CN112876599B - 一种适用于uv光固化体系的固体丙烯酸树脂的制备工艺 - Google Patents
一种适用于uv光固化体系的固体丙烯酸树脂的制备工艺 Download PDFInfo
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- CN112876599B CN112876599B CN201911196742.5A CN201911196742A CN112876599B CN 112876599 B CN112876599 B CN 112876599B CN 201911196742 A CN201911196742 A CN 201911196742A CN 112876599 B CN112876599 B CN 112876599B
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Abstract
本发明公开了一种适用于UV光固化体系的固体丙烯酸树脂的制备工艺,为本体聚合法,具体操作包括:将100质量份的至少一种每分子具有一个可聚合双键的单官能单体与1~10质量份的一种每分子具有两个可聚合双键的双官能单体及0.1~5.0质量份的引发剂和1~10质量份的链转移剂均加入能实现水浴加热的本体聚合反应器中,搅拌混合均匀后,使本体聚合反应器在40~90℃的恒温水浴加热下持续进行聚合反应,直至聚合反应结束。本发明不仅具有制备工艺简单、反应周期短、环保节能、易于实现批量化等优点,而且所制备的固体丙烯酸树脂具有可溶解性、带有双键活性、与多种UV单体能相容且具有高固低粘特性等诸多优点。
Description
技术领域
本发明是涉及一种固体丙烯酸树脂的制备工艺,具体说,是涉及一种适用于UV光固化体系的固体丙烯酸树脂的制备工艺,属于功能材料制备技术领域。
背景技术
近年来,随着人们环保意识进一步加强和我国环保政策的相继出台,工业行业也随之发生巨大的变化,其中化工行业首当其冲,在新环境下面临着新的考验。由于UV光固化技术是一种环保、低VOC排放技术,UV光固化成膜拥有高效、节能、环境友好、经济、适应性强等优点,因此UV光固化技术已成为当今主要发展和研究热点之一。
又由于丙烯酸树脂具有良好的保光保色性、耐候性、干燥快、施工方便、易于施工、重涂和返工等优点,因此现有技术中通常将其添加到UV光固化体系中,以起到调节配方粘度、降低收缩率、降低成本、增加初粘力、加快表干、提高层间附着力等作用。但目前用于UV光固化体系中的丙烯酸树脂主要为饱和树脂,在光固化成膜过程中不能发生进一步交联反应,只是作为惰性添加物/助剂用于UV光固化体系中,这种物理包覆式组合使用方式影响了涂膜硬度、与基材的附着力、耐醇性能和抗腐蚀能力等物化性能,因而局限了其广泛应用。
另外,随着当前环保要求的日益提高,越来越多涂料厂商希望可以将溶剂型涂料的固含提高,但使用现有丙烯酸树脂增加固含会遇到以下两个难题:在高固含下难以继续溶解;在高固含下涂料粘度过大,导致产品无法正常涂布施工;因此,高固低粘特性的丙烯酸树脂也已成为UV光固化应用领域渴求的理想产品。
还有,当前涂料及油墨用固体丙烯酸树脂主要是采用悬浮聚合法生产,因为本体聚合法在聚合中后期的聚合自加速效应,很容易导致产生爆聚及聚合温度难以控制的问题,容易导致所得到的固体丙烯酸树脂存在分子量分布过宽、分子量分布系数大、残留单体多等问题,若使用这样的固体丙烯酸树脂,很容易导致所制造的涂料或油墨存在:储存稳定性差,在储存期间易产生沉淀、分层以及发花现象;气味大;与基材的附着力差;易产生起泡、剥落、变色、收缩等缺陷问题。但由公知常识可知:悬浮聚合法存在废水处理问题,不符合当今环保要求;并且,在聚合末期需要使用阻聚剂来终止反应,工艺控制要求苛刻,产品质量一致性差,不良率高;而本体聚合法,在聚合过程中只需加入单体、引发剂及分子量调节剂,无需溶剂,没有废水产生,环境友好,生产效率高,生产成本低,且产物纯净,产品色泽均一、产品质量一致性好,现已成为当今工业化鼓励发展的聚合工艺。因此,如何实现本体聚合法工业化生产分子量分布窄、残留单体低、综合性能优异的固体丙烯酸树脂,也成为本领域当前热点研究问题之一。
发明内容
针对现有技术存在的上述问题和需求,本发明的目的是提供一种适用于UV光固化体系的固体丙烯酸树脂的制备工艺。
为实现上述发明目的,本发明采用的技术方案如下:
一种适用于UV光固化体系的固体丙烯酸树脂的制备工艺,为本体聚合法,具体操作包括:将100质量份的至少一种每分子具有一个可聚合双键的单官能单体与1~10质量份的一种每分子具有两个可聚合双键的双官能单体及0.1~5.0质量份的引发剂和1~10质量份的链转移剂均加入能实现水浴加热的本体聚合反应器中,搅拌混合均匀后,使本体聚合反应器在40~90℃的恒温水浴加热下持续进行聚合反应,直至聚合反应结束。
一种优选方案,所述制备工艺的具体操作包括:将100质量份的两种每分子具有一个可聚合双键的单官能单体与1~5质量份的一种每分子具有两个可聚合双键的双官能单体及0.3~2.0质量份的引发剂和3~6质量份的链转移剂均加入能实现水浴加热的本体聚合反应器中,搅拌混合均匀后,使本体聚合反应器在50~60℃的恒温水浴加热下持续进行聚合反应,直至聚合反应结束。
一种优选方案,所述的单官能单体选自甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸异辛酯、甲基丙烯酸异冰片酯、甲基丙烯酸月桂酯、甲基丙烯酸、丙烯酸、丙烯酸乙酯、丙烯酸甲酯、丙烯酸丁酯、丙烯酸异辛酯、丙烯酸月桂酯、苯乙烯中的至少一种。
一种优选方案,所述的单官能单体为甲基丙烯酸甲酯与甲基丙烯酸正丁酯的组合。
进一步优选方案,100质量份的单官能单体中,甲基丙烯酸甲酯与甲基丙烯酸正丁酯的组合质量比为2:1~3:1。
一种优选方案,所述的双官能单体选自二丙烯酸乙二醇酯、二丙烯酸己二醇酯、二丙烯酸三丙二醇酯、二丙烯酸丁二醇酯、二丙烯酸新戊二醇酯、二丙烯酸二甘醇酯、二丙烯酸三甘醇酯、二丙烯酸二丙二醇酯、丙烯酸烯丙基酯中的至少一种。
一种优选方案,所述引发剂是由主引发剂和助引发剂组成,其中助引发剂的质量占比为0~20%。
一种优选方案,所述主引发剂选自偶氮二异丁腈、1-叔-戊基偶氮-1-氰基环己烷、过氧化月桂酰、1-叔-丁基偶氮-1-氰基环己烷、过辛酸叔丁酯、过氧化-2-乙基己酸叔丁酯、过苯甲酸叔丁酯、过安息香酸丁酯、过氧化甲酸叔丁酯、过氧化二叔丁基、过氧化氢二异丙苯、叔戊基过氧化氢、叔丁基过氧化氢中的至少一种;所述助引发剂选自2,2-双(过氧化叔丁基)丁烷、2,5-二甲基-2,5-二(叔丁基过氧基)己烷(双二五硫化剂)、叔丁基过氧化六氢对苯二酸酯(KAYAESTER HTP-65W)中的至少一种。
一种优选方案,所述引发剂是由主引发剂和助引发剂组成,其中主引发剂为过氧化月桂酰,助引发剂为2,5-二甲基-2,5-二(叔丁基过氧基)己烷或叔丁基过氧化六氢对苯二酸酯,且主引发剂与助引发剂的质量比为5:1。
一种优选方案,所述链转移剂选自正丙基硫醇、正丁基硫醇、正辛基硫醇、正十二烷基硫醇、二硫酯、α-甲基苯乙烯二聚体中的至少一种。
与现有技术相比,本发明具有如下显著的有益效果:
1)经检测分析得知:采用本发明制备工艺可获得单体残留率低(可低于1%)且分子量分布窄(PD可小于3.0)的固体丙烯酸树脂;
2)经检测分析得知:采用本发明制备工艺获得的固体丙烯酸树脂中带有活性双键,因此,当其用于UV光固化体系中,可参与UV光固化成膜反应,与UV光固化体系中的单体一同生成一体式的三维网状交联结构,从而有利于加快光固化速率和降低涂层的收缩率;
3)经实验验证:采用本发明制备工艺获得的固体丙烯酸树脂在有机溶剂中具有溶解性,可在室温下以30%固含溶解于二甲苯、二氯甲烷、乙酸乙酯等有机溶剂中,尤其在乙酸乙酯中的溶解性可达到60%固含,非常有利于在高固UV光固化体系中使用;
4)经应用试验证明:采用本发明制备工艺获得的固体丙烯酸树脂具有高固低粘特性,30%固含的乙酸乙酯溶液的粘度只有17mpa﹒s,尤其是,50%固含的乙酸乙酯溶液的粘度也只有280mpa﹒s,非常有利于实现高固配方,以降低有机溶剂的使用,更有益于环保要求;
5)经实验验证:采用本发明制备工艺获得的固体丙烯酸树脂可与多种UV光固化单体之间具有很好的相容性,在温度为70℃下,可至少以15%的固含与多种UV光固化单体完全相容得到透明溶液,非常适用于UV光固化体系中;
6)经在PVC板材上涂膜实验得知:对于基材显现出更好的附着力,涂膜硬度达到H铅笔硬度,耐酒精和丁酮的擦拭能力强,耐酸碱和洗刷,涂膜产品无发白、起泡、剥落、变色等现象;
7)经光固化涂层应用试验得知:使用本发明所获得的固体丙烯酸树脂,可使光固化涂层具有更好的硬度(可达2H铅笔硬度)和更佳的耐溶剂性(以0.5公斤力,一个来回记为一次擦拭,可实现耐酒精500次擦拭,耐丁酮195次擦拭),非常适合用于制备UV光固化涂料或油漆中;
8)另外,本发明所述制备工艺还具有操作简单、反应周期短、环保节能、易于实现批量化和连续化生产等优点。
综上所述可见,相对于现有技术,本发明不仅具有显著性进步,而且产生了突出的有益效果。
附图说明
图1所示为饱和固体丙烯酸树脂(不含本发明所述的双官能单体TPGDA,只由MMA与BMA共聚得到)与本发明所获得的固体丙烯酸树脂的核磁共振氢谱对比图。
具体实施方式
下面结合实施例对本发明技术方案做进一步详细、完整地说明。
以下实施例和对比例中关于分子量分布的测定方法如下:
通过凝胶渗透色谱法测定所得固体丙烯酸树脂的分子量分布,使用不同分子量的PS作为标定物,四氢呋喃作为流动相,设置流速为1mL/min,使用RI检测器;使用四氢呋喃对样品进行溶解。
以下实施例和对比例中关于单体残留率的测定方法如下:
准确称量15g聚合物样品,将其溶解在100~150毫升的二氯甲烷中,然后加入1%W/W(相对于聚合物样品)的EMA作为内标;设置GC条件为进样口200摄氏度,柱温从100摄氏度在15分钟内升至230摄氏度保持15分钟,检测器温度200摄氏度,并在GC进样口设置过滤棉,以滤去未溶解物;测试所得残留单体峰面积与内标峰面积之比,即为聚合物中的单体残留率。
实施例1-3
将432克MMA(甲基丙烯酸甲酯)100、150克BMA(甲基丙烯酸正丁酯)、18克TPGDA(二丙烯酸三丙二醇酯)、3克过氧化月桂酰及30克正十二烷基硫醇均加入本体聚合袋中,搅拌使混合均匀后,将本体聚合袋置入水浴中,在水浴恒温加热下持续进行聚合反应,直至聚合反应结束(具体水浴温度和反应时间见表1所示),然后取出本体聚合袋,冷却至室温,将得到的固体丙烯酸树脂粉碎即得最终成品。
表1各实施例反应条件及测试结果
由表1所示结果可见:采用本发明方法可获得分子量分布窄、单体残留率低的固体丙烯酸树脂,尤其在水浴温度为55℃下恒温聚合反应,结果最优,不仅单体残留率低(2.81%),且分子量分布窄(PD值只有2.54)。
对比例1
本对比例与上述实施例2的区别仅在于:将水浴恒温加热替换为电恒温加热方式,即:将本体聚合袋置入55℃的恒温烘箱中进行聚合反应至结束,聚合反应结束后进行分子量分布和单体残留率检测,具体结果见表2所示。
对比例2
本对比例与上述实施例2的区别仅在于:将水浴恒温加热替换为电梯度升温加热方式,即:将本体聚合袋置入电烘箱中,先在55℃聚合反应16小时,然后升温到75℃聚合反应8小时,再升温到95℃聚合反应8小时,最后升温到至120℃聚合反应至结束,聚合反应结束后进行分子量分布和单体残留率检测,具体结果见表2所示。
表2各对比例反应条件及测试结果
对比表1和表2所示结果可见:在同等条件下,采用恒温水浴加热方式相对常规的电加热方式,产生了出乎意料的技术效果:反应周期显著缩短(由50小时缩短为10小时),单体残留率显著降低(由16.13%下降为2.81%),分子量分布得到显著改善(PD值由7.58降低到2.54);虽然采用常规本体聚合加热方式(梯度升温聚合)相对恒温电加热在单体残留率和分子量分布上有些许改善,但改善效果并不明显,且操作麻烦,操作风险高。
实施例4-5
将432克MMA(甲基丙烯酸甲酯)100、150克BMA(甲基丙烯酸正丁酯)、18克TPGDA(二丙烯酸三丙二醇酯)、3克过氧化月桂酰、0.6克2,5-二甲基-2,5-二(叔丁基过氧基)己烷(双二五硫化剂)或叔丁基过氧化六氢对苯二酸酯(KAYAESTER HTP-65W)及30克正十二烷基硫醇均加入本体聚合袋中,搅拌使混合均匀后,将本体聚合袋置入55℃的水浴中,在水浴恒温加热下持续进行聚合反应至聚合反应结束,然后进行分子量分布和单体残留率检测,具体结果见表3所示。
表3各实施例反应条件及测试结果
由表3所示结果可见:在同等条件下,当组合使用一定比例的助引发剂(双二五硫化剂或KAYAESTER HTP-65W)后,可使单体残留率得到显著降低(由2.81%降低到小于1%)。
核磁共振氢谱分析:
将20g两种树脂【饱和固体丙烯酸树脂(不含本发明所述的双官能单体TPGDA,只由MMA与BMA共聚得到)和本发明(可以为实施例2、4或5)所获得的固体丙烯酸树脂】首先在室温下分别溶解在5mL二氯甲烷中,然后将两种溶液分别逐滴加入到250mL正己烷中,边滴加边搅拌,两种树脂分别从二氯甲烷与正己烷的混合溶剂中沉淀出来,过滤后,得到经溶剂洗涤去除残留单体的两种树脂,然后放入40℃烘箱中烘烤直至干燥,冷却后进行核磁共振氢谱测试,得到图1所示图谱。
由图1所示可见:饱和固体丙烯酸树脂在5-7ppm之间无明显出峰,而本发明所获得的固体丙烯酸树脂在5-7ppm之间有明显的三组多重峰,对应为不饱和双键上的三个氢,三者的积分比为1:1:1。众所周知,核磁共振氢谱5-7ppm之间是脂肪族碳碳双键上氢的特征出峰区域,因此,由图1所示结果可见:本发明所获得的固体丙烯酸树脂带有活性双键,是一种不饱和树脂,当该固体丙烯酸树脂用于UV光固化体系中,可与UV单体一同进行光固化聚合,从而形成一体式的三维网状交联结构,可使得到的涂层的物化性能更佳,有利于加快光固化速率和降低涂层收缩率。
溶解性实验:
将本发明(可以为实施例2、4或5)所获得的固体丙烯酸树脂以30%固含于室温下分别溶解于二甲苯和二氯甲烷溶剂中,搅拌一段时间后,发现溶液澄清透明,无不溶物和浑浊现象,说明本发明(可以为实施例2、4或5)所获得的固体丙烯酸树脂在有机溶剂中具有优良的溶解性。
高固低粘特性检验:
将对比树脂,即:饱和固体丙烯酸树脂(不含本发明所述的双官能单体TPGDA,只由MMA与BMA共聚得到)和本发明树脂,即:实施例2、4或5所获得的固体丙烯酸树脂分别以30%,40%,50%,60%固含溶解在乙酸乙酯中,然后观察溶解速度和溶解情况,同时测试在各个固含下的旋转粘度。控制测试和溶解温度均为20摄氏度。
溶解情况观察如下:
在30%、40%和50%的固含下,虽然对比树脂和本发明树脂均可完全溶解,但本发明树脂溶解速度相对要快;而在60%固含下,本发明树脂静置过夜便完全溶解,但对比树脂静置三天也无法完全溶解,说明本发明树脂具有优异的溶解性能。
另外,在不同固含下的两种树脂的乙酸乙酯溶液的粘度测试数据如表4所示:
表4
样品 | 30%固含下粘度 | 40%固含下粘度 | 50%固含下粘度 |
本发明树脂 | 17mpa·s | 40mpa·s | 280mpa·s |
对比树脂 | 31mpa·s | 205mpa·s | >500mpa·s |
由表4所示粘度测试结果可见:本发明树脂具有高固低粘特性,能在UV光固化体系中添加更多的用量,而不会使体系粘度过大增加,可大大降低体系中的溶剂使用量,更有益于安全环保。
与UV单体的相容性实验:
表5显示了本发明树脂(即:实施例2、4或5所获得的固体丙烯酸树脂)在不同固含和温度下与各种UV单体的相容性情况:
表5
由表5所示可见:采用本发明制备工艺获得的固体丙烯酸树脂可与多种UV光固化单体之间具有很好的相容性,在温度为70℃下,可以至少15%的固含与多种UV光固化单体完全相容得到透明溶液,非常适用于UV光固化体系中。
涂膜性能测试:
将对比树脂,即:饱和固体丙烯酸树脂(不含本发明所述的双官能单体TPGDA,只由MMA与BMA共聚得到)和本发明树脂,即:实施例2、4或5所获得的固体丙烯酸树脂在PVC板材上涂膜,然后对形成的涂膜进行附着力、铅笔硬度、耐酒精性、耐丁酮性、耐酸碱性和耐洗刷性能测试,具体测试方法如下:
1)附着力:使用美国Defelsko PosiTest AT-A仪器进行定量测试,此仪器符合ASTM D4541/D7234,ISO 4624/16276-1,AS/NZS 1580.408.5标准。将经过溶剂挥发法手工制得的PVC涂膜样品与50mm锭子通过AB胶粘接在一起,过夜室温固化;仪器拉拔速率设置为0.03MPa/s,仪器量程为0.4-3.8Mpa;当仪器拉拔头将涂膜从基材上撕下时的读数,即为涂膜在该基材上的附着力。
2)铅笔硬度:将铅笔以45度倾角在涂膜上进行匀速刮划,刮划长度约为3厘米,重复5次,然后用橡皮轻轻擦去铅笔痕迹,观察在涂膜上有无留下划痕。首先使用HB铅笔进行第一次测试,若无划痕,则增加铅笔硬度,直至留下划痕;若有划痕,则降低铅笔硬度,直至无划痕出现,最后一次出现无划痕所使用的铅笔的硬度,即为测试结果。
3)耐酒精性:将脱脂棉球在98%的乙醇中完全浸湿,以均匀力在涂膜上来回擦拭,一个来回记为一次擦拭,若涂膜在重复擦拭下被擦除,露出了基材,则此时记下擦拭次数,即为涂膜的耐酒精性。
4)耐丁酮性:测试方法与耐酒精性测试类似,只是将溶剂由乙醇改为丁酮。
5)参考GBT17748-2008进行耐酸碱和耐洗刷性能测试。
具体测试结果见表6所示:
表6
由表6所示结果可见:本发明树脂对于基材显现出更好的附着力,涂膜硬度达到H铅笔硬度,耐酒精和丁酮的擦拭能力强,且耐酸碱和洗刷。
光固化涂层性能测试:
分别使用对比树脂,即:饱和固体丙烯酸树脂(不含本发明所述的双官能单体TPGDA,只由MMA与BMA共聚得到)和本发明树脂,即:实施例2、4或5所获得的固体丙烯酸树脂(15%)与TPGDA单体(80%)和光引发剂二苯甲酮(5%)配成一个简单的光固化配方,进行紫外光固化对比试验及对得到的光固化涂层进行附着力(胶带法;PVC基材)、铅笔硬度、耐酒精性、耐溶剂性测试对比,测试结果见表7所示:
表7
由表7可知:使用本发明所获得的固体丙烯酸树脂,不仅可使光固化涂层具有更好的硬度(可达2H铅笔硬度)和更佳的耐溶剂性(以0.5公斤力,一个来回记为一次擦拭,可实现耐酒精500次擦拭,耐丁酮195次擦拭),而且可加快光固化速率,非常适合用于制备UV光固化涂料或油漆中。
另外,本发明所获得的固体丙烯酸树脂的重均分子量在25000~30000,玻璃化转变温度在30~50℃,特性粘度值为0.08~0.14。
综上所述可见,采用本发明方法制备的固体丙烯酸树脂不仅具有活性双键、可参与后续UV光固化体系中的交联反应,有利于加快光固化速率和降低涂层的收缩率;而且具有有机溶剂溶解性和高固低粘特性,并能与多种UV单体实现至少15%固含的相容性,涂膜和形成的光固化涂层的硬度高,耐溶剂性能显著,非常适合在UV光固化体系中应用,相对于现有技术,本发明产生了显著性进步和出乎意料的技术效果。
最后需要在此指出的是:以上仅是本发明的部分优选实施例,不能理解为对本发明保护范围的限制,本领域的技术人员根据本发明的上述内容做出的一些非本质的改进和调整均属于本发明的保护范围。
Claims (5)
1.一种适用于UV光固化体系、且带有活性双键的不饱和固体丙烯酸树脂的制备方法,为本体聚合法,其特征在于,具体操作包括:将100质量份的两种每分子具有一个可聚合双键的单官能单体与1~5质量份的一种每分子具有两个可聚合双键的双官能单体及0.3~2质量份的引发剂和3~6质量份的链转移剂均加入能实现水浴加热的本体聚合反应器中,搅拌混合均匀后,使本体聚合反应器在50~60℃的恒温水浴加热下持续进行聚合反应,直至聚合反应结束;且,所述的单官能单体选自甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸异辛酯、甲基丙烯酸异冰片酯、甲基丙烯酸月桂酯、甲基丙烯酸、丙烯酸、丙烯酸乙酯、丙烯酸甲酯、丙烯酸丁酯、丙烯酸异辛酯、丙烯酸月桂酯、苯乙烯中的至少一种;所述的双官能单体选自二丙烯酸乙二醇酯、二丙烯酸己二醇酯、二丙烯酸三丙二醇酯、二丙烯酸丁二醇酯、二丙烯酸新戊二醇酯、二丙烯酸二甘醇酯、二丙烯酸三甘醇酯、二丙烯酸二丙二醇酯、丙烯酸烯丙基酯中的至少一种;所述引发剂是由主引发剂和助引发剂组成,所述主引发剂为过氧化月桂酰,所述助引发剂为2,5-二甲基-2,5-二(叔丁基过氧基)己烷或叔丁基过氧化六氢对苯二酸酯,在所述引发剂中,助引发剂的质量占比为0~20%。
2.根据权利要求1所述的制备方法,其特征在于:所述的单官能单体为甲基丙烯酸甲酯与甲基丙烯酸正丁酯的组合。
3.根据权利要求2所述的制备方法,其特征在于:100质量份的单官能单体中,甲基丙烯酸甲酯与甲基丙烯酸正丁酯的组合质量比为2:1~3:1。
4.根据权利要求1所述的制备方法,其特征在于:在所述引发剂中,主引发剂与助引发剂的质量比为5:1。
5.根据权利要求1所述的制备方法,其特征在于:所述链转移剂选自正丙基硫醇、正丁基硫醇、正辛基硫醇、正十二烷基硫醇、二硫酯、α-甲基苯乙烯二聚体中的至少一种。
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