CN103087255A - Crosslinking fluorine modified acrylic ester nanometer polymer emulsion and preparation method thereof - Google Patents
Crosslinking fluorine modified acrylic ester nanometer polymer emulsion and preparation method thereof Download PDFInfo
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Abstract
The invention relates to crosslinking fluorine modified acrylic ester nanometer polymer emulsion and a preparation method thereof. The crosslinking fluorine modified acrylic ester nanometer polymer emulsion is prepared from the following six main components through half-continuous seed emulsion polymerization, wherein in the six main components, a fluorine monomer accounts for 10-25 percent of the whole monomer mass, an acrylic ester monomer accounts for 20-30 percent of the whole monomer mass, a metacrylic ester monomer accounts for 10-25 percent of the whole monomer mass, 4) crosslinking monometer methacrylic acid hydroxyalkyl ether accounts for 5-10 percent of the whole monomer mass, 5) a dimeric surfactant accounts for 1.5-3.5 percent of the whole monomer mass, and 6) a water-soluble azo initiator accounts for 1-3 percent of the whole monomer mass. The crosslinking fluorine modified acrylic ester nanometer polymer emulsion has the advantage that a latex film is high in hydrophobicity, weather resistance, chemical resistance and high-temperature resistance after nano emulsion is subjected to film formation.
Description
Technical field
The present invention relates to a kind of cross-linking type fluorin modified crylic acid ester nanometer polymer emulsion and preparation method thereof, this polymer emulsion can be used for the fields such as coating, tackiness agent, finishing composition and hide finishes.
Background technology
The fluorinated acrylate polymer emulsion had both kept good film-forming properties and the sticking power of polyacrylate dispersion, has to a certain extent again the premium properties of fluoropolymer, show hydrophobic, oleophobic and antifouling surface property, be widely used in fields such as high-performance coating, textile finishing, leather and packings.And the fluorine carbon-nano polymer emulsion also has advantages of following uniqueness: perviousness, wettability are good, to the strong adhesion of ground; Particle diameter is little, can form compactness and film, and the coating film gloss of formation is high; Because particle diameter is little, can realize performance complement with conventional emulsions, improve smoothness and the glossiness of filming; The molecular chain of fluorine carbon-nano polymer emulsion has higher conformational energy, and the shock-resistance of filming, snappiness, hardness, wear resistance are good, and are subject to extensive concern and attention.
Microemulsion polymerization method is a kind of method for preparing the fluorine carbon-nano polymer emulsion commonly used.In common oil/water (O/W) microemulsion system, in order to dissolve the monomer of content relatively low (＜10%), often need high surfactant concentration (7-15%), and have a large amount of hungry area bundles in system, the existence of a large amount of emulsifying agents reduces water tolerance, compactness, the sticking power of filming greatly.Above-mentioned drawbacks limit microemulsion in industrial application, and affect the performance of fluorine carbon-nano polymer emulsion excellent properties, limited further developing of fluorine carbon-nano polymer emulsion.Seeking new emulsification system and the initiator system that adapts thereof, reduce emulsifier, improve emulsion solid content, give full play to the performance of fluorine carbon-nano polymer emulsion, is one of focus of present fluorine carbon-nano polymer emulsion research and development.
Summary of the invention
In order to solve above-mentioned technical problem, an object of the present invention is to provide a kind of cross-linking type fluorin modified crylic acid ester nanometer polymer emulsion, the particle diameter of this nanoemulsions is 30-80nm, after 80 ℃ of lower film forming, the contact angle with water of filming is greater than 90o.Second purpose of the present invention is to provide a kind of preparation method of above-mentioned cross-linking type fluorin modified crylic acid ester nanometer polymer emulsion,
In order to realize first above-mentioned purpose, the present invention has adopted following technical scheme:
A kind of cross-linking type fluorin modified crylic acid ester nanometer polymer emulsion, this polymer emulsion is by following six main ingredients, be prepared from through semi-continuous seed emulsion polymerization, this emulsion appearance is fine and smooth and be translucent with blue-fluorescence, pH value 7.5 ± 0.5, solid content 25 ± 5%, emulsion particle diameter 30-80nm, by weight percentage in six main ingredients:
1) fluorine monomer accounts for the 10-25% of whole monomer mass;
2) acrylic ester monomer accounts for the 20-30% of whole monomer mass;
3) the methyl acrylic ester monomer accounts for the 10-25% of whole monomer mass;
4) cross-linking type monomer hydroxyalkyl methacrylate accounts for the 5-10% of whole monomer mass;
5) Gemini surface active agent accounts for the 1.5-3.5% of whole monomer mass;
6) water-soluble azo initiator accounts for the 1-3% of whole monomer mass.
As preferably, above-mentioned fluorine monomer is selected from one or more in Hexafluorobutyl mathacrylate, vinylformic acid hexafluoro butyl ester, dodecafluoroheptyl methacrylate, methacrylic acid ten trifluoro monooctyl esters and C12 acrylic fluorine ester.
As preferably, above-mentioned acrylic ester monomer is selected from one or more in ethyl propenoate, propyl acrylate, butyl acrylate and Isooctyl acrylate monomer.
As preferably, above-mentioned methyl acrylic ester monomer comprises one or more in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, n octyl methacrylate and Isooctyl methacrylate.
As preferably, above-mentioned cross-linking type monomer comprises one or more in 2-Hydroxy ethyl acrylate, vinylformic acid-2-hydroxyl butyl ester, vinylformic acid-3-hydroxy propyl ester, methacrylic acid-2-hydroxy methacrylate, methacrylic acid-2-hydroxyl butyl ester and methacrylic acid-2-hydroxy propyl ester.
As preferably, the above-mentioned Gemini surface active agent in order to emulsification is quaternary ammonium salt cationic Gemini surface active agent or amide group cation Gemini surfactant or their mixture.
As preferably, the above-mentioned water-soluble azo initiator in order to cause is 2,2'-azo [2-(2-tetrahydroglyoxaline-2-yl) propane] dihydrochloride or 2,2 '-azo 2-methyl-propyl amidine dihydrochloride or their mixture.
In order to realize second above-mentioned purpose, the present invention has adopted following technical scheme:
The preparation method of the cross-linking type fluorin modified crylic acid ester nanometer polymer emulsion that a kind of above-mentioned any one technical scheme is described, the method comprises the following steps:
1) first the 10-30% of mix monomer is prepared into seed emulsion, polymerization reaction time is 20-40min;
2) then adopt semi-continuous seed emulsion polymerization technique, polymerization temperature is that 75-85 ℃, polymerization time are 2.5-4.0h;
3) be warming up at last 90 ℃, continue insulation 30-45min, be cooled to 40 ℃, the ammoniacal liquor with 20% is regulated the pH value, filters discharging.
The present invention utilizes Gemini surface active agent to replace conventional tensio-active agent, use water miscible azo initiator to replace conventional persulfate initiator, and introduce self-cross linking monomer in main monomer, adopt emulsion polymerisation process to prepare cross-linking type fluorin modified crylic acid ester nanometer polymer emulsion.Its outward appearance is fine and smooth and be translucent with blue-fluorescence, pH value 7.5 ± 0.5, and solid content 25 ± 5%, emulsion particle diameter 30-80nm, this polymer emulsion are after 80 ℃ of lower film forming, and the contact angle with water of filming is higher than 90o.The nanoemulsions of gained has the characteristic that particle diameter is little, emulsifier content is little, solid content is high.After the nanoemulsions film forming, latex film has excellent hydrophobicity, weathering resistance, chemical resistant properties and high temperature resistant.
Technical superiority of the present invention is:
1, contain a large amount of fluorine atoms on the molecular chain of emulsion.After polymer emulsion oven dry film forming, most of fluorine atoms all are enriched in the outside surface of filming, and due to the unique property of C-F, causing films has excellent hydrophobicity, weathering resistance, chemical resistant properties and high temperature resistant;
2, the introducing of cross-linking type monomer causes polymer molecule to pass through reaction between functional group and crosslinking curing, and the formation network structure improves polymkeric substance force of cohesion, and after the polymer emulsion film forming, the thermotolerance of filming, water tolerance and use temperature are further enhanced;
3, due to the molecular structure of Gemini surface active agent uniqueness, cause it to have higher surfactivity, lower micelle-forming concentration, better stability of emulsion and froth stability etc. than conventional surfactant.Use Gemini surface active agent as emulsifying agent, reduce emulsifier, improve monomer content, the drawback that the existence that has overcome a large amount of emulsifying agents makes the performances such as the water tolerance of latex film, compactness, sticking power greatly reduce;
4, water miscible azo initiator trigger rate is fast, cause in the vinyl monomer process and induced decomposition can not occur, can reach higher transformation efficiency under relatively mild condition, obtain the polymkeric substance of high molecular weight, and residual initiator not affect the stability of polymkeric substance.
Fig. 1,2: the contact angle with water of filming after the median size of the nanoemulsions that makes by embodiment 1 and emulsion oven dry film forming thereof; Fig. 1 emulsion median size (25.38nm), Fig. 2 contact angle (96.2 °) with water of filming.
Fig. 3,4: the contact angle with water of filming after the median size of the nanoemulsions that makes by embodiment 2 and emulsion oven dry film forming thereof; Fig. 3 emulsion median size (47.80nm), Fig. 4 contact angle (99.0 °) with water of filming.
Embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this.
Embodiment 1
In the 250mL four-hole boiling flask of agitator, reflux condensing tube, dropping funnel is housed, add the Gemini surface active agent of 1.25g and the deionized water of 80.00g, stir and warming-in-water to 80 ℃.The mix monomer of dropping 10% and 10% initiator solution in 15min, dropwise follow-up continuation of insurance temperature 15min respectively.Then remaining initiator emulsion and mix monomer are added drop-wise in 3.0h in four-hole boiling flask, after dropwising, are warming up to 90 ℃, continue insulation 30min.Be cooled to 40 ℃, regulate the pH value with ammoniacal liquor, namely make the fluorine carbon-nano polymer emulsion of cross-linking type after the filtration discharging.The methacrylic acid of the methyl methacrylate of the butyl acrylate that consists of 20.00g of mix monomer, 10.00g, 10.00g vinylformic acid hexafluoro butyl ester, 2.00g-2-hydroxy propyl ester wherein; The content of initiator solution is the water-soluble azo initiator 2 of 0.50g, and 2'-azo [2-(2-tetrahydroglyoxaline-2-yl) propane] dihydrochloride is dissolved in the deionized water of 20.00g.
Embodiment 2
In the 250mL four-hole boiling flask of agitator, reflux condensing tube, dropping funnel is housed, add the Gemini surface active agent of 1.00g and the deionized water of 80.00g, stir and warming-in-water to 80 ℃.The mix monomer of dropping 20% and 20% initiator solution in 20min, dropwise follow-up continuation of insurance temperature 15min respectively.Then remaining initiator emulsion and mix monomer are added drop-wise in 3.0h in four-hole boiling flask, after dropwising, are warming up to 90 ℃, continue insulation 30min.Be cooled to 40 ℃, regulate the pH value with ammoniacal liquor, namely make the fluorine carbon-nano polymer emulsion of cross-linking type after the filtration discharging.The methacrylic acid of the methyl methacrylate of the butyl acrylate that consists of 15.00g of mix monomer, 15.00g, 10.00g dodecafluoroheptyl methacrylate, 2.00g-2-hydroxy propyl ester wherein; The content of initiator solution is the water-soluble azo initiator 2 of 1.00g, and 2 '-azo 2-methyl-propyl amidine dihydrochloride is dissolved in the deionized water of 20.00g.
Embodiment 3
In the 250mL four-hole boiling flask of agitator, reflux condensing tube, dropping funnel is housed, add the Gemini surface active agent of 0.75g and the deionized water of 80.00g, stir and warming-in-water to 80 ℃.The mix monomer of dropping 10% and 10% initiator solution in 15min, dropwise follow-up continuation of insurance temperature 15min respectively.Then remaining initiator emulsion and mix monomer are added drop-wise in 3.0h in four-hole boiling flask, after dropwising, are warming up to 90 ℃, continue insulation 30min.Be cooled to 40 ℃, regulate the pH value with ammoniacal liquor, namely make the fluorine carbon-nano polymer emulsion of cross-linking type after the filtration discharging.The wherein methyl methacrylate of the butyl acrylate that consists of 20.00g of mix monomer, 10.00g, 10.00g Hexafluorobutyl mathacrylate, 2.00g vinylformic acid-2-hydroxyl butyl ester; The content of initiator solution is the water-soluble azo initiator 2 of 1.00g, and 2'-azo [2-(2-tetrahydroglyoxaline-2-yl) propane] dihydrochloride is dissolved in the deionized water of 20.00g.
Embodiment 4
In the 250mL four-hole boiling flask of agitator, reflux condensing tube, dropping funnel is housed, add the Gemini surface active agent of 0.50g and the deionized water of 80.00g, stir and warming-in-water to 80 ℃.The mix monomer of dropping 20% and 20% initiator solution in 20min, dropwise follow-up continuation of insurance temperature 15min respectively.Then remaining initiator emulsion and mix monomer are added drop-wise in 3.0h in four-hole boiling flask, after dropwising, are warming up to 90 ℃, continue insulation 30min.Be cooled to 40 ℃, regulate the pH value with ammoniacal liquor, namely make the fluorine carbon-nano polymer emulsion of cross-linking type after the filtration discharging.The methacrylic acid of the methyl methacrylate of the butyl acrylate that consists of 20.00g of mix monomer, 10.00g, 10.00g dodecafluoroheptyl methacrylate, 2.00g-2-hydroxy propyl ester wherein; The content of initiator solution is the water-soluble azo initiator 2 of 0.75g, and 2 '-azo 2-methyl-propyl amidine dihydrochloride is dissolved in the deionized water of 20.00g.
Embodiment 5
In the 250mL four-hole boiling flask of agitator, reflux condensing tube, dropping funnel is housed, add the Gemini surface active agent of 1.00g and the deionized water of 80.00g, stir and warming-in-water to 80 ℃.The mix monomer of dropping 30% and 30% initiator solution in 25min, dropwise follow-up continuation of insurance temperature 15min respectively.Then remaining initiator emulsion and mix monomer are added drop-wise in 3.0h in four-hole boiling flask, after dropwising, are warming up to 90 ℃, continue insulation 30min.Be cooled to 40 ℃, regulate the pH value with ammoniacal liquor, namely make the fluorine carbon-nano polymer emulsion of cross-linking type after the filtration discharging.The methacrylic acid of the methyl methacrylate of the butyl acrylate that consists of 20.00g of mix monomer, 10.00g, 10.00gC12 acrylic fluorine ester, 2.00g-2-hydroxy methacrylate wherein; The content of initiator solution is the water-soluble azo initiator 2 of 0.75g, and 2'-azo [2-(2-tetrahydroglyoxaline-2-yl) propane] dihydrochloride is dissolved in the deionized water of 20.00g.
Claims (8)
1. cross-linking type fluorin modified crylic acid ester nanometer polymer emulsion, it is characterized in that: this polymer emulsion is by following six main ingredients, be prepared from through semi-continuous seed emulsion polymerization, this emulsion appearance is fine and smooth and be translucent with blue-fluorescence, pH value 7.5 ± 0.5, solid content 25 ± 5%, emulsion particle diameter 30-80nm, by weight percentage in six main ingredients:
1) fluorine monomer accounts for the 10-25% of whole monomer mass;
2) acrylic ester monomer accounts for the 20-30% of whole monomer mass;
3) the methyl acrylic ester monomer accounts for the 10-25% of whole monomer mass;
4) cross-linking type monomer hydroxyalkyl methacrylate accounts for the 5-10% of whole monomer mass;
5) Gemini surface active agent accounts for the 1.5-3.5% of whole monomer mass;
6) water-soluble azo initiator accounts for the 1-3% of whole monomer mass.
2. cross-linking type fluorin modified crylic acid ester nanometer polymer emulsion according to claim 1, it is characterized in that: fluorine monomer is selected from one or more in Hexafluorobutyl mathacrylate, vinylformic acid hexafluoro butyl ester, dodecafluoroheptyl methacrylate, methacrylic acid ten trifluoro monooctyl esters and C12 acrylic fluorine ester.
3. cross-linking type fluorin modified crylic acid ester nanometer polymer emulsion according to claim 1, it is characterized in that: acrylic ester monomer is selected from one or more in ethyl propenoate, propyl acrylate, butyl acrylate and Isooctyl acrylate monomer.
4. cross-linking type fluorin modified crylic acid ester nanometer polymer emulsion according to claim 1, it is characterized in that: the methyl acrylic ester monomer comprises one or more in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, butyl methacrylate, n octyl methacrylate and Isooctyl methacrylate.
5. cross-linking type fluorin modified crylic acid ester nanometer polymer emulsion according to claim 1, it is characterized in that: the cross-linking type monomer comprises one or more in 2-Hydroxy ethyl acrylate, vinylformic acid-2-hydroxyl butyl ester, vinylformic acid-3-hydroxy propyl ester, methacrylic acid-2-hydroxy methacrylate, methacrylic acid-2-hydroxyl butyl ester and methacrylic acid-2-hydroxy propyl ester.
6. according to claim 1 ~ 5 described cross-linking type fluorin modified crylic acid of any one claim ester nanometer polymer emulsions, it is characterized in that: the Gemini surface active agent in order to emulsification is quaternary ammonium salt cationic Gemini surface active agent or amide group cation Gemini surfactant or their mixture.
7. according to claim 1 ~ 5 described cross-linking type fluorin modified crylic acid of any one claim ester nanometer polymer emulsions, it is characterized in that: the water-soluble azo initiator in order to initiation is 2,2'-azo [2-(2-tetrahydroglyoxaline-2-yl) propane] dihydrochloride or 2,2 '-azo 2-methyl-propyl amidine dihydrochloride or their mixture.
8. the preparation method of the described cross-linking type fluorin modified crylic acid of claim 1 ~ 5 an any one claim ester nanometer polymer emulsion, the method comprises the following steps:
1) first the 10-30% of mix monomer is prepared into seed emulsion, polymerization reaction time is 20-40min;
2) then adopt semi-continuous seed emulsion polymerization technique, polymerization temperature is that 75-85 ℃, polymerization time are 2.5-4.0h;
3) be warming up at last 90 ℃, continue insulation 30-45min, be cooled to 40 ℃, the ammoniacal liquor with 20% is regulated the pH value, filters discharging.
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| CN104449154A (en) * | 2014-11-28 | 2015-03-25 | 合肥工业大学 | Water-based chromium-free fingerprint-resistant paint for galvanized steel plate |
| CN104710557A (en) * | 2014-12-31 | 2015-06-17 | 佛山市顺德区巴德富实业有限公司 | Fluorine-containing acrylate emulsion and preparation method thereof |
| CN105601797A (en) * | 2015-12-31 | 2016-05-25 | 徐宪 | Environment-friendly fluorine-containing nanometer positive ion acrylic ester polymer emulsion and preparation method thereof |
| CN106565891A (en) * | 2016-11-10 | 2017-04-19 | 上海英威喷墨科技有限公司 | Organic fluorine modified polyacrylate nanometer emulsion and nanometer composite adhesive |
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| CN112679678A (en) * | 2020-12-28 | 2021-04-20 | 国家能源集团宁夏煤业有限责任公司 | Acrylic ester emulsion and preparation method thereof |
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Effective date of registration: 20130603 Address after: 313300, Zhejiang County, Huzhou Province, Anji County, Zhenkang mountain Kang Shan Industrial Function Zone Applicant after: Anji Wanguo Paint Co., Ltd. Address before: 313300, Zhejiang County, Huzhou Province, Anji County, Zhenkang mountain Kang Shan Industrial Function Zone Applicant before: Shao Yijiang |
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