CN102190759A - Polyester modified fluoro acrylic resin, and preparation method and coating thereof - Google Patents
Polyester modified fluoro acrylic resin, and preparation method and coating thereof Download PDFInfo
- Publication number
- CN102190759A CN102190759A CN 201110068559 CN201110068559A CN102190759A CN 102190759 A CN102190759 A CN 102190759A CN 201110068559 CN201110068559 CN 201110068559 CN 201110068559 A CN201110068559 A CN 201110068559A CN 102190759 A CN102190759 A CN 102190759A
- Authority
- CN
- China
- Prior art keywords
- polyester
- percent
- acrylate resin
- perfluoroalkyl acrylate
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 51
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000011248 coating agent Substances 0.000 title claims abstract description 13
- 238000000576 coating method Methods 0.000 title claims abstract description 13
- 229920000178 Acrylic resin Polymers 0.000 title abstract description 7
- 125000001153 fluoro group Chemical group F* 0.000 title 1
- 239000000178 monomer Substances 0.000 claims abstract description 35
- 239000002253 acid Substances 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 17
- 239000003999 initiator Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000012046 mixed solvent Substances 0.000 claims abstract description 13
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims abstract description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 8
- 239000011737 fluorine Substances 0.000 claims abstract description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 7
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 3
- 238000012986 modification Methods 0.000 claims description 27
- 230000004048 modification Effects 0.000 claims description 27
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 21
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 20
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- -1 t-amyl peroxy Chemical group 0.000 claims description 6
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 5
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 5
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 5
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 claims description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 4
- OZCWUNHGNVXCCO-UHFFFAOYSA-N oxiran-2-ylmethyl hydrogen carbonate Chemical group OC(=O)OCC1CO1 OZCWUNHGNVXCCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 230000002745 absorbent Effects 0.000 claims description 3
- 239000002250 absorbent Substances 0.000 claims description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 abstract description 2
- 150000002221 fluorine Chemical class 0.000 abstract 4
- 239000002243 precursor Substances 0.000 abstract 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 abstract 1
- GNEPLYVYORHREW-UHFFFAOYSA-N 1,1,3,3,6-pentamethyl-7-nitro-2h-inden-5-amine Chemical compound CC1=C(N)C=C2C(C)(C)CC(C)(C)C2=C1[N+]([O-])=O GNEPLYVYORHREW-UHFFFAOYSA-N 0.000 abstract 1
- OAOABCKPVCUNKO-UHFFFAOYSA-N 8-methyl Nonanoic acid Chemical compound CC(C)CCCCCCC(O)=O OAOABCKPVCUNKO-UHFFFAOYSA-N 0.000 abstract 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract 1
- 239000005977 Ethylene Substances 0.000 abstract 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 150000007513 acids Chemical class 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses polyester modified fluorine-containing acrylic resin, and a preparation method and a coating thereof. The polyester modified fluorine-containing acrylic resin is prepared by carrying out a polymerization reaction on a polyester precursor, a mixed monomer and an initiator in a mixed solvent, wherein the amount of the mixed monomer for reaction accounts for 56.7 percent of the total feeding amount; the mixed monomer comprises the following components by mass percentage of the mixed monomer: 4-8 percent of styrene, 18-22 percent of isobornyl thiocyanoacetate methacrylic acid, 13-17 percent of butyl methacrylate, 13-17 percent of hydroxyethyl methacrylate, 18-22 percent of butyl acrylate, 4-6 percent of methacrylic acid, 4-6 percent of versatic acid ethylene oxidic ester and 13-17 percent of fluorine-containing monomer. In the invention, the polyester precursor and an acrylic acid monomer solution are polymerized to obtain the polyester modified fluorine-containing acrylic resin with high solid components and the polyester modified fluorine-containing acrylic resin is prepared into a skin material which is specially tested to coat by using the coating; the result shows that the resin has excellent performance and is remarkably superior to fluorine-containing acrylic resin for preparing a skin material of a helicopter in the strong reflective characteristics, hardness, acid and alkali resistance, and the like.
Description
Technical field
The present invention relates to polyester modification perfluoroalkyl acrylate resins field, is meant helicopter skining material polyester modification perfluoroalkyl acrylate resin of coating and preparation method thereof especially.
Background technology
Fluorin modified crylic acid resin is more superior than simple acrylic resin at aspects such as non-corrosibility, contamination resistance, chemical-resistant and outdoor overlength weathering resistancies, therefore Chinese disclosure of the Invention number has obtained good effect for CN1923868A is used for the manufacturing of helicopter skining paint with fluorin modified crylic acid resin.Along with the raising that coating is required, be the use that is suitable for wider scope, oceanic climate etc. for example is necessary to continue to promote the overall quality of resin, therefore polyester can be combined with fluorin modified crylic acid resin, obtains the more resin material of excellent properties.At present, to the research of polyester modification perfluoroalkyl acrylate resin seldom, retrieving the resin that Wen Di river etc. is published in " research of vinylformic acid fluorinated ester modified unsaturated polyester resin " literary composition on 34 pages of " New Building Materials " 2008 the 4th phases is to handle and form by cast under the room temperature, thermofixation, and its over-all properties of such resin is difficult to reach design requirements.
Summary of the invention
First purpose of the present invention is in order to overcome the shortcoming and defect that prior art exists, and provides a kind of resin property good, at the polyester modification perfluoroalkyl acrylate resin of aspect superior performances such as clarity, hardness, resistance to acids and bases.
Second purpose of the present invention provides the preparation method of above-mentioned polyester modification perfluoroalkyl acrylate resin.
The 3rd purpose of the present invention provides a kind of coating that utilizes above-mentioned polyester modification perfluoroalkyl acrylate resin configuration.
For realizing first purpose of the present invention, its technical scheme is to be made by polyester presoma, mix monomer and initiator polyreaction in mixed solvent, the reaction used each raw material amount by percentage to the quality:
The amount of polyester presoma accounts for 16.6% of total charging capacity;
The amount of mixed solvent accounts for 25.7% of total charging capacity;
The amount of initiator accounts for 2.0% of total charging capacity
The amount of mix monomer accounts for 55.7% of total charging capacity, and this mix monomer comprises following component, accounts for the mass percent meter of mix monomer:
Vinylbenzene 4-8%; Isobornyl methacrylate 18-22%;
Butyl methacrylate 13%-17%; Hydroxyethyl methylacrylate 13%-17%;
Butyl acrylate 18%-22%; Methacrylic acid 4%-6%;
Tertiary carbonic acid glycidyl ester 4-6%; Fluorochemical monomer 13%-17%.
Further being provided with is that described polyester presoma is prepared from by following mode: with neopentyl glycol (weight percent, 30-36%), TriMethylolPropane(TMP) (10-13%), phthalic anhydride (23-27%), m-phthalic acid (25-30%), toluene (4-6%), Dibutyltin oxide (0.15-0.25%), anti--168 (0.4-0.6%) drop into and have in the four-hole boiling flask of water trap, logical nitrogen, heat up, when material dissolves substantially, start stirring; Continue to heat up, reflux dewatering does not reach 90% of theoretical value in dehydration, and preceding control water trap head temperature is no more than 100 ℃, and the temperature of reaction of flask is controlled at 160-180 ℃; When dehydrating amount reach theoretical water 90% the time, the temperature in the flask raises gradually, but is no more than 210 ℃; When dehydrating amount during near theoretical value, the survey acid number of drawing materials when acid number is 8 mgKOH/g, is reaction end, and cooling adds dimethylbenzene and N-BUTYL ACETATE solvent, and weight ratio 1:1, consumption are about 32% of charging capacity, and latting drown stirs evenly, filtration.This setting, described theoretical water are about 10% of above-mentioned charging capacity.
Further being provided with is that described fluorine monomer is a trifluoroethyl methacrylate, vinylformic acid hexafluoro butyl ester and methacrylic acid hexafluoro butyl ester.
Further being provided with is that described initiator is two t-amyl peroxy things.
Further being provided with is that mixed solvent is dimethylbenzene and N-BUTYL ACETATE, and proportioning is 1:1.
For realizing second purpose of the present invention, technical scheme of the present invention is may further comprise the steps:
(1) raw material is equipped with: this step comprises following each operation, and each operation of this step in no particular order
A) preparation polyester presoma, this polyester presoma consumption is 16.6% of total charging capacity;
B) preparation mix monomer, the amount of mix monomer accounts for 55.7% of total charging capacity, and this mix monomer comprises following component, accounts for the mass percent meter of mix monomer:
Vinylbenzene 4-8%; Isobornyl methacrylate 18-22%;
Butyl methacrylate 13%-17%; Hydroxyethyl methylacrylate 13%-17%;
Butyl acrylate 18%-22%; Methacrylic acid 4%-6%;
Tertiary carbonic acid glycidyl ester 4-6%; Fluorochemical monomer 13%-17%;
C) preparation mixed solvent, this mixed solvent accounts for 25.7% of total charging capacity;
(2) polyreaction: get the bottoming of polyester presoma, logical nitrogen, heat up, stir, be raised to about 125 ℃, reflux the formula ratio that adds mixed solvent down 70% in the four-hole boiling flask that has water-and-oil separator, heat to reflux temperature, mix monomer with 100% is placed in the dropping funnel, with the initiator of 10% dissolution with solvents dilution 80% and be placed in another dropping funnel, simultaneously evenly be added to reactive system with 3～5 hours liquid and carry out polyreaction, after dropwising, under reflux temperature, be incubated 1～2 hour two dropping funnels, then with remaining solvent and initiator, at the uniform velocity added with 1～2 hour and to deepen polymerization in the reactive system, continue reaction 3～4 hours up to the acid number of resin less than set quota, obtain polyester modification perfluoroalkyl acrylate resin material.
For realizing the 3rd purpose of the present invention, its technical scheme is to comprise following component, in mass fraction, and polyester modification perfluoroalkyl acrylate resin, 50 parts; Titanium dioxide, 27 parts; Dispersion agent, 2 parts; Flow agent, 1 part; Ultraviolet-resistant absorbent, 2 parts; Dimethylbenzene, 10 parts; Different fluorine that ketone, 5 parts; 1-Methoxy-2-propyl acetate, 3 parts.
For this reason, the present invention utilizes polyester presoma and Acrylic Acid Monomer solution polymerization to obtain the polyester modification perfluoroalkyl acrylate resin of high-solid level and is mixed with skin material and tries specially to be coated with coating, the result shows that resin property is good, obviously is better than being used to make the perfluoroalkyl acrylate resin of helicopter skining paint at aspects such as clarity, hardness, resistance to acids and basess.
Technique effect:
The polyester modification perfluoroalkyl acrylate resin that the present invention makes has following technical indicator: as clear as crystal liquid, solids constituent 68%-72%; Viscosity (Ge Shi pipe, 25C) 10-15 s; Acid number＜12 mgKOH/g.The actual use properties of resin is coated with investigation by the examination that skin material coats that is used for of preparation, test-results shows: coating performance is good, obviously be better than often being coated with the S04 coating property, also than fluorin modified crylic acid resin in excellence aspect clarity, hardness, the resistance to acids and bases.
Below in conjunction with embodiment the present invention is done further introduction.
Embodiment
Below by embodiment the present invention is carried out concrete description; only be used for the present invention is further specified; can not be interpreted as the qualification to protection domain of the present invention, the technician in this field can make some nonessential improvement and adjustment to the present invention according to the content of foregoing invention.
Embodiment1
The preparation of polyester presoma.With 235 gram neopentyl glycol, 74 gram TriMethylolPropane(TMP)s, 163 gram phthalic anhydrides, 183 gram m-phthalic acids, 33 gram toluene, 1.5 gram Dibutyltin oxides, 3.5 grams anti--168 are put in the four-hole boiling flask that has water trap, logical nitrogen, heat up, when material dissolves substantially, start stirring.Continue to heat up, reflux dewatering, the preceding control water trap head temperature of 90% [theoretical water is 66 grams] that does not reach theoretical value in dehydration is no more than 100 ℃, and the temperature of reaction of flask is controlled at 160-180 ℃; When dehydrating amount reach theoretical water 90% the time, the temperature in the flask raises gradually, but is no more than 210 ℃.When dehydrating amount during near theoretical value, the survey acid number of drawing materials when acid number is 8 mgKOH/g, is reaction end, cools to 80 ℃, adds dimethylbenzene and N-BUTYL ACETATE solvent 216 gram (weight ratio 1:1) latting drowns, stirs evenly filtration.Testing index is: solids constituent 69.5%, acid number are 6.3 mgKOH/g, and viscosity (25 ℃, the Ge Shi pipe) is 23 s.
Polyester modification perfluoroalkyl acrylate resin.Get polyester presoma 208 grams, put into the four-hole boiling flask of water-and-oil separator, heat up, stir, be raised to about 125 ℃.The 70%(225 gram that adds the solvent formula amount) (by dimethylbenzene, N-BUTYL ACETATE 1:1 preparation, total amount is 322 grams) heats to reflux temperature.[amount of mix monomer is 697 grams with 100% mix monomer, vinylbenzene (4%), isobornyl methacrylate (18%), butyl methacrylate (16%), hydroxyethyl methylacrylate (14%), butyl acrylate (19%), methacrylic acid (12%) and fluorochemical monomer (17%, trifluoroethyl methacrylate: vinylformic acid hexafluoro butyl ester: the weight ratio of methacrylic acid hexafluoro butyl ester is 1:2:2)] put into dropping funnel; Contain initiator 20 grams with 10% dissolution with solvents dilution 80%(again) two t-amyl peroxy thing initiators and be injected in another dropping funnel, with 4 hours the liquid in two dropping funnels evenly is added drop-wise in the reactive system.After dropwising, insulation is 1.5 hours under reflux temperature, with remaining solvent and initiator (total amount 20%), at the uniform velocity is added drop-wise in the reactor in 1.5 hours then.Continue reaction 4 hours up to the acid number of resin less than set quota, promptly get polyester modification perfluoroalkyl acrylate resin.The index of measuring is: solids constituent, 69.7%; Viscosity (Ge Shi pipe, 25 ℃, 14 s; Acid number, 10.8 mgKOH/g.
Embodiment 2
The varnish preparation.With the above-mentioned synthetic polyester modification perfluoroalkyl acrylate resin preparation coating that obtains, basic recipe is as follows: polyester modification perfluoroalkyl acrylate resin, 50 parts (weight percent); Titanium dioxide, 27 parts; Dispersion agent, 2 parts; Flow agent, 1 part; Ultraviolet-resistant absorbent, 2 parts; Dimethylbenzene, 10 parts; Different fluorine that ketone, 5 parts; 1-Methoxy-2-propyl acetate, 3 parts.Solidifying agent adopts DESMODUR N-3390 HDI trimer curing agent.The ratio of white paint and solidifying agent is 100: 25.Coat-thickness is about 25 μ m.
Join coating try to be coated with at vertiplane with skin material, the performance that records is as follows:
Claims (10)
1. polyester modification perfluoroalkyl acrylate resin is characterized in that: make by polyester presoma, mix monomer and initiator polyreaction in mixed solvent, the amount of used each raw material of reaction by percentage to the quality:
The amount of polyester presoma accounts for 16.6% of total charging capacity;
The amount of mixed solvent accounts for 25.7% of total charging capacity;
The amount that the amount of initiator accounts for 2.0% mix monomer of total charging capacity accounts for 55.7% of total charging capacity, and this mix monomer comprises following component, accounts for the mass percent meter of mix monomer:
Vinylbenzene 4-8%; Isobornyl methacrylate 18-22%;
Butyl methacrylate 13%-17%; Hydroxyethyl methylacrylate 13%-17%;
Butyl acrylate 18%-22%; Methacrylic acid 4%-6%;
Tertiary carbonic acid glycidyl ester 4-6%; Fluorochemical monomer 13%-17%.
2. a kind of polyester modification perfluoroalkyl acrylate resin according to claim 1, it is characterized in that: described polyester presoma is prepared from by following mode: with neopentyl glycol (weight percent, 30-36%), and TriMethylolPropane(TMP) (weight percent, 10-13%), phthalic anhydride (weight percent, 23-27%), and m-phthalic acid (weight percent, 25-30%), toluene (weight percent, 4-6%), and Dibutyltin oxide (weight percent, 0.15-0.25%), anti--168 (weight percents, 0.4-0.6%) input has in the four-hole boiling flask of water trap, and logical nitrogen heats up, when material dissolves substantially, start stirring; Continue to heat up, reflux dewatering does not reach 90% of theoretical value in dehydration, and preceding control water trap head temperature is no more than 100 ℃, and the temperature of reaction of flask is controlled at 160-180 ℃; When dehydrating amount reach theoretical water 90% the time, the temperature in the flask raises gradually, but is no more than 210 ℃; When dehydrating amount during near theoretical value, the survey acid number of drawing materials when acid number is 8 mgKOH/g, is reaction end, and cooling adds dimethylbenzene and N-BUTYL ACETATE solvent, and weight ratio 1:1, consumption are about 32% of charging capacity, and latting drown stirs evenly, filtration.
3. a kind of polyester modification perfluoroalkyl acrylate resin according to claim 1 is characterized in that: described fluorine monomer is trifluoroethyl methacrylate, vinylformic acid hexafluoro butyl ester and methacrylic acid hexafluoro butyl ester.
4. a kind of polyester modification perfluoroalkyl acrylate resin according to claim 1 is characterized in that: described initiator is two t-amyl peroxy things.
5. a kind of polyester modification perfluoroalkyl acrylate resin according to claim 1, it is characterized in that: mixed solvent is dimethylbenzene and N-BUTYL ACETATE, proportioning is 1:1.
6. the preparation method of a polyester modification perfluoroalkyl acrylate resin as claimed in claim 1 is characterized in that may further comprise the steps:
(1) raw material is equipped with: this step comprises following each operation, and each operation of this step in no particular order
A) preparation polyester presoma, this polyester presoma consumption is 16.6% of total charging capacity;
B) preparation mix monomer, the amount of mix monomer accounts for 55.7% of total charging capacity, and this mix monomer comprises following component, accounts for the mass percent meter of mix monomer:
Vinylbenzene 4-8%; Isobornyl methacrylate 18-22%;
Butyl methacrylate 13%-17%; Hydroxyethyl methylacrylate 13%-17%;
Butyl acrylate 18%-22%; Methacrylic acid 4%-6%;
Tertiary carbonic acid glycidyl ester 4-6%; Fluorochemical monomer 13%-17%;
C) preparation mixed solvent, this mixed solvent accounts for 25.7% of total charging capacity;
(2) polyreaction: get the bottoming of polyester presoma, logical nitrogen, heat up, stir, be raised to about 125 ℃, reflux the formula ratio that adds mixed solvent down 70% in the four-hole boiling flask that has water-and-oil separator, heat to reflux temperature, mix monomer with 100% is placed in the dropping funnel, with the initiator of 10% dissolution with solvents dilution 80% and be placed in another dropping funnel, simultaneously evenly be added to reactive system with 3～5 hours liquid and carry out polyreaction, after dropwising, under reflux temperature, be incubated 1～2 hour two dropping funnels, then with remaining solvent and initiator, at the uniform velocity added with 1～2 hour and to deepen polymerization in the reactive system, continue reaction 3～4 hours up to the acid number of resin less than set quota, obtain polyester modification perfluoroalkyl acrylate resin material.
7. a kind of polyester modification perfluoroalkyl acrylate resin according to claim 6, it is characterized in that: described polyester presoma is prepared from by following mode: with neopentyl glycol (weight percent, 30-36%), TriMethylolPropane(TMP) (10-13%), phthalic anhydride (23-27%), m-phthalic acid (25-30%), toluene (4-6%), Dibutyltin oxide (0.15-0.25%), anti--168 (0.4-0.6%) drop into and have in the four-hole boiling flask of water trap, and logical nitrogen heats up, when material dissolves substantially, start stirring; Continue to heat up, reflux dewatering does not reach 90% of theoretical value in dehydration, and preceding control water trap head temperature is no more than 100 ℃, and the temperature of reaction of flask is controlled at 160-180 ℃; When dehydrating amount reach theoretical water 90% the time, the temperature in the flask raises gradually, but is no more than 210 ℃; When dehydrating amount during near theoretical value, the survey acid number of drawing materials when acid number is 8 mgKOH/g, is reaction end, and cooling adds dimethylbenzene and N-BUTYL ACETATE solvent, and weight ratio 1:1, consumption are about 32% of charging capacity, and latting drown stirs evenly, filtration.
8. a kind of polyester modification perfluoroalkyl acrylate resin according to claim 6, it is characterized in that: described fluorine monomer is a trifluoroethyl methacrylate, vinylformic acid hexafluoro butyl ester and methacrylic acid hexafluoro butyl ester.
9. a kind of polyester modification perfluoroalkyl acrylate resin according to claim 6 is characterized in that: described initiator is two t-amyl peroxy things.
10. a coating that utilizes the described polyester modification perfluoroalkyl acrylate of claim 1 resin to be disposed is characterized in that comprising following component, in parts by weight:
Polyester modification perfluoroalkyl acrylate resin, 50 parts; Titanium dioxide, 27 parts; Dispersion agent, 2 parts; Flow agent, 1 part; Ultraviolet-resistant absorbent, 2 parts; Dimethylbenzene, 10 parts; Different fluorine that ketone, 5 parts; 1-Methoxy-2-propyl acetate, 3 parts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110068559A CN102190759B (en) | 2011-03-22 | 2011-03-22 | Polyester modified fluoro acrylic resin, and preparation method and coating thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110068559A CN102190759B (en) | 2011-03-22 | 2011-03-22 | Polyester modified fluoro acrylic resin, and preparation method and coating thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102190759A true CN102190759A (en) | 2011-09-21 |
| CN102190759B CN102190759B (en) | 2012-10-17 |
Family
ID=44599706
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110068559A Active CN102190759B (en) | 2011-03-22 | 2011-03-22 | Polyester modified fluoro acrylic resin, and preparation method and coating thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102190759B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585108A (en) * | 2012-01-17 | 2012-07-18 | 杭州日耀科技有限公司 | Polyester-modified organic fluorine-silicon acrylic resin and preparation method thereof as well as paint using resin |
| CN102838707A (en) * | 2012-09-19 | 2012-12-26 | 江阴恒兴涂料有限公司 | High-performance water-soluble acrylic resin and preparation method thereof |
| CN103030744A (en) * | 2012-11-30 | 2013-04-10 | 无锡市虎皇漆业有限公司 | Polyester modified acrylic resin for wood lacquer and wood lacquer |
| CN103483503A (en) * | 2013-09-29 | 2014-01-01 | 江苏蓝色星球环保科技股份有限公司 | Polyester modified hydroxyl type fluorinated acrylate resin and preparation method thereof |
| CN105400254A (en) * | 2015-11-27 | 2016-03-16 | 宁波双人新材料有限公司 | Weather-proof polyester powder coating and preparation method thereof |
| CN111234126A (en) * | 2020-03-31 | 2020-06-05 | 南京长江涂料有限公司 | High-solid-content high-performance glycidyl versatate modified alkyd resin and preparation method thereof |
| CN111393622A (en) * | 2020-04-29 | 2020-07-10 | 广东邦弗特新材料有限公司 | Saturated polyester resin modified by hydroxyl acrylic fluorine-containing resin and preparation method thereof |
| CN114437301A (en) * | 2021-11-18 | 2022-05-06 | 江苏沃莱新材料有限公司 | Polyester modified hydroxyl acrylic resin and preparation method thereof, high-durability hydroxyl acrylic resin coating and application thereof |
| CN115477878A (en) * | 2022-09-15 | 2022-12-16 | 海洋化工研究院有限公司 | Solvent type skin finishing varnish and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05186715A (en) * | 1991-12-24 | 1993-07-27 | Mitsubishi Rayon Co Ltd | Antifouling coating composition |
| CN1252423A (en) * | 1999-11-09 | 2000-05-10 | 复旦大学 | Acrylic resin paint with high solid content and its preparation |
| US20050004300A1 (en) * | 2001-08-14 | 2005-01-06 | Overbeek Gerardus Cornelis | Aqueous crosslinkable coating compositions based on vinyl fluoropolymer |
| CN101792639A (en) * | 2010-04-02 | 2010-08-04 | 德莱特恩环保涂料(北京)有限公司 | Wear-resisting scratch-resisting weather-proof polyurethane coating and preparation method thereof |
-
2011
- 2011-03-22 CN CN201110068559A patent/CN102190759B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05186715A (en) * | 1991-12-24 | 1993-07-27 | Mitsubishi Rayon Co Ltd | Antifouling coating composition |
| CN1252423A (en) * | 1999-11-09 | 2000-05-10 | 复旦大学 | Acrylic resin paint with high solid content and its preparation |
| US20050004300A1 (en) * | 2001-08-14 | 2005-01-06 | Overbeek Gerardus Cornelis | Aqueous crosslinkable coating compositions based on vinyl fluoropolymer |
| CN101792639A (en) * | 2010-04-02 | 2010-08-04 | 德莱特恩环保涂料(北京)有限公司 | Wear-resisting scratch-resisting weather-proof polyurethane coating and preparation method thereof |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585108A (en) * | 2012-01-17 | 2012-07-18 | 杭州日耀科技有限公司 | Polyester-modified organic fluorine-silicon acrylic resin and preparation method thereof as well as paint using resin |
| CN102838707A (en) * | 2012-09-19 | 2012-12-26 | 江阴恒兴涂料有限公司 | High-performance water-soluble acrylic resin and preparation method thereof |
| CN103030744A (en) * | 2012-11-30 | 2013-04-10 | 无锡市虎皇漆业有限公司 | Polyester modified acrylic resin for wood lacquer and wood lacquer |
| CN103030744B (en) * | 2012-11-30 | 2014-10-22 | 无锡市虎皇漆业有限公司 | Polyester modified acrylic resin for wood lacquer and wood lacquer |
| CN103483503A (en) * | 2013-09-29 | 2014-01-01 | 江苏蓝色星球环保科技股份有限公司 | Polyester modified hydroxyl type fluorinated acrylate resin and preparation method thereof |
| CN105400254B (en) * | 2015-11-27 | 2017-08-18 | 宁波双人新材料有限公司 | A kind of weatherable polyether powder coating and preparation method thereof |
| CN105400254A (en) * | 2015-11-27 | 2016-03-16 | 宁波双人新材料有限公司 | Weather-proof polyester powder coating and preparation method thereof |
| CN111234126A (en) * | 2020-03-31 | 2020-06-05 | 南京长江涂料有限公司 | High-solid-content high-performance glycidyl versatate modified alkyd resin and preparation method thereof |
| CN111234126B (en) * | 2020-03-31 | 2022-12-06 | 南京长江涂料有限公司 | High-solid-content high-performance glycidyl versatate modified alkyd resin and preparation method thereof |
| CN111393622A (en) * | 2020-04-29 | 2020-07-10 | 广东邦弗特新材料有限公司 | Saturated polyester resin modified by hydroxyl acrylic fluorine-containing resin and preparation method thereof |
| CN114437301A (en) * | 2021-11-18 | 2022-05-06 | 江苏沃莱新材料有限公司 | Polyester modified hydroxyl acrylic resin and preparation method thereof, high-durability hydroxyl acrylic resin coating and application thereof |
| CN115477878A (en) * | 2022-09-15 | 2022-12-16 | 海洋化工研究院有限公司 | Solvent type skin finishing varnish and preparation method and application thereof |
| CN115477878B (en) * | 2022-09-15 | 2023-02-28 | 海洋化工研究院有限公司 | Solvent type skin finishing varnish and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102190759B (en) | 2012-10-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102190759B (en) | Polyester modified fluoro acrylic resin, and preparation method and coating thereof | |
| CN102585108A (en) | Polyester-modified organic fluorine-silicon acrylic resin and preparation method thereof as well as paint using resin | |
| CN101560278B (en) | Methyl methacrylate-styrene copolymer containing fluoro-acrylate and preparation method thereof | |
| CN103360561B (en) | Polyurethane modified acrylic emulsion, preparation method of acrylic emulsion and prepared artificial stone | |
| CN101550218B (en) | Polymer emulsion, preparation method and re-dispersible latex powder | |
| CN105622862A (en) | Concrete polycarboxylate water reducing agent and preparing method thereof | |
| CN103172291B (en) | Polycarboxylic-acid water reducing agent synthesized at normal temperature, and preparation method and application method thereof | |
| KR101200124B1 (en) | High-molecular dispersant for inorganic pigments | |
| CN101619116B (en) | Thermoplastic fluorine-containing acrylic resin and preparation method thereof | |
| CN102030483A (en) | Preparation method of porous antireflection film formed by nanopolymer hollow particles | |
| CN105111998A (en) | Ultraviolet curing adhesive | |
| CN102153711A (en) | Preparation method of slow-setting polycarboxylic acid water reducing agent | |
| CN101935387B (en) | Modified UV photocuring pure acrylic resin and preparation method thereof | |
| CN103131354A (en) | Styrene modified polyvinyl acetate emulsion and preparation method | |
| CN108395494A (en) | A kind of preparation method of the latex particle of gradual change type glass transition temperature | |
| Wang et al. | Study on the dispersion, adsorption and early hydration behavior of cement pastes containing multi-armed polycarboxylate superplasticizers | |
| CN109294460A (en) | A kind of UV solidification Liquid optical clear adhesive of color inhibition and preparation method thereof | |
| CN103304813A (en) | Cured resin, spacing agent and filter, as well as preparation methods and display devices thereof | |
| CN103304727A (en) | Core-shell structural elastic emulsion, coating containing emulsion and preparation method thereof | |
| CN102134415B (en) | Fluorine-containing acrylate leveling agent for solvent type coating | |
| CN110066359A (en) | A kind of water-soluble thermosetting acrylic resin and its preparation method and application | |
| CN101984494A (en) | Anti-settling photosensitive silver paste and preparation method thereof | |
| CN103709315B (en) | The pigment preparation method of high light acrylic ester emulsion | |
| CN102391438B (en) | Vinyl resin and preparation method thereof | |
| CN107722185B (en) | Low-surface-energy fluorine-silicon antifouling resin and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: WU ZHIHUA Free format text: FORMER OWNER: WENZHOU UNIVERSITY Effective date: 20131024 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 325000 WENZHOU, ZHEJIANG PROVINCE TO: 310013 HANGZHOU, ZHEJIANG PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20131024 Address after: Room 633, C building, No. 525 Xixi Road, Xihu District, Zhejiang, Hangzhou 310013, China Patentee after: Wu Zhihua Address before: 325000 Zhejiang province Chashan Wenzhou Higher Education Park Patentee before: Wenzhou University |
|
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20110921 Assignee: Hangzhou Riyao Technology Co., Ltd. Assignor: Wu Zhihua Contract record no.: 2014330000127 Denomination of invention: Polyester modified fluoro acrylic resin, and preparation method and coating thereof Granted publication date: 20121017 License type: Exclusive License Record date: 20140505 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210427 Address after: No.11, Shengyang Road, Shangma Industrial Park, Wenling Economic Development Zone, Wenzhou, Zhejiang, 317500 Patentee after: ZHEJIANG YUTONG NEW MATERIAL Co.,Ltd. Address before: Room 633, C building, No. 525 Xixi Road, Xihu District, Zhejiang, Hangzhou 310013, China Patentee before: Wu Zhihua |
|
| TR01 | Transfer of patent right | ||
| CP02 | Change in the address of a patent holder |
Address after: No.11, Shengyang Road, Shangma Industrial Park, Wenling Economic Development Zone, Wenling City, Taizhou City, Zhejiang Province, 317500 Patentee after: ZHEJIANG YUTONG NEW MATERIAL Co.,Ltd. Address before: No.11, Shengyang Road, Shangma Industrial Park, Wenling Economic Development Zone, Wenzhou, Zhejiang, 317500 Patentee before: ZHEJIANG YUTONG NEW MATERIAL Co.,Ltd. |
|
| CP02 | Change in the address of a patent holder |