CN114752004A - 一种生物基uv固化引发剂的制备方法及其产品和应用 - Google Patents
一种生物基uv固化引发剂的制备方法及其产品和应用 Download PDFInfo
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Abstract
本发明公开一种生物基UV固化引发剂的制备方法及其产品和应用，该UV固化引发剂的制备方法是将植物油多元醇与带羧基的噻吨酮衍生物ATX在催化剂催化下反应，获得以植物油多元醇为核的生物基UV固化引发剂。将该引发剂引发含酰亚胺链段的聚氨酯丙烯酸酯UV固化，获得的UV固化材料透光率85.0–96.0％(400–800nm)，拉伸强度4–12MPa，断裂伸长率为60–180％，铅笔硬度6B–9H，初始热分解温度273.4–286.4℃。该UV引发剂可用作丙烯酸酯基类UV固化油漆、油墨和电子封装领域。
Description
技术领域
本发明属于高分子材料技术领域，涉及一种生物基UV固化引发剂的制备方法及其产品和应用。
背景技术
紫外光(UV)固化是一种节能环保的新技术，具有固化快，环境友好等优点[L.Xue,Y.Y.Zhang,Y.J.Zuo,et al.,Preparation and characterization ofnovel UV-curingsilicone rubber via thiol-ene reaction[J],Mater.Lett.,2013,106(34):425-427]，已被广泛应用于涂料、油墨和电子封装等重要领域。在UV固化体系中，UV引发剂虽然占比很小(1–10wt％)，但直接影响固化速度以及固化材料的综合性能。商业化的小分子UV引发剂在UV固化材料领域得到很好的应用。然而，很多小分子UV引发剂有气味、有一定毒性。另外，小分子UV引发剂在产品存储和使用过程中易迁移到UV固化材料表面；残留引发剂易光降解，使UV固化材料黄变、透光率变差等性能劣化，这使其在很多领域的应用受到限制[LiangQ,Zhang L,Xiong Y,et al.A facile method to prepare a polyethyleneglycolmodified polysilane as a waterborne photoinitiator[J].J.Photoch.Photobio.A,2015,299:9-17；Yagci Y,Jockusch S,Turro N J.,Photoinitiatedpolymerization:advances,challenges,and opportunities[J].Macromolecules,2010,43(15):6245-6260；Decker,C.Kinetic study and new applications of UV radiation curing[J].Macromol.Rapid Comm.,2002,23:1067-1093；Zhou R,Jin M,Malval J,etal.Bicarbazole-based oxalates as photoinitiating systems forphotopolymerization under UV-Vis LEDs[J].J.Polym.Sci.,2020,58:1079-1091]
噻吨酮类UV引发剂在长波区(365–395nm)有较强的吸收，适用于UV-LED光源引发固化，UV固化能耗低。但是，它们多为粉末状，在UV固化预聚物、稀释剂和各类溶剂中的溶解性较差，因而极大限制了其应用。
作为重要的可再生的生物基原料，植物油因为具有来源丰富，低毒性，可生物降解性等优点，在UV固化新材料研究和应用中引起人们的广泛关注。本发明利用生物基多元醇的这些优点，克服现有UV固化引发剂有毒性、有气味、迁移率高、易使UV固化材料黄变、与UV固化树脂基体相容性差等不足，将植物油多元醇与带羧基的噻吨酮衍生物ATX在催化剂催化下反应，获得以植物油多元醇为核的生物基UV固化引发剂，该UV固化引发剂用量仅为PI改性的聚氨酯-丙烯酸酯UV固化预聚物质量的0.01–5.0wt％时，UV固化体系经UV固化10–120s，所得UV固化材料透光率85.0–96.0％(400–800nm)，拉伸强度4–12MPa，断裂伸长率为60–180％，铅笔硬度6B–7H，初始热分解温度273.4–286.4℃。该UV引发剂可用作丙烯酸酯基类UV固化油漆、油墨和电子封装领域。
发明内容
本发明的第一个目的是针对现有技术的不足，提供一种生物基UV固化引发剂的制备方法。
在本发明中，以植物油多元醇为核的生物基UV固化引发剂的制备方法，是将带羧基的噻吨酮衍生物ATX与植物油多元醇在催化剂作用下，于100–150℃/130mmHg反应4–12h即可；其中ATX中羧基与植物油多元醇中羟基的摩尔比为1:1–1:1.5。
所述带羧基的噻吨酮衍生物ATX的化学结构式如下：
作为优选，所述植物油多元醇为蓖麻油、大豆油多元醇、葵花籽油多元醇和棕榈油多元醇中的一种或几种的混合物。更为优选，大豆油多元醇羟值为430mg/g，棕榈油多元醇羟值为498mg/g，葵花籽油多元醇羟值为190mg/g。
作为优选，ATX中羧基与植物油多元醇中羟基的摩尔比为1:1–1:1.15。
作为优选，所述催化剂为98％浓硫酸、三氟甲磺酸、对甲苯磺酸、十二烷基苯磺酸、十八烷基苯磺酸中的一种或几种的混合物；催化剂用量为ATX与植物油多元醇总质量的0.5–5％。更为优选，催化剂选自对甲苯磺酸、十二烷基苯磺酸、十八烷基苯磺酸中的一种或几种的混合物，其用量为ATX与植物油多元醇总质量的0.5–2％。
本发明的第二个目的是提供一种生物基UV固化引发剂。
本发明的第三个目的是提供一种UV固化聚酰亚胺改性的聚氨酯-丙烯酸酯的制备方法，包括如下：
步骤(1)：将两端羧基封端的聚酰亚胺(PI)与聚四氢呋喃(PTMG-2000)、异佛尔酮二异氰酸酯(IPDI)、三羟甲基丙烷(TMP)、丙烯酸羟丙酯(HPA)反应，获得PI改性的聚氨酯-丙烯酸酯UV固化预聚物(PIPUA)。
作为优选，所述两端羧基封端的聚酰亚胺(PI)的制备过程为：向三口反应瓶中依次加入2,2-双[4-(4-氨基苯氧基苯)]六氟丙烷、无水四氢呋喃和六氟二酐，25℃下反应8h。随后，向反应体系中滴加4-氨基苯甲酸、间-二氯代苯、无水四氢呋喃，室温下继续反应16h，再130mmHg/80℃减压脱除溶剂，得到白色粉末，即为PI；其合成路线如下：
作为优选，PIPUA具体制备步骤为：向20-102g PI、100-180g PTMG和2.683gTMP的混合物中加入100g四氢呋喃和0.8g二月桂酸二丁基锡，待溶液澄清透明后，升温至60℃滴加72.244gIPDI后，升温至80℃反应4h，随后加入50.755g HPA继续反应4h，最后在80℃/130mmHg减压脱除溶剂和未反应的原料，获得PIPUA。
步骤(2)：将上述以植物油多元醇为核的生物基UV固化引发剂加入到PIPUA中，经UV固化获得UV固化聚酰亚胺改性的聚氨酯-丙烯酸酯；其中以植物油多元醇为核的生物基UV固化引发剂用量为PIPUA质量的0.01–5.0wt％。
作为优选，以植物油多元醇为核的生物基UV固化引发剂用量为PIPUA质量的0.4–1.2wt％。
作为优选，UV固化体系的UV固化时间为10–120s。
本发明的第四个目的是提供一种UV固化聚酰亚胺改性的聚氨酯-丙烯酸酯，其透光率85.0–96.0％(400–800nm)，拉伸强度4–12MPa，断裂伸长率为60–180％，铅笔硬度6B–7H，初始热分解温度273.4–286.4℃。
本发明的又一个目的是提供UV固化聚酰亚胺改性的聚氨酯-丙烯酸酯在丙烯酸酯基类UV固化油漆、油墨和电子封装领域上的应用。
与现有技术相比，本发明的有益效果如下：
(1)所得生物基UV固化引发剂为粘稠液体，与UV固化体系相容性好，易于均匀分散在UV固化体系中，克服了噻吨酮类衍生物小分子UV引发剂为固体粉末，与UV固体体系相容性差，难于均匀分散在UV固化体系中的缺点。
(2)用所得生物基UV固化引发剂制备的UV固化物无论是拉伸强度还是透光率都明显高于用ATX或Irgacure-1173制备的UV固化物。
(3)所得生物基UV固化引发剂在UV固化物中的迁移率明显低于ATX或Irgacure-1173在UV固化物中的迁移率。
(4)本发明所得噻吨酮生物基大分子引发剂具有非常高的引发效率，其用量为聚合物基体0.01-0.1wt％时也具有非常高的引发活性；当其用量为聚合物基体0.1-5wt％时，所得UV固化材料具有优良的综合性能。说明通过大分子改性噻吨酮，可以大幅提高其引发活性。
附图说明
图1是以蓖麻油为核的ATX生物基UV引发剂的1H NMR谱图；
图2是以蓖麻油为核的ATX生物基UV引发剂的FT-IR谱图；
图3是PIPUA的1HNMR谱图；
图4是不同引发剂制备的UV固化材料的应力-应变曲线；
图5是不同PIPUA经UV固化所得材料的应力-应变曲线。
具体实施方式
如前所述，鉴于现有技术的不足，本案发明人经长期研究和大量实践，提出了本发明的技术方案，其主要是依据至少包括：
(1)将多元醇引入UV固化引发剂中，克服了噻吨酮类衍生物小分子UV引发剂为固体粉末，与UV固体体系相容性差，难于均匀分散在UV固化体系中的这一严重缺点。
(2)通过设计合成噻吨酮生物基大分子引发剂，克服现有UV固化引发剂有毒性、有气味、迁移率高、易使UV固化材料黄变、与UV固化树脂基体相容性差等不足。
(3)所得噻吨酮生物基大分子引发剂具有非常高的引发效率，其用量仅仅为聚合物基体0.01-0.1wt％也具有非常高的引发活性；当其用量为聚合物基体0.1-5wt％时，所得UV固化材料具有优良的综合性能。说明通过大分子改性噻吨酮，可以大幅提高其引发活性；
(4)以植物油多元醇为核的生物基UV固化引发剂可以实现用量极少下完成对PI改性的聚氨酯-丙烯酸酯UV固化；且UV固化产物透光率85.0–96.0％(400–800nm)，拉伸强度4–12MPa，断裂伸长率为60–180％，铅笔硬度6B–7H，初始热分解温度273.4–286.4℃。
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。此外，下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
第一方面，以植物油多元醇为核的生物基UV固化引发剂的制备方法，是将带羧基的噻吨酮衍生物ATX与植物油多元醇在催化剂作用下，于100–150℃/130mmHg反应4–12h即可；其中ATX中羧基与植物油多元醇中羟基的摩尔比为1:1–1:1.5。
所述带羧基的噻吨酮衍生物ATX的化学结构式如下：
作为优选，所述植物油多元醇为蓖麻油、大豆油多元醇、葵花籽油多元醇和棕榈油多元醇中的一种或几种的混合物。更为优选，大豆油多元醇羟值为430mg/g，棕榈油多元醇羟值为498mg/g，葵花籽油多元醇羟值为190mg/g。
以蓖麻油为例，植物油多元醇与ATX反应路线如下：
作为优选，ATX中羧基与植物油多元醇中羟基的摩尔比为1:1–1:1.15。
作为优选，所述催化剂为98％浓硫酸、三氟甲磺酸、对甲苯磺酸、十二烷基苯磺酸、十八烷基苯磺酸中的一种或几种的混合物；催化剂用量为ATX与植物油多元醇总质量的0.5–5％。更为优选，催化剂选自对甲苯磺酸、十二烷基苯磺酸、十八烷基苯磺酸中的一种或几种的混合物，其用量为ATX与植物油多元醇总质量的0.5–2％。
第二方面，一种UV固化聚酰亚胺改性的聚氨酯-丙烯酸酯的制备方法，具体是：
步骤(1)：将两端羧基封端的聚酰亚胺(PI)与聚四氢呋喃(PTMG-2000)、异佛尔酮二异氰酸酯(IPDI)、三羟甲基丙烷(TMP)、丙烯酸羟丙酯(HPA)反应，获得PI改性的聚氨酯-丙烯酸酯UV固化预聚物(PIPUA)。
所述两端羧基封端的聚酰亚胺(PI)的制备过程为：向三口反应瓶中依次加入3.24g(6.25mmol)2,2-双[4-(4-氨基苯氧基苯)]六氟丙烷、25g无水四氢呋喃和8.33g(18.75mmol)六氟二酐，25℃下反应8h。随后，向反应体系中滴加1.80g(13.13mmol)4-氨基苯甲酸、12.5g间-二氯代苯、5g无水四氢呋喃，室温下继续反应16h，再130mmHg/80℃减压脱除溶剂，得到白色粉末，即为PI；其合成路线如下：
PIPUA按照如表1所示物料比进行反应制得，具体步骤为：先向PI、PTMG和TMP的混合物中加入100g四氢呋喃和0.8g二月桂酸二丁基锡，待溶液澄清透明后，升温至60℃滴加IPDI后，升温至80℃反应4h，随后加入HPA继续反应4h，最后在80℃/130mmHg减压脱除溶剂和未反应的原料，获得PIPUA。
表1制备PIPUA的物料比
步骤(2)：将上述以植物油多元醇为核的生物基UV固化引发剂加入到PIPUA中，经UV固化获得UV固化聚酰亚胺改性的聚氨酯-丙烯酸酯；其中以植物油多元醇为核的生物基UV固化引发剂用量为PIPUA质量的0.4–2.0wt％。
作为优选，以植物油多元醇为核的生物基UV固化引发剂用量为PIPUA质量的0.01–5.0wt％。
作为优选，UV固化体系的UV固化时间为10–120s。
上述UV固化聚酰亚胺改性的聚氨酯-丙烯酸酯，其透光率85.0–96.0％(400–800nm)，拉伸强度4–12MPa，断裂伸长率为60–180％，铅笔硬度4B–7H，初始热分解温度273.4–286.4℃。
图1是以蓖麻油为核的ATX生物基UV引发剂的1H NMR谱图；7.64–7.34ppm归属于噻吨酮萘环上-C6H5氢原子的化学位移，5.35–5.20ppm归属于蓖麻油分子链中不饱和双键的氢原子化学位移，4.85–4.68ppm归属于-CH2(CO)OCH(CH2CH2)-和-OCH2COO-氢原子的化学位移，2.38–2.30ppm归属于-CH＝CH-CH2-&-O(OCCH2)-氢原子的化学位移，2.02–0.96ppm归属于蓖麻油分子长烷基链段的氢原子的位移，0.88–1.12ppm归属于末端甲基上氢原子的位移。
图2是以蓖麻油为核的ATX生物基UV引发剂的FT-IR谱图；在1640cm-1处为ATX上羧基特征吸收峰，1500cm-1附近为ATX稠环结构的典型特征峰，而3200cm-1附近蓖麻油羟基的特征吸收峰消失，这说明蓖麻油的羟基完全参与反应。
图3是PIPUA的1HNMR谱图；7.28–7.26ppm为4-氨基苯甲酸苯环上氢原子的化学位移，7.20–7.15ppm为六氟丙烷上氢原子的化学位移，4.4–4.1ppm和3.8–3.5ppm分别是PTMG链段中-OCOCH2和-OCH2氢原子的化学位移，这表明PI链段引入PUA中，获得了PIPUA。
以下结合若干较佳实施例对本发明的技术方案作进一步的解释说明，但其中的实验条件和设定参数不应视为对本发明基本技术方案的局限。并且本发明的保护范围不限于下述的实施例。
在本发明中，分析测试方法如下：
核磁共振：以氘代氯仿(CDCl3)作溶剂，用德国Brucker公司Brucker Advance-400NMR核磁共振仪室温下测氢谱(1H-NMR)。
傅里叶变换红外光谱：用Nicolet 700傅立叶红外光谱仪(美国Nicolet公司)测试4000–650cm-1红外光谱，液体样品采用涂膜法，固体样品采用压片法。
透光率测试：美国Thermo Fisher公司的Evolution 300型紫外可见分光光度计测试聚合物的透光率，测试波长范围为300–800nm，样品厚度10mm；
拉伸强度试验：实验设备为优鸿测控技术(上海)有限公司产UH6503D微机控制电子拉压循环往复试验机，拉伸速度2mm/min，每种薄膜测3次，取平均值。
铅笔硬度：按GB/T 6739—2006《色漆和清漆铅笔法测定漆膜硬度》进行测定。
水接触角：IL4200型接触角测量仪，德国KRUSS公司，将吸有去离子水的针管由微型注射器滴水2微升到待测样品表面，测定蒸馏水在空气中与固体涂膜的接触角，内切法测定其值。平行测定5次取平均值。
吸水率：将涂膜剪成一定形状的方块，室温下在去离子水中浸泡24h，用滤纸吸干涂膜表面的水，按式计算涂膜的吸水率。
其中B代表吸水率(％)；m1表示浸泡前涂膜的质量；m2表示浸泡之后使用滤纸吸干涂膜表面液体后的质量。
实施例1
(1)将7.73g ATX、9.33g蓖麻油、0.86g对甲苯磺酸加入洁净的50mL、插有温度计的三口烧瓶中，升温至120℃减压至130mmHg，反应6h后降温至60℃，获得16.52g黄色粘稠液体，即为以蓖麻油为核的ATX生物基UV引发剂。
(2)向100mL三口烧瓶中依次加入12.96g(25mmol)2,2-双[4-(4-氨基苯氧基苯)]六氟丙烷、100g无水四氢呋喃和33.32g(75mmol)六氟二酐，25℃下反应8h。随后，向反应体系中滴加7.20g(52.52mmol)4-氨基苯甲酸、50.0g间-二氯代苯、20g无水四氢呋喃，室温下继续反应16h，再130mmHg/80℃减压脱除溶剂，得到98g PI白色粉末。
取61.224g所得PI、140g PTMG-2000和2.683g TMP装入500mL三口烧瓶中，然后向混合物中加入100g四氢呋喃和0.8g二月桂酸二丁基锡，待溶液澄清透明后，升温至60℃滴加72.244g IPDI后，升温至80℃反应4h，随后加入50.755g HPA继续反应4h，最后在80℃/130mmHg减压脱除溶剂和未反应的原料，获得216.70g PIPUA-3。
(3)0.4g(1)中所得以蓖麻油为核的ATX生物基UV引发剂，40g(2)中所得PIPUA-3，混合均匀，脱除气泡后，旋涂到载玻片上，厚约0.7mm。经不同UV固化时间固化后，所得固化物性能见表2。
表2UV固化时间对UV固化材料的影响
实施例2
分别按照表1，制备不同的PIPUA，并各取40g，并分别向其中加入实施例1中所得以蓖麻油为核的ATX生物基UV引发剂0.4g，混合均匀，脱除气泡后，旋涂到载玻片上，厚约0.7mm。经UV固化60s后，所得固化物性能见表3、图5。
表3不同PIPUA对UV固化材料的影响
实施例3
取实施例1中所得PIPUA-340g，并分别向其中加入实施例1中所得以蓖麻油为核的ATX生物基UV引发剂，混合均匀，脱除气泡后，旋涂到载玻片上，厚约0.7mm。经UV固化60s后，所得固化物性能见表4。
表4不同UV引发剂用量对UV固化材料的影响
上述ATX生物基UV引发剂用量按照PIPUA-3质量百分数计算
实施例4
(1)将7.73g ATX、3.65g大豆油多元醇、0.0569g 98％浓硫酸加入洁净的50mL、插有温度计的三口烧瓶中，升温至140℃减压至130mmHg，反应12h后降温至60℃，获得10.84g深黄色粘稠液体，即为以大豆油多元醇为核的ATX生物基UV引发剂。
(2)取0.4g(1)中所得以大豆油多元醇为核的ATX生物基UV引发剂，40g实施例1中步骤(2)中所得PIPUA-3，混合均匀，脱除气泡后，旋涂到载玻片上，厚约0.7mm。经UV固化60s后，所得固化物凝胶化率93.2％，吸水率0.12％，铅笔硬度7H，透光率94.6％，拉伸强度10.2MPa，断裂伸长率120％。
实施例5
(1)将7.73g ATX、8.264g葵花籽油多元醇、0.480g十二烷基苯磺酸加入洁净的50mL、插有温度计的三口烧瓶中，升温至100℃减压至130mmHg，反应12h后降温至60℃，获得15.454g黄色粘稠液体，即为以葵花籽油多元醇为核的ATX生物基UV引发剂。
(2)取0.4g(1)中所得以葵花籽油多元醇为核的ATX生物基UV引发剂，40g实施例1中步骤(2)中所得PIPUA-3，混合均匀，脱除气泡后，旋涂到载玻片上，厚约0.7mm。经UV固化60s后，所得固化物凝胶化率93.6％，吸水率0.10％，铅笔硬度7H，透光率98.5％，拉伸强度11.0MPa，断裂伸长率150％。
实施例6
(1)将7.73g ATX、3.153g棕榈油多元醇、0.480g十八烷基苯磺酸加入洁净的50mL、插有温度计的三口烧瓶中，升温至100℃减压至130mmHg，反应12h后降温至60℃，获得10.343g褐色粘稠液体，即为以棕榈油多元醇为核的ATX生物基UV引发剂。
(2)取0.4g(1)中所得以棕榈油多元醇为核的ATX生物基UV引发剂，40g实施例1中步骤(2)中所得PIPUA-3，混合均匀，脱除气泡后，旋涂到载玻片上，厚约0.7mm。经UV固化60s后，所得固化物凝胶化率91.2％，吸水率0.18％，铅笔硬度5H，透光率90.0％，拉伸强度9.6MPa，断裂伸长率110％。
对比例
将0.4gATX、Irgacure-1173UV分别作为引发剂，40g实施例1步骤(2)中所得PIPUA-3，混合均匀，脱除气泡后，旋涂到载玻片上，厚约0.7mm。经UV固化60s后，所得固化物性能见图4，其中CO-AYX表示实施例1UV固化引发剂。图4可以看出，用以蓖麻油为核的ATX生物基UV引发剂制备的UV固化材料拉伸强度和断裂伸长率明显优于用ATX或Irgacure-1173制备的UV固化物。
Claims (10)
1.以植物油多元醇为核的生物基UV固化引发剂的制备方法，其特征在于是将带羧基的噻吨酮衍生物ATX与植物油多元醇在催化剂作用下，于100–150℃下反应4–12h即可；其中ATX中羧基与植物油多元醇中羟基的摩尔比为1:1–1:1.5；
所述带羧基的噻吨酮衍生物ATX的化学结构式如下：
2.如权利要求1所述的以植物油多元醇为核的生物基UV固化引发剂的制备方法，其特征在于所述植物油多元醇为蓖麻油、大豆油多元醇、葵花籽油多元醇和棕榈油多元醇中的一种或几种的混合物。
3.如权利要求1所述的以植物油多元醇为核的生物基UV固化引发剂的制备方法，其特征在于ATX中羧基与植物油多元醇中羟基的摩尔比为1:1–1:1.15。
4.如权利要求1所述的以植物油多元醇为核的生物基UV固化引发剂的制备方法，其特征在于所述催化剂为浓硫酸、三氟甲磺酸、对甲苯磺酸、十二烷基苯磺酸、十八烷基苯磺酸中的一种或几种的混合物；催化剂用量为ATX与植物油多元醇总质量的0.5–5％。
5.如权利要求4所述的以植物油多元醇为核的生物基UV固化引发剂的制备方法，其特征在于所述催化剂选自对甲苯磺酸、十二烷基苯磺酸、十八烷基苯磺酸中的一种或几种的混合物，其用量为ATX与植物油多元醇总质量的0.5–2％。
6.一种生物基UV固化引发剂，采用权利要求1-5任一项所述方法制备得到。
7.一种UV固化聚酰亚胺改性的聚氨酯-丙烯酸酯的制备方法，其特征在于包括如下：
步骤(1)：将两端羧基封端的聚酰亚胺PI与聚四氢呋喃、异佛尔酮二异氰酸酯IPDI、三羟甲基丙烷TMP、丙烯酸羟丙酯HPA反应，获得PI改性的聚氨酯-丙烯酸酯UV固化预聚物PIPUA；
步骤(2)：将权利要求6所述的生物基UV固化引发剂加入到PIPUA中，经UV固化获得UV固化聚酰亚胺改性的聚氨酯-丙烯酸酯；其中生物基UV固化引发剂用量为PIPUA质量的0.01–5.0wt％。
8.如权利要求7所述的一种UV固化聚酰亚胺改性的聚氨酯-丙烯酸酯的制备方法，其特征在于UV固化体系的UV固化时间为10–120s。
9.一种UV固化聚酰亚胺改性的聚氨酯-丙烯酸酯，采用权利要求7-8任一项所述方法制备得到。
10.权利要求9所述的UV固化聚酰亚胺改性的聚氨酯-丙烯酸酯在丙烯酸酯基类UV固化油漆、油墨和电子封装领域上的应用。
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| US5859111A (en) * | 1996-12-18 | 1999-01-12 | National Starch And Chemical Investment Holding Corporation | Processes for making nonionic aqueous polyurethane dispersions |
| WO2012003644A1 (zh) * | 2010-07-06 | 2012-01-12 | 天津久日化学工业有限公司 | 噻吨酮-4-羧酸酯及制备方法和光引发剂组合物与应用 |
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| US5859111A (en) * | 1996-12-18 | 1999-01-12 | National Starch And Chemical Investment Holding Corporation | Processes for making nonionic aqueous polyurethane dispersions |
| WO2012003644A1 (zh) * | 2010-07-06 | 2012-01-12 | 天津久日化学工业有限公司 | 噻吨酮-4-羧酸酯及制备方法和光引发剂组合物与应用 |
| CN104910131A (zh) * | 2015-06-23 | 2015-09-16 | 天津久日化学股份有限公司 | 一种新的噻吨酮羧酸酯光引发剂及其制备方法 |
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