CN103755960B - A kind of methyl phenyl silicone resin and preparation method thereof - Google Patents
A kind of methyl phenyl silicone resin and preparation method thereof Download PDFInfo
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Abstract
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: phenyl alkoxysilane 10～20 parts, methyl alkoxy silane 10～20 parts, base catalyst weight are phenyl alkoxysilane and the 0.2%～15% of methyl alkoxy silane gross weight.Present invention also offers its preparation method.The methyl phenyl silicone resin that the present invention provides, it is different from a kind of new material of existing resin, this resin is not readily dissolved in toluene, dimethylbenzene, heat resistance is good, can be used for preparing the plastics such as fire-retardant polycarbonate, polyethylene, polymethyl methacrylate as nitrogen system or the synergist of phosphorus flame retardant.
Description
Technical field
The present invention relates to a kind of methyl phenyl silicone resin and preparation method thereof.
Background technology
Silicones is the thennoset polysiloxane system with highly cross-linked structure, it is common that by organochlorosilane or alcoxyl
Base silane, resets through hydrolytic condensation and thickening and prepares.Currently mainly there are methyl silicon resin, phenyl polysiloxane and aminomethyl phenyl silicon tree
Fat is several.Methyl silicon resin has the advantages such as hardness is high, wearability is good, but thermoelasticity and compatibility are poor；Phenyl polysiloxane heat
Plasticity is relatively big, and practicality is the strongest；And methyl phenyl silicone resin, hold concurrently containing methyl silica chain link and phenyl silica chain link, have good
Thermoelasticity, good to various base material caking property, 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. are prepared for a kind of high temperature resistant phenyl methyl silicones, and synthetic method is as follows: in there-necked flask, add and steam
Distilled water and toluene, drip the phenyl trichlorosilane of metering, diphenyl dichlorosilane, methyl trichlorosilane and two under fast stirring
Dimethyl dichlorosilane (DMCS), keeps constant temperature.After dropping, standing branch vibration layer, solvent layer washes with water, then titrates by NaOH solution
To neutral, at 60～80 DEG C, decompression steams toluene, then is warmed up to 130～140 DEG C of decompression condensations, obtains a kind of hard resin and produces
Thing, this product initial decomposition temperature in air atmosphere is at about 250 DEG C.Maximum heat weightlessness is 28%, maximum heat weightless temperature
Be 600 DEG C (synthesis of high-temperature resistant organic silicon resin and heat-resisting and curing performance thereof are studied, aeronautical material journal, 2005,2).
Liu Fang is violent etc. is prepared for a kind of novel organosilicon resin fire retardant methyl phenyl silicone resin, and it is with positive silicic acid second
Fat, hexamethyl disiloxane, tetramethyl diphenyl disiloxane are primary raw material, anti-by hydrolytic condensation in acid condition
Should synthesize a kind of methylphenylsiloxane, in its air, at 800 DEG C, residual quantity is that the novel aminomethyl phenyl of 80.8wt%(has
The synthesis of machine silicones and fire-retardant polycarbonate research, Northeast Forestry University, 2012).
Inventor finds through investigation, at present the methyl phenyl silicone resin of report, and all dissolving in toluene or dimethylbenzene etc. has
Machine solvent, after being polymerized, in addition it is also necessary to uses the means such as concentration to remove solvent, operates the most complicated, additionally, presently disclosed certain
The heat resistance of a little methyl phenyl silicone resins need to improve further.
Summary of the invention
It is an object of the invention to provide good methyl phenyl silicone resin of a kind of thermostability and preparation method thereof.
The invention provides a kind of thermostability methyl phenyl silicone resin, it is by the raw material preparation of following weight proportion
Become:
Phenyl alkoxysilane 10～20 parts, methyl alkoxy silane 10～20 parts, base catalyst weight are octadecyloxy phenyl
TMOS and the 0.2%～15% of methyl alkoxy silane gross weight.
Further, phenyl alkoxysilane: methyl alkoxy silane=1:1w/w, base catalyst weight are octadecyloxy phenyl
TMOS and the 0.2%～13.5% of methyl alkoxy silane gross weight.
Wherein, described phenyl alkoxysilane is selected from phenyl triethoxysilane, phenyltrimethoxysila,e or phenyl three
Chlorosilane；Described methyl alkoxy silane is selected from MTMS or MTES；Described base catalysis
Agent 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 phenyl alkoxysilane, methyl alkoxy silane,
Base catalyst and organic solvent mix homogeneously, slowly add water, and waits to add water complete, is heated to reflux, and question response is complete, stands cooling
To room temperature, filter, filter residue and drying, obtain methyl phenyl silicone resin.
Further, described organic solvent is selected from toluene or dimethylbenzene or both mixed solvents.
Further, the addition of described water is phenyl alkoxysilane and the 15%-70% of methyl alkoxy silane total amount
w/w；Described organic solvent addition is phenyl alkoxysilane, methyl alkoxy silane and 1.5-5 times of water gross mass.
Further, the addition of described water is phenyl alkoxysilane and the 20%-of methyl alkoxy silane total amount
40%w/w；Described organic solvent addition is phenyl alkoxysilane, methyl alkoxy silane and 3-5 times of water gross mass.
Wherein, the joining day of water continues 10～60min；Heating reflux reaction 12～72h；Described dry employing vacuum is done
Dry mode.
Further, described vacuum drying condition is as follows: vacuum is-0.08 to-0.096MPa, and temperature is 150-
240℃。
Present invention also offers the preparation method of above-mentioned thermostability methyl phenyl silicone resin, it includes following operating procedure:
At normal temperatures, the mixing of phenyl alkoxysilane, methyl alkoxy silane, base catalyst and organic solvent all
Even, slowly add water, wait to add water complete, be heated to reflux, question response is complete, stands and is cooled to room temperature, filters, filter residue and drying, to obtain final product
Methyl phenyl silicone resin.
Further, described organic solvent is selected from toluene or dimethylbenzene or both mixed solvents.
Further, the addition of described water is phenyl alkoxysilane and the 15%-70% of methyl alkoxy silane total amount
w/w；Described organic solvent addition is phenyl alkoxysilane, methyl alkoxy silane and 1.5-5 times of water gross mass.
Further, the addition of described water is phenyl alkoxysilane and the 20%-of methyl alkoxy silane total amount
40%w/w；Described organic solvent addition is phenyl alkoxysilane, methyl alkoxy silane and 3-5 times of water gross mass.
Wherein, the joining day of water continues 10～60min；Heating reflux reaction 12～72h；Described dry employing vacuum is done
Dry mode.
Further, described vacuum drying condition is as follows: vacuum is-0.08 to-0.096MPa, and temperature is 150-
240℃。
The methyl phenyl silicone resin that the present invention provides, is different from a kind of new material of existing resin, and this resin is less soluble
In toluene, dimethylbenzene, heat resistance is good, can be used for preparing anti-flaming polycarbonate as nitrogen system or the synergist of phosphorus flame retardant
The plastics such as ester, polyethylene, polymethyl methacrylate.
Obviously, according to the foregoing of the present invention, according to ordinary technical knowledge and the means of this area, without departing from this
Under bright above-mentioned basic fundamental thought premise, it is also possible to make the amendment of other various ways, replace or change.
Below by way of the form of specific embodiment, the foregoing of the present invention is described in further detail again.But no
This should being interpreted as, the scope of the above-mentioned theme of the present invention is only limitted to below example.All realized based on foregoing of the present invention
Technology belong to the scope of the present invention.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of the organic siliconresin that embodiment 1 obtains；
Fig. 2 is the organic siliconresin that embodiment 1 obtains29SiNMR silicon spectrogram；
Fig. 3 is the thermal analysis curue of the organic siliconresin that embodiment 1 obtains；
Fig. 4 is the SEM photograph of the organic siliconresin that embodiment 1 obtains.
Detailed description of the invention
Embodiment 1:
In 250mL four-hole boiling flask, be sequentially added into 15g phenyltrimethoxysila,e, 15g MTMS and
0.07g potassium hydroxide and 180g toluene.Then, instilling 6ml water, time for adding is 10min, after dropping, by temperature liter
To 65 DEG C, reflux 12h, reacts complete stratification, treats that solution is cooled to room temperature, filters to obtain whiteness.The white that will obtain
It is 150 DEG C that product puts into vacuum drying oven in temperature, and vacuum is under-0.08MPa, is dried 5h, obtains white powder material.Use
The productivity of the method gained organic siliconresin is 65%.
The organic siliconresin obtained by said method is tested, its method of testing and under the conditions of:
Using Nicolet Magna560 type infrared spectrometer, operate under room temperature (25 DEG C), testing sample is with KBr granule altogether
With tabletting sample preparation after grinding, all samples is both needed to sufficiently thin to meet Beer-Lambert rule, infrared spectrum 2cm-1Grating
Record after scanning 32 times；
Scanning electron microscope (Inspect F, FEI Company), electron excitation voltage is 20kV, by sample liquid nitrogen
Brittle failure, on plated surface, thickness is about 100Golden film；
Use the heat stability of Perkin-Elmer thermal analyzer (METTLER TOLEDO) Study Polymer Melts, about 10mg sample
Product, under air atmosphere, are heated to 800 DEG C with the speed of 20 DEG C/min from room temperature；
29Si-NMR test is carried out in Bruker AV11-400 nuclear magnetic resonance analyser, and using deuterochloroform (CDCl3) is deuterium
For reagent, testing at 25 DEG C, with tetramethylsilane (TMS) as standard specimen, chromium acetylacetonate is relaxation reagent.
Testing result is as follows:
Infrared spectrogram as shown in Figure 1,2970cm-1Place is the absworption peak of the stretching vibration of methyl.And 1274cm-1It is Si-
The stretching vibration of C key absorbs.1440 and 1589cm-1Place occurs in that the stretching vibration peak of Si-Ph；At 1010-1130cm-1Place
Occur in that the stretching vibration peak of Si-O-Si；Infrared spectrogram shows not hydroxyl.
Gained29SiNMR spectrogram such 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 obtained as shown in Figure 4, between mean diameter 10-50 μm.
According to above-mentioned test result, the partial structural formula of methyl phenyl silicone resin prepared by the present invention is:
In conjunction with detection data such as infrared, silicon spectrums, 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 is methyl or phenyl during R1～R4 difference；And this structure
Formula does not contains hydroxyl.
As can be seen here, resin prepared by the present invention is the ladder type silicones with looped cord structure, and structure is the most regular.
(about lexical or textual analysis such as looped cord structure, ladder type resins, can refer to " organic siliconresin and application thereof ", Zhao is old superfine, and chemical industry goes out
Version society, P51 relevant portion)
Embodiment 2:
In 250mL four-hole boiling flask, be sequentially added into 15g phenyl triethoxysilane, 15g MTMS and
0.2g potassium hydroxide and 155g toluene.Then, instilling 6ml water, time for adding is 12min, after dropping, temperature is risen to
65 DEG C, reflux 12h, reacts complete stratification, treats that solution is cooled to room temperature and filters to obtain whiteness, the white product that will obtain
Putting into vacuum drying oven in temperature is 150 DEG C, and vacuum is to be dried 5h under-0.08MPa, obtains white powder material.Use this side
The productivity of method gained organic siliconresin is 55%.
Embodiment 3:
15g phenyltrimethoxysila,e, 15g MTES and 4g it is sequentially added in 250mL four-hole boiling flask
Tetramethylammonium hydroxide and 140g toluene.Then instilling 10ml water, time for adding is 15min, after dropping, by temperature liter
To 65 DEG C, reflux 24h, reacts complete stratification, treats that solution is cooled to room temperature and filters to obtain whiteness, the white product that will obtain
It is 150 DEG C that thing puts into vacuum drying oven in temperature, and vacuum is under-0.08MPa, is dried 5h, obtains white powder material.Use this
The productivity of method gained organic siliconresin is 75%.
Embodiment 4:
In 250mL four-hole boiling flask, be sequentially added into 15g phenyl triethoxysilane, 15g MTMS and
0.15g sodium hydroxide and 170g dimethylbenzene.Then instilling 10ml water, time for adding is 20min, after dropping, by temperature
Rise to 65 DEG C of backflow 48h, react complete stratification, treat that solution is cooled to room temperature and filters to obtain whiteness, the white that will obtain
It is 150 DEG C that product puts into vacuum drying oven in temperature, and vacuum is under-0.08MPa, is dried 5h, obtains white powder material.Use
The productivity of the method gained organic siliconresin is 77%.
Analysis and summary:
(1) methyl phenyl silicone resin reported at present, mostly is disordered structure, is dissolved in the organic solvent such as toluene or dimethylbenzene,
After being polymerized, in addition it is also necessary to use the means such as concentration to remove solvent, operate the most complicated, aminomethyl phenyl silicon prepared by the present invention
Fat, compound with regular structure, for ring type structure ladder type silicones, insoluble in the organic solvent such as toluene, dimethylbenzene, synthesize complete, be powder
Powder material, eliminates the solvent recoverable in the operating procedures such as concentration, and course of reaction, reduces cost, and environmental protection
Energy-conservation.
(2) after measured, the initial thermal weight loss temperature of resin of the present invention is 330 DEG C；Maximum heat weightless temperature is 629 DEG C, this
At a temperature of thermal weight loss be 15%；Temperature is that the weightlessness at 800 DEG C is only 18%；And according to 700-800 DEG C of heat analysis data, this
Invention resin weight after 700 DEG C tends to balance.As can be seen here, the methyl phenyl silicone resin heat resistance that prepared by the present invention
Well.
Resin heat resistance of the present invention is preferable, can be used for preparing resistance as nitrogen system or the synergistic flame retardant of phosphorus flame retardant
The plastics such as combustion Merlon, polyethylene, polymethyl methacrylate, such as:
The methyl phenyl silicone resin embodiment of the present invention 1 prepared, with nitrogen system or phosphorus flame retardant, Merlon (poly-second
Alkene, polymethyl methacrylate) and other auxiliary agent insert mix homogeneously in blending equipment, then this mixture is squeezed at twin screw
Go out machine to be carried out melt, mixing, extrude, cool down, pelletizing, the operation such as be dried and carry out being blended pelletize, obtain methyl phenyl silicone resin
The blend pellet of synergistic fire-retardant polycarbonate (polyethylene, polymethyl methacrylate), then injection mo(u)lding.
In sum, the methyl phenyl silicone resin that the present invention provides, it is different from a kind of new material of existing resin, heat-resisting
Functional, can be used for preparing fire-retardant polycarbonate, polyethylene, poly-methyl-prop as nitrogen system or the synergist of phosphorus flame retardant
The plastics such as e pioic acid methyl ester.
Claims (5)
1. a thermostability methyl phenyl silicone resin, it is characterised in that: it is to be prepared from by the raw material of following weight proportion:
Phenyl alkoxysilane 10～20 parts, methyl alkoxy silane 10～20 parts, base catalyst weight are phenyl
Alkoxy silane and the 0.2%～15% of methyl alkoxy silane gross weight；
Described phenyl alkoxysilane is selected from phenyl triethoxysilane or phenyltrimethoxysila,e；Described methyl alkoxy silicon
Alkane is selected from MTMS or MTES；Described base catalyst be potassium hydroxide, sodium hydroxide, four
One or more combination in ammonium hydroxide；
The preparation method of described methyl phenyl silicone resin is as follows:
At normal temperatures phenyl alkoxysilane, methyl alkoxy silane, base catalyst and organic solvent mix homogeneously, slowly
Adding water, wait to add water complete, be heated to reflux, question response is complete, stands and is cooled to room temperature, filters, filter residue and drying, obtains aminomethyl phenyl
Silicones；
Described organic solvent selected from toluene or/and dimethylbenzene；
The addition of described water is phenyl alkoxysilane and the 15%-70%w/w of methyl alkoxy silane total amount；Described organic molten
Agent is phenyl alkoxysilane, methyl alkoxy silane and 1.5-5 times of water gross mass；
The joining day of water continues 10～60min；Heating reflux reaction 12～72h；Described dry employing is vacuum dried
Mode；
The structural formula of described methyl phenyl silicone resin is:
Wherein, R1～R4One in expression methyl or phenyl, but R1～R4Be asynchronously in methyl or phenyl, and this structural formula not
Containing hydroxyl；
Described methyl phenyl silicone resin does not dissolves in toluene and dimethylbenzene.
2. according to the thermostability methyl phenyl silicone resin described in claim 1, it is characterised in that: phenyl alkoxysilane: methyl
Alkoxy silane=1:1w/w, base catalyst weight are phenyl alkoxysilane and the 0.2% of methyl alkoxy silane gross weight
～13.5%.
Thermostability methyl phenyl silicone resin the most according to claim 1, it is characterised in that: the addition of described water is phenyl
Alkoxy silane and the 20%-40%w/w of methyl alkoxy silane total amount；Described organic solvent is phenyl alkoxysilane, methyl
Alkoxy silane and 3-5 times of water gross mass.
Thermostability methyl phenyl silicone resin the most according to claim 1, it is characterised in that: described vacuum drying condition is such as
Under: vacuum is-0.08 to-0.096MPa, and temperature is 150-240 degree Celsius.
5. the preparation method of thermostability methyl phenyl silicone resin described in claim 1, it is characterised in that: it includes operating as follows step
Rapid:
At normal temperatures phenyl alkoxysilane, methyl alkoxy silane, base catalyst and organic solvent mix homogeneously, slowly
Adding water, wait to add water complete, be heated to reflux, question response is complete, stands and is cooled to room temperature, filters, filter residue and drying, obtains aminomethyl phenyl
Silicones.
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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 |
| CN109232894B (en) * | 2018-09-21 | 2021-04-06 | 广州天宸高新材料有限公司 | Methoxy-terminated methylphenyl polysiloxane resin, organic silicon coating adhesive, preparation method and application |
| 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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| CN101508776A (en) * | 2009-03-13 | 2009-08-19 | 杭州师范大学 | Method of preparing methyl phenyl polysiloxane |
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