JP2024033559A - Copolymer latex for carbon dioxide separation membrane, composition for carbon dioxide separation membrane, carbon dioxide separation membrane, and method for producing carbon dioxide separation membrane - Google Patents
Copolymer latex for carbon dioxide separation membrane, composition for carbon dioxide separation membrane, carbon dioxide separation membrane, and method for producing carbon dioxide separation membrane Download PDFInfo
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- JP2024033559A JP2024033559A JP2022137202A JP2022137202A JP2024033559A JP 2024033559 A JP2024033559 A JP 2024033559A JP 2022137202 A JP2022137202 A JP 2022137202A JP 2022137202 A JP2022137202 A JP 2022137202A JP 2024033559 A JP2024033559 A JP 2024033559A
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- Prior art keywords
- carbon dioxide
- separation membrane
- dioxide separation
- copolymer
- mass
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 322
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 161
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 161
- 229920001577 copolymer Polymers 0.000 title claims abstract description 132
- 239000012528 membrane Substances 0.000 title claims abstract description 122
- 238000000926 separation method Methods 0.000 title claims abstract description 120
- 239000000203 mixture Substances 0.000 title claims abstract description 51
- 229920000126 latex Polymers 0.000 title claims abstract description 50
- 239000004816 latex Substances 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 96
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 35
- 150000001993 dienes Chemical class 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000005345 coagulation Methods 0.000 claims abstract description 11
- 230000015271 coagulation Effects 0.000 claims abstract description 11
- 230000001112 coagulating effect Effects 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 20
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 19
- 239000011787 zinc oxide Substances 0.000 claims description 10
- 230000035699 permeability Effects 0.000 abstract description 32
- 238000010586 diagram Methods 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 36
- 239000000463 material Substances 0.000 description 15
- 238000005259 measurement Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- -1 ethylene, propylene, vinyl Chemical group 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
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- 239000003505 polymerization initiator Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
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- 239000007789 gas Substances 0.000 description 7
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- 230000009477 glass transition Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
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- 229910052757 nitrogen Inorganic materials 0.000 description 6
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 5
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- 238000004378 air conditioning Methods 0.000 description 4
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- 239000003638 chemical reducing agent Substances 0.000 description 4
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- 125000002768 hydroxyalkyl group Chemical group 0.000 description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
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- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000005431 greenhouse gas Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 2
- CTMHWPIWNRWQEG-UHFFFAOYSA-N 1-methylcyclohexene Chemical compound CC1=CCCCC1 CTMHWPIWNRWQEG-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- BYLSIPUARIZAHZ-UHFFFAOYSA-N 2,4,6-tris(1-phenylethyl)phenol Chemical compound C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C(C)C=2C=CC=CC=2)=CC=1C(C)C1=CC=CC=C1 BYLSIPUARIZAHZ-UHFFFAOYSA-N 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 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 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- FSWCCQWDVGZMRD-UHFFFAOYSA-N 4-methylcyclohexene Chemical compound CC1CCC=CC1 FSWCCQWDVGZMRD-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-araboascorbic acid Natural products OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000002211 L-ascorbic acid Substances 0.000 description 2
- 235000000069 L-ascorbic acid Nutrition 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
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- 125000000217 alkyl group Chemical group 0.000 description 2
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
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- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- B01D—SEPARATION
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- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D71/06—Organic material
- B01D71/26—Polyalkenes
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D—SEPARATION
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- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
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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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
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Abstract
【課題】優れた二酸化炭素選択透過性及び十分な二酸化炭素透過性を有し、且つ、優れた強度及び柔軟性を有する二酸化炭素分離膜を提供すること。二酸化炭素分離膜用共重合体ラテックス、二酸化炭素分離膜用組成物、及び、二酸化炭素分離膜の製造方法を提供すること。【解決手段】脂肪族共役ジエン系単量体単位を有する共重合体を含有し、共重合体における脂肪族共役ジエン系単量体単位の含有量が１０～８０質量％である、二酸化炭素分離膜用共重合体ラテックス。当該共重合体を含有する、二酸化炭素分離膜。二酸化炭素分離膜の製造方法であって、二酸化炭素分離膜用組成物を塩凝固法により凝固させる工程を備え、二酸化炭素分離膜用組成物が、当該共重合体を含有する、方法。【選択図】なしAn object of the present invention is to provide a carbon dioxide separation membrane having excellent carbon dioxide permselectivity and sufficient carbon dioxide permeability, as well as excellent strength and flexibility. Provided are a copolymer latex for carbon dioxide separation membranes, a composition for carbon dioxide separation membranes, and a method for producing a carbon dioxide separation membrane. [Solution] Carbon dioxide separation containing a copolymer having an aliphatic conjugated diene monomer unit, the content of the aliphatic conjugated diene monomer unit in the copolymer being 10 to 80% by mass. Copolymer latex for membranes. A carbon dioxide separation membrane containing the copolymer. A method for producing a carbon dioxide separation membrane, the method comprising a step of coagulating a composition for a carbon dioxide separation membrane by a salt coagulation method, wherein the composition for a carbon dioxide separation membrane contains the copolymer. [Selection diagram] None
Description
本発明は、二酸化炭素分離膜用共重合体ラテックス、二酸化炭素分離膜用組成物、二酸化炭素分離膜、及び二酸化炭素分離膜の製造方法に関する。 The present invention relates to a copolymer latex for carbon dioxide separation membranes, a composition for carbon dioxide separation membranes, a carbon dioxide separation membrane, and a method for producing a carbon dioxide separation membrane.
近年、温室効果ガスの排出量を削減することを目的に、温室効果ガスを分離、回収する方法が検討されている。 In recent years, methods of separating and recovering greenhouse gases have been studied with the aim of reducing greenhouse gas emissions.
代表的な温室効果ガスの１つである二酸化炭素を分離、回収する方法としては、例えば、分離膜による分離、吸着体により分離が検討されている。より具体的には、特許文献１では、ポリイミド樹脂及びイオン液体を含有する樹脂組成物からなる樹脂膜により二酸化炭素を分離することが検討されており、特許文献２では、特定の構造を有するポリマーを主成分とし、複数の空孔を有する吸収体により二酸化炭素を吸収・脱離することが検討されている。 As methods for separating and recovering carbon dioxide, which is one of the typical greenhouse gases, separation using a separation membrane and separation using an adsorbent are being considered, for example. More specifically, Patent Document 1 considers separating carbon dioxide using a resin membrane made of a resin composition containing a polyimide resin and an ionic liquid, and Patent Document 2 considers separating carbon dioxide using a resin membrane made of a resin composition containing a polyimide resin and an ionic liquid. It is being considered that carbon dioxide can be absorbed and desorbed using an absorber containing carbon dioxide as the main component and having multiple pores.
ところで、上述の特許文献１に記載の分離膜の他、種々の二酸化炭素分離膜が検討されているが、引き続き二酸化炭素選択透過性に優れた二酸化炭素分離膜が求められている。また、二酸化炭素分離膜には、優れた強度及び柔軟性を有することが求められている。 Incidentally, various carbon dioxide separation membranes have been studied in addition to the separation membrane described in Patent Document 1 mentioned above, but a carbon dioxide separation membrane with excellent carbon dioxide permselectivity is still being sought. Further, carbon dioxide separation membranes are required to have excellent strength and flexibility.
本発明は、優れた二酸化炭素選択透過性及び十分な二酸化炭素透過性を有し、且つ、優れた強度及び柔軟性を有する二酸化炭素分離膜を提供することを目的とする。また、本発明は、二酸化炭素分離膜用共重合体ラテックス、二酸化炭素分離膜用組成物、及び二酸化炭素分離膜の製造方法を提供することを目的とする。 An object of the present invention is to provide a carbon dioxide separation membrane having excellent carbon dioxide permselectivity and sufficient carbon dioxide permeability, as well as excellent strength and flexibility. Another object of the present invention is to provide a copolymer latex for carbon dioxide separation membranes, a composition for carbon dioxide separation membranes, and a method for producing carbon dioxide separation membranes.
本発明者らは、脂肪族共役ジエン系単量体単位を特定の含有量で有する共重合体ラテックスを含有する組成物から形成される二酸化炭素分離膜が、優れた二酸化炭素選択透過性及び十分な二酸化炭素透過性を有し、且つ、優れた膜強度及び柔軟性を有することを見出した。 The present inventors have discovered that a carbon dioxide separation membrane formed from a composition containing a copolymer latex having a specific content of aliphatic conjugated diene monomer units has excellent carbon dioxide permselectivity and sufficient It has been found that the membrane has excellent carbon dioxide permeability, as well as excellent membrane strength and flexibility.
すなわち、本発明は、以下の［１］～［６］を提供する。
［１］脂肪族共役ジエン系単量体単位を有する共重合体を含有し、
前記共重合体における前記脂肪族共役ジエン系単量体単位の含有量が１０～８０質量％である、二酸化炭素分離膜用共重合体ラテックス。
［２］前記共重合体が、エチレン系不飽和カルボン酸単量体単位を更に有し、
前記共重合体における前記エチレン系不飽和カルボン酸単量体単位の含有量が０．１～１０質量％である、［１］に記載の二酸化炭素分離膜用共重合体ラテックス。
［３］［１］又は［２］に記載の二酸化炭素分離膜用共重合体ラテックスを含有する、二酸化炭素分離膜用組成物。
［４］酸化亜鉛を更に含有する、［３］に記載の二酸化炭素分離膜用組成物。
［５］脂肪族共役ジエン系単量体単位を有する共重合体を含有し、
前記共重合体における前記脂肪族共役ジエン系単量体単位の含有量が１０～８０質量％である、二酸化炭素分離膜。
［６］二酸化炭素分離膜の製造方法であって、
二酸化炭素分離膜用組成物を塩凝固法により凝固させる工程を備え、
前記二酸化炭素分離膜用組成物が、脂肪族共役ジエン系単量体単位を有する共重合体を含有し、
前記共重合体における前記脂肪族共役ジエン系単量体単位の含有量が１０～８０質量％である、方法。
That is, the present invention provides the following [1] to [6].
[1] Contains a copolymer having an aliphatic conjugated diene monomer unit,
A copolymer latex for a carbon dioxide separation membrane, wherein the content of the aliphatic conjugated diene monomer unit in the copolymer is 10 to 80% by mass.
[2] The copolymer further has an ethylenically unsaturated carboxylic acid monomer unit,
The copolymer latex for a carbon dioxide separation membrane according to [1], wherein the content of the ethylenically unsaturated carboxylic acid monomer unit in the copolymer is 0.1 to 10% by mass.
[3] A composition for a carbon dioxide separation membrane, comprising the copolymer latex for a carbon dioxide separation membrane according to [1] or [2].
[4] The composition for a carbon dioxide separation membrane according to [3], further containing zinc oxide.
[5] Contains a copolymer having an aliphatic conjugated diene monomer unit,
A carbon dioxide separation membrane, wherein the content of the aliphatic conjugated diene monomer unit in the copolymer is 10 to 80% by mass.
[6] A method for manufacturing a carbon dioxide separation membrane, comprising:
comprising a step of coagulating a composition for a carbon dioxide separation membrane by a salt coagulation method,
The carbon dioxide separation membrane composition contains a copolymer having an aliphatic conjugated diene monomer unit,
The method, wherein the content of the aliphatic conjugated diene monomer unit in the copolymer is 10 to 80% by mass.
本発明によれば、優れた二酸化炭素選択透過性及び十分な二酸化炭素透過性を有し、且つ、優れた強度及び柔軟性を有する二酸化炭素分離膜を提供することができる。また、本発明によれば、二酸化炭素分離膜用共重合体ラテックス、二酸化炭素分離膜用組成物、及び二酸化炭素分離膜の製造方法を提供することができる。 According to the present invention, it is possible to provide a carbon dioxide separation membrane that has excellent carbon dioxide permselectivity and sufficient carbon dioxide permeability, as well as excellent strength and flexibility. Further, according to the present invention, it is possible to provide a copolymer latex for carbon dioxide separation membranes, a composition for carbon dioxide separation membranes, and a method for producing a carbon dioxide separation membrane.
以下、本発明の実施形態について詳細に説明する。ただし、本発明は以下の実施形態に限定されるものではない。 Embodiments of the present invention will be described in detail below. However, the present invention is not limited to the following embodiments.
［二酸化炭素分離膜用共重合体ラテックス］
本発明の一実施形態に係る二酸化炭素分離膜用共重合体ラテックス（以下、単に「共重合体ラテックス」ともいう）は、脂肪族共役ジエン系単量体単位を有する共重合体を含有する。共重合体における脂肪族共役ジエン系単量体単位の含有量は、１０～８０質量％である。以下、この共重合体を「共重合体Ａ」ともいう。
[Copolymer latex for carbon dioxide separation membrane]
A copolymer latex for a carbon dioxide separation membrane (hereinafter also simply referred to as "copolymer latex") according to an embodiment of the present invention contains a copolymer having an aliphatic conjugated diene monomer unit. The content of aliphatic conjugated diene monomer units in the copolymer is 10 to 80% by mass. Hereinafter, this copolymer will also be referred to as "copolymer A."
脂肪族共役ジエン系単量体としては、例えば、１，３－ブタジエン、２－メチル－１，３－ブタジエン、２，３－ジメチル－１，３－ブタジエン、２－クロル－１，３－ブタジエン、ペンタジエン類（例えば、置換直鎖共役ペンタジエン類）、及びヘキサジエン類（例えば、置換及び側鎖共役ヘキサジエン類）が挙げられる。共重合体Ａは、１種又は２種以上の脂肪族共役ジエン系単量体単位を有していてもよい。共重合体Ａは、得られる二酸化炭素分離膜の強度及び柔軟性がより優れる観点から、脂肪族共役ジエン系単量体単位として１，３－ブタジエンに由来する構造単位を有することが好ましい。 Examples of aliphatic conjugated diene monomers include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, and 2-chloro-1,3-butadiene. , pentadienes (eg, substituted linear conjugated pentadienes), and hexadienes (eg, substituted and side chain conjugated hexadienes). Copolymer A may have one or more aliphatic conjugated diene monomer units. Copolymer A preferably has a structural unit derived from 1,3-butadiene as the aliphatic conjugated diene monomer unit, from the viewpoint of improving the strength and flexibility of the resulting carbon dioxide separation membrane.
共重合体Ａにおける脂肪族共役ジエン系単量体単位の含有量は、１０～８０質量％である。脂肪族共役ジエン系単量体単位の含有量が１０質量％以上であることにより、共重合体Ａを含む組成物を成膜することが可能となり、二酸化炭素分離膜を作製することができる。脂肪族共役ジエン系単量体単位の含有量が８０質量％以下であることにより、優れた二酸化炭素選択透過性、十分な二酸化炭素透過性、強度、及び柔軟性を実現することができる。共重合体Ａにおける脂肪族共役ジエン系単量体単位の含有量は、得られる二酸化炭素分離膜の二酸化炭素透過性がより優れる観点から、２０質量％以上であることが好ましく、３０質量％以上であることがより好ましい。共重合体Ａにおける脂肪族共役ジエン系単量体単位の含有量は、得られる二酸化炭素分離膜の強度及び柔軟性がより優れる観点から、７５質量％以下であることが好ましく、７０質量％以下であることがより好ましい。これらの観点から、共重合体Ａにおける脂肪族共役ジエン系単量体単位の含有量は、２０～７５質量％であることが好ましく、３０～７０質量％であることがより好ましい。 The content of aliphatic conjugated diene monomer units in copolymer A is 10 to 80% by mass. When the content of the aliphatic conjugated diene monomer unit is 10% by mass or more, it becomes possible to form a composition containing copolymer A into a film, and a carbon dioxide separation membrane can be produced. When the content of aliphatic conjugated diene monomer units is 80% by mass or less, excellent carbon dioxide permselectivity, sufficient carbon dioxide permeability, strength, and flexibility can be achieved. The content of aliphatic conjugated diene monomer units in copolymer A is preferably 20% by mass or more, and 30% by mass or more, from the viewpoint of better carbon dioxide permeability of the resulting carbon dioxide separation membrane. It is more preferable that The content of aliphatic conjugated diene monomer units in copolymer A is preferably 75% by mass or less, and 70% by mass or less, from the viewpoint of better strength and flexibility of the resulting carbon dioxide separation membrane. It is more preferable that From these viewpoints, the content of aliphatic conjugated diene monomer units in copolymer A is preferably 20 to 75% by mass, more preferably 30 to 70% by mass.
共重合体Ａは、脂肪族共役ジエン系単量体単位に加えて、シアン化ビニル系単量体単位、芳香族ビニル系単量体単位、不飽和カルボン酸アルキルエステル系単量体単位、ヒドロキシアルキル基を含有する不飽和単量体単位、エチレン系不飽和カルボン酸単量体単位、不飽和カルボン酸アミド系単量体単位、不飽和二重結合を２つ以上含有する多官能エチレン系不飽和単量体単位等を有していてもよい。共重合体Ａは、二酸化炭素分離膜の強度及び柔軟性がより優れる観点から、エチレン系不飽和カルボン酸単量体単位を有していてもよい。共重合体Ａは、これらの単量体単位を１種又は２種以上を有していてもよい。 Copolymer A contains, in addition to aliphatic conjugated diene monomer units, vinyl cyanide monomer units, aromatic vinyl monomer units, unsaturated carboxylic acid alkyl ester monomer units, and hydroxyl monomer units. Unsaturated monomer units containing alkyl groups, ethylenically unsaturated carboxylic acid monomer units, unsaturated carboxylic acid amide monomer units, polyfunctional ethylenically unsaturated monomer units containing two or more unsaturated double bonds. It may contain saturated monomer units and the like. Copolymer A may have an ethylenically unsaturated carboxylic acid monomer unit from the viewpoint of improving the strength and flexibility of the carbon dioxide separation membrane. Copolymer A may have one or more of these monomer units.
シアン化ビニル系単量体としては、例えば、アクリロニトリル、メタクリロニトリル、α－クロルアクリロニトリル、及びα－エチルアクリロニトリルが挙げられる。共重合体Ａは、１種又は２種以上のシアン化ビニル系単量体単位を有していてもよい。共重合体Ａは、シアン化ビニル系単量体単位としてアクリロニトリルに由来する構造単位を有していてもよい。 Examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and α-ethyl acrylonitrile. Copolymer A may have one or more types of vinyl cyanide monomer units. Copolymer A may have a structural unit derived from acrylonitrile as a vinyl cyanide monomer unit.
共重合体Ａにおけるシアン化ビニル系単量体単位の含有量は、５０質量％以下であることが好ましく、４０質量％以下であることがより好ましく、３０質量％以下であることが更に好ましい。共重合体Ａにおけるシアン化ビニル系単量体単位の含有量は、１質量％以上、３質量％以上、又は５質量％以上であってもよい。 The content of vinyl cyanide monomer units in copolymer A is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less. The content of vinyl cyanide monomer units in copolymer A may be 1% by mass or more, 3% by mass or more, or 5% by mass or more.
芳香族ビニル系単量体としては、例えば、スチレン、α－メチルスチレン、メチル－α－メチルスチレン、ビニルトルエン、及びジビニルベンゼンが挙げられる。共重合体Ａは、１種又は２種以上の芳香族ビニル系単量体単位を有していてもよい。共重合体Ａは、芳香族ビニル系単量体単位としてスチレンに由来する構造単位を有していてもよい。 Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, methyl-α-methylstyrene, vinyltoluene, and divinylbenzene. Copolymer A may have one or more aromatic vinyl monomer units. Copolymer A may have a structural unit derived from styrene as an aromatic vinyl monomer unit.
共重合体Ａにおける芳香族ビニル系単量体単位の含有量は、８０質量％以下、７０質量％以下、又は６５質量％以下であってよく、２０質量％以上、２５質量％以上、又は３０質量％以上であってもよい。 The content of aromatic vinyl monomer units in copolymer A may be 80% by mass or less, 70% by mass or less, or 65% by mass or less, 20% by mass or more, 25% by mass or more, or 30% by mass or less. It may be more than % by mass.
不飽和カルボン酸アルキルエステル系単量体としては、例えば、メチルアクリレート、メチルメタクリレート、エチルアクリレート、エチルメタクリレート、ブチルアクリレート、グリシジルメタクリレート、ジメチルフマレート、ジエチルフマレート、ジメチルマレエート、ジエチルマレエート、ジメチルイタコネート、モノメチルフマレート、モノエチルフマレート、及び２－エチルヘキシルアクリレートが挙げられる。共重合体Ａは、１種又は２種以上の不飽和カルボン酸アルキルエステル系単量体単位を有していてもよい。共重合体Ａは、不飽和カルボン酸アルキルエステル系単量体単位としてメチルメタクリレートに由来する構造単位を有していてもよい。 Examples of unsaturated carboxylic acid alkyl ester monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, glycidyl methacrylate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl maleate, and dimethyl. Itaconate, monomethyl fumarate, monoethyl fumarate, and 2-ethylhexyl acrylate. Copolymer A may have one or more unsaturated carboxylic acid alkyl ester monomer units. Copolymer A may have a structural unit derived from methyl methacrylate as an unsaturated carboxylic acid alkyl ester monomer unit.
共重合体Ａにおける不飽和カルボン酸アルキルエステル系単量体単位の含有量は、８０質量％以下、７０質量％以下、又は６０質量％以下であってよく、１質量％以上、２質量％以上、又は３質量％以上であってもよい。 The content of unsaturated carboxylic acid alkyl ester monomer units in copolymer A may be 80% by mass or less, 70% by mass or less, or 60% by mass or less, and 1% by mass or more, 2% by mass or more. , or 3% by mass or more.
ヒドロキシアルキル基を含有する不飽和単量体としては、例えば、ヒドロキシエチルアクリレート、ヒドロキシエチルメタクリレート、ヒドロキシプロピルアクリレート、ヒドロキシプロピルメタクリレート、ヒドロキシブチルアクリレート、ヒドロキシブチルメタクリレート、３－クロロ－２－ヒドロキシプロピルメタクリレート、ジ－（エチレングリコール）マレエート、ジ－（エチレングリコール）イタコネート、２－ヒドロキシエチルマレエート、ビス（２－ヒドロキシエチル）マレエート、及び２－ヒドロキシエチルメチルフマレートが挙げられる。共重合体Ａは、１種又は２種以上のヒドロキシアルキル基を含有する不飽和単量体単位を有していてもよい。共重合体Ａは、ヒドロキシアルキル基を含有する不飽和単量体単位としてβ－ヒドロキシエチルアクリレートに由来する構造単位を有していてもよい。 Examples of the unsaturated monomer containing a hydroxyalkyl group include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, Di-(ethylene glycol) maleate, di-(ethylene glycol) itaconate, 2-hydroxyethyl maleate, bis(2-hydroxyethyl) maleate, and 2-hydroxyethylmethyl fumarate. Copolymer A may have unsaturated monomer units containing one or more hydroxyalkyl groups. Copolymer A may have a structural unit derived from β-hydroxyethyl acrylate as an unsaturated monomer unit containing a hydroxyalkyl group.
共重合体Ａにおけるヒドロキシアルキル基を含有する不飽和単量体単位の含有量は、１０質量％以下、５質量％以下、又は３質量％以下であってよく、０．１質量％以上、０．５質量％以上、又は１質量％以上であってもよい。 The content of unsaturated monomer units containing hydroxyalkyl groups in copolymer A may be 10% by mass or less, 5% by mass or less, or 3% by mass or less, 0.1% by mass or more, 0. It may be .5% by mass or more, or 1% by mass or more.
不飽和カルボン酸アミド系単量体としては、例えば、アクリルアミド、メタクリルアミド、Ｎ－メチロールアクリルアミド、Ｎ－メチロールメタクリルアミド、及びＮ，Ｎ－ジメチルアクリルアミドが挙げられる。共重合体Ａは、１種又は２種以上の不飽和カルボン酸アミド系単量体単位を有していてもよい。共重合体Ａは、不飽和カルボン酸アミド系単量体単位としてアクリルアミドに由来する構造単位を有していてもよい。 Examples of the unsaturated carboxylic acid amide monomer include acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, and N,N-dimethylacrylamide. Copolymer A may have one or more unsaturated carboxylic acid amide monomer units. Copolymer A may have a structural unit derived from acrylamide as an unsaturated carboxylic acid amide monomer unit.
エチレン系不飽和カルボン酸単量体としては、例えば、アクリル酸、メタクリル酸、クロトン酸等のモノカルボン酸；及びマレイン酸、フマル酸、イタコン酸等のジカルボン酸を挙げることができる。共重合体Ａは、１種又は２種以上のエチレン系不飽和カルボン酸単量体単位を有していてもよい。共重合体Ａは、エチレン系不飽和カルボン酸単量体単位として、アクリル酸、メタクリル酸、イタコン酸、及びフマル酸からなる群より選ばれる少なくとも一種に由来する構造単位を有していてもよい。 Examples of the ethylenically unsaturated carboxylic acid monomer include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; and dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid. Copolymer A may have one or more ethylenically unsaturated carboxylic acid monomer units. Copolymer A may have a structural unit derived from at least one selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, and fumaric acid as an ethylenically unsaturated carboxylic acid monomer unit. .
共重合体Ａにおけるエチレン系不飽和カルボン酸単量体単位の含有量は、０．１～１０質量％であることが好ましい。エチレン系不飽和カルボン酸単量体単位の含有量が０．１質量％以上であることにより、共重合体Ａを安定して重合することができるため、凝集物の生成を抑制することができ、得られる二酸化炭素分離膜の強度及び柔軟性がより優れる。エチレン系不飽和カルボン酸単量体単位の含有量が１０質量％以下であることにより、共重合体Ａの合成時の粘度が高くなりすぎることを抑制できるため、十分に撹拌することができ、共重合体Ａを安定して重合することができる。さらに、得られる共重合体Ａを成膜しやすい傾向がある。共重合体Ａにおけるエチレン系不飽和カルボン酸単量体単位の含有量は、０．５質量％以上であることがより好ましく、１質量％以上であることが更に好ましい。共重合体Ａにおけるエチレン系不飽和カルボン酸単量体単位の含有量は、８質量％以下であることがより好ましく、７質量％以下であることが更に好ましい。共重合体Ａにおけるエチレン系不飽和カルボン酸単量体単位の含有量は、０．５～８質量％であることがより好ましく、１～７質量％であることが更に好ましい。 The content of ethylenically unsaturated carboxylic acid monomer units in copolymer A is preferably 0.1 to 10% by mass. When the content of the ethylenically unsaturated carboxylic acid monomer unit is 0.1% by mass or more, the copolymer A can be stably polymerized, so that the formation of aggregates can be suppressed. , the resulting carbon dioxide separation membrane has better strength and flexibility. By having a content of ethylenically unsaturated carboxylic acid monomer units of 10% by mass or less, it is possible to suppress the viscosity from becoming too high during the synthesis of copolymer A, so that sufficient stirring is possible, Copolymer A can be stably polymerized. Furthermore, the resulting copolymer A tends to be easily formed into a film. The content of ethylenically unsaturated carboxylic acid monomer units in copolymer A is more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. The content of ethylenically unsaturated carboxylic acid monomer units in copolymer A is more preferably 8% by mass or less, and even more preferably 7% by mass or less. The content of ethylenically unsaturated carboxylic acid monomer units in copolymer A is more preferably from 0.5 to 8% by mass, and even more preferably from 1 to 7% by mass.
不飽和二重結合を２つ以上含有する多官能エチレン系不飽和単量体としては、例えば、アリルメタクリレート；エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート等のポリエチレングリコールジ（メタ）アクリレート；及びジビニルベンゼン等のジビニル化合物が挙げられる。共重合体Ａは、１種又は２種以上の多官能エチレン系不飽和単量体単位を有していてもよい。共重合体Ａは、多官能エチレン系不飽和単量体としてアリルメタクリレート、エチレングリコールジメタクリレート、及びジビニルベンゼンからなる群より選ばれる少なくとも一種に由来する構造単位を有していてもよい。 Examples of polyfunctional ethylenically unsaturated monomers containing two or more unsaturated double bonds include allyl methacrylate; ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and triethylene glycol di(meth)acrylate. Examples include polyethylene glycol di(meth)acrylate such as acrylate; and divinyl compounds such as divinylbenzene. Copolymer A may have one or more polyfunctional ethylenically unsaturated monomer units. Copolymer A may have a structural unit derived from at least one selected from the group consisting of allyl methacrylate, ethylene glycol dimethacrylate, and divinylbenzene as a polyfunctional ethylenically unsaturated monomer.
共重合体Ａは、上述した単量体に加えて、エチレン、プロピレン、酢酸ビニル、プロピオン酸ビニル、塩化ビニル、塩化ビニリデン等の乳化重合において通常使用される任意の単量体に由来する構造単位を有していてもよい。 In addition to the above-mentioned monomers, copolymer A contains structural units derived from arbitrary monomers commonly used in emulsion polymerization, such as ethylene, propylene, vinyl acetate, vinyl propionate, vinyl chloride, and vinylidene chloride. It may have.
共重合体Ａの重合には、公知の乳化剤、界面活性剤を使用することができる。界面活性剤としては、例えば、高級アルコールの硫酸エステル塩、アルキルベンゼンスルホン酸塩（例えば、ドデシルベンゼンスルホン酸ナトリウム）、アルキルジフェニルエーテルジスルホン酸塩（例えば、アルキルジフェニルエーテルジスルホン酸ナトリウム）、脂肪族スルホン酸塩、脂肪族カルボン酸塩、デヒドロアビエチン酸塩、ナフタレンスルホン酸のホルマリン縮合物、非イオン性界面活性剤の硫酸エステル塩等のアニオン性界面活性剤；ポリエチレングリコールのアルキルエステル型、アルキルフェニルエーテル型（例えば、ポリオキシエチレンラウリルエーテル）、アルキルエーテル型等のノニオン性界面活性剤を使用することができる。乳化剤、界面活性剤は１種単独で用いてもよく、２種以上を併用してもよい。 In the polymerization of copolymer A, known emulsifiers and surfactants can be used. Examples of the surfactant include higher alcohol sulfate ester salts, alkylbenzene sulfonates (e.g., sodium dodecylbenzene sulfonate), alkyldiphenyl ether disulfonates (e.g., sodium alkyl diphenyl ether disulfonate), aliphatic sulfonates, Anionic surfactants such as aliphatic carboxylates, dehydroabietates, formalin condensates of naphthalene sulfonic acid, sulfate ester salts of nonionic surfactants; alkyl ester types of polyethylene glycol, alkylphenyl ether types (e.g. , polyoxyethylene lauryl ether), alkyl ether type, and the like can be used. The emulsifier and surfactant may be used alone or in combination of two or more.
共重合体Ａの重合には、公知の連鎖移動剤を使用することができる。連鎖移動剤としては、例えば、ｎ－ヘキシルメルカプタン、ｎ－オクチルメルカプタン、ｔ－オクチルメルカプタン、ｎ－ドデシルメルカプタン、ｔ－ドデシルメルカプタン、ｎ－ステアリルメルカプタン等のアルキルメルカプタン化合物；ジメチルキサントゲンジサルファイド、ジイソプロピルキサントゲンジサルファイド等のキサントゲン化合物；テトラメチルチウラムジスルフィド、テトラエチルチウラムジスルフィド、テトラメチルチウラムモノスルフィド等のチウラム系化合物；２，６－ジ－ｔ－ブチル－４－メチルフェノール、スチレン化フェノール等のフェノール系化合物；アリルアルコール等のアリル化合物；ジクロルメタン、ジブロモメタン、四臭化炭素等のハロゲン化炭化水素化合物；α－ベンジルオキシスチレン、α－ベンジルオキシアクリロニトリル、α－ベンジルオキシアクリルアミド等のビニルエーテル；トリフェニルエタン、ペンタフェニルエタン、アクロレイン、メタアクロレイン、チオグリコール酸、チオリンゴ酸、２－エチルヘキシルチオグリコレート、ターピノレン、及びα－メチルスチレンダイマー等が挙げられる。これらは１種単独で用いてもよく、２種以上を併用してもよい。 In the polymerization of copolymer A, a known chain transfer agent can be used. Examples of chain transfer agents include alkylmercaptan compounds such as n-hexylmercaptan, n-octylmercaptan, t-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, and n-stearylmercaptan; dimethylxanthogen disulfide, diisopropylxanthogen Xanthogen compounds such as disulfide; thiuram compounds such as tetramethylthiuram disulfide, tetraethylthiuram disulfide, and tetramethylthiuram monosulfide; phenolic compounds such as 2,6-di-t-butyl-4-methylphenol and styrenated phenol ; Allyl compounds such as allyl alcohol; Halogenated hydrocarbon compounds such as dichloromethane, dibromomethane, and carbon tetrabromide; Vinyl ethers such as α-benzyloxystyrene, α-benzyloxyacrylonitrile, α-benzyloxyacrylamide; triphenylethane, Examples include pentaphenylethane, acrolein, methacrolein, thioglycolic acid, thiomalic acid, 2-ethylhexylthioglycolate, terpinolene, and α-methylstyrene dimer. These may be used alone or in combination of two or more.
共重合体Ａの重合には、公知の重合開始剤を使用することができる。重合開始剤としては、例えば、過硫酸リチウム、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム等の水溶性重合開始剤；クメンハイドロパーオキサイド、過酸化ベンゾイル、t－ブチルハイドロパーオキサイド、アセチルパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、１，１，３，３－テトラメチルブチルハイドロパーオキサイド等の油溶性重合開始剤が挙げられる。重合開始剤は、過硫酸カリウム、過硫酸ナトリウム、クメンハイドロパーオキサイド、及びt－ブチルハイドロパーオキサイドからなる群より選ばれる少なくとも一種であることが好ましい。重合開始剤の使用量は特に制限されず、単量体の組成、重合反応系のｐＨ、他の添加剤との組み合わせを考慮して適宜調整することができる。 For polymerization of copolymer A, a known polymerization initiator can be used. Examples of the polymerization initiator include water-soluble polymerization initiators such as lithium persulfate, potassium persulfate, sodium persulfate, and ammonium persulfate; cumene hydroperoxide, benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, Examples include oil-soluble polymerization initiators such as diisopropylbenzene hydroperoxide and 1,1,3,3-tetramethylbutyl hydroperoxide. The polymerization initiator is preferably at least one selected from the group consisting of potassium persulfate, sodium persulfate, cumene hydroperoxide, and t-butyl hydroperoxide. The amount of the polymerization initiator to be used is not particularly limited, and can be appropriately adjusted in consideration of the monomer composition, the pH of the polymerization reaction system, and the combination with other additives.
共重合体Ａの重合には、公知の還元剤を使用することができる。還元剤としては、例えば、デキストロース、サッカロース等の還元糖類；ジメチルアニリン、トリエタノールアミン等のアミン類；Ｌ－アスコルビン酸、エリソルビン酸、酒石酸、クエン酸等のカルボン酸類及びその塩；亜硫酸塩、亜硫酸水素塩、ピロ亜硫酸塩、亜ニチオン酸塩、ニチオン酸塩、チオ硫酸塩、ホルムアルデヒドスルホン酸塩、及びベンズアルデヒドスルホン酸塩が挙げられる。還元剤は、Ｌ－アスコルビン酸又はエリソルビン酸であることが好ましい。還元剤の使用量は、単量体の組成、重合反応系のｐＨ、他の添加剤との組み合わせを考慮して適宜調整することができる。 In the polymerization of copolymer A, a known reducing agent can be used. Examples of reducing agents include reducing sugars such as dextrose and sucrose; amines such as dimethylaniline and triethanolamine; carboxylic acids and their salts such as L-ascorbic acid, erythorbic acid, tartaric acid, and citric acid; sulfites and sulfurous acids. Hydrogen salts, pyrosulfites, dithionites, dithionates, thiosulfates, formaldehyde sulfonates, and benzaldehyde sulfonates are mentioned. Preferably, the reducing agent is L-ascorbic acid or erythorbic acid. The amount of the reducing agent to be used can be appropriately adjusted in consideration of the monomer composition, the pH of the polymerization reaction system, and the combination with other additives.
共重合体Ａの重合には、水及び公知の有機溶媒を使用することができる。有機溶媒としては、例えば、ペンタン、ヘキサン、ヘプタン、オクタン、シクロヘキサン、シクロヘプタン等の飽和炭化水素；ペンテン、ヘキセン、ヘプテン、シクロペンテン、シクロヘキセン、シクロヘプテン、４－メチルシクロヘキセン、１－メチルシクロヘキセン等の不飽和炭化水素；ベンゼン、トルエン、キシレン等の芳香族炭化水素などの炭化水素化合物を使用することができる。有機溶媒は、沸点が適度に低く、重合終了後に水蒸気蒸留等によって回収、再利用しやすく、環境保全の観点から、シクロヘキセン又はトルエンであることが好ましい。 For polymerization of copolymer A, water and known organic solvents can be used. Examples of organic solvents include saturated hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, and cycloheptane; unsaturated hydrocarbons such as pentene, hexene, heptene, cyclopentene, cyclohexene, cycloheptene, 4-methylcyclohexene, and 1-methylcyclohexene. Hydrocarbon: Hydrocarbon compounds such as aromatic hydrocarbons such as benzene, toluene, and xylene can be used. The organic solvent is preferably cyclohexene or toluene, which has a suitably low boiling point and can be easily recovered and reused by steam distillation or the like after completion of polymerization, and from the viewpoint of environmental conservation.
共重合体Ａの重合には、必要に応じて酸素捕捉剤、キレート剤、分散剤、消泡剤、老化防止剤、防腐剤、抗菌剤、難燃剤、紫外線吸収剤等の公知の添加剤を用いることができる。これら添加剤は、種類、使用量ともに特に限定されず、適宜使用することができる。 In the polymerization of copolymer A, known additives such as oxygen scavengers, chelating agents, dispersants, antifoaming agents, antiaging agents, preservatives, antibacterial agents, flame retardants, and ultraviolet absorbers are added as necessary. Can be used. These additives are not particularly limited in type or amount, and can be used as appropriate.
共重合体Ａの重合時において、上述した単量体成分及び添加剤等の単量体成分以外の成分を反応系に添加する方法としては、例えば、一括添加方法、分割添加方法、連続添加方法、及びパワーフィード方法が挙げられる。 During the polymerization of copolymer A, methods for adding components other than monomer components such as the above-mentioned monomer components and additives to the reaction system include, for example, a batch addition method, a divided addition method, and a continuous addition method. , and power feed methods.
共重合体Ａは、乳化重合、懸濁重合、溶液重合、塊状重合等の公知の重合方法により上述した単量体を重合させることにより得ることができる。 Copolymer A can be obtained by polymerizing the above-mentioned monomers using known polymerization methods such as emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization.
重合反応の温度は、用いる単量体成分の種類等によって異なるが、例えば、４０～１５０℃であってもよい。重合反応の反応時間は、例えば、５～１５時間であってもよい。 The temperature of the polymerization reaction varies depending on the type of monomer component used, but may be, for example, 40 to 150°C. The reaction time of the polymerization reaction may be, for example, 5 to 15 hours.
共重合体Ａの重合は、反応系に添加した単量体成分の重合反応の終了時におけるポリマー転化率が９７％を超えたことを確認して反応を終了させることが好ましい。すなわち、共重合体Ａの重合反応の終了時におけるポリマー転化率は、９７％超であることが好ましい。ポリマー転化率は、反応系の固形分の質量、又は重合反応器の槽内を冷却した熱量から算出することができる。 The polymerization of copolymer A is preferably terminated after confirming that the polymer conversion rate of the monomer components added to the reaction system exceeds 97% at the end of the polymerization reaction. That is, the polymer conversion rate of copolymer A at the end of the polymerization reaction is preferably over 97%. The polymer conversion rate can be calculated from the mass of solid content in the reaction system or the amount of heat used to cool the inside of the polymerization reactor.
重合反応を終了させるために、重合停止剤を用いてもよい。重合反応の終了後、蒸留等により未反応の単量体成分等を除去してもよい。 A polymerization terminator may be used to terminate the polymerization reaction. After the polymerization reaction is completed, unreacted monomer components may be removed by distillation or the like.
共重合体ラテックスのガラス転移温度、ゲル含有率、及び数平均粒子径は、特に限定されないが、共重合体ラテックスの重合安定性等の観点から、以下の範囲であることが好ましい。共重合体ラテックスのガラス転移温度は、－４０～６０℃であることが好ましく、－３５～３０℃であることがより好ましい。共重合体ラテックスの数平均粒子径は、５０～３００ｎｍであることが好ましく、７０～２５０ｎｍであることがより好ましい。共重合体ラテックスのゲル含有率は、２０～９５質量％であることが好ましい。共重合体ラテックスのガラス転移温度、ゲル含有率、及び数平均粒子径は、共重合体ラテックスの重合時に使用する乳化剤、重合開始剤、連鎖移動剤等の種類、使用量、及び添加方法、並びに、水の割合等を適宜調整することにより調整することができる。共重合体ラテックスのガラス転移温度、ゲル含有率、及び数平均粒子径は、それぞれ後述の実施例に記載の方法により測定することができる。 The glass transition temperature, gel content, and number average particle diameter of the copolymer latex are not particularly limited, but are preferably within the following ranges from the viewpoint of polymerization stability of the copolymer latex. The glass transition temperature of the copolymer latex is preferably -40 to 60°C, more preferably -35 to 30°C. The number average particle diameter of the copolymer latex is preferably 50 to 300 nm, more preferably 70 to 250 nm. The gel content of the copolymer latex is preferably 20 to 95% by mass. The glass transition temperature, gel content, and number average particle diameter of the copolymer latex are determined by the type, amount, and addition method of the emulsifier, polymerization initiator, chain transfer agent, etc. used during polymerization of the copolymer latex, and This can be adjusted by appropriately adjusting the proportion of water, etc. The glass transition temperature, gel content, and number average particle diameter of the copolymer latex can be measured by the methods described in Examples below.
共重合体ラテックスは、加熱減圧蒸留、水蒸気蒸留等の方法により、未反応の単量体成分及び他の低沸点成分が除去されていることが好ましい。 It is preferable that unreacted monomer components and other low-boiling components are removed from the copolymer latex by a method such as heating under reduced pressure distillation or steam distillation.
共重合体ラテックスは、分散安定性及び活物質への被覆性の観点から、アンモニア、水酸化カリウム、水酸化ナトリウム等のｐＨ調整剤を添加することにより、ｐＨを調整してもよい。共重合体ラテックスのｐＨは、５～９であることが好ましく、５．５～８．５であることがより好ましい。 The pH of the copolymer latex may be adjusted by adding a pH adjuster such as ammonia, potassium hydroxide, or sodium hydroxide from the viewpoint of dispersion stability and coverage of the active material. The pH of the copolymer latex is preferably 5 to 9, more preferably 5.5 to 8.5.
［二酸化炭素分離膜用組成物］
上述した共重合体ラテックスは、二酸化炭素分離膜用組成物（以下、「組成物Ｂ」ともいう）として用いることができる。すなわち、本発明の他の一実施形態は、上述した共重合体ラテックスを含有する二酸化炭素分離膜用組成物である。組成物Ｂは、共重合体Ａを少なくとも含有する。組成物Ｂにおける共重合体Ａの含有量は、例えば、８０質量％以上、８５質量％以上、９０質量％以上、９３質量％以上、又は９５質量％以上であってもよい。
[Composition for carbon dioxide separation membrane]
The copolymer latex described above can be used as a composition for a carbon dioxide separation membrane (hereinafter also referred to as "composition B"). That is, another embodiment of the present invention is a composition for a carbon dioxide separation membrane containing the above-mentioned copolymer latex. Composition B contains at least copolymer A. The content of copolymer A in composition B may be, for example, 80% by mass or more, 85% by mass or more, 90% by mass or more, 93% by mass or more, or 95% by mass or more.
組成物Ｂは、共重合体ラテックスに加えて、酸化亜鉛を更に含むことが好ましい。組成物Ｂが酸化亜鉛を更に含むことにより、優れた二酸化炭素選択透過性、十分な二酸化炭素透過性、及び強度を有する二酸化炭素分離膜を得やすくなる。 Composition B preferably further contains zinc oxide in addition to the copolymer latex. When Composition B further contains zinc oxide, it becomes easier to obtain a carbon dioxide separation membrane having excellent carbon dioxide permselectivity, sufficient carbon dioxide permeability, and strength.
酸化亜鉛の含有量は、共重合体ラテックス１００重量部（固形分基準）に対して、０．５質量部以上であることが好ましく、０．８質量部以上、又は１質量部以上であってもよい。酸化亜鉛の含有量は、共重合体ラテックス１００重量部（固形分基準）に対して、３質量部以下であることが好ましく、５質量部以下、４質量部以下、３質量部以下、２．５質量部以下、２質量部以下、１．８質量部以下、又は１．５質量部以下であってもよい。 The content of zinc oxide is preferably 0.5 parts by mass or more, 0.8 parts by mass or more, or 1 part by mass or more based on 100 parts by weight of the copolymer latex (solid content basis). Good too. The content of zinc oxide is preferably 3 parts by mass or less, 5 parts by mass or less, 4 parts by mass or less, 3 parts by mass or less, 2. The amount may be 5 parts by mass or less, 2 parts by mass or less, 1.8 parts by mass or less, or 1.5 parts by mass or less.
組成物Ｂは、天然ゴムラテックス、イソプレンゴムラテックス等のゴムラテックスを更に含有してもよい。すなわち、上述した共重合体ラテックスは、その使用目的に応じて他のラテックスと混合して用いてもよい。 Composition B may further contain rubber latex such as natural rubber latex and isoprene rubber latex. That is, the above-mentioned copolymer latex may be used in combination with other latexes depending on the intended use.
組成物Ｂは、ｐＨ調整剤（水酸化カリウム、水酸化ナトリウム、アンモニア水等）、加硫剤（コロイド硫黄、チウラムジスルフィド等）、加硫促進剤（ジアルキルジチオカルバミン酸塩、キサントゲン酸塩等）、加硫促進助剤（リサージ（ＰｂＯ）、鉛丹（Ｐｂ３Ｏ４）、酸化マグネシウム等）、老化防止剤（スチレン化フェノール、イミダゾール類、パラフェニレンジアミン等）、着色剤（二酸化チタン、ファーストイエロー、フタロシアンブルー、群青等）などを更に含有してもよい。 Composition B contains a pH adjuster (potassium hydroxide, sodium hydroxide, aqueous ammonia, etc.), a vulcanizing agent (colloidal sulfur, thiuram disulfide, etc.), a vulcanization accelerator (dialkyl dithiocarbamate, xanthate, etc.), Vulcanization accelerators (resurge (PbO), red lead (Pb 3 O 4 ), magnesium oxide, etc.), anti-aging agents (styrenated phenol, imidazoles, paraphenylenediamine, etc.), colorants (titanium dioxide, fast yellow) , phthalocyan blue, ultramarine blue, etc.).
［二酸化炭素分離膜］
上述した二酸化炭素分離膜用組成物から二酸化炭素分離膜を形成することができる。二酸化炭素分離膜は、少なくとも共重合体Ａを含有する。すなわち、本発明の他の一実施形態は、脂肪族共役ジエン系単量体単位を有する共重合体を含有し、共重合体における脂肪族共役ジエン系単量体単位の含有量が１０～８０質量％である、二酸化炭素分離膜である。
[Carbon dioxide separation membrane]
A carbon dioxide separation membrane can be formed from the above-described composition for a carbon dioxide separation membrane. The carbon dioxide separation membrane contains at least copolymer A. That is, another embodiment of the present invention contains a copolymer having an aliphatic conjugated diene monomer unit, and the content of the aliphatic conjugated diene monomer unit in the copolymer is 10 to 80. mass%, carbon dioxide separation membrane.
二酸化炭素分離膜は、共重合体Ａに加えて、組成物Ｂが含有し得る成分（例えば、酸化亜鉛、上述した共重合体ラテックス以外のラテックス）を含有してもよい。二酸化炭素分離膜は、酸化亜鉛を含有することにより、より優れた二酸化炭素選択透過性、二酸化炭素透過性、及び強度を実現しやすくなる。 In addition to copolymer A, the carbon dioxide separation membrane may contain components that composition B may contain (for example, zinc oxide, latex other than the above-mentioned copolymer latex). By containing zinc oxide, the carbon dioxide separation membrane can easily achieve superior carbon dioxide selective permeability, carbon dioxide permeability, and strength.
二酸化炭素分離膜の二酸化炭素透過率は、二酸化炭素透過性がより優れる観点から、１０×１０１１ｃｍ３・ｃｍ／ｃｍ２・ｓ・ｃｍＨｇ以上、３０×１０１１ｃｍ３・ｃｍ／ｃｍ２・ｓ・ｃｍＨｇ以上、６０×１０１１ｃｍ３・ｃｍ／ｃｍ２・ｓ・ｃｍＨｇ以上、１００×１０１１ｃｍ３・ｃｍ／ｃｍ２・ｓ・ｃｍＨｇ以上、１５０×１０１１ｃｍ３・ｃｍ／ｃｍ２・ｓ・ｃｍＨｇ以上、２００×１０１１ｃｍ３・ｃｍ／ｃｍ２・ｓ・ｃｍＨｇ以上、２５０×１０１１ｃｍ３・ｃｍ／ｃｍ２・ｓ・ｃｍＨｇ以上、又は３００×１０１１ｃｍ３・ｃｍ／ｃｍ２・ｓ・ｃｍＨｇ以上であってもよい。二酸化炭素分離膜の二酸化炭素透過率は、例えば、５００×１０１１ｃｍ３・ｃｍ／ｃｍ２・ｓ・ｃｍＨｇ以下であってもよい。二酸化炭素分離膜の二酸化炭素透過率は、後述の実施例に記載の方法により測定することができる。 The carbon dioxide permeability of the carbon dioxide separation membrane is 10×10 11 cm 3 ·cm/cm 2 ·s·cmHg or more, 30×10 11 cm 3 ·cm/cm 2 · from the viewpoint of better carbon dioxide permeability. s・cmHg or more, 60×10 11 cm 3・cm/cm 2・s・cmHg or more, 100×10 11 cm 3・cm/cm 2・s・cmHg or more, 150×10 11 cm 3・cm/cm 2・s・cmHg or more, 200×10 11 cm 3・cm/cm 2・s・cmHg or more, 250×10 11 cm 3・cm/cm 2・s・cmHg or more, or 300×10 11 cm 3・cm/ It may be at least cm2 ·s·cmHg. The carbon dioxide permeability of the carbon dioxide separation membrane may be, for example, 500×10 11 cm 3 ·cm/cm 2 ·s·cmHg or less. The carbon dioxide permeability of the carbon dioxide separation membrane can be measured by the method described in Examples below.
二酸化炭素分離膜の窒素透過率は、例えば、１２×１０１１ｃｍ３・ｃｍ／ｃｍ２・ｓ・ｃｍＨｇ以下、９×１０１１ｃｍ３・ｃｍ／ｃｍ２・ｓ・ｃｍＨｇ以下、６×１０１１ｃｍ３・ｃｍ／ｃｍ２・ｓ・ｃｍＨｇ以下、３×１０１１ｃｍ３・ｃｍ／ｃｍ２・ｓ・ｃｍＨｇ以下、又は１．５×１０１１ｃｍ３・ｃｍ／ｃｍ２・ｓ・ｃｍＨｇ以下であってもよい。二酸化炭素分離膜の窒素透過率は、例えば、０．１×１０１１ｃｍ３・ｃｍ／ｃｍ２・ｓ・ｃｍＨｇ以上であってもよい。二酸化炭素分離膜の窒素透過率は、後述の実施例に記載の方法により測定することができる。 The nitrogen permeability of the carbon dioxide separation membrane is, for example, 12×10 11 cm 3 cm/cm 2 s cmHg or less, 9×10 11 cm 3 cm/cm 2 s cmHg or less, 6×10 11 cm 3・cm/cm 2・s・cmHg or less, 3×10 11 cm 3・cm/cm 2・s・cmHg or less, or 1.5×10 11 cm 3・cm/cm 2・s・cmHg or less There may be. The nitrogen permeability of the carbon dioxide separation membrane may be, for example, 0.1×10 11 cm 3 ·cm/cm 2 ·s·cmHg or more. The nitrogen permeability of the carbon dioxide separation membrane can be measured by the method described in Examples below.
二酸化炭素分離膜の二酸化炭素選択透過率（二酸化炭素透過率／窒素透過率）は、二酸化炭素選択透過性がより優れる観点から、２５以上、３０以上、又は３４以上であってもよい。二酸化炭素分離膜の二酸化炭素選択透過率（二酸化炭素透過率／窒素透過率）は、例えば、５０以下であってもよい。 The carbon dioxide permselectivity (carbon dioxide permeability/nitrogen permeability) of the carbon dioxide separation membrane may be 25 or more, 30 or more, or 34 or more from the viewpoint of better carbon dioxide permselectivity. The carbon dioxide separation membrane may have a carbon dioxide permselectivity (carbon dioxide permeability/nitrogen permeability) of, for example, 50 or less.
二酸化炭素分離膜の１００％伸び時応力は、柔軟性がより優れる観点から、１０ＭＰａ以下、８ＭＰａ以下、５ＭＰａ以下、又は３ＭＰａ以下であってもよい。二酸化炭素分離膜の１００％伸び時応力は、例えば、１．０ＭＰａ以上であってもよい。二酸化炭素分離膜の１００％伸び時応力は、後述の実施例に記載の方法により測定することができる。 The stress at 100% elongation of the carbon dioxide separation membrane may be 10 MPa or less, 8 MPa or less, 5 MPa or less, or 3 MPa or less, from the viewpoint of better flexibility. The stress at 100% elongation of the carbon dioxide separation membrane may be, for example, 1.0 MPa or more. The stress at 100% elongation of the carbon dioxide separation membrane can be measured by the method described in Examples below.
二酸化炭素分離膜の破断時応力は、強度がより優れる観点から、５ＭＰａ以上、１０ＭＰａ以上、１５ＭＰａ以上、２０ＭＰａ以上、又は２５ＭＰａ以上であってもよい。二酸化炭素分離膜の破断時応力は、例えば、５０ＭＰａ以下であってもよい。二酸化炭素分離膜の破断時応力は、後述の実施例に記載の方法により測定することができる。 The stress at break of the carbon dioxide separation membrane may be 5 MPa or more, 10 MPa or more, 15 MPa or more, 20 MPa or more, or 25 MPa or more from the viewpoint of better strength. The stress at break of the carbon dioxide separation membrane may be, for example, 50 MPa or less. The stress at break of the carbon dioxide separation membrane can be measured by the method described in Examples below.
二酸化炭素分離膜の厚さは、例えば、５μｍ以上、５０μｍ以上、又は１００μｍ以上であってもよく、１０００μｍ以下、５００μｍ以下、又は３００μｍ以下であってもよい。 The thickness of the carbon dioxide separation membrane may be, for example, 5 μm or more, 50 μm or more, or 100 μm or more, or 1000 μm or less, 500 μm or less, or 300 μm or less.
二酸化炭素分離膜は、例えば、上述した二酸化炭素分離膜用組成物を塩凝固法により凝固させる工程を含む方法により製造することができる。すなわち、本発明の他の一実施形態は、二酸化炭素分離膜用組成物を塩凝固法により凝固させる工程を備え、二酸化炭素分離膜用組成物が、脂肪族共役ジエン系単量体単位を有する共重合体を含有し、共重合体における脂肪族共役ジエン系単量体単位の含有量が１０～８０質量％である、二酸化炭素分離膜の製造方法である。 The carbon dioxide separation membrane can be manufactured, for example, by a method including a step of coagulating the above-mentioned composition for a carbon dioxide separation membrane by a salt coagulation method. That is, another embodiment of the present invention includes a step of coagulating a composition for a carbon dioxide separation membrane by a salt coagulation method, and the composition for a carbon dioxide separation membrane has an aliphatic conjugated diene monomer unit. This is a method for producing a carbon dioxide separation membrane containing a copolymer in which the content of aliphatic conjugated diene monomer units in the copolymer is 10 to 80% by mass.
組成物Ｂを塩凝固法により凝固させる方法ついて説明する。まず、基材の表面に凝固液を塗布する。凝固液は、塩化カルシウム、硝酸カルシウム、酢酸カルシウム等のカルシウム塩；塩化マグネシウム等のマグネシウム塩などの金属塩（凝固剤）を水、又はアルコール、ケトン等の親水性有機溶媒に溶解させたものである。凝固液中の金属塩の濃度は、５～５０質量％であってよく、好ましくは１０～３０質量％である。凝固液は、必要に応じてノニオン性界面活性剤、アニオン性界面活性剤等の界面活性剤；炭酸カルシウム、タルク、シリカゲル等の充填材を含有してもよい。 A method for coagulating composition B by a salt coagulation method will be explained. First, a coagulating liquid is applied to the surface of the base material. The coagulating liquid is a solution in which calcium salts such as calcium chloride, calcium nitrate, and calcium acetate; metal salts (coagulants) such as magnesium salts such as magnesium chloride are dissolved in water or a hydrophilic organic solvent such as alcohol or ketone. be. The concentration of the metal salt in the coagulation liquid may be from 5 to 50% by weight, preferably from 10 to 30% by weight. The coagulating liquid may contain surfactants such as nonionic surfactants and anionic surfactants; fillers such as calcium carbonate, talc, and silica gel, as necessary.
凝固液を基材に塗布した後、乾燥させることにより基材の表面に凝固剤を含む塗膜を形成する。次いで、凝固剤を含む塗膜に二酸化炭素分離膜用組成物を塗布する。このとき、凝固剤と共重合体ラテックスが反応して、基材の表面に被膜が形成される。凝固剤と反応しなかった過剰な二酸化炭素分離膜用組成物を除去した後、基材の表面に形成された被膜を水洗、乾燥させて、基材の表面から被膜を剥離することにより二酸化炭素分離膜が得られる。 After applying the coagulation liquid to the base material, it is dried to form a coating film containing the coagulant on the surface of the base material. Next, a composition for a carbon dioxide separation membrane is applied to the coating film containing a coagulant. At this time, the coagulant and copolymer latex react to form a film on the surface of the base material. After removing excess carbon dioxide separation membrane composition that did not react with the coagulant, the film formed on the surface of the base material is washed with water, dried, and removed from the surface of the base material to remove carbon dioxide. A separation membrane is obtained.
二酸化炭素分離膜は、例えば、上述した二酸化炭素分離膜用組成物を乾燥させる工程を含む方法により製造することができる。すなわち、本発明の他の一実施形態は、二酸化炭素分離膜用組成物を乾燥させる工程を備え、二酸化炭素分離膜用組成物が、脂肪族共役ジエン系単量体単位を有する共重合体を含有し、共重合体における脂肪族共役ジエン系単量体単位の含有量が１０～８０質量％である、二酸化炭素分離膜の製造方法である。 The carbon dioxide separation membrane can be manufactured, for example, by a method including the step of drying the above-mentioned composition for a carbon dioxide separation membrane. That is, another embodiment of the present invention includes a step of drying a composition for a carbon dioxide separation membrane, and the composition for a carbon dioxide separation membrane contains a copolymer having an aliphatic conjugated diene monomer unit. and the content of aliphatic conjugated diene monomer units in the copolymer is 10 to 80% by mass.
二酸化炭素分離膜用組成物を乾燥させる方法としては、例えば、二酸化炭素分離膜用組成物を基材（例えば、ガラス基材）に塗布した後、室温（２０～２５℃において、２４時間以上放置する方法が挙げられる。乾燥時間を短くする観点から、二酸化炭素分離膜を加熱して、乾燥させてもよい。乾燥後、基材に形成された被膜を剥離することにより、二酸化炭素分離膜を得ることができる。 As a method for drying the composition for a carbon dioxide separation membrane, for example, after applying the composition for a carbon dioxide separation membrane to a substrate (for example, a glass substrate), the composition is left at room temperature (20 to 25°C for 24 hours or more). From the viewpoint of shortening the drying time, the carbon dioxide separation membrane may be heated to dry it.After drying, the film formed on the base material is peeled off to remove the carbon dioxide separation membrane. Obtainable.
以下、実施例により、本発明を更に具体的に説明する。ただし、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be explained in more detail with reference to Examples. However, the present invention is not limited to the following examples.
＜共重合体ラテックス１（重合例１）の調製＞
耐圧性の重合反応器に、溶媒として純水９０質量部、界面活性剤としてドデシルベンゼンスルホン酸ナトリウム０．６質量部、重合開始剤として過硫酸カリウム０．６質量部を加えて撹拌した。次いで、重合反応器に、表１に示した単量体成分（単位：質量部）とその他の化合物（単位：質量部）を加えて、７０℃（重合温度）に昇温後、８時間（重合時間）重合を行った。添加した単量体成分のポリマー転化率が９７％を超えたことを確認した後、重合停止剤を添加して重合を終了し、重合反応器の槽内の温度を３５℃以下になるまで冷却した。次いで、ｐＨ調整剤として水酸化ナトリウム水溶液０．４質量部（固形分量）を添加して、３０分間保持した後、加熱減圧蒸留により未反応の単量体成分等を除去して、共重合体ラテックス１（重合例１）を得た。
<Preparation of copolymer latex 1 (polymerization example 1)>
90 parts by mass of pure water as a solvent, 0.6 parts by mass of sodium dodecylbenzenesulfonate as a surfactant, and 0.6 parts by mass of potassium persulfate as a polymerization initiator were added to a pressure-resistant polymerization reactor and stirred. Next, the monomer components (unit: parts by mass) shown in Table 1 and other compounds (unit: parts by mass) were added to the polymerization reactor, and after raising the temperature to 70°C (polymerization temperature), the mixture was heated for 8 hours ( Polymerization time) Polymerization was performed. After confirming that the polymer conversion rate of the added monomer components exceeds 97%, a polymerization terminator is added to terminate the polymerization, and the temperature inside the polymerization reactor is cooled to 35℃ or less. did. Next, 0.4 parts by mass (solid content) of an aqueous sodium hydroxide solution was added as a pH adjuster, and after holding for 30 minutes, unreacted monomer components etc. were removed by heating and vacuum distillation to form a copolymer. Latex 1 (Polymerization Example 1) was obtained.
＜共重合体ラテックス２～１３（重合例２～１３）の調製＞
重合に用いた各成分（単位：質量部）及び重合条件を表１に示す条件に変更したこと以外は、共重合体ラテックス１（重合例１）と同様にして共重合体ラテックスを得た。
<Preparation of copolymer latex 2 to 13 (Polymerization examples 2 to 13)>
A copolymer latex was obtained in the same manner as Copolymer Latex 1 (Polymerization Example 1) except that each component (unit: parts by mass) used in the polymerization and the polymerization conditions were changed to those shown in Table 1.
＜ガラス転移温度の測定＞
調製した各共重合体ラテックスをガラス板に約０．５ｇ塗り、７０℃で４時間乾燥させてフィルムを作製した。フィルムをＤＳＣ試験用のアルミニウムパンにセットし、示差走査熱量計（ＤＳＣ６２００、セイコーインスツルメンツ社製）を用いて測定温度－１００～１００℃、昇温速度１０℃／分でＤＳＣ曲線を得た。得られたＤＳＣ曲線のピークから相変化の吸熱の開始点を読み取り、共重合体ラテックスのガラス転移温度（℃）を求めた。相変化が２つ以上確認された場合は、最も温度が低い吸熱の開始点をガラス転移温度とした。測定結果を表１に示す。
<Measurement of glass transition temperature>
Approximately 0.5 g of each prepared copolymer latex was applied to a glass plate and dried at 70° C. for 4 hours to produce a film. The film was set in an aluminum pan for DSC testing, and a DSC curve was obtained using a differential scanning calorimeter (DSC6200, manufactured by Seiko Instruments) at a measurement temperature of -100 to 100°C and a heating rate of 10°C/min. The starting point of the endothermic phase change was read from the peak of the obtained DSC curve, and the glass transition temperature (° C.) of the copolymer latex was determined. When two or more phase changes were confirmed, the starting point of the endotherm with the lowest temperature was taken as the glass transition temperature. The measurement results are shown in Table 1.
＜ゲル含有量（トルエン不溶分）の測定＞
調製した各共重合体ラテックスを用いて、温度８０℃、湿度８５％の雰囲気にてフィルムを作製した。作製したフィルムを約１ｇ秤量し（秤量値：Ｘ（ｇ））、これを４００ｍＬのトルエンに入れて、４８時間放置し、膨潤溶解させた。その後、３００メッシュの金網で濾過し、金網に捕捉されたトルエン不溶分を乾燥させた後、秤量した（秤量値：Ｙ（ｇ））。作製したフィルムの秤量値Ｘに対する、トルエン不溶分の秤量値Ｙの百分率からゲル含有量を算出した。測定結果を表１に示す。
ゲル含有量（質量％）＝（Ｙ／Ｘ）×１００
<Measurement of gel content (toluene insoluble content)>
Using each of the prepared copolymer latexes, films were produced in an atmosphere with a temperature of 80° C. and a humidity of 85%. Approximately 1 g of the produced film was weighed (weighed value: X (g)), placed in 400 mL of toluene, and left for 48 hours to swell and dissolve. Thereafter, it was filtered through a 300-mesh wire gauze, and the toluene-insoluble matter captured by the wire gauze was dried and then weighed (weighed value: Y (g)). The gel content was calculated from the percentage of the weighed value Y of the toluene-insoluble content to the weighed value X of the produced film. The measurement results are shown in Table 1.
Gel content (mass%) = (Y/X) x 100
＜数平均粒子径の測定＞
調製した各共重合体ラテックスの数平均粒子径（μｍ）を光子相関法による動的光散乱法により測定した。数平均粒子径の測定は、ＦＰＡＲ－１０００（大塚電子製）を用いて行った。測定結果を表１に示す。
<Measurement of number average particle diameter>
The number average particle diameter (μm) of each copolymer latex prepared was measured by a dynamic light scattering method using a photon correlation method. The number average particle diameter was measured using FPAR-1000 (manufactured by Otsuka Electronics). The measurement results are shown in Table 1.
＜二酸化炭素分離膜用組成物の調製＞
（実施例１～１０、比較例１～２）
調製した各共重合体ラテックスに下記の成分を加えて、二酸化炭素分離膜用組成物（固形分濃度：３２質量％）を得た。
＜二酸化炭素分離膜用組成物＞ （固形分量）
共重合体ラテックス １００．０質量部
酸化亜鉛 １．５質量部
コロイド硫黄 ０．６質量部
ジエチルジチオカルバミン酸亜鉛 ０．６質量部
二酸化チタン １．５質量部
水酸化カリウム ０．７質量部
<Preparation of composition for carbon dioxide separation membrane>
(Examples 1 to 10, Comparative Examples 1 to 2)
The following components were added to each prepared copolymer latex to obtain a composition for a carbon dioxide separation membrane (solid content concentration: 32% by mass).
<Composition for carbon dioxide separation membrane> (Solid content)
Copolymer latex 100.0 parts by mass Zinc oxide 1.5 parts by mass Colloidal sulfur 0.6 parts by mass Zinc diethyldithiocarbamate 0.6 parts by mass Titanium dioxide 1.5 parts by mass Potassium hydroxide 0.7 parts by mass
（実施例１１～１４）
用いた共重合体ラテックスの種類、及び共重合体ラテックス１００質量部に対する酸化亜鉛の配合量を表２に示す条件に変更したこと以外は、実施例１～１０と同様に二酸化炭素分離膜用組成物を得た。
(Examples 11 to 14)
The composition for a carbon dioxide separation membrane was prepared in the same manner as in Examples 1 to 10, except that the type of copolymer latex used and the amount of zinc oxide added to 100 parts by mass of the copolymer latex were changed to the conditions shown in Table 2. I got something.
＜二酸化炭素分離膜の作製（塩凝固法）＞
（実施例１～１４、比較例１～２）
凝固液として濃度１５質量％の硝酸カルシウム水溶液を用意し、Ｗｉｒｅｂａｒ＃１２を用いて塗工板紙（基材）の表面に塗布して、１２０℃の熱風循環式乾燥機中で１分間乾燥させた。基材の凝固液を塗布した面が内側となるようにして、箱状の基材を成形した。この箱状の基材に、十分な量の二酸化炭素分離膜用組成物を流延して、３０秒間静置した。凝固していない組成物を除去した後、さらに４０秒間静置して、箱状の基材の凝固液を塗布した面側に被膜を形成した。次いで、被膜が形成された箱状の基材に、十分な量の４５℃の温水を流延して、６０秒間温水洗浄した。箱状の基材に形成された被膜を、室温で２時間乾燥させた後、１２０℃で１５分間加熱処理した。次いで、乾燥後の被膜を基材から剥離し、厚みが約１００μｍの二酸化炭素分離膜を得た。
<Preparation of carbon dioxide separation membrane (salt coagulation method)>
(Examples 1 to 14, Comparative Examples 1 to 2)
A calcium nitrate aqueous solution with a concentration of 15% by mass was prepared as a coagulating liquid, and applied to the surface of coated paperboard (base material) using Wirebar #12, and dried for 1 minute in a hot air circulation dryer at 120 ° C. . A box-shaped base material was molded with the surface of the base material coated with the coagulation liquid facing inside. A sufficient amount of the composition for a carbon dioxide separation membrane was cast onto this box-shaped base material and allowed to stand for 30 seconds. After removing the uncoagulated composition, it was allowed to stand still for another 40 seconds to form a film on the side of the box-shaped base material to which the coagulation liquid was applied. Next, a sufficient amount of 45° C. hot water was cast onto the box-shaped base material on which the film was formed, and hot water washing was performed for 60 seconds. The film formed on the box-shaped base material was dried at room temperature for 2 hours, and then heat-treated at 120° C. for 15 minutes. Next, the dried film was peeled off from the base material to obtain a carbon dioxide separation membrane having a thickness of about 100 μm.
＜二酸化炭素分離膜の作製（乾燥法）＞
（実施例１５～２０）
二酸化炭素分離膜用組成物１００質量部に２質量％カルボキシメチルセルロース（セロゲンＥＰ、第一工業製薬株式会社製）水溶液を固形分量が２質量部となるように添加して塗布液を得た。得られた塗布液をクリアランスが５００μｍのアプリケータを用いてガラス板上に塗布し、室温で２４時間乾燥した後、１２０℃で１５分間加熱処理した。次いで、乾燥後の被膜をガラス板から剥離し、厚みが約１００μｍの二酸化炭素分離膜を得た。
<Preparation of carbon dioxide separation membrane (drying method)>
(Examples 15-20)
A coating liquid was obtained by adding a 2% by mass aqueous solution of carboxymethyl cellulose (Celogen EP, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) to 100 parts by mass of the composition for a carbon dioxide separation membrane so that the solid content was 2 parts by mass. The resulting coating liquid was applied onto a glass plate using an applicator with a clearance of 500 μm, dried at room temperature for 24 hours, and then heat-treated at 120° C. for 15 minutes. Next, the dried coating was peeled off from the glass plate to obtain a carbon dioxide separation membrane with a thickness of about 100 μm.
＜ガス透過率の測定＞
作製した各二酸化炭素分離膜の二酸化炭素の単独ガス及び窒素の単独ガスのガス透過率を以下の測定条件でそれぞれ測定した。測定結果を表２に示す。
測定機器：ガス透過率測定装置 ＧＴＲ－１０ＸＡＣＴ（ＧＴＲテック株式会社製）
検出器：ガスクロマトグラフ Ｇ２７００（ヤナコテクニカルサイエンス株式会社製）
測定温度：２２℃
測定面積：１５．２ｃｍ２
サンプルガス圧力：７６ｃｍＨｇ
<Measurement of gas permeability>
The gas permeability of carbon dioxide alone and nitrogen alone of each of the produced carbon dioxide separation membranes was measured under the following measurement conditions. The measurement results are shown in Table 2.
Measuring equipment: Gas permeability measuring device GTR-10XACT (manufactured by GTR Tech Co., Ltd.)
Detector: Gas chromatograph G2700 (manufactured by Yanaco Technical Science Co., Ltd.)
Measurement temperature: 22℃
Measurement area: 15.2cm2
Sample gas pressure: 76cmHg
＜二酸化炭素選択透過率の算出＞
上述のガス透過率の測定結果を用いて、下記式から二酸化炭素選択透過率を算出した。測定結果を表２に示す。
二酸化炭素選択透過率＝（二酸化炭素のガス透過率）／（窒素のガス透過率）
<Calculation of carbon dioxide selective permeability>
Using the measurement results of the gas permeability described above, the carbon dioxide selective permeability was calculated from the following formula. The measurement results are shown in Table 2.
Carbon dioxide selective permeability = (carbon dioxide gas permeability) / (nitrogen gas permeability)
＜強度及び柔軟性の評価＞
ＪＩＳ Ｋ６２５１に従って、作製した各二酸化炭素分離膜に対して引張試験を行い、１００％伸び時の応力と、破断時応力を測定した。測定結果を表２に示す。
<Evaluation of strength and flexibility>
A tensile test was conducted on each carbon dioxide separation membrane produced in accordance with JIS K6251, and the stress at 100% elongation and the stress at break were measured. The measurement results are shown in Table 2.
上記のとおり、脂肪族共役ジエン系単量体単位を有する共重合体を含有し、共重合体における脂肪族共役ジエン系単量体単位の含有量が１０～８０質量％である、二酸化炭素分離膜用共重合体ラテックスを用いることにより、優れた二酸化炭素選択透過性及び十分な二酸化炭素透過性を有し、且つ、優れた強度及び柔軟性を有する二酸化炭素分離膜を得ることができる。 As mentioned above, the carbon dioxide separation method contains a copolymer having an aliphatic conjugated diene monomer unit, and the content of the aliphatic conjugated diene monomer unit in the copolymer is 10 to 80% by mass. By using the copolymer latex for membranes, it is possible to obtain a carbon dioxide separation membrane that has excellent carbon dioxide permselectivity and sufficient carbon dioxide permeability, as well as excellent strength and flexibility.
上述した二酸化炭素分離膜は、例えば、空調（換気）システムで好適に用いることができる。二酸化炭素分離膜を適用した空調（換気）システムが設置される場所としては、一般家庭、オフィスビル等の建築物；自動車、鉄道、航空機、船舶等の輸送機器などが挙げられる。本発明の一実施形態に係る二酸化炭素分離膜は、優れた強度及び柔軟性を有するため、複雑な形状であっても形成することが可能である。また、本発明の一実施形態に係る二酸化炭素分離膜は、優れた二酸化炭素選択透過性及び十分な二酸化炭素透過性を有するため、狭い空間（例えば、自動車等の輸送機器）に設置される空調（換気）システムに対しても好適に用いることができる。 The carbon dioxide separation membrane described above can be suitably used, for example, in an air conditioning (ventilation) system. Examples of locations where air conditioning (ventilation) systems employing carbon dioxide separation membranes are installed include buildings such as ordinary homes and office buildings; transportation equipment such as automobiles, trains, aircraft, and ships. Since the carbon dioxide separation membrane according to one embodiment of the present invention has excellent strength and flexibility, it can be formed into a complicated shape. In addition, since the carbon dioxide separation membrane according to one embodiment of the present invention has excellent carbon dioxide selective permeability and sufficient carbon dioxide permeability, it can be used in air conditioners installed in narrow spaces (for example, transportation equipment such as automobiles). It can also be suitably used for (ventilation) systems.
また、人は呼吸によって空気中の酸素を取り込み、二酸化炭素を多く含む呼気を吐き出しているため、閉鎖された空間では二酸化炭素濃度が上昇する。特に、空間が狭くなるほど、人の密度が高くなるほど二酸化炭素濃度は顕著に上昇しやすい。二酸化炭素濃度が上昇すると、疲労感の増大、注意力の低下、眠気の誘発等のように人体に影響を及ぼすことが知られている。二酸化炭素濃度は、換気によって外気を導入することで低下させることができるが、冷房、暖房をしている場合、換気により快適な室温を維持できなくなるため、快適な室温に戻すために多くのエネルギーを消費する必要が生じ、エネルギー効率が低くなる。一方、本発明の一実施形態に係る二酸化炭素分離膜を適用した空調（換気）システムによれば、室内に外気を導入せずに二酸化炭素濃度を低減することができるため、冷房、暖房のエネルギー消費を抑制することができ、エネルギー効率を向上させることができる。 Additionally, humans take in oxygen from the air when they breathe and exhale breath that contains a lot of carbon dioxide, so the carbon dioxide concentration increases in a closed space. In particular, the narrower the space and the higher the density of people, the more likely the carbon dioxide concentration will rise. It is known that an increase in carbon dioxide concentration affects the human body, such as increasing fatigue, decreasing alertness, and inducing sleepiness. The carbon dioxide concentration can be lowered by introducing outside air through ventilation, but if you are using air conditioning or heating, it becomes impossible to maintain a comfortable room temperature with ventilation, so it takes a lot of energy to return to a comfortable room temperature. This results in lower energy efficiency. On the other hand, according to the air conditioning (ventilation) system to which the carbon dioxide separation membrane according to one embodiment of the present invention is applied, the carbon dioxide concentration can be reduced without introducing outside air into the room, so the energy for cooling and heating can be reduced. Consumption can be suppressed and energy efficiency can be improved.
Claims (6)
前記共重合体における前記脂肪族共役ジエン系単量体単位の含有量が１０～８０質量％である、二酸化炭素分離膜用共重合体ラテックス。 Contains a copolymer having an aliphatic conjugated diene monomer unit,
A copolymer latex for a carbon dioxide separation membrane, wherein the content of the aliphatic conjugated diene monomer unit in the copolymer is 10 to 80% by mass.
前記共重合体における前記エチレン系不飽和カルボン酸単量体単位の含有量が０．１～１０質量％である、請求項１に記載の二酸化炭素分離膜用共重合体ラテックス。 The copolymer further has an ethylenically unsaturated carboxylic acid monomer unit,
The copolymer latex for a carbon dioxide separation membrane according to claim 1, wherein the content of the ethylenically unsaturated carboxylic acid monomer unit in the copolymer is 0.1 to 10% by mass.
前記共重合体における前記脂肪族共役ジエン系単量体単位の含有量が１０～８０質量％である、二酸化炭素分離膜。 Contains a copolymer having an aliphatic conjugated diene monomer unit,
A carbon dioxide separation membrane, wherein the content of the aliphatic conjugated diene monomer unit in the copolymer is 10 to 80% by mass.
二酸化炭素分離膜用組成物を塩凝固法により凝固させる工程を備え、
前記二酸化炭素分離膜用組成物が、脂肪族共役ジエン系単量体単位を有する共重合体を含有し、
前記共重合体における前記脂肪族共役ジエン系単量体単位の含有量が１０～８０質量％である、方法。 A method for manufacturing a carbon dioxide separation membrane, comprising:
comprising a step of coagulating a composition for a carbon dioxide separation membrane by a salt coagulation method,
The carbon dioxide separation membrane composition contains a copolymer having an aliphatic conjugated diene monomer unit,
The method, wherein the content of the aliphatic conjugated diene monomer unit in the copolymer is 10 to 80% by mass.
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| PCT/JP2023/031243 WO2024048587A1 (en) | 2022-08-30 | 2023-08-29 | Copolymer latex for carbon dioxide separator, composition for carbon dioxide separator, carbon dioxide separator, and method for preparing carbon dioxide separator |
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| WO2024048587A1 (en) | 2024-03-07 |
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