JPS62288630A - Photo-stabilized polyarylene thioether - Google Patents
Photo-stabilized polyarylene thioetherInfo
- Publication number
- JPS62288630A JPS62288630A JP61131672A JP13167286A JPS62288630A JP S62288630 A JPS62288630 A JP S62288630A JP 61131672 A JP61131672 A JP 61131672A JP 13167286 A JP13167286 A JP 13167286A JP S62288630 A JPS62288630 A JP S62288630A
- Authority
- JP
- Japan
- Prior art keywords
- polyarylene thioether
- group
- hydrocarbon
- hydrogen
- halogenated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000412 polyarylene Polymers 0.000 title claims abstract description 69
- 150000003568 thioethers Chemical class 0.000 title claims abstract description 54
- 239000000126 substance Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 30
- 229920000642 polymer Polymers 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 15
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 14
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 13
- 150000002367 halogens Chemical class 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- 238000005695 dehalogenation reaction Methods 0.000 claims abstract description 7
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 6
- 229910052977 alkali metal sulfide Inorganic materials 0.000 claims abstract description 5
- 238000005987 sulfurization reaction Methods 0.000 claims abstract description 5
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 18
- 239000004215 Carbon black (E152) Substances 0.000 claims description 17
- 150000008282 halocarbons Chemical group 0.000 claims description 17
- 229930195733 hydrocarbon Natural products 0.000 claims description 17
- 150000002430 hydrocarbons Chemical class 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 150000007944 thiolates Chemical group 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 9
- 125000000732 arylene group Chemical group 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 238000005554 pickling Methods 0.000 claims description 3
- 239000002798 polar solvent Substances 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 150000002896 organic halogen compounds Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 239000003495 polar organic solvent Substances 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- 150000003857 carboxamides Chemical class 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 230000000176 photostabilization Effects 0.000 abstract 1
- 239000004611 light stabiliser Substances 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- -1 Arylene thioether Chemical class 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 6
- 239000012964 benzotriazole Substances 0.000 description 6
- 238000004040 coloring Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 150000002009 diols Chemical group 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- 150000003573 thiols Chemical class 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 239000000378 calcium silicate Substances 0.000 description 3
- 229910052918 calcium silicate Inorganic materials 0.000 description 3
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 238000009739 binding Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000010128 melt processing Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- 101100272412 Arabidopsis thaliana BIA1 gene Proteins 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- 241001137251 Corvidae Species 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 101000958041 Homo sapiens Musculin Proteins 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229920001283 Polyalkylene terephthalate Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012765 fibrous filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 102000046949 human MSC Human genes 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- PGLTVOMIXTUURA-UHFFFAOYSA-N iodoacetamide Chemical compound NC(=O)CI PGLTVOMIXTUURA-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000012066 reaction slurry Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
Description
[産業上の利用分野]
本発明は光安定性の改良されたポリアリーレンチオエー
テル及びその組成物及びそれ等の製造方法に関する。
[従来技術]
ポリアリーレンチオエーテルは耐熱性、電気絶縁性、?
を燃性などに4れたエンジニアリング樹脂であり、射出
成形物、押出成形物、フィルム、シート、lI維、電線
被mなどに応用することができる。特に本発明者等は、
着色の極めて少ない、ポリアリーレンチオエーテルを経
済的に製造寸ろ方法を開発した(特開昭61−7332
号)。しかしながら、ポリアリーレンチオエーテルは、
一般的に380 nm以下の近紫外部に大きな吸収を有
するために、初めは色調の優れた美麗な成形物であった
ものが、紫外線や日光に暴露すると変色して色調が変っ
てしまうという問題点があった。
従来、汎用樹脂の光安定剤としてはベンシフ1ノン系安
定剤、ベンゾ1〜リアゾール系光定剤四が使用されて来
た。
ベンゾフェノン系安定剤は、
(Arニアリール残基)
の化学構造単位を有しており、基本的にはベンピン1′
:lに結合したカルボニル基と、ベンピン環の■の位置
にあるヒドロキシ基との相互作用により光エネルギーを
吸収し、熱エネルギーに変換して逸散することによって
光安定剤として機能するものである。しかしながらベン
ゾフェノン系安定剤は300nm (=J近に強い吸収
を示すものの350nm付近の吸収は弱いので、ポリア
リーレンチオエーテルの光安定剤としてはあまり有効で
ないことが判明した。
ベンゾトリアゾール系光安定剤は、
の化学構造単位を有しており、7v本的にはベンゼン環
に結合しtこ1−リアゾール1寸とベンゼン環の■の位
置にあるヒドロキシ桔との相り作用により、光エネルギ
ーを吸収し熱エネルギーに変換して逸散することによっ
て、光安定剤として機能するちのであると言われている
(HODGEHAN、 D、C,、G[LLERT、
E、P、J、 of Polymer Sci、、 P
olymer Ct+em、 Ed。
18 1105〜1114(1980) )。
この種の安定剤は400nm付近の紫外線から吸収しは
じめ350 n m付近で極大吸収を示すので、ポリア
リーレンチオエーテルの光安定剤として有効であルコと
が示唆されT イt: (CIBA−G[IG’l’社
丁lNUV■
IN 234力タログ1981年3月版)。
しかしながら、耐熱樹脂であるポリアリーレンチオエー
テルの溶融加工温度は汎用樹脂よりかなり高い温度であ
り、従来の汎用樹脂用のベンゾ1〜リアゾール系光安定
剤を混入さけた場合、分子mが充分大きくないために大
半が溶融加工性に揮発、消失してしまい最終成形品に残
存できる有効量が非常に少なくなり、それを回避するた
めに多7Mに添加する必要があり産業上好ましくなく、
また大量に光安定剤を使用すると成形品の物性に影響が
出る等の問題もあった。
上記のベンゾトリアゾール系光安定剤の高温時の揮発を
低減する目的で、ベンピン環の■の位置にあるじドロー
Vシ基をエステル化して大ぎな分子量のものにしてiL
1合する方法が提案されたが(特開昭(10−7166
3) 、この方法では光安定剤作用に肝腎なヒドロキシ
基が消失してしまうため、期待通りの光に対する安定化
効果が得られないという問題が残った。
[発明の作用効果]
本発明6gは、ベンゼン環に結合したベンゾトリアゾー
ル基及びベンゼン環の■の位置のヒドロキシ基による光
安定効采を有する化学構造を、そのまま保持しながらポ
リアリーレンチオエーテルに化学的に結合すると、光安
定性の改良されたポリアリーレンチオエーテルが得られ
、しかも上記のポリアリーレンチオエーテルにおけるベ
ンゾトリアゾール系光安定剤の使用の問題点を解決し得
ることを見出し、本発明を完成した。
即ち、本発明の光安定化ポリアリーレンチオエーテルは
前記の光安定化効果を有する化学構造単位を分子中に化
学結合されて含有しているので、ポリアリーレンチオエ
ーテルに使用される高い溶融成型温度にさらされても光
安定性を損なうことがない。
従って、本発明の光安定化されたポリアリーレンチオエ
ーテルから製造された溶融成型物は、プ;\外線や光に
暴露した時に色調の変化が少なく、各種モールド品、封
止物、フィルム、シート、パイプ、棒、mu等の加工品
は、長+1Q間光による着色や変質のないまま使用でき
る。また本発明の光安定化ポリアリーレンチオエーテル
もしくはその組成物は、長期間光による着色や変質のな
い塗装として用いることもできる。
[発明の要旨]
本発明は分子中のチオエーテル結合の硫黄原子に対し、
化学構造単位:
を0.002〜02 (tル/グラム硫黄原子)化学結
合させた光安定化ポリアリーレンチオニーデルである。
また本願発明は分子中のチオエーテル結合の硫黄原子に
対し、化学構造単位;
を化学結合さUた光安定化ポリアリーレンチオエーテル
と上記化学構造単位を結合してない非光安定化ポリアリ
ーレンチオエーテルとから成る組成物であって、上記の
化学構造単位は組成物中の全チオエーテル結合硫黄原子
に対し0.002〜0.2モル/グラム硫黄原子である
ことを特徴とづる組成物である。
また本発明は上記の光安定化ポリアリーレンチオエーテ
ルのlFJ造方決方法提供するものである。
即ら本発明の光安定化ポリアリーレンチオエーテルの第
1の製造方法は、有機極性溶媒中でのアルカリ金属硫化
物とジハロゲン化分6族化合物との脱ハロゲン化/硫化
反応によってポリアリーレンチオエーテルを生成させる
際に、化学構造単位:を含むハロゲン化有機化合物を0
.002〜02 (モル/グラム硫黄原子)?f!合中
に加え、次いで反応ポリマーを酸洗することから成る。
また本発明の光安定化ポリアリーレンチオエーテルの第
2の製造方法は、強アルカリ性有機極性溶媒中の、分子
末端にチオラート基もしくはチオールLtを有効吊有す
るポリアリーレンチオエーテルΦ合物に、
化学椙造ji位;
を含むハロゲン化石様化合物を0.002−0.21−
ル/′グラム硫黄原子の割合で加え、脱ハロゲン化反応
させ次いで反応ポリマーを酸洗することから成る。
[発明の詳細な説明]
ポリアリーレンチオエーテルの基本構造本発明のポリア
リーレンチオエーテルの主部は、→Ar−8←(Δ「・
:アリーレン基)の構造からなるものである。アリーレ
ン基としてバラフェニレン基を主成分とするものが耐熱
性、成形性の点から好ましい。パラフェニレンV以外に
も、R:アルキル基、n: 1〜4 ) 、p、p’−
シフにが使用される。
繰返し単位のみからなるポリフェニレンチオエーテルが
好ましい。また溶融加工のし易ざ、叩ら加工温度を低く
し着色の少ないベレッi〜を得易い点では、ポリフェニ
レンチオエーテルの共重合体がたはO−フェニレンチオ
エーテル19位が5モル%以上あれば溶融加工の改良効
果が発現でき、40Tl−ル%を越えなければ耐た性、
機械的性質を著しく低jIi位を60〜95モル%含む
共重合体であればランダ連続したブロック状結合を含む
ブ1]ツク共重合体の方が好ましい。ブロック共重合体
の方がランダム共」口合体J、りも同じ加工性で優れた
耐熱性及び撮械的特性の8終成形物を与えるからである
。このようなブロック共重合体J5 にびくの)′ll
仏法、特開昭61−14228号明細出に記載されてい
る。
ボリアリーレンヂオエーフルは、適当な分子Rもしくは
溶融粘度をbつことが加工上から望ましい。即ち、溶融
粘度(η9)が30000ボイス(温度=310℃、剪
断速度=200秒−1)以下のもの、特に好ましくは2
0000ボイス以下のものが望ましい。
30000ボイズを超過するものでは溶融押出でペレッ
I・状成形物を製造するのが回灯となり、加I rP度
も高くなるので着色を生じ易い。
本発明の光安定化ポリアリーレンチオエーテルを伯の光
に対して安定化してないポリアリーレンチオエーテルに
混入して用いる場合は、光安定化ポリアリーレンチオエ
ーテルは低分子ωのものであってもかまわない。
本発明の光安定化ポリアリ−レンチ第1−アルをi1独
で用いる場合は、所謂「キュアー」にJ:り分子間の増
大を必要としないような高分子r11のポリマーである
べきであり、且つフィルム1シー1−9謀N″g:に容
易に加工でさるために【よ実質的に線状のポリマーであ
るべきである。この、ような実質的に線状の、高分子層
ポリアリーレンチオエーテルは、本発明B 1が開発し
た新しい重合法である水添加二段重合法(特開昭61−
7332号)によって特に経済的に製造することができ
る。
光安定化ポリアリーレンチオエーテルのWBh法本発明
の光安定化ポリアリーレンチオエーテルの製造方法は下
記の化学構造単位:
をポリアリーレンチオエーテルに化学結合の形で導入す
るものであり、このためには前記した以下の方法が有効
である。
即ら第1の方法は、極性有機溶媒中でジハロゲン化芳香
族化合物とアルカリ金属硫化物とから脱ハロゲン化/硫
化反応によってポリアリーレンチオエーテルを生成させ
る方法において、当該反応の際に上記化学構造単位を有
するハロゲン化有改化合物(以後化合物へという)、特
にハロゲン化ベンゾトリアゾール系光安定剤を加えて脱
ハロゲン化/硫化反応を生起せしめ、ポリアリーレンチ
オエーテルに上記化学構造単位を導入する方法である。
この方法は従来の、特開昭45−3368号明細書、同
52−12240号明細書等に記載の重合方法に適用で
きるが、特に特開昭61−7332号明細書に開示され
た、水添加二段重合方法に適用することにより、光安定
性に優れた高分子Mの線状ポリアリーレンチオエーテル
を経済的に1造J”ることができる。
これらの重合方法においては、重合中もしくは1合末期
に、重合系に仕込みアルカリ金属硫化物に対し化合物Δ
を好ましくは上記化学構造中位量が0.002〜0.2
モル1モル、さらに好ましくは0.01〜0.1モル1
モルになるように加え、温度200℃〜290℃で20
分間〜20時間反応させることが好ましい。0.002
(モル1モル)以下では光安定効果が不十分となる可
能性があり、0.2’Eル1モル以上では効果の増加が
頭打ちになる傾向にあり経汎的に不利になる。
反応終了後のポリ7−は、ヒドロキシ基を光安定化に於
て有効に沙j1かせる為に0112未満の酸の溶液中、
0〜200℃の温αで1〜500分間処理することが好
ましい。
本方法にJ3けるポリアリーレンチオエーテルと1−リ
アゾール系光安定剤との結合の191を化′ア反応式で
示すと下記のにうになる。
[上記で使用したi・リアゾール系光安定剤はCrBA
−G[IGY社より市販の 丁INUVIN 327
である(−tBuは3級ブチル基を示す)。]
第2の方法は、予め製造し一口回収したポリアリーレン
チオエーテルを化合物Aと反応させるものであり、この
場合使用するポリアリーレンチオエーテルが化合物へと
反応性の乏しいものでは好ましくない。
未喘閃のチオラート基もしくはヂオール基を2マイクロ
モル/グラム以上、より好ましくは3マイク[]]11
−ル/グラム以上づるポリアリーレンチオエーテルであ
ることが好ましい(末端チオラート基、ヂオール基のm
はヨードアセトアミド法によって定けした)。
結合反応は、強アルカリ性の極性有機溶媒中、200〜
290℃で20分間〜20時間反応させることが好まし
い。
極性有機溶媒としては有機アミドが好ましい。
特にポリマーの安定性の点から、2.5〜25(干♀%
)の水を混入した含水有機アミドであること、及びこの
溶媒が強アルカリ性であることが好ましい。例えば当該
溶媒を10イ8?の水で?l′i釈した場合の水溶液の
pH値が9.5以上であるようなアルカリ強度であるこ
とが望ましい。
ポリアリーレンチオエーテルと、当該ポリマー分子中の
チオエーテル結合fA かaに対し11α記化学構造中
位が0.002〜0.2(モル/グラム硫f?i原子)
となるように化合物へを溶媒に仕込み、200〜290
℃の温度で20分間〜20時聞反応させることが好まし
い。第1の方法と同様に反応終了後のポリマーは、酸で
処理することが好ましい。
本方法にd−34Jる、ポリアリーレンチオエーテルと
トリアゾール系光安定剤との結合の1例を化学反応式で
示すと下記のようになる。
上記の方法により得られる本発明のポリアリーレンチオ
エーテルは、例えば
一般式;
[式中、Rは水素又は01〜C14の炭化水素もしくは
ハロゲン化炭化水素基、X 及び×2は水素。
ハロゲン、チオール基(−8H)、チオラート基IsM
:Mはアルカリ金属である)又は01〜C14の炭化水
素ししくはハロゲン化炭化水素基、Ylは水素、ハロゲ
ン又はC1〜C14の炭化水素もしくはハロゲン化炭化
水素基、Y2はC1〜C14の炭化水素又はハロゲン化
炭化水、11、八rはアリーレン基であり、m及びnは
2以上の整数であって、但しm+nは5へ500の範囲
である1を右Jる。
上述のような光安定化ポリアリーレンチオエーテルをそ
のまま成形材として用いることもで込るが、当該光安定
化ポリマーを、1なも4造が同一もしくは異なる、他の
光に対して特に支足化処理をしていないポリアリーレン
チオニーデルど混合した組成物も成形用、塗装用簀に用
いることがでさ。
る。
この場合でも当該組成物中に含まれる仝ヂΔエーテル結
合硫黄ωに対して、上記の化学(1η造甲イ◇のけが0
002〜(′Fニル/グラム原子)になるように混合す
ることが好ましい。
ベンゾトリアゾール爪光安定〜1(化合物)Aベンゾ1
へリアゾール系光安定剤で本発明のポリアリーレンチオ
ニーデルに化合結合さけることの出来る化合物としては
例えば、
一般式;
[Rは水素又はC−C14の炭化水素もしくはハ0ゲン
化炭化水素阜、Xはハロゲン、Yは水素。
ハロゲン又はC〜C14の炭化水素ししくはハ[−1ゲ
ン化炭化水素基であるコ
を有Jろ化合物であり、1体的には下記の」こうならの
がヤげられる。
′ ポリアリーレンチオエーテル組成物く充填材を混合
した組成物〉
上述のような光安定化ポリアリーレンチオエーテル、も
しくは該光安定化ボリアリーレンヂオエーテルと光安定
化していないポリアリーレンヂオエーテルを混合した組
成物は、そのまま用いることも出来るが、成形に支障を
来たさない限度において、寸法安定性、熱変形温度、難
燃性2機械的強度、硬度などの物性を改良するために、
あるいはコストを低減するために、必要に応じて無機充
填材を上述の基材樹脂に混入することができる。
無機充填材は、粉状もしくは粒子状のものと繊維状のも
のとに大別することができる。前者は一般にコストの安
い充填材、であり、後右は一般にコストは高いが物性改
良の効果が大きいことを特徴とするものである。
このような粉状または粒子状の充填材としては、炭酸カ
ルシウム、珪酸カルシウム、タルり、シリカ、マイカ、
酸化チタン、炭素もしくは黒鉛、アルミノ、シリカアル
ミナ、クレー、ガラス、ベンガラ、7′lil’!、砂
、セメント、珪酸カルシウム、硫酸カルシウム及び各種
金属粉末もしくは微粒子等が使用される。
また繊維状充填材としてはガラス、炭素もしくは黒鉛、
ヂタン酸カリ、シリカ、硅酸カルシウム、硫酸カルシウ
ムtqの繊維もしくはウィスカーを使用することができ
る。
充填材の混入Φは0〜70■帛%の範囲が好ましい。7
0Φ通%以上ぐは組成物の溶融加工が困難になるのでI
JIましくない。
く熱可塑性樹脂を混合した組成物〉
本発明の光安定化ポリアリーレンチオ゛エーテルは、押
出成形加工に支障をきたさない範囲において、他の熱可
塑性樹脂をブレンドして用いることも可能である。化学
構造の同一もしくは異なるボリアリーレンヂオエーテル
を混合し得ることは前述したところである。熱可塑性樹
脂の混入は、潤滑性、熱変形温度、耐候性、耐i撃性等
の物性の改良、あるいはコストの低減等を目的とするも
のである。
混入出来る樹脂は、WJFa加工温度(通常200−3
80℃の範囲)で分解したり、変質したりしないものが
望ましい。このような樹脂としては例えばポリアミド、
ポリエーテルエーテルケトン、ポリスルホン、ポリエー
テルスルホン、ポリフェニレンエーテル、ポリカーボネ
ート、ポリアルキレンテレフタレート(ポリニブレンチ
レフタレ−1〜、ポリブチレンチレフタレ−t” M
) 、ポリオレフィン(ポリエチレン、ポリプロピレン
など)、ABS1ボリスヂレン及びポリ弗化ビニリデン
、ポリテトラフルオルエチレン、テトラフルオルエブレ
ン等の弗素樹脂並びにPEゴム、水添SBR、シリコー
ンゴム、弗素ゴム等のエラストマーが挙げられる。
これ等の熱可塑性樹脂の混入1f3−は組成物の0〜4
0重爪%の範囲が好ましい。40%を越えると、成形物
の特性(耐熱性、耐蝕性等の物性)が大きく変化するお
それがあるので好ましくない。
くその他の添加物〉
色調の改良、熱安定性の改良、防錆、滑性付与、結晶化
速度調整、着色などの目的で必要に応じてアルカリ金属
、アルカリ土類金属の塩、水酸化物、酸化物、ないしヒ
ドロカルビルオキシド、安定剤、滑剤、離型剤、顔料な
どの助剤を添加することしできる。
「実 施 例コ
以下、実施例により本発明をさらに説明する。
友111−ユ
・、1の 法による光 ノーイボリアリーレンチオエ2
01オートクレーブにN−メチル−2−ピロリドン(N
MP> 8.01Kgと46.0i吊%のNa2Sを含
むNa2S・5水塩結品(三協化成社%)3.56Kg
(Na2Sとして21.0モル)を仕込み、窒素雰囲気
下に撹拌しながら徐々に203°CまでnQし、水1.
40に9 、 N M P 0.81に9及び0.98
U−ルの1−12Sを留出させた。
バラジクロロベンゼン(P−DCB)2.97N9(2
0,2モ)Lt、P−DC8/Na25=4.01モル
相当)とN M P 2.81に’Jとを加えて220
℃で5時間中合させ、重合スラリーを19だ。
このスラリーの一部753.59 (P −DCB
1.01モル含有)と水54gを11オートクレーブ中
に仕込み、窒素置換した後が諷し、260 ’Cで5詩
間反応セt、、、 メタ。50℃マチ冷却後rlNII
VIN 327(C[BA−GEIGY社製) 0.
01モルを添加し、再び窒素置換して胃温し、255°
Cで3時間反応せしめた。後処理として冷却後150メ
ツシユの篩でポリマーを分離回収し、plllの塩酸中
に投入し50〜70℃で約30分酸洗処理を行い、その
後ポリマーを脱イオン水次いでアt?I−ンで繰返し洗
浄した後、80℃で減圧乾燥してポリマー■を回収した
。
高化式フローデスタ−(高滓製作所装)を用いて310
℃(余熱5分)でポリマーの溶融粘度を測定したところ
、剪斯速DI 200秒−1に換口して3000ボイス
であった。
一デルの製造
〈ポリアリーレンヂオエーテルの製造〉実施例1のスラ
リーの一部7535g(P −D C810,1モル含
有)と水5409を10pオーI−クレープに仕込み窒
素置換したのち貯温し、260℃5時間反応せしめた。
反応後、反応液スラリーの一部を採取し、末端チオラー
ト基もしくはチオール基の定量を行った。末端チオラー
ト基らしくはチオール基の総量は、20.3(マイクロ
モル/グラム硫黄原子〉であった。
残りのスラリーは重合実施例1と同様に侵処PjIして
、ポリマー■を回収した。ポリマー■の溶tel!粘麿
は3200ボイズであった。
くポリマーの末端基の分析〉
本実施例において末端チオラート基又【ユヂオール基の
分析定量は以下のようにして行なつI、:、。
重合反応終了後、直ちに反応液の一部をリンプリングし
、水中に投入してポリマーを析出さけ、戸別して純水中
で洗浄する。次いで′8塩酸水で処理して末端チAラー
j−樋をチオール基に2え、斗水中で30分間洗浄し、
さらにアセトンで30分間洗浄した後真空乾燥機で減圧
乾燥(室温)してポリマーサンプルを19だ。その中か
らポリマーサンプル10η〜19V?度を精秤して密栓
型試験管に入れ、アセトン2.5me及びヨードアゼド
アミド50ミリモル/1のアセトン溶液2.5dを加え
て密栓し、100℃で60分間加熱し水冷する。その後
開栓して液相部を分離し、紫外線吸光光度晶1を用いて
460nmの吸光度(I2の吸光度)を測定した。
上記の操作における化学は反応を式で示すと以下のよう
になる。
イ、酸性化によるチオラート基のチオール基への変換
一8M−!!ニーSH+M”
(チオラート) (チオール)
口、I2の′iu離(3−ド・アセ1−アミド法)−S
H+ I・CH2C0NI(2篇(〜5CH2CONH
2+ H++ I−)(チオール)[Industrial Application Field] The present invention relates to polyarylene thioethers with improved photostability, compositions thereof, and methods for producing the same. [Prior art] Does polyarylene lentioether have heat resistance, electrical insulation properties, etc.?
It is an engineering resin with high flammability and can be applied to injection molded products, extrusion molded products, films, sheets, II fibers, electric wire coverings, etc. In particular, the inventors
Developed an economical method for producing polyarylene thioether with extremely little coloring (Japanese Patent Application Laid-Open No. 7332/1986)
issue). However, polyarylene thioether
Generally, it has a large absorption in the near-ultraviolet region of 380 nm or less, so the problem is that what was initially a beautiful molded product with an excellent color tone becomes discolored and changes in color tone when exposed to ultraviolet rays or sunlight. There was a point. Hitherto, as light stabilizers for general-purpose resins, benzif-1 non-based stabilizers and benzo-1 to lyazole-based light stabilizers have been used. The benzophenone stabilizer has a chemical structural unit of (Ar-niaryl residue), and is basically benpine 1'
:It functions as a light stabilizer by absorbing light energy through the interaction between the carbonyl group bonded to l and the hydroxyl group at position ■ of the bempine ring, converting it into thermal energy and dissipating it. . However, benzophenone stabilizers show strong absorption near 300 nm (=J), but weak absorption near 350 nm, so it has been found that they are not very effective as light stabilizers for polyarylene thioethers.Benzotriazole light stabilizers are It has a chemical structural unit of 7V, which is basically bonded to the benzene ring and absorbs light energy through the interaction of the 1-lyazole and the hydroxyl at the position of the benzene ring. It is said that it functions as a light stabilizer by converting it into heat energy and dissipating it (HODGEHAN, D, C,, G[LLERT,
E, P, J, of Polymer Sci,, P
olymer Ct+em, Ed. 18 1105-1114 (1980)). This type of stabilizer starts absorbing ultraviolet light around 400 nm and shows maximum absorption around 350 nm, so it has been suggested that it is effective as a light stabilizer for polyarylene thioether. IG'l'Shacho lNUV■ IN 234 Power Talog March 1981 edition). However, the melt processing temperature of polyarylene thioether, which is a heat-resistant resin, is considerably higher than that of general-purpose resins, and if conventional benzo-1-lyazole light stabilizers for general-purpose resins are avoided, the molecule m is not large enough. Most of it evaporates and disappears during melt processability, and the effective amount that can remain in the final molded product becomes very small.To avoid this, it is necessary to add 7M, which is industrially undesirable.
Furthermore, there is also the problem that when a large amount of light stabilizer is used, the physical properties of the molded article are affected. In order to reduce the volatilization of the above-mentioned benzotriazole light stabilizer at high temperatures, the didro V group at the position of the bempine ring is esterified to give it a large molecular weight.
A method was proposed to combine the
3) In this method, the hydroxyl group essential for the action of a photostabilizer disappears, so the problem remains that the expected stabilizing effect against light cannot be obtained. [Operations and Effects of the Invention] The present invention 6g chemically transforms polyarylene thioether while maintaining the chemical structure having a photostabilizing effect due to the benzotriazole group bonded to the benzene ring and the hydroxyl group at the position of the benzene ring. The present invention has been completed based on the discovery that a polyarylene thioether having improved photostability can be obtained by bonding to a polyarylene thioether, and the problems associated with the use of a benzotriazole light stabilizer in the above-mentioned polyarylene thioether can be solved. That is, since the photostabilized polyarylene thioether of the present invention contains the chemical structural unit having the above-mentioned photostabilizing effect chemically bonded in the molecule, it can withstand the high melting temperature used for polyarylene thioether. It does not impair photostability even when exposed to heat. Therefore, the melt-molded products produced from the photostabilized polyarylene thioether of the present invention have little change in color tone when exposed to external radiation or light, and can be used in various molded products, sealed products, films, sheets, etc. Processed products such as pipes, rods, and mu can be used without coloring or deterioration due to long + 1Q light. Furthermore, the photostabilized polyarylene thioether or composition thereof of the present invention can also be used as a coating that does not undergo coloring or deterioration due to light for a long period of time. [Summary of the Invention] The present invention is a light-stabilized polyarylene thionidel in which 0.002 to 0.2 (t/gram sulfur atom) of the chemical structural unit is chemically bonded to the sulfur atom of the thioether bond in the molecule. be. In addition, the present invention is comprised of a photostabilized polyarylene thioether which has a chemical structural unit chemically bonded to the sulfur atom of a thioether bond in the molecule, and a non-photostabilized polyarylene thioether which does not have the chemical structural unit bonded to it. The composition is characterized in that the above chemical structural unit is present in an amount of 0.002 to 0.2 mol/g sulfur atom based on all thioether-bonded sulfur atoms in the composition. The present invention also provides a method for producing an IFJ of the above-mentioned photostabilized polyarylene thioether. That is, the first method for producing a photostabilized polyarylene thioether of the present invention involves producing a polyarylene thioether through a dehalogenation/sulfurization reaction between an alkali metal sulfide and a dihalogenated Group 6 compound in an organic polar solvent. When the halogenated organic compound containing the chemical structural unit:
.. 002~02 (mol/gram sulfur atom)? f! during the reaction and then pickling the reacted polymer. Further, the second method for producing a photostabilized polyarylene thioether of the present invention is to add a chemical compound to a polyarylene thioether Φ compound having a thiolate group or a thiol Lt effectively suspended at the molecular end in a strongly alkaline organic polar solvent. 0.002-0.21-
1/'g sulfur atoms, dehalogenation reaction, and pickling of the reacted polymer. [Detailed Description of the Invention] Basic Structure of Polyarylenethioether The main part of the polyarylenethioether of the present invention is →Ar-8←(Δ"・
:arylene group). As the arylene group, those having a paraphenylene group as a main component are preferable from the viewpoint of heat resistance and moldability. In addition to paraphenylene V, R: alkyl group, n: 1-4), p, p'-
is used for Schiff. Polyphenylenethioether consisting only of repeating units is preferred. In addition, in terms of ease of melt processing, it is easier to obtain beret with less coloring by lowering the beating temperature. The improvement effect of processing can be realized, and the durability can be improved as long as it does not exceed 40 Tl-%.
If the copolymer contains 60 to 95 mol % of the jIi position, which has extremely low mechanical properties, a block copolymer containing land-continuous block-like bonds is preferred. This is because a block copolymer provides a final molded product with excellent heat resistance and mechanical properties with the same processability as a random copolymer. Such a block copolymer J5
Buddhism is described in Japanese Patent Application Laid-Open No. 14228/1983. From the viewpoint of processing, it is desirable that the polyarylene difluoride has an appropriate molecular R or melt viscosity. That is, those having a melt viscosity (η9) of 30,000 voices (temperature = 310°C, shear rate = 200 sec-1) or less, particularly preferably 2
0000 voices or less is desirable. If the number of voids exceeds 30,000, the pellet I-shaped molded product is produced by melt extrusion, and the degree of added IrP is also high, which tends to cause discoloration. When the photostabilized polyarylene thioether of the present invention is used by being mixed with a polyarylene thioether that has not been stabilized against light, the photostabilized polyarylene thioether may have a low molecular weight ω. When the photostabilized polyarylene 1-al of the present invention is used alone, it should be a polymer with a high molecular weight r11 that does not require intermolecular expansion for so-called "curing", And the film should be a substantially linear polymer for easy processing. Arylene thioether is produced by the water-addition two-stage polymerization method (Japanese Patent Application Laid-Open No. 61-1979), which is a new polymerization method developed by the present invention B1.
7332) can be produced particularly economically. WBh method of light-stabilized polyarylene thioether The method for producing light-stabilized polyarylene thioether of the present invention is to introduce the following chemical structural unit into polyarylene thioether in the form of a chemical bond. The following methods are effective. That is, the first method is a method in which a polyarylene thioether is produced by a dehalogenation/sulfurization reaction from a dihalogenated aromatic compound and an alkali metal sulfide in a polar organic solvent, and during the reaction, the above chemical structural unit is This method involves adding a halogenated modified compound (hereinafter referred to as "compound"), especially a halogenated benzotriazole light stabilizer, to cause a dehalogenation/sulfurization reaction, and introducing the above chemical structural unit into polyarylene thioether. . This method can be applied to conventional polymerization methods described in JP-A-45-3368, JP-A-52-12240, etc., but in particular, the polymerization method disclosed in JP-A-61-7332, By applying the two-stage addition polymerization method, it is possible to economically produce a linear polyarylene thioether of polymer M with excellent photostability. At the final stage of synthesis, the compound Δ is charged to the polymerization system and the alkali metal sulfide is
Preferably, the median amount of the chemical structure is 0.002 to 0.2
mol 1 mol, more preferably 0.01 to 0.1 mol 1
Add in a molar amount and add at a temperature of 200℃ to 290℃ for 20
It is preferable to react for minutes to 20 hours. 0.002
(1 mol) or less, the photostabilizing effect may become insufficient, and if it is 0.2'E 1 mol or more, the increase in the effect tends to reach a plateau, which is disadvantageous over time. After completion of the reaction, poly7- is placed in a solution of an acid less than 0.0112 in order to effectively stabilize the hydroxyl group in photostabilizing.
It is preferable to process at a temperature α of 0 to 200°C for 1 to 500 minutes. When the bond 191 between the polyarylene thioether and the 1-lyazole light stabilizer in method J3 of this method is represented by the chemical reaction formula, it is as follows. [The i-lyazole light stabilizer used above is CrBA
-G[DINUVIN 327 commercially available from IGY Co., Ltd.
(-tBu represents a tertiary butyl group). ] The second method is to react a pre-produced and collected polyarylene thioether with the compound A. In this case, it is not preferable that the polyarylenchioether used has poor reactivity to the compound. 2 micromol/g or more, more preferably 3 micromol/g of unsaturated thiolate or diol groups []]11
It is preferable that the polyarylene thioether has a molecular weight of 1000 mol/g or more (terminal thiolate group, diol group m
was determined by the iodoacetamide method). The binding reaction is carried out in a strongly alkaline polar organic solvent at 200~
It is preferable to react at 290°C for 20 minutes to 20 hours. As the polar organic solvent, organic amides are preferred. Especially from the point of view of polymer stability,
) is preferably a water-containing organic amide mixed with water, and the solvent is preferably strongly alkaline. For example, if the solvent is 10-8? With water? It is desirable that the alkaline strength is such that the pH value of the aqueous solution when diluted with l'i is 9.5 or more. Polyarylene lentioether and the thioether bond fA in the polymer molecule The 11α chemical structure median is 0.002 to 0.2 (mol/g sulfur f?i atom)
Prepare the compound in a solvent so that 200 to 290
Preferably, the reaction is carried out at a temperature of 20 minutes to 20 hours. As in the first method, the polymer after the reaction is preferably treated with an acid. An example of the bonding between a polyarylene thioether and a triazole light stabilizer according to d-34J of this method is shown in the following chemical reaction formula. The polyarylene thioether of the present invention obtained by the above method has, for example, the general formula: [wherein R is hydrogen or a 01 to C14 hydrocarbon or halogenated hydrocarbon group, and X and x2 are hydrogen. Halogen, thiol group (-8H), thiolate group IsM
: M is an alkali metal) or 01 to C14 hydrocarbon or halogenated hydrocarbon group, Yl is hydrogen, halogen, or C1 to C14 hydrocarbon or halogenated hydrocarbon group, Y2 is C1 to C14 hydrocarbon hydrogen or halogenated hydrocarbon, 11, 8r is an arylene group, m and n are integers of 2 or more, provided that m+n is 1 to 5 in the range of 500; Although it is possible to use the above-mentioned light-stabilized polyarylene thioether as a molding material, it is also possible to use the light-stabilized polymer as a molding material, but it is also possible to use the light-stabilized polymer as a support for other light, which has the same or different structure. Compositions mixed with untreated polyarylene thionedel may also be used in molding and painting cages. Ru. Even in this case, the above chemical (1η armor construction I◇ injury is 0
It is preferable to mix them so that the ratio is 002 to ('F nyl/gram atom). Benzotriazole nail photostable~1 (compound) A benzo 1
Examples of compounds that can be used as heliazole light stabilizers to form a chemical bond to the polyarylene thionidel of the present invention include the general formula; [R is hydrogen, a C-C14 hydrocarbon, or a halogenated hydrocarbon]; X is halogen, Y is hydrogen. It is a compound having a halogen or a C to C14 hydrocarbon group, or a hydrogenated hydrocarbon group, and examples thereof include the following compounds. 'Composition in which a polyarylene thioether composition is mixed with a filler> A light-stabilized polyarylene thioether as described above, or a mixture of the light-stabilized polyarylene dioether and a non-light-stabilized polyarylene dioether. The composition can be used as is, but in order to improve physical properties such as dimensional stability, heat distortion temperature, flame retardance 2 mechanical strength, and hardness, as long as it does not interfere with molding.
Alternatively, in order to reduce costs, an inorganic filler can be mixed into the above-mentioned base resin as needed. Inorganic fillers can be roughly divided into powder or particulate ones and fibrous ones. The former is generally a low cost filler, while the latter is generally high in cost but is characterized by its great effect in improving physical properties. Such powdery or particulate fillers include calcium carbonate, calcium silicate, tar, silica, mica,
Titanium oxide, carbon or graphite, alumino, silica alumina, clay, glass, red iron, 7'lil'! , sand, cement, calcium silicate, calcium sulfate, and various metal powders or fine particles are used. In addition, fibrous fillers include glass, carbon or graphite,
Fibers or whiskers of potassium ditanate, silica, calcium silicate, calcium sulfate tq can be used. The filler content Φ is preferably in the range of 0 to 70%. 7
I
It's not JI. Composition Blended with Thermoplastic Resin> The light-stabilized polyarylene thiol ether of the present invention can be blended with other thermoplastic resins as long as it does not interfere with extrusion processing. As mentioned above, polyarylene diethers having the same or different chemical structures can be mixed. The purpose of mixing a thermoplastic resin is to improve physical properties such as lubricity, heat distortion temperature, weather resistance, and i-impact resistance, or to reduce costs. The resins that can be mixed are at WJFa processing temperature (usually 200-3
It is desirable that the material does not decompose or change in quality at temperatures (in the range of 80°C). Examples of such resins include polyamide,
Polyether ether ketone, polysulfone, polyether sulfone, polyphenylene ether, polycarbonate, polyalkylene terephthalate (polynylene terephthalate-1~, polybutylene ethylene terephthalate-t" M
), polyolefins (polyethylene, polypropylene, etc.), fluororesins such as ABS1 borisdyrene and polyvinylidene fluoride, polytetrafluoroethylene, tetrafluoroethylene, and elastomers such as PE rubber, hydrogenated SBR, silicone rubber, and fluororubber. It will be done. 1f3- of these thermoplastic resins is 0 to 4 of the composition.
A range of 0 weight nails % is preferable. If it exceeds 40%, the properties of the molded product (physical properties such as heat resistance and corrosion resistance) may change significantly, which is not preferable. Other additives> Alkali metal or alkaline earth metal salts or hydroxides as necessary for the purpose of improving color tone, improving thermal stability, preventing rust, imparting lubricity, adjusting crystallization rate, coloring, etc. Auxiliary agents such as , oxides, hydrocarbyl oxides, stabilizers, lubricants, mold release agents, and pigments may be added. EXAMPLES The present invention will be further explained below with reference to Examples.
01 N-methyl-2-pyrrolidone (N
MP> 8.01Kg and 3.56Kg of Na2S pentahydrate salt containing 46.0i hanging% Na2S (Sankyo Kasei Co., Ltd.)
(21.0 mol as Na2S) was charged, the temperature was gradually heated to 203°C with stirring under a nitrogen atmosphere, and 1.0 mol of water was added.
40 to 9, NMP 0.81 to 9 and 0.98
1-12S of Urol was distilled out. Baladichlorobenzene (P-DCB) 2.97N9 (2
0.2 mo) Lt, P-DC8/Na25 = 4.01 mole equivalent) and N M P 2.81 plus 'J
The polymerization slurry was incubated at 19°C for 5 hours. A portion of this slurry 753.59 (P-DCB
1.01 mol) and 54 g of water were placed in an autoclave, and after purging with nitrogen, a reaction was performed at 260'C for 5 hours. rlNII after cooling at 50℃
VIN 327 (C [manufactured by BA-GEIGY) 0.
01 mol was added, the atmosphere was replaced with nitrogen again, the stomach was warmed, and the temperature was heated to 255°.
The mixture was reacted at C for 3 hours. As a post-treatment, after cooling, the polymer was separated and recovered using a 150 mesh sieve, put into a pll of hydrochloric acid, and pickled at 50 to 70°C for about 30 minutes.Then, the polymer was washed with deionized water and then attenuated. After repeated washing with I-N, it was dried under reduced pressure at 80° C. to recover Polymer ①. 310 using Takaka type flow destar (Takafusa Seisakusho equipment)
The melt viscosity of the polymer was measured at °C (preheated for 5 minutes) and found to be 3000 voices at a shear rate DI of 200 sec-1. Production of polyarylene dioether (Production of polyarylene dioether) A portion of 7535 g of the slurry of Example 1 (containing 1 mole of P-D C810) and 5409 g of water were charged into a 10p O-I-crepe, replaced with nitrogen, and then stored at a temperature. , and reacted at 260°C for 5 hours. After the reaction, a portion of the reaction slurry was collected and the terminal thiolate group or thiol group was quantified. The total amount of thiol groups, which appeared to be terminal thiolate groups, was 20.3 (micromol/gram sulfur atom).The remaining slurry was subjected to PjI invasion in the same manner as in Polymerization Example 1, and polymer ① was recovered.Polymer The melting point of (1) was 3200 voids.Analysis of terminal groups of polymer In this example, the analysis and quantification of terminal thiolate groups or diol groups was carried out as follows.Polymerization Immediately after the completion of the reaction, a portion of the reaction solution is limp-ringed, poured into water to precipitate the polymer, and washed separately in pure water.Then, it is treated with '8' hydrochloric acid water and added to the terminal chiller A j-gutter. was converted into a thiol group, washed in diluted water for 30 minutes,
Furthermore, after washing with acetone for 30 minutes, the polymer sample was dried under reduced pressure in a vacuum dryer (room temperature). Among them, polymer sample 10η~19V? The test tube was placed in a tightly stoppered test tube, and 2.5 d of acetone solution containing 2.5 me of acetone and 50 mmol/1 of iodoazedoamide was added, the tube was tightly stoppered, heated at 100° C. for 60 minutes, and cooled with water. Thereafter, the cap was opened, the liquid phase was separated, and the absorbance at 460 nm (absorbance of I2) was measured using an ultraviolet absorption photometer crystal 1. The chemistry of the above operation is as follows when the reaction is expressed as an equation. B. Conversion of thiolate group to thiol group by acidification -8M-! ! Knee SH+M” (thiolate) (thiol) Mouth, I2’iu separation (3-de-ace1-amide method)-S
H+ I・CH2C0NI (2 stories (~5CH2CONH
2+ H++ I-) (thiol)
〔0〕
→〜5CIT2CONH2+臭ごI2+%H20予めモ
デルチオール化合物(Cj<)−8+−1)に関して作
製しておいた検量線を用いて、吸光度から末端のチオー
ル基濃度を算出した(尚、サンプルmはアセトンスラリ
ー中のチオール基の濃度が0.1〜0.3ミリモルの範
囲になるように選択することが好ましい)。
同一乾燥サンプルにつき3回ずつ分析を行ない、末端ヂ
オール基′a度の平均値を求めた。
くベンゾトリアゾール系光安定剤の結合〉含水NMP
(含水率11重量%) 600gに水酸化リヂウム2
gを加え強アルカリ性としたく水10倍希釈液のpH=
13)。この液にポリマー■を108g(硫黄原子1モ
ル分)とTlN0VIN 3270.01 モルとを
加え、255℃で3時間反応させた。反応後、実施例1
と同様に後処理してポリマー■を19た。
又、ポリマー■とポリマー■を1:1でブレンドしてポ
リマー■を得た。
亙1」L一旦
光安定性の試験
く比較光安定剤〉
[F]
71.58 ’J (0,2Eル) (7) TINU
VIN 327 及Uテレフタル酸クロライド20.
30 g(0,1モル)を無水ピリジンに溶解し、12
0℃で5時間リフラックス状態で反応させた。白色固体
生成物をP別し、アセトンで洗ひし室温で減圧乾燥した
。1!7られた白色固体を、赤外線吸収スペクトル(I
R)、マススペクトル(MS)及び核磁気共鳴(NMR
)で同定した結果、ヒト1]−tシ基(−01−1)の
ない、下記に示寸ようへ構)古のエステルが主成分であ
ることが刊った(光安定剤lとする)。
その他に下記の市販の光安定剤を使用した。
■
光安定剤n : TINUVIN 327(CIB
A−GEIGY社製)[tBuは第3級ブブル塁を表わ
寸。]Φ
光安定剤1[[: TINUVIN P(CIBA
−G[IGY社製〉く試料調製〉
ポリマー■に対し、安定剤I、安定剤■あるいは安定剤
■をそれぞれ0.5fi j1196をI11人し、ペ
ント(Jき押出機で330℃に加熱して溶@混練した。
19られたベレットを窒素雰囲気下でホットプレスを用
い、余熱320℃ 1分間のV2320℃で30秒間加
圧プレスし、急冷して厚さ約0.3mrnのシートに調
製して耐光性試験に供した(順に実施番号5゜6,7で
示す)。
ポリマー■、■、■、■にういても上記と同様にしてシ
ー1へ状の試料に調製した〈実施番号1゜2.3.4>
。
く耐光性試験〉
光安定性の評価方法として、各シート状の試料を光に暴
露し、被V露試料につき着色程度をYellownes
s Indexで評価した。盾色光原はアトラス社製、
室内光促進劣化試験機INDOORACTINIC[X
PO3UR[: 5YST[HIIP−UV (光源;
蛍光灯11木、カラス越しUVランフ2木)を用い、1
20時間暴露試験を行なった(掌内放置18ケ月相当)
。
累露試験後、色差計(東京゛1を色KK製C0LOII
AC[丁CA−1)を用いてYcllowncss
Indexを測定した。
その結果を表−1に示す。
表−1によると、ベンゾトリアゾールが結合したベンぜ
ン環の2の位置に01−1基がある化学構造単位がポリ
アリーレンチオエーテルに結合しだらの、又はそれを混
入したものは優れた耐光性を示すことが判明した。
表−1
手続♀ili正書
昭和61年δ゛月25;口
1、事件の表示 昭和61年特許願第131672
号2、発明の名称 光安定化ポリアリーレンチオエ
ーテル3、補正をする者
事件との関係 特許出願人
名 称 (1101呉羽化学工業株式会社4 代
理 人 東京都新宿区新宿1丁目1114Q
山田ビル8、補正の内容
(1) 明細書中、第16頁第7行のrp、p’−シ
フ」の間にrp、p’−ジフェニレンスル■ 明細書中
、第19頁第2行の「本発明に等が開発した新しい重合
法である」を削除する。
O) 明細書中、第26頁第3行に[0,002〜]と
あるを「0.002〜0.2」と補正する。
(4) 明細書中、第31頁第1行に「ン等の弗素樹
脂」とあるを「ン共重合体等の弗素樹脂」と補正ザる。
■ 明細国中、第33頁第9行及び第38真上から第2
行に「余熱」とあるを「予熱」と補正する。[0] →~5CIT2CONH2+Odor I2+%H20The terminal thiol group concentration was calculated from the absorbance using a calibration curve prepared in advance for the model thiol compound (Cj<)-8+-1). Preferably, m is selected such that the concentration of thiol groups in the acetone slurry is in the range of 0.1 to 0.3 mmol). The same dry sample was analyzed three times, and the average value of the terminal diol group'a degree was determined. Binding of benzotriazole light stabilizer> Water-containing NMP
(Water content: 11% by weight) 600g of lithium hydroxide 2
pH of the solution 10 times diluted with water to make it strong alkaline by adding g
13). To this solution were added 108 g (1 mole of sulfur atom) of polymer (1) and 3270.01 mole of TlN0VIN, and the mixture was reacted at 255° C. for 3 hours. After reaction, Example 1
Polymer 19 was obtained by post-treatment in the same manner as above. Further, Polymer (2) and Polymer (2) were blended at a ratio of 1:1 to obtain Polymer (2). [F] 71.58'J (0,2E) (7) TINU
VIN 327 and U terephthalic acid chloride 20.
Dissolve 30 g (0.1 mol) in anhydrous pyridine and add 12
The reaction was carried out in a reflux state at 0°C for 5 hours. The white solid product was separated from P, washed with acetone, and dried under reduced pressure at room temperature. The infrared absorption spectrum (I
R), mass spectra (MS) and nuclear magnetic resonance (NMR)
), it was found that the main component was an ancient ester (as shown below) without the human 1]-t group (-01-1) (referred to as the light stabilizer l). ). In addition, the following commercially available light stabilizers were used. ■ Light stabilizer n: TINUVIN 327 (CIB
Manufactured by A-GEIGY) [tBu represents the third class bubble base. ]Φ Light stabilizer 1 [[: TINUVIN P(CIBA
-G [manufactured by IGY Co., Ltd.] Sample preparation> To polymer 1. The pellets were melted and kneaded using a hot press under a nitrogen atmosphere, with a preheating temperature of 320°C for 1 minute, and a pressure press of 230°C for 30 seconds, followed by rapid cooling to prepare a sheet with a thickness of about 0.3 mrn. (Example No. 5, 6, and 7)゜2.3.4>
. Light resistance test> As a method for evaluating photostability, each sheet-like sample was exposed to light, and the degree of coloring of the exposed sample was determined by Yellows.
Evaluation was made using s Index. The shield colored light source is manufactured by Atlas Corporation.
Indoor light accelerated deterioration tester INDOORACTINIC[X
PO3UR[: 5YST[HIIP-UV (light source;
Fluorescent lamps (11 trees, UV lamps over the crows 2 trees) were used, 1
A 20-hour exposure test was conducted (equivalent to 18 months left in the palm)
. After the dew test, use a color difference meter (Tokyo ゛1 to color KK C0LOII).
Yclowncss using AC [Cing CA-1)
Index was measured. The results are shown in Table-1. According to Table 1, the chemical structure unit in which the 01-1 group is located at the 2 position of the benzene ring to which benzotriazole is bonded is bonded to polyarylene thioether, or those containing it have excellent light resistance. It was found that it shows. Table-1 Procedure ♀ili official document δ゛ month 25, 1985; mouth 1, indication of incident Patent application No. 131672 of 1985
No. 2, Name of the invention Photo-stabilized polyarylene lentioether 3, Relationship to the amended case Patent applicant name (1101 Kureha Chemical Industry Co., Ltd. 4 Agent 1-1114Q, Shinjuku 1-chome, Shinjuku-ku, Tokyo)
Yamada Building 8, Contents of amendment (1) In the specification, page 16, line 7, rp, p'-diphenylene between ``rp, p'-schiff'' ■ In the specification, page 19, line 2 ``The present invention is a new polymerization method developed by et al.'' is deleted. O) In the specification, the text [0,002~] on page 26, line 3 is corrected to ``0.002~0.2''. (4) In the specification, in the first line of page 31, the phrase ``fluororesin such as n'' has been amended to read ``fluororesin such as n copolymer.'' ■ In the specification, page 33, line 9 and 2nd line from the top of 38
Correct the line ``residual heat'' to ``preheat.''
Claims (8)
割合で化学結合させたポリアリーレンチオエーテル。(1) Chemical structural unit; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Polyarylene thioether chemically bonded at a ratio of 0.002 to 0.2 mole per gram atom of sulfur.
しくはハロゲン化炭化水素基、X_1及びX_2は水素
、ハロゲン、チオール基(−SH)、チオラート基(−
SM:Mはアルカリ金属 である)又はC_1〜C_1_4の炭化水素もしくはハ
ロゲン化炭化水素基、Y_1は水素、ハロゲン又はC_
1〜C_1_4の炭化水素もしくはハロゲン化炭化水素
基、Y_2はC_1〜C_1_4の炭化水素又はハロゲ
ン化炭化水素基、Arはアリーレン基であり、m及びn
は2以上の整数であって、但しm+nは5〜500の範
囲である] のいずれかを有することを特徴とする特許請求の範囲第
1項に記載のポリアリーレンチオエーテル。(2) General formula; ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R is hydrogen or C_1 to C_1_4 Hydrocarbon or halogenated hydrocarbon group, X_1 and X_2 are hydrogen, halogen, thiol group (-SH), thiolate group (-
SM: M is an alkali metal) or C_1 to C_1_4 hydrocarbon or halogenated hydrocarbon group, Y_1 is hydrogen, halogen or C_
1 to C_1_4 hydrocarbon or halogenated hydrocarbon group, Y_2 is C_1 to C_1_4 hydrocarbon or halogenated hydrocarbon group, Ar is an arylene group, m and n
is an integer of 2 or more, provided that m+n is in the range of 5 to 500.] The polyarylene thioether according to claim 1, characterized in that it has one of the following.
と上記化学構造単位を結合していない非光安定化ポリア
リーレンチオエーテルとから成る組成物であって、上記
の化学構造単位が組成物中の硫黄1グラム原子に対し0
.002〜0.2モルの割合で結合されていることを特
徴とする光安定化ポリアリーレンチオエーテル組成物。(3) Chemical structural units; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ A composition consisting of a photostabilized polyarylene thioether chemically bonded to a non-photostabilized polyarylene thioether to which the above chemical structural units are not bonded. and the above chemical structural unit is 0 per gram atom of sulfur in the composition.
.. A light-stabilized polyarylene thioether composition characterized in that the light-stabilized polyarylene thioether composition is bonded in a proportion of 0.002 to 0.2 mole.
; ▲数式、化学式、表等があります▼ 又は ▲数式、化学式、表等があります▼ 又は ▲数式、化学式、表等があります▼ [式中、Rは水素又はC_1〜C_1_4の炭化水素も
しくはハロゲン化炭化水素基、X_1及びX_2は水素
、ハロゲン、チオール基(−SH)、チオラート基(−
SM:Mはアルカリ金属 である)又はC_1〜C_1_4の炭化水素もしくはハ
ロゲン化炭化水素基、Y_1は水素、ハロゲン又はC_
1〜C_1_4の炭化水素もしくはハロゲン化炭化水素
基、Y_2はC_1〜C_1_4の炭化水素又はハロゲ
ン化炭化水素基、Arはアリーレン基であり、m及びn
は2以上の整数であって、但しm+nは5〜500の範
囲である] のいずれかを有する化合物であることを特徴とする特許
請求の範囲第3項に記載の組成物。(4) Photostabilized polyarylene thioether has a general formula; R is hydrogen or a hydrocarbon or halogenated hydrocarbon group of C_1 to C_1_4, X_1 and X_2 are hydrogen, halogen, thiol group (-SH), thiolate group (-
SM: M is an alkali metal) or C_1 to C_1_4 hydrocarbon or halogenated hydrocarbon group, Y_1 is hydrogen, halogen or C_
1 to C_1_4 hydrocarbon or halogenated hydrocarbon group, Y_2 is C_1 to C_1_4 hydrocarbon or halogenated hydrocarbon group, Ar is an arylene group, m and n
is an integer of 2 or more, provided that m+n is in the range of 5 to 500.] The composition according to claim 3, which is a compound having one of the following.
ン化芳香族化合物とから脱ハロゲン化/硫化反応によっ
てポリアリーレンチオエーテルを生成させる際に、化学
構造単位; ▲数式、化学式、表等があります▼ を含むハロゲン化有機化合物を0.002〜0.2モル
/グラム硫黄原子の割合で重合中に加え、次いで反応ポ
リマーを酸洗することから成る、前記化学構造単位を硫
黄1グラム原Tに対して0.002〜0.2モルの割合
で化学結合させたポリアリーレンチオエーテルの製造方
法。(5) When polyarylene thioether is produced from an alkali metal sulfide and a dihalogenated aromatic compound by dehalogenation/sulfurization reaction in an organic polar solvent, the chemical structural unit; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ adding a halogenated organic compound containing 0.002 to 0.2 mol/gram sulfur atom during the polymerization, and then pickling the reaction polymer, A method for producing polyarylene thioether which is chemically bonded with 0.002 to 0.2 moles of polyarylene ether.
ハロゲン化炭化水素基、Xはハロゲン、Yは水素、ハロ
ゲン又はC_1〜C_1_4の炭化水素もしくはハロゲ
ン化炭化水素基である] を有する化合物であることを特徴とする特許請求の範囲
第5項に記載の方法。(6) Halogenated organic compounds have a general formula; ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [R is hydrogen or a hydrocarbon of C_1 to C_1_4 or a halogenated hydrocarbon group, X is halogen, Y is hydrogen, halogen or C_1 ~ C_1_4 hydrocarbon or halogenated hydrocarbon group] The method according to claim 5, wherein the compound has the following.
ラート基もしくはチオール基を有効量有するポリアリー
レンチオエーテル重合物に、 化学構造単位; ▲数式、化学式、表等があります▼ を含むハロゲン化有機化合物を0.002〜0.2モル
/グラム硫黄原子の割合で加え、脱ハロゲン化反応させ
、次いで反応ポリマーを酸洗することから成る、前記化
学構造単位を硫黄1グラム原子に対して0.002〜0
.2モルの割合で化学結合させたポリアリーレンチオエ
ーテルの製造方法。(7) A halogenated organic compound containing a chemical structural unit; 0.002 to 0.2 mol/g of sulfur atom, the chemical structural unit is added at a rate of 0.002 to 0.2 mol/g of sulfur atom, the dehalogenation reaction is carried out, and the reaction polymer is then pickled. ~0
.. A method for producing polyarylene thioether chemically bonded at a ratio of 2 moles.
ハロゲン化炭化水素基、Xはハロゲン、Yは水素、ハロ
ゲン又はC_1〜C_1_4の炭化水素もしくはハロゲ
ン化炭化水素基である] を有する化合物であることを特徴とする特許請求の範囲
第7項に記載の方法。(8) The halogenated organic compound has a general formula; ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [R is hydrogen or a hydrocarbon of C_1 to C_1_4 or a halogenated hydrocarbon group, X is halogen, Y is hydrogen, halogen or C_1 to C_1_4 hydrocarbon or halogenated hydrocarbon group] The method according to claim 7, wherein the compound has the following.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61131672A JPH072848B2 (en) | 1986-06-06 | 1986-06-06 | Light-stabilized polyary lentithioether |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61131672A JPH072848B2 (en) | 1986-06-06 | 1986-06-06 | Light-stabilized polyary lentithioether |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS62288630A true JPS62288630A (en) | 1987-12-15 |
JPH072848B2 JPH072848B2 (en) | 1995-01-18 |
Family
ID=15063527
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP61131672A Expired - Lifetime JPH072848B2 (en) | 1986-06-06 | 1986-06-06 | Light-stabilized polyary lentithioether |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH072848B2 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5268450A (en) * | 1992-11-24 | 1993-12-07 | Phillips Petroleum Company | Compositions comprising sulfur-containing derivatives of hydroxyphenylbenzotriazole and process therefor |
US5274015A (en) * | 1992-11-24 | 1993-12-28 | Phillips Petroleum Company | Compositions comprising sulfur-containing derivatives of hydroxyphenylbenzotriazole and process therefor |
US5319091A (en) * | 1992-11-24 | 1994-06-07 | Phillips Petroleum Company | Process for sulfur containing derivatives of hydroxyphenyl/benzotriazoles |
US5516914A (en) * | 1991-02-12 | 1996-05-14 | Ciba-Geigy Corporation | Compositions stabilized with 5-thio-substituted benzotriazole UV-absorbers |
US6040455A (en) * | 1999-01-21 | 2000-03-21 | Ciba Specialty Chemicals Corporation | One-pot process for the preparation of 5-sulfonyl-substituted benzotriazoles UV absorbers |
-
1986
- 1986-06-06 JP JP61131672A patent/JPH072848B2/en not_active Expired - Lifetime
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5516914A (en) * | 1991-02-12 | 1996-05-14 | Ciba-Geigy Corporation | Compositions stabilized with 5-thio-substituted benzotriazole UV-absorbers |
US5942626A (en) * | 1991-02-12 | 1999-08-24 | Ciba Specialty Chemicals Corporation | Process for making 5-thio-substituted benzotriazole UV absorbers |
US5268450A (en) * | 1992-11-24 | 1993-12-07 | Phillips Petroleum Company | Compositions comprising sulfur-containing derivatives of hydroxyphenylbenzotriazole and process therefor |
US5274015A (en) * | 1992-11-24 | 1993-12-28 | Phillips Petroleum Company | Compositions comprising sulfur-containing derivatives of hydroxyphenylbenzotriazole and process therefor |
US5319091A (en) * | 1992-11-24 | 1994-06-07 | Phillips Petroleum Company | Process for sulfur containing derivatives of hydroxyphenyl/benzotriazoles |
US5410071A (en) * | 1992-11-24 | 1995-04-25 | Phillips Petroleum Company | Process for sulfur-containing derivatives of hydroxyphenylbenzotriazoles |
US6040455A (en) * | 1999-01-21 | 2000-03-21 | Ciba Specialty Chemicals Corporation | One-pot process for the preparation of 5-sulfonyl-substituted benzotriazoles UV absorbers |
Also Published As
Publication number | Publication date |
---|---|
JPH072848B2 (en) | 1995-01-18 |
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