CN103045113B - Preparation method of self-crosslinking IPN (interpenetrating network) organosilicone-acrylate copolymer emulsion pressure-sensitive adhesive - Google Patents
Preparation method of self-crosslinking IPN (interpenetrating network) organosilicone-acrylate copolymer emulsion pressure-sensitive adhesive Download PDFInfo
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Abstract
The invention belongs to the technical field of adhesive, and particularly relates to a preparation method of a self-crosslinking IPN (interpenetrating network) organosilicone-acrylate copolymer emulsion pressure-sensitive adhesive. The method comprises the following steps: firstly synthetizing a polymer emulsion serving as a seed, then adding an organosilicone monomer, silane hydrolysis inhibitors, a crosslinking agent and a catalyst in the seed emulsion step by step by adopting a organic silicon monomer after-dropping technology and a method of adding silane hydrolysis inhibitor and the like, making the organosilicone monomer further polymerize and crosslink on the surface of the seminal emulsion, and then preparing a self-crosslinking IPN (interpenetrating network) organosilicone-acrylate copolymer emulsion pressure-sensitive adhesive with excellent combination property. The method can be used for solving the problems that the polymerization stability is reduced due to hydrolysis of organosilicone in the reaction, and the water resistance and weatherability of the organosilicone modified acrylate pressure-sensitive adhesive products are bad, and the like.
Description
Technical field
the invention belongs to adhesive technology field, be specifically related to a kind of preparation method of self-crosslinked interpenetrating net type Silicone-Acrylic Copolymer Emulsion pressure-sensitive adhesive.
Background technology
along with progressively development economic and science and technology, industry, agricultural, traffic, medical treatment, national defence and civil area increase day by day to the demand of pressure-sensitive adhesive, and requirement is also more and more higher.Country's 12 planning also clearly propose research high-performance, high-quality pressure sensitive adhesive and goods.From the practical situations of current pressure sensitive adhesive in general, prepare that intensity is high, the pressure sensitive adhesive of good heat resistance, use merely the resin of a type, be difficult to obtain good effect, must carry out compound and modification.Polyacrylate pressure-sensitive adhesive is with its good adhesiveproperties and chemical stability, and the advantage such as nontoxic, harmless and with low cost, be used widely, but polyacrylate pressure-sensitive resistance toheat is general, the acrylate pressure-sensitive adhesive maximum operation (service) temperature after being cross-linked is only 150
o
c short-term is used, and at higher temperature, thermal-oxidative aging property is poor, easily loses pressure-sensitive, and this is very restricted the application of acrylate pressure-sensitive adhesive.Organic pressure-sensitive gel not only has the characteristic of common pressure sensitive adhesive, also has wider use temperature (70 ~ 250
o
c) advantage such as scope and good unreactiveness, but the stripping strength of organic pressure-sensitive gel is low, is difficult to meet the bonding requirements of some high-peeling strengths.Therefore, adopt organosilicon to carry out chemical modification to polyacrylate pressure-sensitive, with advantages such as the resistance to elevated temperatures of organic pressure-sensitive gel and the high-peeling strengths of polyacrylate pressure-sensitive, not only can guarantee certain stripping strength, and can improve resistance to elevated temperatures and the medium-resistance of polyacrylate pressure-sensitive, there is actual application value.
secondly, along with people are to environmental protection, safety, energy-conservation etc. attention and the continuous expansion of pressure sensitive adhesive application, impel pressure sensitive adhesive towards low pollution, the province energy, high-performance and multifunction future development, particularly western developed country proposes using nuisanceless, pollution-free, resource-saving, province's energy after the prerequisite of development adhesives industries, and emulsion adhesive pollution-free, Water-borne modification causes the great interest of people.But the aspect such as the cohesive strength of the existing kind of coventional type emulsion-type organosilicon-modified acrylate pressure sensitive adhesive, water tolerance, weathering resistance is poor compared with solvent pressure-sensitive adhesive, has limited its more wide development.Therefore, find a kind of superior performance and again free of contamination emulsion-type organosilicon-modified acrylate pressure-sensitive adhesive and related production technology be very important, more existing pertinent literatures reports in this respect.
at present, the method for conventional organosilicon-modified acrylate polymerized emulsion has two kinds, i.e. physical modification method and chemical copolymerization method.Open special permission number was once reported organic pressure-sensitive gel physical blending in organic solvent of the acrylate pressure-sensitive adhesive of 100 parts of weight and 1 ~ 30 part for the Japanese Patent of 60-197780, obtain organosilicon-modified acrylate pressure sensitive adhesive, the blending and modifying of this method, because there is no bonding between acrylate and organosilicon, easily produce and be separated, the poor stability of product.Japanese Patent No. 94157758(1994.7.6) first use vinyl benzene methyl dimethoxysilane, octamethylcyclotetrasiloxane are made to poly organic silicon alkane emulsion, get 10 parts and acroleic acid polymerization, and then with the condensation of 10 parts of hexaphenyl trisiloxanes, the polymer emulsion film making has good weathering resistance, water tolerance and resistance to crocking, and snappiness and sticking power are good.U.S. Patent No. 4,791,163 have also introduced a kind of emulsion-type organosilicon-modified acrylate pressure sensitive adhesive.Application number is that 200510060865.8 Chinese patent was reported organosilane monomer modified polyacrylate pressure-sensitive adhesive, be by monomer mixtures such as acrylate under the condition of solution polymerization, the method that adopts substep to drip, carry out radical polymerization and prepare performed polymer, by regulating solvent to regulate molecular weight and the distribution of product, by adding linking agent, can obtain excellent performance again.Application number is that 02134207.5 Chinese patent has reported that silicone-modified polyacrylate is high temperature resistant, the preparation method of high-temperature insulation pressure-sensitive stick and adhesive tape, first it is to synthesize the pressure-sensitive gluing prepolymer of a kind of grafting interpenetrating(polymer)networks by solution polymerization, then obtains silicone-modified polyacrylate pressure-sensitive adhesive by aftertreatment.
but still there are many deficiencies in above-mentioned disclosed patent of invention, for example, because organosilane monomer is very easily hydrolyzed, condensation, in polymerization process, generate early stage crosslinking structure and cause the cohesion of system unstability, therefore find the method that effectively suppresses organosilane monomer hydrolysis, become a technical barrier in organosilicon-modified acrylate emulsion polymerization process for preparing; Secondly, in acrylic emulsion pressure sensitive adhesive, generally contain the emulsifying agent of 1%-2%, the normally tensio-active agent of anionic and non-ionic type, the existence of these emulsifying agents makes pressure sensitive adhesive easily absorb water and bleach, the glue-line transparency and cohesive strength decline, and emulsifying agent also may move to and glued joint interface enrichment there, cause that interfacial adhesion declines, especially water resistance declines, and therefore reduces the consumption of emulsifying agent or adopts special emulsifying agent can improve pressure sensitive adhesive water tolerance; In addition, complex process, the cost of aforesaid method are higher, and obtain and in organic silicon-acrylate system, have microphase-separated, cause the adhesiveproperties of such organosilicon-modified acrylate system not ideal enough, water tolerance and weathering resistance require also not up to standard, are difficult to industrial applications, need to adopt several different methods for this reason, strengthen the consistency of organosilicon and polyacrylic ester component, to improve its adhesiveproperties.
emulsion interpenetrating polymer networks (LIPN) is exactly the network structure that two kinds of blending emulsion polymer molecular chains mutually run through and form with the each self-crosslinking of mode of chemical bond.In the time of synthetic LIPN, normally adopt Multi-stage seed emulsion polymerization to carry out, first the synthetic cross-linking polymer emulsion as seed, then in seed emulsion, add another kind of monomer (or mix monomer), linking agent, initiator, initiation reaction in the situation that not adding new emulsifier, makes another monomer or mix monomer carry out polymerization and crosslinked on the surface of seed emulsion particle, thereby generates LIPN, therefore, LIPN generally has nucleocapsid structure.This material is the basis of its excellent properties tens to the phase separation structure on hundreds of nanoscale space, has the organosilicon modified acrylic ester copolymer emulsion of inierpeneirating network structure, can be applicable to high performance pressure sensitive field.
Summary of the invention
problem to be solved by this invention is to overcome the defect of prior art, adopt the organosilicon modified acrylic ester copolymer emulsion of the synthetic a kind of polymerization-stable of emulsion interpenetrating polymer networks method, and then prepare the self-crosslinked interpenetrating net type organosilicon modified acrylic ester copolymer emulsion pressure sensitive adhesive of excellent combination property.
the preparation method of a kind of self-crosslinked interpenetrating net type Silicone-Acrylic Copolymer Emulsion pressure-sensitive adhesive that the present invention proposes, concrete steps are as follows:
(1) function monomer of the particular monomers of the hard monomer of the soft monomer of 40 ~ 60 weight parts, 80 ~ 90 weight parts, 5 ~ 15 weight parts, 5 ~ 10 weight parts is mixed, and add the reactive emulsifier of 0.5 ~ 1.5 weight part and the deionized water of 100 ~ 200 weight parts, on high speed agitator, pre-emulsification obtains pre-emulsion for 0.5 ~ 1.5 hour;
(2) take respectively the initiator of 0.5 ~ 1.5 weight part and the deionized water of 5 ~ 15 weight parts, dissolve and obtain initiator solution completely;
(3) take 1/10 ~ 1/4 of the middle pre-emulsion weight part of step (1); in step (2), the pH adjusting agent of 1/4 ~ 1/2,0.5 ~ 1.5 weight part of initiator solution weight part adjusting pH is 7-8, adds in reactor; logical nitrogen protection, controlling temperature of reaction is 70 ~ 90
o
c, rotating speed is controlled at 100 ~ 600 revs/min, after becoming micro-blue seed emulsion gradually, the material in reactor starts to drip respectively residue pre-emulsion and initiator solution, control approximately 20 ~ 80 droplets/minute of rate of addition, controlling time for adding is 2 ~ 4 hours, after dripping, again in 80 ~ 90 ℃ of insulations 1 ~ 2 hour, obtain a kind of polyacrylic ester seed emulsion;
(4) in the polyacrylic ester seed emulsion obtaining in step (3), drip respectively the organosilane monomer of 5 ~ 15 weight parts, initiator, the catalyzer of 0.1 ~ 0.5 weight part and the silane hydrolyzate inhibitor of 5 ~ 15 weight parts of 0.1 ~ 0.5 weight part simultaneously; logical nitrogen protection, controlling temperature of reaction is 70 ~ 90
o
c, control approximately 20 ~ 80 droplets/minute of rate of addition, controlling time for adding is 2 ~ 4 hours, after dropwising, be warming up to 80 ~ 90 ℃, be incubated 1 ~ 2 hour, be cooled to room temperature, add ammoniacal liquor and regulate pH value 7 ~ 8, add the linking agent of mixture weight 1～10%, after fully stirring, obtain a kind of self-crosslinked interpenetrating net type Silicone-Acrylic Copolymer Emulsion;
(5) copolymer emulsion step (4) being obtained is coated on polyester film base material, and oven dry can obtain self-crosslinked interpenetrating net type Silicone-Acrylic Copolymer Emulsion pressure-sensitive adhesive.
preferably, soft monomer in described step (1), is one or more mixture in butyl acrylate, Isooctyl acrylate monomer and decyl acrylate; Hard monomer in described step (1) is one or more mixture in methyl methacrylate, vinylbenzene or vinyl cyanide; Function monomer in described step (1) is one or more the mixture in (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) glycidyl acrylate, n-methylolacrylamide, acrylamide, diacetone acrylamide, two amido ethyl-methyl acrylate, γ-(methacryloxypropyl) propyl trimethoxy silicane etc.; Particular monomers in described step (1), is diacetone-acryloamide(DAA), N hydroxymethyl acrylamide, N, the mixture of one or more in N'-methylene-bisacrylamide, the two Methacrylamides of methylol; Reactive emulsifier in described step (1) is one or more the mixture in 2-acrylamide-2-methyl propane sulfonic, acrylamido sodium isopropyl xanthate, methacrylic acid hydroxide sodium dimercaptosulphanatein, allyloxy hydroxypropyl azochlorosulfonate acid sodium, allyloxy polyoxyethylene nonylphenol ether ammonium sulfate, allyloxy decyl polyoxyethylene ether ammonium sulfate.
preferably, the initiator in described step (2) and (4), is one or more the mixture in tertbutyl peroxide, sodium formaldehyde sulphoxylate, hydrogen peroxide, Sodium Persulfate, Potassium Persulphate or ammonium persulphate.
preferably, pH adjusting agent in described step (3), is one or more the mixture in SODIUM PHOSPHATE, MONOBASIC, primary ammonium phosphate, sodium hydrogen phosphate or bicarbonate of ammonia.
preferably, organosilane monomer in described step (4) is one or more the mixture in γ-(methacryloxy) propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl group methyl dimethoxysilane, γ-(methacryloxy) propyl group dimethoxy chlorosilane, γ-(methacryloxy) propyl-triethoxysilicane, γ-(methacryloxy) propyl group three isopropoxy silane; Catalyzer described in described step (4) is selected from one or more the mixture in diethylamine, triethylamine, diethanolamine or trolamine; Silane hydrolyzate inhibitor is selected from one or more the mixture in ethylene glycol, propylene glycol, butyleneglycol in described step (4); Linking agent in described step (4) is selected from acid amides and other aminated compounds, is one or more the mixture in succinic diamide, adipamide, black tropine, ethylenediamine tetraacetic acid (EDTA) (EDTA), succinyl hydrazine, adipic dihydrazide, adipic dihydrazide.
a second aspect of the present invention, the self-crosslinked interpenetrating net type Silicone-Acrylic Copolymer Emulsion pressure-sensitive adhesive of protecting a kind of aforesaid method to prepare.
the preparation method of the self-crosslinked interpenetrating net type organosilicon modified acrylic ester copolymer emulsion pressure sensitive adhesive that the present invention proposes, the method is take 2-acrylamide-2-methyl propane sulfonic etc. as reactive emulsifier, Isooctyl acrylate monomer and/or butyl acrylate etc. are soft monomer, methyl methacrylates etc. are hard monomer, Hydroxyethyl acrylate and/or vinylformic acid etc. are function monomer, the two Methacrylamides of diacetone-acryloamide(DAA) and/or methylol etc. are particular monomers, first synthesize a kind of polymer emulsion as seed, and then the method such as dropping technology and interpolation silane hydrolyzate inhibitor after employing organosilane monomer, in this seed emulsion, progressively add organosilane monomer, silane hydrolyzate inhibitor, linking agent and catalyzer, initiation reaction, make organosilane monomer in the further polymerization in the surface of seed emulsion particle and crosslinked, and then prepare the self-crosslinked interpenetrating net type Silicone-Acrylic Copolymer Emulsion pressure-sensitive adhesive of excellent combination property.
advantage of the present invention is: the 1. preparation method of a kind of self-crosslinked interpenetrating net type organosilicon modified acrylic ester copolymer emulsion pressure sensitive adhesive of the present invention, and the method has solved that the polymerization stability that causes because of organosilicon hydrolyzation in reaction process reduces preferably, the water tolerance of organosilicon modified pressure-sensitive acrylate product and the difficult problem such as weathering resistance is poor; Polymerization stability is good, environmental protection, the advantage such as technique is simple and convenient, quality product is high, input-output ratio is high, with low cost and application prospect is extensive.
2. compared with common organosilicon modified acrylic ester copolymer emulsion pressure sensitive adhesive, utilize the consistency of self-crosslinked interpenetrating net type organosilicon modified acrylic ester copolymer emulsion pressure sensitive adhesive prepared by the present invention good, having obvious advantage aspect high temperature resistant, water tolerance and weathering resistance, it is new generation of green environment-friendly and high-performance adhesive products.
3. the self-crosslinked interpenetrating net type organosilicon modified acrylic ester copolymer emulsion pressure sensitive adhesive that utilizes the present invention to prepare, its adhesive property and water resistance excellence, industrial applications has a extensive future, and can be applicable to multiple fields such as vehicle, engineering machinery, metallurgy, industrial plants, aircraft, military applications.
Accompanying drawing explanation
below in conjunction with drawings and Examples, the invention will be further described:
fig. 1 is the preparation flow figure of self-crosslinked interpenetrating net type Silicone-Acrylic Copolymer Emulsion pressure-sensitive adhesive.
Embodiment
below in conjunction with specific embodiment, such scheme is described further.Should be understood that these embodiment are not limited to limit the scope of the invention for the present invention is described.The implementation condition adopting in embodiment can be done further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in normal experiment.
describe the present invention in detail below in conjunction with embodiment, should be appreciated that described herein giving an example only in order to explain the present invention, be not intended to limit the present invention.
embodiment 1
the Hydroxyethyl acrylate of the diacetone-acryloamide(DAA) of the methyl methacrylate of the butyl acrylate of 50 weight parts, 80 weight parts, 9 weight parts, 6 weight parts is mixed, and add the 2-acrylamide-2-methyl propane sulfonic of 0.9 weight part and the deionized water of 150 weight parts, on high speed agitator, pre-emulsification obtains pre-emulsion for 1.0 hours.Take respectively the Potassium Persulphate of 1.25 weight parts and the deionized water of 12.5 weight parts, dissolve and obtain initiator solution completely.
take 1/6 of above-mentioned pre-emulsion weight part, the sodium bicarbonate of 1/3,0.8 weight part of above-mentioned initiator solution weight part, adds in reactor, logical nitrogen protection, and controlling temperature of reaction is 82
o
c, rotating speed is controlled at 300 revs/min, after becoming micro-blue seed emulsion gradually, the material in reactor starts to drip residue pre-emulsion and initiator solution, control approximately 45 droplets/minute of rate of addition, controlling time for adding is 2.5 hours, after dripping, again in 90 ℃ of insulations 1.5 hours, obtain a kind of polyacrylic ester seed emulsion.
in above-mentioned polyacrylic ester seed emulsion, drip the 3-methacryloxypropyl trimethoxy silane of 12 weight parts, Potassium Persulphate, the diethanolamine of 0.15 weight part and the ethylene glycol of 10 weight parts of 0.25 weight part; logical nitrogen protection, controlling temperature of reaction is 82
o
c, controls approximately 35 droplets/minute of rate of addition, and controlling time for adding is 3.5 hours, after dropwising, is warming up to 86
o
c, is incubated 1.5 hours, is cooled to room temperature, adds ammoniacal liquor and regulates pH value in 7.5 left and right, adds the adipic dihydrazide of mixture weight 2%, after fully stirring, obtains a kind of self-crosslinked interpenetrating net type Silicone-Acrylic Copolymer Emulsion.
finally self-crosslinked interpenetrating net type Silicone-Acrylic Copolymer Emulsion obtained above being coated on polyester film base material, is 90 in temperature
o
under the condition of C, dry 2-4h, obtain a kind of self-crosslinked interpenetrating net type Silicone-Acrylic Copolymer Emulsion pressure sensitive adhesive.
embodiment 2
identical with embodiment 1, but step (1) 2-acrylamide-2-methyl propane sulfonic replaces with acrylamido sodium isopropyl xanthate, and other are constant.
embodiment 3
identical with embodiment 1, but step (1) 2-acrylamide-2-methyl propane sulfonic replaces with allyloxy hydroxypropyl azochlorosulfonate acid sodium, and other are constant.
embodiment 4
identical with embodiment 1, but step (4) γ-(methacryloxy) propyl trimethoxy silicane replaces with γ-(methacryloxypropyl) propyl group methyl dimethoxysilane, and other are constant.
embodiment 5
identical with embodiment 1, but step (4) γ-(methacryloxy) propyl trimethoxy silicane replaces with γ-(methacryloxy) propyl group three isopropoxy silane, and other are constant.
table 1 and table 2 are compatibility performance and the pressure-sensitive adhesive salient features of self-crosslinked interpenetrating net type Silicone-Acrylic Copolymer Emulsion of the present invention.
The compatibility performance of table 1 self-crosslinked interpenetrating net type Silicone-Acrylic Copolymer Emulsion
| Embodiment | Self-crosslinked interpenetrating net type Silicone-Acrylic Copolymer Emulsion | Emulsion applicable time/moon | T g/ oC | Consistency |
| 1 | Good water tolerance, weathering resistance and gloss retention | > 3 | 36 | Well |
| 2 | Good water tolerance, weathering resistance and gloss retention | > 3 | 35 | Well |
| 3 | Good water tolerance, weathering resistance and gloss retention | > 3 | 35 | Well |
| 4 | Good water tolerance, weathering resistance and gloss retention | > 3 | 33 | Well |
| 5 | Good water tolerance, weathering resistance and gloss retention | > 3 | 38 | Well |
The salient features of table 2 self-crosslinked interpenetrating net type Silicone-Acrylic Copolymer Emulsion pressure sensitive adhesive
| Embodiment | 1 | 2 | 3 | 4 | 5 |
| Tack/(ball number) | 16 | 16 | 16 | 18 | 18 |
| Hold viscosity/h | > 96 | > 96 | > 96 | > 96 | > 96 |
| 180 oStripping strength/(kN/m) | 0.34 | 0.32 | 0.35 | 0.38 | 0.38 |
| Shearing resistance/MPa | 0.21 | 0.22 | 0.22 | 0.25 | 0.26 |
| Water tolerance/sky | > 18 | > 18 | > 18 | > 18 | > 18 |
| High temperature resistant temperature/℃ | 180 | 180 | 180 | 180 | 180 |
above-mentioned example is only explanation technical conceive of the present invention and feature, and its object is to allow person skilled in the art can understand content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalent transformations that spirit is done according to the present invention or modification, within all should being encompassed in protection scope of the present invention.
Claims (2)
1. the preparation method of self-crosslinked interpenetrating net type Silicone-Acrylic Copolymer Emulsion pressure-sensitive adhesive, comprise the steps: the Hydroxyethyl acrylate of the diacetone-acryloamide(DAA) of the methyl methacrylate of the butyl acrylate of 50 weight parts, 80 weight parts, 9 weight parts, 6 weight parts to mix, and add the 2-acrylamide-2-methyl propane sulfonic of 0.9 weight part and the deionized water of 150 weight parts, on high speed agitator, pre-emulsification obtains pre-emulsion for 1.0 hours; Take respectively the Potassium Persulphate of 1.25 weight parts and the deionized water of 12.5 weight parts, dissolve and obtain initiator solution completely;
Take 1/6 of above-mentioned pre-emulsion weight part, 1/3 of above-mentioned initiator solution weight part, the sodium bicarbonate of 0.8 weight part, add in reactor, logical nitrogen protection, controlling temperature of reaction is 82 ℃, rotating speed is controlled at 300 revs/min, after becoming micro-blue seed emulsion gradually, the material in reactor starts to drip residue pre-emulsion and initiator solution, control 45 droplets/minute of rate of addition, controlling time for adding is 2.5 hours, after dripping, again in 90 ℃ of insulations 1.5 hours, obtains a kind of polyacrylic ester seed emulsion;
In above-mentioned polyacrylic ester seed emulsion, drip γ-(methacryloxy) propyl group three isopropoxy silane of 12 weight parts, the Potassium Persulphate of 0.25 weight part, the ethylene glycol of the diethanolamine of 0.15 weight part and 10 weight parts, logical nitrogen protection, controlling temperature of reaction is 82 ℃, control 35 droplets/minute of rate of addition, controlling time for adding is 3.5 hours, after dropwising, be warming up to 86 ℃, be incubated 1.5 hours, be cooled to room temperature, adding ammoniacal liquor regulates pH value in 7.5 left and right, add the adipic dihydrazide of mixture weight 2%, after fully stirring, obtain a kind of self-crosslinked interpenetrating net type Silicone-Acrylic Copolymer Emulsion,
Finally self-crosslinked interpenetrating net type Silicone-Acrylic Copolymer Emulsion obtained above is coated on polyester film base material, be to dry 2-4h under the condition of 90 ℃ in temperature, obtain a kind of self-crosslinked interpenetrating net type Silicone-Acrylic Copolymer Emulsion pressure sensitive adhesive.
2. the self-crosslinked interpenetrating net type Silicone-Acrylic Copolymer Emulsion pressure-sensitive adhesive that preparation method prepares according to claim 1.
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| CN110935199B (en) * | 2019-11-26 | 2021-01-12 | 广东省测试分析研究所（中国广州分析测试中心） | Organosilicon foam with interpenetrating network pH responsiveness |
| CN112266751A (en) * | 2020-11-04 | 2021-01-26 | 扬州工业职业技术学院 | Corrosion-resistant composite binder, and preparation method and application thereof |
| CN116836657B (en) * | 2023-06-12 | 2024-04-05 | 广东荣鼎光学新材料科技有限公司 | Water-based optical adhesive and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1629202A (en) * | 2004-10-22 | 2005-06-22 | 同济大学 | High-silicon content shell-core structured silicon/acrylic emulsion and method for preparing same |
| CN101092468A (en) * | 2006-06-22 | 2007-12-26 | 广东鸿昌化工有限公司 | Method for preparing fluorin silicon modified self cross-linking microemulsion of polyacryl acid (ester) |
| CN102321219A (en) * | 2011-06-03 | 2012-01-18 | 北京化工大学 | Method for preparing organic-silicon grafted acrylate copolymer emulsion |
-
2012
- 2012-08-31 CN CN201210319507.4A patent/CN103045113B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1629202A (en) * | 2004-10-22 | 2005-06-22 | 同济大学 | High-silicon content shell-core structured silicon/acrylic emulsion and method for preparing same |
| CN101092468A (en) * | 2006-06-22 | 2007-12-26 | 广东鸿昌化工有限公司 | Method for preparing fluorin silicon modified self cross-linking microemulsion of polyacryl acid (ester) |
| CN102321219A (en) * | 2011-06-03 | 2012-01-18 | 北京化工大学 | Method for preparing organic-silicon grafted acrylate copolymer emulsion |
Non-Patent Citations (5)
| Title |
|---|
| "Morphological Prediction and Its Application to the Synthesis of Polyacrylate/Polysiloxane Core/Shell Latex Particles";Chen You Kan et al;《Journal of Applied Polymer Science》;20010326;第80卷(第12期);第2251-2258页，实验部分 * |
| "Preparation and Performance in Paper Coating of Silicone-Modified Styrene–Butyl Acrylate Copolymer Latex";Yumin Wu et al;《Journal of Applied Polymer Science》;20001113;第79卷(第2期);第333-336页，实验部分 * |
| Chen You Kan et al."Morphological Prediction and Its Application to the Synthesis of Polyacrylate/Polysiloxane Core/Shell Latex Particles".《Journal of Applied Polymer Science》.2001,第80卷(第12期),第2251-2258页，实验部分. |
| Yumin Wu et al."Preparation and Performance in Paper Coating of Silicone-Modified Styrene–Butyl Acrylate Copolymer Latex".《Journal of Applied Polymer Science》.2000,第79卷(第2期),第333-336页，实验部分. |
| 袁才登."反应性乳化剂".《乳液胶黏剂》.化学工业出版社材料科学与工程中心,2004,第22-23页. |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108299829A (en) * | 2018-03-16 | 2018-07-20 | 武汉大学 | Organosilicon interpenetrating net polymer and preparation method thereof |
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