CN1823133A - Curing composition and method for producing curing composition - Google Patents
Curing composition and method for producing curing composition Download PDFInfo
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- CN1823133A CN1823133A CN 200480020303 CN200480020303A CN1823133A CN 1823133 A CN1823133 A CN 1823133A CN 200480020303 CN200480020303 CN 200480020303 CN 200480020303 A CN200480020303 A CN 200480020303A CN 1823133 A CN1823133 A CN 1823133A
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- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- CIQDYIQMZXESRD-UHFFFAOYSA-N dimethoxy(phenyl)silane Chemical group CO[SiH](OC)C1=CC=CC=C1 CIQDYIQMZXESRD-UHFFFAOYSA-N 0.000 description 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 1
- LQRUPWUPINJLMU-UHFFFAOYSA-N dioctyl(oxo)tin Chemical compound CCCCCCCC[Sn](=O)CCCCCCCC LQRUPWUPINJLMU-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- ZVJXKUWNRVOUTI-UHFFFAOYSA-N ethoxy(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(OCC)C1=CC=CC=C1 ZVJXKUWNRVOUTI-UHFFFAOYSA-N 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 description 1
- VQPKAMAVKYTPLB-UHFFFAOYSA-N lead;octanoic acid Chemical compound [Pb].CCCCCCCC(O)=O VQPKAMAVKYTPLB-UHFFFAOYSA-N 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 229960003511 macrogol Drugs 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 1
- BKXVGDZNDSIUAI-UHFFFAOYSA-N methoxy(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(OC)C1=CC=CC=C1 BKXVGDZNDSIUAI-UHFFFAOYSA-N 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N methyl undecanoic acid Natural products CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical group 0.000 description 1
- RZRNAYUHWVFMIP-UHFFFAOYSA-N monoelaidin Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-UHFFFAOYSA-N 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- ADGJZVKOKVENDN-UHFFFAOYSA-N n-(butoxymethyl)-2-methylprop-2-enamide Chemical compound CCCCOCNC(=O)C(C)=C ADGJZVKOKVENDN-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- HRYSOBDFNHXNTM-UHFFFAOYSA-N n-butylbutan-1-amine;1,3,5-triazine Chemical class C1=NC=NC=N1.CCCCNCCCC HRYSOBDFNHXNTM-UHFFFAOYSA-N 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- FXQLMXPTQYAUPK-UHFFFAOYSA-N n-ethyl-n-methoxy-2-methylprop-2-enamide Chemical compound CCN(OC)C(=O)C(C)=C FXQLMXPTQYAUPK-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- UBVMBXTYMSRUDX-UHFFFAOYSA-N n-prop-2-enyl-3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCNCC=C UBVMBXTYMSRUDX-UHFFFAOYSA-N 0.000 description 1
- TWSLRROKQREASH-UHFFFAOYSA-N naphthalene-1-carboxylic acid;tin Chemical compound [Sn].C1=CC=C2C(C(=O)O)=CC=CC2=C1 TWSLRROKQREASH-UHFFFAOYSA-N 0.000 description 1
- LKEDKQWWISEKSW-UHFFFAOYSA-N nonyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCOC(=O)C(C)=C LKEDKQWWISEKSW-UHFFFAOYSA-N 0.000 description 1
- LYJZNXAVZMEXDH-UHFFFAOYSA-N octadecan-8-yl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCC(OC(=O)C(C)=C)CCCCCCC LYJZNXAVZMEXDH-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002899 organoaluminium compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000005968 oxazolinyl group Chemical group 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- GYUPBLLGIHQRGT-UHFFFAOYSA-N pentane-2,4-dione;titanium Chemical compound [Ti].CC(=O)CC(C)=O GYUPBLLGIHQRGT-UHFFFAOYSA-N 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UWHMFGKZAYHMDJ-UHFFFAOYSA-N propane-1,2,3-trithiol Chemical compound SCC(S)CS UWHMFGKZAYHMDJ-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
- AKQNYQDSIDKVJZ-UHFFFAOYSA-N triphenylsilane Chemical compound C1=CC=CC=C1[SiH](C=1C=CC=CC=1)C1=CC=CC=C1 AKQNYQDSIDKVJZ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical group [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Disclosed herein is a curable composition excellent in workability, adhesion properties, rubber-like properties, storage stability, and quick curability. The curable composition comprises (A) a crosslinkable silyl group-containing organic polymer and (B) a (meth)acrylic polymer obtained by polymerizing a (meth)acrylic monomer having a polymerizable unsaturated bond in the presence of a metallocene compound and a crosslinkable silyl group-containing thiol compound, at least one end of the (meth)acrylic polymer being bonded to a residue, -S-R 3 (where R 3 represents a group having a crosslinkable silyl group) obtained by removing a hydrogen atom from the crosslinkable silyl group-containing thiol compound.
Description
Technical field
The present invention is relevant solidification compound, more specifically, is the relevant solidification compound that has good binding property, rubber rerum natura, the voltinism of tachy steroling and make stability.
Background technology
A kind of acrylic polymer that uses the particular polymeric polymerization catalyst and get is disclosed in the patent documentation 1.In addition, disclose in the patent documentation 1, but the binding property of this solidification compound and rubber rerum natura etc. are still not enough by this special acrylic polymer and the formed solidification compound of silane coupling agent.
In addition, the industrial ambient cure composition that comprises the organic polymer that contains the bridging property silyl is widely used in sealing agent, tackiness agent, purposes such as coating.General these solidification compounds are to utilize various metal catalysts to be cured, and according to its kind and addition what and be used in various uses.
Known this catalyzer is the reactant of organotin and ester cpds (for example referring to Patent Document 2 to 5).In the described ester cpds, the catalyzer of phthalate is particularly used in use usually, economizes VOC policy formulation material but this phthalate is defined as primary work, so seek non-phthalate catalyst design in recent years.
In addition, the voice of the voltinism type goods that require on the market to tachy sterol is surging, but exist in producer's the fast curing goods at present make in the undesirable situation of solidified.For example patent documentation 5 grades disclose comprise in the reactant organic polymer that contains the bridging property silyl, and the oxidation dialkyl tin, with the solidification compound of ester based compound, and contain in the described organic polymer that contains the bridging property silyl-the bridging property silyl shown in the SiX3, but make the bad problem of goods solidified in the manufacturing because of reactive high being present in.In addition, can't obtain tachy steroling voltinism when using active lower organotin to be curing catalysts when considering to make stability, when using active higher organotin to be curing catalysts, can't obtain making stable with the reactant of oxidation dialkyl tin and ester based compound when considering to tachy sterol voltinism.
It is producer's favorable comment of goods that the equipment of being developed recently that can produce catalyzer in complete enclosed system is subjected to ambient cure deeply, but amount of additives is limited and equipment is very expensive, so be not suitable for.Therefore present inventors are that curing catalysts is attentively examined at can obtain highly active organotin after after a while, and finish the present invention.
Patent documentation 1: the spy opens the 2001-40037 communique
Patent documentation 2: the spy opens flat 1-58219 communique
Patent documentation 3: specially permit communique No. 3062625
Patent documentation 4: the spy opens flat 8-337713 communique
Patent documentation 5: the spy opens the 2003-138151 communique
Patent documentation 6: the spy opens flat 11-12480 communique
Patent documentation 7: the spy opens clear 52-73998 communique
Patent documentation 8: the spy opens clear 55-9669 communique
Patent documentation 9: the spy opens clear 59-122541 communique
Patent documentation 10: the spy opens clear 60-6747 communique
Patent documentation 11: the spy opens clear 61-233043 communique
Patent documentation 12: the spy opens clear 63-112642 communique
Patent documentation 13: the spy opens flat 3-79627 communique
Patent documentation 14: the spy opens flat 4-283259 communique
Patent documentation 15: the spy opens flat 5-70531 communique
Patent documentation 16: the spy opens flat 5-287186 communique
Patent documentation 17: the spy opens flat 11-80571 communique
Patent documentation 18: the spy opens flat 11-116763 communique
Patent documentation 19: the spy opens flat 11-130931 communique
Patent documentation 20: specially permit communique No. 3313360
Summary of the invention
In view of above-mentioned prior art problems, the 1st purpose of the present invention is, provide have good operation, the solidification compound of binding property, rubber rerum natura and storage stability.The 2nd purpose of the present invention is, the voltinism of tachy steroling of not using having of phthalate good is provided, makes stability, goods are stable and fusible solidification compound.
In order to solve above-mentioned problem, the 1st form of solidification compound of the present invention is characterised in that, contain following (methyl) acrylic polymer, should (methyl) acrylic polymer be the organic polymer that contains the bridging property silyl at (A) promptly, and (B) under the compound of metallocenes (metallocene) shown in the following formula (1) and the existence of mercaptan compound that contains the bridging property silyl, making (methyl) propylene with polymerizability unsaturated link(age) is that monomer polymerization obtains, on at least 1 end of this (methyl) acrylic polymer, bonding has the mercaptan compound that contains the bridging property silyl to break away from the residue-S-R of hydrogen atom gained
3(R wherein
3For containing the group of bridging property silyl).In addition, in this specification sheets with propenyl and methylpropenyl and be called (methyl) propenyl.
(wherein, in the formula (1), M is selected metal from the group that metal, chromium, ruthenium and palladium constituted of periodictable 4 families, 5 families, 14 families; R
1And R
2Represent independently of one another by having substituent aliphatic alkyl, can have substituent alicyclic alkyl, can have substituent aromatic hydrocarbyl and can having the substituent at least a kind of selected group among the silica-based group who constitutes that contains, or any in hydrogen atom or the singly-bound, in addition, R
1And R
225 yuan of ring keies in the compound close shown in the wushu (1) jointly, and the R of a plurality of adjacency
1Or R
2Can form atoll texture jointly; A and b independently are 1 to 4 integer separately; Alkyl or the halogen atom of Y for being replaced by halogen atom to the small part hydrogen atom, n are 0 or the integer of the valence mumber-2 of metal M.)
The main chain of above-mentioned (methyl) acrylic polymer (B) is preferably, and has the repeating unit shown in the following following formula (2) of 99 weight % and has polymerizable unsaturated compound monomer institute repeat units derived beyond the repeating unit, contain an above bridging property silyl from molecule shown in the formula (2) of 1 to 50 weight %.
(in the formula (2), R
4To R
6Independent separately is the alkyl of hydrogen atom, halogen atom or carbon number 1 to 3; R
7Be hydrogen atom, alkali metal atom, (this alkyl can be the straight chain shape or has side chain the alkyl of carbon number 1 to 22, and this alkyl or form in the group of side chain of this alkyl to the small part hydrogen atom can be by by the chlorine atom, fluorine atom, primary amine groups, secondary amine, tertiary amine groups, the quaternary ammonium salts group, amide group, isocyanate group, the alkylene oxide base, the hydroxyl silyl, the methoxy silyl, the methylamino ethoxy silylation, the third oxygen silyl, the chloromethane silylation, selected at least a polar group or reactive functional group replace among silyl bromide base and epoxypropyl constituted the group, this alkyl can have two keys in addition, and this alkyl can have atoll texture).)
The bridging property silyl of above-mentioned (methyl) acrylic polymer (B) is preferably, shown in following general formula (3).
-SiX
3 ……(3)
(in the formula (3), X is hydroxyl or hydrolization group, and 3 X can be identical or different.)
Bridging property silyl in above-mentioned (methyl) acrylic polymer (B) preferably also has bridging property silyl shown in bridging property silyl shown in the following general formula (3) and the following general formula (4).
-SiX
3 …………………(3)
(in formula (3) and the formula (4), X is hydroxyl or hydrolization group, and can be identical or different when having a plurality of X; R in the formula (4)
8Be 1 valency organic group of the replacement or the non-replacement of carbon number 1 to 20, and have a plurality of R
8The time can be identical or different; C is 1 or 2.)
Above-mentioned (methyl) acrylic polymer (B) is preferably, and contains (methyl) acrylic polymer of bridging property silyl shown in the following general formula (3) and contains the mixture of (methyl) acrylic polymer of bridging property silyl shown in the following general formula (4).
-SiX
3…………………(3)
(in formula (3) and the formula (4), X is hydroxyl or hydrolization group, and can be identical or different when having a plurality of X; In the formula (4), R
8Be the replacement or the non-replacement 1 valency organic group of carbon number 1 to 20, and have a plurality of R
8The time can be identical or different, c is 1 or 2.)
The 1st form of solidification compound of the present invention is preferably, and also contains (C) curing catalysts.Organotin is good to described curing catalysts (C) shown in (C1) following general formula (5) to contain.
R
9R
10SnO ……(5)
(in the formula, R
9And R
10Be respectively 1 valency alkyl.)
In the 1st form of solidification compound of the present invention, be preferably during as curing catalysts, the solidification compound that contains described composition (A), described composition (B) and described composition (C1) is carried out reaction treatment again with described organotin (1).
Being characterized as of the 2nd form of solidification compound of the present invention contained organic polymer that (A) contain the bridging property silyl, and (C1) organotin shown in the following general formula (5).
R
9R
10SnO ……(5)
(in the formula, R
9And R
10Be respectively 1 valency alkyl.)
The 2nd form of solidification compound of the present invention is preferably, and the solidification compound that contains described composition (A) and described composition (C1) is carried out reaction treatment again.
In the 1st and the 2nd form of solidification compound of the present invention, described polymkeric substance (A) preferably contains the organic polymer of bridging property silyl shown in the following general formula (3).
-SiX
3 ……(3)
(in the formula (3), X is hydroxyl or hydrolization group, and 3 X can phase or different.)
In the 1st and the 2nd form of solidification compound of the present invention, described polymkeric substance (A) preferably and the organic polymer of bridging property silyl shown in bridging property silyl shown in the following general formula (3) and the following general formula (4) arranged.
-SiX
3 …………………(3)
(in formula (3) and (4), X is hydroxyl or hydrolization group, and these can be identical or different when having a plurality of X; In the formula (4), R
8Be the replacement or the non-replacement 1 valency organic group of carbon number 1 to 20, and have a plurality of R
8The time these can be identical or different; C is 1 or 2.)
In the 1st and the 2nd form of solidification compound of the present invention, described polymkeric substance (A) is preferably the organic polymer that contains bridging property silyl shown in the following general formula (3), and contains the mixture of the organic polymer of bridging property silyl shown in the following general formula (4).
-SiX
3 …………………(3)
(in formula (3) and (4), X is hydroxyl or hydrolization group, and these can be identical or different when having a plurality of X; In the formula (4), R
8Be the replacement or the non-replacement 1 valency organic group of carbon number 1 to 20, and have a plurality of R
8The time these can be identical or different; C is 1 or 2.)
In the 1st and the 2nd form of solidification compound of the present invention, described polymkeric substance (A) preferably be selected from by the polyoxyalkylene based polymer that contains the bridging property silyl, contain the bridging property silyl (methyl) propenyl modification polyoxyalkylene based polymer, contain the polyisobutene based polymer of bridging property silyl and contain in one group that (methyl) acrylic polymer of bridging property silyl forms at least a kind.
In the 1st and the 2nd form of solidification compound of the present invention, preferably also add (D) silane coupling agent.
Being characterized as of the manufacture method of solidification compound of the present invention, at least contain in the manufacture method of solidification compound of described polymkeric substance (A) and described organotin (C1), to containing the solidification compound in the encloses container of being enclosed in of described polymkeric substance (A) and described organotin (C1), carry out reaction treatment again.
According to the present invention, the 1st can provide have good operation, the solidification compound of binding property, rubber rerum natura, storage stability, deep solidified nature and the voltinism of tachy steroling.So the 2nd can provide do not use phthalate to have high security, the good voltinism of tachy steroling, make stability, goods are stable and fusible solidification compound.
Description of drawings
Fig. 1 is the measurement result graphic representation of the drying time of finger-touching of expression embodiment 10 and comparative example 5.
Embodiment
Below example of the present invention will be described, this example is illustrative, but do not break away under the scope of technological thought of the present invention various variations can not arranged.
Being characterized as of the 1st form of solidification compound of the present invention contained following ingredients (A) and composition (B).
(A) contain the organic polymer of bridging property silyl,
(B) at Metallocenic compound shown in the following formula (1) and contain in the presence of the mercaptan compound of bridging property silyl, make (methyl) propylene with polymerizability unsaturated link(age) be monomer polymerization and, the residue-S-R that breaks away from the hydrogen atom gained from the mercaptan compound that contains the bridging property silyl is arranged at least one terminal bonding
3(R wherein
3For having the group of bridging property silyl) (methyl) acrylic polymer.
(in the formula (1), M is a selected metal in metal, chromium, ruthenium and the palladium of periodictable 4 families, 5 families, 14 families; R
1And R
2Independently serve as reasons separately and can have substituent aliphatic alkyl, can have substituent alicyclic alkyl, can have substituent aromatic hydrocarbyl and can have selected at least a group in a group that substituent silicon-containing group constitutes, or hydrogen atom, singly-bound, in addition, R
1And R
225 yuan of rings in the compound shown in the bonded (1), and the R of a plurality of adjacency jointly
1Or R
2Can form atoll texture jointly; A and b independently are 1 to 4 integer separately; Alkyl or the halogen atom of Y for being replaced by halogen atom to the small part hydrogen atom, n are 0 or the integer of the valence mumber-2 of metal M.)
Employed described composition (A) is, has the hydroxyl that is bonded to Siliciumatom or hydrolization group, siloxane bond is crosslinkable to be contained silica-basedly by forming, and promptly contains the organic polymer of bridging property silyl.This organic polymer (A) that contains the bridging property silyl is as, the material that is disclosed in the patent documentation 2 to 20.This contain the bridging property silyl organic polymer (A) concrete example as, intramolecularly contains the polyoxyalkylene based polymer that 1 above bridging property silyl and main chain can contain organo-siloxane separately, vinyl modification polyoxyalkylene based polymer, (methyl) propenyl modification polyoxyalkylene based polymer, vinyl based polymer, polyester based polymer, (methyl) acrylic ester polymer and multipolymer, mixture etc.
There is no particular restriction for bridging property silicomethane radix, but with regard to the solidified nature of solidification compound and the viewpoints such as rerum natura after the curing, general intramolecularly contains 1 to 6.In addition, the material shown in this bridging property silyl following general formula (6) that is preferably easily crosslinked and that easily make.
(in the formula (6), R
81 valency organic group for the replacement or the non-replacement of carbon number 1 to 20 is preferably the alkyl of carbon number 1 to 20, the aryl of carbon number 6 to 20 or the aralkyl of carbon number 7 to 20, and the best is a methyl, and has a plurality of R
8The time these can be identical or different; X is hydroxyl or hydrolization group, be preferably selected group in halogen atom, hydrogen atom, hydroxyl, alkoxyl group, acyloxy, ketoxime alkali, amide group, sour amide group, sulfydryl, alkenyloxy and the azyloxy, be more preferred from alkoxyl group, the best is a methoxyl group, and these can be identical or different when having a plurality of X; D is 1,2 or 3, and the viewpoint of the voltinism of just tachy steroling considers that the best is 3.)
When having a plurality of bridging property silyl in the above-mentioned organic compound (A) that contains the bridging property silyl, this group can be identical or different, and in addition, the quantity of d can be identical or different in the described formula (6).For example can use the organic polymer that has bridging property silyl shown in bridging property silyl shown in the following formula (3) and the following formula (4) simultaneously.In addition, be suitable for and organic polymer that contains the bridging property silyl shown in the following formula (3) and the mixture that contains the organic polymer of bridging property silyl shown in the following formula (4).
-SiX
3 …………………(3)
(in formula (3) and (4), X and R
8Cotype (6) separately, c is 1 or 2.)
The above-mentioned main chain that contains the organic polymer (A) of bridging property silyl, consider from the viewpoint of solidifying rerum naturas such as back draft binding property, modulus, organo-siloxane be can contain, polyoxyalkylene based polymer, (methyl) propenyl modification polyoxyalkylene polymers, polyisobutene based polymer, (methyl) acrylic polymer and their multipolymer are preferably.
The described organic polymer that contains the bridging property silyl is special good to be, at least a kind of selected polymkeric substance from the polyoxyalkylene based polymer that contains the bridging property silyl and (methyl) propenyl modification polyoxyalkylene based polymer of containing the bridging property silyl.The described number-average molecular weight that contains the organic polymer (A) of bridging property silyl is 1, more than 000 100, below 000, lower and the easy processing of viscosity before solidify, and have rerum naturas such as intensity after the preferable curing, extensibility, modulus and consider, the narrow person of 3,000 to 50,000 molecular weight distribution is suitable.The described organic polymer (A) that contains the bridging property silyl can use separately or also use more than 2 kinds.
Employed described composition (B) is (methyl) acrylic polymer shown in the patent documentation 1.That is, (methyl) acrylic polymer of composition (B) is, is catalyzer with Metallocenic compound shown in the following formula (1) and the mercaptan compound that contains the bridging property silyl, under the existence of catalyzer, make the polymerizable unsaturated compound polymerization and polymkeric substance.Therefore, the residue (S-R of gained after the terminal upward bonding of at least one of this polymkeric substance has catalyzer with the mercaptan compound disengaging hydrogen atom that contains the bridging property silyl
3).R wherein
3For having the group of bridging property silyl.
The above-mentioned Metallocenic compound of polymerizing catalyst that is used as is shown in following formula (1).
In the above-mentioned formula (1), M is a selected metal in metal, chromium, ruthenium and the palladium of periodictable 4 families, 5 families, 14 families.Particularly, M is titanium, zirconium, chromium, ruthenium, vanadium, palladium, tin etc.In addition, in the above-mentioned formula (1), R
1And R
2Independent of separately from by having substituent aliphatic alkyl, can have substituent alicyclic alkyl, can have substituent aromatic hydrocarbyl and can having selected at least a group a group that substituent silicon-containing group forms, or hydrogen atom, any in the singly-bound.
R in addition
1And R
225 yuan of rings in the compound shown in the above-mentioned formula of bonding (1), and the R of a plurality of adjacency jointly
1And R
2Can form atoll texture jointly.In addition, in the above-mentioned formula (1), a and b independently are 1 to 4 integer separately, and alkyl or the halogen atom of Y for being replaced by halogen atom to the small part hydrogen atom, n are 0 or the integer of the valence mumber-2 of metal M.
As described Metallocenic compound concrete example as, Dicyclopentadiene (DCPD)-Ti-dichloride, Dicyclopentadiene (DCPD)-Ti-biphenyl, Dicyclopentadiene (DCPD)-Ti-two-2,3,4,5,6-penta fluoro benzene-1-base, Dicyclopentadiene (DCPD)-Ti-two-2,3,5,6-tetra fluoro benzene-1-base, Dicyclopentadiene (DCPD)-Ti-two-2,5,6-trifluoro-benzene-1-base, Dicyclopentadiene (DCPD)-Ti-two-2,6-two fluorobenzene-1-base, Dicyclopentadiene (DCPD)-Ti-pair-2,4 difluorobenzene-1-base, dimethyl cyclopentadienyl-Ti-two-2,3,4,5,6-penta fluoro benzene-1-base, dimethyl cyclopentadienyl-Ti-two-2,3,5,6-tetra fluoro benzene-1-base, dimethyl cyclopentadienyl-Ti-is two-2,6-two fluorobenzene-1-base, dimethyl cyclopentadienyl-Ti-is two-2,6-two fluoro-3-(hat-1-yl)-benzene-two cyclopentadiene titanium compounds such as 1-base; Dicyclopentadienyl-Zr-dichloride, Dicyclopentadiene (DCPD)-Zr-biphenyl, Dicyclopentadiene (DCPD)-Zr-2,3,4,5,6-penta fluoro benzene-1-base, Dicyclopentadiene (DCPD)-Zr-two-2,3,5,6-tetra fluoro benzene-1-base, Dicyclopentadiene (DCPD)-Zr-two-2,5,6-trifluoro-benzene-1-base, Dicyclopentadiene (DCPD)-Zr-is two-2,6-two fluorobenzene-1-base, Dicyclopentadiene (DCPD)-Zr-two-2,4-two fluorobenzene-1-base, dimethyl cyclopentadienyl-Zr-two-2,3,4,5,6-penta fluoro benzene-1-base, dimethyl cyclopentadienyl-Zr-two-2,3,5,6-tetra fluoro benzene-1-base, dimethyl cyclopentadienyl-Zr-two-2,6-two fluorobenzene-1-base, dimethyl cyclopentadienyl-Zr-is two-2,6-two fluoro-3-(hat-1-yl)-benzene-Bis(cyclopentadienyl)zirconium compounds such as 1-base; Dicyclopentadienyl-V-muriate, two methyl cyclopentadienyl-V-muriate, two pentamethyl-cyclopentadienyl-V-muriate, dicyclopentadienyl-Ru-muriate, dicyclopentadienyl-Cr-muriate etc.This Metallocenic compound can be used alone or in combination.
The usage quantity of described Metallocenic compound can be general catalytic amount, particularly, polymerization is generally 1 to 0.001 weight part with polymerizable unsaturated compound 100 weight parts, is preferably 0.01 to 0.005 weight part.
In addition, among the present invention with the shared mercaptan compound of above-mentioned Metallocenic compound be, have the mercaptan compound of bridging property silyl, generally this mercaptan compound that contains the bridging property silyl is following formula HS-R
3Shown in compound.
Wherein, R
3For having the group of bridging property silyl, illustrative bridging property silyl during employed bridging property silyl is can congruent (A) illustrated, special good for being selected from least a kind of bridging property silyl in a group that forms by hydroxyl silyl, methoxy methyl silylation, (ethoxymethyl) silylation, propoxy-silyl, chloromethane silylation and silyl bromide base.R
3Concrete example as, 3-sulfydryl propyl group-Trimethoxy silane, 3-sulfydryl propyl group-triethoxyl silane, 3-sulfydryl propyl group-monomethyl dimethoxy silane, 3-sulfydryl propyl group-single phenyl dimethoxy silane, 3-sulfydryl propyl group-dimethyl mono methoxy silane, 3-sulfydryl propyl group-monomethyl diethoxy silane, 4-sulfydryl butyl-Trimethoxy silane and 3-sulfydryl butyl-Trimethoxy silane etc.
This mercaptan compound that contains the bridging property silyl mainly is to utilize organometallic compound to choose hydrogen atom and generate S-R when reaction
3Free radical, and make this free radical import at least one end of formed polymkeric substance.Therefore, the bridging property silyl that is directed to polymer ends like this can be owing to this reaction lose activity, the activity that silyl had that the former state maintenance is imported into.
Contain the mercaptan compound HS-R of bridging property silyl by this
3Break away from hydrogen atom and generate S-R
3Free radical, and this free radical and polymerizable unsaturated compound bonding, activation begin polymerization thus.In addition, use the purpose of above-mentioned Metallocenic compound to be, by the mercaptan compound HS-R that contains the bridging property silyl
3The hydrogen atom of choosing, and make the mercaptan compound activation that contains the bridging property silyl.So use the mercaptan compound HS-R that contains the bridging property silyl separately
3The time can obviously reduce percent polymerization, that is, use when containing the mercaptan compound of bridging property silyl in fact separately, polymerizable unsaturated compound will not react.In addition, the main application target of above-mentioned Metallocenic compound is, make the mercaptan compound activation that contains the bridging property silyl, general its structure is with the previous Metallocenic compound that uses, promptly exist in compound mode shown in the above-mentioned formula (1), but sometimes its part can and the mercaptan compound that contains the bridging property silyl, polymerizable unsaturated compound and their derivative bonding, in addition, reaction when carrying out this organometallic compound can decompose and make in the reactive system system and contain metal.
The above-mentioned usage quantity that contains the mercaptan compound of bridging property silyl can be done suitably to select under the characteristic of considering resulting polymers.That is, when increasing the concentration of the mercaptan compound that contains the bridging property silyl in the reactive system, can promote the percent polymerization of time per unit and arrive percent polymerization.Though increase the percent polymerization that the Metallocenic compound amount can promote time per unit this moment, do not have big influence to arriving percent polymerization.In addition, the usage quantity of Metallocenic compound influences hardly to the molecular weight of resulting polymers, but when not using Metallocenic compound, can't effectively react.In addition, when increasing the mercaptan compound usage quantity, can improve polymerization velocity.Because have this tendency, so be considered to composition of the present invention (B) with in the catalyzer, Metallocenic compound plays the effect of the whole deactivated catalyst of reaction, and mercaptan compound has polymerization initiation (polymerization causes the effect of planting).So composition of the present invention (B), contains the usage quantity decision molecular weight and the percent polymerization of the mercaptan compound of bridging property silyl with in the catalyzer.
Therefore the usage quantity that contains the mercaptan compound of bridging property silyl can be considered the molecular weight of resulting polymers, polymerization velocity etc. and do suitably to select, but in order successfully to react, and do not make runaway reaction, the common metal cyclopentadinyl compound is 100: 1 to 1: 50000 with the mol ratio that contains the mercaptan compound of bridging property silyl, is preferably 10: 1 to 1: 10000.
In addition, this mercaptan compound that contains the bridging property silyl can all add when the reaction beginning, or the initial mercaptan compound that contains the bridging property silyl that adds, react and append the mercaptan compound that contains the bridging property silyl again after the desirable time, or append simultaneously the mercaptan compound that contains the bridging property silyl and polymerizable unsaturated compound both.In addition, append the mercaptan compound that contains the bridging property silyl, or can promote percent polymerization when appending the mercaptan compound that contains the bridging property silyl and polymerizable unsaturated compound simultaneously.
Composition of the present invention (B) (methyl) acrylic polymer is, use Metallocenic compound shown in the above-mentioned specific formula (1) and contain the mercaptan compound of bridging property silyl, the polymkeric substance that polymerizable unsaturated compound is reacted and get, but except this contains the mercaptan compound of bridging property silyl, the present invention can and use ethanethio, butanethiol, hexyl mercaptans, uncle's dodecyl mercaptan, positive dodecyl mercaptan, octyl mercaptan etc. are not had the alkyl sulfide alcohols of the functional group beyond the thiol group, phenyl mercaptan, benzyl mercaptan etc. are not had mercaptan compounds such as fragrant family thio-alcohol that palace beyond the thiol group can base, and β-Qiu Jibingsuan, mercaptoethanol, phenylmercaptans etc. contain the mercaptan compound of the functional group beyond the thiol group, and trithioglycerin or tetramethylolmethane are through multi-functional thiol's compound of β-Qiu Jibingsuan esterification, polysulphide based polymer etc. has the polymer-type mercaptan of active sulphur alcohol radical.
In addition, the present invention causes the above-mentioned Metallocenic compound of catalyzer except use as polymerization and contains the mercaptan compound of bridging property silyl, in order to adjust the polymerization velocity and the polymerization degree, can use disulfide, trisulfide, four sulphur compounds.Can be used as this moment polymerization adjust disulfide that agent uses, trisulfide, four sulphur compounds as, diethyl trisulphide, dibutyl tetrasulfide, phenylbenzene disulphide, two (2-hydroxyethyl) disulphide, two (4-hydroxyl butyl) tetrasulfide, two (3-hydroxypropyl) trisulphide, two (3-carboxylic propyl group) trisulphide, two (3-carboxylic propyl group) tetrasulfide, two (3-propyl trimethoxy silicane) disulphide, two (3-propyl-triethoxysilicane) tetrasulfide etc.These sulphur compounds can be used alone or in combination.Employed sulphur compound amount can be in the polymerization of the present invention, does not make the degree of polymerization inactivation, particularly, polymerization is generally 50 to 0 weight parts with polymerizable unsaturated compound 100 weight parts, is preferably 20 to 0.005 weight parts.
The main chain of formation composition of the present invention (B) (methyl) acrylic polymer is to make by the following polymerizable unsaturated compound polymerization of putting down in writing to get.This polymerizable unsaturated compound is as, polymerizable unsaturated compound shown in the following formula (7) to (9).
In the described formula (7), R
4To R
6Independent separately is the alkyl of hydrogen atom, halogen atom or carbon number 1 to 3, R
7Be hydrogen atom, alkali metal atom, (this alkyl can be the straight chain shape or has side chain the alkyl of carbon number 1 to 22, in addition, this alkyl or form in the group of side chain of this alkyl to the small part hydrogen atom can be by by the chlorine atom, fluorine atom, primary amine groups, secondary amine, tertiary amine groups, the quaternary ammonium salts group, amide group, isocyanate group, the alkylene oxide base, the hydroxyl silyl, the methoxy methyl silylation, the (ethoxymethyl) silylation, the propoxy-silyl, the chloromethane silylation, selected at least a polar group among the group that silyl bromide base and epoxypropyl are formed, or the reactive functional group replacement, this alkyl can have two keys and atoll texture in addition).That is R,
7As alkyl, cycloalkyl, aryl, alkenyl, cycloalkenyl, alkoxyl group, alkylether radicals.Constitute this R
7The base to the small part hydrogen atom can be by replacements such as halogen atom, sulfonic group, epoxypropyl.
In the following formula (8), R
11To R
13With above-mentioned R
4To R
6, R
14For hydroxyl ,-CO-NH
2Base ,-CN base, epoxypropyl, alkyl, alkoxyl group, alkenyl, cycloalkenyl, aryl, allyl ether, alkylether radicals at least a group.Constitute this R
14The base to the small part hydrogen atom can be by replacements such as halogen atoms.In addition, this R
14Base can be, and has from the group of deutero-structure unit of alkylene glycol institute, methylol, alkoxyl group amide group.
In the following formula (9), R
15And R
17With above-mentioned R
4To R
6, R
16And R
18Independent separately be carboxyl, hydroxyl ,-CO-NH
2Base ,-CN base, epoxypropyl, alkyl, alkoxyl group, alkenyl, cycloalkenyl, aryl in any one group.Constitute R
16And R
18The base to the small part hydrogen atom can be by replacements such as halogen atoms.In addition, this R
16And R
18Group can with R
15And R
172 carbon atoms of institute's bonding form atoll texture, and this atoll texture can have two keys.
The concrete example of this polymerizable unsaturated compound as, following shown in compound.The salt of vinylformic acid and alkali metal salts of acrylic acids etc.; The salt of methacrylic acid and methacrylic acid alkali metal salt etc.; Alkyl acrylates such as methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, ethyl acrylate, Octyl acrylate, vinylformic acid ester in the ninth of the ten Heavenly Stems, decyl acrylate, lauryl acrylate; Vinylformic acid such as phenyl acrylate, benzyl acrylate aryl ester; Vinylformic acid alcoxyl base alkane esters such as vinylformic acid methoxyl group ethyl ester, vinylformic acid ethoxy ethyl ester, vinylformic acid propoxy-ethyl ester, vinylformic acid butoxy ethyl ester, vinylformic acid oxyethyl group propyl ester; Alkyl methacrylates such as methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, methacrylic acid pentyl ester, the own ester of methylpropanoic acid, methacrylic acid-2-ethylhexyl, Octyl methacrylate, nonyl methacrylate, decyl-octyl methacrylate, lauryl methacrylate(LMA); Aryl methacrylate such as phenyl methacrylate, benzyl methacrylate; Methacrylic acid alkoxy alkyls such as methacrylic acid methoxy base ethyl ester, methacrylic acid ethoxy ethyl ester, methacrylic acid propoxy-ethyl ester, methacrylic acid butoxy ethyl ester, methacrylic acid oxyethyl group propyl ester; The contract diacrylate of (gathering) alkylene glycols such as diacrylate of tripropylene glycol of the diacrylate of the diacrylate of the diacrylate of ethylene glycol, the diacrylate of glycol ether, triglycol, the diacrylate of polyoxyethylene glycol, propylene glycol, the diacrylate, three of dipropylene glycol; The contract dimethacrylate of (gathering) alkylene glycols such as dimethacrylate of tripropylene glycol of the dimethacrylate of the dimethacrylate of the dimethacrylate of ethylene glycol, the dimethacrylate of glycol ether, triglycol, the diacrylate of polyoxyethylene glycol, propylene glycol, the dimethacrylate, three of dipropylene glycol; Multivalence acrylate such as Viscoat 295; Multivalence methyl acrylates such as trimethylolpropane tris methyl acrylate; Vinyl cyanide; Methacrylonitrile; Vinyl-acetic ester; Vinylidene chloride; Vinylformic acid-2-chloroethene ester, methacrylic acid-ethylene halide based compounds such as 2-chloroethene ester; The acrylate of ester ring type alcohol such as cyclohexyl acrylate; The methyl acrylate of ester ring type alcohol such as cyclohexyl methacrylate; The polymerizable compound of 2-vinyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-pseudoallyl-Han oxazolinyls such as 2-oxazoline; The polymerizable compound of acryl ethylenimine, methacryloyl ethylenimine, vinylformic acid-2-ethylenimine base ethyl ester, methacrylic acid-nitrogen heterocyclic ring propyls such as 2-ethylenimine base ethyl ester; Glycidyl allyl ether, vinylformic acid glycidyl ether, methyl propenoic acid glycidyl ether, vinylformic acid glycidyl ether, acrylic acid-2-ethyl glycidyl ether, methacrylic acid-2-ethyl ether etc. contain the vinyl monomer of epoxy group(ing); The vinyl compound of the hydroxyls such as affixture of vinylformic acid-2-hydroxyl ethyl ester, 2-hydroxyethyl methacrylate, vinylformic acid-2-hydroxypropyl acrylate, acrylic or methacrylic acid and polypropylene glycol or poly-alcoholic acid monoesters, lactone and (methyl) vinylformic acid-2-hydroxyl ethyl ester; The fluorine-containing vinyl monomer of fluorine substituent methyl alkyl acrylate, fluorine substitutional crylic acid alkyl ester etc.; (part) ester cpds, the acid anhydrides of unsaturated carboxylic acids such as the methylene-succinic acid except that (methyl) vinylformic acid, Ba Dousuan, toxilic acid, fumaric acid and salt and these materials; 2-chloroethyl vinyl ether, monochloro vinyl-acetic ester etc. contain the reactive halogen vinyl monomer; Amide-containing vinyl monomers such as Methacrylamide, N-methylol methacrylamide, N-methoxy ethyl Methacrylamide, N-butoxymethyl Methacrylamide; Diolefins such as ethylidene norbornene, isoprene, pentadiene, vinyl cyclohexene, chloroprene, divinyl, dimethyl butadiene, cyclobutadiene, dimethyl butadiene.
Other as, in polymerization have the big monomer class etc. (for example, fluorine is monomer, silicon-containing monomer, big monomer, vinylbenzene, silicon etc.) of free-radical polymerised vinyl on the monomer end of vinyl.This polymerizable unsaturated compound can be used alone or in combination.These polymerizable unsaturated compounds can be liquid, solid or gas according to reaction conditions, but with regard to ease-to-operate, are preferably during reaction and use liquid monomer.
Composition of the present invention (B) (methyl) acrylic polymer is, in the presence of by above-mentioned Metallocenic compound and the above-mentioned formed catalyst for polymerization of mercaptan compound that contains the bridging property silyl, with various polymerization polymerization unsaturated compounds polymkeric substance, and bonding has by the mercaptan compound that contains the bridging property silyl and breaks away from the hydrogen be bonded to sulphur atom and the S-R3 of gained on its at least one end.During the aforesaid polymerizable unsaturated compound of polymerization, can corresponding employed polymerizable unsaturated compound, and in its main chain, form the repeating unit shown in for example following formula (2), (10) and (11).
In the following formula (2), R
4To R
6Independent separately is the alkyl of hydrogen atom, halogen atom or carbon number 1 to 3, R
7Be hydrogen atom, alkali metal atom, (this alkyl can be the straight chain shape or has side chain the alkyl of carbon number 1 to 22, in addition, this alkyl or form in the group of side chain of this alkyl, to the small part hydrogen atom can be by by the chlorine atom, fluorine atom, primary amine groups, secondary amine, tertiary amine groups, the quaternary ammonium salts group, amide group, isocyanate group, the alkylene oxide base, the hydroxyl silyl, the methoxy methyl silylation, the (ethoxymethyl) silylation, the propoxy-silyl, the chloromethane silylation, silyl bromide base and epoxypropyl constituted in one group at least a kind of selected polar group, or the reactive functional group replacement, this alkyl can have two keys and atoll texture in addition).That is R,
7As alkyl, cycloalkyl, aryl, alkenyl, cycloalkenyl, alkoxyl group, alkylether radicals.Constitute this R
7The base to the small part hydrogen atom can be by replacements such as halogen atom, sulfate, epoxypropyl.
In the following formula (10), R
11To R
13With above-mentioned R
4To 6, R
14For hydroxyl ,-CO-NH
2Base ,-CN base, epoxypropyl, alkyl, alkoxyl group, alkenyl, cycloalkenyl, aryl, allyl ether, alkylether radicals in any group.Constitute this R
14The base to the small part hydrogen atom can be by replacements such as halogen atoms.In addition, this R
14Base can be, and has from the group of deutero-structure unit of alkylene glycol institute, alkoxysilyl, alkyl alkoxy silyl, methylol, alkoxyl group amide group.
In the following formula (11), R
15And R
17With above-mentioned R
4To R
6, R
16And R
18Independent separately be carboxyl, hydroxyl ,-CO-NH
2Base ,-CN base, epoxypropyl, alkyl, alkoxyl group, alkenyl, cycloalkenyl, aryl in any group.Constitute this R
16And R
18Can being replaced by halogen atom to the small part hydrogen atom of base.In addition, this R
16And R
18Base can with R
15And R
172 carbon atoms of institute's bonding form atoll texture, and this atoll texture can have two keys.
There is no particular restriction for the main chain of composition of the present invention (B) (methyl) acrylic polymer, is preferably repeating unit shown in the formula (2) that contains 50 to 100 weight %.
In addition, when making composition of the present invention (B) (methyl) acrylic polymer, can with polymerizability unsaturated monomer [E] copolymerization with bridging property silyl.Employed this bridging property silyl can be because of the illustrated bridging property silyl illustration of composition (A), and special good is selected at least a bridging property silyl in a group that is made up of hydroxyl silyl, methoxy methyl silylation, (ethoxymethyl) silylation, propoxy-silyl, chloromethane silylation and silyl bromide base.Here employed have the polymerizability unsaturated monomer [E] of bridging property silyl shown in following formula (12).
In the following formula, R
21, R
23With above-mentioned R
4To R
6, R
22For hydrogen atom, halogen atom ,-CN base, epoxypropyl, alkyl, alkoxyl group, alkenyl, cycloalkenyl, aryl, allyl ether, alkylether radicals, alcoxyl silyl, alkyl alcoxyl silyl in any group or atom.This R
22When base is a group beyond the hydrogen atom, halogen atom, constitute this group to the small part hydrogen atom can be by replacements such as halogen atoms.In addition, this R
22Base can be the group that has from deutero-structure unit of alkylene glycol institute, alkoxysilyl, alkyl alkoxy silyl, methylol, alkoxyl group amide group.R
24For-CO-O-,-CH
2-,-C
2H
4-,-CO-O-C
2H
4-,-CO-O-C
2H
4Divalent base or singly-bounds such as-O-.R
25, R
26, R
27Independent separately is any in alkyl, alkoxyl group, hydrogen atom, the halogen atom.
When making compound copolymerization shown in the formula (12), repeating unit shown in the following formula (13) can be imported in the main chain.
(in the following formula (13), R
21To R
27Same following formula (12).)
In the main chain of composition of the present invention (B) (methyl) acrylic polymer, be good with repeating unit shown in the following formula (13) that whole repeating units is imported 1 to 50 weight %, special good for importing 5 to 30 weight % (this importing rate is the monomer scaled value).When importing the repeating unit (13) of this amount, can make this (methyl) acrylic polymer (B) have the autoreaction solidified nature, and can form good cured article when having the resin combination reaction of alkoxysilyl with metallo-chelate such as alcoxyl metal, metal alkoxides such as the silane coupling agent that for example has the bridging property alkoxysilyl, silanol compound, purity titanium tetraethoxide or polyorganosiloxane resin etc.In addition, the method that imports repeating unit shown in the following formula (13) is except can using polymerizability unsaturated monomer [E] importing with bridging property silyl, after also can modulating (methyl) acrylic polymer, make the reaction of compound with bridging property silyl and gained (methyl) acrylic polymer and import.
The monomer [E] that can form repeating unit shown in the above-mentioned formula (13) as, on the vinyl of vinyltrimethoxy silane, γ-vinyl-monochloro dimethoxy silane, γ-vinyl-trichlorosilane, γ-vinyl-two chloro-monomethyl silane etc., directly imported the vinyl compound monomer of bridging property silyl; In higher (methyl) acryl of γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxyl silane, γ-methacryloxypropyl monomethyl dimethoxy silane, γ-acryloxy propyl trimethoxy silicane isoreactivity, import the bridging property silyl and (methyl) propylene be monomer; Allyltrimethoxysilanis, trimethoxy-silylpropyl allyl amine etc. have import the bridging property silyl in the compound of polymerizability unsaturated group and polymerizable monomer.
Mentioned component (B) (methyl) acrylic polymer, particularly have repeating unit shown in the following formula (13) (methyl) acrylic polymer can by, there is compound shown in the formula (1) and contains under the mercaptan compound of bridging property silyl, make (being total to) polymerization of above-mentioned polymerizable unsaturated compound and get.This reaction can be carried out in being regardless of under the solvent-free and dispersion solvent of existence, but considers with regard to the stable aspect of bridging property silyl, is preferably non-water system polymerization.
This polyreaction generally is to carry out in inert gas atmosphere, and can use the condition of carrying out in the common radical polymerization.Therefore, there are not activated gas such as oxygen in this polymerization reaction system.Employed rare gas element as, nitrogen, argon gas, helium and carbonic acid gas.In addition, composition of the present invention (B), can above-mentioned specific organometallic compound and contain the bridging property silyl mercaptan compound in the presence of, make the polymerizable unsaturated compound polymerization and get, and be to go up bonding at least one end (in most cases being the nearly all end of polymkeric substance) residue (S-R that breaks away from the hydrogen atom gained that is bonded to sulphur atom from the mercaptan compound that contains the bridging property silyl is arranged
3) polymkeric substance.
In this polymerization, use as catalyzer by Metallocenic compound shown in the formula (1) and contain the formed catalyst for polymerization amount of mercaptan compound of bridging property silyl, can be general catalytic amount, to the unsaturated group of described polymerizable unsaturated compound several 1 mole, Metallocenic compound shown in the formula (1) is generally 0.0000001 to 0.0001 mole, by the employed mole number that contains the mercaptan compound of bridging property silyl, the preferable alloy cyclopentadinyl compound is 10: 1 to 1: 10000 with the mol ratio that contains the mercaptan compound of bridging property silyl.The usage quantity that contains the mercaptan compound of bridging property silyl is generally 0.00001 to 0.7 mole, is preferably 0.0001 to 0.5 mole.
Above-mentioned polyreaction can be according to the kind of polymerizable unsaturated compound, carry out in heating or under heating, or refrigerative carries out simultaneously, but polymeric reaction temperature is preferably, and is set in 0 to 150 ℃, is more preferred from and is set in 25 to 120 ℃.When polymeric reaction temperature is set in this scope, can prevents runaway reaction and stably carry out.In addition, though be subjected to that the unsaturated group of employed polymerizable unsaturated compound is active to be influenced, even but under the situation of using higher (methyl) acrylic ester polymerizable unsaturated compound of polymerizability, when temperature of reaction is below 0 ℃ the time, Metallocenic compound shown in the formula (1) and the mercaptan compound that contains the bridging property silyl still can reduce with activity as catalyzer, reach abundant percent polymerization required time increase and make, so efficient is poor.In addition, even under the situation of using the lower compound of polymerization activity such as styrene type unsaturated compound, when condition is still can reach sufficient percent polymerization more than 25 ℃ the time.
In addition, temperature of reaction is more than 150 ℃ the time, can the system of Himdu logic in the polyreaction shows heating and produces the danger of runaway reaction.Therefore when being set at polymerization temperature below 120 ℃, do not carry out having to keep successful reaction under the situation of runaway reaction.In the polymerization of the present invention, can consider the suitable setting reaction times such as percent polymerization, molecular weight, under for example above-mentioned condition, the reaction times was generally 2 to 12 hours, was preferably 2 to 8 hours.
This polyreaction can be utilized the method that reduces temperature of charge, is preferably the method end that polyreactions such as adding benzoquinones stops agent.When carrying out polymerization with aforesaid method, generally can get percent polymerization is more than 40%, is preferably the polymkeric substance more than 60%.In addition, utilize the weight-average molecular weight (Mw) of the resulting polymers of gel permeation chromatography (GPC) mensuration to be generally 500 to 1000000, be preferably 1000 to 300000, number-average molecular weight (Mw) is generally 500 to 1000000, is preferably 1000 to 100000.Dispersion index (=number-average molecular weight/weight-average molecular weight) is generally 1.02 to 9.0 in addition, is preferably 1.2 to 3.0.
The utilizing the polymerizing catalyst polymerization of composition of the present invention (B) usefulness and polymkeric substance in, will not be mixed with organometallic compound when particularly carrying out the deliming step.In addition, can contain sulfenyl by employed thio-alcohol deutero-by bonding at least a portion end of resulting polymers molecule.Promptly, though cause kind as polymerization with the mercaptan compound that contains the bridging property silyl when using above-mentioned polymerization catalyst, but these mercaptan compounds that contain the bridging property silyl do not have the activity of planting as the polymerization initiation usually, and during organometallic compound shown in the use formula (1), can become by the mercaptan compound that contains the bridging property silyl the thiol group that obtains of being derived with bridging property silyl, utilize organo-metallic catalyst and can begin the polymeric spike, so can be used as monomeric initiation kind.Therefore, in this reaction, increase to amount of monomer contain the mercaptan compound amount of bridging property silyl the time, can promote the percent polymerization of time per unit.In addition, can begin that bonding contains sulfenyl by the employed mercaptan compound institute deutero-that contains the bridging property silyl on the end in the polymerization of resulting polymers.But the employed mercaptan compound that contains the bridging property silyl causes kind of the effect except having polymerization, also has the chain-transfer agent effect, so molecular weight (polymerization degree) and percent polymerization are contained the influence of the mercaptan compound of bridging property silyl deeply.Phenomenon can infer in this reaction that polymeric carries out and stops is radical polymerization thus.In addition, take out the sulphur free radical (S) that mercaptan compound had that contains the bridging property silyl of hydrogen, cause kind of an attack monomers as polymerization once again because of chain transfer.So the polymkeric substance of this polymerization gained is not subject to the usage quantity of the mercaptan compound that contains the bridging property silyl, can make the polymer ends bonding that is generated contain sulfenyl by the employed mercaptan compound institute deutero-that contains the bridging property silyl.
The reactive system of composition of the present invention (B), in dispersion medium such as pure isopolarity organic solvent or water, still can be with carrying out polymerization as solution polymerization or the mass polymerization, so polymerization reaction system is arranged by free radical reaction.Derive out because of chain transfer breaks away from hydrogen so the reaction of resulting polymers stops the mercaptan compound that end is considered to contain silyl, or the thio-alcohol with free radical sulphur free radical and polymkeric substance growth free radical with free radical coupling must the mercaptan compound of silane-group containing derived out contain sulfenyl.
In the resulting polymers, above-mentioned Metallocenic compound can be directly with this form, or residual with metal form with other organic group bondings.In addition, because of the mercaptan compound that contains the bridging property silyl directly helps the formation reaction of polymkeric substance, the oneself reacts when decomposing, so can be from containing the mercaptan compound institute deutero-terminal group importing polymer ends of bridging property silyl.
Be bonded to terminally from the mercaptan compound institute deutero-group that contains the bridging property silyl like this, the activity of bridging property silyl is not influenced by above-mentioned polymeric, still keeps its activity in resulting polymers.The carrying out of above-mentioned inference and reaction can reasonably released by present inventors, but the present invention be not limited to this by various phenomenons in the present invention's reaction.
Composition of the present invention (B), the mercaptan compound that particularly has a bridging property silyl in Metallocenic compound and molecule shown in the above-mentioned formula (1) at least exists down, by (methyl) propylene with polymerizability unsaturated link(age) be monomer polymerization and polymkeric substance, (methyl) acrylic polymer (B1) that wherein is preferably as follows, being included at least one terminal bonding of going up has the residue-S-R that is broken away from gained behind the hydrogen atom by mercaptan compound
3(this R
3For having the group of bridging property silyl) (methyl) acrylic polymer, main chain that preferably should (methyl) acrylic polymer has that 99 weight % are following, repeating unit shown in the following formula (2) that is preferably 95 to 70 weight %, and (methyl) acrylic polymer (B1) of the repeating unit beyond the repeating unit shown in 1 to the 50 weight %, polymerizable unsaturated compound monomer [E] the institute deutero-that has an above bridging property silyl from molecule that is preferably 5 to 30 weight %, formula (2).
Should (methyl) acrylic polymer (B1) have repeating unit shown in the following formula (2), and by outside the polymerizable unsaturated compound monomer institute repeat units derived shown in the following formula (12) etc., can have the monomer institute repeat units derived that repeating unit shown in following formula (10), (11) for example and other (ethene or propylene etc. two, trimer) etc. have reactive unsaturated link(age).These copolymerization amounts from other monomer institute repeat units derived are generally 0 to 40 weight %, are preferably 0 to 20 weight %.In addition, polymerization amount of the present invention is meant, the copolymerization amount of each repeating unit in (being total to) polymkeric substance when all being 100 weight %.
The weight-average molecular weight (Mw) of utilizing gel permeation chromatography (GPC) to measure to this (methyl) acrylic polymer (B1) is generally 500 to 1000000, be preferably 1000 to 300000, number-average molecular weight (Mn) is generally 500 to 1000000, is preferably 1000 to 100000.In addition, dispersion index (=number-average molecular weight/weight-average molecular weight) is generally 1.02 to 9.0, is preferably 1.2 to 3.0.
Be somebody's turn to do (methyl) acrylic polymer (B1) under the state of state that contains solvent or resinous principle 100%, be generally thick liquid, but reaction backs such as adding solidifying agent are curable.In addition, this cured article has elasticity and flexible.Have and have on above-mentioned repeating unit and the polymer ends in mercaptan compound institute deutero-composition unitary (methyl) acrylic polymer that contains silyl, because of the bridging property silyl that imports the bridging property silyl that comes self-ascending type (12) in the main chain and import molecular end has hyperergy, can utilize self-condensation reaction, condensation cross-linking reaction or merge self-condensation reaction and condensation cross-linking reacts and property such as solidified so should (methyl) acrylic polymer (B1) have.
There is no particular restriction for the cooperation ratio of composition (B), is 0.01 to 100 weight part to composition (A) 1 weight part, and special good is 0.1 to 90 weight part.In addition, these (methyl) acrylic polymers can use separately or also use more than 2 kinds.
Preferably go back added ingredients (C) curing catalysts in the solidification compound of the present invention.There is no particular restriction for this composition (C) curing catalysts, for example organometallic compound or amine etc., and special good is silanol condensation catalyst.Described silanol condensation catalyst is as organo-tin compounds such as, stannous octoate, two sad two fourth tin, dibutyl tin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyl diacetyl acetone tin, dibutyl tin oxide, two triethoxy silicic acid dibutyl tin, distearyl acid dibutyl tin, two lauric acid dioctyl tins, dioctyl two tertiary monocarboxylic acid tin, stannous octoate and naphthoic acid tin; Organo-tin compound (C1) shown in the following general formula (5); The reactant of dibutyltin oxide and phthalate etc.; Titanate esters such as tetrabutyl titanate ester, tetrapropyl titanic acid ester; Organo-aluminium compound classes such as praseodynium aluminium, aluminium tris(ethylacetoacetate), diisopropoxy ethyl acetoacetic acid aluminium; Tetrem acyl acetone zirconium, four titanium acetylacetone isochela combination compound classes; Organic lead plumbate such as lead octoate 36 and lead naphthenate; Organic acid bismuths such as Bismuth Octoate, neodecanoic acid bismuth, roseolic acid bismuth; The known an acidic catalyst that other are used as silanol condensation catalyst and basic catalyst etc.
R
9R
10SnO ……(5)
In the formula (5), R
9And R
10The 1 valency alkyl of respectively doing for oneself.This R
9And R
101 valency alkyl there is no particular restriction, preferable alkyl as carbon numbers 1 to 20 such as methyl, ethyl, propyl group, butyl, amyl group, dodecyl, lauryl, propenyl, phenyl, tolyls.R
9And R
10Can be identical or different.Organotin (C1) shown in the above-mentioned general formula (5) is special good to be dialkyl tin oxides such as tin methide oxide compound, dibutyl tin oxide, dioctyltin oxide.
, preferably will contain mentioned component (A), (B) and solidification compound (C1) at least and be enclosed in the encloses container during with organotin (C1) shown in the above-mentioned general formula (5), carry out reaction treatment again to obtain the voltinism of tachy steroling as composition (C).The method of reaction treatment is with the manufacture method of aftermentioned solidification compound of the present invention.
With regard to viewpoints such as rate of crosslinking, cured article rerum naturas, composition (C) is 0.1 to 30 weight part to the cooperation ratio of composition (A) 100 weight parts, and is special good for using 0.5 to 20 weight part.This curing catalysts can use separately or also use more than 2 kinds.
In order to promote binding property and promote to solidify, preferred added ingredients (D) silane coupling agent again in solidification compound of the present invention.This silane coupling agent can be the use thing of previously known, and there is no particular restriction, for example aminosilane classes such as aminoethyl aminopropyl trimethoxysilane, aminoethyl aminopropyl methyl dimethoxysilane, aminoethyl aminopropyl methyl methoxy base silane; Epoxy silane classes such as γ-glycidoxypropyltrime,hoxysilane; γ-methacryloxypropyl trimethoxy silane etc. (methyl) acryloyl silicane; Hydrosulphonyl silane classes such as γ-Qiu Jibingjisanjiayangjiguiwan; Isocynate silane classes such as γ-isocyanic ester propyl trimethoxy silicane etc.
There is no particular restriction for the cooperation ratio of this composition (D), and composition (A) 100 weight parts are preferably 0.1 to 30 weight part, is more preferred from 0.3 to 15 weight part.This silane coupling agent can use separately or also use more than 2 kinds.
Solidification compound of the present invention is except mentioned component, can add rerum natura in case of necessity adjusts agent, weighting agent, softening agent, thixotropic agent, dewatering agent (storage stability modifying agent), adhesion imparting agent, the anti-materials such as agent, UV light absorber, antioxidant, fire retardant, tinting material, radical polymerization initiator that hang, reaches all kinds of SOLVENTS such as toluene, alcohol, in addition, but other polymkeric substance that mix of fusion.
Add above-mentioned rerum natura and adjust the purpose of agent for improving the stretching rerum natura.This rerum natura adjust agent as, the silicon compound that has a silanol group in 1 molecule, for example tri-phenyl-silane alcohol, trialkyl silica alkanol, dialkyl phenyl organic silanol, diphenyl alkyl silanol etc., other as, can generate the various silane coupling agents such as silicon compound that have the compound of a silanol group in 1 molecule after the hydrolysis, for example triphenyl methoxy silane, trialkyl methoxy silane, dialkyl benzene methoxylsilane, diphenyl alkyl methoxy silane, triphenyl Ethoxysilane, trialkyl Ethoxysilane etc.This rerum natura adjustment agent can be used separately or also use more than 2 kinds.
The purpose of adding above-mentioned weighting agent is the reinforcement cured article.This weighting agent as, lime carbonate, magnesiumcarbonate, diatomite silicate hydrate, silicate hydrate, silicic anhydride, Calucium Silicate powder, silicon-dioxide, titanium dioxide, clay, talcum, carbon black, slabstone powder, mica, kaolin, zeolite etc., wherein be preferably lime carbonate, be more preferred from fatty acid treatment lime carbonate.In addition, can use granulated glass sphere, silica beads, alumina bead, carbon pearl, vinylbenzene pearl, phenol pearl, vinylformic acid pearl, porous silica, silica bead, glass sphere, silica spheres, Sha to take turns ball, vinylformic acid ball etc., the few viewpoint of ductile reduction after wherein solidifying from composition is more preferred from the vinylformic acid ball.This weighting agent can use separately or also use more than 2 kinds.
The purpose of adding above-mentioned plasticizer is, but the extensibility that improves after solidifying reaches low modulusization.This softening agent is as, phosphoric acid esters such as tributyl phosphate, tritolyl phosphate; Phthalates such as trioctylphosphine phthalate (DOP), dibutyl phthalate, butyl benzyl phthalate; Fatty acid monovalent esters of gallic acid such as glyceryl monooleate; Lipid acid such as Polycizer W 260, Octyl adipate dibasic ester class; Binary alcohol esters classes such as polypropylene glycol; Aliphatic ester; The epoxy plasticizer class; Polyester is a softening agent; Polyethers; Polystyrene type, acrylic acid series softening agent etc.This softening agent can use separately or also use more than 2 kinds.
Above-mentioned thixotropic agent is as, inorganic thixotropic agent such as colloidal silica, asbestos powder; Organic thixotropic agent such as bentonite, modified poly ester polyalcohols, fatty acid amide; Hydrogenated castor oil derivative, fatty acid amide wax, aluminum stearate, barium stearate etc.This catalyzer agent can be used separately or also use more than 2 kinds.
The purpose of adding above-mentioned dewatering agent is to remove the moisture in preserving.This dewatering agent is as, silane compounds such as vinyltrimethoxy silane, dimethyldimethoxysil,ne, tetraethoxysilane, methyltrimethoxy silane, Union carbide A-162.
Use the purpose of above-mentioned antioxidant to be, the oxidation that prevents to solidify sealing material to be to improve weathering resistance, for example the antioxidant of bulky amine system and sterically hindered phenol system etc.Bulky amine be antioxidant as, N, N ' N "; N -four-(4, two (butyl-(N-methyl-2,2; 6, the 6-tetramethyl piperidine-4-yl) amido)-triazine-2-yls of 6-)-4,7-diaza decane-1; 10-diamines; dibutylamine 1,3,5-triazines N; N '-two-(2,2,6; 6-tetramethyl--4-piperidyl-1,6-hexamethylene-diamine N-(2,2; 6,6-tetramethyl--4-piperidyl) polycondensate of butylamine; it is poly-that [{ 6-(1,1; 3, the 3-tetramethyl butyl) amido-1,3; 5-triazine-2,4-two bases } { (2,2; 6,6-tetramethyl--4-piperidyl) imido grpup } hexa-methylene { (2,2; 6,6-tetramethyl--4-piperidyl) imido grpup }]; Succinic acid dimethylester and 4-hydroxyl-2,2; 6; 6-tetramethyl--1-piperidines alcoholic acid polymkeric substance; [decane diacid two (2,2,6; 6-tetramethyl--1 (octyloxy)-4-piperidyl) ester; 1; the resultant of reaction of 1-dimethyl ethyl hydroperoxide and octane (70%)]-polypropylene (30%); two (1,2,2; 6; 6-pentamethyl--4-piperidyl) [[3, two (1, the 1-the dimethyl ethyl)-4-hydroxy phenyls of 5-] methyl] butyl malonic acid ester; methyl 1; 2; 2,6,6-pentamethyl--4-piperidyl sebate; two (2; 2; 6,6-tetramethyl--4-piperidyl) sebate; two (1,2; 2; 6,6-pentamethyl--4-piperidyl) sebate; 1-[2-[3-[3,5-two-tertiary butyl-4-hydroxyphenyl] propionyloxy] ethyl]-4-[3-(3; 5-two-tertiary butyl-4-hydroxyphenyl) propionyloxy]-2; 2,6, the 6-tetramethyl piperidine; 4-benzoyloxy group-2; 2; 6, the 6-tetramethyl piperidine; 8-ethanoyl-3-dodecyl-7,7; 9; 9-tetramethyl--1,3,8-thriazaspiro [4.5] decane-2; 4-diketone etc., but non-this example that is limited to.Sterically hindered phenol be antioxidant as, [3-(3 for tetramethylolmethane-four, 5-two-tert-butyl-hydroxy phenyl) propionic ester], [3-(3 for sulphur diethylene-two, 5-two-tert-butyl-hydroxy phenyl) propionic ester], octadecyl-3-(3,5-two-tert-butyl-hydroxy phenyl) propionic ester, N, N '-hexane-1,6-two bases are two, and [3-(3,5-two-tertiary butyl-4-hydroxyphenyl propionic acid amide), phenylpropionic acid 3,5-two (1, the 1-dimethyl ethyl)-4-hydroxyl C7-C9 branched alkyl ester, 2,4-dimethyl-6-(1-methyl pentadecyl) phenol, diethyl [[3, two (1, the 1-the dimethyl ethyl)-4-hydroxy phenyls of 5-] methyl] phosphonic acid ester, 3,3 '; 3 " 5,5 ', 5 "-and hexane-tertiary butyl-4-a; a '; a "-(sym-trimethylbenzene-2,4,6-tolyl) three-p-cresol, calcium diethyl two [[3,5-two-(1, the 1-dimethyl ethyl)-and the 4-hydroxyphenyl] methyl] phosphonic acid ester], 4, two (octyl group the thiomethyl)-ortho-cresols of 6-, two (ethylene oxide) two [3-(5-tertiary butyl-4-hydroxy-m-tolyl) propionic esters] of ethylene, hexamethylene two [3-(3,5-two-tert-butyl-hydroxy phenyl) propionic ester], 1,3,5-three (3,5-two-tertiary butyl-4-acrinyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-triketone, N-phenylaniline and 2,4, the resultant of reaction of 4-2,4,4-Trimethyl-1-pentene, 2,6-two-tertiary butyl-4-(4, two (the octyl group sulphur)-1 of 6-, 3,5-triazine-2-base amido) phenol etc., but non-this example that is limited to.This antioxidant can use separately or also use more than 2 kinds.
Use the purpose of above-mentioned UV light absorber to be, prevent to solidify sealing material light deterioration to improve weathering resistance, for example benzotriazole is, triazine system, benzophenone series, UV light absorber such as benzoic ether system etc., it for example, 2,4-two-tert-butyl-6-(5-chlorobenzotriazole-2-yl) phenol, 2-(2H-benzotriazole-2-yl)-4,6-two-tetr-amyl phenol, 2-(2H-benzotriazole-2-yl)-4-(1,1,3, the 3-tetramethyl butyl) phenol, the resultant of reaction of methyl 3-(3-(2H-benzotriazole-2-yl)-5-tetr-butyl-4-hydroxy phenyl) propionic ester/Liquid Macrogol, (straight chain and side chain dodecyl)-benzotriazoles such as 4-methylphenol are UV light absorber to 2-(2H-benzotriazole-2-yl)-6-; 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5-[(hexyl) oxygen base]-triazines such as phenol are UV light absorber; Benzophenone series UV light absorber such as eight benzoins; 2,4-two-tetr-butyl phenyl-3,5-two-retr-butyl-4-hydroxybenzoate is a UV light absorber etc., but non-this example that is limited to.This UV light absorber can be used separately or also use more than 2 kinds.
The 2nd form of solidification compound of the present invention is, contains (A) and contains the organic polymer of bridging property silyl and (C1) organotin shown in the following general formula (5).
R
9R
10SnO……(5)
(in the formula, R9 and the R10 1 valency alkyl of respectively doing for oneself.)
This composition (A) and (C1) with the 1st form of above-mentioned solidification compound of the present invention.In addition, employed composition (A) can be, (methyl) acrylic polymer (B) with bridging property silyl that patent documentation 1 is disclosed.Mentioned component (C1) is with the 1st form of above-mentioned solidification compound of the present invention, and its cooperation ratio can be with the 1st form of above-mentioned solidification compound of the present invention.Except this composition, can contain additive with the 1st form.
There is no particular restriction for solidification compound of the present invention, but owing to can promote the solidification compound that therefore solidified nature preferably utilizes the manufacture method of solidification compound of the present invention to make.The manufacture method of solidification compound of the present invention is, the solidification compound that will contain the above-mentioned organotin (C1) that above-mentioned polymkeric substance (A) and curing catalysts use at least is enclosed in the encloses container, carries out the method for the reaction treatment used for the voltinism that obtains to tachy sterol again.
Tachy steroling as above-mentioned acquisition, there is no particular restriction for the reaction treatment that voltinism uses, and for example can keep to the normal temperature till the voltinism of finding to tachy sterol at low temperature, or carry out heat treated.This heat treated is preferably, and carries out under 30 ℃ to 150 ℃ 30 minutes to 3 days.Use above-mentioned organotin (C1) to have higher manufacturing stability and solidified nature mitigation as the solidification compound of the present invention of curing catalysts (C), usually preserve at normal temperatures and still can find original voltinism of tachy steroling after one month, but can obviously promote solidified nature after applying above-mentioned heat treated.In addition, can according to circumstances suitably carry out this heating.
Embodiment
To specify the present invention with embodiment below, but this embodiment is only non-limiting for illustration.
(synthesis example 1)
Dimethylbenzene 43 weight parts, methyl methacrylate 80 weight parts, stearyl methacrylate 20 weight parts, γ-methacryloxypropyl trimethoxy silane 20 weight parts and metal catalyst put into ruthenocene dichloride 0.1 weight part have the flask that whipping appts, nitrogen ingress pipe, temperature are taken into account the reflux cooling pipe, import under the nitrogen flask contents is heated to 80 ℃.
Then, stir adding next time fully with 3-sulfydryl propyl trimethoxy silicane 20 weight parts of nitrogen replacement, behind adding 3-sulfydryl propyl trimethoxy silicane 20 weight parts, carry out heating in 4 hours and cooling, the temperature maintenance that makes flask contents in the stirring is 80 ℃.Under agitation with 5 minute in clockwise flask append fully with nitrogen metathetical 3-sulfydryl propyl trimethoxy silicane 20 weight parts thereafter.After appending 3-sulfydryl propyl trimethoxy silicane 20 weight part full doses, limit cooling and heat so that in stirring the temperature maintenance of flask contents be 90 ℃, the limit carries out reacting in 4 hours.
As above-mentioned, after 8 hours 5 minutes the reaction of total, temperature of charge is returned room temperature, again benzoquinones solution (95%THF solution) 20 weight parts are added in the reactant to stop polymerization.Then add 150 weight parts as the match li SAT-200 that contains the organic polymer (A) of bridging property silyl (the polyoxyalkylene based polymer, the bridging property silyl that contain the bridging property silyl: methyl dimethoxy oxygen base silyl, clock deep pool chemical industry (thigh) system).
Then the gained reactant is moved in the vaporizer, decompression slowly is heated to 80 ℃ down with after removing dimethylbenzene, THF, remaining monomer and remaining mercaptan compound, has obtained containing the polyoxyalkylene based polymer (A) of bridging property silyl and the mixture 1 of (methyl) acrylic polymer (B).
(synthesis example 2)
Except replace methyl methacrylate 80 weight parts in the flask contents with n-butyl acrylate 10 weight parts and methyl methacrylate 70 weight parts, other are synthetic with synthesis example 1, have obtained containing the polyoxyalkylene based polymer (A) of bridging property silyl and the mixture 2 of (methyl) acrylic polymer (B).
(synthesis example 3)
Except replace dimethylbenzene 43 weight parts, methyl methacrylate 80 weight parts and octadecyl acrylate 20 weight parts in the flask contents with n-butyl acrylate 10 weight parts, methyl methacrylate 70 weight parts and octadecyl acrylate 20 weight parts, other are synthetic with synthesis example 1, have obtained containing the polyoxyalkylene based polymer (A) of bridging property silyl and the mixture 3 of (methyl) acrylic polymer (B).
(synthesis example 4)
Except with ES-GX3440ST (the polyoxyalkylene based polymer, the bridging property silyl that contain the bridging property silyl: trimethoxysilyl, Asahi Glass (thigh) system) conduct in the 150 weight parts replacement flask contents contains match li SAT-200 (the bridging property silyl: methyl dimethoxy oxygen base silyl) outside 150 weight parts of the organic polymer (A) of bridging property silyl, other are synthetic with synthesis example 3, obtain containing the polyoxyalkylene based polymer (A) of bridging property silyl and the mixture 4 of (methyl) acrylic polymer (B).
(synthesis example 5)
Except with match li SAT-200 (bridging property silyl: 75 weight parts and ES-GX3440ST (bridging property silyl: trimethoxysilyl) 75 weight parts methyl dimethoxy oxygen base silyl), conduct in the replacement flask contents contains match li SAT-200 (the bridging property silyl: 150 weight parts methyl dimethoxy oxygen base silyl) of the organic polymer (A) of bridging property silyl, other are synthetic with synthesis example 3, have obtained containing the polyoxyalkylene based polymer (A) of bridging property silyl and the mixture 5 of (methyl) acrylic polymer (B).
(synthesis example 6)
Except with match li MA-440 ((methyl) propenyl modification polyoxyalkylene polymers that contains the bridging property silyl, bridging property silyl: methyl dimethoxy oxygen base silyl, clock deep pool chemical industry (thigh) system) conduct in the 150 weight parts replacement flask contents contains match li SAT-200 (the bridging property silyl: the methyl dimethoxysilane base) outside 150 weight parts of the organic polymer (A) of bridging property silyl, other are synthetic with synthesis example 3, have obtained containing (methyl) propenyl modification polyoxyalkylene polymers (A) of bridging property silyl and the mixture 6 of (methyl) acrylic polymer (B).
(relatively synthesis example 1)
Dimethylbenzene 43 weight parts, methyl methacrylate 80 weight parts, stearyl methacrylate 20 weight parts, γ-methacryloxypropyl trimethoxy silane 20 weight parts and metal catalyst ruthenocene dichloride 0.1 weight part put into have the flask that whipping appts, nitrogen ingress pipe, temperature are taken into account the reflux cooling pipe, the limit imports nitrogen bottom flask contents is heated to 80 ℃.
Then, under agitation abundant 3-sulfydryl propyl trimethoxy silicane 20 weight parts with nitrogen replacement are once added in the flask.Carry out heating in 4 hours and cooling after adding 3-sulfydryl propyl trimethoxy silicane 20 weight parts, the temperature maintenance that makes flask contents in the stirring is in 80 ℃.Stir down 5 minute to append fully 3-sulfydryl propyl trimethoxy silicane 20 weight parts with nitrogen replacement thereafter.After appending 3-sulfydryl propyl trimethoxy silicane 20 weight parts, the limit is cooled off and is heated so that the temperature maintenance of flask contents is in 90 ℃ in stirring, and reacted 4 hours on the limit.
Add up to reaction after 8 hours 5 minutes like this, make temperature of charge get back to room temperature, add benzoquinones solution (95%THF solution) 20 weight parts again and make reactant stop polymerization.
The gained reactant is moved in the vaporizer, and decompression slowly is heated to 80 ℃ to remove THF and remaining monomer, remaining mercaptan compound down, has obtained (methyl) acrylic polymer 1 (B).
(relatively synthesis example 2)
Except replace methyl methacrylate 80 weight parts in the flask contents with n-butyl acrylate 10 weight parts, methyl methacrylate 70 weight parts, other have obtained (methyl) acrylic polymer 2 (B) with relatively synthesis example 1 is synthetic.
(relatively synthesis example 3)
Except replace dimethylbenzene 43 weight parts, methyl methacrylate 80 weight parts and octadecyl acrylate 20 weight parts in the flask contents with n-butyl acrylate 10 weight parts, methyl acrylate 70 weight parts and stearyl acrylate 20 weight parts, other have obtained (methyl) acrylic polymer 3 (B) with relatively synthesis example 1 is synthetic.
(relatively synthesis example 4)
To be heated to 110 ℃ dimethylbenzene 45 weight parts, methyl methacrylate 80 weight parts, stearyl methacrylate 20 weight parts, γ-methacryloxypropyl trimethoxy silane 2.5 weight parts, 3-sulfydryl propyl trimethoxy silicane 2.1 weight parts as flask contents, splashed into the solution that is dissolved with polymerization starter azobis isobutyronitrile 7.4 weight parts with 6 hours again, polymerization adds after 2 hours as match li SAT-200 (the bridging property silyl: the 150 weight parts methyl dimethoxysilane base) that contains the polyoxyalkylene based polymer (A) of bridging property silyl.
Then the gained reactant is moved in the vaporizer, decompression slowly is heated to 80 ℃ down to remove dimethylbenzene and remaining monomer, has obtained containing the polyoxyalkylene based polymer (A) of bridging property silyl and the mixture 7 of (methyl) acrylic polymer.
(embodiment 1)
According to polyoxyalkylene polymers that contains the bridging property silyl (A) of adding a certain amount of synthesis example 1 gained shown in the table 1 respectively and mixture 1, vinyltrimethoxy silane, amino silane compounds and curing catalysts (C) No.918 (reactant of dibutyl tin oxide and phthalate) that contains (methyl) acrylic polymer (B) of bridging property silyl, the modulation solidification compound.
Table 1
| Embodiment | Comparative example | |||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 1 | 2 | 3 | |
| Mixture 1 (A)+(B) *1 | 100 | - | - | - | - | - | 100 | - | - | - |
| Mixture 2 (A)+(B) *2 | - | 100 | - | - | - | - | - | - | - | - |
| Mixture 3 (A)+(B) *3 | - | - | 100 | - | - | - | - | - | - | - |
| Mixture 4 (A)+(B) *4 | - | - | - | 100 | - | - | - | - | - | - |
| Mixture 5 (A)+(B) *5 | - | - | - | - | 100 | - | - | - | - | - |
| Mixture 6 (A)+(B) *6 | - | - | - | - | - | 100 | - | - | - | - |
| (methyl) acrylic polymer 1 (B) *7 | - | - | - | - | - | - | - | 143 | - | - |
| (methyl) acrylic polymer 2 (B) *8 | - | - | - | - | - | - | - | 143 | - | |
| (methyl) acrylic polymer 3 (B) *9 | - | - | - | - | - | - | - | - | - | 100 |
| No.918(C) *10 | 2 | 2 | 2 | 2 | 2 | 2 | - | 2 | 2 | 2 |
| ネオスンU-300(C1) *11 | - | - | - | - | - | - | 2 | - | - | - |
| Amino silane compounds (D) *12 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 |
| Vinyltrimethoxy silane | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
The addition of the substance of table 1 be weight part,
*1 to
*12 is as follows.
*1: synthesis example 1 gained contains the polyoxyalkylene polymers (A:150 weight part) and the mixture 1 that contains (methyl) acrylic polymer (B:100 weight part) of bridging property silyl of bridging property silyl
*2: synthesis example 2 gained contain the polyoxyalkylene polymers (A) and the mixture 2 that contains (methyl) acrylic polymer (B) of bridging property silyl of bridging property silyl
*3: synthesis example 3 gained contain the polyoxyalkylene polymers (A:150 weight part) and the mixture 3 that contains (methyl) acrylic polymer (B:100 weight part) of bridging property silyl of bridging property silyl
*4: synthesis example 4 gained contain the polyoxyalkylene polymers (A:150 weight part) and the mixture 4 that contains (methyl) acrylic polymer (B:100 weight part) of bridging property silyl of bridging property silyl
*5: synthesis example 5 gained contain the polyoxyalkylene polymers (A:150 weight part) and the mixture 5 that contains (methyl) acrylic polymer (B:100 weight part) of bridging property silyl of bridging property silyl
*6: synthesis example 6 gained contain the polyoxyalkylene polymers (A:150 weight part) and the mixture 6 that contains (methyl) acrylic polymer (B:100 weight part) of bridging property silyl of bridging property silyl
*7: relatively synthesis example 1 gained contains (methyl) acrylic polymer (B) of bridging property silyl
*8: relatively synthesis example 2 gained contain (methyl) acrylic polymer (B) of bridging property silyl
*9: relatively synthesis example 3 gained contain (methyl) acrylic polymer (B) of bridging property silyl
*10: three total machine synthetic (thigh) system trade(brand)name: No.918 (reactant of dibutyl tin oxide and phthalate)
*11: day east changes into (thigh) system trade(brand)name: ネ オ ス Application U-300 (dibutyl tin oxide)
*12:N-β (amino-ethyl) gamma-amino propyl trimethoxy silicane
(embodiment 2 to 6)
Except according to change shown in the table 1 substance and the adding proportion, other experimentize with embodiment 1.
(embodiment 7)
According to inserting in the tube (cartridge) that covers with aluminium so that the No.918 (reactant of dibutyltin oxide and phthalate) of a certain amount of ネ オ ス Application U-300 (dibutyl tin oxide) substitute ingredient (C) back is airtight shown in the table 1, again with 50 ℃ of heating curings 3 days.With embodiment 1 experimentize thereafter.
(comparative example 1 to 3)
Except according to change shown in the table 1 substance and the adding proportion, other experimentize with embodiment 1.
Above-mentioned gained solidification compound is carried out following mensuration, and the result is as shown in table 2.1. binding property
According to the tension fracture bonding strength test method of JIS K 6850 rigidity adhesion materials, and with alumite and Tsuga sieboldii plate as bur.For collapse state, will condense to destroy and be shown zero, interfacial failure is shown *.
2. rubber rerum natura
According to the stretching test method of JIS K 6521 vulcanized rubbers, and use dumbbell shaped No. 3.Be shown in the time of can not surveying *.
3. deep solidified nature
The solidification compound that is adjusted into 23 ℃ is filled in the container of the only direction porous more than the diameter 4cm, more than the high 2cm, and makes the surface be level and smooth shape.Measure 23 ℃, following 24 hours after fixing thickness of 50%RH environment with dial ga(u)ge.
4. storage stability
With solidification compound respectively after placing 24 hours under 23 ℃, 50%RH environment, to record the result as the initial stage with Brookfield viscometer (No. 7 10rpm of eastern machine industry system BS rotor), in 50 ℃ of moisture eliminators, placed for 2 weeks then, placed 24 hours down in 23 ℃, 50%RH environment again, after the liquid temperature was adjusted into 23 ℃, the viscosity results that will record with identical method was as storage back viscosity.The storage back/the initial stage value be lower than 1.3 be shown being shown more than zero, 1.3 *.
5. drying time of finger-touching
Measure drying time of finger-touching according to JIS A 1,439 4.19.Drying time of finger-touching be lower than 10 minutes be shown being shown more than zero, 10 minute *.
Table 2
| Embodiment | Comparative example | ||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 1 | 2 | 3 | ||
| Binding property | Final strength (N/mm 2) | 3.1 | 2.7 | 2.1 | 2.1 | 2.2 | 2.7 | 3.2 | 2.6 | 2.4 | 1.6 |
| The destruction situation | ○ | ○ | ○ | ○ | ○ | ○ | ○ | × | × | × | |
| The rubber rerum natura | Final strength (N/mm 2) | 4.1 | 3.7 | 1.5 | 1.5 | 1.6 | 3.8 | 4.2 | × | × | × |
| Extensibility (%) | 125 | 130 | 110 | 110 | 120 | 90 | 130 | × | × | × | |
| The deep solidified nature | 1.6 | 1.7 | 1.7 | 1.5 | 1.5 | 1.3 | 1.5 | 0.7 | 0.9 | 0.9 | |
| The storage stability | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |
| Drying time of finger-touching | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |
According to shown in the table 2, have good adhesive property, rubber rerum natura, deep solidified nature and storage stability with respect to embodiment 1 to 7, the comparative example 1 to 3 that does not contain composition (A) has binding property and rubber rerum natura problem, and the deep solidified nature is relatively poor.
(embodiment 8)
According to behind the polyoxyalkylene polymers that contains the bridging property silyl (A) of adding a certain amount of synthesis example 1 gained shown in the table 3 respectively and the mixture 1, weighting agent, vinyltrimethoxy silane that contain (methyl) propene polymer (B) of bridging property silyl, mix stirring 2 hours with 110 ℃ of heating decompressions, again additive is dewatered.Add a certain amount of amino silane compounds and No.918 (reactant of dibutyl tin oxide and phthalate) then respectively, modulated solidification compound.
Table 3
| Embodiment 8 | Embodiment 9 | Comparative example 4 | |
| Mixture 1 (A)+(B) *1 | 100 | - | - |
| Mixture 4 (A)+(B) *4 | - | 100 | - |
| Mixture 7 (A) *13 | - | - | 100 |
| No.918(C) *10 | 2 | 2 | 2 |
| Amino silane compounds (D) *12 | 3 | 3 | 3 |
| Weighting agent *14 | 40 | 40 | 40 |
| Vinyltrimethoxy silane | 2 | 2 | 2 |
The addition of the substance of table 3 is a weight part,
*1,
*4,
*10 reach
*12 with table 1,
*13 reach
*14 is as follows.
*13: the polyoxyalkylene polymers that contains the bridging property silyl (A:150 weight part) and the mixture that contains (methyl) acrylic polymer (100 weight part) of bridging property silyl that compare synthesis example 4 gained
*14: fatty acid treatment lime carbonate (trade(brand)name: the card non-200M in road, ball tail calcium (thigh) system)
(embodiment 9 and comparative example 4)
Except according to change shown in the table 3 substance and the adding proportion, other experimentize with embodiment 8.
Above-mentioned gained solidification compound is measured binding property, storage stability and drying time of finger-touching.In addition, according to the tension fracture bonding strength test method of JIS K 6850 rigidity adhesion materials, measure the binding property of various burs shown in the table 4.The method of measuring storage stability and drying time of finger-touching is with embodiment 1, and the result is as shown in table 4.
Table 4
| Embodiment 8 | Embodiment 9 | Comparative example 4 | ||
| Binding property | Alumite | 4.1 | 4.0 | 3.2 |
| Vinylformic acid | 4.0 | 4.1 | 3.0 | |
| Polycarbonate | 4.1 | 4.1 | 3.1 | |
| Polystyrene | 2.9 | 2.8 | 2.5 | |
| ABS | 3.5 | 3.7 | 2.8 | |
| Storage stability | ○ | ○ | ○ | |
| Drying time of finger-touching (branch) | ＜10 | ＜10 | 15 | |
As shown in table 4, have good adhesive property and bonding strength with respect to embodiment 8 and 9, the bonding strength of comparative example 4 is lower.
(synthesis example 7)
With glycerine is initiator, and uses under the zinc six cyanogen cobalt catalyst and carry out the propylene oxide polymerization, gets the poly(propylene oxide) triol.Add the isocyanic ester propyl trimethoxy silicane then and carry out the urethane reaction, make end be transformed to trimethoxysilyl, get the polymer P 1 of molecular weight 18000.
(synthesis example 8)
The isocyanic ester propyl trimethoxy silicane is joined the system UH-2000 of East Asia Synesis Company (molecular weight 11000, viscosity 14000mPas/25 ℃, Tg-55 ℃/DSC, OHV 20mg-KOH/g-resin) carries out the urethane reaction in, make end be transformed to trimethoxysilyl, obtained polymer P 2.
(embodiment 10)
After putting into a certain amount of organic polymer (A), protective agent, lime carbonate and vinyltrimethoxy silane that contains the bridging property silyl shown in the table 5 respectively, 110 ℃ down the heating decompression mix and stirred 2 hours, again substance is dewatered.Then add amino silane compounds (D) and dibutyl tin oxide (C1), decompression mixing stirring is airtight after 10 minutes inserts in the aluminium lining tube modulation solidification compound.In addition, the employed stirrer of present embodiment is made omnipotent mixing and blending machine for product river industry (thigh).
Table 5
| Embodiment | Comparative example | ||||||
| 10 | 11 | 12 | 13 | 14 | 5 | 6 | |
| Polymer P 1 (A) *15 | 100 | - | 50 | - | 100 | 100 | 100 |
| Polymer P 2 (A) *16 | - | 100 | - | - | - | - | - |
| SAT-200(A) *17 | - | - | 50 | 100 | - | - | - |
| STANN BO(C1) *18 | 2 | 2 | 2 | 2 | - | - | - |
| ネオスン U-800(C1) *19 | - | - | - | - | 3 | - | - |
| No.918(C) *10 | - | - | - | - | - | 4 | - |
| ネオスン U-200(C1) *20 | - | - | - | - | - | - | 4 |
| Amino silane compounds (D) *12 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
| Protective agent *21 | 3 | 3 | 3 | 3 | 3 | 3 | 3 |
| Weighting agent *14 | 70 | 70 | 70 | 70 | 70 | 70 | 70 |
| Vinyltrimethoxy silane | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
The addition of the substance of table 5 is (g),
*10,
*12 reach
*14 with table 1 and table 3,
*15 to
*21 is as follows.
*15: the polymer P 1 of above-mentioned synthesis example 7 gained
*16: the polymer P 2 of above-mentioned synthesis example 8 gained
*17: the polyoxyalkylene polymers (clock deep pool chemistry (thigh) system trade(brand)name SAT-200, the bridging property silyl is 2 officials energy) that contains the bridging property silyl
*18: three total machine synthetic (thigh) system trade(brand)name STANN BO (dibutyl tin oxide)
*19: day east changes into (thigh) system trade(brand)name ネ オ ス Application U-800 (oxidation two hot tin)
*20: day east changes into (thigh) system trade(brand)name ネ オ ス Application U-220 (dibutyl diacetyl acetone tin)
*21: Ji Basi (thigh) system commodity well-known saying slave compares B75
(embodiment 11 to 14 and comparative example 5,6)
Except according to change shown in the table 5 substance and the adding proportion, other are with embodiment 10 modulation solidification compounds.
Described gained solidification compound is carried out following performance test.
1) drying time of finger-touching
To embodiment 10 and comparative example 5 gained solidification compounds carry out under 20 ℃, 50 ℃ and 80 ℃ through the time drying time of finger-touching the variation test.In addition, be to measure drying time of finger-touching according to JIS A 14394.19, the result is as shown in Figure 1.
As shown in Figure 1, with respect to the solidification compound of embodiment 10 after according to manufacturings such as temperature and elapsed time treatment condition and drying time of finger-touching changes, the drying time of finger-touching of comparative example 5 is a certain value, is not subjected to the influence in temperature and elapsed time.
Solidification compound to embodiment 10 to 14 and comparative example 5,6 gained, measure drying time of finger-touching soon after making, and the solidification compound after carrying out reaction treatment under the condition shown in the table 6 has been measured drying time of finger-touching, and the result is shown in table 6 and table 7 (measurement result of reaction treatment after fixing composition).
Table 6
| Embodiment | Comparative example | ||||||
| 10 | 11 | 12 | 13 | 14 | 5 | 6 | |
| After the manufacturing (branch) soon | 480 | 460 | 720 | 1440 | 1200 | 5 | 5 |
| 20 ℃ 14 days (branch) | 5 | 5 | 15 | 30 | 20 | 5 | 5 |
| 50 ℃ 3 days (branch) | 5 | 5 | 15 | 30 | 20 | 5 | 5 |
| 80 ℃ 1 day (branch) | 5 | 5 | 15 | 30 | 20 | 5 | 5 |
2) make stability
According to soon drying time of finger-touching after the manufacturing of above-mentioned gained solidification compound, estimate and make stability.Drying time of finger-touching was shown zero more than 30 minutes, be lower than 30 minutes be shown *, the result is as shown in table 7.
3) goods stability
Will be in embodiment 10 to 14 at the solidification compound of 50 ℃ of reaction treatment after 3 days, and soon solidification compound after in comparative example 5,6, will making, under 23 ℃, 50%RH environment, place after 24 hours respectively, (No. 7 10rpm of eastern machine industry system BS rotor) record the result with Brookfield viscometer, and with this result as the initial stage, after then above-mentioned solidification compound being placed for 2 weeks again in 50 ℃ of drying machines, placed 24 hours down in 23 ℃, 50%RH environment, the liquid temperature is adjusted into 23 ℃, similarly carry out the mensuration of viscosity, and with this result as the storage after value.The storage back/the initial stage value be lower than 1.3 be shown being shown more than zero, 1.3 *, the result is as shown in table 7.
4) binding property
Will be among the embodiment 10 to 14 at the solidification compound of 50 ℃ of reaction treatment after 3 days, and soon solidification compound after in comparative example 5,6, will making, with wide 30mm, long 50mm, high 5mm mode separate application on alumite as bur, under 23 ℃, 50%RH maintenance after 14 days test film.After utilizing cutting machine incision end, solidification compound is peeled off from bur with hand.In addition, solidification compound occurs being shown zero when cohesion destroys, be shown during interfacial failure *, the result is as shown in table 7.
Table 7
| Embodiment | Comparative example | ||||||
| 10 | 11 | 12 | 13 | 14 | 5 | 6 | |
| Make stability | ○ | ○ | ○ | ○ | ○ | × | × |
| Drying time of finger-touching (branch) | 5 | 5 | 15 | 30 | 20 | 5 | 5 |
| Goods stability | ○ | ○ | ○ | ○ | ○ | × | × |
| Binding property | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
Shown in table 6 and table 7, have good manufacturing stability, the voltinism of tachy steroling, goods stability and binding property with respect to embodiment 10 to 14, there is the problem of making stability and goods stability in comparative example 5 and 6.
Utilize possibility on the industry
Solidification compound of the present invention can be one-pack-type or dual liquid type as required, and special good is one-pack-type. Solidification compound of the present invention is applicable to encapsulant, bonding agent, adhesive, coating material, pottery making material etc. Solidification compound of the present invention is special good for being used in bonding agent, in addition, can be used in other various buildings and use with, electric and electronic field with, building with, automobile etc.
Claims (15)
1. solidification compound, contain:
(A) contain the organic polymer of bridging property silyl, and
(B) Metallocenic compound shown in the following formula (1) with contain the bridging property silyl mercaptan compound in the presence of, make (methyl) propylene with polymerizability unsaturated link(age) be monomer polymerization and, bonding at least one end have break away from hydrogen atom from the mercaptan compound that contains the bridging property silyl after the residue-S-R of gained
3(R
3For having the group of bridging property silyl) (methyl) acrylic polymer;
(in the formula (1), M is for from metal, chromium, ruthenium and palladium constituted the one group selected metal by periodictable 4 families, 5 families, 14 families; R
1And R
2Represent independently of one another from by having substituent aliphatic alkyl, can have substituent alicyclic alkyl, can have substituent aromatic hydrocarbyl and can having the substituent at least a kind of selected group silica-based a group of constituting that contains, or any in hydrogen atom or the singly-bound, in addition, R
1And R
225 yuan of ring keies in the compound close shown in the wushu (1) jointly, and the R of a plurality of adjacency
1Or R
2Can form atoll texture jointly; A and b independently are 1 to 4 integer separately; Alkyl or the halogen atom of Y for being replaced by halogen atom to the small part hydrogen atom, n are 0 or the integer of the valence mumber-2 of metal M.)
2. solidification compound according to claim 1, wherein, the main chain of (methyl) acrylic polymer (B) has the repeating unit shown in the following following formula (2) of 99 weight % and has polymerizable unsaturated compound monomer institute repeat units derived beyond the repeating unit, contain an above bridging property silyl from molecule shown in the formula (2) of 1 to 50 weight %;
(in the formula (2), R
4To R
6Independent separately is the alkyl of hydrogen atom, halogen atom or carbon number 1 to 3; R
7Be hydrogen atom, alkali metal atom, (this alkyl can be the straight chain shape or has side chain the alkyl of carbon number 1 to 22, and this alkyl or form in the group of side chain of this alkyl to the small part hydrogen atom can selected free chlorine atom, fluorine atom, primary amine groups, secondary amine, tertiary amine groups, the quaternary ammonium salts group, amide group, isocyanate group, the alkylene oxide base, the hydroxyl silyl, the methoxy methyl silylation, the (ethoxymethyl) silylation, the propoxy-silyl, the chloromethane silylation, silyl bromide base and epoxypropyl constituted in one group at least a polar group or reactive functional group replace, this alkyl can have two keys in addition, and this alkyl can have atoll texture)).
3. solidification compound according to claim 1 and 2, wherein, the bridging property silyl in (methyl) acrylic polymer (B) is shown in following general formula (3):
-SiX
3(3) (in the formula (3), X is hydroxyl or hydrolization group, and 3 X can be identical or different).
4. according to any described solidification compound in the claim 1～3, wherein, the bridging property silyl in above-mentioned (methyl) acrylic polymer (B) has the bridging property silyl shown in bridging property silyl shown in the following general formula (3) and the following general formula (4) simultaneously;
-SiX
3 ……(3)
(in formula (3) and the formula (4), X is hydroxyl or hydrolization group, and they can be identical or different when having a plurality of X; R in the formula (4)
8Be 1 valency organic group of the replacement or the non-replacement of carbon number 1 to 20, and have a plurality of R
8The time they can be identical or different; C is 1 or 2.)
5. according to any described solidification compound in the claim 1～4, wherein, above-mentioned (methyl) acrylic polymer (B) is, contains (methyl) acrylic polymer of bridging property silyl shown in the following general formula (3) and contains the mixture of (methyl) acrylic polymer of bridging property silyl shown in the following general formula (4).
-SiX
3 …………………(3)
(in formula (3) and the formula (4), X is hydroxyl or hydrolization group, and they can be identical or different when having a plurality of X; In the formula (4), R
8Be the replacement or the non-replacement 1 valency organic group of carbon number 1 to 20, and have a plurality of R
8The time they can be identical or different, c is 1 or 2.)
6. according to any described solidification compound in the claim 1～5, wherein also contain (C) curing catalysts.
7. solidification compound according to claim 6, wherein said curing catalysts (C) contains organotin shown in (C1) following general formula (5).
R
9R
10SnO ... (5) (in the formula, R
9And R
10Be respectively 1 valency alkyl.)
8. solidification compound contains organic polymer that (A) contain the bridging property silyl, and (C1) organotin shown in the following general formula (5)
R
9R
10SnO ... (5) (in the formula, R
9And R
10Be respectively 1 valency alkyl.)
9. according to claim 7 or 8 described solidification compounds, wherein described solidification compound is carried out reaction treatment again.
10. according to any described solidification compound in the claim 1～9, wherein said polymkeric substance (A) is the organic polymer that contains bridging property silyl shown in the following general formula (3),
-SiX
3 ……(3)
(in the formula (3), X is hydroxyl or hydrolization group, and 3 X can phase or different.)
11. according to any described solidification compound in the claim 1～10, wherein said polymkeric substance (A) is the organic polymer that has bridging property silyl shown in bridging property silyl shown in the following general formula (3) and the following general formula (4) simultaneously.
-SiX
3 …………………(3)
(in formula (3) and (4), X is hydroxyl or hydrolization group, and these can be identical or different when having a plurality of X; In the formula (4), R
8Be the replacement or the non-replacement 1 valency organic group of carbon number 1 to 20, and have a plurality of R
8The time these can be identical or different; C is 1 or 2.)
12. according to any described solidification compound in the claim 1～11, wherein said polymkeric substance (A) is for to contain the organic polymer of bridging property silyl shown in the following general formula (3), and contains the mixture of the organic polymer of bridging property silyl shown in the following general formula (4).
-SiX
3 …………………(3)
(in formula (3) and (4), X is hydroxyl or hydrolization group, and these can be identical or different when having a plurality of X; In the formula (4), R
8Be the replacement or the non-replacement 1 valency organic group of carbon number 1 to 20, and have a plurality of R
8The time these can be identical or different; C is 1 or 2.)
13. according to any described solidification compound in the claim 1～12, wherein said polymkeric substance (A) be selected from by the polyoxyalkylene based polymer that contains the bridging property silyl, contain the bridging property silyl (methyl) propenyl modification polyoxyalkylene polymers, contain the polyisobutene based polymer of bridging property silyl and contain in one group that (methyl) acrylic polymer of bridging property silyl forms at least a kind.
14., wherein also add (D) silane coupling agent according to any described solidification compound in the claim 1～13.
15. the manufacture method of a solidification compound, it is the method for making any described solidification compound in the claim 7～14, to containing described organotin (C1) as curing catalysts and be enclosed in solidification compound in the encloses container, carry out reaction treatment again.
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|---|---|---|---|
| CN2009100064661A Expired - Lifetime CN101486822B (en) | 2003-08-01 | 2004-07-30 | Curing composition and method for producing curing composition |
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| CN (2) | CN101486822B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102947370A (en) * | 2010-04-23 | 2013-02-27 | 汉高公司 | Silicone-acrylic copolymer |
| CN103926795A (en) * | 2013-01-16 | 2014-07-16 | 施敏打硬株式会社 | Photocurable Composition |
| CN105829485A (en) * | 2013-12-13 | 2016-08-03 | 思美定株式会社 | Photocurable Composition Having Adhesive Properties |
| CN109952116A (en) * | 2016-11-02 | 2019-06-28 | 陶氏环球技术有限责任公司 | Solid non aqueous gels air fumet |
| CN111989379A (en) * | 2018-04-20 | 2020-11-24 | 思美定株式会社 | Building with wall structure and method for manufacturing wall structure |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2011111797A1 (en) * | 2010-03-12 | 2013-06-27 | 旭硝子株式会社 | Curable composition |
| CN108138501B (en) * | 2015-09-30 | 2020-11-10 | 盛势达技研株式会社 | Anti-skid structure and anti-skid treatment composition |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05125271A (en) * | 1991-11-06 | 1993-05-21 | Sanraizu Meisei Kk | Nonstaining sealing composition |
| TW250486B (en) * | 1992-08-24 | 1995-07-01 | Gen Electric | |
| CN1155562A (en) * | 1995-10-11 | 1997-07-30 | 陶氏康宁公司 | Curable organopolysiloxane compositions with improved adhesion |
| DE69840831D1 (en) * | 1997-07-28 | 2009-06-25 | Kaneka Corp | HARDENABLE ADHESIVE COMPOSITION |
| JP4398123B2 (en) * | 2001-11-06 | 2010-01-13 | 株式会社カネカ | Curable composition |
-
2004
- 2004-07-30 CN CN2009100064661A patent/CN101486822B/en not_active Expired - Lifetime
- 2004-07-30 CN CNB2004800203034A patent/CN100475901C/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102947370A (en) * | 2010-04-23 | 2013-02-27 | 汉高公司 | Silicone-acrylic copolymer |
| CN102947370B (en) * | 2010-04-23 | 2016-05-11 | 汉高知识产权控股有限责任公司 | silicone-acrylic copolymer |
| CN103926795A (en) * | 2013-01-16 | 2014-07-16 | 施敏打硬株式会社 | Photocurable Composition |
| CN105829485A (en) * | 2013-12-13 | 2016-08-03 | 思美定株式会社 | Photocurable Composition Having Adhesive Properties |
| CN105829485B (en) * | 2013-12-13 | 2018-10-12 | 思美定株式会社 | Photocurable composition with adhesiveness |
| CN109952116A (en) * | 2016-11-02 | 2019-06-28 | 陶氏环球技术有限责任公司 | Solid non aqueous gels air fumet |
| CN109952116B (en) * | 2016-11-02 | 2021-02-09 | 陶氏环球技术有限责任公司 | Solid non-aqueous gel air odorants |
| CN111989379A (en) * | 2018-04-20 | 2020-11-24 | 思美定株式会社 | Building with wall structure and method for manufacturing wall structure |
| CN111989379B (en) * | 2018-04-20 | 2024-02-20 | 思美定株式会社 | Building with wall structure and method for manufacturing wall structure |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100475901C (en) | 2009-04-08 |
| CN101486822A (en) | 2009-07-22 |
| CN101486822B (en) | 2011-07-06 |
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