CN107033274A - 一种两性离子共聚物薄膜材料及其制备方法 - Google Patents
一种两性离子共聚物薄膜材料及其制备方法 Download PDFInfo
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- CN107033274A CN107033274A CN201710206998.4A CN201710206998A CN107033274A CN 107033274 A CN107033274 A CN 107033274A CN 201710206998 A CN201710206998 A CN 201710206998A CN 107033274 A CN107033274 A CN 107033274A
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- Prior art keywords
- acrylate
- poly
- copolymer
- vinylpridine
- vinyl pyridine
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 91
- 239000000463 material Substances 0.000 title claims abstract description 46
- 239000010409 thin film Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 21
- 238000012986 modification Methods 0.000 claims abstract description 8
- 230000004048 modification Effects 0.000 claims abstract description 8
- 238000010276 construction Methods 0.000 claims abstract description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000003282 alkyl amino group Chemical group 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 238000006467 substitution reaction Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 91
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 34
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- 150000008053 sultones Chemical class 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 15
- 238000001556 precipitation Methods 0.000 claims description 15
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical group CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 14
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 13
- OJYDUYJRKAUKGT-UHFFFAOYSA-N acetyl bromide 2-hydroxybenzoic acid Chemical compound OC1=C(C(=O)O)C=CC=C1.C(C)(=O)Br OJYDUYJRKAUKGT-UHFFFAOYSA-N 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- -1 dimethylaminoethyl Chemical group 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 4
- 239000013049 sediment Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- JFVDVTQULBGLET-UHFFFAOYSA-N 2-[(3-ethenylpyridin-2-yl)methyl]prop-2-enoic acid Chemical compound C(=C)C=1C(=NC=CC=1)CC(C(=O)O)=C JFVDVTQULBGLET-UHFFFAOYSA-N 0.000 claims description 2
- UUYQSLQNSVVXCC-UHFFFAOYSA-N CN.C(C=C)(=O)OCCN(C)C Chemical compound CN.C(C=C)(=O)OCCN(C)C UUYQSLQNSVVXCC-UHFFFAOYSA-N 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 229920000075 poly(4-vinylpyridine) Polymers 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- XHIOOWRNEXFQFM-UHFFFAOYSA-N ethyl prop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(=O)C=C XHIOOWRNEXFQFM-UHFFFAOYSA-N 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 18
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 13
- 239000010408 film Substances 0.000 abstract description 11
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- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 abstract description 3
- 229920003228 poly(4-vinyl pyridine) Polymers 0.000 description 46
- 239000000243 solution Substances 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
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- 125000003368 amide group Chemical group 0.000 description 4
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- 125000001453 quaternary ammonium group Chemical group 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- OJVSQAJBHTXMCC-UHFFFAOYSA-N 2-ethenylpyridine;ethyl prop-2-enoate Chemical compound CCOC(=O)C=C.C=CC1=CC=CC=N1 OJVSQAJBHTXMCC-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
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- 150000001412 amines Chemical group 0.000 description 1
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- 229940088710 antibiotic agent Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- JGPIKFZCMVIHJN-UHFFFAOYSA-N ethenyl 3-pyridin-2-ylprop-2-enoate Chemical compound C=COC(=O)C=CC1=CC=CC=N1 JGPIKFZCMVIHJN-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
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- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 210000004885 white matter Anatomy 0.000 description 1
Classifications
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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Abstract
本发明公开了一种两性离子共聚物薄膜材料,其为聚4‑乙烯基吡啶‑丙烯酸酯共聚物经离子化试剂进行季胺化修饰后的产物,所述的聚4‑乙烯基吡啶‑丙烯酸酯共聚物为由摩尔比为1:9~6:4的式Ⅰ表示的结构单元和式Ⅱ表示的结构单元无规则排列的分子量为50000~200000的共聚物,式中R1为氢或甲基,R2为选自C1~C12烷基和C1~C12烷基氨基取代的C1~C12烷基中的一种或多种。本发明还公开了该两性离子共聚物薄膜材料的制备方法。该两性离子聚合物共聚物功能薄膜具有优异的抗菌、抗污性能,而且具有成膜性能好、不易降解的特点。
Description
技术领域
本发明属于抗菌材料技术领域,特别涉及一种基于聚4-乙烯基吡啶-丙烯酸酯类的两性离子共聚物薄膜材料及其制备方法。
背景技术
非特异性蛋白质在材料表面的吸附一直以来都是科学界关注的问题,因为它与许多重要的科学和工业生产密切相关。一方面,在海洋涂料领域,船体表面接触大量的细菌、藻类以及贝壳等海洋微生物、微生物的黏附不仅损耗了能量,更加速了船体的腐蚀,极大地减少了船体保养周期。另一方面,非特异性蛋白吸附会造成生物污染,比如血液在输液导管上的凝结以及植入人体材料引起的血栓以及生物垢等问题。如何设计出一种抗生物黏附的涂料成为许多研究人员面临的重大任务及挑战。因此,对抗非特异性蛋白吸附材料的研究是生物医用材料、生化分析检测、生物化工、海洋防污等领域的重要课题。
目前,抗非特异性蛋白材料主要是以PEG为代表。PEG是一种中性的亲水高分子,由重复的氧乙烯基(-CH2CH2O-)组成,由于分子本身独特的结构,能够与水形成氢键,赋予PEG链高度的亲水性和良好的水溶性。围绕PEG链的氢键可以结合大量的水分子,同时分子链本身的高度流动以及具有很大的空间排斥力,防止了蛋白质分子的吸附。但是PEG本身也存在一些天热缺陷,比如PEG的蛋白不吸附性对分子排列有一定要求,过于紧密或分子量太大都会失去效果。更为重要的是,PEG在氧气和过渡金属离子存在的条件下会自然氧化,从而限制了其应用。
目前基于侧链含有酯键或者酰胺键的两性离子聚合物已成为普遍的一类新型的抗菌防污材料,与同类聚合物PEG有所不同,PEG是通过氢键与水分子结合,该两性离子聚合物则是通过离子溶剂化作用与水分子结合,在材料表层形成致密的水合层,赋予材料抗蛋白质非特异性吸附性能。两性离子聚合物种类繁多,并且有更大的分子设计空间。在工程领域,两性离子因其具有更好的抗菌防污和抗细胞粘附特性足以取代PEG。但是,两性离子聚合物存在力学性能差,吸水性强,其均聚物不宜直接使用等问题。另一方面,由于两性离子聚合物侧链含有酯键或者酰胺键等不稳定基团,极易得造成其发生水解,使得功能性基团发生剥离,从而使得其失去两性离子聚合物的优异属性。上述存在的问题,很大程度上限制了其在涂层和抗菌膜领域的应用。本领域技术人员仍需致力于开发新的具有较佳的抗菌、抗污性能和力学性能且不易水解的两性离子聚合物,以期应用于涂层和抗菌膜领域。
发明内容
本发明的目的在于提供一种具有较佳的抗菌、抗污性能和力学性能且不易降解的两性离子共聚物薄膜材料,其为聚4-乙烯基吡啶-丙烯酸酯共聚物经离子化试剂进行季胺化修饰后的产物,所述的聚4-乙烯基吡啶-丙烯酸酯共聚物为由摩尔比为1:9~6:4的式Ⅰ表示的结构单元和式Ⅱ表示的结构单元无规则排列的分子量为50000~200000的共聚物,
式中R1为氢或甲基;
R2为选自C1~C12烷基和C1~C12烷基氨基取代的C1~C12烷基中的一种或多种,具体的,R2优选自甲基、乙基、丙基、正丁基、异丁基、十二烷基和二甲氨基乙基中的一种或多种,更优选甲基、乙基或二甲氨基乙基。
所述的两性离子共聚物薄膜材料可由以下步骤制得:
(a)由单体4-乙烯基吡啶和单体丙烯酸酯通过自由基溶液聚合的方式聚合后分离得到聚4-乙烯基吡啶-丙烯酸酯共聚物,4-乙烯基吡啶和丙烯酸酯的摩尔比为1:9~6:4;
(b)由步骤(a)得到的聚4-乙烯基吡啶-丙烯酸酯共聚物与离子化试剂在乙醇中反应后分离得到两性离子共聚物薄膜材料,所述的离子化试剂为丙磺内酯或溴乙酰水杨酸酯,聚4-乙烯基吡啶-丙烯酸酯共聚物中的吡啶官能团与离子化试剂的摩尔比为1:9~6:4。
步骤(a)中,所述的丙烯酸酯为丙烯酸乙酯、甲基丙烯酸二甲氨乙酯、丙烯酸甲酯、丙烯酸正丁酯、丙烯酸异丁酯、甲基丙烯酸正丁酯、甲基丙烯酸月桂酯、甲基丙烯酸烷基酯中的一种或它们的组合,优选丙烯酸乙酯或甲基丙烯酸二甲氨乙酯;4-乙烯基吡啶和丙烯酸酯的摩尔比优选1:9~5:5,更优选2:8~5:5;
较佳的,聚合反应在无水无氧条件下进行,溶剂为乙醇,引发剂为偶氮二异丁腈,反应温度为60~80℃,反应时间为12~48h。
步骤(b)中,聚4-乙烯基吡啶-丙烯酸酯共聚物中的吡啶官能团与离子化试剂的摩尔比优选1:1;
较佳的,离子化反应温度为60~65℃,反应时间为12~36h。
本发明的另一目的在于提供所述的两性离子共聚物薄膜材料的制备方法,包括步骤:
(a)聚4-乙烯基吡啶-丙烯酸酯共聚物的制备
由单体4-乙烯基吡啶和单体丙烯酸酯通过自由基溶液聚合的方式聚合后分离得到聚4-乙烯基吡啶-丙烯酸酯共聚物,所述的丙烯酸酯为丙烯酸乙酯、甲基丙烯酸二甲氨乙酯、丙烯酸甲酯、丙烯酸正丁酯、丙烯酸异丁酯、甲基丙烯酸正丁酯、甲基丙烯酸月桂酯、甲基丙烯酸烷基酯中的一种或它们的组合,4-乙烯基吡啶和丙烯酸酯的摩尔比为1:9~6:4;
(b)聚4-乙烯基吡啶-丙烯酸酯共聚物的离子化修饰
由步骤(a)制得的聚4-乙烯基吡啶-丙烯酸酯共聚物与离子化试剂在乙醇中反应后分离得到两性离子共聚物薄膜材料,所述的离子化试剂为丙磺内酯或溴乙酰水杨酸酯,聚4-乙烯基吡啶-丙烯酸酯共聚物中的吡啶官能团与离子化试剂的摩尔比为1:9~6:4。
优选的,步骤(a)中,所述的丙烯酸酯为丙烯酸乙酯或甲基丙烯酸二甲氨乙酯;聚合反应在无水无氧条件下进行,溶剂为乙醇,引发剂为偶氮二异丁腈,引发剂质量为单体总投料质量的0.01%~0.2%,反应温度为60~80℃,反应时间为12~48h。
优选的,步骤(b)中,所述的离子化试剂为丙磺内酯或溴乙酰水杨酸酯;离子化反应温度为60~65℃,反应时间为12~36h。
本发明的制备方法的一些较佳实施例中,
步骤(a)具体为:在无水无氧条件下,向摩尔比为1:9~4:6的4-乙烯基吡啶和丙烯酸乙酯的乙醇溶液中,加入偶氮二异丁腈的乙醇溶液,于60~80℃反应12~36h,然后加入乙醚和/或正己烷产生沉淀,沉淀物经分离干燥得到聚4-乙烯基吡啶-丙烯酸乙酯共聚物;其中乙醇质量与4-乙烯基吡啶和丙烯酸乙酯质量之和的比为20~30:1优选25:1,偶氮二异丁腈的质量为4-乙烯基吡啶和丙烯酸乙酯质量之和的0.01%~0.1%;
步骤(b)具体为:向步骤(a)制得的聚4-乙烯基吡啶-丙烯酸乙酯共聚物的乙醇溶液中滴加丙磺内酯或溴乙酰水杨酸酯的乙醇溶液,于60~65℃反应12~36h,反应后的溶液滴到乙醚和/或正己烷中产生沉淀,沉淀经分离干燥得到两性离子共聚物薄膜材料;其中乙醇质量与聚4-乙烯基吡啶-丙烯酸乙酯共聚物质量的比为20~30:1优选25:1。
本发明的制备方法的另一些较佳实施例中,
步骤(a)具体为:在无水无氧条件下,向摩尔比为2:8~5:5的4-乙烯基吡啶和甲基丙烯酸二甲氨乙酯的乙醇溶液中,加入偶氮二异丁腈的乙醇溶液,于60~80℃反应24~48h,然后加入乙醚和/或正己烷产生沉淀,沉淀物经分离干燥得到聚4-乙烯基吡啶-甲基丙烯酸二甲氨乙酯共聚物;其中乙醇质量与4-乙烯基吡啶和甲基丙烯酸二甲氨乙酯质量之和的比为5~15:1优选8:1,偶氮二异丁腈的质量为4-乙烯基吡啶和甲基丙烯酸二甲氨乙酯质量之和的0.01%~0.2%;
步骤(b)具体为:向步骤(a)制得的聚4-乙烯基吡啶-甲基丙烯酸二甲氨乙酯共聚物的乙醇溶液中滴加丙磺内酯或溴乙酰水杨酸酯的乙醇溶液,于60~65℃反应12~36h,反应后的溶液滴到乙醚和/或正己烷中产生沉淀,沉淀经分离干燥得到两性离子共聚物薄膜材料,其中乙醇质量与聚4-乙烯基吡啶-甲基丙烯酸二甲氨乙酯共聚物质量的比为20~30:1优选25:1。
与现有技术相比,本发明的积极效果如下:
本发明在制备基于聚4-乙烯基吡啶-丙烯酸酯的两性离子共聚物薄膜材料时,一方面,引入丙烯酸酯类作为共聚物单体,用于改善聚合物的成膜性能、力学性能、机械性能、耐水性能;另一方面,引入4-乙烯基吡啶作为共聚物单体,其不含有酯键或者酰胺键,与丙烯酸酯聚合后通过丙磺内酯或溴乙酰水杨酸酯修饰可形成不易降解的两性离子聚合物共聚物功能薄膜。该薄膜具有优异的抗菌、抗污性能,而且稳定性高,不易降解,可大大延长使用周期,作为新型抗菌防污材料,在生物、环保、化学工业等领域具有良好的应用前景。
附图说明
图1为P4VP-co-EA,P4VP/SA-co-EA和P4VP/SO3 --co-EA的红外谱图;
图2为P4VP-co-DMAEMA和P4VP/SO3 --co-DMAEMA/SO3 -的红外谱图;
图3为P4VP-co-EA、P4VP-co-DMAEMA、P4VP/SO3 --co-DMAEMA/SO3 -、P4VP/SO3 --co-EA和P4VP/SA-co-EA的应力应变曲线;
图4为P4VP-co-EA、P4VP-co-DMAEMA、P4VP/SO3 --co-DMAEMA/SO3 -、P4VP/SO3 --co-EA和P4VP/SA-co-EA的热失重曲线;
图5为P4VP/SA-co-EA(a),P4VP/SO3 --co-EA(b),空白样品(c)和P4VP/SO3 --co-DMAEMA/SO3 -(d)的抗大肠杆菌效果照片;
图6为空白样品(a),P4VP/SO3 --co-EA(b),P4VP/SA-co-EA(c)和P4VP/SO3 --co-DMAEMA/SO3 -(d)抗大肠杆菌黏附效果的显微镜照片。
具体实施方式
以下结合具体实施例,对本发明作进一步说明。应理解,以下实施例仅用于说明本发明而非用于限定本发明的范围。
实施例1a1~1d1和1a2~1d2
(1)聚4-乙烯基吡啶-丙烯酸乙酯共聚物(P4VP-co-EA)的制备
分别按照表1-1所示实施例1a1~1d1和1a2~1d2的投料量和反应参数,在无水无氧条件下,向4-乙烯基吡啶(4VP)和丙烯酸乙酯(EA)的乙醇溶液(25mL)中,加入偶氮二异丁腈(AIBN)的乙醇溶液(10mL),于T1温度下反应,反应时间为t1,然后加入乙醚进行沉淀并形成絮状物,过滤得到絮状物;然后将过滤得到的絮状物再用乙醇溶解,加入乙醚使其析出再过滤,如此重复操作2~4次,于20~30℃真空干燥得到聚4-乙烯基吡啶-丙烯酸乙酯共聚物,共聚物中两种单体单元的摩尔比如表1-1所示。
表1-1实施例1a1~1d1和1a2~1d2聚合反应的投料量及反应参数
(2)基于聚4-乙烯基吡啶-丙烯酸乙酯共聚物的磺酸型薄膜材料(P4VP/SO3 --co-EA)的制备
分别按照表1-2所示实施例1a1~1d1的投料量和反应参数,将步骤(1)制备的聚4-乙烯基吡啶-丙烯酸乙酯共聚物溶于乙醇(30mL)中得到共聚物溶液,将丙磺内酯的乙醇溶液(10mL)逐滴加到共聚物溶液中,控制反应温度为T2,反应时间为t2。将反应后的溶液滴到乙醚中,逐渐生成沉淀并形成絮状物,过滤得到絮状物;然后将过滤得到的絮状物再用乙醇溶解,加入乙醚使其析出再过滤,如此重复操作2~4次,于20~30℃真空干燥得到基于聚4-乙烯基吡啶-丙烯酸乙酯共聚物的磺酸型薄膜材料。
表1-2实施例1~4离子化反应的投料量及反应参数
(3)基于聚4-乙烯基吡啶-丙烯酸乙酯共聚物的羧酸型薄膜材料(P4VP/SA-co-EA)的制备
分别按照表1-3所示实施例1a2~1d2的投料量和反应参数,将步骤(1)制备的聚4-乙烯基吡啶-丙烯酸乙酯共聚物溶于乙醇(25mL)中得到共聚物溶液,将溴乙酰水杨酸酯的乙醇溶液(10mL)逐滴加到共聚物溶液中,控制反应温度为T2,反应时间为t2。将反应后的溶液滴到乙醚中,逐渐生成沉淀并形成絮状物,过滤得到絮状物;然后将过滤得到的絮状物再用乙醇溶解,加入乙醚使其析出再过滤,如此重复操作2~4次,于20~30℃真空干燥得到基于聚4-乙烯基吡啶-丙烯酸乙酯共聚物的磺酸型薄膜材料。
表1-3实施例1a2~1d2离子化反应的投料量及反应参数
P4VP-co-EA、P4VP/SO3 --co-EA和P4VP/SA-co-EA的红外谱图如图1所示,P4VP-co-EA上的吡啶环在1598cm-1很强烈的吸收峰,且在1730cm-1出现了丙烯酸乙酯结构单元的酯键C=O吸收峰。随着吡啶环在丙磺内酯或溴乙酰水杨酸酯发生如下所示的季胺化反应以后,P4VP/SO3 --co-EA和P4VP/SA-co-EA中的吡啶环吸收峰1598cm-1彻底消失,随之C-N+吡啶盐吸收峰开始出现在1643cm-1。
实施例2a~2d
(1)聚4-乙烯基吡啶-甲基丙烯酸二甲氨乙酯共聚物(P4VP-co-DMAEMA)的制备
分别按照表2-1所示实施例2a~2d的投料量和反应参数,在无水无氧条件下,向4-乙烯基吡啶和甲基丙烯酸二甲氨乙酯的乙醇溶液(30mL)中,加入偶氮二异丁腈的乙醇溶液(10mL),于65℃条件下反应48h得到粘稠的微黄色透明液体。然后加入正己烷进行沉降,过滤得到白色固体,于20真空干燥得到聚4-乙烯基吡啶-甲基丙烯酸二甲氨乙酯共聚物。
表2-1实施例2a~2d聚合反应的投料量及反应参数
(2)基于聚4-乙烯基吡啶-甲基丙烯酸二甲氨乙酯共聚物磺酸型膜材料(P4VP/SO3 --co-DMAEMA/SO3 -)的制备
将步骤(1)制备的聚4-乙烯基吡啶-甲基丙烯酸二甲氨乙酯共聚物溶于乙醇中得到共聚物溶液,将丙磺内酯的乙醇溶液逐滴加到共聚物溶液中,于60℃反应12h。实施例2a~2d分别控制丙磺内酯摩尔量占总单体摩尔量的20%、30%、40%、50%,可生成不同电荷修饰度的共聚物。将反应后的溶液滴到乙醚中,共聚物会在乙醚中沉淀并形成絮状物,过滤得到絮状物;然后将过滤得到的絮状物再用乙醇溶解,加入乙醚使其析出再过滤,如此重复操作2~4次,于20℃真空干燥得到基于聚4-乙烯基吡啶-甲基丙烯酸二甲氨乙酯共聚物磺酸型膜材料。
P4VP-co-DMAEMA和P4VP/SO3 --co-DMAEMA SO3 -的红外谱图如图2所示,P4VP-co-DMAEMA上的吡啶环吸收峰在1589cm-1很强烈,随着吡啶环在丙磺内酯发生季胺化反应以后,P4VP/SO3 --co-DMAEMA中的吡啶环吸收峰1589cm-1彻底消失,随之C-N+吡啶盐吸收峰开始出现在1644cm-1。同时1033cm-1处产生了新的磺酸基团吸收峰。而甲基丙烯酸二甲氨乙酯单元的N也发生如下所示的季胺化反应。
测试上述实施例制备的P4VP-co-EA、P4VP-co-DMAEMA、P4VP/SO3 --co-DMAEMA/SO3 -、P4VP/SO3 --co-EA和P4VP/SA-co-EA的力学性能,应力应变曲线如图3所示,可知未离子化的P4VP-co-EA、P4VP-co-DMAEMA韧性良好,而季胺化之后的P4VP/SO3 --co-DMAEMA/SO3 -、P4VP/SO3 --co-EA和P4VP/SA-co-EA的韧性有所降低,不过相比于较脆的均聚物P4VP/SO3 -(韧性低且吸水性较强)成膜性能大大提高。
P4VP-co-EA、P4VP-co-DMAEMA、P4VP/SO3 --co-DMAEMA/SO3 -、P4VP/SO3 --co-EA和P4VP/SA-co-EA的热重分析结果如图4所示,250℃时仍能保持结构的稳定,可见具有较高的稳定性。
效果实施例1
分别取实施例1a1-1d1制备的基于聚4-乙烯基吡啶-丙烯酸乙酯共聚物的磺酸型薄膜材料(P4VP/SO3 --co-EA)、实施例1a2-1d2制备的基于聚4-乙烯基吡啶-丙烯酸乙酯共聚物的羧酸型薄膜材料(P4VP/SA-co-EA)和实施例2a-2d制备的基于聚4-乙烯基吡啶-甲基丙烯酸二甲氨乙酯共聚物磺酸型薄膜材料(P4VP/SO3 --co-DMAEMA/SO3 -)各50mg,加入到OD=2.5的25mL大肠杆菌菌液中(其中,大肠杆菌的配制方法为将4mL菌种加入到250mL营养液中,37℃环境下培养4h,大肠杆菌的来源于市售),恒温震荡时间4h。同时平行地进行空白对比例试验。然后,将培养好的菌液通过无菌的0.85%NaCl溶液稀释至10-7倍。最后,少许稀释后的菌液涂敷在琼脂培养基上,培养条件为温度37℃,时间12-16h。图5为实施例1c1,1c2,2c制备的薄膜经过上述步骤处理过的平板以及空白对照处理的平板。通过平板计数法观察活菌数,得到原菌液的浓度,计算实施例1-4的抗菌粒子的抗菌率,结果如表3-1所示,抗菌率的计算公式为:
抗菌率=(起始大肠杆菌数-大肠杆菌存活数)/起始大肠杆菌数×100%。
表3-1各实施例制备的薄膜抗菌率
效果实施例2
首先,分别取实施例1c1制备的基于聚4-乙烯基吡啶-丙烯酸乙酯共聚物的磺酸型薄膜材料(P4VP/SO3 --co-EA)、实施例1c2制备的基于聚4-乙烯基吡啶-丙烯酸乙酯共聚物的羧酸型薄膜材料(P4VP/SA-co-EA)和实施例2c制备的基于聚4-乙烯基吡啶-甲基丙烯酸二甲氨乙酯共聚物磺酸型薄膜材料(P4VP/SO3 --co-DMAEMA/SO3 -),配制成0.025g/mL的溶液,在载玻片表面滴加5滴左右已经配制好的0.025g/mL的上述三种聚合物溶液,增加一组滴加去离子水的载玻片作为空白对照,置于干燥箱内烘干。用菌龄为4h(OD600nm=2.5)的大肠杆菌菌液浸润空白载玻片、载玻片表面涂覆(P4VP/SO3 --co-EA)以及表面涂覆(P4VP/SA-co-EA)和(P4VP/SO3 --co-DMAEMA/SO3 -)的载玻片,维持60秒左右,然后进行去离子水清洗,烘干载玻片,利用美蓝染色法对四种载玻片进行染色,最后在倒置光学显微镜(CCD cameramounted on a Nikon Eclipse Ti series microscope with a 40×lens)条件下观察大肠杆菌在四种载玻片上的粘附程度。结果如图6所示,可知本发明的P4VP/SO3 --co-EA、P4VP/SA-co-EA和P4VP/SO3 --co-DMAEMA/SO3 -具有优异的抗细菌粘附效果。
综上,本发明在制备两性离子聚合物共聚物薄膜时,一方面,引入丙烯酸酯类作为共聚物单体,用于改善聚合物的成膜性能、力学性能、机械性能。另一方面,引入4-乙烯基吡啶作为共聚物单体,其不含有酯键或者酰胺键,与丙烯酸酯聚合后通过丙磺内酯或溴乙酰水杨酸酯修饰可形成不可降解的两性离子聚合物共聚物功能薄膜。效果实施例的结果显示该薄膜具有优异的抗菌效果和抗细菌粘附效果,而且稳定性高,使用周期可大大延长,作为新型抗菌防污材料,在生物、环保、化学工业等领域具有良好的应用前景。
Claims (8)
1.一种两性离子共聚物薄膜材料,其特征在于,其为聚4-乙烯基吡啶-丙烯酸酯共聚物经离子化试剂进行季胺化修饰后的产物,所述的聚4-乙烯基吡啶-丙烯酸酯共聚物为由摩尔比为1:9~6:4的式Ⅰ表示的结构单元和式Ⅱ表示的结构单元无规则排列的分子量为50000~200000的共聚物,
式中R1为氢或甲基,R2为选自C1~C12烷基和C1~C12烷基氨基取代的C1~C12烷基中的一种或多种;
所述的两性离子共聚物薄膜材料可由以下步骤制得:
(a)由单体4-乙烯基吡啶和单体丙烯酸酯通过自由基溶液聚合的方式聚合后分离得到聚4-乙烯基吡啶-丙烯酸酯共聚物,4-乙烯基吡啶和丙烯酸酯的摩尔比为1:9~6:4;
(b)由步骤(a)得到的聚4-乙烯基吡啶-丙烯酸酯共聚物与离子化试剂在乙醇中反应后分离得到两性离子共聚物薄膜材料,所述的离子化试剂为丙磺内酯或溴乙酰水杨酸酯,聚4-乙烯基吡啶-丙烯酸酯共聚物中的吡啶官能团与离子化试剂的摩尔比为1:9~6:4。
2.如权利要求1所述的两性离子共聚物薄膜材料,其特征在于,R2选自甲基、乙基、丙基、正丁基、异丁基、十二烷基和二甲氨基乙基中的一种或多种。
3.如权利要求2所述的两性离子共聚物薄膜材料,其特征在于,所述的两性离子共聚物薄膜材料可由以下步骤制得:
(a)由单体4-乙烯基吡啶和单体丙烯酸酯通过自由基溶液聚合的方式聚合后分离得到聚4-乙烯基吡啶-丙烯酸酯共聚物,所述的丙烯酸酯丙烯酸乙酯、甲基丙烯酸二甲氨乙酯、丙烯酸甲酯、丙烯酸正丁酯、丙烯酸异丁酯、甲基丙烯酸正丁酯、甲基丙烯酸月桂酯、甲基丙烯酸烷基酯中的一种或它们的组合,4-乙烯基吡啶和丙烯酸酯的摩尔比为1:9~5:5;聚合反应在无水无氧条件下进行,溶剂为乙醇,引发剂为偶氮二异丁腈,反应温度为60~80℃,反应时间为12~48h;
(b)由步骤(a)得到的聚4-乙烯基吡啶-丙烯酸酯共聚物与离子化试剂在乙醇中反应后分离得到两性离子共聚物薄膜材料,所述的离子化试剂为丙磺内酯或溴乙酰水杨酸酯,聚4-乙烯基吡啶-丙烯酸酯共聚物中的吡啶官能团与离子化试剂的摩尔比为1:1;离子化反应温度为60~65℃,反应时间为12~36h。
4.一种两性离子共聚物薄膜材料的制备方法,其特征在于,包括步骤:
(a)聚4-乙烯基吡啶-丙烯酸酯共聚物的制备
由单体4-乙烯基吡啶和单体丙烯酸酯通过自由基溶液聚合的方式聚合后分离得到聚4-乙烯基吡啶-丙烯酸乙酯共聚物,所述的丙烯酸酯为丙烯酸乙酯、甲基丙烯酸二甲氨乙酯、丙烯酸甲酯、丙烯酸正丁酯、丙烯酸异丁酯、甲基丙烯酸正丁酯、甲基丙烯酸月桂酯、甲基丙烯酸烷基酯中的一种或它们的组合,4-乙烯基吡啶和丙烯酸酯的摩尔比为1:9~6:4;
(b)聚4-乙烯基吡啶-丙烯酸酯共聚物的离子化修饰
由步骤(a)制得的聚4-乙烯基吡啶-丙烯酸酯共聚物与离子化试剂在乙醇中反应后分离得到两性离子共聚物薄膜材料,所述的离子化试剂为丙磺内酯或溴乙酰水杨酸酯,聚4-乙烯基吡啶-丙烯酸酯共聚物中的吡啶官能团与离子化试剂的摩尔比为1:9~6:4。
5.如权利要求4所述的方法,其特征在于,步骤(a)中,所述的丙烯酸酯为丙烯酸乙酯或甲基丙烯酸二甲氨乙酯;聚合反应在无水无氧条件下进行,溶剂为乙醇,引发剂为偶氮二异丁腈,引发剂质量为单体总投料质量的0.01%~0.2%,反应温度为60~80℃,反应时间为12~48h。
6.如权利要求4所述的方法,其特征在于,步骤(b)中,所述的离子化试剂为丙磺内酯或溴乙酰水杨酸酯;离子化反应温度为60~65℃,反应时间为12~36h。
7.如权利要求4所述的方法,其特征在于,
步骤(a)具体为:在无水无氧条件下,向摩尔比为1:9~4:6的4-乙烯基吡啶和丙烯酸乙酯的乙醇溶液中,加入偶氮二异丁腈的乙醇溶液,于60~80℃反应12~36h,然后加入乙醚和/或正己烷产生沉淀,沉淀物经分离干燥得到聚4-乙烯基吡啶-丙烯酸乙酯共聚物;其中乙醇质量与4-乙烯基吡啶和丙烯酸乙酯质量之和的比为20~30:1,偶氮二异丁腈的质量为4-乙烯基吡啶和丙烯酸乙酯质量之和的0.01%~0.1%;
步骤(b)具体为:向步骤(a)制得的聚4-乙烯基吡啶-丙烯酸乙酯共聚物的乙醇溶液中滴加丙磺内酯或溴乙酰水杨酸酯的乙醇溶液,于60~65℃反应12~36h,反应后的溶液滴到乙醚和/或正己烷中产生沉淀,沉淀经分离干燥得到两性离子共聚物薄膜材料;其中乙醇质量与聚4-乙烯基吡啶-丙烯酸乙酯共聚物质量的比为20~30:1。
8.如权利要求4所述的方法,其特征在于,
步骤(a)具体为:在无水无氧条件下,向摩尔比为2:8~5:5的4-乙烯基吡啶和甲基丙烯酸二甲氨乙酯的乙醇溶液中,加入偶氮二异丁腈的乙醇溶液,于60~80℃反应24~48h,然后加入乙醚和/或正己烷产生沉淀,沉淀物经分离干燥得到聚4-乙烯基吡啶-甲基丙烯酸二甲氨乙酯共聚物;其中乙醇质量与4-乙烯基吡啶和甲基丙烯酸二甲氨乙酯质量之和的比为5~15:1,偶氮二异丁腈的质量为4-乙烯基吡啶和甲基丙烯酸二甲氨乙酯质量之和的0.01%~0.2%;
步骤(b)具体为:向步骤(a)制得的聚4-乙烯基吡啶-甲基丙烯酸二甲氨乙酯共聚物的乙醇溶液中滴加丙磺内酯的乙醇溶液,于60~65℃反应12~36h,反应后的溶液滴到乙醚和/或正己烷中产生沉淀,沉淀经分离干燥得到两性离子共聚物薄膜材料;其中乙醇质量与聚4-乙烯基吡啶-甲基丙烯酸二甲氨乙酯共聚物质量的比为20~30:1。
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