CN101942064B - Modified polyester and water-borne middle coating composition - Google Patents
Modified polyester and water-borne middle coating composition Download PDFInfo
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- CN101942064B CN101942064B CN2010105045797A CN201010504579A CN101942064B CN 101942064 B CN101942064 B CN 101942064B CN 2010105045797 A CN2010105045797 A CN 2010105045797A CN 201010504579 A CN201010504579 A CN 201010504579A CN 101942064 B CN101942064 B CN 101942064B
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- 229920000728 polyester Polymers 0.000 title claims abstract description 135
- 239000008199 coating composition Substances 0.000 title claims abstract description 34
- 239000000178 monomer Substances 0.000 claims abstract description 79
- 239000000203 mixture Substances 0.000 claims abstract description 65
- 239000002253 acid Substances 0.000 claims abstract description 39
- -1 acrylic ester Chemical class 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 239000013067 intermediate product Substances 0.000 claims abstract description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001336 alkenes Chemical class 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 8
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 83
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 45
- 239000003795 chemical substances by application Substances 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 239000003112 inhibitor Substances 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 16
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 13
- 230000000694 effects Effects 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 9
- QAGHEHQMRFEQMB-UHFFFAOYSA-N 2-ethylidenepropanedioic acid Chemical compound CC=C(C(O)=O)C(O)=O QAGHEHQMRFEQMB-UHFFFAOYSA-N 0.000 claims description 9
- 230000003472 neutralizing effect Effects 0.000 claims description 9
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 8
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 8
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 8
- 235000011150 stannous chloride Nutrition 0.000 claims description 8
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 8
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 7
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 229960002887 deanol Drugs 0.000 claims description 6
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 6
- 239000012972 dimethylethanolamine Substances 0.000 claims description 6
- 239000005056 polyisocyanate Substances 0.000 claims description 6
- 229920001228 polyisocyanate Polymers 0.000 claims description 6
- 229920003180 amino resin Polymers 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 229960004418 trolamine Drugs 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 229940086542 triethylamine Drugs 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract description 2
- 239000003963 antioxidant agent Substances 0.000 abstract 1
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- VQLYBLABXAHUDN-UHFFFAOYSA-N bis(4-fluorophenyl)-methyl-(1,2,4-triazol-1-ylmethyl)silane;methyl n-(1h-benzimidazol-2-yl)carbamate Chemical compound C1=CC=C2NC(NC(=O)OC)=NC2=C1.C=1C=C(F)C=CC=1[Si](C=1C=CC(F)=CC=1)(C)CN1C=NC=N1 VQLYBLABXAHUDN-UHFFFAOYSA-N 0.000 abstract 1
- 239000006184 cosolvent Substances 0.000 abstract 1
- 150000007519 polyprotic acids Polymers 0.000 abstract 1
- 150000005846 sugar alcohols Polymers 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- 238000010792 warming Methods 0.000 description 22
- 239000003973 paint Substances 0.000 description 20
- 238000009413 insulation Methods 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 239000004575 stone Substances 0.000 description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- 230000035939 shock Effects 0.000 description 9
- 238000010907 mechanical stirring Methods 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 6
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 6
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 6
- 238000007667 floating Methods 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 239000002987 primer (paints) Substances 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000001530 fumaric acid Substances 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 4
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 4
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 4
- 238000009736 wetting Methods 0.000 description 4
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 3
- 229920003270 Cymel® Polymers 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 150000003512 tertiary amines Chemical group 0.000 description 3
- 239000000080 wetting agent Substances 0.000 description 3
- DSCFFEYYQKSRSV-UHFFFAOYSA-N 1L-O1-methyl-muco-inositol Natural products COC1C(O)C(O)C(O)C(O)C1O DSCFFEYYQKSRSV-UHFFFAOYSA-N 0.000 description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical group [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000001038 titanium pigment Substances 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 229920003275 CYMEL® 325 Polymers 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- GLDOVTGHNKAZLK-UHFFFAOYSA-N n-octadecyl alcohol Natural products CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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Abstract
The invention provides modified polyester, which is prepared by the following steps of: a) under the action of an antioxidant and a catalyst, reacting polyhydric alcohol and alkene diacid with polybasic acid to obtain polyester; b) adding an aqueous cosolvent into the polyester to obtain a polyester mixture; c) adding a first monomer, a second monomer, a third monomer and a radical initiator into the polyester mixture, and continuously reacting to obtain a first intermediate product, wherein the first monomer is one or two of crylic acid and methacrylic acid, the second monomer is one or more of acrylic ester and styrene, and the third monomer is crylic acid hydroxy ester; and d) adding a neutralizer into the first intermediate product, and stirring for neutralization to obtain the modified polyester. The invention also provides a water-borne middle coating composition. Experiments show that the water-borne middle coating composition has the stone-chip resistance of less than or equal to 3 grade, the impact strength of more than or equal to 50kg.cm and the lustre of 70 to 80 percent at 60 DEG C.
Description
Technical field
The present invention relates to technical field of coatings, relate in particular in a kind of modified poly ester and the water-based and be coated with coating composition.
Background technology
The body of a motor car coating is a multilayer system, generally includes electrophoretic deposition prime coat, floating coat and top coat layer etc.Floating coat not only can increase the sticking power of priming paint and finish paint, can also cushion the impact that sandstone forms car surface on the road surface, and protection primer coating and ground are injury-free, improves the weather resistance of primer coating film greatly.In addition, floating coat can also be adjusted the ground planeness, fill and lead up defectives such as the sand holes of coating surface, pin hole, forms smoothly to be coated with the surface in careful, improves the vividness and the plentiful type of topcoat, obtains better decorative effect.
Prior art disclose multiple formation floating coat in coating, wherein, the paint film that waterborne polyester coating obtains has good glossiness, good anti-stone and hits performance, good toughness and hardness and obtained extensive studies and application.Like application number is that 200780003337.6 Chinese patent document discloses in a kind of water-based and is coated with coating composition; Comprise that hydroxyl value is that 100～200mgKOH/g, acid number are polyester, solidifying agent and the flats pigment particles of 20～50mgKOH/g; The paint film that this coating obtains has good smoothness; But, cause the water tolerance of coating relatively poor because the hydroxyl value and the acid number of the polyester that uses are all higher.In order to improve the water tolerance of coating; Application number is that 01138041.1 Chinese patent document discloses the water-dispersed paint that a kind of automobile floating coat is used; This coating by acid number be 20～25, hydroxyl value is that 50～100 polyester, color stuffing, linking agent, catalyzer, auxiliary agent and water are formed; Though this coating has water resistance preferably, the adhesive ability of itself and primer coating and topcoat is relatively poor.
Application number is the preparation method that 200710027673.6 Chinese patent document discloses coating in a kind of water-based; Mainly may further comprise the steps: with polyvalent alcohol, dimethylol propionic acid, vinylformic acid is raw material, under the effect of isocyanic ester, forms the aqueous dispersion type resin; , with polyoxyethylene nonylphenol isophorone diisocyanate (IPDI) or hexamethylene diisocyanate (HDI) are carried out modification, but obtain the wetting ability dispersible polyisocyanate as catalyzer with organotin; But aqueous dispersion type resin, color stuffing, catalyzer, auxiliary agent and water are mixed with the wetting ability dispersible polyisocyanate; Coating in can obtaining; Have good sticking power between this coating and primer coating and the topcoat, also have excellent flexibility, anti-stone hits performance and water resistance.But the glossiness of this coating is lower, shock resistance is relatively poor.
Summary of the invention
In view of this, technical problem to be solved by this invention is to provide in a kind of modified poly ester and the water-based and is coated with coating composition, is coated with coating composition in the water-based provided by the invention and has good anti-stone and hit performance, shock resistance and glossiness.
The invention provides a kind of modified poly ester, said modified poly ester prepares according to following method:
A) polyvalent alcohol, alkene diacid and polyprotonic acid reaction under the effect of oxidation inhibitor and catalyzer obtains polyester;
B) in said polyester, add the water-based solubility promoter, obtain polyester mixture;
C) in said polyester mixture, add first monomer, second monomer, the 3rd monomer and radical initiator; Continue reaction and obtain first intermediate product; Said first monomer is one or both in vinylformic acid and the methylacrylic acid; Said second monomer is one or more in propenoate and the vinylbenzene, and said the 3rd monomer is a crylic acid hydroxy ester;
D) in said first intermediate product, add neutralizing agent, stir neutralization, obtain modified poly ester.
Preferably, said polyvalent alcohol is NSC 6366,2-butyl-2-ethyl-1, one or more in ammediol, TriMethylolPropane(TMP) and the 1,4 cyclohexane dimethanol.
Preferably, said alkene diacid is two or three in butene dioic acid, propene dicarboxylic acid and the octadecene diacid.
Preferably, said polyprotonic acid is a m-phthalic acid, 1, one or more in 4-cyclohexane dicarboxylic acid, hexanodioic acid and the Tetra hydro Phthalic anhydride.
Preferably, said catalyzer is one or more in dibutyl tin laurate, tin protochloride and the Dibutyltin oxide.
Preferably, said neutralizing agent is triethylamine, dimethylethanolamine, trolamine or diethylolamine.
Preferably, in the said step a), the temperature of said reaction is 180 ℃～210 ℃.
Preferably, in the said step c), the temperature of said reaction is 120 ℃～140 ℃.
The present invention also provides in a kind of water-based and has been coated with coating composition, comprising:
The described modified poly ester of the technique scheme of 35～100 weight parts;
5～30 parts by weight of cross-linking agent;
3～15 weight part water-based auxiliary agents;
The color stuffing of 10～35 weight parts;
0.3 the water-based flow agent of～1.7 weight parts;
0.6 the water-based skimmer of～1.3 weight parts.
Preferably, said linking agent is aminoresin or blocked polyisocyanate.
Compared with prior art; The present invention is that properties-correcting agent carries out modification to polyester with first monomer, second monomer and the 3rd monomer; Wherein, first monomer is one or both in vinylformic acid and the methylacrylic acid, and second monomer is one or more in propenoate and the vinylbenzene; The 3rd monomer is a crylic acid hydroxy ester, and first monomer, second monomer and the 3rd monomer reaction generation propenoate are grafted to then and obtain acrylic ester grafted modified poly ester on the polyester.Said propenoate has excellent weathering resistance and clarity, also is the main raw of top coat layer, therefore has good sticking power; Said waterborne polyester has good anti-stone and hits performance, shock resistance and toughness, and therefore, the modified poly ester that obtains has excellent weathering resistance, clarity, anti-stone and hits performance, shock resistance and toughness.In addition, said modified poly ester has lower acid number and lower hydroxyl value, and therefore, its water tolerance is better.With modified poly ester provided by the invention is main raw material, adds to be coated with coating composition in the water-based that obtains behind the materials such as linking agent, aqueous promoter, pigment and filler and to have good anti-stone and hit performance, shock resistance, glossiness, water tolerance and sticking power.Experiment shows, the anti-stone that is coated with coating composition in the water-based provided by the invention hits performance≤3 grade, resistance to impact shock>=50kg.cm, and 60 ° of gloss can reach 70%～80%.
Description of drawings
The proton nmr spectra spectrogram of the modified poly ester that Fig. 1 provides for the embodiment of the invention.
Embodiment
The invention provides a kind of modified poly ester, prepare according to following method:
A), polyvalent alcohol, alkene diacid and polyprotonic acid react under the effect of oxidation inhibitor and catalyzer, obtain polyester;
B), in said polyester, add the water-based solubility promoter, obtain polyester mixture;
C), in said polyester mixture, add first monomer, second monomer, the 3rd monomer and radical initiator; Continue reaction and obtain first intermediate product; Said first monomer is one or both in vinylformic acid and the methylacrylic acid; Said second monomer is one or more in propenoate and the vinylbenzene, and said the 3rd monomer is a crylic acid hydroxy ester;
D), in said first intermediate product, add neutralizing agent, stir neutralization, obtain modified poly ester.
Under the effect of catalyzer and oxidation inhibitor, polyvalent alcohol and alkene diacid and polyprotonic acid generation polycondensation generate polyester.The temperature of said reaction is preferably 180 ℃～210 ℃, more preferably 185 ℃～205 ℃.According to the present invention, said polycondensation specifically may further comprise the steps:
With polyvalent alcohol, alkene diacid, polyprotonic acid, oxidation inhibitor and catalyst mix; Slowly be warming up to 180 ℃～200 ℃ reflux dewaterings; Then preferably with 10 ℃/30min～20 ℃/30min, more preferably the speed of 12 ℃/30min～18 ℃/30min is warming up to 210 ℃, insulation back flow reaction 2h～7h; Preferred 2h～5h obtains polyester behind the 2h～3h that reduces pressure then.
Owing to comprise alkene diacid in the reaction raw materials, so contain unsaturated link(age) in the polyester that obtains.
According to the present invention; Said polyvalent alcohol is preferably NSC 6366,2-butyl-2-ethyl-1; In ammediol, TriMethylolPropane(TMP) and the 1,4 cyclohexane dimethanol one or more, more preferably NSC 6366,2-butyl-2-ethyl-1; Ammediol, TriMethylolPropane(TMP) or 1,4 cyclohexane dimethanol;
Said alkene diacid is preferably two or three in butene dioic acid, propene dicarboxylic acid and the octadecene diacid, also can be for wherein a kind of;
Said polyprotonic acid is preferably m-phthalic acid, 1, one or more in 4-cyclohexane dicarboxylic acid, hexanodioic acid and the Tetra hydro Phthalic anhydride, m-phthalic acid, 1 more preferably, 4-cyclohexane dicarboxylic acid, adipic-or phthalic acid acid anhydride;
Said oxidation inhibitor is preferably one or both in four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol esters and the β-positive octadecanol ester of (3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid;
Said catalyzer is preferably one or more in dibutyl tin laurate, tin protochloride and the Dibutyltin oxide.
The mass ratio of said polyvalent alcohol, alkene diacid, polyprotonic acid, oxidation inhibitor and catalyzer is preferably 278～492: 47～176: 236～453: 0.5～0.9: 0.4～1; More preferably 300～450: 60～150: 300～430: 0.5～0.9: 0.4～0.9, most preferably be 350～400: 100～120: 350～400: 0.5～0.9: 0.4～0.8.
After obtaining polyester,, obtain polyester mixture to wherein adding the water-based solubility promoter.The present invention preferably is cooled to 50 ℃～70 ℃ with said polyester, after more preferably 55 ℃～65 ℃, adds the water-based solubility promoter again, obtains polyester mixture after stirring according to method well known to those skilled in the art.
According to the present invention; Said water-based solubility promoter is preferably one or more in 1-Methoxy-2-propyl acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, Virahol and the glycol-12, more preferably one or more in ethylene glycol monobutyl ether, diethylene glycol monobutyl ether and the propylene glycol monobutyl ether.The mass ratio of said water-based solubility promoter and said polyvalent alcohol is preferably 278～492: 60～95, more preferably 300～450: 65～80, most preferably be 350～400: 70～75.According to the present invention, the time of said stirring is preferably 15min～30min, more preferably 20min～25min.
After obtaining polyester mixture; In said polyester mixture, add first monomer, second monomer, the 3rd monomer and radical initiator; Continue reaction and obtain first intermediate product; Said first monomer is one or both in vinylformic acid and the methylacrylic acid, and said second monomer is one or more in propenoate and the vinylbenzene, and said the 3rd monomer is a crylic acid hydroxy ester.Under action of free radical initiator, said first monomer, second monomer, the 3rd monomer and the said polyester generation Raolical polymerizable that contains unsaturated link(age) obtain first intermediate product, specifically may further comprise the steps:
First monomer, second monomer, the 3rd monomer and radical initiator are mixed, obtain the propenoate mixture;
In said polyester mixture, drip said propenoate mixture under the nitrogen protection, insulation reaction obtains first intermediate product.
Under action of free radical initiator, first monomer, second monomer and the 3rd monomer generation Raolical polymerizable obtain the propenoate mixture.According to the present invention, said first monomer is one or more in vinylformic acid and the methylacrylic acid; Said second monomer is one or more in propenoate and the vinylbenzene, and said propenoate is preferably one or more in Bing Xisuandingzhi and the Isooctyl acrylate monomer; Said the 3rd monomer is a crylic acid hydroxy ester, is preferably in Hydroxyethyl acrylate and the Propylene glycol monoacrylate one or both.Said first monomer, second monomer and the 3rd monomeric mass ratio are preferably 10～70: 2～50: 3～80, more preferably 20～60: 5～30: 5～50, most preferably be 25～55: 10～25: 10～30.Said first monomer, second monomer and the 3rd monomeric quality and be preferably 36～96 with the mass ratio of said polyvalent alcohol: 278～492, more preferably 40～90: 300～450, most preferably be 45～85: 350～400.
After being added drop-wise to said propenoate mixture in the polyester mixture; Unsaturated group in the propenoate mixture and the unsaturated group in the polyester mixture react; Obtain first intermediate product, said first intermediate product is acrylic ester grafted polyester.
Said propenoate mixture is being added drop-wise in the polyester mixture when generating said first intermediate product, the temperature of said reaction is preferably 120 ℃～140 ℃, more preferably 125 ℃～135 ℃; The time of said reaction is preferably 2h～7h, more preferably 3h～5h.
React completely in order to make, the present invention is added drop-wise to said propenoate mixture in the polyester mixture, and said rate of addition is preferably 10mL/min～16mL/min, more preferably 11mL/min～15mL/min.
After obtaining first intermediate product, in said first intermediate product, add neutralizing agent, after the stirring neutralization, can obtain modified poly ester.The main effect of said neutralizing agent is sour with acrylic or methacrylic in being, makes the modified poly ester that obtains have lower acid number.According to the present invention, said neutralizing agent is preferably tertiary amine, more preferably triethylamine, dimethylethanolamine, trolamine or diethylolamine.The mass ratio of said neutralizing agent and said polyvalent alcohol is preferably 20～80: 278～492, more preferably 22～72: 300～450, most preferably be 30～65: 350～400.
Underway with the time temperature be preferably 40 ℃～60 ℃, more preferably 45 ℃～55 ℃; The time of said stirring is preferably 10min～30min, more preferably 15min～25min.The present invention does not have particular restriction to said stirring, is mechanical stirring well known to those skilled in the art.
The modified poly ester that obtains through technique scheme, monomeric different according to first monomer, second monomer selected with the 3rd, can various structure; As being vinylformic acid when first monomer, second monomer is propenoate and vinylbenzene, and when the 3rd monomer was crylic acid hydroxy ester, the modified poly ester that obtains had formula (I) structure:
Wherein, R
1Be polyester based;
R
2Be tertiary amine groups;
P, m, s and t are the polymerization degree, 20≤p≤50,1≤m≤23,1≤s≤10,1≤t≤10;
R is 0 or 1.
In formula (I) structure, R
1For polyester diol except that two polyester based the hydroxyl; R
2Be tertiary amine groups, include but not limited to triethyamino, dimethyl ethanol amido, trolamine base, N, N-dimethyl ethanol amido or di-alcohol amido.P is the polymerization degree of modified poly ester, and 20≤p≤50 are preferred, 25≤p≤40; 1≤m≤23, preferred, 3≤m≤20; 1≤s≤10, preferred, 2≤s≤8; 1≤t≤10, preferred, 2≤t≤8; R is 0 or 1.
The present invention is that properties-correcting agent carries out modification to polyester with first monomer, second monomer and the 3rd monomer; Wherein, First monomer is one or both in vinylformic acid and the methylacrylic acid; Second monomer is one or more in propenoate and the vinylbenzene, and the 3rd monomer is a crylic acid hydroxy ester, and first monomer, second monomer and the 3rd monomer reaction generation propenoate are grafted to then and obtain acrylic ester grafted modified poly ester on the polyester.Said propenoate has excellent weathering resistance and clarity, also is the main raw of top coat layer, therefore has good sticking power; Said waterborne polyester has good anti-stone and hits performance, shock resistance and toughness, and therefore, the modified poly ester that obtains has excellent weathering resistance, clarity, anti-stone and hits performance, shock resistance and toughness.In addition, said modified poly ester has lower acid number and lower hydroxyl value, and therefore, its water tolerance is better.
The present invention also provides in a kind of water-based and has been coated with coating composition, comprising:
The described modified poly ester of the technique scheme of 35～100 weight parts;
5～30 parts by weight of cross-linking agent;
3～15 weight part water-based auxiliary agents;
The color stuffing of 10～35 weight parts;
0.3 the water-based flow agent of～1.7 weight parts;
0.6 the water-based skimmer of～1.3 weight parts.
Said modified poly ester is the chief component that is coated with coating composition in the said water-based, and its content is 35～100 weight parts, is preferably 40～95 weight parts, and more preferably 45～90 weight parts most preferably are 50～85 weight parts.
The effect of said linking agent is to make to be coated with coating composition in the said water-based in the curing of substrate surfaces such as steel plate, forms paint film.According to the present invention; Said linking agent is preferably aminoresin or blocked polyisocyanate: when said linking agent was aminoresin, more preferably the special company of the U.S.'s cyanogen model of producing was one or more in the aminoresin of Cymel303, Cymel 325, Cymel 327, Cymel 370 and Cymel 373; When said linking agent was blocked polyisocyanate, the model of Beyer Co., Ltd's production more preferably was Bayhydur BL 5140 or Bayhydur BL 5235.The content of said linking agent is 5～30 weight parts, is preferably 10～25 weight parts, more elects 15～20 weight parts as.
Be coated with coating composition in the water-based provided by the invention and also comprise color stuffing, the content of said color stuffing is 10～35 weight parts, is preferably 15～30 weight parts, more preferably 20～25 weight parts.According to the present invention, said color stuffing comprises pigment and filler, and said pigment optimization is white titanium pigment and carbon black, and wherein white titanium pigment and sooty weight ratio are preferably 18～53: 0.1～0.35; Said filler is preferably one or both in talcum powder and the lime carbonate, is preferably talcum powder and lime carbonate; When being talcum powder and lime carbonate, the weight ratio of said talcum powder and said lime carbonate is preferably 5～11: 3～12.In said color stuffing, the weight ratio of said pigment and said filler is preferably 18.5～53.5: 8～23, more preferably 20～50: 10～20.In order not influence the character of the paint film that obtains, the particle diameter of said color stuffing is preferably more than 1000 orders, more preferably more than 1250 orders, most preferably is more than 1500 orders.
Be coated with in the said water-based and also comprise the water-based flow agent in the coating composition, the effect of said water-based flow agent is to make the paint film of formation more smooth, smooth, even.The present invention does not have particular restriction to said water-based flow agent, is preferably model that BYK company produces and is in the flow agent of BYK-381N, BYK-307, BYK-341 and BYK-381 one or both.The content of said water-based flow agent is 0.3～1.7 weight part, is preferably 0.4～1.5 weight part, and more preferably 0.5～1.2 weight part most preferably is 0.8～1 weight part.
Be coated with in the water-based provided by the invention and also contain the water-based skimmer in the coating composition, the content of said water-based skimmer is 0.6～1.3 weight part, is preferably 0.8～1.2 weight part, more preferably 0.9～1.1 weight part.The present invention does not have particular restriction to said water-based skimmer, is preferably model that BYK company produces and is in the water-based skimmer of BYK-019, BYK-024 and BYK-028 one or both.
Be coated with in the said water-based and also comprise aqueous promoter in the coating composition, said aqueous promoter includes but not limited to water-based wetting dispersing agent and anti-precipitation aid, can be for a kind of, and also can be for multiple.The total content of said aqueous promoter is 3～15 weight parts, is preferably 5～12 weight parts, more preferably 8～10 weight parts.
Said aqueous wetting agent can provide the wetting ability that is coated with coating composition in the said water-based, makes said compsn more easily by water-wet.The present invention does not have particular restriction to said aqueous wetting agent; Being preferably the model that BYK company produces is the aqueous wetting agent of DisperBYK-180, DisperBYK-182, DisperBYK-184, DisperBYK-190, DisperBYK-191, DisperBYK-192 and DisperBYK-194, can be wherein one or more.
The effect of said anti-precipitation aid is to prevent to produce deposition, is preferably aerosil.
Be coated with coating composition in the water-based provided by the invention preferably according to following method preparation:
Aqueous promoter, water-based flow agent, water-based skimmer and color stuffing are added in the impeller, and the rotating speed stirring 20min～50min with 1400rpm～1800rmp, preferred 1500rpm～1700rpm behind preferred 25min～40min, obtains mixture;
Said mixture is ground 15h～25h, and preferred 17h～23h makes the fineness≤15 μ m of said mixture, and is preferred≤10 μ m;
Mixture after grinding is mixed with modified poly ester, linking agent; With 1600rpm～2000rpm, preferred 1700rpm～1900rpm, more preferably the rotating speed of 1750rpm～1850rpm stirs 15min～30min; More preferably behind 20min～25min, obtain being coated with in the water-based coating composition.
With being coated with in the said water-based on the steel plate that coating composition is sprayed on primer coating; Preferred spraying 2～3 roads are behind levelling 10min～20min, in the time of 80 ℃～90 ℃ behind baking 6min～8min; After 130 ℃～150 ℃ 25min～30min is toasted in continuation down, can obtain the floating coat paint film.The thickness of said paint film is preferably 32 μ m～38 μ m, more preferably 34 μ m～36 μ m.
Said paint film is carried out performance test, and the result shows, is coated with paint film that coating composition obtains in the water-based provided by the invention and has good opacifying power, gloss, hardness, impact resistance, sticking power, snappiness, grinability and anti-stone and hit performance.
In order to further specify the present invention, be described in detail being coated with coating composition in modified poly ester provided by the invention and the water-based below in conjunction with embodiment.
Embodiment 1
In the four-hole bottle that mechanical stirrer, TM, condensing surface, water trap and logical nitrogen protection device are housed, add 138g NSC 6366,95g2-butyl-2-ethyl-1; Ammediol, 30g TriMethylolPropane(TMP), 18g1,4-cyclohexanedimethanol, 35g FUMARIC ACID TECH GRADE, 52g propene dicarboxylic acid, 206g m-phthalic acid, 30g1, the model of 4-cyclohexane dicarboxylic acid, 0.5g Switzerland vapour Bagong department is 1010 oxidation inhibitor and 0.4g tin protochloride; Four-hole bottle slowly is warming up to 180 ℃ of reflux dewaterings; Speed with 15 ℃/30min is warming up to 210 ℃ then, insulation backflow 3h, and 3h then reduces pressure; After being cooled to 60 ℃; Add the 60g propylene glycol monobutyl ether, stir 20min, obtain polyester mixture;
With 15g Acrylic Acid Monomer, 8g methacrylic acid monomer, 7.5g Isooctyl acrylate monomer monomer, 12g Hydroxyethyl acrylate and 2.6g Diisopropyl azodicarboxylate, mix, obtain the propenoate mixture;
Said polyester mixture is warming up to 130 ± 5 ℃ under nitrogen protection, drips said propenoate mixture, rate of addition is 13mL/min.After dropwising, continue insulation reaction 3h, be cooled to 55 ℃ then, add 24g triethylamine and 1040g deionized water, behind the mechanical stirring 20min, obtain modified poly ester.
Said modified poly ester is carried out nucleus magnetic resonance, and the result is referring to Fig. 1, and the proton nmr spectra spectrogram of the modified poly ester that Fig. 1 provides for the embodiment of the invention can be known by Fig. 1, its hydrogen spectrum as follows:
1H NMR:0.92ppm, 1.11ppm, 1.21～1.29ppm, 1.33ppm, 1.52ppm, 1.58ppm, 1.66ppm, 1.91ppm, 2.01ppm, 2.07ppm, 2.26ppm, 2.31ppm, 2.41ppm, 2.49ppm, 3.58ppm, 3.86ppm, 3.91ppm, 4.03ppm, 4.12ppm, 4.27ppm, 4.3ppm, 7.18ppm, 7.44ppm, 7.48ppm, 7.92ppm, 8.11ppm, 8.46ppm.This shows that said modified poly ester is by acrylic ester grafted polyester.
Said modified poly ester is tested, and its acid number is 20mgKOH/g, and its hydroxyl value is 36mgKOH/g, and its number-average molecular weight is 18000 dalton, and its solid content is 38%.
In the four-hole bottle that mechanical stirrer, TM, condensing surface, water trap and logical nitrogen protection device are housed, add 231g NSC 6366,28g TriMethylolPropane(TMP), 46g1; 4-cyclohexanedimethanol, 58g FUMARIC ACID TECH GRADE, 39g propene dicarboxylic acid, 62g octadecene diacid, 210g1; The model of 4-cyclohexane dicarboxylic acid, 70g hexanodioic acid, 10g Tetra hydro Phthalic anhydride, 0.1g Switzerland vapour Bagong department is that the model of 1010 oxidation inhibitor, 0.8g Switzerland vapour Bagong department is 1076 oxidation inhibitor, 0.3g tin protochloride and 0.2g Dibutyltin oxide, and four-hole bottle slowly is warming up to 200 ℃ of reflux dewaterings, and the speed with 15 ℃/30min is warming up to 210 ℃ then; Insulation backflow 3h; The 3h that reduces pressure then, be cooled to 60 ℃ after, add 40g propylene glycol monobutyl ether and 38g diethylene glycol monobutyl ether; Stir 20min, obtain polyester mixture;
With 40g Acrylic Acid Monomer, 18g Hydroxyethyl acrylate, 16g Propylene glycol monoacrylate, 20g vinylbenzene and 5.1g Lucidol, mix, obtain the propenoate mixture;
Said polyester mixture is warming up to 130 ± 5 ℃ under nitrogen protection, drips said propenoate mixture, rate of addition is 111mL/min.After dropwising, continue insulation reaction 3h, be cooled to 55 ℃ then, add 72g dimethylethanolamine and 1500g deionized water, behind the mechanical stirring 20min, obtain modified poly ester.
Said modified poly ester is carried out nucleus magnetic resonance, and its hydrogen is composed as follows:
1H NMR:0.96ppm, 1.11～1.31ppm, 1.50ppm, 1.56ppm, 1.68ppm, 1.90ppm, 1.99ppm, 2.03ppm, 2.28ppm, 2.43ppm, 2.55ppm, 3.50ppm, 3.63ppm, 3.81ppm, 3.88ppm, 4.04ppm, 4.15ppm, 4.30ppm, 7.08ppm, 7.12ppm, 7.23ppm, 7.44ppm, 7.94ppm.This shows that said modified poly ester is by acrylic ester grafted polyester.
Said modified poly ester is tested, and its acid number is 23mgKOH/g, and its hydroxyl value is 89mgKOH/g, and its number-average molecular weight is 13800 dalton, and its solid content is 40%.
Embodiment 3
In the four-hole bottle that mechanical stirrer, TM, condensing surface, water trap and logical nitrogen protection device are housed, add 287g NSC 6366,152g2-butyl-2-ethyl-1; The model of ammediol, 23g FUMARIC ACID TECH GRADE, 24g propene dicarboxylic acid, 153g m-phthalic acid, 300g hexanodioic acid, 0.6g Switzerland vapour Bagong department is 1010 oxidation inhibitor, 0.2g dibutyl tin laurate and 0.3g tin protochloride, and four-hole bottle slowly is warming up to 190 ℃ of reflux dewaterings, and the speed with 15 ℃/30min is warming up to 210 ℃ then; Insulation backflow 3h; The 3h that reduces pressure then, be cooled to 60 ℃ after, add the 95g ethylene glycol monobutyl ether; Stir 20min, obtain polyester mixture;
With 23g Acrylic Acid Monomer, 13g Hydroxyethyl acrylate and 2.1g Diisopropyl azodicarboxylate, mix, obtain the propenoate mixture;
Said polyester mixture is warming up to 130 ± 5 ℃ under nitrogen protection, drips said propenoate mixture, rate of addition is 12mL/min.After dropwising, continue insulation reaction 3h, be cooled to 55 ℃ then, add 22g dimethylethanolamine and 1080g deionized water, behind the mechanical stirring 20min, obtain modified poly ester.
Said modified poly ester is carried out nucleus magnetic resonance, and its hydrogen is composed as follows:
1H NMR:0.98ppm, 1.10ppm, 1.26ppm, 1.28ppm, 1.59ppm, 1.71ppm, 1.93ppm, 2.29ppm, 2.53ppm, 3.65ppm, 3.84ppm, 3.90ppm, 4.01ppm, 4.16ppm, 4.21ppm, 4.33ppm, 7.15ppm, 7.49ppm, 8.18ppm, 8.48ppm.This shows that said modified poly ester is by acrylic ester grafted polyester.
Said modified poly ester is tested, and its acid number is 15mgKOH/g, and its hydroxyl value is 47mgKOH/g, and its number-average molecular weight is 16000 dalton, and its solid content is 39%.
In the four-hole bottle that mechanical stirrer, TM, condensing surface, water trap and logical nitrogen protection device are housed, add 268g NSC 6366,40g TriMethylolPropane(TMP), 20g1; 4-cyclohexanedimethanol, 60g FUMARIC ACID TECH GRADE, 63g octadecene diacid, 160g1; The model of 4-cyclohexane dicarboxylic acid, 100g Tetra hydro Phthalic anhydride, 0.5g Switzerland vapour Bagong department is 1067 oxidation inhibitor and 0.8g tin protochloride, and four-hole bottle slowly is warming up to 180 ℃ of reflux dewaterings, and the speed with 15 ℃/30min is warming up to 210 ℃ then; Insulation backflow 3h; The 3h that reduces pressure then, be cooled to 60 ℃ after, add 20g propylene glycol monobutyl ether and 50g ethylene glycol monobutyl ether; Stir 20min, obtain polyester mixture;
With 53g methacrylic acid monomer, 28g Butyl Acrylate Monomer, 10g Hydroxyethyl acrylate and 5.8g Lucidol, mix, obtain the propenoate mixture;
Said polyester mixture is warming up to 130 ± 5 ℃ under nitrogen protection, drips said propenoate mixture, rate of addition is 12mL/min.After dropwising, continue insulation reaction 3h, be cooled to 55 ℃ then, add 33g triethylamine and 1130g deionized water, behind the mechanical stirring 20min, obtain modified poly ester.
Said modified poly ester is carried out nucleus magnetic resonance, and its hydrogen is composed as follows:
1H NMR:1.03ppm, 1.26ppm, 1.35ppm, 1.55ppm, 1.63ppm, 1.96ppm, 2.05ppm, 2.24ppm, 2.43ppm, 2.49ppm, 3.33ppm, 3.58ppm, 3.86ppm, 3.90ppm, 4.00ppm, 4.13～4.18ppm, 4.25ppm, 7.10ppm, 7.41ppm, 7.52ppm.This shows that said modified poly ester is by acrylic ester grafted polyester.
Said modified poly ester is tested, and its acid number is 14mgKOH/g, and its hydroxyl value is 93mgKOH/g, and its number-average molecular weight is 11950 dalton, and its solid content is 41%.
Embodiment 5
In the four-hole bottle that mechanical stirrer, TM, condensing surface, water trap and logical nitrogen protection device are housed, add 210g2-butyl-2-ethyl-1; Ammediol, 278g TriMethylolPropane(TMP), 60g FUMARIC ACID TECH GRADE, 50g propene dicarboxylic acid, 230g1; The model of 4-cyclohexane dicarboxylic acid, 71g hexanodioic acid, 0.7g Switzerland vapour Bagong department is that model that 1010 oxidation inhibitor, 0.1g Switzerland vapour Bagong department produce is 1067 oxidation inhibitor and 0.6g tin protochloride, and four-hole bottle slowly is warming up to 180 ℃ of reflux dewaterings, and the speed with 15 ℃/30min is warming up to 210 ℃ then; Insulation backflow 3h; The 3h that reduces pressure then, be cooled to 60 ℃ after, add the 90g diethylene glycol monobutyl ether; Stir 20min, obtain polyester mixture;
With 15g Acrylic Acid Monomer, 26g methacrylic acid monomer, 23g Hydroxyethyl acrylate, 13g Propylene glycol monoacrylate, 10g vinylbenzene and 4.5g Diisopropyl azodicarboxylate, mix, obtain the propenoate mixture;
Said polyester mixture is warming up to 130 ± 5 ℃ under nitrogen protection, drips said propenoate mixture, rate of addition is 13mL/min.After dropwising, continue insulation reaction 3h, be cooled to 55 ℃ then, add 36g dimethylethanolamine and 1580g deionized water, behind the mechanical stirring 20min, obtain modified poly ester.
Said modified poly ester is carried out nucleus magnetic resonance, and its hydrogen is composed as follows:
1H NMR:0.89ppm, 1.24ppm, 1.31ppm, 1.52～1.69ppm, 1.91ppm, 2.05ppm, 2.30ppm, 2.52～2.61ppm, 3.56ppm, 3.63ppm, 3.81ppm, 3.93ppm, 4.07ppm, 4.13～4.30ppm, 7.10ppm, 7.18ppm.This shows that said modified poly ester is by acrylic ester grafted polyester.
Said modified poly ester is tested, and its acid number is 26mgKOH/g, and its hydroxyl value is 97mgKOH/g, and its number-average molecular weight is 12000 dalton, and its solid content is 38%.
In the four-hole bottle that mechanical stirrer, TM, condensing surface, water trap and logical nitrogen protection device are housed, add 67g NSC 6366,105g2-butyl-2-ethyl-1; Ammediol, 320g1; The model of 4-cyclohexanedimethanol, 82g propene dicarboxylic acid, 94g octadecene diacid, 103g m-phthalic acid, 96g hexanodioic acid, 45g Tetra hydro Phthalic anhydride, 0.9g Switzerland vapour Bagong department is 1010 oxidation inhibitor, 0.3g dibutyl tin dilaurate and 0.7g Dibutyltin oxide, and four-hole bottle slowly is warming up to 180 ℃ of reflux dewaterings, and the speed with 15 ℃/30min is warming up to 210 ℃ then; Insulation backflow 3h; The 3h that reduces pressure then, be cooled to 60 ℃ after, add 50g propylene glycol monobutyl ether and 30g ethylene glycol monobutyl ether; Stir 20min, obtain polyester mixture;
With 34g methacrylic acid monomer, 41g Hydroxyethyl acrylate, 21g vinylbenzene and 6.1g Diisopropyl azodicarboxylate, mix, obtain the propenoate mixture;
Said polyester mixture is warming up to 130 ± 5 ℃ under nitrogen protection, drips said propenoate mixture, rate of addition is 13mL/min.After dropwising, continue insulation reaction 3h, be cooled to 55 ℃ then, fall into 32g triethylamine and 1200g deionized water, behind the mechanical stirring 20min, obtain modified poly ester.
Said modified poly ester is carried out nucleus magnetic resonance, and its hydrogen is composed as follows:
1H NMR:0.93ppm, 1.16ppm, 1.28ppm, 1.35ppm, 1.57ppm, 1.66ppm, 1.98ppm, 2.08ppm, 2.23～2.46ppm, 2.61ppm, 3.83ppm, 3.93ppm, 4.06ppm, 4.15ppm, 4.29ppm, 7.06～7.19ppm, 7.46ppm, 7.90ppm, 8.08ppm, 8.32ppm.This shows that said modified poly ester is by acrylic ester grafted polyester.
Said modified poly ester is tested, and its acid number is 18mgKOH/g, and its hydroxyl value is 1200mgKOH/g, and its number-average molecular weight is 10000 dalton, and its solid content is 41%.
Comparative example 1
In the four-hole bottle that mechanical stirrer, TM, condensing surface, water trap and logical nitrogen protection device are housed, add 67g NSC 6366,105g2-butyl-2-ethyl-1; Ammediol, 320g1; The model of 4-cyclohexanedimethanol, 82g propene dicarboxylic acid, 94g octadecene diacid, 103g m-phthalic acid, 96g hexanodioic acid, 45g Tetra hydro Phthalic anhydride, 0.9g Switzerland vapour Bagong department is 1010 oxidation inhibitor, 0.3g dibutyl tin dilaurate and 0.7g Dibutyltin oxide, and four-hole bottle slowly is warming up to 180 ℃ of reflux dewaterings, and the speed with 15 ℃/30min is warming up to 210 ℃ then; Insulation backflow 3h; The 3h that reduces pressure then, be cooled to 60 ℃ after, add 50g propylene glycol monobutyl ether and 30g ethylene glycol monobutyl ether; Stir 20min, obtain polyester mixture;
Said polyester mixture is cooled to 55 ℃, falls into 32g triethylamine and 1200g deionized water, behind the mechanical stirring 20min, obtain polyester.
Said modified poly ester is carried out nucleus magnetic resonance, and its hydrogen is composed as follows:
1H NMR:1.12ppm, 1.28ppm, 1.46ppm, 1.55ppm, 1.67ppm, 2.23ppm, 2.39ppm, 3.37ppm, 3.43ppm, 3.65ppm, 4.09ppm, 4.16ppm, 4.32ppm.This shows that said polyester does not pass through modification.
Embodiment 7
According to the material ratio of table 1, prepare according to following method and to be coated with coating composition in the water-based:
Aqueous promoter, water-based flow agent, water-based skimmer and color stuffing are added in the impeller, behind the rotating speed stirring 20min～50min with 1400rpm～1800rmp, obtain mixture;
Said mixture is ground 15h～25h, make the fineness≤15 μ m of said mixture;
Mixture after grinding is mixed with modified poly ester, linking agent, behind the rotating speed stirring 15min～30min with 1600rpm～2000rpm, obtain being coated with in the water-based coating composition, be designated as WP1, WP2, WP3, WP4, WP5, WP6 and WP7 respectively.
Be coated with the material ratio of coating composition in the table 1 preparation water-based
With in be coated with coating composition WP1, WP2, WP3, WP4, WP5, WP6 and WP7 and be sprayed on respectively on the steel plate that has applied electrophoretic primer; Spraying 2～3 roads; Levelling 15min; Baking 6min～8min under 80 ℃～90 ℃ toasts 25min～30min down at 140 ℃ then, and obtaining thickness is paint film WP1, WP2, WP3, WP4, WP5, WP6 and the WP7 of 32 μ m～38 μ m.
Said paint film is carried out performance test, and the result is referring to table 2, and table 2 is the The performance test results of the paint film that is coated with coating composition in the water-based provided by the invention and obtains.
Be coated with the The performance test results of the paint film that coating composition obtains in table 2 water-based provided by the invention
In the table 2, anti-stone hits and performance adopts stone to hit appearance to detect, and test sample plate amine is evaluated for 0～10 grade, and 0 grade is not had puncture for paint film, and 10 grades are the puncture of paint film big area.
Can know by table 2; Compare with being coated with the paint film WP7 that coating composition WP7 obtains in the water-based that the polyester of non-modified is formed, be coated with the paint film that coating composition WP1, WP2, WP3, WP4, WP5 and WP6 obtain in the water-based of forming through acrylate modified polyester and hit aspect of performances such as performance and sticking power and all make moderate progress at gloss, hardness, snappiness, resistance to impact shock, anti-stone.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (9)
1. a modified poly ester that is used for coating is characterized in that, said modified poly ester prepares according to following method:
A) polyvalent alcohol, alkene diacid and polyprotonic acid reaction under the effect of oxidation inhibitor and catalyzer obtains polyester, and said alkene diacid is two or three in butene dioic acid, propene dicarboxylic acid and the octadecene diacid;
B) in said polyester, add the water-based solubility promoter, obtain polyester mixture;
C) in said polyester mixture, add first monomer, second monomer, the 3rd monomer and radical initiator; Continue reaction and obtain first intermediate product; Said first monomer is one or both in vinylformic acid and the methylacrylic acid; Said second monomer is one or more in propenoate and the vinylbenzene, and said the 3rd monomer is a crylic acid hydroxy ester;
D) in said first intermediate product, add neutralizing agent, stir neutralization, obtain modified poly ester.
2. modified poly ester according to claim 1 is characterized in that, said polyvalent alcohol is NSC 6366,2-butyl-2-ethyl-1, one or more in ammediol, TriMethylolPropane(TMP) and the 1,4 cyclohexane dimethanol.
3. modified poly ester according to claim 1 is characterized in that, said polyprotonic acid is a m-phthalic acid, 1, one or more in 4-cyclohexane dicarboxylic acid and the hexanodioic acid.
4. modified poly ester according to claim 1 is characterized in that, said catalyzer is one or more in dibutyl tin laurate, tin protochloride and the Dibutyltin oxide.
5. modified poly ester according to claim 1 is characterized in that, said neutralizing agent is triethylamine, dimethylethanolamine, trolamine or diethylolamine.
6. modified poly ester according to claim 1 is characterized in that, in the said step a), the temperature of said reaction is 180 ℃～210 ℃.
7. modified poly ester according to claim 1 is characterized in that, in the said step c), the temperature of said reaction is 120 ℃～140 ℃.
8. be coated with coating composition in a water-based, comprise:
Any described modified poly ester of the claim 1～7 of 35～100 weight parts;
5～30 parts by weight of cross-linking agent;
3～15 weight part water-based auxiliary agents;
The color stuffing of 10～35 weight parts;
0.3 the water-based flow agent of～1.7 weight parts;
0.6 the water-based skimmer of～1.3 weight parts.
9. be coated with coating composition in the water-based according to claim 8, it is characterized in that, said linking agent is aminoresin or blocked polyisocyanate.
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| CN2010105045797A CN101942064B (en) | 2010-10-13 | 2010-10-13 | Modified polyester and water-borne middle coating composition |
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| CN2010105045797A CN101942064B (en) | 2010-10-13 | 2010-10-13 | Modified polyester and water-borne middle coating composition |
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| CN102260445B (en) * | 2011-02-17 | 2014-04-16 | 晟通科技集团有限公司 | Polyester-modified acrylate resin aqueous paint, and preparation method thereof |
| CN103387643B (en) * | 2012-05-08 | 2015-11-25 | 长春市三化实业有限责任公司 | Polyester modification water-and acrylate and automobile water-miscible paint composition |
| CN103525267A (en) * | 2012-07-04 | 2014-01-22 | 长春市三化实业有限责任公司 | Automobile water-based primer surfacer with excellent chip resistance and preparation method thereof |
| CN103554381A (en) * | 2013-10-21 | 2014-02-05 | 北京金汇利应用化工制品有限公司 | Water-based acrylic acid modified saturated polyester resin and preparation method thereof |
| FR3037589B1 (en) * | 2015-06-17 | 2020-02-28 | Arkema France | HYDROXYLATED AND / OR CARBOXYLATED POLYESTER RESIN WITH HIGH EXTRACT DRIED AND HIGH COVERING FOR METAL SHEET COATING |
| US9567475B1 (en) * | 2016-06-03 | 2017-02-14 | Sirrus, Inc. | Coatings containing polyester macromers containing 1,1-dicarbonyl-substituted 1 alkenes |
| CN110591062A (en) * | 2019-09-01 | 2019-12-20 | 合众（佛山）化工有限公司 | Melamine derivative modified waterborne polyester flame-retardant resin and preparation method thereof |
| CN111838895B (en) * | 2020-08-11 | 2022-12-16 | 浙江伟星实业发展股份有限公司 | Aluminum button and preparation method thereof |
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| GB2226566B (en) * | 1988-12-12 | 1992-04-08 | Croda Applic Chemicals Limited | Automotive sealing process |
| CN1687271A (en) * | 2005-04-18 | 2005-10-26 | 重庆芬斯特工业(集团)有限公司 | Primer of modified polyester coiled material |
| CN101798373B (en) * | 2010-03-31 | 2011-09-28 | 鞍山润德精细化工有限公司 | Production process and production line for water-borne acrylic acid modified polyester resin |
| CN101792639B (en) * | 2010-04-02 | 2012-09-05 | 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 |
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