CN104761662B - 一种水溶性二苯甲酮光引发剂及其制备方法 - Google Patents
一种水溶性二苯甲酮光引发剂及其制备方法 Download PDFInfo
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- 239000003999 initiator Substances 0.000 title claims abstract description 62
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 title claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract description 3
- -1 carboxyl diphenyl ketone Chemical compound 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 13
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 9
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 claims description 8
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 8
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 8
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- JOZZAIIGWFLONA-UHFFFAOYSA-N 3-methylbutan-2-amine Chemical compound CC(C)C(C)N JOZZAIIGWFLONA-UHFFFAOYSA-N 0.000 claims description 4
- HTJDQJBWANPRPF-UHFFFAOYSA-N Cyclopropylamine Chemical compound NC1CC1 HTJDQJBWANPRPF-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- 229940043279 diisopropylamine Drugs 0.000 claims description 4
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 4
- 238000007142 ring opening reaction Methods 0.000 claims description 4
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 claims description 4
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 4
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 2
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 2
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims description 2
- 150000003512 tertiary amines Chemical group 0.000 claims description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims 1
- 235000011118 potassium hydroxide Nutrition 0.000 claims 1
- 235000017550 sodium carbonate Nutrition 0.000 claims 1
- 235000011121 sodium hydroxide Nutrition 0.000 claims 1
- 238000000016 photochemical curing Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000002159 abnormal effect Effects 0.000 abstract description 2
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- 230000000977 initiatory effect Effects 0.000 abstract description 2
- 230000035943 smell Effects 0.000 abstract description 2
- 150000008064 anhydrides Chemical class 0.000 abstract 1
- 230000001988 toxicity Effects 0.000 abstract 1
- 231100000419 toxicity Toxicity 0.000 abstract 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 12
- 239000000243 solution Substances 0.000 description 8
- 239000012965 benzophenone Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 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 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 238000003848 UV Light-Curing Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 2
- 229940043276 diisopropanolamine Drugs 0.000 description 2
- 229940093495 ethanethiol Drugs 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
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- 239000007787 solid Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
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- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
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- Polymerisation Methods In General (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种水溶性二苯甲酮光引发剂及其制备方法。以二苯甲酮四酸二酐为原料,在特定物质的作用下,酸酐开环制备了一类水溶性二苯甲酮光引发剂。该类水性二苯甲酮光引发剂与水性低聚物相容性好,在水介质中光活性高,引发效率高,毒性低、气味小、挥发性低、安全环保,在水性光固化领域中有着广泛的应用。水溶性二苯甲酮光引发剂结构式如下:
Description
技术领域:
本发明涉及一种光引发剂及其制备方法,特点是水性二苯甲酮光引发剂及其制备方法。
背景技术:
紫外光固化技术是指经过紫外光的辐射作用,液态低聚物能在瞬间发生聚合、交联和固化的过程。紫外光固化技术相比于传统的固化技术,具有如下优点:固化速率快,节约能源,环境友好,可涂装各种基材。然而,光固化技术仍然存在一些不足之处,尤其是一些体系需要加入挥发性的有机溶剂以调节体系黏度及提高固化膜的性能,而这些挥发性有机溶剂会损害人体健康及污染环境。因此,水性紫外光固化技术结合光固化技术和水性涂料技术,使用水代替有机溶剂,安全环保,成为研究和开发紫外光固化技术的一个新领域。
光引发剂是光聚合技术的重要组成部分,它对光固化涂料的光固化速率起决定性作用。为了满足水性紫外光固化技术的全面发展,水性光引发剂的开发引起高度重视,水性光引发剂是水性光固化技术的关键组成部分,要求其在水性低聚物中相容性好,在水介质中引发效率高,以及其它光引发剂要求的低挥发性、无毒、无味、无色等。
二苯甲酮是一种应用广泛的夺氢型光引发剂,因为它表面固化良好、溶解性能好、价格低廉且容易得到。但是,它气味强烈,容易升华,对人身体产生不良影响。二苯甲酮类水性光引发剂在水性光引发剂中占有重要的地位,是近年来研究最广泛的水溶性光引发剂。该类引发剂主要是在二苯甲酮母核上引入离子性或亲水性非离子基团而得。但是目前合成的水性二苯甲酮光引发剂,制备方法比较复杂,需要在高温高压条件下进行,成本高,并且在水中的溶解度还有待提高,还不符合水性光敏涂料的发展需求。迫切需要开发出一种环境友好型,低VOC排放的水性光引发剂。
发明内容:
本发明为了解决以上水性光引发剂存在的问题,提供了一种水性二苯甲酮光引发剂及其制备方法,所得引发剂与树脂体系相容性好,在水中溶解度高(溶解度大约为60g/100g水),可代替二苯甲酮作为光引发剂使用,而且其制备成本低,操作简便,产品产率高。
本发明制备的水性二苯甲酮光引发剂,其化学结构如下式所示:
R1=H+,Na+、K+,NH4+或伯、仲、叔胺。
R2=OH,ONa,OK,NH2或n=1-5,X为-O,-S,-NH-或
本发明水性二苯甲酮光引发剂制备方法如下:
(1)将二苯甲酮四酸二酐与开环剂按摩尔比为1:1-1:5加入到三口烧瓶中,加热搅拌至60-120℃,加入用量是上述两种原料总质量0.1%-0.5%的催化剂,搅拌反应1-5小时,得到含端羧基二苯甲酮光引发剂。
(2)将上述制得的含端羧基二苯甲酮光引发剂和碱性溶液中的碱性溶质按摩尔比1:2溶于水中,中和成盐,除去水分后制得水溶性二苯甲酮光引发剂。
本发明制备水性二苯甲酮光引发剂的整个反应方程式可表示为:
(1)
(2)
进一步,上述步骤(1)所用的开环剂为正丁醇,异丁醇,仲丁醇,叔丁醇,正丙醇,异丙醇,乙醇,甲醇,氨水,乙胺,二乙胺,乙二胺,乙醇胺,二乙醇胺,正丙胺,二丙胺,异丙胺,二异丙胺,1,2-二甲基丙胺,1,2-丙二胺,2-丙烯胺,环丙胺,正丁胺,二正丁胺,异丁胺,仲丁胺,1,4-丁二胺,二异丁胺,巯基乙烷,巯基乙酸,巯基乙醇或1,3-二巯基丙烷。
进一步,上述步骤(2)所用的碱性物质为氢氧化钠,氢氧化钾,碳酸钠,碳酸钾,碳酸氢钠,碳酸氢钾,氨水,一乙胺,二乙胺,三乙胺,乙二胺,正丙胺,二丙胺,三丙胺,异丙胺,二异丙胺,1,2-二甲基丙胺,1,2-丙二胺,2-丙烯胺,环丙胺,正丁胺,二正丁胺,异丁胺,仲丁胺,1,4-丁二胺,叔丁胺,二异丁胺,己胺,2-乙基己胺,己二胺,一乙醇胺,二乙醇胺,三乙醇胺,3-丙醇胺,一异丙醇胺,二异丙醇胺,三异丙醇胺,或N,N-二甲基乙醇胺。
本发明提供了一种新型水性二苯甲酮光引发剂的制备方法,通过分子结构设计,将羧基引入二苯甲酮光引发剂分子中,产生一种水性的光引发剂,提高了水性引发剂与水性低聚物的相容性,非常适用于目前发展迅猛的水性光固化技术。
附图说明
图1是实施例反应制得的光引发剂的紫外吸收光谱
图2是实施例反应制得的光引发剂用于引发丙烯酸羟乙酯固化。
具体实施方式:
下述实施例详细说明本发明,但不限制本发明的范围。
实施例1:
(1)将0.03mol(10g)二苯甲酮四酸二酐加入到三口烧瓶中,再将0.03mol(1.86g)正丙醇加到上述三口烧瓶中,加热搅拌至60℃,加入0.0593g的三苯基磷,搅拌反应4小时,得到含端羧基二苯甲酮光引发剂。
(2)将上述制得的含端羧基二苯甲酮光引发剂溶于水中,加入60ml,1mol/L的氢氧化钠溶液,除去水分后制得水溶性二苯甲酮光引发剂。
实施例2:
(1)将0.03mol(10g)二苯甲酮四酸二酐加入到三口烧瓶中,再将0.03mol(4.44g)正丁醇加到上述三口烧瓶中,加热搅拌至80℃,加入0.0289g对甲苯磺酸,搅拌反应4.5小时,得到含端羧基二苯甲酮光引发剂。
(2)将上述制得的含端羧基二苯甲酮光引发剂溶于水中,加入60ml,1mol/L的氢氧化钾溶液,除去水分后制得水溶性二苯甲酮光引发剂。
实施例3:
(1)将0.03mol(10g)二苯甲酮四酸二酐加入到三口烧瓶中,再将0.03mol(1.86g)异丙醇加到上述三口烧瓶中,加热搅拌至100℃,加入0.0119g的固体磺酸催化剂,搅拌反应3小时,得到含端羧基二苯甲酮光引发剂。
(2)将上述制得的含端羧基二苯甲酮光引发剂溶于水中,加入60ml,1mol/L的碳酸钾溶液,除去水分后制得水溶性二苯甲酮光引发剂。
实施例4:
(1)将0.03mol(10g)二苯甲酮四酸二酐加入到三口烧瓶中,再将0.06mol(4.08g)乙醇胺加到上述三口烧瓶中,加热搅拌至120℃,加入0.0141g三苯基磷,搅拌反应3小时,得到含端羧基二苯甲酮光引发剂。
(2)将上述制得的含端羧基二苯甲酮光引发剂溶于水中,加入60ml,1mol/L的氢氧化钾溶液,除去水分后制得水溶性二苯甲酮光引发剂。
实施例5:
(1)将0.03mol(10g)二苯甲酮四酸二酐加入到三口烧瓶中,再将0.06mol(4.08g)乙醇胺加到上述三口烧瓶中,加热搅拌至80℃,加入0.0704g的对甲苯磺酸,搅拌反应4小时,得到含端羧基二苯甲酮光引发剂。
(2)将上述制得的含端羧基二苯甲酮光引发剂溶于水中,加入60ml,1mol/L的碳酸氢钠溶液,除去水分后制得水溶性二苯甲酮光引发剂。
实施例6:
(1)将0.03mol(10g)二苯甲酮四酸二酐加入到三口烧瓶中,再将0.06mol(2.1g)氨水加到上述三口烧瓶中,加热搅拌至100℃,加入0.0121g的固体磺酸,搅拌反应5小时,得到含端羧基二苯甲酮光引发剂。
(2)将上述制得的含端羧基二苯甲酮光引发剂溶于水中,加入60ml,1mol/L的异丁胺溶液,除去水分后制得水溶性二苯甲酮光引发剂。
实施例7:
(1)将0.03mol(10g)二苯甲酮四酸二酐加入到三口烧瓶中,再将0.09mol(5.58g)巯基乙烷加到上述三口烧瓶中,加热搅拌至90℃,加入0.0467g的三苯基磷,搅拌反应4小时,得到含端羧基二苯甲酮光引发剂。
(2)将上述制得的含端羧基二苯甲酮光引发剂溶于水中,加入60ml,1mol/L的氢氧化钾溶液,除去水分后制得水溶性二苯甲酮光引发剂。
实施例8:
(1)将0.03mol(10g)二苯甲酮四酸二酐加入到三口烧瓶中,再将0.12mol(5.58g)正丙醇加到上述三口烧瓶中,加热搅拌至100℃,加入0.0156g的三苯基磷,搅拌反应3小时,得到含端羧基二苯甲酮光引发剂。
(2)将上述制得的含端羧基二苯甲酮光引发剂溶于水中,加入60ml,1mol/L的乙胺溶液,除去水分后制得水溶性二苯甲酮光引发剂。
实施例9:
(1)将0.03mol(10g)二苯甲酮四酸二酐加入到三口烧瓶中,再将0.15mol(9.3g)异丙醇加到上述三口烧瓶中,加热搅拌至80℃,加入0.0965g的对甲苯磺酸,搅拌反应3小时,得到含端羧基二苯甲酮光引发剂。
(2)将上述制得的含端羧基二苯甲酮光引发剂溶于水中,加入60ml,1mol/L的正丁胺溶液,除去水分后制得水溶性二苯甲酮光引发剂。
实施例10:
(1)将0.03mol(10g)二苯甲酮四酸二酐加入到三口烧瓶中,再将0.03mol(2.76g)巯基乙酸加到上述三口烧瓶中,加热搅拌至100℃,加入0.0128g的三苯基磷,搅拌反应4.5小时,得到含端羧基二苯甲酮光引发剂。
(2)将上述制得的含端羧基二苯甲酮光引发剂溶于水中,加入60ml,1mol/L的氢氧化钠溶液,除去水分后制得水溶性二苯甲酮光引发剂。
实施例11:
(1)将0.03mol(10g)二苯甲酮四酸二酐加入到三口烧瓶中,再将0.06mol(5.52g)巯基乙酸加到上述三口烧瓶中,加热搅拌至90℃,加入0.0466g的催化剂,搅拌反应3.5小时,得到含端羧基二苯甲酮光引发剂。
(2)将上述制得的含端羧基二苯甲酮光引发剂溶于水中,加入60ml,1mol/L的氨水,除去水分后制得水溶性二苯甲酮光引发剂。
所有实施例所得引发剂与树脂体系相容性好,在水中溶解度高(溶解度大于60g/100g水),可代替二苯甲酮作为光引发剂使用。
Claims (4)
1.水性二苯甲酮光引发剂,其特征在于该水性二苯甲酮光引发剂的化学结构如下式所示:
R1=H+,Na+、K+,NH4+或伯、仲、叔胺基团;R2=OH,ONa,OK,NH2或n=1-5,X为-O-,-S-,-NH-或
2.如权利要求1所述水性二苯甲酮光引发剂的制备方法,其特征在于:
(1)将二苯甲酮四酸二酐与开环剂按摩尔比为1:1-1:5加入到三口烧瓶中,加热搅拌至60-120℃,加入用量是上述两种原料总质量0.1%-0.5%的催化剂,搅拌反应1-5小时,得到含端羧基二苯甲酮光引发剂;
(2)将上述制得的含端羧基二苯甲酮光引发剂和碱性溶液中的碱性溶质按摩尔比1:2溶于水中,中和成盐,除去水分后制得水溶性二苯甲酮光引发剂。
3.如权利要求2所述水性二苯甲酮光引发剂的制备方法,其特征在于:上述步骤(1)所用的开环剂为正丁醇,异丁醇,仲丁醇,叔丁醇,正丙醇,异丙醇,乙醇,甲醇,氨水,乙胺,二乙胺,乙二胺,乙醇胺,二乙醇胺,正丙胺,二丙胺,异丙胺,二异丙胺,1,2-二甲基丙胺,1,2-丙二胺,2-丙烯胺,环丙胺,正丁胺,二正丁胺,异丁胺,仲丁胺,1,4-丁二胺,二异丁胺,巯基乙烷,巯基乙酸,巯基乙醇或1,3-二巯基丙烷。
4.如权利要求2所述水性二苯甲酮光引发剂的制备方法,其特征在于:上述步骤(2)所用的碱性物质为氢氧化钠,氢氧化钾,碳酸钠,碳酸钾,碳酸氢钠,碳酸氢钾,氨水,一乙胺,二乙胺,三乙胺,乙二胺,正丙胺,二丙胺,三丙胺,异丙胺,二异丙胺,1,2-二甲基丙胺,1,2-丙二胺,2-丙烯胺,环丙胺,正丁胺,二正丁胺,异丁胺,仲丁胺,1,4-丁二胺,叔丁胺,二异丁胺,己胺,2-乙基己胺,己二胺,一乙醇胺,二乙醇胺,三乙醇胺,3-丙醇胺,一异丙醇胺,二异丙醇胺,三异丙醇胺,或N,N-二甲基乙醇胺。
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