CN102391297A - 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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Abstract
The invention discloses a polysiloxane low polymer with a side epoxy group and a preparation method thereof. The method comprises the steps of: firstly mixing gamma-chloropropyl methyl dialkoxysilane and phenyl trialkoxysilane with methylbenzene, heating to 85-90 DEG C, dropping diluted hydrochloric acid for reaction for 5-8h, adding end-capping agent for continuous reaction and cooling to obtain polychloropropyl phenylsilane methylbenzene solution; then bisphenol A sodium salt or kali salt solution into the polychloropropyl phenylsilane methylbenzene solution, adding phase transfer catalysts and heating for reaction for 4-6h; and adding epoxy chloropropane for reaction, cooling, separating, removing water layers and methylbenzene and drying in vacuum to obtain the polysiloxane low polymer with the side epoxy group. The polysiloxane low polymer with the side epoxy group has a good thermal and oxidative stability, is flame-retardant, can be used as compatilizer for the blending systems of high-molecular materials, can introduce the high-temperature and low-temperature resistance, the flame retardance and the like of polysiloxane structures and is adaptive to comparatively high processing temperature.
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 is made up of the Si-O-Si key, has good resistant of high or low temperature, flame retardant resistance, weathering resistance, biocompatibility etc., and the kind of silica ratio, side group, molecular weight etc. also can influence its performance largely in the molecular structure.The ZGK 5 reactive behavior of side group band epoxy group(ing) is higher; The reaction that can utilize epoxide group and amido, alcoholic extract hydroxyl group, phenolic hydroxyl group, carboxyl, thiol group etc. is as reaction intermediate, and also the reactivity of epoxide group capable of using is as the compatilizer of polar macromolecule material co-mixing system.General ethylene-propylene acid butyl ester-glycidyl methacrylate copolymer (PTW), the ethylene-methyl acrylate-glycidyl methacrylate copolymer heat-resisting oxidative stabilities of high molecular compatible agent such as (X8900) that has an epoxy group(ing) is poor; 5% quality weightless temperature is merely about 250 ℃ in air atmosphere; And the heat-resisting oxidative stability of ZGK 5 of side group band epoxy group(ing) is good; And difficult combustion; 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 is 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 oxygen based polysiloxane has three kinds: (1) hydrogen silication additive process; (2) different sense condensation method; (3) open loop additive process, the epoxy group(ing) structure of being introduced are generally
GE and in patents such as CN93106016.8, CN93106980.7, have prepared band oxygen based polysiloxane with the silane that contains SiH or siloxanes and olefin epoxide silicon hydrogen addition under platinum or rhodium compound effect; (wherein R1, R3 are hydrogen, alkyl or phenyl to Chinese patent CN200910107756.5 independently of one another with
; X is the chlorine atom) with epoxy monochloroethane in the perhydronaphthalene solvent; Under the palladium-carbon catalyst effect; React the ZGK 5 that condensation has obtained side group band epoxy group(ing) down at 120～160 ℃, above patent synthesizing epoxy based polysiloxane all need adopt precious metal chemical complex to make catalyzer, and reaction conditions is harsh.Patent CN201010115028.1 adopts the silane monomer hydrolytie polycondensation contain epoxy group(ing) or has prepared band oxygen based polysiloxane with the method for other silane monomer hydrolysis copolycondensations, but in this method silane monomer under acid and alkaline condition in the hydrolytie polycondensation its epoxy group(ing) can produce more serious ring-opening reaction.
Summary of the invention
The objective 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 will have the silane monomer of chloropropyl and the ZGK 5 that phenyl tri-alkoxy hydrolysis copolycondensation obtains reactive chloropropyl of side group band and high heat resistance phenyl earlier; Utilize chloropropyl and the dihydroxyphenyl propane nucleophilic substitution reaction under the phase-transfer catalyst effect to introduce dihydroxyphenyl propane sodium salt or sylvite then, utilize the reaction of itself and epoxy chloropropane to connect epoxide group again.
The object of the invention realizes through following technical scheme:
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) comprises the steps:
Step 1, γ-chloropropyl methyl dialkoxy silicane, phenyl trialkoxy silane and toluene are mixed, heat temperature raising to 85～90 ℃ drip the Hydrogen chloride of mass concentration 5～7%; Behind reaction 5～8h; Add end-capping reagent, continue reaction 3～5h, remove water layer after the cooling; Clean toluene layer to neutral, get polychlorostyrene propylbenzene radical siloxane toluene solution; Said 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 said toluene is γ-chloropropyl methyl dialkoxy silicane and phenyl trialkoxy silane total mass 2～4 times; The add-on of said Hydrogen chloride is γ-chloropropyl methyl dialkoxy silicane and phenyl trialkoxy silane total mass 0.3～0.6 times; Said end-capping reagent is SWS-F 221, trimethylchlorosilane, and the add-on of end-capping reagent is 2～10% of γ-chloropropyl methyl dialkoxy silicane and a phenyl trialkoxy silane total moles;
Said phase-transfer catalyst is tetradecyl dimethyl benzyl ammonium chloride, cetalkonium chloride, stearyl dimethyl benzyl ammonium chloride, and add-on is 5～10% of a dihydroxyphenyl propane mole number;
The preparation method of said dihydroxyphenyl propane sodium salt or potassium salt soln is: at N
2Under the atmosphere, add dihydroxyphenyl propane, Pottasium Hydroxide or sodium hydroxide and deionized water, mix post-heating and be warming up to 80～100 ℃, promptly get behind stirring refluxed reaction 1～2h; 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 Pottasium 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, and cooling afterreaction system is divided into water layer and toluene layer, separates and removes water layer; Toluene layer is washed till neutrality with zero(ppm) water, steam removes behind the toluene polysiloxane oligomers that promptly gets side group band epoxy group(ing) 80～100 ℃ of following 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 characteristic:
(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, and reaction conditions is gentle, is easy to realize that 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 TMOS monomer Direct Water solution, avoided the ring-opening reaction of epoxy group(ing) well.
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
Below in conjunction with accompanying drawing and embodiment the present invention is further described, but embodiments of the invention are not limit so.
Embodiment 1
Step 1,, the 250ml four-hole boiling flask of whisking appliance, reflux condensing tube, TM, tap funnel adds 0.08mol gamma-chloropropylmethyldimethoxysilane, 0.1mol phenyl triethoxysilane, 116g toluene in being housed; With reaction system heat temperature raising to 85 ℃, drip the Hydrogen chloride 17.5g of massfraction 7%, behind the reaction 5h; Add the 0.0108mol trimethylchlorosilane; Continue reaction 3h, remove water layer after the cooling, clean toluene layer to neutral with saturated aqueous sodium sulfate; Obtain polychlorostyrene propylbenzene radical siloxane toluene solution, this solution is all transferred in the 250ml four-hole boiling flask that whisking appliance, reflux condensing tube, TM, tap funnel are housed;
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 to remove water layer, toluene layer is washed till neutrality with zero(ppm) water, steam and remove behind the toluene polysiloxane oligomers that promptly gets thick colourless side group band epoxy group(ing) 80 ℃ of following 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 ir spectra (FTIR) and proton nmr spectra test, and the gained spectrogram is as depicted in figs. 1 and 2 respectively.The ownership that product FTIR spectrogram (Fig. 1) is gone up each main peaks is: 912cm
-1Be epoxide group charateristic avsorption band, 1088cm
-1, 1042cm
-1For the Si-O-Si stretching vibration bimodal, 1182cm
-1Be aryl oxide C-O stretching vibration peak, 1248cm
-1Be Si-CH
3Stretching vibration peak, 1607cm
-1Be phenyl ring skeletal vibration peak, 3648cm
-1Be the O-H stretching vibration peak on the silanol.
In order simply to conclusively show product
1H-NMR (CDCl
3) each hydrogenation displacement study (δ) ownership on the spectrogram, existing hydrogen on the polysiloxane oligomers structural formula of side group band epoxy group(ing) is indicated as follows with a, b, c, d, e, f, g, h, Ph (expression phenyl ring):
Hydrogen on embodiment 2～6 product structures adopts same sign.The δ that can be known each hydrogen by Fig. 2 is respectively: 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, the δ of hydrogen is 4.40 on the silanol in addition.
Step 1,, the 250ml four-hole boiling flask of whisking appliance, reflux condensing tube, TM, tap funnel adds 0.02mol γ-chloropropyl methyldiethoxysilane, 0.1mol phenyltrimethoxysila,e, 96g toluene in being housed; With reaction system heat temperature raising to 85 ℃, drip the Hydrogen chloride 14.4g of massfraction 5%, behind the reaction 8h; Add the 0.012mol SWS-F 221; Continue reaction 3h, remove water layer after the cooling, clean toluene layer to neutral with saturated aqueous sodium sulfate; Obtain polychlorostyrene propylbenzene radical siloxane toluene solution, this solution is all transferred in the 250ml four-hole boiling flask that whisking appliance, reflux condensing tube, TM, tap funnel are housed;
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 to remove water layer, toluene layer is washed till neutrality with zero(ppm) water, steam and remove behind the toluene polysiloxane oligomers that promptly gets light yellow arborescens side group band epoxy group(ing) 85 ℃ of following 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 ir spectra (FTIR) and proton nmr spectra test.
The ownership of each main peaks is on the product FTIR spectrogram: 910cm
-1Be epoxide group charateristic avsorption band, 1131cm
-1, 1049cm
-1For the Si-O-Si stretching vibration bimodal, 1172cm
-1Be aryl oxide C-O stretching vibration peak, 1248cm
-1Be Si-CH
3Stretching vibration peak, 1607cm
-1Be phenyl ring skeletal vibration peak, 3650cm
-1Be the O-H stretching vibration peak on the silanol.
Product
1H-NMR (CDCl
3) each hydrogen δ ownership is on the 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, the δ of hydrogen is 4.37 on the silanol in addition.
Embodiment 3
Step 1,, the 250ml four-hole boiling flask of whisking appliance, reflux condensing tube, TM, tap funnel adds 0.05mol γ-chloropropyl methyldiethoxysilane, 0.1mol phenyltrimethoxysila,e, 91g toluene in being housed; With reaction system heat temperature raising to 90 ℃, drip the Hydrogen chloride 12.1g of massfraction 7%, behind the reaction 6h; Add the 0.003mol SWS-F 221; Continue reaction 4h, remove water layer after the cooling, clean toluene layer to neutral with saturated aqueous sodium sulfate; Obtain polychlorostyrene propylbenzene radical siloxane toluene solution, this solution is all transferred in the 250ml four-hole boiling flask that whisking appliance, reflux condensing tube, TM, tap funnel are housed;
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 to remove water layer, organic layer is washed till neutrality with zero(ppm) water, steam and remove behind the toluene polysiloxane oligomers that promptly gets light yellow arborescens side group band epoxy group(ing) 100 ℃ of following 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 ir spectra (FTIR) and proton nmr spectra test.
The ownership of each main peaks is on the product FTIR spectrogram: 914cm
-1Be epoxide group charateristic avsorption band, 1117cm
-1, 1040cm
-1For the Si-O-Si stretching vibration bimodal, 1181cm
-1Be aryl oxide C-O stretching vibration peak, 1248cm
-1Be Si-CH
3Stretching vibration peak, 1607cm
-1Be phenyl ring skeletal vibration peak.
Product
1H-NMR (CDCl
3) each hydrogen δ ownership is on the 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,, the 250ml four-hole boiling flask of whisking appliance, reflux condensing tube, TM, tap funnel adds 0.1mol γ-chloropropyl methyldiethoxysilane, 0.1mol phenyltrimethoxysila,e, 82g toluene in being housed; With reaction system heat temperature raising to 85 ℃, drip the Hydrogen chloride 12.3g of massfraction 7%, behind the reaction 7h; Add the 0.008mol trimethylchlorosilane; Continue reaction 5h, remove water layer after the cooling, clean toluene layer to neutral with saturated aqueous sodium sulfate; Obtain polychlorostyrene propylbenzene radical siloxane toluene solution, this solution is all transferred in the 250ml four-hole boiling flask that whisking appliance, reflux condensing tube, TM, tap funnel are housed;
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 to remove water layer, toluene layer is washed till neutrality with zero(ppm) water, steam and remove behind the toluene polysiloxane oligomers that promptly gets thick colourless side group band epoxy group(ing) 90 ℃ of following 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 ir spectra (FTIR) and proton nmr spectra test.
The ownership of each main peaks is on the product FTIR spectrogram: 916cm
-1Be epoxide group charateristic avsorption band, 1106cm
-1, 1042cm
-1For the Si-O-Si stretching vibration bimodal, 1173cm
-1Be aryl oxide C-O stretching vibration peak, 1246cm
-1Be Si-CH
3Stretching vibration peak, 1605cm
-1Be phenyl ring skeletal vibration peak, 3646cm
-1Be the O-H stretching vibration peak on the silanol.
Product
1H-NMR (CDCl
3) each hydrogen δ ownership is on the 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, the δ of hydrogen is 4.38 on the silanol in addition.
Embodiment 5
Step 1,, the 250ml four-hole boiling flask of whisking appliance, reflux condensing tube, TM, tap funnel adds 0.06mol gamma-chloropropylmethyldimethoxysilane, 0.1mol phenyl triethoxysilane, 140g toluene in being housed; With reaction system heat temperature raising to 90 ℃, drip the Hydrogen chloride 17.5g of massfraction 5%, behind the reaction 6h; Add the 0.0128mol trimethylchlorosilane; Continue reaction 5h, remove water layer after the cooling, clean toluene layer to neutral with saturated aqueous sodium sulfate; Obtain polychlorostyrene propylbenzene radical siloxane toluene solution, this solution is all transferred in the 250ml four-hole boiling flask that whisking appliance, reflux condensing tube, TM, tap funnel are housed;
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 to remove water layer, toluene layer is washed till neutrality with zero(ppm) water, steam and remove behind the toluene polysiloxane oligomers that promptly gets light yellow arborescens side group band epoxy group(ing) 95 ℃ of following 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 ir spectra (FTIR) and proton nmr spectra test.
The ownership of each main peaks is on the product FTIR spectrogram: 914cm
-1Be epoxide group charateristic avsorption band, 1128cm
-1, 1045cm
-1Be Si-O-Si stretching vibration peak, 1188cm
-1Be aryl oxide C-O stretching vibration peak, 1248cm
-1Be Si-CH
3Stretching vibration peak, 1608cm
-1Be phenyl ring skeletal vibration peak.
Product
1H-NMR (CDCl
3) each hydrogen δ ownership is on the 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,, the 250ml four-hole boiling flask of whisking appliance, reflux condensing tube, TM, tap funnel adds 0.1mol γ-chloropropyl methyldiethoxysilane, 0.1mol phenyltrimethoxysila,e and 82g toluene in being housed; With reaction system heat temperature raising to 85 ℃, drip the Hydrogen chloride 12.3g of massfraction 5%, behind the reaction 5h; Add the 0.008mol SWS-F 221; Continue reaction 5h, remove water layer after the cooling, clean toluene layer to neutral with saturated aqueous sodium sulfate; Obtain polychlorostyrene propylbenzene radical siloxane toluene solution, this solution is all transferred in the 250ml four-hole boiling flask that whisking appliance, reflux condensing tube, TM, tap funnel are housed;
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 to remove water layer, toluene layer is washed till neutrality with zero(ppm) water, steam and remove behind the toluene polysiloxane oligomers that promptly gets thick colourless side group band epoxy group(ing) 90 ℃ of following 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 ir spectra (FTIR) and proton nmr spectra test.
The ownership of each main peaks is on the product FTIR spectrogram: 914cm
-1Be epoxide group charateristic avsorption band, 1096cm
-1, 1044cm
-1For the Si-O-Si stretching vibration bimodal, 1180cm
-1Be aryl oxide C-O stretching vibration peak, 1246cm
-1Be Si-CH
3Stretching vibration peak, 1607cm
-1Be phenyl ring skeletal vibration peak, 3650cm
-1Be the O-H stretching vibration peak on the silanol.
Product
1H-NMR (CDCl
3) each hydrogen δ ownership is on the 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, the δ of hydrogen is 4.35 on the silanol in addition.
Through test; 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 equally be used as the compatilizer of polymer blended material as the ethylene-propylene acid butyl ester-glycidyl methacrylate copolymer (PTW) that has epoxy group(ing), the high molecular compatible agent commonly used such as (X8900) of ethylene-methyl acrylate-glycidyl methacrylate copolymer.The heat-resisting oxidative stability of high molecular compatible agent commonly used such as PTW, X8900 is poor; 5% quality weightless temperature is merely about 250 ℃ in air atmosphere; Be not suitable for using above in 250 ℃ the systems such as engineering plastics, semi-aromatic nylon and special engineering plastics in processing temperature; The polysiloxane oligomers of this side group band epoxy group(ing) then has higher heat-resisting oxidative stability; Can under the high temperature about 300 ℃, use, and self difficult combustion, therefore particularly fairly obvious to the demanding system application advantage of flame retardant resistance at expanding material as the high temperature process system.
Claims (3)
1. the polysiloxane oligomers of a side group band epoxy group(ing) is characterized in that structural formula is:
Wherein R be-H ,-Si (CH
3)
3, m, n are integer, 1≤m≤5,1≤n≤5.
2. the preparation method of the polysiloxane oligomers of the described side group band of claim 1 epoxy group(ing) is characterized in that comprising the steps:
Step 1, γ-chloropropyl methyl dialkoxy silicane, phenyl trialkoxy silane and toluene are mixed, heat temperature raising to 85～90 ℃ drip the Hydrogen chloride of mass concentration 5～7%; Behind reaction 5～8h; Add end-capping reagent, continue reaction 3～5h, remove water layer after the cooling; Clean toluene layer to neutral, get polychlorostyrene propylbenzene radical siloxane toluene solution; Said 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 said toluene is γ-chloropropyl methyl dialkoxy silicane and phenyl trialkoxy silane total mass 2～4 times; The add-on of said Hydrogen chloride is γ-chloropropyl methyl dialkoxy silicane and phenyl trialkoxy silane total mass 0.3～0.6 times; Said end-capping reagent is SWS-F 221, trimethylchlorosilane, and the add-on of end-capping reagent is 2～10% of γ-chloropropyl methyl dialkoxy silicane and a phenyl trialkoxy silane total moles;
Step 2, dihydroxyphenyl propane sodium salt or potassium salt soln are joined in the polychlorostyrene propylbenzene radical siloxane toluene solution, add phase-transfer catalyst again, refluxed reaction 4～6h is stirred in heat temperature raising to 70～85 ℃;
Said phase-transfer catalyst is tetradecyl dimethyl benzyl ammonium chloride, cetalkonium chloride, stearyl dimethyl benzyl ammonium chloride, and add-on is 5～10% of a dihydroxyphenyl propane mole number;
The preparation method of said dihydroxyphenyl propane sodium salt or potassium salt soln is: at N
2Under the atmosphere, add dihydroxyphenyl propane, Pottasium Hydroxide or sodium hydroxide and deionized water, mix post-heating and be warming up to 80～100 ℃, promptly get behind stirring refluxed reaction 1～2h; 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 Pottasium 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, and cooling afterreaction system is divided into water layer and toluene layer, separates and removes water layer; Toluene layer is washed till neutrality with zero(ppm) water, steam removes behind the toluene polysiloxane oligomers that promptly gets side group band epoxy group(ing) 80～100 ℃ of following vacuum-dryings.
3. the preparation method of the polysiloxane oligomers of side group band epoxy group(ing) according to claim 2 is characterized in that: described cleaning toluene layer to neutrality is to clean toluene layer to neutral with saturated aqueous sodium sulfate.
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| CN103044919A (en) * | 2012-12-20 | 2013-04-17 | 涌奇材料技术（上海）有限公司 | Halogen-free phosphate-free environment-friendly synergistic flame retardant and use thereof |
| CN103965481A (en) * | 2013-02-01 | 2014-08-06 | 常州化学研究所 | Epoxy function group-containing silicone resin preparation method |
| CN107686555A (en) * | 2017-08-04 | 2018-02-13 | 山东交通学院 | A kind of modified polyorganosiloxane containing ester group and preparation method and application |
| CN109851759A (en) * | 2018-11-06 | 2019-06-07 | 中国神华能源股份有限公司 | Modifying epoxy resin by organosilicon, preparation method and modifying epoxy resin by organosilicon adhesive |
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| CN1712425A (en) * | 2005-07-18 | 2005-12-28 | 南京大学 | Production of Redix with 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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| US20040197284A1 (en) * | 2003-04-04 | 2004-10-07 | Frederic Auguste | Cosmetic composition comprising a volatile fatty phase |
| 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 | Production of Redix with 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 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103044919A (en) * | 2012-12-20 | 2013-04-17 | 涌奇材料技术（上海）有限公司 | Halogen-free phosphate-free environment-friendly synergistic flame retardant and use thereof |
| CN103044919B (en) * | 2012-12-20 | 2014-09-17 | 涌奇材料技术（上海）有限公司 | Halogen-free phosphate-free environment-friendly synergistic flame retardant and use thereof |
| CN103965481A (en) * | 2013-02-01 | 2014-08-06 | 常州化学研究所 | Epoxy function group-containing silicone resin preparation method |
| CN107686555A (en) * | 2017-08-04 | 2018-02-13 | 山东交通学院 | A kind of modified polyorganosiloxane containing ester group and preparation method and application |
| CN109851759A (en) * | 2018-11-06 | 2019-06-07 | 中国神华能源股份有限公司 | Modifying epoxy resin by organosilicon, preparation method and modifying epoxy resin by organosilicon adhesive |
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