JPH0480059B2 - - Google Patents
Info
- Publication number
- JPH0480059B2 JPH0480059B2 JP16910385A JP16910385A JPH0480059B2 JP H0480059 B2 JPH0480059 B2 JP H0480059B2 JP 16910385 A JP16910385 A JP 16910385A JP 16910385 A JP16910385 A JP 16910385A JP H0480059 B2 JPH0480059 B2 JP H0480059B2
- Authority
- JP
- Japan
- Prior art keywords
- butyl
- stabilizer
- bis
- piperazine
- weight
- 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.)
- Expired
Links
- 229920000098 polyolefin Polymers 0.000 claims description 8
- 239000003381 stabilizer Substances 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 150000003053 piperidines Chemical class 0.000 claims description 2
- -1 polyethylene Polymers 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 8
- 229920003002 synthetic resin Polymers 0.000 description 8
- 239000000057 synthetic resin Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 230000006866 deterioration Effects 0.000 description 6
- 239000004611 light stabiliser Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 4
- 239000012760 heat stabilizer Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002530 phenolic antioxidant Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 238000001103 continuous-wave nuclear magnetic resonance spectrum Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 150000004885 piperazines Chemical class 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- ROHFBIREHKPELA-UHFFFAOYSA-N 2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]prop-2-enoic acid;methane Chemical compound C.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O ROHFBIREHKPELA-UHFFFAOYSA-N 0.000 description 1
- PHXLONCQBNATSL-UHFFFAOYSA-N 2-[[2-hydroxy-5-methyl-3-(1-methylcyclohexyl)phenyl]methyl]-4-methyl-6-(1-methylcyclohexyl)phenol Chemical compound OC=1C(C2(C)CCCCC2)=CC(C)=CC=1CC(C=1O)=CC(C)=CC=1C1(C)CCCCC1 PHXLONCQBNATSL-UHFFFAOYSA-N 0.000 description 1
- WWYDYZMNFQIYPT-UHFFFAOYSA-L 2-phenylpropanedioate Chemical compound [O-]C(=O)C(C([O-])=O)C1=CC=CC=C1 WWYDYZMNFQIYPT-UHFFFAOYSA-L 0.000 description 1
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 1
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
- MDWVSAYEQPLWMX-UHFFFAOYSA-N 4,4'-Methylenebis(2,6-di-tert-butylphenol) Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 MDWVSAYEQPLWMX-UHFFFAOYSA-N 0.000 description 1
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 1
- 239000002656 Distearyl thiodipropionate Substances 0.000 description 1
- 241000156978 Erebia Species 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000003042 antagnostic effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008395 clarifying agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229920003020 cross-linked polyethylene Polymers 0.000 description 1
- 239000004703 cross-linked polyethylene Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 235000019305 distearyl thiodipropionate Nutrition 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Chemical class 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- XKIVKIIBCJIWNU-UHFFFAOYSA-N o-[3-pentadecanethioyloxy-2,2-bis(pentadecanethioyloxymethyl)propyl] pentadecanethioate Chemical compound CCCCCCCCCCCCCCC(=S)OCC(COC(=S)CCCCCCCCCCCCCC)(COC(=S)CCCCCCCCCCCCCC)COC(=S)CCCCCCCCCCCCCC XKIVKIIBCJIWNU-UHFFFAOYSA-N 0.000 description 1
- RZKVVRUHAVARMF-UHFFFAOYSA-N octadecyl 3-[4-(3-octadecoxy-3-oxopropyl)piperazin-1-yl]propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCN1CCN(CCC(=O)OCCCCCCCCCCCCCCCCCC)CC1 RZKVVRUHAVARMF-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- NYCWWRBJMYYWHT-UHFFFAOYSA-N tetradecyl 3-[4-(3-oxo-3-tetradecoxypropyl)piperazin-1-yl]propanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCN1CCN(CCC(=O)OCCCCCCCCCCCCCC)CC1 NYCWWRBJMYYWHT-UHFFFAOYSA-N 0.000 description 1
- XZHNPVKXBNDGJD-UHFFFAOYSA-N tetradecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C=C XZHNPVKXBNDGJD-UHFFFAOYSA-N 0.000 description 1
- 229940071127 thioglycolate Drugs 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-M thioglycolate(1-) Chemical compound [O-]C(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-M 0.000 description 1
- IVIIAEVMQHEPAY-UHFFFAOYSA-N tridodecyl phosphite Chemical compound CCCCCCCCCCCCOP(OCCCCCCCCCCCC)OCCCCCCCCCCCC IVIIAEVMQHEPAY-UHFFFAOYSA-N 0.000 description 1
- QOQNJVLFFRMJTQ-UHFFFAOYSA-N trioctyl phosphite Chemical compound CCCCCCCCOP(OCCCCCCCC)OCCCCCCCC QOQNJVLFFRMJTQ-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、オレフイン重合体に配合して該樹脂
の熱酸化的劣化及び光による劣化を抑制する新規
な安定剤に関するものである。このオレフイン重
合体の加工品はビールクレート、農業用フイル
ム、自動車の外装品、中空容器として有用であ
る。
〔従来の技術〕
一般に、ポリエチレン、ポリプロピレン、ポリ
塩化ビニル、ABS等の合成樹脂は、成型加工時
の熱劣化あるいは酸化、もしくは、製品となつた
後も紫外線及び酸素を主体とする耐候性劣化など
により、色の変化、機械的強度の低下等を引き起
こし長期の使用に耐えないことが知られている。
かかる欠点を除くために、一種又は、数種の熱
安定剤あるいは光安定剤等を該合成樹脂に添加し
て、種々の劣化を抑制する必要がある。かかる熱
安定剤としては一般に、テトラキス〔メチレン−
３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシ
フエニル）−プロピオネート〕メタン（チバガイ
キー社(株)製商品名、RA−1010）等のフエノール
系酸化防止剤が主に使用され、光安定剤としては
ビス（２，２，６，６−テトラメチル−４−ピペ
リジニル）セバケート（三共(株)製商品名、サノー
ルLS770）等のヒンダードアミン系化合物が一般
に知られている。
しかし、ある種の熱安定剤と光安定剤との間に
は、拮抗作用が存在する欠点がある。すなわち、
合成樹脂の耐熱老化性と耐候性を共に向上させる
目的で、例えば、熱安定剤としてRA−1010、光
安定剤としてサノールLS770を、併用して合成樹
脂に添加した場合、おのおの単独で、配合した場
合と比較して、耐熱老化性が著しく低下するとい
う現象が知られている。
〔問題点を解決する具体的な手段〕
本発明者は、かかる現状に鑑み、鋭意検討を重
ねた結果、オレフイン重合体の耐熱老化性向上の
目的で、各種フエノール系酸化防止剤を配合する
際、下記一般式（）で表わされるピペラジン誘
導体を併用して添加することにより、耐熱老化性
のみならず、耐候性も著しく改善された高分子材
料が得られることを見い出した。
（発明の構成）
本発明は、次の一般式（）で示されるピペリ
ジン誘導体よりなるオレフイン重合体用安定剤を
提供するものである。
〔式中、ＲとR′は水素原子あるいはメチル基
を示し、R2とR4は炭素数１〜18のアルキル基を
示す。ｎとｍは１〜３の数である。〕
かかる式（）で示される安定剤として代表的
な化合物の示性式を次に示す。
Ｎ，N′−ビス〔２−（テトラデシルオキシカル
ボニル）エチル〕ピペラジン
（融点約44℃）
Ｎ，N′−ビス〔２−（テトラデシルオキシカル
ボニル）−１−メチルエチル〕
（融点約52〜53℃）
Ｎ，N′−ビス〔２−（テトラデシルオキシカル
ボニル）エチル〕−２，５−ジメチルピペラジン
（融点約43℃）
Ｎ，N′−ビス〔２−（オクタデシルオキシカル
ボニル）エチル〕ピペラジン
（融点約57〜59℃）
Ｎ，N′−ビス〔２−（テトラデシルオキシカル
ボニル）メチル〕ピペラジン
（融点約87〜88℃）
Ｎ，N′−ビス〔２−（トリデシルカルボニルオ
キシ）エチル〕ピペラジン
（融点約48〜50℃）
本発明の前記一般式（）で表わせるピペラジ
ン誘導体の添加量は、合成樹脂100重量部に対し
て0.05〜１重量部、好ましくは0.08〜0.5重量部の
割合で通常使用される。
（併用する他の添加剤）
本発明の安定剤は、フエノール系酸化防止剤、
硫黄系抗酸化剤や光安定剤と併用して用いると熱
安定性、耐候性に優れた樹脂加工品を製造するこ
とができる。
かかるフエノール系酸化防止剤としては、例え
ば、２，６−ジ−ｔ−ブチル−ｐ−クレゾール、
ステアリル−（３，６−ジ−ｔ−メチル−４−ヒ
ドロキシベンジル）チオグリコレート、ステアリ
ル−β−（４−ヒドロキシ−３，５−ジ−ｔ−ブ
チルフエニル）、プロピオネート、ジステアリル
（４−ヒドロキシ−３−メチル−５−ｔ−ブチル）
ベンジルマロネート、２，2′−メチレンビス（４
−メチル−６−ｔ−ブチルフエノール）、４，
4′−メチレンビス（２，６−ジ−ｔ−ブチルフエ
ノール）、２，2′−メチレンビス〔６−（１−メチ
ルシクロヘキシル）ｐ−クレゾール〕、ビス〔３，
３−ビス（４−ヒドロキシ−３−ｔ−ブチルフエ
ニル）ブチリツクアシド〕グリコールエステル、
４，4′−ブチリデンビス（６−ｔ−ブチル−ｍ−
クレゾール）、１，１，３−トリス（２−メチル
−４−ヒドロキシ−５−ｔ−ブチルフエニル）ブ
タン、１，３，５−トリス（３，５−ジ−ｔ−ブ
チル−４−ヒドロキシベンジル）−２，４，６−
トリメチルベンゼン、テトラキス〔メチレン−３
−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフ
エニル）プロピオネート〕メタン、１，３，５−
トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキ
シベンジル）イソシアヌレート、１，３，５−ト
リス〔（３，５−ジ−ｔ−ブチル−４−ヒドロキ
シフエニル）プロピオニルオキシエチル）イソシ
アヌレート、２−オクチルチオ−４，６−ジ（４
−ヒドロキシ−３，５−ジ−ｔ−ブチル）フエノ
キシ−１，３，５−トリアジン、４，4′−チオビ
ス（６−ｔ−ブチル−ｍ−クレゾール）などがあ
げられる。
また、硫黄系抗酸化剤としては、ジステアリル
チオジプロピオネート、ジラウリルチオジプロピ
オネート、ペンタエリスリトールテトラ（β−ラ
ウリルチオプロピオネート）、１，３，５−トリ
ス−β−ラテアリルチオプロピオニルオキシエチ
ルイソシアヌレートなどがあげられる。これら安
定剤は合成樹脂100重量部に対し、0.05〜１重量
部の割合で用いられる。
本発明の安定剤を含有する樹脂組成物に、さら
に、ホスフアイト系の化合物を添加することによ
つて耐熱性及び耐候性をさらに改良することがで
きる。かかる化合物としては、トリオクチルホス
フアイト、トリラウリルフオスフアイト、トリフ
エニルホスフアイト、トリス（ノニルフエニル）
ホスフアイト、ジステアリルペンタエリスリトー
ルジホスフアイト等のホスフアイト系化合物があ
げられる。
その他に、使用に応じて、光安定剤（紫外線吸
収剤）をさらに添加することにより耐候性を向上
させうる。これらには、ベンゾフエノン系、ベン
ゾトリアゾール系、サクシネート系、置換アクリ
ロニトリル系、ニツケル錯塩系などの化合物が包
含される。これは合成樹脂100重量部に対し、
0.05〜５重量部、好ましくは0.1〜２重量部の割
合で用いる。
その他、必要に応じて、例えば、顔料、充填
剤、発泡剤、帯電防止剤、防曇剤、表面処理剤、
滑剤、難燃剤、金属不活性剤、増核剤、金属石け
ん、透明化剤、加工助剤、防黴剤、殺菌剤、離型
剤などを包含させることもできる。
（合成樹脂）
本発明の安定剤が配合されるオレフイン重合体
の例を挙げれば、ポリエチレン、ポリプロピレ
ン、ポリブテン、ポリ−３−メチルブテン、架橋
ポリエチレンなどのα−オレフイン重合体または
エチレン−酢酸ビニル共重合体、エチレン−プロ
ピレン共重合体などのポリオレフインおよびこれ
らの共重合体、を挙げることができる。
実施例 １（例示化合物番号１）
四ツ口フラスコ内に、アクリル酸ミリスチル
10.0ｇ、ピペラジン1.61ｇ及びエタノール60mlを
加え、窒素気流中で攪拌し、加熱を開始した。温
度60℃で５時間加熱を続行した後、室温まで冷却
すると、白色の結晶が析出した。
この結果を別し、エタノールにより再結晶を
行ない、目的物10.6ｇを得た（収率91％）。
（分析値）
H1−NMR吸収スペクトル〔CDC3，δ
（ppm）〕0.70〜1.76（54H，ｍ），2.26〜2.87（16H，
ｍ），4.05（4H，ｔ）
IR吸収スペクトル〔KBr 波数（Cm-1）〕
2910，1730，1325，1310，1185，1155，720。
MS 〔ｍ／ｅ、精密質量分析〕
622，６（M+）
実施例 ２（例示化合物番号２）
四ツ口フラスコ内に、クロトン酸ミリスチル
10.0ｇ、ピペラジン1.53ｇ及びエタノール60mlを
加え、窒素気流中で攪拌し、加熱を開始した。温
度60℃で10時間加熱を続行した後、室温まで冷却
すると白色の結晶が析出した。
この結果を別し、エタノールにより再結晶を
行い、目的物2.7ｇを得た（収率23.4％）。
（分析値）
H1−NMR吸収スペクトル〔CDC3，δ
（ppm）〕0.66〜1.83（60H，ｍ）、2.07〜2.75（12H，
ｍ）、2.90〜3.33（2H，ｍ）、4.03（4H，ｔ）。
IR吸収スペクトル〔KBr 波数（Cm-1）〕
2940，1735，1330，1195，1155。
MS 〔ｍ／ｅ（相対強度）〕
650（43，M+），394（62），326（43），113
（100），87（41）
次に、応用例によつて、本発明の化合物の安定
化効果を例示する。
応用例１〜８、比較応用例１〜５
135℃テトラリン中で測定した極限粘度が1.9で
アイソタクチツクなものが98％のポリプロピレン
粉末100重量部に、第１表に示す各添加剤を配合
して、ミキサーで充分混合した。
そしてシリンダー温度260℃、Ｌ／Ｄ＝20，20
mm径の押出機によつてこの混合物を溶融混練して
造粒した。こうして得られたペレツトを230℃で
厚さ0.5mmのシートに圧縮成形して試験片とした。
耐熱老化性は、150℃の循環式空気炉中で試験
片を加熱して試験片が酸化劣化によつて褐変脆化
するまでの所要時間を測定した。
耐候性はアトラス社製65／XW−WR型キセノ
ンウエザーオメーターを用い、ブラツクパネル温
度80℃で試験片に光照射し、試験片を180℃折り
曲げたとき、試験片が脆化してクラツクを発生す
るまでの所要時間を測定した。
結果は、第１表に示す通りであつた。
なお、表中の略号は次の通りである。
〓１ テトラキス〔３−（３，５−ジ−ｔ−ブ
チル−４−ヒドロキシフエニル）プロピオニ
ルオキシメチル〕メタン
〓２ 商品名 三共(株)製サノールLS770（商品
名）
〓３ 商品名 アデカアーガス社製チヌビン
326（商品名）
〓４ 商品名 マークPEP−８（アデカアーガ
ス社製）
【表】DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel stabilizer that is incorporated into an olefin polymer to suppress thermal oxidative deterioration and photo-induced deterioration of the resin. Processed products of this olefin polymer are useful as beer crates, agricultural films, automobile exterior parts, and hollow containers. [Prior art] In general, synthetic resins such as polyethylene, polypropylene, polyvinyl chloride, and ABS suffer from thermal deterioration or oxidation during molding, or deterioration of weather resistance mainly due to ultraviolet rays and oxygen even after they are made into products. It is known that this causes color changes, decreases in mechanical strength, etc., and that it cannot withstand long-term use. In order to eliminate such drawbacks, it is necessary to add one or more types of heat stabilizers or light stabilizers to the synthetic resin to suppress various types of deterioration. Such heat stabilizers generally include tetrakis[methylene-
Phenolic antioxidants such as 3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate]methane (trade name, RA-1010, manufactured by Ciba Gaiki Co., Ltd.) are mainly used. As light stabilizers, hindered amine compounds such as bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate (trade name, Sanol LS770, manufactured by Sankyo Co., Ltd.) are generally known. However, the drawback is that there is an antagonistic effect between certain heat and light stabilizers. That is,
For the purpose of improving both the heat aging resistance and weather resistance of synthetic resins, for example, when RA-1010 as a heat stabilizer and Sanol LS770 as a light stabilizer are added together to a synthetic resin, each of them may be added individually. It is known that the heat aging resistance is significantly reduced compared to the conventional case. [Specific Means for Solving the Problems] In view of the current situation, the present inventors have made extensive studies and found that when blending various phenolic antioxidants with the aim of improving the heat aging resistance of olefin polymers, It has been discovered that by adding a piperazine derivative represented by the following general formula () in combination, a polymer material having significantly improved weather resistance as well as heat aging resistance can be obtained. (Structure of the Invention) The present invention provides a stabilizer for olefin polymers comprising a piperidine derivative represented by the following general formula (). [In the formula, R and R' represent a hydrogen atom or a methyl group, and R 2 and R 4 represent an alkyl group having 1 to 18 carbon atoms. n and m are numbers from 1 to 3. ] The formula of a typical compound as a stabilizer represented by the formula () is shown below. N,N'-bis[2-(tetradecyloxycarbonyl)ethyl]piperazine (melting point approx. 44℃) N,N'-bis[2-(tetradecyloxycarbonyl)-1-methylethyl] (melting point approximately 52-53℃) N,N'-bis[2-(tetradecyloxycarbonyl)ethyl]-2,5-dimethylpiperazine (melting point: approx. 43°C) N,N'-bis[2-(octadecyloxycarbonyl)ethyl]piperazine (melting point approximately 57-59℃) N,N'-bis[2-(tetradecyloxycarbonyl)methyl]piperazine (melting point approximately 87-88℃) N,N'-bis[2-(tridecylcarbonyloxy)ethyl]piperazine (melting point: about 48-50°C) The amount of the piperazine derivative represented by the above general formula () of the present invention is based on 100 parts by weight of the synthetic resin. It is usually used in a proportion of 0.05 to 1 part by weight, preferably 0.08 to 0.5 part by weight. (Other additives used in combination) The stabilizer of the present invention includes a phenolic antioxidant,
When used in combination with sulfur-based antioxidants and light stabilizers, resin processed products with excellent thermal stability and weather resistance can be produced. Examples of such phenolic antioxidants include 2,6-di-t-butyl-p-cresol,
Stearyl-(3,6-di-t-methyl-4-hydroxybenzyl)thioglycolate, Stearyl-β-(4-hydroxy-3,5-di-t-butylphenyl), Propionate, Distearyl(4-hydroxy -3-methyl-5-t-butyl)
Benzyl malonate, 2,2'-methylenebis(4
-methyl-6-t-butylphenol), 4,
4'-methylenebis(2,6-di-t-butylphenol), 2,2'-methylenebis[6-(1-methylcyclohexyl)p-cresol], bis[3,
3-bis(4-hydroxy-3-t-butylphenyl)butyric acid] glycol ester,
4,4'-Butylidene bis(6-t-butyl-m-
cresol), 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl) -2,4,6-
Trimethylbenzene, tetrakis [methylene-3
-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, 1,3,5-
Tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris[(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxyethyl)isocyanurate nurate, 2-octylthio-4,6-di(4
Examples thereof include -hydroxy-3,5-di-t-butyl)phenoxy-1,3,5-triazine and 4,4'-thiobis(6-t-butyl-m-cresol). In addition, sulfur-based antioxidants include distearylthiodipropionate, dilaurylthiodipropionate, pentaerythritol tetra (β-laurylthiopropionate), 1,3,5-tris-β-latearylthio Examples include propionyloxyethyl isocyanurate. These stabilizers are used in a proportion of 0.05 to 1 part by weight per 100 parts by weight of the synthetic resin. Heat resistance and weather resistance can be further improved by further adding a phosphite-based compound to the resin composition containing the stabilizer of the present invention. Such compounds include trioctyl phosphite, trilauryl phosphite, triphenyl phosphite, tris(nonylphenyl)
Examples include phosphite compounds such as phosphite and distearyl pentaerythritol diphosphite. In addition, depending on the use, weather resistance can be improved by further adding a light stabilizer (ultraviolet absorber). These include compounds such as benzophenone, benzotriazole, succinate, substituted acrylonitrile, and nickel complex salts. This is based on 100 parts by weight of synthetic resin.
It is used in a proportion of 0.05 to 5 parts by weight, preferably 0.1 to 2 parts by weight. In addition, if necessary, for example, pigments, fillers, foaming agents, antistatic agents, antifogging agents, surface treatment agents,
Lubricants, flame retardants, metal deactivators, nucleating agents, metal soaps, clarifying agents, processing aids, fungicides, bactericidal agents, mold release agents, and the like can also be included. (Synthetic resin) Examples of olefin polymers to which the stabilizer of the present invention is blended include α-olefin polymers such as polyethylene, polypropylene, polybutene, poly-3-methylbutene, crosslinked polyethylene, and ethylene-vinyl acetate copolymers. Polyolefins such as polymers, ethylene-propylene copolymers, and copolymers thereof can be mentioned. Example 1 (Exemplary Compound No. 1) In a four-necked flask, myristyl acrylate
10.0 g, piperazine 1.61 g, and ethanol 60 ml were added, stirred in a nitrogen stream, and started heating. After continuing heating at a temperature of 60°C for 5 hours, white crystals were precipitated when the mixture was cooled to room temperature. The results were separated and recrystallized with ethanol to obtain 10.6 g of the desired product (yield 91%). (Analytical value) H 1 −NMR absorption spectrum [CDC 3 , δ
(ppm)〕0.70~1.76 (54H, m), 2.26~2.87 (16H,
m), 4.05 (4H, t) IR absorption spectrum [KBr wave number (Cm -1 )] 2910, 1730, 1325, 1310, 1185, 1155, 720. MS [m/e, accurate mass spectrometry] 622,6 (M + ) Example 2 (Exemplary Compound No. 2) In a four-necked flask, myristyl crotonate
10.0 g of piperazine, 1.53 g of piperazine, and 60 ml of ethanol were added, stirred in a nitrogen stream, and started heating. After continuing heating at a temperature of 60°C for 10 hours, white crystals were precipitated when the mixture was cooled to room temperature. The results were separated and recrystallized with ethanol to obtain 2.7 g of the target product (yield 23.4%). (Analytical value) H 1 −NMR absorption spectrum [CDC 3 , δ
(ppm)〕0.66~1.83 (60H, m), 2.07~2.75 (12H,
m), 2.90-3.33 (2H, m), 4.03 (4H, t). IR absorption spectrum [KBr wave number (Cm -1 )] 2940, 1735, 1330, 1195, 1155. MS [m/e (relative intensity)] 650 (43, M + ), 394 (62), 326 (43), 113
(100), 87(41) Next, the stabilizing effect of the compounds of the present invention will be illustrated by application examples. Application Examples 1 to 8, Comparative Application Examples 1 to 5 Each additive shown in Table 1 was blended with 100 parts by weight of polypropylene powder with an intrinsic viscosity of 1.9 measured in tetralin at 135°C and 98% isotactic. and thoroughly mixed with a mixer. And cylinder temperature 260℃, L/D=20,20
This mixture was melt-kneaded and granulated using a mm diameter extruder. The pellets thus obtained were compression molded at 230°C into a sheet with a thickness of 0.5 mm to obtain test pieces. Heat aging resistance was determined by heating a test piece in a circulating air oven at 150°C and measuring the time required for the test piece to brown and become brittle due to oxidative deterioration. Weather resistance was measured using an Atlas 65/XW-WR xenon weather meter. When the test piece was irradiated with light at a black panel temperature of 80°C and the test piece was bent at 180°C, the test piece became brittle and cracked. The time required to do so was measured. The results were as shown in Table 1. The abbreviations in the table are as follows. 〓1 Tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxymethyl]methane 〓2 Product name Sanol LS770 (product name) manufactured by Sankyo Co., Ltd. 〓3 Product name Adeka Argus Co., Ltd. Made of Tinuvin
326 (Product name) 〓4 Product name Mark PEP-8 (manufactured by Adeka Argus) [Table]
Claims (1)
を示し、R2とR4は炭素数１〜18のアルキル基を
示す。ｎとｍは１〜３の数である。〕で表わされ
るピペリジン誘導体よりなるオレフイン重合体用
安定剤。[Claims] 1 (1) General formula, [In the formula, R and R' represent a hydrogen atom or a methyl group, and R 2 and R 4 represent an alkyl group having 1 to 18 carbon atoms. n and m are numbers from 1 to 3. ] A stabilizer for olefin polymers comprising a piperidine derivative represented by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16910385A JPS6230135A (en) | 1985-07-31 | 1985-07-31 | Stabilizer for synthetic resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16910385A JPS6230135A (en) | 1985-07-31 | 1985-07-31 | Stabilizer for synthetic resin |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20610091A Division JPH0678452B2 (en) | 1991-07-24 | 1991-07-24 | Method for stabilizing polyolefin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6230135A JPS6230135A (en) | 1987-02-09 |
| JPH0480059B2 true JPH0480059B2 (en) | 1992-12-17 |
Family
ID=15880360
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16910385A Granted JPS6230135A (en) | 1985-07-31 | 1985-07-31 | Stabilizer for synthetic resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6230135A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5929837B2 (en) * | 2013-05-30 | 2016-06-08 | 信越化学工業株式会社 | Nitrogen-containing cyclic compound protected with silyl group and process for producing the same |
| CN115010991A (en) * | 2020-11-11 | 2022-09-06 | 绍兴瑞康生物科技有限公司 | Steric hindrance adjustable weak base light stabilizer, and preparation method and application thereof |
-
1985
- 1985-07-31 JP JP16910385A patent/JPS6230135A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6230135A (en) | 1987-02-09 |
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