CN102167831A - Functional trapezoid polysilsequioxane and preparation method thereof - Google Patents
Functional trapezoid polysilsequioxane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses functional trapezoid polysilsequioxane and a preparation method thereof. The preparation method comprises the following steps of: dissolving silane into an organic solvent; adding deionized water solution dropwise at the temperature of between -15 and 15 DEG C; reacting for 2 to 48 hours to obtain a prepolymer; standing and layering; washing an oil phase system with water until the pH value is 6 to 7; adding a basic catalyst; performing a condensation reaction for 3 to 20 hours at the temperature of between 40 and 120 DEG C; washing the obtained polymer organic solution with water until the pH value is 6 to 7; adding a proper catalyst and alkoxy silane with active functional groups; reacting for 0.5 to 12 hours at the temperature of between 30 and 160 DEG C and under inert atmosphere; adding the reaction product into methanol; and purifying a precipitate to obtain the functional trapezoid polysilsequioxane. In the technical scheme, the raw material monomers have wide sources and low price; the synthetic process is easy to control; and the obtained product has the characteristics of simpleness and convenience in separation and purification, high trapezoid structure content and the like, so the functional trapezoid polysilsequioxane has low production cost and is easy to produce on a large scale.
Description
Technical field
The present invention relates to a kind of hybrid inorganic-organic high polymer material technology, particularly a kind of trapezoidal polysilsesquioxane that contains active function groups and preparation method thereof belongs to technical field of polymer materials.
Background technology
Trapezoidal polysilsesquioxane is the novel organic-inorganic hybrid macromolecular material of the double-stranded shape structure formed of a kind of silica chain link by trifunctional (T chain link), particular structure is given its outstanding over-all properties, comprise excellent electric insulating, optical transparence, water-repellancy and flame retardant resistance, outstanding heat-resisting, weather-proof, water-fast and chemical resistance and high hardness and physical strength etc., thereby demonstrate great application prospect in a plurality of leading-edge fields such as aerospace, national defense and military.Because the thermostability of trapezoidal polysilsesquioxane side group is higher than other organic group, existing trapezoidal polysilsesquioxane is the most excellent with the over-all properties of poly methyl silsesquioxane and polyphenylene silsesquioxane, application potential is maximum.
An important use of trapezoidal polysilsesquioxane is the synthetic and modification that is used for the novel high-performance polymkeric substance, and therefore, the design that contains the trapezoidal polysilsesquioxane of active function groups is synthesized with preparation just significant.Before the present invention makes, about the synthetic technology of trapezoidal poly methyl silsesquioxane and trapezoidal polyphenyl base silsesquioxane is appeared in the newspapers, can reduce two kinds, first kind is by coupling synthetic method progressively, as with hydrazine to monomers such as phenyl-trichloro-silicane carry out pre-ammonia separate obtain coupling dimerization template after, hydrolysis under acidic conditions successively, condensation under the alkaline condition, remove open in the literature (the Zhong-xing Zhang of the technology that obtains high-sequential trapezoidal phenyl polysilsesquioxane after the hydrazine template, Jinkun Hao, etal.Chem Mater, 2008,20,1322-1330).But this method is not suitable for the synthetic of trapezoidal poly-methyl/polyphenylene silsesquioxane of containing active function groups, and synthesis procedure is loaded down with trivial details and expense is expensive.Second method is under the condition of acidity or basic catalyst existence, adopts the method for hydrolysis and condensation methyl/phenyl trialkoxy silane or methyl/phenyl-trichloro-silicane to synthesize.The two kinds of functionalized trapezoidal polysilsesquioxanes that disclose the hydrolysis of alkyltrialkoxysilaneand of alkyltrialkoxysilaneand by containing active function groups and non-functional group and condensation prepared as Chinese invention patent (CN 1454919).Yet,, and then cause being difficult to obtain containing the trapezoidal polysilsesquioxane of high ladder structure content because the hydrolysis of different alkyl trimethoxysilane and condensation speed is different; Disclose also in the document that to utilize a chlorosilane that contains active function groups that silicon hydroxyl remaining in the trapezoidal polysilsesquioxane is carried out partially end-blocked, and then obtained containing the trapezoidal polysilsesquioxane of active function groups.But, the end-blocking monomeric species that this method adopted is few, the source is narrow, cost is high, need import mostly, and limited the preparation of the trapezoidal polysilsesquioxane that contains other active function groups (as aminopropyl, mercapto propyl group or methacryloxypropyl etc.), simultaneously, this end-capping reagent can produce a large amount of hydrogen chloride gas in the end-blocking process, often cause the uncontrollable and reaction system of end capping may produce gel, and the hydrochloric acid that reaction generates can cause corrosion to equipment; In addition, this method adopts washing and distillation method that the trapezoidal polysilsesquioxane of gained is purified, obviously make its purifying technique become loaded down with trivial details, simultaneously can not remove the polysilsesquioxane and the unreacted end-capping reagent of the random and low ladder structure content in the resulting polymers effectively, thereby be unfavorable for obtaining the trapezoidal polysilsesquioxane of high ladder structure content.
Structural performance, synthetic method and the relevant existing problem of starting raw material at existing trapezoidal poly-methyl/phenyl silsesquioxane, the preparation method of the poly-methyl/phenyl silsesquioxane that contains active function groups and high ladder structure content that a kind of monomer source is wide, cost is low, technology is easy to control is provided, has important use and be worth and academic significance.
Summary of the invention
In order to overcome the deficiency that prior art exists, functionalized trapezoidal polysilsesquioxane that the object of the present invention is to provide that a kind of starting monomer source is wide, technology is easy to control, production cost is low and preparation method thereof.
Realize that the technical scheme that the object of the invention adopted is: a kind of functionalized trapezoidal polysilsesquioxane, its structural formula is:
In the formula, P is a methyl or phenyl; R
1And R
2Be active function groups, described active function groups is aminopropyl, N-2-aminoethyl-3-aminopropyl, mercapto propyl group or methacryloxypropyl, R
1With R
2Identical or different; N is 10～1000.
A kind of method for preparing above-mentioned functionalized trapezoidal polysilsesquioxane comprises the steps:
(1) under agitation condition, silane is dissolved in the organic solvent, drip the mixing solutions of forming by deionized water and an acidic catalyst again, reacted 2～48 hours under-15～15 ℃ the condition in temperature, obtain pre-polymer solution; The concentration of silane in organic solvent is 0.5～4mol/kg solvent; An acidic catalyst is hydrochloric acid or sulfuric acid, and the mol ratio of an acidic catalyst and silane is 0～0.15:1; The mol ratio of deionized water and silane is 3:1～20:1;
(2) with the pre-polymer solution standing demix, it is 6～7 that the oil phase system that obtains is washed to pH, adds basic catalyst, is condensation reaction 3～20 hours under 40～120 ℃ the condition in temperature, obtains polymer organic solution; The basic catalyst that is added is 2.5～10wt% of washing back oil phase system;
(3) the polymer organic solution water being washed till pH is 6～7, adds the organoalkoxysilane of catalyst A and band active function groups, in temperature is under 30～160 ℃ the inert atmosphere conditions, to react 0.5～12 hour, obtains crude product; The organoalkoxysilane of described band active function groups, a kind of in the organoalkoxysilane of the organoalkoxysilane of the organoalkoxysilane of the organoalkoxysilane of band aminopropyl active function groups, band N-2-aminoethyl-3-aminopropyl active function groups, band mercapto propyl group active function groups or band methacryloxypropyl active function groups, or their arbitrary combination; The organoalkoxysilane of catalyst A that is added and band active function groups is respectively 0.01:1～0.10:1 and 0.1:1～3:1 in molar ratio with silane in the step (1);
(4) crude product is joined in the methyl alcohol, throw out is carried out purification process, obtain functionalized trapezoidal polysilsesquioxane.
In the technique scheme, described silane is phenyltrimethoxysila,e, methyltrimethoxy silane, phenyl triethoxysilane, Union carbide A-162, phenyl-trichloro-silicane or METHYL TRICHLORO SILANE.
Organic solvent of the present invention is toluene, dimethylbenzene or hexone.
Described basic catalyst is that concentration is the potassium hydroxide of 0.1mg/mL or the methanol solution of sodium hydroxide.
Described catalyst A is that quaternary ammonium salt, lithium chloride, trolamine, triphenyl phosphorus, aluminium acetylacetonate, aluminum benzoate, potassium hydroxide, sodium hydroxide, Potassium ethanoate, sodium-acetate, titanic acid ester or carbonatoms are 1～20 carboxylic acid.
The organoalkoxysilane of described band aminopropyl active function groups is 3-aminopropyl trimethoxysilane or γ-An Bingjisanyiyangjiguiwan.The organoalkoxysilane of described band N-2-aminoethyl-3-aminopropyl active function groups is N-2-aminoethyl-3-aminopropyl trimethoxysilane.The organoalkoxysilane of described band mercapto propyl group active function groups is 3-mercaptopropyltriethoxysilane or 3-mercaptopropyl trimethoxysilane.The organoalkoxysilane of described band methacryloxypropyl active function groups is 3-(methacryloxypropyl) propyl trimethoxy silicane.
Compared with prior art, the beneficial effect obtained of the present invention is:
1, employing contains the end-capping reagent of the alkyl trimethoxysilane of active function groups as end capping in the trapezoidal polysilsesquioxane of preparation, can successfully introduce various active organo-functional group in trapezoidal polysilsesquioxane structure.
2, employing contains the alkyl trimethoxysilane of active function groups as end-capping reagent, can by the precipitator method polysilsesquioxane of unreacted end-capping reagent and low ladder structure content be separated effectively easily, and then prepare the trapezoidal polysilsesquioxane of high ladder structure content, be more suitable in scale operation and application.
3, the prepared trapezoidal polysilsesquioxane of active function groups that contains has high ladder structure content, thereby has more outstanding heat-resisting, dielectric, fire-retardant and mechanical property.
4, because reaction monomers source is wide, low price, and has technology and be easy to control, products therefrom separates purifies easy and hydrolyzate characteristics such as contaminated equipment not, therefore, and low production cost.
Description of drawings
Fig. 1 is the FTIR spectrogram of the trapezoidal polyphenyl base silsesquioxane of the band aminopropyl active group that provides of the embodiment of the invention;
Fig. 2 is the XRD spectra of the trapezoidal polyphenyl base silsesquioxane of the band aminopropyl active group that provides of the embodiment of the invention;
Fig. 3 is the trapezoidal polyphenyl base silsesquioxane of the band aminopropyl active group that provides of the embodiment of the invention
29The Si-NMR spectrogram.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment one
1, be that 36.5% hydrochloric acid soln is formed mixed solution with the deionized water of 5.40g and 0.08g mass concentration, stir and-15 ℃ temperature condition under, in 0.5 hour, dropwise join in the mixed solution of forming by the toluene of the phenyltrimethoxysila,e of 19.80g and 200.00g, after dropwising, reacted 2 hours down at-15 ℃, obtain pre-polymer solution;
2,, the oil phase system is washed to pH=7 with the pre-polymer solution standing demix;
3, in the oil phase system after washing, add the methanol solution (consumption of control basic catalyst is the 2.5wt% of washing back oil phase system) of the potassium hydroxide of an amount of 0.1mg/mL,, obtain trapezoidal polysilsesquioxane organic solution in 40 ℃ of reactions 3 hours;
The trapezoidal polysilsesquioxane organic solution that 4, will obtain is washed to pH=7, adds 0.08g sodium-acetate and 2.21g γ-An Bingjisanyiyangjiguiwan, under 30 ℃ temperature condition and inert atmosphere, reacts 0.5 hour, obtains crude product; Crude product joined in the 100mL methyl alcohol precipitate, obtain white powder; And then it is dissolved in the tetrahydrofuran (THF), use the methanol extraction of 2 times of concentrated solution volumes again, after the purification process, promptly obtain trapezoidal polyphenyl base silsesquioxane powder with aminopropyl.Its structural formula is:
Wherein, P is a phenyl, R
1And R
2Be aminopropyl.Its weight-average molecular weight is 13897(n ≈ 55), molecular weight distribution is 1.61.
Its FT-IR, XRD,
29The SiNMR spectrogram is respectively as Fig. 1, shown in 2 and 3.
Referring to accompanying drawing 1, it is the FTIR spectrogram of the trapezoidal polyphenyl base silsesquioxane of the band aminopropyl that provides of present embodiment; Fig. 2 is the XRD spectra of the trapezoidal polyphenyl base silsesquioxane of the band aminopropyl that provides of present embodiment; Fig. 3 is the trapezoidal polyphenyl base silsesquioxane of the band aminopropyl that provides of present embodiment
29The Si-NMR spectrogram.
As can be seen from Figure 1, institute of the present invention synthetic polyphenylene silsesquioxane contains amino and hydroxyl; From Fig. 2 and 3 as can be seen, institute of the present invention synthetic polyphenylene silsesquioxane has the ladder structure of high ladder structure content.
Embodiment two
1, be that 36.5% hydrochloric acid soln is formed mixed solution with the deionized water of 36.00g and 1.25g mass concentration, stir and 15 ℃ of conditions under, in 0.5 hour, dropwise join in the mixed solution of forming by 24.00g phenyl triethoxysilane and 25.00g dimethylbenzene, dropwise the back 15 ℃ of reactions 48 hours, obtain prepolymer;
2, with behind the pre-polymer solution standing demix, the oil phase system is washed to pH=7;
3, in the oil phase system after washing, add the methanol solution (consumption of control basic catalyst is the 10wt% of washing back oil phase system) of the potassium hydroxide of an amount of 0.1mg/mL,, obtain trapezoidal polysilsesquioxane organic solution in 120 ℃ of reactions 20 hours;
The trapezoidal polysilsesquioxane organic solution that 4, will obtain is washed to pH=7, adds 3.3g aluminium acetylacetonate and 50.80g γ-An Bingjisanyiyangjiguiwan, in 160 ℃ with inert atmosphere under, reacted 12 hours, obtain crude product; Crude product added in the 100mL methyl alcohol precipitate, obtain white powder; And then carry out purification process, its method is: it is dissolved in the tetrahydrofuran (THF), uses the methanol extraction of 2 times of concentrated solution volumes again; Repeat purification step 10 times, promptly obtain trapezoidal polyphenyl base silsesquioxane powder with aminopropyl.Its weight-average molecular weight is 2560(n ≈ 10), molecular weight distribution is 1.74.
Embodiment three
1, the deionized water of 10.80g and the concentrated hydrochloric acid solution of 0.17g (mass concentration is 36.5%) are formed mixed solution, under the condition of stirring and-5 ℃ of temperature, in 0.5 hour, dropwise join in the mixed solution of 13.60g methyltrimethoxy silane and 100.00g dimethylbenzene composition, dropwise the back-5 ℃ of reactions 8 hours, obtain prepolymer;
2, with behind the pre-polymer solution standing demix, the oil phase system is washed to pH=7;
3, add the methanol solution (consumption of control basic catalyst is the 5wt% of washing back oil phase system) of the potassium hydroxide of an amount of 0.1mg/mL in the oil phase system after washing,, obtain trapezoidal polysilsesquioxane organic solution in 100 ℃ of reactions 8 hours;
The trapezoidal polysilsesquioxane organic solution that 4, will obtain is washed to pH=7, adds suitable 0.11g potassium hydroxide and 74.40g3-(methacryloxypropyl) propyl trimethoxy silicane, under 120 ℃ and inert atmosphere, reacts 6 hours, obtains crude product; Crude product added in the 100mL methyl alcohol precipitate, obtain white powder; Then it is dissolved in the tetrahydrofuran (THF), uses the methanol extraction of 2 times of concentrated solution volumes again, repeat purification step 3 times, promptly obtain trapezoidal polyphenyl base silsesquioxane powder with methacryloxypropyl.Its weight-average molecular weight is 138000(n ≈ 1000), molecular weight distribution is 1.56.
Embodiment four
1, with the deionized water of 12.80g and 0.28g mass concentration is the mixed solution that 98.5% concentrated sulfuric acid solution is formed, stir and 0 ℃ of temperature condition under, in 0.5 hour, dropwise join in the mixed solution of forming by 17.83g Union carbide A-162 and 150.00g hexone, dropwise the back 0 ℃ of reaction 5 hours, obtain prepolymer;
2, with behind the pre-polymer solution standing demix, the oil phase system is washed to pH=7;
3, add the methanol solution (consumption of control basic catalyst is the 5wt% of washing back oil phase system) of the potassium hydroxide of an amount of 0.1mg/mL in the oil phase system after washing,, obtain trapezoidal polysilsesquioxane organic solution in 110 ℃ of reactions 6 hours;
The trapezoidal polysilsesquioxane organic solution that 4, will obtain is washed to pH=7, adds suitable 0.49g Potassium ethanoate and 37.23g3-(methacryloxypropyl) propyl trimethoxy silicane, under 140 ℃ and inert atmosphere, reacts 4 hours, obtains crude product; Crude product with precipitating in its adding 100mL methyl alcohol, is obtained white powder; And then it is dissolved in the tetrahydrofuran (THF), use the methanol extraction of 2 times of concentrated solution volumes again, repeat purification step 3 times, promptly obtain trapezoidal polyphenyl base silsesquioxane powder with methacryloxy.Its weight-average molecular weight is 35678(n ≈ 266), molecular weight distribution is 1.68.
Embodiment five
1, stir and 5 ℃ of conditions under, the deionized water of 14.80g was dropwise joined in 0.5 hour in the mixed solution that 17.83g METHYL TRICHLORO SILANE and 150.00g hexone form, obtain prepolymer at 0 ℃ after reacting 20 hours;
2, with behind the pre-polymer solution standing demix, the oil phase system is washed to pH=7;
3, the methanol solution (consumption of control basic catalyst is the 7.5wt% of washing back oil phase system) that adds the potassium hydroxide of an amount of 0.1mg/mL in the oil phase system after the washing that obtains, in 100 ℃ of reactions 16 hours, obtain trapezoidal polysilsesquioxane organic solution;
The trapezoidal polysilsesquioxane organic solution that 4, will obtain is washed to pH=7, adds suitable 0.08g lithium chloride and 38.53g3-mercaptopropyl trimethoxysilane, under 100 ℃ and inert atmosphere, reacts 3 hours, obtains crude product; Crude product with precipitating in its adding 100mL methyl alcohol, is obtained white powder; And then it is dissolved in the tetrahydrofuran (THF), use the methanol extraction of 2 times of concentrated solution volumes again, repeat purification step 3 times, promptly obtain trapezoidal polyphenyl base silsesquioxane powder with the mercapto propyl group.Its weight-average molecular weight is 15670(n ≈ 120), molecular weight distribution is 1.86.
Embodiment six
1, stir with 5 ℃ of conditions under, the deionized water of 14.80g was dropwise joined in 0.5 hour in the mixed solution of being made up of 21.16g phenyl-trichloro-silicane and 120.00g hexone, obtain prepolymer at 0 ℃ after reacting 10 hours;
2, with behind the pre-polymer solution standing demix, the oil phase system is washed to pH=7;
3, add the methanol solution (consumption of control basic catalyst is the 7.5wt% of washing back oil phase system) of the potassium hydroxide of an amount of 0.1mg/mL in the oil phase system after washing,, obtain trapezoidal polysilsesquioxane organic solution in 90 ℃ of reactions 18 hours;
The trapezoidal polysilsesquioxane organic solution that 4, will obtain is washed to pH=7, adds suitable 0.68g titanic acid ester and 17.93g3-aminopropyl trimethoxysilane, under 110 ℃ and inert atmosphere, reacts 2 hours, obtains crude product; Crude product added in the 100mL methyl alcohol precipitate, obtain white powder; And then it is dissolved in the tetrahydrofuran (THF), use the methanol extraction of 2 times of concentrated solution volumes again, repeat purification step 3 times, promptly obtain trapezoidal polyphenyl base silsesquioxane powder with aminopropyl.Its weight-average molecular weight is 15455(n ≈ 60), molecular weight distribution is 1.76.
Embodiment seven
1, stir with 5 ℃ of conditions under, the deionized water of 14.80g was dropwise joined in 0.5 hour in the mixed solution of being made up of 21.16g phenyl-trichloro-silicane and 120.00g hexone, obtain prepolymer at 0 ℃ after reacting 10 hours;
2, with behind the pre-polymer solution standing demix, the oil phase system is washed to pH=7;
3, add the methanol solution (consumption of control basic catalyst is the 7.5wt% of washing back oil phase system) of the potassium hydroxide of an amount of 0.1mg/mL in the oil phase system after washing,, obtain trapezoidal polysilsesquioxane organic solution in 90 ℃ of reactions 18 hours;
The trapezoidal polysilsesquioxane organic solution that 4, will obtain is washed to pH=7, add suitable 0.68g titanic acid ester, 13.45g3-mercaptopropyl trimethoxysilane and 17.93g3-aminopropyl trimethoxysilane are under 110 ℃ and inert atmosphere, reacted 2 hours, and obtained crude product; Crude product added in the 100mL methyl alcohol precipitate, obtain white powder; And then it is dissolved in the tetrahydrofuran (THF), use the methanol extraction of 2 times of concentrated solution volumes again, repeat purification step 3 times, promptly obtain trapezoidal polyphenyl base silsesquioxane powder with mercapto propyl group and aminopropyl.Its weight-average molecular weight is 134000(n ≈ 520), molecular weight distribution is 1.96.
Embodiment eight
1, the mixed solution that the deionized water of 36.00g and the concentrated hydrochloric acid solution of 1.25g (mass concentration is 36.5%) are formed, stir and 15 ℃ of conditions under, in 0.5 hour, dropwise join by 24.00g phenyl triethoxysilane and 25.00g dimethylbenzene form mixed solution in, dropwise the back 15 ℃ of reactions 48 hours, obtain prepolymer;
2, with behind the pre-polymer solution standing demix, the oil phase system is washed to pH=7;
3, in the oil phase system after washing, add the methanol solution (consumption of control basic catalyst is the 10wt% of washing back oil phase system) of the potassium hydroxide of an amount of 0.1mg/mL,, obtain trapezoidal polysilsesquioxane organic solution in 120 ℃ of reactions 20 hours;
The trapezoidal polysilsesquioxane organic solution that 4, will obtain is washed to pH=7, adds the aluminium acetylacetonate and the 3-aminopropyl triethoxysilane of 66.31g of 3.3g, in 160 ℃ with inert atmosphere under, reacted 12 hours, obtain crude product; Crude product added in the 100mL methyl alcohol precipitate, obtain white powder; And then it is dissolved in the tetrahydrofuran (THF), use the methanol extraction of 2 times of concentrated solution volumes again, repeat purification step 10 times, promptly obtain trapezoidal polyphenyl base silsesquioxane powder with aminopropyl.Its weight-average molecular weight is 89045(n ≈ 350), molecular weight distribution is 1.55.
Embodiment nine
1, the mixed solution that deionized water and the 0.17g concentrated hydrochloric acid solution (mass concentration is 36.5%) of 10.80g are formed, stir and-5 ℃ of conditions under, in 0.5 hour, dropwise join in the mixed solution of forming by the dimethylbenzene of the methyltrimethoxy silane of 13.60g and 100.00g, dropwise the back-5 ℃ of reactions 8 hours, obtain prepolymer;
2, with behind the pre-polymer solution standing demix, the oil phase system is washed to pH=7;
3, add the methanol solution (consumption of control basic catalyst is the 5wt% of washing back oil phase system) of the potassium hydroxide of an amount of 0.1mg/mL in the oil phase system after washing,, obtain trapezoidal polysilsesquioxane organic solution in 100 ℃ of reactions 8 hours;
The trapezoidal polysilsesquioxane organic solution that 4, will obtain is washed to pH=7, adds suitable 0.11g potassium hydroxide and 14.80g3-aminopropyl triethoxysilane, under 120 ℃ and inert atmosphere, reacts 6 hours, obtains crude product; Crude product added in the 100mL methyl alcohol precipitate, obtain white powder; And then it is dissolved in the tetrahydrofuran (THF), use the methanol extraction of 2 times of concentrated solution volumes again, repeat purification step 3 times, promptly obtain trapezoidal polyphenyl base silsesquioxane powder with aminopropyl.Its weight-average molecular weight is 76332(n ≈ 570), molecular weight distribution is 1.75.
Embodiment ten
1, the mixed solution that the deionized water of 12.80g and the concentrated sulfuric acid solution of 0.28g (mass concentration is 98.5%) are formed, stir and 0 ℃ of condition under, in 0.5 hour, dropwise join in the mixed solution of forming by the hexone of the Union carbide A-162 of 17.83g and 150.00g, dropwise the back 0 ℃ of reaction 5 hours, obtain prepolymer;
2, with behind the pre-polymer solution standing demix, the oil phase system is washed to pH=7;
3, add the methanol solution (consumption of control basic catalyst is the 5wt% of washing back oil phase system) of the potassium hydroxide of an amount of 0.1mg/mL in the oil phase system after washing,, obtain trapezoidal polysilsesquioxane organic solution in 110 ℃ of reactions 6 hours;
The trapezoidal polysilsesquioxane organic solution that 4, will obtain is washed to pH=7, adds the Potassium ethanoate and the 3-aminopropyl triethoxysilane of 37.23g of 0.49g, in 140 ℃ with inert atmosphere under, reacted 4 hours, obtain crude product; Crude product with precipitating in its adding 100mL methyl alcohol, is obtained white powder; And then it is dissolved in the tetrahydrofuran (THF), use the methanol extraction of 2 times of concentrated solution volumes again, repeat purification step 3 times, promptly obtain trapezoidal polyphenyl base silsesquioxane powder with aminopropyl.Its weight-average molecular weight is 24567(n ≈ 180), molecular weight distribution is 1.90.
Embodiment 11
1, the mixed solution that deionized water and the 0.28g concentrated sulfuric acid solution (mass concentration is 98.5%) of 12.80g are formed, stir and 0 ℃ of condition under, in 0.5 hour, dropwise join in the mixed solution of 17.83g Union carbide A-162 and 150.00g hexone composition, dropwise the back 0 ℃ of reaction 5 hours, obtain prepolymer;
2, with behind the pre-polymer solution standing demix, the oil phase system is washed to pH=7;
3, add the methanol solution (consumption of control basic catalyst is the 5wt% of washing back oil phase system) of the potassium hydroxide of an amount of 0.1mg/mL in the oil phase system after washing,, obtain trapezoidal polysilsesquioxane organic solution in 110 ℃ of reactions 6 hours;
The trapezoidal polysilsesquioxane organic solution that 4, will obtain is washed to pH=7, adds the organoalkoxysilane of 0.49g Potassium ethanoate and 43.23gN-2-aminoethyl-3-aminopropyl active function groups, in 140 ℃ with inert atmosphere under, reacted 4 hours, obtain crude product; Crude product with precipitating in its adding 100mL methyl alcohol, is obtained white powder; And then it is dissolved in the tetrahydrofuran (THF), use the methanol extraction of 2 times of concentrated solution volumes again, repeat purification step 3 times, promptly obtain trapezoidal polyphenyl base silsesquioxane powder with N-2-aminoethyl-3-aminopropyl.Its weight-average molecular weight is 25400(n ≈ 190), molecular weight distribution is 1.82.
Claims (10)
1. functionalized trapezoidal polysilsesquioxane is characterized in that its structural formula is:
In the formula, P is a methyl or phenyl; R
1And R
2Be active function groups, described active function groups is aminopropyl, N-2-aminoethyl-3-aminopropyl, mercapto propyl group or methacryloxypropyl, R
1With R
2Identical or different; N is 10～1000.
2. a method for preparing functionalized trapezoidal polysilsesquioxane as claimed in claim 1 is characterized in that comprising the steps:
(1) under agitation condition, silane is dissolved in the organic solvent, drip the mixing solutions of forming by deionized water and an acidic catalyst again, reacted 2～48 hours under-15～15 ℃ the condition in temperature, obtain pre-polymer solution; The concentration of silane in organic solvent is 0.5～4mol/kg solvent; An acidic catalyst is hydrochloric acid or sulfuric acid, and the mol ratio of an acidic catalyst and silane is 0～0.15:1; The mol ratio of deionized water and silane is 3:1～20:1;
(2) with the pre-polymer solution standing demix, it is 6～7 that the oil phase system that obtains is washed to pH, adds basic catalyst, is condensation reaction 3～20 hours under 40～120 ℃ the condition in temperature, obtains polymer organic solution; The basic catalyst that is added is 2.5～10wt% of washing back oil phase system;
(3) the polymer organic solution water being washed till pH is 6～7, adds the organoalkoxysilane of catalyst A and band active function groups, in temperature is under 30～160 ℃ the inert atmosphere conditions, to react 0.5～12 hour, obtains crude product; The organoalkoxysilane of described band active function groups, a kind of in the organoalkoxysilane of the organoalkoxysilane of the organoalkoxysilane of the organoalkoxysilane of band aminopropyl active function groups, band N-2-aminoethyl-3-aminopropyl active function groups, band mercapto propyl group active function groups or band methacryloxypropyl active function groups, or their arbitrary combination; The organoalkoxysilane of catalyst A that is added and band active function groups is respectively 0.01:1～0.10:1 and 0.1:1～3:1 in molar ratio with silane in the step (1);
(4) crude product is joined in the methyl alcohol, throw out is carried out purification process, obtain functionalized trapezoidal polysilsesquioxane.
3. a kind of method for preparing functionalized trapezoidal polysilsesquioxane according to claim 2 is characterized in that: described silane is phenyltrimethoxysila,e, methyltrimethoxy silane, phenyl triethoxysilane, Union carbide A-162, phenyl-trichloro-silicane or METHYL TRICHLORO SILANE.
4. a kind of method for preparing functionalized trapezoidal polysilsesquioxane according to claim 2 is characterized in that: described organic solvent is toluene, dimethylbenzene or hexone.
5. a kind of method for preparing functionalized trapezoidal polysilsesquioxane according to claim 2 is characterized in that: described basic catalyst is that concentration is the potassium hydroxide of 0.1mg/mL or the methanol solution of sodium hydroxide.
6. a kind of method for preparing functionalized trapezoidal polysilsesquioxane according to claim 2 is characterized in that: described catalyst A is that quaternary ammonium salt, lithium chloride, trolamine, triphenyl phosphorus, aluminium acetylacetonate, aluminum benzoate, potassium hydroxide, sodium hydroxide, Potassium ethanoate, sodium-acetate, titanic acid ester or carbonatoms are 1～20 carboxylic acid.
7. a kind of method for preparing functionalized trapezoidal polysilsesquioxane according to claim 2 is characterized in that: the organoalkoxysilane of described band aminopropyl active function groups is 3-aminopropyl trimethoxysilane or γ-An Bingjisanyiyangjiguiwan.
8. a kind of method for preparing functionalized trapezoidal polysilsesquioxane according to claim 2 is characterized in that: the organoalkoxysilane of described band N-2-aminoethyl-3-aminopropyl active function groups is N-2-aminoethyl-3-aminopropyl trimethoxysilane.
9. a kind of method for preparing functionalized trapezoidal polysilsesquioxane according to claim 2 is characterized in that: the organoalkoxysilane of described band mercapto propyl group active function groups is 3-mercaptopropyltriethoxysilane or 3-mercaptopropyl trimethoxysilane.
10. a kind of method for preparing functionalized trapezoidal polysilsesquioxane according to claim 2 is characterized in that: the organoalkoxysilane of described band methacryloxypropyl active function groups is 3-(methacryloxypropyl) propyl trimethoxy silicane.
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| CN106009016A (en) * | 2016-08-11 | 2016-10-12 | 潘忠宁 | Method for preparing monodisperse polysilsesquioxane spherical film |
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| CN114031779A (en) * | 2021-11-01 | 2022-02-11 | 兰州瑞朴科技有限公司 | Phosphorus-containing ladder-shaped polysiloxane, preparation method thereof and application of phosphorus-containing ladder-shaped polysiloxane as flame-retardant synergist |
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