CN104710553A - Styrene-acrylate core-shell emulsion and preparation method thereof - Google Patents
Styrene-acrylate core-shell emulsion and preparation method thereof Download PDFInfo
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- CN104710553A CN104710553A CN201410847939.1A CN201410847939A CN104710553A CN 104710553 A CN104710553 A CN 104710553A CN 201410847939 A CN201410847939 A CN 201410847939A CN 104710553 A CN104710553 A CN 104710553A
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Abstract
The invention relates to a styrene-acrylate core-shell emulsion and a preparation method thereof. The styrene-acrylate core-shell emulsion comprises the following components by mass percentage: a core monomer comprising 20-40% of styrene, 50-75% of butyl acrylate monomer, 0-5% of acrylic acid, 0-5% of acrylamide; and a shell monomer comprising 75-100% of styrene, 0-15% of butyl acrylate monomer, 0-5% of acrylic acid and 0-5% of acrylamide; based on total mass percentage of the components, 1-5% of emulsifier and 0.2-0.6% of persulfate are added. The styrene-acrylate core-shell emulsion has the beneficial effect that 1) employing a core-shell emulsion polymerization preparation method, the particle size of the emulsion is controlled at 0.1-0.2mum, a core-shell structure is a soft core-shell structure; wherein the soft shell can provide good film forming ability for the emulsion, the hard shell can provide intensity and contamination resistance performance for the emulsion; 2)total vitrification point (Tg) of a polymer is no less than 20 DEG C, and optimal scope is between 25 and 40 DEG C; and 3)minimum film-forming temperature (MFT) of the polymer is no higher than 25 DEG C.
Description
Technical field
The present invention relates to a kind of building coating compounding process field, specifically a kind of styrene-acrylate core/shell emulsion and preparation method thereof.
Background technology
Vinylbenzene-acrylic ester emulsion is obtained through letex polymerization by vinylbenzene and acrylate monomer.Because it has excellent water tolerance, erosion resistance, contamination resistance and relative low price, be widely used in construction coating for internal wall.Because it in use needs certain hardness, therefore require that Tg can not too low (as can not lower than 15 DEG C).But the too high minimum film-forming temperature of emulsion (MFT) that easily causes of Tg is too high, causing it can not film forming in room temperature, in use needs to add film coalescence aid.Film coalescence aid is a kind of volatile organic matter (VOC), causes environmental pollution.Along with environmental regulation, to the restriction of VOC content in coating, increasingly strict and people are to the concern of own health, and low VOC even Diamond Search becomes the important directions of paint development, and core-shell emulsion is one of method effectively reducing emulsion minimum film-forming temperature.
Summary of the invention
The present invention is intended at least to solve one of technical problem existed in prior art.
For this reason, it is low at interior wall coating film-forming temperature that one object of the present invention is to propose one, styrene-acrylate core/shell emulsion that water tolerance and scrub resistance also meet the demands and preparation method thereof.
According to a kind of styrene-acrylate core/shell emulsion of the present invention, it is characterized in that: the mass percentage content of each monomer component content is:
Nuclear monomer:
Vinylbenzene 20-40%
Butyl acrylate 50-75%
Vinylformic acid 0-5%
Acrylamide 0-5%
Shell monomer:
Vinylbenzene 75-100%
Butyl acrylate 0-15%
Vinylformic acid 0-5%
Acrylamide 0-5%
Based on all monomer total mass degrees, add emulsifying agent 1-5% and persulphate 0.2-0.6%.
In addition, according to a kind of styrene-acrylate core/shell emulsion of the present invention, also there is following additional technical feature: according to some embodiments of the present invention, further concrete, the second-order transition temperature (Tg) of described nuclear monomer is-35 DEG C to 10 DEG C, the Tg of shell monomer is 80 DEG C to 110 DEG C, and total Tg of all monomers is not less than 20 DEG C.Second-order transition temperature is according to FOX formulae discovery:
Wherein, Wi is the massfraction of i-th kind of monomer, and Tgi is the second-order transition temperature of the corresponding homopolymer of i-th kind of monomer, unit K.
Concrete further, described emulsifying agent is wherein one or both the mixture arbitrarily of fatty alcohol-polyoxyethylene ether sulfosuccinic acid semiester disodium salt or alkyl polyoxyethylene ether.
Concrete further, described persulphate is ammonium persulphate or Potassium Persulphate or Sodium Persulfate wherein one or more mixture arbitrarily.
A preparation method for styrene-acrylate core/shell emulsion, its step is as follows:
Step S1: after vinylbenzene 20-40%, butyl acrylate 50-75%, vinylformic acid 0-5% and acrylamide 0-5%, emulsifying agent 1-5% and persulphate 0.2% to 0.6% being mixed, prepare the pre-emulsion 1 of nuclear monomer;
Step S2: after vinylbenzene 75-100%, butyl acrylate 0-15%, vinylformic acid 0-5%, acrylamide 0-5%, emulsifying agent 1-5% and persulphate 0.2%-0.6% being mixed, prepare the pre-emulsion 2 of shell monomer;
Step S3: make initiator solution with the mass ratio 96%:4% of water and ammonium persulphate;
Step S4: the pre-emulsion 1 preparing nuclear monomer wherein in step S1 or the optional one of the pre-emulsion 2 preparing shell monomer in step S2, water 400g is added in reactor, be warming up to 80 DEG C, start to drip pre-emulsion 1, start to drip initiator solution simultaneously, pre-emulsion time for adding 144min to 240 min, initiator solution drips 240min, after pre-emulsion 1 or emulsion 2 are added dropwise to complete, initiator solution suspends dropping, reaction mixture is incubated 0.5 h to 1.5h at 80 DEG C to 83 DEG C, then 45 DEG C are cooled to, add 25% of ammoniacal liquor 10g, stir 5min discharging.
Further concrete, in step s 4 which, after pre-emulsion 1 or emulsion 2 are added dropwise to complete, start to drip another kind of pre-emulsion 1 or pre-emulsion 2, initiator continues to drip simultaneously, pre-emulsion 2 time for adding 96min, after pre-emulsion 1 or emulsion 2 drip off, reaction mixture is incubated 1.5h at 81 DEG C at 83 DEG C.
The invention has the beneficial effects as follows: 1, adopt core-shell emulsion polymerization preparation method, emulsion particle diameter controls at 0.1-0.2 μm, and nucleocapsid structure is soft core duricrust; Wherein, soft endorsing thinks that emulsion provides good film-forming properties, and duricrust can provide intensity and contamination resistance for emulsion; 2, the second-order transition temperature (Tg) that polymkeric substance is total is not less than 20 DEG C, and preferred scope is between 25-40 DEG C; 3, the minimum film-forming temperature (MFT) of polymkeric substance is not higher than 25 DEG C.
Embodiment
Be described below in detail embodiments of the invention, shown in the example of described embodiment, wherein same or similar label represents same or similar element or has element that is identical or similar functions from start to finish.Below by being exemplary with reference to the embodiment described, only for explaining the present invention, and limitation of the present invention can not be interpreted as.
A kind of styrene-acrylate core/shell emulsion according to the embodiment of the present invention is described below.
According to a kind of styrene-acrylate core/shell emulsion of the present invention, it is characterized in that: the mass percentage content of each monomer component content is:
Nuclear monomer:
Vinylbenzene 20-40%
Butyl acrylate 50-75%
Vinylformic acid 0-5%
Acrylamide 0-5%
Shell monomer:
Vinylbenzene 75-100%
Butyl acrylate 0-15%
Vinylformic acid 0-5%
Acrylamide 0-5%
Based on all monomer total mass degrees, add emulsifying agent 1-5% and persulphate 0.2-0.6%.
In addition, according to a kind of styrene-acrylate core/shell emulsion of the present invention, also there is following additional technical feature: according to some embodiments of the present invention, further concrete, the second-order transition temperature (Tg) of described nuclear monomer is-35 DEG C to 10 DEG C, the Tg of shell monomer is 80 DEG C to 110 DEG C, and total Tg of all monomers is not less than 20 DEG C.Second-order transition temperature is according to FOX formulae discovery:
Wherein, Wi is the massfraction of i-th kind of monomer, and Tgi is the second-order transition temperature of the corresponding homopolymer of i-th kind of monomer, unit K.
Concrete further, described emulsifying agent is wherein one or both the mixture arbitrarily of fatty alcohol-polyoxyethylene ether sulfosuccinic acid semiester disodium salt or alkyl polyoxyethylene ether.
Concrete further, described persulphate is ammonium persulphate or Potassium Persulphate or Sodium Persulfate wherein one or more mixture arbitrarily.
A preparation method for styrene-acrylate core/shell emulsion, its step is as follows:
Step S1: after vinylbenzene 20-40%, butyl acrylate 50-75%, vinylformic acid 0-5% and acrylamide 0-5%, emulsifying agent 1-5% and persulphate 0.2-0.6% being mixed, prepare the pre-emulsion 1 of nuclear monomer;
Step S2: after vinylbenzene 75-100%, butyl acrylate 0-15%, vinylformic acid 0-5%, acrylamide 0-5%, emulsifying agent 1-5% and persulphate 0.2-0.6% being mixed, prepare the pre-emulsion 2 of shell monomer;
Step S3: make initiator solution with the mass ratio 96%:4% of water and ammonium persulphate;
Step S4: the pre-emulsion 1 preparing nuclear monomer wherein in step S1 or the optional one of the pre-emulsion 2 preparing shell monomer in step S2, water 400g is added in reactor, be warming up to 80 DEG C, start to drip pre-emulsion 1, start to drip initiator solution simultaneously, pre-emulsion time for adding 144min to 240 min, initiator solution drips 240min, after pre-emulsion 1 or emulsion 2 are added dropwise to complete, initiator solution suspends dropping, reaction mixture is incubated 0.5 h to 1.5h at 80 DEG C to 83 DEG C, then 45 DEG C are cooled to, add 25% of ammoniacal liquor 10g, stir 5min discharging.
Further concrete, in step s 4 which, after pre-emulsion 1 or emulsion 2 are added dropwise to complete, start to drip another kind of pre-emulsion 1 or pre-emulsion 2, initiator continues to drip simultaneously, pre-emulsion 2 time for adding 96min, after pre-emulsion 1 or emulsion 2 drip off, reaction mixture is incubated 1.5h at 81 DEG C at 83 DEG C.
The formula composition of the embodiment of the present invention is described below by some embodiments.
Embodiment 1
With water 33%, vinylbenzene 27%, butyl acrylate 36%, vinylformic acid 1%, acrylamide 1%, AEROSOL A-102 emulsifying agent 2%(succinic acid alkyl polyoxyethylene ether monoesters disodium sulfonate, from cyanogen specialization work) make monomer pre-emulsion 1.
Monomer pre-emulsion 2 is made with water 24.5%, vinylbenzene 47.8%, vinylformic acid 0.7%, acrylamide 0.7%, AEROSOL A-10 emulsifying agent 26.3%.
With water 96%: ammonium persulphate 4% makes initiator solution.
Water 400g is added in reactor, be warming up to 80 DEG C, start to drip pre-emulsion 1, start to drip initiator solution simultaneously, pre-emulsion 1 time for adding 144min, initiator solution drips 240min, and after pre-emulsion 1 is added dropwise to complete, initiator solution suspends dropping, reaction mixture is incubated 0.5h at 80 DEG C at 82 DEG C, then start to drip pre-emulsion 2, initiator continues to drip simultaneously, pre-emulsion 2 time for adding 96min.After pre-emulsion 2 drips off, reaction mixture is incubated 1.5h at 81 DEG C at 83 DEG C, is then cooled to 45 DEG C, adds the ammoniacal liquor 10g of 25%, stirs 5min discharging.
Embodiment 2
With water 33%, vinylbenzene 28%, butyl acrylate 36%, vinylformic acid 0.9%, acrylamide 0.9%, RHODIAPEX CO-436 emulsifying agent 1.2%(polyoxyethylene nonylphenol ether ammonium sulfate, from Luo Diya group) make monomer pre-emulsion 1.
Monomer pre-emulsion 2 is made with water 33%, vinylbenzene 64%, vinylformic acid 0.9%, acrylamide 0.9%, RHODIAPEX CO-436 emulsifying agent 1.2%.
With water 96%: ammonium persulphate 4% makes initiator solution.
Water 400g is added in reactor, be warming up to 80 DEG C, start to drip pre-emulsion 1, start to drip initiator solution simultaneously, pre-emulsion 1 time for adding 144min, initiator solution drips 240min, and after pre-emulsion 1 is added dropwise to complete, initiator solution suspends dropping, reaction mixture is incubated 0.5h at 80 DEG C at 82 DEG C, then start to drip pre-emulsion 2, initiator continues to drip simultaneously, pre-emulsion 2 time for adding 96min.After pre-emulsion 2 drips off, reaction mixture is incubated 1.5h at 81 DEG C at 83 DEG C, is then cooled to 45 DEG C, adds 25% of ammoniacal liquor 10g, stirs 5min discharging.
Comparative example 3
Technique is similar to Example 1, but the dropping order of pre-emulsion 1 and pre-emulsion 2 is exchanged.
Comparative example 4
Monomer pre-emulsion is made with water 32.7%, vinylbenzene 30.7%, butyl acrylate 32.7%, vinylformic acid 0.9%, acrylamide 0.9%, AEROSOL A-102 emulsifying agent 2.1%.
With water 96%: ammonium persulphate 4% makes initiator solution.
In reactor, add water 400g, be warming up to 80 DEG C, start to drip pre-emulsion and initiator solution, time for adding 240min, after being added dropwise to complete, reaction mixture is incubated 1.5h at 81 DEG C at 83 DEG C, then be cooled to 45 DEG C, add the ammoniacal liquor 10g of 25%, stir 5min discharging.
Masking: the line rod masking on a glass product that above-mentioned three examples obtain being used respectively 100 μm, then 25 DEG C, dry in the thermostatic constant wet chamber of relative humidity 60%, observe its film forming situation, the results are shown in Table 1.
By test result, these the above embodiments have following features: 1, adopt core-shell emulsion polymerization preparation method, emulsion particle diameter controls at 0.1 μm to 0.2 μm, and nucleocapsid structure is soft core duricrust; Wherein, soft endorsing thinks that emulsion provides good film-forming properties, and duricrust can provide intensity and contamination resistance for emulsion; 2, the second-order transition temperature (Tg) that polymkeric substance is total is not less than 20 DEG C, and preferred scope is between 25 DEG C to 40 DEG C; 3, the minimum film-forming temperature (MFT) of polymkeric substance is not higher than 25 DEG C.
Although illustrate and describe embodiments of the invention, those having ordinary skill in the art will appreciate that: can carry out multiple change, amendment, replacement and modification to these embodiments when not departing from principle of the present invention and aim, scope of the present invention is by claim and equivalents thereof.
Claims (6)
1. a styrene-acrylate core/shell emulsion, is characterized in that: the mass percentage content of each monomer component content is:
Nuclear monomer:
Vinylbenzene 20-40%
Butyl acrylate 50-75%
Vinylformic acid 0-5%
Acrylamide 0-5%
Shell monomer:
Vinylbenzene 75-100%
Butyl acrylate 0-15%
Vinylformic acid 0-5%
Acrylamide 0-5%
Based on all monomer total mass degrees, add emulsifying agent 1-5% and persulphate 0.2-0.6%.
2. a kind of styrene-acrylate core/shell emulsion according to claim 1, is characterized in that: the second-order transition temperature (Tg) of described nuclear monomer is-35 DEG C to 10 DEG C, and the Tg of shell monomer is 80 DEG C to 110 DEG C, and total Tg of all monomers is not less than 20 DEG C,
Second-order transition temperature is according to FOX formulae discovery:
Wherein, Wi is the massfraction of i-th kind of monomer, and Tgi is the second-order transition temperature of the corresponding homopolymer of i-th kind of monomer, unit K.
3. a kind of styrene-acrylate core/shell emulsion according to claim 1, is characterized in that: described emulsifying agent is wherein one or both the mixture arbitrarily of fatty alcohol-polyoxyethylene ether sulfosuccinic acid semiester disodium salt or alkyl polyoxyethylene ether.
4. a kind of styrene-acrylate core/shell emulsion according to claim 1, is characterized in that: described persulphate is ammonium persulphate or Potassium Persulphate or Sodium Persulfate wherein one or more mixture arbitrarily.
5. a preparation method for styrene-acrylate core/shell emulsion, its step is as follows:
Step S1: after vinylbenzene 20-40%, butyl acrylate 50-75%, vinylformic acid 0-5% and acrylamide 0-5%, emulsifying agent 1-5% and persulphate 0.2-0.6% being mixed, prepare the pre-emulsion 1 of nuclear monomer;
Step S2: after vinylbenzene 75-100%, butyl acrylate 0-15%, vinylformic acid 0-5%, acrylamide 0-5%, emulsifying agent 1-5% and persulphate 0.2-0.6% being mixed, prepare the pre-emulsion 2 of shell monomer;
Step S3: make initiator solution with the mass ratio 96%:4% of water and ammonium persulphate;
Step S4: the pre-emulsion 1 preparing nuclear monomer wherein in step S1 or the optional one of the pre-emulsion 2 preparing shell monomer in step S2, water 400g is added in reactor, be warming up to 80 DEG C, start to drip pre-emulsion 1, start to drip initiator solution simultaneously, pre-emulsion time for adding 144min to 240 min, initiator solution drips 240min, after pre-emulsion 1 or emulsion 2 are added dropwise to complete, initiator solution suspends dropping, reaction mixture is incubated 0.5 h to 1.5h at 80 DEG C to 83 DEG C, then 45 DEG C are cooled to, add 25% of ammoniacal liquor 10g, stir 5min discharging.
6. the preparation method of a kind of styrene-acrylate core/shell emulsion according to claim 5, its step is as follows:
In step s 4 which, after pre-emulsion 1 or emulsion 2 are added dropwise to complete, start to drip another kind of pre-emulsion 1 or pre-emulsion 2, initiator continues to drip simultaneously, pre-emulsion 2 time for adding 96min, after pre-emulsion 1 or emulsion 2 drip off, reaction mixture is incubated 1.5h at 81 DEG C at 83 DEG C.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105175600A (en) * | 2015-10-13 | 2015-12-23 | 三棵树涂料股份有限公司 | Core-shell-type styrene-acrylic emulsion with dual-gradient structures contained in shell layers and preparing method thereof |
| CN105331307A (en) * | 2015-10-16 | 2016-02-17 | 上海晶华胶粘新材料股份有限公司 | Core-shell styrene-acrylic emulsion impregnating agent, and preparation method thereof |
| CN108948268A (en) * | 2018-07-09 | 2018-12-07 | 上海三瑞高分子材料股份有限公司 | A kind of preparation method of sub-micron acrylic acid ester emulsion |
| CN109280121A (en) * | 2018-09-17 | 2019-01-29 | 肖连发 | A kind of acrylic acid base-material lotion |
| CN109971287A (en) * | 2019-03-25 | 2019-07-05 | 镇江市朗悦塑业有限公司 | A kind of limited slip plate and its production technology |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0348565A1 (en) * | 1984-07-25 | 1990-01-03 | Rohm And Haas Company | Polymers comprising alkali-insoluble core/alkali-soluble shell and compositions thereof |
| CN101092467A (en) * | 2007-06-25 | 2007-12-26 | 常州光辉化工有限公司 | Interpolymer latex of polystyrene and acrylic ester in hud polymerization type, and preparation method |
| CN101275005A (en) * | 2008-05-14 | 2008-10-01 | 恒昌涂料（惠阳）有限公司 | Preparation for acroleic acid emulsion having nucleocapsid structure, acroleic acid emulsion and water-based gloss oil therefrom |
-
2014
- 2014-12-31 CN CN201410847939.1A patent/CN104710553A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0348565A1 (en) * | 1984-07-25 | 1990-01-03 | Rohm And Haas Company | Polymers comprising alkali-insoluble core/alkali-soluble shell and compositions thereof |
| CN101092467A (en) * | 2007-06-25 | 2007-12-26 | 常州光辉化工有限公司 | Interpolymer latex of polystyrene and acrylic ester in hud polymerization type, and preparation method |
| CN101275005A (en) * | 2008-05-14 | 2008-10-01 | 恒昌涂料（惠阳）有限公司 | Preparation for acroleic acid emulsion having nucleocapsid structure, acroleic acid emulsion and water-based gloss oil therefrom |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105175600A (en) * | 2015-10-13 | 2015-12-23 | 三棵树涂料股份有限公司 | Core-shell-type styrene-acrylic emulsion with dual-gradient structures contained in shell layers and preparing method thereof |
| CN105331307A (en) * | 2015-10-16 | 2016-02-17 | 上海晶华胶粘新材料股份有限公司 | Core-shell styrene-acrylic emulsion impregnating agent, and preparation method thereof |
| CN108948268A (en) * | 2018-07-09 | 2018-12-07 | 上海三瑞高分子材料股份有限公司 | A kind of preparation method of sub-micron acrylic acid ester emulsion |
| CN109280121A (en) * | 2018-09-17 | 2019-01-29 | 肖连发 | A kind of acrylic acid base-material lotion |
| CN109971287A (en) * | 2019-03-25 | 2019-07-05 | 镇江市朗悦塑业有限公司 | A kind of limited slip plate and its production technology |
| WO2020191794A1 (en) * | 2019-03-25 | 2020-10-01 | 江苏朗悦新材料科技有限公司 | Anti-skid board and production process therefor |
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Application publication date: 20150617 |