CN1337416A - Prepn process of fluororubber modified polyacrylate emulsion - Google Patents

Prepn process of fluororubber modified polyacrylate emulsion Download PDF

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Publication number
CN1337416A
CN1337416A CN 01131115 CN01131115A CN1337416A CN 1337416 A CN1337416 A CN 1337416A CN 01131115 CN01131115 CN 01131115 CN 01131115 A CN01131115 A CN 01131115A CN 1337416 A CN1337416 A CN 1337416A
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ratio
gram
emulsion
miniemulsion
water
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CN1131250C (en
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唐黎明
张侃
潘志存
刘德山
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Tsinghua University
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Tsinghua University
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Abstract

The preparation method of fluororubber modified polyacrylate emulsion includes the following steps: firstly, preparing monomer mixture formed from methyl methacrylate, butyl acrylate and acrylic acid, dissolving the fluororubber said mixture, and dissolving the emulsion adjuvant in said mixture to form oil phase for stand-by; dissoling non-ionic emulsifier and anionic emulsifier in water to form water phase; mixing said oil phase and water phase, stirring at high speed to obtain fine emulsion, adding initiating agent in the fine emulsion, under the protection of nitrogen gas adding fine emulsion, deionized water and initiating agent, then drop adding the fine emulsion in which the initiating agent is added into a container, finally adding initiating agent, regulating pH value to obtain the fluororubber modified polyacrylate emulsion. It possesses good cohesive force with base material and good surface performance of formed film, and has no pollution, so that it can be used for modifying surface of base material in the fields required for resisting pollution, heat resistance, water-proofing property, resistance to chemical reagent and inadhesion property.

Description

A kind of preparation method of fluororubber modified polyacrylate dispersion
Technical field:
The present invention relates to the preparation method of the polyacrylate dispersion of a kind of viton (vinylidene-hexafluoropropylene copolymer) modification, specifically providing a kind of is the modified polyacrylate emulsion and preparation method thereof of properties-correcting agent with the viton, the performance of the paint film that utilizes this modified emulsion preparation is provided again simultaneously, has belonged to polymeric material field.
Background technology:
Characteristics such as the polyacrylate(s) emulsion is a medium with water, has advantages such as cost is low, safe in utilization, low in the pollution of the environment, and that its film forming matter has is pliable and tough, weather-proof, viscosity is good, therefore as building materials be widely used in decorate and inner, external wall coating in.But along with the rise of urban skyscraper, the waterproof of buildings, didirtresistance and outward appearance come into one's own day by day, and skin coating is had higher requirement.
High performance skin coating is except must having higher intensity, elasticity and sticking power, still need have higher weathering resistance, water tolerance, resistance to acids and bases, anti-pollution and ventilation property preferably, could satisfy the requirement of modern coating, and common polyacrylate(s) emulsion coatings is can not satisfy these requirements far away.Address these problems, just must carry out modification, improve its performance this emulsion.
Fluoropolymer has the performance of many excellences, and as outstanding weathering resistance, water tolerance, oil-proofness, chemical resistance etc., its paint film has the good mechanical performance.But also there are 3 deficiencies:
1. general fluoro-resin all indissoluble is separated, and selects for use organic solvent to cause problem of environmental pollution.Separating as the easy crystallization indissoluble of PVDF resin, when it is used as coating, is to dissolve with intensive polar solvent, and voltalef, tetrafluoroethylene difficulty especially are dissolved in common solvent.Limit the new regulation that solvent discharges for observing, require further to reduce the use of organic solvent in the coating, this has promoted the development and application of solventless coatings product innovation, and this also is the shortcoming for the insoluble that overcomes conventional fluorocarbon polymer coating existence.
2. high temperature sintering.Fluoropolymer needs during as coating high temperature sintering could form the film of one deck densification.Therefore its purposes is very limited, and particularly just can not use at main equipment or when carrying out outdoor construction.
3. cost an arm and a leg.The fluorine-containing latex coating of fluorocarbon polymer coating, particularly Air drying, excellent performance, but cost an arm and a leg, use is restricted.
The fluoropolymer coating of being reported at present mainly is the polyvinylidene difluoride (PVDF) class: as U.S. Pat 3,34, and 222,3,324,069,4,383,075,4,557,977 etc., it is to be dissolved in polyvinylidene difluoride (PVDF) in the organic solvent and the polyacrylate resin mixing, and by film forming behind the hot setting.Cause environmental pollution because use a large amount of organic solvents, and need hot setting and be unfavorable for construction.
Summary of the invention:
The objective of the invention is to propose a kind of preparation method of fluororubber modified polyacrylate dispersion, with fluororubber modified polyacrylate(s) emulsion, further improve the performance of polyacrylate coating, make it have higher weathering resistance, solvent resistance and stain resistance etc., and can prevent the influence of solvent to environment, the excellent performance and the price that make coating are more much lower than fluoropolymer.
The preparation method of the fluororubber modified polyacrylate dispersion that the present invention proposes comprises following each step:
1. prepare the monomer mixture that methyl methacrylate, butyl acrylate and vinylformic acid are formed, its ratio is 1: 1: 0.05~0.1, again according to the ratio of weight ratio 1: 5~50, viton is dissolved in the above-mentioned monomeric mixture, then according to 1: 200~250 ratio, assistant for emulsifying agent is dissolved in the said mixture, and it is standby to form oil phase; Ratio according to 1: 50~70 is dissolved in nonionic emulsifying agent and anionic emulsifier in the water, forms water, wherein, the ratio of nonionic emulsifying agent and anionic emulsifier is 1: 0.5~2, then, oil phase and water are mixed, and at room temperature stirred 5 ~ 20 minutes;
2. adopt homogenizer with the said mixture high-speed stirring, become miniemulsion;
3. add initiator in miniemulsion, wherein the ratio of the add-on of initiator and total viton is 1: 5-30;
4; under nitrogen protection; the miniemulsion that in container, adds above-mentioned second step; deionized water and initiator; wherein; the viton total amount is 1 with the ratio of miniemulsion: 4-60; the ratio of viton total amount and deionized water is 1: 4-40; the ratio of viton total amount and initiator is 4-40: 1; stirring also is warming up to 60-90 ℃; react after 1-3 hour; in 1-3 hour, the above-mentioned the 3rd miniemulsion that goes on foot at the uniform velocity is added drop-wise in the container by constant pressure funnel, the viton total amount is 1 with the ratio of miniemulsion: 4-60; after dropwising; add initiator again, its consumption is 1/5~1/30 of a viton total amount, is incubated after 1-3 hour; add ammoniacal liquor and regulate pH value to 7.5~9.5, be fluororubber modified polyacrylate dispersion.
Among the present invention,, used assistant for emulsifying agent in order to reach thin emulsive purpose; Can enumerate tensio-active agents such as n-Hexadecane, hexadecanol as assistant for emulsifying agent, but be not limited to these.
Among the present invention, emulsifying agent has used nonionic surface active agent; Can enumerate Voranol EP 2001 class, polyoxyethylene alkyl phenyl ether class etc. as nonionic surface active agent, but be not limited to these.In particular, can list polyoxyethylene lauryl ether, polyoxyethylene cetyl base ether etc. as the Voranol EP 2001 class; The polyoxyethylene alkyl phenyl ether class can list polyoxyethylene nonylplenyl ether, polyoxyethylene octyl phenyl ether etc.
Among the present invention, emulsifying agent has used aniorfic surfactant, can enumerate alkyl-sulphate, alkylsulfonate, Voranol EP 2001 class vitriol, polyoxyethylene alkyl phenyl ether class vitriol etc. as aniorfic surfactant, but be not limited to these.In particular, can list sodium lauryl sulphate, Sodium palmityl sulfate as alkyl-sulphate; Can list sodium laurylsulfonate, sodium cetanesulfonate as alkylsulfonate; Can list polyoxyethylene lauryl ether sodium sulfate, polyoxyethylene cetyl base ether sulfuric acid amine as Voranol EP 2001 class vitriol; Can list polyoxyethylene nonylplenyl ether sodium sulfate, polyoxyethylene octyl phenyl ether sulfuric acid amine etc. as polyoxyethylene alkyl phenyl ether class vitriol etc.
In the composition of the present invention, acrylic ester monomer comprises methyl methacrylate, butyl acrylate, acrylic acid epoxy propyl ester, vinylformic acid, vinylbenzene etc., but is not limited to these.
In the composition of the present invention, the fluoropolymer of use has better solvability in acrylic ester monomer.Except vinylidene-hexafluoro-propylene class elastomerics, for example can also enumerate vinylidene class elastomerics, R 1216-vinyl elastomerics, tetrafluoroethylene-vinyl elastomericss etc. such as vinylidene-hexafluoropropylene (HFP)/tetrafluoroethylene (TFE) class, but be not limited to these.
In composition of the present invention, initiator comprises persulfuric acid salt, azo class and organic peroxy class initiator, but is not limited to these.
The present invention is because good with the cohesive force of base material, and the surface property of paint film is good after the film forming, and pollution-free.Therefore can require anti-pollution, thermotolerance, water tolerance, the field of drug-resistant and non-viscosity is used for the surface modification of base material.As be used for the field such as water-fast, oil-proof composition of external wall, weaving, leatherware.It is low that method of the present invention also has a synthetic cost, little to the contaminative of environment, and characteristics such as easy to operate are adapted at adopting in the suitability for industrialized production.
The specific embodiment:
Below by embodiment technology of the present invention is given to illustrate further.
Embodiment 1: the preparation 1 of modified emulsion
1.0 gram fluorubber are dissolved in by 20 gram methyl methacrylates, 20 gram butyl acrylates and 1.5 gram acrylic acid In the monomer mixture that causes, 0.2 gram oil-soluble assistant for emulsifying agent hexadecane is dissolved in the said mixture, forms oil phase; The OPEO of 0.5 gram and the lauryl sodium sulfate of 0.5 gram are dissolved in 60 gram deionized waters, form water Phase; Two-phase at room temperature stirred 10 minutes after mixing, and the emulsion that stirs is put into IKA-T25B type high speed disintegrator, With 23,000 rev/mins rotating speed high-speed stirred 1 minute, then with 16,000 rev/mins rotating speed high-speed stirred 5 minutes Clock becomes miniemulsion.
Under nitrogen protection, add 1/3 miniemulsion, 30 gram deionized waters and 0.2 gram in the glass reactor and cause The agent ammonium persulfate. Stir, be warming up to 74 ℃, react after 2 hours, in 2 hours, will contain 0.2 by constant pressure funnel The residue miniemulsion of gram ammonium persulfate at the uniform velocity is added drop-wise in the reactor. After dropwising, add 0.2 gram ammonium persulfate, protect Temperature two hours; After being cooled to 50 ℃, adding ammoniacal liquor and regulate pH value to 8~9, discharging.
Gel-free in the emulsion after the polymerization is coated in emulsion on the slide, in 40 ℃ baking oven after dry 24 hours, Visualization finds that the gained paint film transparency is good, with OCA20 type surface contact angle instrument (DataPhysics company product) Measure paint film to the contact angle of water, the results are shown in Table 1.
Embodiment 2: the preparation 2 of modified emulsion
2.0 gram fluorubber are dissolved in by 20 gram methyl methacrylates, 20 gram butyl acrylates and 1.5 gram acrylic acid In the monomer mixture that causes, 0.2 gram oil-soluble assistant for emulsifying agent hexadecane is dissolved in the said mixture, forms oil phase; The OPEO of 0.4 gram and the lauryl sodium sulfate of 0.6 gram are dissolved in 60 gram deionized waters, form water Phase; Two-phase at room temperature stirred 15 minutes after mixing, and the emulsion that stirs is put into IKA-T25B type high speed disintegrator, With 23,000 rev/mins rotating speed high-speed stirred 1 minute, then with 16,000 rev/mins rotating speed high-speed stirred 5 minutes Clock becomes miniemulsion.
Under nitrogen protection, add 1/3 miniemulsion, 30 gram deionized waters and 0.2 gram in the glass reactor and cause The agent ammonium persulfate. Stir, be warming up to 76 ℃, react after 2 hours, in 2 hours, will contain 0.2 by constant pressure funnel The residue miniemulsion of gram ammonium persulfate at the uniform velocity is added drop-wise in the reactor. After dropwising, add 0.2 gram ammonium persulfate, protect Temperature two hours; After being cooled to 50 ℃, adding ammoniacal liquor and regulate pH value to 8~9, discharging.
Gel-free in the emulsion after the polymerization is coated in emulsion on the slide, in 40 ℃ baking oven after dry 24 hours, Visualization finds that the gained paint film transparency is good, measures paint film to the contact angle of water, the results are shown in Table 1.
Embodiment 3: the preparation 3 of modified emulsion
3.0 gram fluorubber are dissolved in by 20 gram methyl methacrylates, 20 gram butyl acrylates and 1.5 gram acrylic acid In the monomer mixture that causes, 0.2 gram oil-soluble assistant for emulsifying agent hexadecane is dissolved in the said mixture, forms oil phase; The OPEO of 0.6 gram and the lauryl sodium sulfate of 0.4 gram are dissolved in 60 gram deionized waters, form water Phase; Two-phase at room temperature stirred 20 minutes after mixing, and the emulsion that stirs is put into IKA-T25B type high speed disintegrator, With 23,000 rev/mins rotating speed high-speed stirred 1 minute, then with 16,000 rev/mins rotating speed high-speed stirred 5 minutes Clock becomes miniemulsion.
Under nitrogen protection, add 1/3 miniemulsion, 30 gram deionized waters and 0.2 gram in the glass reactor and cause The agent ammonium persulfate. Stir, be warming up to 80 ℃, react after 2 hours, in 2 hours, will contain 0.2 by constant pressure funnel The residue miniemulsion of gram ammonium persulfate at the uniform velocity is added drop-wise in the reactor. After dropwising, add 0.2 gram ammonium persulfate, protect Temperature 2.5 hours; After being cooled to 45 ℃, adding ammoniacal liquor and regulate pH value to 8~9, discharging.
Gel-free in the emulsion after the polymerization is coated in emulsion on the slide, in 40 ℃ baking oven after dry 24 hours, Visualization finds that the gained paint film transparency is good, measures paint film to the contact angle of water, the results are shown in Table 1.
Embodiment 4: the preparation 4 of modified emulsion
4.0 gram fluorubber are dissolved in by 20 gram methyl methacrylates, 20 gram butyl acrylates and 1.5 gram acrylic acid In the monomer mixture that causes, 0.2 gram oil-soluble assistant for emulsifying agent hexadecane is dissolved in the said mixture, forms oil phase; The OPEO of 0.5 gram and the lauryl sodium sulfate of 0.5 gram are dissolved in 60 gram deionized waters, form water Phase; Two-phase at room temperature stirred 10 minutes after mixing, and the emulsion that stirs is put into IKA-T25B type high speed disintegrator, With 23,000 rev/mins rotating speed high-speed stirred 1 minute, then with 16,000 rev/mins rotating speed high-speed stirred 5 minutes Clock becomes miniemulsion.
Under nitrogen protection, add 1/3 miniemulsion, 30 gram deionized waters and 0.2 gram in the glass reactor and cause The agent ammonium persulfate. Stir, be warming up to 78 ℃, react after 2 hours, in 2.5 hours, will contain by constant pressure funnel There is the residue miniemulsion of 0.2 gram ammonium persulfate at the uniform velocity to be added drop-wise in the reactor. After dropwising, add 0.2 gram persulfuric acid Ammonium is incubated two hours; After being cooled to 50 ℃, adding ammoniacal liquor and regulate pH value to 8~9, discharging.
0.38% gel (weight is take the gross weight of emulsion compositions as benchmark) is arranged in the emulsion after the polymerization. With emulsion Be coated on the slide, after dry 24 hours, visualization finds that the gained paint film transparency is good in 40 ℃ baking oven, Measure paint film to the contact angle of water, the results are shown in Table 1.
Embodiment 5: the preparation 5 of modified emulsion
5.0 gram fluorubber are dissolved in by 20 gram methyl methacrylates, 20 gram butyl acrylates and 1.5 gram acrylic acid In the monomer mixture that causes, 0.2 gram oil-soluble assistant for emulsifying agent hexadecane is dissolved in the said mixture, forms oil phase; The OPEO of 0.5 gram and the lauryl sodium sulfate of 0.5 gram are dissolved in 60 gram deionized waters, form water Phase; Two-phase at room temperature stirred 20 minutes after mixing, and the emulsion that stirs is put into IKA-T25B type high speed disintegrator, With 23,000 rev/mins rotating speed high-speed stirred 1 minute, then with 16,000 rev/mins rotating speed high-speed stirred 5 minutes Clock becomes miniemulsion.
Under nitrogen protection, add 1/3 miniemulsion, 30 gram deionized waters and 0.2 gram in the glass reactor and cause The agent ammonium persulfate. Stir, be warming up to 72 ℃, react after 2 hours, in 1.5 hours, will contain by constant pressure funnel There is the residue miniemulsion of 0.2 gram ammonium persulfate at the uniform velocity to be added drop-wise in the reactor. After dropwising, add 0.2 gram persulfuric acid Ammonium is incubated two hours; After being cooled to 50 ℃, adding ammoniacal liquor and regulate pH value to 8~9, discharging.
0.76% gel (weight is take the gross weight of emulsion compositions as benchmark) is arranged in the emulsion after the polymerization, show with The increase of fluorubber addition, system begins to occur unstable. Emulsion is coated on the slide, at 40 ℃ baking oven After middle dry 24 hours, visualization finds that the gained paint film transparency is good, and the mensuration paint film is to the contact angle of water, result See Table 1.
Embodiment 6: the preparation 6 of modified emulsion
Fluorubber 6.0 grams are dissolved in by 20 gram methyl methacrylates, 20 gram butyl acrylates and 1.5 gram acrylic acid In the monomer mixture that forms, 0.2 gram oil-soluble assistant for emulsifying agent hexadecane is dissolved in the said mixture, forms oil phase; The OPEO of 0.5 gram and the lauryl sodium sulfate of 0.5 gram are dissolved in 60 gram deionized waters, form water Phase; Two-phase at room temperature stirred 20 minutes after mixing, and the emulsion that stirs is put into IKA-T25B type high speed disintegrator, With 23,000 rev/mins rotating speed high-speed stirred 1 minute, then with 16,000 rev/mins rotating speed high-speed stirred 5 minutes Clock becomes miniemulsion.
Under nitrogen protection, add 1/3 miniemulsion, 30 gram deionized waters and 0.2 gram in the glass reactor and cause The agent ammonium persulfate. Stir, be warming up to 72 ℃, react after 2 hours, in 1.5 hours, will contain by constant pressure funnel There is the residue miniemulsion of 0.2 gram ammonium persulfate at the uniform velocity to be added drop-wise in the reactor. After dropwising, add 0.2 gram persulfuric acid Ammonium is incubated two hours; After being cooled to 50 ℃, adding ammoniacal liquor and regulate pH value to 8~9, discharging.
0.69% gel (weight is take the gross weight of emulsion compositions as benchmark) is arranged in the emulsion after the polymerization, show with The further increase of fluorubber addition, system is further unstable. Emulsion is coated on the slide, at 40 ℃ After dry 24 hours, visualization finds that the gained paint film transparency is good, measures paint film to the contact angle of water in the baking oven, The results are shown in Table 1.
Comparative example: the preparation of unmodified emulsion
The OPEO of 0.5 gram and the lauryl sodium sulfate of 0.5 gram are dissolved in 60 gram deionized waters, will 0.2 gram oil-soluble assistant for emulsifying agent hexadecane is dissolved in by 20 gram methyl methacrylates, 20 gram butyl acrylates and 1.5 In the monomer mixture that gram acrylic acid forms. Two-phase at room temperature stirred 10 minutes after mixing, and the emulsion that stirs is put Enter IKA-T25B type high speed disintegrator, with 23,000 rev/mins rotating speed high-speed stirred 1 minute, then with 16,000 Rev/min rotating speed high-speed stirred 5 minutes, this moment, system was miniemulsion.
Under nitrogen protection, add 1/3 miniemulsion, 30 gram deionized waters and 0.2 gram in the glass reactor and cause The agent ammonium persulfate. Speed of agitator is 270 rev/mins, is warming up to 74 ℃, reacts after 2 hours, will remain miniemulsion and (contain 0.2 gram initiator ammonium persulfate is arranged), in 2 hours, at the uniform velocity be added drop-wise in the reactor by constant pressure funnel. Dropwise After, add 0.2 gram initiator ammonium persulfate, be incubated two hours; After being cooled to 50 ℃, adding ammoniacal liquor and regulate pH value extremely Alkalescence, discharging. Emulsion is coated on the slide, and after dry 24 hours, institute is found in visualization in 40 ℃ baking oven It is good to get the paint film transparency, measures paint film to the contact angle of water, the results are shown in Table 1.
By above embodiment as seen, when the addition of fluorubber is 3.0 grams when following, gel-free in the emulsion, stable system Property is good.
The different emulsion paint films of table 1 are to the contact angle of water
Project The comparative example Embodiment
1     2     3     4     5     6
Contact angle/° 59.85 73.86   77.23   81.59   76.44   75.76     73.91
Be can clearly be seen that by table 1 contact angle of fluororubber modified polyacrylate dispersion paint film is much higher than unmodified The contact angle of emulsion paint film shows that the hydrophobic performance of film coated surface is greatly improved. In addition, prepared emulsion is steady Qualitative good, can long preservation. Fluororubber modified polyacrylate dispersion of the present invention is applicable to construction material, fabric Deng covering with paint.

Claims (1)

1, a kind of preparation method of fluororubber modified polyacrylate dispersion is characterized in that this method comprises following each step:
(1) monomer mixture of preparation methyl methacrylate, butyl acrylate and vinylformic acid composition, its ratio is 1: 1: 0.05~0.1, again according to the ratio of weight ratio 1: 5~50, viton is dissolved in the above-mentioned monomeric mixture, then according to 1: 200~250 ratio, assistant for emulsifying agent is dissolved in the said mixture, and it is standby to form oil phase; Ratio according to 1: 50~70 is dissolved in nonionic emulsifying agent and anionic emulsifier in the water, forms water, wherein, the ratio of nonionic emulsifying agent and anionic emulsifier is 1: 0.5~2, then, oil phase and water are mixed, and at room temperature stirred 5 ~ 20 minutes;
(2) adopt homogenizer with the said mixture high-speed stirring, become miniemulsion;
(3) add initiator in miniemulsion, wherein the ratio of the add-on of initiator and total viton is 1: 5-30;
(4) under nitrogen protection; the miniemulsion that in container, adds above-mentioned second step; deionized water and initiator; wherein; the viton total amount is 1 with the ratio of miniemulsion: 4-60; the ratio of viton total amount and deionized water is 1: 4-40; the ratio of viton total amount and initiator is 4-40: 1; stirring also is warming up to 60-90 ℃; react after 1-3 hour; in 1-3 hour, the above-mentioned the 3rd miniemulsion that goes on foot at the uniform velocity is added drop-wise in the container by constant pressure funnel, the viton total amount is 1 with the ratio of miniemulsion: 4-60; after dropwising; add initiator again, its consumption is 1/5~1/30 of a viton total amount, is incubated after 1-3 hour; add ammoniacal liquor and regulate pH value to 7.5~9.5, be fluororubber modified polyacrylate dispersion.
CN 01131115 2001-08-31 2001-08-31 Prepn process of fluororubber modified polyacrylate emulsion Expired - Fee Related CN1131250C (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003064486A2 (en) * 2002-01-14 2003-08-07 Eastman Chemical Company Rubber modified acrylic and/or vinyl hybrid resins
CN1300203C (en) * 2005-01-19 2007-02-14 南京工业大学 Fluoro resin/acrylic ester mixed emulsion and method for preparation thereof
CN102167772A (en) * 2011-01-20 2011-08-31 安徽大学 Fluorine-containing easily processed acrylate rubber and preparation method thereof
CN105418850A (en) * 2015-11-30 2016-03-23 何晨旭 Nano-scale core-shell type wax-acrylic polymer emulsion for coating and preparation method of nano-scale core-shell type wax-acrylic polymer emulsion

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003064486A2 (en) * 2002-01-14 2003-08-07 Eastman Chemical Company Rubber modified acrylic and/or vinyl hybrid resins
WO2003064486A3 (en) * 2002-01-14 2004-04-22 Eastman Chem Co Rubber modified acrylic and/or vinyl hybrid resins
US7396871B2 (en) 2002-01-14 2008-07-08 Eastman Chemical Comapny Rubber modified acrylic and/or vinyl hybrid resins
CN1300203C (en) * 2005-01-19 2007-02-14 南京工业大学 Fluoro resin/acrylic ester mixed emulsion and method for preparation thereof
CN102167772A (en) * 2011-01-20 2011-08-31 安徽大学 Fluorine-containing easily processed acrylate rubber and preparation method thereof
CN102167772B (en) * 2011-01-20 2013-05-29 安徽大学 Fluorine-containing easily processed acrylate rubber and preparation method thereof
CN105418850A (en) * 2015-11-30 2016-03-23 何晨旭 Nano-scale core-shell type wax-acrylic polymer emulsion for coating and preparation method of nano-scale core-shell type wax-acrylic polymer emulsion

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