CN1214036C - Imino-silane composition - Google Patents
Imino-silane composition Download PDFInfo
- Publication number
- CN1214036C CN1214036C CN 99118188 CN99118188A CN1214036C CN 1214036 C CN1214036 C CN 1214036C CN 99118188 CN99118188 CN 99118188 CN 99118188 A CN99118188 A CN 99118188A CN 1214036 C CN1214036 C CN 1214036C
- Authority
- CN
- China
- Prior art keywords
- silane
- imino
- group
- undersaturated
- glass fibre
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- SBVCEDLIWDSBGE-UHFFFAOYSA-N iminosilane Chemical compound [SiH2]=N SBVCEDLIWDSBGE-UHFFFAOYSA-N 0.000 title claims description 20
- 239000000203 mixture Substances 0.000 title abstract description 24
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 100
- -1 unsaturated imino silicane Chemical compound 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910000077 silane Inorganic materials 0.000 claims description 100
- 239000000463 material Substances 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 125000003368 amide group Chemical group 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- 150000008064 anhydrides Chemical class 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000005864 Sulphur Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229920005992 thermoplastic resin Polymers 0.000 claims description 4
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical compound C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 claims description 2
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 239000012764 mineral filler Substances 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 125000003968 arylidene group Chemical group [H]C(c)=* 0.000 claims 1
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical compound OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000003999 initiator Substances 0.000 claims 1
- 239000003365 glass fiber Substances 0.000 abstract description 36
- 238000002360 preparation method Methods 0.000 abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 22
- 150000003254 radicals Chemical class 0.000 abstract description 10
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract description 3
- 229910003480 inorganic solid Inorganic materials 0.000 abstract description 3
- 239000011343 solid material Substances 0.000 abstract 2
- 239000006227 byproduct Substances 0.000 abstract 1
- 239000003380 propellant Substances 0.000 abstract 1
- 239000012260 resinous material Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 29
- 239000011347 resin Substances 0.000 description 29
- 239000000243 solution Substances 0.000 description 24
- 239000000047 product Substances 0.000 description 19
- 239000004743 Polypropylene Substances 0.000 description 17
- 229920001155 polypropylene Polymers 0.000 description 17
- 239000003795 chemical substances by application Substances 0.000 description 16
- 239000011521 glass Substances 0.000 description 15
- 239000000835 fiber Substances 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000002585 base Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 229910010272 inorganic material Inorganic materials 0.000 description 11
- 239000011147 inorganic material Substances 0.000 description 11
- 238000004513 sizing Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 9
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 8
- 239000000945 filler Substances 0.000 description 8
- 229920000728 polyester Polymers 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 150000008065 acid anhydrides Chemical class 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000004677 Nylon Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000008878 coupling Effects 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
- 238000005859 coupling reaction Methods 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 150000003949 imides Chemical class 0.000 description 5
- 125000001841 imino group Chemical group [H]N=* 0.000 description 5
- 229920001778 nylon Polymers 0.000 description 5
- 150000002978 peroxides Chemical class 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- PWKSKIMOESPYIA-BYPYZUCNSA-N L-N-acetyl-Cysteine Chemical compound CC(=O)N[C@@H](CS)C(O)=O PWKSKIMOESPYIA-BYPYZUCNSA-N 0.000 description 4
- 229920002292 Nylon 6 Polymers 0.000 description 4
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 230000000887 hydrating effect Effects 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 230000037452 priming Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- KWQPWOQUXSQDNN-UHFFFAOYSA-N (2,3,4-trimethylphenyl) dihydrogen phosphate Chemical compound CC1=CC=C(OP(O)(O)=O)C(C)=C1C KWQPWOQUXSQDNN-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical group C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical group OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000010301 surface-oxidation reaction Methods 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- ZMMNUJFRPXPLOG-UHFFFAOYSA-N 1-methyl-4-azatricyclo[5.2.1.02,6]dec-8-ene-3,5-dione Chemical compound O=C1NC(=O)C2C1C1(C)C=CC2C1 ZMMNUJFRPXPLOG-UHFFFAOYSA-N 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- ZLPORNPZJNRGCO-UHFFFAOYSA-N 3-methylpyrrole-2,5-dione Chemical compound CC1=CC(=O)NC1=O ZLPORNPZJNRGCO-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical class CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- NEEGXVHYIQQTNF-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)OOC(C1=CC=CC=C1)=O.C(C1=CC=CC=C1)(=O)OOC(C1=CC=CC=C1)=O.C(C1=CC=CC=C1)(=O)OOC(C1=CC=CC=C1)=O Chemical compound C(C1=CC=CC=C1)(=O)OOC(C1=CC=CC=C1)=O.C(C1=CC=CC=C1)(=O)OOC(C1=CC=CC=C1)=O.C(C1=CC=CC=C1)(=O)OOC(C1=CC=CC=C1)=O NEEGXVHYIQQTNF-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- MSPCIZMDDUQPGJ-UHFFFAOYSA-N N-methyl-N-(trimethylsilyl)trifluoroacetamide Chemical compound C[Si](C)(C)N(C)C(=O)C(F)(F)F MSPCIZMDDUQPGJ-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- NOKSMMGULAYSTD-UHFFFAOYSA-N [SiH4].N=C=O Chemical compound [SiH4].N=C=O NOKSMMGULAYSTD-UHFFFAOYSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000004646 arylidenes Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- FGZBFIYFJUAETR-UHFFFAOYSA-N calcium;magnesium;silicate Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])([O-])[O-] FGZBFIYFJUAETR-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- ZFTFAPZRGNKQPU-UHFFFAOYSA-L carboxylato carbonate Chemical compound [O-]C(=O)OC([O-])=O ZFTFAPZRGNKQPU-UHFFFAOYSA-L 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004643 material aging Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- RFPMGSKVEAUNMZ-UHFFFAOYSA-N pentylidene Chemical group [CH2+]CCC[CH-] RFPMGSKVEAUNMZ-UHFFFAOYSA-N 0.000 description 1
- 229940083254 peripheral vasodilators imidazoline derivative Drugs 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- OSFBJERFMQCEQY-UHFFFAOYSA-N propylidene Chemical group [CH]CC OSFBJERFMQCEQY-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Chemical group 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- XJKVPKYVPCWHFO-UHFFFAOYSA-N silicon;hydrate Chemical compound O.[Si] XJKVPKYVPCWHFO-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The present invention relates to unsaturated imino silicane which does not basically contain siloxane, and the unsaturated imino silicane can be used for treating surfaces of inorganic solid materials. A new method for preparing the silicane is provided, and side products of water or the siloxane do not generate in the preparation process of the silicane. Basically, the imino silicane is used for treating the inorganic solid materials, resinous materials and a composition which is composed of optional free radical propellants, particularly a glass fiber intensifying composition.
Description
Technical field
The present invention relates to a kind of imino-silane.
Background technology
The organo-functional group silane compound has been used to the processing of various material surfaces, metal oxide for example, silicate, grain silicon fiber and colorant, and fiber, for example glass fibre, steel fiber and aluminum fiber.(oxide surface can be regarded in the metallic surface, because though that their subsurface does not have is oxidized, their upper layer is oxidized).Some functional organic silane finish comprises that organic, the water-solution organic or water with silane is coated with the described surface of stain or cooperates the solution of other compound to be coated with the stain surface with silane.
These treatment agents have strengthened the bonding action between inorganic oxide and the resin medium.Correspondingly, silane by use as coating, caking agent and sealing agent be applied to inorganic oxide surface priming paint component and by being used as a kind of pretreated filler, for example those mix the filler of glass fibre, thereby improve the intensity of such potting resin composition and the integrity of structure.Silane this functional organic, hydrolyzable is referred to as " coupler " or " adhesion promotor ".
The effectiveness major part of functional organic silane depends on the chemical reaction ability or the binding ability of it and resin medium.When thermosetting resin cured reaction, the reactivity of organo-functional group will be complementary with the reactivity of thermosetting resin or solidifying agent.It must become the part of the organic polymer that constitutes the resin medium.In making thermoplastic article, organo-functional group silane also will become the part of resin medium, and it is by organo-functional group and polymer reaction or is grafted on the main chain of polymkeric substance.
Functional organic silane does not also reach the integrity of the structure that strengthens the goods that are mixed into this silane with the reaction of all resins medium.Usually, if silane only with part resin medium or with the additive reaction compatible with the resin medium, this enhancement may realize.For example, pure polypropylene is appointed as the reinforcing agent of glass fibre, generally is and maleinization polypropylene (polypropylene of a.k.a. coupling) bonded that this example sees US Patent No.5,300,547.The maleinization polypropylene is meant unsaturated organic acid or its acid anhydrides and propylene grafting or multipolymer.For example, the general maleic anhydride-propylene copolymer that generates of maleic anhydride and propylene reaction.These two kinds of polypropylene, pure and maleinization and glass fibre is sent into coextrusion machine and tabletting machine simultaneously.In this process, make glass fibre and carry out surface treatment (gluing), so that comprise the silane that mates with the maleic anhydride chemistry.A kind of aminosilane such as SILQUEST
A-1100
TMThe 3-aminopropyltriethoxywerene werene is an example with the silane of maleic anhydride coupling.When compound (squeezing action), silane above the glass fibre and maleinization polypropylene form chemical bond.Silane not with the reaction of pure polypropylene.The polyacrylic chemical bonding effect of glass fibre and maleinization is the reason place of glass Reinforced Polypropylene excellent property.Using one of polyacrylic shortcoming of maleinization is that its cost is than non-coupling or pure polypropylene height.Using the polyacrylic another kind of shortcoming of maleinization is that the maximum that can not reach structural integrity and intensity strengthens degree.The maleinization polypropylene is with pure polyacrylic to mix or disperse may be uneven.Because pure polyacrylic existence has hindered the chemical reaction ability of organo-functional group of the silane of they and inorganic surfaces.Can not cause the composition undesirable property as making the resin medium more hydrophilic, and therefore reduce the ability of the wet degraded of moisture resistance with the polyacrylic toxilic acid functional group of silane reaction.Glass fibre to the responding property of (pure) polypropylene of non-coupling is provided, and is of great use for the high-performance that obtains glass fibre enhanced virgin pp.
In addition, other organic resin (for example nylon) that is used to connect inorganic materials insufficient or non-reacted functional group of responding property usually.With these materials effectively the new silane of bonding require (needs) it strengthens the character of organic resin when being used for inorganic materials.Imino-silane when being used in combination separately or with free radical generating agent be unique can with the silane of coupling of various resin medium or bonding.
Imino-silane is known, see US Patent Nos 3,755,354 and 3,249,461 and EP Patent No.0 50861, but these imino-silanes is problematic, and wherein the existence of water is institute's inherent among the said silane preparation method.Water causes silane hydrolyzate, generates siloxanes and also makes silane become pasty state by liquid, and mashed prod can not be used for coating or applying glue system component, and they require silane to dissolve and in the surface flow of inorganic materials.See the example 1 of US Patent No 3,755,354.Other synthetic method has muriate to exist, and muriate can decomposition and combination thing matrix.
Summary of the invention
That the present invention discloses is new, undersaturated imino-silane and comprise the composition of these silane.In addition, also disclose the method for this class imino-silane of new preparation, the result of this method does not have siloxanes and muriate basically in silane.
The present invention describes the bonding improvement to inorganic surfaces of doing of organic resin that mineral filler strengthens and wet physical strength and organic resin, and they obtain by with the free radical generating agent of choosing any one kind of them inorganic surfaces or filler being carried out surface treatment with unsaturated imino-silane.With the filler of the silane treatment of ethene functional groupization mix and grafting that optional radical brings out provides higher performance.Specifically, use filler, especially glass fiber-reinforced thermoplastic and heat cured resin, filler is handled with undersaturated imino-silane and optional free radical generating agent, can offer significantly doing and wet flexural strength of reinforcement of mixture.
Among the present invention, undersaturated imino-silane structural formula (I) is
((R
1)
bY)
aR
2 3-aSiR
3N (C=O)
2X, wherein R
1And R
2Be monovalent group, R
3It is the group of divalence, X is that the group of divalence comprises at least one undersaturated thiazolinyl, the group of two kinds of valence states is to connect with the carbon atom that is connected with nitrogen-atoms (promptly to form one to contain-C (=O) NC (=O)-ring of group) herein, Y is Sauerstoffatom, nitrogen-atoms or sulphur atom, a=1-3 and b=1 or the 2 valence state decisions by Y.
In above-mentioned structural formula I, each R
1Be the univalent group, for example hydrogen, imino-, dialkyl amido or preferred a kind of hydrocarbon functional group include but not limited to that aryl, allyl group, cycloalkyl, alkyl (straight or branched) maybe may include the aralkyl of heteroatoms such as oxygen, nitrogen or sulphur.R
1Also may be (as the ethanoyl) of acyl group functionality.R
1Example be-N=C (CH
3)
2And-CH=CHCH
3Most preferred R
1Be the alkyl of 1-10 carbon atom, as methyl, ethyl, sec.-propyl, cyclohexyl or isobutyl-.
The value of b depends on the valence state of Y, and Y was a nitrogen-atoms when promptly Y was oxygen or sulphur atom and b=2 during b=1.Preferred Y is a Sauerstoffatom.
Preferred a is 3, if but a＜3, each R
2Be univalent perssad, include, but not limited to hydrocarbon group, saturated hydrocarbon group, undersaturated hydrocarbon group or cyano group.Preferred R
2Be cycloalkyl, alkyl (straight or branched) or the aralkyl that possible comprise heteroatoms such as oxygen, nitrogen or sulphur and 1-10 carbon atom.Typical R
2Comprise phenyl, styroyl or 2-methoxy-propyl.Most preferred R
2Be methyl or ethyl.
R
3Be the abutment group of divalence, include, but not limited to alkylidene group, alkylene group, alkarylene, arylidene or poly-alkylene oxide group, but C preferably
1-C
12Alkylidene group, for example propylidene or inferior normal-butyl, and may be for example new pentylidene of side chain, cyclic is Dimethylenecyclohexacompound for example, or undersaturated for example dimethylene cyclohexenyl or phenylene.
In new silane, R
3May comprise hetero atom substituents, for example R
3May comprise the amino that is connected in the main chain or is attached to main chain.R
3Concrete example be ethylene propylene amine, diphenylene amine, diethylidene ethamine.This silane is included in R particularly
3In contain the silane of amido, be advantageous, because further chemical transformation may take place in the manufacturing processed of composition for they.
X is a divalence, and each valency is connected with carbonyl herein, and carbonyl is connected with nitrogen-atoms, forms a ring so at least.In addition, X comprises at least one undersaturated thiazolinyl in its ring or outside the ring.X may be that wherein arbitrary ring has undersaturated dicyclo.Preferred X is a hydrocarbon group, and they form ring 5-12 atom and that have imide.X (it incorporates acylimino (C (=O) NC (=O)-) functionality) object lesson into is (I) isobutenyl dimaleoyl imino, (II) (+/-)-2-octenyl-1-dimaleoyl imino, (III) clothing health imide, (IV) 2-dodecylene-1-base dimaleoyl imino, (V) suitable-1,2,3,6-tetrahydrochysene phthalimide base, (VI) suitable-5-norbornylene-Nei-2,3-dicarboximide base, (VII) interior-dicyclo (2.2.2) suffering-5-alkene-2,3-dicarboximide base, (VIII) methyl-5-norbornylene-2,3-dicarboximide base, (IX) outer-3,6-epoxy-1,2,3,6-tetrahydrochysene phthalimide base, (X) dimaleoyl imino, (XI) citraconimide base, (XII) 2,3-dimethyl dimaleoyl imino, (XIII) 1-cyclopentenyl-1,2-dicarboximide base, (XIV) 3,4,5,6-tetrahydrochysene phthalimide base.
Preferred undersaturated imino-silane is not contain siloxanes basically.The water that generates in synthetic causes the premature hydrolysis of organoalkoxysilane and generates siloxanes.Preferably, have by the quality of silane to be less than 5% (wt/wt) siloxanes, more preferably for less than 2% (wt/wt) be most preferably less than 0.5% (wt/wt) and paramount being preferably and do not have siloxanes.Be substantially free of siloxanes and be following new preparation method's consequence.The benefit of this kind anhydride is not disturb the reaction of silane.In addition, the existence of water causes the hydrolysis of organoalkoxysilane and is condensed into siloxanes that this siloxanes can be solid-state or mashed prod, and can not be directly used in the processing of glass fibre.
Preferred silane should be not halogen-containing yet, and chlorine element specifically is because halogen may be to the deleterious material of composition.The content of halogen should be lower than 1% (wt/wt), and preferred content is 0% (wt/wt) for being lower than 0.01% (wt/wt) and most preferred content of halogen.
The composition that comprises silane
Silane may be included among the composition, and composition comprises inorganic surfaces, as filler or plane surface, resin medium and optional free radical generating agent.Compound silane comprises organic, water-organic or the solution of water or the solution-treated inorganic surfaces of silane and other compound of using silane to the pattern in the composition, or is coated on the surface with the silane that does not have secondary solvent.The surface of these silane treatment can combine with resin medium and the free radical generating agent of choosing wantonly.In some example application, silane can directly be added in the resin medium in being referred to as " the whole mixing " technology.Be connected with the resin medium at the inorganic surfaces of crossing with silane treatment, the pattern that can adopt, for molding, for example comprise and push, inject, prolong pressure, casting, compression, lamination and transfer molding, for coating, comprise varnish, film viscose glue, colored paint, priming paint, China ink, dyestuff, tackiness agent and glass fibre glue.
The inorganic surfaces of available silane treatment is a solid inorganic material, and oxide compound or hydroxy are arranged on its exposed surface and comprise may be with any material of coupler processing known in the art.Solid inorganic material can be any form, comprises non-rule or well-regulated particle, for example sphere, line fiber, braided fiber seat or fabric, or the successive surface is as sheet, film, plate and shaped state.
The concrete example that is fit to the application solid inorganic material has, the trihydrate of the copper metal of the brass of surface oxidation, surface oxidation, iron, steel, aluminum oxide, aluminium for example, silicon materials such as silicon-dioxide, hydrated SiO 2, white carbon black (siliceous reinforcing agent), pure aluminium silicate, calcium magnesium silicate, clay, mica, molecular sieve, wollastonite, E-glass, S-glass, A-glass and analogue.
The consumption of silane be for can change the surface property of solid inorganic material, make its surface be more suitable in and/or be adhered to they compound resin media and be degree.When silane offers resin with whole blended method, the effective quantitative change scope of silane is about 0.05% (wt/wt)-15% (wt/wt), and preferred range is 0.1% (wt/wt)-2.0% (wt/wt), its percentage calculation be based on the weight of the solid mineral material of resin compounded.
When silane is directly supplied with solid inorganic material surface with filler, colorant or the analogue of fiber or coating of particles, the variation range of its significant quantity is about 0.01% (wt/wt)-10% (wt/wt), preferred range is 0.1% (wt/wt)-about 0.5% (wt/wt), and its per-cent serves as to calculate the basis with the solid inorganic material quality.When silane is used as the priming paint of inorganic solid surfaces, be used for the about 0.005 gram/rice of variation range of the significant quantity of surperficial silane
2-1.5 gram/rice
2, and preferred range is about 0.01 gram/rice
2-0.1 gram/rice
2, by the weight calculating of the surperficial every square metre of silane of institute's solid inorganic material of handling.
The resin medium can be thermoplastic or thermosetting material, and the use of " resin medium " term do not get rid of following possibility, i.e. the material that generates at the scene, with when solid inorganic material contacts from monomer material deutero-material.The present invention preferably uses thermoplastic resin.
The resin medium that is suitable for the silane application comprises a large amount of resins, and they react with the unsaturated imino-functional group of independent silane or with the free radical generating agent one of choosing any one kind of them.For purposes of illustration, the resin medium may be Synolac, undersaturated polyester, vinyl acetate, nylon, thermoplastic polyester, polyethylene, polypropylene, polybutene, polystyrene, copolymer from styrene and butadiene, copolymer from ethylene and propylene, SBR, natural rubber and analogue.Most preferably adopt polypropylene herein.
Sizing material may comprise free radical generating agent; be selected from one group of water-soluble or oily molten superoxide; hydrogen peroxide for example; ammonium persulphate; Potassium Persulphate; for example two alkyl peroxides of various organo-peroxides such as di-isopropyl superoxide; the dilauryl superoxide; two-tert-butyl peroxide; two-(2-t-butyl peroxy sec.-propyl) benzene; dicumyl peroxide; alkyl hydroperoxide such as tert-butyl hydroperoxide; uncle-amyl group hydroperoxide; the cumyl hydroperoxide; two acyl peroxides are acetyl pexoxide for example; lauroyl peroxide; benzoyl peroxide, peroxy esters class such as benzoyl hydroperoxide ethyl ester and azo-compound such as 2-azo two (isopropyl cyanide).Possible free radical generating agent be with high shear process bonded resin material, particularly thermoplastic resin.High-shear degraded thermoplastic resin is created on the main polymer chain or the terminated group.
The coating that is used to handle inorganic surfaces can be independent silane organically, water-organically or the aqueous solution or with other compound solution.Other compound is as wetting agent, static inhibitor, levelling agent, tackiness agent, lubricant, fiber protective material, membrane-forming agent and analogue.
When solution of silane was used to handle glass fibre, they were called as " sizing material ".This composition may comprise film-forming polymer, this polymkeric substance is generally the emulsion state, for example polyurethane, epoxy, unsaturated polyester, epoxy ester, bisphenol-A epoxy, bis-phenol base polyester, polyvinyl acetate, vinyl-acetic ester and acrylic copolymer, polyethylene, ethene, vinyl acetate copolymer, melamine-based formaldehyde and analogue.Sizing material also may comprise softening agent, as phthalic ester, phosphoric acid ester, polyester etc.Sizing material also may comprise for example polyvinylamine, Microcrystalline Wax, aliphatic group polyamine and the analogue that replace of the fatty acid amide, polyene oxide compound, alkyl imidazoline derivatives, acid amides of cationic acid solubilising of a kind of lubricant.Sizing material may comprise acid (for example acetate or suitable-butene dioic acid), water, tensio-active agent, defoamer, emulsifying agent or other silane (for example ethene unsaturated silane).Water in the sizing material is necessary, and it can activate the effect of silane to glass fibre.Other is used for the book of the compound of sizing material with reference to K.L.Loewenstein, continuous glass fibre manufacturing technology, revised edition (Elsevier Amsterdam, 1993) for the third time.
Silane and water added together silane is distributed in the sizing material; Therefore, water combines in advance with silane and makes sizing material aging more than 72 hours, and the result can produce useless siloxane glue.
Sizing material preferably is applied to glass fibre, and this glass fibre is compound in the composition of polymkeric substance.This preparation of compositions from document as can be known.The composition of gained has enhanced to be done and wet tenacity, enhanced soakage and improved stranded integrity.
Imino-silane is by aminoalkyl group dialkoxy silicane or amino-trialkoxy silane (for example aminopropyl trialkoxy silane, or N-amino-ethyl-3-aminopropyl dialkoxy silicane) and the preparation of undersaturated acid anhydrides.The silane that halogen need not be arranged is preferential selection, because they will produce undesired halogenide.This reaction produces the silane of open loop.The typical acid anhydrides that adopts is the isobutenyl succinyl oxide, (+/-)-2-octenyl-1-succinyl oxide, itaconic anhydride, 2-dodecylene-1-succinyl oxide, suitable-1,2,3,6-tetrahydrochysene phthalic anhydride, suitable-5-norbornylene-Nei-2, the 3-dicarboxylic anhydride, in-dicyclo (2.2.2)-Xin-5-alkene-2, the 3-dicarboxylic anhydride, methyl-5-norbornylene-2, the 3-dicarboxylic anhydride, outward-3,6-epoxy-1,2,3,6-tetrahydrochysene phthalic anhydride, maleic anhydride, citraconic anhydride, 2, the 3-dimethyl maleic anhydride, 1-cyclopentenyl-1, the 2-dicarboxylic anhydride, with 3,4,5,6-tetrahydrochysene phthalic anhydride.
The first step reaction can have or solvent-free, carries out under heating or the condition that do not heat, does not preferably heat, because heating can generate water.Suitable solvent comprises methylene dichloride, chloroform, alcohols, aliphatics and aromatic hydrocarbons and ethers.
The silane of open loop (being amido acid silane) is used the end-blocking material processing, produces water when avoiding into ring with this.This step is not preferably carrying out under the heating condition.Suitable end-blocking material is a sillylation reagent, comprise trialkylsilkl halogenide, two-(trimethyl silyl) trifluoroacetamide, N, the mixture of two (trimethyl silyl) ethanamides of O-, N-methyl-N-trimethyl silyl trifluoroacetamide, 1-(trimethyl-silyl-imidazole), N-trimethyl silyl diethylamide, hexamethyldisilazane and these compounds, useful especially is trimethylchlorosilane.
Other end-blocking material is the material that carboxylic acid is converted into the ester class, as chlorating hydrocarbon polymer, dialkyl carbonate, dialkyl group pyrocarbonate, dialkyl group sulphonate, diazomethane and analogue.Yet the alcohols that is commonly used to acid is converted into the ester class is inappropriate, because they produce water when end capping.When end-blocking material production hydrogen halide, this reactions steps is preferably carried out having under acid scavenger (for example alkali) existence condition.Alkali is to be used to remove halogenide.The example of suitable alkali comprises triethylamine, pyridine or dimethyl aminopyridine or any tertiary amine compounds.
Three-step reaction is that the end capped amido acid silane of heating generates imino-silane.When the end-blocking material is sillylation reagent, need two equivalents.Sillylation reagent while and the hydroxyl of carboxylic acid and the NH-radical reaction of acid amides.Under vacuum condition, temperature of reaction is controlled in the 40-80 ℃ of scope.In this step, the reaction product of end-blocking material (for example hexamethyldisiloxane (MM)) and the oxygen evolution of raw material acid anhydrides are come out.The end-capping reagent of described reaction preferably is distilled or flash distillation extraction from imino-silane.If the end-blocking material generates a kind of carboxylicesters, cyclic action can promote by heating carboxylic acid amide esters silane so.The temperature of reaction should be between 40-220 ℃, and preferred temperature is 80-120 ℃.In this step, will produce alcohol.
Products therefrom avoid siloxanes to exist and halide content low.
The method for preparing imino-silane that another kind avoids water (and siloxanes) to generate is the method by undersaturated acid anhydrides and isocyanic acid silane single step reaction, and this reaction discharges CO
2And imino-silane.At catalyzer, preferably ph ospholene exists down, and acid anhydrides and isocyanic ester are pressed the chemical reaction metering than adding and reflux, cooling and filtration.
In addition, the unsaturated acyl imines with ethene functionality can carry out hydrosilylation with hydrogen alcoxyl silane.The hydrosilylation effect is carried out as described in known references.For example, see what Marciniec compiled
Hydrogen The silanization composition handbook(1992) relative section is quoted as a reference here.
In the 4th step, dehydration is from two (amide group silane), and (have or the catalyst-free condition under) be heated to about 190 °-240 ℃, the result obtains imino-silane and aminosilane.
Embodiment
Embodiment
Embodiment 1, silane A's is synthetic
Under nitrogen atmosphere (bubbler), in 5000 milliliters reactor, add powdered maleic anhydride 352 grams and 574 gram methylene dichloride.Under agitation condition, progressively add 796 gram 3-aminopropyltriethoxywerene werene (SILQUEST to reactor in two hours
A-1100
TM(WitcoCorp.)).Bathe reactor cooling to 10 ℃ with cryosel.In reactor, add 723 gram triethylamines.Continue cooling, in reactor, add 777 gram trimethyl silicane chlorine again.To the terminal point that trimethyl silicane chlorine adds, in reactor, add 300 gram methylene dichloride and also continue to stir to spend the night.Reaction mixture is through 30 micron filters and 0.5 micron filter pressure filtration.Filtrate is packed in 5000 milliliters the flask, at room temperature, slow gas clean-up to 200 mmhg height, methylene dichloride is steamed flask.Under decompression and thermal condition, carry out cyclic action, obtain the finished product.Thick product is by the vacuum distilling purifying.
1H,
13C and
29Si nuclear magnetic resonance spectrum (NMR) is consistent with Maleimide base propyl-triethoxysilicane.This process is shown in reaction formula I.
Reaction formula I
Than the material example I
Synthesizing of U.S.P.3 755 354 maleimide amine silanes
The restrain oneself mixture of alkane of 23.2 gram 3-aminopropyltriethoxywerene werene, 10.3 gram maleic anhydrides, 0.53 gram pyridine and 316 is added at the bottom of 1000 milliliter of three neck garden of band Dean Stark cold-trap in the flask.Mixture refluxed 13 hours.Form two-layer.Lower floor is told and does 29-Si NMR spectrum analysis.The result shows the 35mol% siloxanes, and this shows that silane has water to exist between synthesis phase.
Silane-water solution in the preparation present embodiment.The mixture of 0.2 gram silane, 0.1 gram glacial acetic acid, 0.6 gram methyl alcohol and 0.2 gram water was stirred 20 minutes.The limit is stirred and is slowly added 18.95 gram water again.Almost produce the light yellow solid precipitation immediately.Make limpid, the stable and uniform aqueous solution of silane A by above-mentioned blending means.
Embodiment 2, no peroxide condition are handled glass fibre with silane A down
By preparing the gluing bath of a kind of glass fibre in the hydrating solution that silane A is joined deposit.The hydrating solution of deposit is made up of 1440 gram 2-propyl alcohol and 160 gram distilled water.This solution is adjusted to pH 4 with Glacial acetic acid.1.5 gram silane A are joined in the solution of 298.5 gram deposits of continuous stirring and make 0.5% (wt/wt) silane A solution.This solution restir 30 minutes is to guarantee the silane complete hydrolysis.The fiberglass fabric is cut into strip and immerses solution of silane.It is dry and be placed in 135 ℃ of stoves 2.5 minutes again that impregnated bar hangs in the baking oven blowing air.
Embodiment 3 usefulness silane A and peroxide treatment glass fibre
The glass fibre of handling with silane A among the embodiment 2 is coated with stain with peroxide solutions again.With 0.45 the gram dicumyl peroxide be dissolved in 299.55 the gram toluene in make 0.15% (wt/wt) peroxide solutions.The glasscloth bar that silane treatment is crossed immerses peroxide solutions and through dry air 1 hour.
Embodiment 4 presses the preparation and the check of layer product by the nylon of silane A, the preparation of no superoxide
The glass fibre bar of handling among the embodiment 2 cuts into the square of 8 inches * 8 inches (20.3 centimetres of 20.3 cm x).10 mils (0.025 centimetre) nylon, 6 films and the glass fabric multilayer of handling alternately are used to make 11 layers pressure layer product.Many laminate layers product is compressed to 0.125 inch (0.317 centimetre) with Q230H type PHI pressing machine and kept 0.75 hour 1500 pounds of (680 kilograms) ram pressures at 260 ℃.
Be used for the sample employing diamond saw cutting that dried wet elasticity test and loss on ignition (%LOI) are analyzed.It is wide that test sample is of a size of 0.5 inch (1.77 centimetres), 0.125 inch (0.317 centimetre) high and 3.5 inches (8.89 centimetres) length.According to ASTM D790, dry elasticity test with 0.2 inch (0.51 centimetre)/minute pinblock speed and 2 inches wide parameters of (5.08 centimetres) spacing carry out, used instrument is Instron 1123 checking machines.Sample soaks in boiled water and carries out the wet elasticity test after 24 hours.The sample size of wet test is all identical with dry test with method.%LOIs analyzes and carries out according to ASTM D4963-94.The results are shown among the Table I.
Embodiment 5
The preparation of the nylon 6 stratiform things that made by silane A and superoxide and test prepare according to the mode of embodiment 4 and test nylon 6 stratiform things, and its difference is to use the glass fibre bar of the processing of embodiment 3.The results are shown in Table I.
Comparing embodiment II
According to the step of embodiment 2, the glass fibre that preparation is handled, but use the 3-aminopropyltriethoxywerene werene.Step preparation and check nylon 6 according to embodiment 4 are pressed layer product.The results are shown in the Table I.
Comparing embodiment III
Step according to embodiment 2 and 3 prepares the glass fibre of handling, but uses maleinamide silane.Being prepared as follows of silane: under nitrogen atmosphere (whisking machine), in 5000 milliliters of reactors, add powdered maleic anhydride 352 grams and 574 gram methylene dichloride.Under agitation condition, progressively in reactor, drop into 796 gram SILQUEST in two hours
A-1100
TMThe 3-aminopropyltriethoxywerene werene of (Witco Corp.).At ambient temperature, methylene dichloride is by slow gas clean-up to 200 mmhg height, and is discharged from flask.
Press layer product according to preparation of the step among the embodiment 4 and check nylon 6.
The polypropylene of embodiment 6 usefulness silane A and superoxide preparation is pressed the manufacturing and the check of layer product
The glass fibre bar of handling among the embodiment 3 is cut into the square of 8 inches * 8 inches (20.3 centimetres of 20.3 cm x).15 mils (0.038 centimetre) polypropylene film and the glass fabric of handling are alternately made 9 layers pressure layer product.Many laminate layers product is compressed to 0.125 inch (0.317 centimetre) with Q230H type PHI pressing machine and kept 1 hour 1500 pounds of (680 kilograms) ram pressures at 232 ℃.Check many laminate layers product according to the step of embodiment 4.The results are shown in the Table I.
Comparing embodiment IV
Step according to embodiment 2 and 3 prepares the glass fibre of handling, but uses Witco Corp. sells, commodity SILQUEST by name
The vinyltrimethoxy silane of A-171.According to the preparation of the step of embodiment 6 with check many laminate layers product.The results are shown in the Table I.
Comparing embodiment V
Step according to embodiment 2 and 3 prepares the glass fibre of handling, but uses Witco Corp. sells, commodity SILQUEST by name
3-methacrylic (methacryl) the oxygen base propyl trimethoxy silicane of A-174.According to the preparation of the step of embodiment 6 with check many laminate layers product.The results are shown in the Table I.
Comparing embodiment VI
Step according to embodiment 2 and 3 prepares the glass fibre of handling, but uses the silane of comparing embodiment III preparation.According to the preparation of the step of embodiment 6 with check many laminate layers product.The results are shown in the Table I.
Comparing embodiment VII
Step according to embodiment 2 prepares the glass fibre of handling, but uses Witco Corp. sells, commodity SILQUEST by name
The 3-aminopropyltriethoxywerene werene of A-1100.According to the preparation of the step of embodiment 6 with check many laminate layers product.The results are shown in the Table I.
Comparing embodiment VIII
According to glass fibre and many laminate layers product of comparing embodiment VII preparation processing, but the polypropylene film of maleinization includes the grafted maleic anhydride of 1500ppm.The results are shown in the Table I.
Comparing embodiment IX
According to glass fibre and many laminate layers product of comparing embodiment VII preparation processing, but the maleinization polypropylene film comprises the 3000ppm grafted maleic anhydride.The results are shown in the Table I.
The preparation and the check of the Pultruded polyester rod of embodiment 7 usefulness silane A preparation
Silane A is joined make a kind of glass fiber size in the hydrating solution of deposit and bathe.The hydrating solution of deposit is made up of the distilled water of 1440 gram 2-propyl alcohol and 160 grams.Solution is adjusted to pH 4 with glacial acetic acid.Under agitation condition, 1.5 gram silane A are progressively joined in the solution of deposits of 298.5 grams and make a kind of 0.5% (wt/wt) silane A solution.This solution was continued to stir 30 minutes, to guarantee that the silane complete hydrolysis is its silanol form.The single-ended rove of glue waterborne comprises 2040, and Owens Corning sells, and commodity be called OCF 861, is immersed in the sizing material bath with the pulling rate of 25 feet per minute clocks (762 cm per minute).This fiber is by carrying out drying in the pipe that is heated to 420 (215 ℃), and fiber is 25 feet per minute clocks (762 cm per minute) by the pulling rate in the pipe, is trapped in pipe interior 0.8 minute.The exsiccant fiber is 22 circles on the spool, and the diameter of tube is 36 inches (91.4 centimetres).Fiber is removed from tube, fixes an end and cuts the other end.The Ashland Chemical that fiber immersion 1200 is restrained sell, AROPOL 7241 polyester and 12 gram LUPERCO ATC, a kind of trimethylphenyl phosphoric acid ester (50%wt/wt) solution of benzoyl peroxide 30 minutes, wherein the trimethylphenyl phosphoric acid ester is that Pennwalt sells.Impregnated fiber draws in the meticulous hollow glass tube of 0.25 inch of an internal diameter (0.635 centimetre), and solidifies 30 minutes at 221 °F (105 ℃).Rod takes out and cuts into 2.25 inches (5.71 centimetres) length from pipe.According to ASTM D790, measure dry elasticity intensity with Instron 1123 checking machines, the pinblock speed of checking machine be 0.2 inch (0.51 centimetre)/minute and 1.75 inches of spacings (4.45 centimetres).Wet sample is checked boiling bubbly water 24 hours and with identical method.Scaling loss is lost (%LOI) and is measured according to ASTM D4963-94.Adopt Instron 1123 checking machines in the mensuration of the glass roving elastic strength of handling, firmly span is 1 inch (2.54 centimetres), pinblock speed be 0.2 inch (0.51 centimetre)/minute.Report value is unit with the gram, makes the crooked necessary maximum, force of glass yarn.The result is reported in the Table II.
Comparing embodiment X
Prepare glass fibre and the rod of handling and do test according to embodiment 7, but the toxilic acid acid amides silane for preparing in comparing embodiment III is used as silane.The results are shown in the Table II.
Comparing embodiment XI
Prepare glass fibre and the rod of handling and do test according to embodiment 7, but silane is that Witco Corp. sells, commodity SILQUEST by name
The 3-metacryloxy propyl trimethoxy silicane of A-174.The results are shown in the Table II.
Table I uses the glasscloth of silane treatment to prepare
Glass fiber-reinforced assay of pressing layer product
Nylon
| Embodiment 45 II III | Crooked (doing) MPa 468.5 427.2 372.1 420.3 | Crooked (wetting) MPa 254.9 206.7 179.1 227.4 | Per-cent maintenance 54.4 48.4 48.1 54.1 | Per-cent glass 58 53 54 54 | Superoxide does not have dicumyl peroxide and does not have dicumyl peroxide |
Polypropylene
| Embodiment | |||||
| 6 IV V VI VII VIII IX | 246.1 170.9 144.7 192.9 124.0 199.8 213.6 | 224.6 150.2 125.4 165.4 96.5 179.1 186.0 | 91.3 87.9 86.7 85.7 77.8 89.6 87.1 | 57 52 51 51 47 52 51 | Dicumyl peroxide dicumyl peroxide dicumyl peroxide dicumyl peroxide does not have |
The assay of the Pultruded glass fibre rod of the glass roving preparation of Table II usefulness silane treatment
Polyester
| Embodiment 7 X XI | Crooked (doing) MPa 764.8 737.2 785.5 | Crooked (wetting) MPa 716.6 496.1 702.8 | Per-cent maintenance 93.7 67.3 89.5 | Per-cent glass 61.5 62.3 62.5 | Superoxide benzoyl peroxide benzoyl peroxide benzoyl peroxide | Glass bending (g) 61 37 39 |
Claims (3)
1. one kind prepares and has formula ((R
1)
bY)
aR
2 3-aSiR
3N (C=O)
2The method of the silane of X, wherein, R
1It is the aralkyl that the alkyl of hydrogen, imino-, dialkyl amido, aryl, allyl group, cycloalkyl, a 1-10 carbon atom maybe can contain aerobic, nitrogen or sulphur; R
2It is the aralkyl that the alkyl of cycloalkyl, a 1-10 carbon atom maybe can contain aerobic, nitrogen or sulphur; R
3Be C
1-C
12Alkylidene group, alkylene group, alkarylene, arylidene or poly-alkylene oxide group and R
3Can comprise the amino that is connected in the main chain or is attached to main chain; X is a hydrocarbon group, and is that they form 5-12 atom and have-N (C=O)
2-ring and in its ring or outside encircling, comprise at least one undersaturated thiazolinyl; Y is oxygen, nitrogen or sulphur, a=1-3 and b=1 or 2, this is by the valence state decision of Y, wherein this method comprises: (a) a kind of aminoalkyl group dialkoxy silicane or amino-trialkoxy silane and a kind of undersaturated anhydride reaction generate a kind of amido acid silane, (b) with the end-blocking material processing amido acid silane that is selected from sillylation reagent, chlorating hydrocarbon polymer, dialkyl carbonate, dialkyl group pyrocarbonate, dialkyl group sulphonate and diazomethane, (c) material that will handle is heated to 40-220 ℃, produces a kind of imino-silane.
2. material comprises undersaturated imino-silane according to claim 1, thermoplastic resin material and the mineral filler that can react with imino-.
3. according to the material of claim 2, also comprise free-radical initiator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99118188 CN1214036C (en) | 1999-08-30 | 1999-08-30 | Imino-silane composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99118188 CN1214036C (en) | 1999-08-30 | 1999-08-30 | Imino-silane composition |
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|---|---|---|---|
| CN 200510050972 Division CN1654468A (en) | 1999-08-30 | 1999-08-30 | Imino-silane composition |
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| CN1214036C true CN1214036C (en) | 2005-08-10 |
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| WO2021160575A1 (en) * | 2020-02-14 | 2021-08-19 | Evonik Operations Gmbh | Stabilized silane composition |
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