CN115594852A - Trapezoidal organic silicon resin, preparation method thereof and flame-retardant material containing trapezoidal organic silicon resin - Google Patents
Trapezoidal organic silicon resin, preparation method thereof and flame-retardant material containing trapezoidal organic silicon resin Download PDFInfo
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- CN115594852A CN115594852A CN202211287967.3A CN202211287967A CN115594852A CN 115594852 A CN115594852 A CN 115594852A CN 202211287967 A CN202211287967 A CN 202211287967A CN 115594852 A CN115594852 A CN 115594852A
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- substituted
- unsubstituted
- diisocyanate
- organic silicon
- silicon resin
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- 229920005989 resin Polymers 0.000 title claims abstract description 41
- 239000011347 resin Substances 0.000 title claims abstract description 41
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 40
- 239000010703 silicon Substances 0.000 title claims abstract description 40
- 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 title claims abstract description 21
- 239000003063 flame retardant Substances 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 14
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910000077 silane Inorganic materials 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 16
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 13
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 13
- 229920002050 silicone resin Polymers 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 11
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 11
- 239000007795 chemical reaction product Substances 0.000 claims description 11
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 11
- 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 11
- 239000002994 raw material Substances 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- 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 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 claims description 6
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 6
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 6
- 125000006835 (C6-C20) arylene group Chemical group 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 0.000 claims description 4
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 3
- 239000007822 coupling agent Substances 0.000 claims description 3
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 3
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 claims description 2
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-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
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 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
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 2
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 125000001424 substituent group Chemical group 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
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002861 polymer material Substances 0.000 abstract description 21
- 229920002396 Polyurea Polymers 0.000 abstract description 12
- -1 polysiloxane Polymers 0.000 description 14
- 229920003023 plastic Polymers 0.000 description 10
- 239000004033 plastic Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000004417 polycarbonate Substances 0.000 description 7
- 229920000515 polycarbonate Polymers 0.000 description 7
- 229920001296 polysiloxane Polymers 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000003377 acid catalyst Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000005054 phenyltrichlorosilane Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 3
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 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
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004653 anthracenylene group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000004977 cycloheptylene group Chemical group 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- 125000004978 cyclooctylene group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000005567 fluorenylene group Chemical group 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000005560 phenanthrenylene group Chemical group 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920000734 polysilsesquioxane polymer Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012798 spherical particle Substances 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
- HPEPIADELDNCED-UHFFFAOYSA-N triethoxysilylmethanol Chemical compound CCO[Si](CO)(OCC)OCC HPEPIADELDNCED-UHFFFAOYSA-N 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/458—Block-or graft-polymers containing polysiloxane sequences containing polyurethane sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
Abstract
The invention provides a trapezoidal organic silicon resin, a preparation method thereof and a flame-retardant material containing the same. The ladder-shaped organic silicon resin has a structure shown in a formula I or a formula II. The preparation method of the trapezoidal organic silicon resin comprises the following steps: reacting an amino-containing silane coupling agent with diisocyanate to obtain an intermediate; and reacting the intermediate with a silane monomer to obtain the trapezoidal organic silicon resin. According to the trapezoid organic silicon resin provided by the invention, the polyurea chain segment is introduced, so that the trapezoid organic silicon resin has excellent flame retardant property and mechanical property, is good in flexibility and has good compatibility with a high polymer material, the flame retardant property of the material can be improved when the trapezoid organic silicon resin is added into the high polymer material, and the mechanical property of the high polymer material cannot be greatly reduced.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a trapezoidal organic silicon resin and a preparation method and application thereof.
Background
The trapezoidal silicone resin is polysiloxane with a special rigid structure and a trapezoidal double-chain or multi-chain structure, is more excellent in heat resistance, radiation resistance, chemical resistance, mechanics and the like compared with single-chain polysiloxane and body type cross-linked polysiloxane, and has wide application prospects due to the performances.
In recent years, trapezoidal silicone resin is also used in the field of flame retardation, but the current trapezoidal silicone resin has the problems of poor mechanical properties, poor compatibility with general polymer materials and the like, and the application of the trapezoidal silicone resin is limited.
For example, CN101838394a discloses a highly regular trapezoidal polyphenylsilsesquioxane and a method for preparing the same, the method comprising: mixing phenyltrichlorosilane, a solvent and deionized water to hydrolyze the phenyltrichlorosilane, taking an upper layer, adding a metal chloride aqueous solution, heating, adding a catalyst, and refluxing at 80-120 ℃ to obtain a solid-liquid mixture; filtering, adding precipitant into the filtrate, suction filtering, washing, and vacuum drying to obtain white spherical particle with diameter of 0.5-1 μm and weight average molecular weight of 3000-8000. The trapezoidal polyphenyl silsesquioxane bridging group is an oxygen bridging group, no hydroxyl is arranged in the structure, the molecular chain regularity is high, and the thermal stability is good. However, the trapezoidal polyphenylsilsesquioxane has poor compatibility with the high polymer material, and the transparency and the mechanical property of the high polymer material are influenced.
CN1284513A discloses a tubular structure material composed of organic bridging ladder polysiloxane, wherein the organic bridging group in the organic bridging ladder polysiloxane comprises 13 structures. The tubular structure material is prepared by an in-situ embedding or displacement embedding method, and object molecules matched with the tubular polymer can be selectively embedded according to the difference of the size and the chemical affinity of the tubular polymer, so that various supramolecular complexes are formed and the tubular structure material has wide application prospects in the fields of molecular devices, molecular recognition catalysis, separation, novel optical materials, novel electrical materials and the like. However, the heat resistance of the organobridged ladder-type polysiloxane is slightly poor.
Patents JP2005312503 and JP2012005935 disclose the use of ladder-type polysilsesquioxane as a protective material for optical elements having high heat resistance, light resistance, and gas barrier properties, but its application in industry is limited due to its low flexibility and poor compatibility with general polymers.
Therefore, the development of a trapezoidal organic silicon resin which has good compatibility with a high polymer material, good flexibility and flame retardant property and mechanical property is a technical problem to be solved in the field.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a trapezoidal organic silicon resin, a preparation method thereof and a flame-retardant material containing the same. The polyurea chain segment is introduced into the bridge group, so that the trapezoidal organic silicon resin has excellent flame retardant property and mechanical property, is good in flexibility and excellent in compatibility with a high polymer material, can improve the flame retardance of the high polymer material, and cannot influence the mechanical property of the high polymer material when added into the high polymer material.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a ladder-shaped silicone resin having any one of the following structures:
wherein R is selected from
R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 Each independently selected from any one of H, substituted or unsubstituted C1-C6 straight chain or branched chain alkyl, substituted or unsubstituted C1-C6 alkoxy, substituted or unsubstituted phenyl or hydroxyl; r 11 Selected from substituted or unsubstituted C1-C6 linear or branched alkylene, substituted or unsubstituted C6-C20 arylene, substituted or unsubstituted C6-C15 cycloalkylene, -Ar 1 -L-Ar 2 -any one of; ar (Ar) 1 、Ar 2 Each independently selected from any one of substituted or unsubstituted C6-C20 arylene, substituted or unsubstituted C6-C15 cycloalkylene; l is selected from a single bond or methylene; r is 12 、R 13 Each independently selected from substituted or unsubstituted C1-C6 linear or branched alkylene, -CH 2 CH 2 NHCH 2 CH 2 -、-CH 2 CH 2 NHCH 2 CH 2 CH 2 -any of; r is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 The substituted substituent group in (1) comprises any one of halogen, unsubstituted or halogenated C1-C6 straight-chain or branched-chain alkyl and hydroxyl; n is an integer of 2 to 1000; m is an integer of 0 to 1000.
In the invention, the polyurea structure is introduced into the structure of the trapezoidal organic silicon resin, so that the compatibility, flexibility, heat resistance and mechanical property of the trapezoidal organic silicon resin are improved; the trapezoid organic silicon resin has excellent flame retardant property and mechanical property, has excellent compatibility with other high polymer materials, is beneficial to improving the flame retardant property of other high polymer materials, and cannot cause the loss of the mechanical property of other high polymer materials. And the polarity of the polyurea structure is greatly different from that of the siloxane structure, when the polyurea structure is positioned at a bridge group, the polyurea structure can form microphase separation with a siloxane chain segment, so that the mechanical property of the resin is improved, and when the polyurea structure is positioned at a side chain, the polyurea structure cannot form the polyurea structure, and is more easily oxidized and thermally degraded, so that the weather resistance and the heat resistance are reduced.
In the present invention, the C1 to C6 linear or branched alkyl group includes C1, C2, C3, C4, C5, C6 linear or branched alkyl groups, and exemplarily includes but is not limited to methyl, ethyl, propyl, isopropyl, butyl, isobutyl, etc.
Preferably, the C1-C6 alkoxy group includes C1, C2, C3, C4, C5, C6 alkoxy groups, illustratively including but not limited to methoxy, ethoxy, propoxy, and the like.
In the present invention, the C1 to C6 linear or branched alkylene group includes C1, C2, C3, C4, C5, C6 linear or branched alkylene groups, and exemplarily includes but is not limited to methylene, ethylene, propylene, isopropylene, butylene, isobutylene, pentylene, hexylene, and the like.
Preferably, the C6-C20 arylene group includes C6. C7, C8, C9, C10, C12, C14, C16, C18 aryl, and the like, illustratively including but not limited to: phenylene, biphenylene, naphthylene, fluorenylene, anthracenylene, indenylene, phenanthrenylene, pyrenylene, acenaphthylene, triphenylene, phenylene
Acenaphthylene, peryleneylene, and the like.
Preferably, the C6 to C15 cycloalkylene group includes C6, C7, C8, C9, C10, C11, C12, C13, C14 cycloalkyl groups and the like, and exemplarily includes but is not limited to cyclohexylene, cycloheptylene, cyclooctylene and the like.
In the present invention, the halogen includes fluorine, chlorine, bromine or iodine; the following relates to the same description with the same meaning.
In the present invention, the "halo" means that at least one H in the group is substituted by a halogen (e.g., F, cl, br or I).
Preferably, n is an integer of 2 to 1000, and may be, for example, 20, 40, 60, 80, 100, 200, 400, 600, 800, or the like. From the viewpoint of flame retardancy and dispersibility, an integer of 10 to 200 is more preferable.
Preferably, R 1 、R 2 Each independently selected from any one of substituted or unsubstituted C1-C3 straight chain or branched chain alkyl and substituted or unsubstituted C1-C3 alkoxy.
Preferably, R 3 、R 4 、R 7 、R 8 Each independently selected from any one of substituted or unsubstituted C1-C3 straight chain or branched chain alkyl, substituted or unsubstituted phenyl and hydroxyl.
Preferably, R 5 、R 6 、R 9 、R 10 Each independently selected from any one of substituted or unsubstituted C1-C3 straight chain or branched chain alkyl, substituted or unsubstituted phenyl and hydroxyl.
Preferably, R 11 Selected from the group consisting of hexamethylene,
Any one of the above, wherein denotes a ligation site.
Preferably, R 12 、R 13 Each independently selected from substituted or unsubstituted C1-C3 linear or branched alkylene, -CH 2 CH 2 NHCH 2 CH 2 -、-CH 2 CH 2 NHCH 2 CH 2 CH 2 -any of the above.
Preferably, the raw materials of the ladder-shaped organic silicon resin comprise an amino-containing silane coupling agent, diisocyanate and a silane monomer.
Preferably, the aminosilane-containing coupling agent comprises at least one of gamma-aminopropyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, or gamma-aminopropylmethyldiethoxysilane.
Preferably, the diisocyanate comprises at least one of toluene diisocyanate, isophorone diisocyanate, m-xylylene isocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane-1,4-diisocyanate or hexamethylene diisocyanate, and derivatives or homologues thereof.
Preferably, the molar ratio of the amino-containing silane coupling agent to diisocyanate is (2-4): 1, and can be, for example, 2.2.
Preferably, the silane monomer has a functionality of 2 to 3.
Preferably, the silane monomer comprises at least one of dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, propyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, and isobutyltrimethoxysilane.
Preferably, the molar ratio of the silane monomer to the amino-containing silane coupling agent and diisocyanate reaction product is 1 (1-20), and can be 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1.
In a second aspect, the present invention provides a method for producing the ladder-shaped silicone resin according to the first aspect, the method comprising the steps of;
(1) Reacting an amino-containing silane coupling agent with diisocyanate to obtain an intermediate;
(2) And (2) reacting the intermediate obtained in the step (1) with a silane monomer to obtain the trapezoidal organic silicon resin.
In the present invention, the intermediate refers to the reaction product of the above-mentioned aminosilane-containing coupling agent and diisocyanate.
Preferably, the reaction of step (1) is carried out in a protective atmosphere.
Preferably, the protective atmosphere comprises nitrogen.
Preferably, the reaction temperature in step (1) is 10 to 80 ℃, for example, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ and the like.
Preferably, the reaction time in step (1) is 1 to 4 hours, and for example, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours and the like can be mentioned.
Preferably, the raw materials for the reaction of step (2) further comprise water.
Preferably, the molar ratio of water to intermediate is (2 to 10): 1, for example, 2.2.
In the invention, the water provides hydrolysis conditions for silane hydrolysis condensation.
Preferably, the reaction of step (2) is carried out in the presence of a catalyst.
Preferably, the catalyst comprises an acidic catalyst.
Preferably, the acidic catalyst comprises an organic acid and/or an inorganic acid.
Preferably, the organic acid comprises at least one of sulfonic acid, formic acid, acetic acid, citric acid, or oxalic acid.
Preferably, the inorganic acid comprises at least one of hydrochloric acid, sulfuric acid, nitric acid, or phosphoric acid.
Preferably, the catalyst is used in an amount of 0.1 to 5% by mass of the total mass of the intermediate and the silane monomer, and may be, for example, 0.2%, 0.5%, 0.8%, 1%, 1.2%, 1.4%, 1.5%, 1.6%, 1.8%, 2%, 2.2%, 2.4%, 2.6%, 2.8%, 3%, 3.2%, 3.4%, 3.6%, 3.8%, 4%, 4.2%, 4.4%, 4.6%, 4.8%, or the like.
Preferably, the reaction temperature in step (2) is 60 to 150 ℃, for example, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ and the like.
Preferably, the reaction time in step (2) is 4 to 8 hours, and for example, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours and the like can be realized.
Preferably, the reaction of step (2) further comprises a post-treatment step.
Preferably, the post-treatment comprises neutralization, washing and separation.
In the invention, the neutralization refers to adjusting the pH value to be neutral by adopting an alkaline solution.
Preferably, the solvent used for the washing comprises water.
As a preferred technical solution of the present invention, the preparation method comprises:
(1) Under the protection atmosphere, reacting an amino-containing silane coupling agent with diisocyanate at the temperature of 10-80 ℃ for 1-4 h to obtain an intermediate;
(2) And (2) mixing the intermediate obtained in the step (1) with silane monomer and water in the presence of a catalyst, and reacting for 4-8 h at the temperature of 60-150 ℃ to obtain the trapezoidal organic silicon resin.
In a third aspect, the present invention provides a flame retardant material comprising the ladder-shaped silicone resin according to the first aspect.
The recitation of numerical ranges herein includes not only the above-recited values, but also any values between any of the above-recited numerical ranges not recited, and for brevity and clarity, is not intended to be exhaustive of the specific values encompassed within the range.
Compared with the prior art, the invention has the following beneficial effects:
according to the trapezoid organic silicon resin provided by the invention, the polyurea chain segment is introduced into the bridge group, so that the trapezoid organic silicon resin has excellent flame retardant property and mechanical property, is good in flexibility and excellent in compatibility with a high polymer material, can improve the flame retardant property and toughness of the material, and cannot influence the mechanical property of the high polymer material when added into the high polymer material.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a trapezoidal organic silicon resin, wherein raw materials of the trapezoidal organic silicon resin comprise gamma-aminopropyltriethoxysilane, isophorone diisocyanate and dimethyldiethoxysilane; the molar ratio of the gamma-aminopropyltriethoxysilane to the isophorone diisocyanate is 2:1; the molar ratio of the dimethyl diethoxysilane to the reaction product of the gamma-aminopropyltriethoxysilane and the isophorone diisocyanate is 1.
The embodiment provides a preparation method of the trapezoidal organic silicon resin, which specifically comprises the following steps:
(1) Adding gamma-aminopropyltriethoxysilane and isophorone diisocyanate into a reaction kettle, introducing nitrogen, starting stirring, and reacting at 60 ℃ for 2 hours to obtain an intermediate;
(2) Reacting the intermediate obtained in the step (1) with dimethyl diethoxy silane and water at the temperature of 100 ℃ for 6 hours in the presence of an acid catalyst, and neutralizing, washing, concentrating and separating the obtained product to obtain the trapezoidal organic silicon resin; the acid catalyst is sulfuric acid, and the use amount of the sulfuric acid is 2% of the total mass of the intermediate and the dimethyl diethoxy silane; the molar ratio of water to intermediate is 5:1.
1 H NMR(400HMz，CDCl 3 ，298K)：δ＝6.44(4H,-HN-CO-NH-),3.1-3.25(4H,HN-C 2 H-CH 2 -CH 2 -Si),1.45-1.55(4H,HN-CH 2 - 2 CH-CH 2 -Si),0.5-0.6(4H,NH-CH 2 -CH 2 -C 2 H-Si-),6.35(2H,-OH),0.15(24H,Si-CH 3 )。
Example 2
The embodiment provides a ladder-shaped silicone resin, and raw materials of the ladder-shaped silicone resin comprise N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, 4,4' -diphenylmethane diisocyanate and phenyltrimethoxysilane; the molar ratio of the N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane to the 4,4' -diphenylmethane diisocyanate is 2.5; the molar ratio of the phenyltrimethoxysilane to the reaction product of the N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane and 4,4' -diphenylmethane diisocyanate is 1:8.
The embodiment provides a preparation method of the trapezoidal organic silicon resin, which specifically comprises the following steps:
(1) Adding N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane and 4,4' -diphenylmethane diisocyanate into a reaction kettle, introducing nitrogen, starting stirring, and reacting at 80 ℃ for 1h to obtain an intermediate;
(2) Reacting the intermediate obtained in the step (1) with phenyltrimethoxysilane and water at 130 ℃ for 5 hours in the presence of an acid catalyst, and neutralizing, washing, concentrating and separating the obtained product to obtain the trapezoidal organic silicon resin; the acid catalyst is acetic acid, and the using amount of the acetic acid is 4% of the total mass of the intermediate and the phenyl trimethoxy silane; the molar ratio of water to intermediate is 8:1.
1 H NMR(400HMz，CDCl 3 ，298K)：δ＝6.44(4H,-HN-CO-NH-),1.48(2H,-NH-),2.5-2.55(4H,HN-C 2 H-CH 2 -CH 2 -Si),1.35-1.4(4H,HN-CH 2 -C 2 H-CH 2 -Si),0.5-0.6(4H,NH-CH 2 -CH 2 -C 2 H-Si-),3.25-3.3(4H,-CONH-C 2 H-CH 2 -NH-),2.75-2.8(4H,-CONH-CH 2 -C 2 H-NH-),6.35(2H,-OH),7.18-7.27(-C 6 H 5 ),6.35(2H,-C 6 H 5 -Si-OH)。
Example 3
The embodiment provides a trapezoidal organic silicon resin, and raw materials of the trapezoidal organic silicon resin comprise gamma-aminopropyl methyl diethoxysilane, cyclohexane-1,4-diisocyanate and silane monomers; the molar ratio of the gamma-aminopropyl methyl diethoxysilane to the cyclohexane-1,4-diisocyanate is 3:1; the molar ratio of the silane monomer to the reaction product of gamma-aminopropylmethyldiethoxysilane and cyclohexane-1,4-diisocyanate is 1; the silane monomer comprises diphenyldimethoxysilane and isobutyltrimethoxysilane in a molar ratio of 1:1.
The embodiment provides a preparation method of the trapezoidal organic silicon resin, which specifically comprises the following steps:
(1) Adding gamma-aminopropyl methyl diethoxysilane and cyclohexane-1,4-diisocyanate into a reaction kettle, introducing nitrogen, starting stirring, and reacting at 35 ℃ for 4 hours to obtain an intermediate;
(2) Reacting the intermediate obtained in the step (1) with diphenyldimethoxysilane, isobutyltrimethoxysilane and water at 60 ℃ for 8 hours in the presence of an acidic catalyst, and neutralizing, washing, concentrating and separating the obtained product to obtain the trapezoidal organic silicon resin; the acid catalyst is oxalic acid, and the dosage of the oxalic acid is 3 percent of the total mass of the intermediate and the silane monomer; the molar ratio of water to intermediate is 10.
Example 4
This example provides a ladder-type silicone resin which differs from example 1 only in that the molar ratio of the dimethyldiethoxysilane to the reaction product of gamma-aminopropyltriethoxysilane and isophorone diisocyanate is 1:5, and the other raw materials, amounts and preparation methods are the same as those of example 1.
Example 5
This example provides a ladder-type silicone resin, which is different from example 1 only in that the molar ratio of the dimethyldiethoxysilane to the reaction product of γ -aminopropyltriethoxysilane and isophorone diisocyanate is 1.
Example 6
This example provides a ladder-type silicone resin which differs from example 1 only in that the molar ratio of the dimethyldiethoxysilane to the reaction product of gamma-aminopropyltriethoxysilane and isophorone diisocyanate is 1:2, and the other raw materials, amounts and preparation methods are the same as those of example 1.
Example 7
This example provides a ladder-type silicone resin, which is different from example 1 only in that the molar ratio of the dimethyldiethoxysilane to the reaction product of γ -aminopropyltriethoxysilane and isophorone diisocyanate is 1.
Example 8
This example provides a ladder-type silicone resin, which differs from example 1 only in that the isophorone diisocyanate is replaced with 4,4' -diphenylmethane diisocyanate, the dimethyldiethoxysilane is replaced with diphenyldiethoxysilane, and the other raw materials, amounts, and preparation methods are the same as example 1.
Comparative example 1
This comparative example provides a ladder type silicone resin which is different from example 1 only in that the gamma-aminopropyltriethoxysilane is replaced with an equimolar amount of hydroxymethyltriethoxysilane, and the other raw materials, amounts and preparation methods are the same as those of example 1.
Comparative example 2
This comparative example provides a ladder-shaped silicone resin selected from the siloxane bridged ladder-shaped polysiloxane graft copolymers disclosed in patent document CN108003348a, example 31.
Performance testing
100g of Polycarbonate (PC) and 4g of the trapezoidal silicone resin provided in examples 1-8 and comparative examples 1 and 2 were mixed, and then placed in a double-screw mixer for melt extrusion, cooling and granulation to obtain the flame-retardant PC, wherein the melt extrusion temperature is 250 ℃, the screw rotation speed is 25r/min, and the melt extrusion pressure is 2MPa. The flame-retardant PC thus obtained was tested in the following manner, and the results are shown in Table 1. And PC without the addition of the ladder silicone resin was used as a blank for comparison.
(1) Tensile strength: testing according to GB/T528 standard;
(2) Impact strength: the determination is carried out according to the Izod impact performance detection standard of plastics specified in ASTM D256-1997;
(3) Limiting oxygen index: testing according to the GB/T2406 standard;
(4) UL-94 vertical burning rating: testing according to ANLIIUL-94-1985;
(5) Evaluation of transparency: the flame retardant PC was made into a 2mm thick test piece and tested by a light transmittance tester.
The specific test results are shown in table 1:
TABLE 1
The above table shows that the trapezoidal organic silicon resin provided by the invention has good flexibility, excellent mechanical properties and excellent flame retardant property by introducing the polyurea chain segment into the bridge group part. After the trapezoidal organic silicon resin is mixed with the plastic, the transparency of the plastic is hardly influenced, which shows that the compatibility of the plastic and the plastic is good. In addition, the trapezoid organic silicon resin can improve the flame retardant property of the plastic, and the mechanical property of the plastic is not influenced.
From examples 1 to 5, it is understood that the polycarbonate composite material comprising the trapezoidal silicone resin has a tensile strength of 57.3 to 59.6MPa, which is not much different from that of polycarbonate plastic; the impact strength is 478-489%, the limited oxygen index is 30-36%, the UL-94 vertical burning grade reaches V-0 grade, and the toughness and the flame retardance are improved; the light transmittance is 86.8-88.5%, and the transparency of the plastic is not influenced.
As can be seen from comparison between example 1 and example 8, the introduction of the benzene ring structure is advantageous for further improving the flame retardancy and compatibility of the plastic.
As is clear from comparison between example 1 and examples 6 to 7, the molar ratio of the amino-containing silane coupling agent to diisocyanate or the molar ratio of the reaction product of the amino-containing silane coupling agent to diisocyanate to the silane monomer is not within a specific range, and the mechanical properties, flame retardancy and compatibility of the ladder-shaped silicone resin are deteriorated; as can be seen from comparison of example 1 with comparative examples 1 and 2, the ladder-shaped silicone resin is not a specific structure of the present invention, and the mechanical properties, flame retardancy, and compatibility of the ladder-shaped silicone resin are deteriorated.
In conclusion, the polyurea chain segment is introduced into the bridge group, so that the trapezoidal organic silicon resin provided by the invention has excellent flame retardant property and mechanical property, good flexibility and excellent compatibility with a high polymer material, and cannot cause the mechanical property reduction of the high polymer material when being added into the high polymer material, and the trapezoidal organic silicon resin has a wide application prospect particularly when being used for preparing a flame retardant material.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A ladder silicone resin, wherein the ladder silicone resin has any one of the following structures:
wherein,r is selected from
R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 Each independently selected from any one of H, substituted or unsubstituted C1-C6 straight chain or branched chain alkyl, substituted or unsubstituted C1-C6 alkoxy, substituted or unsubstituted phenyl and hydroxyl;
R 11 selected from substituted or unsubstituted C1-C6 linear or branched alkylene, substituted or unsubstituted C6-C20 arylene, substituted or unsubstituted C6-C15 cycloalkylene, -Ar 1 -L-Ar 2 -any of;
Ar 1 、Ar 2 each independently selected from any one of substituted or unsubstituted C6-C20 arylene, substituted or unsubstituted C6-C15 cycloalkylene;
l is selected from a single bond or methylene;
R 12 、R 13 each independently selected from substituted or unsubstituted C1-C6 linear or branched alkylene, -CH 2 CH 2 NHCH 2 CH 2 -、-CH 2 CH 2 NHCH 2 CH 2 CH 2 -any one of;
R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 the substituted substituent group in (1) comprises any one of halogen, unsubstituted or halogenated C1-C6 straight-chain or branched-chain alkyl and hydroxyl;
n is an integer of 2 to 1000; m is an integer of 0 to 1000.
2. The ladder silicone resin of claim 1, wherein R is 1 、R 2 Each independently selected from any one of substituted or unsubstituted C1-C3 straight-chain or branched alkyl and substituted or unsubstituted C1-C3 alkoxy;
preferably, R 3 、R 4 、R 7 、R 8 Each independently selected from any one of substituted or unsubstituted C1-C3 straight chain or branched chain alkyl, substituted or unsubstituted phenyl and hydroxyl;
preferably, R 5 、R 6 、R 9 、R 10 Each independently selected from any one of substituted or unsubstituted C1-C3 straight chain or branched chain alkyl, substituted or unsubstituted phenyl and hydroxyl.
3. The ladder silicone resin of claim 1 or 2, wherein R is 11 Selected from the group consisting of hexamethylene,
Any one of the above, wherein denotes a ligation site;
preferably, R 12 、R 13 Each independently selected from substituted or unsubstituted C1-C3 linear or branched alkylene, -CH 2 CH 2 NHCH 2 CH 2 -、-CH 2 CH 2 NHCH 2 CH 2 CH 2 -any of the above.
4. The ladder-shaped silicone resin according to any one of claims 1 to 3, wherein the raw materials of the ladder-shaped silicone resin comprise an amino-containing silane coupling agent, diisocyanate, and a silane monomer;
preferably, the aminosilane-containing coupling agent comprises at least one of gamma-aminopropyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, or gamma-aminopropylmethyldiethoxysilane;
preferably, the diisocyanate comprises at least one of toluene diisocyanate, isophorone diisocyanate, m-xylylene isocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane-1,4-diisocyanate or hexamethylene diisocyanate;
preferably, the molar ratio of the amino-containing silane coupling agent to the diisocyanate is (2-4): 1.
5. The ladder silicone resin of any one of claims 1 to 4, wherein the silane monomer has a functionality of 2 to 3;
preferably, the silane monomer comprises at least one of dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, propyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and isobutyltrimethoxysilane;
preferably, the molar ratio of the silane monomer to the reaction product of the amino-containing silane coupling agent and the diisocyanate is 1 (1-20).
6. A method for producing a ladder-shaped silicone resin according to any one of claims 1 to 5, characterized by comprising the steps of;
(1) Reacting an amino-containing silane coupling agent with diisocyanate to obtain an intermediate;
(2) And (2) reacting the intermediate obtained in the step (1) with a silane monomer to obtain the trapezoidal organic silicon resin.
7. The method according to claim 6, wherein the reaction of step (1) is carried out in a protective atmosphere;
preferably, the temperature of the reaction in the step (1) is 10-80 ℃;
preferably, the reaction time of the step (1) is 1-4 h.
8. The production method according to claim 6 or 7, wherein the raw material for the reaction of step (2) further comprises water;
preferably, the molar ratio of the water to the intermediate is (2-10): 1;
preferably, the reaction of step (2) is carried out in the presence of a catalyst;
preferably, the catalyst comprises an acidic catalyst;
preferably, the acidic catalyst comprises an organic acid and/or an inorganic acid;
preferably, the organic acid comprises at least one of sulfonic acid, formic acid, acetic acid, citric acid, or oxalic acid;
preferably, the inorganic acid comprises at least one of hydrochloric acid, sulfuric acid, nitric acid, or phosphoric acid;
preferably, the amount of the catalyst is 0.1-5% of the total mass of the intermediate and the silane monomer;
preferably, the temperature of the reaction in the step (2) is 60-150 ℃;
preferably, the reaction time of the step (2) is 4-8 h.
9. The production method according to any one of claims 6 to 8, characterized by comprising:
(1) Under the protection atmosphere, reacting an amino-containing silane coupling agent with diisocyanate at the temperature of 10-80 ℃ for 1-4 h to obtain an intermediate;
(2) And (2) mixing the intermediate obtained in the step (1) with silane monomer and water in the presence of a catalyst, and reacting for 4-8 h at the temperature of 60-150 ℃ to obtain the trapezoidal organic silicon resin.
10. A flame retardant material, characterized in that it comprises a ladder-shaped silicone resin according to any one of claims 1 to 5.
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| EP0761707A1 (en) * | 1995-08-31 | 1997-03-12 | Bayer Ag | Binders containing isocyanurate-polyisocyanates based on 1,4-diisocyanate butane and their use as coating |
| CN101058640A (en) * | 2006-04-18 | 2007-10-24 | 汉高股份两合公司 | Organic silicon polyurea base polymer, elastic body prepared by the same, preparation method and application thereof |
| CN102827340A (en) * | 2011-06-13 | 2012-12-19 | 中国科学院化学研究所 | Organosilicon-modified waterborne polyurethane composite material and applications thereof |
| CN104321385A (en) * | 2012-05-25 | 2015-01-28 | 株式会社大赛璐 | Curable resin composition, and cured product, sealing agent, and optical semiconductor device using same |
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