CN107903372A - 一种uv光固化柔性超支化聚氨酯丙烯酸酯树脂及其制备方法与应用 - Google Patents
一种uv光固化柔性超支化聚氨酯丙烯酸酯树脂及其制备方法与应用 Download PDFInfo
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Abstract
本发明属于光敏性功能高分子材料领域,公开了一种UV光固化柔性超支化聚氨酯丙烯酸酯树脂及其制备方法与应用。制备方法如下:1)二异氰酸酯单体与单氨基多羟基单体通过“一步法”制得不同代数的端羟基超支化聚氨酯;2)将二异氰酸酯单体与含柔性链段的二元醇反应,制得中间体R,再将R与丙烯酸羟烷基酯单体反应,制得半加成产物F;3)将F与端羟基超支化聚氨酯反应,即制得UV光固化柔性超支化聚氨酯丙烯酸酯树脂。所制备的树脂,由于分子末端含有大量的光敏基团,可快速光固化成型;通过柔性链段的调控可对固化制品的固化时间与柔韧性进行调节;该制备方法简单、环保、节能,可用于光固化涂料、膜材料与光固化3D打印等领域。
Description
技术领域
本发明属于光敏性功能高分子材料领域,特别涉及一种UV光固化柔性超支化聚氨酯丙烯酸酯树脂及其制备方法与应用。
背景技术
超支化聚合物是具有三维球形结构的高度支化的大分子,由于分子链末端带有大量的活性基团,以及分子链间缠结较少不易结晶等结构特性,呈现出反应活性高、粘度低、溶解性好等许多独特的理化性能。超支化聚氨酯丙烯酸酯树脂是一种新型的功能性树脂,不仅具有聚氨酯丙烯酸树脂的UV光反应活性、耐磨性、耐化学腐蚀性等性能,还具有超支化聚合物的反应活性高、粘度低、溶解性好等特性。目前,合成超支化聚氨酯丙烯酸酯主要有两种方法:一种是通过二异氰酸酯或多异氰酸酯制得超支化聚氨酯,然后再与丙烯酸酯反应而制得超支化聚氨酯丙烯酸酯(曾幸荣,2008,2011;CN102361620B;);另一种是先合成分子末端为羟基的端羟基超支化聚合物,再利用氨基甲酸酯和丙烯酸酯对其改性后而制得超支化聚氨酯丙烯酸酯(施文芳,2014;CN103709373A)。目前,超支化聚氨酯丙烯酸酯主要作为功能型添加剂被添加到油漆、涂料、胶粘剂等领域中用于改善基础树脂的反应速率、粘度、力学性能和溶解性等。Kwak等人(Polymer,2004,45,6889-6896)研究表明由于超支化聚氨酯丙烯酸酯光固化后体系交联密度大、链缠结少以及缺少柔性链段等因素,导致光固化成型制品柔韧性低、易脆裂、力学性能差,因此很难直接利用超支化聚氨酯丙烯酸酯树脂的光固化交联来制备柔性器件。孙宁等通过在超支化聚合物的合成过程中引入柔性链段,但由于柔性链段被限制于超支化聚合物的“核”内,固化物的柔韧性与力学性能未能得到有效改善,仍只能作为添加剂使用。(高分子材料科学与工程,2015,31(2):22-26;CN104693409A和CN103724582A)。
发明内容
为了克服现有技术中UV光固化超支化聚氨酯丙烯酸酯在固化过程中存在的缺点与不足,本发明的首要目的在于提供一种UV光固化柔性超支化聚氨酯丙烯酸酯树脂,该超支化聚氨酯丙烯酸酯树脂是通过在超支化聚氨酯的硬“核”上接枝柔性聚氨酯丙烯酸酯“臂”,可在UV光照下快速固化成型为柔性制品。
本发明的另一目的在于提供一种上述UV光固化柔性超支化聚氨酯丙烯酸酯树脂的制备方法。
本发明的再一目的在于提供上述一种UV光固化柔性超支化聚氨酯丙烯酸酯树脂的应用。
本发明的目的通过下述技术方案实现:
一种UV光固化柔性超支化聚氨酯丙烯酸酯树脂,该树脂是通过在端羟基超支化聚氨酯上接枝柔性聚氨酯丙烯酸酯得到,其中端羟基超支化聚氨酯中的羟基与柔性聚氨酯丙烯酸酯中异氰酸酯基摩尔比1~1.5:1。
所述的端羟基超支化聚氨酯是由摩尔比1:1的二异氰酸酯单体和单氨基多羟基单体通过“一步法”缩聚合成而得。
所述二异氰酸酯单体为甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、4,4’-二环已基甲烷二异氰酸酯、六亚甲基二异氰酸酯、赖氨酸二异氰酸酯、间苯二甲基异氰酸酯、对苯二异氰酸酯、四甲基间苯二亚甲基二异氰酸酯和1,5-萘二异氰酸酯中的一种以上。
所述单氨基多羟基单体为二甲醇胺、二乙醇胺、二异丙醇胺、二羟基联苯胺和三羟甲基氨基甲烷中的一种以上。
所述柔性聚氨酯丙烯酸酯是由二异氰酸酯单体和含柔性链段的二元醇反应,得到两端为异氰酸酯基的中间体R,然后将中间体R与丙烯酸羟烷基酯单体中的一种以上进行反应,得到柔性聚氨酯丙烯酸酯;其中二异氰酸酯单体、含柔性链段的二元醇和丙烯酸羟烷基酯单体的摩尔比为1:0.5:0.5~0.7。
所述二异氰酸酯单体为甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、4,4’-二环已基甲烷二异氰酸酯、六亚甲基二异氰酸酯、赖氨酸二异氰酸酯、间苯二甲基异氰酸酯、对苯二异氰酸酯、四甲基间苯二亚甲基二异氰酸酯和1,5-萘二异氰酸酯中的一种以上;所述含柔性链段的二元醇为丁二醇、戊二醇、己二醇、庚二醇、聚乙二醇、聚丙二醇、聚酯二醇、聚四氢呋喃二醇和α,ω-二羟基聚硅氧烷中的一种以上。
所述聚乙二醇为PEG200、PEG400、PEG600或PEG1000;
所述α,ω-二羟基聚硅氧烷的粘度为750~3000cSt;
所述聚四氢呋喃二醇为PTMEG250、PTMEG650、PTMEG1000或PTMEG1400。
所述丙烯酸羟烷基酯单体为丙烯酸羟乙酯、丙烯酸羟丙酯和4-羟基丁基丙烯酸酯中一种以上。
上述的UV光固化柔性超支化聚氨酯丙烯酸酯树脂的制备方法,包括以下操作步骤:
(1)先将二异氰酸酯单体在-10~0℃下搅拌冷却30min,再将单氨基多羟基单体滴入,先在-10~0℃下反应1~3h,然后在40~60℃下反应,直到其NCO含量达到其理论值,加入二正丁胺封端,经过无水乙醚沉淀分离、真空干燥后就得到不同代数的端羟基超支化聚氨酯;
(2)将含柔性链段的二元醇滴入二异氰酸酯单体中,在40~70℃下反应,直到达到NCO理论值,得到两端为异氰酸酯基的反应中间体R;
(3)将丙烯酸羟烷基酯单体中的一种或两种,与二月桂酸二丁基锡一起滴入反应中间体R中,在10~35℃下反应,直到NCO达到其理论值,得到柔性聚氨酯丙烯酸酯;
(4)将步骤(3)所得柔性聚氨酯丙烯酸酯与步骤(1)所得端羟基超支化聚氨酯,在50~80℃下反应,直至NCO达到理论值,加入二正丁胺封端,经过无水乙醚沉淀、丙酮洗涤、真空干燥后即可得到UV光固化柔性超支化聚氨酯丙烯酸酯树脂。
上述的UV光固化柔性超支化聚氨酯丙烯酸酯树脂在光固化涂料、柔性膜和光固化3D打印领域中的应用。
本发明相对于现有技术具有如下的优点及效果:
本发明利用二异氰酸酯单体与单氨基多羟基单体的自缩聚反应,通过调控“一步法”的反应条件可制得不同代数的端羟基超支化聚氨酯;通过二异氰酸酯单体、含柔性链段的二元醇、丙烯酸羟烷基酯单体反应,得到柔性聚氨酯丙烯酸酯半加成产物;将柔性聚氨酯丙烯酸酯半加成产物与端羟基超支化聚氨酯反应,即可制得UV光固化柔性超支化聚氨酯丙烯酸酯树脂。通过在超支化聚合物的“臂”上引入柔性链段,通过柔性链段类型与长度的改变可实现对光固化制品的固化时间与柔韧性的调节。所制备的UV光固化柔性超支化聚氨酯丙烯酸酯树脂,由于分子链末端含有大量的活性光敏基团,在UV辐照下可快速光固化成型;该工艺简单、高效、环保和节能,能有效地解决UV光固化超支化聚氨酯丙烯酸酯树脂固化后柔韧性差、力学性能低等问题。
具体实施方式
下面结合实施例对本发明作进一步详细的描述,但本发明的实施方式不限于此。
实施例1第二代端羟基超支化聚氨酯的制备
在装有温度计、氮气管、机械搅拌器和滴液漏斗的250mL四口烧瓶中,加入33.33g异佛尔酮二异氰酸酯和等质量N,N′-二甲基乙酰胺,待溶液冷却至0℃时,缓慢滴加15.77g(二乙醇胺)和等质量N,N′-二甲基乙酰胺,滴完后在0℃条件下反应2h;缓慢升温至50℃,每隔20min对其进行NCO含量测定,当NCO含量达到1.2%时,加入过量二正丁胺进行封端,最后用无水乙醚进行沉降分离、真空干燥后得到第二代端羟基超支化聚氨酯HPU-OH-2。
实施例2第三代端羟基超支化聚氨酯的制备
在装有温度计、氮气管、机械搅拌器和滴液漏斗的250mL四口烧瓶中,加入26.12g甲苯二异氰酸酯和等质量N,N′-二甲基乙酰胺,待溶液冷却至-5℃时,缓慢滴加15.77g二乙醇胺和等质量N,N′-二甲基乙酰胺,滴完后在-5℃条件下反应3h;缓慢升温至40℃,每隔20min对其进行NCO含量测定,当测定NCO含量达到0.65%,加入过量二正丁胺进行封端,最后用无水乙醚进行沉降分离、真空干燥后得到第二代端羟基超支化聚氨酯HPU-OH-3。
实施例3第四代端羟基超支化聚氨酯的制备
在装有温度计、氮气管、机械搅拌器和滴液漏斗的250mL四口烧瓶中,加入37.54g二苯基甲烷二异氰酸酯和等质量N,N′-二甲基乙酰胺,待溶液冷却至0℃时,缓慢滴加20.0g二异丙醇胺和等质量N,N′-二甲基乙酰胺,滴完后在-10℃条件下反应3h;缓慢升温至60℃,每隔20min对其进行NCO含量测定,当NCO含量达到0.43%,加入过量二正丁胺进行封端,最后用无水乙醚进行沉降分离、真空干燥后得到第四代端羟基超支化聚氨酯HPU-OH-4。
实施例4第五代端羟基超支化聚氨酯的制备
在装有温度计、氮气管、机械搅拌器和滴液漏斗的250mL四口烧瓶中,加入25.23g六亚甲基二异氰酸酯和等质量N,N′-二甲基乙酰胺,待溶液冷却至-5℃时,缓慢滴加32.44g二羟基联苯胺和等质量N,N′-二甲基乙酰胺,滴完后在0℃条件下反应2h;缓慢升温至40℃,每隔20min对其进行NCO含量测定,当NCO含量达到0.25%,加入过量二正丁胺进行封端,最后用无水乙醚进行沉降分离、真空干燥后得到第五代端羟基超支化聚氨酯HPU-OH-5。
实施例5 IPDI/PEG200/HEA预聚体的制备
在装有温度计、搅拌器和冷凝管的四口瓶中,在60℃,氮气条件下,加入22.22g异佛尔酮二异氰酸酯(IPDI)和等质量N,N′-二甲基乙酰胺,缓慢滴加10g PEG200和等质量N,N′-二甲基乙酰胺,当NCO值达到理论值后,降温至35℃后,缓慢滴加溶有0.0375wt.%二月桂酸二丁基锡和0.2wt.%对羟基苯甲醚、7.55g HEA(丙烯酸羟乙酯)和等质量N,N′-二甲基乙酰胺混合溶液,滴完后每隔20min测NCO值,当达到理论值时停止反应,得到IPDI/PEG200/HEA预聚体。
实施例6 H12MDI/PEG600/HPA预聚体的制备
在装有温度计、搅拌器和冷凝管的250mL四口瓶中,在50℃,氮气条件下,加入52.47g 4,4’-二环已基甲烷二异氰酸酯和等质量N,N′-二甲基乙酰胺,缓慢滴加60gPEG600和等质量N,N′-二甲基乙酰胺,当NCO值达到理论值后,,降温至25℃后,缓慢滴0.0375wt.%二月桂酸二丁基锡、0.2wt.%对羟基苯甲醚、8.46g HPA(丙烯酸羟丙酯)和7.55g N,N′-二甲基乙酰胺混合溶液,滴完后每隔20min进行NCO测定,当达到理论值时降至室温后待用,得到H12MDI/PEG600/HPA预聚体。
实施例7 IPDI/BDO/HBA预聚体的制备
在装有温度计、搅拌器和冷凝管的250mL四口瓶中,在40℃,氮气条件下,加入44.44g异佛尔酮二异氰酸酯(IPDI)和等质量N,N′-二甲基乙酰胺,缓慢滴加10.41g BDO(异戊二醇)和等质量N,N′-二甲基乙酰胺,当NCO值达到理论值后,降温至30℃后,缓慢滴0.0375wt.%二月桂酸二丁基锡、0.2wt.%对羟基苯甲醚、9.37g HBA(4-羟基丁基丙烯酸酯)和等质量的N,N′-二甲基乙酰胺混合溶液,滴完后每隔20min进行NCO测定,当达到理论值时降至室温后待用,得到IPDI/BDO/HBA预聚体。
实施例8 IPDI/PTMEG250/HEA预聚体的制备
在装有温度计、搅拌器和冷凝管的250mL四口瓶中,在55℃,氮气条件下,加入44.44g异佛尔酮二异氰酸酯(IPDI)和等质量N,N′-二甲基乙酰胺,缓慢滴加25g PTMEG250和等质量N,N′-二甲基乙酰胺,当NCO值达到理论值后,降温至20℃后,缓慢滴0.0375wt.%二月桂酸二丁基锡、0.2wt.%对羟基苯甲醚、7.55g HEA(丙烯酸羟乙酯)和等质量的N,N′-二甲基乙酰胺混合溶液,滴完后每隔20min进行NCO测定,当达到理论值时降至室温后待用,得到IPDI/PTMEG250/HEA预聚体。
实施例9 HDI/PTMEG1000/HPA预聚体的制备
在装有温度计、搅拌器和冷凝管的250mL四口瓶中,在60℃,氮气条件下,加入33.64g HDI(六亚甲基二异氰酸酯)和等质量N,N′-二甲基乙酰胺,缓慢滴加100gPTMEG1000和等质量N,N′-二甲基乙酰胺,当NCO值达到理论值后,降温至35℃后,缓慢滴0.0375wt.%二月桂酸二丁基锡、0.2wt.%对羟基苯甲醚、8.46g HPA(丙烯酸羟丙酯)和7.55gN,N′-二甲基乙酰胺混合溶液,滴完后每隔20min进行NCO测定,当达到理论值时降至室温后待用,得到HDI/PTMEG1000/HPA预聚体。
实施例10 IPDI/HO-PDMS-OH/HBA预聚体的制备
在装有温度计、搅拌器和冷凝管的250mL四口瓶中,在40℃,氮气条件下,加入44.44g异佛尔酮二异氰酸酯(IPDI)和等质量N,N′-二甲基乙酰胺,缓慢滴加140.58g HO-PDMS-OH(α,ω-二羟基聚硅氧烷,粘度为2000cSt)和等质量N,N′-二甲基乙酰胺,滴完后反应2h,降温至15℃后,缓慢滴0.0375wt.%二月桂酸二丁基锡、0.2wt.%对羟基苯甲醚、9.37g HBA(4-羟基丁基丙烯酸酯)和等质量的N,N′-二甲基乙酰胺混合溶液,滴完后每隔20min进行NCO测定,当达到理论值时降至室温后待用,得到IPDI/HO-PDMS-OH/HBA预聚体。
实施例11 HPUA-2-PEG600的制备
将实施例1所制备的HPU-OH-2,0.1wt.%二月桂酸二丁基锡和0.2wt.%对羟基苯甲醚搅拌均匀,缓慢滴加等羟基摩尔量的实施例6所制备的H12MDI/PEG600/HPA预聚体,滴完后升温至80℃反应,每隔20min测定NCO值,直至NCO值不变后加入过量二正丁胺进行封端。通过无水乙醚沉淀,再用丙酮洗涤、过滤,最后真空干燥后即可得到柔性超支化聚氨酯丙烯酸酯HPUA-2-PEG600。
实施例12 HPUA-3-PEG600的制备
将实施例2所制备的HPU-OH-3,0.1wt.%二月桂酸二丁基锡和0.2wt.%对羟基苯甲醚搅拌均匀,缓慢滴加等羟基摩尔量的实施例6所制备的H12MDI/PEG600/HPA预聚体,滴完后升温至55℃反应,每隔20min测定NCO值,直至NCO值不变后加入过量二正丁胺进行封端。通过无水乙醚沉淀,再用丙酮洗涤、过滤,最后真空干燥后即可得到柔性超支化聚氨酯丙烯酸酯HPUA-3-PEG600。
实施例13 HPUA-4-PEG600的制备
将实施例3所制备的HPU-OH-4,0.1wt.%二月桂酸二丁基锡和0.2wt.%对羟基苯甲醚搅拌均匀,缓慢滴加等羟基摩尔量的实施例6所制备的H12MDI/PEG600/HPA预聚体,滴完后升温至60℃反应,每隔20min测定NCO值,直至NCO值不变后加入过量二正丁胺进行封端。通过无水乙醚沉淀,再用丙酮洗涤、过滤,最后真空干燥后即可得到柔性超支化聚氨酯丙烯酸酯HPUA-4-PEG600。
实施例14 HPUA-5-PEG600的制备
将实施例4所制备的HPU-OH-5,0.1wt.%二月桂酸二丁基锡和0.2wt.%对羟基苯甲醚搅拌均匀,缓慢滴加等羟基摩尔量的实施例6所制备的H12MDI/PEG600/HPA预聚体,滴完后升温至65℃反应,每隔20min测定NCO值,直至NCO值不变后加入过量二正丁胺进行封端。通过无水乙醚沉淀,再用丙酮洗涤、过滤,最后真空干燥后即可得到柔性超支化聚氨酯丙烯酸酯HPUA-5-PEG600。
实施例15 HPUA-4-PEG200的制备
将实施例3所制备的HPU-OH-4,0.1wt.%二月桂酸二丁基锡和0.2wt.%对羟基苯甲醚搅拌均匀,缓慢滴加等羟基摩尔量的实施例5所制备的IPDI/PEG200/HEA预聚体,滴完后升温至70℃反应,每隔20min测定NCO值,直至NCO值不变后加入过量二正丁胺进行封端。通过无水乙醚沉淀,再用丙酮洗涤、过滤,最后真空干燥后即可得到柔性超支化聚氨酯丙烯酸酯HPUA-4-PEG200。
实施例16 HPUA-4-PTMEG250的制备
将实施例3所制备的HPU-OH-4,0.1wt.%二月桂酸二丁基锡和0.2wt.%对羟基苯甲醚搅拌均匀,缓慢滴加等羟基摩尔量的实施例8所制备的IPDI/PTMEG250/HEA预聚体,滴完后升温至50℃反应,每隔20min测定NCO值,直至NCO值不变后加入过量二正丁胺进行封端。通过无水乙醚沉淀,再用丙酮洗涤、过滤,最后真空干燥后即可得到柔性超支化聚氨酯丙烯酸酯HPUA-4-PTMEG250。
实施例17 HPUA-4-PTMEG1000的制备
将实施例3所制备的HPU-OH-4,0.1wt.%二月桂酸二丁基锡和0.2wt.%对羟基苯甲醚搅拌均匀,缓慢滴加等羟基摩尔量的实施例9所制备的HDI/PTMEG1000/HPA预聚体,滴完后升温至70℃反应,每隔20min测定NCO值,直至NCO值不变后加入过量二正丁胺进行封端。通过无水乙醚沉淀,再用丙酮洗涤、过滤,最后真空干燥后即可得到柔性超支化聚氨酯丙烯酸酯HPUA-4-PTMEG1000。
实施例18 HPUA-4-PDMS的制备
将实施例3所制备的HPU-OH-4,0.1wt.%二月桂酸二丁基锡和0.2wt.%对羟基苯甲醚搅拌均匀,缓慢滴加等羟基摩尔量的实施例10所制备的IPDI/HO-PDMS-OH/HBA预聚体,滴完后升温至55℃反应,每隔20min测定NCO值,直至NCO值不变后加入过量二正丁胺进行封端。通过无水乙醚沉淀,再用丙酮洗涤、过滤,最后真空干燥后即可得到柔性超支化聚氨酯丙烯酸酯HPUA-4-PDMS。
实施例19 HPUA-4-BDO的制备
将实施例3所制备的HPU-OH-4,0.1wt.%二月桂酸二丁基锡和0.2wt.%对羟基苯甲醚搅拌均匀,缓慢滴加等羟基摩尔量的实施例7所制备的IPDI/BDO/HBA预聚体,滴完后升温至65℃反应,每隔20min测定NCO值,直至NCO值不变后加入过量二正丁胺进行封端。通过无水乙醚沉淀,再用丙酮洗涤、过滤,最后真空干燥后即可得到柔性超支化聚氨酯丙烯酸酯HPUA-4-BDO。
对比例1 HPUA-4的制备
将实施例3所制备的HPU-OH-4,0.1wt.%二月桂酸二丁基锡和0.2wt.%对羟基苯甲醚搅拌均匀,缓慢滴加等羟基摩尔量的IPDI/HEA预聚体,滴完后升温至80℃反应,每隔20min测定NCO值,直至NCO小于0.2%后加入过量二正丁胺进行封端,冷却至室温后通过无水乙醚进行沉降,再用丙酮进行洗涤,过滤,最后真空干燥后得到无柔性链段的超支化聚氨酯丙烯酸酯HPUA-4。
对比例2 HPUA-5的制备
将实施例2所制备的HPU-OH-5,0.1wt.%二月桂酸二丁基锡和0.2wt.%对羟基苯甲醚搅拌均匀,缓慢滴加等羟基摩尔量的HDI/HEA预聚体,滴完后升温至45℃反应,每隔20min测定NCO值,直至NCO小于0.2%后加入过量二正丁胺进行封端,冷却至室温后通过无水乙醚进行沉降,再用丙酮进行洗涤,过滤,最后真空干燥后得到无柔性链段的超支化聚氨酯丙烯酸酯HPUA-5。
表1本发明的实施例11~19与对比例的固化时间与柔韧性
采用压指法测固化时间,经紫外光固化后,用手指轻压膜材料,若无压痕,则合格,反之不合格。光固化膜的柔韧性测定依照国标(GB/T1731-1993),利用QTX—漆膜柔韧性测试仪进行测试。
表1为本发明实施例11-19所提供的光固化柔性超支化聚氨酯丙烯酸酯的固化速度与柔韧性。结果表明,随着超支化聚合物代数从二代增大到五代(实施例11~14),聚合物分子链末端的活性光敏丙烯酸酯基团数量增大,固化膜的固化时间缩短;此外,随着代数增大,超支化聚合物的臂变得更柔软,所以固化膜的柔韧性也随之增大。与对比例1~2相比,随着柔性链段链长增大,固化膜的固化时间缩短,因为柔性链段的引入,有助于末端活性基团的扩散运动;固化膜的柔韧性也随链长的增大而提高,因为随链长的增加,分子链的柔韧性增大。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (10)
1.一种UV光固化柔性超支化聚氨酯丙烯酸酯树脂,其特征在于:该树脂是通过在端羟基超支化聚氨酯上接枝柔性聚氨酯丙烯酸酯得到,其中端羟基超支化聚氨酯中的羟基与柔性聚氨酯丙烯酸酯中异氰酸酯基摩尔比1~1.5:1。
2.根据权利要求1所述的一种UV光固化柔性超支化聚氨酯丙烯酸酯树脂,其特征在于:所述的端羟基超支化聚氨酯是由摩尔比1:1的二异氰酸酯单体和单氨基多羟基单体通过“一步法”缩聚合成而得。
3.根据权利要求2所述的一种UV光固化柔性超支化聚氨酯丙烯酸酯树脂,其特征在于:所述二异氰酸酯单体为甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、4,4’-二环已基甲烷二异氰酸酯、六亚甲基二异氰酸酯、赖氨酸二异氰酸酯、间苯二甲基异氰酸酯、对苯二异氰酸酯、四甲基间苯二亚甲基二异氰酸酯和1,5-萘二异氰酸酯中的一种以上。
4.根据权利要求2所述的一种UV光固化柔性超支化聚氨酯丙烯酸酯树脂,其特征在于:所述单氨基多羟基单体为二甲醇胺、二乙醇胺、二异丙醇胺、二羟基联苯胺和三羟甲基氨基甲烷中的一种以上。
5.根据权利要求1所述的一种UV光固化柔性超支化聚氨酯丙烯酸酯树脂,其特征在于:所述柔性聚氨酯丙烯酸酯是由二异氰酸酯单体和含柔性链段的二元醇反应,得到两端为异氰酸酯基的中间体R,然后将中间体R与丙烯酸羟烷基酯单体中的一种以上进行反应,得到柔性聚氨酯丙烯酸酯;其中二异氰酸酯单体、含柔性链段的二元醇和丙烯酸羟烷基酯单体的摩尔比为1:0.5:0.5~0.7。
6.根据权利要求5所述的一种UV光固化柔性超支化聚氨酯丙烯酸酯树脂,其特征在于:所述二异氰酸酯单体为甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、4,4’-二环已基甲烷二异氰酸酯、六亚甲基二异氰酸酯、赖氨酸二异氰酸酯、间苯二甲基异氰酸酯、对苯二异氰酸酯、四甲基间苯二亚甲基二异氰酸酯和1,5-萘二异氰酸酯中的一种以上;所述含柔性链段的二元醇为丁二醇、戊二醇、己二醇、庚二醇、聚乙二醇、聚丙二醇、聚酯二醇、聚四氢呋喃二醇和α,ω-二羟基聚硅氧烷中的一种以上。
7.根据权利要求6所述的一种UV光固化柔性超支化聚氨酯丙烯酸酯树脂,其特征在于:所述聚乙二醇为PEG200、PEG400、PEG600或PEG1000;
所述α,ω-二羟基聚硅氧烷的粘度为750~3000cSt;
所述聚四氢呋喃二醇为PTMEG250、PTMEG650、PTMEG1000或PTMEG1400。
8.根据权利要求5所述的一种UV光固化柔性超支化聚氨酯丙烯酸酯树脂,其特征在于:所述丙烯酸羟烷基酯单体为丙烯酸羟乙酯、丙烯酸羟丙酯和4-羟基丁基丙烯酸酯中一种以上。
9.根据权利要求1所述的UV光固化柔性超支化聚氨酯丙烯酸酯树脂的制备方法,其特征在于包括以下操作步骤:
(1)先将二异氰酸酯单体在-10~0℃下搅拌冷却30min,再将单氨基多羟基单体滴入,先在-10~0℃下反应1~3h,然后在40~60℃下反应,直到其NCO含量达到其理论值,加入二正丁胺封端,经过无水乙醚沉淀分离、真空干燥后就得到不同代数的端羟基超支化聚氨酯;
(2)将含柔性链段的二元醇滴入二异氰酸酯单体中,在40~70℃下反应,直到达到NCO理论值,得到两端为异氰酸酯基的反应中间体R;
(3)将丙烯酸羟烷基酯单体中的一种或两种,与二月桂酸二丁基锡一起滴入反应中间体R中,在10~35℃下反应,直到NCO达到其理论值,得到柔性聚氨酯丙烯酸酯;
(4)将步骤(3)所得柔性聚氨酯丙烯酸酯与步骤(1)所得端羟基超支化聚氨酯,在50~80℃下反应,直至NCO达到理论值,加入二正丁胺封端,经过无水乙醚沉淀、丙酮洗涤、真空干燥后即可得到UV光固化柔性超支化聚氨酯丙烯酸酯树脂。
10.根据权利要求1所述的UV光固化柔性超支化聚氨酯丙烯酸酯树脂在光固化涂料、柔性膜和光固化3D打印领域中的应用。
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