add obtained poly-(BA-St) emulsion of initiator emulsion polymerization, then methyl methacrylate is added drop-wise in this emulsion and is polymerized to obtain core-shell emulsion.This core-shell emulsion 30-50 part, water 15-20 part, color stuffing 30-40 part, auxiliary agent 4-7 part is mixed to get coating.The nucleocapsid structure particle diameter of synthesis is smaller, and size distribution is also relatively more even, and stability of emulsion is better.The coating of preparation, its film has excellent elasticity, weathering resistance, water tolerance, contamination resistance and higher hardness.
Description
Technical field:
The present invention relates to a kind of hud typed elastic emulsion, particularly a kind of hud typed elastic emulsion, coating and preparation method thereof containing hud typed elastic emulsion, belong to letex polymerization, technical field of coatings.
Background technology:
In recent years, along with the continuous reinforcement of environmental protection consciousness and the day by day perfect of legislations of environmental protection, the water-borne coatings of energy-conserving and environment-protective obtains high speed development.Compared with solvent based coating, water-borne coatings has that price is low, use safety, saving resource and the energy, reduces the advantage such as environmental pollution and public hazards.Water soluble acrylic acid grease coating material is with fastest developing speed in water-borne coatings, that kind is maximum pollution-free coating.Esters of acrylic acid coating is owing to having excellent cohesive force and water-fast, alkaline-resisting, ageing-resistant performance obtains and applies widely.In butyl polyacrylate emulsion, butyl polyacrylate elastic microsphere has excellent elasticity, as stress raiser in coating use procedure, both can bring out crazing and shear zone absorption energy, and can stop crazing again.When it is used as elastic coating, when crack appears in base material, film is subject to tensile deformation and can not cracking destruction, and still complete film keeps original various iris action, prevents the base material place ftractureed directly to be exposed among air.But butyl polyacrylate poor dimensional stability, and second-order transition temperature is too low, not easily film forming under room temperature.This severely limits its application in elastic coating.
Summary of the invention:
The object of the invention is to overcome above-mentioned deficiency and provide a kind of hud typed elastic emulsion and preparation method thereof, this emulsion can make paint film have the two-fold advantage of polyacrylic ester and polymethylmethacrylate concurrently.
Another object of the present invention is to provide a kind of coating containing described hud typed elastic emulsion and preparation method thereof, and this coating film has excellent performance.
The technical scheme that the present invention takes is:
A kind of hud typed elastic emulsion, it is for core with poly-(BA-St), take polymethylmethacrylate as poly-(BA-St)/polymethylmethacrylate nucleocapsid structure aqueous polymer emulsion of shell, obtained by butyl acrylate, vinylbenzene and methyl methacrylate letex polymerization.
Described hud typed elastic emulsion solid content is 20 ~ 40%, and particle size range is at 50 ~ 100nm.
The preparation method of described hud typed elastic emulsion, comprises step as follows:
(1) preparation of poly-(BA-St) seed emulsion:
0.15 ~ 0.25:0.03 in mass ratio ~ 0.05:0.001 ~ 0.003:0.004 ~ 0.006:0.001 ~ 0.003:0.001 ~ 0.003:1 takes butyl acrylate (BA), vinylbenzene (St), sodium lauryl sulphate (SDS), OP-10, ethylene glycol dimethacrylate (EDMA), allyl methacrylate(AMA) (ALMA) and deionized water, add reaction flask, 80 DEG C are warming up in stirring, constant temperature stirs 20-30min, take initiator potassium persulfate (KPS), the consumption of KPS is 0.006 ~ 0.008 times of water, join in reaction flask, 80 DEG C are stirred 10-15min and obtain seed emulsion,
(2) preparation of poly-(BA-St) emulsion,
Raw material is taken according to the ratio described in step (1), amount expands the 8-10 of step (1) to doubly, butyl acrylate, vinylbenzene, sodium lauryl sulphate, OP-10, ethylene glycol dimethacrylate, allyl methacrylate(AMA) and deionized water are mixed with pre-emulsion, pre-emulsion is slowly added drop-wise in prepared seed emulsion, add initiator KPS initiation reaction, 80 DEG C of stirring reaction 2 ± 0.1h, are gathered (BA-St) emulsion;
(3) methyl methacrylate (MMA) is added drop-wise in emulsion prepared in step (2), take initiator KPS and add initiation reaction, 80 DEG C of reaction 30-35min, can be gathered (BA-St)/polymethylmethacrylate core-shell emulsion; The consumption of methyl methacrylate is 0.3 ~ 0.5 times of aforesaid propylene acid butyl ester total amount, and the consumption of KPS is 0.02 ~ 0.04 times of methyl methacrylate consumption.
In above-mentioned preparation method, stirring velocity controls at 1500-2000r/min, and the rate of addition of monomers methyl methacrylate controls at 1-3ml/min; The rate of addition of pre-emulsion controls to add in 30min.
Coating containing above-mentioned hud typed elastic emulsion.
The weight part ratio composition of described coating is preferred: above-mentioned hud typed elastic emulsion i.e. poly-(BA-St)/polymethylmethacrylate core-shell emulsion 30-50 part, water 15-20 part, color stuffing 30-40 part, auxiliary agent 4-7 part; The weight part ratio of auxiliary agent consists of propylene glycol 1-2 part, dispersion agent 0.1-0.5 part, wetting agent 0.1-0.5 part, defoamer 0.1-0.5 part, film coalescence aid 0.5-1 part, multifunctional assistant 0.1-0.5 part, anticorrosion and bactericidal agent 0.1 ~ 0.5 part, thickening material 0.6 ~ 1.5 part.
Described color stuffing weight part ratio consists of titanium dioxide 10-15 part, water-ground limestone (1250 order) 15-20 part, water-washed kaoline (2000 order) 5-10 part.
Described auxiliary agent is specially: dispersion agent 5040; Wetting agent PE-100; Defoamer NXZ; Film coalescence aid alcohol ester-12; Multifunctional assistant AMP95; Anticorrosion and bactericidal agent LXE; Thickening material ATM-60, SD-301.
The preparation method of above-mentioned coating, step is:
By part water, titanium dioxide, water-ground limestone (1250 order), water-washed kaoline (2000 order), the mixing of propylene glycol, dispersion agent, wetting agent, defoamer, film coalescence aid, multifunctional assistant, with high speed dispersor dispersion sand milling to fineness≤30 μm;
Hud typed elastic emulsion, anticorrosion and bactericidal agent, thickening material, excess water stirring at low speed is added successively evenly to it again according to recipe ratio.
The present invention adopts the method preparing poly-(the BA-St)/polymethylmethacrylate composite material of core-shell structure of nucleocapsid structure to overcome the defect of virgin pp acid butyl ester as elastic coating emulsion.Wherein, Shell Materials polymethylmethacrylate, as duricrust, can keep the dimensional stability of inner elastomeric core and give inner elastomeric core certain hardness on the one hand, can increase the consistency of inner elastomeric core and matrix on the other hand.And cinnamic existence can regulate the second-order transition temperature of multipolymer further, realize film forming under room temperature.The nucleocapsid structure particle diameter of synthesis is smaller, and size distribution is also relatively more even, and stability of emulsion is better.
Core-shell type aqueous elastic coating prepared by the present invention, environmental protection, low VOC discharge; Its film has excellent elasticity, weathering resistance, water tolerance, contamination resistance and higher hardness, effectively can prevent cracking and make up matrix minute crack, having high application value.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of poly-(BA-St)/polymethylmethacrylate core-shell emulsion that the present invention obtains;
Fig. 2 be the present invention obtain poly-(BA-St)/polymethylmethacrylate core-shell emulsion sample breakdown of emulsion, drying, carry out the infrared spectrogram that infrared test obtains after washing;
Fig. 3 is the grain size distribution of poly-(BA-St)/polymethylmethacrylate core-shell emulsion that the present invention obtains.
Embodiment
Below in conjunction with embodiment to further instruction of the present invention:
Embodiment 1: a kind of preparation of the coating containing hud typed elastic emulsion, step is as follows:
1. the preparation of poly-(BA-St)/polymethylmethacrylate core-shell emulsion
A. the preparation of poly-(BA-St) seed emulsion
Take butyl acrylate (BA) 3.6g, vinylbenzene (St) 0.96g, sodium lauryl sulphate (SDS) 0.072g, OP-100.096g, ethylene glycol dimethacrylate (EDMA) 0.048g, allyl methacrylate(AMA) (ALMA) 0.072g and deionized water 24g in four-hole boiling flask.Be warming up to 80 DEG C and stir 20min.Taking initiator potassium persulfate (KPS) 0.144g joins in flask, stirs 15min and obtains seed emulsion.
B. poly-(BA-St) seed emulsion is expanding
Expand 8 times according to the preparation formula equal proportion amount of seed emulsion in step a to join, butyl acrylate, vinylbenzene, sodium lauryl sulphate, OP-10, ethylene glycol dimethacrylate, allyl methacrylate(AMA) and deionized water are mixed with pre-emulsion, pre-emulsion are slowly added drop-wise in the seed emulsion prepared by step a.Add initiator KPS initiation reaction, 80 DEG C of reaction 2h, are gathered (BA-St) emulsion.
C. the preparation of poly-(BA-St)/polymethylmethacrylate emulsion
Take methyl methacrylate (MMA) 9.72g to be added drop-wise in emulsion prepared in step b.Take initiator KPS0.389g initiation reaction, 80 DEG C of reaction 30min, can be gathered (BA-St)/polymethylmethacrylate core-shell emulsion.
2. the preparation of coating
The formula of coating is as follows:
First, by part water, titanium dioxide, water-ground limestone (1250 order), water-washed kaoline (2000 order), propylene glycol, dispersion agent (5040), wetting agent (PE-100), defoamer (NXZ), film coalescence aid (alcohol ester-12), multifunctional assistant (AMP95) mixing, with high speed dispersor dispersion sand milling to fineness≤30 μm;
Poly-(BA-St)/polymethylmethacrylate core-shell emulsion, anticorrosion and bactericidal agent (LXE), thickening material (ATM-60), thickening material (SD-301), excess water stirring at low speed is added successively evenly again according to recipe ratio.
Embodiment 2: a kind of preparation of the coating containing hud typed elastic emulsion, step is as follows:
1. the preparation of poly-(BA-St)/polymethylmethacrylate core-shell emulsion
A. the preparation of poly-(BA-St) seed emulsion
Take butyl acrylate (BA) 4.8g, vinylbenzene (St) 0.72g, sodium lauryl sulphate (SDS) 0.024g, OP-100.12g, ethylene glycol dimethacrylate (EDMA) 0.072g, allyl methacrylate(AMA) (ALMA) 0.024g and deionized water 24g in four-hole boiling flask.Be warming up to 80 DEG C and stir 20min.Taking initiator potassium persulfate (KPS) 0.168g joins in flask, stirs 15min and obtains seed emulsion.
B. poly-(BA-St) seed emulsion is expanding
Expand 9 times according to the preparation formula equal proportion of seed emulsion in step a to join.Butyl acrylate, vinylbenzene, sodium lauryl sulphate, OP-10, ethylene glycol dimethacrylate, allyl methacrylate(AMA) and deionized water are mixed with pre-emulsion, pre-emulsion are slowly added drop-wise in the seed emulsion prepared by step a.Add initiator KPS initiation reaction, 80 DEG C of reaction 2h, are gathered (BA-St) emulsion.
C. the preparation of poly-(BA-St)/polymethylmethacrylate emulsion
Take methyl methacrylate (MMA) 19.2g to be added drop-wise in emulsion prepared in step b.Take initiator KPS0.576g initiation reaction, 80 DEG C of reaction 30min, can be gathered (BA-St)/polymethylmethacrylate core-shell emulsion.
2. the preparation of coating
The formula of coating is as follows:
First, by part water, titanium dioxide, water-ground limestone (1250 order), water-washed kaoline (2000 order), propylene glycol, dispersion agent (5040), wetting agent (PE-100), defoamer (NXZ), film coalescence aid (alcohol ester-12), multifunctional assistant (AMP95) mixing, with high speed dispersor dispersion sand milling to fineness≤30 μm;
Poly-(BA-St)/polymethylmethacrylate core-shell emulsion, anticorrosion and bactericidal agent (LXE), thickening material (ATM-60), thickening material (SD-301), excess water stirring at low speed is added successively evenly again according to recipe ratio.
Embodiment 3: a kind of preparation of the coating containing hud typed elastic emulsion, step is as follows:
1. the preparation of poly-(BA-St)/polymethylmethacrylate core-shell emulsion
A. the preparation of poly-(BA-St) seed emulsion
Take butyl acrylate (BA) 6g, vinylbenzene (St) 1.2g, sodium lauryl sulphate (SDS) 0.048g, OP-100.144g, ethylene glycol dimethacrylate (EDMA) 0.024g, allyl methacrylate(AMA) (ALMA) 0.048g and deionized water 24g in four-hole boiling flask.Be warming up to 80 DEG C and stir 20min.Taking initiator potassium persulfate (KPS) 0.192g joins in flask, stirs 15min and obtains seed emulsion.
B. poly-(BA-St) seed emulsion is expanding
Expand 10 times of preparations according to the preparation formula equal proportion of seed emulsion in step a, pre-emulsion is slowly added drop-wise in the seed emulsion prepared by step a.Add initiator KPS initiation reaction, 80 DEG C of reaction 2h, are gathered (BA-St) emulsion.
C. the preparation of poly-(BA-St)/polymethylmethacrylate emulsion
Take methyl methacrylate (MMA) 33g to be added drop-wise in emulsion prepared in step b.Take initiator KPS0.66g initiation reaction, 80 DEG C of reaction 30min, can be gathered (BA-St)/polymethylmethacrylate core-shell emulsion.
2. the preparation of coating
The formula of coating is as follows:
Concrete steps are as follows:
First, by part water, titanium dioxide, water-ground limestone (1250 order), water-washed kaoline (2000 order), propylene glycol, dispersion agent (5040), wetting agent (PE-100), defoamer (NXZ), film coalescence aid (alcohol ester-12), multifunctional assistant (AMP95) mixing, with high speed dispersor dispersion sand milling to fineness≤30 μm;
Poly-(BA-St)/polymethylmethacrylate emulsion, anticorrosion and bactericidal agent (LXE), thickening material (ATM-60), thickening material (SD-301), excess water stirring at low speed is added successively evenly again according to recipe ratio.
Embodiment 4: a kind of preparation of the coating containing hud typed elastic emulsion, step is as follows:
1. the preparation of poly-(BA-St)/polymethylmethacrylate core-shell emulsion
A. the preparation of poly-(BA-St) seed emulsion
Take butyl acrylate (BA) 4.8g, vinylbenzene (St) 0.96g, sodium lauryl sulphate (SDS) 0.048g, OP-100.12g, ethylene glycol dimethacrylate (EDMA) 0.048g, allyl methacrylate(AMA) (ALMA) 0.048g and deionized water 24g in four-hole boiling flask.Be warming up to 80 DEG C and stir 20min.Taking initiator potassium persulfate (KPS) 0.168g joins in flask, stirs 15min and obtains seed emulsion.
B. poly-(BA-St) seed emulsion is expanding
9 times of preparations are expanded according to the preparation formula equal proportion of seed emulsion in step a, butyl acrylate, vinylbenzene, sodium lauryl sulphate, OP-10, ethylene glycol dimethacrylate, allyl methacrylate(AMA) and deionized water are mixed with pre-emulsion, pre-emulsion are slowly added drop-wise in the seed emulsion prepared by step a.Add initiator KPS initiation reaction, 80 DEG C of reaction 2h, are gathered (BA-St) emulsion.
C. the preparation of poly-(BA-St)/polymethylmethacrylate emulsion
Take methyl methacrylate (MMA) 19.2g to be added drop-wise in emulsion prepared in step b.Take initiator KPS0.576g initiation reaction, 80 DEG C of reaction 30min, can be gathered (BA-St)/polymethylmethacrylate core-shell emulsion.
2. the preparation of coating
The formula of coating is as follows:
Concrete steps are as follows:
First, by part water, titanium dioxide, water-ground limestone (1250 order), water-washed kaoline (2000 order), propylene glycol, dispersion agent (5040), wetting agent (PE-100), defoamer (NXZ), film coalescence aid (alcohol ester-12), multifunctional assistant (AMP95) mixing, with high speed dispersor dispersion sand milling to fineness≤30 μm;
Poly-(BA-St)/polymethylmethacrylate emulsion, anticorrosion and bactericidal agent (LXE), thickening material (ATM-60), thickening material (SD-301), excess water stirring at low speed is added successively evenly again according to recipe ratio.
Embodiment 5: a kind of preparation of the coating containing hud typed elastic emulsion, step is as follows:
1. the preparation of poly-(BA-St)/polymethylmethacrylate core-shell emulsion
A. the preparation of poly-(BA-St) seed emulsion
Take butyl acrylate (BA) 3.6g, vinylbenzene (St) 0.72g, sodium lauryl sulphate (SDS) 0.024g, OP-100.96g, ethylene glycol dimethacrylate (EDMA) 0.024g, allyl methacrylate(AMA) (ALMA) 0.048g and deionized water 24g in four-hole boiling flask.Be warming up to 80 DEG C and stir 20min.Taking initiator potassium persulfate (KPS) 0.144g joins in flask, stirs 15min and obtains seed emulsion.
B. poly-(BA-St) seed emulsion is expanding
8 times of preparation pre-emulsions are expanded according to the preparation formula equal proportion of seed emulsion in step a.Pre-emulsion is slowly added drop-wise in the seed emulsion prepared by step a.Add initiator KPS initiation reaction, 80 DEG C of reaction 2h, are gathered (BA-St) emulsion.
C. the preparation of poly-(BA-St)/polymethylmethacrylate emulsion
Take methyl methacrylate (MMA) 12.96g to be added drop-wise in emulsion prepared in step b.Take initiator KPS0.259g initiation reaction, 80 DEG C of reaction 30min, can be gathered (BA-St)/polymethylmethacrylate core-shell emulsion.
2. the preparation of coating
The formula of coating is as follows:
Concrete steps are as follows:
First, by part water, titanium dioxide, water-ground limestone (1250 order), water-washed kaoline (2000 order), propylene glycol, dispersion agent (5040), wetting agent (PE-100), defoamer (NXZ), film coalescence aid (alcohol ester-12), multifunctional assistant (AMP95) mixing, with high speed dispersor dispersion sand milling to fineness≤30 μm;
Hud typed elastic emulsion, anticorrosion and bactericidal agent (LXE), thickening material (ATM-60), thickening material (SD-301), excess water stirring at low speed is added successively evenly again according to recipe ratio.
Embodiment 6: a kind of preparation of the coating containing hud typed elastic emulsion, step is as follows:
1. the preparation of poly-(BA-St)/polymethylmethacrylate core-shell emulsion
A. the preparation of poly-(BA-St) seed emulsion
Take butyl acrylate (BA) 4.8g, vinylbenzene (St) 0.72g, sodium lauryl sulphate (SDS) 0.072g, OP-100.12g, ethylene glycol dimethacrylate (EDMA) 0.072g, allyl methacrylate(AMA) (ALMA) 0.024g and deionized water 24g in four-hole boiling flask.Be warming up to 80 DEG C and stir 20min.Taking initiator potassium persulfate (KPS) 0.168g joins in flask, stirs 15min and obtains seed emulsion.
B. poly-(BA-St) seed emulsion is expanding
9 times of preparation pre-emulsions are expanded according to the preparation formula equal proportion of seed emulsion in step a.Pre-emulsion is slowly added drop-wise in the seed emulsion prepared by step a.Add initiator KPS initiation reaction, 80 DEG C of reaction 2h, are gathered (BA-St) emulsion.
C. the preparation of poly-(BA-St)/polymethylmethacrylate emulsion
Take methyl methacrylate (MMA) 14.4g to be added drop-wise in emulsion prepared in step b.Take initiator KPS0.288g initiation reaction, 80 DEG C of reaction 30min, can be gathered (BA-St)/polymethylmethacrylate core-shell emulsion.
2. the preparation of coating
The formula of coating is as follows:
Concrete steps are as follows:
First, by part water, titanium dioxide, water-ground limestone (1250 order), water-washed kaoline (2000 order), propylene glycol, dispersion agent (5040), wetting agent (PE-100), defoamer (NXZ), film coalescence aid (alcohol ester-12), multifunctional assistant (AMP95) mixing, with high speed dispersor dispersion sand milling to fineness≤30 μm;
Poly-(BA-St)/polymethylmethacrylate emulsion, anticorrosion and bactericidal agent (LXE), thickening material (ATM-60), thickening material (SD-301), excess water stirring at low speed is added successively evenly again according to recipe ratio.
Following table is that the emulsion particle Tg of poly-(the BA-St)/polymethylmethacrylate emulsion of different IPs shell mass ratio of the present invention contrasts
Claims (3)
1. the preparation method of a hud typed elastic emulsion, it is characterized in that, it is for core with poly-(BA-St), take polymethylmethacrylate as poly-(BA-St)/polymethylmethacrylate nucleocapsid structure aqueous polymer emulsion of shell, obtained by butyl acrylate, vinylbenzene and methyl methacrylate letex polymerization, comprise step as follows:
(1) preparation of poly-(BA-St) seed emulsion:
0.15 ~ 0.25:0.03 in mass ratio ~ 0.05:0.001 ~ 0.003:0.004 ~ 0.006:0.001 ~ 0.003:0.001 ~ 0.003:1 takes butyl acrylate, vinylbenzene, sodium lauryl sulphate, OP-10, ethylene glycol dimethacrylate, allyl methacrylate(AMA) and deionized water, add reaction flask, 80 DEG C are warming up in stirring, constant temperature stirs 20 ~ 30min, take initiator potassium persulfate KPS, the consumption of KPS is 0.006 ~ 0.008 times of water, join in reaction flask, 80 DEG C are stirred 10 ~ 15min and obtain seed emulsion;
(2) preparation of poly-(BA-St) emulsion, raw material is taken according to the ratio described in step (1), amount expands 8 ~ 10 times of step (1) to, butyl acrylate, vinylbenzene, sodium lauryl sulphate, OP-10, ethylene glycol dimethacrylate, allyl methacrylate(AMA) and deionized water are mixed with pre-emulsion, pre-emulsion is slowly added drop-wise in prepared seed emulsion, add initiator KPS initiation reaction, 80 DEG C of stirring reaction 2 ± 0.1h, are gathered (BA-St) emulsion;
(3) be added drop-wise to by methyl methacrylate in emulsion prepared in step (2), take initiator KPS and add initiation reaction, 80 DEG C of reaction 30 ~ 35min, can be gathered (BA-St)/polymethylmethacrylate core-shell emulsion; The consumption of methyl methacrylate is 0.3 ~ 0.5 times of aforesaid propylene acid butyl ester total amount, and the consumption of KPS is 0.02 ~ 0.04 times of methyl methacrylate consumption.
2. the preparation method of hud typed elastic emulsion according to claim 1, is characterized in that, stirring velocity controls at 1500 ~ 2000r/min, and the rate of addition of monomers methyl methacrylate controls at 1 ~ 3ml/min; The rate of addition of pre-emulsion controls to add in 30min.
3. the preparation method of a kind of hud typed elastic emulsion according to claim 1, is characterized in that, described hud typed elastic emulsion solid content is 20 ~ 40%, and particle size range is at 50 ~ 100nm.
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| CN104263118A (en) * | 2014-10-20 | 2015-01-07 | 济南玛博伦环保涂料有限公司 | Water-in-water faux marble paint and preparation method thereof |
| CN108192017B (en) * | 2017-12-29 | 2021-02-12 | 嘉力丰科技股份有限公司 | Core-shell type anti-impact wallpaper base film and preparation method thereof |
| CN110804136B (en) * | 2019-11-05 | 2022-04-26 | 济南大学 | Preparation method of core-shell type fluorine-containing emulsion microsphere and application of core-shell type fluorine-containing emulsion microsphere in super-hydrophobic coating |
| CN114456304B (en) * | 2020-12-28 | 2023-09-22 | 海南必凯水性新材料有限公司 | High-barrier and high-water-resistance aqueous acrylic emulsion and preparation method thereof |
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| KR100274658B1 (en) * | 1997-12-30 | 2000-12-15 | 하영준, 마르코스 고메즈 | A preparing method of core-shell composite particles for toughening agent of polymethyl methacrylate resin and composition containing the same |
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| US4952635A (en) * | 1987-08-20 | 1990-08-28 | Norsolor | Process for the manufacture of an impact resistant thermoplastic resin |
| CN101190992A (en) * | 2006-11-18 | 2008-06-04 | 沂源瑞丰高分子材料有限公司 | Transparent acrylic ester impact-resisting modifier for PVC |
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| Title |
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| 聚苯乙烯/聚甲基丙烯酸甲酯核/壳结构复合乳液的制备与形貌的研究;朱莉芳等;《高分子材料科学与工程》;20000731;第16卷(第4期);第168-169页 * |
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