CN102268138A - Aqueous organosilicon grafted (methyl) acrylic polymer and preparation method of emulsion thereof - Google Patents
Aqueous organosilicon grafted (methyl) acrylic polymer and preparation method of emulsion thereof Download PDFInfo
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- CN102268138A CN102268138A CN2011101266297A CN201110126629A CN102268138A CN 102268138 A CN102268138 A CN 102268138A CN 2011101266297 A CN2011101266297 A CN 2011101266297A CN 201110126629 A CN201110126629 A CN 201110126629A CN 102268138 A CN102268138 A CN 102268138A
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Abstract
The invention discloses an aqueous organosilicon grafted (methyl) acrylic polymer and a preparation method of an emulsion thereof. The method comprises the following steps that 100 weight parts of poly(methyl)acrylate emulsion, 15-50 weight parts of polysiloxane cation emulsion and 0.1-0.5 weight part of catalyst react at 60-90 DEG C for 3-8h; and organic solvents are deprived to obtain the aqueous organosilicon grafted (methyl) acrylic polymer emulsion. The invention employs long-chain alkyl benzene sulfonic acid as a reactive emulsifier, so the emulsion has a good emulsification effect; meanwhile, an emulsion film has no residual emulsifier therein, so the emulsion has a better film performance. The final polymer emulsion has a high organosilicon content; and the grafted siloxane chain is long and is not easily embedded or covered by an acrylate main chain, so as to fully play a modification effect of the organosilicon. The operation method of the invention has low requirements of equipment and raw materials, and is beneficial for the realization of industrialized production.
Description
Technical field
The present invention relates to the polymer materials field, particularly a kind of waterborne organic silicon grafting (methyl) acrylic ester polymer and emulsion preparation method thereof.
Background technology
Therefore characteristics such as (methyl) acrylic ester polymer has that cohesiveness is strong, good film-forming property, oil-resistant weather-resistant are good, with low cost are widely used in fields such as coating, binding agent, weaving, leather, papermaking.But simultaneously because its constructional feature, particularly its linear polymer have water tolerance, water vapour permeability and shortcomings such as polluting proofing property difference and hot sticky cold crisp, therefore, can be to its modification to improve emulsion property.
Organosilicon has excellent resistant of high or low temperature, durability in oxidative degradation, weathering resistance, hydrophobicity, electrical insulating property, shock-resistance, wear resistant, and have series of advantages such as softness, oxygen perviousness are good, ultraviolet resistance, physiology inertia, but then, the adhesive power of organosilicon and base material is relatively poor, therefore, the monomer that esters of acrylic acid and this two classes polarity of organosilicon can be differed greatly carries out polymeric modification, and preparation has the novel material of both excellent properties concurrently.
Prepare the most frequently used method of organosilicon crylic acid latex and be that to utilize the organosilane monomer that contains reactive functional groups and acrylic ester monomer to carry out free-radical polymerized, thus on main polymer chain introducing silicon segment, obtain stable organosilicon crylic acid latex.The common organosilane monomer that contains reactive functional groups is based on silane coupling agent.But, use silane coupling agent to come with some shortcomings separately, for example its common molecular chain is shorter, and easily by acrylate chains covering, embedding, organosilyl modified effect embodies not obvious in the reaction; And its hydrolysising group activity is bigger, easily reacts and crosslinked entanglement each other, and shelf-stability is poor.Therefore, if can increase grafted organosilicon chain length, then modified effect is better.And cyclosiloxane can carry out ring-opening polymerization, forms the siloxane prepolymer of long-chain, and is easy to react with the hydrolysising group of silane coupling agent, is to carry out the good selection that graft reaction increases organosilicon chain and compatible organic-silicon-modified effect.
Summary of the invention
First purpose of the present invention provides a kind of waterborne organic silicon grafting (methyl) acrylic ester polymer.
Second purpose of the present invention provides the preparation method of a kind of homogeneous, stabilized aqueous organosilicon inarch (methyl) acrylate polymer emulsion.
The 3rd purpose of the present invention provides the emulsion of waterborne organic silicon grafted (methyl) acrylic ester polymer that a kind of method for preparing obtains.
To achieve these goals, technical scheme of the present invention is as follows:
A kind of waterborne organic silicon grafting (methyl) acrylic ester polymer, be formed by connecting with any order and quantity by structural unit (1)+structural unit (2)+C, described C is a kind of and structural unit (4) combination in structural unit (3) and the structural unit (7), the perhaps combination of a kind of and structural unit (6) in structural unit (5) and the structural unit (8), its structural unit adds up to 20-10000, wherein (1) or (2) unit number is 10-3000, (3), (5), (7) or (8) unit number be 10-3000, (4) or (6) unit number be 0-1000, the structural unit structure is as follows:
Wherein, n is the natural number of 5-200; R
1And R
3Be methyl (CH
3) or hydrogen is (H); R
2And R
4Be carbon number be the saturated alkyl of 1-10 or hydrogen (H); R
5, R
6, R
7, R
8, R
9Can be hydrogen (H) or carbon number be the saturated alkoxyl group of 1-5, also can be siloxane chain (
M is the natural number of 5-200); R
10Be methyl or hydrogen.
The preparation method of the emulsion of above-mentioned waterborne organic silicon grafted (methyl) acrylic ester polymer is poly-(methyl) acrylic ester emulsion (latex A), the silicone, cationic emulsion (emulsion B) of 15-50 weight part and the catalyzer of 0.1-0.5 weight part with 100 weight parts, under 60-90 ℃ of condition, react 3-8h, remove organic solvent, get waterborne organic silicon grafted (methyl) acrylate polymer emulsion.
Described catalyzer is dibutyl tin dilaurate, dioctyl two lauric acid tin, metatitanic acid tetra isopropyl ester or metatitanic acid four isobutyl.
The preparation method of described poly-(methyl) acrylic ester emulsion (latex A) is:
(methyl) acrylate monomer of 100 weight parts, the silane coupling agent of 2-15 weight part, the organic solvent of 150-300 weight part are mixed, be warming up to 60-90 ℃, the initiator that adds the 1-5 weight part, stirring reaction 2-6h under refluxad, the solution that reaction obtains is cooled to room temperature, keeping solution temperature is 0 ℃, with the weakly alkaline pH regulator agent pH=6-8 that neutralizes, the deionized water that under agitation condition, adds the 80-120 weight part again, make emulsion, promptly get and gather (methyl) acrylic ester emulsion (latex A).
Preferred vinylformic acid of described (methyl) acrylate monomer and carbonatoms are not higher than the acrylate that 10 alcohol forms, or methacrylic acid and carbonatoms are not higher than the methacrylic ester of 10 alcohol formation or two kinds and mix.
The soft or hard monomer mass ratio preferred 1 of described (methyl) acrylate monomer: 4-4: 1.
Preferred azo class of described initiator or organic peroxy type free base polymerization starter.
The preferred Diisopropyl azodicarboxylate of described azo-initiator (AIBN); The preferred dibenzoyl peroxide of organic peroxy class initiator (BPO).
The preferred dehydrated alcohol of described organic solvent, butanone or acetone.
Described silane coupling agent optimal ethylene base silane or methacryloxy silane.
Described vinyl silanes preferred vinyl dimethoxy silane (KH-161), vinyltriethoxysilane (A-151) or methyl ethylene diethoxy silane; Preferred gamma-methyl allyl acyloxypropyl trimethoxysilane of methacryloxy silane (KH-570) or methacryloxypropyl three (isopropoxy) silane (C-1757).
Described dosage of silane coupling agent is preferably the 3-10 weight part.
Preferred triethylamine of described weakly alkaline pH regulator agent or yellow soda ash.
The preparation method of described silicone, cationic emulsion (emulsion B) is:
The cyclosiloxane of 100 weight parts, the reactive emulsifier of 2.5-15 weight part and the deionized water of 150-300 weight part are mixed, be warming up to 60-90 ℃, under refluxad stirring reaction 0.5-3h gets siloxanes cation emulsion (emulsion B).
One or more mixtures in the preferred octamethylcyclotetrasiloxane of described cyclosiloxane, octaethyl cyclotetrasiloxane and the hexamethyl cyclotrisiloxane.
Described reactive emulsifier preferred alkyl carbonatoms is at the chain alkyl Phenylsulfonic acid of 8-25.
Preferred Witco 1298 Soft Acid of described chain alkyl Phenylsulfonic acid or hexadecyl Phenylsulfonic acid.
A kind of emulsion of waterborne organic silicon grafted (methyl) acrylic ester polymer that obtains by method for preparing.
Because the present invention is that the siloxane prepolymer that will be formed by cyclosiloxane open loop pre-polymerization is grafted on (methyl) acrylate backbone by silane coupling agent, therefore the selection of silane coupling agent kind and consumption is crucial, at first require silane coupling agent to carry out copolymerization with (methyl) acrylic ester monomer, so preferable methyl acryloyl-oxy base silane and vinyl silanes; Secondly, if dosage of silane coupling agent very little, then the tie point of the polysiloxane that is formed by cyclosiloxane open loop pre-polymerization and (methyl) acrylate backbone very little, can not carry out fully effectively graft modification, and dosage of silane coupling agent is too many, again easily mutually between reaction, form crosslinking structure, not only unfavorable to graft reaction, and gel fraction is improved greatly, reaction can't be carried out.Therefore dosage of silane coupling agent is the 2%-15% of (methyl) acrylate monomer, is preferably the 3%-10% of (methyl) acrylate monomer.
The selection of (methyl) acrylate monomer also is crucial, can with monomer rough be divided into soft monomer and hard monomer (in general, the monomer low second-order transition temperature is referred to as soft monomer, and the high monomer of second-order transition temperature is referred to as hard monomer), soft monomer can cause the polymer glass temperature to reduce, hard monomer can improve the second-order transition temperature of polymkeric substance, make polymkeric substance promptly have certain mechanical strength, allow it that enough toughness is arranged again, therefore, the soft or hard monomer mass ratio preferred 1 of (methyl) acrylate monomer: 4-4: 1.
The present invention compared with prior art has following advantage:
(1) the present invention has adopted the chain alkyl Phenylsulfonic acid as reactive emulsifier in the preparation process of emulsion B, makes the emulsion emulsify well, and residual because of emulsifier-free in the emulsion film makes that the emulsion film performance is better simultaneously.
(2) the present invention has utilized the reaction between silane coupling agent hydrolysising group and the siloxanes positive ion, with siloxanes positive ion emulsion (emulsion B) and poly-(methyl) acrylic ester emulsion (latex A) mixing carrying out graft reaction, make that organosilicon content is higher in the final polymer emulsion, the grafted siloxane chain is longer, be difficult for having been given full play to organosilyl modified effect by acrylate backbone embedding, covering.
(3) working method of the present invention is lower to the requirement of equipment raw material, is beneficial to the realization suitability for industrialized production.
Specific embodiment
The present invention is described further below in conjunction with embodiment, but implementation of the present invention is not limited thereto.
Embodiment 1
The emulsion of table 1 a waterborne organic silicon grafted (methyl) acrylic ester polymer
Physicals and film performance thereof
Wherein, latex A
1Synthetic method be: with methyl methacrylate, methyl acrylate, methacrylic acid, gamma-methyl allyl acyloxypropyl trimethoxysilane (KH-570), butanone by 20: 25: 4: feed intake at 1: 100, cause by Diisopropyl azodicarboxylate (ATBN), controlled temperature is at 80 ℃, under refluxad stirring reaction 4h and, the solution that reaction obtains is cooled to room temperature, adds 50 parts of deionized waters and make latex A under stirring condition
1
Emulsion B
1Synthetic method be: prestox ring+tetrasiloxane, Witco 1298 Soft Acid and deionized water were fed intake by 19: 1: 40, and controlled temperature is at 75 ℃, stirring reaction 1h under refluxad, emulsion B
1
Emulsion C
1Composition and latex A
1The same.
Emulsion C
2With C
3Synthetic method be: with latex A
1With emulsion B
2Feed intake in the ratio in the table, under the catalysis of 0.2 part of dibutyl tin dilaurate, controlled temperature is at 80 ℃, and reaction 4h removes organic solvent and obtains waterborne organic silicon grafted (methyl) acrylate polymer emulsion.
As can be seen from Table 1, the shelf-stability height of the emulsion of waterborne organic silicon grafted (methyl) acrylic ester polymer that present embodiment makes, the film dynamic performance that is coated with is good, water-intake rate is low, has reached purpose of the present invention.And along with the increase of emulsion B content, every performance index of final emulsion all increases.
Above-mentioned test is all by following standard:
The tensile strength of filming: press GB/T 23805-2009 and measure;
The elongation at break of filming: press GB/T 6344-1996 and measure;
Shelf-stability: press GB/T 16497-2007 and measure;
The water-intake rate of filming: press GB/T 2834-1998 and measure.
Embodiment 2
The emulsion of the another kind of waterborne organic silicon grafted of table 2 (methyl) acrylic ester polymer
Physicals and film performance thereof
Wherein, latex A
2Synthetic method be: with butyl methacrylate, butyl acrylate, gamma-methyl allyl acyloxypropyl trimethoxysilane (KH-570) and dehydrated alcohol by 30: 18: 2: 100 feed intake, with the dehydrated alcohol is solvent, cause by Diisopropyl azodicarboxylate (AIBN), controlled temperature is at 75 ℃, stirring reaction 5.5h under refluxad, the solution that reaction obtains is cooled to room temperature, adds 50 parts of deionized waters and make latex A under stirring condition
2
Emulsion B
2Synthetic method be: octamethylcyclotetrasiloxane, hexadecyl Phenylsulfonic acid, deionized water were fed intake by 9: 1: 20, and controlled temperature is at 70 ℃, stirring reaction 1.5h under refluxad, emulsion B
2
Emulsion D
1Composition and latex A
1The same.
Emulsion D
2With D
3Synthetic method be: with latex A
2With emulsion B
2Feed intake in the ratio in the table, under the catalysis of 0.25 part of dioctyl two lauric acid tin, controlled temperature reacts 4.5h at 85 ℃, removes organic solvent and obtains waterborne organic silicon grafted (methyl) acrylate polymer emulsion.
As can be seen from Table 2, the emulsion of waterborne organic silicon grafted (methyl) acrylic ester polymer that present embodiment makes, if part changes the synthesis material of latex A in the claim scope, still the shelf-stability height of prepared emulsion, the film dynamic performance that is coated with is good, water-intake rate is low, has reached purpose of the present invention.And along with the increase of emulsion B content, every performance index of final emulsion all increases.
Above-mentioned test is all by following standard:
The tensile strength of filming: press GB/T 23805-2009 and measure;
The elongation at break of filming: press GB/T 6344-1996 and measure;
Shelf-stability: press GB/T 16497-2007 and measure;
The water-intake rate of filming: press GB/T 2834-1998 and measure.
Embodiment 3
The emulsion of another waterborne organic silicon grafted (methyl) acrylic ester polymer of table 3
Physicals and film performance thereof.
Wherein, latex A
3Synthetic method be: (methyl) acrylate monomer, gamma-methyl allyl acyloxypropyl trimethoxysilane (KH-570) and butanone were fed intake by 48: 2: 100, cause by dibenzoyl peroxide (BPO), controlled temperature is at 80 ℃, stirring reaction 4.5h under refluxad, the solution that reaction obtains is cooled to room temperature, adds 50 parts of deionized waters and make latex A under stirring condition
3In (methyl) acrylate monomer, the selection propyl methacrylate is a hard monomer, and butyl acrylate is a soft monomer, and both are in the ratio reaction that feeds intake in the table.
Emulsion B
3Synthetic method be: octamethylcyclotetrasiloxane, Witco 1298 Soft Acid, deionized water were fed intake by 19: 1: 40, and controlled temperature is at 70 ℃, stirring reaction 1.5h under refluxad, emulsion B
3
Emulsion E
1, E
2, E
3Synthetic method be: with latex A
3With emulsion B
3Fed intake by 10: 1, under the catalysis of 0.2 part of dibutyl tin dilaurate, controlled temperature is at 75 ℃, and reaction 5.5h removes organic solvent and obtains waterborne organic silicon grafted (methyl) acrylate polymer emulsion.
As can be seen from Table 3, if the emulsion of (methyl) acrylic ester polymer of the use organosilicon inarch that present embodiment makes is the control latex A
3With emulsion B
3Feed ratio constant, and emulsion B
3Composition also constant, and latex A
3In the monomeric feed ratio of (methyl) acrylate soft or hard when changing, final emulsion still has good shelf-stability, and the film dynamic performance that is coated with is good, water-intake rate is low, has reached purpose of the present invention.
Above-mentioned test is all by following standard:
The tensile strength of filming: press GB/T 23805-2009 and measure;
The elongation at break of filming: press GB/T 6344-1996 and measure;
Shelf-stability: press GB/T 16497-2007 and measure;
The water-intake rate of filming: press GB/T 2834-1998 and measure.
Embodiment 4
14g butyl methacrylate, 21g decyl acrylate, 1.8g gamma-methyl allyl acyloxypropyl trimethoxysilane (KH-570), 105g dehydrated alcohol are joined in the 250ml three-necked bottle that has reflux condensing tube, thermometer and hollow glass plug, controlled temperature is at 75 ℃, under magnetic agitation, add 1.3g Diisopropyl azodicarboxylate (AIBN) (being dissolved in the dehydrated alcohol) earlier, add 0.5gAIBN behind the 30min again, get water white transparency polyacrylic ester pre-polymer solution behind the reaction 4h.Above-mentioned solution is put to room temperature, and under ice bath, added the 40g deionized water, make polyacrylate dispersion, standby.
5g octamethylcyclotetrasiloxane, 0.13g Witco 1298 Soft Acid and 8g deionized water are joined in the 100ml three-necked bottle that has reflux condensing tube, thermometer and hollow glass plug, be warming up to 75 ℃, reaction 1h gets oyster white silicone, cationic emulsion, and is standby.
The above-mentioned 40g polyacrylic ester pre-polymer emulsion that has made, 20g silicone, cationic emulsion, 0.08g dibutyl tin dilaurate are joined in the 100ml three-necked bottle that has reflux condensing tube, thermometer and hollow glass plug, be warming up to 60 ℃, reaction 4h gets the oyster white viscous emulsion.Revolve to steam and remove dehydrated alcohol, get the graft type organosilicon crylic acid latex, have blue light after the dilution.This emulsion viscosity is 5.4mPaS, and surface tension is 23.42N/m.
The polymer chemistry structural formula is as follows in the emulsion, wherein n
1=2000-3000, n
2=150-200.
Ir data is as follows:
FT-IR (500-4000cm
-1): 1254cm
-1, 838cm
-1, 755cm
-1(Si-CH
3); 1720cm
-1(C=O); 1026cm
-1, 991cm
-1(Si-O-Si); 2840cm
-1, 1095cm
-1(Si-O-CH
3); 1163cm
-1(C-O); 723cm
-1(chain alkyl).
Embodiment 5
27g butyl methacrylate, 25.5g methacrylic acid pentyl ester, 4.8g methacrylic acid, 3g methyl ethylene diethoxy silane, 120g butanone are joined in the 500ml three-necked bottle that has reflux condensing tube, thermometer and hollow glass plug, controlled temperature is at 80 ℃, under magnetic agitation, add 1.8g Diisopropyl azodicarboxylate (AIBN) (being dissolved in the butanone) earlier, add 0.6gAIBN behind the 30min again, get water white transparency polyacrylic ester pre-polymer solution behind the reaction 4.5h.Above-mentioned solution is put to room temperature, and under ice bath, added the 5.5g triethylamine, solution is transferred to pH=7, add 60g again and remove sub-water, make emulsion, standby.
5g octaethyl cyclotetrasiloxane, 0.8g Witco 1298 Soft Acid and 15g deionized water are joined in the 100ml three-necked bottle that has reflux condensing tube, thermometer and hollow glass plug, be warming up to 75 ℃, reaction 1.5h gets oyster white silicone, cationic emulsion, and is standby.
Above-mentioned 40g polyacrylic ester pre-polymer emulsion, 10g polysiloxane emulsion, the 0.12g dibutyl tin dilaurate that has made joined in the 100ml three-necked bottle that has reflux condensing tube, thermometer and hollow glass plug, be warming up to 60 ℃, reaction 3h gets the oyster white viscous emulsion.Revolve to steam and remove butanone, get the graft type organosilicon crylic acid latex, have blue light after the dilution.This emulsion viscosity is 5.1mPaS, and surface tension is 24.36N/m.
The polymer chemistry structural formula is as follows in the emulsion, wherein n
1=1200-1500, n
2=120-150.
Ir data is as follows:
FT-IR (500-4000cm
-1): 1254cm
-1, 840cm
-1, 750cm
-1(Si-C
2H
5); 1720cm
-1(ester C=O); 1026cm
-1, 991cm
-1(Si-O-Si); 2840cm
-1, 1090cm
-1(Si-O-C
2H
5); 1163cm
-1(C-O); 724cm
-1(chain alkyl); 2209cm
-1(Si-H); 1760cm
-1(sour C=O).
Embodiment 6
36g butyl methacrylate, 34g methyl acrylate, 6.4g vinylformic acid, 13g gamma-methyl allyl acyloxypropyl trimethoxysilane (KH-570), 160g acetone are joined in the 500ml three-necked bottle that has reflux condensing tube, thermometer and hollow glass plug, controlled temperature is at 55 ℃, under magnetic agitation, add 0.7g dibenzoyl peroxide (BPO) (being dissolved in the acetone) earlier, add 0.2gBPO behind the 1h again, get water white transparency polyacrylic ester pre-polymer solution behind the reaction 6h.Above-mentioned solution is put to room temperature, and under ice bath, added the 7.0g triethylamine, solution is transferred to pH=7, add the 80g deionized water again, make emulsion, standby.
5g octaethyl cyclotetrasiloxane, 0.25g Witco 1298 Soft Acid and 10g deionized water are joined in the 100ml three-necked bottle that has reflux condensing tube, thermometer and hollow glass plug, be warming up to 75 ℃, reaction 1h gets oyster white silicone, cationic emulsion, and is standby.
The above-mentioned 40g polyacrylic ester pre-polymer emulsion that has made, 6.3g polysiloxane emulsion, 0.12g metatitanic acid tetra isopropyl ester are joined in the 100ml three-necked bottle that has reflux condensing tube, thermometer and hollow glass plug, be warming up to 60 ℃, reaction 4h gets the oyster white viscous emulsion.Revolve to steam and remove acetone, get the graft type organosilicon crylic acid latex, have blue light after the dilution.This emulsion viscosity is 4.9mPaS, and surface tension is 23.14N/m.
The polymer chemistry structural formula is as follows in the emulsion, wherein n
1=1500-2000, n
2=250-300.
Ir data is as follows:
FT-IR (500-4000cm
-1): 1254cm
-1, 840cm
-1, 750cm
-1(Si-C
2H
5); 1720cm
-1(ester C=O); 1026cm
-1, 991cm
-1(Si-O-Si); 2845cm
-1, 1092cm
-1(Si-O-CH
3); 1163cm
-1(C-O); 725cm
-1(chain alkyl); 1760cm
-1(sour C=O).
Embodiment 7
21g propyl methacrylate, 21g butyl acrylate, 3.2g vinylformic acid, 2g vinyl-dimethyl TMOS (KH-161), 80g butanone are joined in the 250ml three-necked bottle that has reflux condensing tube, thermometer and hollow glass plug, controlled temperature is at 75 ℃, under magnetic agitation, add 1.2g Diisopropyl azodicarboxylate (AIBN) (being dissolved in the butanone) earlier, add 0.4gAIBN behind the 30min again, get water white transparency polyacrylic ester pre-polymer solution behind the reaction 3.5h.Above-mentioned solution is put to room temperature, and adding 1.6g yellow soda ash is neutralized to pH value of solution=7.5 under ice bath, adds the 40g deionized water again, makes emulsion, standby.
5g octamethylcyclotetrasiloxane, 0.35g hexadecyl Phenylsulfonic acid and 10g deionized water are joined in the 100ml three-necked bottle that has reflux condensing tube, thermometer and hollow glass plug, be warming up to 75 ℃, reaction 1.5h gets oyster white silicone, cationic emulsion, and is standby.
The above-mentioned 40g polyacrylic ester pre-polymer emulsion that has made, 6.3g polysiloxane emulsion, 0.15g metatitanic acid four isobutyl are joined in the 100ml three-necked bottle that has reflux condensing tube, thermometer and hollow glass plug, be warming up to 60 ℃, reaction 3h gets the oyster white viscous emulsion.Revolve to steam and remove butanone, get the graft type organosilicon crylic acid latex, have blue light after the dilution.This emulsion viscosity is 5.8mPaS, and surface tension is 23.88N/m.
The polymer chemistry structural formula is as follows in the emulsion, wherein n
1=1300-1800, n
2=100-150.
Ir data is as follows:
FT-IR (500-4000cm
-1): 1254cm
-1, 838cm
-1, 755cm
-1(Si-CH
3); 1720cm
-1(ester C=O); 1026cm
-1, 991cm
-1(Si-O-Si); 2840cm
-1, 1095cm
-1(Si-O-CH
3); 1163cm
-1(C-O); 725cm
-1(chain alkyl); 2209cm
-1(Si-H); 1760cm
-1(sour C=O).
Embodiment 8
20g butyl methacrylate, 20g isobutyl acrylate, 5g vinylformic acid, 3g vinyltriethoxysilane (A-151), 80g dehydrated alcohol are joined in the 250ml three-necked bottle that has reflux condensing tube, thermometer and hollow glass plug, controlled temperature is at 75 ℃, under magnetic agitation, add 1g dibenzoyl peroxide (BPO) (being dissolved in the dehydrated alcohol) earlier, add 0.4gBPO behind the 30min again, get water white transparency polyacrylic ester pre-polymer solution behind the reaction 4h.Above-mentioned solution is put to room temperature, and under ice bath, added 2.5g yellow soda ash, solution is transferred to pH=7.5, add the 40g deionized water again, make emulsion, standby.
5g hexamethyl cyclotrisiloxane, 0.25g Witco 1298 Soft Acid and 10g deionized water are joined in the 100ml three-necked bottle that has reflux condensing tube, thermometer and hollow glass plug, be warming up to 75 ℃, reaction 1h gets oyster white silicone, cationic emulsion, and is standby.
Above-mentioned 40g polyacrylic ester pre-polymer emulsion, 6.3g polysiloxane emulsion, the 0.08g dibutyl tin dilaurate that has made joined in the 100ml three-necked bottle that has reflux condensing tube, thermometer and hollow glass plug, be warming up to 60 ℃, reaction 4h gets the oyster white viscous emulsion.Revolve to steam and remove dehydrated alcohol, get the graft type organosilicon crylic acid latex, have blue light after the dilution.This emulsion viscosity is 6.2mPaS, and surface tension is 23.54N/m.
The polymer chemistry structural formula is as follows in the emulsion, wherein n
1=1800-2000, n
2=220-250.
Ir data is as follows:
FT-IR (500-4000cm
-1): 1254cm
-1, 838cm
-1, 755cm
-1(Si-CH
3); 1720cm
-1(ester C=O); 1026cm
-1, 991cm
-1(Si-O-Si); 2840cm
-1, 1090cm
-1(Si-O-C
2H
5); 1163cm
-1(C-O); 725cm
-1(chain alkyl); 2209cm
-1(Si-H); 1760cm
-1(sour C=O).
Embodiment 9
With 15g butyl methacrylate, 15g Octyl acrylate, 15g isobutyl acrylate, 5g methacrylic acid, 2.5g methacryloxypropyl three (isopropoxy) silane (C-1757), 75g dehydrated alcohol join in the 250ml three-necked bottle that has reflux condensing tube, thermometer and hollow glass plug, controlled temperature is at 75 ℃, under magnetic agitation, add 1.2g Diisopropyl azodicarboxylate (AIBN) (being dissolved in the dehydrated alcohol) earlier, add 0.4gAIBN behind the 30min again, get water white transparency polyacrylic ester pre-polymer solution behind the reaction 4h.Above-mentioned solution is put to room temperature, and under ice bath, added the 40g deionized water, make emulsion, standby.
5g hexamethyl cyclotrisiloxane, 0.25g Witco 1298 Soft Acid and 10g deionized water are joined in the 100ml three-necked bottle that has reflux condensing tube, thermometer and hollow glass plug, be warming up to 75 ℃, reaction 1h gets oyster white silicone, cationic emulsion, and is standby.
The above-mentioned 40g polyacrylic ester pre-polymer emulsion that has made, 6.3g polysiloxane emulsion, 0.08g dioctyl two lauric acid tin are joined in the 100ml three-necked bottle that has reflux condensing tube, thermometer and hollow glass plug, be warming up to 60 ℃, reaction 6h gets the oyster white viscous emulsion.Revolve to steam and remove dehydrated alcohol, get the graft type organosilicon crylic acid latex, have blue light after the dilution.This emulsion viscosity is 5.6mPaS, and surface tension is 24.08N/m.
The polymer chemistry structural formula is as follows in the emulsion, wherein n
1=1600-2000, n
2=280-300.
Ir data is as follows:
FT-IR (500-4000cm
-1): 1254cm
-1, 840cm
-1, 750cm
-1(Si-C
2H
5); 1720cm
-1(ester C=O); 1026cm
-1, 991cm
-1(Si-O-Si); 2842cm
-1, 1095cm
-1(Si-O-C
3H
7); 1163cm
-1(C-O); 723cm
-1(chain alkyl); 1760cm
-1(sour C=O).
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. a waterborne organic silicon grafting (methyl) acrylic ester polymer, it is characterized in that: described polymkeric substance is formed by connecting with any order and quantity by structural unit (1)+structural unit (2)+C, described C is a kind of and structural unit (4) combination in structural unit (3) and the structural unit (7), the perhaps combination of a kind of and structural unit (6) in structural unit (5) and the structural unit (8), its structural unit adds up to 20-10000, wherein (1) or (2) unit number is 10-3000, (3), (5), (7) or (8) unit number be 10-3000, (4) or (6) unit number be 0-1000, the structural unit structure is as follows:
Wherein, n is the natural number of 5-200; R
1And R
3Be methyl or hydrogen; R
2And R
4Be that carbon number is saturated alkyl or the hydrogen of 1-10; R
10Be methyl or hydrogen;
R
5, R
6, R
7, R
8, R
9Be hydrogen, carbon number be 1-5 saturated alkoxyl group,
Or
M is the natural number of 5-200).
2. preparation method who comprises the emulsion of the described waterborne organic silicon grafted of claim 1 (methyl) acrylic ester polymer, it is characterized in that comprising following operation steps: with poly-(methyl) acrylic ester emulsion, the silicone, cationic emulsion of 15-50 weight part and the catalyzer of 0.1-0.5 weight part of 100 weight parts, under 60-90 ℃ of condition, react 3-8h, remove organic solvent, get waterborne organic silicon grafted (methyl) acrylate polymer emulsion.
3. preparation method according to claim 2 is characterized in that: described catalyzer is dibutyl tin dilaurate, dioctyl two lauric acid tin, metatitanic acid tetra isopropyl ester or metatitanic acid four isobutyl.
4. preparation method according to claim 2 is characterized in that: described poly-(methyl) preparing acrylate emulsion method is:
(methyl) acrylate monomer of 100 weight parts, the silane coupling agent of 2-15 weight part, the organic solvent of 150-300 weight part are mixed, be warming up to 60-90 ℃, the initiator that adds the 1-5 weight part, stirring reaction 2-6h under refluxad, the solution that reaction obtains is cooled to room temperature, keeping solution temperature is 0 ℃, with the weakly alkaline pH regulator agent pH=6-8 that neutralizes, the deionized water that under agitation condition, adds the 80-120 weight part again, make emulsion, promptly get and gather (methyl) acrylic ester emulsion;
Described (methyl) acrylate monomer is that vinylformic acid and carbonatoms are not higher than the acrylate that 10 alcohol forms, or methacrylic acid and carbonatoms are not higher than the methacrylic ester of 10 alcohol formation or two kinds and mix; The soft or hard monomer mass ratio preferred 1 of described (methyl) acrylate monomer: 4-4: 1;
Described initiator is azo class or organic peroxy type free base polymerization starter;
Described silane coupling agent is vinyl silanes or methacryloxy silane.
5. preparation method according to claim 4 is characterized in that: described azo-initiator is a Diisopropyl azodicarboxylate; Organic peroxy class initiator is a dibenzoyl peroxide; Described vinyl silanes is vinyl-dimethyl TMOS, vinyltriethoxysilane or methyl ethylene diethoxy silane; Methacryloxy silane is gamma-methyl allyl acyloxypropyl trimethoxysilane or methacryloxypropyl three (isopropoxy) silane.
6. preparation method according to claim 4 is characterized in that: described dosage of silane coupling agent is the 3-10 weight part.
7. preparation method according to claim 4 is characterized in that: the agent of described weakly alkaline pH regulator is triethylamine or yellow soda ash; Described organic solvent is dehydrated alcohol, butanone or acetone.
8. preparation method according to claim 2 is characterized in that: the preparation method of described silicone, cationic emulsion is:
The cyclosiloxane of 100 weight parts, the reactive emulsifier of 2.5-15 weight part and the deionized water of 150-300 weight part are mixed, be warming up to 60-90 ℃, under refluxad stirring reaction 0.5-3h gets the siloxanes cation emulsion;
Described cyclosiloxane is one or more mixtures in octamethylcyclotetrasiloxane, octaethyl cyclotetrasiloxane and the hexamethyl cyclotrisiloxane;
Described reactive emulsifier is the chain alkyl Phenylsulfonic acid of alkyl carbon atoms number at 8-25.
9. preparation method according to claim 8 is characterized in that: described chain alkyl Phenylsulfonic acid is Witco 1298 Soft Acid or hexadecyl Phenylsulfonic acid.
10. the emulsion of waterborne organic silicon grafted (methyl) acrylic ester polymer for preparing by each described method of claim 2-9.
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| CN103087256A (en) * | 2013-01-23 | 2013-05-08 | 中科院广州化学有限公司 | (Methyl) acrylic resin with high organic silicon content and preparation method thereof |
| CN103210906A (en) * | 2013-02-26 | 2013-07-24 | 中国中化股份有限公司 | Application of organosilicon-modified high-molecular compound as seed coating film-forming agent |
| CN103396509B (en) * | 2013-06-27 | 2015-10-28 | 中科院广州化学有限公司 | Organic-silicon-modified fluorine-containing (methyl) acrylate polymer emulsion of long side chain |
| CN109575681A (en) * | 2018-11-09 | 2019-04-05 | 何国雄 | A kind of water-based free radical-cationic hybrid light-curable ink and its application |
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| CN110862737A (en) * | 2018-08-28 | 2020-03-06 | 郑州珊瑚纳米科技有限公司 | Polyacrylate super-hydrophobic leather brightener containing organic silicon long side chains and preparation method of coating thereof |
| CN111607092A (en) * | 2020-04-02 | 2020-09-01 | 安徽嘉智信诺化工股份有限公司 | Preparation method of novel epoxy silicone oil modified acrylate anti-doodling emulsion |
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| CN103087256B (en) * | 2013-01-23 | 2015-11-18 | 中科院广州化学有限公司 | (methyl) acrylic resin of a kind of high silicone content and preparation method thereof |
| CN103210906A (en) * | 2013-02-26 | 2013-07-24 | 中国中化股份有限公司 | Application of organosilicon-modified high-molecular compound as seed coating film-forming agent |
| CN103210906B (en) * | 2013-02-26 | 2015-03-11 | 中国中化股份有限公司 | Application of organosilicon-modified high-molecular compound as seed coating film-forming agent |
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| CN110862737A (en) * | 2018-08-28 | 2020-03-06 | 郑州珊瑚纳米科技有限公司 | Polyacrylate super-hydrophobic leather brightener containing organic silicon long side chains and preparation method of coating thereof |
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| CN109575681B (en) * | 2018-11-09 | 2022-04-19 | 中山布瑞特环保油墨有限公司 | Water-based free radical-cation hybrid photocuring ink and application thereof |
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| CN109942762B (en) * | 2019-02-21 | 2021-10-22 | 上海普信高分子材料有限公司 | Preparation method of surface treating agent with flame retardant property |
| CN111607092A (en) * | 2020-04-02 | 2020-09-01 | 安徽嘉智信诺化工股份有限公司 | Preparation method of novel epoxy silicone oil modified acrylate anti-doodling emulsion |
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