CN105968132A - 一种柠檬酸酯复合金属螯合型粉末涂料螯合型锆钛化合物 - Google Patents
一种柠檬酸酯复合金属螯合型粉末涂料螯合型锆钛化合物 Download PDFInfo
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- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical class [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 title claims abstract description 24
- -1 Citric acid ester Chemical class 0.000 title claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 title claims description 15
- 239000000843 powder Substances 0.000 title description 9
- 239000011248 coating agent Substances 0.000 title description 6
- 238000000576 coating method Methods 0.000 title description 5
- 229910052751 metal Inorganic materials 0.000 title description 3
- 239000002184 metal Substances 0.000 title description 3
- 239000002131 composite material Substances 0.000 title 1
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 11
- 239000010936 titanium Substances 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims description 35
- 150000001875 compounds Chemical class 0.000 claims description 35
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 8
- HDDLVZWGOPWKFW-UHFFFAOYSA-N trimethyl 2-hydroxypropane-1,2,3-tricarboxylate Chemical group COC(=O)CC(O)(C(=O)OC)CC(=O)OC HDDLVZWGOPWKFW-UHFFFAOYSA-N 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 7
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- 239000003973 paint Substances 0.000 claims description 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical group CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical group CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 claims description 4
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 4
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims description 4
- 150000004702 methyl esters Chemical class 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- 239000001069 triethyl citrate Chemical group 0.000 claims description 4
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Chemical group CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 claims description 4
- 235000013769 triethyl citrate Nutrition 0.000 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical compound C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- 241000040710 Chela Species 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 235000005979 Citrus limon Nutrition 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- 0 CC=NOC(CC(CC(O*)=O)(C(O*)=O)OC)=O Chemical compound CC=NOC(CC(CC(O*)=O)(C(O*)=O)OC)=O 0.000 description 1
- ZRMXXCULMPGSEY-UHFFFAOYSA-N COC(C(CC(O)OI)(CC(ON=C)=O)[O]=C)=O Chemical compound COC(C(CC(O)OI)(CC(ON=C)=O)[O]=C)=O ZRMXXCULMPGSEY-UHFFFAOYSA-N 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000009503 electrostatic coating Methods 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- VPVSTMAPERLKKM-UHFFFAOYSA-N glycoluril Chemical compound N1C(=O)NC2NC(=O)NC21 VPVSTMAPERLKKM-UHFFFAOYSA-N 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 150000007519 polyprotic acids Chemical class 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
- C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
- C07C215/12—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic the nitrogen atom of the amino group being further bound to hydrocarbon groups substituted by hydroxy groups
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
- C07C69/675—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids of saturated hydroxy-carboxylic acids
- C07C69/704—Citric acid esters
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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Abstract
本发明涉及以下通式的螯合型锆钛化合物，其中，M表示Zr或Ti；R1和R2各自独立地表示C1‑C10的支链或直链烷基；C1‑C10的支链或直链不饱和烷基；C1‑C10的支链或直链卤素单取代或多取代烷基；C1‑C10的支链或直链芳基取代烷基。
Description
技术领域
本发明涉及一种柠檬酸酯复合金属螯合型锆钛化合物。
背景技术
市场上已知的螯合型锆、钛化合物或螯合型锆钛酸酯主要是烷氧基、磷酸酯基、亚磷酸酯基、焦磷酸酯基或磺酸酯基的单螯合型化合物，主要作用是偶联剂，应用于填料改性、塑料、橡胶、液态涂料、油墨等领域。在这些螯合型锆钛化合物中，烷氧基型具有反应活性，但遇水分解就失去了反应活性；磷酸酯基、亚磷酸酯基、焦磷酸酯基或磺酸酯基型没有反应活性，因此不能作为交联(固化)剂。
目前，广泛使用的聚合物特别是聚酯粉末涂料的交联(固化)剂的品种主要有：异氰脲酸三缩水甘油酯固化剂、羟烷基酰胺类固化剂、多元酸缩水甘油酯固化剂、异氰脲酸三-β-甲基缩水甘油酯固化剂、噁唑啉类固化剂、聚酯/封闭型异氰酸酯、羟基树脂/甘脲、丙烯酸缩水甘油酯/脂肪酸等固化剂。这些固化剂用于粉末涂料在耐候性、光泽、膜面效果、流平性、价格等方面的表现各有不同，其中异氰脲酸三缩水甘油酯固化剂的表现最好，某些性能其他固化剂还不能替代，因此成为市场上主要的聚酯粉末涂料的交联(固化)剂。
但是，异氰脲酸三缩水甘油酯有一定的致癌性，并且在生产和使用过程中，接触其粉尘的人们绝大部分会严重过敏，因此已经被欧洲禁止使用，含有异氰脲酸三缩水甘油酯(TGIC)的粉末涂料也被中国列入限制发展类项目。所以人们不遗余力地寻求其替代产品。
众所周知，锆酸酯或钛酸酯能与含有羟基和羧基的化合物，特别是含有羟基和羧基的高分子化合物发生交联反应。但是一般的锆酸酯或钛酸酯遇水分解而失去反应活性，因此，提供一种既保留锆酸酯或钛酸酯的交联反应活性，又保证它们在遇水情况下不分解，具有特别的意义。
发明内容
本发明的目的是提供一种新型螯合型锆钛化合物、其制备方法和应用。
本发明提供一种螯合型锆钛化合物，其具有通式I：
其中：
M表示Zr和/或Ti；
R1和R2各自独立地表示：C1-C10的支链或直链烷基；C1-C10的支链或直链不饱和烷基；C1-C10的支链或直链卤素单取代或多取代烷基；C1-C10的支链或直链芳基取代烷基。
在本发明的一个实施方案中，锆和/或钛的四个键是全螯合或交叉螯合的。
在本发明的一个实施方案中，通式I的化合物使用通式II的化合物、通式III的化合物和通式IV的化合物制备得到，其中
通式II的化合物为：
其中：
R3表示C2-C10的支链或直链烷基，优选为C2H5，C3H7，C4H9；
通式II的钛酸酯优选为钛酸四甲酯、钛酸四乙酯、钛酸四异丙酯、钛酸四正丙酯、钛酸四正丁酯、钛酸四异丁酯、钛酸四叔丁酯、钛酸四戊酯、钛酸四辛酯；
通式II的锆酸酯优选为锆酸四甲酯、锆酸四乙酯、锆酸四异丙酯、锆酸四正丙酯、锆酸四正丁酯、锆酸四异丁酯、锆酸四叔丁酯、锆酸四戊酯、锆酸四辛酯；
通式III的化合物为：
其中：
通式III的化合物优选为三乙醇胺、三异丙醇胺、三叔丁基醇胺；
通式IV的化合物为：
其中：
R2优选为柠檬酸三甲酯、柠檬酸三乙酯、柠檬酸三丁酯、柠檬酸三异丙酯。
在本发明的一个实施方案中，反应类型为全螯合，醇胺可以结构不同交叉螯合。
在本发明的一个实施方案中，通式II的化合物可以是单一化合物或混合物。
在本发明的一个实施方案中，通式III的化合物可以是单一化合物或混合物。
在本发明的一个实施方案中，通式IV的化合物可以是单一化合物或混合物。
本发明提供一种螯合型锆钛化合物作为聚合物的交联剂的用途。
本发明提供一种螯合型锆钛化合物作为粉末涂料的交联剂的用途。
在本发明的一个实施方案中，M为Zr或Ti。
在本发明的一个实施方案中，M为Zr和Ti的混合物，称之为螯合型锆、钛化合物或螯合型锆钛化合物；或螯合型锆、钛酸酯或螯合型钛酸酯。
在本发明的一个实施方案中，使用通式II的锆酸酯或钛酸酯与通式III的含三羟基烷胺和通式IV的柠檬酸酯化合物反应制备，优选的三羟基烷胺化合物是三乙醇胺和三异丙醇胺，优选的二羟基化合物是乙二醇、丙二醇、丁二醇，优选的柠檬酸酯是柠檬酸三甲酯、柠檬酸三乙酯和柠檬酸三丙酯。
在本发明的一个实施方案中，使用通式II的锆酸酯或钛酸酯与通式III的含三羟基烷胺和通式IV的柠檬酸酯化合物在20-150℃反应。
在本发明的一个实施方案中，在溶剂中反应，优选溶剂是醇、甲苯、二甲苯、石油醚和醚类溶剂。
在本发明的一个实施方案中，也可以不用溶剂。
本发明的新型螯合型锆钛化合物作为聚合物的交联剂(固化剂)。螯合型锆钛化合物特别优选作为用于聚酯或聚丙烯酸酯作为聚合物的粉末涂料的交联剂(固化剂)。
本发明的螯合型锆钛化合物可以单独作为螯合型锆钛化合物(固化剂)，也可以和其他螯合型锆钛化合物(固化剂)混合使用。
合成例
以下合成例作为本发明螯合型锆钛化合物的制备参考，但本发明不仅限于以下实施例。
合成例1：
将钛酸四正丁酯34克、三乙醇胺14.9克(摩尔比1∶1)置于装有搅拌器、温度计和回流冷凝器的250毫升的四颈圆底烧瓶中，在80-100℃反应2-3小时。再加入柠檬酸三甲酯23.4克(与钛酸四正丁酯摩尔比1∶1)，保温1小时。反应结束后，蒸出反应生成的丁醇，直至丁醇蒸尽(80℃，10mmHg无馏分)。加入甲苯150毫升回流2小时，冷却结晶，滤出固体，再在80℃真空下干燥。得白色粉末41克，产物即为复合的全螯合型的钛酸酯，编号TM1041。元素分析钛含量11.06％，理论值11.22％。
合成例2：
将钛酸四正丁酯34克、三异丙醇胺19.2克(摩尔比1∶1)置于装有搅拌器、温度计和回流冷凝器的250毫升的四颈圆底烧瓶中，在80-100℃反应2-3小时。反应结束后，再加入柠檬酸三乙酯27.6克(与钛酸四正丁酯摩尔比1∶1)，保温1小时，反应结束后，蒸出反应生成的丁醇，直至丁醇蒸尽(80℃，10mmHg无馏分)。加入甲苯150毫升回流2小时，冷却结晶，滤出固体，再在80℃真空下干燥。得白色结晶粉末48克，产物即为复合的全螯合型的钛酸酯，编号TM2011。元素分析钛含量9.21％，理论值9.36％。
合成例3：
将锆酸四正丙酯70％丙醇溶液59.8克、三异丙醇胺19.2克(摩尔比1∶1)置于装有搅拌器、温度计和回流冷凝器的250毫升的四颈圆底烧瓶中，在60-100℃反应2-3小时。反应结束后，再加入柠檬酸三乙酯27.6克(与锆酸四丙酯摩尔比1∶1)，保温1小时，反应结束后，蒸出反应生成的丙醇，直至丙醇蒸尽(80℃，10mmHg无馏分)。加入甲苯150毫升回流2小时，冷却结晶，滤出固体，再在60℃真空下干燥。得类白色粉末63克，产物即为复合的全螯合型的锆酸酯，编号ZM2144。元素分析锆含量13.8％，理论值14.07％。
实施例1-4：
分别将上述合成例1至3的产物14.4克加入到345.6克羧基聚酯(酸值为20-80mgKOH/g，Tg50-80℃)、6克流平剂、120克钛白粉和114克硫酸钡中，混合均匀，经双螺杆挤出机在110℃挤出，粉碎成200目的细粉。
上述粉末，用静电喷涂的方式喷涂在铝片或铁片上，喷涂厚度在60-150μm，然后在190℃烘烤10分钟。
烘烤后的铝片或铁片，涂膜及性能测试结果如下：
测试方法：按照国家标准《热固性粉末涂料HG/T2006-2006》测试。
1)羟基型聚酯树脂(羟基值26-34)
2)羧基型聚酯树脂(酸值20-25)
Claims (9)
1.一种螯合型锆钛化合物，其具有通式I：
其中：
M表示Zr和/或Ti；
R1和R2各自独立地表示：C1-C10的支链或直链烷基；C1-C10的支链或直链不饱和烷基；C1-C10的支链或直链卤素单取代或多取代烷基；C1-C10的支链或直链芳基取代烷基。
2.权利要求1的螯合型锆钛化合物，其中锆和/或钛的四个键是全螯合或交叉螯合的。
3.权利要求1的螯合型锆钛化合物，其中通式I的化合物使用通式II的化合物、通式III的化合物和通式IV的化合物制备得到，其中
通式II的化合物为：
其中：
R3表示C2-C10的支链或直链烷基，优选为C2H5，C3H7，C4H9；
通式II的钛酸酯优选为钛酸四甲酯、钛酸四乙酯、钛酸四异丙酯、钛酸四正丙酯、钛酸四正丁酯、钛酸四异丁酯、钛酸四叔丁酯、钛酸四戊酯、钛酸四辛酯；
通式II的锆酸酯优选为锆酸四甲酯、锆酸四乙酯、锆酸四异丙酯、锆酸四正丙酯、锆酸四正丁酯、锆酸四异丁酯、锆酸四叔丁酯、锆酸四戊酯、锆酸四辛酯；
通式III的化合物为：
其中：
通式III的化合物优选为三乙醇胺、三异丙醇胺、三叔丁基醇胺；
通式IV的化合物为：
其中：
R2优选为柠檬酸三甲酯、柠檬酸三乙酯、柠檬酸三丁酯、柠檬酸三异丙酯。
4.权利要求3的螯合型锆钛化合物，其中反应类型为全螯合，醇胺可以结构不同交叉螯合。
5.权利要求3的螯合型锆钛化合物，其中通式II的化合物可以是单一化合物或混合物。
6.权利要求3的螯合型锆钛化合物，其中通式III的化合物可以是单一化合物或混合物。
7.权利要求3的螯合型锆钛化合物，其中通式IV的化合物可以是单一化合物或混合物。
8.权利要求1的螯合型锆钛化合物作为聚合物的交联剂的用途。
9.权利要求1的螯合型锆钛化合物作为粉末涂料的交联剂的用途。
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1104663A (zh) * | 1993-05-19 | 1995-07-05 | 泰奥塞特殊品有限公司 | 聚酯树脂粉末涂料组合物 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1104663A (zh) * | 1993-05-19 | 1995-07-05 | 泰奥塞特殊品有限公司 | 聚酯树脂粉末涂料组合物 |
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| 崔桂陵等: "调剖用部分水解聚丙烯酰胺- 柠檬酸钛缓交联体系", 《油田化学》 * |
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