JP2021098815A - Polyarylene sulfide, and purification method and production method of the same - Google Patents
Polyarylene sulfide, and purification method and production method of the same Download PDFInfo
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- JP2021098815A JP2021098815A JP2019231478A JP2019231478A JP2021098815A JP 2021098815 A JP2021098815 A JP 2021098815A JP 2019231478 A JP2019231478 A JP 2019231478A JP 2019231478 A JP2019231478 A JP 2019231478A JP 2021098815 A JP2021098815 A JP 2021098815A
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- polyarylene sulfide
- crude
- carbon atoms
- water
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- 229920000412 polyarylene Polymers 0.000 title claims abstract description 111
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000000746 purification Methods 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 91
- 239000000203 mixture Substances 0.000 claims abstract description 43
- 239000002245 particle Substances 0.000 claims abstract description 38
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000002798 polar solvent Substances 0.000 claims abstract description 14
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 28
- 239000007864 aqueous solution Substances 0.000 claims description 26
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- 229910052783 alkali metal Chemical group 0.000 claims description 14
- 150000001491 aromatic compounds Chemical class 0.000 claims description 12
- 150000001340 alkali metals Chemical group 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 6
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 230000001133 acceleration Effects 0.000 claims 2
- 239000013078 crystal Substances 0.000 claims 2
- 239000002253 acid Substances 0.000 abstract description 10
- 150000002894 organic compounds Chemical class 0.000 abstract 4
- 238000005486 sulfidation Methods 0.000 abstract 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 32
- 229920000069 polyphenylene sulfide Polymers 0.000 description 29
- 239000004734 Polyphenylene sulfide Substances 0.000 description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 238000005406 washing Methods 0.000 description 26
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 21
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 20
- 239000002002 slurry Substances 0.000 description 20
- -1 alkali metal salt Chemical class 0.000 description 19
- 238000002425 crystallisation Methods 0.000 description 17
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- 238000001914 filtration Methods 0.000 description 15
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 238000000465 moulding Methods 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 9
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 229910052977 alkali metal sulfide Inorganic materials 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
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- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
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- 239000007787 solid Substances 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000000691 measurement method Methods 0.000 description 4
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- BUYMVQAILCEWRR-UHFFFAOYSA-N naled Chemical compound COP(=O)(OC)OC(Br)C(Cl)(Cl)Br BUYMVQAILCEWRR-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 239000005456 alcohol based solvent Substances 0.000 description 3
- 229910001508 alkali metal halide Inorganic materials 0.000 description 3
- 150000008045 alkali metal halides Chemical class 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
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- 239000010408 film Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 3
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 2
- ROWKJAVDOGWPAT-UHFFFAOYSA-N Acetoin Chemical compound CC(O)C(C)=O ROWKJAVDOGWPAT-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 208000015943 Coeliac disease Diseases 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 125000004181 carboxyalkyl group Chemical group 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
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- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000000816 ethylene group Polymers [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
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- 229920000647 polyepoxide Polymers 0.000 description 2
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical class O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
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- RLUFBDIRFJGKLY-UHFFFAOYSA-N (2,3-dichlorophenyl)-phenylmethanone Chemical compound ClC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1Cl RLUFBDIRFJGKLY-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、ポリアリーレンスルフィド（以下、ＰＡＳと略称することがある）の精製方法および製造方法に関する。更に詳しくは、従来の各種の強酸（塩酸、硫酸など）を用いた精製方法と較べて製造設備や成形時の金型に対する腐食性を低減することができ、且つ、ポリアリーレンスルフィドの品質を向上させることが可能な精製方法および製造方法に関する。また、本発明の目的の一つは、各種成形材料やフィルム、繊維、電気・電子部品、自動車用部品、塗料等の幅広い用途材料として好適なポリアリーレンスルフィドを提供することでもある。 The present invention relates to a method for purifying polyarylene sulfide (hereinafter, may be abbreviated as PAS) and a method for producing the polyarylene sulfide. More specifically, it is possible to reduce the corrosiveness to the manufacturing equipment and the mold at the time of molding as compared with the conventional purification method using various strong acids (hydrochloric acid, sulfuric acid, etc.), and improve the quality of polyarylene sulfide. The present invention relates to a purification method and a production method that can be used. Another object of the present invention is to provide polyarylene sulfide suitable as a material for a wide range of applications such as various molding materials, films, fibers, electric / electronic parts, automobile parts, and paints.
ポリアリーレンスルフィドの中でも代表的なポリフェニレンスルフィド（以下、ＰＰＳと略称することがある）は、通常、特許文献１などに記載されているように、Ｎ−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチル−ε−カプロラクタム等の比較的極性の高い有機溶媒中で、硫化ナトリウムに代表される硫化アルカリ金属、あるいは水硫化ナトリウムに代表される水硫化アルカリ金属と水酸化ナトリウムに代表される水酸化アルカリ金属と、ｐ−ジクロルベンゼンに代表されるポリハロ芳香族化合物とを反応させる方法などによって得られる（特許文献１参照）。 Typical polyphenylene sulfides among polyarylene sulfides (hereinafter, may be abbreviated as PPS) are usually N-methyl-2-pyrrolidone, N, N-dimethyl, as described in Patent Document 1 and the like. Alkali metal sulfide typified by sodium sulfide, or alkali metal sulfide typified by sodium hydroxide and sodium hydroxide in relatively highly polar organic solvents such as acetoamide and N-methyl-ε-caprolactam. It can be obtained by a method of reacting an alkali metal hydroxide with a polyhalo aromatic compound typified by p-dichlorobenzene or the like (see Patent Document 1).
重合反応は、通常、高温加圧、アルカリ条件下で行われ、重合反応の進行に伴い食塩が生成し、重合反応後のいわゆる粗反応生成物には、少なくとも、ポリアリーレンスルフィド及びアルカリ金属ハロゲン化物や、そのほかに、未反応の原料や、環状ないし線状オリゴマー、さらには、下記構造式（１） The polymerization reaction is usually carried out under high temperature pressurization and alkaline conditions, and as the polymerization reaction progresses, sodium chloride is produced, and the so-called crude reaction products after the polymerization reaction include at least polyarylene sulfide and alkali metal halide. In addition, unreacted raw materials, cyclic or linear oligomers, and the following structural formula (1)
さらに、ポリアリーレンスルフィドの製造時に、ポリアリーレンスルフィドの製造原料として、例えば、アミド系溶媒がＮ−メチル−２−ピロリドン、ポリハロ芳香族化合物がｐ−ジクロロベンゼンである場合には前記カルボキシアルキルアミノ基含有化合物として、下記一般式（２） Further, during the production of polyarylene sulfide, for example, when the amide solvent is N-methyl-2-pyrrolidone and the polyhaloaromatic compound is p-dichlorobenzene, the carboxyalkylamino group is used as a raw material for producing polyarylene sulfide. As the contained compound, the following general formula (2)
（式中、Ｘは水素原子又はアルカリ金属原子を表す。）で表されるものが得られる（この化合物を“ＣＰ−ＭＡＢＡ”と略記し、特にＸが水素原子の場合を“ＣＰ−ＭＡＢＡ（水素型）”、アルカリ金属原子の場合を“ＣＰ−ＭＡＢＡ（アルカリ金属塩型）”、特にＸがナトリウム原子の場合は“ＣＰ−ＭＡＢＡ（Ｎａ塩型）”と略記することがある）。 (In the formula, X represents a hydrogen atom or an alkali metal atom.) (This compound is abbreviated as "CP-MABA", and particularly when X is a hydrogen atom, "CP-MABA (" Hydrogen type) ”, the case of alkali metal atom may be abbreviated as“ CP-MABA (alkali metal salt type) ”, and in particular, when X is a sodium atom, it may be abbreviated as“ CP-MABA (Na salt type) ”).
重合反応後の粗反応生成物は適当な容器に取り出され、それに含有される溶媒は適当な手段（減圧留去法、遠心分離法、スクリューデカンター法、減圧濾過法、加圧濾過法など適当な方法が選択可能である）により、分離回収されて（ここではこの操作を「脱溶媒」という）再利用されたり、必要に応じて更に精製されて再利用される。 The crude reaction product after the polymerization reaction is taken out into a suitable container, and the solvent contained therein is suitable by a suitable means (vacuum distillation method, centrifugation method, screw decanter method, vacuum filtration method, pressure filtration method, etc.). Depending on the method (selectable method), it can be separated and recovered (here, this operation is referred to as "desolvation") and reused, or if necessary, further purified and reused.
一方、脱溶媒させて、有機極性溶媒を分離除去した後、粗反応生成物に含まれていたポリアリーレンスルフィド（以下、粗ポリアリーレンスルフィド）を含む混合物に、一般には水洗と濾過を繰り返し行い、主に食塩やアルカリ性物質等の不純物を除去した後に乾燥することでポリアリーレンスルフィドが得られる。 On the other hand, after removing the solvent to separate and remove the organic polar solvent, the mixture containing polyarylene sulfide (hereinafter referred to as crude polyarylene sulfide) contained in the crude reaction product is generally washed with water and filtered repeatedly. Polyarylene sulfide can be obtained mainly by removing impurities such as salt and alkaline substances and then drying.
このようにして得られたポリアリーレンスルフィドはその優れた耐薬品性、電気的特性、機械的特性のために、繊維、フィルム、塗料、射出成形材料用コンパウンド及び繊維強化複合材料などに使用されているが、靭性改善のために、ポリマー鎖末端のカルボキシ基量を高めることにより、エポキシシランや官能基含有エラストマーとの反応性（以下、単に「反応性」という）に優れるポリアリーレンスルフィドが切望されている。 The polyarylene sulfide thus obtained is used in fibers, films, paints, compounds for injection molding materials, fiber-reinforced composite materials, etc. due to its excellent chemical resistance, electrical properties, and mechanical properties. However, in order to improve toughness, polyarylene sulfide having excellent reactivity with epoxy silane and functional group-containing elastomer (hereinafter, simply referred to as "reactivity") is desired by increasing the amount of carboxy group at the end of the polymer chain. ing.
このため、粗ポリアリーレンスルフィドを含む混合物の精製工程で、粗ポリアリーレンスルフィドを酸と接触させてポリマー鎖末端のカルボキシ基量を向上させる方法（特許文献２参照）が提案されているが、強酸を使用する方法が多く、装置や設備に対する腐食性の面で重大な問題を有していると共に、得られたポリアリーレンスルフィドの色調の悪化や製品の特性の低下を招く原因になっていた。 Therefore, in the purification step of a mixture containing crude polyarylene sulfide, a method of contacting crude polyarylene sulfide with an acid to improve the amount of carboxy groups at the end of the polymer chain has been proposed (see Patent Document 2), but a strong acid has been proposed. There are many methods of using the above, which has a serious problem in terms of corrosiveness to equipment and facilities, and has caused deterioration of the color tone of the obtained polyarylene sulfide and deterioration of product characteristics.
そこで、ＮＭＰで洗浄した後、炭酸ガスまたは炭酸水を系内に導入して炭酸ガスまたは炭酸水と該粗ポリアリーレンスルフィドとを接触させる方法が提案されている（特許文献３、４参照）。しかし、この方法で得られたポリアリーレンスルフィドは反応性に優れるものの結晶化速度が速いという特徴があった。このような結晶化速度の速いポリアリーレンスルフィドを使用して成形品を製造する際、近年、金属部品代替目的から需要が多くなってきている、大型化成形品や肉厚化成形品に適用とすると、成形不良を起こすことがあった。 Therefore, a method has been proposed in which carbon dioxide gas or carbonated water is introduced into the system after washing with NMP to bring the carbon dioxide gas or carbonated water into contact with the crude polyarylene sulfide (see Patent Documents 3 and 4). However, although the polyarylene sulfide obtained by this method has excellent reactivity, it has a characteristic that the crystallization rate is high. When manufacturing a molded product using such a polyarylene sulfide having a high crystallization rate, it is applied to a large-sized molded product or a thick-walled molded product, which has been in increasing demand in recent years for the purpose of replacing metal parts. Then, molding defects may occur.
そこで本発明が解決しようとする課題は、反応性に優れつつ、かつ、結晶化速度の遅いポリアリーレンスルフィドの精製方法、当該工程を含む反応性に優れつつ、かつ、結晶化速度の遅いポリアリーレンスルフィドの製造方法、および、反応性に優れつつ、かつ、結晶化速度の遅いポリアリーレンスルフィドを提供することにある。 Therefore, the problem to be solved by the present invention is a method for purifying polyarylene sulfide having excellent reactivity and slow crystallization rate, and polyarylene having excellent reactivity including the step and having a slow crystallization rate. It is an object of the present invention to provide a method for producing a sulfide, and to provide a polyarylene sulfide having excellent reactivity and a slow crystallization rate.
本願発明者らは種々の検討を行った結果、粗ポリアリーレンスルフィドを含む混合物を、特定有機溶媒と接触、および、水と接触させて多孔質化した後、多孔質化した粗ポリアリーレンスルフィドと、１００℃超の水とを接触させる精製方法により、残存するカルボキシアルキルアミノ基含有化合物に代表される副生成物を特定含有量に調整した結果、反応性に優れ、かつ、結晶化速度の遅いポリアリーレンスルフィドが得られることを見出し、本発明を完成するに至った。 As a result of various studies, the inventors of the present application made the mixture containing the crude polyarylene sulfide into a porous material by contacting it with a specific organic solvent and water, and then forming it into a porous crude polyarylene sulfide. As a result of adjusting the residual by-products typified by the carboxyalkylamino group-containing compound to a specific content by a purification method in which water is brought into contact with water at a temperature exceeding 100 ° C., the reactivity is excellent and the crystallization rate is slow. They have found that polyarylene sulfide can be obtained, and have completed the present invention.
すなわち、本発明は、有機極性溶媒中、ポリハロ芳香族化合物とスルフィド化剤とを反応させて得られるポリアリーレンスルフィドを含有する粗反応生成物を脱溶媒させることにより、粗ポリアリーレンスルフィドを含む混合物を得る工程（１）、粗ポリアリーレンスルフィドを含む混合物を、精製して前記粗ポリアリーレンスルフィドを比表面積３０〔ｍ２／ｇ〕以上の範囲の多孔質粒子とする工程（２）と、前記粗ポリアリーレンスルフィドを比表面積３０〔ｍ２／ｇ〕以上の範囲の多孔質粒子とする工程（２）、得られた多孔質粒子と１００℃超の水とを接触させる工程（３）とを有し、
前記工程（２）が、炭素原子数１〜３の酸素原子含有溶媒と接触させる工程（２Ｓｓ）と、水と接触させる工程（２Ｓｗ）とをそれぞれ少なくとも１回ずつ行う工程を有し、
工程（３）後の多孔質粒子中に含まれる下記構造式（１）で表される化合物（１）の割合が、１０００〔ｐｐｍ〕超から、３０００〔ｐｐｍ〕以下の範囲であることを特徴とするポリアリーレンスルフィドの精製方法
That is, the present invention is a mixture containing crude polyarylene sulfide by desolving a crude reaction product containing polyarylene sulfide obtained by reacting a polyhalo aromatic compound with a sulfidizing agent in an organic polar solvent. The step (1) of obtaining the crude polyarylene sulfide, and the step (2) of purifying the crude polyarylene sulfide to form porous particles having a specific surface area of 30 [m 2 / g] or more. The step of forming the crude polyarylene sulfide into porous particles having a specific surface area of 30 [m 2 / g] or more (2) and the step of bringing the obtained porous particles into contact with water over 100 ° C. (3) are performed. Have and
The step (2) includes a step of contacting with an oxygen atom-containing solvent having 1 to 3 carbon atoms (2Ss) and a step of contacting with water (2Sw) at least once.
The proportion of the compound (1) represented by the following structural formula (1) contained in the porous particles after the step (3) is in the range of more than 1000 [ppm] to 3000 [ppm] or less. Method for purifying polyarylene sulfide
また、本発明は、前記記載の精製方法によりポリアリーレンスルフィドを精製する工程を有することを特徴とするポリアリーレンスルフィドの製造方法に関する。 The present invention also relates to a method for producing polyarylene sulfide, which comprises a step of purifying polyarylene sulfide by the purification method described above.
また、本発明は、比表面積１０〔ｍ２／ｇ〕以上の範囲の多孔質粒子であり、
下記構造式（１）で表される化合物（１）の含有量の割合が、１０００〔ｐｐｍ〕超から、３０００〔ｐｐｍ〕以下の範囲であることを特徴とするポリアリーレンスルフィド
Further, the present invention is a porous particle having a specific surface area of 10 [m 2 / g] or more.
Polyarylene sulfide characterized in that the content ratio of the compound (1) represented by the following structural formula (1) is in the range of more than 1000 [ppm] to 3000 [ppm] or less.
本発明によれば、反応性に優れつつ、かつ、結晶化速度の遅いポリアリーレンスルフィドの精製方法、当該工程を含む反応性に優れつつ、かつ、結晶化速度の遅いポリアリーレンスルフィドの製造方法、および、反応性に優れつつ、かつ、結晶化速度の遅いポリアリーレンスルフィドを提供することができる。 According to the present invention, a method for purifying polyarylene sulfide having excellent reactivity and a slow crystallization rate, and a method for producing polyarylene sulfide having excellent reactivity and a slow crystallization rate including the step. Further, it is possible to provide a polyarylene sulfide having excellent reactivity and a slow crystallization rate.
本発明の精製方法は、有機極性溶媒中、ポリハロ芳香族化合物とスルフィド化剤とを反応させて得られるポリアリーレンスルフィドを含有する粗反応生成物を脱溶媒させることにより、粗ポリアリーレンスルフィドを含む混合物を得る工程（１）を有する。 The purification method of the present invention contains crude polyarylene sulfide by desolving a crude reaction product containing polyarylene sulfide obtained by reacting a polyhalo aromatic compound with a sulfidizing agent in an organic polar solvent. It has a step (1) of obtaining a mixture.
ポリアリーレンスルフィドは、通常、Ｎ−メチル−２−ピロリドンなどを代表とする有機極性溶媒中で、少なくとも１種のポリハロ芳香族化合物と少なくとも１種のスルフィド化剤とを適当な重合条件下で反応させて合成される。 Polyarylene sulfide is usually obtained by reacting at least one polyhaloaromatic compound with at least one sulfidizing agent under appropriate polymerization conditions in an organic polar solvent typified by N-methyl-2-pyrrolidone or the like. It is synthesized.
本発明で用いられるポリハロ芳香族化合物とは、例えば、芳香族環に直接結合した２個以上のハロゲン原子を有するハロゲン化芳香族化合物であり、具体的には、ｐ−ジクロルベンゼン、ｏ−ジクロルベンゼン、ｍ−ジクロルベンゼン、トリクロルベンゼン、テトラクロルベンゼン、ジブロムベンゼン、ジヨードベンゼン、トリブロムベンゼン、ジブロムナフタレン、トリヨードベンゼン、ジクロルジフェニルベンゼン、ジブロムジフェニルベンゼン、ジクロルベンゾフェノン、ジブロムベンゾフェノン、ジクロルジフェニルエーテル、ジブロムジフェニルエーテル、ジクロルジフェニルスルフィド、ジブロムジフェニルスルフィド、ジクロルビフェニル、ジブロムビフェニル等のジハロ芳香族化合物及びこれらの混合物が挙げられ、これらの化合物をブロック共重合してもよい。これらの中でも好ましいのはジハロゲン化ベンゼン類であり、特に好ましいのはｐ−ジクロルベンゼンを８０モル％以上含むものである。 The polyhaloaromatic compound used in the present invention is, for example, a halogenated aromatic compound having two or more halogen atoms directly bonded to an aromatic ring, and specifically, p-dichlorobenzene, o-. Dichlorobenzene, m-dichlorobenzene, trichlorobenzene, tetrachlorobenzene, dibrombenzene, diiodobenzene, tribrombenzene, dibromnaphthalene, triiodobenzene, dichlorodiphenylbenzene, dibrom diphenylbenzene, dichlorobenzophenone , Dihalo-aromatic compounds such as dibrom benzophenone, dichlorodiphenyl ether, dibrom diphenyl ether, dichlorodiphenyl sulfide, dibrom diphenyl sulfide, dichlorobiphenyl, dibrombiphenyl and mixtures thereof, and blocks these compounds. It may be polymerized. Among these, benzene dihalogenates are preferable, and those containing 80 mol% or more of p-dichlorobenzene are particularly preferable.
また、枝分かれ構造とすることによってポリアリーレンスルフィドの粘度増大を図る目的で、１分子中に３個以上のハロゲン置換基を有するポリハロ芳香族化合物を分岐剤として所望に応じて用いてもよい。このようなポリハロ芳香族化合物としては、例えば、１，２，４−トリクロルベンゼン、１，３，５−トリクロルベンゼン、１，４，６−トリクロルナフタレン等が挙げられる。 Further, for the purpose of increasing the viscosity of the polyarylene sulfide by forming a branched structure, a polyhaloaromatic compound having three or more halogen substituents in one molecule may be used as a branching agent, if desired. Examples of such polyhalo aromatic compounds include 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene, 1,4,6-trichloronaphthalene and the like.
更に、アミノ基、チオール基、ヒドロキシル基等の活性水素を持つ官能基を有するポリハロ芳香族化合物を挙げることが出来、具体的には、２，６−ジクロルアニリン、２，５−ジクロルアニリン、２，４−ジクロルアニリン、２，３−ジクロルアニリン等のジハロアニリン類；２，３，４−トリクロルアニリン、２，３，５−トリクロルアニリン、２，４，６−トリクロルアニリン、３，４，５−トリクロルアニリン等のトリハロアニリン類；２，２’−ジアミノ−４，４’−ジクロルジフェニルエーテル、２，４’−ジアミノ−２’，４−ジクロルジフェニルエーテル等のジハロアミノジフェニルエーテル類およびこれらの混合物においてアミノ基がチオール基やヒドロキシル基に置き換えられた化合物などが例示される。 Further, polyhaloaromatic compounds having a functional group having an active hydrogen such as an amino group, a thiol group and a hydroxyl group can be mentioned, and specifically, 2,6-dichloroaniline and 2,5-dichloroaniline. , 2,4-Dichloroaniline, 2,3-dichloroaniline and other dihaloanilines; 2,3,4-trichloroaniline, 2,3,5-trichloroaniline, 2,4,6-trichloroaniline, 3, Trihaloanilines such as 4,5-trichloroaniline; dihaloaminodiphenyl ethers such as 2,2'-diamino-4,4'-dichlorodiphenyl ether, 2,4'-diamino-2', 4-dichlorodiphenyl ether And compounds in which the amino group is replaced with a thiol group or a hydroxyl group in a mixture thereof and the like are exemplified.
また、これらの活性水素含有ポリハロ芳香族化合物中の芳香族環を形成する炭素原子に結合した水素原子が他の不活性基、例えばアルキル基などの炭化水素基に置換している活性水素含有ポリハロ芳香族化合物も使用出来る。 Further, the active hydrogen-containing polyhalo in which the hydrogen atom bonded to the carbon atom forming the aromatic ring in these active hydrogen-containing polyhaloaromatic compounds is replaced with another inactive group, for example, a hydrocarbon group such as an alkyl group. Aromatic compounds can also be used.
これらの各種活性水素含有ポリハロ芳香族化合物の中でも、好ましいのは活性水素含有ジハロ芳香族化合物であり、特に好ましいのはジクロルアニリンである。 Among these various active hydrogen-containing polyhaloaromatic compounds, an active hydrogen-containing dihaloaromatic compound is preferable, and dichloroaniline is particularly preferable.
ニトロ基を有するポリハロ芳香族化合物としては、例えば、２，４−ジニトロクロルベンゼン、２，５−ジクロルニトロベンゼン等のモノまたはジハロニトロベンゼン類；２−ニトロ−４，４’−ジクロルジフェニルエーテル等のジハロニトロジフェニルエーテル類；３，３’−ジニトロ−４，４’−ジクロルジフェニルスルホン等のジハロニトロジフェニルスルホン類；２，５−ジクロル−３−ニトロピリジン、２−クロル−３，５−ジニトロピリジン等のモノまたはジハロニトロピリジン類；あるいは各種ジハロニトロナフタレン類などが挙げられる。 Examples of the polyhaloaromatic compound having a nitro group include mono- or dihalonitrobenzenes such as 2,4-dinitrochlorobenzene and 2,5-dichloronitrobenzene; 2-nitro-4,4'-dichlorodiphenyl ether and the like. Dihalonitrodiphenyl ethers; dihalonitrodiphenylsulfones such as 3,3'-dinitro-4,4'-dichlorodiphenylsulfone; 2,5-dichloro-3-nitropyridine, 2-chlor-3,5 -Mono or dihalonitropyridines such as dinitropyridine; or various dihalonitronaphthalene and the like.
本発明で用いられるスルフィド化剤としては、硫化リチウム、硫化ナトリウム、硫化ルビジウム、硫化セシウム及びこれらの混合物などの硫化アルカリ金属が含まれる。かかる硫化アルカリ金属は、水和物あるいは水性混合物あるいは無水物として使用することが出来る。また、硫化アルカリ金属は水硫化アルカリ金属と水酸化アルカリ金属との反応によっても導くことが出来る。 Sulfidating agents used in the present invention include alkali metals sulfides such as lithium sulfide, sodium sulfide, rubidium sulfide, cesium sulfide and mixtures thereof. Such alkali metal sulfides can be used as hydrates, aqueous mixtures or anhydrides. The alkali metal sulfide can also be derived by the reaction between the alkali metal hydroxide and the alkali metal hydroxide.
尚、通常、硫化アルカリ金属中に微量存在する水硫化アルカリ金属、チオ硫酸アルカリ金属と反応させるために、少量の水酸化アルカリ金属を加えても差し支えない。 It should be noted that a small amount of alkali metal hydroxide may be added in order to react with the alkali metal hydrosulfide and the alkali metal thiosulfate which are usually present in a trace amount in the alkali metal sulfide.
本発明で用いられる有機極性溶媒としては、Ｎ−メチル−２−ピロリドン、ホルムアミド、アセトアミド、Ｎ−メチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、２−ピロリドン、Ｎ−メチル−ε−カプロラクタム、ε−カプロラクタム、ヘキサメチルホスホルアミド、テトラメチル尿素、Ｎ−ジメチルプロピレン尿素、１，３−ジメチル−２−イミダゾリジノン酸のアミド尿素、及びラクタム類；スルホラン、ジメチルスルホラン等のスルホラン類；ベンゾニトリル等のニトリル類；メチルフェニルケトン等のケトン類及びこれらの混合物を挙げることが出来る。 Examples of the organic polar solvent used in the present invention include N-methyl-2-pyrrolidone, formamide, acetamide, N-methylformamide, N, N-dimethylacetamide, 2-pyrrolidone, N-methyl-ε-caprolactam and ε-caprolactam. , Hexamethylphosphoramide, tetramethylurea, N-dimethylpropyleneurea, amide urea of 1,3-dimethyl-2-imidazolidinone acid, and lactams; sulfolanes such as sulfolane, dimethylsulfolane; benzonitrile and the like. Nitriles; ketones such as methylphenylketone and mixtures thereof can be mentioned.
これらの有機極性溶媒の存在下、上記のスルフィド化剤とポリハロ芳香族化合物との重合条件は一般に、温度２００〜３３０℃であり、圧力は重合溶媒及び重合モノマーであるポリハロ芳香族化合物を実質的に液層に保持するような範囲であるべきであり、一般には０．１〜２０ＭＰａ、好ましくは０．１〜２ＭＰａの範囲より選択される。反応時間は温度と圧力により異なるが、一般に１０分乃至７２時間の範囲であり、望ましくは１時間乃至４８時間の範囲である。 In the presence of these organic polar solvents, the conditions for polymerization of the above-mentioned sulfidating agent and the polyhalo aromatic compound are generally a temperature of 200 to 330 ° C., and the pressure is substantially the same as that of the polymerization solvent and the polyhalo aromatic compound which is a polymerization monomer. The range should be such that it is retained in the liquid layer, and is generally selected from the range of 0.1 to 20 MPa, preferably 0.1 to 2 MPa. The reaction time varies depending on the temperature and pressure, but is generally in the range of 10 minutes to 72 hours, preferably 1 hour to 48 hours.
本発明においては、粗反応生成物がスルフィド化剤及び有機極性溶媒の存在下に、ポリハロ芳香族化合物及び有機極性溶媒を連続的、乃至、断続的に加えながら反応させることにより得られる形態も包含する。 The present invention also includes a form obtained by reacting the crude reaction product in the presence of a sulfidizing agent and an organic polar solvent while continuously or intermittently adding a polyhalo aromatic compound and an organic polar solvent. To do.
本発明においては、重合反応にて得られたポリアリーレンスルフィドを含有する粗反応生成物を適当な手段（減圧留去法、遠心分離法、スクリューデカンター法、減圧濾過法、加圧濾過法など適当な方法が選択可能である）により「脱溶媒」させて、有機極性溶媒を分離除去した後、粗ポリアリーレンスルフィドを含む混合物を得ることができる。有機極性溶媒の分離除去の程度は特に限定されないが、該混合物中の固形分の割合（固形分濃度）が、該混合物１００質量部に対して、好ましくは４０質量部以上、より好ましくは５０質量部以上、更に好ましくは５５質量部以上である。上限値は限定されないが、好ましくは１００質量部以下であり、より好ましくは１００質量部未満、さらに好ましくは９９質量部以下である。 In the present invention, the crude reaction product containing the polyarylene sulfide obtained by the polymerization reaction is appropriately used by an appropriate means (vacuum distillation method, centrifugation method, screw decanter method, vacuum filtration method, pressure filtration method, etc.). The organic polar solvent can be separated and removed by "desolventization" (these methods can be selected), and then a mixture containing crude polyarylene sulfide can be obtained. The degree of separation and removal of the organic polar solvent is not particularly limited, but the ratio of solid content (solid content concentration) in the mixture is preferably 40 parts by mass or more, more preferably 50 parts by mass with respect to 100 parts by mass of the mixture. More than parts, more preferably 55 parts by mass or more. The upper limit is not limited, but is preferably 100 parts by mass or less, more preferably less than 100 parts by mass, and further preferably 99 parts by mass or less.
本発明の精製方法は、続いて、粗ポリアリーレンスルフィドを含む混合物を、精製して前記粗ポリアリーレンスルフィドを比表面積３０〔ｍ２／ｇ〕以上の範囲の多孔質粒子とする工程（２）を有する。前記工程（２）は、炭素原子数１〜３の酸素原子含有溶媒と接触させる工程（２Ｓｓ）と、水と接触させる工程（２Ｓｗ）とをそれぞれ少なくとも１回ずつ行う工程を有する。 The purification method of the present invention subsequently purifies a mixture containing crude polyarylene sulfide to form the crude polyarylene sulfide into porous particles having a specific surface area of 30 [m 2 / g] or more (2). Has. The step (2) includes a step of contacting with an oxygen atom-containing solvent having 1 to 3 carbon atoms (2Ss) and a step of contacting with water (2Sw) at least once.
本発明において工程（２Ｓｓ）は、炭素原子数１〜３の酸素原子含有溶剤を用いて、粗ポリアリーレンスルフィドを含む混合物と接触させ、洗浄する工程である。炭素原子数１〜３の酸素原子含有溶媒を加える際の温度としては特に限定されないが、好ましくは１０℃以上、より好ましくは２０℃以上から、好ましくは９０℃以下、より好ましくは７０℃以下の範囲である。一回の洗浄に使用する該溶剤の量には特に制限は無いが、好ましくはポリアリーレンスルフィド１００質量部に対して、好ましくは２０質量部以上、より好ましくは５０質量部以上、さらに好ましくは１００質量部以上から、好ましくは５０００質量部以下、より好ましくは１８００質量部以下、さらに好ましくは６００質量部以下である。 In the present invention, the step (2Ss) is a step of using an oxygen atom-containing solvent having 1 to 3 carbon atoms to bring it into contact with a mixture containing crude polyarylene sulfide for washing. The temperature at which the oxygen atom-containing solvent having 1 to 3 carbon atoms is added is not particularly limited, but is preferably 10 ° C. or higher, more preferably 20 ° C. or higher, preferably 90 ° C. or lower, and more preferably 70 ° C. or lower. The range. The amount of the solvent used for one washing is not particularly limited, but is preferably 20 parts by mass or more, more preferably 50 parts by mass or more, and further preferably 100 parts by mass with respect to 100 parts by mass of polyarylene sulfide. From parts by mass or more, it is preferably 5000 parts by mass or less, more preferably 1800 parts by mass or less, and further preferably 600 parts by mass or less.
本発明において工程（２Ｓｗ）は、前工程（１）で得られた、少なくとも、粗ポリアリーレンスルフィドを含む混合物に適量の水を加えて接触させ、洗浄する。水を加える際の温度としては特に限定されないが、好ましくは１０℃以上、より好ましくは２０℃以上から、好ましくは１００℃以下、より好ましくは９０℃以下、さらに好ましくは８０℃以下の範囲である。洗浄した後、濾過等により固液分離して、ケーキ状物とすることが好ましい。一回の洗浄に使用する水の量には特に制限は無いが、好ましくはポリアリーレンスルフィド１００質量部に対して、好ましくは２０質量部以上、より好ましくは５０質量部以上、さらに好ましくは１００質量部以上から、好ましくは１００００質量部以下、より好ましくは５０００質量部以下、さらに好ましくは２０００質量部以下である。 In the present invention, the step (2Sw) is carried out by adding an appropriate amount of water to the mixture containing at least the crude polyarylene sulfide obtained in the previous step (1), contacting the mixture, and washing the mixture. The temperature at which water is added is not particularly limited, but is preferably in the range of 10 ° C. or higher, more preferably 20 ° C. or higher, preferably 100 ° C. or lower, more preferably 90 ° C. or lower, still more preferably 80 ° C. or lower. .. After washing, it is preferably solid-liquid separated by filtration or the like to form a cake-like product. The amount of water used for one washing is not particularly limited, but is preferably 20 parts by mass or more, more preferably 50 parts by mass or more, and further preferably 100 parts by mass with respect to 100 parts by mass of polyarylene sulfide. From the parts of parts or more, it is preferably 10000 parts by mass or less, more preferably 5000 parts by mass or less, and further preferably 2000 parts by mass or less.
粗ポリアリーレンスルフィドを含む混合物を、工程（２Ｓｓ）と工程（２Ｓｗ）の順番は特に問わず、粗ポリアリーレンスルフィドを含む混合物を、水と接触させて洗浄する工程（２Ｓｗ）を行ってから、粗ポリアリーレンスルフィドを含む混合物を、炭素原子数１〜３の酸素原子含有溶媒と接触させて洗浄する工程（２Ｓｓ）を行ってもよいし、または、工程（２Ｓｓ）を行ってから工程（２Ｓｗ）を行ってもよい。それぞれの工程は、まとめて、または交互に、任意の一又は複数回、実施することもできる。工程（２Ｓｓ）または工程（２Ｓｗ）を行ってから、次の工程を行う前に、固液分離により、洗浄に用いた水または炭素原子数１〜３の酸素原子含有溶媒を除去しておくことが好ましい。 The order of the steps (2Ss) and the steps (2Sw) for the mixture containing the crude polyarylene sulfide is not particularly limited, and the mixture containing the crude polyarylene sulfide is brought into contact with water to be washed (2Sw). The mixture containing the crude polyarylene sulfide may be washed by contacting it with an oxygen atom-containing solvent having 1 to 3 carbon atoms (2Ss), or the step (2Ss) may be performed and then the step (2Sw) is performed. ) May be performed. Each step can also be carried out collectively or alternately, any one or more times. After performing the step (2Ss) or the step (2Sw) and before performing the next step, the water used for washing or the oxygen atom-containing solvent having 1 to 3 carbon atoms used for washing should be removed by solid-liquid separation. Is preferable.
ここで粗ポリアリーレンスルフィドを含む混合物と接触させる炭素原子数１〜３の酸素原子含有溶媒としては、例えば、アルコール系溶媒およびケトン系溶媒からなる群から選ばれる少なくとも一つが挙げられる。アルコール系溶媒（アルコール溶媒ともいう）としては、メチルアルコール、エチルアルコール、ｎ−プロピルアルコール、イソプロピルアルコール、ｎ−ブチルアルコール、イソブチルアルコール、ｔ−ブチルアルコール、エチレングリコール、プロピレングリコール、トリメチロールプロパン、ベンジルアルコール等の炭素原子数が１０以下のアルコール；２−メトキシエチルアルコール、２−エトキシエチルアルコール、１−メトキシ−２−プロピルアルコール、１−エトキシ−２−プロピルアルコール、３−メトキシ−１−ブチルアルコール、２−イソプロポキシエチルアルコール等のエーテル結合を含む炭素原子数が１０以下のアルコール；３−ヒドロキシ−２−ブタノン等のケトン基を含む炭素原子数が１０以下のアルコール；ヒドロキシイソ酪酸メチル等のようなエステル基を含む炭素原子数が１０以下のアルコールが例示される。また、ケトン系溶媒（ケトン溶媒ともいう）としては、アセトン、メチルエチルケトン、シクロヘキサノン、γ−ブチルラクトン又はＮ−メチルピロリジノンが例示される。本発明において、炭素原子数１０以下の一価アルコールを用いることが、残留する前記カルボキシアルキルアミノ基含有化合物を効率的に除去可能なことから好ましく、さらに、炭素原子数３以下の一価アルコールが好ましい。また、炭素原子数１〜３の酸素原子含有溶媒に水を加えた水溶液とし、濃度を低くした上で工程（２Ｓｓ）を実施してもよい。その際、水溶液中の炭素原子数１〜３の酸素原子含有溶媒の濃度は特に限定されないが、水溶液１００質量部に対して、好ましくは９０質量部以下の範囲である。より好ましくは８５質量部以下の範囲から、好ましくは２５質量部以上、より好ましくは４５質量部以上の範囲である。 Here, examples of the oxygen atom-containing solvent having 1 to 3 carbon atoms to be brought into contact with the mixture containing crude polyarylene sulfide include at least one selected from the group consisting of alcohol-based solvents and ketone-based solvents. Examples of alcohol-based solvents (also referred to as alcohol solvents) include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, ethylene glycol, propylene glycol, trimethylolpropane, and benzyl. Alcohols with 10 or less carbon atoms such as alcohols; 2-methoxyethyl alcohol, 2-ethoxyethyl alcohol, 1-methoxy-2-propyl alcohol, 1-ethoxy-2-propyl alcohol, 3-methoxy-1-butyl alcohol , 2-Isopropoxyethyl alcohols and other alcohols with 10 or less carbon atoms containing ether bonds; 3-hydroxy-2-butanone and other alcohols with 10 or less carbon atoms; methyl hydroxyisobutyrate and the like An example is an alcohol containing such an ester group and having 10 or less carbon atoms. Examples of the ketone solvent (also referred to as a ketone solvent) include acetone, methyl ethyl ketone, cyclohexanone, γ-butyl lactone and N-methylpyrrolidinone. In the present invention, it is preferable to use a monohydric alcohol having 10 or less carbon atoms because the residual carboxyalkylamino group-containing compound can be efficiently removed, and further, a monohydric alcohol having 3 or less carbon atoms is preferable. preferable. Further, the step (2Ss) may be carried out after making an aqueous solution obtained by adding water to an oxygen atom-containing solvent having 1 to 3 carbon atoms and lowering the concentration. At that time, the concentration of the oxygen atom-containing solvent having 1 to 3 carbon atoms in the aqueous solution is not particularly limited, but is preferably in the range of 90 parts by mass or less with respect to 100 parts by mass of the aqueous solution. It is more preferably in the range of 85 parts by mass or less, preferably in the range of 25 parts by mass or more, and more preferably in the range of 45 parts by mass or more.
本発明は、粗ポリアリーレンスルフィドを、炭素原子数１〜３の酸素原子含有溶媒と接触させる工程（２Ｓｓ）と、水と接触させる工程（２Ｓｗ）とをそれぞれ一回または複数回繰り返して行うことにより、粗ポリアリーレンスルフィドを比表面積３０〔ｍ２／ｇ〕以上の範囲の多孔質粒子、好ましくは４３〔ｍ２／ｇ〕以上から、２００〔ｍ２／ｇ〕以下の範囲の多孔質粒子、より好ましくは６０〔ｍ２／ｇ〕以上から、１２０〔ｍ２／ｇ〕以下の範囲の多孔質粒子とする。 In the present invention, the step of contacting the crude polyarylene sulfide with an oxygen atom-containing solvent having 1 to 3 carbon atoms (2Ss) and the step of contacting the crude polyarylene sulfide with water (2Sw) are repeated once or a plurality of times, respectively. As a result, the crude polyarylene sulfide is composed of porous particles having a specific surface area of 30 [m 2 / g] or more, preferably 43 [m 2 / g] or more and 200 [m 2 / g] or less. , More preferably, the porous particles are in the range of 60 [m 2 / g] or more and 120 [m 2 / g] or less.
粗ポリアリーレンスルフィドを、このような比表面積の範囲を有する多孔質粒子とすることは、粗ポリアリーレンスルフィド中のカルボキシアルキルアミノ基含有化合物を所望の範囲まで容易に低減することが可能となり好ましい。 It is preferable that the crude polyarylene sulfide is made into porous particles having such a range of specific surface area because the carboxyalkylamino group-containing compound in the crude polyarylene sulfide can be easily reduced to a desired range.
本発明の精製方法は、続いて、得られた多孔質粒子と１００℃超の水（以下、「熱水」とも称する）とを接触させる工程（３）を有する。これにより多孔質粒子中に含まれるスルフィド化剤（硫化アルカリ金属、水硫化アルカリ金属）などの未反応原料や、カルボキシアルキルアミノ基含有化合物、アルカリ金属ハロゲン化物などの副生成物を洗浄することができる（以下、熱水を接触させて多孔質粒子を洗浄することを「熱水洗」とも称する）。 The purification method of the present invention subsequently includes a step (3) of bringing the obtained porous particles into contact with water having a temperature of over 100 ° C. (hereinafter, also referred to as “hot water”). This makes it possible to clean unreacted raw materials such as sulfidizing agents (alkali sulfide metal, alkali metal hydrosulfide) contained in porous particles and by-products such as carboxyalkylamino group-containing compounds and alkali metal halides. (Hereinafter, cleaning porous particles by contacting them with hot water is also referred to as "hot water washing").
本発明において、前工程（２）で得られた多孔質粒子を、１００℃超の水と接触させる際の条件は、１００℃超以上、より好ましくは１２０℃以上、さらに好ましくは１４０℃以上から、好ましくは２８０℃以下、より好ましくは２７５℃以下、さらに好ましくは２６０℃以下までの範囲である。圧力は反応器内の気相の圧力が加圧下であればよく、好ましくは０．２ＭＰａ（ゲージ圧、以下同じ）以上から、４．６ＭＰａ以下までの範囲である。 In the present invention, the conditions for contacting the porous particles obtained in the previous step (2) with water over 100 ° C. are from over 100 ° C. or higher, more preferably 120 ° C. or higher, still more preferably 140 ° C. or higher. It is preferably in the range of 280 ° C. or lower, more preferably 275 ° C. or lower, and further preferably 260 ° C. or lower. The pressure may be as long as the pressure of the gas phase in the reactor is under pressure, and is preferably in the range of 0.2 MPa (gauge pressure, the same applies hereinafter) or more to 4.6 MPa or less.
前記多孔質粒子と接触させる際に用いる１００℃超の水の量についても特に制限は無いが、多孔質粒子と１００℃超の水との接触が良好に行われ、精製効率がさらに好適となることから、多孔質粒子１００質量部に対して、好ましくは５０質量部以上、より好ましくは１００質量部以上、さらに好ましくは２００質量部以上から、好ましくは１００００質量部以下、より好ましくは５０００質量部以下、さらに好ましくは１０００質量部以下の範囲である。この量の熱水を２回以上に分けて熱水洗を行ってもよい。例えば、熱水洗を２回繰り返す場合、１回目の熱水洗と２回目の熱水洗の間にはろ過を行い、１回目の熱水洗で抽出したスルフィド化剤（硫化アルカリ金属、水硫化アルカリ金属）などの未反応原料や、カルボキシアルキルアミノ基含有化合物、アルカリ金属ハロゲン化物などの副生成物を、ポリアリーレンスルフィド樹脂と濾別することが好ましい。また、熱水洗を一回実施した後に濾過を行い、１００℃以下、より好ましくは室温での水洗を実施しても良い。この操作によっても副生成物ないし未反応原料と、ポリアリーレンスルフィド樹脂との分離、除去がより促進されうる。また１回目の熱水洗工程と２回目の熱水洗工程の条件は前記の条件より任意に選ぶことができるものの、１回目の熱水洗工程の温度は例えば１２０℃〜２００℃の範囲にある温度に設定して、まず高アルカリ性の濾液を濾別して除去した後に、２回目の熱水洗工程の温度を１回目の熱水洗工程の温度より高い温度、例えば１５０℃〜２７５℃の範囲にある温度に設定して実施することが前記熱水洗で用いられる装置の耐薬品性の観点から好ましい。 The amount of water above 100 ° C. used for contacting the porous particles is not particularly limited, but the porous particles are well contacted with water above 100 ° C., and the purification efficiency becomes more preferable. Therefore, with respect to 100 parts by mass of the porous particles, preferably 50 parts by mass or more, more preferably 100 parts by mass or more, still more preferably 200 parts by mass or more, preferably 10,000 parts by mass or less, more preferably 5000 parts by mass. Hereinafter, it is more preferably in the range of 1000 parts by mass or less. This amount of hot water may be washed with hot water in two or more times. For example, when hot water washing is repeated twice, filtration is performed between the first hot water washing and the second hot water washing, and the sulfidizing agent (alkali metal sulfide, alkali metal hydrosulfide) extracted in the first hot water washing is performed. It is preferable to filter out unreacted raw materials such as, carboxyalkylamino group-containing compounds, and by-products such as alkali metal halides from the polyarylene sulfide resin. Further, the hot water washing may be carried out once and then the filtration may be carried out, and then the water washing may be carried out at 100 ° C. or lower, more preferably at room temperature. This operation can also further promote the separation and removal of the by-product or unreacted raw material from the polyarylene sulfide resin. The conditions of the first hot water washing step and the second hot water washing step can be arbitrarily selected from the above conditions, but the temperature of the first hot water washing step is, for example, a temperature in the range of 120 ° C. to 200 ° C. After setting, the highly alkaline filtrate is first filtered and removed, and then the temperature of the second hot water washing step is set to a temperature higher than the temperature of the first hot water washing step, for example, a temperature in the range of 150 ° C. to 275 ° C. From the viewpoint of chemical resistance of the apparatus used in the hot water washing, it is preferable.
なお、工程（３）において、前記水溶液（ｂ）に酸や塩基を添加してｐＨ調整をすることができ、特に熱水洗後のｐＨが１０．０以上１３．０未満の範囲になるように制御することが好ましい。その際に用いる酸としては、例えば、塩酸、硫酸、炭酸、酢酸、シュウ酸等が挙げられ、これらの中でも炭酸、酢酸、シュウ酸が好ましい。また、常圧または加圧下で炭酸ガスを導入し接触させても良い。一方、塩基としては水酸化リチウム、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物、または炭酸ナトリウム、炭酸アンモニウム、リン酸ナトリウム等が挙げられ、これらの中でも水酸化ナトリウムが好ましい。 In the step (3), the pH can be adjusted by adding an acid or a base to the aqueous solution (b), so that the pH after washing with hot water is in the range of 10.0 or more and less than 13.0. It is preferable to control. Examples of the acid used at that time include hydrochloric acid, sulfuric acid, carbonic acid, acetic acid, oxalic acid and the like, and among these, carbonic acid, acetic acid and oxalic acid are preferable. Further, carbon dioxide gas may be introduced and brought into contact under normal pressure or pressure. On the other hand, examples of the base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, sodium carbonate, ammonium carbonate and sodium phosphate, and among these, sodium hydroxide is preferable.
本発明の利点の一つは、強酸を用いた場合にはポリアリーレンスルフィド中に残存する酸を除去するために、強酸を用いた洗浄の後に大量の水と洗浄回数を要して残存する酸を除去する必要があるのに対して、本発明の１００℃超の水を用いた精製方法の場合には、１００℃超の水による洗浄の後に使用する水の量も少なく洗浄回数も削減出来るため、工程能力においても非常にメリットがある上に、環境対策の面からも適した方法と言える。 One of the advantages of the present invention is that when a strong acid is used, a large amount of water and a large number of washings are required after washing with a strong acid in order to remove the acid remaining in the polyarylene sulfide. However, in the case of the purification method using water of more than 100 ° C. of the present invention, the amount of water used after washing with water of more than 100 ° C. is small and the number of washings can be reduced. Therefore, it can be said that it is a suitable method not only in terms of process capacity but also in terms of environmental measures.
本発明の１００℃超の水と前記多孔質粒子とを接触させて精製する際の系内の固形分濃度は、１〜５０重量％となる割合であることが好ましい。該固形分濃度がこの範囲内にあればポリアリーレンスルフィド粒子と１００℃超の水との接触が良好に行われ精製効率が好適でありより好ましい。 The solid content concentration in the system when the water of the present invention exceeding 100 ° C. and the porous particles are brought into contact with each other for purification is preferably a ratio of 1 to 50% by weight. When the solid content concentration is within this range, the polyarylene sulfide particles are in good contact with water having a temperature of more than 100 ° C., and the purification efficiency is preferable, which is more preferable.
本発明は１００℃超の水とポリアリーレンスルフィドの多孔質粒子との接触を、容器内部に撹拌翼を有し、且つ、底部に濾過用フィルターが配設された開放型容器内で行うことができる。密閉型あるいは密閉可能な混合機能を有す容器内で行う必要性はないが、当然、このような容器内で行うこともできる。 In the present invention, the contact between water exceeding 100 ° C. and the porous particles of polyarylene sulfide can be performed in an open container having a stirring blade inside the container and a filter for filtration at the bottom. it can. It is not necessary to carry out in a container having a closed type or a container having a mixing function that can be closed, but of course, it can be carried out in such a container.
尚、本発明の態様は、上述するように、有機極性溶媒中、ポリハロ芳香族化合物とスルフィド化剤とを反応させて得られるポリアリーレンスルフィドを含有する粗反応生成物を脱溶媒させた後、有機溶媒と接触させてポリアリーレンスルフィドを比表面積３０〔ｍ２／ｇ〕以上の範囲の多孔質粒子とし、得られた多孔質粒子と１００℃超の水とを接触させることを特徴とするポリアリーレンスルフィドの精製方法に係るものである。 In the embodiment of the present invention, as described above, the crude reaction product containing polyarylene sulfide obtained by reacting a polyhalo aromatic compound with a sulfidizing agent is desolvated in an organic polar solvent, and then the solvent is removed. Polyarylene sulfide is made into porous particles having a specific surface area of 30 [m 2 / g] or more by contacting with an organic solvent, and the obtained porous particles are brought into contact with water having a specific surface area of more than 100 ° C. It relates to a method for purifying allylene sulfide.
そして、本発明の他の態様の一つとしては、当該精製方法によりポリアリーレンスルフィドを精製する工程を有する、ポリアリーレンスルフィドの製造方法にかかるものである。すなわち、当該ポリアリーレンスルフィドの製造方法に係る発明は、有機極性溶媒中、ポリハロ芳香族化合物とスルフィド化剤とを反応して得られるポリアリーレンスルフィドを含有する粗反応生成物を脱溶媒させることにより、粗ポリアリーレンスルフィドを含む混合物を得る工程、粗ポリアリーレンスルフィドを含む混合物を、精製して前記粗ポリアリーレンスルフィドを比表面積３０〔ｍ２／ｇ〕以上の範囲の多孔質粒子とする工程、得られた多孔質粒子と１００℃超の水とを接触させる工程（３）とを有し、
前記工程（２）が、炭素原子数１〜３の酸素原子含有溶媒と接触させる工程（２Ｓｓ）と、水と接触させる工程（２Ｓｗ）とをそれぞれ少なくとも１回ずつ行う工程を有し、
工程（３）後の前記多孔質粒子中に含まれる前記構造式（１）で表される化合物（１）の割合が、該ポリアリーレンスルフィド中に１０００〔ｐｐｍ〕超から、３０００〔ｐｐｍ〕以下の範囲であることを特徴とする。
Then, one of the other aspects of the present invention relates to a method for producing polyarylene sulfide, which comprises a step of purifying polyarylene sulfide by the purification method. That is, the invention according to the method for producing the polyarylene sulfide is obtained by desolving a crude reaction product containing polyarylene sulfide obtained by reacting a polyhalo aromatic compound with a sulfidizing agent in an organic polar solvent. , A step of obtaining a mixture containing crude polyarylene sulfide, a step of purifying the mixture containing crude polyarylene sulfide to form the crude polyarylene sulfide into porous particles having a specific surface area of 30 [m 2 / g] or more. It has a step (3) of bringing the obtained porous particles into contact with water having a temperature of over 100 ° C.
The step (2) includes a step of contacting with an oxygen atom-containing solvent having 1 to 3 carbon atoms (2Ss) and a step of contacting with water (2Sw) at least once.
The proportion of the compound (1) represented by the structural formula (1) contained in the porous particles after the step (3) is from more than 1000 [ppm] to 3000 [ppm] or less in the polyarylene sulfide. It is characterized in that it is in the range of.
本発明の精製方法ないし製造方法を経て得られたポリアリーレンスルフィドは、そのまま乾燥しても良いし、更に水洗や有機溶剤洗を適宜行った後、固液分離し、乾燥を行っても良い。 The polyarylene sulfide obtained through the purification method or the production method of the present invention may be dried as it is, or may be further washed with water or an organic solvent as appropriate, then solid-liquid separated and dried.
乾燥は実質的に水等の溶媒が蒸発する温度に加熱して行う。乾燥は真空下で行っても良いし、空気中あるいは窒素のような不活性雰囲気下で行っても良い。 Drying is carried out by heating to a temperature at which a solvent such as water evaporates substantially. Drying may be carried out under vacuum, in air or in an inert atmosphere such as nitrogen.
上述した本発明の精製方法ないし製造方法を経て得られたポリアリーレンスルフィド（単に、「精製ポリアリーレンスルフィド」ということがある）は以下の特徴を有する。すなわち、
本発明の精製ポリアリーレンスルフィドは、比表面積が、１０〔ｍ２／ｇ〕以上、好ましくは１５〔ｍ２／ｇ〕以上、より好ましくは２０〔ｍ２／ｇ〕以上から、好ましくは１８０〔ｍ２／ｇ〕以下、より好ましくは１５０〔ｍ２／ｇ〕以下、さらに好ましくは１００〔ｍ２／ｇ〕以下、特に好ましくは５０〔ｍ２／ｇ〕以下までの範囲の多孔質粒子である。
The polyarylene sulfide obtained through the above-mentioned purification method or production method of the present invention (sometimes simply referred to as "purified polyarylene sulfide") has the following characteristics. That is,
The purified polyarylene sulfide of the present invention has a specific surface area of 10 [m 2 / g] or more, preferably 15 [m 2 / g] or more, more preferably 20 [m 2 / g] or more, and preferably 180 [m 2 / g] or more. Porous particles in the range of m 2 / g] or less, more preferably 150 [m 2 / g] or less, still more preferably 100 [m 2 / g] or less, and particularly preferably 50 [m 2 / g] or less. is there.
また、本発明の精製ポリアリーレンスルフィドは、構造式（１）で表される化合物（１）の含有量の割合が該ポリアリーレンスルフィド中に１０００〔ｐｐｍ〕超、好ましくは１１００〔ｐｐｍ〕から、３０００〔ｐｐｍ〕以下、好ましくは２０００〔ｐｐｍ〕以下の範囲である。 Further, the purified polyarylene sulfide of the present invention has a content ratio of the compound (1) represented by the structural formula (1) of more than 1000 [ppm], preferably 1100 [ppm] in the polyarylene sulfide. The range is 3000 [ppm] or less, preferably 2000 [ppm] or less.
さらに、本発明の精製ポリアリーレンスルフィドは、結晶化速度が遅い傾向を有する。結晶化速度について特に限定されるものではないが、等温結晶化速度が、好ましくは４〔分〕以上、より好ましくは５〔分〕以上から、９〔分〕以下、好ましくは８〔分〕以下までの範囲である。ただし、等温結晶化温度は、試料を、示差走査熱量測定装置を用いて、３５０℃／３分溶融させた後、３５０℃から２４０℃に急冷却（２１０℃／分）し、冷却した温度（２４０℃）で１５分間保持した際の測定値である。 Furthermore, the purified polyarylene sulfide of the present invention tends to have a slow crystallization rate. The crystallization rate is not particularly limited, but the isothermal crystallization rate is preferably 4 [minutes] or more, more preferably 5 [minutes] or more, 9 [minutes] or less, preferably 8 [minutes] or less. The range is up to. However, the isothermal crystallization temperature is the temperature at which the sample is melted at 350 ° C./3 minutes using a differential scanning calorimetry device and then rapidly cooled from 350 ° C. to 240 ° C. (210 ° C./min). It is a measured value when it was held at 240 ° C.) for 15 minutes.
本発明の精製方法ないし製造方法を経て得られたポリアリーレンスルフィドは従来と同様、そのまま各種成形材料等に利用できるが、空気あるいは酸素富化空気中あるいは減圧下で熱処理することにより増粘することが可能であり、必要に応じてこのような増粘操作を行った後、各種成形材料等に利用しても良い。この熱処理温度は処理時間によっても異なるし処理する雰囲気によっても異なるので一概に規定できないが、通常は１８０℃以上で行うことが好ましい。熱処理温度が１８０℃未満では増粘速度が非常に遅く生産性が悪く好ましくない。熱処理は押出機等を用いて重合体の融点以上で、溶融状態で行っても良い。但し、重合体の劣化の可能性あるいは作業性等から、融点プラス１００℃以下で行うことが好ましい。 The polyarylene sulfide obtained through the purification method or production method of the present invention can be used as it is for various molding materials as in the conventional case, but it is thickened by heat treatment in air or oxygen-enriched air or under reduced pressure. If necessary, after performing such a thickening operation, it may be used for various molding materials and the like. This heat treatment temperature varies depending on the treatment time and the atmosphere to be treated, and therefore cannot be unconditionally specified, but it is usually preferably performed at 180 ° C. or higher. If the heat treatment temperature is less than 180 ° C., the thickening rate is very slow and the productivity is poor, which is not preferable. The heat treatment may be carried out in a molten state at a temperature equal to or higher than the melting point of the polymer using an extruder or the like. However, it is preferable to carry out the process at a melting point of 100 ° C. or lower because of the possibility of deterioration of the polymer or workability.
本発明により得られたポリアリーレンスルフィドは、従来と同様、充填剤や他の樹脂と配合して溶融混練後、直接または一旦ペレットに成形した後、射出成形、押出成形、圧縮成形、ブロー成形のごとき各種溶融加工法により、耐熱性、成形加工性、寸法安定性等に優れた成形物にすることができる。しかしながら強度、耐熱性、寸法安定性等の性能をさらに改善するために、本発明の目的を損なわない範囲で各種充填材と組み合わせて使用することも可能である。充填材としては、繊維状充填材、無機充填材等が挙げられる。また、成形加工の際に添加剤として本発明の目的を逸脱しない範囲で少量の、離型剤、着色剤、耐熱安定剤、紫外線安定剤、発泡剤、防錆剤、難燃剤、滑剤、カップリング剤を含有せしめることができる。更に、同様に下記のごとき合成樹脂及びエラストマーを混合して使用できる。これら合成樹脂としては、ポリエステル、ポリアミド、ポリイミド、ポリエーテルイミド、ポリカーボネート、ポリフェニレンエーテル、ポリスルフォン、ポリエーテルスルフォン、ポリエーテルエーテルケトン、ポリエーテルケトン、ポリアリーレン、ポリエチレン、ポリプロピレン、ポリ四弗化エチレン、ポリ二弗化エチレン、ポリスチレン、ＡＢＳ樹脂、エポキシ樹脂、シリコーン樹脂、フェノール樹脂、ウレタン樹脂、液晶ポリマー等が挙げられ、エラストマーとしては、ポリオレフィン系ゴム、弗素ゴム、シリコーンゴム等が挙げられる。 The polyarylene sulfide obtained by the present invention can be mixed with a filler or other resin, melt-kneaded, directly or once molded into pellets, and then injection-molded, extrusion-molded, compression-molded, or blow-molded, as in the conventional case. By various melt processing methods such as, it is possible to obtain a molded product having excellent heat resistance, molding processability, dimensional stability and the like. However, in order to further improve performance such as strength, heat resistance, and dimensional stability, it can be used in combination with various fillers as long as the object of the present invention is not impaired. Examples of the filler include a fibrous filler and an inorganic filler. In addition, a small amount of mold release agent, colorant, heat-resistant stabilizer, ultraviolet stabilizer, foaming agent, rust preventive, flame retardant, lubricant, cup, as an additive during molding, as long as it does not deviate from the object of the present invention. A ring agent can be contained. Further, similarly, the following synthetic resin and elastomer can be mixed and used. Examples of these synthetic resins include polyester, polyamide, polyimide, polyetherimide, polycarbonate, polyphenylene ether, polysulphon, polyethersulphon, polyetheretherketone, polyetherketone, polyarylene, polyethylene, polypropylene, polytetrafluorinated ethylene, and the like. Examples thereof include polydifluorinated ethylene, polystyrene, ABS resin, epoxy resin, silicone resin, phenol resin, urethane resin, liquid crystal polymer and the like, and examples of the elastomer include polyolefin rubber, fluororubber, silicone rubber and the like.
本発明のポリアリーレンスルフィドまたはそれを含む樹脂組成物を溶融成形してなる成形品は、従来の方法で得られるＰＰＳ同様耐熱性、寸法安定性等が優れるので、例えば、コネクタ・プリント基板・封止成形品などの電気・電子部品、ランプリフレクター・各種電装部品などの自動車部品、各種建築物や航空機・自動車などの内装用材料、あるいはＯＡ機器部品・カメラ部品・時計部品などの精密部品等の射出成形・圧縮成形品、あるいは繊維・フィルム・シート・パイプなどの押出成形・引抜成形品等として幅広く利用可能である。さらに、結晶化速度が従来の方法で得られるＰＰＳよりも遅いことから、射出成型時にゲート部の固化を遅め肉厚部まで圧力を加えることができ、これによりこれまでの充填不足を解消し、強度低下を防止することができる。このことから、特に、大型ないし肉厚の成形品、好ましくは射出成形品に適しており、例えば、４ｍｍ以上の肉厚部を有する射出成形品、一辺が２００ｍｍ以上の大型の射出成形品成型品として特に好ましく利用可能である。 The molded product obtained by melt-molding the polyarylene sulfide of the present invention or the resin composition containing the same is excellent in heat resistance, dimensional stability, etc. like the PPS obtained by the conventional method. Therefore, for example, a connector, a printed substrate, or a seal. Electrical and electronic parts such as stop moldings, automobile parts such as lamp reflectors and various electrical parts, interior materials such as various buildings, aircraft and automobiles, and precision parts such as OA equipment parts, camera parts and clock parts. It can be widely used as injection-molded / compression-molded products, or extrusion-molded / draw-molded products such as fibers, films, sheets, and pipes. Furthermore, since the crystallization rate is slower than the PPS obtained by the conventional method, it is possible to delay the solidification of the gate portion and apply pressure to the thick portion at the time of injection molding, thereby eliminating the conventional filling shortage. , It is possible to prevent a decrease in strength. From this, it is particularly suitable for a large-sized or thick-walled molded product, preferably an injection-molded product. For example, an injection-molded product having a wall thickness of 4 mm or more, or a large-sized injection-molded product having a side of 200 mm or more. It is particularly preferably available as.
以下に実施例を挙げて本発明を具体的に説明する。これら例は例示的なものであって限定的なものではない。 Hereinafter, the present invention will be specifically described with reference to examples. These examples are exemplary and not limiting.
（測定法１）ポリアリーレンスルフィド樹脂中のＣＰ−ＭＡＢＡ濃度の定量
（１）ポリアリーレンスルフィド中のＣＰ−ＭＡＢＡの抽出：ＮａＯＨ０．０５％水溶液をポリアリーレンスルフィドに対して、２０倍を入れて、２００℃に昇温して３０分加熱し、固液分離することで、ポリアリーレンスルフィド樹脂中のＣＰ−ＭＡＢＡをろ液に抽出した。
(Measurement method 1) Quantification of CP-MABA concentration in polyarylene sulfide resin (1) Extraction of CP-MABA in polyarylene sulfide: Add 20 times of NaOH 0.05% aqueous solution to polyarylene sulfide. CP-MABA in the polyarylene sulfide resin was extracted into a filtrate by heating to 200 ° C. for 30 minutes and separating into solid and liquid.
（２）〔ＣＰ−ＭＡＢＡの測定方法〕
得られたろ液中のＣＰ−ＭＡＢＡ濃度は、（１）で作製したろ液サンプルのＨＰＬＣ測定を行い、下記の方法で作製した標準サンプルと同じ保持時間のピーク面積と検量線とから液中の濃度を求め、算出した。
(2) [Measurement method of CP-MABA]
The CP-MABA concentration in the obtained filtrate was measured by HPLC measurement of the filtrate sample prepared in (1), and the peak area and calibration curve of the same retention time as the standard sample prepared by the following method were used to determine the concentration in the filtrate. The concentration was calculated and calculated.
（サンプル調製）
ろ液中のＣＰ−ＭＡＢＡは、そのまま移動相を加えて調製し測定した。
(Sample preparation)
CP-MABA in the filtrate was prepared and measured by adding the mobile phase as it was.
（標準サンプル：ＣＰ−ＭＡＢＡの合成）
４８％ＮａＯＨ水溶液８３．４ｇ（１．０モル）とＮ‐メチル‐２‐ピロリドン２９７．４ｇ（３．０モル）を、撹拌機付き耐圧容器に仕込み、２３０℃で３時間撹拌した。この撹拌が終了した後、温度２３０℃のままバルブを開き、放圧し、Ｎ‐メチル‐２‐ピロリドンの蒸気圧程度である２３０℃において０．１ＭＰａまで圧力を低下させ、水を留去した。その後、再び密閉し２００℃程度まで温度を低下させた。
(Standard sample: Synthesis of CP-MABA)
83.4 g (1.0 mol) of a 48% NaOH aqueous solution and 297.4 g (3.0 mol) of N-methyl-2-pyrrolidone were placed in a pressure-resistant container equipped with a stirrer and stirred at 230 ° C. for 3 hours. After the stirring was completed, the valve was opened at a temperature of 230 ° C., the pressure was released, the pressure was lowered to 0.1 MPa at 230 ° C., which is about the vapor pressure of N-methyl-2-pyrrolidone, and water was distilled off. Then, it was sealed again and the temperature was lowered to about 200 ° C.
ｐ−ジクロロベンゼン１４７．０ｇ（１．０モル）を６０℃以上の温度条件下で加熱溶解して反応混合物中に投入し、２５０℃まで昇温後４時間撹拌した。この撹拌が終了した後、室温まで冷却した。ｐ−ジクロロベンゼンの反応率は３１モル％であった。冷却後、内容物を取り出し、水を加えて撹拌後、未反応のｐ−ジクロロベンゼンが不溶物となって残ったものをろ過によって取り除いた。 147.0 g (1.0 mol) of p-dichlorobenzene was heated and dissolved under a temperature condition of 60 ° C. or higher, charged into the reaction mixture, heated to 250 ° C., and stirred for 4 hours. After this stirring was completed, the mixture was cooled to room temperature. The reaction rate of p-dichlorobenzene was 31 mol%. After cooling, the contents were taken out, water was added, and the mixture was stirred, and then the unreacted p-dichlorobenzene that remained as an insoluble matter was removed by filtration.
次いで、ろ液である水溶液に塩酸を加えて該水溶液のｐＨを４に調整した。このとき水溶液中に褐色オイル状のＣＰ−ＭＡＢＡ（水素型）が生じた。そこにクロロホルムを加えて褐色オイル状物質を抽出した。このときの水相には、Ｎ−メチル−２−ピロリドン及びその開環物である４−メチルアミノ酪酸（以下「ＭＡＢＡ」と略記する。）が含まれるため水相は廃棄した。クロロホルム相は水洗を２回繰り返した。 Next, hydrochloric acid was added to the aqueous solution as a filtrate to adjust the pH of the aqueous solution to 4. At this time, a brown oil-like CP-MABA (hydrogen type) was generated in the aqueous solution. Chloroform was added thereto to extract a brown oily substance. Since the aqueous phase at this time contained N-methyl-2-pyrrolidone and 4-methylaminobutyric acid (hereinafter abbreviated as "MABA") which is a ring-opening product thereof, the aqueous phase was discarded. The chloroform phase was washed twice with water.
クロロホルム相に水を加えてスラリー化した状態で４８％ＮａＯＨ水溶液を加え、該スラリーのｐＨを１３に調整した。このときＣＰ−ＭＡＢＡはナトリウム塩となって水相に移り、クロロホルム相には副生成物であるｐ−クロロ−Ｎ−メチルアニリン及びＮ−メチルアニリンが溶解しているためクロロホルム相は廃棄した。水相はクロロホルム洗浄を２回繰り返した。 Water was added to the chloroform phase to form a slurry, and a 48% NaOH aqueous solution was added to adjust the pH of the slurry to 13. At this time, CP-MABA became a sodium salt and moved to the aqueous phase, and the chloroform phase was discarded because the by-products p-chloro-N-methylaniline and N-methylaniline were dissolved in the chloroform phase. The aqueous phase was washed with chloroform twice.
水溶液に希塩酸を加えて該水溶液のｐＨを１以下に調整した。このときＣＰ−ＭＡＢＡは塩酸塩となって水溶液中にとどまるので、水溶液にクロロホルムを加えて、副生成物であるｐ−クロロフェノールを抽出した。ｐ−クロロフェノールが溶解したクロロホルム相は廃棄した。 Dilute hydrochloric acid was added to the aqueous solution to adjust the pH of the aqueous solution to 1 or less. At this time, CP-MABA became a hydrochloride and remained in the aqueous solution, so chloroform was added to the aqueous solution to extract p-chlorophenol as a by-product. The chloroform phase in which p-chlorophenol was dissolved was discarded.
残った水溶液に４８％ＮａＯＨ水溶液を加え、該水溶液のｐＨを４に調整した。これにより、ＣＰ−ＭＡＢＡの塩酸塩が中和され、褐色オイル状のＣＰ−ＭＡＢＡ（水素型）が水溶液から析出した。ＣＰ−ＭＡＢＡ（水素型）をクロロホルムで抽出し、クロロホルムを減圧除去することによってＣＰ−ＭＡＢＡ（水素型）を得た。 A 48% NaOH aqueous solution was added to the remaining aqueous solution to adjust the pH of the aqueous solution to 4. As a result, the hydrochloride salt of CP-MABA was neutralized, and CP-MABA (hydrogen type) in the form of brown oil was precipitated from the aqueous solution. CP-MABA (hydrogen type) was extracted with chloroform, and chloroform was removed under reduced pressure to obtain CP-MABA (hydrogen type).
（ＨＰＬＣの測定）
よく攪拌した溶液から、１ｍｌをサンプリングし、そこにＨＰＬＣの移動相を９ｍｌ加え、ろ液を測定サンプルとした。測定サンプルのＨＰＬＣ測定を行い、下記の方法で作成した標準サンプルと同じ保持時間のピーク面積と検量線とから液中の濃度を求めた。ＨＰＬＣ測定条件は以下の通り。
装置名：株式会社 島津製作所製「高速液体クロマトグラム Ｐｒｏｍｉｎｅｎｃｅ」
カラム：株式会社 島津ジーエルシー製
「Ｐｈｅｎｏｍｅｎｅｘ Ｌｕｎａ ５ｕ Ｃ１８（２） １００Ａ」
検出器：ＤＡＤ （Ｄｉｏｄｅ Ａｒｒａｙ Ｄｅｔｅｃｔｏｒ）
データ処理：株式会社 島津製作所製「ＬＣｓｏｌｕｔｉｏｎ」
測定条件：カラム温度４０℃
移動相：メタノール/酢酸水溶液１ｖｏｌ％＝６/４(ｖｏｌ比)
流速 ：１．０ｍｌ／分
(Measurement of HPLC)
From the well-stirred solution, 1 ml was sampled, 9 ml of the mobile phase of HPLC was added thereto, and the filtrate was used as a measurement sample. The HPLC measurement of the measurement sample was performed, and the concentration in the liquid was determined from the peak area and the calibration curve having the same retention time as the standard sample prepared by the following method. The HPLC measurement conditions are as follows.
Device name: "High Performance Liquid Chromatogram Prominence" manufactured by Shimadzu Corporation
Column: "Phenomenex Luna 5u C18 (2) 100A" manufactured by Shimadzu LLC Co., Ltd.
Detector: DAD (Diode Array Detector)
Data processing: "LC solution" manufactured by Shimadzu Corporation
Measurement conditions: Column temperature 40 ° C
Mobile phase: Methanol / acetic acid aqueous solution 1 vol% = 6/4 (vol ratio)
Flow velocity: 1.0 ml / min
（測定法２） 比表面積（ＢＥＴ比表面積）の分析方法
比表面積の測定には株式会社 島津製作所製トライスターＩＩ３０２０を使用した。得られたポリフェニレンスルフィドの多孔質粒子（試料）をセルに入れた後、脱気した後ヘリウム置換、冷却し、窒素置換させることによって比表面積を測定した。
(Measurement method 2) Analysis method of specific surface area (BET specific surface area) Tristar II 3020 manufactured by Shimadzu Corporation was used for measuring the specific surface area. The obtained porous particles (sample) of polyphenylene sulfide were placed in a cell, degassed, replaced with helium, cooled, and replaced with nitrogen to measure the specific surface area.
（測定法３） ポリアリーレンスルフィドの等温結晶化速度の測定
サンプル４ｍｇを示差走査熱量測定装置（パーキンエルマー製「Ｄｉａｍｏｎｄ ＤＳＣ」）を用いて、３５０℃／３分溶融させた後、３５０℃から２４０℃に急冷却（２１０℃／分）し、冷却した温度（２４０℃）で１５分間保持した時の等温結晶化速度を測定した。得れた等温結晶化速度を「Ｔｍａｘ＠２４０℃」と表示した。
(Measurement method 3) 4 mg of a sample for measuring the isothermal crystallization rate of polyarylene sulfide was melted at 350 ° C./3 minutes using a differential scanning calorimetry device (“Diamond DSC” manufactured by PerkinElmer), and then 350 ° C. to 240 ° C. The isothermal crystallization rate was measured when the mixture was rapidly cooled to ° C. (210 ° C./min) and held at the cooled temperature (240 ° C.) for 15 minutes. The obtained isothermal crystallization rate was indicated as "Tmax @ 240 ° C.".
（測定例４）反応性評価方法
得られたポリアリーレンスルフィドの多孔質粒子を小型粉砕機で粉砕した後、日本工業規格Ｚ８８０１の目開き０．５ｍｍの試験用篩いを用いて篩った。篩いを通過したＰＰＳ樹脂１００質量部に対し、３−グリシドキシプロピルトリメトキシシラン０．５質量部を配合し、均一に混合した後に溶融粘度Ｖ６（島津製作所製フローテスター、ＣＦＴ−５００Ｄを用い、３００℃、荷重：１．９６×１０６Ｐａ、Ｌ／Ｄ＝１０（ｍｍ）／１（ｍｍ）にて、６分間保持した後に測定した値）を測定した。添加後の溶融粘度Ｖ６／添加前の溶融粘度Ｖ６の比から粘度上昇度を倍率として算出した。粘度上昇度が大きいほど反応性が高く、優れていることを示す。
(Measurement Example 4) Reactivity Evaluation Method The obtained porous particles of polyarylene sulfide were pulverized with a small pulverizer, and then sieved using a test sieve having a mesh size of 0.5 mm according to Japanese Industrial Standard Z8801. 0.5 parts by mass of 3-glycidoxypropyltrimethoxysilane was mixed with 100 parts by mass of PPS resin that had passed through the sieve, and after uniformly mixing, a melt viscosity V6 (a flow tester manufactured by Shimadzu Corporation, CFT-500D) was used. , 300 ° C., load: 1.96 × 10 6 Pa, L / D = 10 (mm) / 1 (mm), and the value measured after holding for 6 minutes) was measured. The degree of increase in viscosity was calculated as a magnification from the ratio of the melt viscosity V6 after the addition / the melt viscosity V6 before the addition. The larger the degree of increase in viscosity, the higher the reactivity and the better.
（測定例５）キャビティーバランス
実施例１〜４ないし比較例１、２で得られた精製ＰＰＳ６５質量部、住友化学株式会社製オレフィン系熱可塑性エラストマー「ボンドファースト−Ｅ」５質量部をタンブラーで均一に混合した。その後、ベント付き２軸押出機（日本製鋼所、ＴＥＸ３０α）の投入口（トップフィーダ）に前記配合材料を投入し、サイドフィーダから、ガラス繊維（チョップドストランド、繊維径１０μｍ、繊維長３ｍｍ、エポキシ樹脂集束剤）３０質量部を投入して、樹脂成分吐出量３０ｋｇ／ｈｒ、スクリュー回転数２２０ｒｐｍ、設定樹脂温度を３２０℃に設定して溶融混練し、吐出口より吐出したストランド状物をカットしてＰＰＳコンパウンドのペレットを得た。
続いて、上記のペレットをシリンダー温度３１０℃に設定した住友重機製射出成形機（ＳＥ７５Ｄ−ＨＰ）に供給し、次の条件下で射出成形した。すなわち、４０個分のキャビティーを有するワッシャー金型を用いて、一次スプルーに最も近い位置のキャビティー（Ｃ１）が完全に充填される限りで最低の成形条件とした。他の成形条件は７５トン成形機、シリンダー温度３２０℃、金型温度１４０℃、保圧無しとした。
成型後の、キャビティー（Ｃ１）と同じランナーにある一次スプルーから最も遠いキャビティー（Ｃ１０）の充填度を比較した。充填度(質量％）は、キャビティー（Ｃ１）の成形品に対する、キャビティー（Ｃ１０）の成形品の質量比から求めた。キャビティー（Ｃ１０）の充填度が高いほど、キャビティーバランスが優れていると言える。充填度に基づいて、各組成物のキャビティーバランスを以下の基準で判定した。
ＡＡ：１００質量％以下から、９０質量％以上の範囲
Ａ：９０質量％未満から、８０質量％以上の範囲
Ｂ：８０質量％未満から、７０質量％以上の範囲
Ｃ：７０質量％未満から、６０質量％以上の範囲
Ｄ：６０質量％未満以下の範囲
(Measurement Example 5) Cavity Balance 65 parts by mass of the purified PPS obtained in Examples 1 to 4 to Comparative Examples 1 and 2 and 5 parts by mass of the olefin-based thermoplastic elastomer "Bond First-E" manufactured by Sumitomo Chemical Co., Ltd. were tumbled. Mixed uniformly. After that, the compounding material is charged into the inlet (top feeder) of a twin-screw extruder with a vent (Japan Steel Works, TEX30α), and glass fiber (chopped strand, fiber diameter 10 μm, fiber length 3 mm, epoxy resin) is fed from the side feeder. 30 parts by mass of the sizing agent) is added, the resin component discharge amount is 30 kg / hr, the screw rotation speed is 220 rpm, the set resin temperature is set to 320 ° C., melt-kneading is performed, and the strand-shaped material discharged from the discharge port is cut. PPS compound pellets were obtained.
Subsequently, the pellets were supplied to an injection molding machine (SE75D-HP) manufactured by Sumitomo Heavy Industries, which was set to a cylinder temperature of 310 ° C., and injection molded under the following conditions. That is, using a washer mold having 40 cavities, the minimum molding conditions were set as long as the cavity (C1) at the position closest to the primary sprue was completely filled. Other molding conditions were a 75-ton molding machine, a cylinder temperature of 320 ° C., a mold temperature of 140 ° C., and no holding pressure.
After molding, the filling degree of the cavity (C10) farthest from the primary sprue in the same runner as the cavity (C1) was compared. The filling degree (mass%) was determined from the mass ratio of the molded product of the cavity (C10) to the molded product of the cavity (C1). It can be said that the higher the filling degree of the cavity (C10), the better the cavity balance. Based on the filling degree, the cavity balance of each composition was determined according to the following criteria.
AA: From 100% by mass or less to 90% by mass or more A: From less than 90% by mass to 80% by mass or more B: From less than 80% by mass to 70% by mass or more C: From less than 70% by mass Range of 60% by mass or more D: Range of less than 60% by mass
〔合成例１〕 ポリアリーレンスルフィドの重合工程
圧力計、温度計、コンデンサー、デカンター、精留塔を付けた撹拌翼付き１５０Ｌオートクレーブにｐ−ジクロロベンゼン（以下、ＤＣＢと略す）３３．２２２ｋｇ（２２６ｍｏｌ）、ＮＭＰ２．２８０ｋｇ（２３ｍｏｌ）、４７．２３質量％水硫化ソーダ２７．３００ｋｇ（２３０ｍｏｌ）、及び４９．２１質量％苛性ソーダ１８．５３３ｋｇ（２２８ｍｏｌ）を仕込み、撹拌しながら窒素雰囲気下で１７３℃まで５時間掛けて昇温して、水２７．３ｋｇを留出させた後、釜を密閉した。脱水時に共沸により留出したＤＣＢはデカンターで分離して随時釜内に戻し、脱水終了後の釜内は無水硫化ナトリウム組成物がDCB中に分散した状態であった。更に、内温を１６０℃に冷却し、ＮＭＰ４７．４９２ｋｇ（４７９ｍｏｌ）を仕込み、１８５℃まで昇温した。圧力が０．００ＭＰａに到達した時点で、精留塔を連結したバルブを開放し、内温２００℃まで１時間掛けて昇温した。この際、精留塔出口温度が１１０℃以下になる様に冷却とバルブ開度で制御した。留出したＤＣＢと水の混合蒸気はコンデンサーで凝縮し、デカンターで分離して、ＤＣＢは釜へ戻した。留出水量は１７９ｇであった。次に、内温２００℃から２３０℃まで３時間かけて昇温し、１時間撹拌した後、２５０℃まで昇温し１時間撹拌して反応終了後、オートクレーブの内温を２５０℃から２３５℃に冷却し、到達後にオートクレープの底弁を開いて減圧状態のまま撹拌翼付き１５０リットル真空撹拌乾燥機（脱溶媒機ジャケット温度１２０度）にフラッシュさせてＮ−メチル−２−ピロリドンを抜き取り、室温まで冷却し、サンプリングした結果、Ｎ.Ｖ.５５％の粗ＰＰＳ混合物を得た。
[Synthesis Example 1] Polymerization process of polyarylene sulfide p-dichlorobenzene (hereinafter abbreviated as DCB) 33.222 kg (226 mol) in a 150 L autoclave with a stirring blade equipped with a pressure gauge, a thermometer, a condenser, a decanter, and a rectification tower. , NMP 2.280 kg (23 mol), 47.23 mass% hydrosulfide soda 27.300 kg (230 mol), and 49.21 mass% caustic soda 18.533 kg (228 mol), and stir to 173 ° C. under a nitrogen atmosphere. The temperature was raised over time to distill out 27.3 kg of water, and then the kettle was sealed. The DCB distilled by azeotrope during dehydration was separated by a decanter and returned to the kettle at any time, and the anhydrous sodium sulfide composition was dispersed in the kettle after the dehydration was completed. Further, the internal temperature was cooled to 160 ° C., NMP 47.492 kg (479 mol) was charged, and the temperature was raised to 185 ° C. When the pressure reached 0.00 MPa, the valve connected to the rectification column was opened, and the temperature was raised to an internal temperature of 200 ° C. over 1 hour. At this time, cooling and valve opening were controlled so that the rectification tower outlet temperature was 110 ° C. or lower. The distilled steam of DCB and water was condensed by a condenser, separated by a decanter, and the DCB was returned to the kettle. The amount of distilled water was 179 g. Next, the internal temperature was raised from 200 ° C. to 230 ° C. over 3 hours, stirred for 1 hour, then raised to 250 ° C. and stirred for 1 hour, and after the reaction was completed, the internal temperature of the autoclave was raised from 250 ° C. to 235 ° C. After reaching the temperature, open the bottom valve of the autoclave and flush it with a 150 liter vacuum stirring dryer with a stirring blade (solvent remover jacket temperature 120 degrees) to remove N-methyl-2-pyrrolidone. The mixture was cooled to room temperature and sampled to obtain a crude PPS mixture of NV 55%.
（実施例１）
合成例１で得た粗ＰＰＳ混合物４００ｇとイソプロピルアルコール（富士フイルム和光純薬株式会社製「試薬特級」）６３４ｇをフラスコに入れ、４０℃で３０分間撹拌混合し、そのスラリーを桐山ロートで減圧濾過し、上から押し固め、さらに上から８０ｗｔ％イソプロピルアルコール水溶液（富士フイルム和光純薬株式会社製「試薬特級」８０質量部に水２０質量部を加えたもの）４２２ｇを数回に分けて注ぎろ過した。更に、そのろ過して作製したケーキをビーカーに移して薬さじで粉末状に砕き、そこに２０℃の水を６３４ｇ注ぎ、３０分間攪拌混合した。そのスラリーを桐山ロートで減圧ろ過し、上から押し固め、更に上から２０℃の水４２２ｇを数回に分けて注ぎろ過した。上記ケーキと水３４２ｇをオートクレーブに仕込み、２４０℃に加熱し３０分間攪拌させた。そのスラリーを桐山ロートで減圧ろ過し、上から押し固め、更に上から水４４２ｇを数回に分けて注ぎろ過した。そのろ過して作製したケーキをバットに移して薬さじで粉末状に砕き、１２０℃×４時間で乾燥し、精製ＰＰＳを得た。得られた精製ＰＰＳについて測定を行った。その結果を表１に示す。
(Example 1)
400 g of the crude PPS mixture obtained in Synthesis Example 1 and 634 g of isopropyl alcohol (“Reagent Special Grade” manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) are placed in a flask, stirred and mixed at 40 ° C. for 30 minutes, and the slurry is filtered under reduced pressure with a Kiriyama funnel. Then, compact from the top, and then pour 422 g of an 80 wt% isopropyl alcohol aqueous solution (80 parts by mass of "Reagent Special Grade" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. plus 20 parts by mass of water) in several batches and filter. did. Further, the cake prepared by filtration was transferred to a beaker, crushed into powder with a spatula, 634 g of water at 20 ° C. was poured therein, and the cake was stirred and mixed for 30 minutes. The slurry was filtered under reduced pressure with a Kiriyama funnel, compacted from above, and 422 g of water at 20 ° C. was poured from above in several portions and filtered. The cake and 342 g of water were placed in an autoclave, heated to 240 ° C., and stirred for 30 minutes. The slurry was filtered under reduced pressure with a Kiriyama funnel, compacted from above, and 442 g of water was further poured from above in several portions and filtered. The filtered cake was transferred to a vat, crushed into powder with a spatula, and dried at 120 ° C. for 4 hours to obtain purified PPS. The obtained purified PPS was measured. The results are shown in Table 1.
（実施例２）
合成例１で得た粗ＰＰＳ混合物４００ｇとイソプロピルアルコール（富士フイルム和光純薬株式会社製「試薬特級」）６３４ｇをフラスコに入れ、４０℃で３０分間撹拌混合し、そのスラリーを桐山ロートで減圧濾過し、上から押し固め、さらに上から５０ｗｔ％イソプロピルアルコール水溶液（富士フイルム和光純薬株式会社製「試薬特級」５０質量部に水５０質量部を加えたもの）４２２ｇを数回に分けて注ぎろ過した。更に、そのろ過して作製したケーキをビーカーに移して薬さじで粉末状に砕き、そこに２０℃の水を６３４ｇ注ぎ、３０分間攪拌混合した。そのスラリーを桐山ロートで減圧ろ過し、上から押し固め、更に上から２０℃の水４２２ｇを数回に分けて注ぎろ過した。上記ケーキと水３４２ｇをオートクレーブに仕込み、２４０℃に加熱し３０分間攪拌させた。そのスラリーを桐山ロートで減圧ろ過し、上から押し固め、更に上から水４４２ｇを数回に分けて注ぎろ過した。そのろ過して作製したケーキをバットに移して薬さじで粉末状に砕き、１２０℃×４時間で乾燥し、精製ＰＰＳを得た。
得られた精製ＰＰＳについて測定を行った。その結果を表１に示す。
(Example 2)
400 g of the crude PPS mixture obtained in Synthesis Example 1 and 634 g of isopropyl alcohol (“Reagent Special Grade” manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) are placed in a flask, stirred and mixed at 40 ° C. for 30 minutes, and the slurry is filtered under reduced pressure with a Kiriyama funnel. Then, compact from the top, and then pour 422 g of a 50 wt% isopropyl alcohol aqueous solution (50 parts by mass of "Reagent Special Grade" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. plus 50 parts by mass of water) from the top into several batches for filtration. did. Further, the cake prepared by filtration was transferred to a beaker, crushed into powder with a spatula, 634 g of water at 20 ° C. was poured therein, and the cake was stirred and mixed for 30 minutes. The slurry was filtered under reduced pressure with a Kiriyama funnel, compacted from above, and 422 g of water at 20 ° C. was poured from above in several portions and filtered. The cake and 342 g of water were placed in an autoclave, heated to 240 ° C., and stirred for 30 minutes. The slurry was filtered under reduced pressure with a Kiriyama funnel, compacted from above, and 442 g of water was further poured from above in several portions and filtered. The filtered cake was transferred to a vat, crushed into powder with a spatula, and dried at 120 ° C. for 4 hours to obtain purified PPS.
The obtained purified PPS was measured. The results are shown in Table 1.
（実施例３）
合成例１で得た粗ＰＰＳ混合物４００ｇとイソプロピルアルコール（富士フイルム和光純薬株式会社製「試薬特級」）６３４ｇをフラスコに入れ、４０℃で３０分間撹拌混合し、そのスラリーを桐山ロートで減圧濾過し、上から押し固め、さらに上から３０ｗｔ％イソプロピルアルコール水溶液（富士フイルム和光純薬株式会社製「試薬特級」３０質量部に水７０質量部を加えたもの）４２２ｇを数回に分けて注ぎろ過した。更に、そのろ過して作製したケーキをビーカーに移して薬さじで粉末状に砕き、そこに２０℃の水を６３４ｇ注ぎ、３０分間攪拌混合した。そのスラリーを桐山ロートで減圧ろ過し、上から押し固め、更に上から２０℃の水４２２ｇを数回に分けて注ぎろ過した。上記ケーキ上記ケーキと水３４２ｇをオートクレーブに仕込み、２４０℃に加熱し３０分間攪拌させた。そのスラリーを桐山ロートで減圧ろ過し、上から押し固め、更に上から水４４２ｇを数回に分けて注ぎろ過した。そのろ過して作製したケーキをバットに移して薬さじで粉末状に砕き、１２０℃×４時間で乾燥し精製ＰＰＳを得た。得られた精製ＰＰＳについて測定を行った。その結果を表１に示す。
(Example 3)
400 g of the crude PPS mixture obtained in Synthesis Example 1 and 634 g of isopropyl alcohol (“Reagent Special Grade” manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) are placed in a flask, stirred and mixed at 40 ° C. for 30 minutes, and the slurry is filtered under reduced pressure with a Kiriyama funnel. Then, compact from the top, and then pour 422 g of a 30 wt% isopropyl alcohol aqueous solution (30 parts by mass of "Reagent Special Grade" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. plus 70 parts by mass of water) from the top into several batches for filtration. did. Further, the cake prepared by filtration was transferred to a beaker, crushed into powder with a spatula, 634 g of water at 20 ° C. was poured therein, and the cake was stirred and mixed for 30 minutes. The slurry was filtered under reduced pressure with a Kiriyama funnel, compacted from above, and 422 g of water at 20 ° C. was poured from above in several portions and filtered. The cake The cake and 342 g of water were placed in an autoclave, heated to 240 ° C., and stirred for 30 minutes. The slurry was filtered under reduced pressure with a Kiriyama funnel, compacted from above, and 442 g of water was further poured from above in several portions and filtered. The cake prepared by filtration was transferred to a vat, crushed into powder with a spatula, and dried at 120 ° C. for 4 hours to obtain purified PPS. The obtained purified PPS was measured. The results are shown in Table 1.
（実施例４）
合成例１で得た粗ＰＰＳ混合物４００ｇとメタノール（富士フイルム和光純薬株式会社製「試薬特級」）６３４ｇをフラスコに入れ、４０℃で３０分間撹拌混合し、そのスラリーを桐山ロートで減圧濾過し、上から押し固め、さらに上から３０ｗｔ％メタノール水溶液（富士フイルム和光純薬株式会社製「試薬特級」３０質量部に水７０質量部を加えたもの）４２２ｇを数回に分けて注ぎろ過した。更に、そのろ過して作製したケーキをビーカーに移して薬さじで粉末状に砕き、そこに２０℃の水を６３４ｇ注ぎ、３０分間攪拌混合した。そのスラリーを桐山ロートで減圧ろ過し、上から押し固め、更に上から２０℃の水４２２ｇを数回に分けて注ぎろ過した。上記ケーキ上記ケーキと水３４２ｇをオートクレーブに仕込み、２４０℃に加熱し３０分間攪拌させた。そのスラリーを桐山ロートで減圧ろ過し、上から押し固め、更に上から水４４２ｇを数回に分けて注ぎろ過した。そのろ過して作製したケーキをバットに移して薬さじで粉末状に砕き、１２０℃×４時間で乾燥し精製ＰＰＳを得た。得られた精製ＰＰＳについて測定を行った。その結果を表１に示す。
(Example 4)
400 g of the crude PPS mixture obtained in Synthesis Example 1 and 634 g of methanol (“Reagent Special Grade” manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were placed in a flask, stirred and mixed at 40 ° C. for 30 minutes, and the slurry was filtered under reduced pressure with a Kiriyama funnel. , Compacted from above, and 422 g of a 30 wt% methanol aqueous solution (30 parts by mass of "Reagent Special Grade" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. plus 70 parts by mass of water) was poured and filtered in several times. Further, the cake prepared by filtration was transferred to a beaker, crushed into powder with a spatula, 634 g of water at 20 ° C. was poured therein, and the cake was stirred and mixed for 30 minutes. The slurry was filtered under reduced pressure with a Kiriyama funnel, compacted from above, and 422 g of water at 20 ° C. was poured from above in several portions and filtered. The cake The cake and 342 g of water were placed in an autoclave, heated to 240 ° C., and stirred for 30 minutes. The slurry was filtered under reduced pressure with a Kiriyama funnel, compacted from above, and 442 g of water was further poured from above in several portions and filtered. The cake prepared by filtration was transferred to a vat, crushed into powder with a spatula, and dried at 120 ° C. for 4 hours to obtain purified PPS. The obtained purified PPS was measured. The results are shown in Table 1.
（比較例１）
合成例１で得た粗ＰＰＳ混合物４００ｇとＮＭＰ４２２ｇをフラスコに入れ、４０℃で３０分間撹拌混合し、そのスラリーを桐山ロートで減圧濾過し、上から押し固め、さらに上からＮＭＰ４２２ｇを数回に分けて注ぎろ過した。更に、そのろ過して作製したケーキをビーカーに移して薬さじで粉末状に砕き、そこに７０℃の水を４４２ｇ注ぎ、３０分間攪拌混合した。そのスラリーをそのスラリーを桐山ロートで減圧ろ過し、上から押し固め、更に上から７０℃の水４４２ｇを数回に分けて注ぎろ過した。そのろ過して作製したケーキと炭酸水６３４ｇをオートクレーブに仕込み、１６０℃で１時間攪拌混合した。そのスラリーを桐山ロートで減圧ろ過し、上から押し固め、更に上から２５℃の炭酸水４２２ｇを数回に分けて注ぎろ過した。そのろ過して作製したケーキをバットに移して薬さじで粉末状に砕き、１２０℃×４時間で乾燥し、精製ＰＰＳを得た。得られた精製ＰＰＳについて測定を行った。その結果を表１に示す。
(Comparative Example 1)
400 g of the crude PPS mixture and 422 g of NMP obtained in Synthesis Example 1 are placed in a flask, stirred and mixed at 40 ° C. for 30 minutes, the slurry is filtered under reduced pressure with a Kiriyama funnel, compacted from above, and 422 g of NMP is further divided into several times from above. Pour and filter. Further, the cake prepared by filtration was transferred to a beaker, crushed into powder with a spatula, 442 g of water at 70 ° C. was poured therein, and the cake was stirred and mixed for 30 minutes. The slurry was filtered under reduced pressure with a Kiriyama funnel, compacted from above, and 442 g of water at 70 ° C. was poured from above in several portions and filtered. The filtered cake and 634 g of carbonated water were placed in an autoclave and stirred and mixed at 160 ° C. for 1 hour. The slurry was filtered under reduced pressure with a Kiriyama funnel, compacted from above, and 422 g of carbonated water at 25 ° C. was poured from above in several portions and filtered. The filtered cake was transferred to a vat, crushed into powder with a spatula, and dried at 120 ° C. for 4 hours to obtain purified PPS. The obtained purified PPS was measured. The results are shown in Table 1.
（比較例２）
合成例１で得た粗ＰＰＳ混合物４００ｇとＮＭＰ４２２ｇをフラスコに入れ、４０℃で３０分間撹拌混合し、そのスラリーを桐山ロートで減圧濾過し、上から押し固め、さらに上からＮＭＰ４２２ｇを数回に分けて注ぎろ過した。更に、そのろ過して作製したケーキをビーカーに移して薬さじで粉末状に砕き、そこに７０℃の水を４４２ｇ注ぎ、３０分間攪拌混合した。そのスラリーをそのスラリーを桐山ロートで減圧ろ過し、上から押し固め、更に上から７０℃の水４４２ｇを数回に分けて注ぎろ過した。そのろ過して作製したケーキと炭酸水６３４ｇをフラスコに入れ、２５℃で１時間攪拌混合した。そのスラリーを桐山ロートで減圧ろ過し、上から押し固め、更に上から２５℃の炭酸水４２２ｇを数回に分けて注ぎろ過した。そのろ過して作製したケーキをバットに移して薬さじで粉末状に砕き、１２０℃×４時間で乾燥し、精製ＰＰＳを得た。得られた精製ＰＰＳについて測定を行った。その結果を表１に示す。
(Comparative Example 2)
400 g of the crude PPS mixture and 422 g of NMP obtained in Synthesis Example 1 are placed in a flask, stirred and mixed at 40 ° C. for 30 minutes, the slurry is filtered under reduced pressure with a Kiriyama funnel, compacted from above, and 422 g of NMP is further divided into several times from above. Pour and filter. Further, the cake prepared by filtration was transferred to a beaker, crushed into powder with a spatula, 442 g of water at 70 ° C. was poured therein, and the cake was stirred and mixed for 30 minutes. The slurry was filtered under reduced pressure with a Kiriyama funnel, compacted from above, and 442 g of water at 70 ° C. was poured from above in several portions and filtered. The filtered cake and 634 g of carbonated water were placed in a flask and stirred and mixed at 25 ° C. for 1 hour. The slurry was filtered under reduced pressure with a Kiriyama funnel, compacted from above, and 422 g of carbonated water at 25 ° C. was poured from above in several portions and filtered. The filtered cake was transferred to a vat, crushed into powder with a spatula, and dried at 120 ° C. for 4 hours to obtain purified PPS. The obtained purified PPS was measured. The results are shown in Table 1.
比較例１、２と実施例１〜４とを対比すると、いずれのＰＰＳも反応性には優れる一方で、実施例１〜４のＰＰＳは、キャビティーバランスが大幅に向上したことが明らかとなった。 Comparing Comparative Examples 1 and 2 with Examples 1 to 4, it was clarified that the cavity balance of the PPSs of Examples 1 to 4 was significantly improved while all the PPSs were excellent in reactivity. It was.
Claims (11)
前記工程（２）が、炭素原子数１〜３の酸素原子含有溶媒と接触させる工程（２Ｓｓ）と、水と接触させる工程（２Ｓｗ）とをそれぞれ少なくとも１回ずつ行う工程を有し、
工程（３）後の多孔質粒子中に含まれる下記構造式（１）で表される化合物（１）の割合が、１０００〔ｐｐｍ〕超から、３０００〔ｐｐｍ〕以下の範囲であることを特徴とするポリアリーレンスルフィドの精製方法。
The step (2) includes a step of contacting with an oxygen atom-containing solvent having 1 to 3 carbon atoms (2Ss) and a step of contacting with water (2Sw) at least once.
The proportion of the compound (1) represented by the following structural formula (1) contained in the porous particles after the step (3) is in the range of more than 1000 [ppm] to 3000 [ppm] or less. A method for purifying polyarylene sulfide.
下記構造式（１）で表される化合物（１）の含有量の割合が、１０００〔ｐｐｍ〕超から、３０００〔ｐｐｍ〕以下の範囲であることを特徴とするポリアリーレンスルフィド。
A polyarylene sulfide having a content ratio of the compound (1) represented by the following structural formula (1) in the range of more than 1000 [ppm] to 3000 [ppm] or less.
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