CN106008779B - 一种交联聚对苯乙烯磺酸钠凝胶微球制作方法 - Google Patents
一种交联聚对苯乙烯磺酸钠凝胶微球制作方法 Download PDFInfo
- Publication number
- CN106008779B CN106008779B CN201610381707.0A CN201610381707A CN106008779B CN 106008779 B CN106008779 B CN 106008779B CN 201610381707 A CN201610381707 A CN 201610381707A CN 106008779 B CN106008779 B CN 106008779B
- Authority
- CN
- China
- Prior art keywords
- sodium
- styrenesulfonate
- distilled water
- gel micro
- ball
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000004132 cross linking Methods 0.000 title claims abstract description 7
- 239000011806 microball Substances 0.000 title claims abstract 7
- 229920001464 poly(sodium 4-styrenesulfonate) Polymers 0.000 title claims abstract 6
- 238000004519 manufacturing process Methods 0.000 title claims abstract 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000012153 distilled water Substances 0.000 claims abstract description 21
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 claims abstract description 12
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001856 Ethyl cellulose Substances 0.000 claims abstract description 10
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920001249 ethyl cellulose Polymers 0.000 claims abstract description 10
- 235000019325 ethyl cellulose Nutrition 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims description 2
- -1 N, N '-methylene Chemical group 0.000 claims 1
- 235000019441 ethanol Nutrition 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 5
- 239000003431 cross linking reagent Substances 0.000 abstract description 2
- 239000002270 dispersing agent Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000010557 suspension polymerization reaction Methods 0.000 abstract description 2
- 125000002091 cationic group Chemical group 0.000 abstract 2
- 238000013270 controlled release Methods 0.000 abstract 1
- 238000000605 extraction Methods 0.000 abstract 1
- 229930014626 natural product Natural products 0.000 abstract 1
- 239000010865 sewage Substances 0.000 abstract 1
- 230000002459 sustained effect Effects 0.000 abstract 1
- 238000013268 sustained release Methods 0.000 abstract 1
- 230000008961 swelling Effects 0.000 abstract 1
- 239000004005 microsphere Substances 0.000 description 21
- 239000000499 gel Substances 0.000 description 20
- 239000002245 particle Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 7
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 238000012674 dispersion polymerization Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012673 precipitation polymerization Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000012688 inverse emulsion polymerization Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/32—Polymerisation in water-in-oil emulsions
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Graft Or Block Polymers (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明属于凝胶微球制备的技术领域，具体涉及一种交联聚对苯乙烯磺酸钠凝胶微球制作方法，采用反相悬浮聚合法，以甲苯为分散介质、乙基纤维素为分散剂构成油相；以对苯乙烯磺酸钠(SSS)为功能单体，N,N’‑亚甲基双丙烯酰胺为交联剂，过硫酸铵为引发剂，以及蒸馏水构成水相制得粒径为150～250um左右的交联聚对苯乙烯磺酸钠凝胶微球(CPSSS)。具有很好地溶胀性能，而且其表面和内部携带大量的负电荷，可以用于药物缓控释、污水中阳离子的清除、阳离子天然产物的分离提取等领域。
Description
技术领域
本发明属于凝胶微球制备的技术领域,具体涉及一种交联聚对苯乙烯磺酸钠凝胶微球制作方法。
背景技术
凝胶微球是一类内部具有交联结构、在水介质中可充分溶胀而不溶解的微米级聚合物微球。凝胶微球不仅具有大尺寸宏观凝胶的环境响应性特点，当外界环境 (如温度、pH、溶剂等) 条件发生改变，凝胶微球会快速产生溶胀-消胀响应行为，而且具有独特的界面效应、表面效应、尺寸效应、体积效应、渗流效应等，因此凝胶微球在许多领域具有重要的应用，如药物控制释放、物质分离、环境治理等（Bekhit M., Sanchez-
Gonzalez L., Ben Messaoud G., Desobry S. J. Food Eng., 2016, 180:1）。
凝胶微球的制备的方法有多种，主要包括乳液聚合、溶液聚合、沉淀聚合和分散聚合。不同聚合方法制备出的微球粒径大小不同，一般乳液聚合法可以制备出粒径为0.02-100 um的凝胶微球；沉淀聚合法制备粒径为0.5-10 um左右的凝胶微球；分散聚合法制备0.1-10um左右的凝胶微球。乳液聚合是制备凝胶微球的常用方法，主要有反相乳液聚合、种子乳液聚合和无皂乳液聚合。用于制备凝胶微球的单体主要为甲基丙烯酸、丙烯酸、丙烯酰胺以及海藻酸盐、聚乙烯醇等大分子。而以水溶性单体为功能单体，制备粒径较大的便于吸附的凝胶微球多采用反相悬浮聚合(徐锐, 高保娇,杨青.过程工程学报，2014,
14:86)，而采用对苯乙烯磺酸阴离子单体制备的凝胶微球尚未见报道。
发明内容
本发明所要解决的技术问题是如何提供一种交联聚对苯乙烯磺酸钠凝胶微球制作方法。
本发明所采用的技术方案是：一种交联聚对苯乙烯磺酸钠凝胶微球制作方法，其步骤如下：
第一步,在四口瓶中，在通氮气保护条件下，将乙基纤维素与质量为其20倍的甲苯混合，在一定温度下保温，使完全溶解。
第二步，将对苯乙烯磺酸钠，N,N’-亚甲基双丙烯酰胺溶于蒸馏水直接加入至上述四口瓶中，搅拌条件下，再将引发剂过硫酸铵，滴加至上述溶液中，形成反相悬浮体系，恒温条件下，继续搅拌，使反应完全，过滤，乙醇，蒸馏水反复洗涤，干燥至恒重，制得交联聚对苯乙烯磺酸钠凝胶微球CPSSS。
作为一种优选方式：第一步中所述的甲苯与乙基纤维素的保温温度为60℃～70℃，保温时间为0.5～2h。
作为一种优选方式：第二步中，反相悬浮体系中，甲苯与蒸馏水的体积比为2:1，所述的单体对苯乙烯磺酸钠为强阴离子电解质，在反相悬浮体系中，对苯乙烯磺酸钠的浓度为 0.92～1.02 mol/L ，N,N’-亚甲基双丙烯酰胺的浓度为 6.82×10-2～7.79×10-2 mol/L，过硫酸铵的浓度为1.04×10-2～1.08×10-2 mol/L，恒温温度为55～65℃，反应时间为4～6 h，使用搅拌机搅拌，搅拌速度为250～400 rpm，所制得的交联聚对苯乙烯磺酸钠凝胶微球的粒径为150～250 um。
本发明的有益效果是：以甲苯为分散介质、乙基纤维素为分散剂构成连续相油相，首次以阴离子单体对苯乙烯磺酸纳（SSS）为功能单体，N,N'-亚甲基双丙烯酰胺（MBA）为交联剂，过硫酸铵为引发剂以及蒸馏水构成水相；采用反相悬浮聚合法，通过阴离子单体对苯乙烯磺酸纳的交联聚合，制备粒径为150～250 um的新型交联聚对苯乙烯磺酸钠凝胶微球（CPSSS）。本发明工艺简单，价格低廉，容易操作，具有很好地稳定性等优点。
具体实施方式
下面以实例来说明一种阴离子凝胶微球制备方法。
实施例1：在四口瓶中，将1.7g乙基纤维素加入至40mL甲苯中，于60℃下加热2小时溶解,通氮气保护。搅拌条件下，将3.8g对苯乙烯磺酸钠，0.21g N,N’-亚甲基双丙烯酰胺溶于15mL蒸馏水中加入至上述四口瓶后；将溶于5mL蒸馏水的0.0475g过硫酸铵滴加入上述溶液中，滴加时间约为10min；搅拌速度为250rpm，65℃下，恒温反应4 h后，过滤，乙醇，蒸馏水反复洗涤，干燥至恒重，制得粒径为250 um的交联聚对苯乙烯磺酸钠（CPSSS）。
实施例2：在四口瓶中，将1.7g乙基纤维素加入至40mL甲苯中，于70℃下加热1小时溶解,通氮气保护。搅拌条件下，将4.2 g对苯乙烯磺酸钠，0.24g N,N’-亚甲基双丙烯酰胺溶于15 mL蒸馏水中加入至上述四口瓶后；将溶于5 mL蒸馏水的0.0495g过硫酸铵滴加入上述溶液中，滴加时间约为10min；搅拌速度为400 rpm，55℃下，恒温反应6 h后，过滤，乙醇，蒸馏水反复洗涤，干燥至恒重，制得粒径为150 um的交联聚对苯乙烯磺酸钠（CPSSS）。
实施例3：在四口瓶中，将1.7g乙基纤维素加入至40mL甲苯中，于65℃下加热1.5小时溶解,通氮气保护。搅拌条件下，将4.0 g对苯乙烯磺酸钠，0.22g N,N’-亚甲基双丙烯酰胺溶于15 mL蒸馏水中加入至上述四口瓶后；将溶于5 mL蒸馏水的0.0485g过硫酸铵滴加入上述溶液中，滴加时间约为10min；搅拌速度为300 rpm，60℃下，恒温反应5 h后，过滤，乙醇，蒸馏水反复洗涤，干燥至恒重，制得粒径为200 um的交联聚对苯乙烯磺酸钠（CPSSS）。
实施例4：在四口瓶中，将1.7g乙基纤维素加入至40mL甲苯中，于65℃下加热2小时溶解,通氮气保护。搅拌条件下，将3.8 g对苯乙烯磺酸钠，0.23g N,N’-亚甲基双丙烯酰胺溶于15 mL蒸馏水中加入至上述四口瓶后；将溶于5 mL蒸馏水的0.0495g过硫酸铵滴加入上述溶液中，滴加时间约为10min；搅拌速度为300 rpm，55℃下，恒温反应6 h后，过滤，乙醇，蒸馏水反复洗涤，干燥至恒重，制得粒径为230 um的交联聚对苯乙烯磺酸钠（CPSSS）。
Claims (2)
1.一种交联聚对苯乙烯磺酸钠凝胶微球制作方法，其特征在于按照如下步骤进行：
第一步,在四口瓶中，在通氮气保护条件下，将乙基纤维素与质量为其20倍的甲苯混合，在一定温度下保温，使完全溶解；
第二步，将对苯乙烯磺酸钠，N,N’-亚甲基双丙烯酰胺溶于蒸馏水直接加入至上述四口瓶中，搅拌条件下，再将溶于蒸馏水的引发剂过硫酸铵，滴加至上述溶液中，形成反相悬浮体系，甲苯与蒸馏水的体积比为2:1；所述的单体对苯乙烯磺酸钠为强阴离子电解质，水相中，对苯乙烯磺酸钠的浓度（溶质的量与溶剂水量的比）为 0.92～1.02 mol/L，N,N’-亚甲基双丙烯酰胺的浓度（溶质的量与溶剂水量的比）为 6.82×10-2～7.79×10-2 mol/L，过硫酸铵在水相中的浓度（溶质的量与溶剂水量的比）为1.04×10-2～1.08×10-2 mol/L，于恒温55～65℃条件下，250～400 rpm继续搅拌4～6 h，使反应完全，过滤，乙醇，蒸馏水反复洗涤，干燥至恒重，制得交联聚对苯乙烯磺酸钠凝胶微球。
2.根据权利要求1所述的一种交联聚对苯乙烯磺酸钠凝胶微球制作方法，其特征在于：第一步中所述的甲苯与乙基纤维素的保温温度为60℃～70℃，保温时间为0.5～2h。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610381707.0A CN106008779B (zh) | 2016-06-02 | 2016-06-02 | 一种交联聚对苯乙烯磺酸钠凝胶微球制作方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610381707.0A CN106008779B (zh) | 2016-06-02 | 2016-06-02 | 一种交联聚对苯乙烯磺酸钠凝胶微球制作方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106008779A CN106008779A (zh) | 2016-10-12 |
| CN106008779B true CN106008779B (zh) | 2018-11-27 |
Family
ID=57092096
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610381707.0A Active CN106008779B (zh) | 2016-06-02 | 2016-06-02 | 一种交联聚对苯乙烯磺酸钠凝胶微球制作方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106008779B (zh) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106749907A (zh) * | 2016-11-25 | 2017-05-31 | 合众（佛山）化工有限公司 | 一种atrp技术合成的嵌段聚合物分散剂 |
| CN108905656B (zh) * | 2018-07-12 | 2021-02-19 | 中北大学 | 一种接枝聚对苯乙烯磺酸钠聚砜微孔滤膜制备方法及应用 |
| CN112679658B (zh) * | 2020-12-25 | 2022-04-15 | 江南大学 | 一种水不溶性温度pH双敏感微凝胶及其制备方法 |
| CN116440877B (zh) * | 2023-05-22 | 2024-10-29 | 福州大学 | 一种nmp体系中痕量金属离子吸附剂 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5749602A (en) * | 1980-09-10 | 1982-03-23 | Kao Corp | Preparation of bead polymer |
| JP2938920B2 (ja) * | 1990-01-31 | 1999-08-25 | 住友精化株式会社 | 吸水性樹脂の製造方法 |
-
2016
- 2016-06-02 CN CN201610381707.0A patent/CN106008779B/zh active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106008779A (zh) | 2016-10-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106008779B (zh) | 一种交联聚对苯乙烯磺酸钠凝胶微球制作方法 | |
| Cornwell et al. | Expanding the scope of gels–combining polymers with low-molecular-weight gelators to yield modified self-assembling smart materials with high-tech applications | |
| CN101412792B (zh) | 一种珠状高分子酰化试剂的合成方法 | |
| CN103804700B (zh) | 一种颜色可调的化学交联的光子晶体水凝胶的制备方法 | |
| JPH0830124B2 (ja) | 大孔質粒子の製造方法 | |
| CN112457838B (zh) | 一种新型耐酸耐盐缩膨剂及其制备方法 | |
| CN103087257B (zh) | pH和温度双重敏感的离子微水凝胶的制备方法 | |
| CN104892833B (zh) | 一种聚丙烯酸中空微凝胶的制备方法 | |
| CN101092494A (zh) | 大分子印迹聚丙烯酸钙/海藻酸钙杂化微球及其制备方法 | |
| CN102827330A (zh) | 一种温敏性核壳结构凝胶纳米粒子的制备方法及其产物的应用 | |
| Zhong et al. | Organic polymer-constructed chiral particles: preparation and chiral applications | |
| CN107474263B (zh) | 以聚离子多糖作为大分子交联剂的温度-pH敏感嵌段纳米水凝胶的制备方法 | |
| Wu et al. | Template size matched film thickness for effectively in situ surface imprinting: A model study of glycoprotein imprints | |
| Štefanec et al. | Aryl acrylate porous functional polymer supports from water‐in‐oil‐in‐water multiple emulsions | |
| CN104761673A (zh) | 一种卡波姆及其制备方法 | |
| CN103113509B (zh) | 以l-甲状腺素为亲和配基的再生型亲和沉淀剂及制备方法和应用以及相关再生型聚合物 | |
| CN105175750A (zh) | 一种水凝胶微球的制备方法 | |
| CN108998036A (zh) | 自缔合型阳离子聚合物包覆腐殖酸固沙缓释剂及其制备方法 | |
| CN105693909B (zh) | 基于氧化石墨烯牺牲材料制备表面分子印迹微球的方法及应用 | |
| CN103709339B (zh) | 内核为微纳碳球的离子型球型聚电解质刷及其制备方法 | |
| CN102558422B (zh) | 多孔pH敏感型P(AAc-co-AAPheEt)手性水凝胶 | |
| CN102796219B (zh) | 一种复合微球的制备方法 | |
| CN107805295B (zh) | 一种具有超支化结构的pH敏感型水凝胶及其制备方法与应用 | |
| CN108341914B (zh) | 一种核壳结构的两性亲和聚合物微球制备方法 | |
| CN104387539A (zh) | 一种pH响应的荧光碳纳米颗粒杂化微凝胶及其制备方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Men Jiying Inventor after: Shi Hongxing Inventor after: Dong Chengya Inventor after: Shi Nan Inventor after: Dang Lifang Inventor after: Li Huan Inventor after: Lei Tian Inventor after: Li Xinyan Inventor after: Gao Baojiao Inventor before: Men Jiying Inventor before: Shi Nan Inventor before: Li Huan Inventor before: Lei Tian Inventor before: Li Xinyan Inventor before: Gao Baojiao |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220601 Address after: 570100 room 219-032, building a and B, Fuxiu community, Xiangrong Road, Xiuying District, Haikou City, Hainan Province Patentee after: Tieju Technology (Hainan) Co.,Ltd. Address before: 030051, Xueyuan Road, Shanxi Province, Taiyuan Province, No. 3 Patentee before: NORTH University OF CHINA |