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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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 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.
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 side group band epoxy group(ing) claimed in claim 1, is characterized in that comprising 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.
3. the preparation method of the polysiloxane oligomers of side group band epoxy group(ing) according to claim 2, it is characterized in that: described cleaning toluene layer is to use saturated aqueous sodium sulfate to neutrality.
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| CN103965481A (en) * | 2013-02-01 | 2014-08-06 | 常州化学研究所 | Epoxy function group-containing silicone resin preparation method |
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| US20040197284A1 (en) * | 2003-04-04 | 2004-10-07 | Frederic Auguste | Cosmetic composition comprising a volatile fatty phase |
| 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 |
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