CN101033279A - 用作聚乙烯加工助剂的超支化聚合物及合成方法 - Google Patents
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Abstract
本发明涉及一种可作为聚乙烯加工助剂的超支化聚合物及其合成方法，具体涉及一种以由丙烯酸高碳醇酯和苯乙烯构成的超支化聚合物及其采用原子转移自由基聚合的合成方法。本发明首先通过以下配方合成超支化聚合物(重量份)：对氯甲基苯乙烯1，苯乙烯6.84～13.68，丙烯酸十二醇酯7.88～23.64，联二吡啶(Bpy)0.21～0.63，氯化亚铜(CuCl)0.065～0.196，以上组分经过抽真空，充氩气或氮气5次以上，密闭后磁力搅拌下于100～130℃中反应4～12小时，产物用丙酮溶解，经氧化铝柱过滤，在乙醇中沉淀，25～40℃下真空干燥数小时得超支化聚合物。本发明的熔体粘度相对于纯HDPE有明显下降，拉伸性能测试表明其强度变化很小。
Description
技术领域
本发明涉及一种可作为聚乙烯加工助剂的超支化聚合物及其合成方法，具体涉及一种以由丙烯酸高碳醇酯和苯乙烯构成的超支化聚合物及其采用原子转移自由基聚合的合成方法。
背景技术
近20年来，超支化聚合物(Hyperbranched polymer)在高分子学术和工业界被广泛关注，它是指分子中无明显主链，而具有丰富的支化结构和表面官能团的聚合物。超支化聚合物具有近似球形的三维分子结构，分子间和分子内链缠结很少，溶液和熔体粘度较低。因而在高固体份涂料，药物和催化剂载体，橡塑加工助剂等方面有广阔的应用前景(Yan D，Prog.Polym.Sci.，2004，29，183)。超支化聚合物的合成方法主要包括Flory在1952年提出的通过ABx类单体的缩聚反应合成法(Flory P.J，J.Am.Chem.Soc 1952，74，2718)，以及Fréchet在1995年提出的自缩合乙烯基聚合(SCVP)(Fréchet J.M.J，Science 1995，269，1080)。由缩聚反应合成的超支化聚合物一般是聚酯，聚酰胺等，其中瑞典Perstorp公司生产的超支化聚酯Boltorn已经商品化生产。超支化聚酯，聚酰胺等作为塑料加工流变改性剂已被广泛报道，表1列出了已公开的相关中国专利。
表1 缩聚法合成的超支化聚合物作为流变改性剂与塑料共混相关专利
| 专利公开号 | 内容 |
| CN1370790 | 采用支化度为0.4-0.8的高度支化脂肪族聚酯作为聚氯乙烯(PVC)的优良增塑剂而使用，其与PVC相容性好，不会流出。 |
| CN1488668 | 采用超支化聚酯-酰胺与超高分子量聚乙烯共混，发现可以显著降低聚乙烯的熔体粘度。 |
| CN1615342 | 公开了采用高度支化的聚酯，聚酯酰胺，聚酰胺作为加工助剂与聚烯烃，聚酰胺等热塑性聚合物共混，可以提高热塑性聚合物的加工流动性。 |
| CN1760252 | 采用三元或四元醇与对苯二甲酸酯反应合成的超支化聚酯与聚丙烯共混可明显提高聚丙烯的熔体流动性。 |
自缩合乙烯基聚合合成超支化聚合物要涉及到一种特殊的自引发单体AB*，其单体结构中包含一个在一定催化条件下可以转化为活性种的官能团B*和一个可聚合的官能团A，如乙烯基。根据B*官能团的不同，SCVP可以是离子或自由基聚合，单体结构可以根据需要设计，同时还可选择适当的普通单体与自引发单体进行共聚。因此，采用SCVP可以在较温和的反应条件下得到结构丰富的超支化聚合物，如超支化聚苯乙烯，超支化聚丙烯酸酯，超支化聚异丁烯，超支化马来酰亚胺共聚物等都已被成功合成。对氯甲基苯乙烯(CMS)是一种可以进行原子转移自由基聚合(ATRP)且已经商品化生产的自引发单体(Gaynor S.G.，Macromolecules 1996，29，1079)，采用其合成超支化聚合物作为聚合物加工的流动改性剂，工业化前景良好。到目前为止，国内所有公开专利中用以改善聚合物加工流动性的超支化聚合物都是聚酯，聚酰胺等缩聚物，存在结构单一，分子量较低，且成本较高的缺点。如CN1488668采用1％～10％超支化聚酯-酰胺与分子量为100～300万的超高分子聚乙烯共混，发现可显著降低超高分子量聚乙烯的熔体粘度，但并未给出所采用超支化聚合物的合成方法。而采用条件更为温和的ATRP方法合成的超支化聚合物用以改进聚乙烯加工流动性方面尚未见有相关专利。
发明内容
本发明的目的是提供一种可以有效改善聚乙烯加工流动性的超支化聚合物助剂及其合成方法。
首先通过以下配方合成超支化聚合物(重量份)：
对氯甲基苯乙烯 1
苯乙烯 6.84～13.68
丙烯酸十二醇酯 7.88～23.64
联二吡啶(Bpy) 0.21～0.63
氯化亚铜(CuCl) 0.065～0.196
该配方中对氯甲基苯乙烯是产生支化点的自引发单体，其用量越高，所合成的超支化聚合物的支化程度越高，但体系也更易交联。丙烯酸十二醇酯是用来提供与PE相容性的第二单体，CuCl/Bpy是催化剂，其用量太低将会导致体系合成的聚合物是线性而非超支化的，用量太高会使体系中催化剂残留不易除尽。
以上组分经过抽真空，充氩气或氮气5次以上，密闭后磁力搅拌下于100～130℃中反应4～12小时，产物用丙酮溶解，经氧化铝柱过滤，在乙醇中沉淀，25～40℃下真空干燥数小时得超支化聚合物。
将所得超支化聚合物按1％～4％的比例加入到高密度聚乙烯中混合均匀后，在HaakeRheocord 90转矩流变仪上混炼，发现可以显著降低加工转矩。将所得共混物在PhysicaMCR锥板流变仪上进行流变性能测试，发现共混物的熔体粘度相对于纯HDPE有明显下降，拉伸性能测试表明其强度变化很小。
附图说明
图1超支化聚合物的1H-NMR图
图2纯PE和PE/超支化聚合物(HBP)共混物的流变曲线
具体实施方式
(1)超支化聚合物的合成实施例1
将对氯甲基苯乙烯5.08g(0.0333mol)，丙烯酸十二醇酯39.96g(0.167mol)，苯乙烯34.66g(0.3333mol)，氯化亚铜0.495g(0.005mol)，联二吡啶1.56g(0.01mol)加入到250mL圆底烧瓶中，磁力搅拌下于110℃下反应8小时，将所得产物用600mL丙酮溶解，经氧化铝柱过滤，滤液滴入大量乙醇中沉淀，过滤，35℃下真空干燥48小时得目标超支化聚合物(HBP)，产率75％。超支化聚合物的1H-NMR图见附图1，根据1H-NMR图计算共聚物中丙烯酸十二醇酯结构单元的摩尔含量为30％，与投料时单体组成31.3％接近。产物采用凝胶渗透色谱(GPC)测得
Mw，GPC＝9.4×104，
Mn，GPC＝3.4×104，多角度激光光散射(MALLS)测得Mw，MALLS＝1.3×105。光散射测得的绝对重均分子量明显大于以线性聚苯乙烯为标样采用凝胶渗透色谱测得的相对重均分子量，证实所得聚合物具有高度支化的结构。
(2)超支化聚合物的合成实施例2
将对氯甲基苯乙烯2.54g(0.0167mol)，丙烯酸十二醇酯39.96g(0.167mol)，苯乙烯26g(0.25mol)，氯化亚铜0.331g(0.00333mol)，联二吡啶1.039g(0.00666mol)加入到250mL圆底烧瓶中，磁力搅拌下于115℃下反应6小时，将所得产物用500mL丙酮溶解，氧化铝柱过滤，滤液滴入大量乙醇中沉淀，过滤，35℃下真空干燥48小时得超支化聚合物，产率73.2％。产物采用凝胶渗透色谱(GPC)测得
Mw，GPC＝7.2×104，
Mn，GPC＝2.3×104，多角度激光光散射测得
Mw，MALLS＝1.4×105。
(3)超支化聚合物合成实施例3
将对氯甲基苯乙烯1.693g(0.0111mol)，丙烯酸十二醇酯40.08g(0.167mol)，苯乙烯23.088g(0.222mol)，氯化亚铜0.330g(0.00333mol)，联二吡啶1.039g(0.00666mol)加入到250mL圆底烧瓶中，磁力搅拌下于120℃下反应10小时，将所得产物用500mL丙酮溶解，氧化铝柱过滤，滤液滴入大量乙醇中沉淀，过滤，30℃下真空干燥72小时得超支化聚合物，产率70.0％。产物采用凝胶渗透色谱(GPC)测得
Mw，GPC＝1×105，
Mn，GPC＝5×104，多角度激光光散射测得
Mw，MALLS＝1.6×105。
(4)超支化聚合物与高密度聚乙烯的共混
将实施例(1)所得超支化聚合物按1％，2％和4％的比例加入到高密度聚乙烯中手动混合均匀后，在Haake Rheocord 90转矩流变仪上混炼，记录转矩随时间的变化情况，结果示于表2。然后将所得共混物在Physica MCR锥板流变仪上进一步进行流变性能测试，测得其表观粘度与剪切速率之间的关系见附图2所示，取剪切速率为100 s-1时的粘度示于表2第4列。
表2 支化聚合物对聚乙烯流变扭矩的影响
| HBP添加量(wt％) | 混合熔体扭矩(N·m) | 扭矩值降低程度(％) | 剪切速率100s-1时表观粘度(Pa.S) | 粘度降低程度(％) |
| 0 | 22.1 | 0 | 1983 | 0 |
| 1.0 | 21.8 | 1.4％ | 1905 | 3.9 |
| 2.0 | 21.4 | 3.2％ | 1832 | 7.6 |
| 4.0 | 20.2 | 8.6％ | 1668 | 15.9 |
将所得共混物制成样条进行拉伸性能测试，其结果如表3所示：
表3 共混物的拉伸性能
| HBP添加量(wt％) | 断裂伸长率(％) | 断裂伸长率下降程度％ | 拉伸强度(MPa) | 拉伸强度下降程度％ |
| 0 | 1039 | 0 | 28.5 | 0 |
| 1.0 | 997 | 4.0 | 27.3 | 4.2 |
| 2.0 | 1021 | 1.7 | 28.3 | 0.7 |
| 4.0 | 982 | 5.5 | 27.5 | 3.5 |
从以上数据看出，当在聚乙烯中加入4％重量的超支化聚合物，即可降低熔体粘度15.9％，拉伸强度仅下降3.5％，断裂伸长率仅下降5.5％。
Claims (2)
1.一种作为聚乙烯加工助剂的超支化聚合物，其特征在于：通过以下配方合成的超支化聚合物，以重量份计：
对氯甲基苯乙烯 1
苯乙烯 6.84～13.68
丙烯酸十二醇酯 7.88～23.64
联二吡啶Bpy 0.21～0.63
氯化亚铜CuCl 0.065～0.196
2.权利要求1所述的一种作为聚乙烯加工助剂的超支化聚合物的合成方法，其特征是：所述配方组分经过抽真空，充氩气或氮气5次以上，密闭后磁力搅拌下于100～130℃中反应4～12小时，产物用丙酮溶解，经氧化铝柱过滤，在乙醇中沉淀，25～40℃下真空干燥得超支化聚合物。
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151483A (zh) * | 2014-06-04 | 2014-11-19 | 常州大学 | 一种端羟基超支化聚丙烯酸酯的制备方法 |
| CN104804197A (zh) * | 2015-04-16 | 2015-07-29 | 科达斯特恩(常州)汽车塑件系统有限公司 | 无卤超支化聚合物及含该聚合物的改性聚丙烯 |
| CN108794847A (zh) * | 2017-04-28 | 2018-11-13 | 中国石油化工股份有限公司 | 滚塑聚烯烃组合物及其制备方法 |
| CN115008851A (zh) * | 2022-07-01 | 2022-09-06 | 江苏欧晟新材料科技有限公司 | 一种高密度聚乙烯复合薄膜及其加工工艺 |
| WO2023155574A1 (zh) * | 2022-02-21 | 2023-08-24 | 天津金发新材料有限公司 | 一种高阻隔、耐低温、耐环境应力开裂的hdpe材料及其制备方法和应用 |
-
2007
- 2007-03-22 CN CNB2007100210156A patent/CN100551943C/zh active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151483A (zh) * | 2014-06-04 | 2014-11-19 | 常州大学 | 一种端羟基超支化聚丙烯酸酯的制备方法 |
| CN104151483B (zh) * | 2014-06-04 | 2016-02-10 | 常州大学 | 一种端羟基超支化聚丙烯酸酯的制备方法 |
| CN104804197A (zh) * | 2015-04-16 | 2015-07-29 | 科达斯特恩(常州)汽车塑件系统有限公司 | 无卤超支化聚合物及含该聚合物的改性聚丙烯 |
| CN108794847A (zh) * | 2017-04-28 | 2018-11-13 | 中国石油化工股份有限公司 | 滚塑聚烯烃组合物及其制备方法 |
| WO2023155574A1 (zh) * | 2022-02-21 | 2023-08-24 | 天津金发新材料有限公司 | 一种高阻隔、耐低温、耐环境应力开裂的hdpe材料及其制备方法和应用 |
| CN115008851A (zh) * | 2022-07-01 | 2022-09-06 | 江苏欧晟新材料科技有限公司 | 一种高密度聚乙烯复合薄膜及其加工工艺 |
| CN115008851B (zh) * | 2022-07-01 | 2024-10-01 | 南通睿华科技服务有限公司 | 一种高密度聚乙烯复合薄膜及其加工工艺 |
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| CN100551943C (zh) | 2009-10-21 |
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