CN1597719A - Low temperature elasticity polyacrylate waterproof emulsion - Google Patents
Low temperature elasticity polyacrylate waterproof emulsion Download PDFInfo
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- CN1597719A CN1597719A CN 03158350 CN03158350A CN1597719A CN 1597719 A CN1597719 A CN 1597719A CN 03158350 CN03158350 CN 03158350 CN 03158350 A CN03158350 A CN 03158350A CN 1597719 A CN1597719 A CN 1597719A
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Abstract
A water-proof low-temp elastic polyacrylate emulsion contains deionized water, trigger, the mixture of soft monomer and hard monomer, emulsifier, special monomer and neutralizing agent. Regulating the ratio of soft monomer and hard monomer can change its vitrifying temp, so obtaining different products.
Description
Technical field
The present invention relates to a kind of coating composition of the multipolymer based on the aliphatic unsaturated hydrocarbon that has only a carbon-to-carbon double bond, particularly a kind of low temperature elasticity polyacrylic ester water-proof emulsion.
Background technology
The production of existing elastomeric polypropylenes acid esters water-proof emulsion, many employing vinylbenzene, methyl methacrylate are hard monomer, with the butyl acrylate is that soft monomer is polymerized by semicontinuous pre-emulsification technology, the emulsifying agent that adopts is non-response type anionic emulsifier, the emulsion polymer second-order transition temperature Tg that is obtained≤0 ℃.Because the butyl acrylate soft monomer has pressure-sensitive character, its ester chain carbon atom number is lower, a little less than the internal plasticization ability, hydrophobicity is poor, and as the second-order transition temperature Tg that reduces emulsion polymer, butyl acrylate soft monomer proportion in prescription is just bigger, and therefore, the quick after tackiness of the resistance to compression of emulsion polymer, resistance to deterioration, water tolerance are also poor thereupon.Like this, prior art is difficult to obtain the polyacrylic ester water-proof emulsion of each side high comprehensive performance under lower second-order transition temperature condition.
Invention constitutes
The objective of the invention is to overcome weak point of the prior art and the low temperature elasticity polyacrylic ester water-proof emulsion of the each side high comprehensive performances such as the quick after tackiness of resistance to compression, resistance to deterioration and water tolerance of emulsion under the lower condition of a kind of second-order transition temperature is provided.
The objective of the invention is to realize by following approach.
Low temperature elasticity polyacrylic ester water-proof emulsion, comprise deionized water, initiator, mix monomer, emulsifying agent, extraordinary monomer and neutralizing agent, mix monomer comprise soft monomer and hard monomer, its structural feature is: with the high vinylformic acid higher alkyl esters of ester chain carbon atom number is main soft monomer, its ester chain carbon atom number 〉=8.
The present invention adopts the high vinylformic acid higher alkyl esters of ester chain carbon atom number as the main soft monomer in the mix monomer, its ester chain carbon atom number is more than or equal to 8, it has following characteristic: first, after the ester chain carbon atom number of acrylate monomer increases, its internal plasticization ability and hydrophobicity are strengthened, thereby improve the resistance to deterioration and the water tolerance of reacted emulsion polymer; The second, vinylformic acid higher alkyl esters of the present invention does not have pressure-sensitive character, thereby makes emulsion polymer have the quick after tackiness of good resistance to compression; The 3rd, when the ratio of vinylformic acid higher alkyl esters in prescription is bigger, the second-order transition temperature of polymkeric substance reduces, and therefore, can obtain to have different and second-order transition temperature that temperature is lower, this second-order transition temperature Tg≤-15 ℃ by the ratio of adjusting soft monomer.Therefore, the present invention not only can obtain to have the various low temperature elasticity polyacrylic ester water-proof emulsions of different glass temperature value, and have good resistance to compression quick after tackiness, resistance to deterioration and water tolerance in the ratio of adjusting soft monomer vinylformic acid higher alkyl esters.
Have mix monomer in the prescription of the anti-emulsion of low temperature elasticity polyacrylic ester, mix monomer comprises soft monomer and hard monomer, and soft monomer is the vinylformic acid higher alkyl esters, and hard monomer is a methyl methacrylate.And this mix monomer comprises mix monomer one and mix monomer two.
The component of mix monomer one and consumption are:
| Component | Consumption (total weight parts: 1000) |
| Methyl methacrylate | ????50～75 |
| Methacrylic acid dodecane ester | ????150～125 |
| Methacrylic acid | ????5 |
The component of mix monomer two and consumption are:
| Component | Consumption (total weight parts: 1000) |
| Methyl methacrylate | ????75～150 |
| Octyl acrylate | ????280～205 |
| Methacrylic acid | ????6 |
Like this, can adjust according to the amount ranges of the hard monomer methyl methacrylate in mix monomer one and the mix monomer two and soft monomer methacrylic acid dodecane ester and Octyl acrylate, and obtain various different glass temperature.
Has the surface tension that can reduce by two kinds or the multiple liquid that can not mix mutually in the prescription of the anti-emulsion of low temperature elasticity polyacrylic ester, make it form the additive of stable emulsion, emulsifying agent, this emulsifying agent comprises emulsifying agent one and emulsifying agent two, wherein emulsifying agent one is a reactive emulsifier, and emulsifying agent two is non-reactive emulsifier.
Like this, on non-reactive emulsifier basis, introduce reactive emulsifier, thereby strengthened the chemical stability of emulsion.
The component of reactive emulsifier one and consumption are:
| Component | Consumption (total weight parts: 1000) |
| The allyl group hydroxypropyl azochlorosulfonate acid sodium | ????2 |
| Sodium lauryl sulphate | ????2.9 |
| ??OP-50 | ????2.9 |
| ??H 2O | ????50 |
The component of non-reactive emulsifier two and consumption are:
| Component | Consumption (total weight parts: 1000) |
| Sodium lauryl sulphate | ????4 |
| ????OP-50 | ????3.6 |
| ????H 2O | ????80 |
Initiator in the prescription of low temperature elasticity polyacrylic ester water-proof emulsion comprises initiator one, initiator two and initiator three.
The component of initiator one and consumption are:
| Component | Consumption (total weight parts: 1000) |
| ????K 2S 2O 8 | ????0.3 |
| ????H 2O | ????10 |
The component of initiator two and consumption are:
| Component | Consumption (total weight parts: 1000) |
| ????K 2S 2O 8 | ????1.2 |
| ????H 2O | ????60 |
The component of initiator three and consumption are:
| Component | Consumption (total weight parts: 1000) |
| Tertbutyl peroxide | ????1.5 |
| ????H 2O | ????50 |
The component and the consumption of the neutralizing agent in the prescription of the anti-emulsion of low temperature elasticity polyacrylic ester are:
| Component | Consumption (total weight parts: 1000) |
| ????NaOH | ????10 |
| ????H 2O | ????30 |
Other components are respectively extraordinary monomer 70% allyl urea in the prescription of the anti-emulsion of low temperature elasticity polyacrylic ester, and its consumption is 4.6 per 1000 weight parts; Sanitas Kathon, its consumption are 2 per 1000 weight parts; Defoamer NXZ, consumption are 3 per 1000 weight parts; The consumption of deionized water is 115 per 1000 weight parts.
The production method of low temperature elasticity polyacrylic ester water-proof emulsion includes following steps:
1. preparation initiator one is prepared initiator two, preparation mix monomer one, preparation initiator three, preparation mix monomer two; A kind of header tank is provided, with the initiator one for preparing, initiator two, initiator three, mix monomer one, mix monomer two is squeezed into header tank, and is standby;
2. a kind of pre-emulsifying tank A is provided, each component raw material in the emulsifying agent one is added among pre-ization groove A stirring and dissolving and mixes, and progressively drip mix monomer one in the header tank, the limit edged is stirred to the stable pre-emulsion A of formation, and is standby.
3. a kind of pre-emulsifying tank B is provided, each component raw material in the emulsifying agent two is added, and add mix monomer two in the high groove, be stirred to and form stable pre-emulsion B, standby.
4. a kind of reactor is provided, and a kind of agitator adds deionized water in reactor, and the startup agitator stirs, heats up, add 1/5 pre-emulsion A, and add the initiator one in the header tank, initiation reaction fast, when temperature of reaction is increased to top temperature, first step of reaction is finished, and the adjustment temperature is a constant temperature, and balance drips initiator two and the remaining 4/5 pre-emulsion A in the header tank simultaneously, dropwise, keep constant temperature.
5. initiator three and the pre-emulsion B in the header tank of balance average rate dropping simultaneously dropwises, and adds extraordinary monomer, continues to keep constant temperature.
6. cooling adds neutralizing agent and neutralizes, and adds sanitas and defoamer respectively, and reinforced finishing stirs, and storage tank is squeezed in discharging.
Like this, produce this low temperature elasticity polyacrylic ester water-proof emulsion, when total weight parts is 1000, at first, 0.3 part of Potassium Persulfate K
2S
2O
8With 10 parts of water H
2One, 1.2 part of Potassium Persulfate K of O preparation initiator
2S
2O
8With 60 parts of water H
2O preparation two, 1.5 parts of tertbutyl peroxides of initiator and 50 parts of water H
2O prepares initiator three, 75 parts of methyl methacrylates, 125 parts of methacrylic acid dodecane esters and 5 parts of methacrylic acid preparation mix monomers one, 110 parts of methyl methacrylates, 245 parts of Octyl acrylates and 6 parts of methacrylic acid preparation mix monomers two are squeezed into header tank, and are standby; Then, in pre-emulsifying tank A, add the each component in the emulsifying agent one, 2 parts of allyl group hydroxypropyl azochlorosulfonate acid sodiums, 2.9 parts of sodium lauryl sulphate, 2.9 parts of polyoxyethylene nonylphenol ether OP-50 and 50 parts of water H
2O, stirring and dissolving and mix after, progressively drip the mix monomer one for preparing in the header tank, the limit edged is stirred to and forms stable pre-emulsion A, and is standby; In pre-emulsifying tank B, add the each component in the emulsifying agent two, 4 parts of sodium lauryl sulphate, 3.6 parts of polyoxyethylene nonylphenol ether OP-50,1 part of S-WAT and 80 parts of water H
2O, stirring and dissolving and mix after, add mix monomer two, be stirred to and form stable pre-emulsion B, standby; Then enter first step of reaction, in reactor, add 115 parts of deionized waters, and the startup agitator stirs, be warming up to 75 ℃, add 1/5 pre-emulsion A, and add the initiator one for preparing in the header tank, initiation reaction fast, when temperature of reaction was increased to top temperature, first step of reaction was promptly finished.After first step of reaction is finished, adjust homo(io)thermism, keeping constant temperature is 78～82 ℃, and balance drips initiator two and the residue 4/5 pre-emulsion A for preparing in the header tank simultaneously, and the dropping time is 1.5 hours, dropwises the back and continues to keep constant temperature 20 minutes; Continue simultaneously that the balance average rate drips initiator three and the pre-emulsion B for preparing in the header tank, the dropping time is 1 hour, after dropwising, adds 4.6 part of 70% allyl urea of extraordinary monomer, continues to keep 78～82 ℃ of constant temperature 2 hours; Be cooled to 40 ℃ then, add 10 parts of sodium hydroxide of neutralizing agent and 30 parts of water, and add 2 parts of loose Kathon of card of sanitas respectively, 3 parts of big gun agent NXZ that disappear, reinforced finishing continues to stir 0.5 hour, storage tank is squeezed in discharging, and the production of low temperature elasticity polyacrylic ester water-proof emulsion is finished.
In sum, the utility model has the following advantages compared to existing technology: adjust the monomeric ratio of soft or hard, can obtain to have the various low temperature elasticity polyacrylic ester water-proof emulsions of different glass temperature value, various emulsion polymers all have the quick after tackiness of good resistance to compression, resistance to deterioration and anti-, and reactive emulsifier makes the chemical stability of emulsion strengthen the consistency when having improved with the cement interworking.
Embodiment
Most preferred embodiment:
Low temperature elasticity polyacrylic ester water-proof emulsion, comprise deionized water, initiator, mix monomer, emulsifying agent, extraordinary monomer and neutralizing agent, mix monomer comprise soft monomer and hard monomer, be main soft monomer wherein with the high vinylformic acid higher alkyl esters of ester chain carbon atom number, its ester chain carbon atom number 〉=8.Hard monomer is a methyl methacrylate, and this mix monomer comprises mix monomer one and mix monomer two.
The component of mix monomer one and consumption are:
| Component | Consumption (total weight parts: 1000) |
| Methyl methacrylate | ????75 |
| Methacrylic acid dodecane ester | ????125 |
| Methacrylic acid | ????5 |
The component of mix monomer two and consumption are:
| Component | Consumption (total weight parts: 1000) |
| Methyl methacrylate | ????110 |
| Octyl acrylate | ????245 |
| Methacrylic acid | ????6 |
Has the surface tension that can reduce by two kinds or the multiple liquid that can not mix mutually in the prescription of the anti-emulsion of low temperature elasticity polyacrylic ester, make it form the additive of stable emulsion, emulsifying agent, this emulsifying agent comprises emulsifying agent one and emulsifying agent two, wherein emulsifying agent one is a reactive emulsifier, and emulsifying agent two is non-reactive emulsifier.
The component of reactive emulsifier one and consumption are:
| Component | Consumption (total weight parts: 1000) |
| The allyl group hydroxypropyl azochlorosulfonate acid sodium | ????2 |
| Sodium lauryl sulphate | ????2.9 |
| ??OP-50 | ????2.9 |
| ??H 2O | ????50 |
The component of non-reactive emulsifier two and consumption are:
| Component | Consumption (total weight parts: 1000) |
| Sodium lauryl sulphate | ????4 |
| ????OP-50 | ????3.6 |
| ????H 2O | ????80 |
Initiator in the prescription of low temperature elasticity polyacrylic ester water-proof emulsion comprises initiator one, initiator two and initiator three, and the component of initiator one and consumption are:
| Component | Consumption (total weight parts: 1000) |
| ????K 2S 2O 8 | ????0.3 |
| ????H 2O | ????10 |
The component of initiator two and consumption are:
| Component | Consumption (total weight parts: 1000) |
| ????K 2S 2O 8 | ????1.2 |
| ????H 2O | ????60 |
The component of initiator three and consumption are:
| Component | Consumption (total weight parts: 1000) |
| Tertbutyl peroxide | ????1.5 |
| ????H 2O | ????50 |
The component and the consumption of the neutralizing agent in the prescription of the anti-emulsion of low temperature elasticity polyacrylic ester are:
| Component | Consumption (total weight parts: 1000) |
| ????NaOH | ????10 |
| ????H 2O | ????30 |
Other components are respectively extraordinary monomer 70% allyl urea in the prescription of the anti-emulsion of low temperature elasticity polyacrylic ester, and its consumption is 4.6 per 1000 weight parts; Sanitas Kathon, its consumption are 2 per 1000 weight parts; Digestive pharmaceutical NXZ, consumption are 3 per 1000 weight parts; The consumption of deionized water is 115 per 1000 weight parts.
The production method of low temperature elasticity polyacrylic ester water-proof emulsion, when total weight parts is 1000,
1. 0.3 part of Potassium Persulfate K
2S
2O
8With 10 parts of water H
2One, 1.2 part of Potassium Persulfate K of O preparation initiator
2S
2O
8With 60 parts of water H
2O preparation two, 1.5 parts of tertbutyl peroxides of initiator and 50 parts of water H
2O prepares initiator three, 75 parts of methyl methacrylates, 125 parts of methacrylic acid dodecane esters and 5 parts of methacrylic acid preparation mix monomers one, 110 parts of methyl methacrylates, 245 parts of Octyl acrylates and 6 parts of methacrylic acid preparation mix monomers two are squeezed into header tank, and are standby;
2. in pre-emulsifying tank A, add the each component in the emulsifying agent one, 2 parts of allyl group hydroxypropyl azochlorosulfonate acid sodiums, 2.9 parts of sodium lauryl sulphate, 2.9 parts of polyoxyethylene nonylphenol ether OP-50 and 50 parts of water H
2O, stirring and dissolving and mix after, progressively drip the mix monomer one for preparing in the header tank, the limit edged is stirred to and forms stable pre-emulsion A, and is standby;
3. in pre-emulsifying tank B, add the each component in the emulsifying agent two, 4 parts of sodium lauryl sulphate, 3.6 parts of polyoxyethylene nonylphenol ether OP-50,1 part of S-WAT and 80 parts of water H
2O, stirring and dissolving and mix after, add mix monomer two, be stirred to and form stable pre-emulsion B, standby;
4. in reactor, add 115 parts of deionized waters, and start the agitator stirring, be warming up to 75 ℃, add 1/5 pre-emulsion A, and add the initiator one for preparing in the header tank, initiation reaction fast, when temperature of reaction was increased to top temperature, first step of reaction was promptly finished.After first step of reaction is finished, adjust homo(io)thermism, keeping constant temperature is 78～82 ℃, and balance drips initiator two and the residue 4/5 pre-emulsion A for preparing in the header tank simultaneously, and the dropping time is 1.5 hours, dropwises the back and continues to keep constant temperature 20 minutes;
5. continue in reactor simultaneously that the balance average rate drips initiator three and the pre-emulsion B for preparing in the header tank, the dropping time is 1 hour, after dropwising, adds 4.6 part of 70% allyl urea of extraordinary monomer, continues to keep 78～82 ℃ of constant temperature 2 hours;
6. be cooled to 40 ℃, add 10 parts of sodium hydroxide of neutralizing agent and 30 parts of water, and add 2 parts of loose Kathon of card of sanitas respectively, 3 parts of defoamer NXZ, reinforced finishing continues to stir 0.5 hour, and storage tank is squeezed in discharging.
It is same as the prior art that present embodiment is not stated part.
Claims (7)
1. low temperature elasticity polyacrylic ester water-proof emulsion, comprise deionized water, initiator, mix monomer, emulsifying agent, extraordinary monomer and neutralizing agent, mix monomer comprises soft monomer and hard monomer, it is characterized in that, be main soft monomer with the high vinylformic acid higher alkyl esters of ester chain carbon atom number, its ester chain carbon atom number 〉=8.
2. low temperature elasticity polyacrylic ester water-proof emulsion according to claim 1 is characterized in that: mix monomer comprises mix monomer one and mix monomer two, and mix monomer one adopts following component consumption:
Component Consumption (total weight parts: 1000)
Methyl methacrylate ????50～75
Methacrylic acid dodecane ester ????150～125
Methacrylic acid ????5
Mix monomer two adopts following component consumption:
Component Consumption (total weight parts: 1000)
Methyl methacrylate ????75～150
Octyl acrylate ????280～205
Methacrylic acid ????6
3. low temperature elasticity polyacrylic ester water-proof emulsion according to claim 1 is characterized in that: emulsifying agent comprises emulsifying agent one and emulsifying agent two, and wherein emulsifying agent one is a reactive emulsifier, and emulsifying agent two is non-reactive emulsifier.
4. low temperature elasticity polyacrylic ester water-proof emulsion according to claim 3 is characterized in that: reactive emulsifier one adopts following component consumption:
Component Consumption (total weight parts: 1000)
The allyl group hydroxypropyl azochlorosulfonate acid sodium ????2
Sodium lauryl sulphate ????2.9
??OP-50 ????2.9
??H
2O
????50
Non-reaction emulsifier two adopts following component consumption:
Component Consumption (total weight parts: 1000)
Sodium lauryl sulphate ????4
????OP-50 ????3.6
????H
2O
????80
5. low temperature elasticity polyacrylic ester water-proof emulsion according to claim 1, it is characterized in that: extraordinary monomer adopts 70% allyl urea, and consumption is 4.6 per 1000 weight parts.
6. low temperature elasticity polyacrylic ester water-proof emulsion according to claim 1, it is characterized in that: initiator comprises initiator one, initiator two and initiator three, initiator one adopts following component consumption:
Component Consumption (total weight parts: 1O00)
????K
2S
2O
8 ????0.3
????H
2O
????10
Initiator two adopts following component consumption:
Component Consumption (total weight parts: 1000)
????K
2S
2O
8 ????1.2
????H
2O
????60
Initiator three adopts following component consumption:
Component Consumption (total weight parts: 1000)
Tertbutyl peroxide ????1.5
????H
2O
????50
Neutralizing agent adopts following component consumption:
Component Consumption (total weight parts: 1000)
????NaOH ????10
????H
2O
????30
7. low temperature elasticity polyacrylic ester water-proof emulsion according to claim 1 is characterized in that: also have the Kathon sanitas of 2 parts of per 1000 weight parts and the NXZ defoamer of 3 parts of per 1000 weight parts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03158350 CN1246354C (en) | 2003-09-15 | 2003-09-15 | Low temperature elasticity polyacrylate waterproof emulsion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03158350 CN1246354C (en) | 2003-09-15 | 2003-09-15 | Low temperature elasticity polyacrylate waterproof emulsion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1597719A true CN1597719A (en) | 2005-03-23 |
| CN1246354C CN1246354C (en) | 2006-03-22 |
Family
ID=34660446
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03158350 Expired - Fee Related CN1246354C (en) | 2003-09-15 | 2003-09-15 | Low temperature elasticity polyacrylate waterproof emulsion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1246354C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102140266A (en) * | 2011-04-15 | 2011-08-03 | 北京秀珀科技发展有限公司 | Polymethylmethacrylate waterproof paint and preparation method thereof |
| CN101319124B (en) * | 2008-07-01 | 2012-05-02 | 山东诺贝特化工科技股份有限公司 | Preparation method of environment friendly high-density aqueous woodenware emulsion paint |
| CN103709310A (en) * | 2013-12-20 | 2014-04-09 | 西南石油大学 | Methacrylic acid-methyl methacrylate copolymer emulsion and preparation method and applications thereof |
| CN107304239A (en) * | 2016-04-19 | 2017-10-31 | 中建西部建设新疆有限公司 | A kind of new airtight dose and preparation method thereof for corrosion resistant concrete |
| CN107964069A (en) * | 2017-12-24 | 2018-04-27 | 王琪宇 | A kind of preparation method of tenacity acrylic's ester water-repellent paint |
| CN114656586A (en) * | 2022-04-08 | 2022-06-24 | 浙江理工大学 | Composite fluoride-free polyacrylate waterproof emulsion and preparation method and application thereof |
-
2003
- 2003-09-15 CN CN 03158350 patent/CN1246354C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101319124B (en) * | 2008-07-01 | 2012-05-02 | 山东诺贝特化工科技股份有限公司 | Preparation method of environment friendly high-density aqueous woodenware emulsion paint |
| CN102140266A (en) * | 2011-04-15 | 2011-08-03 | 北京秀珀科技发展有限公司 | Polymethylmethacrylate waterproof paint and preparation method thereof |
| CN102140266B (en) * | 2011-04-15 | 2013-05-29 | 广州秀珀化工股份有限公司 | Polymethylmethacrylate waterproof paint and preparation method thereof |
| CN103709310A (en) * | 2013-12-20 | 2014-04-09 | 西南石油大学 | Methacrylic acid-methyl methacrylate copolymer emulsion and preparation method and applications thereof |
| CN107304239A (en) * | 2016-04-19 | 2017-10-31 | 中建西部建设新疆有限公司 | A kind of new airtight dose and preparation method thereof for corrosion resistant concrete |
| CN107964069A (en) * | 2017-12-24 | 2018-04-27 | 王琪宇 | A kind of preparation method of tenacity acrylic's ester water-repellent paint |
| CN114656586A (en) * | 2022-04-08 | 2022-06-24 | 浙江理工大学 | Composite fluoride-free polyacrylate waterproof emulsion and preparation method and application thereof |
| CN114656586B (en) * | 2022-04-08 | 2023-03-28 | 浙江理工大学 | Composite fluoride-free polyacrylate waterproof emulsion and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1246354C (en) | 2006-03-22 |
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