CN102585108A - Polyester-modified organic fluorine-silicon acrylic resin and preparation method thereof as well as paint using resin - Google Patents
Polyester-modified organic fluorine-silicon acrylic resin and preparation method thereof as well as paint using resin Download PDFInfo
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- CN102585108A CN102585108A CN201210013155XA CN201210013155A CN102585108A CN 102585108 A CN102585108 A CN 102585108A CN 201210013155X A CN201210013155X A CN 201210013155XA CN 201210013155 A CN201210013155 A CN 201210013155A CN 102585108 A CN102585108 A CN 102585108A
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- polyester
- fluorine
- organic silicon
- vinyl resin
- polyester modification
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- 239000011347 resin Substances 0.000 title claims abstract description 38
- 229920005989 resin Polymers 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 11
- 239000003973 paint Substances 0.000 title abstract description 7
- 229920000178 Acrylic resin Polymers 0.000 title abstract 6
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 title abstract 5
- 229920000728 polyester Polymers 0.000 claims abstract description 43
- 239000000178 monomer Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 239000012046 mixed solvent Substances 0.000 claims abstract description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 10
- 239000011737 fluorine Substances 0.000 claims abstract description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 7
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims abstract description 6
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 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 abstract description 5
- 229940119545 isobornyl methacrylate Drugs 0.000 claims abstract description 5
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims abstract description 5
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000012986 modification Methods 0.000 claims description 27
- 230000004048 modification Effects 0.000 claims description 27
- 229920002554 vinyl polymer Polymers 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 229920001296 polysiloxane Polymers 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- -1 t-amyl peroxy Chemical group 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 5
- JGWUKKFNKOUBPW-UHFFFAOYSA-N 2-ethenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical class C=C[SiH]1O[SiH2]O[SiH2]O[SiH2]O1 JGWUKKFNKOUBPW-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 claims description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- 230000002745 absorbent Effects 0.000 claims description 3
- 239000002250 absorbent Substances 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 239000003518 caustics Substances 0.000 claims description 3
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 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
- 238000009413 insulation Methods 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- OZCWUNHGNVXCCO-UHFFFAOYSA-N oxiran-2-ylmethyl hydrogen carbonate Chemical group OC(=O)OCC1CO1 OZCWUNHGNVXCCO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000001038 titanium pigment Substances 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000013067 intermediate product Substances 0.000 claims description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- VDRSDNINOSAWIV-UHFFFAOYSA-N [F].[Si] Chemical compound [F].[Si] VDRSDNINOSAWIV-UHFFFAOYSA-N 0.000 claims 1
- 229910052728 basic metal Inorganic materials 0.000 claims 1
- 150000003818 basic metals Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 claims 1
- KXNVYIMVNJZBOS-UHFFFAOYSA-N fluoromethane;prop-2-enoic acid Chemical compound FC.OC(=O)C=C KXNVYIMVNJZBOS-UHFFFAOYSA-N 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 abstract 2
- 230000000379 polymerizing effect Effects 0.000 abstract 2
- 239000002243 precursor Substances 0.000 abstract 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 abstract 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000006096 absorbing agent Substances 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 abstract 1
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 235000010215 titanium dioxide Nutrition 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 9
- 150000007513 acids Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000001458 anti-acid effect Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000000126 substance Substances 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
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- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses polyester-modified organic fluorine-silicon acrylic resin and a preparation method thereof as well as paint using the resin. The polyester-modified organic fluorine-silicon acrylic resin is prepared by polymerizing a polyester precursor, a mixed monomer and an initiator in a mixed solvent, wherein the mixed monomer used in reaction comprises the following components: ethyl acrylate, methacrylic acid, isobornyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, butyl acrylate, glycidyl tertcarbonate, fluorine-containing methacrylate monomer and organic silicon intermediate. The paint comprises the following components: the polyester-modified organic fluorine-silicon acrylic resin, titanium white, a dispersing agent, a flatting agent, an ultraviolet-resistant absorber, dimethylbenzene, isophorone and propylene glycol methyl ether acetate. According to the invention, the polyester-modified organic fluorine-silicon acrylic resin is obtained by polymerizing the polyester precursor with an acrylic acid monomer solution, and is prepared into the paint; the resin has good property and is superior to fluorine-acrylic resin in the aspects of distinctness of image, hardness, acid-alkali resistance, high-low temperature resistance and the like.
Description
Technical field
The present invention relates to polyester modification organic silicon-fluorine vinyl resin preparation field, is meant that especially lower run machine skin material is with polyester modification organic silicon-fluorine vinyl resin of coating and preparation method thereof.
Background technologyOrganosilicon material is because silica bond energy (460 kJ/mol) is higher than carbon-oxygen bond (351 kJ/mol) and carbon-carbon bond (347 kJ/mol), and the coating that therefore contains organosilicon material has characteristics such as high-weatherability, excellent anti-stain characteristic, strong antiacid rain property.Fluorin modified crylic acid resin is then having advantageous characteristic aspect non-corrosibility, contamination resistance, chemical-resistant and the outdoor overlength weathering resistance.Fluorin modified crylic acid resin has certain report, but is used for patent of invention that coating makes seldom, and Chinese disclosure of the Invention number is used for the manufacturing of helicopter skining paint for CN1923868A has reported a kind of fluorin modified crylic acid resin, has obtained good result.Along with the raising that coating is required; When satisfying characteristics such as weathering resistance, anti-stain characteristic, antiacid rain property, chemical-resistant; Be necessary to continue to promote the overall quality of resin at aspects such as clarity, hardness and high-low temperature resistants; Therefore can polyester and fluorin modified crylic acid be contained the resin-bonded of silicone intermediate, obtained performance is the resin material of excellence more.At present, organic-silicon-modified resin is a lot, studies also comparatively fully, but to the research of polyester modification perfluoroalkyl acrylate resin seldom, and the perfluoroalkyl acrylate resin that will contain silicone intermediate carries out polyester modification, and report is not arranged so far.
Summary of the invention
The present invention has three targets; First target is to overcome some shortcoming and defect that prior art exists; Provide a kind of resin property good, especially at the polyester modification organic silicon-fluorine vinyl resin of aspect superior performances such as clarity, hardness, resistance to acids and bases, high-low temperature resistant.Second target of the present invention provides the preparation method of above-mentioned polyester modification organic silicon-fluorine vinyl resin.The 3rd target of the present invention provides a kind of above-mentioned polyester modification organic silicon-fluorine vinyl resin coatings formulated of utilizing.
For realizing first target of the present invention; Its technical scheme is to be made by polyester presoma, mix monomer (containing silicone intermediate and fluorine-containing methacrylate 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 the 13-16% of total charging capacity;
The amount of mixed solvent accounts for the 28-32% of total charging capacity;
The amount of initiator accounts for total charging capacity (1.8-2.2%);
The amount of mix monomer accounts for the 51-55% of total charging capacity,
This mix monomer comprises following component, accounts for the mass percent meter of mix monomer:
Ethyl propenoate 4-8%; Methylacrylic acid 6%-8%; Isobornyl methacrylate 16-20%; NSC 20956 11%-15%; Rocryl 400 15%-19%; Bing Xisuandingzhi 16%-20%; Tertiary carbonic acid glycidyl ester 6-8%; Fluorine-containing methacrylate monomer 11%-15%; Silicone intermediate 2-4%.
Above-mentioned described polyester presoma is prepared by following mode: with TriMethylolPropane(TMP) (12-15%), and NSC 6366 (28-34%), phthalic anhydride (21-25%); M-phthalic acid (27-32%), toluene (5-7%), Dibutyltin oxide (0.20-0.30%); Anti--168 (0.35-0.65%) drop into and have in the flask of water trap, and fully logical nitrogen heats up then gradually; Basically dissolve to material; Start to stir and also to continue to heat up,, keep reflux dewatering and control the water trap head temperature being controlled at 160-180 ° of C at 100 ° below the C, the temperature of reaction of flask to refluxing; When dehydrating amount reach theoretical water 90% the time, the temperature in the flask can raise gradually, but is controlled at 210 ° below the C; When dehydrating amount during near theoretical value, get material and measure acid number, when acid number is 8 mgKOH/g, be reaction end; Stop heating, cool to about 80 ° of C naturally, add YLENE and N-BUTYL ACETATE solvent (weight ratio 1:1) latting drown then; Consumption is about 33% of total charging capacity, stirs, and filters.Described theoretical dehydrating amount is about 12% of above-mentioned total charging capacity.
Above-mentioned described fluorine-containing methacrylate monomer is a trifluoroethyl methacrylate, vinylformic acid hexafluoro butyl ester and methylacrylic acid hexafluoro butyl ester.
Above-mentioned described silicone intermediate is prepared from following mode: eight vinyl cyclotetrasiloxanes and octamethylcyclotetrasiloxane carry out polymerization and obtain (eight vinyl cyclotetrasiloxanes and octamethylcyclotetrasiloxane mass percent are 65-73:35-27) under alkali metal hydroxide catalysis.Catalyzer can be a sodium hydroxide, Pottasium Hydroxide, volatile caustic; Butyl alcohol-tert potassium, consumption (mass percent) is 0.5-2%, temperature of reaction 80-140 ° of C; Reaction times 5-7 hour, gained organosilicon intermediate product water white transparency, purity 100%; Viscosity (being coated with-4 glasss) is 160-210 second, and molecular weight is 650-970 (gel chromatography).
Above-mentioned described initiator is two t-amyl peroxy things.
Above-mentioned described mixed solvent is YLENE and N-BUTYL ACETATE, and proportioning (mass ratio) is 1:1.
For realizing second target of the present invention, technical scheme of the present invention 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 mix monomer, the amount of mix monomer accounts for the 51-55% of total charging capacity, and this mix monomer comprises following component, accounts for the mass percent meter of mix monomer:
Ethyl propenoate 4-8%; Methylacrylic acid 6%-8%; Isobornyl methacrylate 16-20%; NSC 20956 11%-15%; Rocryl 400 15%-19%; Bing Xisuandingzhi 16%-20%; Tertiary carbonic acid glycidyl ester 6-8%; Fluorine-containing methacrylate monomer 11%-15%; Silicone intermediate 2-4%.
B) preparation polyester presoma, this polyester presoma consumption is the 13-16% of total charging capacity;
C) preparation mixed solvent, this mixed solvent accounts for the 28-32% of total charging capacity;
Polyreaction: get the bottoming of polyester presoma, logical nitrogen heats up; Stir, be raised to about 125 ° of C, the formula ratio that adds mixed solvent down of refluxing 65% in the flask that has water-and-oil separator; Heat to reflux temperature, the mix monomer with 100% is placed in the tap funnel, with the initiator of 10% dissolution with solvents dilution 75% and be placed in another tap funnel; Simultaneously evenly be added to reactive system with 3～4 hours liquid with two tap funnels and carry out polyreaction, after dropwising, insulation is 2～3 hours under reflux temperature; 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 3～5 hours up to the acid number of resin less than set quota, obtain polyester modification perfluoroalkyl acrylate resin material.
For realizing the 3rd target of the present invention, its technical scheme is to comprise following component, in mass fraction, and polyester modification organic silicon-fluorine vinyl resin, 48 parts; White titanium pigment, 28 parts; Dispersion agent, 2 parts; Flow agent, 1 part; Ultraviolet-resistant absorbent, 2 parts; YLENE, 9 parts; Different fluorine that ketone, 5 parts; 1-Methoxy-2-propyl acetate, 4 parts.
For this reason; The present invention utilizes polyester presoma and silicone intermediate, Acrylic Acid Monomer solution polymerization to obtain polyester modification organic silicon-fluorine vinyl resin and be mixed with skin material to carry out application with coating; The application result shows that resin property is excellent, obviously is superior to being used for the skining paint of perfluoroalkyl acrylate resins at aspects such as clarity, hardness, resistance to acids and bases, high-low temperature resistants.
Technique effect
The polyester modification organic silicon-fluorine vinyl resin that the present invention makes has following technical indicator: as clear as crystal liquid, solids constituent 64-66%; Viscosity (Ge Shi pipe, 25 ° of C) 9-13s; Acid number < 11 mgKOH/>g.The actual use properties of resin is investigated through the application that skin material coats that is used for of preparation; Test-results shows: coating performance is good; For example obviously be superior to often being coated with the S04 coating property, especially at aspect excellent performances such as clarity, hardness, resistance to acids and bases, high-low temperature resistants.
Embodiment
Through embodiment the present invention is carried out concrete description below; 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.
Embodiment 1
The preparation of organosilicon intermediate: with eight vinyl cyclotetrasiloxanes, 227 grams, octamethylcyclotetrasiloxane 74 grams join in the four-hole boiling flask of 500mL, stir; Add each 3 gram of volatile caustic and butyl alcohol-tert potassium again, heat up, maintain the temperature at 135-145 ° of C and reacted 5.5 hours down; Stopped reaction, cooling obtains silicone intermediate; The product water white transparency, viscosity (being coated with-4 glasss) is 195 seconds, molecular weight 913 (gel chromatography).
Embodiment 2
The preparation of polyester presoma.With 259 gram NSC 6366s, 81 gram TriMethylolPropane(TMP)s, 179 gram phthalic anhydrides, 201 gram m-phthalic acids; 36 gram toluene, 1.7 gram Dibutyltin oxides, 3.9 grams anti--168 are put in the four-hole boiling flask that has water trap, logical nitrogen; Heat up, when material dissolves basically, start stirring.Continue to heat up, reflux dewatering, the preceding control water trap head temperature of 90% [theoretical water is 73 grams] that does not reach theoretical value in dehydration is no more than 100 ° of C, and the temperature of reaction of flask is controlled at 160-180 ° of C; When dehydrating amount reach theoretical water 90% the time, the temperature in the flask raises gradually, but is no more than 210 ° of C.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 ° of C, adds YLENE and N-BUTYL ACETATE solvent 238 gram (weight ratio 1:1) latting drowns, stirs filtration.Testing index is: solids constituent 69.2%, acid number are 6.6 mgKOH/g, and viscosity (25 ° of C, Ge Shi pipe) is 24s.
Embodiment 3
Polyester modification organic silicon-fluorine vinyl resin.Get polyester presoma 180 grams, put into the four-hole boiling flask of water-and-oil separator, heat up, stir, be raised to about 125 ° of C.Add 65% (234 gram) (by YLENE, N-BUTYL ACETATE 1:1 preparation, total amount is 360 grams) of solvent formula amount, heat to reflux temperature.[amount of mix monomer is 636 grams with 100% mix monomer; Ethyl propenoate (4%), isobornyl methacrylate (18%), NSC 20956 (16%), Rocryl 400 (14%), Bing Xisuandingzhi (19%), methylacrylic acid (12%) and fluorine-containing methacrylate monomer (15%; Trifluoroethyl methacrylate: methylacrylic acid hexafluoro butyl ester: the weight ratio of methylacrylic acid hexafluoro isopropyl ester is 1:2:2), silicone intermediate (2%) is put into tap funnel; With two t-amyl peroxy thing initiators of 15% dissolution with solvents dilution 80% (containing initiator 19 grams) and be injected in another tap funnel, the liquid in two tap funnels evenly is added drop-wise in the reactive system again with 4 hours.After dropwising, insulation is 1.5 hours under reflux temperature, with remaining solvent and initiator (total amount 20%), in 1.5 hours, at the uniform velocity is added drop-wise in the reaction kettle 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, 64.8%; Viscosity (Ge Shi pipe, 25 ° of C), 12 s; Acid number, 9.7 mgKOH/g.
Embodiment 4
The varnish preparation.With the above-mentioned synthetic polyester modification organic silicon-fluorine vinyl resin preparation coating that obtains, basic recipe is following: polyester modification organic silicon-fluorine vinyl resin, 48 parts (mass percent); White titanium pigment, 28 parts; Dispersion agent, 2 parts; Flow agent, 1 part; Ultraviolet-resistant absorbent, 2 parts; YLENE, 9 parts; Different fluorine that ketone, 5 parts; 1-Methoxy-2-propyl acetate, 4 parts.Solidifying agent adopts DESMODUR N-3390 HDI trimer curing agent.The ratio of white paint and solidifying agent is 100: 27.Coat-thickness is about 25 μ m.Join coating try to be coated with at low flyer with skin material, the performance that records is following:
Claims (8)
1. polyester modification organic silicon-fluorine vinyl resin, it is characterized in that: it is made 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 the 13-16% of total charging capacity;
The amount of mixed solvent accounts for the 28-32% of total charging capacity;
The amount of initiator accounts for the 1.8-2.2% of total charging capacity;
The amount of mix monomer accounts for the 51-55% of total charging capacity, and said mix monomer comprises following component, accounts for the mass percent meter of mix monomer:
Ethyl propenoate 4-8%; Methylacrylic acid 6%-8%; Isobornyl methacrylate 16-20%; NSC 20956 11%-15%; Rocryl 400 15%-19%; Bing Xisuandingzhi 16%-20%; Tertiary carbonic acid glycidyl ester 6-8%; Fluorine-containing methacrylate monomer 11%-15%; Silicone intermediate 2-4%.
2. a kind of polyester modification organic silicon-fluorine vinyl resin according to claim 1; It is characterized in that: described polyester presoma prepares in the following manner: by mass percent TriMethylolPropane(TMP) 12-15%, NSC 6366 28-34%, phthalic anhydride 21-25%, m-phthalic acid 27-32%, toluene 5-7%, Dibutyltin oxide 0.20-0.30% and anti--168 0.35-0.65% input are had in the flask of water trap; Fully logical nitrogen; Heat up gradually then; Basically dissolve to material, start to stir and continue and heat up, to refluxing; Keep reflux dewatering and control the water trap head temperature at 100 ° below the C, the temperature of reaction of flask is controlled at 160-180 ° of C; When dehydrating amount reach theoretical water 90% the time, the temperature in the flask can raise gradually, but is controlled at 210 ° below the C; When dehydrating amount during near theoretical value; Getting material and measure acid number, is reaction end when acid number is 8 mgKOH/g, stops heating; Naturally cool to 80 ° of C; Add YLENE and N-BUTYL ACETATE solvent latting drown that the mass percent weight ratio is 1:1 then, its consumption is 33% of total charging capacity, stirs at last, filters.
3. a kind of polyester modification organic silicon-fluorine vinyl resin according to claim 1 is characterized in that: described initiator is two t-amyl peroxy things.
4. a kind of polyester modification organic silicon-fluorine vinyl resin according to claim 1, it is characterized in that: mixed solvent is YLENE and N-BUTYL ACETATE, proportioning is 1:1.
5. a kind of polyester modification organic silicon-fluorine vinyl resin according to claim 1 is characterized in that: described methyl fluoride acrylate monomer is any one or a few in trifluoroethyl methacrylate, methylacrylic acid hexafluoro butyl ester, the methylacrylic acid hexafluoro isopropyl ester.
6. a kind of polyester modification organic silicon-fluorine vinyl resin according to claim 1; It is characterized in that: described silicone intermediate is prepared from following mode: with mass percent is that eight vinyl cyclotetrasiloxanes and the octamethylcyclotetrasiloxane of 65-73:35-27 carries out polymerization and obtain under alkali metal hydroxide catalysis; Said basic metal catalytic materials is a kind of in sodium hydroxide, Pottasium Hydroxide, volatile caustic, the butyl alcohol-tert potassium; Its consumption is 0.5-2%, temperature of reaction 80-140 ° of C, reaction times 5-7 hour; Gained silicone intermediate product water white transparency, its purity are 100%, viscosity is 160-210 second, molecular weight is 650-970.
7. the preparation method of a kind of polyester modification organic silicon-fluorine vinyl resin according to claim 1 is characterized in that: described polyester modification organic silicon-fluorine vinyl resin is prepared from following polyreaction: get the bottoming of polyester presoma, logical nitrogen; Heat up, stir, be raised to 125 ° of C; Reflux the formula ratio that adds mixed solvent down 65% in the flask that has water-and-oil separator, heat to reflux temperature, the mix monomer with 100% is placed in the tap funnel; With the initiator of 10% dissolution with solvents dilution 75% and be placed in another tap funnel; Simultaneously evenly be added to reactive system with 3～4 hours liquid with two tap funnels and carry out polyreaction, after dropwising, insulation is 2～3 hours under reflux temperature; 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 3～5 hours up to the acid number of resin less than set quota, obtain polyester modification perfluoroalkyl acrylate resin material.
8. one kind is utilized the described polyester modification organic silicon-fluorine of claim 1 vinyl resin institute coatings formulated, and it is characterized in that: it comprises following component, in parts by weight:
Polyester modification organic silicon-fluorine vinyl resin: 48 parts; White titanium pigment: 28 parts; Dispersion agent: 2 parts; Flow agent: 1 part; Ultraviolet-resistant absorbent: 2 parts; YLENE: 9 parts; Different fluorine that ketone: 5 parts; 1-Methoxy-2-propyl acetate: 4 parts.
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| CN103214632A (en) * | 2013-04-15 | 2013-07-24 | 湖北大学 | Water-soluble fluoroacrylic acid-polyester transparent insulating resin and preparation method thereof |
| CN103275330A (en) * | 2013-06-07 | 2013-09-04 | 苏州兴业材料科技股份有限公司 | Fluorine-containing organosilicone dual-modified acrylic resin material for aircraft skin coating |
| CN103666165A (en) * | 2013-09-11 | 2014-03-26 | 东莞上海大学纳米技术研究院 | Preparation method of organic fluorine-silicon bionic anti-fouling resin and product |
| CN104002061A (en) * | 2014-05-21 | 2014-08-27 | 广州柏仕达新材料有限公司 | High-performance high-stability nanometer soldering paste 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 |
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| CN110684186A (en) * | 2019-10-12 | 2020-01-14 | 杭州金质丽科技有限公司 | Organosilicon modified fluorine-containing powder resin, preparation method and super-lubricating powder coating |
| CN111363130A (en) * | 2020-04-29 | 2020-07-03 | 广东邦弗特新材料有限公司 | Epoxy acrylic fluorine-containing resin modified saturated polyester resin and preparation method thereof |
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| CN103214632A (en) * | 2013-04-15 | 2013-07-24 | 湖北大学 | Water-soluble fluoroacrylic acid-polyester transparent insulating resin and preparation method thereof |
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| 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 |
| 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 |
| CN109734884A (en) * | 2019-01-14 | 2019-05-10 | 浙江天女集团制漆有限公司 | A kind of resistance to deep-draw water-borne acrylic acid modified polyester resin and preparation method thereof |
| CN109734884B (en) * | 2019-01-14 | 2021-04-09 | 浙江天女集团制漆有限公司 | Deep drawing resistant waterborne acrylic modified polyester resin and preparation method thereof |
| CN110684186A (en) * | 2019-10-12 | 2020-01-14 | 杭州金质丽科技有限公司 | Organosilicon modified fluorine-containing powder resin, preparation method and super-lubricating powder coating |
| CN111363130A (en) * | 2020-04-29 | 2020-07-03 | 广东邦弗特新材料有限公司 | Epoxy acrylic fluorine-containing resin modified saturated polyester 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 |
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Application publication date: 20120718 |