CN109589947A - 一种含多酚羟基聚苯乙烯系大孔吸附树脂制备方法及应用 - Google Patents
一种含多酚羟基聚苯乙烯系大孔吸附树脂制备方法及应用 Download PDFInfo
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Abstract
本发明公开了一种含多酚羟基聚苯乙烯系大孔吸附树脂制备方法及应用,属于高分子材料技术领域,其特征在于制备方法为一锅法制备,包括有机相制备、水相制备和悬浮聚合,共聚珠体经过蒸汽蒸馏,致孔剂全部蒸出后,向反应釜依次加入引发剂Ⅱ、邻苯三酚,本发明的有益效果是:本发明采用了一锅法制备,大大缩短了工艺时间,简化了工艺步骤,避免因频繁导料而占用大量的生产设备和生产场地;创造性的利用了邻苯三酚,采用一步法以聚苯乙烯为骨架,制备的含多酚羟基聚苯乙烯系大孔吸附树脂,具有较高比表面,具有多个酚羟基易于蛋白形成氢键簇体,使其蛋白质吸附力强、吸附量高、选择性好、易再生、使用寿命长、性能稳定等优良特性。
Description
技术领域:
本发明属于高分子材料技术领域,更具体地涉及一种含多酚羟基聚苯乙烯系大孔吸附树脂制备方法及应用。
背景技术:
头孢菌素类的产量占世界抗生素产量的60%以上,而我国头孢菌素C(CPC)产量占到了世界总产量的80%以上。它一般由微生物发酵法生产,发酵法生产头孢菌素C发酵液中含有大量的蛋白质、菌丝体等杂质。其主要来源于培养基和发酵过程中产生的。发酵液中蛋白质等杂质的存在对CPC滤液的过滤澄清以及后续的纯化不利。发酵液的预处理是CPC分离与纯化的首要条件,对CPC的产品质量、收率、成本以及生产效率有着极大的影响。
因此,去除发酵液中的蛋白质等杂质成为CPC纯化中尤为关键的一步。传统去除蛋白的方法有溶剂沉淀法、真空鼓式过滤机、板框加压过滤、平板超滤膜等。有机溶剂沉淀法不仅会消耗大量的有机溶剂,而且不利于其他单元的纯化操作。真空鼓式过滤与板框加压过滤,虽然滤布容易清洗但是由于发酵液粘稠,需要使用助滤剂,操作工艺繁琐,滤液质量与收率低。
在生产过程中为了保证高生产效率,选择合适的超滤膜的孔径尤为重要,若膜孔径太大,没有过滤效果;若膜孔径太小不但过滤速度慢而且头孢菌素有效成损失过高。发酵液的质量波动大,蛋白质成分复杂,分子大小不一。这就使分子小于膜孔径的杂质和CPC一起通过膜,导致去除不彻底,对后面的分离纯化不利,而且极易污染后面的吸附树脂柱。故在超滤的后面增加一个预处理树脂显的尤为必要,不但可以保护后面的吸附柱不受污染,而且利于CPC发酵液的纯化分离。一般的大孔吸附树脂单纯依靠疏水作用,蛋白质等杂质吸附量低,树脂易污染、再生不彻底,导致树脂衰减快。
发明内容:
为解决上述问题,克服现有技术的不足,本发明提供了一种含多酚羟基聚苯乙烯系大孔吸附树脂制备方法及应用;
解决的第一个技术问题是:一般大孔吸附树脂在处理头孢菌素C滤液(超滤后的发酵液)工艺中易污染、吸附量低、再生困难、树脂衰减快导致成本高。
解决的第二个技术问题是:现有的多酚羟基聚苯乙烯系大孔吸附树脂生产工艺繁琐,占用设备和场地较多;
解决的第三个技术问题是:溶剂沉淀法、真空鼓式过滤机、板框加压过滤、平板超滤膜等传统去除蛋白的方法,存在弊端,操作工艺繁琐,滤液质量与收率低的问题;
解决的第四个技术问题是:现有的大孔吸附树脂对蛋白亲和性差且吸附不牢,易被水冲洗下来,导致吸附量低、发酵液纯化效果欠佳的问题。
本发明解决上述技术问题的具体技术方案为:所述的含多酚羟基聚苯乙烯系大孔吸附树脂制备方法,其特征在于所述制备方法为一锅法制备,包括:有机相制备、水相制备和悬浮聚合;
所述有机相制备的步骤为将苯乙烯、交联剂Ⅰ、致孔剂和引发剂Ⅰ混溶得到有机相;
所述水相制备的步骤为将分散剂加入到水中,升温至40-45 ℃溶解30min,冷却至室温加入硼酸和氢氧化钠,调节溶液pH为10-10.5,得到水相;
所述悬浮聚合的步骤为将所述有机相加入到所述水相中,分散成球,粒度均匀后,在75-80℃反应2-4小时,在85-95℃反应12-16小时得到悬浮聚合物;
将所述悬浮聚合物进行蒸馏、水洗后得到共聚珠体。
进一步地,所述的共聚珠体经过蒸汽蒸馏,致孔剂全部蒸出后,降温至40-45 ℃,向反应釜依次加入引发剂Ⅱ、邻苯三酚,升温至75-80℃反应12-16小时,水洗即可制得含多酚羟基聚苯乙烯系大孔吸附树脂。
进一步地,交联剂Ⅰ为二乙烯基苯的溶液,所述二乙烯基苯的溶液浓度为63%或80%的一种;所述交联剂Ⅰ和苯乙烯的质量比为:90:10-95:5。
进一步地,所述的引发剂Ⅰ和引发剂Ⅱ均为过氧化苯甲酰或过氧化2-乙基己酸叔丁酯一种或两种的混合物;所述引发剂Ⅰ和引发剂Ⅱ均为交联剂Ⅰ和苯乙烯总重量的0.5%-1.5%。
进一步地,所述的邻苯三酚为交联剂Ⅰ和苯乙烯总重量50-100%。
进一步地,所述致孔剂为甲苯、白油、异丁醇、甲基异丁基甲醇、聚乙二醇、线性聚苯乙烯中的一种或者几种的混合;所述致孔剂为交联剂Ⅰ和苯乙烯总重量的120%-200%。
进一步地,所述的水为纯化水,重量为交联剂、苯乙烯和致孔剂总重量的200%-300%;所述的分散剂为明胶、羟乙基纤维素、木质素磺酸钠、聚乙烯醇中的一种或者几种的混合物;所述的分散剂为水质量的1%-1.5%。
进一步地,多酚羟基聚苯乙烯系大孔吸附树脂由上述方法制备而成。
进一步地,多酚羟基聚苯乙烯系大孔吸附树脂含有式Ⅰ和式Ⅱ。
进一步地,多酚羟基聚苯乙烯系大孔吸附树脂用于去除头孢菌素C虑液中蛋白质。
本发明的有益效果是:
本发明采用了一锅法制备,大大缩短了工艺时间,简化了工艺步骤,避免因频繁导料而占用大量的生产设备和生产场地;
本发明创造性的利用了邻苯三酚,采用一步法以聚苯乙烯为骨架,制备的含多酚羟基聚苯乙烯系大孔吸附树脂,不但具有较高比表面,而且具有多个酚羟基易于蛋白形成氢键簇体,使其蛋白质吸附力强、吸附量高、选择性好、易再生、使用寿命长、性能稳定等优良特性。
附图说明:
附图1是本发明多酚羟基聚苯乙烯系大孔吸附树脂Ⅰ型结构示意图;
附图2是本发明多酚羟基聚苯乙烯系大孔吸附树脂Ⅱ型结构示意图;
具体实施方式:
在本发明的描述中具体细节仅仅是为了能够充分理解本发明的实施例,但是作为本领域的技术人员应该知道本发明的实施并不限于这些细节。另外,公知的结构和功能没有被详细的描述或者展示,以避免模糊了本发明实施例的要点。对于本领域的普通技术人员而言,可以具体情况理解上述术语在本发明中的具体含义。
本发明的具体实施方式:
实施例一:
含多酚羟基聚苯乙烯系大孔吸附树脂制备方法,其特征在于所述制备方法为一锅法制备,包括:水相制备、有机相制备、蒸馏、水洗;
具体为:将14.5g明胶分散剂加入到1450g水中,升温至40-45 ℃溶解30min,冷却至室温加入1.4g氢氧化钠和2.44g硼酸,测定溶液pH为10.2。将混匀含有20g苯乙烯、180g二乙烯基苯、180g异丁醇和150g甲苯、2g过氧化苯甲酰引发剂1的有机相,加入到水相中,分散成球,调节转速粒度均匀后升温至反应温度,进行悬浮聚合,在78℃反应2小时。在85-95℃反应14小时,保温结束后用每次使用1000g无盐水洗涤二至三次、然后开启蒸汽蒸馏,致孔剂全部蒸出后,降温至40-45 ℃,向反应釜依次加入过氧化苯甲酰2g、120g邻苯三酚,升温至75-80℃反应12-16小时,水洗即可制得含多酚羟基聚苯乙烯系大孔吸附树脂。
实施例二:
具体为:18g明胶分散剂加入到1800g水中,升温至40-45 ℃溶解30min,冷却至室温加入1.4g氢氧化钠和2.44g硼酸,测定溶液pH为10.1。将混匀含有10g苯乙烯、190g二乙烯基苯、200g甲基异丁基甲醇和200g甲苯、3g过氧化苯甲酰引发剂1的有机相,加入到水相中,分散成球,调节转速粒度均匀后升温至反应温度,进行悬浮聚合,在78℃反应2小时。在85-95℃反应14小时,保温结束后用每次使用1000g无盐水洗涤二至三次、然后开启蒸汽蒸馏,致孔剂全部蒸出后,降温至40-45 ℃,向反应釜依次加入过氧化苯甲酰2g、200g邻苯三酚,升温至75-80℃反应12-16小时,水洗即可制得含多酚羟基聚苯乙烯系大孔吸附树脂。
为了更加直观的展现本发明的产品优势,特以本发明制备的1#样品:多酚羟基聚苯乙烯系大孔吸附树脂与对比样品、2#样品、3#样品和4#样品进行对比;
其中:
1#样品:本发明得到含有多酚羟基聚苯乙烯系大孔吸附树脂;
2#样品:以援引的方式引用的专利号为《200910308251.5》的中国发明专利公开的方法制备的苯乙烯多酚羟基树脂
3#样品:市场上购买的DM1180型树脂
4#样品:市场上购买的H20大孔吸附树脂;
试验条件:采用玻璃试验柱,树脂装量分别为100ml;树脂预处理按照常规方法进行,预处理后树脂备用;定量上柱,发酵液为工业化生产头孢菌素C滤液。5-10℃以1.0~1.2BV/hr的吸附流速通过树脂柱;一定浓度的弱碱溶液解析,流速0.8~1BV/hr。实验组基本参数见表1;实验结果见表2(多批实验数据平均值),树脂评价见表3。
表1:各试验组树脂基本参数
样品名称 | 试验组描述 | 树脂类型 | 工艺 | 反应物 |
1# | 本发明 | 聚苯乙烯系多酚羟基树脂 | 一锅法 | 邻苯三酚 |
2# | 援引 | 聚苯乙烯系多酚羟基树脂 | 多步法 | 苯酚 |
3# | DM1180 | 聚苯乙烯系大孔树脂 | 一步法 | 无 |
4# | H20 | 聚苯乙烯系大孔树脂 | 一步法 | 无 |
表2:各试验组树脂去除头孢菌素C滤液蛋白质效果的对照试验结果
注:1:CPC即头孢菌素C;
2:蛋白截留率即发酵液原有蛋白含量减去处理后发酵液蛋白含量与发酵液原有蛋白含量的比值;
3:420nm透光率主要反映解析液的澄清度和颜色
4: 发酵液CPC损失率即其初始浓度和过完树脂后浓度差与初始浓度的比值。
表3:各试验组树脂性能综合评价
树脂样品 | 发酵液有效成分CPC损失 | pH | 420nm透光率 | CPC液相纯度% | 蛋白截留率% | 综合评价 |
1<sup>#</sup> | 最低 | 略高 | 最高 | 最高 | 最高 | 最优 |
2<sup>#</sup> | 最高 | 略低 | 其次 | 最低 | 其次 | 略差 |
3<sup>#</sup> | 略低 | 其次 | 略低 | 其次 | 略低 | 其次 |
4<sup>#</sup> | 其次 | 略低 | 最低 | 略低 | 最低 | 最差 |
以上数据分析可知:
1#试验组与2#试验组对比可知:采用以苯酚作为反应剂以多步法的常规手段制备的树脂在应用时,头孢菌素C损失率高,单一的酚羟基蛋白结合力弱去除效果也不如本实施例。
1#试验组与3#试验组对比可知:本发明具有蛋白吸附量大、蛋白去除率高、滤液透光率好、头孢菌孙损失少的优点。
1#试验组与4#试验组对比可知:本发明具有蛋白吸附量大、蛋白去除率高、滤液透光率好、头孢菌孙损失少的优点。
综上所述:本发明采用一步法以聚苯乙烯为骨架,创造性的引入邻苯三酚,制备的含多酚羟基聚苯乙烯系大孔吸附树脂,相对于其他常规手段制备的大孔吸附树脂:不但具有较高比表面,而且具有多个酚羟基易于蛋白形成氢键簇体,使其蛋白质吸附力强、吸附量高、选择性好、易再生、使用寿命长、性能稳定等优良特性。
Claims (10)
1.一种含多酚羟基聚苯乙烯系大孔吸附树脂制备方法,其特征在于所述制备方法为一锅法制备,包括:有机相制备、水相制备和悬浮聚合;
所述有机相制备的步骤为将苯乙烯、交联剂Ⅰ、致孔剂和引发剂Ⅰ混溶得到有机相;
所述水相制备的步骤为将分散剂加入到水中,升温至40-45 ℃溶解30min,冷却至室温加入硼酸和氢氧化钠,调节溶液pH为10-10.5,得到水相;
所述悬浮聚合的步骤为将所述有机相加入到所述水相中,分散成球,粒度均匀后,在75-80℃反应2-4小时,在85-95℃反应12-16小时得到悬浮聚合物;
将所述悬浮聚合物进行蒸馏、水洗后得到共聚珠体。
2.根据权利要求1所述的含多酚羟基聚苯乙烯系大孔吸附树脂制备方法,其特征在于所述的共聚珠体经过蒸汽蒸馏,致孔剂全部蒸出后,降温至40-45 ℃,向反应釜依次加入引发剂Ⅱ、邻苯三酚,升温至75-80℃反应12-16小时,水洗即可制得含多酚羟基聚苯乙烯系大孔吸附树脂。
3.根据权利要求2所述的含多酚羟基聚苯乙烯系大孔吸附树脂制备方法,其特征在于交联剂Ⅰ为二乙烯基苯的溶液,所述二乙烯基苯的溶液浓度为63%或80%的一种;所述交联剂Ⅰ和苯乙烯的质量比为:90:10-95:5。
4.根据权利要求3所述的含多酚羟基聚苯乙烯系大孔吸附树脂制备方法,其特征在于所述的引发剂Ⅰ和引发剂Ⅱ均为过氧化苯甲酰或过氧化2-乙基己酸叔丁酯一种或两种的混合物;所述引发剂Ⅰ和引发剂Ⅱ均为交联剂Ⅰ和苯乙烯总重量的0.5-1.5%。
5.根据权利要求3所述的含多酚羟基聚苯乙烯系大孔吸附树脂制备方法,其特征在于所述的邻苯三酚为交联剂Ⅰ和苯乙烯总重量50-100%。
6.根据权利要求3所述的含多酚羟基聚苯乙烯系大孔吸附树脂制备方法,其特征在于所述致孔剂为甲苯、白油、异丁醇、甲基异丁基甲醇、聚乙二醇、线性聚苯乙烯中的一种或者几种的混合;所述致孔剂为交联剂Ⅰ和苯乙烯总重量的120-200%。
7.根据权利要求3所述的含多酚羟基聚苯乙烯系大孔吸附树脂制备方法,其特征在于所述的水为纯化水,重量为交联剂、苯乙烯和致孔剂总重量的200-300%;所述的分散剂为明胶、羟乙基纤维素、木质素磺酸钠、聚乙烯醇中的一种或者几种的混合物;所述的分散剂为水质量的1%-1.5%。
8.一种多酚羟基聚苯乙烯系大孔吸附树脂由权利要求1-7任意一项权利要求所述的方法制备而成。
9.根据权利要求8所述的多酚羟基聚苯乙烯系大孔吸附树脂,其特征在于含有式Ⅰ和式Ⅱ。
10.根据权利要求8或9所述的多酚羟基聚苯乙烯系大孔吸附树脂,其特征在于用于去除头孢菌素C虑液中蛋白质。
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