CN102807643B - Emulsifying agent for emulsion polymerization and preparation method thereof - Google Patents
Emulsifying agent for emulsion polymerization and preparation method thereof Download PDFInfo
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- CN102807643B CN102807643B CN201210309287.7A CN201210309287A CN102807643B CN 102807643 B CN102807643 B CN 102807643B CN 201210309287 A CN201210309287 A CN 201210309287A CN 102807643 B CN102807643 B CN 102807643B
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Abstract
The invention relates to an emulsifying agent for emulsion polymerization and a preparation method thereof. The emulsifying agent is an esterification derivative of a styrene-maleic anhydride (SMA) copolymer, which is obtained by performing catalytic esterification reaction of the SMA copolymer, saturated fatty alcohol and an acrylate monomer containing hydroxyl, wherein a side chain of the esterification derivative contains carbon-carbon double bonds; raw materials for the catalytic esterification reaction comprise the following component in percentage by mass: 10 to 30 percent of SMA polymer, 1 to 10 percent of saturated fatty alcohol, 0.5 to 5 percent of acrylate monomer containing hydroxyl, 0.001 to 5 percent of esterification catalyst and 40 to 70 percent of solvent; and the SMA polymer is a polymer of styrene and maleic anhydride in a molar ratio of 1:(1-3):1. According to a polymer emulsion prepared from the emulsifying agent for the emulsion polymerization, the water tolerance of a coating film is superior to that of the similar conventional emulsion, so that the emulsifying agent has an obvious effect on the aspect of enhancing the water tolerance of the coating film.
Description
Technical field
The present invention relates to a kind of emulsifier for emulsion polymerization and preparation method thereof.
Background technology
In polymer emulsion building-up process, mostly adopt emulsifying agent, as sodium lauryl sulphate (SDS) etc., its role is to: pattern and size and the stable latex particle of controlling latex particle.Conventionally emulsifying agent is all surperficial at latex particle with the formal distribution of physical adsorption, but in actual applications, due to physical adsorption in the emulsifying agent on latex particle surface very easily from forming the latex particle surface desorption of filming, migrate to film coated surface or enrichment and form hydrophilic region, thereby affect the performances such as gloss, water tolerance, physical strength of paint film.In recent ten years, report has the novel method much addressing the above problem both at home and abroad, comprises and adopts macromole emulsifying agent or polymerisable small-molecular emulsifier and adopt emulsifier-free emulsion polymerization method.But these methods still exist problem more or less, adopt macromole emulsifying agent can only slow down desorb odds and speed, the problem that can not fundamentally avoid desorb to cause; Although adopt the polymerisable small-molecular emulsifier can be with polymerization single polymerization monomer together copolymerization in emulsion polymerization process principle, but the polymerization activity of emulsifying agent is Tai Gao or too low usually, if the too high meeting of activity causes emulsifying agent autohemagglutination, thereby forming polyelectrolyte is dissolved in water, the water tolerance that is unfavorable for emulsion paint film, the too low emulsifying agent that can cause of activity can not be with polymerization single polymerization monomer copolymerization, and still the form with small-molecular emulsifier exists; The large multistability of emulsion that emulsifier-free emulsion polymerization method obtains is not fine, sometimes still needs to add a small amount of small-molecular emulsifier.Therefore, emulsifying agent has become to affect the key of polymer emulsion quality, has also affected the development of water-borne coatings.
Summary of the invention
First object of the present invention is: provide a kind of can with the emulsifier for emulsion polymerization of letex polymerization monomer copolymerization.
The technical scheme that realizes first object of the present invention is: a kind of emulsifier for emulsion polymerization is the esterified derivative that the acrylate monomer of styrene-maleic anhydride copolymer and saturated fatty alcohol and hydroxyl carries out the styrene-maleic anhydride copolymer of the side chain carbon-carbon double bonds that catalytic esterification obtains, in the raw materials used total mass of catalytic esterification, styrene-maleic anhydride copolymer accounts for 10%～30%, saturated fatty alcohol accounts for 1～10%, the acrylate monomer of hydroxyl accounts for 0.5%～5%, esterifying catalyst accounts for 0.001%～5%, solvent accounts for 40%～70%, the percentage ratio sum of above-mentioned each raw material consumption is 100%,
Described styrene-maleic anhydride copolymer is that mol ratio is the vinylbenzene of 1:1～3:1 and the multipolymer of two kinds of monomers of maleic anhydride, the number-average molecular weight that its gel permeation chromatography records is 1000～10000g/mol, molecular weight distribution coefficient is 1.1～3.0, and acid number is 200～500mg KOH/g;
Described saturated fatty alcohol is one or more in propyl carbinol, Pentyl alcohol, n-Octanol, isooctyl alcohol, lauryl alcohol, tetradecyl alcohol, hexadecanol, stearyl alcohol;
The acrylate monomer of described hydroxyl is a kind of in Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, vinylformic acid hydroxy butyl ester, methacrylic acid hydroxy butyl ester.
Second object of the present invention is: a kind of convenient operation is provided, for the preparation of can with the method for the emulsifying agent of letex polymerization monomer copolymerization.
The technical scheme that realizes second object of the present invention is: a kind of preparation method of mentioned emulsifier, and its concrete steps are as follows:
1. prepare raw material
Acrylate monomer, esterifying catalyst and the solvent of the styrene-maleic anhydride copolymer using by above-mentioned emulsifier ratio preparation catalytic esterification, saturated fatty alcohol, hydroxyl;
2. preparation
In reaction vessel, be sequentially added into acrylate monomer and the esterifying catalyst of styrene-maleic anhydride copolymer that 1. step prepare, solvent, saturated fatty alcohol, hydroxyl and stir, be warming up to 60～150 ℃, after insulation reaction 2～20 hours, gained material is cooled to 40 ℃, then under stirring, pour in the container that water is housed and generate throw out, leach throw out, dry and be emulsifier for emulsion polymerization.
In above-mentioned preparation method, described styrene-maleic anhydride copolymer is that mol ratio is the vinylbenzene of 1:1～3:1 and the multipolymer of two kinds of monomers of maleic anhydride, the number-average molecular weight that its gel permeation chromatography records is 1000～10000g/mol, molecular weight distribution coefficient is 1.1～3.0, and acid number is 200～500mg KOH/g;
Described saturated fatty alcohol is one or more in propyl carbinol, Pentyl alcohol, n-Octanol, isooctyl alcohol, lauryl alcohol, tetradecyl alcohol, hexadecanol, stearyl alcohol;
The acrylate monomer of described hydroxyl is a kind of in Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, vinylformic acid hydroxy butyl ester, methacrylic acid hydroxy butyl ester;
Described esterifying catalyst is a kind of in tosic acid, Dimethylamino pyridine, dibutyl tin dilaurate;
Described solvent is one or more in acetone, butanone, tetrahydrofuran (THF), DMF and Isosorbide-5-Nitrae-dioxane.
Technique effect of the present invention is: the emulsifying agent of technical solution of the present invention takes full advantage of each maleic anhydride unit in styrene-maleic anhydride copolymer (hereinafter to be referred as SMA multipolymer) molecule and contains a characteristic with the anhydride group of good reactive behavior, select the SMA multipolymer that ratio is suitable and molecular weight is suitable of maleic anhydride and styrene units, with the acrylate monomer of suitable saturated fatty alcohol and hydroxyl, the part anhydride group of SMA multipolymer is carried out to esterification, the side chain carbon-carbon double bonds of the esterified derivative of the SMA multipolymer obtaining after esterification.With the esterified derivative of the SMA multipolymer of this side chain carbon-carbon double bonds as benzene emulsion, organosilicon crylic acid latex, during the emulsifying agent of the letex polymerizations such as acrylate and vinyl acetate emulsion, at letex polymerization initial stage emulsifying agent of the present invention, first form micella, vinylbenzene subsequently, monomer polymerizations in micella such as vinylformic acid (ester), polymerization process or polymerization latter stage, the contained carbon-carbon double bond of emulsifying agent side chain of the present invention just can with the vinylbenzene for the synthesis of emulsion, the monomer copolymerizations such as vinylformic acid (ester), emulsifying agent is just combined in emulsion particle surface by chemical bonded refractory like this, avoided using emulsifying agent migration that conventional small-molecular emulsifier and macromole emulsifying agent bring and from the problem of latex particle surface desorption, solved again the unmanageable problem of reactive behavior of polymerizable small-molecular emulsifier, thereby improved after emulsion film forming, film long-term water tolerance and mechanical property, accelerate coating Water-borne modification process, meet environmental requirement.
Embodiment
Below in conjunction with embodiment, the present invention is described further, but is not limited to this.
Embodiment and comparative example be raw materials used is unless otherwise indicated commercially available industrial goods, can buy by commercial channel.
Embodiment 1～3 prepares emulsifying agent A, B, C
Prepare the main chemical reactions that emulsifying agent A, B, C relate to:
Wherein:
M:n is 1:1～3:1
R
1for carbonatoms 20 is with interior alkyl;
R
2for hydrogen or methyl;
R
3for carbonatoms 4 is with interior alkyl or polyoxyethylene group.
1. prepare raw material
Each raw material consumption of emulsion of the present invention is as follows: in the raw materials used total mass of catalytic esterification, styrene-maleic anhydride copolymer accounts for 10%～30%, saturated fatty alcohol accounts for 1～10%, the acrylate monomer of hydroxyl accounts for 0.5%～5%, esterifying catalyst accounts for 0.001%～5%, solvent accounts for 40%～70%, and the percentage ratio sum of above-mentioned each raw material consumption is 100%.
Embodiment 1～3 each raw material consumption is in Table 1, and the chemical structural formula of each raw material is in Table 2.
Table 1
Note: 1, in bracket, data are this raw material shared percentage ratio in raw materials used total mass;
2, SMA1000P is the trade name of Satomer company, it is that mol ratio is the vinylbenzene of 1:1 and the multipolymer of two kinds of monomers of maleic anhydride, the number-average molecular weight that its gel permeation chromatography records is 2060g/mol, and molecular weight distribution coefficient is 2.0, and acid number is 480mgKOH/g;
SMA2000 is the trade name of Satomer company, it is that mol ratio is the vinylbenzene of 2:1 and the multipolymer of two kinds of monomers of maleic anhydride, the number-average molecular weight that its gel permeation chromatography records is 3000g/mol, and molecular weight distribution coefficient is 2.2, and acid number is 350mgKOH/g;
SMA3000 is the trade name of Satomer company, it is that mol ratio is the vinylbenzene of 3:1 and the multipolymer of two kinds of monomers of maleic anhydride, the number-average molecular weight that its gel permeation chromatography records is 3800g/mol, and molecular weight distribution coefficient is 2.3, and acid number is 280mgKOH/g.
2. preparation
Respectively in 500ml reaction flask, be sequentially added into acrylate monomer and the esterifying catalyst of styrene-maleic anhydride copolymer that 1. step prepare, solvent, saturated fatty alcohol, hydroxyl and stir, be warming up to 65 ℃, after insulation reaction 9～10 hours, gained material is cooled to 40 ℃, under then stirring, pours in the container that 500g water is housed and generates throw out, leaches throw out, oven dry is emulsifier for emulsion polymerization A, B, C, and its chemical structural formula is in Table 2.
Embodiment 4 prepares polymer emulsion A
In 500mL reaction flask, be sequentially added into emulsifying agent A, 220g deionized water and 8g ammoniacal liquor that 20g embodiment 1 makes, be warming up to 70 ℃, keep stirring until emulsifying agent A dissolves completely.Now, the in the situation that of stirring and logical nitrogen, temperature is risen to 85 ℃, then, by the mixture of 60g vinylbenzene and 30g butyl acrylate and at the solution being formed by 50g deionized water and 0.6g ammonium persulphate, be added drop-wise in reaction flask, after dropwising in 3 hours, at 85 ℃, continue to stir after 2 hours, under stirring at low speed, be cooled to room temperature, obtain polymer emulsion A, outward appearance is translucent, without condensation product.
The median size that records the emulsion particle of polymer emulsion A by nano-particle size analysis instrument is 41nm left and right, and the actual measurement solids content of polymer emulsion A is 29.4wt%, and it is 118mPas that rotational viscosimeter records viscosity.
Embodiment 5 prepares polymer emulsion B
In 500mL reaction flask, be sequentially added into emulsifying agent B, 190g deionized water and 5g ammoniacal liquor that 15g embodiment 2 makes, be warming up to 70 ℃, keep stirring until emulsifying agent B dissolves completely.Now, the in the situation that of stirring and logical nitrogen, temperature is risen to 85 ℃, then the mixture of 20g methyl methacrylate and 40g butyl acrylate and the solution that is comprised of 30g deionized water and 0.4g ammonium persulphate are added drop-wise in reaction flask, after dropwising in 3 hours, at 85 ℃, continue to stir after 2 hours, under stirring at low speed, be cooled to room temperature, obtain polymer emulsion B, outward appearance is translucent, without condensation product.
By nano-particle size analysis instrument record polymer emulsion B the median size of emulsion particle be 47nm, the actual measurement solid content of polymer emulsion B is 24.3wt%, it is 82mPas that rotational viscosimeter records viscosity.
Embodiment 6 prepares polymer emulsion C
In 500mL reaction flask, be sequentially added into emulsifying agent C, 160g deionized water and 5g ammoniacal liquor that 15g embodiment 3 makes, be warming up to 70 ℃, keep stirring until emulsifying agent C dissolves completely.Now, the in the situation that of stirring and logical nitrogen, temperature is risen to 85 ℃, then by the mixture of 10g methyl methacrylate, 20g vinylbenzene and 35g butyl acrylate and the solution that formed by 40g deionized water and 0.4g ammonium persulphate, be added drop-wise in reaction flask, after dropwising in 3 hours, at 85 ℃, continue to stir after 2 hours, under stirring at low speed, be cooled to room temperature, obtain polymer emulsion C, outward appearance is translucent.
The median size that records the emulsion particle of polymer emulsion C by nano-particle size analysis instrument is 55nm, and the actual measurement solids content of polymer emulsion C is 29.3wt%, and it is 107mPas that rotational viscosimeter records viscosity
Reference examples 1 adopts conventional small-molecular emulsifier sodium lauryl sulphate to prepare emulsion
In 500mL reaction flask, be sequentially added into 0.45g emulsifier sodium lauryl sulfate, 170g deionized water, be warming up to 70 ℃, keep stirring until the whole dissolution system clears of emulsifying agent.Now, the in the situation that of stirring and logical nitrogen, temperature is risen to 85 ℃, then by the mixture of 60g vinylbenzene and 30g butyl acrylate and the solution that formed by 40g deionized water and 0.4g ammonium persulphate, be added drop-wise in reaction flask, after dropwising in 3 hours, at 85 ℃, continue to stir after 2 hours, under stirring at low speed, be cooled to room temperature, obtain reference examples 1 polymer emulsion, outward appearance is oyster white.
The median size that records the emulsion particle of reference examples 1 polymer emulsion by nano-particle size analysis instrument is 112nm, and the actual measurement solid content of emulsion is 29.8wt%, and it is 208mPas that rotational viscosimeter records viscosity.
Reference examples 2 adopts commercially available SMA1000(not containing polymerizable double bond) as macromole emulsifying agent, prepare emulsion
In 500mL reaction flask, be sequentially added into 5g emulsifying agent SMA1000P, 160g deionized water and 3g ammoniacal liquor, be warming up to 70 ℃, keep stirring until emulsifying agent dissolves completely.Now, the in the situation that of stirring and logical nitrogen, temperature is increased to 85 ℃, then by the mixture of 5g methyl methacrylate and 12g butyl acrylate and the solution that formed by 40g deionized water and 0.08g ammonium persulphate, be added drop-wise in reaction flask, after dropwising in 3 hours, at 85 ℃, continue to stir after 2 hours, under stirring at low speed, be cooled to room temperature, obtain reference examples 2 polymer emulsions, outward appearance is translucent, wherein emulsifying agent SMA1000P is Satomer company name of product, it is that mol ratio is the vinylbenzene of 1:1 and the SMA multipolymer that maleic anhydride forms,
The median size that records the emulsion particle of reference examples 1 polymer emulsion by nano-particle size analysis instrument is 52nm, and the actual measurement solids content of emulsion is 9.6wt%, and it is 34mPas that rotational viscosimeter records viscosity.
The polymer emulsion that embodiment 4～6 and reference examples 1～2 are made adds film coalescence aid (Lauryl Alcohol ester) high-speed stirring of mass ratio 0.1%～1% to make after varnish, is coated on ABS plastic plate, makes detection model, and detects as follows correlated performance:
Sticking power is tested according to standard GB/T/T9286-98; Pencil hardness is tested according to standard GB/T/T6739-96; Water resistance test is according to standard GB/T/T1733-93(first method) test.The performance of respectively filming recording is listed in table 3.
Table 3
| Emulsion title | Sticking power, level | Pencil hardness, H | Water tolerance |
| Polymer emulsion A | 0 | 2 | 72h does not whiten, non-foaming |
| Polymer emulsion B | 0 | 2 | 72h does not whiten, non-foaming |
| Polymer emulsion C | 0 | 2 | 72h does not whiten, non-foaming |
| Reference examples 1 polymer emulsion | 0 | 1 | 48h slightly whitens, non-foaming |
| Reference examples 2 polymer emulsions | 1 | 2 | 24h whiting, comes off |
As can be seen from Table 3, the polymer emulsion making with emulsifying agent of the present invention, its water-resistance property of coating is all better than conventional emulsion (reference examples 1 and 2), particularly use and do not contain the SMA multipolymer of polymerizable double bond as the reference examples 2 of emulsifying agent, its water-resistance property of coating is the poorest, has more proved that emulsifying agent of the present invention (esterified derivative of the SMA multipolymer of side chain carbon-carbon double bonds) is having positive effect aspect enhancing water-resistance property of coating energy.
Practical application shows, emulsion of the present invention is as the emulsifying agent of the letex polymerizations such as benzene emulsion, organosilicon crylic acid latex, acrylate and vinyl acetate emulsion, all can make the water-resistance property of coating of the polymer emulsion that makes be significantly improved, and do not repeat them here.
Claims (3)
1. an emulsifier for emulsion polymerization, it is characterized in that, it is the esterified derivative that the acrylate monomer of styrene-maleic anhydride copolymer and saturated fatty alcohol and hydroxyl carries out the styrene-maleic anhydride copolymer of the side chain carbon-carbon double bonds that catalytic esterification obtains, in the raw materials used total mass of catalytic esterification, styrene-maleic anhydride copolymer accounts for 10%～30%, saturated fatty alcohol accounts for 1～10%, the acrylate monomer of hydroxyl accounts for 0.5%～5%, esterifying catalyst accounts for 0.001%～5%, solvent accounts for 40%～70%, the percentage ratio sum of above-mentioned each raw material consumption is 100%,
Described styrene-maleic anhydride copolymer is that mol ratio is the vinylbenzene of 1:1～3:1 and the multipolymer of two kinds of monomers of maleic anhydride, the number-average molecular weight that its gel permeation chromatography records is 1000～10000g/mol, molecular weight distribution coefficient is 1.1～3.0, and acid number is 200～500mgKOH/g;
Described saturated fatty alcohol is one or more in propyl carbinol, Pentyl alcohol, n-Octanol, isooctyl alcohol, lauryl alcohol, tetradecyl alcohol, hexadecanol, stearyl alcohol;
The acrylate monomer of described hydroxyl is a kind of in Hydroxyethyl acrylate, Propylene glycol monoacrylate, vinylformic acid hydroxy butyl ester.
2. a preparation method for claim 1 emulsifying agent, is characterized in that, concrete steps are as follows:
1. prepare raw material
Acrylate monomer, esterifying catalyst and the solvent of the styrene-maleic anhydride copolymer using by the proportioning preparation catalytic esterification of claim 1, saturated fatty alcohol, hydroxyl;
2. preparation
In reaction vessel, be sequentially added into acrylate monomer and the esterifying catalyst of styrene-maleic anhydride copolymer that 1. step prepare, solvent, saturated fatty alcohol, hydroxyl and stir, be warming up to 60～150 ℃, after insulation reaction 2～20 hours, gained material is cooled to 40 ℃, then under stirring, pour in the container that water is housed and generate throw out, leach throw out, dry and be emulsifier for emulsion polymerization.
3. preparation method according to claim 2, it is characterized in that, described styrene-maleic anhydride copolymer is that mol ratio is the vinylbenzene of 1:1～3:1 and the multipolymer of two kinds of monomers of maleic anhydride, the number-average molecular weight that its gel permeation chromatography records is 1000～10000g/mol, molecular weight distribution coefficient is 1.1～3.0, and acid number is 200～500mg KOH/g;
Described saturated fatty alcohol is one or more in propyl carbinol, Pentyl alcohol, n-Octanol, isooctyl alcohol, lauryl alcohol, tetradecyl alcohol, hexadecanol, stearyl alcohol;
The acrylate monomer of described hydroxyl is a kind of in Hydroxyethyl acrylate, Propylene glycol monoacrylate, vinylformic acid hydroxy butyl ester;
Described esterifying catalyst is a kind of in tosic acid, Dimethylamino pyridine, dibutyl tin dilaurate;
Described solvent is one or more in acetone, butanone, tetrahydrofuran (THF), DMF and Isosorbide-5-Nitrae-dioxane.
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| CN105693944B (en) * | 2014-11-27 | 2019-01-29 | 合众（佛山）化工有限公司 | A kind of preparation method of heat resist modification styrene-acrylic emulsion |
| CN105506643A (en) * | 2015-12-20 | 2016-04-20 | 中国海洋石油总公司 | Polymerized imidazoline corrosion inhibitor and preparation method thereof |
| CN110698579B (en) * | 2019-09-18 | 2022-04-05 | 中科院广州化学有限公司 | Alcohol-resistant water-based resin emulsion binder for quick-drying ink and preparation method thereof |
| TWI792436B (en) * | 2020-07-23 | 2023-02-11 | 法商阿科瑪法國公司 | (meth)acrylate functional dispersant |
| CN113881003B (en) * | 2021-09-27 | 2024-02-27 | 万华化学(四川)有限公司 | ABS grafted polymerizable emulsifier, preparation method and application thereof, and preparation method of ABS grafted latex |
| CN115197381B (en) * | 2022-09-16 | 2022-11-25 | 广州鹿山新材料股份有限公司 | Unsaturated SMA resin modified polypropylene and preparation method thereof |
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Effective date of registration: 20161020 Address after: 213016 Changzhou Zhong Road, Jiangsu Province, No. 22 Longjiang Road Patentee after: CNOOC CHANGZHOU PAINT CHEMICAL RESEARCH INSTITUTE CO., LTD. Patentee after: CNOOC Energy Development Co., Ltd. Patentee after: CNOOC Changzhou EP Coating Co., Ltd. Address before: 100010 Dongcheng District, Chaoyangmen, North Street, No. 4705, No. 25, box office, Beijing Patentee before: China National Offshore Oil Corporation Patentee before: CNOOC CHANGZHOU PAINT CHEMICAL RESEARCH INSTITUTE CO., LTD. Patentee before: CNOOC Energy Development Co., Ltd. Patentee before: CNOOC Changzhou EP Coating Co., Ltd. |