JPH0546375B2 - - Google Patents
Info
- Publication number
- JPH0546375B2 JPH0546375B2 JP50163683A JP50163683A JPH0546375B2 JP H0546375 B2 JPH0546375 B2 JP H0546375B2 JP 50163683 A JP50163683 A JP 50163683A JP 50163683 A JP50163683 A JP 50163683A JP H0546375 B2 JPH0546375 B2 JP H0546375B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- silicone
- group
- organic
- norbornane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920001577 copolymer Polymers 0.000 description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 239000004642 Polyimide Substances 0.000 description 11
- 229920001721 polyimide Polymers 0.000 description 11
- 229920001296 polysiloxane Polymers 0.000 description 11
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 10
- 150000004985 diamines Chemical class 0.000 description 9
- 150000002430 hydrocarbons Chemical group 0.000 description 8
- 125000000962 organic group Chemical group 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical compound C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 125000002993 cycloalkylene group Chemical group 0.000 description 3
- 125000006159 dianhydride group Chemical group 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000012212 insulator Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 2
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 2
- SGEWZUYVXQESSB-UHFFFAOYSA-N 3-methylheptane-1,7-diamine Chemical compound NCCC(C)CCCCN SGEWZUYVXQESSB-UHFFFAOYSA-N 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- -1 ether anhydride Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 150000003949 imides Chemical group 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- XGKKWUNSNDTGDS-UHFFFAOYSA-N 2,5-dimethylheptane-1,7-diamine Chemical compound NCC(C)CCC(C)CCN XGKKWUNSNDTGDS-UHFFFAOYSA-N 0.000 description 1
- YXOKJIRTNWHPFS-UHFFFAOYSA-N 2,5-dimethylhexane-1,6-diamine Chemical compound NCC(C)CCC(C)CN YXOKJIRTNWHPFS-UHFFFAOYSA-N 0.000 description 1
- YTGIXGHANIPQGU-UHFFFAOYSA-N 2-[3-(1-amino-2-methylpropan-2-yl)-4-methylphenyl]-2-methylpropan-1-amine Chemical compound CC1=CC=C(C(C)(C)CN)C=C1C(C)(C)CN YTGIXGHANIPQGU-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- QPIOXOJERGNNMX-UHFFFAOYSA-N 3-(3-aminopropylsulfanyl)propan-1-amine Chemical compound NCCCSCCCN QPIOXOJERGNNMX-UHFFFAOYSA-N 0.000 description 1
- POTQBGGWSWSMCX-UHFFFAOYSA-N 3-[2-(3-aminopropoxy)ethoxy]propan-1-amine Chemical compound NCCCOCCOCCCN POTQBGGWSWSMCX-UHFFFAOYSA-N 0.000 description 1
- GPXCORHXFPYJEH-UHFFFAOYSA-N 3-[[3-aminopropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-amine Chemical compound NCCC[Si](C)(C)O[Si](C)(C)CCCN GPXCORHXFPYJEH-UHFFFAOYSA-N 0.000 description 1
- YEEIWUUBRYZFEH-UHFFFAOYSA-N 3-methoxyhexane-1,6-diamine Chemical compound NCCC(OC)CCCN YEEIWUUBRYZFEH-UHFFFAOYSA-N 0.000 description 1
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 1
- ZWIBGDOHXGXHEV-UHFFFAOYSA-N 4,4-dimethylheptane-1,7-diamine Chemical compound NCCCC(C)(C)CCCN ZWIBGDOHXGXHEV-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- IPDXWXPSCKSIII-UHFFFAOYSA-N 4-propan-2-ylbenzene-1,3-diamine Chemical compound CC(C)C1=CC=C(N)C=C1N IPDXWXPSCKSIII-UHFFFAOYSA-N 0.000 description 1
- LQOPXMZSGSTGMF-UHFFFAOYSA-N 6004-79-1 Chemical compound C1CC2C3C(=O)OC(=O)C3C1C2 LQOPXMZSGSTGMF-UHFFFAOYSA-N 0.000 description 1
- KNDQHSIWLOJIGP-UHFFFAOYSA-N 826-62-0 Chemical compound C1C2C3C(=O)OC(=O)C3C1C=C2 KNDQHSIWLOJIGP-UHFFFAOYSA-N 0.000 description 1
- CRFXKCZAYILCOU-UHFFFAOYSA-N C[Si](O[Si](C)(C)C1C2C(C(C(C1)C2)C(=O)O)C(=O)O)(C)C1C2C(C(C(C1)C2)C(=O)O)C(=O)O Chemical compound C[Si](O[Si](C)(C)C1C2C(C(C(C1)C2)C(=O)O)C(=O)O)(C)C1C2C(C(C(C1)C2)C(=O)O)C(=O)O CRFXKCZAYILCOU-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- YMHMDTCJFJDMPW-UHFFFAOYSA-N [butyl(methyl)silyl]oxy-trimethylsilane Chemical compound CCCC[SiH](C)O[Si](C)(C)C YMHMDTCJFJDMPW-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- CBLAIDIBZHTGLV-UHFFFAOYSA-N dodecane-2,11-diamine Chemical compound CC(N)CCCCCCCCC(C)N CBLAIDIBZHTGLV-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KMBPCQSCMCEPMU-UHFFFAOYSA-N n'-(3-aminopropyl)-n'-methylpropane-1,3-diamine Chemical compound NCCCN(C)CCCN KMBPCQSCMCEPMU-UHFFFAOYSA-N 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- CHWKGJOTGCSFNF-UHFFFAOYSA-N norbornene anhydride Chemical compound C1CC2C3C(=O)OC(=O)C3=C1C2 CHWKGJOTGCSFNF-UHFFFAOYSA-N 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229910052990 silicon hydride Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Silicon Polymers (AREA)
Description
請求の範囲
1 次式():
のノルボルナン終端ポリジオルガノシロキサンと
次式():
のポリイミドとが化学結合してなるシリコーン−
イミド共重合体。
式()中のRは一価C(1-13)炭化水素基及び一
価置換C(1-13)炭化水素基から選択され、R1〜R6
水素、ハロゲン及び同じまたは異なる一価C(1-13)
炭化水素基及び一価置換C(1-13)炭化水素基から選
択され、R7は(a)6〜20個の炭素原子を有する芳
香族炭化水素基及びそのハロゲン化誘導体、(b)2
〜20個の炭素原子を有するアルキレン基及びシク
ロアルキレン基、C(2-8)アルキレン終端ポリジオ
ルガノシロキサン、及び(c)次式:
に包含される二価の基よりなる群から選択される
二価C(2-20)有機基であり、Q′は
−O−、Claim 1 Formula (): Norbornane-terminated polydiorganosiloxane with the following formula (): Silicone formed by chemical bonding with polyimide.
Imide copolymer. R in formula () is selected from a monovalent C (1-13) hydrocarbon group and a monovalent substituted C (1-13) hydrocarbon group, R 1 to R 6
Hydrogen, halogen and the same or different monovalent C (1-13)
selected from hydrocarbon groups and monovalently substituted C (1-13) hydrocarbon groups, R 7 being (a) aromatic hydrocarbon groups having 6 to 20 carbon atoms and halogenated derivatives thereof; (b) 2
alkylene and cycloalkylene groups having ~20 carbon atoms, C (2-8) alkylene-terminated polydiorganosiloxanes, and (c) the following formula: is a divalent C (2-20) organic group selected from the group consisting of divalent groups included in
【式】−S−及び
−CXH2X−
よりなる群から選択される基であり、xは1〜5
の整数であり、Zは−O−及び−C(R1)2−から
選択される二価の基であり、nは1〜2000に等し
い整数であり;
式()中のQは[Formula] A group selected from the group consisting of -S- and -C X H 2X -, where x is 1 to 5
is an integer of , Z is a divalent group selected from -O- and -C(R 1 ) 2 -, n is an integer equal to 1 to 2000; Q in formula () is
【式】および[expression] and
【式】
よりなる群から選択される四価有機基であり、D
は
−O−、−S−、[Formula] is a tetravalent organic group selected from the group consisting of D
is -O-, -S-,
【式】【formula】
【式】−OR9O−及び
から選択される基であり、R8は水素及びRから
選択され、R9は[Formula] −OR 9 O− and R 8 is selected from hydrogen and R 9 is a group selected from
【式】【formula】
及び一般式;
の二価有機基よりなる群から選択される基であ
り、Xは次式:
−CYH2Y−、 and general formula; is a group selected from the group consisting of divalent organic groups, and X is of the following formula: -C Y H 2Y -,
【式】及び
−S−、
の二価の基よりなる群から選択される基であり、
mは0または1であり、yは1〜5の整数であ
り、R7は(a)6〜20個の炭素原子を有する芳香族
炭化水素基及びそのハロゲン化誘導体、(b)2〜20
個の炭素原子を有するアルキレン基及びシクロア
ルキレン基、C(2-8)アルキレン終端ポリジオルガ
ノシロキサン、及び(c)次式:
に包含される二価の基よりなる群から選択される
二価C(2-20)有機基であり、Q′は
−O−、A group selected from the group consisting of divalent groups of [Formula] and -S-,
m is 0 or 1, y is an integer of 1 to 5, and R7 is (a) an aromatic hydrocarbon group having 6 to 20 carbon atoms and a halogenated derivative thereof, (b) 2 to 20
alkylene and cycloalkylene groups having C (2-8) alkylene-terminated polydiorganosiloxanes, and (c) the following formula: is a divalent C (2-20) organic group selected from the group consisting of divalent groups included in
【式】−S−及び
−CXH2X−
よりなる群から選択される基であり、xは1〜5
の整数であり、aは1〜1000に等しい整数であ
り、bは0〜200に等しい整数であり、a+bの
和は10〜1000に等しい。
2 Rがメチルである特許請求の範囲第1項記載
のシリコーン−イミド共重合体。
3 Qが
である特許請求の範囲第1項記載のシリコーン−
イミド共重合体。
4 Qが
である特許請求の範囲第1項記載のシリコーン−
イミド共重合体。
5 R7が
である特許請求の範囲第1項記載のシリコーン−
イミド共重合体。
6 R7が
である特許請求の範囲第1項記載のシリコーン−
イミド共重合体。
7 R1〜R6が水素で、Zが−CH2−である特許
請求の範囲第1項記載のシリコーン−イミド共重
合体。
8 次式のノルボルナン終端ポリジオルガノシロ
キサンが化学結合してなる特許請求の範囲第1項
記載のシリコーン−イミド共重合体。
式中R7は二価のC(2-20)有機基である。
9 R7が
である特許請求の範囲第8項記載のシリコーン−
イミド共重合体。
10 R7が
である特許請求の範囲第8項記載のシリコーン−
イミド共重合体。
関連出願の提示
本出願は、同日付で出願され本発明と同一譲受
人に譲渡された本発明者の特表昭59−501208「シ
リルノルボルナン無水物および製造方法」に関連
した出願である。
発明の背景
本発明は、ノルボルナン無水物終端オルガノポ
リシロキサンおよび有機ジアミンの使用に基づく
オルガノポリシロキサン−ポリイミド共重合体に
関する。
本発明以前には、Holubの米国特許第3325450
号およびHeathらの米国特許第3847867号に示さ
れているように、芳香族ビス(無水物)とアミン
オルガノ終端ポリジオルガノシロキサンとの反応
によつてシリコーン−ポリイミド共重合体を製造
した。例えばHolubは他のジアミン、例えばm−
フエニレンジアミンの使用と共にアミノプロピル
ポリジメチルシロキサンおよびアミンブチルテト
ラメチルジシロキサンを使用することを示してい
る。このようなシリコーン−ポリイミドブロツク
重合体の製造により、例えば耐熱性電気絶縁体と
して有用な価値の高い組成物が得られる。
関連出願特表昭59−501208号公報に示されてい
るように、次式:
〔式中のRは一価C(1-13)炭化水素基および一価置
換C(1-13)炭化水素基から選択され、R1〜R6は水
素、ハロゲンおよび同じまたは異なる一価C(1-13)
炭化水素基および一価置換C(1-13)炭化水素基から
選択され、Zは−O−および−C(R1)2−から選
択される二価の基であり、YはRおよび
から選択される基であり、nは0〜2000に等しい
整数、mは0〜500に等しい整数であり、n+m
の和は0〜2000に等しい〕のノルボルナン終端ポ
リジオルガノシロキサンは、次の反応式で示され
るように、白金触媒の存在下でノルボンネン無水
物およびその誘導体と水素化珪素とのヒドロシラ
ン化反応(hydrosilation)によつて形成できる。
ここでR1〜R6、Zおよびnは前記定義の通り。
R内に包含される基の例には、アリール基およ
びハロゲン化アリール基、例えばフエニル、クロ
ロフエニル、トリル、キシリル、ビフエニル、ナ
フチルなど;アルケニル基、例えばビニル、アリ
ル、シクロヘキセニルなど;C(1-8)アルキル基お
よびハロゲン化アルキル、例えばメチル、エチ
ル、プロピル、ブチル、オクチルなどがある。
R1〜R6内に包含される基は、例えば水素、ク
ロロおよび上で定義した通りのR基である。
関連出願特表昭59−501208号公報に示された別
の方法は、nが2000より小さい式(1)の範囲内に二
無水物を環状オルガノポリシロキサン、例えばオ
クタメチルシクロテトラシロキサンと酸触媒、例
えば硫酸の存在下で平衡化反応させる方法であ
る。
本発明は、熱酸化安定性に優れ熱変形温度が非
常に高いシリコーン−ポリイミド共重合体が、式
(1)のノルボルナン無水物終端ポリジオルガノシロ
キサンおよび次式:
NH2R7NH2 (2)
の有機ジアミンおよび所望に応じて次式:
の有機二無水物間の反応を行うことによつて形成
できるとの知見に基づく。ここでQは[Formula] A group selected from the group consisting of -S- and -C X H 2X -, where x is 1 to 5
, a is an integer equal to 1 to 1000, b is an integer equal to 0 to 200, and the sum of a+b is equal to 10 to 1000. 2. The silicone-imide copolymer according to claim 1, wherein R is methyl. 3 Q is The silicone according to claim 1 which is
Imide copolymer. 4 Q is The silicone according to claim 1 which is
Imide copolymer. 5 R 7 The silicone according to claim 1 which is
Imide copolymer. 6 R 7 is The silicone according to claim 1 which is
Imide copolymer. 7. The silicone-imide copolymer according to claim 1, wherein R1 to R6 are hydrogen and Z is -CH2- . 8. The silicone-imide copolymer according to claim 1, which is formed by chemically bonding norbornane-terminated polydiorganosiloxane of the following formula. In the formula, R 7 is a divalent C (2-20) organic group. 9 R 7 The silicone according to claim 8 which is
Imide copolymer. 10 R 7 The silicone according to claim 8 which is
Imide copolymer. Presentation of related applications This application is related to the inventor's Japanese Patent Publication No. 59-501208 "Silynorbornane Anhydride and Manufacturing Method" filed on the same date and assigned to the same assignee as the present invention. BACKGROUND OF THE INVENTION The present invention relates to organopolysiloxane-polyimide copolymers based on the use of norbornane anhydride-terminated organopolysiloxanes and organic diamines. Prior to this invention, Holub U.S. Patent No. 3,325,450
Silicone-polyimide copolymers were prepared by the reaction of aromatic bis(anhydrides) with amine organo-terminated polydiorganosiloxanes as shown in US Pat. No. 3,847,867 to Heath et al. For example, Holub can be used with other diamines, such as m-
The use of aminopropylpolydimethylsiloxane and the amine butyltetramethyldisiloxane is shown along with the use of phenylenediamine. The preparation of such silicone-polyimide block polymers results in valuable compositions useful, for example, as high temperature electrical insulators. As shown in the related Japanese Patent Application Publication No. 59-501208, the following formula: [wherein R is selected from a monovalent C (1-13) hydrocarbon group and a monovalent substituted C (1-13) hydrocarbon group, and R 1 to R 6 are hydrogen, halogen, and the same or different monovalent C (1-13)
selected from hydrocarbon groups and monovalent substituted C (1-13) hydrocarbon groups, Z is a divalent group selected from -O- and -C(R 1 ) 2 -, Y is R and n is an integer equal to 0 to 2000, m is an integer equal to 0 to 500, and n+m
equal to 0 to 2000], the norbornane-terminated polydiorganosiloxane is produced by a hydrosilation reaction between norbornene anhydride and its derivatives and silicon hydride in the presence of a platinum catalyst, as shown in the following reaction formula. ) can be formed by Here, R 1 to R 6 , Z and n are as defined above. Examples of groups encompassed within R include aryl and halogenated aryl groups, such as phenyl, chlorophenyl, tolyl, xylyl, biphenyl, naphthyl, etc.; alkenyl groups, such as vinyl, allyl, cyclohexenyl, etc.; C (1- 8) Alkyl groups and alkyl halides, such as methyl, ethyl, propyl, butyl, octyl, etc. Groups included within R 1 to R 6 are, for example, hydrogen, chloro and R groups as defined above. Another method disclosed in related Japanese Patent Publication No. 59-501208 is to combine a dianhydride within the range of formula (1) where n is less than 2000 with a cyclic organopolysiloxane, such as octamethylcyclotetrasiloxane, and an acid catalyst. For example, this is a method in which an equilibration reaction is carried out in the presence of sulfuric acid. The present invention uses a silicone-polyimide copolymer with excellent thermal oxidative stability and a very high heat distortion temperature, which has the formula
(1) a norbornane anhydride-terminated polydiorganosiloxane of the formula: NH 2 R 7 NH 2 (2) an organic diamine of the formula: Based on the knowledge that it can be formed by carrying out a reaction between organic dianhydrides. Here Q is
【式】および[expression] and
【式】
よりなる群から選択される四価有機基であり、D
は
−O−、−S−、[Formula] is a tetravalent organic group selected from the group consisting of D
is -O-, -S-,
【式】−C−、− OR9O− および[Formula] -C-, -OR 9 O- and
【式】
から選択される基であり、R8は水素およびRか
ら選択され、R9はis a group selected from [Formula], R 8 is selected from hydrogen and R, and R 9 is
【式】【formula】
および一般式:
の二価有機基よりなる群から選択される基であ
り、Xは次式:
−CyH2y−、 and general formula: is a group selected from the group consisting of divalent organic groups of the following formula: -C y H 2y -,
【式】および−S−
の二価の基よりなる群から選択される基であり、
mは0または1で、yは1〜5の整数で、R7は
(a)6〜20個の炭素原子を有する芳香族炭化水素基
およびそのハロゲン化誘導体、(b)2〜20個の炭素
原子を有するアルキレン基およびシクロアルキレ
ン基、C(2-8)アルキレン終端ポリジオルガノシロ
キサン、および(c)次式:
に包含される二価の基よりなる群から選択される
二価C(2-20)有機基であり、Q′は
−O−、A group selected from the group consisting of a divalent group of [Formula] and -S-,
m is 0 or 1, y is an integer from 1 to 5, R 7 is
(a) Aromatic hydrocarbon groups and halogenated derivatives thereof having 6 to 20 carbon atoms, (b) Alkylene and cycloalkylene groups having 2 to 20 carbon atoms, C (2-8) alkylene termination polydiorganosiloxane, and (c) the following formula: is a divalent C (2-20) organic group selected from the group consisting of divalent groups included in
【式】−S−および−CX
H2X−
よりなる群から選択される基であり、xは1〜5
の整数である。
発明の開示
式(1)のノルボルナン終端ポリジオルガノシロキ
サンから、次式のノルボルナン終端ポリジオルガ
ノシロキサンを含むシリコーン−ポリイミド共重
合体が予想された。
ここでR〜R7、Z、mおよびnは前記定義の
通り、Y′はRおよび次式:
を有する基から選択される。
本発明に包含されるシリコーン−イミド共重合
体は、次式:
のノルボルナン終端ポリジオルガノシロキサンと
次式:
のポリイミドとが化学結合してなる。ここでR〜
R7、QおよびZは前記定義の通りnは1〜2000
に等しい整数、aは1〜1000に等しい整数、bは
0〜200に等しい整数であり、a+bの和は10〜
1000に等しい。
本発明の実施にあたつて式(1)のノルボルナン無
水物終端シロキサンと組合せて使用できる式(3)の
有機二無水物は、例えばピロメリツト酸二無水
物、ベンゾフエノン二無水物、本発明と同じ譲受
人に譲渡されたHeathらの米国特許第3879428号
の芳香族ビス(エーテル無水物)、次式:
の二無水物、およびこれらの混合物である。ここ
でR7およびR8は前記定義の通り。
式(2)の有機ジアミンに含まれる化合物は、例え
ば次の通り。
m−フエニレンジアミン、
p−フエニレンジアミン、
4,4′−ジアミノジフエニルプロパン、
4,4′−ジアミノジフエニルメタン、
ベンジジン、
4,4′−ジアミノジフエニルスルフイド
4,4′−ジアミノジフエニルスルホン、
4,4′−ジアミノジフエニルエーテル、
1,5−ジアミノナフタレン、
3,3′−ジメチルベンジジン、
3.3′−ジメトキシベンジジン、
2,4−ジアミノトルエン、
2,6−ジアミノトルエン、
2,4−ビス(アミノ−t−ブチル)トルエン、
1,3−ジアミノ−4−イソプロピルベンゼン、
1,2−ビス(3−アミノプロポキシ)エタン、
m−キシリレンジアミン、
p−キシリレンジアミン、
ビス(4−アミノシクロヘキシル)メタン、
デカメチレンジアミン、
3−メチルヘプタメチレンジアミン、
4,4−ジメチルヘプタメチレンジアミン、
2,11−ドデカンジアミン、
2,2−ジメチルプロピレンジアミン、
オクタメチレンジアミン、
3−メトキシヘキサメチレンジアミン、
2,5−ジメチルヘキサメチレンジアミン、
2,5−ジメチルヘプタメチレンジアミン、
3−メチルヘプタメチレンジアミン、
5−メチルノナチレンジアミン、
1,4−シクロヘキサンジアミン、
1,15−オクタデカンジアミン、
ビス(3−アミノプロピル)スルフイド、
N−メチル−ビス(3−アミノプロピル)アミ
ン、
ヘキサメチレンジアミン、
ヘプタメチレンジアミン、
2,4−ジアミノトルエン、
ノナメチレンジアミン、
2,6−ジアミノトルエン、
ビス−(3−アミノプロピル)テトラメチルジシ
ロキサン
など。
シリコーン−ポリイミド共重合体は2工程の手
順で合成でき、ほゞ等モル量の式(2)の有機ジアミ
ンおよび式(1)のノルボルナン終端ポリジオルガノ
シロキサンの反応を、または所望に応じて式(3)の
有機二無水物と共に、有機ジアミンと二無水物の
合計モル数をほゞ同じにし、周囲温度で不活性有
機溶剤の存在下で行う。室温で最初に形成された
中間体ポリアミド酸を次に高温、例えば150℃〜
220℃で環化脱水する。
シリコーン−イミド共重合体を形成するのに使
用できる別の方法では、ほゞ等モル量の式(2)の有
機ジアミンおよびノルボルナン二無水物および所
望に応じて他の有機二無水物を不活性有機溶剤、
例えばo−ジクロロベンゼン、m−クレゾールな
どの中で還流させる。
双極性中性溶剤、例えばジメチルホルムアミ
ド、ジメチルアセトアミド、N−メチルピロリド
ンをプレポリマーの製造に使用することができ
る。ノルボルナン無水物終端ポリジオルガノシオ
ロサンと少くとも1種の他の有機二無水物とを
種々のモル割合で配合したものを、ぼゞ等モル量
の有機ジアミンと反応させて広範なシリコーン−
ポリイミドブロツク重合体を生成することができ
る。
本発明のシリコーン−ポリイミド共重合体は、
電気導体用の絶縁体、接着剤、成形用コンパウン
ド、コーテイングとして、また積層品および強靭
なエラストマーを製造するために使用することが
できる。
当業者が本発明をよく実施できるように、以下
に実施例を限定としてでなく、例示として示す。
部はすべて重量部である。
実施例
69.4g(0.42モル)の5−ノルボルネン−2,
3−ジカルボン酸無水物、26.8g(0.2モル)の
1,1,3,3−テトラメチルジシロキサンおよ
び100mlの乾燥クロロベンゼンの混合物に、かき
まぜながら、本発明と同じ譲受人に譲渡された
Karstedtの米国特許第3775442号に従つて調製し
た5%白金触媒10滴を加えた。得られた混合物を
かきまぜながら70〜80℃に4時間、次いで100〜
110℃に1夜加熱した。冷却後、カーボンブラツ
クを加え、溶液を室温で30分間かきまぜた。過
し、溶剤を真空ポンプで100℃で除去し、乾燥ジ
エチルエーテルを加えたところ、白色の結晶質固
体が沈澱した。製造法に基づいて、この生成物は
次式を有する5,5′−(1,1,3,3−テトラ
メチル−1,3−ジシロキサンジイル)−ビス−
ノルボルナン−2,3−ジカルボン酸無水物であ
つた。
ブロツク共重合体を含めて一連のシリコーン−
イミド共重合体を、上記5,5′−(1,1,3,
3−テトラメチル−1,3−ジシロキサンジイ
ル)−ビス−ノルボルナン−2,3−ジカルボン
酸二無水物(以下NSDAと称す)およびベンゾ
フエソンテトラカルボン酸二無水物(BPDA)
の種々の混合物から製造した。
0.991g(5×10-3モル)のメチレンジアニリ
ンおよび5mlのジメチルホルムアミドの溶液に、
窒素中でかきまぜながら、0.457g(10-3モル)
のNSDA、1.289g(4×10-3モル)のBPDAお
よび5mlのジメチルホルムアミドの混合物を加え
た。得られた溶液を室温で2時間かきまぜた。シ
リコーン−アミド酸共重合体が得られた。次に溶
液をガラス皿に注ぎ、窒素流中に保つた炉内で80
℃で1時間、次いで150℃で2時間乾燥した。製
造法、IRおよびNMR分析に基づいて、実質的に
次式:
のノルボルナン終端ジメチルシロキサン単位と次
式:
のイミド単位とが化学結合してなるシリコーン−
ポリイミド共重合体が得られた。
同じ手順を繰返して、次式で示されるような、
別のシリコーン−イミドブロツク共重合体を製造
した。
これら共重合体のガラス転移温度(Tg)を差
動走査熱量法(DSC)で測定し、下記の表に示
す。下表には上式中のb、cおよびdの値も示
す。これら共重合体の熱酸化安定性を熱重量分析
(TGA)で測定した。これら共重合体のN2およ
び空気中での10%減量温度も示す。[Formula] A group selected from the group consisting of -S- and -C X H 2X -, where x is 1 to 5
is an integer. Disclosure of the Invention From the norbornane-terminated polydiorganosiloxane of formula (1), a silicone-polyimide copolymer containing a norbornane-terminated polydiorganosiloxane of the following formula was predicted. Here, R to R 7 , Z, m and n are as defined above, and Y' is R and the following formula: selected from the group having The silicone-imide copolymer encompassed by the present invention has the following formula: Norbornane-terminated polydiorganosiloxane with the following formula: is chemically bonded with polyimide. Here R~
R 7 , Q and Z are as defined above, n is 1 to 2000
an integer equal to , a is an integer equal to 1 to 1000, b is an integer equal to 0 to 200, and the sum of a + b is 10 to
Equals 1000. In carrying out the present invention, the organic dianhydride of formula (3) that can be used in combination with the norbornane anhydride-terminated siloxane of formula (1) is, for example, pyromellitic dianhydride, benzophenone dianhydride, the same as in the present invention. Aromatic bis(ether anhydride) of Heath et al., U.S. Pat. No. 3,879,428, assigned to Assignee, formula: dianhydrides, and mixtures thereof. Here, R 7 and R 8 are as defined above. Examples of the compounds contained in the organic diamine of formula (2) are as follows. m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, benzidine, 4,4'-diaminodiphenyl sulfide 4,4'- Diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 2,4-diaminotoluene, 2,6-diaminotoluene, 2,4-bis(amino-t-butyl)toluene, 1,3-diamino-4-isopropylbenzene, 1,2-bis(3-aminopropoxy)ethane, m-xylylenediamine, p-xylylenediamine, Bis(4-aminocyclohexyl)methane, decamethylenediamine, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 2,11-dodecanediamine, 2,2-dimethylpropylenediamine, octamethylenediamine, 3- Methoxyhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 3-methylheptamethylenediamine, 5-methylnonethylenediamine, 1,4-cyclohexanediamine, 1,15-octadecanediamine , bis(3-aminopropyl) sulfide, N-methyl-bis(3-aminopropyl)amine, hexamethylenediamine, heptamethylenediamine, 2,4-diaminotoluene, nonamethylenediamine, 2,6-diaminotoluene, bis -(3-aminopropyl)tetramethyldisiloxane, etc. Silicone-polyimide copolymers can be synthesized in a two-step procedure, involving the reaction of approximately equimolar amounts of an organic diamine of formula (2) and a norbornane-terminated polydiorganosiloxane of formula (1), or optionally Together with the organic dianhydride in step 3), the total number of moles of organic diamine and dianhydride is approximately the same, and the reaction is carried out at ambient temperature in the presence of an inert organic solvent. The intermediate polyamic acid initially formed at room temperature is then heated to a higher temperature, e.g.
Cyclization and dehydration at 220℃. Another method that can be used to form the silicone-imide copolymer involves inactivating approximately equimolar amounts of the organic diamine of formula (2) and norbornane dianhydride and optionally other organic dianhydrides. Organic solvent,
For example, it is refluxed in o-dichlorobenzene, m-cresol, or the like. Dipolar neutral solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone can be used in the preparation of the prepolymer. Blends of norbornane anhydride-terminated polydiorganosiolosan and at least one other organic dianhydride in various molar proportions are reacted with equimolar amounts of organic diamines to form a wide range of silicone-
Polyimide block polymers can be produced. The silicone-polyimide copolymer of the present invention is
It can be used as an insulator, adhesive, molding compound, coating for electrical conductors, and to produce laminates and tough elastomers. The following examples are presented by way of illustration and not by way of limitation, to enable those skilled in the art to better practice the invention.
All parts are parts by weight. Example 69.4 g (0.42 mol) of 5-norbornene-2,
3-dicarboxylic anhydride, 26.8 g (0.2 mol) of 1,1,3,3-tetramethyldisiloxane and 100 ml of dry chlorobenzene, with stirring, are added to a mixture of the same assignee as the present invention.
Ten drops of 5% platinum catalyst prepared according to Karstedt US Pat. No. 3,775,442 were added. The resulting mixture was heated to 70-80°C for 4 hours with stirring, then to 100-80°C for 4 hours.
Heated to 110°C overnight. After cooling, carbon black was added and the solution was stirred for 30 minutes at room temperature. The solvent was removed with a vacuum pump at 100° C. and dry diethyl ether was added to precipitate a white crystalline solid. Based on the method of preparation, the product is 5,5'-(1,1,3,3-tetramethyl-1,3-disiloxanediyl)-bis-
It was norbornane-2,3-dicarboxylic acid anhydride. A range of silicones including block copolymers
The above 5,5′-(1,1,3,
3-Tetramethyl-1,3-disiloxanediyl)-bis-norbornane-2,3-dicarboxylic dianhydride (hereinafter referred to as NSDA) and benzofethonetetracarboxylic dianhydride (BPDA)
prepared from various mixtures of. In a solution of 0.991 g (5 x 10 -3 mol) methylene dianiline and 5 ml dimethylformamide,
0.457g (10 -3 mol) while stirring in nitrogen
of NSDA, 1.289 g (4 x 10 -3 moles) of BPDA and 5 ml of dimethylformamide were added. The resulting solution was stirred at room temperature for 2 hours. A silicone-amic acid copolymer was obtained. The solution was then poured into a glass dish and placed in a furnace kept under nitrogen flow for 80 min.
It was dried at 150°C for 1 hour and then at 150°C for 2 hours. Based on the manufacturing method, IR and NMR analysis, essentially the following formula: with norbornane-terminated dimethylsiloxane units of the following formula: Silicone formed by chemically bonding imide units of
A polyimide copolymer was obtained. By repeating the same procedure, we get the following formula:
Another silicone-imide block copolymer was prepared. The glass transition temperatures (T g ) of these copolymers were measured by differential scanning calorimetry (DSC) and are shown in the table below. The table below also shows the values of b, c and d in the above formula. The thermo-oxidative stability of these copolymers was measured by thermogravimetric analysis (TGA). Also shown are the 10% weight loss temperatures in N2 and air for these copolymers.
【表】
上記の結果から、本発明のシリコーン−イミド
共重合体を、優れた酸化安定性を有する金属導体
用高温絶縁体として使用できることがわかる。例
えば、銅線をシリコーン−アミド酸共重合体のジ
メチルホルムアミド溶液に浸漬し、溶液から引抜
き、空気乾燥する。被覆銅線を次に200℃に加熱
して銅線上のアミド酸被膜をイミド状態に転化す
る。得られたシリコーン−イミド共重合体被膜は
優れた酸化安定性を有する優れた高温絶縁体であ
る。
上記実施例は本発明のシリコーン−イミド共重
合体の非常に多数の例の数例に言及しているにす
ぎないが、本発明は、これらの実施例に先立つ説
明で既に教示した通りに、式(1)のノルボルナン無
水物終端ポリジオルガノシロキサンを式(2)の有機
ジアミンと、また所望に応じて式(1)のノボルナン
無水物終端ポリジオルガノシロキサンを式(3)の他
の有機二無水物と混合して使用することに基づ
く、ブロツク共重合体を含む極めて広範な種々の
シリコーン−イミド共重合体に関することを理解
すべきである。[Table] The above results show that the silicone-imide copolymer of the present invention can be used as a high-temperature insulator for metal conductors having excellent oxidation stability. For example, a copper wire is dipped into a dimethylformamide solution of a silicone-amic acid copolymer, pulled out of the solution, and air-dried. The coated copper wire is then heated to 200°C to convert the amic acid coating on the copper wire to an imide state. The resulting silicone-imide copolymer coating is an excellent high temperature insulator with excellent oxidative stability. Although the above examples refer to only a few of the numerous examples of silicone-imide copolymers of the present invention, the present invention, as already taught in the description preceding these examples, The norbornane anhydride-terminated polydiorganosiloxane of formula (1) is combined with an organic diamine of formula (2), and optionally the nobornane anhydride-terminated polydiorganosiloxane of formula (1) is combined with another organic dianhydride of formula (3). It should be understood that there is a wide variety of silicone-imide copolymers, including block copolymers, for use in admixture with silicone-imide copolymers.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US395933FREGB | 1982-07-07 | ||
PCT/US1983/000507 WO1984000374A1 (en) | 1982-07-07 | 1983-04-11 | Silicone-imide copolymers and method for making |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP4171462A Division JPH0713144B2 (en) | 1983-04-11 | 1992-05-20 | Polydiorganosiloxane for silicone-imide copolymer |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS59501215A JPS59501215A (en) | 1984-07-12 |
JPH0546375B2 true JPH0546375B2 (en) | 1993-07-13 |
Family
ID=22174982
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP50163683A Granted JPS59501215A (en) | 1982-07-07 | 1983-04-11 | Silicone-imide copolymer and manufacturing method |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS59501215A (en) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0243221A (en) * | 1988-06-10 | 1990-02-13 | Occidental Chem Corp | New soluble polyimide siloxane and its manufacture and use |
JPH0598234A (en) * | 1991-10-14 | 1993-04-20 | Sumitomo Bakelite Co Ltd | Thermally contact-bondable filmy adhesive |
JPH0598235A (en) * | 1991-10-14 | 1993-04-20 | Sumitomo Bakelite Co Ltd | Thermally contact-bondable filmy adhesive |
JP2740064B2 (en) * | 1991-10-14 | 1998-04-15 | 住友ベークライト株式会社 | Thermo-compressible film adhesive |
JP2716609B2 (en) * | 1991-10-14 | 1998-02-18 | 住友ベークライト株式会社 | Thermo-compressible film adhesive |
JPH05117597A (en) * | 1991-10-29 | 1993-05-14 | Sumitomo Bakelite Co Ltd | Film adhesive having high thermal conductivity and bondable by hot melt bonding |
JPH05117599A (en) * | 1991-10-29 | 1993-05-14 | Sumitomo Bakelite Co Ltd | Film adhesive having high thermal conductivity and bondable by hot melt bonding |
JP2716612B2 (en) * | 1991-10-29 | 1998-02-18 | 住友ベークライト株式会社 | High thermal conductive film adhesive that can be thermocompressed |
JPH05125334A (en) * | 1991-11-01 | 1993-05-21 | Sumitomo Bakelite Co Ltd | Hot melt bonding electrically conductive filmy adhesive |
JP2740590B2 (en) * | 1991-11-01 | 1998-04-15 | 住友ベークライト株式会社 | Thermoconductive adhesive film |
JP2733157B2 (en) * | 1991-11-01 | 1998-03-30 | 住友ベークライト株式会社 | Thermoconductive adhesive film |
JP6024234B2 (en) * | 2011-06-21 | 2016-11-09 | 日立化成株式会社 | Adhesive and method for producing the same |
JP6810677B2 (en) * | 2017-12-05 | 2021-01-06 | 信越化学工業株式会社 | New tetracarboxylic dianhydride, polyimide resin and its manufacturing method, photosensitive resin composition, pattern forming method and cured film forming method, interlayer insulating film, surface protective film, electronic parts |
-
1983
- 1983-04-11 JP JP50163683A patent/JPS59501215A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS59501215A (en) | 1984-07-12 |
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