CN102391297B - Polysiloxane low polymer with side epoxy group and preparation method thereof - Google Patents
Polysiloxane low polymer with side epoxy group and preparation method thereof Download PDFInfo
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- CN102391297B CN102391297B CN201110252005XA CN201110252005A CN102391297B CN 102391297 B CN102391297 B CN 102391297B CN 201110252005X A CN201110252005X A CN 201110252005XA CN 201110252005 A CN201110252005 A CN 201110252005A CN 102391297 B CN102391297 B CN 102391297B
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- toluene
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- -1 Polysiloxane Polymers 0.000 title claims abstract description 55
- 125000003700 epoxy group Chemical group 0.000 title claims abstract description 38
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920000642 polymer Polymers 0.000 title description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 177
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000243 solution Substances 0.000 claims abstract description 25
- 238000001816 cooling Methods 0.000 claims abstract description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 11
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract 4
- WGMBWDBRVAKMOO-UHFFFAOYSA-L disodium;4-[2-(4-oxidophenyl)propan-2-yl]phenolate Chemical compound [Na+].[Na+].C=1C=C([O-])C=CC=1C(C)(C)C1=CC=C([O-])C=C1 WGMBWDBRVAKMOO-UHFFFAOYSA-L 0.000 claims abstract 3
- 238000006243 chemical reaction Methods 0.000 claims description 58
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- 238000010992 reflux Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 229920006395 saturated elastomer Polymers 0.000 claims description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 8
- 235000011152 sodium sulphate Nutrition 0.000 claims description 8
- KEZMLECYELSZDC-UHFFFAOYSA-N 3-chloropropyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(OCC)CCCCl KEZMLECYELSZDC-UHFFFAOYSA-N 0.000 claims description 6
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical group C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 5
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 5
- KNTKCYKJRSMRMZ-UHFFFAOYSA-N 3-chloropropyl-dimethoxy-methylsilane Chemical group CO[Si](C)(OC)CCCCl KNTKCYKJRSMRMZ-UHFFFAOYSA-N 0.000 claims description 4
- SXPWTBGAZSPLHA-UHFFFAOYSA-M cetalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SXPWTBGAZSPLHA-UHFFFAOYSA-M 0.000 claims description 4
- 229960000228 cetalkonium chloride Drugs 0.000 claims description 4
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims 11
- 229930185605 Bisphenol Natural products 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- OCBHHZMJRVXXQK-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;chloride Chemical group [Cl-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 OCBHHZMJRVXXQK-UHFFFAOYSA-M 0.000 claims 1
- HLWSWQPKCVYQCL-UHFFFAOYSA-N ethoxysilane trimethoxy(phenyl)silane Chemical compound C(C)O[SiH3].C1(=CC=CC=C1)[Si](OC)(OC)OC HLWSWQPKCVYQCL-UHFFFAOYSA-N 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- 150000004756 silanes Chemical class 0.000 claims 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical group CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 239000002861 polymer material Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 42
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 28
- 238000009835 boiling Methods 0.000 description 24
- 239000001257 hydrogen Substances 0.000 description 16
- 229910052739 hydrogen Inorganic materials 0.000 description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 15
- 150000003254 radicals Chemical class 0.000 description 15
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 14
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 14
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 14
- 230000001590 oxidative effect Effects 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 11
- 229910000077 silane Inorganic materials 0.000 description 11
- 150000002924 oxiranes Chemical group 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- XBFGOORMDPGOIC-UHFFFAOYSA-N [K].OC(CC)(C1=CC=CC=C1)O Chemical compound [K].OC(CC)(C1=CC=CC=C1)O XBFGOORMDPGOIC-UHFFFAOYSA-N 0.000 description 8
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 229910002808 Si–O–Si Inorganic materials 0.000 description 7
- CXBMSGCGKSYSDZ-UHFFFAOYSA-N [Na].OC(CC)(C1=CC=CC=C1)O Chemical compound [Na].OC(CC)(C1=CC=CC=C1)O CXBMSGCGKSYSDZ-UHFFFAOYSA-N 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 6
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 6
- 230000002902 bimodal effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 4
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 3
- 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 2
- 0 C[*+]O[S+]C(C)(C)C(C)(C)O[S+](*)Cc1ccccc1 Chemical compound C[*+]O[S+]C(C)(C)C(C)(C)O[S+](*)Cc1ccccc1 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012675 alcoholic extract Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 230000002508 compound effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- QHGSGZLLHBKSAH-UHFFFAOYSA-N hydridosilicon Chemical compound [SiH] QHGSGZLLHBKSAH-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- 229920006012 semi-aromatic polyamide Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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Abstract
本发明公开了一种侧基带环氧基的聚硅氧烷低聚物及其制备方法。该方法先将γ-氯丙基甲基二烷氧基硅烷、苯基三烷氧基硅烷和甲苯混合，加热升温至85~90℃，滴加稀盐酸，反应5~8h后，加入封端剂，继续反应，冷却后得聚氯丙基苯基硅氧烷甲苯溶液；然后将双酚A钠盐或钾盐溶液加入到聚氯丙基苯基硅氧烷甲苯溶液中，再加入相转移催化剂，加热升温至，反应4~6h；加入环氧氯丙烷反应，冷却后分离除去水层和甲苯后，真空干燥即得侧基带环氧基的聚硅氧烷低聚物。本发明侧基带环氧基的聚硅氧烷低聚物耐热氧稳定性好、难燃，用作高分子材料共混体系的相容剂可引入聚硅氧烷结构的耐高低温性、难燃性等，且适合较高的加工温度。The invention discloses a polysiloxane oligomer with epoxy groups on side groups and a preparation method thereof. This method first mixes γ-chloropropylmethyldialkoxysilane, phenyltrialkoxysilane and toluene, heats up to 85~90℃, adds dilute hydrochloric acid dropwise, reacts for 5~8 hours, and then adds capping agent, continue to react, and obtain polychloropropylphenylsiloxane toluene solution after cooling; then add bisphenol A sodium salt or potassium salt solution to polychloropropylphenylsiloxane toluene solution, and then add phase transfer Catalyst, heat up to 100°C, react for 4-6 hours; add epichlorohydrin to react, separate and remove the water layer and toluene after cooling, and vacuum dry to obtain a polysiloxane oligomer with epoxy groups in side groups. The polysiloxane oligomer with epoxy groups on the side groups of the present invention has good heat-resistant oxygen stability and flame retardancy, and can be used as a compatibilizer for a polymer material blending system to introduce high and low temperature resistance of the polysiloxane structure, Flame retardancy, etc., and suitable for higher processing temperatures.
Description
Technical field
The present invention relates to polysiloxane oligomers of a kind of side group band epoxy group(ing) and preparation method thereof.
Background technology
The organopolysiloxane main chain consists of the Si-O-Si key, has good resistant of high or low temperature, flame retardant resistance, weathering resistance, biocompatibility etc., and in molecular structure, the kind of silica ratio, side group, molecular weight etc. also can affect its performance largely.The polysiloxane reactive behavior of side group band epoxy group(ing) is higher, can utilize the reaction of epoxide group and amido, alcoholic extract hydroxyl group, phenolic hydroxyl group, carboxyl, thiol group etc. as reaction intermediate, also can utilize the compatilizer of the reactivity of epoxide group as the polar macromolecule material co-mixing system.general Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer with epoxy group(ing) (PTW), the heat-resisting oxidative stabilities of polymer compatilizer such as ethylene-methyl acrylate-glyceryl methacrylate multipolymer (X8900) are poor, 5% quality weightless temperature is only 250 ℃ of left and right in air atmosphere, and the heat-resisting oxidative stability of polysiloxane of side group band epoxy group(ing) is good, and difficult combustion, can introduce the resistant of high or low temperature of polysiloxane structure as the compatilizer of macromolecular material co-mixing system, flame retardancy etc., and be fit to higher processing temperature, has the incomparable advantage of normal tape epoxy group(ing) multipolymer compatilizer.
The main preparation methods of side group band epoxy based polysiloxane has three kinds: (1) hydrosilylation method; (2) different sense condensation method; (3) open loop additive process, the epoxy group(ing) structure of introducing is generally
GE has prepared band epoxy based polysiloxane with the silane that contains SiH or siloxanes and olefin epoxide silicon hydrogen addition under platinum or rhodium compound effect in the patents such as CN93106016.8, CN93106980.7; Chinese patent CN200910107756.5 will
(wherein R1, R3 are hydrogen, alkyl or phenyl independently of one another; X is the chlorine atom) with epoxy monochloroethane in the perhydronaphthalene solvent, under the palladium-carbon catalyst effect, the reaction condensation has obtained the polysiloxane of side group band epoxy group(ing) under 120～160 ℃, and above patent synthesizing epoxy based polysiloxane all need adopt precious metal chemical complex to make catalyzer, and reaction conditions is harsher.Patent CN201010115028.1 adopts the silane monomer hydrolytie polycondensation contain epoxy group(ing) or with the method for other silane monomers hydrolysis copolycondensations, has prepared band epoxy based polysiloxane, but in the method silane monomer under acid and alkaline condition in hydrolytie polycondensation its epoxy group(ing) can produce more serious ring-opening reaction.
Summary of the invention
The object of the invention is to overcome the deficiency of above-mentioned prior art, provide a kind of heat-resisting oxidative stability good, the polysiloxane oligomers of the side group band epoxy group(ing) of the activity that responds and difficult combustion; The preparation method of this oligopolymer is the polysiloxane that first will obtain the reactive chloropropyl of side group band and high heat resistance phenyl with silane monomer and the phenyl tri-alkoxy hydrolysis copolycondensation of chloropropyl, then utilize chloropropyl and the dihydroxyphenyl propane nucleophilic substitution reaction under the phase-transfer catalyst effect to introduce dihydroxyphenyl propane sodium salt or sylvite, the reaction that recycles itself and epoxy chloropropane connects epoxide group.
The object of the invention is achieved through the following technical solutions:
A kind of polysiloxane oligomers of side group band epoxy group(ing), its structural formula is:
Wherein R be-H ,-Si (CH
3)
3, m, n are integer, 1≤m≤5,1≤n≤5.
The preparation method of the polysiloxane oligomers of side group band epoxy group(ing), comprise the steps:
Step 1, γ-chloropropyl methyl dialkoxy silicane, phenyl trialkoxy silane and toluene are mixed, be heated to 85～90 ℃, drip the dilute hydrochloric acid of mass concentration 5～7%, after reaction 5～8h, add end-capping reagent, continue reaction 3～5h, remove water layer after cooling, clean toluene layer to neutral, obtain polychlorostyrene propylbenzene radical siloxane toluene solution; Described γ-chloropropyl methyl dialkoxy silicane is gamma-chloropropylmethyldimethoxysilane or γ-chloropropyl methyldiethoxysilane, and the phenyl trialkoxy silane is phenyltrimethoxysila,e or phenyl triethoxysilane; γ-chloropropyl methyl dialkoxy silicane and phenyl trialkoxy silane mol ratio are 0.2～1: 1; The add-on of described toluene is γ-chloropropyl methyl dialkoxy silicane and phenyl trialkoxy silane total mass 2～4 times; The add-on of described dilute hydrochloric acid is γ-chloropropyl methyl dialkoxy silicane and phenyl trialkoxy silane total mass 0.3～0.6 times; Described end-capping reagent is hexamethyldisiloxane, trimethylchlorosilane, and the add-on of end-capping reagent is 2～10% of γ-chloropropyl methyl dialkoxy silicane and phenyl trialkoxy silane total moles;
Step 2, dihydroxyphenyl propane sodium salt or potassium salt soln are joined in polychlorostyrene propylbenzene radical siloxane toluene solution, then add phase-transfer catalyst, be heated to 70～85 ℃, stir lower back flow reaction 4～6h;
Described phase-transfer catalyst is 1427, cetalkonium chloride, stearyl dimethyl benzyl ammonium chloride, and add-on is 5～10% of dihydroxyphenyl propane mole number;
The preparation method of described dihydroxyphenyl propane sodium salt or potassium salt soln is: at N
2Under atmosphere, add dihydroxyphenyl propane, potassium hydroxide or sodium hydroxide and deionized water, mix post-heating and be warming up to 80～100 ℃, after stirring lower back flow reaction 1～2h and get final product; By mole number, the add-on of dihydroxyphenyl propane is 0.8～1 times of γ-chloropropyl methyl dialkoxy silicane, and the add-on of potassium hydroxide or sodium hydroxide is 2～2.1 times of dihydroxyphenyl propane, and the add-on of deionized water is 50～150 times of dihydroxyphenyl propane;
Step 3, above-mentioned reaction system is cooled to 40～50 ℃, add epichlorohydrin reaction 2～4h, the add-on of epoxy chloropropane is 1～5 times of dihydroxyphenyl propane mole number, cooling afterreaction system is divided into water layer and toluene layer, separate and remove water layer, toluene layer is washed till neutrality with distilled water, steams except namely obtain the polysiloxane oligomers of side group band epoxy group(ing) after toluene 80～100 ℃ of lower vacuum-dryings.
Described cleaning toluene layer to neutrality is to clean toluene layer to neutral with saturated aqueous sodium sulfate.
With respect to prior art, the present invention has following feature:
(1) good, the difficult combustion of the heat-resisting oxidative stability of polysiloxane oligomers of side group band epoxy group(ing) of the present invention, the compatilizer that is used as the macromolecular material co-mixing system can be introduced the resistant of high or low temperature of polysiloxane structure, flame retardancy etc., and be fit to higher processing temperature, have the incomparable advantage of normal tape epoxy group(ing) multipolymer compatilizer;
(2) compare with silicon hydrogen addition method, reaction raw materials of the present invention is easy to get, and temperature of reaction is lower, reaction conditions is gentle, be easy to realize, the present invention also utilizes phase-transfer catalyst to realize the nucleophilic substitution reaction of dihydroxyphenyl propane and chloropropyl and epoxy chloropropane, and reaction efficiency is high;
(3) compare with band epoxy radicals silicone hydride monomer direct hydrolysis method, avoided well the ring-opening reaction of epoxy group(ing).
Description of drawings
Fig. 1 is the infrared spectrogram (FTIR) of the polysiloxane oligomers of embodiment 1 gained side group band epoxy group(ing);
Fig. 2 be the polysiloxane oligomers of embodiment 1 gained side group band epoxy group(ing) the hydrogen nuclear magnetic resonance spectrogram (
1H-NMR).
Embodiment
The present invention is further illustrated below in conjunction with drawings and Examples, but embodiments of the invention are not limit so.
Embodiment 1
step 1, agitator is being housed, reflux condensing tube, thermometer, add the 0.08mol gamma-chloropropylmethyldimethoxysilane in the 250ml four-hole boiling flask of dropping funnel, 0.1mol phenyl triethoxysilane, 116g toluene, reaction system is heated to 85 ℃, drip the dilute hydrochloric acid 17.5g of massfraction 7%, after reaction 5h, add the 0.0108mol trimethylchlorosilane, continue reaction 3h, remove water layer after cooling, clean toluene layer to neutral with saturated aqueous sodium sulfate, obtain polychlorostyrene propylbenzene radical siloxane toluene solution, this solution is all transferred to agitator is housed, reflux condensing tube, thermometer, in the 250ml four-hole boiling flask of dropping funnel,
Step 2, in being equipped with the 250ml four-hole boiling flask of agitator, reflux condensing tube, thermometer, another passes into N
2, add 0.07mol dihydroxyphenyl propane, 0.14mol sodium hydroxide and 90g deionized water, be heated to 90 ℃, stir lower back flow reaction 1.5h, after cooling the dihydroxyphenyl propane sodium salt solution; Prepared dihydroxyphenyl propane sodium salt solution is all joined in the 250ml four-hole boiling flask that fills polychlorostyrene propylbenzene radical siloxane toluene solution, separately add the 2.21g stearyl dimethyl benzyl ammonium chloride, be heated to 80 ℃, stir lower back flow reaction 6h;
Step 3, above-mentioned reaction system is cooled to 50 ℃, add 0.35mol epichlorohydrin reaction 3h, cooling afterreaction system is divided into water layer and toluene layer, separate and remove water layer, toluene layer is washed till neutrality with distilled water, steams except namely obtain the polysiloxane oligomers of thick colourless side group band epoxy group(ing) after toluene 80 ℃ of lower vacuum-dryings.The heat-resisting oxidative stability of this oligopolymer is good, and 5% quality weightless temperature is 321 ℃ in air atmosphere, and it is carried out infrared spectra (FTIR) and proton nmr spectra test, and the gained spectrogram respectively as depicted in figs. 1 and 2.Being attributed to of upper each main peaks of product FTIR spectrogram (Fig. 1): 912cm
-1For epoxide group charateristic avsorption band, 1088cm
-1, 1042cm
-1For the Si-O-Si stretching vibration bimodal, 1182cm
-1For aryl oxide C-O stretching vibration peak, 1248cm
-1For Si-CH
3Stretching vibration peak, 1607cm
-1For phenyl ring skeletal vibration peak, 3648cm
-1For the O-H stretching vibration peak on silanol.
In order simply to conclusively show product
1H-NMR (CDCl
3) each Hydrochemistry displacement (δ) ownership on spectrogram, now indicate as follows with a, b, c, d, e, f, g, h, Ph (expression phenyl ring) hydrogen on the polysiloxane oligomers structural formula of side group band epoxy group(ing):
Hydrogen on embodiment 2～6 product structures adopts same sign.The δ of each hydrogen is respectively as shown in Figure 2: H
a≈ 0.15, H
b≈ 0.69, H
c≈ 1.65, H
d≈ 1.84, H
e≈ 2.76, H
f≈ 2.90, H
g≈ 3.37, H
h≈ 4.13, H
Ph=6.71～7.25, on silanol, the δ of hydrogen is 4.40 in addition.
Embodiment 2
step 1, agitator is being housed, reflux condensing tube, thermometer, add 0.02mol γ-chloropropyl methyldiethoxysilane in the 250ml four-hole boiling flask of dropping funnel, 0.1mol phenyltrimethoxysila,e, 96g toluene, reaction system is heated to 85 ℃, drip the dilute hydrochloric acid 14.4g of massfraction 5%, after reaction 8h, add the 0.012mol hexamethyldisiloxane, continue reaction 3h, remove water layer after cooling, clean toluene layer to neutral with saturated aqueous sodium sulfate, obtain polychlorostyrene propylbenzene radical siloxane toluene solution, this solution is all transferred to agitator is housed, reflux condensing tube, thermometer, in the 250ml four-hole boiling flask of dropping funnel,
Step 2, in being equipped with the 250ml four-hole boiling flask of agitator, reflux condensing tube, thermometer, another passes into N
2, add 0.02mol dihydroxyphenyl propane, 0.06mol potassium hydroxide and 81g deionized water, be heated to 80 ℃, stir lower back flow reaction 1h, after cooling the dihydroxyphenyl propane potassium salt soln; Prepared dihydroxyphenyl propane potassium salt soln is all joined in the 250ml four-hole boiling flask that fills polychlorostyrene propylbenzene radical siloxane toluene solution, separately add the 0.79g cetalkonium chloride, be heated to 70 ℃, stir lower back flow reaction 4h;
Step 3, above-mentioned reaction system is cooled to 48 ℃, add 0.06mol epichlorohydrin reaction 4h, cooling afterreaction system is divided into water layer and toluene layer, separate and remove water layer, toluene layer is washed till neutrality with distilled water, steams except namely obtain the polysiloxane oligomers of light yellow arborescens side group band epoxy group(ing) after toluene 85 ℃ of lower vacuum-dryings.The heat-resisting oxidative stability of this oligopolymer is good, and 5% quality weightless temperature is 334 ℃ in air atmosphere, and it is carried out infrared spectra (FTIR) and proton nmr spectra test.
Being attributed to of each main peaks on product FTIR spectrogram: 910cm
-1For epoxide group charateristic avsorption band, 1131cm
-1, 1049cm
-1For the Si-O-Si stretching vibration bimodal, 1172cm
-1For aryl oxide C-O stretching vibration peak, 1248cm
-1For Si-CH
3Stretching vibration peak, 1607cm
-1For phenyl ring skeletal vibration peak, 3650cm
-1For the O-H stretching vibration peak on silanol.
Product
1H-NMR (CDCl
3) each hydrogen δ is attributed on spectrogram: H
a≈ 0.15, H
b≈ 0.68, H
c≈ 1.64, H
d≈ 1.85, H
e≈ 2.77, H
f≈ 2.91, H
g≈ 3.35, H
h≈ 4.18, H
Ph=6.68～7.03, on silanol, the δ of hydrogen is 4.37 in addition.
Embodiment 3
step 1, agitator is being housed, reflux condensing tube, thermometer, add 0.05mol γ-chloropropyl methyldiethoxysilane in the 250ml four-hole boiling flask of dropping funnel, 0.1mol phenyltrimethoxysila,e, 91g toluene, reaction system is heated to 90 ℃, drip the dilute hydrochloric acid 12.1g of massfraction 7%, after reaction 6h, add the 0.003mol hexamethyldisiloxane, continue reaction 4h, remove water layer after cooling, clean toluene layer to neutral with saturated aqueous sodium sulfate, obtain polychlorostyrene propylbenzene radical siloxane toluene solution, this solution is all transferred to agitator is housed, reflux condensing tube, thermometer, in the 250ml four-hole boiling flask of dropping funnel,
Step 2, add and pass into N in another is equipped with the four-hole boiling flask of agitator, reflux condensing tube, thermometer
2, 0.05mol dihydroxyphenyl propane, 0.1mol sodium hydroxide and 108g deionized water, be heated to 100 ℃, stirs lower back flow reaction 2h, after cooling the dihydroxyphenyl propane sodium salt solution; Prepared dihydroxyphenyl propane sodium salt solution is all joined in the 250ml four-hole boiling flask that fills polychlorostyrene propylbenzene radical siloxane toluene solution, separately add the 1.47g 1427, be heated to 75 ℃, stir lower back flow reaction 6h;
Step 3, above-mentioned reaction system is cooled to 50 ℃, add 0.25mol epichlorohydrin reaction 2h, cooling afterreaction system is divided into water layer and organic layer, separate and remove water layer, organic layer is washed till neutrality with distilled water, steams except namely obtain the polysiloxane oligomers of light yellow arborescens side group band epoxy group(ing) after toluene 100 ℃ of lower vacuum-dryings.The heat-resisting oxidative stability of this oligopolymer is good, and 5% quality weightless temperature is 330 ℃ in air atmosphere, and it is carried out infrared spectra (FTIR) and proton nmr spectra test.
Being attributed to of each main peaks on product FTIR spectrogram: 914cm
-1For epoxide group charateristic avsorption band, 1117cm
-1, 1040cm
-1For the Si-O-Si stretching vibration bimodal, 1181cm
-1For aryl oxide C-O stretching vibration peak, 1248cm
-1For Si-CH
3Stretching vibration peak, 1607cm
-1For phenyl ring skeletal vibration peak.
Product
1H-NMR (CDCl
3) each hydrogen δ is attributed on spectrogram: H
a≈ 0.15, H
b≈ 0.69, H
c≈ 1.66, H
d≈ 1.85, H
e≈ 2.77, H
f≈ 2.92, H
g≈ 3.38, H
h≈ 4.20, H
Ph=6.72～7.33.
Embodiment 4
step 1, agitator is being housed, reflux condensing tube, thermometer, add 0.1mol γ-chloropropyl methyldiethoxysilane in the 250ml four-hole boiling flask of dropping funnel, 0.1mol phenyltrimethoxysila,e, 82g toluene, reaction system is heated to 85 ℃, drip the dilute hydrochloric acid 12.3g of massfraction 7%, after reaction 7h, add the 0.008mol trimethylchlorosilane, continue reaction 5h, remove water layer after cooling, clean toluene layer to neutral with saturated aqueous sodium sulfate, obtain polychlorostyrene propylbenzene radical siloxane toluene solution, this solution is all transferred to agitator is housed, reflux condensing tube, thermometer, in the 250ml four-hole boiling flask of dropping funnel,
Step 2, in being equipped with the 250ml four-hole boiling flask of agitator, reflux condensing tube, thermometer, another passes into N
2, add 0.08mol dihydroxyphenyl propane, 0.168mol potassium hydroxide and 108g deionized water, be heated to 80 ℃, stir lower back flow reaction 2h, after cooling the dihydroxyphenyl propane potassium salt soln; Prepared dihydroxyphenyl propane potassium salt soln is all joined in the 250ml four-hole boiling flask that fills polychlorostyrene propylbenzene radical siloxane toluene solution, separately add the 2.53g cetalkonium chloride, be heated to 75 ℃, stir lower back flow reaction 5h;
Step 3, above-mentioned reaction system is cooled to 50 ℃, add 0.16mol epichlorohydrin reaction 3h, cooling afterreaction system is divided into water layer and toluene layer, separate and remove water layer, toluene layer is washed till neutrality with distilled water, steams except namely obtain the polysiloxane oligomers of thick colourless side group band epoxy group(ing) after toluene 90 ℃ of lower vacuum-dryings.The heat-resisting oxidative stability of this oligopolymer is good, and 5% quality weightless temperature is 316 ℃ in air atmosphere, and it is carried out infrared spectra (FTIR) and proton nmr spectra test.
Being attributed to of each main peaks on product FTIR spectrogram: 916cm
-1For epoxide group charateristic avsorption band, 1106cm
-1, 1042cm
-1For the Si-O-Si stretching vibration bimodal, 1173cm
-1For aryl oxide C-O stretching vibration peak, 1246cm
-1For Si-CH
3Stretching vibration peak, 1605cm
-1For phenyl ring skeletal vibration peak, 3646cm
-1For the O-H stretching vibration peak on silanol.
Product
1H-NMR (CDCl
3) each hydrogen δ is attributed on spectrogram: H
a≈ 0.15, H
b≈ 0.68, H
c≈ 1.64, H
d≈ 1.82, H
e≈ 2.75, H
f≈ 2.86, H
g≈ 3.30, H
h≈ 4.09, H
Ph=6.68～7.08, on silanol, the δ of hydrogen is 4.38 in addition.
Embodiment 5
step 1, agitator is being housed, reflux condensing tube, thermometer, add the 0.06mol gamma-chloropropylmethyldimethoxysilane in the 250ml four-hole boiling flask of dropping funnel, 0.1mol phenyl triethoxysilane, 140g toluene, reaction system is heated to 90 ℃, drip the dilute hydrochloric acid 17.5g of massfraction 5%, after reaction 6h, add the 0.0128mol trimethylchlorosilane, continue reaction 5h, remove water layer after cooling, clean toluene layer to neutral with saturated aqueous sodium sulfate, obtain polychlorostyrene propylbenzene radical siloxane toluene solution, this solution is all transferred to agitator is housed, reflux condensing tube, thermometer, in the 250ml four-hole boiling flask of dropping funnel,
Step 2, in being equipped with the 250ml four-hole boiling flask of agitator, reflux condensing tube, thermometer, another passes into N
2, add 0.05mol dihydroxyphenyl propane, 0.1mol potassium hydroxide and 120g deionized water, be heated to 100 ℃, stir lower back flow reaction 1h, after cooling the dihydroxyphenyl propane potassium salt soln; Prepared dihydroxyphenyl propane potassium salt soln is all joined in the 250ml four-hole boiling flask that fills polychlorostyrene propylbenzene radical siloxane toluene solution, separately add the 0.92g 1427, be heated to 70 ℃, stir lower back flow reaction 6h;
Step 3, above-mentioned reaction system is cooled to 49 ℃, add 0.20mol epichlorohydrin reaction 4h, cooling afterreaction system is divided into water layer and toluene layer, separate and remove water layer, toluene layer is washed till neutrality with distilled water, steams except namely obtain the polysiloxane oligomers of light yellow arborescens side group band epoxy group(ing) after toluene 95 ℃ of lower vacuum-dryings.The heat-resisting oxidative stability of this oligopolymer is good, and 5% quality weightless temperature is 327 ℃ in air atmosphere, and it is carried out infrared spectra (FTIR) and proton nmr spectra test.
Being attributed to of each main peaks on product FTIR spectrogram: 914cm
-1For epoxide group charateristic avsorption band, 1128cm
-1, 1045cm
-1For Si-O-Si stretching vibration peak, 1188cm
-1For aryl oxide C-O stretching vibration peak, 1248cm
-1For Si-CH
3Stretching vibration peak, 1608cm
-1For phenyl ring skeletal vibration peak.
Product
1H-NMR (CDCl
3) each hydrogen δ is attributed on spectrogram: H
a≈ 0.15, H
b≈ 0.67, H
c≈ 1.63, H
d≈ 1.82, H
e≈ 2.79, H
f≈ 2.93, H
g≈ 3.39, H
h≈ 4.16, H
Ph=6.73～7.20.
Embodiment 6
step 1, agitator is being housed, reflux condensing tube, thermometer, add 0.1mol γ-chloropropyl methyldiethoxysilane in the 250ml four-hole boiling flask of dropping funnel, 0.1mol phenyltrimethoxysila,e and 82g toluene, reaction system is heated to 85 ℃, drip the dilute hydrochloric acid 12.3g of massfraction 5%, after reaction 5h, add the 0.008mol hexamethyldisiloxane, continue reaction 5h, remove water layer after cooling, clean toluene layer to neutral with saturated aqueous sodium sulfate, obtain polychlorostyrene propylbenzene radical siloxane toluene solution, this solution is all transferred to agitator is housed, reflux condensing tube, thermometer, in the 250ml four-hole boiling flask of dropping funnel,
Step 2, in being equipped with the four-hole boiling flask of agitator, reflux condensing tube, thermometer, another passes into N
2, add 0.1mol dihydroxyphenyl propane, 0.2mol potassium hydroxide and 90g deionized water, be heated to 90 ℃, stir lower back flow reaction 1h, obtain the dihydroxyphenyl propane potassium salt soln after cooling; Prepared dihydroxyphenyl propane potassium salt soln is all joined in the 250ml four-hole boiling flask that fills polychlorostyrene propylbenzene radical siloxane toluene solution, separately add the 2.12g stearyl dimethyl benzyl ammonium chloride, be heated to 75 ℃, stir lower back flow reaction 4h;
Step 3, above-mentioned reaction system is cooled to 50 ℃, add 0.1mol epichlorohydrin reaction 2h, cooling afterreaction system is divided into water layer and toluene layer, separate and remove water layer, toluene layer is washed till neutrality with distilled water, steams except namely obtain the polysiloxane oligomers of thick colourless side group band epoxy group(ing) after toluene 90 ℃ of lower vacuum-dryings.The heat-resisting oxidative stability of this oligopolymer is good, and 5% quality weightless temperature is 322 ℃ in air atmosphere, and it is carried out infrared spectra (FTIR) and proton nmr spectra test.
Being attributed to of each main peaks on product FTIR spectrogram: 914cm
-1For epoxide group charateristic avsorption band, 1096cm
-1, 1044cm
-1For the Si-O-Si stretching vibration bimodal, 1180cm
-1For aryl oxide C-O stretching vibration peak, 1246cm
-1For Si-CH
3Stretching vibration peak, 1607cm
-1For phenyl ring skeletal vibration peak, 3650cm
-1For the O-H stretching vibration peak on silanol.
Product
1H-NMR (CDCl
3) each hydrogen δ is attributed on spectrogram: H
a≈ 0.15, H
b≈ 0.68, H
c≈ 1.67, H
d≈ 1.88, H
e≈ 2.80, H
f≈ 2.96, H
g≈ 3.35, H
h≈ 4.18, H
Ph=6.75～7.28, on silanol, the δ of hydrogen is 4.35 in addition.
After tested, the polysiloxane oligomers of the side group band epoxy group(ing) that the present invention is prepared, heat-resisting oxidative stability is good, 5% quality weightless temperature is all more than 315 ℃ in air atmosphere, its structural epoxy group(ing) has good reactivity, can be used as the compatilizer of polymer blended material as the high molecular weight compatibilizers commonly used such as the Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer with epoxy group(ing) (PTW), ethylene-methyl acrylate-glyceryl methacrylate multipolymer (X8900).The heat-resisting oxidative stability of the high molecular weight compatibilizer commonly used such as PTW, X8900 is poor, 5% quality weightless temperature is only 250 ℃ of left and right in air atmosphere, be not suitable for surpassing in the systems such as engineering plastics, semi-aromatic nylon and special engineering plastics of 250 ℃ and using in processing temperature, the polysiloxane oligomers of this side group band epoxy group(ing) has higher heat-resisting oxidative stability, can use under the high temperature of 300 ℃ of left and right, and self difficult combustion, therefore particularly fairly obvious to the demanding system application advantage of flame retardant resistance at the expanding material as the high temperature process system.
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| CN1712425A (en) * | 2005-07-18 | 2005-12-28 | 南京大学 | A kind of preparation method of epoxy resin containing siloxane structural unit |
| CN101103064A (en) * | 2004-12-07 | 2008-01-09 | 罗狄亚化学公司 | Method of preparing polyorganosiloxane with functional groups in the presence of lithium silanolate |
| WO2010121873A1 (en) * | 2009-04-20 | 2010-10-28 | Evonik Degussa Gmbh | Composition containing quaternary amino-functional organosilicon compounds and production and use thereof |
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| CN101103064A (en) * | 2004-12-07 | 2008-01-09 | 罗狄亚化学公司 | Method of preparing polyorganosiloxane with functional groups in the presence of lithium silanolate |
| CN1712425A (en) * | 2005-07-18 | 2005-12-28 | 南京大学 | A kind of preparation method of epoxy resin containing siloxane structural unit |
| WO2010121873A1 (en) * | 2009-04-20 | 2010-10-28 | Evonik Degussa Gmbh | Composition containing quaternary amino-functional organosilicon compounds and production and use thereof |
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