CN103755960A - Methylphenyl silicon resin and preparation method thereof - Google Patents
Methylphenyl silicon resin and preparation method thereof Download PDFInfo
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- CN103755960A CN103755960A CN201410021048.0A CN201410021048A CN103755960A CN 103755960 A CN103755960 A CN 103755960A CN 201410021048 A CN201410021048 A CN 201410021048A CN 103755960 A CN103755960 A CN 103755960A
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- silicone resin
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- alkoxy silane
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- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical compound C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229920005989 resin Polymers 0.000 title claims abstract description 23
- 239000011347 resin Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- -1 phenyl alkoxy silane Chemical compound 0.000 claims abstract description 40
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 36
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 31
- 229910000077 silane Inorganic materials 0.000 claims abstract description 30
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 28
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 28
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 229920002050 silicone resin Polymers 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000003960 organic solvent Substances 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 7
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical group CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 230000004044 response Effects 0.000 claims description 4
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 125000003944 tolyl group Chemical group 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
- 239000003063 flame retardant Substances 0.000 abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 10
- 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 abstract description 7
- 229920000515 polycarbonate Polymers 0.000 abstract description 7
- 239000004417 polycarbonate Substances 0.000 abstract description 7
- 239000004698 Polyethylene Substances 0.000 abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 abstract description 6
- 229920000573 polyethylene Polymers 0.000 abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 5
- 239000011574 phosphorus Substances 0.000 abstract description 5
- 229920003023 plastic Polymers 0.000 abstract description 4
- 239000004033 plastic Substances 0.000 abstract description 4
- 239000004926 polymethyl methacrylate Substances 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000012747 synergistic agent Substances 0.000 abstract 1
- 239000008096 xylene Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000013517 stratification Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- NCWQJOGVLLNWEO-UHFFFAOYSA-N methylsilicon Chemical compound [Si]C NCWQJOGVLLNWEO-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- WBODDOZXDKQEFS-UHFFFAOYSA-N 1,2,3,4-tetramethyl-5-phenylbenzene Chemical compound CC1=C(C)C(C)=CC(C=2C=CC=CC=2)=C1C WBODDOZXDKQEFS-UHFFFAOYSA-N 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- CCDWGDHTPAJHOA-UHFFFAOYSA-N benzylsilicon Chemical compound [Si]CC1=CC=CC=C1 CCDWGDHTPAJHOA-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 1
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000001367 organochlorosilanes Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
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Abstract
The invention provides a high-heat-stability methylphenyl silicon resin which is prepared from the following raw materials in parts by weight: 10-20 parts of phenyl alkoxy silane, 10-20 parts of methyl alkoxy silane and alkaline catalyst accounting for 0.2-15 wt% of the phenyl alkoxy silane and methyl alkoxy silane. The invention also provides a preparation method of the methylphenyl silicon resin. The methylphenyl silicon resin provided by the invention is a new material different from the existing resins. The methylphenyl silicon resin can not be easily dissolved in toluene and xylene, has favorable heat resistance, and can be used as a synergistic agent of a nitrogen or phosphorus flame retardant for preparing flame-retardant polycarbonate, polyethylene, polymethyl methacrylate and other plastic products.
Description
Technical field
The present invention relates to a kind of methyl phenyl silicone resin and preparation method thereof.
Background technology
Silicone resin is the thermoset polysiloxane system with highly cross-linked structure, normally by organochlorosilane or organoalkoxysilane, through hydrolytic condensation and multiviscosisty rearrangement, makes.Mainly contain at present methyl silicon resin, phenyl polysiloxane and methyl phenyl silicone resin are several.Methyl silicon resin has the advantages such as hardness is high, wear resistance is good, but thermo-elasticity and compatibleness are poor; Phenyl polysiloxane thermoplasticity is larger, and practicality is not strong; And methyl phenyl silicone resin, hold concurrently containing methyl silica chain link and phenyl silica chain link, have good thermo-elasticity, good to various base material cohesiveness, mechanical property is good, glossiness is good, has been widely used as high-temperature insulating paint, high-temperature resistant coating, high-temperature resistance adhesive and ablator etc.
Sun Jutao etc. have prepared a kind of high temperature resistant phenyl methyl silicone resin, synthetic method is as follows: in there-necked flask, add distilled water and toluene, under rapid stirring, drip phenyl-trichloro-silicane, diphenyl dichlorosilane, METHYL TRICHLORO SILANE and the dimethyldichlorosilane(DMCS) of metering, keep constant temperature.After dropwising, standing branch vibration layer, solvent layer washes with water, then with NaOH solution, be titrated to neutrality, at 60～80 ℃, decompression steams toluene, be warmed up to 130～140 ℃ of decompression condensations again, obtain a kind of solid resin product, the initial decomposition temperature of this product in air atmosphere is 250 ℃ of left and right.Maximum heat weightlessness is 28%, and maximum heat weightless temperature is 600 ℃ (synthetic and the heat-resisting and curing performance research of high-temperature resistant organic silicon resin, aeronautical material journal, 2005,2).
Liu Fang suddenly waits and has prepared a kind of novel organosilicon resin fire retardant methyl phenyl silicone resin, it is take tetraethoxysilance, hexamethyldisiloxane, tetramethyl-phenylbenzene sily oxide as main raw material, by the hydrolysis-condensation reaction under acidic conditions, synthesized a kind of methylphenylsiloxane, in its air, at 800 ℃, residual quantity is the synthetic of the novel methylphenylsiloxane of 80.8wt%(and fire-retardant polycarbonate research, Northeast Forestry University, 2012).
Contriver finds through investigation, the methyl phenyl silicone resin of report at present, all dissolve in the organic solvents such as toluene or dimethylbenzene, after polymerization completes, also need the means such as employing concentrates except desolventizing, operate comparatively complicatedly, in addition, at present the resistance toheat of disclosed some methyl phenyl silicone resin need further raising.
Summary of the invention
The object of the present invention is to provide good methyl phenyl silicone resin of a kind of thermotolerance and preparation method thereof.
The invention provides a kind of thermostability methyl phenyl silicone resin, it is to be prepared from by the raw material of following weight proportion:
10～20 parts of octadecyloxy phenyl TMOSs, 10～20 parts, methyl alkoxy silane, basic catalyst weight are 0.2%～15% of octadecyloxy phenyl TMOS and methyl alkoxy silane gross weight.
Further, octadecyloxy phenyl TMOS: methyl alkoxy silane=1:1w/w, basic catalyst weight are 0.2%～13.5% of octadecyloxy phenyl TMOS and methyl alkoxy silane gross weight.
Wherein, described octadecyloxy phenyl TMOS is selected from phenyl triethoxysilane, phenyltrimethoxysila,e or phenyl-trichloro-silicane; Described methyl alkoxy silane is selected from methyltrimethoxy silane or Union carbide A-162; Described basic catalyst is one or more the combination in potassium hydroxide, sodium hydroxide, Tetramethylammonium hydroxide.
Wherein, the preparation method of described resin is as follows: at normal temperatures octadecyloxy phenyl TMOS, methyl alkoxy silane, basic catalyst and organic solvent are mixed, slowly add water, water to be added is complete, reflux, and question response is complete, the standing room temperature that is cooled to, filter, filter residue and drying, obtains methyl phenyl silicone resin.
Further, described organic solvent is selected from toluene or dimethylbenzene or both mixed solvents.
Further, the add-on of described water is the 15%-70%w/w of octadecyloxy phenyl TMOS and methyl alkoxy silane total amount; Described organic solvent add-on is octadecyloxy phenyl TMOS, methyl alkoxy silane and water total mass 1.5-5 times.
Further, the add-on of described water is the 20%-40%w/w of octadecyloxy phenyl TMOS and methyl alkoxy silane total amount; Described organic solvent add-on is octadecyloxy phenyl TMOS, methyl alkoxy silane and water total mass 3-5 times.
Wherein, the joining day of water continues 10～60min; Heating reflux reaction 12～72h; Described dry employing vacuum-drying mode.
Further, described vacuum drying condition is as follows: vacuum tightness is-0.08 to-0.096MPa, and temperature is 150-240 ℃.
The present invention also provides the preparation method of above-mentioned thermostability methyl phenyl silicone resin, and it comprises following operation steps:
At normal temperatures, octadecyloxy phenyl TMOS, methyl alkoxy silane, basic catalyst and organic solvent are mixed, slowly add water, water to be added is complete, reflux, question response is complete, the standing room temperature that is cooled to, filter, filter residue and drying, obtains methyl phenyl silicone resin.
Further, described organic solvent is selected from toluene or dimethylbenzene or both mixed solvents.
Further, the add-on of described water is the 15%-70%w/w of octadecyloxy phenyl TMOS and methyl alkoxy silane total amount; Described organic solvent add-on is octadecyloxy phenyl TMOS, methyl alkoxy silane and water total mass 1.5-5 times.
Further, the add-on of described water is the 20%-40%w/w of octadecyloxy phenyl TMOS and methyl alkoxy silane total amount; Described organic solvent add-on is octadecyloxy phenyl TMOS, methyl alkoxy silane and water total mass 3-5 times.
Wherein, the joining day of water continues 10～60min; Heating reflux reaction 12～72h; Described dry employing vacuum-drying mode.
Further, described vacuum drying condition is as follows: vacuum tightness is-0.08 to-0.096MPa, and temperature is 150-240 ℃.
Methyl phenyl silicone resin provided by the invention, it is a kind of novel material that is different from existing resin, this resin is not soluble in toluene, dimethylbenzene, resistance toheat is good, can be used as the synergist of nitrogen system or phosphorus flame retardant, for the preparation of plastics such as fire-retardant polycarbonate, polyethylene, polymethylmethacrylates.
Obviously, according to foregoing of the present invention, according to ordinary skill knowledge and the means of this area, not departing under the above-mentioned basic fundamental thought of the present invention prerequisite, can also make modification, replacement or the change of other various ways.
By the form of specific embodiment, foregoing of the present invention is described in further detail again below.But this should be interpreted as to the scope of the above-mentioned theme of the present invention only limits to following embodiment.All technology realizing based on foregoing of the present invention all belong to scope of the present invention.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of the silicone resin that obtains of embodiment 1;
Fig. 2 is the silicone resin that obtains of embodiment 1
29siNMR silicon spectrogram;
Fig. 3 is the thermogram of the silicone resin that obtains of embodiment 1;
Fig. 4 is the SEM photo of the silicone resin that obtains of embodiment 1.
Embodiment
Embodiment 1:
In 250mL four-hole boiling flask, add successively 15g phenyltrimethoxysila,e, 15g methyltrimethoxy silane and 0.07g potassium hydroxide and 180g toluene.Then, splash into 6ml water, time for adding is 10min, after dropwising, temperature is risen to 65 ℃, and backflow 12h, reacts complete stratification, treats that solution is cooled to room temperature, filters to obtain white mass.It is 150 ℃ in temperature that the white product obtaining is put into vacuum drying oven, vacuum tightness is-0.08MPa under, dry 5h, obtains white powder material.Adopting the productive rate of this method gained silicone resin is 65%.
The silicone resin that aforesaid method is obtained is tested, under its testing method and condition:
Use Nicolet Magna560 type infrared spectrometer, the lower operation of room temperature (25 ℃), compressing tablet sample preparation after the common grinding of testing sample and KBr particle, it is enough thin to meet Beer-Lambert rule that all samples all needs, infrared spectra 2cm
-1record after raster scanning 32 times;
Scanning electronic microscope (Inspect F, FEI Company), electron excitation voltage is 20kV, by sample liquid nitrogen brittle failure, on plated surface, thickness is approximately 100
golden film;
The thermostability that adopts Perkin-Elmer thermal analyzer (METTLER TOLEDO) Study Polymer Melts, about 10mg sample, under air atmosphere, is heated to 800 ℃ with the speed of 20 ℃/min from room temperature;
29si-NMR test is carried out in Bruker AV11-400 nuclear magnetic resonance analyser, and using deuterochloroform (CDCl3) is deuterated reagent, test at 25 ℃, and take tetramethylsilane (TMS) as standard specimen, chromium acetylacetonate is relaxation reagent.
Detected result is as follows:
Infrared spectrogram as shown in Figure 1,2970cm
-1place is the absorption peak of the stretching vibration of methyl.And 1274cm
-1the stretching vibration that is Si-C key absorbs.1440 and 1589cm
-1there is the stretching vibration peak of Si-Ph in place; At 1010-1130cm
-1there is the stretching vibration peak of Si-O-Si in place; Infrared spectrogram shows not hydroxyl.
Gained
29siNMR spectrogram is as Fig. 2; As shown in Figure 3, the maximum heat weightless temperature of this resin is 629 ℃ to Thermal Chart; The scanning electron microscope (SEM) photograph obtaining as shown in Figure 4, between median size 10-50 μ m.
Known according to above-mentioned test result, the partial structural formula of methyl phenyl silicone resin prepared by the present invention is:
In conjunction with infrared, silicon spectrum etc., detect data, the structural formula of methyl phenyl silicone resin prepared by the present invention can be expressed as:
Wherein, R1～R4 represents the one in methyl or phenyl, but R1～R4 is methyl or phenyl when different; And in this structural formula, do not contain hydroxyl.
As can be seen here, resin prepared by the present invention is the ladder type silicone resin with looped cord structure, and structure is comparatively regular.(about lexical or textual analysis such as looped cord structure, ladder type resins, can be with reference to " silicone resin and application thereof ", Zhao is old superfine, Chemical Industry Press, P51 relevant portion)
Embodiment 2:
In 250mL four-hole boiling flask, add successively 15g phenyl triethoxysilane, 15g methyltrimethoxy silane and 0.2g potassium hydroxide and 155g toluene.Then, splash into 6ml water, time for adding is 12min, after dropwising, temperature is risen to 65 ℃, backflow 12h, react complete stratification, treat that solution is cooled to room temperature and filters to obtain white mass, it is 150 ℃ in temperature that the white product obtaining is put into vacuum drying oven, vacuum tightness is-0.08MPa under dry 5h, obtain white powder material.Adopting the productive rate of this method gained silicone resin is 55%.
Embodiment 3:
In 250mL four-hole boiling flask, add successively 15g phenyltrimethoxysila,e, 15g Union carbide A-162 and 4g Tetramethylammonium hydroxide and 140g toluene.Then splash into 10ml water, time for adding is 15min, after dropwising, temperature is risen to 65 ℃, backflow 24h, react complete stratification, treat that solution is cooled to room temperature and filters to obtain white mass, it is 150 ℃ in temperature that the white product obtaining is put into vacuum drying oven, vacuum tightness is-0.08MPa under, dry 5h, obtains white powder material.Adopting the productive rate of this method gained silicone resin is 75%.
Embodiment 4:
In 250mL four-hole boiling flask, add successively 15g phenyl triethoxysilane, 15g methyltrimethoxy silane and 0.15g sodium hydroxide and 170g dimethylbenzene.Then splash into 10ml water, time for adding is 20min, after dropwising, temperature is risen to 65 ℃ of backflow 48h, react complete stratification, treat that solution is cooled to room temperature and filters to obtain white mass, it is 150 ℃ in temperature that the white product obtaining is put into vacuum drying oven, vacuum tightness is-0.08MPa under, dry 5h, obtains white powder material.Adopting the productive rate of this method gained silicone resin is 77%.
Analyze and sum up:
(1) methyl phenyl silicone resin of reporting at present, mostly be random structure, be dissolved in the organic solvents such as toluene or dimethylbenzene, after polymerization completes, also need the means such as employing concentrates except desolventizing, operate comparatively complicated, aminomethyl phenyl silicone grease prepared by the present invention, compound with regular structure, for ring type structure ladder type silicone resin, be insoluble to the organic solvents such as toluene, dimethylbenzene, synthetic complete, be dusty material, the operation stepss such as concentrated have been saved, and the solvent recoverable in reaction process, has reduced cost, and environmental protection and energy saving.
(2) after measured, the initial thermal weight loss temperature of resin of the present invention is 330 ℃; Maximum heat weightless temperature is 629 ℃, and at this temperature, thermal weight loss is 15%; Temperature is that the weightlessness at 800 ℃ is only 18%; And known according to 700-800 ℃ of heat analysis data, resin of the present invention weight after 700 ℃ tends to balance.As can be seen here, the methyl phenyl silicone resin resistance toheat that prepared by the present invention is good.
Resin resistance toheat of the present invention is better, can be as the synergistic flame retardant of nitrogen system or phosphorus flame retardant, for example, for the preparation of plastics such as fire-retardant polycarbonate, polyethylene, polymethylmethacrylates:
Methyl phenyl silicone resin prepared by the embodiment of the present invention 1, with nitrogen system or phosphorus flame retardant, polycarbonate (polyethylene, polymethylmethacrylate) and other auxiliary agent insert in blending equipment and mix, then this mixture is carried out in twin screw extruder melting, mixing, extrude, cooling, pelletizing, the operation such as dry carry out blend granulation, obtain methyl phenyl silicone resin synergistic fire-retardant polycarbonate (polyethylene, polymethylmethacrylate) blend pellet, then injection moulding.
In sum, methyl phenyl silicone resin provided by the invention, is a kind of novel material that is different from existing resin, and resistance toheat is good, can be used as the synergist of nitrogen system or phosphorus flame retardant, for the preparation of plastics such as fire-retardant polycarbonate, polyethylene, polymethylmethacrylates.
Claims (10)
1. a thermostability methyl phenyl silicone resin, is characterized in that: it is to be prepared from by the raw material of following weight proportion:
10～20 parts of octadecyloxy phenyl TMOSs, 10～20 parts, methyl alkoxy silane, basic catalyst weight are 0.2%～15% of octadecyloxy phenyl TMOS and methyl alkoxy silane gross weight.
2. thermostability methyl phenyl silicone resin according to claim 1, is characterized in that: octadecyloxy phenyl TMOS: methyl alkoxy silane=1:1w/w, basic catalyst weight are 0.2%～13.5% of octadecyloxy phenyl TMOS and methyl alkoxy silane gross weight.
3. thermostability methyl phenyl silicone resin according to claim 1 and 2, is characterized in that:
Described octadecyloxy phenyl TMOS is selected from phenyl triethoxysilane, phenyltrimethoxysila,e or phenyl-trichloro-silicane; Described methyl alkoxy silane is selected from methyltrimethoxy silane or Union carbide A-162; Described basic catalyst is one or more the combination in potassium hydroxide, sodium hydroxide, Tetramethylammonium hydroxide.
4. according to the thermostability methyl phenyl silicone resin described in claim 1～3 any one, it is characterized in that: the preparation method of described resin is as follows:
At normal temperatures octadecyloxy phenyl TMOS, methyl alkoxy silane, basic catalyst and organic solvent are mixed, slowly add water, water to be added is complete, reflux, question response is complete, the standing room temperature that is cooled to, filter, filter residue and drying, obtains methyl phenyl silicone resin.
5. thermostability methyl phenyl silicone resin according to claim 4, is characterized in that: described organic solvent is selected from toluene or/and dimethylbenzene.
6. thermostability methyl phenyl silicone resin according to claim 4, is characterized in that: the add-on of described water is the 15%-70%w/w of octadecyloxy phenyl TMOS and methyl alkoxy silane total amount; Described organic solvent is octadecyloxy phenyl TMOS, methyl alkoxy silane and water total mass 1.5-5 times.
7. thermostability methyl phenyl silicone resin according to claim 6, is characterized in that: the add-on of described water is the 20%-40%w/w of octadecyloxy phenyl TMOS and methyl alkoxy silane total amount; Described organic solvent is octadecyloxy phenyl TMOS, methyl alkoxy silane and water total mass 3-5 times.
8. thermostability methyl phenyl silicone resin according to claim 3, is characterized in that: the joining day of water continues 10～60min; Heating reflux reaction 12～72h; Described dry employing vacuum-drying mode.
9. thermostability methyl phenyl silicone resin according to claim 7, is characterized in that: described vacuum drying condition is as follows: vacuum tightness is-0.08 to-0.096MPa, and temperature is 150-240 degree Celsius.
10. the preparation method of thermostability methyl phenyl silicone resin described in claim 1～3 any one, is characterized in that: it comprises following operation steps:
At normal temperatures octadecyloxy phenyl TMOS, methyl alkoxy silane, basic catalyst and organic solvent are mixed, slowly add water, water to be added is complete, reflux, question response is complete, the standing room temperature that is cooled to, filter, filter residue and drying, obtains methyl phenyl silicone resin.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107962650A (en) * | 2017-11-29 | 2018-04-27 | 黄桂凤 | A kind of fire retardant and preparation method thereof |
| CN108707231A (en) * | 2018-04-11 | 2018-10-26 | 哈尔滨工程大学 | A kind of preparation method of methyl phenyl silicone resin and coating |
| CN109232894A (en) * | 2018-09-21 | 2019-01-18 | 广州天宸高新材料有限公司 | Methoxy group methyl phenyl silicone resin, organosilicon coating glue and preparation method and application |
| CN110820323A (en) * | 2019-10-31 | 2020-02-21 | 哈尔滨工业大学 | Preparation method of Si-C-O ceramic antioxidant coating on surface of carbon fiber |
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| CN101508776A (en) * | 2009-03-13 | 2009-08-19 | 杭州师范大学 | Method of preparing methyl phenyl polysiloxane |
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| CN101508776A (en) * | 2009-03-13 | 2009-08-19 | 杭州师范大学 | Method of preparing methyl phenyl polysiloxane |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107962650A (en) * | 2017-11-29 | 2018-04-27 | 黄桂凤 | A kind of fire retardant and preparation method thereof |
| CN108707231A (en) * | 2018-04-11 | 2018-10-26 | 哈尔滨工程大学 | A kind of preparation method of methyl phenyl silicone resin and coating |
| CN109232894A (en) * | 2018-09-21 | 2019-01-18 | 广州天宸高新材料有限公司 | Methoxy group methyl phenyl silicone resin, organosilicon coating glue and preparation method and application |
| CN110820323A (en) * | 2019-10-31 | 2020-02-21 | 哈尔滨工业大学 | Preparation method of Si-C-O ceramic antioxidant coating on surface of carbon fiber |
| CN110820323B (en) * | 2019-10-31 | 2022-08-09 | 哈尔滨工业大学 | Preparation method of Si-C-O ceramic antioxidant coating on surface of carbon fiber |
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