JPH01132604A - Liquid hydroxylated modified alpha-olefin polymer, its production and its use - Google Patents
Liquid hydroxylated modified alpha-olefin polymer, its production and its useInfo
- Publication number
- JPH01132604A JPH01132604A JP28929187A JP28929187A JPH01132604A JP H01132604 A JPH01132604 A JP H01132604A JP 28929187 A JP28929187 A JP 28929187A JP 28929187 A JP28929187 A JP 28929187A JP H01132604 A JPH01132604 A JP H01132604A
- Authority
- JP
- Japan
- Prior art keywords
- olefin
- liquid
- olefin polymer
- polymer
- carbon atoms
- 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
- 239000004711 α-olefin Substances 0.000 title claims abstract description 122
- 239000007788 liquid Substances 0.000 title claims abstract description 106
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 102
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 56
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 40
- 239000003973 paint Substances 0.000 claims abstract description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 21
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims abstract 4
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 claims description 11
- 238000013329 compounding Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims 1
- 239000000654 additive Substances 0.000 abstract description 15
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 abstract description 8
- 238000001228 spectrum Methods 0.000 abstract description 5
- 230000000996 additive effect Effects 0.000 abstract description 2
- 239000003879 lubricant additive Substances 0.000 abstract 1
- 238000000214 vapour pressure osmometry Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 32
- 239000010687 lubricating oil Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 18
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 15
- 239000000203 mixture Substances 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 10
- 238000005227 gel permeation chromatography Methods 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000010689 synthetic lubricating oil Substances 0.000 description 8
- 239000002199 base oil Substances 0.000 description 7
- 238000009472 formulation Methods 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
- -1 benzyl squalane Chemical compound 0.000 description 6
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000012208 gear oil Substances 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000007665 sagging Methods 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- AMKGKYQBASDDJB-UHFFFAOYSA-N 9$l^{2}-borabicyclo[3.3.1]nonane Chemical compound C1CCC2CCCC1[B]2 AMKGKYQBASDDJB-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 235000012216 bentonite Nutrition 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000010835 comparative analysis Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000006197 hydroboration reaction Methods 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 238000005555 metalworking Methods 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 239000010705 motor oil Substances 0.000 description 2
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920013639 polyalphaolefin Polymers 0.000 description 2
- 150000004291 polyenes Chemical class 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 150000003755 zirconium compounds Chemical class 0.000 description 2
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- IKAACYWAXDLDPM-UHFFFAOYSA-N 1,2,3,4,4a,5-hexahydronaphthalene Chemical compound C1=CCC2CCCCC2=C1 IKAACYWAXDLDPM-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 229940106006 1-eicosene Drugs 0.000 description 1
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- ZZLCFHIKESPLTH-UHFFFAOYSA-N 4-Methylbiphenyl Chemical compound C1=CC(C)=CC=C1C1=CC=CC=C1 ZZLCFHIKESPLTH-UHFFFAOYSA-N 0.000 description 1
- WTQBISBWKRKLIJ-UHFFFAOYSA-N 5-methylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C)CC1C=C2 WTQBISBWKRKLIJ-UHFFFAOYSA-N 0.000 description 1
- FEJUGLKDZJDVFY-UHFFFAOYSA-N 9-borabicyclo[3.3.1]nonane Substances C1CCC2CCCC1B2 FEJUGLKDZJDVFY-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- NLDGJRWPPOSWLC-UHFFFAOYSA-N deca-1,9-diene Chemical compound C=CCCCCCCC=C NLDGJRWPPOSWLC-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N dodecahydrosqualene Natural products CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 229940032094 squalane Drugs 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 101150054171 thf1 gene Proteins 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/06—Oxidation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、液状ヒドロキシル化変性α−オレフィン系重
合体、その製法およびその用途に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a liquid hydroxylated modified α-olefin polymer, its production method, and its use.
さらに詳細には、潤滑油配合剤、塗料用配合剤、樹脂用
改質剤などの用途に優れた性能を発揮することのできる
液状ヒドロキシル化変性α−オレフィン系重合体に関す
る。なお、本発明において重合体という語は、単独重合
体のみならず共重合体を含めた意味で用いられることが
ある。More specifically, the present invention relates to a liquid hydroxylated modified α-olefin polymer that can exhibit excellent performance in applications such as lubricating oil formulations, paint formulations, and resin modifiers. Note that in the present invention, the term polymer is sometimes used to include not only homopolymers but also copolymers.
［従来の技術１
ギヤ油、エンジン油、グリース、金属加工油、離型剤な
どの潤滑油にはその使用目的に応じてその性能を向上さ
せるために種々の添加剤が配合されており、これらの添
加剤の大部分は極性化合物である。これらの添加剤が初
期の目的を達成するためには、これらの潤滑油基油に対
して溶解することが望ましいが、これらの添加剤の中に
は基油に対する親和性の低いものもあり、その場合は溶
解することなく、基油中に単に分散している状態のもの
も多かった。ｉ＆近、潤滑油基油は従来の鉱油からオレ
フィン系重合体油に代表される合成潤滑油への代替が進
行しつつあるが、これらの合成潤滑油では上記の傾向が
一層明瞭になっており、潤滑油の性能向上効果が充分に
現われないことが多かった。従って、潤滑油用途の分野
においては種々の潤滑油用添加剤の基油に対する溶解性
を向上させることのできる相溶化剤が強く求められてい
る。[Prior art 1] Lubricating oils such as gear oil, engine oil, grease, metal working oil, mold release agent, etc. are blended with various additives to improve their performance depending on the purpose of use. The majority of additives are polar compounds. Although it is desirable for these additives to be soluble in these lubricating base oils in order to achieve their initial purpose, some of these additives have a low affinity for the base oil; In that case, many of them were simply dispersed in the base oil without being dissolved. As for lubricating oil base oils, the replacement of conventional mineral oils with synthetic lubricating oils represented by olefinic polymer oils is progressing, but the above trends are becoming even clearer with these synthetic lubricating oils. However, the performance improvement effect of lubricating oils was often not fully realized. Therefore, in the field of lubricating oil applications, there is a strong demand for compatibilizers that can improve the solubility of various lubricating oil additives in base oils.
また、塗料の分野においても種々の目的に応じた添加剤
が配合されている。たとえば、フィラー沈降防止剤、タ
レ防止剤、低温可撓性付与剤としては従来から超微粉シ
リカ、超微細沈降性炭酸カルシウム、ベントナイト、有
機ベントナイト類などが用いられているが、使用目的に
よってはいずれも充分な性能を発揮しているとは言い難
い。従って、塗料用途の分野においても上記性能に優れ
た塗料用配合剤が強く要望されている。Additionally, in the field of paints, additives are added for various purposes. For example, ultrafine silica, ultrafine precipitated calcium carbonate, bentonite, organic bentonites, etc. have traditionally been used as filler anti-settling agents, anti-sagging agents, and low-temperature flexibility imparting agents, but depending on the purpose of use, However, it is difficult to say that it is exhibiting sufficient performance. Therefore, in the field of paint applications, there is a strong demand for paint formulations that have excellent properties as described above.
［発明が解決しようとする問題点Ｊ
本発明者らは、従来の潤滑油用配合剤において上述の問
題点のあることを認識し、さらに優れた性能を発揮する
ことのできるこれらの配合剤について鋭意検討した結果
、特定の性状の液状ヒドロキシル化変性α−オレフィン
系重合体が新規物質であり、該液状ヒドロキシル化変性
α−オレフィン系重合体が上記目的を達成できることを
見出し、本発明に到達したものである。[Problems to be Solved by the Invention J The present inventors have recognized that there are the above-mentioned problems in conventional lubricating oil formulations, and have proposed these formulations that can exhibit even better performance. As a result of intensive studies, it was discovered that a liquid hydroxylated modified α-olefin polymer with specific properties is a new substance, and that the liquid hydroxylated modified α-olefin polymer can achieve the above object, and the present invention was achieved. It is something.
本発明の目的は、新規物質である液状ヒドロキシル化変
性α−オレフイン系重合体、その製法およびその用途を
提供することにある。An object of the present invention is to provide a new liquid hydroxylated modified α-olefin polymer, a method for producing the same, and uses thereof.
Ｅ問題点を解決するための手段１
本発明によれば、炭素原子数が３ないし２０のα−オレ
フィンから構成される液状α−オレフィン系重合体のヒ
ドロキシル化変性物であって、（ｉ） 該液状ヒドロ
キシル化変性α−オレフィン系重合体の”Ｃ−ＮＭＲス
ペクトル中において重合体主鎖中の隣接した２個の３級
炭素原子間に２個の連続したメチレン連鎖に基づくシグ
ナルが観測されないこと、
（ｉｉ） 該液状ヒドロキシル化変性α−オレフイン
Ｍ１１＋体のベーパープレツシヤーオスモメーター （
ｖ ｐ ｏ ）で測定した数平均分子ｔ（ｆａｎ）が２
００ないし１００００の範囲にあること、および（ｉｉ
ｉ） ヒドロキシル基が該液状α−オレフイン系重合
体の分子末端に位置するα−オレフィンに由来する炭素
原子に結合しており、ヒドロキシル基の含有割合が該液
状ヒドロキシル化変性α−オレフイン系重合体１００ｇ
あたり０．０１ないし１．０モルの範囲にあること、
によって特徴づけられる液状ヒドロキシル変性α−オレ
フィン系重合体が提供される。Means for Solving Problem E 1 According to the present invention, a hydroxylated modified product of a liquid α-olefin polymer composed of an α-olefin having 3 to 20 carbon atoms, comprising (i) No signal based on two consecutive methylene chains between two adjacent tertiary carbon atoms in the polymer main chain is observed in the C-NMR spectrum of the liquid hydroxylated modified α-olefin polymer. , (ii) Vapor pressure osmometer of the liquid hydroxylated modified α-olefin M11+ body (
The number average molecular t(fan) measured at v p o ) is 2
00 to 10000, and (ii
i) A hydroxyl group is bonded to a carbon atom derived from an α-olefin located at the molecular end of the liquid α-olefin polymer, and the content of the hydroxyl group is higher than that of the liquid hydroxylated modified α-olefin polymer. 100g
There is provided a liquid hydroxyl-modified alpha-olefin polymer characterized by the following:
さらに、本発明によれば、該液状ヒドロキシル化変性α
−オレフィン系重合体の下記製法（１）、（２）および
（３）が提供される。Furthermore, according to the present invention, the liquid hydroxylated modified α
- The following methods (1), (2) and (3) for producing olefin polymers are provided.
（１） 炭素原子数が３ないし２０のα−オレフインか
ら構成されかつ、
（ｉ） Ｉ３Ｃ−ＮＭＲスペクトル中において重合体
主鎖中の隣接した２個の３ａ炭素原子開に２個のメチレ
ン連鎖に基づくシグナルが観測されないこと、および
（ｉｉ） ベーパープレツシヤーオスモメーター（Ｖ
ＰＯ）で測定した数平均分子量（ｒｗｎ）が２００ない
しｉ ｏｏｏｏの範囲にあること、
によって表わされる重合体分子末端に炭素・炭素不飽和
結合を有する液状α−オレフイン系重合体に、ジボラン
またはハイドロボランを反応させた後、過酸化水素を反
応させることを特徴とする液状ヒドロキシル化変性α−
オレフイン系重合体の製法。(1) It is composed of an α-olefin having 3 to 20 carbon atoms, and (i) In the I3C-NMR spectrum, two adjacent 3a carbon atoms in the polymer main chain open to form two methylene chains. (ii) no signal is observed based on the vapor pressure osmometer (V
The number average molecular weight (rwn) measured by PO) is in the range of 200 to ioooo. Liquid hydroxylated modified α- characterized by reacting borane and then reacting hydrogen peroxide.
Method for producing olefin polymers.
（２）炭素原子数が３ないし２０のα−オレフィンから
構成される装置
（ｉ）”Ｃ−ＮＭＲスペクトル中において重合体主鎖中
の隣接した２個の３級炭素原子間に２個のメチレン連鎖
に基づくシグナルが観測されないこと、および
（ｉｉ） ベーパープレツシヤーオスモメーター（Ｖ
ＰＯ）で測定した数平均分子量（ｊａｎ）が２００ない
し１００００の範囲にあること、
によって表わされる重合体分子末端に炭素・炭素不飽和
結合を有する液状α−オレフィン系重合体に、有機酸の
存在下に過酸化水素を反応させさらに必要に応じて加水
分解することを特徴とする液状ヒドロキシル化変性α−
オレフイン系重合体の製法。(2) A device composed of an α-olefin having 3 to 20 carbon atoms (i) In the C-NMR spectrum, there are two methylenes between two adjacent tertiary carbon atoms in the polymer main chain. (ii) no linkage-based signal is observed; and (ii) a vapor pressure osmometer (V
The presence of an organic acid in the liquid α-olefin polymer having a carbon-carbon unsaturated bond at the end of the polymer molecule represented by: Liquid hydroxylated modified α- characterized by reacting with hydrogen peroxide and further hydrolyzing as necessary
Method for producing olefin polymers.
（３） 炭素原子数が３ないし２０のα−オレフインか
ら構成されかつ、
（ｉ ） １３Ｃ−ＮＭＲスペクトル中においで重合
体主鎖中の隣接した２個の３級炭素原子間に２個のメチ
レン連鎖に基づくシグナルがｉＩａ＋されないこと、お
よび
（ｉｉ） ベーパープレツシヤーオスモメーター（Ｖ
ＰＯ）で測定した数平均分子量（ｘｎ）が２００ないし
１００００の範囲にあること、
によって表わされる重合体分子末端に炭素・炭素不飽和
結合を有する液状α−オレフィン系重合体に、有機過酸
化物を反応させた後に加水分解することを特徴とする液
状ヒドロキシル化変性α−オレフイン系重合体の製法。(3) It is composed of an α-olefin having 3 to 20 carbon atoms, and (i) In the 13C-NMR spectrum, two methylenes are present between two adjacent tertiary carbon atoms in the polymer main chain. (ii) the vapor pressure osmometer (V
The number average molecular weight (xn) measured by PO) is in the range of 200 to 10,000. 1. A method for producing a liquid hydroxylated modified α-olefin polymer, which comprises reacting and then hydrolyzing.
またさらに、本発明によれば、
炭素原子数が３ないし２０のα−オレフィンから構成さ
れる液状α−オレフィン系重合体のヒドロキシル化変性
物であって、
（ｉ） 該液状ヒドロキシル化変性α−オレフィン系
重合体の’３Ｃ−ＮＭＲスペクトル中において重合体主
鎖中の隣接した２個の３級炭素原子間に２個の連続した
メチレン連鎖に基づくシグナルが観測されないこと１
、（ｉｉ ） 該液状ヒドロキシル化変性α−オレフ
イン系重合体のベーパープレツシヤーオスモメーター（
ｖｐｏ）で測定した数平均分子量（Ｍｎ）が２゜Ｏない
し１００００の範囲にあること、および（ｉｉ） ヒ
ドロキシル基が該液状α−オレフイン系重合体の分子末
端に位置するα−オレフィンに由来する炭素原子に結合
しており、ヒドロキシル基の含有割合が該液状ヒドロキ
シル化変性α−オレフイン系重合体１００ｇあたり０．
０１ないし１．０モルの範囲にあること、
によって特徴づけられる液状ヒドロキシル化変性α−オ
レフイン系重合体からなる潤滑油配合剤、および
炭素原子数が３ないし２０のα−オレフィンから構成さ
れる液状α−オレフイン系重合体のヒドロキシル化変性
物であって、
（ｉ） 該液状ヒドロキシル化変性α−オレフイン系
重合体の目Ｃ−ＮＭＲスペクトル中において重合体主鎖
中の隣接した２個の３級炭素原子間に２個の連続したメ
チレン連鎖に基づくシグナルが観測されないこと、
（ｉｉ） 該液状ヒドロキシル化変性α−オレフイン
［ｃ合体のベーパープレツシヤーオスモメーター（ｖｐ
ｏ）で測定した数平均分子量（ｒｎｎ）が２００ないし
１００００の範囲にあること、および（ｉｉｉ） ヒ
ドロキシル基が該液状α−オレフイン系重合体の分子末
端に位置するα−オレフィンに由来する炭素原子に結合
しており、ヒドロキシル基の含有割合が該液状ヒドロキ
シル化変性α−オレフィン系重合体１００ｇあたり０．
０１ないし０．５モルの範囲にあること、
によって特徴づけられる液状ヒドロキシル化変性α−オ
レフィン系重合体からなる塗料用配合剤が提供される。Furthermore, according to the present invention, there is provided a hydroxylated modified product of a liquid α-olefin polymer composed of an α-olefin having 3 to 20 carbon atoms, comprising: (i) the liquid hydroxylated modified α-olefin; No signal based on two consecutive methylene chains between two adjacent tertiary carbon atoms in the polymer main chain is observed in the '3C-NMR spectrum of the olefinic polymer. (ii) The liquid state Hydroxylated modified α-olefin polymer vapor pressure osmometer (
(ii) the hydroxyl group is derived from an α-olefin located at the molecular end of the liquid α-olefin polymer; It is bonded to a carbon atom, and the content of hydroxyl groups is 0.00 g per 100 g of the liquid hydroxylated modified α-olefin polymer.
01 to 1.0 mol of a lubricating oil compounding agent comprising a liquid hydroxylated modified α-olefin polymer, and a liquid comprising an α-olefin having 3 to 20 carbon atoms. A hydroxylated modified product of an α-olefin polymer, wherein (i) two adjacent tertiary groups in the polymer main chain are detected in the C-NMR spectrum of the liquid hydroxylated modified α-olefin polymer; (ii) no signal based on two consecutive methylene chains between carbon atoms is observed; (ii) a vapor pressure osmometer (VP) of the liquid hydroxylated modified α-olefin
The number average molecular weight (rnn) measured in step o) is in the range of 200 to 10,000, and (iii) the hydroxyl group is a carbon atom derived from an α-olefin located at the molecular end of the liquid α-olefin polymer. and the content of hydroxyl groups is 0.0 g per 100 g of the liquid hydroxylated modified α-olefin polymer.
There is provided a paint formulation comprising a liquid hydroxylated modified alpha-olefin polymer characterized by:
本発明の液状ヒドロキシル化変性α−オレフィン系重合
体は、炭素原子数が３ないし２ｏのα−オレフィンから
構成される液状α−オレフィン系重合体のヒドロキシル
化変性物であって、ヒドロキシル基は該液状α−オレフ
ィン系重合体の分子末端に位置するα−オレフインに由
来する炭素・炭素不飽和結合を介して形成しており、少
なくとも１個のヒドロキシル基が結合したものであり、
たとえばＪＩＳ Ｋ−２２６９に基づき測定した流動
点が５０℃以下テあり、ＪＩＳ Ｋ−’２２８３に基
づき測定した１００℃における動粘度が１×１０５セン
チストークス以下のものである。The liquid hydroxylated modified α-olefin polymer of the present invention is a hydroxylated modified liquid α-olefin polymer composed of an α-olefin having 3 to 2 carbon atoms, and the hydroxyl group is It is formed through a carbon-carbon unsaturated bond derived from the α-olefin located at the molecular end of the liquid α-olefin polymer, and has at least one hydroxyl group bonded to it,
For example, the pour point measured in accordance with JIS K-2269 is 50°C or less, and the kinematic viscosity at 100°C measured in accordance with JIS K-'2283 is 1 x 105 centistokes or less.
該液状ヒドロキシル化変性α−オレフイン系重合体は、
その１３ｃｍＮＭＲスペクトル中において重合体主鎖中
の隣接した２個の３級炭素原子間に２個の連続したメチ
レン連鎖に基づくシグナルが観測されない。The liquid hydroxylated modified α-olefin polymer is
In its 13 cm NMR spectrum, no signal based on two consecutive methylene chains between two adjacent tertiary carbon atoms in the polymer main chain is observed.
また、該液状ヒドロキシル化変性α−オレフィン系重合
体のベーパープレツシヤーオスモメーター（ｖｐｏ）で
測定した数平均分子量（Ｍ ｎ ）は２００ないし１０
０００．好ましくは３００ないし８０００、とくに好ま
しくは５００ないし５０００の範囲にある。また、１３
５℃のデカリン中で測定した極限粘度［η］は０．０１
ないし０．４ｄｌ／ｇ、好ましくは０．０２ないし０．
３５ｄｊ！ ／ｇ。The liquid hydroxylated modified α-olefin polymer has a number average molecular weight (M n ) of 200 to 10 as measured by a vapor pressure osmometer (VPO).
000. It is preferably in the range of 300 to 8,000, particularly preferably 500 to 5,000. Also, 13
The intrinsic viscosity [η] measured in decalin at 5°C is 0.01
from 0.4 dl/g, preferably from 0.02 to 0.
35dj! /g.
とくに好ましくは０．０３ないし０．３ｄｌ／ｇの範囲
である。Particularly preferred is a range of 0.03 to 0.3 dl/g.
該液状ヒドロキシル化変性α−オレフィン系重合体のゲ
ルパーミエイションクロマトグラフイー（Ｇ Ｐ Ｃ）
によって測定した分子量分布（Ｍｗ／ｕｎ）は１．１な
いし４．０、好ましくは１．２ないし３．０、とくに好
ましくは１．３ないし２．５の範囲である。Gel permeation chromatography (GPC) of the liquid hydroxylated modified α-olefin polymer
The molecular weight distribution (Mw/un) measured by the method is in the range of 1.1 to 4.0, preferably 1.2 to 3.0, particularly preferably 1.3 to 2.5.
該液状ヒドロキシル化変性α−オレフィン系重合体のヒ
ドロキシル基の含有割合は該液状ヒドロキシル化変性α
−オレフイン系重全体１００ｇ中に０．０１ないし０．
５モル、好ましくは０．０１５ないし０．３モル、とく
に好ましくは０．０２ないし０．２モルの範囲である。The content of hydroxyl groups in the liquid hydroxylated modified α-olefin polymer is determined by the liquid hydroxylated modified α-olefin polymer.
-0.01 to 0.00% in 100g of total olefin weight.
5 mol, preferably 0.015 to 0.3 mol, particularly preferably 0.02 to 0.2 mol.
本発明の液状ヒドロキシル化変性α−オレフイン系重合
体の製造に使用される該液状α−オレフィン系重合体の
１３５℃のデカリン中で測定した極限粘度［η１は通常
は０．０１ないし０．４ｄｊ！／ｇ、好ましくは０．０
３ないし０．３ｄｊ！／ｇの範囲にあり、ベーパープレ
ツシヤーオスモメーター（ｖ ｐ ｏ ）によって測定
した数平均分子量は通常は２００ないし１００００、好
ましくは３００ないし８０００、とくに好ましくは５０
０ないし５０００にあり、ＧＰＣ法によって測定した分
子量分布（Ｍｗ／Ｍｎ）は通常は４．０以下、好ましく
は３．０以下、とくに２．５以下の範囲にある。The intrinsic viscosity of the liquid α-olefin polymer used in the production of the liquid hydroxylated modified α-olefin polymer of the present invention measured in decalin at 135°C [η1 is usually 0.01 to 0.4 dj ! /g, preferably 0.0
3 to 0.3 dj! /g, and the number average molecular weight measured by a vapor pressure osmometer (v p o ) is usually 200 to 10,000, preferably 300 to 8,000, particularly preferably 50
0 to 5,000, and the molecular weight distribution (Mw/Mn) measured by GPC method is usually in the range of 4.0 or less, preferably 3.0 or less, particularly 2.5 or less.
該液状α−オレフィン系重合体の沃素価は１ないし１２
５、好ましくは２ないし８５の範囲にある。該液状α−
オレフィン系重合体はその重合体分子の片末端にα−オ
レフイン単位に基づく炭素・炭素不飽和結合を有してい
るか、または片末端にα−オレフイン単位に基づく炭素
・炭素不飽和結合を有しているものと重合体分子の片末
端に炭素・炭素不飽和結合を有していないものとの混合
物である。The liquid α-olefin polymer has an iodine value of 1 to 12.
5, preferably in the range of 2 to 85. The liquid α-
Olefinic polymers have a carbon-carbon unsaturated bond based on an α-olefin unit at one end of the polymer molecule, or a carbon-carbon unsaturated bond based on an α-olefin unit at one end. It is a mixture of polymers that have no carbon-carbon unsaturated bonds at one end of the polymer molecule.
本発明の液状ヒドロキシル化変性α−オレフイン系重合
体をうるための変性反応に用いる場合には、重合体分子
の片末端がすべて炭素・炭素不飽和結合であるものが好
ましい。When used in the modification reaction to obtain the liquid hydroxylated modified α-olefin polymer of the present invention, it is preferable that one end of the polymer molecule is a carbon-carbon unsaturated bond.
該液状α−オレフィン系重合体の構成成分である炭素原
子数が３ないし２０のα−オレフイン成分として具体的
には、プロピレン、１−ブテン、１−ヘキセン、４−メ
チル−１−ペンテン、３−メチル−１−ペンテン、°１
−オクテン、１−デセン、１−ドデセン、１−テトラデ
セン、１−ヘキサデセン、１−オクタデセン、１−エイ
コセンなどを例示することができる。′また、非共役ポ
リエン成分として、具体的には、１，４−ヘキサジエン
、１，４−ペンタノエン、１，７−オクタジエン、１．
８−ノナツエン、１，９−デカジエン、４−メチル−１
，４−ヘキサノエン、５−メチル−１，４−ヘキサノエ
ン、５−エチリデン−２−ノルボルネン
ノルボルネン、５−メチレン−２−ノルボルネン、１、
５−シ・クロオクタノエン、５，８−エンドメチレンへ
キサヒドロナフタレンなどを例示することがでとる。Specifically, the α-olefin component having 3 to 20 carbon atoms, which is a constituent component of the liquid α-olefin polymer, includes propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 3 -Methyl-1-pentene, °1
Examples include -octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. 'Moreover, as the non-conjugated polyene component, specifically, 1,4-hexadiene, 1,4-pentanoene, 1,7-octadiene, 1.
8-nonatsuene, 1,9-decadiene, 4-methyl-1
, 4-hexanoene, 5-methyl-1,4-hexanoene, 5-ethylidene-2-norbornene norbornene, 5-methylene-2-norbornene, 1,
Examples include 5-cyclooctanoene, 5,8-endomethylene hexahydronaphthalene, and the like.
該液状α−オレフィン系重合体において、該α−オレフ
ィン成分は、その配列状態についてみると、該重合体の
’３Ｃ−ＮＭＲスペクトルには、重合体主鎖中の隣接し
た２個の三級炭素原子間の２個の連続したメチレン連鎖
に基づくシグナルが観測されない。In the liquid α-olefin polymer, the α-olefin component has two adjacent tertiary carbons in the main chain of the polymer. No signal based on two consecutive methylene chains between atoms is observed.
例えば、１−ヘキセン重合体において下記結合、ＣＨ２
ＣＨＣＨ２ＣＨＣＨ２ＣＨ−
Ｃ，Ｈ，Ｃ，Ｈ，Ｃ，Ｈ。For example, in a 1-hexene polymer, the following bond, CH2
CHCH2CHCH2CH- C,H,C,H,C,H.
では、いずれの隣接した２個の三級炭素原子間には１個
の孤立したメチレン基シグナルが観測されるが、２個の
連続したメチレン連鎖に基づくシグナルは観測されない
。このことは、該重合体において、１−ヘキセン成分が
重合する際に、いずれの成分も規則正しい頭尾結合配列
をしていることを示している。In this case, one isolated methylene group signal is observed between any two adjacent tertiary carbon atoms, but no signal based on two consecutive methylene chains is observed. This indicates that in this polymer, when the 1-hexene component is polymerized, all components have a regular head-to-tail bond arrangement.
一方、１−ヘキセン重合体において、下記結合、Ｃ，Ｈ
，Ｃ，Ｈ，Ｃ，Ｈ，Ｃ，Ｈ。On the other hand, in 1-hexene polymer, the following bonds, C, H
,C,H,C,H,C,H.
では、隣接した２個の炭素原子間には２個の連続したメ
チレン連鎖に基づくシグナルが観測される。In this case, a signal based on two consecutive methylene chains between two adjacent carbon atoms is observed.
このことは、該重合体において１−ヘキセン成分が重合
する際に、頭頭結合、属地結合が存在することを示して
いる。This indicates that head-to-head bonds and local bonds are present when the 1-hexene component is polymerized in the polymer.
さらに、該液状α−オレフィン系重合体、特にプロピレ
ン又は１−ブテン重合体の［３個のモノマーユニット連
鎖」でみたミクロアイソタフティシティは０．３５以下
、好ましくは０．３以下、より好ましく０．２８以下で
ある。該ミクロアイソタフティシティの値は、該液状α
−オレフィン系重合体連鎖におけるモノマーユニット連
鎖の中で、立体構造の最小単位である「３個のモノマー
ユニット連鎖」の可能な岨み合わせ数の総数のＸ（例え
ば３個のモノマーユニット連鎖単位の場合は１．４個の
モノマーユニット連鎖単位の場合は３）に対して、上記
［３個のモノマーユニット連鎖」がと９得る三種の配列
、すなわち−・−配列（アイツタクチイック配列）、論
・ｒ配列及びｒ’ｒ配列の中で、―・輸配列をとってい
る該［３個のモノマーユニット連鎖」の数ｙの割合（ｙ
／ｘ）を示す。Furthermore, the microisotoughness of the liquid α-olefin polymer, particularly the propylene or 1-butene polymer, in terms of [three monomer unit chains] is 0.35 or less, preferably 0.3 or less, more preferably It is 0.28 or less. The value of the microisotoughness is the value of the liquid α
- X of the total number of possible modifications of the "3 monomer unit chain" which is the smallest unit of steric structure in the monomer unit chain in the olefinic polymer chain (for example, In the case of 1.4 monomer unit chain units, in contrast to 3), the above [3 monomer unit chain] yields three types of arrangements, namely - - arrangement (it's tactical arrangement).・Among the r and r'r sequences, the ratio of the number y of the [three monomer unit chains] that have a ---transfer arrangement (y
/x).
上述のように、本発明で３個のモノマーユニット連鎖で
みたミクロアイソタフティシティとは、それ自体公知の
１３Ｃ核磁気共鳴スペクトルの手法によって３個のモノ
マーユニット連鎖に着目し、該３個のモノマーユニット
連鎖単位における３個のモノマーユニットがアイツタク
チイックに配列している分率を定量したものである。As mentioned above, in the present invention, microisotoughness seen in terms of a chain of three monomer units is determined by focusing on a chain of three monomer units using a method of 13C nuclear magnetic resonance spectroscopy, which is known per se. This is a quantification of the fraction in which three monomer units in a monomer unit chain unit are arranged in a tactical manner.
なお、該重合体の”Ｃ−ＮＭＲの測定は、例えば、１０
ｍ＋ｓφの試料管中で約２００ｍｇの重合体を１ｍｌの
へキサクロロブタノエンに溶解した溶液を、通常、測定
温度１２０℃、測定周波数２５゜０５ＭＨ２、スペクト
ル幅１５００Ｈ２，フィルター幅１５００Ｈ２，パルス
繰返し時間４．２秒、パルス幅７μ秒積算回数２０００
〜５０００回の条件で測定した。In addition, the measurement of "C-NMR" of the polymer is carried out, for example, at 10
A solution of about 200 mg of polymer dissolved in 1 ml of hexachlorobutanoene in a sample tube of m+sφ is usually measured at a measurement temperature of 120°C, a measurement frequency of 25°05MH2, a spectral width of 1500H2, a filter width of 1500H2, and a pulse repetition time. 4.2 seconds, pulse width 7 μs, cumulative number of 2000
The measurement was performed under the conditions of ~5000 times.
スペクトルの解析はＬ 、 Ｐ 、 Ｌ １ｎｄｅ＋ｍ
ａｎ、 Ａ ｎａｌ。Spectrum analysis is L, P, L 1nde+m
an, A nal.
Ｃｈｅｗ、 、４３．１２４５（１９７１）、Ｊ、Ｃ，
ＲａｎｄａｌｌｖＭａｃｒｏｅ＋ｏｌｅｃｕｌａｒ、
に１，５９２（１９７８）らの報告に基づいて行った。Chew, , 43.1245 (1971), J.C.
Randall v Macroe+olecular,
1,592 (1978) et al.
該液状α−オレフィン重合体は、
（Ａ） 共役π電子を有する基を配位子としたジルコ
ニウム化合物、および
（Ｂ） アルミノオキサン
からなる触媒の存在下に、炭素原子数が３ないし２０の
α−オレフィンおよび必要に応じて非共役ポリエンを共
重合せしめることにより調製することができる。The liquid α-olefin polymer is prepared by adding a zirconium compound having 3 to 20 carbon atoms in the presence of a catalyst consisting of (A) a zirconium compound having a group having conjugated π electrons as a ligand, and (B) an aluminoxane. It can be prepared by copolymerizing an α-olefin and, if necessary, a non-conjugated polyene.
該液状α−オレフイン系重合体は、本出願人の出願に係
る特開昭６１−２２１２０７号公報および特願昭６１−
１５６１６８号に提案した方法、具体的には、
［Ａ］ 周期律表のＩＶｂ族、ｖｂ族およびｖｔｂ族
よりなる群から選ばれた遷移金属の化合物、および
［Ｂ］ −船底（Ｉ［［）または−船底（ＩＶ）■
（式中、Ｒは炭化水素基を示し、ｍは好ましくは５以上
の整数を示す）
で表わされるアルミノオキサン、
から形成される触媒の存在下に、α−オレフィンを重合
させる方法において適宜条件を選択することにより製造
することができる。The liquid α-olefin polymer is disclosed in Japanese Unexamined Patent Application Publication No. 61-221207 and Japanese Patent Application No. 1983-1981 filed by the present applicant.
The method proposed in No. 156168, specifically, [A] a compound of a transition metal selected from the group consisting of IVb group, Vb group, and Vtb group of the periodic table, and [B] -bottom (I[[) or - bottom (IV) ■ (wherein R represents a hydrocarbon group and m preferably represents an integer of 5 or more) an aluminoxane, in the presence of a catalyst formed from an α-olefin It can be produced by selecting appropriate conditions in the method of polymerizing.
本発明の液状ヒドロキシル化変性α−オレフイン系重合
体を製造する方法としては、以下の方法を具体的に例示
することができる。As a method for producing the liquid hydroxylated modified α-olefin polymer of the present invention, the following method can be specifically exemplified.
（１）該液状α−オレフイン系重合体にジボラン又は９
− Ｂ Ｂ Ｎ（９−ｂｏｒａｂｉｃｙｃｌｏ［３、３
、１］ｎｏｎａｎｅ）などのハイドロボランを添加し、
ハイドロボレーション反応を行った後、過酸化水素で酸
化する方法。(1) Diborane or 9 is added to the liquid α-olefin polymer.
-BBN(9-borabicyclo[3,3
, 1] nonane), etc.
A method of oxidizing with hydrogen peroxide after a hydroboration reaction.
（２）該液状α−オレフイン系重合体にギ酸又は酢酸な
どの有機酸と過酸化水素との混合物を添加し酸化する方
法。(2) A method of oxidizing the liquid α-olefin polymer by adding a mixture of an organic acid such as formic acid or acetic acid and hydrogen peroxide.
（３） 該液状α−オレフィン系重合体に過酢酸、−一
クロロ過安息香酸などの有機過酸化物を添加しエポキシ
化した後加水分解する方法６（２）の方法においては、
ヒドロキシル化およびエステル化が同時に進行し、モノ
ヒドロキシモノエステル化した液状変性α−オレフィン
系重合体が得られる。更に、エステル基はケン化により
ヒドロキシル基に変えることも可能であり、この際、ジ
ヒドロキジル化した液状変性α−オレフイン系重合体が
得られる。(3) In method 6 (2), in which an organic peroxide such as peracetic acid or -monochloroperbenzoic acid is added to the liquid α-olefin polymer to epoxidize it and then hydrolyze it,
Hydroxylation and esterification proceed simultaneously to obtain a liquid modified α-olefin polymer that is monohydroxy monoesterified. Furthermore, the ester group can be converted into a hydroxyl group by saponification, and in this case, a dihydroxylated liquid modified α-olefin polymer is obtained.
さらに、詳細には、（１）の方法において、該液状α−
オレフィン系重合体の不飽和結合１モルに対しハイドロ
ボロンの添加量は１ないし１０モル、好ましくは２ない
し５モルであり、ハイドロボロン１モルに対し過酸化水
素の添加量は工ないし１０モル、好ましくは２ないし５
モルの範囲である。Further, in detail, in the method (1), the liquid α-
The amount of hydroboron added is 1 to 10 mol, preferably 2 to 5 mol, per mol of unsaturated bonds of the olefin polymer, and the amount of hydrogen peroxide added is 1 to 10 mol, per mol of hydroboron. Preferably 2 to 5
It is in the molar range.
また、ハイドロボレーションおよび酸化反応の温度は−
２０ないし６０℃、好ましくは０ないし４０℃であり、
それに要する時間は０．５ないし２０時間、好ましくは
１ないし１０時間である。さらに、ポリマー濃度として
は５ないし２００ｇ／２、好ましくは１０ないし１００
ｇ／尼の範囲である。Also, the temperature of hydroboration and oxidation reaction is -
20 to 60°C, preferably 0 to 40°C,
The time required for this is 0.5 to 20 hours, preferably 1 to 10 hours. Furthermore, the polymer concentration is 5 to 200 g/2, preferably 10 to 100 g/2.
It is in the range of g/am.
（２）の方法において、該液状α−オレフイン系重合体
の不飽和結合１モルに対し、有機酸の添加量は１ないし
２００モル、好ましくは５ないし１００モルであり、過
酸化水素の添加量は１ないし５０モル、好ましくは２な
いし２０モルの範囲にある。また反応の温度は０ないし
６０℃、好ましくは１０ないし５０℃であり、それに要
する時間は０．５ないし２０時間、好ましくは１ないし
１０時間である。さらに、ポリマー濃度としては５ない
し４００ｇ／１．好ましくは１０ないし３００ｇ／２の
範囲である。In the method (2), the amount of organic acid added is 1 to 200 mol, preferably 5 to 100 mol, per 1 mol of unsaturated bonds of the liquid α-olefin polymer, and the amount of hydrogen peroxide added is is in the range of 1 to 50 mol, preferably 2 to 20 mol. The reaction temperature is 0 to 60°C, preferably 10 to 50°C, and the time required is 0.5 to 20 hours, preferably 1 to 10 hours. Furthermore, the polymer concentration is 5 to 400 g/1. Preferably it is in the range of 10 to 300 g/2.
（３）の方法において、該液状α−オレフイン系重合体
の不飽和結合１モルに対し有機過酸化物の添加量は１な
いし１０モル、好ましくは１ないし５モルの範囲にある
。また反応の温度は０ないし１００℃、好ましくは１０
ないし８０℃であり、それに要する時間は０．１ないし
１０時間、好ましくは０．５ないし５時間の範囲である
。さらに、ポリマー濃度としては５ないし４００ｇ／ｌ
、好ましくは１０ないし３００ｇ／Ｊ２の範囲である。In the method (3), the amount of organic peroxide added is in the range of 1 to 10 moles, preferably 1 to 5 moles, per mole of unsaturated bonds in the liquid α-olefin polymer. The reaction temperature is 0 to 100°C, preferably 10°C.
The temperature ranges from 0.1 to 10 hours, preferably from 0.5 to 5 hours. Furthermore, the polymer concentration is between 5 and 400 g/l.
, preferably in the range of 10 to 300 g/J2.
次に加水分解においては酸濃度として０．５ないし５Ｎ
、好ましくは１ないし４Ｎの水溶液を上記ポリマー１ｇ
＋、：討し１０ないし１００ｍｊｌ！、好ましくは５な
いし５０ｍ１添加する。また、反応の温度は２０ないし
１００℃、好ましくは４０ないし８０℃であり、それに
要する時間は１ないし２０時間、好ましくは２ないし１
０時間である。Next, in hydrolysis, the acid concentration is 0.5 to 5N.
, preferably 1 to 4N aqueous solution to 1 g of the above polymer.
+,: 10 to 100 mjl! , preferably 5 to 50 ml. Further, the reaction temperature is 20 to 100°C, preferably 40 to 80°C, and the time required for the reaction is 1 to 20 hours, preferably 2 to 1 hour.
It is 0 hours.
本発明の液状ヒドロキシル化変性α−オレフイン系重合
体を製造する際に用いる溶媒としては、ベンゼン、トル
エン、キシレンなどの芳香族炭化水素溶媒、エチルエー
テル、テトラヒドロフラン、ジオキサンなどのエーテル
溶媒を挙げることができる。Examples of the solvent used in producing the liquid hydroxylated modified α-olefin polymer of the present invention include aromatic hydrocarbon solvents such as benzene, toluene, and xylene, and ether solvents such as ethyl ether, tetrahydrofuran, and dioxane. can.
本発明の液状ヒドロキシル化変性α−オレフイン系重合
体は潤滑油用配合剤として利用することができる。潤滑
油用配合剤としては、鉱油潤滑油基油、オレフィン系重
合体または共重合体油などのオレフィン系合成潤滑油、
シリコン系合成潤滑油、エステル系合成潤滑油等の合成
潤滑油のいずれにも利用することができる。該液状ヒド
ロキシル化変性α−オレフイン系重合体の配合割合は上
記潤滑油基油１００重量部に対して通常０．５ないし３
００重量部、好ましくは０．８ないし２００重量部、と
くに好ましくは１ないし１５０重量部の範囲である。該
潤滑油には、該液状ヒドロキシル化変性α−オレフイン
系重合体の他に、潤滑油に配合されることが知られてい
る種々の添加剤を配合することができる。該潤滑油用添
加剤として具体的には鉱油にュートラオイル）、低分子
量α−オレフイン重合体、シリコン系合成潤滑油、エス
テル系合成潤滑油、酸化安定剤、極圧剤、さゾどめ添加
剤、消泡剤、摩耗防止剤などを配合することができる。The liquid hydroxylated modified α-olefin polymer of the present invention can be used as a compounding agent for lubricating oils. Compounding agents for lubricating oils include mineral oil lubricating oil base oils, olefinic synthetic lubricating oils such as olefinic polymer or copolymer oils,
It can be used for any synthetic lubricating oil such as silicone-based synthetic lubricating oil and ester-based synthetic lubricating oil. The blending ratio of the liquid hydroxylated modified α-olefin polymer is usually 0.5 to 3 parts by weight per 100 parts by weight of the above lubricating base oil.
00 parts by weight, preferably 0.8 to 200 parts by weight, particularly preferably 1 to 150 parts by weight. In addition to the liquid hydroxylated modified α-olefin polymer, the lubricating oil may contain various additives known to be incorporated into lubricating oils. Examples of additives for the lubricating oil include mineral oil and eutra oil), low molecular weight α-olefin polymers, silicone-based synthetic lubricating oils, ester-based synthetic lubricating oils, oxidation stabilizers, extreme pressure agents, and stop additives. , an antifoaming agent, an anti-wear agent, etc. can be added.
これらの成分の配合割合は適宜の範囲である。The blending ratio of these components is within an appropriate range.
該液状ヒドロキシル化変性α−オレフィン系重合体が配
合された潤滑油は、ギヤ油、エンジン油、グリース、金
属加工油、雛形刑などの用途に利用される。Lubricating oils containing the liquid hydroxylated modified α-olefin polymers are used in applications such as gear oils, engine oils, greases, metal working oils, and molding oils.
本発明の液状ヒドロキシル化変性α−オレフイン系重合
体は塗料配合剤として用いることができる。本発明の液
状ヒドロキシル化変性α−オレフイン系重合体が配合さ
れる塗料として具体的には、塗膜形成用樹脂成分として
フルキッド樹脂またはその変性物、不飽和ポリエステル
またはその変性物、フェノール樹脂、エポキシ樹脂また
はその変性物、尿素樹脂、メラミン樹脂などの７ミノ樹
脂、ポリツレクン樹脂、乾性油などの縮合系塗料用樹脂
；アクリル系樹脂、ゴム系塗料用樹脂などの重合系塗料
用樹脂などを含む塗料を例示することができる。該液状
ヒドロキシル化変性α−オレフイン系重合体の配合割合
は塗料中の塗膜形成要素成分１００重量部に対して通常
０．０１ないし２０重量部、好ましくは０．１ないし１
０重量部の範囲である。本発明の液状ヒドロキシル化変
性α−オレフイン系重合体が配合された塗料には、その
他に従来から知られている種々の添加剤、たとえば顔料
、溶剤（溶剤型塗料の場合）、分散媒（エマルション型
塗料の場合）、レベリング剤、耐候安定剤などの適宜量
が配合される。The liquid hydroxylated modified α-olefin polymer of the present invention can be used as a paint formulation agent. Specifically, paints to which the liquid hydroxylated modified α-olefin polymer of the present invention is blended include fluid resins or modified products thereof, unsaturated polyesters or modified products thereof, phenolic resins, epoxy resins, etc. Paints containing resins or their modified products, condensation resins for paints such as 7-mino resins such as urea resins and melamine resins, polyurekne resins, and drying oils; resins for polymerization paints such as acrylic resins and resins for rubber paints. can be exemplified. The blending ratio of the liquid hydroxylated modified α-olefin polymer is usually 0.01 to 20 parts by weight, preferably 0.1 to 1 part by weight, per 100 parts by weight of the film-forming component in the paint.
It is in the range of 0 parts by weight. Paints containing the liquid hydroxylated modified α-olefin polymer of the present invention may also contain various conventionally known additives, such as pigments, solvents (in the case of solvent-based paints), dispersion media (emulsions), etc. (in the case of mold paints), leveling agents, weathering stabilizers, etc. are added in appropriate amounts.
本発明の液状ヒドロキシル化変性α−オレフイン系重合
体は前記潤滑油用配合剤およ１前記塗料用配合剤の他に
、種々の用途、たとえば潤滑油への固形添加剤の分散剤
、ゴム又は樹脂の加工助剤、繊維加工助剤、ゴム又は樹
脂の改質剤、可塑剤、インキの添加剤、金属イオン補足
剤、イオン交換剤、農薬展着剤、塗料の可塑性付与剤、
塗料用プライマー改質剤、接着剤の改質剤などの用途に
利用することができる。The liquid hydroxylated modified α-olefin polymer of the present invention can be used in a variety of applications, such as as a dispersant for solid additives in lubricating oils, as a dispersant for solid additives in lubricating oils, in addition to the above-mentioned lubricating oil compounding agents and the above-mentioned paint compounding agents. Resin processing aids, textile processing aids, rubber or resin modifiers, plasticizers, ink additives, metal ion scavengers, ion exchange agents, pesticide spreading agents, paint plasticizers,
It can be used as a primer modifier for paints, a modifier for adhesives, etc.
［実施例１ 次に本発明を実施例によって具体的に説明する。[Example 1 Next, the present invention will be specifically explained with reference to Examples.
なお、本発明の液状ヒドロキシル化変性α−オレフイン
系重合体およびその原料の液状α−オレフイン系重合体
の組成および物性値の測定方法ならびにその評価法を以
下に示した。In addition, methods for measuring and evaluating the composition and physical property values of the liquid hydroxylated modified α-olefin polymer of the present invention and the liquid α-olefin polymer as a raw material thereof are shown below.
（１）１３Ｃ−ＮＭＲの測定により、α−オレフイン、
ヒドロキシル基およびエステル基の含量を求めた。通常
、測定条件は前記のα−オレフインの配列状態の処で述
べた測定条件と同一である。(1) By 13C-NMR measurement, α-olefin,
The content of hydroxyl groups and ester groups was determined. Generally, the measurement conditions are the same as those described above regarding the alignment state of α-olefin.
（２）数平均分子量の測定方法
ベーパープレツシヤーオスモメーター（ｖ ｐ ｏ ）
を用い、分子量既知の標準サンプルとしてベンジルお上
りスクアランを使用し、トルエン溶媒、８０℃の条件に
て常法により、数平均分子量（Ｍｎ）を測定した。(2) Method for measuring number average molecular weight Vapor pressure osmometer (vpo)
The number average molecular weight (Mn) was measured by a conventional method in a toluene solvent at 80° C. using benzyl squalane as a standard sample with a known molecular weight.
（３）分子量分布（Ｍｗ／Ｍｎ）の測定は武内着、丸善
発行の「ゲルパーミェーション・クロマトグラフィー」
に準じて次の如く行う。(3) Molecular weight distribution (Mw/Mn) was measured using “gel permeation chromatography” published by Takeuchi and Maruzen.
In accordance with the following.
■ 分子量既知の標準ポリスチレン（東洋ソーブ（株）
製、単分散ポリスチレン）を使用して分子量ＭとそのＧ
Ｐ Ｃ（Ｇ ｅｌ Ｐ ｅｒｍｅａｔｉｏｎ Ｃ
ｈｒｏｍａｔｏｇｒａｐｈ ）カウントを測定し、分子
量ＭとＶ ｅ（Ｅ Ｉｕｔｉ。■ Standard polystyrene with known molecular weight (Toyo Sorb Co., Ltd.)
(monodispersed polystyrene) to determine the molecular weight M and its G
P C (Gel P ermeation C
chromatography) counts and molecular weights M and V e (E Iuti.
ｎ Ｖｏｌｕｍｅ）の相関図較正曲線を作製する。こ
の時の濃度は０．０２ｗｔ％とする。Create a correlation diagram calibration curve for nVolume). The concentration at this time is 0.02 wt%.
■ ＧＰＣ測定法により試料のＧＰＣクロマトグラフを
と９、前記（１）によりポリスチレン換算の数平均分子
量Ｍｎｓ重量平均分子量Ｍｌｌ＋を算出し、Ｍｗ／Ｍｎ
値を求める。その際のサンプル調製条件お上びＧＰＣ測
定条件は以下の通りである。■ Obtain a GPC chromatograph of the sample using the GPC measurement method9, calculate the number average molecular weight Mns weight average molecular weight Mll+ in terms of polystyrene using (1) above, and calculate Mw/Mn.
Find the value. The sample preparation conditions and GPC measurement conditions at that time are as follows.
［サンプル調製］
（イ）試料を０，１ｗｔ％になるようにトルエン溶媒と
ともに三角フラスコに採取する。[Sample Preparation] (a) Collect a sample into an Erlenmeyer flask together with toluene solvent so that the concentration is 0.1 wt%.
（ロ）三角フラスコを７０℃において１時間加温したの
ちステンレス製フィルター（孔径０．５μ）でｔ濾過し
、その１戸液をＧＰＣにか１する。(b) After heating the Erlenmeyer flask at 70°C for 1 hour, filter it with a stainless steel filter (pore size 0.5μ), and transfer the resulting solution to GPC.
［Ｇ Ｐ Ｃ条件］ 次の条件で実施した。[GPC conditions] It was conducted under the following conditions.
（イ） 装置：Ｗａｔｅｒｓ社製（１５０Ｃ−ＡＬＣ／
ＧＰＣ）
（ロ） カラム：東洋ソーダ製（Ｇ４０００Ｈ，Ｇ３０
００Ｈ，Ｇ２０００Ｈ）
（ハ） 温度ニア０℃
（ニ）流速：１，５ｍｌ／ｗｉｎ
参考例１
［アルミノオキサンの調製］
充分に窒素置換した２００１の７ラスコにＡ１□（ＳＯ
４）３・１４Ｈ２０７，５ｇとトルエン２５ｕ１を装入
し、０℃に冷却後、トルエン２５ｍ１で希釈したトリメ
チルアルミニウム１００Ｉ＠ｍｏｌを滴下した。次に、
４０℃まで昇温し、その温度で３２時間反応を続けた。(b) Equipment: Waters (150C-ALC/
GPC) (b) Column: Toyo Soda (G4000H, G30
00H, G2000H) (c) Temperature near 0°C (d) Flow rate: 1.5 ml/win Reference example 1 [Preparation of aluminoxane] A1□ (SO
4) 207.5 g of 3.14H and 25 ul of toluene were charged, and after cooling to 0° C., 100 I@mol of trimethylaluminum diluted with 25 ml of toluene was added dropwise. next,
The temperature was raised to 40°C, and the reaction was continued at that temperature for 32 hours.
反応後、濾過により固液分離を行い、更に炉液よりトル
エンを除去することによって白色固体のアルミノオキサ
ン２．９Ｆ１を得た。ベンゼン中での凝固点降下により
求めた分子量は１３４０であり、触ｔ＆成分［Ｂｌ中に
示した■値は２１であった。重合にはトルエンに再溶解
して用いた。After the reaction, solid-liquid separation was performed by filtration, and toluene was further removed from the furnace solution to obtain white solid aluminoxane 2.9F1. The molecular weight determined by freezing point depression in benzene was 1,340, and the value of ■ shown in t&component [Bl] was 21. For polymerization, it was used after being redissolved in toluene.
［重合１
充分に窒素置換した２１のオートクレーブに４−メチル
−１−ペンテン１２を装入し、４５℃まで昇温しな。そ
の後、アルミノオキサンをアルミニウム原子換算で５ミ
リグラム原子、トルエンに溶解したビス（シクロペンタ
ジェニル）ノルコニウムジクロリドをジルコニウム原子
換算で０．０２ミリグラム原子装入し、５０℃で２時間
重合を行なった。生成したポリマー溶液に水を加え脱灰
を行なった後、未重合の４−メチル−１−ペンテンをエ
バポレーターにより除去し、更に１２０℃で１２時間減
圧乾燥することにより数平均分子量８４０、［り１０，
０３ｄｌ ／ｇ−Ｍｗ／Ｍｎ＝２．２１、沃素価３０の
液状ポリ４−メチル−１−ペンテン６９ｇを得た。[Polymerization 1 4-methyl-1-pentene 12 was charged into a No. 21 autoclave which was sufficiently purged with nitrogen, and the temperature was raised to 45°C. Thereafter, 5 milligram atoms of aluminoxane in terms of aluminum atoms and 0.02 milligram atoms in terms of zirconium atoms of bis(cyclopentadienyl)norconium dichloride dissolved in toluene were charged, and polymerization was carried out at 50°C for 2 hours. Ta. After adding water to the resulting polymer solution and deashing it, unpolymerized 4-methyl-1-pentene was removed using an evaporator, and further dried under reduced pressure at 120°C for 12 hours to obtain a number average molecular weight of 840, [10 ，
03 dl/g-Mw/Mn=2.21 and 69 g of liquid poly-4-methyl-1-pentene having an iodine value of 30 was obtained.
該ポリマーを実施例１の変性に用いた。The polymer was used for modification in Example 1.
参考例２
［重合］
充分に窒素置換した２２のオートクレーブに精製トルエ
ン１１を装入し、プロピレンガスを２００β／ｈｒで流
通させた。その後３０℃に昇温し、アルミノオキサンを
アルミニウム原子換算で５ミリグラム原子、トルエンに
溶解したビス（シクロペンタジェニル）ノルコニウムジ
クロリドをツルコニウム原子換算で０．０２ミリグラム
原子装入し、３０℃で２時間常圧で重合を行なった。生
成したポリマー溶液に水を加え脱灰を行なった後、トル
エンを除去し１２０℃で１２時間減圧乾燥することによ
り数平均分子量１２１０、〔りＪＯ００６ｄｌ ／ｇ、
Ｍｗ／ Ｍｎ’ ２ 、０５、沃素価２１の液状ポリ
プロピレン４８ｇを得た。該ポリマーを実施例２の変性
に用いた。Reference Example 2 [Polymerization] Purified toluene 11 was charged into 22 autoclaves which were sufficiently purged with nitrogen, and propylene gas was passed through the autoclave at a rate of 200β/hr. Thereafter, the temperature was raised to 30°C, and 5 milligram atoms of aluminoxane in terms of aluminum atoms and 0.02 milligram atoms in terms of turconium atoms of bis(cyclopentagenyl)norconium dichloride dissolved in toluene were charged, and the temperature was raised to 30°C. Polymerization was carried out at normal pressure for 2 hours. After adding water to the resulting polymer solution and deashing it, toluene was removed and drying under reduced pressure at 120°C for 12 hours resulted in a number average molecular weight of 1210, [JO006dl/g,
48 g of liquid polypropylene having a Mw/Mn' 2 of 05 and an iodine value of 21 was obtained. The polymer was used for modification in Example 2.
参考例３
［重合１
参考例２においてトルエン５００ｍＡ、４−メチル−１
−ペンテン５００ＩＩＩＪ１プロピレン〃スフ５ｊ！／
ｈｒ、重合温度５０℃で２時間重合した以外は参考例２
と同様に行ないプロピレン含量１９モル％、数平均分子
量６８０、［η］０．０２ｄｌ／ｇ、Ｍｕ／Ｍｎ＝２．
３５、沃素価′３７の液状プロピレン−４−メチル−１
−ペンテン共ｍ 合体２３ ｇを得た。該ポリマーを実
施例３の変性に用いた。Reference Example 3 [Polymerization 1 In Reference Example 2, toluene 500 mA, 4-methyl-1
-Pentene 500IIIJ1 Propylene Sufu 5j! /
hr, Reference Example 2 except that polymerization was performed at a polymerization temperature of 50°C for 2 hours.
Propylene content was 19 mol%, number average molecular weight was 680, [η] was 0.02 dl/g, Mu/Mn was 2.
35, liquid propylene-4-methyl-1 with iodine number '37
- 23 g of pentene co-merge was obtained. The polymer was used for modification in Example 3.
実施例１
充分に窒素置換した１００ｍｊ！の〃ラス製フラスコに
ＴＨＦ７論！と液状α−オレフイン重合体（参考例１）
５．０ｇを装入し、室温下で更にギ酸１２゜４８、引艶
続き３５ｗｔ％の過酸化水素２．６ｇを加、えた。その
後４０℃に昇温し、その温度で８時間激しく攪拌を続け
た。次に室温まで降温し、１０ｗｔ％のＮ ａ２ Ｓ
Ｏｓ水溶液６８−を１０分間で滴下した。更に、室温下
で３０分間攪拌した後へキサンによりポリマーを抽出し
乾燥することにより数平均分子量８９０、Ｍｗ／Ｍｎ２
，３５、ヒドロキシル基０．１０モル／ １００ ｇ重
合体、ギ酸エステル０．１０モル／１００．重合体、［
η］０．０４ｄ１７ｇの無色透明な液状ヒドロキシル化
変性α−オレフィン重合体５．０ｇが得られた。尚、該
重合体の’コＣ−ＮＭＲスペクトルには重合体主鎖中の
隣接した２個の３級炭素原子間に２個の連続したメチレ
ン連鎖に基づくシグナルは検出されなかった。Example 1 100 mj with sufficient nitrogen substitution! THF7 theory in a glass flask! and liquid α-olefin polymer (Reference Example 1)
5.0 g of the solution was charged, and at room temperature, 12.48 g of formic acid and 2.6 g of 35 wt % hydrogen peroxide were further added. Thereafter, the temperature was raised to 40°C, and vigorous stirring was continued at that temperature for 8 hours. Next, the temperature was lowered to room temperature, and 10 wt% Na2S
An Os aqueous solution 68- was added dropwise over 10 minutes. Furthermore, after stirring for 30 minutes at room temperature, the polymer was extracted with hexane and dried to obtain a number average molecular weight of 890 and Mw/Mn2.
, 35, hydroxyl group 0.10 mol/100 g polymer, formate ester 0.10 mol/100. Polymer, [
η]0.04d17 g of a colorless and transparent liquid hydroxylated modified α-olefin polymer was obtained. In addition, no signal based on two consecutive methylene chains between two adjacent tertiary carbon atoms in the main chain of the polymer was detected in the C-NMR spectrum of the polymer.
実施例２
充分に窒素置換した５００ｍ１のガラス製フラスコに０
．５Ｍの９−ＢＢＮ（９ｂｏｒａｂｉｃｙｅｌ。Example 2 Into a 500ml glass flask that was sufficiently purged with nitrogen,
．． 5M of 9-BBN (9borabicyel.
［３、３、１１ｎｏｎａｎｅ）のＴＨＦ溶液４０−２を
入れ１０℃に冷却した。１０℃に保持しながらＴＨＦ１
０７ｍｊ２で希釈した液状α−オレフィン重合体（参考
例３）５．ｏｇを５分間で滴下した０滴下終了後、室温
で５時間攪拌を続けた。その後、０℃に冷却し、３Ｎの
ＮａＯＨ水溶液水溶液２奢
５ｗｔ％の過酸化水素水６．８ｇを１５分間で滴下した
。その際、反応系内の温度は０℃から２０℃まで昇温し
な．引き続！３０℃まで昇温し、その温度で２時間反応
を続けた。反応終了後、１５℃まで降温し、飽和Ｋ ２
Ｃ Ｏ ３水溶液５０ｖｊ！を加えた。その後、ヘキ
サンによりポリマーを抽出し更にヘキサンを除去、乾燥
することにより数平均分子量１２２０、Ｍｗ／Ｍｎ２．
１ ３、ヒドロキシル基０．０８モルフ１００ｇ重合体
、［り１０，０６ｄｌ ／ｇの無色透明な液状ヒドロキ
シル化変性ａーオレフイン重合体４．９ｇが得られた．
尚、該重合体の１３ｃｍＮＭＲスペクトルには重合体主
鎖中の隣接した２個の３級炭素原子間に２個の連続した
メチレン連鎖に基づくシグナルは検出されなかった。A THF solution 40-2 of [3, 3, 11 nonane) was added and cooled to 10°C. THF1 while keeping at 10℃
Liquid α-olefin polymer diluted with 07mj2 (Reference Example 3)5. After 0 dropwise addition of 0.0 g over 5 minutes, stirring was continued at room temperature for 5 hours. Thereafter, the mixture was cooled to 0° C., and 6.8 g of 3N NaOH aqueous solution and 5 wt % hydrogen peroxide solution were added dropwise over 15 minutes. At that time, the temperature inside the reaction system should not be raised from 0°C to 20°C. Continue! The temperature was raised to 30°C, and the reaction was continued at that temperature for 2 hours. After the reaction is completed, the temperature is lowered to 15°C, and the saturated K2
C O 3 aqueous solution 50vj! added. Thereafter, the polymer was extracted with hexane, the hexane was further removed, and the number average molecular weight was 1220, Mw/Mn2.
13. 100 g of a polymer with 0.08 morph of hydroxyl groups and 4.9 g of a colorless and transparent liquid hydroxylated modified a-olefin polymer with a concentration of 10.06 dl/g were obtained.
In addition, no signal based on two consecutive methylene chains between two adjacent tertiary carbon atoms in the polymer main chain was detected in the 13 cm NMR spectrum of the polymer.
実施例３
実施例１において液状α−オレフイン系重合体として参
考例３で得られたものを５．４ｇ用いた以外は実施例１
と同様に行ない、プロピレン含量１９モル％、数平均分
子量７４０、Ｍｗ／ｘｎ２。Example 3 Example 1 except that 5.4 g of the liquid α-olefin polymer obtained in Reference Example 3 was used in Example 1.
Propylene content was 19 mol%, number average molecular weight was 740, Mw/xn2.
３１、ヒドロキシル基０．３モル／１００ｇ重合体、ギ
酸エステル０．１３モル／１００．重合体、［η１０．
０ ３ｄｌ ／ｇの無色透明な液状ヒドロキシル化変性
ａーオレフィン系重合体４．８ｇを得た。31, hydroxyl group 0.3 mol/100g polymer, formate ester 0.13 mol/100. Polymer, [η10.
0.3 dl/g of a colorless and transparent liquid hydroxylated modified a-olefin polymer was obtained.
尚、該重合体の１３ｃｍＮＭＲスペクトルには共重合体
主鎖中の隣接した２個の３級炭素原子間に２個の連続し
たメチレン連鎖に基づくシグナルは検出されなかった。In addition, no signal based on two consecutive methylene chains between two adjacent tertiary carbon atoms in the main chain of the copolymer was detected in the 13 cm NMR spectrum of the polymer.
応用例１
下記の方法によって、本発明の液状ヒドロキシル化変性
ａーオレフィン系重合体の潤滑油用配合剤としての性能
を評価した。Application Example 1 The performance of the liquid hydroxylated modified a-olefin polymer of the present invention as a lubricating oil compounding agent was evaluated by the following method.
（１）試料の調製
３００ｍ１ビーカーにポリミーオレフィンオリゴｖ−Ａ
（Ｍｏｂｉｌ Ｃｈｅｓｅｉｃａ１社製Ｍｏｂｉｌ
５ＨＦ−１００１）６５重量部とポリα−オレフィン
オリゴｖ−Ｂ（Ｃｈｅｖｒｏｎ Ｃｈｅｍｉｃａ１社
製５ｙｎｆｌｕｉｄ６ｃｓｔ ＰＡＯ）３５重量部を
採り、〃ラス棒を用いてよく混合した後、市販ギヤ油°
パッケージ型添加剤（Ｔｅｘａｅｏ社製、ＴＣ９５３５
：Ｓ ２４，１％、Ｐ １．８％）１重量部およびそ
れぞれ実施例１お上り３によって得られた液状ヒドロキ
シル化変性α−オレフィン系重合体３重量部を加えて更
にかきまぜ、２つの評価用潤滑油試料（１）を調製した
。また、同様の方法で、液状ヒドロキシル化変性α−オ
レフィン系重合体を加えずに調製して、比較評価用潤滑
油試料（Ｕ）を得た。(1) Sample preparation Polymyolefin oligo v-A in a 300ml beaker
(Mobil made by Chesica1)
5HF-1001) and 35 parts by weight of poly α-olefin oligo V-B (5ynfluid 6cst PAO manufactured by Chevron Chemica 1) were taken, mixed thoroughly using a lath rod, and mixed with commercially available gear oil.
Packaged additive (Texaeo, TC9535
:S 24.1%, P 1.8%) 1 part by weight and 3 parts by weight of the liquid hydroxylated modified α-olefin polymer obtained in Example 1 and 3 were added and further stirred, and two evaluations were performed. A lubricating oil sample (1) was prepared. A lubricating oil sample (U) for comparative evaluation was also prepared in the same manner without adding the liquid hydroxylated modified α-olefin polymer.
（２）評価方法
（ｉ） 相溶性
直径４０＋ｍの〃ラス製容器に試料１００＠ｊ！を採取
し、−夜静置後、分光光度計を用い、波長６６０ｎｍの
光の吸光度（セル：硝子・５０＋ａｍ、対称：ヘキサン
）を測定し、透明性を調べた。(2) Evaluation method (i) Compatibility 100 samples in a lath container with a diameter of 40+ m! was collected, and after being allowed to stand overnight, the absorbance of light at a wavelength of 660 nm (cell: glass, 50+am, symmetry: hexane) was measured using a spectrophotometer to examine transparency.
〈評価〉
（ｉｉ） 加熱安定性
相溶性試験後の試料の入ったままのガラスｇＩ容器を８
０℃の恒温槽に１力月問入れた後、取り出して室温下に
一夜放冷し、上記（ｉ）と同様の方法で透明性を評価し
た。<Evaluation> (ii) The glass gI container containing the sample after the heat stability compatibility test was
After placing it in a constant temperature bath at 0° C. for one month, it was taken out and left to cool at room temperature overnight, and the transparency was evaluated in the same manner as in (i) above.
（ｉｉｉ＞ 抗乳化性
ＪＩＳ Ｋ２５２０の方法に従って乳化層の消滅時間
を調べた。(iii> Demulsification property The disappearance time of the emulsified layer was investigated according to the method of JIS K2520.
〈評価〉
（３）評価結果
応用例２
下記の方法によって、本発明の液状ヒドロキシル化変性
α−オレフィン系重合体の塗料用配合剤としての性能を
評価した。<Evaluation> (3) Evaluation Results Application Example 2 The performance of the liquid hydroxylated modified α-olefin polymer of the present invention as a paint compounding agent was evaluated by the following method.
（１）試料の調製
エポキシ樹脂Ａ（三井石油化学工業（株）社製、エポミ
ツクＲ−１４０）８５重量部、エポキシ樹脂（同、エポ
ミツクＲ−０９４）１５重量部および実施例２によって
得られた液状ヒドロキシル化変性ポリプロピレン５重量
部をよく混合したのち、これに砕石粉（竜森工業社製り
リスタライ）Ａ−１）３５重量部を加えて更によくかき
まぜ、評価用エポキシ塗料（１）を得た。また、同様の
方法で、液状ヒドロキシル化変性ポリプロピレンの代わ
りに市販の植物油重合系沈降防止剤を用いて比較評価用
エポキシ塗料（Ｉ［）を調製した。(1) Preparation of samples: 85 parts by weight of epoxy resin A (manufactured by Mitsui Petrochemical Industries, Ltd., Epomic R-140), 15 parts by weight of epoxy resin (Epomic R-094) obtained in Example 2. After thoroughly mixing 5 parts by weight of liquid hydroxylated modified polypropylene, 35 parts by weight of crushed stone powder (Ristaly A-1, manufactured by Ryumori Kogyo Co., Ltd.) was added thereto, and the mixture was further stirred to obtain an epoxy paint for evaluation (1). Ta. In addition, in the same manner, an epoxy paint (I[) for comparative evaluation was prepared using a commercially available vegetable oil polymerized anti-settling agent instead of the liquid hydroxylated modified polypropylene.
（２）評価方法
（ｉ） 顔料沈降率
内径１８ａ＋ａ＋、高さ４５ｍ５＋のキャップ付ガラス
容器に高さ４０＋ａｍになるように試料を入れ、１力月
静置後の顔料沈降率を下式によって求めた。(2) Evaluation method (i) Pigment sedimentation rate A sample was placed in a capped glass container with an inner diameter of 18a+a+ and a height of 45m5+ to a height of 40+am, and the pigment sedimentation rate after standing for one month was determined by the formula below. .
顔料沈降率（％）＝−Ｘ１００ ｉ。Pigment sedimentation rate (%) = -X100 i.
ここで、Ｘ 、：＠料の充填高さ（４０ｍｍ）ｌ：１力
月静置により顔料が沈降し
て出来な上部清澄層の高さ（ａｍ）
（ｉｉ） タレ性
評価用塗料１００重量部に対し変性ポリアミン系硬化剤
（三井石油化学工業（株）社製、エポミ゛ツクＱ−６３
６）２８重量部を加えてよく混合し、ガラス板に塗布し
、その直後に垂直固定して静置したまま硬化させ、タレ
度合いを観察しながらタレない最高塗布厚を求めた。Here, Modified polyamine curing agent (manufactured by Mitsui Petrochemical Industries, Ltd., Epomic Q-63)
6) 28 parts by weight were added, mixed well, and coated on a glass plate. Immediately thereafter, it was fixed vertically and allowed to harden while standing still. The maximum coating thickness without sagging was determined while observing the degree of sagging.
（３）評価結果
［発明の効果］
本発明により新規な液状ヒドロキシル化変性α−オレフ
イン系重合体が得られる。(3) Evaluation Results [Effects of the Invention] The present invention provides a novel liquid hydroxylated modified α-olefin polymer.
本発明の液状ヒドロキシル化変性α−オレフィン系重合
体は、潤滑油用配合剤および塗料用配合剤として優れた
効果を示す。The liquid hydroxylated modified α-olefin polymer of the present invention exhibits excellent effects as a compounding agent for lubricating oils and a compounding agent for paints.
外１名1 other person
Claims (6)
構成される液状α−オレフイン系重合体のヒドロキシル
化変性物であって、 （ｉ）該液状ヒドロキシル化変性α−オレフイン系重合
体の＾１＾３Ｃ−ＮＭＲスペクトル中において重合体主
鎖中の隣接した２個の３級炭素原子間に２個の連続した
メチレン連鎖に基づくシグナルが観測されないこと、 （ｉｉ）該液状ヒドロキシル化変性α−オレフイン系重
合体のベーパープレツシヤーオスモメーター（ＶＰＯ）
で測定した数平均分子量（＠Ｍ＠ｎ）が２００ないし１
００００の範囲にあること、および（ｉｉｉ）ヒドロキ
シル基が該液状α−オレフイン系重合体の分子末端に位
置するα−オレフインに由来する炭素原子に結合してお
り、ヒドロキシル基の含有割合が該液状ヒドロキシル化
変性α−オレフイン系重合体１００ｇあたり０．０１な
いし１．０モルの範囲にあること、 によって特徴づけられる液状ヒドロキシル化変性α−オ
レフイン系重合体。(1) A hydroxylated modified product of a liquid α-olefin polymer composed of an α-olefin having 3 to 20 carbon atoms, (i) a hydroxylated modified product of the liquid hydroxylated modified α-olefin polymer; (ii) no signal based on two consecutive methylene chains between two adjacent tertiary carbon atoms in the polymer main chain is observed in the 1^3C-NMR spectrum; Olefin polymer vapor pressure osmometer (VPO)
The number average molecular weight (@M@n) measured in
0000, and (iii) the hydroxyl group is bonded to a carbon atom derived from the α-olefin located at the molecular end of the liquid α-olefin polymer, and the content of the hydroxyl group is within the range of A liquid hydroxylated modified α-olefin polymer characterized by the following: 0.01 to 1.0 mol per 100 g of the hydroxylated modified α-olefin polymer.
構成されかつ、 （ｉ）＾１＾３Ｃ−ＮＭＲスペクトル中において重合体
主鎖中の隣接した２個の３級炭素原子間に２個のメチレ
ン連鎖に基づくシグナルが観測されないこと、および （ｉｉ）ベーパープレツシヤーオスモメーター（ＶＰＯ
）で測定した数平均分子量（＠Ｍ＠ｎ）が２００ないし
１００００の範囲にあること、 によって表わされる重合体分子末端に炭素・炭素不飽和
結合を有する液状α−オレフイン系重合体に、ジボラン
またはハイドロボランを反応させた後、過酸化水素を反
応させることを特徴とする液状ヒドロキシル化変性α−
オレフィン系重合体の製法。(2) It is composed of α-olefin having 3 to 20 carbon atoms, and (i) In the ^1^3C-NMR spectrum, two carbon atoms are present between two adjacent tertiary carbon atoms in the polymer main chain. (ii) the vapor pressure osmometer (VPO
) has a number average molecular weight (@M@n) in the range of 200 to 10,000, diborane or Liquid hydroxylated modified α- characterized by reacting hydroborane and then reacting hydrogen peroxide.
A method for producing olefin polymers.
構成されかつ、 （ｉ）＾１＾３Ｃ−ＮＭＲスペクトル中において重合体
主鎖中の隣接した２個の３級炭素原子間に２個のメチレ
ン連鎖に基づくシグナルが観測されないこと、および （ｉｉ）ベーパープレツシヤーオスモメーター（ＶＰＯ
）で測定した数平均分子量（＠Ｍ＠ｎ）が２００ないし
１００００の範囲にあること、 によって表わされる重合体分子末端に炭素・炭素不飽和
結合を有する液状α−オレフイン系重合体に、有機酸の
存在下に過酸化水素を反応させさらに必要に応じて加水
分解することを特徴とする液状ヒドロキシル化変性α−
オレフイン系重合体の製法。(3) It is composed of α-olefin having 3 to 20 carbon atoms, and (i) In the ^1^3C-NMR spectrum, two carbon atoms are present between two adjacent tertiary carbon atoms in the polymer main chain. (ii) the vapor pressure osmometer (VPO
) has a number average molecular weight (@M@n) in the range of 200 to 10,000. A liquid hydroxylated modified α-
Method for producing olefin polymers.
構成されかつ、 （ｉ）＾１＾３Ｃ−ＮＭＲスペクトル中において重合体
主鎖中の隣接した２個の３級炭素原子間に２個のメチレ
ン連鎖に基づくシグナルが観測されないこと、および （ｉｉ）ベーパープレツシヤーオスモメーター（ＶＰＯ
）で測定した数平均分子量（＠Ｍ＠ｎ）が２００ないし
１００００の範囲にあること、 によって表わされる重合体分子末端に炭素・炭素不飽和
結合を有する液状α−オレフイン系重合体に、有機過酸
化水素を反応させた後に加水分解することを特徴とする
液状ヒドロキシル化変性α−オレフイン系重合体の製法
。(4) It is composed of an α-olefin having 3 to 20 carbon atoms, and (i) In the ^1^3C-NMR spectrum, there are two tertiary carbon atoms between two adjacent tertiary carbon atoms in the polymer main chain. (ii) the vapor pressure osmometer (VPO
) has a number average molecular weight (@M@n) in the range of 200 to 10,000. A method for producing a liquid hydroxylated modified α-olefin polymer, which comprises reacting with hydrogen oxide and then hydrolyzing it.
構成される液状α−オレフイン系重合体のヒドロキシル
化変性物であって、 （ｉ）該液状ヒドロキシル化変性α−オレフイン系重合
体の＾１＾３Ｃ−ＮＭＲスペクトル中において重合体主
鎖中の隣接した２個の３級炭素原子間に２個の連続した
メチレン連鎖に基づくシグナルが観測されないこと、 （ｉｉ）該液状ヒドロキシル化変性α−オレフィン系重
合体のベーパープレツシヤーオスモメータ（ＶＰＯ）で
測定した数平均分子量（＠Ｍ＠ｎ）が２００ないし１０
０００の範囲にあること、および（ｉｉ）ヒドロキシル
基が該液状α−オレフイン系重合体の分子末端に位置す
るα−オレフインに由来する炭素原子に結合しており、
ヒドロキシル基の含有割合が該液状ヒドロキシル化変性
α−オレフイン系重合体１００ｇあたり０．０１ないし
１．０モルの範囲にあること、 によって特徴づけられる液状ヒドロキシル化変性α−オ
レフイン系重合体からなる潤滑油配合剤。(5) A hydroxylated modified product of a liquid α-olefin polymer composed of an α-olefin having 3 to 20 carbon atoms, (i) a hydroxylated modified product of the liquid hydroxylated modified α-olefin polymer; (ii) no signal based on two consecutive methylene chains between two adjacent tertiary carbon atoms in the polymer main chain is observed in the 1^3C-NMR spectrum; The number average molecular weight (@M@n) of the olefin polymer measured with a vapor pressure osmometer (VPO) is 200 to 10.
000, and (ii) the hydroxyl group is bonded to a carbon atom derived from α-olefin located at the molecular end of the liquid α-olefin polymer;
A lubricant comprising a liquid hydroxylated modified α-olefin polymer characterized by the following: the content of hydroxyl groups is in the range of 0.01 to 1.0 mol per 100 g of the liquid hydroxylated modified α-olefin polymer. Oil compound.
構成される液状α−オレフイン系重合体のヒドロキシル
化変性物であって、 （ｉ）該液状ヒドロキシル化変性α−オレフイン系重合
体の＾１＾３Ｃ−ＮＭＲスペクトル中において重合体主
鎖中の隣接した２個の３級炭素原子間に２個の連続した
メチレン連鎖に基づくシグナルが観測されないこと、 （ｉｉ）該液状ヒドロキシル化変性α−オレフイン系重
合体のベーパープレツシヤーオスモメーター（ＶＰＯ）
で測定した数平均分子量（＠Ｍ＠ｎ）が２００ないし１
００００の範囲にあること、および（ｉｉ）ヒドロキシ
ル基が該液状α−オレフイン系重合体の分子末端に位置
するα−オレフインに由来する炭素原子に結合しており
、ヒドロキシル基の含有割合が該液状ヒドロキシル化変
性α−オレフイン系重合体１００ｇあたり０．０１ない
し０．５モルの範囲にあること、 によって特徴づけられる液状ヒドロキシル化変性α−オ
レフィン系重合体からなる塗料用配合剤。(6) A hydroxylated modified product of a liquid α-olefin polymer composed of an α-olefin having 3 to 20 carbon atoms, comprising: (i) a hydroxylated modified product of the liquid hydroxylated modified α-olefin polymer; (ii) no signal based on two consecutive methylene chains between two adjacent tertiary carbon atoms in the polymer main chain is observed in the 1^3C-NMR spectrum; Olefin polymer vapor pressure osmometer (VPO)
The number average molecular weight (@M@n) measured in
0000, and (ii) the hydroxyl group is bonded to the carbon atom derived from the α-olefin located at the molecular end of the liquid α-olefin polymer, and the content of the hydroxyl group is within the range of A paint compounding agent comprising a liquid hydroxylated modified α-olefin polymer characterized by the following: 0.01 to 0.5 mol per 100 g of the hydroxylated modified α-olefin polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28929187A JPH0757774B2 (en) | 1987-11-18 | 1987-11-18 | Liquid hydroxylated modified .ALPHA.-olefin polymer, its production and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28929187A JPH0757774B2 (en) | 1987-11-18 | 1987-11-18 | Liquid hydroxylated modified .ALPHA.-olefin polymer, its production and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01132604A true JPH01132604A (en) | 1989-05-25 |
| JPH0757774B2 JPH0757774B2 (en) | 1995-06-21 |
Family
ID=17741278
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28929187A Expired - Lifetime JPH0757774B2 (en) | 1987-11-18 | 1987-11-18 | Liquid hydroxylated modified .ALPHA.-olefin polymer, its production and use |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0757774B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5674950A (en) * | 1994-03-07 | 1997-10-07 | Exxon Chemical Patents Inc. | Polymers having terminal hydroxyl aldehyde, or alkylamino substitutents and derivatives thereof |
| US5691422A (en) * | 1994-03-07 | 1997-11-25 | Exxon Chemical Patents Inc. | Saturated polyolefins having terminal aldehyde or hydroxy substituents and derivatives thereof |
| EP1424347A4 (en) * | 2001-08-21 | 2005-03-09 | Univ School Nihon Juridic Per | Ethylene/vinyl alcohol copolymer and process for producing the same |
| JP2006056918A (en) * | 2004-08-17 | 2006-03-02 | Mitsui Chemicals Inc | Additive for coating and coating comprising the same |
-
1987
- 1987-11-18 JP JP28929187A patent/JPH0757774B2/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5674950A (en) * | 1994-03-07 | 1997-10-07 | Exxon Chemical Patents Inc. | Polymers having terminal hydroxyl aldehyde, or alkylamino substitutents and derivatives thereof |
| US5691422A (en) * | 1994-03-07 | 1997-11-25 | Exxon Chemical Patents Inc. | Saturated polyolefins having terminal aldehyde or hydroxy substituents and derivatives thereof |
| US5777041A (en) * | 1994-03-07 | 1998-07-07 | Exxon Chemical Patents Inc | Saturated polyolefins having terminal aldehyde or hydroxy substituents and derivatives thereof |
| US5780554A (en) * | 1994-03-07 | 1998-07-14 | Exxon Chemical Patents Inc. | Saturated polyolefins having terminal aldehyde or hydroxy substituents and derivatives thereof |
| US5880219A (en) * | 1994-03-07 | 1999-03-09 | Exxon Chemical Patents Inc. | Polymers having terminal hydroxyl, aldehyde, or alkylamino substituents and derivatives thereof |
| US5919869A (en) * | 1994-03-07 | 1999-07-06 | Exxon Chemical Patents, Inc. | Polymers having terminal hydroxyl, aldehyde, or alkylamino substituents and derivatives thereof |
| EP1424347A4 (en) * | 2001-08-21 | 2005-03-09 | Univ School Nihon Juridic Per | Ethylene/vinyl alcohol copolymer and process for producing the same |
| US7019095B2 (en) | 2001-08-21 | 2006-03-28 | Nihon University, School Juridical Person | Ethylene-vinyl alcohol copolymer and process for producing the same |
| JP2006056918A (en) * | 2004-08-17 | 2006-03-02 | Mitsui Chemicals Inc | Additive for coating and coating comprising the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0757774B2 (en) | 1995-06-21 |
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