CN115960359B - Organosilicon treating agent, preparation method thereof and powder containing organosilicon treating agent - Google Patents
Organosilicon treating agent, preparation method thereof and powder containing organosilicon treating agent Download PDFInfo
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- CN115960359B CN115960359B CN202310079324.8A CN202310079324A CN115960359B CN 115960359 B CN115960359 B CN 115960359B CN 202310079324 A CN202310079324 A CN 202310079324A CN 115960359 B CN115960359 B CN 115960359B
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- Prior art keywords
- treating agent
- hydroxy
- organosilicon
- powder
- monomer
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- 239000000843 powder Substances 0.000 title claims abstract description 82
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 29
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 25
- -1 silane compound Chemical class 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 239000010703 silicon Substances 0.000 claims abstract description 12
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 10
- 239000012948 isocyanate Substances 0.000 claims abstract description 10
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- 229920001971 elastomer Polymers 0.000 claims abstract description 6
- 239000003973 paint Substances 0.000 claims abstract description 6
- 239000004033 plastic Substances 0.000 claims abstract description 6
- 229920003023 plastic Polymers 0.000 claims abstract description 6
- 239000005060 rubber Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 45
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 34
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 27
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 13
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 9
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 8
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- UMFJXASDGBJDEB-UHFFFAOYSA-N triethoxy(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(OCC)OCC UMFJXASDGBJDEB-UHFFFAOYSA-N 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- JPPHEZSCZWYTOP-UHFFFAOYSA-N trimethoxysilylmethyl prop-2-enoate Chemical compound CO[Si](OC)(OC)COC(=O)C=C JPPHEZSCZWYTOP-UHFFFAOYSA-N 0.000 claims description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- ZUQABTLQDXJZFK-UHFFFAOYSA-N 10-hydroxydecyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCCCCCO ZUQABTLQDXJZFK-UHFFFAOYSA-N 0.000 claims description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 2
- WULAHPYSGCVQHM-UHFFFAOYSA-N 2-(2-ethenoxyethoxy)ethanol Chemical compound OCCOCCOC=C WULAHPYSGCVQHM-UHFFFAOYSA-N 0.000 claims description 2
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 claims description 2
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 claims description 2
- NJRHMGPRPPEGQL-UHFFFAOYSA-N 2-hydroxybutyl prop-2-enoate Chemical compound CCC(O)COC(=O)C=C NJRHMGPRPPEGQL-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 claims description 2
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 claims description 2
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 claims description 2
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 claims description 2
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 claims description 2
- SBVKVAIECGDBTC-UHFFFAOYSA-N 4-hydroxy-2-methylidenebutanamide Chemical compound NC(=O)C(=C)CCO SBVKVAIECGDBTC-UHFFFAOYSA-N 0.000 claims description 2
- YKXAYLPDMSGWEV-UHFFFAOYSA-N 4-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCO YKXAYLPDMSGWEV-UHFFFAOYSA-N 0.000 claims description 2
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 2
- XFOFBPRPOAWWPA-UHFFFAOYSA-N 6-hydroxyhexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCO XFOFBPRPOAWWPA-UHFFFAOYSA-N 0.000 claims description 2
- OCIFJWVZZUDMRL-UHFFFAOYSA-N 6-hydroxyhexyl prop-2-enoate Chemical compound OCCCCCCOC(=O)C=C OCIFJWVZZUDMRL-UHFFFAOYSA-N 0.000 claims description 2
- YPMOAQISONSSNL-UHFFFAOYSA-N 8-hydroxyoctyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCCCO YPMOAQISONSSNL-UHFFFAOYSA-N 0.000 claims description 2
- LIIKVCVIMXKWJX-UHFFFAOYSA-N 8-triethoxysilyloctyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCCCCCCOC(=O)C(C)=C LIIKVCVIMXKWJX-UHFFFAOYSA-N 0.000 claims description 2
- DDVHXZANLAFDSZ-UHFFFAOYSA-N 8-triethoxysilyloctyl prop-2-enoate Chemical compound CCO[Si](CCCCCCCCOC(=O)C=C)(OCC)OCC DDVHXZANLAFDSZ-UHFFFAOYSA-N 0.000 claims description 2
- GAYWTJPBIQKDRC-UHFFFAOYSA-N 8-trimethoxysilyloctyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCCCCCCOC(=O)C(C)=C GAYWTJPBIQKDRC-UHFFFAOYSA-N 0.000 claims description 2
- JOVCTEPPTIOAPX-UHFFFAOYSA-N 8-trimethoxysilyloctyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCCCCCCOC(=O)C=C JOVCTEPPTIOAPX-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- IIXYEVUNJFXWEB-UHFFFAOYSA-N n-hydroxy-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NO IIXYEVUNJFXWEB-UHFFFAOYSA-N 0.000 claims description 2
- 239000011863 silicon-based powder Substances 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- UZIAQVMNAXPCJQ-UHFFFAOYSA-N triethoxysilylmethyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)COC(=O)C(C)=C UZIAQVMNAXPCJQ-UHFFFAOYSA-N 0.000 claims description 2
- WDUXKFKVDQRWJN-UHFFFAOYSA-N triethoxysilylmethyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)COC(=O)C=C WDUXKFKVDQRWJN-UHFFFAOYSA-N 0.000 claims description 2
- UOKUUKOEIMCYAI-UHFFFAOYSA-N trimethoxysilylmethyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)COC(=O)C(C)=C UOKUUKOEIMCYAI-UHFFFAOYSA-N 0.000 claims description 2
- 229940065472 octyl acrylate Drugs 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 14
- 125000003545 alkoxy group Chemical group 0.000 abstract description 6
- 239000004814 polyurethane Substances 0.000 abstract description 4
- 229920002635 polyurethane Polymers 0.000 abstract description 4
- 229910000077 silane Inorganic materials 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000000463 material Substances 0.000 description 18
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 230000008034 disappearance Effects 0.000 description 10
- 238000012544 monitoring process Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 125000002947 alkylene group Chemical group 0.000 description 7
- 239000000155 melt Substances 0.000 description 6
- 239000003607 modifier Substances 0.000 description 6
- QCDFRRQWKKLIKV-UHFFFAOYSA-M chloroplatinum Chemical compound [Pt]Cl QCDFRRQWKKLIKV-UHFFFAOYSA-M 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052990 silicon hydride Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- HLOLETUOZGAKMT-UHFFFAOYSA-N trimethoxysilyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)OC(=O)C(C)=C HLOLETUOZGAKMT-UHFFFAOYSA-N 0.000 description 3
- 125000006835 (C6-C20) arylene group Chemical group 0.000 description 2
- GCYHRYNSUGLLMA-UHFFFAOYSA-N 2-prop-2-enoxyethanol Chemical compound OCCOCC=C GCYHRYNSUGLLMA-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 2
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 1
- NPGANJGGHAXWBF-UHFFFAOYSA-N 1-[diethoxy(propyl)silyl]oxyethanamine Chemical compound CCC[Si](OCC)(OCC)OC(C)N NPGANJGGHAXWBF-UHFFFAOYSA-N 0.000 description 1
- IQEWHTMQTSAPLG-UHFFFAOYSA-N 10-hydroxydecyl prop-2-enoate Chemical compound OCCCCCCCCCCOC(=O)C=C IQEWHTMQTSAPLG-UHFFFAOYSA-N 0.000 description 1
- AEZJNQZYZFLLIY-UHFFFAOYSA-N 12-hydroxydodecyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCCCCCCCO AEZJNQZYZFLLIY-UHFFFAOYSA-N 0.000 description 1
- NKYRAXWYDRHWOG-UHFFFAOYSA-N 12-hydroxydodecyl prop-2-enoate Chemical compound OCCCCCCCCCCCCOC(=O)C=C NKYRAXWYDRHWOG-UHFFFAOYSA-N 0.000 description 1
- JSCDRVVVGGYHSN-UHFFFAOYSA-N 8-hydroxyoctyl prop-2-enoate Chemical compound OCCCCCCCCOC(=O)C=C JSCDRVVVGGYHSN-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000004653 anthracenylene group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000005567 fluorenylene group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 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
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 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
- 239000007788 liquid Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 125000005562 phenanthrylene group Chemical group 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920006294 polydialkylsiloxane Polymers 0.000 description 1
- 239000011160 polymer matrix composite Substances 0.000 description 1
- 229920013657 polymer matrix composite Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000005548 pyrenylene group Chemical group 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention provides an organosilicon treating agent, a preparation method thereof and powder containing the organosilicon treating agent, wherein the preparation raw materials of the organosilicon treating agent comprise organosilicon prepolymer containing side hydrogen, a first monomer, a second monomer and isocyanate; the first monomer comprises a compound containing a carbon-carbon double bond and a hydroxyl group; the second monomer includes a silane compound having a carbon-carbon double bond and an alkoxy group. According to the invention, the organic silicon treating agent is prepared from specific raw materials, so that the molecular structure of the organic silicon treating agent is provided with a polysiloxane main chain, a polyurethane organic chain segment and a siloxane side chain, the compatibility of inorganic powder and a polymer can be improved, the inorganic powder is dispersed in the polymer, and the obtained product is excellent in mechanical property, smooth, good in hand feeling, wide in application field and suitable for multiple fields such as plastics, rubber, paint, daily chemicals and the like.
Description
Technical Field
The invention belongs to the technical field of powder treatment, and particularly relates to an organosilicon treating agent, a preparation method thereof and powder containing the organosilicon treating agent.
Background
In some polymer material industry and polymer composite material fields, the powder material is an indispensable filler or component in the polymer matrix composite material as an incremental material, and the dosage of the powder material can be 5% -80% of the composite material. The inorganic mineral powder such as kaolin, mica, quartz, alumina, talcum, calcium carbonate and the like is used as the filler, so that the production cost of the material is reduced, the mechanical property and stability of the composite material are improved, and even certain special physical and chemical properties can be endowed to the material. However, since the inorganic powder has many hydrophilic groups on the surface, it has poor compatibility with the organic polymer, and therefore, it is often necessary to surface-modify the inorganic powder to improve its compatibility with the organic polymer.
The surface modification method of inorganic powder can be divided into two main types of surface physical modification and surface chemical modification. The powder modifier commonly used at present is a silane coupling agent, and the siloxy groups in the silane coupling agent have reactivity to inorganic powder, and the organic functional groups have reactivity or compatibility to organic matters, so that the compatibility between the inorganic powder and the polymer can be improved. The common silane coupling agents include vinyl triethoxysilane, gamma-methacryloxypropyl trimethoxysilane, amino propyl triethoxysilane and the like, but the compatibility of the silane coupling agents with high molecular polymers still has insufficient due to the low organic content, and the obtained finished product has poor handiness.
In addition, CN110922534a discloses a method for preparing an inorganic powder modifier, which comprises dissolving polyvinyl butyral into a liquid, improving toughness and cohesiveness, grafting organosilicon, improving thermal softening point temperature, and grafting lipophilic functional group, hydrophobic functional group and bonding functional group, so that the inorganic powder modifier can be used as an inorganic powder modifier to modify inorganic powder, and has a good coating rate. However, the mechanical properties of the materials obtained with the modifier are to be further improved.
Therefore, developing a powder modifier which can make inorganic powder and polymer have good compatibility, good hand feeling of finished products, excellent mechanical property and good processing property is a technical problem to be solved in the field.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide an organosilicon treating agent, a preparation method thereof and powder containing the organosilicon treating agent. The organic silicon treating agent has polysiloxane main chain, polyurethane organic chain segment and siloxane side chain in the molecular structure by selecting specific preparation raw materials, can improve the compatibility of inorganic powder and polymer, ensures that the inorganic powder has good dispersing effect in the polymer, and the obtained product has excellent mechanical property, smooth and good hand feeling, has wide application field and is suitable for a plurality of fields such as plastics, rubber, paint, daily chemicals and the like.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a silicone treatment, wherein the silicone treatment comprises a side hydrogen-containing silicone prepolymer, a first monomer, a second monomer, and isocyanate; the first monomer comprises a compound containing a carbon-carbon double bond and a hydroxyl group; the second monomer includes a silane compound having a carbon-carbon double bond and an alkoxy group.
In the invention, the organosilicon prepolymer containing side hydrogen is selected, so that the organosilicon treating agent has a polysiloxane main chain, the heat resistance and the lubricity of the powder can be improved, the melt index is improved, and the powder is endowed with excellent handfeel; the silane compound containing carbon-carbon double bonds and alkoxy is selected, so that the organosilicon treating agent is provided with a siloxane side chain, a firm chemical bond can be formed between the organosilicon treating agent and the surface of the powder, and the compatibility between the powder and a high polymer material can be improved and the mechanical property of the material can be improved by introducing an organic chain segment side chain into the molecular structure of the organosilicon treating agent through a first monomer and isocyanate; the three are matched with each other, so that the dispersibility of the inorganic powder in the polymer is further improved, and the material has good flexibility and good hand feeling.
The hydrogen content in the side hydrogen-containing silicone prepolymer is preferably 0.2 to 0.4%, and may be, for example, 0.25%, 0.3%, 0.35%, 0.4%, or the like.
The number average molecular weight of the side hydrogen-containing silicone prepolymer is preferably 500 to 10000, and may be 600, 700, 800, 900, 1000, 1200, 1400, 1500, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, or the like, for example.
Preferably, in the preparation raw material, the molar ratio of the silicon hydrogen to the carbon-carbon double bond is 1 (1-1.5), for example, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5 and the like can be adopted.
Preferably, the first monomer comprises at least one of allyl alcohol, hydroxy methacrylamide, hydroxy ethylacrylamide, allyl hydroxyethyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, 8-hydroxyoctyl acrylate, 8-hydroxyoctyl methacrylate, 10-hydroxydecyl acrylate, 10-hydroxydecyl methacrylate, 12-hydroxylauryl acrylate or 12-hydroxylauryl methacrylate.
Preferably, the molar ratio of the first monomer to the second monomer is 1 (0.2-9.5), for example, 1:0.25, 1:0.3, 1:0.35, 1:0.4, 1:0.45, 1:0.5, 1:0.55, 1:0.6, 1:0.65, 1:0.7, 1:0.8, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, etc., and further preferably 1 (0.4-5).
In the invention, the first monomer and the second monomer are in a specific molar ratio range, so that the mechanical property of the material and the dispersibility of the inorganic powder in the polymer are better.
Preferably, the second monomer includes at least one of allyltrimethoxysilane, allyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 8-methacryloxyoctyltrimethoxysilane, 8-methacryloxyoctyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 8-acryloxyoctyltrimethoxysilane, or 8-acryloxyoctyltriethoxysilane.
Preferably, the isocyanate comprises at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate or hexamethylene diisocyanate.
Preferably, the molar ratio of hydroxyl groups to isocyanate groups in the preparation raw material is 1 (0.9-1), and for example, may be 1:0.91, 1:0.92, 1:0.93, 1:0.94, 1:0.95, 1:0.96, 1:0.97, 1:0.98, 1:0.99, etc.
Preferably, the organosilicon treating agent has a structure shown in formula I:
wherein R is 1 Selected from the group consisting of substituted or unsubstituted C1-C6 linear or branched alkylene, substituted or unsubstituted C6-C20 arylene, substituted or unsubstituted C6-C15 aralkylene, -R 11 CONHR 12 -、-R 11 OR 12 -、-R 11 OCH 2 CH 2 OR 12 -or-R 11 COOR 12 -any one of the following; r is R 11 、R 12 Each independently selected from substituted or unsubstituted C1 to C15 linear or branched alkylene; r is R 2 Selected from the group consisting of Represents a junction site; r is R 4 Selected from the group consisting of substituted or unsubstituted C1-C6 linear or branched alkylene, substituted or unsubstituted C6-C20 arylene, substituted or unsubstituted C6-C20 aralkylene, and R 41 COOR 42 -any one of the following; r is R 41 、R 42 Each independently selected from substituted or unsubstituted C1 to C12 linear or branched alkylene; r is R 5 Selected from methyl or ethyl; r is R 3 、R 6 、R 7 、R 8 Each independently selected from any one of hydrogen, substituted or unsubstituted C1-C6 linear or branched alkyl, substituted or unsubstituted C1-C6 linear or branched alkoxy, substituted or unsubstituted C6-C20 aryl or substituted or unsubstituted C6-C20 aralkyl; a. c are each independently selected from integers of 1 to 100, and may be, for example, 2, 4, 8, 10, 20, 30, 40, 50, 60, 70, 80, 90, etc.; b is an integer selected from 0 to 100, and may be, for example, 2, 4, 8, 10, 20, 30, 40, 50, 60, 70, 80, 90, etc.; the substituted substituent includes any one of halogen, hydroxy, carboxyl or amino.
In the present invention, the C1-C6 linear or branched alkylene group includes a C1, C2, C3, C4, C5, C6 linear or branched alkyl group, and illustratively includes, but is not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and the like.
In the present invention, the C6 to C20 arylene includes C6, C7, C8, C9, C10, C12, C14, C16, C18 aryl, etc., exemplarily including but not limited to: phenylene, biphenylene, naphthylene, fluorenylene, anthrylene, indenylene, phenanthrylene, pyrenylene, acenaphthylene, triphenylene, and phenyleneA base, acenaphthylene base, perylene base, etc.
In the present invention, the C1-C12 straight or branched chain alkylene group includes C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12 straight or branched chain alkylene groups, and illustratively includes, but is not limited to, methylene, ethylene, propylene, isopropylene, butylene, isobutylene, pentylene, hexylene, heptylene, decylene, and the like.
In the present invention, the C1-C6 straight or branched alkyl group includes a C1, C2, C3, C4, C5, C6 straight or branched alkyl group, and illustratively includes, but is not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and the like.
In the present invention, the C1-C6 straight-chain or branched-chain alkoxy group includes a C1, C2, C3, C4, C5, C6 straight-chain or branched-chain alkoxy group, and exemplary includes, but is not limited to, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, and the like.
In a second aspect, the present invention provides a method for producing the silicone treatment according to the first aspect, the method comprising the steps of:
(1) In the presence of a catalyst, reacting a side hydrogen-containing organosilicon prepolymer, a first monomer and a second monomer to obtain a hydroxyl-containing intermediate;
(2) And (3) reacting the hydroxyl-containing intermediate obtained in the step (1) with isocyanate to obtain the organosilicon treating agent.
Preferably, the catalyst of step (1) comprises a transition metal catalyst.
In the present invention, the transition metal catalyst includes, but is not limited to, a chloro-platinum catalyst.
Preferably, the catalyst is used in an amount of 40 to 60ppm, for example, 42ppm, 44ppm, 46ppm, 48ppm, 50ppm, 52ppm, 54ppm, 56ppm, 58ppm, etc.
Preferably, the temperature of the reaction in the step (1) is 80 to 120 ℃, for example, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃ and the like; the time is 2 to 8 hours, and may be, for example, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, or the like.
In the invention, the reaction in the step (1) is carried out under the protection of nitrogen; and the progress of the reaction was confirmed by infrared monitoring of the disappearance of the characteristic peak of the hydrogen-silicon.
In the present invention, the step of removing water from the hydroxyl group-containing intermediate at 100 to 110 ℃ (for example, 102 ℃, 104 ℃, 106 ℃, 108 ℃ and the like) for 1 to 3 hours (for example, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours, 2 hours, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours and the like) is further included before the reaction of the hydroxyl group-containing intermediate with isocyanate.
Preferably, the reaction system in the step (2) further comprises a solvent and a catalyst.
Preferably, the catalyst in step (2) is used in an amount of 0.1 to 0.7% by weight of the total mass of the reactants, for example, 0.2%, 0.3%, 0.4%, 0.5%, 0.6% and the like.
In the present invention, the catalyst of step (2) includes, but is not limited to, organobismuth catalysts.
In the present invention, the solvent of step (2) includes, but is not limited to butanone; the solvent may be used in an amount of 5 to 15% by weight based on the total mass of the system, for example, 6%, 8%, 10%, 12%, 14% by weight, etc.
Preferably, the temperature of the reaction in step (2) is 70 to 90 ℃, for example, 75 ℃, 80 ℃, 85 ℃ and the like; the time is 3 to 6 hours, and may be, for example, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, or the like.
In the invention, the reaction in the step (2) further comprises a step of removing the solvent. In step (2), the progress of the reaction was confirmed by infrared monitoring for the disappearance of the NCO characteristic peak.
In a third aspect, the present invention provides a modified powder, wherein the raw materials of the modified powder comprise 0.5 to 10% by mass (for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% etc.) of the organosilicon treating agent according to the first aspect and 90 to 99.5% by mass (for example, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99% etc.) of the inorganic powder.
Preferably, the inorganic powder includes at least one of calcium carbonate powder, talc powder, titanium dioxide powder, silicon powder, toner or flame retardant powder.
Preferably, the modified powder is prepared by a method comprising: the silicone treating agent and the inorganic powder are mixed at 50 to 70 ℃ (for example, 55 ℃, 60 ℃, 65 ℃ and the like) for 0.5 to 2 hours (for example, 1 hour, 1.5 hours, 2 hours and the like) to obtain the modified powder.
In a fourth aspect, the invention provides an application of the organosilicon treating agent according to the first aspect and/or the modified powder according to the second aspect in the fields of plastics, paint, daily chemicals, rubber and the like.
The numerical ranges recited herein include not only the recited point values, but also any point values between the recited numerical ranges that are not recited, and are limited to, and for the sake of brevity, the invention is not intended to be exhaustive of the specific point values that the recited range includes.
Compared with the prior art, the invention has the beneficial effects that:
the organosilicon treating agent provided by the invention adopts specific preparation raw materials, so that the organosilicon treating agent has a polysiloxane main chain, a polyurethane organic chain segment and a siloxane side chain, and can endow powder with excellent dispersibility, wherein the main chain can improve the heat resistance and lubricity of the powder, improve the melt index, endow the powder with excellent hand feeling, firm chemical bonds can be formed between the siloxane side chain and the surface of the powder, and the compatibility between the powder and a high polymer material and the mechanical property of the organic chain segment side chain can be improved. The modified powder obtained by modifying the organosilicon treating agent is applied to products in the fields of plastics, rubber, paint, daily chemicals and the like, and can improve the smoothness and mechanical properties of the products and keep good flexibility.
Drawings
FIG. 1 is an infrared spectrum of the silicone treating agent obtained in example 1 of the present invention.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The materials used in the invention are as follows:
organobismuth catalyst: biCAT8106, leading in the United states
Side hydrogen organosilicon prepolymer
The preparation method comprises the following steps:
s1, 250.3g of octamethyl cyclotetrasiloxane, 42.7g of high hydrogen silicone oil (202, hydrogen content is 1.58%) and 6.97g of hexamethyldisiloxane as well as 4g of concentrated sulfuric acid are added into a reaction kettle, the temperature is raised to 55 ℃, the heat preservation reaction is carried out for 6 hours, a sodium carbonate neutralizer is added, filtration and the temperature is raised to 140 ℃ to remove micromolecular substances, and hydrogenated polydialkylsiloxane with the hydrogen content of 0.22% is obtained after cooling.
Example 1
The embodiment provides an organosilicon treating agent, wherein the preparation raw materials of the organosilicon treating agent comprise a side hydrogen organosilicon prepolymer, allyl alcohol, allyl trimethoxysilane and isophorone diisocyanate (IPDI); the molar ratio of allyl alcohol to allyl trimethoxysilane is 2:8, the molar ratio of silicon hydrogen to carbon-carbon double bond in the system is 1:1.05, and the molar ratio of hydroxyl to isocyanate group is 1:0.95.
The embodiment provides a preparation method of an organosilicon treating agent, which specifically comprises the following steps:
(1) According to the formula amount, adding the side hydrogen organosilicon prepolymer, allyl alcohol and allyl trimethoxy silane into a reaction kettle, adding 50ppm of a chloro-platinum catalyst, starting stirring, introducing nitrogen, heating to 90 ℃, and reacting for 6 hours to obtain a hydroxyl-containing intermediate; in the reaction process, confirming the progress of the reaction by infrared monitoring of disappearance of characteristic peaks of the silicon hydride;
(2) Adding the hydroxyl-containing intermediate obtained in the step (1) into a reaction kettle, dewatering at 105 ℃ for 2 hours, cooling to 80 ℃, adding butanone with the mass of 10% of the system, adding IPDI into the reaction kettle, adding an organobismuth catalyst with the mass of 0.5% of the reactant, controlling the reaction temperature to 80 ℃, reacting for 5 hours, removing the solvent, and obtaining the organosilicon treating agent, wherein the reaction is confirmed by infrared monitoring of disappearance of NCO characteristic peaks in the reaction process.
The structure of the silicone treatment obtained in example 1 was characterized by using an infrared spectrometer, and the results are shown in fig. 1.
Example 2
The embodiment provides an organosilicon treating agent, wherein the preparation raw materials of the organosilicon treating agent comprise a side hydrogen organosilicon prepolymer, allyl alcohol, allyl triethoxysilane and diphenylmethane diisocyanate (MDI); the mol ratio of allyl alcohol to allyl triethoxysilane is 4:6, the mol ratio of silicon hydrogen to carbon-carbon double bond in the system is 1:1.1, and the mol ratio of hydroxyl to isocyanate group is 1:0.98.
The embodiment provides a preparation method of an organosilicon treating agent, which specifically comprises the following steps:
(1) According to the formula amount, adding the side hydrogen organosilicon prepolymer, allyl alcohol and allyl triethoxysilane into a reaction kettle, adding 60ppm of chloro-platinum catalyst, starting stirring, introducing nitrogen, heating to 80 ℃, and reacting for 8 hours to obtain a hydroxyl-containing intermediate; in the reaction process, confirming the progress of the reaction by infrared monitoring of disappearance of characteristic peaks of the silicon hydride;
(2) Adding the hydroxyl-containing intermediate obtained in the step (1) into a reaction kettle, dewatering at 105 ℃ for 2 hours, cooling to 70 ℃, adding butanone with the mass of 10% of the system, adding MDI into the reaction kettle, adding an organobismuth catalyst with the mass of 0.5% of the reactants, controlling the reaction temperature to 80 ℃, reacting for 6 hours, removing the solvent, and obtaining the organosilicon treating agent, wherein the reaction is confirmed by infrared monitoring of disappearance of NCO characteristic peaks in the reaction process.
Example 3
The embodiment provides an organosilicon treating agent, wherein the preparation raw materials of the organosilicon treating agent comprise a side hydrogen organosilicon prepolymer, allyl alcohol, methacryloxy trimethoxy silane and diphenylmethane diisocyanate (MDI); the mol ratio of allyl alcohol to methacryloxy trimethoxy silane is 7:3, the mol ratio of silicon to carbon double bond is 1:1.2, and the mol ratio of hydroxyl to isocyanate group is 1:0.97 in the system.
The embodiment provides a preparation method of an organosilicon treating agent, which specifically comprises the following steps:
(1) Adding side hydrogen organosilicon prepolymer, allyl alcohol and methacryloxy trimethoxy silane into a reaction kettle according to the formula amount, adding 60ppm of chloro-platinum catalyst, starting stirring, introducing nitrogen, heating to 120 ℃, and reacting for 3 hours to obtain a hydroxyl-containing intermediate; in the reaction process, confirming the progress of the reaction by infrared monitoring of disappearance of characteristic peaks of the silicon hydride;
(2) Adding the hydroxyl-containing intermediate obtained in the step (1) into a reaction kettle, dewatering at 105 ℃ for 2 hours, cooling to 90 ℃, adding butanone with the mass of 10% of the system, adding MDI into the reaction kettle, adding an organobismuth catalyst with the mass of 0.5% of the reactants, controlling the reaction temperature to 80 ℃, reacting for 3 hours, removing the solvent, and obtaining the organosilicon treating agent, wherein the reaction is confirmed by infrared monitoring of disappearance of NCO characteristic peaks in the reaction process.
Example 4
The embodiment provides an organosilicon treating agent, wherein the preparation raw materials of the organosilicon treating agent comprise a side hydrogen organosilicon prepolymer, allyl hydroxyethyl ether, acryloxymethyl trimethoxysilane and isophorone diisocyanate (IPDI); the molar ratio of the 2-hydroxyethyl vinyl ether to the acryloxymethyl trimethoxysilane is 3.3:6.7, the molar ratio of the silicon hydrogen to the carbon-carbon double bond is 1:1.1, and the molar ratio of the hydroxyl group to the isocyanate group is 1:0.95 in the system.
The embodiment provides a preparation method of an organosilicon treating agent, which specifically comprises the following steps:
(1) According to the formula amount, adding the side hydrogen organosilicon prepolymer, allyl alcohol and allyl trimethoxy silane into a reaction kettle, adding 50ppm of a chloro-platinum catalyst, starting stirring, introducing nitrogen, heating to 85 ℃, and reacting for 7 hours to obtain a hydroxyl-containing intermediate; in the reaction process, confirming the progress of the reaction by infrared monitoring of disappearance of characteristic peaks of the silicon hydride;
(2) Adding the hydroxyl-containing intermediate obtained in the step (1) into a reaction kettle, dewatering at 105 ℃ for 2 hours, cooling to 80 ℃, adding butanone with the mass of 10% of the system, adding IPDI into the reaction kettle, adding an organobismuth catalyst with the mass of 0.5% of the reactant, controlling the reaction temperature to 80 ℃, reacting for 3 hours, removing the solvent, and obtaining the organosilicon treating agent, wherein the reaction is confirmed by infrared monitoring of disappearance of NCO characteristic peaks in the reaction process.
Example 5
This example provides a silicone treatment which differs from example 1 only in that the total molar amount of allyl alcohol and allyltrimethoxysilane is unchanged, the molar ratio of the allyl alcohol to allyltrimethoxysilane is 1:9, and other materials, amounts and preparation methods are the same as in example 1.
Example 6
This example provides a silicone treatment which differs from example 1 only in that the total molar amount of allyl alcohol and allyltrimethoxysilane is unchanged, the molar ratio of the allyl alcohol to allyltrimethoxysilane is 8:2, and other materials, amounts and preparation methods are the same as in example 1.
Comparative example 1
This comparative example provides a silicone treatment differing from example 1 only in that the total molar amount of allyl alcohol and allyltrimethoxysilane was unchanged, no allyltrimethoxysilane was present, and other materials, amounts, and preparation methods were the same as in example 1.
Application example 1
A modified powder comprising, in parts by weight, 2 parts of a silicone treatment (example 1) and 98 parts of calcium carbonate powder; the preparation method of the modified powder comprises the following steps: and mixing the organosilicon treating agent with calcium carbonate powder for 1h at 60 ℃ to obtain the modified powder.
Application examples 2 to 6
The modified powder was different from application example 1 only in that the silicone treatment agents were the silicone treatment agents provided in examples 2 to 6, respectively, and other components, amounts and preparation methods were the same as those of application example 1.
Comparative application example 1
The modified powder is different from the modified powder in application example 1 only in that the organosilicon treating agent is the organosilicon treating agent provided in comparative example 1, and other components, amounts and preparation methods are the same as those in application example 1.
Comparative application example 2
The modified powder was different from application example 1 only in that the organosilicon treating agent was a hydroxyl group-containing intermediate obtained in step (1) of example 1, and other components, amounts and preparation methods were the same as those of application example 1.
Comparative application example 3
A modified powder which is different from application example 1 only in that the silicone treating agent is replaced with KH550 of equal weight part, and other components, amounts and preparation methods are the same as application example 1.
Comparative application example 4
Unmodified calcium carbonate powder.
Performance testing
100 parts by mass of polypropylene, 28 parts of modified calcium carbonate powder or unmodified calcium carbonate powder provided by the application examples and the comparative application examples and 0.2 part of antioxidant 1010 are mixed uniformly, then are added into an internal mixer to be mixed for 8 minutes at 210 ℃, and then are granulated by an extruder to obtain test master batches, and after the test master batches are prepared into test templates, the impact property, the tensile property and the melt flow rate of the test master batches are tested;
(1) Notched impact strength: notched impact strength was measured according to ASTM D256;
(2) Tensile strength: testing according to standard ASTM D638-2014;
(3) Melt flow rate: measured according to ASTM D1238-2004 at 230℃under a load of 2.16 kg;
(4) Dispersibility: test master batches were prepared as 100mm x 1mm test plates, and the number of spots and appearance of the sample plate surface were observed, and the sample plate surface was classified into 5 stages according to the difference in the number of spots on the surface and the uniformity of the appearance, with 1 stage being the best, 5 stages being the worst, and 1 stage: the number of spots is less than 2, the appearance is very uniform, and the level is 2: 3-6, 3 stages: 7-10, 4 grades: 11-13, 5 stages: more than 14.
The specific test results are shown in table 1:
TABLE 1
As can be seen from the table, the organic silicon treating agent provided by the invention has a polysiloxane main chain, a polyurethane organic chain segment and a siloxane side chain in the molecular structure by selecting specific preparation raw materials, so that the compatibility of inorganic powder and a polymer can be improved, the dispersion effect of the inorganic powder in the polymer is good, and the obtained product has excellent mechanical property, smoothness and good hand feeling; in the optimal technical scheme of the invention (application examples 1-4), the impact strength of the material reaches 32.2-34.8 KJ/m 2 The tensile strength reaches 41.5-43.9 MPa, the melt flow rate is 16.92-19.53 g/10min, and the dispersibility of the inorganic powder in the polymer is good.
As is clear from the comparison of application example 1 with application examples 5 and 6, the molar ratio of the first monomer to the second monomer is not in a further preferable range, and the mechanical properties and dispersibility of the obtained material are slightly inferior.
As is clear from the comparison of application example 1 with comparative application examples 1 to 2, the silicone treatment agent of a not specific structure is remarkably deteriorated in mechanical properties, melt flow rate and dispersibility of the finally obtained material. As can be seen from application example 1 and comparative application examples 3 and 4, the modification of the organosilicon treating agent to the inorganic powder greatly improves the compatibility of the inorganic powder and the polymer, and improves the mechanical property and the melt flow rate of the material.
In summary, the organosilicon treating agent provided by the invention selects specific preparation raw materials, and the raw materials are used for modifying inorganic powder within a specific molar ratio range, so that the powder can be endowed with excellent dispersibility, the mechanical property and the melt flow rate of the composite material are improved, and the organosilicon treating agent can be used for preparing products in the fields of plastics, rubber, paint, daily chemicals and the like.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (15)
1. The organosilicon treating agent for modifying inorganic powder is characterized in that the preparation raw materials of the organosilicon treating agent comprise organosilicon prepolymer containing side hydrogen, a first monomer, a second monomer and isocyanate;
the mol ratio of the first monomer to the second monomer is 1 (0.4-5);
the hydrogen content in the side hydrogen-containing organosilicon prepolymer is 0.2-0.4%;
the first monomer is at least one of allyl alcohol, hydroxy methacrylamide, hydroxy ethylacrylamide, 2-hydroxy ethyl vinyl ether, 4-hydroxy butyl vinyl ether, diethylene glycol monovinyl ether, 2-hydroxy ethyl acrylate, 2-hydroxy ethyl methacrylate, 2-hydroxy propyl acrylate, 2-hydroxy propyl methacrylate, 3-hydroxy propyl acrylate, 3-hydroxy propyl methacrylate, 2-hydroxy butyl acrylate, 2-hydroxy butyl methacrylate, 4-hydroxy butyl acrylate, 4-hydroxy butyl methacrylate, 6-hydroxy hexyl acrylate, 6-hydroxy hexyl methacrylate, 8-hydroxy octyl acrylate, 8-hydroxy octyl methacrylate, 10-hydroxy decyl acrylate, 10-hydroxy decyl methacrylate, 12-hydroxy lauryl acrylate or 12-hydroxy lauryl methacrylate;
the second monomer is at least one of allyl trimethoxysilane, allyl triethoxysilane, methacryloxymethyl trimethoxysilane, methacryloxymethyl triethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl triethoxysilane, 8-methacryloxyoctyl trimethoxysilane, 8-methacryloxyoctyl triethoxysilane, acryloxymethyl trimethoxysilane, acryloxymethyl triethoxysilane, 3-acryloxypropyl trimethoxysilane, 3-acryloxypropyl triethoxysilane, 8-acryloxyoctyl trimethoxysilane or 8-acryloxyoctyl triethoxysilane;
the isocyanate comprises at least one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate or hexamethylene diisocyanate;
the organosilicon treating agent is prepared by the following method, which comprises the following steps:
(1) In the presence of a catalyst, reacting a side hydrogen-containing organosilicon prepolymer, a first monomer and a second monomer to obtain a hydroxyl-containing intermediate;
(2) And (3) reacting the hydroxyl-containing intermediate obtained in the step (1) with isocyanate to obtain the organosilicon treating agent.
2. The silicone treatment according to claim 1, wherein the side hydrogen-containing silicone prepolymer has a number average molecular weight of 500 to 10000.
3. The organosilicon treating agent according to claim 1, wherein the molar ratio of silicon hydrogen to carbon-carbon double bonds in the preparation raw material is 1 (1-1.5).
4. The silicone treatment according to claim 1, wherein the molar ratio of hydroxyl groups to isocyanate groups in the preparation raw material is 1 (0.9 to 1).
5. A method for producing the silicone treatment according to any one of claims 1 to 4, comprising the steps of:
(1) In the presence of a catalyst, reacting a side hydrogen-containing organosilicon prepolymer, a first monomer and a second monomer to obtain a hydroxyl-containing intermediate;
(2) And (3) reacting the hydroxyl-containing intermediate obtained in the step (1) with isocyanate to obtain the organosilicon treating agent.
6. The method of claim 5, wherein the catalyst of step (1) comprises a transition metal catalyst.
7. The method for preparing the catalyst according to claim 5, wherein the catalyst is used in an amount of 40 to 60 ppm.
8. The method according to claim 5, wherein the reaction in the step (1) is carried out at a temperature of 80 to 120 ℃ for 2 to 8 hours.
9. The method according to claim 5, wherein the reaction system in the step (2) further comprises a solvent and a catalyst.
10. The method of claim 9, wherein the catalyst in step (2) is used in an amount of 0.1 to 0.7% based on the total mass of the reactants.
11. The method according to claim 5, wherein the reaction in the step (2) is carried out at a temperature of 70-90 ℃ for 3-6 hours.
12. The modified powder is characterized in that the raw materials of the modified powder comprise 0.5-10% of the organic silicon treating agent according to any one of claims 1-4 and 90-99.5% of inorganic powder in percentage by mass.
13. The modified powder of claim 12, wherein the inorganic powder comprises at least one of calcium carbonate powder, talc, titanium dioxide powder, silicon powder, toner, or flame retardant powder.
14. The modified powder of claim 12, wherein the modified powder is prepared by a process comprising: and mixing the organosilicon treating agent with inorganic powder for 0.5-2 hours at 50-70 ℃ to obtain the modified powder.
15. Use of the organosilicon treating agent according to any one of claims 1 to 4 and/or the modified powder according to any one of claims 12 to 14 in plastics, paints, daily chemicals, rubber fields.
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| CN101260190A (en) * | 2008-04-28 | 2008-09-10 | 华南理工大学 | Multiple functionality degree polysiloxane coupling agent and preparation method thereof |
| CN114541148A (en) * | 2022-03-16 | 2022-05-27 | 广东德美精细化工集团股份有限公司 | Closed isocyanate modified silicon wax for textile water resistance and preparation method thereof |
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| ES2865325T3 (en) * | 2016-12-16 | 2021-10-15 | Henkel Ag & Co Kgaa | Process for the preparation of polysiloxanes having hydroxyl functional groups |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101260190A (en) * | 2008-04-28 | 2008-09-10 | 华南理工大学 | Multiple functionality degree polysiloxane coupling agent and preparation method thereof |
| CN114541148A (en) * | 2022-03-16 | 2022-05-27 | 广东德美精细化工集团股份有限公司 | Closed isocyanate modified silicon wax for textile water resistance and preparation method thereof |
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