CN1030709C - 水分散性聚合物组合物及其制备方法 - Google Patents
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Abstract
本发明涉及被疏水气相法二氧化硅所包裹的水溶性聚合物组合物可快速溶于水，还涉及改善水溶性聚合物的水分散性的方法。
Description
此项发明涉及到水溶性聚合物的组合物及改善其水分散性的方法。
水溶性高分子量聚合物通常被制成稀水溶液使用。尽管所制备的聚合物可分散于水中形成均相溶液，但必须精心操作，以使聚合物在水中达到初级分散。除非采取适当保护措施，否则聚合物很可能被水润湿而聚结，形成颗粒状部分水合的结块聚合物，这种聚合物很难一下子溶解。此外，结块的聚合物有堵塞液体处理设备的可能。尽管结块的聚合物有可能完全溶解，但这需要很长的溶解时间或进行特殊处理，以促进凝胶体的快速溶解。从溶液中除去结块的聚合物虽是一种可供选择的方法，但这样会造成聚合物的浪费。
因此，可快速分散上述聚合物的方法对现有技术的改进将作出显著贡献。
这项发明的一个目的是要制成一种更易于分散在水中的新型聚合物(即组合物)，另一个目的是提供一种改善水溶性高分子量聚合物水分散性的方法。
本发明其它方面的目的将在下文详细介绍。
根据本发明，聚合物颗粒与疏水气相法二氧化硅(fumedsilica)相接触，以使气相法二氧化硅能隔离包裹聚合物颗粒，从而得到具有较好水分散性的水溶性高分子量聚合物组合物。
适用于本发明的水溶性聚合物是现有技术中众所周知的。此聚合物应为固体颗粒且一般其粒径可在1到1000微米的范围内。
这种水溶性聚合物选自乙醚纤维素，淀粉、树胶、乙烯基聚合物，丙烯酸聚合物和生物多糖。
合适的乙醚纤维素选自羧甲基纤维素、甲基纤维素、羧甲基羟乙基纤维素、羟丙基甲基纤维素、羟丙基纤维素、羟乙基纤维素、乙羟基纤维素等。
合适的淀粉可选自羧甲基淀粉、羟乙基淀粉和羟丙基淀粉。
合适的树胶选自阿拉伯树胶特拉加肯胶(trajacanth)，刺梧桐树胶、沙提胶(shatti)，刺槐豆胶、瓜耳(树)胶、欧车前籽胶、榅桲籽胶、琼脂、藻酸铵、角叉(菜)胶、帚叉藻聚糖胶(furcellaran)、果胶、明胶和叶落松胶。
合适的丙烯酸聚合物选自聚丙烯酸、聚丙烯酰胺、丙烯酰胺——丙烯酸共聚物、丙烯酰胺—甲基丙烯酸共聚物和聚丙烯腈。
合适的乙烯基聚合物选自聚乙烯基吡咯烷酮、聚乙烯醇、羧乙烯基聚合物。
本发明中所用到的生物聚合物是在微生物存在条件下通过碳水化合物的微生物转变而得到的，最终聚合产物的组成，性质和结构均不同于聚合母体。合适的碳水化合物包含戊糖或己糖等糖类物质，例如葡萄糖、蔗糖、果糖、麦芽糖、乳糖、半乳糖和淀粉如可溶性淀粉、玉米淀粉等，可使用碳水化合物含量较高的粗制产品。合适的粗制产品有粗糖、原糖浆等。促进碳水化合物的微生物转变的合适的微生物可以是例如植物病原菌如植物病原体，它能够在被感染植物的划裂处产生渗出液。常用微生物有黄单胞菌属，例如杂多糖生物聚合物可由葡萄糖通过野油菜黄单胞菌(XC聚合物)的作用制备。
市售呫吨胶生物聚合物可选用Kelco Div.，Merk&Co.，Inc.公司的“Kelzan”牌产品和GeneralMills，Inc.公司生产的“Biopolymer XB23”牌产品。制备生物聚合物所用的其它黄单胞菌包括：菜豆黄单胞菌、锦葵黄单胞菌、胡罗卜黄单胞菌、常春藤黄单胞菌、半透明黄单胞菌和罂粟黄单胞菌。本发明所用其它生物聚合物即所谓的合成胶有：称为明串珠菌属(Leuconostor Van Tieghemend)的细菌与蔗糖作用合成的葡聚糖胶〔参见Bailey等，美国专利2,360,237〕；亨利豪斯提酵母(Hansenula holstii)NRRL-Y2448与葡萄糖作用合成的磷酸化甘露聚糖胶〔参见美国农业部农业研究局北方应用研究开发处，1958年10月CA-N-7号公报，Peoria，伊利诺伊州〕；通过粘性节杆菌(Arthrobacter Viscous)NRRLB—1973及粘性节杆菌(Archrobacter Viscous)NRRLB—1797等白喉菌作用产生的胶〔参见Cadmus等的美国专利3,228,855〕；通过粘膜甲基单胞菌(Methy lomonasMucosa)作用产生的胶〔参见Finn等，美国专利3,923,782〕；通过塔氏欧文氏菌(Erwinia tahitica)作用产生的胶〔参见Kang等，美国专利3,933,788〕；和通过固氮菌(Azotobacter indicus VarMgxogenes)作用产生的胶〔参见Kang等，美国专利3,960,832〕。
合适的生物多糖选自在野油菜黄单胞菌，菜豆黄单胞菌，锦葵黄单胞菌，胡罗卜黄单胞菌，半透明黄单胞菌、常春藤黄单胞菌，罂粟黄单胞菌，亨利豪斯提酵母(Hansenule holstii)，粘性节杆菌(Arthrobacter Viscous)，粘膜甲基单胞菌(Methylomonas macosa)，塔氏欧文氏菌(Erwinia tahitica)和固氮菌(Azotobacterindicus)的作用下制成的多糖。
除水溶性聚合物而外，新型组合物还含有疏水气相法二氧化硅。这种二氧化硅可通过四氯化硅在氢——氧炉中产生氧化而制得。反应产物二氧化硅经硅烷处理后具有疏水性。在优选的实施方案中疏水气相法二氧化硅的比表面应达到100平方米/克。
只要使疏水气相法二氧化硅将聚合物颗粒包覆起来气相法二氧化硅即可以任何方式与所选择的水溶性聚合物进行配料。
最终组合物中疏水气相法二氧化硅的重量百分含量在0.1～10％的范围内，如果聚合物是乙醚纤维素、淀粉、乙烯基聚合物或丙烯酸聚合物，则含量优选为1～2％。若聚合物是树胶或生物多糖，则优选含量范围为2.5～3.5％。
本发明的最终组合物能够快速溶于水，并形成半透明溶液。若想获得透明溶液只须向溶液中随意加入一种表面活性剂即可。一般来说，表面活性剂用量为0.1～5％(重量)，合适的表面活性剂选自长链胺。烷基——芳基磺酸的碱金属盐，短链石油磺酸的碱式盐、铵皂、胺皂和碱金属皂。
下面通过举例对该项发明作进一步说明。
实例I
本实例目的在于验证该组合物与水接触时是否能使乙醚纤维素类聚合物快速溶解。
将50克羧甲基纤维素与足量疏水气相法二氧化硅相混合，并控制硅重量百分含量为2％，制成样品。
再将50克羧甲基羟乙基纤维素与足量疏水气相法二氧化硅相混合，并控制硅重量百分含量为2％制成另一种样品。
将上述处理过的样品与二个未作上述处理的样品进行比较。对每个样品每克聚合物均加入250ml冷水并机械搅拌30秒钟。30秒钟过后，经过疏水气相法二氧化硅处理的两个样品中的乙醚纤维素全部溶解，而未作处理的两个样品中的聚合物没有溶解，而是在试验容器底部集结成块。
实例II
两个不同粒径的聚丙烯酰胺样品(Alcomer 120和DSCO DBX)与疏水气相法二氧化硅进行干混，并控制最终产品气相法二氧化硅重量百分含量为2％。
将上述样品分别与按如下方式制备的每一种未处理的聚丙烯酰胺样品相比较。每种样品一克均加入250ml冷水，并机械搅拌40秒钟， 40秒钟后，经疏水气相法二氧化硅处理的聚丙烯酰胺样品全部溶解，未作处理的两个聚丙烯酰胺样品没有溶解且集结成块。
实例III
本实例目的在于验证疏水气相法二氧化硅处理的生物聚合物是否能快速分散。
将野油菜黄单胞菌作用所产生的多糖与一定量的疏水气相法二氧化硅混合，并控制疏水气相法二氧化硅重量百分含量为3％，这样便制得了一个样品。
将处理过的聚合物样品与相同聚合物的未处理样品相比较。每克样品均加入280ml冷水并机械搅拌30秒钟。
结果经处理过的样品金部溶解，而未作处理的样品在测试容器底部集结成大块。
上述实例表明，由于本发明所提出的疏水气相法二氧化硅对乙醚纤维素、丙烯聚合物或生物多糖的包裹作用，结果改善了聚合物在水中的分散性。
很明显，对本技术领域的普通技术人员来说，可参考上述公开内容作出各种改进、而不会偏离本发明的构思和保护范围。
Claims (22)
1. 水分散性聚合物组合物，由重量含量为9.0—99.9％的水溶性聚合物和重量含量为0.1—10％的疏水气相法二氧化硅组成；其中水溶性聚合物主要选自：
a)乙醚纤维素
b)树胶
c)淀粉
d)乙烯基聚合物
e)丙烯酸聚合物和
f)生物多糖
2. 权利要求1所述组合物，其中的乙醚纤维素选自羧甲基纤维素、甲基纤维素、羟丙基甲基纤维素、羟丙基纤维素、羟乙基纤维素、乙羟基纤维素、羧甲基羟乙基纤维素。
3. 权利要求2所述组合物，其中的乙醚纤维素是羧甲基纤维素。
4. 权利要求2所述组合物，其中的乙醚纤维素是羧甲基羟乙基纤维素。
5. 权利要求1所述组合物，其中的淀粉选自羧甲基淀粉、羟乙基淀粉和羟丙基淀粉。
6. 权利要求1所述组合物，其中的树胶选自阿拉伯树胶，特拉加肯胶、刺梧桐树胶、沙提胶、刺槐豆胶、瓜耳(树)胶、欧车前籽胶、榅桲籽胶、琼脂、藻酸胺、角叉(菜)胶帚叉藻聚糖胶、果胶、明胶、叶落松胶。
7. 权利要求1所述组合物，其中的乙烯基聚合物选自聚乙烯吡咯烷酮、聚乙烯醇、羧乙烯基聚合物。
8. 权利要求1所述组合物，其中的丙烯酸聚合物选自聚丙烯酸、聚丙烯酰胺、丙烯酰胺—丙烯酸共聚物、丙烯酰胺—甲基丙烯酸共聚物，聚丙烯腈。
9. 权利要求8所述组合物，其中的丙烯酸聚合物是聚丙烯酰胺。
10. 权利要求1所述组合物，其中的生物多糖选自通过野油菜黄单胞菌、菜豆黄单胞菌、锦葵黄单胞菌、胡罗卜黄单胞菌、半透明黄单胞菌、常春藤黄单胞菌、罂粟黄单胞菌、亨利豪斯提酵母、粘性节杆菌、粘膜甲基单胞菌、塔氏欧文氏菌和固氮菌的作用产生的多糖。
11. 权利要求10所述组合物，其中的多糖是通过野油菜黄单胞菌作用产生的。
12. 改善水溶性聚合物水分散性的方法包括：将选自乙醚纤维素、淀粉、树胶、乙烯基、聚合物、丙烯酸聚合物和生物多糖的颗粒状水溶性聚合物与重量百分含量在0.1—10％范围内的疏水气相法二氧化硅相接触，而使疏水气相法二氧化硅包裹每个水溶性聚合物颗粒。
13. 权利要求12所述方法，其中的乙醚纤维素选自羧甲基纤维素、甲基纤维素、羟丙基甲基纤维素、羟丙基纤维素、羟乙基纤维素、乙羟基纤维素羧甲基羟乙基纤维素。
14. 权利要求13所述方法，其中的乙醚纤维素是羧甲基纤维素。
15. 权利要求13所述方法，其中的乙醚纤维素是羧甲基羟乙基纤维素。
16. 权利要求12所述方法，其中的淀粉选自羧甲基淀粉、羟乙基淀粉、和羟丙基淀粉。
17. 权利要求12所述方法，其中的树胶选自阿拉伯树胶、特拉加肯胶、刺梧桐树胶、沙提胶、刺槐豆胶、瓜耳(树)胶、欧车前籽胶、榅桲籽胶、琼脂、藻酸铵、角叉(菜)胶、帚叉藻聚糖胶、果胶、明胶和叶落松胶。
18. 权利要求12所述方法，其中的乙烯基聚合物选自聚乙烯吡咯烷酮、聚乙烯醇、羧乙烯基聚合物。
19. 权利要求12所述方法，其中的丙烯酸聚合物选自聚丙烯酸、聚丙烯酰胺、丙烯酰胺—丙烯酸共聚物、丙烯酰胺—甲基丙烯酸共聚物，聚丙烯腈
20. 权利要求19所述方法，其中的丙烯酸聚合物是聚丙烯酰胺。
21. 权利要求12所述方法，其中的生物多糖选自通过野油菜黄单胞菌、菜豆黄单胞菌、锦葵黄单胞菌、常春藤黄单胞菌、罂粟黄单胞菌，亨利豪斯提酵母、粘性节杆菌、粘膜甲基单胞菌、塔氏欧文氏菌和固氮菌的作用产生的多糖。
22. 权利要求21所述方法，其中的生物多糖是通过野油菜黄单胞菌作用产生的。
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| CN107418552A (zh) * | 2017-08-14 | 2017-12-01 | 中国石油天然气股份有限公司 | 一种遇水膨胀纳米材料及基于此的控水增油压裂方法 |
Also Published As
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| JPS6348341A (ja) | 1988-03-01 |
| AR241142A1 (es) | 1991-11-29 |
| EP0256538B1 (en) | 1994-08-24 |
| CN87105225A (zh) | 1988-03-09 |
| DE3750418D1 (de) | 1994-10-06 |
| NO873457D0 (no) | 1987-08-17 |
| NO169018C (no) | 1992-04-29 |
| EP0256538A2 (en) | 1988-02-24 |
| NO873457L (no) | 1988-02-19 |
| CA1277186C (en) | 1990-12-04 |
| FI873545L (fi) | 1988-02-19 |
| FI92328C (fi) | 1994-10-25 |
| MX7634A (es) | 1993-12-01 |
| DE3750418T2 (de) | 1994-12-15 |
| NO169018B (no) | 1992-01-20 |
| BR8704242A (pt) | 1988-04-12 |
| FI873545A0 (fi) | 1987-08-17 |
| EP0256538A3 (en) | 1989-02-22 |
| AR241142A2 (es) | 1991-11-29 |
| US4735659A (en) | 1988-04-05 |
| FI92328B (fi) | 1994-07-15 |
| IN168443B (zh) | 1991-04-06 |
| JPH0668036B2 (ja) | 1994-08-31 |
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