CN100564427C - A kind of fluorine-containing POSS acrylate block copolymer resin and synthetic method thereof - Google Patents
A kind of fluorine-containing POSS acrylate block copolymer resin and synthetic method thereof Download PDFInfo
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Abstract
A kind of fluorine-containing POSS acrylate block copolymer resin and synthetic method thereof relate to a kind of acrylate copolymer resin and synthetic method thereof.A kind of fluorine-containing polyhedral oligomeric silsesquioxane acrylate block copolymer resin and synthetic method thereof are provided.Molecular weight of copolymer Mn=20000～60000, Mn/Mw=1.1～1.5, the contact angle of coating and water is 85～120 ° after the film forming.Add by each component and to react to such an extent that have an end capped methyl methacrylate performed polymer of Br in reaction vessel; Again with CuBr, PMDETA, F-POSS reaction; To react back solution remove behind the catalyzer with methanol extraction filter, vacuum-drying is to constant weight, get final product organic-inorganic hybrid nanometer bunch fluorinated acrylate block copolymer resin.This polymer powder is dissolved in ethyl acetate, acetone, 1, the 2-ethylene dichloride, dioxane in pimelinketone or their mixture, can carry out the brushing film forming.
Description
Technical field
The present invention relates to a kind of acrylate copolymer resin and synthetic method thereof, especially organic-inorganic hybrid nanometer bunch fluorine-containing polyhedral oligomeric silsesquioxane (POSS) replaces (methyl) acrylate based block copolymer.
Background technology
Fluorine is the element of electronegativity maximum in the periodic table of elements, has the strongest electronegativity, minimum polarizability, and atomic radius is only second to hydrogen, short and the bond energy big (up to 485kJ/mol, being far longer than the bond energy 422kJ/mol of carbon-carbon bond) of the bond distance of carbon-fluorine bond (Yang Tingting, etc. the polymer circular, 2003,6:13-18).In the fluoropolymer because the carbon-fluorine bond bond distance is short, can encase the carbon carbon backbone chain closely, simultaneously when the fluorinated polymer film forming, fluoro-containing group can be sent to the top layer enrichment certainly, make the fluoropolymer stable physical property, weather resistance and chemical proof good (Zhou Xiaodong, Sun Daoxing. coating technology and digest, 2004,25 (3): 7-10).
For the utilization that improves fluorine resin and with the over-all properties that improves resin, can adopt two kinds of methods of blend and copolymerization to prepare the fluorine modified resins.Blending and modifying is that fluorochemical acrylate polymer is mixed according to a certain ratio with other polymkeric substance.Zhang Kan etc. (Zhang Kan, etc. Tsing-Hua University's journal (natural science edition), 2001,41 (12); Zhang Kan, etc. fine chemistry industry, 2001,18 (2): 100-102) adopt blend and two kinds of methods of in-situ emulsion polymerization to prepare the polyacrylate dispersion of fluorine emulsion modification.When the fluorine emulsion massfraction was big, the water tolerance and the hardness of glued membrane were significantly improved, and just are significantly improved with the performance of emulsion polymerization in situ modification glued membrane under fluorine emulsion add-on situation seldom.Its advantage of the method for blend is relatively simple, and shortcoming is that homogeneity is relatively poor, and required fluorine-containing composition has good performance than the great talent.
Copolymerization is to introduce fluorine-containing unit in multipolymer is formed, and for example adopts fluorine monomer and other monomer copolymerizations, and this method can change the structure of polymer lateral chain, effectively changes the surface property of multipolymer, compares blending method and has more realistic meaning.Because the fluorochemical monomer price is higher, thereby copolymerization method also is the effective ways that reduce the fluoro-resin cost.
Fluorine element is introduced acrylate resin, can reduce resin-coated surface energy greatly.(Zhang Qinghua such as Zhang Qinghua, Deng. textile journal, 2005,26 (2): 4-7) in composite emulsification system (fluorocarbon surfactant F-300 and NP-40), stable fluoro acrylic ester (FA), lauryl methacrylate(LMA) (LMA), methyl methacrylate (MMA) copolymer emulsion have been synthesized, fluorine content reaches at 33% o'clock in system, and the contact angle to water of filming is greater than 111 °, to the contact angle of n-Hexadecane also greater than 90 °.Xia Jianhan (Xia Jianhan. the Guangzhou chemistry, 2004,29 (2): 25-28) utilize 1,1-dihydro perfluor undecyl alcohol acrylate (FUA) is made solvent with dioxane, with acrylic acid copolymer.Along with the increase of FUA content, surface energy polymer reduces, and with the contact angle increase of water, when the molar content of FUA in polymkeric substance was 2.35%, this multipolymer and water contact angle reached 120 °.
Silicone resin has good low-temperature performance, snappiness, erosion resistance is also better, cooperate with organic fluorine, except the low-temperature performance deficiency that can improve fluoro-resin, also have advantage (Ni Yong such as good wetting permeability and self-cleaning performance, Deng. organosilicon material, 2005,19 (2): 14-16), thereby be subjected to people's attention.
Huang Yuewen (Huang Yuewen, Deng. polymer material science and engineering, 2006,22 (1): 32-35) γ-methacryloxypropyl three (trimethyl silicon based) silane (WD), γ-methacryloxypropyl triethoxyl silane and isobornyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester and fluorine-containing methacrylate are carried out copolymerization, in the method that all monomers add simultaneously, polymkeric substance easily forms random arrangement, and the co-polymer membrane surface energy descends little, and it is less that water contact angle increases degree.Adopt time-delay to drip the then more formation grafting of silane monomer technology, block or from the polymkeric substance of poly structure, the organosilicon part that helps low surface energy is to surface transport, water contact angle increases obviously, and both maximums differ 6 ° (WD content was all) at 20% o'clock.Zhao Xingshun (Zhao Xingshun, Deng. the polymer journal, 2004, (2): 196-200) with sodium lauryl sulphate (SDS) and OP-10 blending emulsifiers, methacrylic acid perfluoro capryl ethyl ester (FMA8), butyl methacrylate (BMA) and methacrylic acid (MAA) are carried out emulsion copolymerization, when the massfraction of perfluorinated monomers to 25% the time, its surface energy is reduced to 19.74mJ/m
2
Above-described is the main method of current preparation acrylate containing fluorine resin.Mainly there is following shortcoming in these methods: 1. fluorinated acrylate monomer generally is insoluble to organic solvent commonly used, needs higherly with some costs, just can carry out solution polymerization to the solvent of contaminate environment; 2. fluorinated acrylate monomer in use often utilizes it after emulsifying agent emulsification, and polymerization forms emulsion, though water-based emulsion in use, water solvent does not pollute environment, because the existence of emulsifying agent increases the coating surface water-absorbent; 3. the acrylate containing fluorine emulsion in order to improve monomeric utilization ratio, reduces the surface energy of coating in the preparation, often use fluorine-containing tensio-active agent, so cost is higher, has environmental pollution; 4. the acrylate containing fluorine coating hardness also is not very desirable.
Summary of the invention
Purpose of the present invention aims to provide a kind of fluorine-containing polyhedral oligomeric silsesquioxane (POSS) acrylate block copolymer resin and synthetic method thereof.
Technical scheme of the present invention is that to replace (methyl) acrylate with fluorine-containing polyhedral oligomeric silsesquioxane be raw material, adopts the synthetic organic-inorganic hybrid nanometer bunch fluoro-acrylate copolymer resin with low surface energy of atom transition free radical polymerization reaction (ATRP).
A kind of fluorine-containing POSS acrylate block copolymer resin of the present invention is fluorine-containing polyhedral oligomeric silsesquioxane (POSS) substituted acrylic ester segmented copolymer or fluorine-containing polyhedral oligomeric silsesquioxane (POSS) substituted methacrylic acid ester based block copolymer, molecular weight of copolymer Mn=20000～60000, Mn/Mw=1.1～1.5, the contact angle of coating and water is 85～120 ° after the film forming.The structural formula of multipolymer is as follows:
Wherein: R=-CH
3,-C
6H
11,-C
4H
9,-C
8H
17,-C
6H
5
X＝-OCH
2(CH
2)
pCH
2(CF
2)
5CF
3；
Y＝-H，-CH
3；
q＝1～5；
p＝1～6；
M, n are the structural unit number of polymkeric substance.
The reaction equation of multipolymer of the present invention is as follows:
In the formula, m, n are the structural unit number of polymkeric substance, and ATRP is an atom transfer radical polymerization.
The synthetic method of a kind of fluorine-containing POSS acrylate block copolymer resin of the present invention is as follows:
1) with Catalysts Cu Br/N, N, N ', N ", N "-pentamethyl--diethylenetriamine (PMDETA) joins in the reaction vessel, and sealing vacuumizes, logical nitrogen replacement; Initiator ethyl (EBriB) is dissolved in the monomers methyl methacrylate (MMA), logical nitrogen deoxygenation, add in the reactor in the lump then, vacuumize, lead to nitrogen replacement, the mass ratio of each component materials is EBriB: CuBr: PMDETA: MMA=1 in the system: (1～4): (2～12): (1000～2000);
2), or under the microwave irradiation of 200～450W, react 1～5h in 75～85 ℃ of following reacting by heating 8～24h;
3) tetrahydrofuran (THF) of quality such as adding and MMA dilution in reaction system, remove unnecessary catalyzer and initiator by alumina adsorption, use methanol extraction then, filter, room temperature vacuum-drying is to constant weight, get final product to such an extent that have an end capped methyl methacrylate performed polymer of Br;
4) in another reaction vessel, add with the tetrahydrofuran (THF) of quality such as methyl methacrylate performed polymer, add CuBr, PMDETA, methyl methacrylate performed polymer more successively, concentration is the F-POSS tetrahydrofuran solution of 0.2g/mL, the massfraction of the F-POSS that adds be in the performed polymer MMA quality 1%～5%, CuBr and PMDETA are respectively 1%～4%, 2%～8% of F-POSS quality, sealing vacuumizes, leads to nitrogen replacement; Under 75～85 ℃, continue reacting by heating 24～36h, or react 1～5h down in the microwave irradiation of 200～450W;
4) will react back solution and remove catalyzer by alumina adsorption, use methanol extraction then, filtration, vacuum-drying get a kind of fluorine-containing POSS acrylate block copolymer resin, i.e. organic-inorganic hybrid nanometer bunch fluorinated acrylate block copolymer resin to constant weight.
This polymer powder is dissolved in ethyl acetate, acetone, 1, the 2-ethylene dichloride, dioxane in pimelinketone or their mixture, can carry out the brushing film forming.
The present invention has adopted the method for controlled polymerization to prepare fluorine-containing and non-fluorine segmental segmented copolymer, because containing FPOSS helps fluorine-containing section to surface enrichment, improve fluorine-containing unitary utilising efficiency, only need a spot of fluorochemical monomer that the skin of polymeric film is almost covered by the FPOSS layer, obtain having the polymeric film of low surface energy.The polyhedral oligomeric silsesquioxane nano structure of introducing among the present invention in addition, this monomer can play the effect of nano-filled phase in resin, thereby has higher hardness.And this monomer can be dissolved in the organic solvent of multiple low toxicity, avoids introducing tensio-active agent, has improved the hydrophobic performance on top layer.The process of reacting has been accelerated in synthetic employing microwave heating, makes production efficiency improve, and helps to promote this resin material and realizes suitability for industrialized production.
Embodiment
The present invention is further illustrated below by specific embodiment.
Embodiment 1:
Step 1, with load weighted CuBr0.144g and PMDETA0.346g, put into two-mouth bottle, with its sealing, vacuumize, logical nitrogen, this replacement process carries out 3 times.
Step 2, initiator EBriB0.195g are dissolved among the monomer M MA100g, and nitrogen is guided to bubbling deoxygenation under the monomer liquid level, after 1 minute, add in the lump in the two-mouth bottle, vacuumize, lead to nitrogen, and this replacement process carries out 3 times.The ratio of amount of substance is EbriB: CuBr: PMDETA: MMA=1 in this system: 1: 2: 1000.Then two-mouth bottle is placed in 85 ℃ the silicone oil bath reaction 24h.
Step 3, will react back solution, remove unnecessary catalyzer and initiator, use methanol extraction then, filter, room temperature vacuum-drying is to constant weight, obtains having Br end-blocking methyl methacrylate performed polymer by alumina adsorption with the dilution of 100g tetrahydrofuran (THF);
Step 4, get another two-mouth bottle, add the 10g tetrahydrofuran (THF), CuBr0.001g, PMDETA 0.002g, methyl methacrylate performed polymer 10g, 0.5mlF-POSS (R=-C in its structural formula
6H
5, X=-OCH
2(CH
2)
2CH
2(CF
2)
5CF
3, q=1, Y=-CH
3) tetrahydrofuran solution (wherein the quality of F-POSS is 0.1g), sealing vacuumizes, leads to nitrogen, and this replacement process carries out 3 times.In 85 ℃ silicone oil bath, continue reacting by heating 24h.
Step 5, will react back solution and remove catalyzer, with methyl alcohol 206ml precipitation, filter then by alumina adsorption, and with methyl alcohol suction filtration 5 times.Vacuum-drying is to constant weight.Promptly get organic-inorganic hybrid nanometer bunch fluorine-containing ester block copolymer.
Step 6, this multipolymer is dissolved in ethyl acetate and pimelinketone mass ratio is in 90: 10 the mixed solvent, is made into solid content and is 20% solution, is coated on the sheet glass and can obtains low surface energy coat.
The GPC method records molecular weight of copolymer Mn=25000, and Mn/Mw=1.2, the contact angle of coating and water are 85 °.
Embodiment 2:
Step 1, with good CuBr0.288g of weighing and PMDETA0.692g, put into two-mouth bottle, with its sealing, vacuumize, logical nitrogen, this replacement process carries out 3 times.
Step 2, initiator EbriB0.195g are dissolved among the monomer M MA100g, and nitrogen is guided to bubbling deoxygenation under the monomer liquid level, after 1 minute, add in the lump in the two-mouth bottle, vacuumize, lead to nitrogen, and this replacement process carries out 3 times.The ratio of amount of substance is EbriB: CuBr: PMDETA: MMA=1 in this system: 2: 6: 1500.Then two-mouth bottle is placed in 80 ℃ the silicone oil bath reaction 20h.
Step 3, will react the tetrahydrofuran (THF) dilution that back solution such as uses at 100g, remove unnecessary catalyzer and initiator, use methanol extraction then, filter, room temperature vacuum-drying is to constant weight, obtains having Br end-blocking methyl methacrylate performed polymer by alumina adsorption;
Step 4, get another two-mouth bottle, add the 10g tetrahydrofuran (THF), CuBr0.006g, PMDETA 0.012g, methyl methacrylate performed polymer 10g, 1.5mlF-POSS (R=-CH in its structural formula
3, X=-OCH
2CH
2CH
2(CF
2)
5CF
3, q=5, Y=-H.) tetrahydrofuran solution (wherein the quality of F-POSS is 0.3g), sealing vacuumizes, logical nitrogen, this replacement process carries out 3 times, in 80 ℃ silicone oil bath, continues reacting by heating 30h.
Step 5, will react back solution and remove catalyzer, with methyl alcohol 350ml precipitation, filter then by alumina adsorption, and with methyl alcohol suction filtration 5 times.Vacuum-drying is to constant weight.Promptly get organic-inorganic hybrid nanometer bunch fluorine-containing ester block copolymer.
Step 6, this multipolymer is dissolved in ethyl acetate and pimelinketone mass ratio is in 90: 10 the mixed solvent, is made into solid content and is 20% solution, is coated on the sheet glass and can obtains low surface energy coat.
The GPC method records molecular weight of copolymer Mn=40000, and Mn/Mw=1.15, the contact angle of coating and water are 110 °.
Embodiment 3:
Step 1, with good CuBr0.28gg of weighing and PMDETA0.692g, put into two-mouth bottle, put into two-mouth bottle, with its sealing, vacuumize, logical nitrogen, this replacement process carries out 3 times.
Step 2, initiator EbriB0.195g are dissolved among the monomer M MA100g, and nitrogen is guided to bubbling deoxygenation under the monomer liquid level, after 1 minute, add in the lump in the two-mouth bottle, vacuumize, lead to nitrogen, and this replacement process carries out 3 times.The ratio of amount of substance is EbriB: CuBr: PMDETA: MMA=1 in this system: 3: 8: 1000.Two-mouth bottle is placed in the microwave oven, and it is 300W that power is set, reaction 4h.
Step 3, will react the tetrahydrofuran (THF) dilution that back solution such as uses at 100g, remove unnecessary catalyzer and initiator, use methanol extraction then, filter, room temperature vacuum-drying is to constant weight, obtains having Br end-blocking methyl methacrylate performed polymer by alumina adsorption;
Step 4, get another two-mouth bottle, add the 10g tetrahydrofuran (THF), CuBr0.006g, PMDETA 0.012g, methyl methacrylate performed polymer 10g, 1.5mlF-POSS (R=-n-C in its structural formula
6H
11, X=-OCH
2(CH
2)
3CH
2(CF
2)
5CF
3, q=3, Y=-H.) tetrahydrofuran solution (wherein the quality of F-POSS is 0.3g), sealing vacuumizes, logical nitrogen, this replacement process carries out 3 times, and two-mouth bottle is placed in the microwave oven, it is 300W that power is set, and continues reaction 4h.
Step 5, polymers soln is removed catalyzer by alumina adsorption, with methyl alcohol 200ml precipitation, filter then, and with methyl alcohol suction filtration 5 times.Vacuum-drying is to constant weight.
Step 6, the synthetic multipolymer is dissolved in ethyl acetate and pimelinketone mass ratio is in 90: 10 the mixed solvent, is made into solid content and is 20% solution, is coated on the sheet glass and can obtains low surface energy coat.
The GPC method records molecular weight of copolymer Mn=50000, and Mn/Mw=1.3, the contact angle of coating and water are 115 °.
Embodiment 4:
Step 1, with good CuBr0.576g of weighing and PMDETA2.076g, put into two-mouth bottle, with its sealing, vacuumize, logical nitrogen, this replacement process carries out 3 times.
Step 2, initiator EbriB0.195g are dissolved among the monomer M MA200g, and nitrogen is guided to bubbling deoxygenation under the monomer liquid level, after 1 minute, add in the lump in the two-mouth bottle, vacuumize, lead to nitrogen, and this replacement process carries out 3 times.The ratio of amount of substance is EbriB: CuBr: PMDETA: MMA=1 in this system: 4: 12: 2000.Two-mouth bottle is placed in the microwave oven, and it is 400W that power is set, reaction 2.5h.
Step 3, will react the tetrahydrofuran (THF) dilution that back solution such as uses at 200g, remove unnecessary catalyzer and initiator, use methanol extraction then, filter, room temperature vacuum-drying is to constant weight, obtains having Br end-blocking methyl methacrylate performed polymer by alumina adsorption;
Step 4, get another two-mouth bottle, add the 20g tetrahydrofuran (THF), CuBr0.006g, PMDETA 0.012g, methyl methacrylate performed polymer 20g, 2.5mlF-POSS (R=-n-C in its structural formula
4H
9, X=-OCH
2(CH
2)
6CH
2(CF
2)
5CF
3, q=2, Y=-CH
3) tetrahydrofuran solution (wherein the quality of F-POSS is 0.5g), sealing vacuumizes, leads to nitrogen, and this replacement process carries out 3 times, and two-mouth bottle is placed in the microwave oven, and it is 400W that power is set, and continues reaction 2.5h.
Step 5, will react back solution and remove catalyzer, with methyl alcohol 300ml precipitation, filter then by alumina adsorption, and with methyl alcohol suction filtration 5 times.Vacuum-drying is to constant weight.
Step 6, the synthetic multipolymer is dissolved in ethyl acetate and pimelinketone mass ratio is in 90: 10 the mixed solvent, is made into solid content and is 20% solution, is coated on the sheet glass and can obtains low surface energy coat.
The GPC method records molecular weight of copolymer Mn=20000, and Mn/Mw=1.5, the contact angle of coating and water are 100 °.
Claims (2)
1. fluorine-containing POSS acrylate block copolymer resin, it is characterized in that being fluorine-containing polyhedral oligomeric silsesquioxane substituted acrylic ester segmented copolymer or fluorine-containing polyhedral oligomeric silsesquioxane substituted methacrylic acid ester based block copolymer, molecular weight of copolymer Mn=20000～60000, Mn/Mw=1.1～1.5, the contact angle of coating and water is 85～120 ° after the film forming, and the structural formula of multipolymer is as follows:
Wherein: R=-CH
3,-C
6H
11,-C
4H
9,-C
8H
17,-C
6H
5
X＝-OCH
2(CH
2)
pCH
2(CF
2)
5CF
3；
Y＝-H，-CH
3；
q＝1～5；
p＝1～6；
M, n are the structural unit number of polymkeric substance.
2. the synthetic method of a kind of fluorine-containing POSS acrylate block copolymer resin as claimed in claim 1 is characterized in that its step is as follows:
1) with Catalysts Cu Br/N, N, N ', N ", N "-pentamethyl--diethylenetriamine joins in the reaction vessel, and sealing vacuumizes, logical nitrogen replacement; The initiator ethyl is dissolved in the monomers methyl methacrylate, logical nitrogen deoxygenation, add in the reactor in the lump then, vacuumize, lead to nitrogen replacement, the mass ratio of each component materials is ethyl: CuBr: N in the system, N, N '; N ", N "-pentamethyl--diethylenetriamine: methyl methacrylate=1: 1～4: 2～12: 1000～2000;
2), or under the microwave irradiation of 200～450W, react 1～5h in 75～85 ℃ of following reacting by heating 8～24h;
3) tetrahydrofuran (THF) of quality such as adding and methyl methacrylate dilution in reaction system, remove unnecessary catalyzer and initiator by alumina adsorption, use methanol extraction then, filter, room temperature vacuum-drying is to constant weight, get final product to such an extent that have an end capped methyl methacrylate performed polymer of bromine;
4) in another reaction vessel, add with the tetrahydrofuran (THF) of quality such as methyl methacrylate performed polymer, add CuBr, N more successively, N, N '; N "; N "-pentamethyl--diethylenetriamine, methyl methacrylate performed polymer, concentration are the F-POSS tetrahydrofuran solution of 0.2g/mL, the massfraction of the F-POSS that adds be in the performed polymer methyl methacrylate quality 1%～5%, CuBr and N, N, N ', N ", N "-pentamethyl--diethylenetriamine is respectively 1%～4%, 2%～8% of F-POSS quality, sealing vacuumizes, leads to nitrogen replacement; Under 75～85 ℃, continue reacting by heating 24～36h, or react 1～5h down in the microwave irradiation of 200～450W;
5) will react back solution and remove catalyzer by alumina adsorption, and use methanol extraction then, filtration, vacuum-drying get fluorine-containing POSS acrylate block copolymer resin to constant weight.
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| US6586548B2 (en) * | 2000-12-19 | 2003-07-01 | Bausch & Lomb Incorporated | Polymeric biomaterials containing silsesquixane monomers |
| US20060057402A1 (en) * | 2002-07-15 | 2006-03-16 | Augustine Brian H | Hybrid polymers for functional tuning of microfluidic device surfaces |
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2007
- 2007-03-09 CN CNB2007100086854A patent/CN100564427C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6586548B2 (en) * | 2000-12-19 | 2003-07-01 | Bausch & Lomb Incorporated | Polymeric biomaterials containing silsesquixane monomers |
| US20020182541A1 (en) * | 2001-03-12 | 2002-12-05 | Gonsalves Kenneth E. | High resolution resists for next generation lithographies |
| US20060057402A1 (en) * | 2002-07-15 | 2006-03-16 | Augustine Brian H | Hybrid polymers for functional tuning of microfluidic device surfaces |
Non-Patent Citations (6)
| Title |
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| POSS改性传统聚合物的研究进展. 刘玉荣.宇航材料工艺，第2期. 2005 |
| POSS改性传统聚合物的研究进展. 刘玉荣.宇航材料工艺，第2期. 2005 * |
| 含多面低聚倍半硅氧烷新型杂化聚合物的合成. 王冠海.化学进展，第18卷第4期. 2006 |
| 含多面低聚倍半硅氧烷新型杂化聚合物的合成. 王冠海.化学进展，第18卷第4期. 2006 * |
| 活性聚合合成POSSCl/PMMA. 王文平.2005年全国高分子学术论文报告会. 2005 |
| 活性聚合合成POSSCl/PMMA. 王文平.2005年全国高分子学术论文报告会. 2005 * |
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| CN101029137A (en) | 2007-09-05 |
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