CN110452191B - 一种改性丙烯酸酯、制备方法及其导电胶粘剂的应用 - Google Patents
一种改性丙烯酸酯、制备方法及其导电胶粘剂的应用 Download PDFInfo
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Abstract
本发明公开了一种改性丙烯酸酯、制备方法及其导电胶粘剂的应用,本发明将多元醇丙烯酸酯类单体中羟基转变为含α‑H的缩醛基团,得到所述改性丙烯酸酯。本发明通过减少羟基,得到的改性丙烯酸酯粘度较低,可作为活性稀释剂有效应用于光固化涂料配方中;且含有具有促进光聚合活性的含α‑H的缩醛基团,能够提高光固化活性,促进光交联,无需添加氢供体助剂,能够避免氧阻聚的问题。该改性丙烯酸酯用于制备光固化组合物时,制得的光固化组合物易固化、表干快。本发明还提供采用烯醇醚与多元醇丙烯酸酯类单体的羟基进行反应得到含α‑H的缩醛基团的制备方法,并提供该改性丙烯酸酯在制备光固化组合物及其导电胶粘剂的应用。
Description
技术领域
本发明涉及光固化高分子材料技术领域,更具体地,涉及一种改性丙烯酸酯、制备方法及其导电胶粘剂的应用。
背景技术
辐射(UV/EB)固化因其节能环保、固化效率高、经济效益良好,无VOCs排放等优点而广泛应用于印刷包装、木器、塑料等领域,紫外光固化涂料可作为木器、纸张、金属、塑料、光线等表面保护涂层。紫外光固化涂料一般由低聚物或称树脂或低聚物、单体、光引发剂、助剂,四部分组成。其中单体又称活性稀释剂,是一种含有可聚合官能团的有机小分子,起到溶解和稀释低聚物,调节体系黏度的作用,并参与光固化过程中,影响光固化产品的固化速率和固化膜的各种性能,其为光固化涂料配方中的一个重要组成。常见的丙烯酸酯类活性稀释剂有单官、双官以及多官的丙烯酸酯化合物,一般官能度越大,其黏度越大,黏度范围为0~600mPaS(25℃)。其中,低粘度单官、双官及三官的丙烯酸酯类单体作为活性稀释剂应用于光固化涂料配方中最为广泛。
理想状态下,多元醇和丙烯酸酯化可达到100%酯化,即将所有羟基都酯化成为丙烯酸酯基,但在实际合成生产中,多元醇中不同羟基活性不一样,尤其是叔醇活性较差,且受位阻影响,很难与丙烯酸发生酯化反应,所以多元醇和丙烯酸酯化后产物含有不同量的羟基。其残余的羟基由于氢键作用,会导致所得酯化产物粘度大,耐水性差等缺点,不利于作为活性稀释剂使用。
而且,紫外光固化涂料中常用的TypeⅡ型光引发剂一般需要搭配氢供体助剂使用,如叔胺类,才可以快速有效产生活性自由基,引发双键聚合。如果不添加氢供体助剂,制得的紫外光固化涂料光固化较慢,存在氧阻聚的问题。
此外,随着终端电子设备朝着小、轻、薄方向的发展,电子元器件之间窄间距、密引脚的贴合成为目前粘合剂研究的一个主流方向。异方性导电树脂膜凭借着其粘结精细、贴合脚距薄等优点,已经被应用于各种便携式电子产品的组装中。然而,国内目前使用的异方性导电树脂膜仍然主要依赖进口。丙烯酸酯单体作为导电胶粘剂的成分之一,现有的单体与导电粒子相容性较差,粘接时容易发生胶层断裂,不利于制备导电胶粘剂。
因此,需要开发出粘度较低、能够提高光固化活性、无需添加氢供体助剂、与导电粒子相容性更好的改性丙烯酸酯。
发明内容
本发明为克服上述现有技术所述的丙烯酸酯类单体粘度大、光固化较慢的缺陷,提供一种改性丙烯酸酯,提供的改性丙烯酸酯有效减少羟基,粘度较低,且含有具有促进光聚合活性的含α-H的缩醛基团,能够提高光固化活性,促进光交联,与导电粒子相容性好。
本发明的另一目的在于提供上述改性丙烯酸酯的制备方法。
本发明的还一目的在于提供上述改性丙烯酸酯在制备光固化组合物中的应用。
为解决上述技术问题,本发明采用的技术方案是:
一种改性丙烯酸酯,将多元醇丙烯酸酯类单体中羟基转变为含α-H的缩醛基团,得到所述改性丙烯酸酯。
本发明将多元醇丙烯酸酯类单体中羟基转变为含α-H的缩醛基团,得到改性丙烯酸酯,有效减少羟基,粘度较低,且含有具有促进光聚合活性的含α-H的缩醛基团,能够提高光固化活性,促进光交联,无需添加氢供体助剂,能够避免氧阻聚的问题。该改性丙烯酸酯用于制备光固化组合物时,制得的光固化组合物易固化、表干快。而且,该改性丙烯酸酯与导电粒子相容性好,用于导电胶粘剂时,粘接时不容易发生胶层断裂。
优选地,所述改性丙烯酸酯的化学结构如式(Ⅰ)或式(Ⅱ)所示:
其中,R1为H或甲基;
R为碳原子数为1~10的直链烷基、支链烷基或环烷基,或者(甲基)丙烯酸酯基团取代的直链烷基或支链烷基,或者缩醛基团取代的直链烷基或支链烷基;
R2为碳原子数为1~11的直链烷基或支链烷基;
R3为碳原子数为1~11的直链烷基或支链烷基;
R4为烷基,R4与相邻的碳原子和氧原子形成五元环或六元环。
优选地,所述改性丙烯酸酯由含有残余羟基的丙烯酸酯单体与烯醇醚通过亲核加成反应得到。
针对多元醇与丙烯酸反应酯化残余羟基问题,本发明采用烯醇醚将残余羟基消耗掉,减少分子间的氢键作用,所得单体粘度低,可作为活性稀释剂有效应用于光固化涂料配方中;同时,其生成具有促进光聚合活性的含α-H的缩醛基团,缩醛基团α-H为活泼氢,该氢原子可促进光交联,可作为氢供体或者过氧化物以及氧气猝灭剂使用,有效抑制氧阻聚,有利于提高光固化速率,促进光交联。
优选地,将多元醇丙烯酸酯类单体中羟基与烯醇醚反应转变为α-H的缩醛基团。
本发明还保护上述改性丙烯酸酯的制备方法,所述制备方法包括如下步骤:
S1.将多元醇与丙烯酸类化合物反应,得到式(Ⅲ)化合物;
其中,R5为碳原子数为1~10的直链烷基、支链烷基或环烷基,或者(甲基)丙烯酸酯基团取代的直链烷基或支链烷基,或者羟基取代的直链烷基或支链烷基;
S2.将步骤S1.制得的式(Ⅲ)化合物与烯醇醚通过亲核加成反应制得式(Ⅰ)化合物或式(Ⅱ)化合物。
步骤S1.的具体步骤如下:
1)多元醇和丙烯酸类化合物在催化剂、对羟基苯甲醚、次磷酸条件下,加入甲苯,加热升温,并开启真空泵抽真空,保持反应体系负压,真空度控制绝压在20KPa~70KPa之间,温度控制在75~100℃之间,反应生成的水随着丙烯酸和甲苯或甲苯和环己烷的混合溶剂共沸并通过分水器上回流冷凝进行气液交换,气相冷却为液体后分层,下层水不断分出,上层(甲基)丙烯酸和甲苯回流进反应瓶中,直至反应出水量小于0.1g/h;
2)然后降温至40~45℃,补加甲苯,然后加入水洗涤并静置分水,然后加入碳酸氢钠水溶液和氢氧化钠水溶液中和,并静置分水;
3)中和结束后,补加对羟基苯甲醚,然后真空脱溶剂,除掉甲苯或甲苯和环己烷的混合溶剂,温度控制在70~75℃,真空度控制在5~10KPa,得到式(Ⅲ)化合物。
所述丙烯酸类化合物可以为(甲基)丙烯酸。
步骤S2.中式(Ⅲ)化合物与烯醇醚通过亲核加成反应制得化合物M,得到烯醇醚改性的丙烯酸酯单体,产物中不含有羟基且含有α-H的缩醛基团。所收集产物可以是化合物M,还可以是化合物M与酯化反应生成的多官能丙烯酸酯单体的混合物,该多官能丙烯酸酯单体作为可聚合多官能成分存在。
优选地,步骤S1.的反应在四口烧瓶中进行,四口烧瓶上安装有电动搅拌装置、温度计、分水器、冷凝管和真空泵。
优选地,步骤S1.的所述催化剂为硫酸、硫酸氢盐、有机磺酸或过硫酸氢盐中的一种或两种以上的组合。
优选地,步骤S1.中多元醇、丙烯酸类化合物、甲苯或甲苯与环己烷混合溶剂、对羟基苯甲醚、次磷酸和有机磺酸的质量用量比为1:2~8:2.5~7:0.1~0.15:0.02~0.04:0.06~0.15。
所述有机磺酸为甲基磺酸或对甲苯磺酸。
优选地,步骤S1.中所述中反应体系压力控制在绝压25KPa~65KPa之间,温度控制在80~95℃之间。
优选地,所述多元醇至少含有2个羟基,所述多元醇为含有碳原子数为3~15的直链、支链或环烷基结构的多元醇。
优选地,所述多元醇含2~8个羟基。
优选地,所述烯醇醚的化学结构如式(Ⅳ)或式(Ⅴ)所示:
其中,R6为H或碳原子数为1~10的直链烷基或支链烷基;
R7为H或碳原子数为1~10的直链烷基或支链烷基;
R8为烷基,式(Ⅴ)构成五元环或六元环。
优选地,所述烯醇醚为乙烯基异丁醚、乙烯基丁醚、甲基-1-丙烯基醚、乙烯基异丙基醚、2,3-二氢呋喃或3,4-二氢吡喃中的一种或两种以上的组合。
所述步骤S2.中,按照测定式(Ⅲ)化合物羟值计算式(Ⅲ)化合物的投料量。
优选地,所述烯醇醚的摩尔数与式(Ⅲ)化合物的羟基摩尔数的比值为1~1.5。
优选地,所述烯醇醚的摩尔数与式(Ⅲ)化合物的羟基摩尔数的比值为1~1.05。
优选地,步骤S2.反应温度为30~80℃,反应时间为3~24h。
本发明还保护上述改性丙烯酸酯在制备光固化组合物或导电胶粘剂中的应用。
与现有技术相比,本发明的有益效果是:
本发明将多元醇丙烯酸酯类单体中羟基转变为含α-H的缩醛基团,得到改性丙烯酸酯,有效减少羟基,粘度较低,可作为活性稀释剂有效应用于光固化涂料配方中;且含有具有促进光聚合活性的含α-H的缩醛基团,能够提高光固化活性,促进光交联,无需添加氢供体助剂,能够避免氧阻聚的问题。该改性丙烯酸酯用于制备光固化组合物时,制得的光固化组合物易固化、表干快。而且,该改性丙烯酸酯与导电粒子相容性好,用于导电胶粘剂时,粘接时不容易发生胶层断裂。
另外,本发明具体采用烯醇醚与含有残余羟基的丙烯酸酯单体发生亲核加成反应,从而消耗掉残余的羟基,获得低粘度的改性丙烯酸酯,同时生成含α-H的缩醛基团。
具体实施方式
下面结合具体实施方式对本发明作进一步的说明。
实施例中的原料均可通过市售得到;
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。
实施例中1N碳酸氢钠和1N氢氧化钠水溶液,1N=1mol/L。
实施例1
一种改性丙烯酸酯,制备方法如下:
S1.甘油丙三醇和丙烯酸酯化后所得单体A1,为三种分子的混合物,结构如下,其中R1为H:
操作步骤:四口烧瓶配以搅拌桨,温度计,分水器,分水器上部连接回流冷凝管。82.8g丙三醇和200g丙烯酸置于500mL四口烧瓶中,加入4.5g对羟基苯甲醚,9g甲基磺酸,2g次磷酸,100g甲苯,搅拌均匀后,开启真空泵30KPa,升温至体系温度为82℃时,回流冷凝管中溶剂回流流速稳定,分水器中出现水层,每小时记录一次出水量,当出水量小于0.1g/h时,反应结束,反应时长16~18h。
反应结束后,降温至45℃,向上述反应后产物中加入100g甲苯,加入50g水洗涤,于40℃搅拌5min后置于分液漏斗中静置分水。于40℃,再加入50g 1N碳酸氢钠和1N氢氧化钠水溶液中和,静置分水,此操作重复3遍。中和完成后,加入0.3g对羟基苯甲醚,旋干溶剂,得无色透明粘稠单体A1,1H NMR(400MHz,CDCl3)δ6.43(d,1H,-CH=CH2),6.12(m,1H,-CH=CH2),5.86(d,1H,-CH=CH2),5.29(m,0.5,-OH),4.40(m,1.6H,-CH2-),4.19(m,1.9H,-CH2-),3.74(m,3H,-CH2-),核磁结果表明成功将丙烯酸接到甘油丙三醇上,但有羟基残余。单体A1酸值1.58mg KOH/g样品,粘度3500~4000cps@30℃,羟值436.21mg KOH/g样品。
S2.烯醇醚改性丙烯酸酯化合物
单体M1合成,单体M1由化合物M1(Ⅱ)和化合物M1(Ⅲ)组成并混有化合物A1(Ⅰ),结构如下:
操作步骤:100g实施例1步骤S1.反应所得单体A1,加入57.80g 2,3-二氢呋喃,于50℃搅拌,直至羟值低于3mg KOH/g样品时,停止反应,反应时长约12h。所得单体M1各项参数:羟值1.43mg KOH/g样品,粘度275cps@30℃。结果表明2,3-二氢呋喃与甘油丙烯酸酯化后残余羟基发生反应,有效降低甘油丙烯酸酯化产物粘度。
实施例2
本实施例的改性丙烯酸酯的制备方法如下:
S1.季戊四醇和丙烯酸酯化后所得单体A2,即化合物A2,结构如下
操作步骤:四口烧瓶配以搅拌桨,温度计,分水器,分水器上部连接回流冷凝管。100g季戊四醇和168g丙烯酸置于500ml四口烧瓶中,加入4.4g对羟基苯甲醚,8.9g对甲苯磺酸,1.98g次磷酸,100g甲苯,搅拌均匀后,开启真空泵30KPa,升温至体系温度为82℃时,回流冷凝管中溶剂回流流速稳定,分水器中出现水层,每小时记录一次出水量,当出水量小于0.1g/h时,反应结束,反应时长16~18h。
反应结束后,降温至45℃,向上述反应后产物中加入100g甲苯,加入50g水洗涤,于40℃搅拌5min后置于分液漏斗中静置分水。于40℃,再加入50g 1N碳酸氢钠和1N氢氧化钠水溶液中和,静置分水,此操作重复3遍。中和完成后,加入0.3g对羟基苯甲醚,旋干溶剂,得无色透明粘稠单体A2,1H NMR(400MHz,CDCl3)δ6.48(d,3H,-CH=CH2),6.16(m,3H,-CH=CH2),5.81(d,3H,-CH=CH2),4.19(m,1.2H,-OH),3.95(s,6H,-CH2-),3.89(m,2.3H,-CH2-OH),核磁结果表明成功将丙烯酸接到季戊四醇上,但有羟基残余。单体A2酸值1.58mg KOH/g样品,粘度1250cps@30℃,羟值208.13mg KOH/g样品。
S2.烯醇醚改性丙烯酸酯化合物
单体M2合成,结构如下:
操作步骤:100g实施例2步骤S1反应所得单体A2,加入39.07g乙烯基正丁醚,于45℃搅拌,直至羟值低于3mg KOH/g样品时,停止反应,反应时长约18h。所得单体M2各项参数:羟值1.43mg KOH/g样品,粘度468cps@30℃。结果表明乙烯基正丁醚与季戊四醇丙烯酸酯化后残余羟基发生反应,有效降低季戊四醇丙烯酸酯化产物粘度。
实施例3
本实施例的改性丙烯酸酯的制备方法如下:
S1.对羟甲基环己醇和丙烯酸酯化后所得单体A3,为两种分子的混合物,结构如下:
操作步骤:四口烧瓶配以搅拌桨,温度计,分水器,分水器上部连接回流冷凝管。150.2g对羟甲基环己醇和92g丙烯酸置于500mL四口烧瓶中,加入4.2g对羟基苯甲醚,8.6g对甲苯磺酸,1.95g次磷酸,80g甲苯,搅拌均匀后,开启真空泵30KPa,升温至体系温度为86℃时,回流冷凝管中溶剂回流流速稳定,分水器中出现水层,每小时记录一次出水量,当出水量小于0.1g/h时,反应结束,反应时长16~18h。
反应结束后,降温至45℃,向上述反应后产物中加入80g甲苯,加入50g水洗涤,于40℃搅拌5min后置于分液漏斗中静置分水。于40℃,再加入50g 1N碳酸氢钠和1N氢氧化钠水溶液中和,静置分水,此操作重复3遍。中和完成后,加入0.3g对羟基苯甲醚,旋干溶剂,得无色透明粘稠单体A3,1H NMR(400MHz,CDCl3)δ6.43(d,1H,-CH=CH2),6.15(m,1H,-CH=CH2),5.79(d,1H,-CH=CH2),4.83(m,0.3H,-OH),4.05(d,1.5H),3.48(m,0.7H),2.03(m,0.7H),1.75(m,1.5H),1.60(m,1.6H),1.40(m,1.7H),1.38(m,1.4H).核磁结果表明成功将丙烯酸接到对羟甲基环己醇上,但有羟基残余。单体A3酸值1.58mg KOH/g样品,粘度60cps@30℃,羟值98mg KOH/g样品。
S2.烯醇醚改性丙烯酸酯化合物
单体M3合成,单体M3由化合物M3组成,混合有化合物A3(Ⅰ),结构如下:
操作步骤:100g实施例3步骤S1.反应所得单体A3,加入13g 2,3-二氢呋喃,于50℃搅拌,直至羟值低于3mg KOH/g样品时,停止反应,反应时长约12h。所得单体M3各项参数:羟值1.54mg KOH/g样品,粘度30cps@30℃。结果表明2,3-二氢呋喃与对羟甲基环己醇丙烯酸酯化后残余羟基发生反应,降低甘油丙烯酸酯化产物粘度。
试验例1~6及对照例1~2
配制光固化组合物,如表1所示,试验例1~6以实施例1~3制得的改性丙烯酸酯M1~M3作为活性稀释剂,对照例1~2以三羟甲基丙烷三丙烯酸酯(TMPTA)活性稀释剂,其中对照例2还添加了助剂BDMA(N,N-二甲基苄胺)。
步骤:取活性稀释剂50g、活性稀释剂聚乙二醇200双丙烯酸酯PEGDA-20050g、六官能聚氨酯丙烯酸酯B605(广东博兴新材料有限公司)150g,光引发剂异丙基硫杂蒽酮ITX2.5g(1wt%),助剂BDMA 2.5g(1wt%)搅拌均匀,线棒涂膜玻璃板上,控制膜厚约25μm。分别以不同光源辐照固化,1000W中压汞灯辐照光强24.9mW/cm2,375UV LED辐照光强260mW/cm2,辐照时间10sec。以指触法检测表面固化情况,涂层表面出现指纹压痕,以×表示,表明存在显著表面氧阻聚;涂层表面未出现指纹压痕,以⊙表示,表明光固化表面氧阻聚得到克服,即表明表层光交联较好。试验结果如表1所示。
以上试验例1~6及对照例1~2所采用的光引发剂均为异丙基硫杂蒽酮ITX,该光引发剂为TypeⅡ型光引发剂,需搭配氢供体助剂如叔胺类使用,才可以快速有效产生活性自由基,引发双键聚合。实施例1~3制备的改性丙烯酸酯具有含活泼α-氢的缩醛基团,可作为氢供体,搭配ITX使用,无需添加额外氢供体助剂,有效提高光引发体系的引发性能,促进体系光交联。
根据表1的结果可知,实施例1~3制备的改性丙烯酸酯粘度低且具有可提高光固化活性的特点,制得的光固化组合物易固化、表干快,可有效解决表面氧阻聚问题,促进光交联。
表1不同活性稀释剂对体系表面氧阻聚的影响
活性稀释剂体系 | 辐照方式 | 指触法结果 | |
试验例1 | 单体M<sub>1</sub> | 中压汞灯 | ⊙ |
试验例2 | 单体M<sub>2</sub> | 中压汞灯 | ⊙ |
试验例3 | 单体M<sub>3</sub> | 中压汞灯 | ⊙ |
试验例4 | 单体M<sub>1</sub> | 375UVLED | ⊙ |
试验例5 | 单体M<sub>2</sub> | 375UVLED | ⊙ |
试验例6 | 单体M<sub>3</sub> | 375UVLED | ⊙ |
对照例1 | 单体TMPTA | 中压汞灯 | × |
对照例2 | 单体TMPTA+助剂BDMA | 中压汞灯 | ⊙ |
试验例7~9
试验例7~9为制备的改性丙烯酸酯在导电胶粘剂中的应用。
配方:石墨烯包裹镀铜粒子5wt%,环氧树脂B-183 30wt%,光引发剂TPO5wt%,聚氨酯丙烯酸酯2111 50wt%,分散助剂路博润24000 4wt%,改性丙烯酸酯5wt%。试验例7~9采用实施例1~3制备的改性丙烯酸酯,对照例3采用TMPTA。
实验操作:依次将环氧树脂、分散助剂、石墨烯包裹镀铜粒子加入混合分散1~2小时,之后加入光引发剂,聚氨酯丙烯酸酯及单体,搅拌30min。
断裂强度测试:将上述混合物固化成膜,膜厚50微米,WDS单臂式数显电子拉力试验机;
根据表2,本发明制备的改性丙烯酸酯有助于石墨烯包裹镀铜粒子与体系的结合,增强内聚强度,石墨烯包裹镀铜粒子在实施例1~3制备的改性丙烯酸酯的体系中的断裂强度更高。
表2不同单体体系在制备导电胶粘剂时的影响
显然,本发明的上述实施例仅仅是为清楚地说明本发明所作的举例,而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明权利要求的保护范围之内。
Claims (6)
3.根据权利要求2所述的制备方法,其特征在于,所述烯醇醚为乙烯基丁醚或2,3-二氢呋喃中的一种或几种。
4.根据权利要求2所述的制备方法,其特征在于,所述烯醇醚的摩尔数与式(Ⅲ)化合物的羟基摩尔数的比值为1~1.5。
5.根据权利要求2所述的制备方法,其特征在于,步骤S2.反应温度为30~80℃,反应时间为3~24h。
6.权利要求1所述改性丙烯酸酯在制备光固化组合物或导电胶粘剂中的应用。
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