CN102321219B - Method for preparing organic-silicon grafted acrylate copolymer emulsion - Google Patents
Method for preparing organic-silicon grafted acrylate copolymer emulsion Download PDFInfo
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- CN102321219B CN102321219B CN2011101487815A CN201110148781A CN102321219B CN 102321219 B CN102321219 B CN 102321219B CN 2011101487815 A CN2011101487815 A CN 2011101487815A CN 201110148781 A CN201110148781 A CN 201110148781A CN 102321219 B CN102321219 B CN 102321219B
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Abstract
The invention discloses a method for preparing water dispersion organic-silicon grafted acrylate copolymer emulsion, belonging to the field of emulsion polymerization and overcoming deficiencies of waterborne modified acrylate. According to the method provided by the invention, the emulsion has the advantages of good mechanical stability, water resistance, mechanical property and acid and alkali resistance; the highest solid content of the emulsion is up to 58 percent; the prepared organic-silicon modified acrylate emulsion with a high solid content has a good mechanical stability and a calcium ion stability; and simultaneously compared with other polymerization methods, the method provided by the invention also has the economic advantages of simple preparation method, low equipment cost, and capability of wide application.
Description
Technical field
The invention belongs to the letex polymerization field, be specifically related to the preparation method of water dispersible organosilicon inarch acrylate polymer emulsion.
Technical background
The water soluble acrylic acid ester paint has obtained develop rapidly in recent years, because the water soluble acrylic acid ester paint has preferably resistance to acids and bases, anti-stain characteristic, performance such as environmentally friendly, so it occupies an important position in paint field.But it is relatively poor relatively in water tolerance, mechanical properties, so people have carried out a large amount of research to it; Chinese patent CN 1038106A discloses a kind of acrylic acid modified resin that contains aldehyde radical, and it is applied to the dewatered sludge of anti-impact modifier, but the more organic-silicon-modified performance of its modification performance has weak point; Chinese patent CN 1887926A discloses a kind of preparation method and application of silicone modified polyacrylate, and solvent has used organic solvent in its polymkeric substance, but its preparation process is comparatively complicated; Simultaneously, the stability of high solid polymerized emulsion is also relatively poor, and the higher film temperature that is baked into also is a major issue can not ignoring; Chinese patent CN 1362433A discloses a kind of grafted-organosilicon modified acrylic ester copolymer emulsion that relates to, and mainly solve the problem that there is poor stability in emulsion in the past, but its solid content has only 40%.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of organosilicon inarch acrylate copolymer emulsion makes a kind of polymerized emulsion that overcomes watersoluble modified acrylic acid ester weak point.
The present invention realizes through following technical scheme: with monomer, emulsifying agent, that water carries out preparatory emulsification is subsequent use; The preparation of seed emulsion; Pre-emulsion is added in the seed emulsion, adds initiator simultaneously and carry out polyreaction, insulation for some time, the pH value of regulation system, discharging, filtration, preservation, thus can get the organosilicon inarch acrylate copolymer emulsion.
Concrete process step is following:
A. the preparation of pre-emulsion: the compound emulsifying agent of 3～6 mass parts is dissolved in the deionized water of 200～570 mass parts; Transfer in the reactor drum then; At propenoate hard monomer, the propenoate soft monomer of 80～100 mass parts and (methyl) vinylformic acid of 1～3 mass parts of continuing to add under the stirring 100 mass parts; Continue to continue to stir 30～60min and can make milky pre-emulsion, insert in the container it for use;
B. the preparation of seed emulsion: get the compound emulsifying agent of 1～2 mass parts and the pH buffer reagent of 0.01～1 mass parts, make mixing solutions, then it is transferred in the reactor drum, at the uniform velocity stir, be heated to 75～90 ℃ with the deionized water dissolving of 120～400 mass parts; The initiator of 2～4 mass parts is obtained initiator solution with the deionized water dissolving of 20～30 mass parts, get 1/10～1/5 and be added in the reactor drum; The pre-emulsion 1/100～1/25 of getting the steps A preparation simultaneously adds in the reactor drum, and controlled temperature is at 75～90 ℃, and after waiting blue light to occur, then the seed emulsion preparation finishes;
C. polymerization: in the seed emulsion of step B preparation, drip remaining pre-emulsion and initiator solution, 1.5～2.5h drips, and adds the silane coupling agent of 1～20 mass parts then; After being incubated 75～90 ℃ of stirring 1～1.5h; Cool to 20～40 ℃, regulate pH to 7～8, discharging with the pH regulator agent; Filter, promptly get the organosilicon inarch acrylate copolymer emulsion.
Described propenoate hard monomer is: one or more in TEB 3K, methacrylic tert-butyl acrylate, vinylbenzene, vinyl cyanide, the acrylic amide.
Described propenoate soft monomer is: in lauryl methacrylate(LMA), NSC 20956, acrylic acid-2-ethyl ester, the Hydroxyethyl acrylate one or more.
Described silane coupling agent general formula can be expressed as: CH
2=CH-R-Si (OR
1), wherein the R base is C
1～C
6Carbalkoxy or alkyl, R
1For containing C
1～C
2Alkyl.
Described silane coupling agent is specially organosilicon KH-560, KH-570, A-151 or A-171.
Described compound emulsifying agent is: the mixture that anionic emulsifier and nonionic emulsifying agent are made into by 3: 1～1: 3 mass ratio; Wherein anionic emulsifier is X 2073 or dialkyl benzene sulfonic acids sodium, and nonionic emulsifying agent is OP-X emulsifying agent or TX-100.
Described initiator is the water soluble starter persulphate.
Described initiator is specially Potassium Persulphate, ammonium persulphate or Sodium Persulfate.
Described pH buffer reagent is: sodium hydrogencarbonate or saleratus.
Described pH regulator agent is the ammoniacal liquor of 20～30wt%.
Beneficial effect of the present invention: the emulsion of the present invention's preparation has favorable mechanical stability, water resistance, mechanical property, acid-proof alkaline, and its solid content reaches as high as 58%.The high solid emulsion of the organosilicon-modified acrylate that adopts this method to prepare has favorable mechanical stability and Calcium ion stability is arranged; Simultaneously, compare with other polymerization method, the preparation method is simple, the economic advantages of the cheap widespread use of equipment cost but this method also has.
Embodiment
Embodiment one:
Is OP: SDBS=1 with 0.70g with the quality proportioning: 1 compound emulsifying agent is dissolved in the 30g deionized water and makes emulsifier solution; Transfer in the reactor drum then; Under continuing stirring, use and add 16.54g TEB 3K, 14.18g Bing Xisuandingzhi, 2.48g vinyl cyanide, 0.67g methylacrylic acid to reactor drum; Continue to stir 40min and can make milky pre-emulsion, insert in the container it for use; Getting 0.20g is OP: SDBS=1 with the quality proportioning: 1 compound emulsifying agent and sodium hydrogencarbonate 0.10g, make mixing solutions with the 40g deionized water dissolving, and then it is transferred in the reactor drum; After at the uniform velocity stirring, be heated to 75 ℃, initiator potassium persulfate 0.25g is dissolved in the 5.0g deionized water, get 0.6g and be added in the reactor drum; Add the 1.0g pre-emulsion simultaneously; Controlled temperature is at 75 ℃, wait to occur obvious blue light after, then the seed emulsion preparation finishes; After seed emulsion preparation is accomplished, drip residue pre-emulsion and initiator solution, 2h adds, and 2.5g organosilicon KH-570 is added in the reactor drum after adding pre-emulsion; After being incubated 75 ℃ of stirring 1.5h, be cooled to 40 ℃, regulate pH to 7.2 with the ammoniacal liquor of 25wt%; Discharging is filtered, and preserves.
Embodiment two:
Is OP: SDBS=2 with 0.60g with the quality proportioning: 1 compound emulsifying agent is dissolved in the 40g deionized water and makes emulsifier solution; Transfer in the reactor drum then; Under continuing stirring, use and add 16.52g methacrylic tert-butyl acrylate, 16.52g acrylic acid-2-ethyl ester, 3.02g vinylbenzene, 0.67g vinylformic acid to reactor drum; Continue to stir 30min and can make milky pre-emulsion, insert in the container it for use; Getting 0.21g is OP: SDBS=2 with the quality proportioning: 1 compound emulsifying agent and sodium hydrogencarbonate 0.10g, make mixing solutions with the 30g deionized water dissolving, and then it is transferred in the reactor drum; After at the uniform velocity stirring, be heated to 80 ℃, initiator potassium persulfate 0.30g is dissolved in the 4.5g deionized water, get 0.5g and be added in the reactor drum; Add the 0.7g pre-emulsion simultaneously; Controlled temperature is at 80 ℃, wait to occur obvious blue light after, then the seed emulsion preparation finishes; After seed emulsion preparation is accomplished, drip residue pre-emulsion and initiator solution, 1.5h adds, and 2.0g organosilicon A-151 is added in the reactor drum after adding pre-emulsion; After being incubated 80 ℃ of stirring 1.5h, be cooled to 30 ℃, regulate pH to 7.5 with the ammoniacal liquor of 25wt%; Discharging is filtered, and preserves.
Embodiment three:
Is OP: SDBS=1 with 0.65g with the quality proportioning: 2 compound emulsifying agent is dissolved in the 25g deionized water and makes emulsifier solution; Transfer in the reactor drum then; Under continuing stirring, use and add 13.00g TEB 3K, 9.02g Bing Xisuandingzhi consumption, 9.50g Hydroxyethyl acrylate, 3.09g vinylbenzene, 3.11g vinyl cyanide, 0.70g methylacrylic acid to reactor drum; Continue to stir 50min and can make milky pre-emulsion, insert in the container it for use; Getting 0.30g is OP: SDBS=1 with the quality proportioning: 2 compound emulsifying agent and saleratus 0.10g, make mixing solutions with the 20g deionized water dissolving, and then it is transferred in the reactor drum; After at the uniform velocity stirring, be heated to 85 ℃, initiator potassium persulfate 0.35g is dissolved in the 5.0g deionized water, get 0.5g and be added in the reactor drum; Add the 2.0g pre-emulsion simultaneously; Controlled temperature is at 85 ℃, wait to occur obvious blue light after, then the seed emulsion preparation finishes; After seed emulsion preparation is accomplished, drip residue pre-emulsion and initiator solution, 2h adds, and 2.0g organosilicon KH-570 is added in the reactor drum after adding pre-emulsion; After being incubated 85 ℃ of stirring 1.5h, be cooled to 20 ℃, regulate pH to 7 with the ammoniacal liquor of 25wt%; Discharging is filtered, and preserves.
Embodiment four:
Is OP: SDBS=1 with 0.80g with the quality proportioning: 2 compound emulsifying agent is dissolved in the 15g deionized water and makes emulsifier solution, transfers to then in the reactor drum, is continuing under the stirring with adding the 16.39g TEB 3K; 15.58g NSC 20956; 1.56g vinylbenzene, the mix monomer of 0.51g methylacrylic acid is after finishing; Continue to stir 60min and can make milky pre-emulsion, insert in the container it for use; Getting 0.32g is OP: SDBS=1 with the quality proportioning: 2 compound emulsifying agent and saleratus 0.11g, make mixing solutions with the 18g deionized water dissolving, and then it is transferred in the reactor drum; After at the uniform velocity stirring, be heated to 85 ℃, the 0.30g initiator is used the 3g deionized water dissolving, get 0.45g and be added in the reactor drum; Add the 1.0g pre-emulsion simultaneously; Controlled temperature is at 85 ℃, wait to occur obvious blue light after, then the seed emulsion preparation finishes; After seed emulsion preparation is accomplished, drip residue pre-emulsion and initiator solution, about 2.5h adds, and adds behind the pre-emulsion in the 2.5g organosilicon KH-560 adding reactor drum; After being incubated 85 ℃ of stirring 1.5h, be cooled to 40 ℃, regulate pH to 7.8 with the ammoniacal liquor of 25wt%; Discharging is filtered, and preserves.
Embodiment five:
Is OP: SDBS=1 with 0.75g with the quality proportioning: 1 compound emulsifying agent is dissolved in the 15g deionized water and makes emulsifier solution, transfers to then in the reactor drum, is continuing to add TEB 3K 16.52g under the stirring; Bing Xisuandingzhi 14.18g; Vinyl cyanide 2.48g, the mix monomer of methylacrylic acid 0.36g is after finishing; Continue to stir 40min and can make milky pre-emulsion, insert in the container it for use; Getting 0.24g is OP: SDBS=1 with the quality proportioning: 1 compound emulsifying agent and saleratus 0.10g, make mixing solutions with the 15g deionized water dissolving, and then it is transferred in the reactor drum; After at the uniform velocity stirring, be heated to 90 ℃, the 0.35g initiator is used the 4g deionized water dissolving, get 0.5g and be added in the reactor drum; Add the 0.7g pre-emulsion simultaneously; Controlled temperature is at 90 ℃, wait to occur obvious blue light after, then the seed emulsion preparation finishes; After seed emulsion preparation is accomplished, drip residue pre-emulsion and initiator solution, about 2.5h adds, and adds behind the pre-emulsion in the 2.35g organosilicon KH-570 adding reactor drum; After being incubated 90 ℃ of stirring 1h, be cooled to 30 ℃, regulate pH to 8 with the ammoniacal liquor of 25wt%; Discharging is filtered, and preserves.
The organosilicon inarch acrylate copolymer emulsion performance that embodiment one～embodiment five makes, see the following form:
Can know by last table, can prepare low solid emulsion, also can prepare the emulsion of higher solids content, the mechanical stability of the emulsion of preparation, package stability, Ca through the method among the present invention
2+Have good stability.
Claims (7)
1. the preparation method of an organosilicon inarch acrylate copolymer emulsion is characterized in that, its concrete process step is following:
A. the preparation of pre-emulsion: the compound emulsifying agent of 3～6 mass parts is dissolved in the deionized water of 200～570 mass parts; Transfer in the reactor drum then; At propenoate hard monomer, the propenoate soft monomer of 80～100 mass parts and (methyl) vinylformic acid of 1～3 mass parts of continuing to add under the stirring 100 mass parts; Continue to continue to stir 30～60min and can make milky pre-emulsion, insert in the container it for use;
B. the preparation of seed emulsion: get the compound emulsifying agent of 1～2 mass parts and the pH buffer reagent of 0.01～1 mass parts, make mixing solutions, then it is transferred in the reactor drum, at the uniform velocity stir, be heated to 75～90 ℃ with the deionized water dissolving of 120～400 mass parts; The initiator of 2～4 mass parts is obtained initiator solution with the deionized water dissolving of 20～30 mass parts, get 1/10～1/5 and be added in the reactor drum; The pre-emulsion 1/100～1/25 of getting the steps A preparation simultaneously adds in the reactor drum, and controlled temperature is at 75～90 ℃, and after waiting blue light to occur, then the seed emulsion preparation finishes;
C. polymerization: in the seed emulsion of step B preparation, drip remaining pre-emulsion and initiator solution, 1.5～2.5h drips, and adds the silane coupling agent of 1～20 mass parts then; After being incubated 75～90 ℃ of stirring 1～1.5h; Cool to 20～40 ℃, regulate pH to 7～8, discharging with the pH regulator agent; Filter, promptly get the organosilicon inarch acrylate copolymer emulsion;
Described propenoate hard monomer is: one or more in TEB 3K, methacrylic tert-butyl acrylate, vinylbenzene, vinyl cyanide, the acrylic amide;
Described propenoate soft monomer is: in lauryl methacrylate(LMA), NSC 20956, acrylic acid-2-ethyl ester, the Hydroxyethyl acrylate one or more;
Described compound emulsifying agent is: the mixture that anionic emulsifier and nonionic emulsifying agent are made into by the mass ratio of 3:1～1:3; Wherein anionic emulsifier is X 2073 or dialkyl benzene sulfonic acids sodium, and nonionic emulsifying agent is OP-X emulsifying agent or TX-100.
2. the preparation method of a kind of organosilicon inarch acrylate copolymer emulsion according to claim 1 is characterized in that, described silane coupling agent general formula can be expressed as: CH
2=CH-R-Si (OR
1), wherein the R base is C
1～C
6Carbalkoxy or alkyl, R
1For containing C
1～C
2Alkyl.
3. the preparation method of a kind of organosilicon inarch acrylate copolymer emulsion according to claim 2 is characterized in that, described silane coupling agent is specially organosilicon KH-560, KH-570, A-151 or A-171.
4. the preparation method of a kind of organosilicon inarch acrylate copolymer emulsion according to claim 1 is characterized in that, described initiator is the water soluble starter persulphate.
5. the preparation method of a kind of organosilicon inarch acrylate copolymer emulsion according to claim 4 is characterized in that, described initiator is specially Potassium Persulphate, ammonium persulphate or Sodium Persulfate.
6. the preparation method of a kind of organosilicon inarch acrylate copolymer emulsion according to claim 1 is characterized in that, described pH buffer reagent is: sodium hydrogencarbonate or saleratus.
7. the preparation method of a kind of organosilicon inarch acrylate copolymer emulsion according to claim 1 is characterized in that, described pH regulator agent is the ammoniacal liquor of 20～30wt%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101487815A CN102321219B (en) | 2011-06-03 | 2011-06-03 | Method for preparing organic-silicon grafted acrylate copolymer emulsion |
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| CN2011101487815A CN102321219B (en) | 2011-06-03 | 2011-06-03 | Method for preparing organic-silicon grafted acrylate copolymer emulsion |
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| CN102321219B true CN102321219B (en) | 2012-10-31 |
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| CN103045113B (en) * | 2012-08-31 | 2014-07-02 | 江苏创基新材料有限公司 | Preparation method of self-crosslinking IPN (interpenetrating network) organosilicone-acrylate copolymer emulsion pressure-sensitive adhesive |
| CN112358566A (en) * | 2020-12-07 | 2021-02-12 | 衡水新光新材料科技有限公司 | Preparation method of two-in-one emulsion for multicolor paint |
| CN114230710A (en) * | 2022-01-26 | 2022-03-25 | 上海保立佳化学技术有限公司 | Low-odor pure silicone acrylate acrylic emulsion and preparation method thereof |
| CN117468268B (en) * | 2023-12-27 | 2024-03-22 | 湖南大道新材料有限公司 | Water-blocking paper bag and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1362432A (en) * | 2001-01-03 | 2002-08-07 | 中国石油化工股份有限公司 | Organosilicon grafted and mofiied acrylic ester copolymer emulsion |
| CN1546542A (en) * | 2003-11-28 | 2004-11-17 | 顺德鸿昌化工有限公司 | Method for preparing organic silicon modified polyacrylic acid (polyacrylate) emulsion |
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|---|---|---|---|---|
| US6169149B1 (en) * | 1998-12-04 | 2001-01-02 | General Electric Company | Emulsion polymerized silicone-acrylate rubber impact modifiers thermoplastic blends, and methods for making |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1362432A (en) * | 2001-01-03 | 2002-08-07 | 中国石油化工股份有限公司 | Organosilicon grafted and mofiied acrylic ester copolymer emulsion |
| CN1546542A (en) * | 2003-11-28 | 2004-11-17 | 顺德鸿昌化工有限公司 | Method for preparing organic silicon modified polyacrylic acid (polyacrylate) emulsion |
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