CN103980441A - Associated thickening agent generated by rheologic and modified monomer and preparation method of associated thickening agent - Google Patents
Associated thickening agent generated by rheologic and modified monomer and preparation method of associated thickening agent Download PDFInfo
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- CN103980441A CN103980441A CN201410210590.0A CN201410210590A CN103980441A CN 103980441 A CN103980441 A CN 103980441A CN 201410210590 A CN201410210590 A CN 201410210590A CN 103980441 A CN103980441 A CN 103980441A
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Abstract
The invention discloses an associated thickening agent generated by a rheologic and modified monomer and a preparation method of the associated thickening agent. The associated thickening agent generated by the rheologic and modified monomer is characterized by being a polymer emulsion with solid content of 28-32%, wherein the polymer emulsion is formed by carrying out emulsion polymerization reaction on methacrylic acid (MAA) accounting for 38-42% of the total mass of a monomer, ethyl acrylate (EA) accounting for 46-50% of the total mass of the monomer and a docosyl-polyoxyethylene methacrylate and tristyrylphenol ethoxylate methacrylate mixture HPM-400 accounting for 10-13% of the total mass of the monomer; the adding amount of an emulsifier accounts for 6-9% of the weight of the monomer. The thickening agent prepared by the invention can be used for remarkably increasing the viscosity of water and can also be used for increasing the viscosity of a waterborne paint and improving the splashing resistance of the waterborne paint when used for the waterborne paint.
Description
Technical field
The present invention relates to a kind of thickener for coating, associative thickener of a kind of rheology modified monomer generation and preparation method thereof is particularly disclosed, belong to the thickening material field in coatings additive(s), thickening material of the present invention can be directly used in water-borne coatings, effectively improve the viscosity of water-borne coatings, improve the anti-performance of splashing of water-borne coatings.
Background technology
Thickening material is for improving water-based system viscosity and a kind of polymer builder that improves rheological.In the system that needs thickening, add a little thickening material, can increase the apparent viscosity of system, make it to reach requirement.Especially at water-borne coatings and sizing agent etc., can give workability and the physical and chemical stability energy of product fine.In coating, thickening material, as adjusting the rheological property of coating and the functional agent of water retention property, plays an important role in coating coating operation and coating performance improvement, and what application was wider at present is associative thickener.Associative thickener essence is the water-soluble polymers of hydrophobically modified, can be divided into hydrophobically modified association type urethane (HEUR) by its structure, the swelling emulsion of hydrophobically-modified alkali (HASE) and Natrosol Plus (HMHEC).Compared with traditional coating thickening material, associative thickener has good rheological property and good water retention property, is therefore applied to and in coating, has good effect.
Growing along with China's economy, the enhancing of Chinese air quality index PM2.5 Continued and national awareness of environment protection, organic solvent-free, oligosaprobic water-borne coatings are by the developing direction that is China's coating industry.
Emulsion paint is a kind of water-based system taking water as dispersion medium, and viscosity is conventionally lower, easily causes the sedimentation of pigment, filler, is not easy to construction, therefore, often need to improve viscosity, to ensure the package stability of emulsion paint and to ensure its brushing performance.Thickening material is in the market of a great variety, and wherein topmost have: clay, modified-cellulose and derivative thereof; Alkali swelling type polyacrylate(s); Associative thickener class.Compared with traditional thickening material, associative thickener with its excellent rheological property make coating in construction, show film plentiful, prevent the feature such as sagging, good leveling property.In synthetic thickening agent, the copolymer emulsion of vinylformic acid and lower alkyl ester thereof is a class efficient thickeners.Because this class thickening material has that own viscosity is low, thickening capabilities is strong, good stability, be difficult for the features such as mildew, the industry such as water-based adhesive and water-borne coatings, leather and paper conversion are widely used in abroad at present, and can partly replace natural cellulose thickening material, become indispensable additive in water-borne coatings.
The hydrophobically modified associative thickener of monomer processability excellence is stablized in the rheology modified monomer of this research and utilization Belgium Sol dimension and copolymerization, and rheology modified monomer is the mixture of docosyl polyethenoxy ether metacrylic acid ester and triphen ethylphenol polyethenoxy ether metacrylic acid ester.Low-shear viscosity and the high-shear viscosity of this thickening material to water-borne coatings has good balance, can meet the requirement of water-borne coatings to stability in storage and brushing performance.
Associative thickener has relevant patent report, such as CN1398929A, CN1840588A, CN101787231A and CN102675951A etc.Wherein CN1398929A discloses and has prepared associative thickener with vulcabond, alkyl alcohol and polyoxyethylene glycol etc.CN1840588A discloses in use polyoxyethylene glycol and vulcabond and has introduced associating monomer, and single functionality or two functionality compounds, prepare thickening material.CN101787231A discloses and has adopted hydrophobically modified monomer and unsaturated carboxylic acid monomer, carboxy-containing acid group's monoethylenically unsaturated monomer is not prepared thickening material.CN102675951A discloses and has adopted hydrophobically modified monomer and unsaturated carboxylic acid monomer, carboxy-containing acid group's monoethylenically unsaturated monomer and a kind of linking agent monomer that contains at least two unsaturated double-bonds are not prepared thickening material.
Summary of the invention
The object of the invention is to solve the not good problem of prior art products performance, associative thickener of a kind of rheology modified monomer generation and preparation method thereof is provided, it is a kind of polymerization stability, go out the quantity of slag few, can balance low-shear viscosity and high-shear viscosity, the associative thickener of the anti-excellent performance that splashes, can be used for multiple system, and suitability is wider.
The present invention is achieved in that the associative thickener that a kind of rheology modified monomer generates, it is characterized in that: described thickening material is to account for 38～42% of monomer total mass with methacrylic acid MAA, ethyl propenoate EA accounts for 46～50% of monomer total mass, phosphoric acid ester function monomer COPS-3 accounts for 0.2～0.5% of monomer total mass, the mixture HPM-400 of docosyl polyethenoxy ether metacrylic acid ester and triphen ethylphenol polyethenoxy ether metacrylic acid ester accounts for 10～13% of monomer total mass, the polymer emulsion that the solid content forming through emulsion polymerization is 28～32%, the addition of emulsifying agent is 6～9% of monomer weight, described phosphoric acid ester function monomer is the monomer with copolymerization stability, the emulsifying agent adopting in described emulsion polymerization is anionic emulsifier,
Described rheology modified monomer is the monomer with rheology modified function: docosyl polyethenoxy ether metacrylic acid ester, triphen ethylphenol polyethenoxy ether metacrylic acid ester,
The structural formula of described docosyl polyethenoxy ether metacrylic acid ester is:
，
The structural formula of described triphen ethylphenol polyethenoxy ether metacrylic acid ester is:
。
Described anionic emulsifier is not containing any one in carbon tridecanol sodium sulfate, straight-chain fatty alcohol sodium sulfate salt, fatty alcohol ether sulfate sodium salt, tridecyl ether sodium sulfate, sodium lauryl sulphate, fatty alcohol (ether) phosphate and the alcohol ether succinic acid monoester sodium salt of alkylphenol polyoxyethylene compounds APEO.
A preparation method for the associative thickener that above-mentioned rheology modified monomer generates, is characterized in that: described preparation method's concrete steps are:
The configuration of A, reaction raw materials, the composition of described reaction raw materials and mass percent are:
(1) monomer pre-emulsion:
Deionized water 15～20%,
Anionic emulsifier (carbon tridecanol sodium sulfate) 2～3%,
MAA (methacrylic acid) 11～13%,
EA 13～15%，
Rheology improves monomer (HPM-400) 2～5%,
(2) still bed material:
Deionized water 36～40%,
Anionic emulsifier (carbon tridecanol sodium sulfate) 0.3～0.5%,
Polymerization stabilizer (COPS-3) 0.1～0.2%,
(3) seed initiator:
Deionized water 1～2%,
Ammonium persulphate 0.05～0.1%,
(4) enter altogether initiator:
Deionized water 8～9%,
Ammonium persulphate 0.02～0.06%,
(5) after, add initiator:
Deionized water 1.5～2.0%,
Tertbutyl peroxide 0.03～0.05%,
Saccharosonic acid 0.03～0.04;
B, nitrogen protection, add still bed material and be heated to 85 DEG C;
C, anionic emulsifier and HPM-400 monomer dissolve, and add EA and MAA, and high-speed stirring, prepares pre-emulsion;
D, prepare seed initiator respectively, enter initiator and rear interpolation initiator altogether;
At the bottom of E, still, temperature is warmed up to 85 DEG C, adds 5% pre-emulsion and seed initiator, waits 10～15 minutes;
F, remaining monomer is entered to initiator together within three hours, drip;
G, slaking 30 minutes;
H, add rear interpolation initiator, be incubated 30～45 minutes;
Below I, cooling emulsion to 40 DEG C, regulate 8～9, the 120 orders filtration dischargings of pH value, make associative thickener.
The initiator adopting in emulsion polymerization process is scarcely dissolved in monomer, and is dissolved in external phase.Initiator has considerable influence to particle nucleation in emulsion polymerization systems.Bibliographical information, has surface-active initiator and has higher efficiency of initiation, and particle nucleation mechanism is mainly micella mechanism, and particle growth process occurs in micella, and particle stability is good.Ammonium persulphate has good surfactivity, easily separated go out SO
4(R), produce free group initiation reaction.So the present invention adopts ammonium persulphate to make initiator.
Above-mentioned rheology modified monomer also can be the mixture of docosyl polyethenoxy ether metacrylic acid ester and triphen ethylphenol polyethenoxy ether metacrylic acid ester and other compounds.
The described monomer with copolymerization stability also has: allyl hydroxyl sodium sulfonate, phosphoric acid ester function monomer, methyl-propyl sodium sulfonate, vinyl carbinol b-oxide, vinyl carbinol b-oxide ammonium sulfate etc.
Described fatty alcohol (ether) phosphate is: aromatic phosphoric acid ester, fatty alcohol (ether) phosphate etc.
Described alcohol ether succinic acid monoester sodium salt is: double tridecyl succinate sodium sulfonate etc.
The invention has the beneficial effects as follows:
1. phosphoric acid ester function monomer provides the stability in associative thickener building-up process, and less emulsion particle diameter improves freeze-thaw stability, improves mechanical stability, goes out the quantity of slag few, improves the white property of water resistant of water-borne coatings, reduces the addition of tensio-active agent;
2. rheology modified monomer HPM-400 is triphenyl ethyl phenoxy group polyethoxye ether metacrylic acid ester (SEM-25) and docosyl polyethoxye methacrylic ester (BEM) and other compounds, wherein BEM has unusual effect to increasing low-shear viscosity, SEM-25 has unusual effect to increasing high-shear viscosity, and HPM-400 has merged both advantages, can balance high-shear viscosity and low-shear viscosity under viscosity control there is more excellent performance and the wider scope of application.
Embodiment
Below by embodiment, the invention will be further described.
The associative thickener that a kind of rheology modified monomer of the present invention generates, with methacrylic acid MAA account for monomer total mass 38～42%, ethyl propenoate EA account for monomer total mass 46～50%, phosphoric acid ester function monomer COPS-3 account for monomer total mass 0.2～0.5%, the mixture HPM-400 of docosyl polyethenoxy ether metacrylic acid ester and triphen ethylphenol polyethenoxy ether metacrylic acid ester accounts for 10～13% of monomer total mass, the polymer emulsion that the solid content forming through emulsion polymerization is 28～32%; The addition of emulsifying agent is 6～9% of monomer weight.
Embodiment 1:
The preparation method's of the associative thickener that the rheology modified monomer of the present invention generates concrete steps are as follows:
The configuration of A, reaction raw materials, the composition of described reaction raw materials and weight part ratio are:
(1) monomer pre-emulsion:
Deionized water 89.21
Anionic emulsifier (carbon tridecanol sodium sulfate) 11.00
MAA 58.93
EA 70.71
Rheology improves monomer (HPM-400) 18.07
(2) still bed material:
Deionized water 192.38
Anionic emulsifier (carbon tridecanol sodium sulfate) 1.61
Polymerization stabilizer (COPS-3) 0.74
(3) seed initiator:
Deionized water 6.44
Ammonium persulphate 0.40
(4) enter altogether initiator:
Deionized water 40.23
Ammonium persulphate 0.22
(5) after, add initiator:
Deionized water 9.66
Tertbutyl peroxide 0.24
Saccharosonic acid 0.16
B, nitrogen protection, add still bed material and be heated to 85 DEG C;
C, anionic emulsifier and HPM-400 monomer dissolve, and add EA and MAA, and high-speed stirring, prepares pre-emulsion;
D, prepare seed initiator respectively, enter initiator and rear interpolation initiator altogether;
At the bottom of E, still, temperature is warmed up to 85 DEG C, adds 5% pre-emulsion and seed initiator, waits 10～15 minutes;
F, remaining monomer is entered to initiator together within three hours, drip;
G, slaking 30 minutes;
H, add rear interpolation initiator, be incubated 30～45 minutes;
Below I, cooling emulsion to 40 DEG C, regulate 8～9, the 120 orders filtration dischargings of pH value, make associative thickener.
The thickening material 1% concentration of aqueous solution viscosity that the present embodiment makes is (lower No. 4 rotors of room temperature, 60 revs/min) 3300mPaS, to pure-acrylic emulsion (viscosity < 100 mPaS), add 2% thickening material after viscosity reach 96.5KU.
Embodiment 2:
The preparation method's of the associative thickener that the rheology modified monomer of the present invention generates concrete steps are as follows:
The configuration of A, reaction raw materials, the composition of described reaction raw materials and weight part ratio are:
(1) monomer pre-emulsion:
Deionized water 89.21
Anionic emulsifier (carbon tridecanol sodium sulfate) 10.97
MAA 57.80
EA 71.89
Rheology improves monomer (HPM400) 17.57
(2) still bed material:
Deionized water 192.81
Anionic emulsifier (carbon tridecanol sodium sulfate) 1.61
Polymerization stabilizer (COPS-3) 0.69
(3) seed initiator:
Deionized water 6.44
Ammonium persulphate 0.40
(4) enter altogether initiator:
Deionized water 40.23
Ammonium persulphate 0.22
(5) after, add initiator:
Deionized water 9.66
Tertbutyl peroxide 0.24
Saccharosonic acid 0.16
Other are with embodiment 1.
The thickening material 1% concentration of aqueous solution viscosity that the present embodiment makes is (lower No. 4 rotors of room temperature, 60 revs/min) 3000mPaS, to pure-acrylic emulsion (viscosity < 100 mPaS), add 2% thickening material after viscosity reach 94.5KU.
Embodiment 3:
The preparation method's of the associative thickener that the rheology modified monomer of the present invention generates concrete steps are as follows:
The configuration of A, reaction raw materials, the composition of described reaction raw materials and weight part ratio are:
(1) monomer pre-emulsion:
Deionized water 89.21
Anionic emulsifier (carbon tridecanol sodium sulfate) 10.97
MAA 58.93
EA 70.71
Rheology improves monomer (HPM-400) 18.07
(2) still bed material:
Deionized water 192.40
Anionic emulsifier (carbon tridecanol sodium sulfate) 1.61
Polymerization stabilizer (COPS-3) 0.69
(3) seed initiator:
Deionized water 6.44
Ammonium persulphate 0.40
(4) enter altogether initiator:
Deionized water 40.23
Ammonium persulphate 0.22
(5) after, add initiator:
Deionized water 9.66
Tertbutyl peroxide 0.24
Saccharosonic acid 0.16
Other are with embodiment 1.
The thickening material 1% concentration of aqueous solution viscosity that the present embodiment makes is (lower No. 4 rotors of room temperature, 60 revs/min) 3500mPaS, to pure-acrylic emulsion (viscosity < 100 mPaS), add 2% thickening material after viscosity reach 98.0KU.
Claims (3)
1. the associative thickener that rheology modified monomer generates, it is characterized in that: described thickening material be with methacrylic acid MAA account for monomer total mass 38～42%, ethyl propenoate EA account for monomer total mass 46～50%, phosphoric acid ester function monomer COPS-3 account for monomer total mass 0.2～0.5%, the mixture HPM-400 of docosyl polyethenoxy ether metacrylic acid ester and triphen ethylphenol polyethenoxy ether metacrylic acid ester accounts for 10～13% of monomer total mass, the polymer emulsion that the solid content forming through emulsion polymerization is 28～32%; The addition of emulsifying agent is 6～9% of monomer weight; Described phosphoric acid ester function monomer is the monomer with copolymerization stability; The emulsifying agent adopting in described emulsion polymerization is anionic emulsifier;
Described rheology modified monomer is the monomer with rheology modified function: docosyl polyethenoxy ether metacrylic acid ester, triphen ethylphenol polyethenoxy ether metacrylic acid ester,
The structural formula of described docosyl polyethenoxy ether metacrylic acid ester is:
，
The structural formula of described triphen ethylphenol polyethenoxy ether metacrylic acid ester is:
。
2. the associative thickener generating according to the rheology modified monomer described in claim 1, is characterized in that: described anionic emulsifier is not containing any one in carbon tridecanol sodium sulfate, straight-chain fatty alcohol sodium sulfate salt, fatty alcohol ether sulfate sodium salt, tridecyl ether sodium sulfate, sodium lauryl sulphate, fatty alcohol (ether) phosphate and the alcohol ether succinic acid monoester sodium salt of alkylphenol polyoxyethylene compounds APEO.
3. a preparation method for the associative thickener that in claim 1 or 2, described in any one, rheology modified monomer generates, is characterized in that: described preparation method's concrete steps are:
The configuration of A, reaction raw materials, the composition of described reaction raw materials and mass percent are:
Monomer pre-emulsion:
Deionized water 15～20%,
Anionic emulsifier (carbon tridecanol sodium sulfate) 2～3%,
MAA (methacrylic acid) 11～13%,
EA 13～15%，
Rheology improves monomer (HPM-400) 2～5%,
(2) still bed material:
Deionized water 36～40%,
Anionic emulsifier (carbon tridecanol sodium sulfate) 0.3～0.5%,
Polymerization stabilizer (COPS-3) 0.1～0.2%,
(3) seed initiator:
Deionized water 1～2%,
Ammonium persulphate 0.05～0.1%,
(4) enter altogether initiator:
Deionized water 8～9%,
Ammonium persulphate 0.02～0.06%,
(5) after, add initiator:
Deionized water 1.5～2.0%,
Tertbutyl peroxide 0.03～0.05%,
Saccharosonic acid 0.03～0.04;
B, nitrogen protection, add still bed material and be heated to 85 DEG C;
C, anionic emulsifier and HPM-400 monomer dissolve, and add EA and MAA, and high-speed stirring, prepares pre-emulsion;
D, prepare seed initiator respectively, enter initiator and rear interpolation initiator altogether;
At the bottom of E, still, temperature is warmed up to 85 DEG C, adds 5% pre-emulsion and seed initiator, waits 10～15 minutes;
F, remaining monomer is entered to initiator together within three hours, drip;
G, slaking 30 minutes;
H, add rear interpolation initiator, be incubated 30～45 minutes;
Below I, cooling emulsion to 40 DEG C, regulate 8～9, the 120 orders filtration dischargings of pH value, make associative thickener.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105801767A (en) * | 2016-03-30 | 2016-07-27 | 山东源根化学技术研发有限公司 | Preparing method for paint rheolytic moisture holding regulator |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060008431A1 (en) * | 2004-06-15 | 2006-01-12 | Celine Farcet | Copolymer functionalized with an iodine atom, compositions comprising the copolymer and treatment processes |
| CN101787231A (en) * | 2010-01-27 | 2010-07-28 | 济南大学 | Hydrophobic modified associative thickener and preparation method thereof |
| CN102675951A (en) * | 2012-05-22 | 2012-09-19 | 济南大学 | Water-repellent modified association thickening agent and preparation method thereof |
| CN103788283A (en) * | 2014-01-17 | 2014-05-14 | 广州市东雄化工有限公司 | Hydrophobic modified associative thickener and preparation method thereof |
-
2014
- 2014-05-19 CN CN201410210590.0A patent/CN103980441A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060008431A1 (en) * | 2004-06-15 | 2006-01-12 | Celine Farcet | Copolymer functionalized with an iodine atom, compositions comprising the copolymer and treatment processes |
| CN101787231A (en) * | 2010-01-27 | 2010-07-28 | 济南大学 | Hydrophobic modified associative thickener and preparation method thereof |
| CN102675951A (en) * | 2012-05-22 | 2012-09-19 | 济南大学 | Water-repellent modified association thickening agent and preparation method thereof |
| CN103788283A (en) * | 2014-01-17 | 2014-05-14 | 广州市东雄化工有限公司 | Hydrophobic modified associative thickener and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105801767A (en) * | 2016-03-30 | 2016-07-27 | 山东源根化学技术研发有限公司 | Preparing method for paint rheolytic moisture holding regulator |
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Application publication date: 20140813 |