CN116903798A - 一种光固化液体硅橡胶及其制备方法 - Google Patents
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Abstract
本发明公开一种光固化液体硅橡胶及其制备方法,该硅橡胶包括以下原料:有机硅聚氨酯丙烯酸酯树脂、SEBS橡胶和活性稀释剂。所述有机硅聚氨酯丙烯酸酯树脂的合成原料包括二元异氰酸酯单体、双羟基封端聚二甲基硅氧烷、单羟基丙烯酸酯单体、多羟基支化单体。本发明采用光固化技术极大的缩短了液体硅橡胶的硫化时间,并结合了SEBS橡胶提高了液体硅橡胶的抗压缩永久变形及力学性能。
Description
技术领域
本发明属于液体硅橡胶技术领域,具体涉及一种光固化液体硅橡胶及其制备方法。
背景技术
硅橡胶因其特殊的的分子结构,在电子信息设备、机械工程设备、汽车及其制造设备等领域中起着至关重要的作用。
传统热固化液体硅橡胶采用含氢硅油及乙烯基硅油,固化能耗高、速度慢、工艺复杂、设备成本及占地面积大,且单组份液体硅橡胶储存稳定性较差。光固化技术能有效减少工业能耗、可以极大提高工作效率,只需紫外光照射数秒便能实现固化。工艺简单,危险系数低,无需增加大型设备;也可采用手持紫外灯源固化,在在线固化垫圈技术领域具有极高的应用价值。能在汽车、电子、建筑等多个领域均具有广泛应用。
中国专利CN202310536870.X披露了一种低温快速硫化的加成型液态硅橡胶及其制备方法,具体的说:采用白炭黑、乙烯基封端聚硅氧烷、催化剂、抑制剂、交联剂制备了一种操作时间≥120min,硫化温度80℃的硫化速度T90为88s的加成型液态硅橡胶,解决了液态硅橡胶低温固化慢、操作时间短的问题。
中国专利CN202211596853.7披露了一种电子束辐照交联硅橡胶及其制备工艺,具体的说:采用甲基乙烯基生胶、气相白炭黑与氢氧化铝微粉在140~160℃下混合制得生胶,将生胶与硅油、偶联剂、双二五硫化剂等在140~160℃下混合制得混合胶,经电子束辐射处理,得电子束辐射交联硅橡胶。结合了高温硫化和电子束辐射硫化的优点。
因此,现有液体硅橡胶存在以下问题:①以热固化为主:固化效率低、设备成本高、能耗大;②较难适用于各类不同形状,各类大小的装配件;③操作时间较短;④储存稳定性较差;现有技术需要进一步改进。
发明内容
为解决上述问题本发明提供了一种光固化液体硅橡胶及其制备方法,包括以下原料:有机硅聚氨酯丙烯酸酯树脂、SEBS橡胶和活性稀释剂。其中,有机硅聚氨酯丙烯酸酯树脂1-5g、SEBS橡胶1-2.5g、活性稀释剂1-10g。
进一步地,所述有机硅聚氨酯丙烯酸酯树脂的合成原料包括二元异氰酸酯单体、双羟基封端聚二甲基硅氧烷、单羟基丙烯酸酯单体、多羟基支化单体。
进一步地,所述二元异氰酸酯单体为异弗尔酮二异氰酸酯。
进一步地,所述双羟基封端聚二甲基硅氧烷为4000分子量的羟丙基聚二甲基硅氧烷或2000分子量的羟丙基聚二甲基硅氧烷中的一种。
进一步地,所述单羟基丙烯酸酯单体为丙烯酸羟乙酯。
进一步地,所述多羟基支化单体为丙三醇。
进一步地,所述有机硅聚氨酯丙烯酸酯树脂由以下方法合成:
步骤a1、扩链:将二异氰酸酯单体和溶剂加入带有搅拌装置、温度计、冷凝管和恒压滴液漏斗的四颈烧瓶中,取双羟基封端聚二甲基硅氧烷与催化剂混合液,在45~65℃下缓慢滴加入烧瓶中,滴加完后升温至60~75℃后再反应2~4h;
步骤a2、封端:再将温度降至45~65℃,缓慢滴加入单羟基丙烯酸酯单体、催化剂、阻聚剂和溶剂的混合物,滴加完后在60~75℃下反应2~4h;
步骤a3、支化:再缓慢滴加多羟基支化单体与催化剂的混合溶液,继续反应2~4h,反应完后除去溶剂即得有机硅聚氨酯丙烯酸酯树脂。
进一步地,所述二异氰酸酯单体与双羟基封端聚二甲基硅氧烷摩尔用量比为1:(0.5~0.7),二异氰酸酯单体与单羟基丙烯酸酯单体摩尔用量比为1:(0.3~0.55),二异氰酸酯单体与多羟基支化单体摩尔用量比为1:(0.07~0.16)。
进一步地,所述一种光固化液体硅橡胶的制备方法,包括以下步骤:
步骤b1、将SEBS橡胶(苯乙烯-乙烯-丁二烯-苯乙烯嵌段共聚物)与活性稀释剂在70~110℃下混合均匀;
步骤b2、将b1制备的混合液加入到有机硅聚氨酯丙烯酸酯树脂中,并加入光引发剂和气相二氧化硅搅拌均匀。采用UV固化即得硅橡胶。
进一步地,所述活性稀释剂为四氢呋喃丙烯酸酯。
采用上述技术方案,本发明可取得的有益效果是:
①本发明制备的一种光固化液体硅橡胶采用异氰酸酯改性有机硅,并引入可光固化基团丙烯酰氧基,使得本发明所制备的液体硅橡胶在100Mw/cm2功率的紫外灯下,辐照30s即可实现固化,固化效率快,极大地缩短了液体硅橡胶硫化时间。
②本发明制备的一种光固化液体硅橡胶,共混了部分SEBS硅橡胶,SEBS较好的耐压缩变形及力学性能,提高了硅橡胶弹性体的压缩回弹性能和拉伸强度。
③本发明制备的一种光固化液体硅橡胶,反应性基团为丙烯酰氧基,较添加有铂催化剂的含氢硅油与乙烯基硅油的体系,具有更好的稳定性。
附图说明
图1为本发明的工艺流程图;
图2为实施例1中甘油、IPDI、HEA和支化型有机硅聚氨酯丙烯酸酯预聚体红外光谱;
图3为实施案例2中样品反应过程中扩链、封端和支化后的红外光谱图;
图4为实施例5-10的应力-应变图。
具体实施方式
下面结合实施例对本发明进一步详细的阐明,但本发明的内容不仅仅局限于下面的实施例。
以下实施例1-3为支化型有机硅聚氨酯丙烯酸酯树脂的合成,实施例4-6、对比例1-4为光固化液体硅橡胶的制备。
实施例1:
支化型有机硅聚氨酯丙烯酸酯树脂的合成:
(1)扩链:将异佛尔酮二异氰酸酯(IPDI,0.25mol)和溶剂丙酮加入配备聚四氟乙烯搅拌杆、温度计、冷凝管和恒压滴液漏斗的四颈烧瓶中,将羟丙基聚二甲基硅氧烷(PDMS,Mn=2000,0.125mol)与催化剂二月桂酸二丁基锡(DBTDL,0.2wt.%,0.65g)混合均匀后,55℃下将混合溶液逐滴加入到反应体系中,将温度升至60℃后再反应3h。
(2)封端:将反应体系温度降至55℃后,将定量的丙烯酸羟乙酯(HEA,0.135mol)、DBTDL(0.2wt.%,0.65g)和丙酮稀释后的阻聚剂对羟基苯甲醚(MEHQ,0.5wt.%,1.62g)混合均匀,缓慢滴入反应体系中,65℃下反应2h。
(3)支化:再加入丙三醇(0.0385mol)与DBTDL(0.1wt.%,0.32g),继续反应3h,并使用傅里叶红外光谱监测反应终点,直至-NCO的特征吸收峰2270cm-1完全反应消失,即得支化型有机硅聚氨酯丙烯酸酯树脂。。
实施例2:
支化型有机硅聚氨酯丙烯酸酯树脂的合成:
(1)扩链:将异佛尔酮二异氰酸酯(IPDI,0.25mol)和溶剂丙酮加入配备聚四氟乙烯搅拌杆、温度计、冷凝管和恒压滴液漏斗的四颈烧瓶中,将羟丙基聚二甲基硅氧烷(PDMS,Mn=4000,0.125mol)与催化剂二月桂酸二丁基锡(DBTDL,0.2wt.%,1.148g)混合均匀后,55℃下按比例将混合溶液逐滴加入到反应体系中,将温度升至60℃后再反应2h。
(2)封端:将反应体系温度降至55℃后,将定量的丙烯酸羟乙酯(HEA,0.135mol)、DBTDL(0.2wt.%,1.148g)和丙酮稀释后的阻聚剂对羟基苯甲醚(MEHQ,0.5wt.%,2.87g)混合均匀,缓慢滴入反应体系中,60℃下反应3h。
(3)支化:再加入丙三醇(0.0385mol)与DBTDL(0.1wt.%,0.574g),继续反应3h,并使用傅里叶红外光谱监测反应终点,直至-NCO的特征吸收峰2270cm-1完全反应消失,即得支化型有机硅聚氨酯丙烯酸酯树脂。。
实施例3:
支化型有机硅聚氨酯丙烯酸酯树脂的合成:
(1)扩链:将异佛尔酮二异氰酸酯(IPDI,0.25mol)和溶剂丙酮加入配备聚四氟乙烯搅拌杆、温度计、冷凝管和恒压滴液漏斗的四颈烧瓶中,将羟丙基聚二甲基硅氧烷(PDMS,Mn=2000,0.125mol)与催化剂二月桂酸二丁基锡(DBTDL,0.2wt.%,0.66g)混合均匀后,55℃下按比例将混合溶液逐滴加入到反应体系中,将温度升至60℃后再反应2h。
(2)封端:将反应体系温度降至55℃后,将定量的丙烯酸羟乙酯(HEA,0.18mol)、DBTDL(0.2wt.%,0.66g)和丙酮稀释后的阻聚剂对羟基苯甲醚(MEHQ,0.5wt.%,1.64g)混合均匀,缓慢滴入反应体系中,60℃下反应3h。
(3)支化:再加入丙三醇(0.023mol)与DBTDL(0.1wt.%,0.328g),继续反应3h,并使用傅里叶红外光谱监测反应终点,直至-NCO的特征吸收峰2270cm-1完全反应消失,即得支化型有机硅聚氨酯丙烯酸酯树脂。
实施例4:
光固化液体硅橡胶弹性体的制备:
(1)将2.5g SEBS橡胶(苯乙烯-乙烯-丁二烯-苯乙烯嵌段共聚物)与10g稀释剂四氢呋喃丙烯酸酯(THFA)混合,100℃下充分搅拌至二者完全相溶。
(2)将实例1制备的5g支化型有机硅聚氨酯丙烯酸酯与5g上述混合溶液混合搅拌5min,再加入1g气相二氧化硅和0.5g光引发剂2-羟基-2-甲基苯基丙酮(1173)避光混合搅拌5min,再将配置好的预聚物倒入聚四氟乙烯模具中,在紫外光固化机上光照30s后,得到弹性体。
实施例5:
光固化液体硅橡胶弹性体的制备:
(1)将2.5g SEBS橡胶(苯乙烯-乙烯-丁二烯-苯乙烯嵌段共聚物)与10g稀释剂四氢呋喃丙烯酸酯(THFA)混合,100℃下充分搅拌至二者完全相溶。
(2)将实例2制备的5g支化型有机硅聚氨酯丙烯酸酯与5g上述混合溶液混合搅拌5min,再加入1g气相二氧化硅和0.5g光引发剂2-羟基-2-甲基苯基丙酮(1173)避光混合搅拌5min,再将配置好的预聚物倒入聚四氟乙烯模具中,在紫外光固化机上光照30s后,得到弹性体。
实施例6:
光固化液体硅橡胶弹性体的制备:
(1)将2.5g SEBS橡胶(苯乙烯-乙烯-丁二烯-苯乙烯嵌段共聚物)与10g稀释剂四氢呋喃丙烯酸酯(THFA)混合,100℃下充分搅拌至二者完全相溶。
(2)将实例3制备的5g支化型有机硅聚氨酯丙烯酸酯与5g上述混合溶液混合搅拌5min,再加入1g气相二氧化硅和0.5g光引发剂2-羟基-2-甲基苯基丙酮(1173)避光混合搅拌5min,再将配置好的预聚物倒入聚四氟乙烯模具中,在紫外光固化机上光照30s后,得到弹性体。
对比例1:
光固化液体硅橡胶弹性体的制备:
将实例1制备的5g支化型有机硅聚氨酯丙烯酸酯与0.55gTHFA混合搅拌5min,再加入0.2775g气相二氧化硅和0.111g光引发1173避光混合搅拌5min,再将配置好的预聚物倒入聚四氟乙烯模具中,在紫外光固化机上光照30s后,得到弹性体。
对比例2:
光固化液体硅橡胶弹性体的制备:
将实例2制备的5g支化型有机硅聚氨酯丙烯酸酯和0.1g光引发剂1173避光混合搅拌5min,再将配置好的预聚物倒入聚四氟乙烯模具中,在紫外光固化机上光照30s后,得到弹性体。
对比例3:
光固化液体硅橡胶弹性体的制备:
将实例2制备的5g支化型有机硅聚氨酯丙烯酸酯和0.55gTHFA混合搅拌5min,再加入0.111g光引发剂1173避光混合搅拌5min,再将配置好的预聚物倒入聚四氟乙烯模具中,在紫外光固化机上光照30s后,得到弹性体。
对比例4:
光固化液体硅橡胶弹性体的制备:
将实例3制备的5g支化型有机硅聚氨酯丙烯酸酯与0.55gTHFA混合搅拌5min,再加入0.2775g气相二氧化硅和0.111g光引发1173避光混合搅拌5min,再将配置好的预聚物倒入聚四氟乙烯模具中,在紫外光固化机上光照30s后,得到弹性体。
效果验证例1
对上述实施例4~6、对比例1-4进行应力应变测试(参照标准GB/T528-1998)、压缩永久变形测试(参照标准GB 6669-2008)和储存稳定性测试(60℃下储存,观察粘度变化)
表1实施例4-6、对比例1-4的拉伸测试结果
实施例 | 拉伸强度/MPa | 断裂伸长率/% | 回弹性/% | 热储稳定性(d) |
实施例4 | 0.989 | 53.11 | 95 | 30天无明显变化 |
实施例5 | 0.319 | 169.17 | 90 | 30天无明显变化 |
实施例6 | 0.585 | 62.77 | 91 | 30天无明显变化 |
对比例1 | 0.52 | 26.32 | 83 | 30天无明显变化 |
对比例2 | 0.042 | 128.34 | 81 | 30天无明显变化 |
对比例3 | 0.051 | 135.72 | 78 | 30天无明显变化 |
对比例4 | 0.359 | 56.195 | 85 | 30天无明显变化 |
上述实施例4-6、对比例1-4所制备的光固化液体硅橡胶弹性体的性能测试结果见表1及图4。
由表1、图4可见,对比例1-4要么只具有较高的拉伸强度,要么只具有较高的断裂伸产率,而采用本发明方法制备的光固化液体硅橡胶实施例4-6相比对比例1-4,在增大机械强度的同时具有优异的回弹性。
Claims (12)
1.一种光固化液体硅橡胶,其特征在于,其原料包括:有机硅聚氨酯丙烯酸酯树脂1-5g、SEBS橡胶1-2.5g,和活性稀释剂1-10g。
2.根据权利要求1所述的光固化液体硅橡胶,其特征在于,所述有机硅聚氨酯丙烯酸酯树脂的合成原料包括二元异氰酸酯单体、双羟基封端聚二甲基硅氧烷、单羟基丙烯酸酯单体、多羟基支化单体。
3.根据权利要求2所述的光固化液体硅橡胶,其特征在于,二异氰酸酯单体与双羟基封端聚二甲基硅氧烷摩尔用量比为1:(0.5~0.7);
二异氰酸酯单体与单羟基丙烯酸酯单体摩尔用量比为1:(0.3~0.55);
二异氰酸酯单体与多羟基支化单体摩尔用量比为1:(0.07~0.16)。
4.根据权利要求2所述的光固化液体硅橡胶,其特征在于,二元异氰酸酯单体为异弗尔酮二异氰酸酯。
5.根据权利要求2所述的光固化液体硅橡胶,其特征在于,双羟基封端聚二甲基硅氧烷为4000分子量的羟丙基聚二甲基硅氧烷或2000分子量的羟丙基聚二甲基硅氧烷中的一种。
6.根据权利要求2所述的光固化液体硅橡胶,其特征在于,单羟基丙烯酸酯单体为丙烯酸羟乙酯。
7.根据权利要求2所述的光固化液体硅橡胶,其特征在于,多羟基支化单体为丙三醇。
8.根据权利要求2所述的光固化液体硅橡胶,其特征在于,所述有机硅聚氨酯丙烯酸酯树脂由以下方法合成:
步骤a1、扩链:将二异氰酸酯单体和溶剂加入带有搅拌装置、温度计、冷凝管和恒压滴液漏斗的四颈烧瓶中,取双羟基封端聚二甲基硅氧烷与催化剂混合液,在45~65℃下缓慢滴加入烧瓶中,滴加完后升温至60~75℃后再反应2~4h;
步骤a2、封端:再将温度降至45~65℃,缓慢滴加入单羟基丙烯酸酯单体、催化剂、阻聚剂和溶剂的混合物,滴加完后在60~75℃下反应2-4h;
步骤a3、支化:再缓慢滴加多羟基支化单体与催化剂的混合溶液,继续反应2-4h,反应完后除去溶剂即得有机硅聚氨酯丙烯酸酯树脂。
9.根据权利要求8所述的光固化液体硅橡胶,其特征在于,二异氰酸酯单体与双羟基封端聚二甲基硅氧烷摩尔用量比为1:(0.5~0.7);
二异氰酸酯单体与单羟基丙烯酸酯单体摩尔用量比为1:(0.3~0.55);
二异氰酸酯单体与多羟基支化单体摩尔用量比为1:(0.07~0.16)。
10.根据权利要求8所述的光固化液体硅橡胶,其特征在于,步骤a3中,反应完后的判断方法是:使用傅里叶红外光谱监测反应终点,直至-NCO的特征吸收峰2270cm-1完全反应消失。
11.一种光固化液体硅橡胶的制备方法,其特征在于,包括以下步骤:
(1)按权利要求8中的方法合成支化型有机硅聚氨酯丙烯酸酯树脂;
(2)光固化液体硅橡胶的制备及固化:
步骤b1、将SEBS橡胶(苯乙烯-乙烯-丁二烯-苯乙烯嵌段共聚物)与活性稀释剂在70~110℃下混合均匀;
步骤b2、加入到(1)中制备的有机硅聚氨酯丙烯酸酯树脂中,并加入光引发剂和气相二氧化硅搅拌均匀,采用UV固化即得硅橡胶。
12.根据权利要求11所述的制备方法,其特征在于,活性稀释剂为四氢呋喃丙烯酸酯。
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