CN115010898A - 一种用于提高金属涂层附着力的低聚物及其制备方法与应用 - Google Patents
一种用于提高金属涂层附着力的低聚物及其制备方法与应用 Download PDFInfo
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- CN115010898A CN115010898A CN202210529733.9A CN202210529733A CN115010898A CN 115010898 A CN115010898 A CN 115010898A CN 202210529733 A CN202210529733 A CN 202210529733A CN 115010898 A CN115010898 A CN 115010898A
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- Prior art keywords
- oligomer
- acrylate
- diisocyanate
- metal coating
- meth
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- 238000000576 coating method Methods 0.000 title claims abstract description 48
- 239000011248 coating agent Substances 0.000 title claims abstract description 44
- 239000002184 metal Substances 0.000 title claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 33
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- 238000000034 method Methods 0.000 claims abstract description 25
- -1 mercapto compound Chemical class 0.000 claims abstract description 15
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 6
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- 239000002904 solvent Substances 0.000 claims description 22
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 17
- 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 11
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- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 7
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 7
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
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- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 4
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- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 claims description 4
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- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 claims description 3
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 3
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 claims description 3
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 claims description 2
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- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 2
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 2
- SRZXCOWFGPICGA-UHFFFAOYSA-N 1,6-Hexanedithiol Chemical compound SCCCCCCS SRZXCOWFGPICGA-UHFFFAOYSA-N 0.000 claims description 2
- ZRKMQKLGEQPLNS-UHFFFAOYSA-N 1-Pentanethiol Chemical compound CCCCCS ZRKMQKLGEQPLNS-UHFFFAOYSA-N 0.000 claims description 2
- PUGOMSLRUSTQGV-UHFFFAOYSA-N 2,3-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OCC(OC(=O)C=C)COC(=O)C=C PUGOMSLRUSTQGV-UHFFFAOYSA-N 0.000 claims description 2
- HAQZWTGSNCDKTK-UHFFFAOYSA-N 2-(3-sulfanylpropanoyloxy)ethyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCCOC(=O)CCS HAQZWTGSNCDKTK-UHFFFAOYSA-N 0.000 claims description 2
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 claims description 2
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 claims description 2
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 2
- VSYDLUXFKAXBBY-UHFFFAOYSA-N C(C=1C(C(=O)O)=CC=CC1)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(COCCO)O Chemical compound C(C=1C(C(=O)O)=CC=CC1)(=O)O.C(C=C)(=O)O.C(C=C)(=O)O.C(COCCO)O VSYDLUXFKAXBBY-UHFFFAOYSA-N 0.000 claims description 2
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- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 2
- IYPNRTQAOXLCQW-UHFFFAOYSA-N [4-(sulfanylmethyl)phenyl]methanethiol Chemical compound SCC1=CC=C(CS)C=C1 IYPNRTQAOXLCQW-UHFFFAOYSA-N 0.000 claims description 2
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- 239000003085 diluting agent Substances 0.000 claims description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims description 2
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C333/02—Monothiocarbamic acids; Derivatives thereof
- C07C333/04—Monothiocarbamic acids; Derivatives thereof having nitrogen atoms of thiocarbamic groups bound to hydrogen atoms or to acyclic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
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- C—CHEMISTRY; METALLURGY
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Abstract
Description
技术领域
本发明涉及低聚物制备技术领域,尤其是涉及一种用于提高金属涂层附着力的低聚物及其制备方法与应用。
背景技术
光聚合技术作为一项节能环保且高效的绿色技术,近年来得到飞速发展。其中丙烯酸酯类低聚物由于其固化速度快,成本低廉成为光固化领域应用最为广泛的树脂。但是,快速固化过程中双键聚合产生的收缩应力以及绝大多数金属致密的表面共同导致了金属涂层附着力差的问题。
目前提升光固化金属涂层附着力措施主要分为两种,一是基材表面处理,主要有基材表面打磨、溶剂清洗、酸碱处理、基材表面磷化或钝化,但是此类方面工艺复杂、成本较高并且容易产生大量粉尘或者废水污染环境。二是通过涂料配方设计降低收缩应力,主要是通过降低官能团密度、延长松弛时间、补偿收缩体积来降低涂层收缩应力带来的影响,以上方法不可避免地损害了涂层力学性能,同时并不能完全耗散收缩应力,只能在一定程度上减少产生的收缩应力。因此应用的范围仍然受到很大程度的限制。
发明内容
针对现有技术存在的上述问题,本发明申请提供了一种用于提高金属涂层附着力的低聚物及其制备方法与应用。本发明通过在涂料配方中引入含有动态硫氨酯键的低聚物丙烯酸树脂,通过热处理驱动硫代氨基甲酸酯动态交换耗散固化过程的收缩应力。
本发明的技术方案如下:
一种用于提高金属涂层附着力的低聚物,所述低聚物的结构如通式(1)所示:
通式(1)中,R1表示为巯基化合物中除去两端巯基的部分;R2表示为二异氰酸酯中除去两端的异氰酸酯基团的部分;R3表示为丙烯酸酯光敏单体除去羟基的部分;n为≥1的整数。
进一步地,所述低聚物的数均分子量为500~5000g/mol。
进一步地,所述巯基化合物为乙二硫醇、1,3-丙二硫醇、1,4-丁二硫醇、1,5-戊二硫醇、1,6-己二硫醇、1,8-辛二硫醇、3,6-二氧杂-1,8-辛烷二硫醇、二(巯基乙酸)丁二醇酯、二(3-巯基丙酸)乙二醇酯、对苯二甲硫醇中的一种或多种。
进一步地,所述二异氰酸酯为二苯基甲烷-4,4二异氰酸酯、1,5-萘二异氰酸酯、甲苯二异氰酸酯、二环己基甲烷二异氰酸酯、苯二亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯中的一种或多种。
进一步地,所述丙烯酸酯光敏单体为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯、丙烯酸羟丁酯、甲基丙烯酸羟丁酯、季戊四醇三丙烯酸酯、双季戊四醇五丙烯酸酯中的一种或多种。
一种所述用于提高金属涂层附着力的低聚物的制备方法,所述制备方法包括如下步骤:
(1)将二异氰酸酯与巯基化合物反应,在催化剂的作用下得到端异氰酸酯聚硫氨酯低聚物;
所述催化剂为三乙胺、三丁胺、1,5-二氮杂双环[4.3.0]-5-壬烯、二月桂酸二丁基锡、三苯基磷中的一种或多种。
二异氰酸酯与巯基化合物的摩尔比为1.1:1~2:1。
(2)将步骤(1)得到的端异氰酸酯低聚物与丙烯酸酯光敏单体反应,挥发溶剂,得到含动态聚硫氨酯键的聚硫氨酯丙烯酸酯低聚物,即所述用于提高金属涂层附着力的低聚物;
丙烯酸酯光敏单体的摩尔数为剩余异氰酸酯基团数的1~1.1倍。
进一步地,所述用于提高金属涂层附着力的低聚物的制备方法包括如下步骤:
(1)将巯基化合物缓慢滴加至含有二异氰酸酯和适量溶剂的三口烧瓶中,控制反应温度在20~30℃,在0.05%~0.1%巯基化合物质量分数的催化剂的作用下反应2~4h得到端异氰酸酯聚硫氨酯低聚物;所述溶剂为丙酮、乙酸乙酯、四氢呋喃、三氯甲烷、N,N-二甲基甲酰胺中的一种或多种。
(2)将丙烯酸酯光敏单体、0.05%~0.1%丙烯酸酯光敏单体质量分数的阻聚剂对羟基苯甲醚、0.1%~0.2%丙烯酸酯光敏单体质量分数的二月桂酸二丁基锡滴加至上述含有端异氰酸酯聚硫氨酯低聚物的三口烧瓶中,控制反应温度为50~70℃,反应2~4h后挥发溶剂,得到含动态聚硫氨酯键的聚硫氨酯丙烯酸酯低聚物,即所述用于提高金属涂层附着力的低聚物。
一种所述用于提高金属涂层附着力的低聚物的应用,其特征在于用于制备金属涂料,涂料涂覆在基材紫外光固化或电子束固化后,再进一步加热处理;所述加热方式分为烘箱加热或近红外光源辐照加热,加热温度为70℃~120℃。
进一步地,所述金属涂料所含原料及各原料的重量分数为:
进一步地,所述丙烯酸酯类低聚物为环氧丙烯酸酯、聚氨酯丙烯酸酯、聚酯丙烯酸酯中的一种或多种。
进一步地,所述丙烯酸酯类活性稀释剂为(甲基)丙烯酸四氢糠基酯、(甲基)丙烯酸异冰片酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸异癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸羟乙酯、1,4-丁二醇二丙烯酸酯、三羟甲基丙烷三丙烯酸酯、邻苯二甲酸二乙二醇二丙烯酸酯、丙氧基化新戊二醇双丙烯酸酯、三缩三丙二醇双丙烯酸酯、乙氧基化三羟甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、丙氧基化甘油三丙烯酸酯、季戊四醇四丙烯酸酯中的一种或多种。
进一步地,所述光引发剂为2-羟基-2-甲基-1-苯基丙酮、1-羟基环己基苯基甲酮、2-甲基-2-(4-吗啉基)-1-[4-(甲硫基)苯基]-1-丙酮、2,4,6-三甲基苯甲酰基-二苯基氧化膦中的一种;所述附着力促进剂为γ-氨丙基三甲氧基硅烷、γ-(2,3-环氧丙氧基)丙基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、γ-巯丙基三甲氧基硅烷、乙烯基三甲氧基硅烷、β-(3,4-环氧环己基)乙基三甲氧基硅烷、2-甲基-2-丙烯酸-2-羟乙基酯磷酸酯、羟乙基甲基丙烯酸磷酸酯中的一种或多种。
金属涂料在紫外光固化时需要光引发剂的参与,选择电子束固化时无需光引发剂即可固化。
本发明有益的技术效果在于:
本发明申请利用了硫氨酯动态共价键在高温下的动态交换耗散体系中积累的收缩应力,动态共价键在刺激下键断开改变网络的交联密度使得网络链段自由运动,去除刺激后成键,在此过程中网络结构拓扑重排耗散了聚合过程中的收缩应力。涂层的收缩应力耗散以后,使得涂层和基材的浸润程度增加,涂层和基材的相互作用更加显著导致了附着力的提升。
本发明申请将动态聚硫氨酯应用于金属涂层时,常温下稳定且具有与聚氨酯相类似的优异力学性能,额外的动态特性使得可以热处理以后耗散涂层固化过程种的收缩应力提高附着力。
本发明提供的制备方法简单,工艺成熟,适用于工业化生产。
附图说明
图1为本发明实施例1-3及对比例1-3涂层样品的储能模量及损耗因子与温度变化关系图;
图2为本发明实施例1及对比例1低聚物的红外结构表征;
图3为本发明实施例1-3及对比例1-3低聚物分子量表征。
具体实施方式
下面结合附图和实施例,对本发明进行具体描述。
实施例1
一种用于提高金属涂层附着力的低聚物的制备方法,所述制备方法包括如下步骤:
(1)取0.5mol的3,6-二氧杂-1,8-辛烷二硫醇(EDDT),在氮气保护下滴加进含0.09g三乙胺和1mol异佛尔酮二异氰酸酯(IPDI)以无水丙酮做溶剂的溶液中,并在温度20℃反应2h,得到端异氰酸酯聚硫氨酯低聚物(IPDI-EDDT);
(2)再加入1mol丙烯酸羟乙酯、0.09g对羟基苯甲醚、0.2g二月桂酸二丁基锡,并在温度60℃反应4h,将得到的聚合物溶液旋蒸除去溶剂,得到含有动态硫氨酯键的丙烯酸低聚物树脂,即所述低聚物。
按照所述低聚物70份、丙烯酸四氢糠基酯30份、光引发剂2-羟基-2-甲基-1-苯基丙酮2份、羟乙基甲基丙烯酸磷酸酯1份进行混合。配方命名为PTUA-1。
实施例2
一种用于提高金属涂层附着力的低聚物的制备方法,所述制备方法包括如下步骤:
(1)取0.4mol的3,6-二氧杂-1,8-辛烷二硫醇,在氮气保护下滴加进含0.065g三乙胺和0.6mol异佛尔酮二异氰酸酯以无水丙酮做溶剂的溶液中,并在温度20℃反应2h,得到端异氰酸酯聚硫氨酯低聚物;
(2)再加入0.4mol丙烯酸羟乙酯、0.045g对羟基苯甲醚和0.08g二月桂酸二丁基锡,并在温度60℃反应4h,将得到的聚合物溶液旋蒸除去溶剂,得到含有动态硫氨酯键的丙烯酸低聚物树脂,即所述低聚物。
按照所述低聚物70份、丙烯酸四氢糠基酯30份、2-羟基-2-甲基-1-苯基丙酮2份、羟乙基甲基丙烯酸磷酸酯1份进行混合。配方命名为PTUA-2。
实施例3
一种用于提高金属涂层附着力的低聚物的制备方法,所述制备方法包括如下步骤:
(1)取0.6mol的3,6-二氧杂-1,8-辛烷二硫醇,在氮气保护下滴加进含0.1g三乙胺和0.8mol异佛尔酮二异氰酸酯以无水丙酮做溶剂的溶液中,并在温度20℃反应2h,得到端异氰酸酯聚硫氨酯低聚物;
(2)再加入0.4mol丙烯酸羟乙酯、0.045g对羟基苯甲醚和0.08g二月桂酸二丁基锡,并在温度60℃反应4h,将得到的聚合物溶液旋蒸除去溶剂,得到含有动态硫氨酯键的丙烯酸低聚物树脂,即所述低聚物。
按照所述低聚物70份、丙烯酸四氢糠基酯30份、2-羟基-2-甲基-1-苯基丙酮2份、羟乙基甲基丙烯酸磷酸酯1份进行混合。配方命名为PTUA-3。
对比例1
制备方法同实施例1,区别在于将3,6-二氧杂-1,8-辛烷二硫醇替换成三乙二醇制备了相同分子量的对照样PUA-1。
对比例2
制备方法同实施例2,区别在于将3,6-二氧杂-1,8-辛烷二硫醇替换成三乙二醇制备了相同分子量的对照样PUA-2。
对比例3
制备方法同实施例3,区别在于将3,6-二氧杂-1,8-辛烷二硫醇替换成三乙二醇制备了相同分子量的对照样PUA-3。
本发明实施例1及对比例1低聚物的红外结构表征如图2所示,由图2可以看出IPDI-EDDT中硫醇峰的完全消失,异氰酸酯峰的明显变小,说明中间产物端异氰酸酯聚硫氨酯低聚物的成功制备,与丙烯酸羟乙酯反应后异氰酸酯基团的完全消失以及双键峰的出现,说明低聚物PTUA-1/PUA-1的成功制备。
本发明实施例1-3及对比例1-3低聚物分子量表征如图3所示,实施例和其对比例中所制备的低聚物的分子量是极其相近的,说明用于对比加热前后的附着力提升程度具有可比性。
实施例4
一种用于提高金属涂层附着力的低聚物的制备方法,所述制备方法包括如下步骤:
(1)取0.5mol的3,6-二氧杂-1,8-辛烷二硫醇,在氮气保护下滴加进0.08g的三乙胺和0.55mol份异佛尔酮二异氰酸酯以无水丙酮做溶剂的溶液中,并在温度30℃反应4h,得到端异氰酸酯聚硫氨酯低聚物;
(2)而后再加入0.1mol丙烯酸羟乙酯、0.02g的对羟基苯甲醚和0.02g的二月桂酸二丁基锡,并在温度60℃反应4h,将得到的聚合物溶液旋蒸除去溶剂,得到含有动态硫氨酯键的丙烯酸低聚物树脂,即所述低聚物。
按照所述低聚物70份与1,4-丁二醇二丙烯酸酯(BDDA)/三羟甲基丙烷三甲基丙烯酸酯(TMPTA)/季戊四醇三丙烯酸酯(PET4A)30份、2-羟基-2-甲基-1-苯基丙酮2份、羟乙基甲基丙烯酸磷酸酯1.5份进行混合。配方分别命名为PTUA-BDDA、PTUA-TMPTA、PTUA-PET4A。
实施例5
一种用于提高金属涂层附着力的低聚物的制备方法,所述制备方法包括如下步骤:
(1)取0.4mol的己二硫醇,在氮气保护下滴加进含0.08g的1,5-二氮杂双环[4.3.0]-5-壬烯和0.6mol甲苯二异氰酸酯以乙酸乙酯做溶剂的溶液中,并在温度30℃反应2h,得到端异氰酸酯聚硫氨酯低聚物;
(2)再加入0.4mol甲基丙烯酸羟乙酯、0.065g对羟基苯甲醚和0.1g二月桂酸二丁基锡,并在温度70℃反应4h,将得到的聚合物溶液旋蒸除去溶剂,得到含有动态硫氨酯键的丙烯酸低聚物树脂,即所述低聚物。
按照所述低聚物70份、丙烯酸异冰片酯30份、RY1101标准环氧丙烯酸酯20份、1-羟基环己基苯基甲酮2份、γ-巯丙基三甲氧基硅烷2份进行混合。配方命名为PTUA-5。
实施例6
一种用于提高金属涂层附着力的低聚物的制备方法,所述制备方法包括如下步骤:
(1)取0.4mol二巯基丙酸乙二醇酯,在氮气保护下滴加进含0.07g三丁胺和0.5mol六亚甲基二异氰酸酯以三氯甲烷做溶剂的溶液中,并在温度30℃反应3h,得到端异氰酸酯聚硫氨酯低聚物;
(2)再加入0.22mol份季戊四醇三丙烯酸酯、0.065g阻聚剂对羟基苯甲醚和0.12g催化剂二月桂酸二丁基锡,并在温度80℃反应4h,将得到的聚合物溶液旋蒸除去溶剂,得到含有动态硫氨酯键的丙烯酸低聚物树脂,即所述低聚物。
按照所述低聚物80份、三缩三丙二醇双丙烯酸酯10份、DRE524聚酯丙烯酸酯10份、1-羟基环己基苯基甲酮2份、β-(3,4-环氧环己基)乙基三甲氧基硅1.5份进行混合。配方命名为PTUA-6。
实施例7
一种用于提高金属涂层附着力的低聚物的制备方法,所述制备方法包括如下步骤:
(1)取0.4mol二巯基丙酸乙二醇酯,在氮气保护下滴加进含0.08g的三丁胺和0.5mol六亚甲基二异氰酸酯以三氯甲烷做溶剂的溶液中,并在温度30℃反应3h,得到端异氰酸酯聚硫氨酯低聚物;
(2)再加入0.21mol季戊四醇三丙烯酸酯、0.08g对羟基苯甲醚和0.1g二月桂酸二丁基锡,并在温度80℃反应4h,将得到的聚合物溶液旋蒸除去溶剂,得到含有动态硫氨酯键的丙烯酸低聚物树脂,即所述低聚物。
按照所述低聚物2份、三缩三丙二醇双丙烯酸酯2份、DRE524聚酯丙烯酸酯6份、1-羟基环己基苯基甲酮3份、β-(3,4-环氧环己基)乙基三甲氧基硅1.5份进行混合。配方命名为PTUA-7。
实施例8
一种用于提高金属涂层附着力的低聚物的制备方法,所述制备方法包括如下步骤:
(1)取0.6mol二巯基丙酸乙二醇酯,在氮气保护下滴加进含0.1g的三丁胺和0.7mol六亚甲基二异氰酸酯以三氯甲烷做溶剂的溶液中,并在温度30℃反应3h,得到端异氰酸酯聚硫氨酯低聚物;
(2)再加入0.2mol甲基丙烯酸羟乙酯、0.045g对羟基苯甲醚和0.08g二月桂酸二丁基锡,并在温度60℃反应4h,将得到的聚合物溶液旋蒸除去溶剂,得到含有动态硫氨酯键的丙烯酸低聚物树脂,即所述低聚物。
按照所述低聚物80份、三缩三丙二醇双丙烯酸酯10份、DRE524聚酯丙烯酸酯10份、1-羟基环己基苯基甲酮3份、乙烯基三甲氧基硅烷2.5份进行混合。配方命名为PTUA-8。
实施例9
按照实施例7制备得到的低聚物60份、三缩三丙二醇双丙烯酸酯20份、DRE524聚酯丙烯酸酯20份、羟乙基甲基丙烯酸磷酸酯2份进行混合。配方命名为PTUA-9
实施例10
按照实施例8制备得到的低聚物60份、三缩三丙二醇双丙烯酸酯20份、DRE524聚酯丙烯酸酯20份、羟乙基甲基丙烯酸磷酸酯2份进行混合。配方命名为PTUA-10
测试例:
(1)用丙酮对钢板进行反复擦拭除去钢板表面的油脂,利用框式刮膜器将实施例1-8和对比例1-3所得涂料在钢板表面涂布湿膜厚度为90微米的涂层,在30℃的烘箱中流平5分钟后使用UV固化机曝光5次,履带速度为5.4米/分钟,将固化完成后的钢板置于烘箱中加热。实施例1-3和对比例1-3加热温度为110℃,加热时间为15min。实施例4-5加热温度为120℃,加热时间为10min。
实施例6-8加热温度为70℃,加热时间为20min。
按照美标ASTM-D4514对涂层进行拉拔附着力测试。经过热处理或未经过热处理的样品测试结果分别如表1所示:
表1
实施例 | 样品 | 拉拔附着力/MPa-热处理前 | 拉拔附着力/MPa-热处理后 |
实施例1 | PTUA-1 | 0.55±0.13 | 2.08±0.55 |
实施例2 | PTUA-2 | 1.35±0.27 | 4.02±0.63 |
实施例3 | PTUA-3 | 1.88±0.54 | 4.45±1.31 |
对比例1 | PUA-1 | 0.62±0.13 | 0.95±0.25 |
对比例2 | PUA-2 | 1.28±0.24 | 2.02±0.73 |
对比例3 | PUA-3 | 1.95±0.71 | 2.51±0.85 |
本发明实施例1-3及对比例1-3涂层样品的储能模量及损耗因子与温度变化关系如图1所示。由图1可以看出,实施例1-3所得PTUA-1、PTUA-2、PTUA-3固化材料在110℃~130℃由于动态硫氨酯的解离可以观察到储能模量的显著降低,其参照样PUA-1、PUA-2、PUA-3没有观察到类似的现象,说明了硫代氨基甲酸酯键具有的动态特性。并且从表1中可以看到对比例的附着力略微提升是由于加热导致的链段运动释放了部分应力,而实施例的附着力提升十分显著归因于动态键交换导致的大幅应力耗散。
实施例4的测试结果如表2所示。
表2
样品 | 拉拔附着力/MPa-热处理前 | 拉拔附着力/MPa-热处理后 |
PTUA-BDDA | 1.25±0.33 | 2.35±0.24 |
PTUA-TMPTA | 0.75±0.17 | 1.98±0.43 |
PTUA-PET4A | 0.11±0.03 | 1.45±0.13 |
实施例5-8的测试结果如表3所示。
表3
实施例 | 样品 | 拉拔附着力/MPa-热处理前 | 拉拔附着力/MPa-热处理后 |
实施例5 | PTUA-5 | 1.25±0.53 | 3.08±0.55 |
实施例6 | PTUA-6 | 2.35±0.71 | 4.44±1.15 |
实施例7 | PTUA-7 | 1.66±0.52 | 4.85±1.31 |
实施例8 | PTUA-8 | 0.88±0.11 | 3.34±0.71 |
(2)用丙酮对钢板进行反复擦拭除去钢板表面的油脂,利用框式刮膜器将实施例9-10和对所得涂料在钢板表面涂布湿膜厚度为90微米的涂层,在30℃的烘箱中流平5分钟后使用EB固化设备固化涂层,电压为200kV,剂量90kGy。将固化完成后的钢板置于烘箱中加热,加热温度为120℃,加热时间为15min。
按照美标ASTM-D4514对涂层进行拉拔附着力测试。经过热处理或未经过热处理的样品测试结果分别如表4所示:
表4
实施例 | 样品 | 拉拔附着力/MPa-热处理前 | 拉拔附着力/MPa-热处理后 |
实施例9 | PTUA-9 | 1.44±0.37 | 3.52±0.88 |
实施例10 | PTUA-10 | 2.15±0.62 | 4.26±1.15 |
Claims (10)
2.根据权利要求1所述的低聚物,其特征在于,所述低聚物的数均分子量为500~5000g/mol。
3.根据权利要求1所述的低聚物,其特征在于,所述巯基化合物为乙二硫醇、1,3-丙二硫醇、1,4-丁二硫醇、1,5-戊二硫醇、1,6-己二硫醇、1,8-辛二硫醇、3,6-二氧杂-1,8-辛烷二硫醇、二(巯基乙酸)丁二醇酯、二(3-巯基丙酸)乙二醇酯、对苯二甲硫醇中的一种或多种;所述二异氰酸酯为二苯基甲烷-4,4二异氰酸酯、1,5-萘二异氰酸酯、甲苯二异氰酸酯、二环己基甲烷二异氰酸酯、苯二亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯中的一种或多种。
4.根据权利要求1所述的低聚物,其特征在于,所述丙烯酸酯光敏单体为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯、丙烯酸羟丁酯、甲基丙烯酸羟丁酯、季戊四醇三丙烯酸酯、双季戊四醇五丙烯酸酯中的一种或多种。
5.一种权利要求1所述用于提高金属涂层附着力的低聚物的制备方法,其特征在于,所述制备方法包括如下步骤:
(1)将二异氰酸酯与巯基化合物反应,在催化剂的作用下得到端异氰酸酯聚硫氨酯低聚物;
(2)将步骤(1)得到的端异氰酸酯低聚物与丙烯酸酯光敏单体反应,挥发溶剂,得到含动态聚硫氨酯键的聚硫氨酯丙烯酸酯低聚物,即所述用于提高金属涂层附着力的低聚物。
6.根据权利要求5所述的制备方法,其特征在于,步骤(1)中,所述催化剂为三乙胺、三丁胺、1,5-二氮杂双环[4.3.0]-5-壬烯、二月桂酸二丁基锡、三苯基磷中的一种或多种;二异氰酸酯与巯基化合物的摩尔比为1.1:1~2:1。
7.根据权利要求5所述的制备方法,其特征在于,步骤(2)中,丙烯酸酯光敏单体的摩尔数为剩余异氰酸酯基团数的1~1.1倍。
8.一种权利要求1所述用于提高金属涂层附着力的低聚物的应用,其特征在于用于制备金属涂料,涂料涂覆在基材紫外光固化或电子束固化后,再进一步加热处理;所述加热方式分为烘箱加热,加热温度为70℃~120℃,加热时间为10~20min。
10.根据权利要求8所述的应用,其特征在于,所述丙烯酸酯类低聚物为环氧丙烯酸酯、聚氨酯丙烯酸酯、聚酯丙烯酸酯中的一种或多种;所述丙烯酸酯类活性稀释剂为(甲基)丙烯酸四氢糠基酯、(甲基)丙烯酸异冰片酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸异癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸羟乙酯、1,4-丁二醇二丙烯酸酯、三羟甲基丙烷三丙烯酸酯、邻苯二甲酸二乙二醇二丙烯酸酯、丙氧基化新戊二醇双丙烯酸酯、三缩三丙二醇双丙烯酸酯、乙氧基化三羟甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、丙氧基化甘油三丙烯酸酯、季戊四醇四丙烯酸酯中的一种或多种;所述光引发剂为2-羟基-2-甲基-1-苯基丙酮、1-羟基环己基苯基甲酮、2-甲基-2-(4-吗啉基)-1-[4-(甲硫基)苯基]-1-丙酮、2,4,6-三甲基苯甲酰基-二苯基氧化膦中的一种;所述附着力促进剂为γ-氨丙基三甲氧基硅烷、γ-(2,3-环氧丙氧基)丙基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、γ-巯丙基三甲氧基硅烷、乙烯基三甲氧基硅烷、β-(3,4-环氧环己基)乙基三甲氧基硅烷、2-甲基-2-丙烯酸-2-羟乙基酯磷酸酯、羟乙基甲基丙烯酸磷酸酯中的一种或多种。
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