CN105801791B - 一种蓖麻油基uv固化聚氨酯丙烯酸酯及其制备方法和应用 - Google Patents
一种蓖麻油基uv固化聚氨酯丙烯酸酯及其制备方法和应用 Download PDFInfo
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- CN105801791B CN105801791B CN201610169042.7A CN201610169042A CN105801791B CN 105801791 B CN105801791 B CN 105801791B CN 201610169042 A CN201610169042 A CN 201610169042A CN 105801791 B CN105801791 B CN 105801791B
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- Prior art keywords
- castor oil
- base
- cured polyurethane
- polyurethane acrylates
- diisocyanate
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Classifications
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
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Abstract
本发明属于UV固化高分子材料领域,具体公开了一种蓖麻油基UV固化聚氨酯丙烯酸酯及其制备方法和应用。本发明首先将二元醇和蓖麻油减压脱水后,加入二异氰酸酯和催化剂的混合物,反应2~3h后,加入溶有双酚A和2,2‑二羟甲基丙酸的N,N‑二甲基甲酰胺及丙酮混合溶液制得中间产物;然后搅拌下加入(甲基)丙烯酸羟烷酯与阻聚剂的混合物,反应2~3h,得到蓖麻油基UV固化聚氨酯丙烯酸酯。本发明将蓖麻油用于聚氨酯原材料,对于减轻石油化工压力、拓宽天然油脂类产品应用和提高其附加值,将具有积极的借鉴价值;且由于蓖麻油的引入和双酚A的高绝缘性,制得的蓖麻油基UV固化聚氨酯丙烯酸酯具有较好的低温性能、耐水解性以及优良的电绝缘性。
Description
技术领域
本发明属于UV固化高分子材料领域,具体涉及一种蓖麻油基UV固化聚氨酯丙烯酸酯及其制备方法和应用。
背景技术
随着多媒体信息设备的与日俱增,触摸屏因具有坚固耐用、反应速度快、节省空间、易于交流等许多优点,已经在各个领域越来越多地被使用到。触摸屏的关键材料是透明导电涂层材料氧化铟锡(ITO)弱导电体,是所有电阻技术触摸屏及电容技术触摸屏都用到的主要材料,而在触摸屏的生产流程中,在基板上镀上ITO膜后,需要进行各种加工工序,这时就需要丝网印刷UV光固化绝缘油墨于绝缘、保护等相关区域,经UV固化形成绝缘保护膜,然后附着于触摸屏上。UV固化绝缘油墨主要应用于触摸屏、ITO玻璃、ITO薄膜的绝缘、保护和支撑作用,可通过丝网印刷在ITO膜和ITO玻璃上,在使用过程中起到防止ITO玻璃与ITO薄膜相互接触,从而避免无触摸时造成短路而产生误动作。此产品要求在广泛的温度和湿度范围内体现良好的综合性能,成膜性极好,具有极好的附着力和绝缘性。
聚氨酯丙烯酸酯是一类重要的光固化交联性树脂,其应用广泛程度仅次于环氧丙烯酸酯,其分子结构中主要包含氨基甲酸酯链段、多元醇的主链、丙烯酸酯羟烷基酯链段,固化特性由位于链段的丙烯酸酯决定,树脂主链的结构与组成对产品的性能影响最大。全球性化石资源的消耗和由此带来的环境污染问题使人们深刻认识到资源问题不仅影响我们的生态环境,也阻碍以化石原料为基础的有机高分子化工的发展,而且由于日益激烈的国际争端,开始威胁我国的战略安全,而生物质资源是目前唯一可以持续利用的原料和化学资源。因此,以综合利用生物质资源制造高性能生物基化学品和生物基材料为重点,加强生物基材料和化学品制造过程中的生物转化、化学转化、复合成型等核心关键技术的研究具有重要的理论和现实意义。
公开号为CN105348487A的中国发明专利公开了一种蓖麻油酸基UV固化水性树脂的制备方法,该方法所用蓖麻油酸是蓖麻油水解后得到的直链的含羟基羧酸,并非将蓖麻油直接作为原材料,本发明采用蓖麻油直接作为原材料,合成的是一种星型结构的PUA预聚物。公开号CN103881341A和CN102604015A的中国发明专利申请分别公开了一种桐油衍生物改性不饱和聚酯树脂组合物和甲酯化桐油改性水性聚氨酯乳液,虽然也都涉及到以天然植物油资源制备UV固化树脂,但没有涉及到蓖麻油基UV固化PUA的制备。
发明内容
为了克服上述现有技术的缺点与不足,本发明的首要目的在于提供一种蓖麻油基UV固化聚氨酯丙烯酸酯。
本发明另一目的在于提供上述蓖麻油基UV固化聚氨酯丙烯酸酯的制备方法。
本发明再一个目的在于提供上述蓖麻油基UV固化聚氨酯丙烯酸酯在UV固化绝缘油墨等方面的应用。
一种蓖麻油基UV固化聚氨酯丙烯酸酯的制备方法,包括如下步骤:
(1)在反应釜中依次加入计量好的二元醇和蓖麻油,搅拌并升温至115~125℃,减压脱水2~3h后降温至65~75℃,随后加入二异氰酸酯和催化剂的混合物,注意控制其滴加速度优选在2~3h滴完,反应2~3h后,将溶有双酚A和2,2-二羟甲基丙酸的N,N-二甲基甲酰胺及丙酮混合溶液加到反应釜里,继续反应,期间取样测量-NCO基团含量直到达到理论值,第一步反应结束;
(2)将步骤(1)制得的中间产物降温为45~55℃,搅拌下加入(甲基)丙烯酸羟烷酯与阻聚剂的混合物,反应2~3h,跟踪-NCO基团的含量,当游离的-NCO含量低于0.1%时,停止反应蒸出溶剂降温出料,得到蓖麻油基UV固化聚氨酯丙烯酸酯。
步骤(1)中所述的二异氰酸酯与二元醇的摩尔比为1:1~1:1.01;蓖麻油、双酚A、2,2-二羟甲基丙酸的用量分别为二异氰酸酯用量的1~10%、10~30%、10~30%。
步骤(1)中所述的二元醇为聚酯二元醇和/或聚醚二元醇,其分子量为1000~3000,优选为聚乙二醇、聚丙二醇、聚乙二酸乙二醇和聚己二酸丁二醇中的至少一种;步骤(1)中所述的二异氰酸酯为芳香族和/或脂肪族二异氰酸酯,优选为二异氰酸酯为六亚甲基二异氰酸酯、甲苯二异氰酸酯、对苯二异氰酸酯、4,4’-二苯基甲烷二异氰酸酯和异佛尔酮二异氰酸酯中的至少一种;
步骤(1)中所述的催化剂为二月桂酸二丁基锡,以蓖麻油基UV固化聚氨酯丙烯酸酯100重量份计,所述催化剂为0.1~0.15重量份。
步骤(1)中所述的二异氰酸酯和催化剂的混合物与步骤(2)中所述的(甲基)丙烯酸羟烷酯及阻聚剂的混合物,其加入方式包括一次加入或者滴加等其他加入方式,优选为以1~10g/min的速度加入,或者控制在0.5~1h内加完。
步骤(2)中所述的(甲基)丙烯酸羟烷酯与步骤(1)中所述的二异氰酸酯的摩尔比为1:1。本发明反应中采用二异氰酸酯与二元醇的摩尔比为1:(1~1.01),而(甲基)丙烯酸羟烷酯与二异氰酸酯的摩尔比为1:1,即意味着(甲基)丙烯酸羟烷酯稍稍过量,目的在于保证异氰酸酯完全反应,不残留,且过量的(甲基)丙烯酸羟烷酯还可以起到活性单体的作用,并一起参与紫外光固化。
步骤(2)中所述的(甲基)丙烯酸羟烷酯为丙烯酸羟乙酯、丙烯酸羟丙酯、丙烯酸羟丁酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯和甲基丙烯酸羟丁酯中的至少一种;
步骤(2)中所述的阻聚剂为对羟基苯甲醚或对苯二酚;以(甲基)丙烯酸羟烷酯100重量份计,所述阻聚剂为0.05~1.5重量份。
本发明的蓖麻油基UV固化聚氨酯丙烯酸酯合成过程的化学反应方程式如下式,其中CO为蓖麻油,PEG为聚醚乙二醇,PBA为聚酯乙二醇。
本发明相对于现有合成技术,具有如下的优点及有益效果:
(1)本发明将蓖麻油用于聚氨酯原材料,对于拓宽天然油脂类产品应用和提高其附加值,将具有积极的借鉴价值。且由于蓖麻油的引入,其中的脂肪酸中的不饱和碳碳双键能提供水性聚氨酯与丙烯酸酯单体共聚反应的接枝活性点,成为可与聚氨酯及丙烯酸酯交联的反应型官能团。用蓖麻油为原料制造的蓖麻油基UV固化聚氨酯丙烯酸酯固化成膜后具有较好的低温性能、耐水解性以及优良的电绝缘性。
(2)本发明采用双酚A为扩链剂,制备蓖麻油基UV固化聚氨酯丙烯酸酯,相比其他的UV固化PUA树脂,该蓖麻油基UV固化聚氨酯丙烯酸酯具有高绝缘性的同时还具有较高的附着力,其固化速度快及综合性能忧良。
附图说明
图1为实施例1的PUA低聚物合成过程的FT-IR谱图,其中a为反应前的FT-IR谱图,b为反应中的FT-IR谱图,c为反应完成后的FT-IR谱图。
图2为实施例1的PUA低聚物光固化前后的FT-IR谱图,其中A为固化前的FT-IR谱图,B为固化后的FT-IR谱图。
具体实施方式
下面结合实施例和附图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
(1)在反应器中依次加入计量好的聚乙二醇、聚乙二酸乙二醇和蓖麻油,搅拌并升温至115℃,减压脱水2h后降温至65℃,随后逐渐滴加异佛尔酮二异氰酸酯和二月桂酸二丁基锡(聚氨酯丙烯酸酯预聚物重量的0.1%)的混合物,注意控制其滴加速度,以1g/min的速度加入,反应3h后,将溶于双酚A和2,2-二羟甲基丙酸的N,N-二甲基甲酰胺及丙酮混合溶液加到反应釜里,继续反应,期间取样测量-NCO基团含量直到达到理论值,第一步反应结束;
(2)将上述中间产物降温为45℃,搅拌下逐滴滴加丙烯酸羟乙酯、甲基丙烯酸羟乙酯与对羟基苯甲醚(为丙烯酸羟乙酯和甲基丙烯酸羟乙酯重量的0.05%)的混合物,反应2h,跟踪-NCO基团的含量,当游离的-NCO含量低于0.1%时,停止反应蒸出溶剂降温出料,得到DMPA改性蓖麻油基UV固化聚氨酯丙烯酸酯低聚物(简称PUA低聚物)。
PUA低聚物的红外光谱测试:将待测样涂覆在KBr片上,随后置于德国布鲁克公司VERTEX 70型红外光谱仪上测试。扫描波数范围为4000~400cm-1,分辨率为4cm-1,扫描128次后取平均值得到样品的红外光谱图,如图1所示。
由图1知,随着预聚反应的进行,3349和1540cm-1处出现了氨基甲酸酯-NH-(氢键)的特征吸收峰,1725-1730cm-1范围出现了酯键-C=O的特征吸收峰,而异氰酸酯基-NCO基团在2265-2270cm-1范围内的伸缩振动吸收峰以及羟基-OH在3400-3500cm-1范围内的特征吸收峰不断下降,同时1229和1114cm-1处出现了氨酯基基团中-COC-的伸缩振动吸收峰表明了氨酯基团的存在,说明了异氰酸酯基团-NCO基团与羟基-OH发生反应生成了氨酯键;随着反应的进行-NCO基团特征吸收峰逐渐地降低,此外当丙烯酸酯的封端反应持续150min后-NCO基团特征吸收峰已基本消失,同时这意味着-NCO基团已基本反应完全,表明DMPA改性聚氨酯丙烯酸酯树脂的合成阶段基本结束。
实施例2
(1)在反应器中依次加入计量好的聚乙二醇、聚乙二酸乙二醇和蓖麻油,搅拌并升温至115℃,减压脱水2h后降温至65℃,随后逐渐滴加六亚甲基二异氰酸酯、甲苯二异氰酸酯和二月桂酸二丁基锡(聚氨酯丙烯酸酯预聚物重量的0.1%)的混合物,注意控制其滴加速度,以1g/min的速度加入,反应3h后,将溶于双酚A和2,2-二羟甲基丙酸的N,N-二甲基甲酰胺及丙酮混合溶液加到反应釜里,继续反应,期间取样测量-NCO基团含量直到达到理论值,第一步反应结束;
(2)将上述中间产物降温为45℃,搅拌下逐滴滴加丙烯酸羟丙酯、甲基丙烯酸羟丙酯与对羟基苯甲醚(为丙烯酸羟丙酯和甲基丙烯酸羟丙酯重量的1.5%)的混合物,反应2h,跟踪-NCO基团的含量,当游离的-NCO含量低于0.1%时,停止反应蒸出溶剂降温出料,得到DMPA改性蓖麻油基UV固化聚氨酯丙烯酸酯低聚物(简称PUA低聚物)。
以德国布鲁克公司VERTEX 70型红外光谱仪测试PUA低聚物合成过程的FTIR谱图,所得结果特征峰与实施例1相同。
实施例3
(1)在反应器中依次加入计量好的聚乙二醇、聚乙二酸乙二醇和蓖麻油,搅拌并升温至115℃,减压脱水2h后降温至65℃,随后逐渐滴加对苯二异氰酸酯、4,4’-二苯基甲烷二异氰酸酯和二月桂酸二丁基锡(聚氨酯丙烯酸酯预聚物重量的0.1%)的混合物,注意控制其滴加速度,以1g/min的速度加入,反应3h后,将溶于双酚A和2,2-二羟甲基丙酸的N,N-二甲基甲酰胺及丙酮混合溶液加到反应釜里,继续反应,期间取样测量-NCO基团含量直到达到理论值,第一步反应结束;
(2)将上述中间产物降温为45℃,搅拌下逐滴滴加丙烯酸羟丁酯、甲基丙烯酸羟丁酯与对苯二酚(为丙烯酸羟丁酯和甲基丙烯酸羟丁酯重量的0.05%)的混合物,反应2h,跟踪-NCO基团的含量,当游离的-NCO含量低于0.1%时,停止反应蒸出溶剂降温出料,得到DMPA改性蓖麻油基UV固化聚氨酯丙烯酸酯低聚物(简称PUA低聚物)。
以德国布鲁克公司VERTEX 70型红外光谱仪测试PUA低聚物合成过程的FTIR谱图,所得结果特征峰与实施例1相同。
实施例4
(1)在反应器中依次加入计量好的聚乙二醇、聚乙二酸乙二醇、聚丙二醇、聚己二酸丁二醇和蓖麻油,搅拌并升温至115℃,减压脱水2h后降温至65℃,随后逐渐滴加六亚甲基二异氰酸酯、甲苯二异氰酸酯和二月桂酸二丁基锡(聚氨酯丙烯酸酯预聚物重量的0.1%)的混合物,注意控制其滴加速度,以1g/min的速度加入,反应3h后,将溶于双酚A和2,2-二羟甲基丙酸的N,N-二甲基甲酰胺及丙酮混合溶液加到反应釜里,继续反应,期间取样测量-NCO基团含量直到达到理论值,第一步反应结束;
(2)将上述中间产物降温为45℃,搅拌下逐滴滴加丙烯酸羟丙酯、甲基丙烯酸羟丙酯)与对苯二酚(为丙烯酸羟丙酯和甲基丙烯酸羟丙酯重量的1.5%)的混合物,反应2h,跟踪-NCO基团的含量,当游离的-NCO含量低于0.1%时,停止反应蒸出溶剂降温出料,得到DMPA改性蓖麻油基UV固化聚氨酯丙烯酸酯低聚物(简称PUA低聚物)。
以德国布鲁克公司VERTEX 70型红外光谱仪测试PUA低聚物合成过程的FTIR谱图,所得结果特征峰与实施例1相同。
实施例5
(1)在反应器中依次加入计量好的聚丙二醇、聚己二酸丁二醇和蓖麻油,搅拌并升温至125℃,减压脱水3h后降温至75℃,随后逐渐滴加异佛尔酮二异氰酸酯和二月桂酸二丁基锡(聚氨酯丙烯酸酯预聚物重量的0.15%)的混合物,注意控制其滴加速度,以10g/min的速度加入,反应2h后,将溶于双酚A和2,2-二羟甲基丙酸的N,N-二甲基甲酰胺及丙酮混合溶液加到反应釜里,继续反应,期间取样测量-NCO基团含量直到达到理论值,第一步反应结束;
(2)将上述中间产物降温为55℃,搅拌下逐滴滴加丙烯酸羟丁酯、甲基丙烯酸羟丁酯与对苯二酚(为丙烯酸羟丁酯和甲基丙烯酸羟丁酯重量的1.5%)的混合物,反应3h,跟踪-NCO基团的含量,当游离的-NCO含量低于0.1%时,停止反应蒸出溶剂降温出料,得到DMPA改性蓖麻油基UV固化聚氨酯丙烯酸酯低聚物(简称PUA低聚物)。
以德国布鲁克公司VERTEX 70型红外光谱仪测试PUA低聚物合成过程的FTIR谱图,所得结果特征峰与实施例1相同。
实施例6
(1)在反应器中依次加入计量好的聚丙二醇、聚己二酸丁二醇和蓖麻油,搅拌并升温至125℃,减压脱水3h后降温至75℃,随后逐渐滴加六亚甲基二异氰酸酯、甲苯二异氰酸酯和二月桂酸二丁基锡(聚氨酯丙烯酸酯预聚物重量的0.15%)的混合物,注意控制其滴加速度,以10g/min的速度加入,反应2h后,将溶于双酚A和2,2-二羟甲基丙酸的N,N-二甲基甲酰胺及丙酮混合溶液加到反应釜里,继续反应,期间取样测量-NCO基团含量直到达到理论值,第一步反应结束;
(2)将上述中间产物降温为55℃,搅拌下逐滴滴加丙烯酸羟乙酯、甲基丙烯酸羟乙酯与对羟基苯甲醚(为丙烯酸羟乙酯和甲基丙烯酸羟乙酯重量的1.5%)的混合物,反应3h,跟踪-NCO基团的含量,当游离的-NCO含量低于0.1%时,停止反应蒸出溶剂降温出料,得到DMPA改性蓖麻油基UV固化聚氨酯丙烯酸酯低聚物(简称PUA低聚物)。
以德国布鲁克公司VERTEX 70型红外光谱仪测试PUA低聚物合成过程的FTIR谱图,所得结果特征峰与实施例1相同。
实施例7
(1)在反应器中依次加入计量好的聚乙二醇、聚乙二酸乙二醇和蓖麻油,搅拌并升温至125℃,减压脱水3h后降温至75℃,随后逐渐滴加异佛尔酮二异氰酸酯和二月桂酸二丁基锡(聚氨酯丙烯酸酯预聚物重量的0.15%)的混合物,注意控制其滴加速度,以10g/min的速度加入,反应2h后,将溶于双酚A和2,2-二羟甲基丙酸的N,N-二甲基甲酰胺及丙酮混合溶液加到反应釜里,继续反应,期间取样测量-NCO基团含量直到达到理论值,第一步反应结束;
(2)将上述中间产物降温为55℃,搅拌下逐滴滴加丙烯酸羟乙酯、甲基丙烯酸羟乙酯与对羟基苯甲醚(为丙烯酸羟乙酯和甲基丙烯酸羟乙酯重量的0.05%)的混合物,反应3h,跟踪-NCO基团的含量,当游离的-NCO含量低于0.1%时,停止反应蒸出溶剂降温出料,得到DMPA改性蓖麻油基UV固化聚氨酯丙烯酸酯低聚物(简称PUA低聚物)。
以德国布鲁克公司VERTEX 70型红外光谱仪测试PUA低聚物合成过程的FTIR谱图,所得结果特征峰与实施例1相同。
实施例8
(1)在反应器中依次加入计量好的聚乙二醇、聚乙二酸乙二醇、聚丙二醇、聚己二酸丁二醇和蓖麻油,搅拌并升温至125℃,减压脱水3h后降温至75℃,随后逐渐滴加对苯二异氰酸酯、4,4’-二苯基甲烷二异氰酸酯和二月桂酸二丁基锡(聚氨酯丙烯酸酯预聚物重量的0.15%)的混合物,注意控制其滴加速度,以10g/min的速度加入,反应2h后,将溶于双酚A和2,2-二羟甲基丙酸的N,N-二甲基甲酰胺及丙酮混合溶液加到反应釜里,继续反应,期间取样测量-NCO基团含量直到达到理论值,第一步反应结束;
(2)将上述中间产物降温为55℃,搅拌下逐滴滴加丙烯酸羟丁酯、甲基丙烯酸羟丁酯与对苯二酚(为丙烯酸羟丁酯和甲基丙烯酸羟丁酯重量的1.5%)的混合物,反应3h,跟踪-NCO基团的含量,当游离的-NCO含量低于0.1%时,停止反应蒸出溶剂降温出料,得到DMPA改性蓖麻油基UV固化聚氨酯丙烯酸酯低聚物(简称PUA低聚物)。
以德国布鲁克公司VERTEX 70型红外光谱仪测试PUA低聚物合成过程的FTIR谱图,所得结果特征峰与实施例1相同。
试验实施例1:各实施例产品综合性能测试
将上述各实施例制得的蓖麻油基UV固化聚氨酯丙烯酸酯添加入同等量、同种类的光引发剂制成UV油墨;
表干时间,将UV油墨均匀的涂抹在聚四氟乙烯板表面,在设定的光源和曝光时间下经UV固化。根据GB1728-79,将固化膜用200g干燥砝码压上一片滤纸,一定时间后移去砝码,翻转固化膜,滤纸能自由掉下,即认为表干,测定油墨固化表干时间;
硬度分析,按照GB/T 6739-1996测定漆膜的硬度;
膜体拉伸强度分析,按照GB13022-91使用UTM4204型万能电子试验机测定光固化薄膜的力学性能。各实施例测试结果见表1。
耐水性由吸水率表征,按照GB/T1733–93的方法测试;附着力的测定按照GB/T9286–1998的方法测试。
表1各实施例产品综合性能测试结果
实施例 | 表干/s | 硬度 | 拉伸强度/Mpa | 断裂伸长率/% | 吸水率/% | 附着力/级 |
实施例1 | 26 | H | 35.7 | 7.2 | 1.24 | 0 |
实施例2 | 27 | HB | 34.2 | 8.2 | 1.18 | 1 |
实施例3 | 26 | H | 35.3 | 7.5 | 1.06 | 0 |
实施例4 | 25 | H | 36.4 | 7.5 | 1.01 | 0 |
实施例5 | 23 | H | 37 | 7.4 | 1.21 | 1 |
实施例6 | 26 | H | 36.2 | 7.3 | 1.16 | 0 |
实施例7 | 25 | H | 36.7 | 7.9 | 1.20 | 1 |
实施例8 | 24 | H | 36.7 | 7.1 | 1.17 | 0 |
好的UV固化油墨一般具有固化速率快,硬度适中,成膜后力学性能优异等特点,对于聚氨酯丙烯酸而言,这就要求树脂表干时间越短,拉伸强度越大、柔韧性越好即断裂伸长率越大则树脂综合性能越好,本发明所制备的蓖麻油基UV固化聚氨酯丙烯酸酯表干时间均小于30秒,硬度都在H至HB范围,拉伸强度均大于34Mpa,断裂伸长率均大于7%,因此固化速率,膜力学性能等综合性能完全满足实际应用需要。
热稳定性分析,采用日本Shimadzu公司DTG-60型热重分析仪对树脂进行测试表征,升温速率:20℃/min;气氛:氮气;坩埚材料:铝坩埚。记录各实施例质量损失达5%时的热降解温度。
电绝缘性能测试,将油墨制备成表面平整的固化膜,采用ZC-36型高阻计,按照JB/T 5561-91测定树脂固化膜的电性能。测量各实施例固化膜0.5h时的体积电阻和250h时的体积电阻。
接触角测试,将油墨制备成表面平整的固化膜,接触角测试采用德国Dataphysics公司OCA40接触角测试仪,水滴3μL左右,每个样品测试10次,去掉一个最大值,一个最小值后取平均值。各实施例的测试结果见表2。
表2各实施例产品特异性能测试结果
实施例 | 热降解温度/℃ | 0.5h体积电阻/Ω | 250h体积电阻/Ω | 接触角/° |
实施例1 | 239 | 2.3-2.4×1010 | 2.0-2.15×109 | 90 |
实施例2 | 243 | 3.9-4.0×1010 | 3.6-3.7×108 | 87 |
实施例3 | 271 | 5.5-5.6×1010 | 5.0-5.15×108 | 91 |
实施例4 | 263 | 7.0-7.1×1010 | 7.6-7.75×108 | 88 |
实施例5 | 255 | 1.0-1.05×1011 | 1.0-1.05×109 | 93 |
实施例6 | 264 | 3.1-3.2×1011 | 3.0-3.15×109 | 95 |
实施例7 | 257 | 2.2-2.35×1011 | 2.4-2.5×109 | 89 |
实施例8 | 255 | 7.5-7.65×1011 | 7.3-7.45×109 | 92 |
从以上数据分析,实施例样品制备所得的蓖麻油基UV固化聚氨酯丙烯酸酯其固化速率较快,力学性能优异,且热稳定性好,热降解温度较高,经过本文提供的制备方法制备得的蓖麻油基聚氨酯丙烯酸酯,比一般的聚氨酯丙烯酸酯具有更优良的电绝缘性及附着力,且综合性能优异。
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 (8)
1.一种蓖麻油基UV固化聚氨酯丙烯酸酯的制备方法,其特征在于,包括如下步骤:
(1)将二元醇和蓖麻油减压脱水后,保持温度为65~75℃,加入二异氰酸酯和催化剂的混合物反应2~3h,然后加入溶有双酚A和2,2-二羟甲基丙酸的N,N-二甲基甲酰胺及丙酮混合溶液,继续反应,期间取样测量-NCO基团含量直到达到理论值,第一步反应结束;所述的二异氰酸酯与二元醇的摩尔比为1:1~1:1.01,蓖麻油、双酚A、2,2-二羟甲基丙酸的用量分别为二异氰酸酯用量的1~10%、10~30%、10~30%;
(2)将步骤(1)制得的中间产物降温为45~55℃,搅拌下加入(甲基)丙烯酸羟烷酯与阻聚剂的混合物,反应2~3h,跟踪-NCO基团的含量,当游离的-NCO含量低于0.1%时,停止反应蒸出溶剂降温出料,得到蓖麻油基UV固化聚氨酯丙烯酸酯;所述的蓖麻油基UV固化聚氨酯丙烯酸酯应用于UV固化绝缘油墨。
2.根据权利要求1所述的蓖麻油基UV固化聚氨酯丙烯酸酯的制备方法,其特征在于,步骤(1)中所述的二元醇为聚酯二元醇和/或聚醚二元醇,其分子量为1000~3000,所述的二异氰酸酯为芳香族和/或脂肪族二异氰酸酯。
3.根据权利要求1所述的蓖麻油基UV固化聚氨酯丙烯酸酯的制备方法,其特征在于,所述的二元醇为聚乙二醇、聚丙二醇、聚乙二酸乙二醇和聚己二酸丁二醇中的至少一种;所述的二异氰酸酯为六亚甲基二异氰酸酯、甲苯二异氰酸酯、对苯二异氰酸酯、4,4’-二苯基甲烷二异氰酸酯和异佛尔酮二异氰酸酯中的至少一种。
4.根据权利要求1所述的蓖麻油基UV固化聚氨酯丙烯酸酯的制备方法,其特征在于,步骤(1)中所述的催化剂为二月桂酸二丁基锡,以蓖麻油基UV固化聚氨酯丙烯酸酯100重量份计,所述催化剂为0.1~0.15重量份。
5.根据权利要求1所述的蓖麻油基UV固化聚氨酯丙烯酸酯的制备方法,其特征在于,步骤(2)中所述的(甲基)丙烯酸羟烷酯与步骤(1)中所述的二异氰酸酯的摩尔比为1:1。
6.根据权利要求1所述的蓖麻油基UV固化聚氨酯丙烯酸酯的制备方法,其特征在于,步骤(2)中所述的(甲基)丙烯酸羟烷酯为丙烯酸羟乙酯、丙烯酸羟丙酯、丙烯酸羟丁酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯和甲基丙烯酸羟丁酯中的至少一种。
7.根据权利要求1所述的蓖麻油基UV固化聚氨酯丙烯酸酯的制备方法,其特征在于,步骤(2)中所述的阻聚剂为对羟基苯甲醚或对苯二酚;以(甲基)丙烯酸羟烷酯100重量份计,所述阻聚剂为0.05~1.5重量份。
8.一种蓖麻油基UV固化聚氨酯丙烯酸酯,其特征在于,其由权利要求1至7任一项所述的蓖麻油基UV固化聚氨酯丙烯酸酯的制备方法制备得到。
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