CN103554461A - Epoxy modified alkyd resin and its high hardness fast reaction coating - Google Patents
Epoxy modified alkyd resin and its high hardness fast reaction coating Download PDFInfo
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- CN103554461A CN103554461A CN201310451747.4A CN201310451747A CN103554461A CN 103554461 A CN103554461 A CN 103554461A CN 201310451747 A CN201310451747 A CN 201310451747A CN 103554461 A CN103554461 A CN 103554461A
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 66
- 229920000180 alkyd Polymers 0.000 title claims abstract description 66
- 238000000576 coating method Methods 0.000 title claims abstract description 52
- 239000011248 coating agent Substances 0.000 title claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 35
- 239000003822 epoxy resin Substances 0.000 claims abstract description 53
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 53
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000007787 solid Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000007599 discharging Methods 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 36
- 239000002253 acid Substances 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000003921 oil Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 12
- 238000006757 chemical reactions by type Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 5
- 229920001228 polyisocyanate Polymers 0.000 claims description 5
- 239000005056 polyisocyanate Substances 0.000 claims description 5
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 5
- 229960004418 trolamine Drugs 0.000 claims description 5
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 229940106691 bisphenol a Drugs 0.000 claims description 4
- 229940043232 butyl acetate Drugs 0.000 claims description 4
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 claims description 4
- -1 glycidyl ester Chemical class 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000049 pigment Substances 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- XUNCVWQATLFOFE-UHFFFAOYSA-N butylphosphanium;acetate Chemical compound CC([O-])=O.CCCC[PH3+] XUNCVWQATLFOFE-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 229930185605 Bisphenol Natural products 0.000 claims description 2
- 244000068988 Glycine max Species 0.000 claims description 2
- 235000010469 Glycine max Nutrition 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 239000004841 bisphenol A epoxy resin Substances 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
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000013530 defoamer Substances 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- MUTGBJKUEZFXGO-UHFFFAOYSA-N hexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21 MUTGBJKUEZFXGO-UHFFFAOYSA-N 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
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 claims description 2
- 229940059574 pentaerithrityl Drugs 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 claims description 2
- 239000002383 tung oil Substances 0.000 claims description 2
- 239000000080 wetting agent Substances 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 9
- 238000001035 drying Methods 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000008096 xylene Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract 2
- 239000007888 film coating Substances 0.000 abstract 1
- 238000009501 film coating Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 150000007519 polyprotic acids Chemical class 0.000 abstract 1
- 150000005846 sugar alcohols Polymers 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 238000010792 warming Methods 0.000 description 24
- 238000002360 preparation method Methods 0.000 description 12
- 239000003973 paint Substances 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 230000003628 erosive effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000005028 tinplate Substances 0.000 description 3
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- 101100008050 Caenorhabditis elegans cut-6 gene Proteins 0.000 description 1
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Landscapes
- Paints Or Removers (AREA)
Abstract
Belonging to the field of epoxy resin coatings, the invention discloses an epoxy modified alkyd resin and its high hardness fast reaction coating. The epoxy modified alkyd resin is prepared by the method of: (1) mixing polyhydric alcohol with polyprotic acid, adding xylene, then performing heating reaction for 1-2h, raising the temperature to completely react, thus obtaining alkyd resin; (2) mixing epoxy resin, alkyd resin and a catalyst, performing heating reaction for 2-4h, carrying out filtering and discharging, thus obtaining epoxy modified alkyd resin, which has the advantages of good adhesion (0 level), good fullness, strong toughness (2mm), high epoxy resin mechanical strength (6H), and excellent corrosion resistance. The high hardness fast reaction coating made of the epoxy modified alkyd resin has the characteristics of high hardness, good toughness and fast drying speed (4h). According to the invention, the raw materials are easily available, and the process is simple. The prepared product has a high solid content and good leveling property, and is easy to achieve film coating.
Description
Technical field
The invention belongs to epoxypaint field, particularly a kind of epoxy alkyd resin and high rigidity quick-reaction type coating thereof.
Background technology
Wood furniture is by the external coating of different process, can play the effect of protection furniture, makes loose ground more solid, allows furniture have the good performance such as water-fast, wear-resisting, corrosion-resistant.Timber is carried out to application, and reaching desirable application object is not to be easy to thing, mainly contains several important reasons: the Density inhomogeneity that (1) is wooden and porousness, require coating to have good sticking power.(2) property complicated and changeable of processing environment and environment for use, requires coating to have hardness high, and wear resistance is good, guarantees the persistence of paint film.(3) for speciality coating, because needs are under extreme conditions used, so it is high temperature resistant to require coating to have, chemical resistance, hardness high.Coating in use often can run into, and causes not wear-resisting, the problem of scratch resistant not because coating hardness is not high, and for this problem, the way conventionally adopting is carry out resin modified or add hard filler.But it is far from being enough only depending on wear resistance and the hardness of using hard powders to increase coating, and use hard powders when improving hardness, the snappiness of coating can significantly decline, and the fragility of coating increases, and when being subject to External Force Acting, is very easy to destroyed.So improving hardness by resin modified becomes inevitable.
On epoxy resin molecular chain, contain the groups such as carboxyl, hydroxyl, epoxy group(ing), therefore there is good mechanical property and physicochemical property.Epoxypaint becomes cancellated macromole by crosslinked in drying process, and the paint film after solidifying has that good erosion resistance, hardness are high, wear resistance and the good feature of sticking power.Shortcoming is only to pass through simple epoxy resin cure, poor, the easy efflorescence of paint film fullness ratio.Synolac over-all properties is moderate, and the coating of preparation has good snappiness and from dryness.By epoxide modified from dry alkyd resin, both kept Synolac from dryness and snappiness, there is again good erosion resistance and the high rigidity of epoxy resin.In prior art, for epoxy resin and Synolac modified paint, carried out more research; conventionally epoxy alkyd resin is all to utilize epoxy resin to replace part polyvalent alcohol; in polyreaction, directly epoxy resin is introduced in alkyd polymer, then in the polymerization later stage, added gradually polyprotonic acid to prevent reaction gel.During with this method synthesizing epoxy modified alkyd resin, owing to being single step reaction, the shared ratio of epoxy is conventionally less, because if the shared ratio height of epoxy words can be easy in reaction process, occur gel, so low epoxy content often causes soft.Having in addition research to claim can be first by epoxy resin and fatty acid response synthesizing epoxy ester, and then epoxy ester carries out transesterify with Synolac again.During with this method synthesis modification resin, transesterify extremely difficulty reacts completely, and the by product that produces of transesterify can cause waste to the environment ，Dui manufacturer that works the mischief, and has the slow and not wear-resisting problem of dry speed.
Therefore, seek a kind of technique simple, product possesses again that hardness is high, wear resistance good, the production method of the modified alkyd resin of fast drying simultaneously, and tool is of great significance.
Summary of the invention
In order to overcome the shortcoming and deficiency of above-mentioned prior art, primary and foremost purpose of the present invention is to provide a kind of epoxy alkyd resin.
Another object of the present invention is to provide a kind of preparation method of above-mentioned epoxy alkyd resin.
Still a further object of the present invention is to provide a kind of high rigidity quick-reaction type coating preparing based on above-mentioned epoxy alkyd resin.
Object of the present invention realizes by following proposal:
, by following methods, prepared:
(1) polyvalent alcohol is mixed with polyprotonic acid, add after dimethylbenzene, after reacting by heating 1～2h, temperature reaction, to completely, obtains Synolac;
(2), epoxy resin, Synolac and catalyst mix, reacting by heating 2～4h, filters discharging, obtains epoxy alkyd resin.
Described polyvalent alcohol refers at least one in glycerine, neopentyl glycol, TriMethylolPropane(TMP), tetramethylolmethane, propylene glycol, ethylene glycol, glycol ether, propylene glycol, Viscotrol C, oleum lini, tung oil and soya-bean oil.
Described polyprotonic acid refers at least one in hexanodioic acid, SA, phthalic anhydride, terephthalic acid, phthalic acid, m-phthalic acid, HHPA and trimellitic acid 1,2-anhydride.
In step (1), the mass ratio of polyvalent alcohol used and polyprotonic acid is 1:1.2～1:2.3.By regulating the mass ratio of polyvalent alcohol and polyprotonic acid, control the molecular weight of Synolac and the acid number of resin.
The amount of dimethylbenzene used is that every 100 mass parts polyvalent alcohols are used 16～20 mass parts.
Heating described in step (1) refers to be heated to 120～130 ℃.
Temperature reaction described in step (1) is to referring to be heated to 160～180 ℃ completely, and isothermal reaction is to Suan Zhi≤100mgKOH/g.
Described reaction to after completely by vacuumizing except removal xylene.
In step (2), the mass ratio of epoxy resin used and Synolac is 1:4～1:7.The shared too low meeting of ratio of epoxy resin makes the hardness of modified resin influenced, and the shared ratio of epoxy resin is too high, easily occurs again gel in the process of epoxy alkyd resin.
Described epoxy resin refers at least one in bisphenol A type epoxy resin, bisphenol f type epoxy resin, methylol bisphenol A type epoxy resin, bisphenol-A epoxy resin, organic-silicon-modified bisphenol A type epoxy resin, aliphatic glycidyl ether epoxy resin, glycidyl ester type epoxy resin and glycidyl amine type epoxy resin.
Described catalyzer refers at least one in triphenyl phosphorus, 4-butyl-phosphonium acetate, chromium acetylacetonate, trolamine, benzyldimethylamine and Bian base triphenyl phosphonium muriate.
The amount of used catalyst is 0.15～0.3% of reaction system total mass.
Heating described in step (2) refers to that heating refers to 105～115 ℃.
A kind of high rigidity quick-reaction type coating preparing based on above-mentioned epoxy alkyd resin that the present invention also provides, includes organic coating and solidifying agent, and the weight ratio of organic coating and solidifying agent is 40:60～60:40.
Wherein, the component that organic coating comprises following weight part meter:
Described solidifying agent refers to polyisocyanate-based solidifying agent.
Preferably, described epoxy alkyd resin is 65% with solvent cut to solid content before using.
Described pigment refers at least one in stibium trioxide, titanium dioxide, barba hispanica, phthalocyanine blue, phthalocyanine green and carbon black.
Described filler refers at least one in calcium carbonate, talcum powder, kaolin, magnesium hydroxide and barium sulfate.
Described auxiliary agent refers at least one in wetting agent, dispersion agent, flow agent, defoamer, anti-settling agent and siccative.
Described solvent is the conventional organic solvent of coating.
Preferably, described solvent nail benzene, dimethylbenzene, petroleum naphtha, raffinate oil, at least one in ethyl acetate, butylacetate, 100# solvent oil and 200# solvent oil.
Preferably, described solidifying agent refers at least one in IL1451, N3390, BL3175SN, WB905,2604, TPA-90SB, HX-90B, HX-90, B1358A, HI100, HXR, HX, HK, HLBA, HI190B/S, SC-75LT, N3300, IL1451 and HLBA.
Preferably, before described solidifying agent use, adding ethyl acetate to solid content is 50%.
Preferably, described siccative finger ring alkanoic acid metallic soap and at least one in isocaprylic acid metallic soap.
Preferably, described dispersion agent is at least one in Anti-Terra-P, Anti-Terra-203, Anti-Terra-204 and Anti-Terra-206.
Preferably, described anti-settling agent refers at least one in BENTONE27 and BENTONE34.
When described high rigidity quick-reaction type coating is used, first organic coating dispersed with stirring, then add solidifying agent to mix, can use.
Mechanism of the present invention is:
(1) the present invention selects the synthetic end of polyprotonic acid and polyvalent alcohol carboxyl Synolac, utilizes carboxyl on Synolac and the epoxy group(ing) on epoxy resin to react, and epoxy resin is introduced in Synolac, and generated and have highly active hydroxyl simultaneously.Molecule aspect, epoxy resin is introduced in Synolac, form macromolecular structure, make its existing alkyd structure on molecular chain, have again epoxy construction, not only retained the erosion resistance of epoxy resin, the advantage of high rigidity simultaneously but also have advantages of that the strong adhesion of Synolac, toughness are strong.The present invention is by first synthetic alkyd resin, and then epoxy resin is introduced in Synolac, and whole reaction process is not only gentle, but also without any the generation of by product.Both guaranteed hardness, there will not be again gel, and basis can also be provided for follow-up curing reaction.
(2) high rigidity quick-reaction type coating of the present invention utilizes hydroxyl to react with polyisocyanate-based being cured, therefore speed of response is fast and can at lower temperature, carry out, when guaranteeing material hardness and wear resistance, can effectively improve coating from dryness.
The present invention, with respect to prior art, has following advantage and beneficial effect:
(1) epoxy alkyd resin of the present invention adopts chemical bonds, has improved molecule consistency, has that sticking power good (0 grade), fullness ratio are good, toughness strong (2mm), epoxy resin physical strength high (6H), the good advantage of antiseptic property.
(2) high rigidity quick-reaction type coating of the present invention is comprised of epoxy alkyd resin, pigment, filler, solidifying agent etc., by polyisocyanate-based solidifying agent, be cured, molecular weight and the drying rate of resin have been improved greatly, when not affecting mechanical property, solved the slow defect of dry speed after epoxy alkyd resin, the advantage that integrates various resins, has hardness high (6H), good toughness (2mm), the dry speed feature of (4h) soon.
(3) raw material of the present invention is easy to get, technique is simple.The coating solid content that simultaneously makes is high, good leveling property, be easy to film.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1: the preparation of epoxy alkyd resin
(1) as table 1 formula, polyvalent alcohol and polyprotonic acid are dropped into reactor, be warming up to 120～130 ℃ and add dimethylbenzene, reactant starts after dissolving completely to stir, be incubated 1～2 hour to stable reaction, continue to be warming up to 160～180 ℃, termination reaction when being incubated 4～5 hours and being 40mgKOH/g to acid number, is cooled to 100～110 ℃ and is evacuated to and does not have dimethylbenzene to extract out to obtain Synolac.
(2) as table 1 formula, epoxy resin and Synolac are dropped into reactor, drop into respectively again toluene, triphenyl phosphorus and benzyldimethylamine, be warming up to 105～115 ℃, be incubated 4 hours, with ethyl acetate and butylacetate, being diluted to solid part is 65%, filters discharging, makes epoxy alkyd resin.
Table 1 epoxy alkyd resin prepare formula table
Embodiment 2: the preparation of epoxy alkyd resin
(1) as table 2 formula, polyvalent alcohol and polyprotonic acid are dropped into reactor, be warming up to 120～130 ℃ and add dimethylbenzene, reactant starts after dissolving completely to stir, be incubated 1～2 hour to stable reaction, continue to be warming up to 160～180 ℃, termination reaction when being incubated 4～5 hours and being 96mgKOH/g to acid number, is cooled to 100～110 ℃ and is evacuated to and does not have dimethylbenzene to extract out to obtain Synolac.
(2), as table 2 formula, epoxy resin and Synolac are dropped into reactor, then drop into respectively toluene and 4-butyl-phosphonium acetate, be warming up to 105～115 ℃, be incubated 3 hours, with 200# solvent oil and butylacetate, being diluted to solid part is 65%, filter discharging, make epoxy alkyd resin.
Table 2 epoxy alkyd resin prepare formula table
Embodiment 3: the preparation of epoxy alkyd resin
(1) as table 3 formula, polyvalent alcohol and polyprotonic acid are dropped into reactor, be warming up to 120～130 ℃ and add dimethylbenzene, reactant starts after dissolving completely to stir, be incubated 1～2 hour to stable reaction, continue to be warming up to 160～180 ℃, termination reaction when being incubated 4～5 hours and being 68mgKOH/g to acid number, is cooled to 100～110 ℃ and is evacuated to and does not have dimethylbenzene to extract out to obtain Synolac.
(2) as table 3 formula, epoxy resin and Synolac are dropped into reactor, drop into respectively again toluene, trolamine and chromium acetylacetonate, be warming up to 105～115 ℃, be incubated 2 hours, with dimethylbenzene, ethyl acetate and 100# solvent oil, being diluted to solid part is 65%, filters discharging, makes epoxy alkyd resin.
Table 3 epoxy alkyd resin prepare formula table
Embodiment 4: the preparation of epoxy alkyd resin
(1) as table 4 formula, polyvalent alcohol and polyprotonic acid are dropped into reactor, be warming up to 120～130 ℃ and add dimethylbenzene, reactant starts after dissolving completely to stir, be incubated 1～2 hour to stable reaction, continue to be warming up to 160～180 ℃, termination reaction when being incubated 4～5 hours and being 45mgKOH/g to acid number, is cooled to 100～110 ℃ and is evacuated to and does not have dimethylbenzene to extract out to obtain Synolac.
(2) as table 4 formula, epoxy resin and Synolac are dropped into reactor, then drop into respectively toluene and triphenyl phosphorus, be warming up to 105～115 ℃, be incubated 2 hours, by ethyl acetate, being diluted to solid part is 65%, filters discharging, makes epoxy alkyd resin.
Table 4 epoxy alkyd resin prepare formula table
Embodiment 5: the preparation of epoxy alkyd resin
(1) as table 5 formula, polyvalent alcohol and polyprotonic acid are dropped into reactor, be warming up to 120～130 ℃ and add dimethylbenzene, reactant starts after dissolving completely to stir, be incubated 1～2 hour to stable reaction, continue to be warming up to 160～180 ℃, termination reaction when being incubated 4～5 hours and being 73mgKOH/g to acid number, is cooled to 100～110 ℃ and is evacuated to and does not have dimethylbenzene to extract out to obtain Synolac.
(2), as table 5 formula, epoxy resin and Synolac are dropped into reactor, then drop into respectively toluene and triphenyl phosphorus, be warming up to 105～115 ℃, be incubated 3 hours, by ethyl acetate with raffinate oil that to be diluted to solid part be 65%, filter discharging, make epoxy alkyd resin.
Table 5 epoxy alkyd resin prepare formula table
Embodiment 6: the preparation of epoxy alkyd resin
(1) as table 6 formula, polyvalent alcohol and polyprotonic acid are dropped into reactor, be warming up to 120～130 ℃ and add dimethylbenzene, reactant starts after dissolving completely to stir, be incubated 1～2 hour to stable reaction, continue to be warming up to 160～180 ℃, termination reaction when being incubated 4～5 hours and being 56mgKOH/g to acid number, is cooled to 100～110 ℃ and is evacuated to and does not have dimethylbenzene to extract out to obtain Synolac.
(2), as table 6 formula, epoxy resin and Synolac are dropped into reactor, then drop into respectively toluene and chromium acetylacetonate, be warming up to 105～115 ℃, be incubated 3 hours, with ethyl acetate and 100# solvent oil, being diluted to solid part is 65%, filter discharging, make epoxy alkyd resin.
Table 6 epoxy alkyd resin prepare formula table
Embodiment 7: the preparation of epoxy alkyd resin
(1) as table 7 formula, polyvalent alcohol and polyprotonic acid are dropped into reactor, be warming up to 120～130 ℃ and add dimethylbenzene, reactant starts after dissolving completely to stir, be incubated 1～2 hour to stable reaction, continue to be warming up to 160～180 ℃, termination reaction when being incubated 4～5 hours and being 95mgKOH/g to acid number, is cooled to 100～110 ℃ and is evacuated to and does not have dimethylbenzene to extract out to obtain Synolac.
(2) as table 7 formula, epoxy resin and Synolac are dropped into reactor, drop into respectively again toluene, benzyldimethylamine, trolamine, be warming up to 105～115 ℃, be incubated 4 hours, with ethyl acetate and 200# solvent oil, being diluted to solid part is 65%, filters discharging, makes epoxy alkyd resin.
Table 7 epoxy alkyd resin prepare formula table
Embodiment 8: the preparation of epoxy alkyd resin
(1) as table 8 formula, polyvalent alcohol and polyprotonic acid are dropped into reactor, be warming up to 120～130 ℃ and add dimethylbenzene, reactant starts after dissolving completely to stir, be incubated 1～2 hour to stable reaction, continue to be warming up to 160～180 ℃, termination reaction when being incubated 4～5 hours and being 75mgKOH/g to acid number, is cooled to 100～110 ℃ and is evacuated to and does not have dimethylbenzene to extract out to obtain Synolac.
(2) as table 8 formula, epoxy resin and Synolac are dropped into reactor, drop into respectively again toluene, benzyldimethylamine, trolamine, be warming up to 105～115 ℃, be incubated 2 hours, with ethyl acetate and 200# solvent oil, being diluted to solid part is 65%, filters discharging, makes epoxy alkyd resin.
Table 8 epoxy alkyd resin prepare formula table
Embodiment 9: the preparation of the coating based on epoxy alkyd resin
According to listed each component raw material proportioning in table 9, the epoxy alkyd resin respectively embodiment 1～8 being made mixes high speed dispersion 15 minutes with pigment, filler, auxiliary agent, after adding, stirs solidifying agent as second component, can spray.
The formulation for coating material table of table 9 based on epoxy alkyd resin
In this example, solidifying agent used is for directly buying from market, and before using, adding part ethyl acetate to solid content is 50%.
Those skilled in the art can be according to actual needs, and just can select applicable siccative kind and consumption according to the guidance of textbook or laboratory manual.In this example, siccative is at least one in naphthenic acid metallic soap and isocaprylic acid metallic soap.
Those skilled in the art can be according to actual needs, and just can select applicable siccative kind and consumption according to the guidance of textbook or laboratory manual.In this example, dispersion agent is at least one in Anti-Terra-P, Anti-Terra-203, Anti-Terra-204 and Anti-Terra-206.
Those skilled in the art can be according to actual needs, and just can select applicable siccative kind and consumption according to the guidance of textbook or laboratory manual.In this example, anti-settling agent is at least one in BENTONE27, BENTONE34.
Embodiment 10: the performance test of the coating based on epoxy alkyd resin
The coating that embodiment 10 is prepared carries out performance test, operates as follows:
Sample preparation methods: use tinplate as base material, with sand paper, the tinplate sheet polishing of getting ready is removed to oil stain above, clean, dry with deionized water, finally use line rod spreader to apply.Coat-thickness is at 30 ± 5 μ m, solidifies test performance after 10～60min at 30～60 ℃, the results are shown in Table 6.
(1) mensuration of hardness: with reference to standard GB/T/T6739-86, prepare the drawing pencil that one group of hardness is 6B～6H, measure the pencil hardness of filming by manual method.On the table top that the plate level of filming is placed on, hand-held pencil angle at 45 ° firmly pushes about 1cm, and stay and scratch on filming with uniform speed on coated surface.The pencil of same hardness label is repeated to scratch 5 roads, if any 2 roads or the above base plate that does not scratch model, uses the pencil of the large label of hardness instead, until find film be scratched 2 roads or more than.Than the little label of this pencil hardness, be the pencil hardness of filming.
(2) mensuration of sticking power: with reference to standard GB/T/T9286-1998, cut the 6 parallel cut channels in road with drawing cutter on paint film, should cut the entire depth of wearing paint film; And then cut 6 same roads, vertical with the former, form many lattices, then with wide, for the translucent Pressuresensitive Tape of 25mm is attached to whole cut channel, draw on lattice, wrench adhesive tape, and with standard comparison, determine the progression of film adhesive.
(3) erosion resistance test: with reference to standard GB/T/T1771-91, adopt Q235 steel as base material, after spraying, the thickness of coating is 150 ± 5 μ m, carries out neutral salt spray test after being fully dried,
(4) snappiness test: with reference to standard GB/T/T1731-93.By test plate (panel) paint film upward, with the hands paint film is pressed on the mandrel rod of specified diameter, in 2～3s, around the crooked test plate (panel) of mandrel rod.Observe paint film and whether produce reticulate pattern, crackle and the breakoff phenomenon such as peel off, reference standard is determined suppleness.
(5) test of time of drying: with reference to standard GB/T/T1728-79, paint spay-coating, on tinplate, is measured respectively to the surface drying time of coating, do solid work the time.
The performance index of the coating of table 10 based on epoxy alkyd resin
| Project | 1# | 2# | 3# | 4# | 5# | 6# | 7# | 8# |
| Hardness of paint film | 3 | 3 | 4 | 6 | 5 | 6 | 5 | 5 |
| Sticking power | 1 | 1 | 0 | 0 | 1 | 0 | 0 | 1 |
| Corrosion-resistant (96h) | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified |
| Snappiness (mm) | 4 | 2 | 2 | 3 | 3 | 4 | 2 | 3 |
| Surface drying time (min) | 40 | 50 | 25 | 10 | 20 | 20 | 10 | 30 |
| Do solid work the time (h) | 24 | 30 | 18 | 6 | 12 | 14 | 4 | 22 |
The coating that the present invention prepares as can be seen from Table 10 all has good performance, has both guaranteed the hardness of coating, has kept good snappiness and erosion resistance simultaneously.
To in the research of epoxy, only embody Synolac and epoxy resin hydridization between the two at home and abroad, epoxy alkyd resin both had Synolac from dryness and snappiness, there is again excellent corrosion resistance and the high rigidity of epoxy resin.But the modification of this degree can produce any impact hardly on the dry speed of hybrid resin.Therefore, synthetic a kind of hardness is high, wear resistance good, the fast Synolac of dry speed, is that manufacturer is pursued always, but still blank in this part research at home and abroad.The present invention considers from the angle of molecular designing, the advantage of Synolac, epoxy resin, three kinds of materials of isocyanic ester is organically combined.First utilize carboxyl on Synolac and the epoxy group(ing) on epoxy resin to react, epoxy resin is introduced in Synolac, it is its existing alkyd structure in molecule aspect, there is again epoxy construction, not only retained the erosion resistance of epoxy resin, the advantage of high rigidity and but also have advantages of that the strong adhesion of Synolac, toughness are strong simultaneously.Then utilize the hydroxyl producing in epoxy resin modification Synolac process to react with polyisocyanate-based being cured.Because this curing system speed of response is fast and can carry out at lower temperature, thus can effectively improve coating from dryness.The method provides a kind of ultrahigh hardness coating system and preparation method thereof, has solved the slow problem of low, not wear-resisting, the dry speed of hardness that coating in use run into.The coating obtaining has that hardness is high, erosion resistance is strong, dry speed is fast, have again certain snappiness simultaneously.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. an epoxy alkyd resin, is characterized in that being prepared by following methods:
(1) polyvalent alcohol is mixed with polyprotonic acid, add after dimethylbenzene, after reacting by heating 1～2h, temperature reaction, to completely, obtains Synolac;
(2), epoxy resin, Synolac and catalyst mix, reacting by heating 2～4h, filters discharging, obtains epoxy alkyd resin.
2. epoxy alkyd resin according to claim 1, is characterized in that: the polyvalent alcohol described in step (1) refers at least one in glycerine, neopentyl glycol, TriMethylolPropane(TMP), tetramethylolmethane, propylene glycol, ethylene glycol, glycol ether, propylene glycol, Viscotrol C, oleum lini, tung oil and soya-bean oil; Described polyprotonic acid refers at least one in hexanodioic acid, SA, phthalic anhydride, terephthalic acid, phthalic acid, m-phthalic acid, HHPA and trimellitic acid 1,2-anhydride.
3. epoxy alkyd resin according to claim 1, is characterized in that: in step (1), the mass ratio of polyvalent alcohol used and polyprotonic acid is 1:1.2～1:2.3.
4. epoxy alkyd resin according to claim 1, is characterized in that: in step (1), the amount of dimethylbenzene used is that every 100 mass parts polyvalent alcohols are used 16～20 mass parts; Described heating refers to be heated to 120～130 ℃; Described temperature reaction is to referring to be heated to 160～180 ℃ completely, and isothermal reaction is to Suan Zhi≤100mgKOH/g.
5. epoxy alkyd resin according to claim 1, is characterized in that: in step (2), the mass ratio of epoxy resin used and Synolac is 1:4～1:7.
6. epoxy alkyd resin according to claim 1, is characterized in that: the epoxy resin described in step (2) refers at least one in bisphenol A type epoxy resin, bisphenol f type epoxy resin, methylol bisphenol A type epoxy resin, bisphenol-A epoxy resin, organic-silicon-modified bisphenol A type epoxy resin, aliphatic glycidyl ether epoxy resin, glycidyl ester type epoxy resin and glycidyl amine type epoxy resin; Described catalyzer refers at least one in triphenyl phosphorus, 4-butyl-phosphonium acetate, chromium acetylacetonate, trolamine, benzyldimethylamine and Bian base triphenyl phosphonium muriate; The amount of used catalyst is 0.15～0.3% of reaction system total mass; Described heating refers to that heating refers to 105～115 ℃.
7. the high rigidity quick-reaction type coating that the epoxy alkyd resin based on described in claim 1～6 any one prepares, is characterized in that: include organic coating and solidifying agent; The weight ratio of organic coating and solidifying agent is 40:60～60:40.
8. high rigidity quick-reaction type coating according to claim 7, is characterized in that: the component that described organic coating comprises following weight part meter:
Described solidifying agent refers to polyisocyanate-based solidifying agent.
9. high rigidity quick-reaction type coating according to claim 8, is characterized in that: described epoxy alkyd resin is 65% with solvent cut to solid content before using; Described pigment refers at least one in stibium trioxide, titanium dioxide, barba hispanica, phthalocyanine blue, phthalocyanine green and carbon black; Described filler refers at least one in calcium carbonate, talcum powder, kaolin, magnesium hydroxide and barium sulfate; Described solvent nail benzene, dimethylbenzene, petroleum naphtha, raffinate oil, at least one in ethyl acetate, butylacetate, 100# solvent oil and 200# solvent oil; Described auxiliary agent refers at least one in wetting agent, dispersion agent, flow agent, defoamer, anti-settling agent and siccative; Described solidifying agent refers at least one in IL1451, N3390, BL3175SN, WB905,2604, TPA-90SB, HX-90B, HX-90, B1358A, HI100, HXR, HX, HK, HLBA, HI190B/S, SC-75LT, N3300, IL1451 and HLBA; It is 50% that described solidifying agent adds ethyl acetate to solid content before using.
10. high rigidity quick-reaction type coating according to claim 7, is characterized in that: when described high rigidity quick-reaction type coating is used, first organic coating dispersed with stirring, then add solidifying agent to mix, can use.
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Application publication date: 20140205 |