JPH04258614A - Fluoroelastomer - Google Patents
FluoroelastomerInfo
- Publication number
- JPH04258614A JPH04258614A JP2061691A JP2061691A JPH04258614A JP H04258614 A JPH04258614 A JP H04258614A JP 2061691 A JP2061691 A JP 2061691A JP 2061691 A JP2061691 A JP 2061691A JP H04258614 A JPH04258614 A JP H04258614A
- Authority
- JP
- Japan
- Prior art keywords
- molecular weight
- units
- weight
- extrusion
- elastomer
- 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.)
- Pending
Links
- 229920001973 fluoroelastomer Polymers 0.000 title abstract 3
- 229920001971 elastomer Polymers 0.000 claims abstract description 62
- 239000000806 elastomer Substances 0.000 claims abstract description 60
- 238000009826 distribution Methods 0.000 claims abstract description 20
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical group FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims abstract description 10
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims abstract description 5
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 34
- 229910052731 fluorine Inorganic materials 0.000 claims description 34
- 239000011737 fluorine Substances 0.000 claims description 34
- 238000001125 extrusion Methods 0.000 description 42
- 238000004073 vulcanization Methods 0.000 description 30
- 238000006116 polymerization reaction Methods 0.000 description 26
- 239000000203 mixture Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- 239000000178 monomer Substances 0.000 description 16
- 230000000704 physical effect Effects 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 13
- 229920005862 polyol Polymers 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 238000004898 kneading Methods 0.000 description 10
- 150000003077 polyols Chemical class 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000012986 chain transfer agent Substances 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 238000013329 compounding Methods 0.000 description 7
- -1 polyol compound Chemical class 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 6
- 238000009778 extrusion testing Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 5
- 238000010060 peroxide vulcanization Methods 0.000 description 5
- 229920000768 polyamine Polymers 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 3
- 238000004293 19F NMR spectroscopy Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920006158 high molecular weight polymer Polymers 0.000 description 3
- 229920000609 methyl cellulose Polymers 0.000 description 3
- 239000001923 methylcellulose Substances 0.000 description 3
- 235000010981 methylcellulose Nutrition 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000010558 suspension polymerization method Methods 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000005674 electromagnetic induction Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 150000002497 iodine compounds Chemical class 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- UDPGUMQDCGORJQ-UHFFFAOYSA-N (2-chloroethyl)phosphonic acid Chemical compound OP(O)(=O)CCCl UDPGUMQDCGORJQ-UHFFFAOYSA-N 0.000 description 1
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 description 1
- JNVXRQOSRUDXDY-UHFFFAOYSA-N 1,1-diiodoethane Chemical compound CC(I)I JNVXRQOSRUDXDY-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- LLOXZCFOAUCDAE-UHFFFAOYSA-N 2-diphenylphosphorylbenzene-1,4-diol Chemical compound OC1=CC=C(O)C(P(=O)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 LLOXZCFOAUCDAE-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- UZCPNEBHTFYJNY-UHFFFAOYSA-N benzyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1CP(C=1C=CC=CC=1)C1=CC=CC=C1 UZCPNEBHTFYJNY-UHFFFAOYSA-N 0.000 description 1
- VUUQSOCJUCSVBN-UHFFFAOYSA-M benzyl(trioctyl)phosphanium;chloride Chemical compound [Cl-].CCCCCCCC[P+](CCCCCCCC)(CCCCCCCC)CC1=CC=CC=C1 VUUQSOCJUCSVBN-UHFFFAOYSA-M 0.000 description 1
- USFRYJRPHFMVBZ-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 USFRYJRPHFMVBZ-UHFFFAOYSA-M 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000007975 iminium salts Chemical group 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical group 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- FBEVECUEMUUFKM-UHFFFAOYSA-M tetrapropylazanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CCC FBEVECUEMUUFKM-UHFFFAOYSA-M 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【0001】0001
【産業上の利用分野】本発明は新規な含フッ素エラスト
マーに関する。さらに詳しくは、押出し性に優れ、耐熱
性、耐油性、耐化学薬品性に優れた加硫物を得ることが
出来る含フッ素エラストマーに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a new fluorine-containing elastomer. More specifically, the present invention relates to a fluorine-containing elastomer that has excellent extrudability and can yield a vulcanizate with excellent heat resistance, oil resistance, and chemical resistance.
【0002】0002
【従来の技術】近年、押出し加工性に優れなおかつ加硫
物において優れた耐熱性、耐油性、さらには耐メタノー
ル性などの耐化学薬品性をもったエラストマーが要求さ
れている。代表的な用途としては自動車の燃料ホースが
ある。含フッ素エラストマーは耐熱性、耐油性、耐メタ
ノール性について優れた素材であるが、押出し性の点で
充分満足のいくものではない。押出し速度を上げようと
して、分子量を下げていくと、加硫が充分にかからず満
足のいく物性が得られない。加硫が充分かかるまで分子
量をあげていくと、流動性がわるくなり押出し速度が出
なくなる。このようなジレンマを解決するための方法が
、特開平02−160810に提案されている。すなわ
ち分子量分布を多ピーク型にする方法であり、物性と押
出し加工性を両立させるには非常に有効な方法である。
しかしこの方法は、ロールなどで加硫剤などを混練する
際に分子鎖の切断が起こり、分子量が低下する場合があ
る。特に分子量の高い成分を多く含む場合に顕著である
。そのためロール混練作業時間やロール間隙の違いによ
って、押出し速度や物性のばらつきが出るといった問題
点があった。BACKGROUND OF THE INVENTION In recent years, there has been a demand for elastomers that have excellent extrusion processability and, in the form of vulcanizates, excellent heat resistance, oil resistance, and chemical resistance such as methanol resistance. A typical use is in automobile fuel hoses. Although fluorine-containing elastomers are excellent materials in terms of heat resistance, oil resistance, and methanol resistance, they are not fully satisfactory in terms of extrudability. If the molecular weight is lowered in an attempt to increase the extrusion speed, vulcanization will not be sufficient and satisfactory physical properties will not be obtained. If the molecular weight is increased until vulcanization is sufficient, the fluidity will deteriorate and the extrusion speed will not be high. A method for solving such a dilemma is proposed in Japanese Patent Laid-Open No. 02-160810. That is, this is a method of making the molecular weight distribution multi-peaked, and is a very effective method for achieving both physical properties and extrusion processability. However, in this method, when the vulcanizing agent and the like are kneaded with a roll or the like, molecular chains may be cut, resulting in a decrease in molecular weight. This is particularly noticeable when a large amount of components with high molecular weights are included. Therefore, there was a problem in that extrusion speed and physical properties varied due to differences in roll kneading operation time and roll gap.
【0003】0003
【発明が解決しようとする課題】本発明の目的は押出し
性に優れ、さらに耐熱性、耐油性、耐メタノール性に優
れさらに加硫特性、加硫物性に優れ、しかもロール混練
作業などにおいて、押出し性や物性にばらつきを生ずる
事のない含フッ素エラストマーを提供することにある。[Problems to be Solved by the Invention] The object of the present invention is to have excellent extrudability, heat resistance, oil resistance, methanol resistance, vulcanization properties, and vulcanization physical properties. The object of the present invention is to provide a fluorine-containing elastomer that does not cause variations in properties or physical properties.
【0004】0004
【課題を解決するための手段】本発明者らは、前記課題
を解決するために鋭意研究を重ねた結果、分子鎖の切断
が起こるのはある特定の分子量以上の成分であることを
見いだし、さらに研究を進めた結果、本発明を完成した
。すなわち本発明は(イ)ビニリデンフルオライド単位
と、(ロ)ヘキサフルオロプロピレン単位及び(ハ)0
〜35重量%のテトラフルオロエチレン単位からなり、
かつ(イ)単位と(ロ)単位の重量比が40:60ない
し80:20でありその分子量分布が、(a)多ピーク
型であること
(b)分子量ピークのうち、最も分子量の高いピークの
頂点の分子量が、35万以上55万以下であること(c
)重量平均分子量(Mw)と数平均分子量(Mn)との
比Mw/Mnが4以上10以下であること(d)極限粘
度数が40〜200ml/gであること(e)分子量5
万以下の成分比(M5)と極限粘度数([n])の比、
M5/[n]が0.15〜0.70であること
を特徴とする含フッ素エラストマーである。[Means for Solving the Problems] As a result of extensive research in order to solve the above problems, the present inventors have discovered that molecular chain scission occurs in components with molecular weights above a certain specific level. As a result of further research, the present invention was completed. That is, the present invention comprises (a) vinylidene fluoride units, (b) hexafluoropropylene units, and (c) 0
Consisting of ~35% by weight of tetrafluoroethylene units,
and (a) the weight ratio of units to (b) units is 40:60 to 80:20, and the molecular weight distribution is (a) multi-peak type; (b) among the molecular weight peaks, the peak with the highest molecular weight; The molecular weight of the apex of is from 350,000 to 550,000 (c
) The ratio Mw/Mn of weight average molecular weight (Mw) to number average molecular weight (Mn) is 4 or more and 10 or less (d) The intrinsic viscosity number is 40 to 200 ml/g (e) Molecular weight 5
The ratio of the component ratio (M5) of 10,000 or less and the limiting viscosity number ([n]),
The present invention is a fluorine-containing elastomer characterized in that M5/[n] is 0.15 to 0.70.
【0005】以下、詳細に本発明を説明する。本発明は
ビニリデンフルオライド(以下VDFと略記する)単位
、ヘキサフルオルプロピレン(以下HFPと略記する)
単位及び場合によりテトラフルオロエチレン(以下TF
Eと略記する)単位とからなる含フッ素エラストマーで
あって、これらの含フッ素エラストマーにおける該VD
F単位とHFP単位との割合は、重量比で40:60な
いし80:20の範囲にあることが必要である。該VD
F単位がこれよりも少ないと、重合速度が極めて遅くか
つ高分子量のものか得られにくいし、これよりも多いと
得られる含フッ素エラストマーは樹脂状となって弾性が
低下する傾向になる。また、三元系含フッ素エラストマ
ーにおいては、TFE単位の含有量は35重量%以下、
好ましくは5〜25重量%の範囲にあることが必要であ
り、この含有量が35重量%を超えると得られる含フッ
素エラストマーは、弾性が低下する傾向を生じる。
また、VDF単位とHFP単位との好ましい割合は、二
元系含フッ素エラストマーにおいては重量比55:45
から75:25の範囲で選ばれ、三元系含フッ素エラス
トマーにおいては、45:55から70:30の範囲で
選ばれる。[0005] The present invention will be explained in detail below. The present invention uses vinylidene fluoride (hereinafter abbreviated as VDF) units, hexafluoropropylene (hereinafter abbreviated as HFP) units,
Unit and optionally tetrafluoroethylene (hereinafter TF
A fluorine-containing elastomer consisting of a unit (abbreviated as E), in which the VD in these fluorine-containing elastomers is
The ratio of F units to HFP units needs to be in the range of 40:60 to 80:20 by weight. The VD
If the amount of F units is less than this, the polymerization rate is extremely slow and it is difficult to obtain a product with a high molecular weight. If the amount is more than this, the resulting fluorine-containing elastomer becomes resin-like and tends to have lower elasticity. In addition, in the ternary fluorine-containing elastomer, the content of TFE units is 35% by weight or less,
The content is preferably in the range of 5 to 25% by weight, and if the content exceeds 35% by weight, the resulting fluorine-containing elastomer tends to have reduced elasticity. Further, the preferred ratio of VDF units to HFP units is 55:45 by weight in the binary fluorine-containing elastomer.
For ternary fluorine-containing elastomers, the ratio is selected from 45:55 to 70:30.
【0006】また、この含フッ素エラストマーはその分
子量分布が多ピーク型であることが必要である。1ピー
クの分子量分布をもつ含フッ素エラストマーでは押出し
性と物性の両立は難しい。分子量を多ピーク型にするこ
とにより、高分子量成分で物性をもたせ低分子量成分で
押出し性を改善する。多ピーク型にすることにより、押
出し加工性と物性に両者を満足させることが可能になる
。[0006] Furthermore, the fluorine-containing elastomer must have a multi-peak molecular weight distribution. It is difficult to achieve both extrudability and physical properties with a fluorine-containing elastomer that has a one-peak molecular weight distribution. By making the molecular weight multi-peak, the high molecular weight component provides physical properties and the low molecular weight component improves extrudability. By making it a multi-peak type, it becomes possible to satisfy both extrusion processability and physical properties.
【0007】さらに、分子量ピークのうち、最も高い分
子量ピークの頂点の分子量が55万以下35万以上であ
ることが必要である。55万以上を頂点とする分子量ピ
ークの成分は、ロール等による混練により分子量の低下
がおこり、押出速度、押出し肌さらに物性のばらつきの
原因となる。さらに好ましくは50万以下である。また
、35万未満では実質的に物性と加工性のバランスをと
ることが難しい。好ましくは37万以上である。Furthermore, among the molecular weight peaks, the molecular weight at the top of the highest molecular weight peak must be between 550,000 and 350,000 or more. The molecular weight of components with a peak molecular weight of 550,000 or more is reduced by kneading with rolls, etc., which causes variations in extrusion speed, extrusion texture, and physical properties. More preferably, it is 500,000 or less. Moreover, if it is less than 350,000, it is difficult to achieve a substantial balance between physical properties and workability. Preferably it is 370,000 or more.
【0008】また、重量平均分子量(Mw)と数平均分
子量(Mn)との比、Mw/Mnは4以上10以下であ
ることが必要である。4未満では多ピークの各々の分子
量の差が小さすぎて物性や押出し性のコントロールが難
しく、多ピークにした効果が有効に働かない。又、10
を超えると、低分子量側のピークの分子量が低くなりす
ぎて、ロール混練時のロールへの粘着が激しくなり、ま
た加硫しにくくなるので好ましくない。さらに好ましく
は4〜8である。[0008] Furthermore, the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn), Mw/Mn, needs to be 4 or more and 10 or less. If it is less than 4, the difference in molecular weight of each of the multiple peaks is too small, making it difficult to control physical properties and extrudability, and the effect of having multiple peaks will not work effectively. Also, 10
Exceeding this is not preferable because the molecular weight of the peak on the low molecular weight side becomes too low, resulting in severe adhesion to the rolls during roll kneading and making vulcanization difficult. More preferably, it is 4-8.
【0009】また、極限粘度数は40ml/g以上20
0ml/g以下であることが必要である。極限粘度数が
40ml/g未満では低分子量成分が多くなりすぎて物
性が低下する上、ロールに対する粘着性が増大するとと
もに金型離型性が低下する。一方、200ml/gを超
えると流動性が低下し、良好な押出し成形が不可能にな
る。好ましくは50〜150ml/gである。[0009] In addition, the intrinsic viscosity is 40 ml/g or more 20
It is necessary that it is 0 ml/g or less. If the intrinsic viscosity is less than 40 ml/g, the amount of low molecular weight components will be too large, resulting in poor physical properties, as well as increased adhesion to rolls and poor mold releasability. On the other hand, if it exceeds 200 ml/g, fluidity decreases and good extrusion molding becomes impossible. Preferably it is 50 to 150 ml/g.
【0010】さらに、分子量5万以下の低分子量重合体
量M5 (重量%)と極限粘度数[η](ml/g)と
の比M5 /[η]は、0.15〜0.70、好ましく
は0.20〜0.60の範囲にあることが必要である。
このM5 及び[η]は、たがいに影響しあって押出成
形性を左右しており、M5 が大きくなると押出速度や
押出肌が改善される傾向があり、一方[η]が大きくな
ると押出速度及び押出肌ともに劣化する傾向がある。し
たがって、良好な押出成形性を有するためには、M5
/[η]の値は前記範囲にあることが必要である。この
M5 /[η]が0.15未満では押出しが困難となり
、押出速度や押出肌が著しく劣化するし、0.70を超
えるとグリーン強度が低下し、押出成形時に変化しやす
い上、加硫物の機械的強度が低下するおそれがある。Furthermore, the ratio M5/[η] of the amount M5 (wt%) of the low molecular weight polymer having a molecular weight of 50,000 or less and the intrinsic viscosity [η] (ml/g) is 0.15 to 0.70, It is preferably in the range of 0.20 to 0.60. M5 and [η] influence each other and influence extrusion moldability, and as M5 increases, extrusion speed and extrusion texture tend to improve, while as [η] increases, extrusion speed and extrusion moldability tend to improve. Both extruded skin tends to deteriorate. Therefore, in order to have good extrusion moldability, M5
The value of /[η] needs to be within the above range. If M5/[η] is less than 0.15, extrusion becomes difficult and the extrusion speed and extrusion surface deteriorate significantly. If it exceeds 0.70, the green strength decreases and changes easily during extrusion molding, and vulcanization There is a risk that the mechanical strength of the object will decrease.
【0011】本発明の含フッ素エラストマーは、例えば
、それぞれ別個に製造された高分子量重合体と低分子量
重合体とをブレンドすることによっても製造することが
できるが、懸濁重合法によって製造するのが有利である
。これは、懸濁重合法によると分子量分布の狭いピーク
のポリマーが得られやすく、多段階の重合を組み合わせ
ることにより、比較的シャープな分子量分布の多ピーク
型が得られやすいためである。The fluorine-containing elastomer of the present invention can be produced, for example, by blending a high molecular weight polymer and a low molecular weight polymer that have been produced separately, but it can also be produced by a suspension polymerization method. is advantageous. This is because suspension polymerization tends to yield a polymer with a narrow peak molecular weight distribution, and by combining multiple stages of polymerization, a multi-peak type with a relatively sharp molecular weight distribution can be easily obtained.
【0012】このように、懸濁重合法は、本発明のよう
な超高分子量重合体の含有量が少なく、かつ多ピーク型
のポリマーを得るのに適している。このような多ピーク
型のものは、重合過程において、重合圧力を変更する方
法、触媒を追添する方法、連鎖移動剤を添加する方法な
どによって得ることができるが、これらの中で、重合過
程において連鎖移動剤を添加する方法は、分子量分布の
コントロールが容易であるので好ましい。[0012] As described above, the suspension polymerization method is suitable for obtaining a multi-peak type polymer having a small content of ultra-high molecular weight polymer as in the present invention. Such a multi-peak type can be obtained by changing the polymerization pressure, adding a catalyst, adding a chain transfer agent, etc. during the polymerization process. The method of adding a chain transfer agent in the step is preferable because the molecular weight distribution can be easily controlled.
【0013】この連鎖移動剤による方法においては、例
えばバッチ重合の場合には、連鎖移動剤を全く用いない
か、又は重合初期に少量添加して重合を行い、高分子量
重合体を形成させて、所定量のポリマーを生成させたの
ち、連鎖移動剤を多量に添加することにより、低分子量
重合体を形成させる方法を用いることができる。該連鎖
移動剤としては、低級アルコール類やハロゲン化合物な
ど、従来公知のものを用いることができるが、特に連鎖
移動能力が大きいことから、ジヨードメタンやジヨード
エタンなどのヨウ素化合物、ジブロモメタンやジブロモ
エタンなどの臭素化合物が好ましく、特にジヨードメタ
ンなどのヨウ素化合物が好適である。In this method using a chain transfer agent, for example, in the case of batch polymerization, a chain transfer agent is not used at all or is added in a small amount at the beginning of the polymerization to form a high molecular weight polymer. A method can be used in which a predetermined amount of polymer is produced and then a large amount of chain transfer agent is added to form a low molecular weight polymer. As the chain transfer agent, conventionally known ones such as lower alcohols and halogen compounds can be used, but because of their particularly high chain transfer ability, iodine compounds such as diiodomethane and diiodoethane, dibromomethane and dibromoethane, etc. Bromine compounds are preferred, particularly iodine compounds such as diiodomethane.
【0014】次に、本発明の含フッ素エラストマーを製
造するための懸濁重合法の好適な1例について説明する
と、まず、所定の混合モノマー(仕込モノマー)を溶存
した不活性有機溶媒を水媒体中に分散させ、さらに懸濁
安定剤、油溶性触媒を添加し、機械的にかきまぜながら
温度を好ましくは50〜60℃に保ち、圧力が好ましく
は5〜17kg/cm2 ・Gの範囲で一定となるよう
に新たな前記混合モノマー(追添モノマー)を添加して
重合を進める。生成する含フッ素エラストマー中のモノ
マー単位の組成は仕込みモノマー組成と追添モノマー組
成との関係によって決定される。なお、仕込みモノマー
組成及び追添モノマー組成はガスクロマトグラフにより
、含フッ素エラストマー中のモノマー単位の組成は、該
エラストマーをアセトン溶解後、19F−NMRによっ
て測定する。また、重合の途中で、前記連鎖移動剤を添
加することにより、分子量分布の調整を行う。Next, a preferred example of the suspension polymerization method for producing the fluorine-containing elastomer of the present invention will be explained. First, an inert organic solvent in which a predetermined mixed monomer (feed monomer) is dissolved is added to an aqueous medium Further, a suspension stabilizer and an oil-soluble catalyst are added, and the temperature is preferably kept at 50 to 60°C while stirring mechanically, and the pressure is preferably kept constant in the range of 5 to 17 kg/cm2.G. The polymerization is proceeded by adding new mixed monomers (additional monomers) so that the polymerization is as follows. The composition of monomer units in the produced fluorine-containing elastomer is determined by the relationship between the charged monomer composition and the additional monomer composition. The charged monomer composition and additional monomer composition are measured by gas chromatography, and the composition of monomer units in the fluorine-containing elastomer is measured by 19F-NMR after dissolving the elastomer in acetone. Moreover, the molecular weight distribution is adjusted by adding the chain transfer agent during the polymerization.
【0015】この懸濁音重合法において用いられる不活
性有機溶媒としては、ラジカル連鎖移動を生じやすい炭
素−水素結合をもたない有機溶媒が用いられるが、1,
1,2−トリクロロ−1,2,2−トリフルオロエタン
が性能的にも経済的にも好ましい。懸濁安定剤としては
メチルセルロースが好ましい。油溶性触媒としては、ジ
イソプロピルパーオキシジカーボネートなどのジアルキ
ルパーオキシジカーボネートが高温の分解温度を有して
いるので好ましい。The inert organic solvent used in this suspension sonopolymerization method is an organic solvent that does not have carbon-hydrogen bonds that tend to cause radical chain transfer.
1,2-trichloro-1,2,2-trifluoroethane is preferred from both performance and economical points of view. Methylcellulose is preferred as the suspension stabilizer. As the oil-soluble catalyst, dialkyl peroxydicarbonates such as diisopropyl peroxydicarbonate are preferred because they have a high decomposition temperature.
【0016】本発明の含フッ素エラストマーはポリアミ
ン化合物、ポリオール化合物、パーオキシ化合物などで
加硫可能であり、特にポリオール加硫した場合、本発明
の含フッ素エラストマーの改善された性能が著しく発揮
される。以下、ポリオール加硫法を例として説明する。
含フッ素エラストマーに酸結合剤、ポリオール化合物、
加硫促進剤及び必要に応じて充てん剤を配合して混練、
押出成形後、加熱して加硫する。The fluorine-containing elastomer of the present invention can be vulcanized with a polyamine compound, a polyol compound, a peroxy compound, etc., and particularly when vulcanized with a polyol, the improved performance of the fluorine-containing elastomer of the present invention is significantly exhibited. Hereinafter, a polyol vulcanization method will be explained as an example. Fluorine-containing elastomer with acid binder, polyol compound,
Add vulcanization accelerator and filler if necessary and knead.
After extrusion molding, it is heated and vulcanized.
【0017】酸結合剤としては、二価の金属酸化物又は
水酸化物、例えばマグネシウム、カルシウム、亜鉛、鉛
などの酸化物又は水酸化物が用いられ、その使用量は、
エラストマー100重量部当り1〜30重量部、好まし
くは2〜20重量部の範囲で選ばれる。ポリオール化合
物としてはヒドロキノン、2,2−ビス(4−ヒドロキ
シフェニル)プロパン(ビスフェノールA)、2,2−
ビス(4−ヒドロキシフェニル)パーフルオロプロパン
(ビスフェノールAF)、4,4′−ジヒドロキシジフ
ェニルメタン、2,2−ビス(4−ヒドロイシフェニル
)ブタンなとが、エラストマー100重量部当り0.1
〜10重量部、好ましくは0.6〜5重量部の割合で用
いられる。As the acid binder, divalent metal oxides or hydroxides, such as oxides or hydroxides of magnesium, calcium, zinc, lead, etc., are used, and the amount used is as follows:
The amount is selected in the range of 1 to 30 parts by weight, preferably 2 to 20 parts by weight, per 100 parts by weight of the elastomer. Examples of polyol compounds include hydroquinone, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-
Bis(4-hydroxyphenyl) perfluoropropane (bisphenol AF), 4,4'-dihydroxydiphenylmethane, 2,2-bis(4-hydroycyphenyl)butane, etc., per 100 parts by weight of elastomer.
It is used in a proportion of 10 parts by weight, preferably 0.6 to 5 parts by weight.
【0018】加硫促進剤としては、第四オニウム塩化合
物、第四級ホスホニウム塩、第四級アンモニウム塩又は
イミニウム塩、例えばテトラメチルアンモニウムクロリ
ド、テトラエチルアンモニウムクロリド、テトラプロピ
ルアンモニウムクロリド、テトラブチルアンモニウムク
ロリド、テトラブチルアンモニウムブロミド、ビス(ベ
ンジルジフェニルホスフィン)イミニウムクロリド、テ
トラブチルホスホニウムクロリド、ベンジルトリフェニ
ルホスホニウムクロリド、ベンジルトリオクチルホスホ
ニウムクロリドなどが適当であり、エラストマー100
重量部当り0.05〜2重量部、好ましくは0.1〜1
重量部の割合で用いられる。充てん剤、補強剤としては
、例えばカーボンブラック、シリカ、クレー、タルクな
どが必要に応じて用いられる。As the vulcanization accelerator, quaternary onium salt compounds, quaternary phosphonium salts, quaternary ammonium salts or iminium salts such as tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride are used. , tetrabutylammonium bromide, bis(benzyldiphenylphosphine)iminium chloride, tetrabutylphosphonium chloride, benzyltriphenylphosphonium chloride, benzyltrioctylphosphonium chloride, etc., and elastomer 100
0.05 to 2 parts by weight, preferably 0.1 to 1 part by weight
Used in parts by weight. As fillers and reinforcing agents, for example, carbon black, silica, clay, talc, etc. are used as necessary.
【0019】本発明の含フッ素エラストマーの多ピーク
型分子量分布の低分子量側のピークの少なくとも1つが
、ヨウ素原子や臭素原子を含む連鎖移動剤を用いた重合
により形成されていると、ヨウ素原子や臭素原子はラジ
カル反応活性が高いので、過酸化物を用いるパーオキシ
ド加硫も可能となる。さらに、該含フッ素エラストマー
には低分子量重合体が含まれているので、ポリヒドロキ
シ化合物を用いるポリオール加硫法、あるいはポリアミ
ン化合物を用いるポリアミン加硫法に加え、パーオキシ
ド加硫法も同時に併用することが可能である。このよう
に、パーオキシド加硫法を併用することにより、加工性
の改善に伴って生じる加硫性低下の問題を解決すること
ができる。このパーオキシド共加硫性は、臭素タイプよ
りヨウ素タイプの方が高い。When at least one peak on the low molecular weight side of the multi-peak molecular weight distribution of the fluorine-containing elastomer of the present invention is formed by polymerization using a chain transfer agent containing an iodine atom or a bromine atom, Since bromine atoms have high radical reaction activity, peroxide vulcanization using peroxides is also possible. Furthermore, since the fluorine-containing elastomer contains a low molecular weight polymer, a peroxide vulcanization method can be used simultaneously in addition to a polyol vulcanization method using a polyhydroxy compound or a polyamine vulcanization method using a polyamine compound. is possible. In this way, by using the peroxide vulcanization method in combination, it is possible to solve the problem of decreased vulcanizability that occurs with improvement in processability. This peroxide co-vulcanization is higher in the iodine type than in the bromine type.
【0020】次に、ポリオール加硫法やポリアミン加硫
法に併用してパーオキシド加硫する場合について説明す
る。この場合、ポリオール加硫やポリアミン加硫に用い
る加硫用配合剤に加えて、パーオキシド加硫用の配合剤
である多官能性不飽和化合物、有機過酸化物及び必要に
応じて用いられる添加剤をさらに配合混練する。該多官
能性不飽和化合物としては、例えば、トリアリルシアヌ
レート、トリアリルイソシアヌレート、トリス(ジアリ
ルアミン)−s−トリアジンなどが有用であり、特にト
リアリルイソシアヌレートが好ましく用いられる。Next, the case where peroxide vulcanization is used in combination with polyol vulcanization method or polyamine vulcanization method will be explained. In this case, in addition to the vulcanizing compounding agents used for polyol vulcanization and polyamine vulcanization, polyfunctional unsaturated compounds that are compounding agents for peroxide vulcanization, organic peroxides, and additives used as necessary. Further mix and knead. As the polyfunctional unsaturated compound, for example, triallyl cyanurate, triallyl isocyanurate, tris(diallylamine)-s-triazine, etc. are useful, and triallyl isocyanurate is particularly preferably used.
【0021】有機過酸化物としては、熱によって容易に
パーオキシラジカルを発生するものが好ましく、例えば
、2,5−ジメチル−2,5−ジ(t−ブチルパーオキ
シ)ヘキシン−3、2,5−ジメチル−2,5−ジ(t
−ブチルパーオキシ)ヘキサンなどのジアルキルパーオ
キシドが好適である。また、添加剤としては、補強剤と
してのカーボンブラック、シリカ、クレー、タルクなど
を加工助剤としてのワックス類などをそれぞれ挙げるこ
とができる。[0021] The organic peroxide is preferably one that easily generates peroxy radicals by heat, such as 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3,2, 5-dimethyl-2,5-di(t
Dialkyl peroxides such as -butylperoxy)hexane are preferred. Examples of additives include carbon black, silica, clay, talc, etc. as reinforcing agents, and waxes as processing aids.
【0022】前記の含フッ素エラストマーと各種配合剤
との混合物は、ロールやバンバリミキサーなどで混練後
、押出成形して、その後加熱し加硫する。[0022] The mixture of the fluorine-containing elastomer and various compounding agents is kneaded using a roll or Banbury mixer, extrusion molded, and then heated and vulcanized.
【0023】[0023]
【実施例】次に、実施例により本発明をさらに詳細に説
明するが、本発明はこれらによってなんら限定されるも
のではない。なお、含フッ素エラストマーの各特性や加
硫物の物性、加工性は、次に示す方法により求めた。
(1)極限粘度:メチルエチルケトンを溶媒とする0.
1g/100mlの濃度溶液を毛細管粘度計を用いて3
5℃で測定する。
(2)分子量分布:液体クロマトグラフ:LC−3A型
〔島津製作所(株)製〕カラム:KF−80M(2本)
+KF−800P(プレカラム)〔昭和電工(株)製〕
検出器:ERC−7510S(エマル光学(株)製)イ
ンテグレーター:7000A(システムインスツルメン
ツ社製)
展開溶媒:テトラヒドロフラン
濃 度:0.1重量%
温 度:35℃
分子量検量線用標準ポリマー:単分散ポリスチレン各種
〔東洋曹達(株)製〕〔Mw/Mn=1.2(max)
〕
なお、図1に示すように、多ピーク型の分子量分布にお
いて、各々のピークが重なりあって高分子成分ピークが
明確に表われずショルダー状になっている場合は、クロ
マトの変曲点を高分子成分のピークとして取扱う。
(3)加硫物の機械物性
所定の配合割合の含フッ素エラストマー組成物をロール
により混練して調製したのち、金型に入れプレス加硫し
、次いで金型より取り出し、引き続きオーブン加硫して
、厚さ2mmの加硫シートを作成した。このシートから
3号ダンベル型試験片を打ち抜き、JIS−K6301
に準じて引張試験器(東洋精機(株)製〕を用い、引張
速度50cm/分で機械物性を測定した。
(4)硬度
JIS−K6301に準じて、スプリング式硬さ試験機
A形で測定した。
(5)押出試験
ブラベンダー社製エクストルーダー10DW型(D=1
9.1mm、L/D=10)を用い、チューブダイ(外
径9mm、内径8mm)のダイスを用い、スクリュー温
度80℃、ヘッド温度120℃、スクリュー回転数50
rpmの条件下で行った。EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these in any way. The properties of the fluorine-containing elastomer, the physical properties of the vulcanizate, and the processability were determined by the following methods. (1) Intrinsic viscosity: 0.0 using methyl ethyl ketone as a solvent.
A solution with a concentration of 1 g/100 ml was measured using a capillary viscometer.
Measure at 5°C. (2) Molecular weight distribution: Liquid chromatograph: LC-3A type [manufactured by Shimadzu Corporation] Column: KF-80M (2 columns)
+KF-800P (precolumn) [manufactured by Showa Denko Co., Ltd.]
Detector: ERC-7510S (manufactured by Emul Optical Co., Ltd.) Integrator: 7000A (manufactured by System Instruments) Developing solvent: Tetrahydrofuran concentration: 0.1% by weight Temperature: 35°C Standard polymer for molecular weight calibration curve: Monodisperse polystyrene Various [manufactured by Toyo Soda Co., Ltd.] [Mw/Mn=1.2 (max)
] In addition, as shown in Figure 1, in a multi-peak molecular weight distribution, if each peak overlaps and the polymer component peak does not appear clearly and has a shoulder shape, the inflection point of the chromatography may be Treated as a peak of a polymer component. (3) Mechanical properties of vulcanized product A fluorine-containing elastomer composition with a predetermined blending ratio is prepared by kneading with a roll, then put into a mold and press vulcanized, then taken out from the mold and subsequently vulcanized in an oven. A vulcanized sheet with a thickness of 2 mm was prepared. A No. 3 dumbbell-shaped test piece was punched out from this sheet, and JIS-K6301
Mechanical properties were measured using a tensile tester (manufactured by Toyo Seiki Co., Ltd.) at a tensile speed of 50 cm/min. (4) Hardness Measured using a spring type hardness tester type A according to JIS-K6301. (5) Extrusion test Extruder 10DW model manufactured by Brabender (D=1
9.1 mm, L/D = 10), using a tube die (outer diameter 9 mm, inner diameter 8 mm), screw temperature 80 ° C, head temperature 120 ° C, screw rotation speed 50.
It was carried out under the condition of rpm.
【0024】押出肌は、目視で表面肌のきめの細かさを
みて5段階(優れている順に5から1まで)で示した。
押出速度は、単位時間当りの吐出長さより、ダイスウエ
ルは、チューブ外径及び厚みより算出した。
(6)ロール粘着性
ロール粘着性は、6インチロール混練機を用いて、生ゴ
ム又は加硫剤内添ゴムをロールに巻き付かせて、そのは
がれやすさで評価した。[0024] The extruded skin was visually inspected to determine the fineness of the surface texture, and was rated in five grades (from 5 to 1 in descending order of excellence). The extrusion speed was calculated from the discharge length per unit time, and the die swell was calculated from the outer diameter and thickness of the tube. (6) Roll tackiness Roll tackiness was evaluated by wrapping raw rubber or vulcanizing agent-added rubber around a roll using a 6-inch roll kneader and evaluating how easy it was to peel off.
【0025】[0025]
【実施例1−1】電磁誘導式かくはん機を備えた内容積
約15lのオートクレーブを窒素ガスで十分に掃気し、
減圧−窒素充てんを3回繰り返して、窒素置換したのち
、減圧状態で脱酸素した純水5.44kg、1,1,2
−トリクロロ−1,2,2−トリフルオロエタン(以下
フロン113という)1.07kg及び懸濁安定剤とし
てのメチルセルロース(粘度50cp)5.4gを仕込
み、さらにジヨードメタン0.5gを仕込み600rp
mでかきまぜながら、温度50℃に保った。次いでVD
F14.5重量%、HFP79.4重量%及びTFE6
.1重量%から成る混合モノマーを仕込みガスとして、
15kg/cm2 ・Gとなるまで仕込んだ。次に触媒
として、ジイソプロピルパーオキシジカーボネート20
.1重量%を含有したフロン113溶液26.5gを圧
入し重合を開始させた。重合により圧力が14.5kg
/cm2 ・Gまで低下したらVDF43.7重量%、
HFP29.6重量%、TFE27.0重量%から成る
混合モノマーを追添ガスとして追添し、再び圧力を15
kg/cm2 ・Gに戻した。このような操作を繰り返
し重合反応を行った。[Example 1-1] An autoclave with an internal volume of about 15 liters equipped with an electromagnetic induction stirrer was sufficiently purged with nitrogen gas,
5.44 kg of pure water, 1, 1, 2, deoxygenated under reduced pressure after repeating vacuum-nitrogen filling three times and replacing with nitrogen
- 1.07 kg of trichloro-1,2,2-trifluoroethane (hereinafter referred to as Freon 113) and 5.4 g of methyl cellulose (viscosity 50 cp) as a suspension stabilizer were charged, and further 0.5 g of diiodomethane was charged, and the rotation was carried out at 600 rpm.
The temperature was maintained at 50° C. while stirring at m. Then VD
F14.5% by weight, HFP79.4% by weight and TFE6
.. A mixed monomer consisting of 1% by weight is used as a charging gas,
It was prepared until it reached 15kg/cm2・G. Next, as a catalyst, diisopropyl peroxydicarbonate 20
.. 26.5 g of Freon 113 solution containing 1% by weight was injected under pressure to initiate polymerization. The pressure is 14.5 kg due to polymerization.
/cm2 ・When it decreases to G, VDF43.7% by weight,
A monomer mixture consisting of 29.6% by weight of HFP and 27.0% by weight of TFE was added as additional gas, and the pressure was increased to 15% by weight again.
kg/cm2 - Returned to G. Such operations were repeated to perform a polymerization reaction.
【0026】重合開始後、4.5時間経過した時点で、
ジヨードメタン42.6gを添加し、同様に圧力14.
5〜15.0kg/cm2 ・Gで重合反応をさらに1
0.6時間続け、全体で15.1時間重合反応を行った
。重合反応終了後、残存する混合モノマーを掃気し、得
られた懸濁液を遠心分離機で脱水し、十分水洗したのち
、100℃で真空乾燥してエラストマー約4.4kgを
得た。得られた含フッ素エラストマーを19F−NMR
により分析したところ、VDF単位43.9重量%、H
FP単位30.6重量%、TFE単位25.5重量%で
あった。[0026] After 4.5 hours had passed after the start of polymerization,
42.6 g of diiodomethane was added and the pressure was increased to 14.6 g.
5 to 15.0 kg/cm2 ・Carry out the polymerization reaction by 1 more time with G.
The polymerization reaction continued for 0.6 hours, for a total of 15.1 hours. After the polymerization reaction was completed, the remaining mixed monomers were scavenged, and the resulting suspension was dehydrated using a centrifuge, thoroughly washed with water, and then dried under vacuum at 100°C to obtain about 4.4 kg of elastomer. The obtained fluorine-containing elastomer was subjected to 19F-NMR.
According to analysis, VDF unit was 43.9% by weight, H
The FP units were 30.6% by weight and the TFE units were 25.5% by weight.
【0027】このエラストマーの[η]は71ml/g
、分子量分布のチャートの形状は、図2に示すように2
山型であり、Mnは2.8×104 、Mw/Mnは1
3.7であった。また、高分子成分のピーク分子量は3
88000、Mnは29000、Mw/Mnは6.9で
あった。[η] of this elastomer is 71ml/g
, the shape of the molecular weight distribution chart is 2 as shown in Figure 2.
It is mountain-shaped, Mn is 2.8×104, Mw/Mn is 1
It was 3.7. In addition, the peak molecular weight of the polymer component is 3
88,000, Mn was 29,000, and Mw/Mn was 6.9.
【0028】[0028]
【実施例1−2】実施例1−1で得られたエラストマー
を、ロール混練機(ロールクリアランス0.5mm)を
用いて充分混練の後、GPCを用いて分子量分布を測定
した。高分子量成分のピーク分子量は352000、M
nは31000、Mw/Mnは8.8であり、ロール混
練前後において高分子量成分の大幅な分子量の低下は見
られなかった。[Example 1-2] The elastomer obtained in Example 1-1 was thoroughly kneaded using a roll kneader (roll clearance 0.5 mm), and then its molecular weight distribution was measured using GPC. The peak molecular weight of the high molecular weight component is 352,000, M
n was 31,000, Mw/Mn was 8.8, and no significant decrease in the molecular weight of the high molecular weight component was observed before and after roll kneading.
【0029】[0029]
【実施例1−3】実施例1−1で得られたエラストマー
に、ロール混練機(ロールクリアランス0.5mm)を
用いてポリオール加硫配合剤を配合し、一昼夜放置後さ
らに混練した。このエラストマー加硫配合物の押出試験
をおこなったところ押出速度114cm/min、押出
肌4.5、ダイスウェル内径47、厚み38であった。[Example 1-3] A polyol vulcanization compounding agent was blended into the elastomer obtained in Example 1-1 using a roll kneader (roll clearance 0.5 mm), and after being left overnight, it was further kneaded. When this elastomer vulcanized compound was subjected to an extrusion test, the extrusion speed was 114 cm/min, the extrusion surface was 4.5, the inner diameter of the die well was 47, and the thickness was 38.
【0030】また同様に、得られたエラストマーに、ロ
ール混練機(ロールクリアランス2.5mm)を用いて
ポリオール加硫配合剤を配合した。このエラストマー加
硫配合物の押出試験をおこなったところ押出速度104
cm/min、押出肌4.5、ダイスウエル内径47、
厚み41であった。ロールクリアランスの差及び一昼夜
放置後の混練の有り無しにおいても押出特性に大きな変
化は見られず、いずれの場合も優れた押出特性を示した
。Similarly, a polyol vulcanization compounding agent was blended into the obtained elastomer using a roll kneader (roll clearance 2.5 mm). An extrusion test of this elastomer vulcanized compound revealed that the extrusion speed was 104.
cm/min, extrusion skin 4.5, die well inner diameter 47,
The thickness was 41 mm. No major changes were observed in the extrusion properties regardless of the difference in roll clearance or with or without kneading after standing overnight, and excellent extrusion properties were observed in all cases.
【0031】[0031]
【実施例1−4】実施例1−1で得られたエラストマー
を、前記の方法で加硫し機械物性を測定したところ、破
断強度130kg/cm2 、伸び440%、100%
モジュラス20kg/cm2 、硬度70であった。良
好な加硫物物性が得られた。尚、加硫剤等の配合及び加
硫条件を、次に示す。[Example 1-4] The elastomer obtained in Example 1-1 was vulcanized by the method described above, and its mechanical properties were measured. The breaking strength was 130 kg/cm2, the elongation was 440%, and the mechanical properties were 100%.
It had a modulus of 20 kg/cm2 and a hardness of 70. Good physical properties of the vulcanizate were obtained. The composition of the vulcanizing agent and the vulcanization conditions are shown below.
【0032】
含フッ素エラストマー
100 重量部
高活性マグネシウム1)
3
〃 水酸化カルシウム 2)
6 〃 ビスフェノールAF
2 〃 ビス(ベンジル
ジフェニルホスフィン)
1 〃
イミニウムクロリド
SRFカ
ーボン3)
12 〃
ジメチルスルホン
2
〃 TAIC4)
0.5 〃 パーヘキサ25B−
405)
0.5 〃
熱プレス加硫
155℃×80分
オーブン加硫
180℃×3
hr (注) 1)協和化学工業(株)製品「キョ
ーワマグ50」
2)近江化学工業(株)製品「カルビット」3)旭カー
ボン(株)製品「シーストS」4)トリアリルイソシア
ヌレート
5)日本油脂(株)製品「パーヘキサ25B−40」〔
2,5−ジメチル−2,5−ジ(t−ブチルパーオキシ
)ヘキサン〕[0032] Fluorine-containing elastomer
100 parts by weight Highly active magnesium 1)
3
〃 Calcium hydroxide 2)
6 Bisphenol AF
2 〃 Bis(benzyldiphenylphosphine)
1 〃
iminium chloride
SRF carbon 3)
12 〃
dimethyl sulfone
2
〃TAIC4)
0.5 〃 Perhexa25B-
405)
0.5 〃 Heat press vulcanization
Oven vulcanization at 155℃ x 80 minutes
180℃×3
hr (Note) 1) Kyowa Mag 50, manufactured by Kyowa Chemical Industry Co., Ltd. 2) Calvit, manufactured by Ohmi Chemical Industry Co., Ltd. 3) Seast S, manufactured by Asahi Carbon Co., Ltd. 4) Triallylisocyanurate 5) Japan Yushi Co., Ltd. product “Perhexa 25B-40” [
2,5-dimethyl-2,5-di(t-butylperoxy)hexane]
【0033】[0033]
【比較例1−1】電磁誘導式かくはん機を備えた内容積
約50lのオートクレーブを窒素ガスで十分に掃気し、
減圧−窒素充てんを3回繰り返して、窒素置換したのち
、減圧状態で脱酸素した純水29.5kg、1,1,2
−トリクロロ−1,2,2−トリフルオロエタン(以下
フロン113という)4.6kg及び懸濁安定剤として
のメチルセルロース(粘度50cp)29.5gを仕込
み、480rpmでかきまぜながら、温度50℃に保っ
た。次いでVDF14.7重量%、HFP78.6重量
%及びTFE6.7重量%から成る混合モノマーを仕込
みガスとして、15kg/cm2 ・Gとなるまで仕込
んだ。次に触媒として、ジイソプロピルパーオキシジカ
ーボネート20.1重量%を含有したフロン113溶液
36.9gを圧入し重合を開始させた。重合により圧力
が14.5kg/cm2 ・Gまで低下したらVDF4
3.7重量%、HFP29.6重量%、TFE27.0
重量%から成る混合モノマーを追添ガスとして追添し、
再び圧力を15kg/cm2 ・Gに戻した。このよう
な操作を繰り返し重合反応を行った。[Comparative Example 1-1] An autoclave with an internal volume of about 50 liters equipped with an electromagnetic induction stirrer was sufficiently purged with nitrogen gas,
29.5 kg of pure water, 1, 1, 2, which was deoxidized under reduced pressure after being replaced with nitrogen by repeating decompression and nitrogen filling three times.
- 4.6 kg of trichloro-1,2,2-trifluoroethane (hereinafter referred to as Freon 113) and 29.5 g of methylcellulose (viscosity 50 cp) as a suspension stabilizer were charged, and the temperature was maintained at 50°C while stirring at 480 rpm. . Next, a monomer mixture consisting of 14.7% by weight of VDF, 78.6% by weight of HFP, and 6.7% by weight of TFE was charged as a charging gas until it reached 15 kg/cm2.G. Next, as a catalyst, 36.9 g of Freon 113 solution containing 20.1% by weight of diisopropyl peroxydicarbonate was introduced under pressure to initiate polymerization. When the pressure decreases to 14.5 kg/cm2 ・G due to polymerization, VDF4
3.7% by weight, HFP29.6% by weight, TFE27.0
Adding a mixed monomer consisting of % by weight as an additional gas,
The pressure was returned to 15 kg/cm2.G. Such operations were repeated to perform a polymerization reaction.
【0034】重合開始後、7.5時間経過した時点で、
ジヨードメタン340gを添加し、同様に圧力14.5
〜15.0kg/cm2 ・Gで重合反応をさらに15
.2時間続け、全体で22.7時間重合反応を行った。
重合反応終了後、残存する混合モノマーを掃気し、得ら
れた懸濁液を遠心分離機で脱水し、十分水洗したのち、
100℃で真空乾燥してエラストマー約30kgを得た
。
得られた含フッ素エラストマーを19F−NMRにより
分析したところ、VDF単位43.9重量%、HFP単
位30.6重量%、TFE単位25.5重量%であった
。[0034] After 7.5 hours had passed after the start of polymerization,
Add 340g of diiodomethane and similarly reduce the pressure to 14.5
〜15.0kg/cm2 ・Continue the polymerization reaction with G for another 15
.. The polymerization reaction continued for 2 hours, for a total of 22.7 hours. After the polymerization reaction is completed, the remaining mixed monomers are scavenged, and the resulting suspension is dehydrated using a centrifuge and thoroughly washed with water.
Approximately 30 kg of elastomer was obtained by vacuum drying at 100°C. When the obtained fluorine-containing elastomer was analyzed by 19F-NMR, it was found that VDF units were 43.9% by weight, HFP units were 30.6% by weight, and TFE units were 25.5% by weight.
【0035】このエラストマーの[η]は122ml/
g、分子量分布のチャートの形状は、2山型であり、M
nは2.9×104 、Mw/Mnは17.9であった
。
又、高分子成分のピーク分子量は124.6×104、
Mnは29000、Mw/Mnは17.9であった。[η] of this elastomer is 122ml/
g, the shape of the molecular weight distribution chart is two peaks, and M
n was 2.9×10 4 and Mw/Mn was 17.9. In addition, the peak molecular weight of the polymer component is 124.6×104,
Mn was 29,000, and Mw/Mn was 17.9.
【0036】[0036]
【比較例1−2】比較例1−1で得られたエラストマー
を、ロール混練機(ロールクリアランス0.5mm)を
用いて充分混練の後、GPCを用いて分子量分布を測定
した。高分子量成分のピーク分子量は486000、M
nは30000、Mw/Mnは15.3であり、ロール
混練によって高分子量成分の大幅な分子量の低下がみら
れた。[Comparative Example 1-2] The elastomer obtained in Comparative Example 1-1 was sufficiently kneaded using a roll kneader (roll clearance 0.5 mm), and then its molecular weight distribution was measured using GPC. The peak molecular weight of the high molecular weight component is 486,000, M
n was 30,000, Mw/Mn was 15.3, and a significant decrease in the molecular weight of the high molecular weight component was observed by roll kneading.
【0037】[0037]
【比較例1−3】比較例1−1で得られたエラストマー
に、ロール混練機(ロールクリアランス0.5mm)を
用いてポリオール加硫配合剤を配合し、一昼夜放置後さ
らに混練した。このエラストマー加硫配合物の押出試験
を行ったところ、押出速度149cm/min、押出肌
4.5、ダイスウェル内径27、厚み10であった。[Comparative Example 1-3] A polyol vulcanization compounding agent was blended into the elastomer obtained in Comparative Example 1-1 using a roll kneader (roll clearance 0.5 mm), and the mixture was left to stand overnight and then further kneaded. When this elastomer vulcanized compound was subjected to an extrusion test, the extrusion speed was 149 cm/min, the extrusion surface was 4.5, the inner diameter of the die well was 27, and the thickness was 10.
【0038】また同様に、比較例1−1で得られたエラ
ストマーに、ロール混練機(ロールクリアランス2.5
mm)を用いてポリオール加硫配合剤を配合した。この
エラストマー加硫配合物の押出試験を行ったところ押出
速度99cm/min、押出肌4、ダイスウェル内径3
5、厚み27であった。比較例1−1で得られたエラス
トマーはあきらかに、ロールクリアランスの差および一
昼夜放置後の混練の有り無しによって押出特性に変化が
見られた。すなわち混練度合の不十分なエラストマー加
硫配合物は押出速度が大幅に低下し、押出肌は悪くなり
、ダイスウェルは大きくなった。Similarly, the elastomer obtained in Comparative Example 1-1 was mixed with a roll kneader (roll clearance 2.5).
A polyol vulcanization compounding agent was compounded using a polyol vulcanization compound. An extrusion test of this elastomer vulcanized compound was conducted, and the extrusion speed was 99 cm/min, the extrusion surface was 4, and the die well inner diameter was 3.
5, thickness was 27. The elastomer obtained in Comparative Example 1-1 clearly showed changes in extrusion characteristics depending on the difference in roll clearance and the presence or absence of kneading after standing overnight. In other words, an elastomer vulcanized compound with an insufficient degree of kneading had a significantly reduced extrusion speed, poor extrusion texture, and large die swell.
【0039】[0039]
【実施例2〜7、比較例2】表1および表2に示す重合
条件以外は実施例1−1と同様の方法で、重合を実施し
た。得られたエラストマーのポリマー特性を表3に、同
じく押出特性・加硫物性・ロール粘着性を表4に示す。
尚、この時の加硫剤等の配合、及び加硫条件は実施例1
−4と同一とした。[Examples 2 to 7, Comparative Example 2] Polymerization was carried out in the same manner as in Example 1-1 except for the polymerization conditions shown in Tables 1 and 2. Table 3 shows the polymer properties of the obtained elastomer, and Table 4 shows the extrusion properties, vulcanization properties, and roll tack. The composition of the vulcanizing agent and the vulcanization conditions at this time are the same as in Example 1.
-4.
【0040】[0040]
【比較例3〜4】比較例として市販の押出加工に適した
含フッ素エラストマーの押出試験・加硫特性、ロール粘
着性測定の結果を表−4に示す。なお加硫配合は以下の
ようにした。
含フッ素エラストマー
:100重量部
(比較例3;ダイエルG555)
(比較例4;フローレルFT2320
)
高活性酸化マグネシウム
: 3重
量部 水酸化カルシウム
: 6重量
部 SRFカーボン
: 15重量部
上記配合以外は、実施例1−4の加硫条件と同様に実施
した。実施例2〜7のエラストマーは優れた押出特性、
加硫物性を示す。また、ロール粘着性がなく非常にロー
ル加工性が良好である。[Comparative Examples 3 and 4] Table 4 shows the results of extrusion tests, vulcanization characteristics, and roll tack measurements of commercially available fluorine-containing elastomers suitable for extrusion processing as comparative examples. The vulcanization mixture was as follows. Fluorine-containing elastomer
:100 parts by weight
(Comparative Example 3; Daiel G555)
(Comparative Example 4; Florel FT2320
)
Highly active magnesium oxide
: 3 parts by weight Calcium hydroxide
: 6 parts by weight SRF carbon
: 15 parts by weight Except for the above formulation, vulcanization was carried out under the same conditions as in Example 1-4. The elastomers of Examples 2-7 have excellent extrusion properties;
Indicates vulcanization physical properties. Furthermore, it has no roll stickiness and has very good roll processability.
【0041】比較例2、比較例3は押出特性は良好であ
るが、ロール粘着が激しくロール作業がきわめて困難で
ある。また、比較例4は押出肌が悪く、また押出速度も
遅い。Comparative Examples 2 and 3 have good extrusion properties, but roll adhesion is severe and rolling work is extremely difficult. Furthermore, Comparative Example 4 had poor extrusion texture and slow extrusion speed.
【0042】[0042]
【表1】[Table 1]
【0043】[0043]
【表2】[Table 2]
【0044】[0044]
【表3】[Table 3]
【0045】[0045]
【表4】[Table 4]
【0046】[0046]
【発明の効果】本発明の含フッ素エラストマーを用いれ
ば、押出性に優れ、なおかつ加硫物において優れた耐熱
性、耐油性、耐メタノール性をしめし、さらに機械物性
、圧縮永久歪について優れ、しかも加硫剤等を配合する
際のロール混練による押出加工性、機械物性等の変化の
少ない加硫性含フッ素エラストマー組成物を得る事がで
きる。[Effects of the Invention] When the fluorine-containing elastomer of the present invention is used, it has excellent extrudability, and also exhibits excellent heat resistance, oil resistance, and methanol resistance in the vulcanized product, as well as excellent mechanical properties and compression set. It is possible to obtain a vulcanizable fluorine-containing elastomer composition with little change in extrusion processability, mechanical properties, etc. due to roll kneading when blending a vulcanizing agent and the like.
【図1】分子量分布の一例である。FIG. 1 is an example of molecular weight distribution.
【図2】実施例1−1にて得られたエラストマーの分子
量分布である。FIG. 2 shows the molecular weight distribution of the elastomer obtained in Example 1-1.
Claims (1)
(ロ)ヘキサフルオロプロピレン単位及び(ハ)0〜3
5重量%のテトラフルオロエチレン単位からなり、かつ
(イ)単位と(ロ)単位の重量比が40:60ないし8
0:20でありその分子量分布が、 (a)多ピーク型であること (b)分子量ピークのうち、最も分子量の高いピークの
頂点の分子量が、35万以上55万以下であること(c
)重量平均分子量(Mw)と数平均分子量(Mn)との
比Mw/Mnが4以上10以下であること(d)極限粘
度数が40〜200ml/gであること(e)分子量5
万以下の成分比(M5)と極限粘度数([n])の比、
M5/[n]が0.15〜0.70であること を特徴とする含フッ素エラストマーClaim 1: (a) a vinylidene fluoride unit, (b) a hexafluoropropylene unit, and (c) 0 to 3
Consisting of 5% by weight of tetrafluoroethylene units, and the weight ratio of (a) units to (b) units is 40:60 to 8
0:20 and its molecular weight distribution is (a) multi-peak type (b) among the molecular weight peaks, the molecular weight at the top of the highest molecular weight peak is 350,000 to 550,000 (c
) The ratio Mw/Mn of weight average molecular weight (Mw) to number average molecular weight (Mn) is 4 or more and 10 or less (d) The intrinsic viscosity number is 40 to 200 ml/g (e) Molecular weight 5
The ratio of the component ratio (M5) of 10,000 or less and the limiting viscosity number ([n]),
A fluorine-containing elastomer characterized in that M5/[n] is 0.15 to 0.70.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2061691A JPH04258614A (en) | 1991-02-14 | 1991-02-14 | Fluoroelastomer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2061691A JPH04258614A (en) | 1991-02-14 | 1991-02-14 | Fluoroelastomer |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH04258614A true JPH04258614A (en) | 1992-09-14 |
Family
ID=12032182
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2061691A Pending JPH04258614A (en) | 1991-02-14 | 1991-02-14 | Fluoroelastomer |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH04258614A (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996032428A1 (en) * | 1993-10-15 | 1996-10-17 | E.I. Du Pont De Nemours And Company | Fluoroelastomer |
WO1996034902A1 (en) * | 1995-05-02 | 1996-11-07 | E.I. Du Pont De Nemours And Company | Fluoroelastomer |
WO2002055567A3 (en) * | 2001-01-10 | 2003-10-16 | Solvay | Method for two-step preparation of halogenated polymers and halogenated plurimodal polymers |
JP2007056215A (en) * | 2005-08-26 | 2007-03-08 | Daikin Ind Ltd | Peroxide-crosslinkable fluororubber |
JP2013014785A (en) * | 2012-10-22 | 2013-01-24 | Daikin Industries Ltd | Peroxide-crosslinkable fluorine-containing rubber |
US8912283B2 (en) | 2010-11-02 | 2014-12-16 | Unimatec Co., Ltd. | Fluorine-containing elastomer blend |
WO2019189233A1 (en) * | 2018-03-30 | 2019-10-03 | ダイキン工業株式会社 | Molded article having cooling-liquid-contact surface |
-
1991
- 1991-02-14 JP JP2061691A patent/JPH04258614A/en active Pending
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996032428A1 (en) * | 1993-10-15 | 1996-10-17 | E.I. Du Pont De Nemours And Company | Fluoroelastomer |
WO1996034902A1 (en) * | 1995-05-02 | 1996-11-07 | E.I. Du Pont De Nemours And Company | Fluoroelastomer |
WO2002055567A3 (en) * | 2001-01-10 | 2003-10-16 | Solvay | Method for two-step preparation of halogenated polymers and halogenated plurimodal polymers |
JP2007056215A (en) * | 2005-08-26 | 2007-03-08 | Daikin Ind Ltd | Peroxide-crosslinkable fluororubber |
US8912283B2 (en) | 2010-11-02 | 2014-12-16 | Unimatec Co., Ltd. | Fluorine-containing elastomer blend |
JP2013014785A (en) * | 2012-10-22 | 2013-01-24 | Daikin Industries Ltd | Peroxide-crosslinkable fluorine-containing rubber |
WO2019189233A1 (en) * | 2018-03-30 | 2019-10-03 | ダイキン工業株式会社 | Molded article having cooling-liquid-contact surface |
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