CN102086267A - Amino-containing organic silicon resin fire retardant and preparation method thereof - Google Patents
Amino-containing organic silicon resin fire retardant and preparation method thereof Download PDFInfo
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- CN102086267A CN102086267A CN201010595303.4A CN201010595303A CN102086267A CN 102086267 A CN102086267 A CN 102086267A CN 201010595303 A CN201010595303 A CN 201010595303A CN 102086267 A CN102086267 A CN 102086267A
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- fire retardant
- silicon resin
- organic silicon
- silane
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 50
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229920005989 resin Polymers 0.000 title claims abstract description 25
- 239000011347 resin Substances 0.000 title claims abstract description 25
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 25
- 239000010703 silicon Substances 0.000 title claims abstract description 25
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000012046 mixed solvent Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 3
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 18
- 229910000077 silane Inorganic materials 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 230000003472 neutralizing effect Effects 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000006386 neutralization reaction Methods 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- -1 aminoethyl methyl dimethoxy oxygen Chemical compound 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 5
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- AUEJBKCWXPYRGZ-UHFFFAOYSA-N 1,1'-biphenyl diethoxysilane Chemical compound C(C)O[SiH2]OCC.C1(=CC=CC=C1)C1=CC=CC=C1 AUEJBKCWXPYRGZ-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- YEKZPZKFJZWQLH-UHFFFAOYSA-N C(CC)[Si](C)(C)C.[O] Chemical compound C(CC)[Si](C)(C)C.[O] YEKZPZKFJZWQLH-UHFFFAOYSA-N 0.000 claims description 2
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical group C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 claims description 2
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 claims description 2
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 2
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 claims description 2
- 150000005826 halohydrocarbons Chemical class 0.000 claims description 2
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical group CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002769 thiazolinyl group Chemical group 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
- LSSHHSHIJANGKT-UHFFFAOYSA-N 3-[diethyl(methyl)silyl]propan-1-amine Chemical compound CC[Si](C)(CC)CCCN LSSHHSHIJANGKT-UHFFFAOYSA-N 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- YLBPOJLDZXHVRR-UHFFFAOYSA-N n'-[3-[diethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CCO[Si](C)(OCC)CCCNCCN YLBPOJLDZXHVRR-UHFFFAOYSA-N 0.000 claims 1
- 239000008096 xylene Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- 231100000053 low toxicity Toxicity 0.000 abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 239000002981 blocking agent Substances 0.000 abstract 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 abstract 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 abstract 1
- 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 description 8
- 229920001296 polysiloxane Polymers 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 229920013822 aminosilicone Polymers 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920002050 silicone resin Polymers 0.000 description 3
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical class CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920007019 PC/ABS Polymers 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Silicon Polymers (AREA)
Abstract
The invention discloses an amino-containing organic silicon resin fire retardant and a preparation method thereof. The preparation method comprises the steps of: with amino silane and trialkoxysilane as raw materials or with amino silane, dialkoxysilane and trialkoxysilane as the raw materials, adding water or a mixed solvent of water and an organic solvent, carrying out hydrolytic polycondensation under the action of a catalyst, finally adding blocking agent to block the end, adding a neutralizer to neutralize before the reaction is finished, and then filtering, washing and drying to obtain the amino-containing organic silicon resin fire retardant. The fire retardant contains two fire-retardant elements of nitrogen and silicon, has with high efficiency and low toxicity and is an environment-friendly macromolecular fire retardant; the chemical structure is shown as follows: wherein R1, R2, R3, R4, and R6 are H, CH3 or C6H5; R5 is CH2, CH2CH2, CH2CH2CH2, CH2NHCH2CH2 or C6H5; R7 and R8 are CH3, C2H5 or C6H5; and n, p, q are integers of 1-50.
Description
Technical field
The present invention relates to a kind of fire retardant and preparation method thereof, specifically is a kind of amino organic silicon resin fire retardant and preparation method thereof that contains.
Background technology
The fire retardant that is widely used in fields such as plastics, fiber, coating generally is divided into Halogen and halogen-free flame retardants two big classes, and wherein halogen-free flame retardants is widely used, effect is better, meets the strategy of sustainable development of environment.Silicone flame retardant is a kind of novel halogen-free flame retardants, also is that a kind of one-tenth carbon presses down fumicants, and it has characteristics such as efficient, nontoxic, smokeless, pollution-free as a family macromolecule fire retardant.Polysiloxane can be divided into two kinds from molecular structure, a kind of is line style, and a kind of is branched chain type, and both all can contain aromatic base and aliphatic group.It has been generally acknowledged that the mechanism that organic silicon resin fire retardant can be fire-retardant mainly is fire-retardant because of itself, polysiloxane is compounded to form flame-retardant layer by the carbide with plastics and reaches inhibition incendiary purpose to the migration of frosting appropriateness during burning.Because the consistency of organic silicon fibre retardant and plastics is relatively poor, in silicone resin, introduce amino, by the consistency between reactive compatibilization increase organic silicon resin fire retardant and plastics.The silicone resin thermostability and the flame retardant resistance of existing amino-functional are relatively poor, can not satisfy existing to the high stability of fire retardant and the demand of high flame retardant.
Summary of the invention
The present invention overcomes the deficiencies in the prior art, and a kind of amino organic silicon resin fire retardant that contains is provided, and this fire retardant contains nitrogen and two kinds of ignition-proof elements of silicon simultaneously, and high-efficiency low-toxicity is a kind of environment-friendly type macromolecule fire retardant.And compare with the silicone resin of present amino-functional, the present invention introduces the capping group of different structure in molecular structure, and the phenyl content in the organic silicon resin fire retardant is higher, therefore has excellent thermostability and flame retardant resistance.
Technical scheme of the present invention is: a kind of organic silicon resin fire retardant that contains amino is characterized in that its chemical structure is shown below:
Wherein, R
1, R
2, R
3, R
4Be H, CH
3Or C
6H
5
R
5Be CH
2, CH
2CH
2, CH
2CH
2CH
2, CH
2NHCH
2CH
2Or C
6H
5
R
6Be H, CH
3Or C
6H
5
R
7, R
8Be the end group of molecular chain, be CH
3, C
2H
5Or C
6H
5
N is the integer of 1-50; P is the integer of 1-50; Q is the integer of 1-50.
The present invention also provides the preparation method of this fire retardant, it is characterized in that, with aminosilane and trialkoxy silane is raw material, be raw material with aminosilane, dialkoxy silicane and trialkoxy silane perhaps, add the mixed solvent of entry or water and organic solvent, polycondensation is hydrolyzed under catalyst action, add the end-capping reagent end-blocking at last, in reaction solution, add the neutralizing agent neutralization before reaction finishes, filter then, wash, drying, obtain product (white or little yellow solid matter).
Concrete steps are as follows: the mixed solvent that adds entry or water and organic solvent in the reaction vessel, with aminosilane and trialkoxy silane, join in the constant pressure funnel after perhaps aminosilane, dialkoxy silicane and trialkoxy silane mix, at the uniform velocity be added dropwise under 20～120 ℃ in the reaction vessel, the dropping time is 30-180min; After dropwising, continue hydrolysis 2-6h, add catalyzer then, continue reaction 2-6h down, in reaction solution, add end-capping reagent then, continue reaction 1-6h at temperature 20-120 ℃; Add neutralizing agent neutralization again, filter then, wash, drying, obtain product (white or little yellow solid matter).
The mol ratio of described trialkoxy silane, dialkoxy silicane and aminosilane is 0.01～1.0: 0～1.0: 0.01～1.0, and preferred proportion is: 0.1～0.5: 0.1～0.5: 0.1～0.4; The volumetric molar concentration of described catalyzer is 0.01-1.0mol/1, and the mol ratio of described catalyzer and reaction raw materials (trialkoxy silane, dialkoxy silicane and aminosilane) is 0.01～1.0: 1.0; The mol ratio of described end-capping reagent and reaction raw materials (trialkoxy silane, dialkoxy silicane and aminosilane) is that 0.001～0.1: 1 preferred proportion is: 0.005～0.05: 1; The volumetric molar concentration of described neutralizing agent is 0.01-1.0mol/l, and the mol ratio of described neutralizing agent and catalyzer is 0.1～1.0: 1.0; The volume ratio of organic solvent and water is less than 1 in the mixed solvent of described water and organic solvent.
Described aminosilane comprises any one in N-β-aminoethyl-γ-aminopropyl methyl dimethoxy (second) TMOS, aminoethyl methyl dimethoxy (second) oxygen base, aminopropyl methyl dimethoxy (second) base silane, aminopropyl triethoxysilane, aminopropyl trimethoxysilane, two (trimethyl silicon based) amine.
Described trialkoxy silane comprises: any one in phenyltrimethoxysila,e, phenyl triethoxysilane, methyltrimethoxy silane, Union carbide A-162, the γ-glycidyl ether oxygen propyl trimethyl silane.
Described dialkoxy silicane comprises: any one in dimethoxydiphenylsilane, phenylbenzene diethoxy silane, phenyl methyl dimethoxy silane, dimethyldimethoxysil,ne, the dimethyldiethoxysilane.
Described catalyzer is mineral acid or alkali or organic acid or alkali, comprises in hydrochloric acid, sulfuric acid, phosphoric acid, potassium hydroxide, sodium hydroxide, ammoniacal liquor, the triethylamine any one.
Described end-capping reagent is any one in dimethyl tetraphenyl sily oxide, hexamethyldisiloxane, hexamethyldisilazane, tetrem thiazolinyl sily oxide, the tetramethyl divinyl disiloxane.
Described neutralizing agent comprises triethylamine, pyridine, N, any one in accelerine, sodium hydroxide, potassium hydroxide, hydrochloric acid, sulfuric acid, the phosphoric acid.
Described organic solvent can for: halohydrocarbon organic solvent as, chloroform, 1,2-ethylene dichloride, chlorobenzene; Aromatic hydrocarbon solvent comprises toluene, dimethylbenzene, benzene; Other polar solvents comprise acetonitrile, N, dinethylformamide, N,N-DIMETHYLACETAMIDE, tetrahydrofuran (THF), acetone, methyl iso-butyl ketone (MIBK).
The invention has the beneficial effects as follows: the silicone flame retardant of the present invention's preparation; the high-temperature zone forms silicon dioxide layer of protection at specimen surface; inhibition is with the thermooxidative degradation reaction of the carbon-coating of generation; stop the mass loss of carbon-coating; increase the thermostability of carbon-coating; and it is few to give birth to the cigarette amount during burning, and the etchant gas of generation is few.This fire retardant also can combine with polymeric matrix by modes such as crosslinked, grafting, condensations by the terminal active group in the molecular designing, increase consistency with polymeric matrix, make macromolecular material can obtain lasting flame retardant resistance, and the mechanical property of polymkeric substance and processing characteristics are improved.This fire retardant contains nitrogen and two kinds of ignition-proof elements of silicon simultaneously, and high-efficiency low-toxicity is a kind of environment-friendly type macromolecule fire retardant.It can be applied to be used as fire retardant in the plastics such as polyolefine, polycarbonate, ABS, nylon, PC/ABS, PBT, PET, PBT/PET, PPO, POM, compares high-efficiency low-toxicity with conventional flame retardant, is a kind of environment-friendly type plastic fire retardant.When in above-mentioned macromolecular material, adding different (0.1-40wt%) organic silicon resin fire retardant of massfraction, can make the fire-retardant rank of material reach the V-0 level.
Embodiment
By following examples technical scheme of the present invention is elaborated, but the present invention is not limited to following embodiment.
Embodiment 1
The 2000ml four-hole boiling flask is loaded onto agitator, thermometer, ball prolong and 500ml constant pressure funnel, add 300ml deionized water and 300ml dimethylbenzene mixed solvent, with 41.2g N-β-aminoethyl-γ-aminopropyl methyl dimethoxysilane, 16.8g Union carbide A-162 and 211.2g phenylbenzene diethoxy silane, join in the constant pressure funnel after mixing, temperature is controlled at 40 ℃, at the uniform velocity be added drop-wise in the flask, drip 40-50min and dropwise; Continue hydrolysis 6h, after adding 0.1mol/l hydrochloric acid soln 60ml reaction 4h then, add 5.0 gram hexamethyldisilazanes, behind the reaction 2h, add 40 milliliters of 0.1mol/l sodium hydroxide solution neutralization reaction systems, filtering, wash the also dry white resinous solid that obtains is to contain amino silicone resin.Quality is that 194.8g, yield are 92.3%, and number-average molecular weight is about 20000, and structure is branched polysiloxane.
Embodiment 2
The 1000ml four-hole boiling flask is loaded onto agitator, thermometer, ball prolong and 100ml constant pressure funnel, add in 500ml deionized water and the dimethylbenzene mixed solvent (volume ratio 2: 1), with 25.6 gram aminopropyl methyl dimethoxysilanes, 8.4 gram Union carbide A-162s, 106.5 gram phenylbenzene diethoxy silanes, join in the constant pressure funnel after mixing, temperature of reaction is controlled at 60 ℃, at the uniform velocity drip in the solvent, drip and dropwised in 28-32 minute; Continue hydrolysis 3h, add 0.1mol/l sodium hydroxide solution 30ml then, after continuing reaction 4h, add 4.0 gram dimethyl tetraphenyl sily oxide, behind the reaction 2h, add 0.1mol/l hydrochloric acid soln 30ml neutralization reaction system, filtering, wash the also dry white resinous solid that obtains is to contain amino silicone resin.Quality is that 94.2g, yield are 89.2%, and number-average molecular weight is 15000, and structure is branched polysiloxane.
Embodiment 3
The 1000ml four-hole boiling flask is loaded onto agitator, thermometer, ball prolong and 100ml constant pressure funnel, add the 500ml deionized water, with 60.4 gram aminopropyl trimethoxysilane, 118.8 gram phenyltrimethoxysila,e, join in the constant pressure funnel after mixing, temperature of reaction is controlled at 50 ℃, at the uniform velocity be added drop-wise in the deionized water, drip and dropwised in 30-45 minute; Continue hydrolysis 4h, add 0.1mol/l sulfuric acid dilute solution 25ml then, after continuing reaction 4h, add 4.0 gram dimethyl tetraphenyl sily oxide, behind the reaction 2h, add 50 milliliters of neutralization reaction systems of 0.1mol/l ammonia soln, filtering, wash the also dry white resinous solid that obtains is to contain amino silicone resin.Quality is that 150.9g, yield are 88.7%, and number-average molecular weight is 14000, and structure is branched polysiloxane.
Embodiment 4
The 500ml four-hole boiling flask is loaded onto agitator, thermometer, ball prolong and 100ml constant pressure funnel, add 200ml deionized water and 100ml toluene, with 30.2 gram aminopropyl methyl dimethoxysilanes, 13.6 gram methyltrimethoxy silanes, 138.6 gram phenyltrimethoxysila,e, join in the constant pressure funnel after mixing, temperature of reaction is controlled at 40 ℃, at the uniform velocity be added drop-wise in the deionized water, dropwised in Dropwise 5 5-65 minute; Continue hydrolysis 4h, add 1.0mol/l sodium hydroxide solution 10ml then, after continuing reaction 4h, add 2.0 gram dimethyl tetraphenyl sily oxide, behind the reaction 2h, concentration is 1.0mol/l hydrochloric acid soln 10ml, and the neutralization reaction system is filtered, washed and the dry white resinous solid that obtains is to contain amino silicone resin.Quality is that 152.9g, yield are 93.0%, and number-average molecular weight is about 12300, and structure is branched polysiloxane.
Claims (10)
1. one kind contains amino organic silicon resin fire retardant, it is characterized in that its chemical structure is shown below:
Wherein, R
1, R
2, R
3, R
4Be H, CH
3Or C
6H
5
R
5Be CH
2, CH
2CH
2, CH
2CH
2CH
2, CH
2NHCH
2CH
2Or C
6H
5
R
6Be H, CH
3Or C
6H
5
R
7, R
8Be CH
3, C
2H
5Or C
6H
5
N is the integer of 1-50; P is the integer of 1-50; Q is the integer of 1-50.
2. the preparation method who contains amino organic silicon resin fire retardant as claimed in claim 1, it is characterized in that, with aminosilane and trialkoxy silane is raw material, be raw material with aminosilane, dialkoxy silicane and trialkoxy silane perhaps, add the mixed solvent of entry or water and organic solvent, polycondensation is hydrolyzed under catalyst action, add the end-capping reagent end-blocking at last, in reaction solution, add the neutralizing agent neutralization before reaction finishes, filter then, wash, drying, obtain product.
3. the organic silicon resin fire retardant preparation method who contains amino as claimed in claim 2, it is characterized in that, the mixed solvent that adds entry or water and organic solvent in the reaction vessel, with aminosilane and trialkoxy silane, perhaps aminosilane, dialkoxy silicane and trialkoxy silane, join after mixing in the constant pressure funnel, at the uniform velocity be added dropwise in the reaction vessel under 20～120 ℃, the dropping time is 30-180min; After dropwising, continue hydrolysis 2-6h, add catalyzer then, continue reaction 2-6h down for 20～120 ℃, in reaction solution, add end-capping reagent then, continue reaction 1-6h in temperature; Add neutralizing agent neutralization again, then after filtration, washing, drying, obtain product; The mol ratio of described trialkoxy silane, dialkoxy silicane and aminosilane is 0.01～1.0: 0～1.0: 0.01～1.0, the volumetric molar concentration of described catalyzer is 0.01-1.0mol/1, and the mol ratio of described catalyzer and reaction raw materials is 0.01～1.0: 1.0; The mol ratio of described end-capping reagent and reaction raw materials is 0.001～0.1: 1; The volumetric molar concentration of described neutralizing agent is 0.01-1.0mol/l, and the mol ratio of described neutralizing agent and catalyzer is 0.1～1.0: 1.0; The volume ratio of organic solvent and water is less than 1 in the mixed solvent of described water and organic solvent; Described reaction raw materials is trialkoxy silane, dialkoxy silicane and aminosilane.
4. the organic silicon resin fire retardant preparation method who contains amino as claimed in claim 3 is characterized in that the mol ratio of described trialkoxy silane, dialkoxy silicane and aminosilane is: 0.1～0.5: 0.1～0.5: 0.1～0.4; The mol ratio of described end-capping reagent and reaction raw materials is: 0.005～0.05: 1.
5. as any described organic silicon resin fire retardant preparation method who contains amino among the claim 2-4, it is characterized in that described aminosilane is N-β-aminoethyl-γ-aminopropyl methyl dimethoxysilane, N-β-aminoethyl-γ-aminopropyl methyldiethoxysilane, aminoethyl methyl dimethoxy oxygen base, aminoethyl methyl diethoxy, aminopropyl methyl dimethoxy base silane, aminopropyl methyl diethylsilane, aminopropyl triethoxysilane, aminopropyl trimethoxysilane or two (trimethyl silicon based) amine; Described trialkoxy silane is phenyltrimethoxysila,e, phenyl triethoxysilane, methyltrimethoxy silane, Union carbide A-162 or γ-glycidyl ether oxygen propyl trimethyl silane; Described dialkoxy silicane is dimethoxydiphenylsilane, phenylbenzene diethoxy silane, phenyl methyl dimethoxy silane, dimethyldimethoxysil,ne or dimethyldiethoxysilane.
6. as any described organic silicon resin fire retardant preparation method who contains amino among the claim 2-4, it is characterized in that described catalyzer is mineral acid or alkali or organic acid or alkali; Described neutralizing agent is triethylamine, pyridine, N, accelerine, sodium hydroxide, potassium hydroxide, hydrochloric acid, sulfuric acid or phosphoric acid.
7. the organic silicon resin fire retardant preparation method who contains amino as claimed in claim 6 is characterized in that described catalyzer is hydrochloric acid, sulfuric acid, phosphoric acid, potassium hydroxide, sodium hydroxide, ammoniacal liquor or triethylamine.
8. as any described organic silicon resin fire retardant preparation method who contains amino among the claim 2-4, it is characterized in that described end-capping reagent is dimethyl tetraphenyl sily oxide, hexamethyldisiloxane, hexamethyldisilazane, tetrem thiazolinyl sily oxide or tetramethyl divinyl disiloxane.
9. as any described organic silicon resin fire retardant preparation method who contains amino among the claim 2-4, it is characterized in that described organic solvent is: halohydrocarbon organic solvent, aromatic hydrocarbon solvent or other polar solvents.
10. the organic silicon resin fire retardant preparation method who contains amino as claimed in claim 9, it is characterized in that, described organic solvent is: chloroform, 1,2-ethylene dichloride, chlorine benzene,toluene,xylene, benzene, acetonitrile, N, dinethylformamide, N,N-DIMETHYLACETAMIDE, tetrahydrofuran (THF), acetone or methyl iso-butyl ketone (MIBK).
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| CN102558750A (en) * | 2012-01-29 | 2012-07-11 | 厦门大学 | Organosilicon fire retardant for ABS and preparation method thereof |
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| CN102558750A (en) * | 2012-01-29 | 2012-07-11 | 厦门大学 | Organosilicon fire retardant for ABS and preparation method thereof |
| CN103342817A (en) * | 2013-06-21 | 2013-10-09 | 安徽硅宝翔飞有机硅新材料有限公司 | Method for recycling diamino silicane high boiling substance |
| CN103342817B (en) * | 2013-06-21 | 2016-03-16 | 安徽硅宝翔飞有机硅新材料有限公司 | The method of the recycling of a kind of pair of aminosilane high boiling material |
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| CN105985522A (en) * | 2014-12-24 | 2016-10-05 | 财团法人工业技术研究院 | Highly branched polysiloxanes and hybrid materials and methods of forming the same |
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