CN107501463A - 一种紫外光自交联聚丙烯酸酯及其制备方法 - Google Patents
一种紫外光自交联聚丙烯酸酯及其制备方法 Download PDFInfo
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- CN107501463A CN107501463A CN201710580434.7A CN201710580434A CN107501463A CN 107501463 A CN107501463 A CN 107501463A CN 201710580434 A CN201710580434 A CN 201710580434A CN 107501463 A CN107501463 A CN 107501463A
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- acrylate
- ultraviolet light
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- monomer
- crosslinking
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- 238000007254 oxidation reaction Methods 0.000 description 1
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- 239000011574 phosphorus Substances 0.000 description 1
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- 239000002861 polymer material Substances 0.000 description 1
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Abstract
本发明公开了一种紫外光自交联聚丙烯酸酯及其制备方法。本发明首先合成一种含有潜在巯基基团的丙烯酸酯单体A和含有降冰片烯双键基团的丙烯酸酯单体B,然后将合成的丙烯酸酯单体A和B与可聚合光引发剂,甲基丙烯酸甲酯和丙烯酸丁酯按一定投料比通过热引发自由基共聚反应,得到紫外光自交联聚丙烯酸酯;本发明通过将潜在巯基结构以及双键接入聚丙烯酸酯侧链中,当紫外光照射下才产生巯基,并同时发生巯烯光点击反应实现交联,这样可以解决巯基和烯烃双键共同存在的体系在存放过程中不稳定的问题,制备得到的紫外光自交联聚丙烯酸酯在光固化涂料、光固化粘合剂、光致抗蚀剂、印刷板材、电子工业等方面具有较大的应用前景。
Description
技术领域
本发明属于高分子材料技术领域。更具体地,涉及一种紫外光自交联聚丙烯酸酯及其制备方法。
背景技术
紫外光交联丙烯酸酯在光固化涂料、光固化粘合剂、光致抗蚀剂、印刷板材、电子工业等方面的应用越来越广泛。聚丙烯酸酯成膜后经过光交联处理形成聚合物网络结构,可以提高成膜性能,例如:强度、硬度、耐磨性、耐溶剂性以及抗老化性等。
聚合物光交联的途径有多种,例如分子链上可聚合基团的光聚合反应、光致双自由基耦合反应、光环合加成反应、叠氮基团的光耦合反应、光致巯烯点击反应等等。目前大部分的紫外光交联型丙烯酸酯一般在侧链或主链上引入双键(如 POLYMERIC MATERIALSSCIENCE AND ENGINEERING,第3期,第43-48 页,1993年5月),这种通过自由基聚合或耦合反应交联的途径存在氧阻聚和收缩率高等问题。
而巯烯点击反应具有对氧和水均不敏感,体积收缩小,反应效率高的优点,而且基于巯烯点击交联的聚合物涂膜,由于巯基基团的引入,反应后生成硫醚的结构,硫醚在交联网状结构中旋转位垒较低,使得涂层具有很好的韧性和粘接性,高的折光系数,耐热性、抗氧性和低的吸水性。但是,巯基化合物小分子味道难闻,虽然已有报道将巯基基团引入聚合物分子链上有利于减轻难闻味道,但是巯烯体系的保存期较短(巯基在放置过程中有可能与双键加成反应,或两个巯基之间形成双硫键,从而交联和凝胶化),这阻碍了它在相应工业化中的应用。
发明内容
本发明所要解决的技术问题是克服上述现有技术的缺陷和不足,提供一种紫外光自交联聚丙烯酸酯的制备,通过将潜在巯基结构以及双键接入聚丙烯酸酯侧链中,当紫外光照射下才产生巯基,并同时发生巯烯光点击反应实现交联,这样可以解决巯基和烯烃双键共同存在的体系在存放过程中不稳定的问题。本发明还同时将二苯甲酮结构接入聚合物侧链中,作为光引发基团在光照下引发巯基点击反应,这样在使用时无需外加光引发剂。而且,二苯甲酮在光照下发生氢转移反应而产生的双自由基也具有偶合交联作用,进一步提高交联度。
本发明的目的是提供一种紫外光自交联聚丙烯酸酯。
本发明的另一目的是提供所述紫外光自交联聚丙烯酸酯的制备方法。
本发明的上述目的是通过以下技术方案给予实现的:
一种含有潜在巯基基团的丙烯酸酯单体A,结构式如下式(I)所示:
其中,R1选自甲基或氢;R2选自1~4个亚甲基;R3、R4、R5、R6选自氢或烷基。
优选地,R1为甲基;R2为2个亚甲基;R3、R4、R5、R6均为氢。
优选地,所述含有潜在巯基基团的丙烯酸酯单体A的制备方法如下:
(1)将邻硝基苄溴与3-巯基丙酸在一定缚酸剂,温度条件下反应形成硫醚 (如反应式III所示);
(2)将步骤(1)的反应产物与甲基丙烯酸缩水甘油酯的环氧基在催化剂的作用下发生开环反应,得到丙烯酸酯单体A(如反应式IV所示)。
优选地,所述缚酸剂为氢氧化钠,氢氧化钾,碳酸钠,碳酸钾,三乙胺或吡啶(优选氢氧化钠)。
优选地,步骤(1)中反应温度为30~70℃(优选45℃)。
优选地,步骤(2)中的开环催化剂为三乙胺,四甲基氯化铵,四丁基溴化铵或三苯基膦(优选三苯基膦)。
优选地,所述开环催化剂用量为0.5~3wt%(优选1wt%)。
优选地,步骤(2)中开环反应温度为80~120℃(优选110℃)。
一种含有降冰片烯双键基团的丙烯酸酯单体B,结构式如下式(II)所示:
其中,R1选自甲基或氢;R2选自1~4个亚甲基;R3选自氢或羧基。
优选地,R1为甲基;R2为2个亚甲基;R3为羧基。
优选地,所述含有降冰片烯双键基团的丙烯酸酯单体B的制备方法为:将降冰片烯二酸酐与甲基丙烯酸羟乙酯在一定温度下发生醇解反应,得到丙烯酸酯单体B(如反应式V所示)。
优选地,降冰片烯二酸酐与甲基丙烯酸羟乙酯的投料摩尔比为1:1~1.5(优选1:1.1)。
优选地,醇解反应的温度为100~140℃(优选130℃)。
优选地,醇解反应时间为3~8h(优选5h)。
一种紫外光自交联聚丙烯酸酯的制备方法,将上述含有潜在巯基基团的丙烯酸酯单体A和含有降冰片烯双键基团的丙烯酸酯单体B通过热引发自由基共聚反应,得到紫外光自交联聚丙烯酸酯。
优选地,所述丙烯酸酯单体A投入量为1~50wt%(优选5~10wt%)。
优选地,所述丙烯酸酯单体B投入量为1~50wt%(优选5~10wt%)。
本发明发现,在实际制备聚合物时,丙烯酸酯单体A和丙烯酸酯单体B的添加量并不是越多越好,当丙烯酸酯的单体B的添加量过高时,聚合反应中容易产生凝胶从而影响聚合反应的进行,当丙烯酸酯单体A的添加量多高时,会引起体系变黄;此时,可加入常规的聚合单体来作为共聚和稀释单体来解决丙烯酸酯单体A和B添加量过高时带来的影响,通过试验证明,确定丙烯酸酯单体 A和丙烯酸酯单体B的投入量均为10%时效果最理想,聚合时不会有凝胶产生。
优选地,所述常规聚合单体投入量为0~98wt%(优选50~80wt%)。
优选地,所述聚合反应温度为40~120℃(优选60~90℃,最优75℃)。
优选地,所述聚合反应时间为2~10h(优选3~6h,最优4h)。
优选地,所述常规聚合单体为乙酸乙烯酯、苯乙烯、丙烯酸、甲基丙烯酸、衣康酸、顺丁烯二酸二丁酯、顺丁烯二酸二辛酯、丙烯酰胺、甲基丙烯酰胺或丙烯腈、为丙烯酸甲酯、丙烯酸乙酯、丙烯酸异冰片酯、丙烯酸丁酯、丙烯酸月桂酯、丙烯酸-2-羟乙酯、丙烯酸缩水甘油酯、丙烯酸异丁酯、丙烯酸异癸酯、丙烯酸异辛酯或丙烯酸-2-羟丙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸异冰片酯、甲基丙烯酸丁酯、甲基丙烯酸月桂酯、甲基丙烯酸-2-羟乙酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸异丁酯、甲基丙烯酸异癸酯、甲基丙烯酸异辛酯、甲基丙烯酸二甲基氨基乙酯或甲基丙烯酸-2-羟丙酯中的一种或几种。
优选地,所述热引发使用的热引发剂为过氧化二苯甲酰,过氧化二月桂酰,过氧化二碳酸二异丙酯,过氧化苯甲酸叔丁酯,偶氮二异丁腈或偶氮二异庚腈。
优选地,所述热引发剂用量为0.5~3wt%(优选1%)。
优选地,聚合反应在有机溶剂中进行,有机溶剂为乙酸乙酯,乙酸丁酯、乙二醇乙酸酯、四氢呋喃、二氧六环、苯、甲苯、二甲苯、丙酮、丁酮、甲乙酮、环己酮、乙醇、丙醇、丁醇等常规有机溶剂(优选乙酸丁酯)。
优选地,聚合反应中可加入可聚合光引发剂,其作用不仅可以作为光引发巯烯点击反应,而且还可以通过夺氢使分子链间发生双基耦合,进一步提高交联度;其投入量为0~10wt%(优选0~5wt%)。
更优选地,所述可聚合光引发剂为MHPBP,其结构式如下式(VI)所示,其具体合成方法如ACS Appl.Mater.Interfaces,2015,7(31)pp 17489–17498)。
另外,上述方法制备得到的紫外光自交联聚丙烯酸酯及其在光固化涂料、光固化粘合剂、光致抗蚀剂、印刷板材或电子工业中的应用亦在发明保护范围内。
所述紫外光自交联聚丙烯酸酯的树脂溶液的固含量为5~80%;优选地,固含量为20~50%;更优选地,固含量为35%。
本发通过将潜在巯基结构以及双键接入聚丙烯酸酯侧链中,当紫外光照射下才产生巯基,并同时发生巯烯光点击反应实现交联,这样可以解决巯基和烯烃双键共同存在的体系在存放过程中不稳定的问题。同时将二苯甲酮结构接入聚合物侧链中,作为光引发基团在光照下引发巯基点击反应,这样在使用时无需外加光引发剂。而且,二苯甲酮在光照下发生氢转移反应而产生的双自由基也具有偶合交联作用,进一步提高交联度。
本发明中的紫外光自交联聚丙烯酸酯,在应用时给予光照即可自交联,其光交联机理如下:聚合物侧链上的邻硝基苄基吸收光能后,苄基上α键发生断裂脱去邻亚硝基苯甲醛并且生成巯基;在光引发剂的作用下,巯基与降冰片烯双键发生高活性的巯烯点击反应从而形成交联网络结构(如反应式VII所示)。
在交联过程中所需要的光引发剂,包括但不限于二苯甲酮、异丙基硫杂蒽酮、米氏酮、香豆素、取代二茂铁、2-羟基-2-甲基-1-苯基-1-丙酮、1-羟基环己基苯基甲酮、2-甲基-1-(4-甲硫基苯基)-2-吗啉基-1-丙酮、安息香双甲醚、2,4,6-三甲基苯甲酰基-二苯基氧化磷等。
与现有技术相比,本发明具有以下有益效果:
本发明制备得到了一种紫外光自交联聚丙烯酸酯,通过将潜在巯基结构以及双键接入聚丙烯酸酯侧链中,当紫外光照射下才产生巯基,并同时发生巯烯光点击反应实现交联,解决了巯基和烯烃双键共同存在的体系在存放过程中不稳定的问题;同时在聚合反应中加入可聚合光引发剂,不仅可以作为光引发巯烯点击反应,而且还可以通过夺氢使分子链间发生双基耦合,进一步提高交联度;制备得到的紫外光自交联聚丙烯酸酯在光固化涂料、光固化粘合剂、光致抗蚀剂、印刷板材、电子工业等方面具有较大的应用前景。
附图说明
图1为含有潜在巯基基团的丙烯酸酯单体A的1H NMR图。
图2为含有潜在巯基基团的丙烯酸酯单体A的ESI-MS正谱图。
图3为含有降冰片烯双键基团的丙烯酸酯单体B的1H NMR图。
图4为含有降冰片烯双键基团的丙烯酸酯单体B的ESI-MS负谱图。
具体实施方式
以下结合说明书附图和具体实施例来进一步说明本发明,但实施例并不对本发明做任何形式的限定。除非特别说明,本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
除非特别说明,以下实施例所用试剂和材料均为市购。
实施例1
1、制备紫外光自交联聚丙烯酸酯
(1)丙烯酸酯单体A的制备:
2.46g 3-巯基丙酸溶于20mL的丙酮,加入NaOH水溶液(2.04gNaOH、 14mLH2O);降温至0℃,5g邻硝基苄基溴溶于20mL丙酮,并慢慢滴加;加热至45℃,继续反应4h;溶剂通过减压蒸馏除去,残留物重新溶解于20mL二氯甲烷和20mL水混合液中。水相用二氯甲烷清洗,随后用10%HCl溶液酸化,用 30mL二氯甲烷萃取2遍,合并有机相,用无水硫酸钠干燥,减压旋蒸,得到浅黄色固体。
取5g上述浅黄色固体和三苯基膦溶于甲苯中,加热至110℃,将3.5g甲基丙烯酸缩水甘油酯慢慢滴加,反应5h;减压蒸馏除去甲苯,得到棕色粘稠状液体,然后用硅胶层析柱进一步提纯,流动相为乙酸乙酯和石油醚(v/v=2:3),得到淡黄色粘稠状液体。图1为产物的核磁氢谱1H NMR(400MHz,CDCl3,δ, ppm):8.00(a,1H),7.65~7.40(b,c,d,3H),6.17(m,1H),5.65(n,1H),4.35~4.00 (h,i,j,k,6H),4.12(e,2H),2.76(f,2H),2.65(g,2H),1.99(l,3H);图2 为ESI-MS正谱:特征峰401.1=[M+NH4 +]。
(2)丙烯酸酯单体B的制备:
在150mL三颈烧瓶中加入14.3g甲基丙烯酸羟乙酯、16.4g降冰片烯二酸酐、0.015g对羟基苯甲醚,通入氮气保护,加热至130℃,反应5h,测定酸值达到理论值后,冷却,得到白色固体。图3为产物的核磁氢谱1H NMR(400MHz,CDCl3, δ,ppm):6.30(a,1H),6.25(b,1H),6.15(j,1H),5.61(k,1H),4.42~4.22 (g,h,4H),3.33(c,2H),3.22(d,2H),1.97(i,3H),1.50(e,1H),1.37(f, 1H);图4为ESI-MS负谱:特征峰292.9=[M-H+]。
(3)紫外光自交联聚丙烯酸酯的制备:
将上述合成的1.0g丙烯酸酯单体A、1.0g丙烯酸酯单体B、9.0g甲基丙烯酸甲酯和9.0g丙烯酸丁酯单体,以及0.2g偶氮二异丁氰,加入30g乙酸丁酯为溶剂配成单体溶液。在装有冷凝管、机械搅拌、氮气导管以及滴液漏斗的四口烧瓶,滴入配好的1/3单体溶液,通入氮气,75℃下反应0.5h后,2h内滴加完剩余单体溶液以及引发剂,恒温反应1h,升温至95℃继续反应0.5h,把未反应的单体反应完全。在FT-IR光谱上1652cm-1处为降冰片烯C=C双键吸收峰,710cm-1处为C-S键吸收峰。
2、涂膜及光交联效果测试
上述所合成的聚丙烯酸酯树脂中加入基于树脂固体分的1wt%光引发剂2-羟基-2-甲基-1-苯基-1-丙酮,混合均匀后,用25μm的线棒涂布在聚四氟乙烯板上,将涂覆好的板材置于鼓风烘箱85℃下干燥30min后,在抽屉式的UV固化机上进行UV辐照固化3min,使涂覆好的板材在距光源约20cm处,光强为25.0至 28.5mW/cm2。将薄膜揭下后,采用索氏抽提法测其交联度,结果如表1所示。
表1索氏抽提法测交联度结果
实施例2
将0.5g丙烯酸酯单体A、1.0g丙烯酸酯单体B、9.25g甲基丙烯酸甲酯和 9.25g丙烯酸丁酯单体以及0.2g偶氮二异丁氰,加入30g乙酸丁酯为溶剂配成单体溶液。其余步骤均匀实施例1中相同,得到紫外光自交联聚丙烯酸酯。
涂膜步骤与实施例1相同,当丙烯酸酯A的含量从5%降为2.5%,交联点减少,交联度为35.76%。
实施例3
将2.0g丙烯酸酯单体A、1.0g丙烯酸酯单体B、8.5g甲基丙烯酸甲酯和8.5g 丙烯酸丁酯单体以及0.2g偶氮二异丁氰,加入30g乙酸丁酯为溶剂配成单体溶液。其余步骤均匀实施例1中相同,得到紫外光自交联聚丙烯酸酯。
涂膜步骤与实施例1相同,由于丙烯酸酯A的含量从5%增致10%,交联点增加,交联度为54.91%。
实施例4
将2.0g丙烯酸酯单体A、2.0g丙烯酸酯单体B、8.0g甲基丙烯酸甲酯和8.0g 丙烯酸丁酯单体以及0.2g偶氮二异丁氰,加入30g乙酸丁酯为溶剂配成单体溶液。其余步骤均匀实施例1中相同,得到紫外光自交联聚丙烯酸酯。
涂膜步骤与实施例1相同,同时将丙烯酸酯A和B的含量从5%增致10%,交联点增加,交联度为73.92%。
实施例5
将0.2g可聚合光引发剂,2.0g丙烯酸酯单体A、2.0g丙烯酸酯单体B、7.9g 甲基丙烯酸甲酯和7.9g丙烯酸丁酯单体以及0.2g偶氮二异丁氰,加入30g乙酸丁酯为溶剂配成单体溶液。其余步骤均匀实施例1中相同,得到紫外光自交联聚丙烯酸酯。
将上述所合成的聚丙烯酸酯直接涂布在聚四氟乙烯板上,将涂覆好的板材置于鼓风烘箱85℃下干燥30min后,在抽屉式的UV固化机上进行UV辐照固化 3min。由于聚合物侧链含有二苯甲酮单元,无需外加光引发剂,而且实现双机理交联,与实施例4相比,交联度增致88.48%。
对比例1
将1.0g丙烯酸酯单体B、9.5g甲基丙烯酸甲酯和9.5g丙烯酸丁酯单体以及 0.2g偶氮二异丁氰,加入30g乙酸丁酯为溶剂配成单体溶液。其余步骤均匀实施例1中相同,得到侧链只含降冰片烯双键的聚丙烯酸酯。
涂膜步骤与实施例1相同。由于体系中不含丙烯酸酯单体A,不能产生巯基进行点击交联,仅靠降冰片烯双键固化,活性很低,交联度仅为4.70%。
Claims (10)
1.一种含有潜在巯基基团的丙烯酸酯单体A,其特征在于,结构式如下式(I)所示:
其中,R1选自甲基或氢;R2选自1~4个亚甲基;R3、R4、R5、R6选自氢或烷基。
2.一种含有降冰片烯双键基团的丙烯酸酯单体B,其特征在于,结构式如下式(II)所示:
其中,R1选自甲基或氢;R2选自1~4个亚甲基;R3选自氢或羧基。
3.一种紫外光自交联聚丙烯酸酯的制备方法,其特征在于,将权利要求1和2的丙烯酸酯单体A和B通过热引发自由基共聚反应,得到紫外光自交联聚丙烯酸酯。
4.根据权利要求3所述的制备方法,其特征在于,所述丙烯酸酯单体A投入量为1~50wt%;,丙烯酸酯单体B投入量为1~50wt%。
5.根据权利要求3所述的制备方法,其特征在于,共聚反应体系中加入常规聚合单体,其投加量为0~98%。
6.根据权利要求3所述的制备方法,其特征在于,所述聚合反应温度为40~120℃,聚合反应时间为2~10h。
7.根据权利要求4所述的制备方法,其特征在于,所述常规聚合单体为乙酸乙烯酯、苯乙烯、丙烯酸、甲基丙烯酸、衣康酸、顺丁烯二酸二丁酯、顺丁烯二酸二辛酯、丙烯酰胺、甲基丙烯酰胺或丙烯腈、为丙烯酸甲酯、丙烯酸乙酯、丙烯酸异冰片酯、丙烯酸丁酯、丙烯酸月桂酯、丙烯酸-2-羟乙酯、丙烯酸缩水甘油酯、丙烯酸异丁酯、丙烯酸异癸酯、丙烯酸异辛酯或丙烯酸-2-羟丙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸异冰片酯、甲基丙烯酸丁酯、甲基丙烯酸月桂酯、甲基丙烯酸-2-羟乙酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸异丁酯、甲基丙烯酸异癸酯、甲基丙烯酸异辛酯、甲基丙烯酸二甲基氨基乙酯或甲基丙烯酸-2-羟丙酯中的一种或几种。
8.根据权利要求3所述的制备方法,其特征在于,共聚反应中加入可聚合光引发剂,其投入量为0~10wt%。
9.权利要求3~8任一项所述制备方法制备得到的紫外光自交联聚丙烯酸酯。
10.权利要求9所述紫外光自交联聚丙烯酸酯在光固化涂料、光固化粘合剂、光致抗蚀剂、印刷板材或电子工业中的应用。
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