CN102167831B - Functional trapezoid polysilsequioxane and preparation method thereof - Google Patents
Functional trapezoid polysilsequioxane and preparation method thereof Download PDFInfo
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- CN102167831B CN102167831B CN 201110059023 CN201110059023A CN102167831B CN 102167831 B CN102167831 B CN 102167831B CN 201110059023 CN201110059023 CN 201110059023 CN 201110059023 A CN201110059023 A CN 201110059023A CN 102167831 B CN102167831 B CN 102167831B
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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 ladder-like polysiloxane that contains active function groups and preparation method thereof belongs to technical field of polymer materials.
Background technology
Ladder-like polysiloxane is the novel organic-inorganic hybrid macromolecular material of the double-stranded shape structure that forms of a kind of silica chain link by trifunctional (T chain link), unique structure is given its outstanding over-all properties, comprise good electrical insulating property, 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 huge application prospect in a plurality of leading-edge fields such as aerospace, national defense and military.Because the thermostability of ladder-like polysiloxane side group is higher than other organic group, existing ladder-like polysiloxane is the most excellent with the over-all properties of poly methyl silsesquioxane and polyphenylsilsesquioxane, application potential is maximum.
An important use of ladder-like polysiloxane is for novel high-performance synthetic polymer and modification, and therefore, the design that contains the ladder-like polysiloxane of active function groups is synthesized with preparation just significant.Before the present invention makes, about the synthetic technology of trapezoid polymethylsilsesquioxane and trapezoid polyphenylsilsesquioxane is appeared in the newspapers, can be summarized as two kinds, the first is by the synthetic method of coupling progressively, as with hydrazine the monomers such as phenyl-trichloro-silicane being carried out after pre-ammonia solution obtains coupling dimerization template, under acidic conditions, be hydrolyzed successively, condensation under the alkaline condition, remove technology open (the Zhong-xing Zhang in the literature that obtains high-sequential trapezoidal phenyl polysilsesquioxane after the hydrazine template, Jinkun Hao, etal.Chem Mater, 2008,20,1322-1330).But the method is not suitable for the synthetic of trapezoidal poly-methyl/polyphenylsilsesquioxane of containing active function groups, and synthesis procedure is loaded down with trivial details and somewhat 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 hydrolysis and condensation that discloses the alkyltrialkoxysilaneand of alkyltrialkoxysilaneand by containing active function groups and non-functional group such as Chinese invention patent (CN 1454919) has prepared two kinds of functional trapezoid polysilsequioxanes.Yet, because the difference of the hydrolysis and condensation speed of different alkyl trimethoxysilane, and then cause being difficult to obtain containing the ladder-like polysiloxane of high ladder structure content; Disclose also in the document that to utilize a chlorosilane that contains active function groups that silicon hydroxyl remaining in the ladder-like polysiloxane is carried out partially end-blocked, and then obtained containing the ladder-like polysiloxane of active function groups.But, the end-blocking monomeric species that this method adopts is few, the source is narrow, cost is high, mostly need import, and limited the preparation of the ladder-like polysiloxane that contains other active function groups (such 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, the method adopts washing and distillation method that the gained ladder-like polysiloxane is purified, obviously make its purifying technique become loaded down with trivial details, simultaneously can not effectively remove polysilsesquioxane and the unreacted end-capping reagent of the random and low ladder structure content in the resulting polymers, thereby be unfavorable for obtaining the ladder-like polysiloxane of high ladder structure content.
Structural performance, synthetic method and the relevant existing problem of starting raw material for 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, technique is easy to control is provided, has important using value and academic significance.
Summary of the invention
The deficiency that exists in order to overcome prior art, functional trapezoid polysilsequioxane that the object of the present invention is to provide that a kind of starting monomer source is wide, technique is easy to control, production cost is low and preparation method thereof.
Realize that the technical scheme that the object of the invention adopts is: a kind of functional trapezoid polysilsequioxane, its structural formula is:
In the formula, P is 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 functional trapezoid polysilsequioxane comprises the steps:
(1) under agitation condition, silane is dissolved in the organic solvent, drip again the mixing solutions that is formed by deionized water and an acidic catalyst, 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-based 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 adds is 2.5～10wt% of the rear oil-based system of washing;
(3) the polymer organic solution water being washed till pH is 6～7, adds catalyst A and with the organoalkoxysilane of active function groups, in temperature is under 30～160 ℃ the inert atmosphere conditions, to react 0.5～12 hour, obtains crude product; Described organoalkoxysilane with active function groups, for with the organoalkoxysilane of aminopropyl active function groups, with the organoalkoxysilane of N-2-aminoethyl-3-aminopropyl active function groups, with the organoalkoxysilane of mercapto propyl group active function groups or a kind of with in the organoalkoxysilane of methacryloxypropyl active function groups, or their arbitrary combination; The catalyst A that adds and with the organoalkoxysilane of 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 functional trapezoid polysilsequioxane.
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.
Described organoalkoxysilane with the aminopropyl active function groups is 3-aminopropyl trimethoxysilane or γ-aminopropyl triethoxysilane.Described organoalkoxysilane with N-2-aminoethyl-3-aminopropyl active function groups is N-2-aminoethyl-3-aminopropyl trimethoxysilane.Described organoalkoxysilane with mercapto propyl group active function groups is 3-mercaptopropyltriethoxysilane or 3-mercaptopropyl trimethoxysilane.Described organoalkoxysilane with the 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 alkyl trimethoxysilane of active function groups as the end-capping reagent of end capping in the preparation ladder-like polysiloxane, can successfully introduce various active organo-functional group in the ladder-like polysiloxane 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 ladder-like polysiloxane of high ladder structure content, be more suitable in scale operation and application.
3, the prepared active function groups ladder-like polysiloxane 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 technique and be easy to control, the easy and hydrolyzate of products therefrom separating-purifying is the characteristics such as contaminated equipment not, therefore, and low production cost.
Description of drawings
Fig. 1 is the FTIR spectrogram with the trapezoidal polyphenyl base silsesquioxane of aminopropyl active group that the embodiment of the invention provides;
Fig. 2 is the XRD spectra with the trapezoidal polyphenyl base silsesquioxane of aminopropyl active group that the embodiment of the invention provides;
Fig. 3 is the trapezoidal polyphenyl base silsesquioxane with the aminopropyl active group that the embodiment of the invention provides
29The Si-NMR spectrogram.
Embodiment
The invention will be further described below in conjunction with embodiment:
Embodiment one
1, be that 36.5% hydrochloric acid soln forms 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 that the toluene by the phenyltrimethoxysila,e of 19.80g and 200.00g forms, after dropwising,-15 ℃ of lower reactions 2 hours, obtain pre-polymer solution;
2, with the pre-polymer solution standing demix, oil-based system is washed to pH=7;
3, in the oil-based system after washing, add the methanol solution (consumption of control basic catalyst is the 2.5wt% of the rear oil-based system of washing) of the potassium hydroxide of an amount of 0.1mg/mL, in 40 ℃ of reactions 3 hours, obtain ladder-like polysiloxane organic solution;
4, the ladder-like polysiloxane organic solution that obtains is washed to pH=7, adds 0.08g sodium-acetate and 2.21g γ-aminopropyl triethoxysilane, under 30 ℃ temperature condition and inert atmosphere, reacted 0.5 hour, obtain crude product; Crude product joined in the 100mL methyl alcohol precipitate, obtain white powder; And then it is dissolved in the tetrahydrofuran (THF), use again the methanol extraction of 2 times of concentrated solution volumes, after the purification process, namely obtain the trapezoid polyphenylsilsesquioxane powder with aminopropyl.Its structural formula is:
Wherein, P is 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 such as Fig. 1, shown in 2 and 3.
Referring to accompanying drawing 1, it is the FTIR spectrogram with the trapezoidal polyphenyl base silsesquioxane of aminopropyl that the present embodiment provides; Fig. 2 is the XRD spectra with the trapezoidal polyphenyl base silsesquioxane of aminopropyl that the present embodiment provides; Fig. 3 is the trapezoidal polyphenyl base silsesquioxane with aminopropyl that the present embodiment provides
29The Si-NMR spectrogram.
As can be seen from Figure 1, the polyphenylene silsesquioxane that the present invention synthesized contains amino and hydroxyl; Can find out from Fig. 2 and 3, the polyphenylene silsesquioxane that the present invention synthesized has the ladder structure of high ladder structure content.
Embodiment two
1, be that 36.5% hydrochloric acid soln forms 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 that is formed by 24.00g phenyl triethoxysilane and 25.00g dimethylbenzene, 15 ℃ of reactions 48 hours, obtain prepolymer after dropwising;
2, with behind the pre-polymer solution standing demix, oil-based system is washed to pH=7;
3, in the oil-based system after washing, add the methanol solution (consumption of control basic catalyst is the 10wt% of the rear oil-based system of washing) of the potassium hydroxide of an amount of 0.1mg/mL, in 120 ℃ of reactions 20 hours, obtain ladder-like polysiloxane organic solution;
4, the ladder-like polysiloxane organic solution that obtains is washed to pH=7, adds 3.3g aluminium acetylacetonate and 50.80g γ-aminopropyl triethoxysilane, 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, namely obtain the trapezoid polyphenylsilsesquioxane 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,-5 ℃ of reactions 8 hours, obtain prepolymer after dropwising;
2, with behind the pre-polymer solution standing demix, oil-based system is washed to pH=7;
3, add the methanol solution (consumption of control basic catalyst is the 5wt% of the rear oil-based system of washing) of the potassium hydroxide of an amount of 0.1mg/mL in the oil-based system after washing, in 100 ℃ of reactions 8 hours, obtain ladder-like polysiloxane organic solution;
4, the ladder-like polysiloxane organic solution that obtains is washed to pH=7, adds suitable 0.11g potassium hydroxide and 74.40g3-(methacryloxypropyl) propyl trimethoxy silicane, under 120 ℃ and inert atmosphere, reacted 6 hours, obtain crude product; Crude product added in the 100mL methyl alcohol precipitate, obtain white powder; Then it is dissolved in the tetrahydrofuran (THF), uses again the methanol extraction of 2 times of concentrated solution volumes, repeat purification step 3 times, namely obtain the trapezoid polyphenylsilsesquioxane 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 forms, stir and 0 ℃ of temperature condition under, in 0.5 hour, dropwise join in the mixed solution that is formed by 17.83g Union carbide A-162 and 150.00g hexone, 0 ℃ of reaction 5 hours, obtain prepolymer after dropwising;
2, with behind the pre-polymer solution standing demix, oil-based system is washed to pH=7;
3, add the methanol solution (consumption of control basic catalyst is the 5wt% of the rear oil-based system of washing) of the potassium hydroxide of an amount of 0.1mg/mL in the oil-based system after washing, in 110 ℃ of reactions 6 hours, obtain ladder-like polysiloxane organic solution;
4, the ladder-like polysiloxane organic solution that obtains is washed to pH=7, adds suitable 0.49g Potassium ethanoate and 37.23g3-(methacryloxypropyl) propyl trimethoxy silicane, under 140 ℃ and inert atmosphere, 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 again the methanol extraction of 2 times of concentrated solution volumes, repeat purification step 3 times, namely obtain the trapezoid polyphenylsilsesquioxane 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, oil-based system is washed to pH=7;
3, the methanol solution (consumption of control basic catalyst is the 7.5wt% of the rear oil-based system of washing) that adds the potassium hydroxide of an amount of 0.1mg/mL in the oil-based system after the washing that obtains, in 100 ℃ of reactions 16 hours, obtain ladder-like polysiloxane organic solution;
4, the ladder-like polysiloxane organic solution that obtains is washed to pH=7, adds suitable 0.08g lithium chloride and 38.53g3-mercaptopropyl trimethoxysilane, under 100 ℃ and inert atmosphere, reacted 3 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 again the methanol extraction of 2 times of concentrated solution volumes, repeat purification step 3 times, namely obtain the trapezoid polyphenylsilsesquioxane 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 that is comprised 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, oil-based system is washed to pH=7;
3, add the methanol solution (consumption of control basic catalyst is the 7.5wt% of the rear oil-based system of washing) of the potassium hydroxide of an amount of 0.1mg/mL in the oil-based system after washing, in 90 ℃ of reactions 18 hours, obtain ladder-like polysiloxane organic solution;
4, the ladder-like polysiloxane organic solution that obtains is washed to pH=7, adds suitable 0.68g titanic acid ester and 17.93g3-aminopropyl trimethoxysilane, under 110 ℃ and inert atmosphere, reacted 2 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 again the methanol extraction of 2 times of concentrated solution volumes, repeat purification step 3 times, namely obtain the trapezoid polyphenylsilsesquioxane 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 that is comprised 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, oil-based system is washed to pH=7;
3, add the methanol solution (consumption of control basic catalyst is the 7.5wt% of the rear oil-based system of washing) of the potassium hydroxide of an amount of 0.1mg/mL in the oil-based system after washing, in 90 ℃ of reactions 18 hours, obtain ladder-like polysiloxane organic solution;
4, the ladder-like polysiloxane organic solution that obtains 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 again the methanol extraction of 2 times of concentrated solution volumes, repeat purification step 3 times, namely obtain the trapezoid polyphenylsilsesquioxane 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%) is 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, 15 ℃ of reactions 48 hours, obtain prepolymer after dropwising;
2, with behind the pre-polymer solution standing demix, oil-based system is washed to pH=7;
3, in the oil-based system after washing, add the methanol solution (consumption of control basic catalyst is the 10wt% of the rear oil-based system of washing) of the potassium hydroxide of an amount of 0.1mg/mL, in 120 ℃ of reactions 20 hours, obtain ladder-like polysiloxane organic solution;
4, the ladder-like polysiloxane organic solution that obtains 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 again the methanol extraction of 2 times of concentrated solution volumes, repeat purification step 10 times, namely obtain the trapezoid polyphenylsilsesquioxane powder with aminopropyl.Its weight-average molecular weight is 89045(n ≈ 350), molecular weight distribution is 1.55.
Embodiment nine
1, with the deionized water of 10.80g and the mixed solution of 0.17g concentrated hydrochloric acid solution (mass concentration is 36.5%) composition, stir and-5 ℃ of conditions under, in 0.5 hour, dropwise join in the mixed solution that the dimethylbenzene by the methyltrimethoxy silane of 13.60g and 100.00g forms,-5 ℃ of reactions 8 hours, obtain prepolymer after dropwising;
2, with behind the pre-polymer solution standing demix, oil-based system is washed to pH=7;
3, add the methanol solution (consumption of control basic catalyst is the 5wt% of the rear oil-based system of washing) of the potassium hydroxide of an amount of 0.1mg/mL in the oil-based system after washing, in 100 ℃ of reactions 8 hours, obtain ladder-like polysiloxane organic solution;
4, the ladder-like polysiloxane organic solution that obtains is washed to pH=7, adds suitable 0.11g potassium hydroxide and 14.80g3-aminopropyl triethoxysilane, under 120 ℃ and inert atmosphere, reacted 6 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 again the methanol extraction of 2 times of concentrated solution volumes, repeat purification step 3 times, namely obtain the trapezoid polyphenylsilsesquioxane 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%) is formed, stir and 0 ℃ of condition under, in 0.5 hour, dropwise join in the mixed solution that the hexone by the Union carbide A-162 of 17.83g and 150.00g forms, 0 ℃ of reaction 5 hours, obtain prepolymer after dropwising;
2, with behind the pre-polymer solution standing demix, oil-based system is washed to pH=7;
3, add the methanol solution (consumption of control basic catalyst is the 5wt% of the rear oil-based system of washing) of the potassium hydroxide of an amount of 0.1mg/mL in the oil-based system after washing, in 110 ℃ of reactions 6 hours, obtain ladder-like polysiloxane organic solution;
4, the ladder-like polysiloxane organic solution that obtains 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 again the methanol extraction of 2 times of concentrated solution volumes, repeat purification step 3 times, namely obtain the trapezoid polyphenylsilsesquioxane powder with aminopropyl.Its weight-average molecular weight is 24567(n ≈ 180), molecular weight distribution is 1.90.
Embodiment 11
1, with the deionized water of 12.80g and the mixed solution of 0.28g concentrated sulfuric acid solution (mass concentration is 98.5%) composition, 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, 0 ℃ of reaction 5 hours, obtain prepolymer after dropwising;
2, with behind the pre-polymer solution standing demix, oil-based system is washed to pH=7;
3, add the methanol solution (consumption of control basic catalyst is the 5wt% of the rear oil-based system of washing) of the potassium hydroxide of an amount of 0.1mg/mL in the oil-based system after washing, in 110 ℃ of reactions 6 hours, obtain ladder-like polysiloxane organic solution;
4, the ladder-like polysiloxane organic solution that obtains 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 again the methanol extraction of 2 times of concentrated solution volumes, repeat purification step 3 times, namely obtain the trapezoid polyphenylsilsesquioxane powder with N-2-aminoethyl-3-aminopropyl.Its weight-average molecular weight is 25400(n ≈ 190), molecular weight distribution is 1.82.
Claims (5)
1. method for preparing functional trapezoid polysilsequioxane, the structural formula of described functional trapezoid polysilsequioxane is:
In the formula, P is 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;
It is characterized in that comprising the steps:
(1) under agitation condition, silane is dissolved in the organic solvent, drip again the mixing solutions that is formed by deionized water and an acidic catalyst, 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-based 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 adds is 2.5～10wt% of the rear oil-based system of washing;
(3) the polymer organic solution water being washed till pH is 6～7, adds catalyst A and with the organoalkoxysilane of active function groups, in temperature is under 30～160 ℃ the inert atmosphere conditions, to react 0.5～12 hour, obtains crude product; Described organoalkoxysilane with active function groups, for with the organoalkoxysilane of aminopropyl active function groups, with the organoalkoxysilane of N-2-aminoethyl-3-aminopropyl active function groups, with the organoalkoxysilane of mercapto propyl group active function groups or a kind of with in the organoalkoxysilane of methacryloxypropyl active function groups, or their arbitrary combination; The catalyst A that adds and with the organoalkoxysilane of 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 functional trapezoid polysilsequioxane.
2. a kind of method for preparing functional trapezoid polysilsequioxane according to claim 1, it is characterized in that: described silane is phenyltrimethoxysila,e, methyltrimethoxy silane, phenyl triethoxysilane, Union carbide A-162, phenyl-trichloro-silicane or METHYL TRICHLORO SILANE.
3. a kind of method for preparing functional trapezoid polysilsequioxane according to claim 1, it is characterized in that: described organic solvent is toluene, dimethylbenzene or hexone.
4. a kind of method for preparing functional trapezoid polysilsequioxane according to claim 1, it 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.
5. a kind of method for preparing functional trapezoid polysilsequioxane according to claim 1, it 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.
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| WO2016048736A1 (en) * | 2014-09-22 | 2016-03-31 | 3M Innovative Properties Company | Curable polymers comprising silsesquioxane polymer core silsesquioxane polymer outer layer, and reactive groups |
| CN106009016A (en) * | 2016-08-11 | 2016-10-12 | 潘忠宁 | Method for preparing monodisperse polysilsesquioxane spherical film |
| CN107759789A (en) * | 2017-10-27 | 2018-03-06 | 黑龙江大学 | A kind of polysilsesquioxane with electrochromic property and its preparation method and application |
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| CN112646187A (en) * | 2020-05-21 | 2021-04-13 | 中国科学院上海硅酸盐研究所 | Self-crosslinking trapezoidal polysilsesquioxane polymer and preparation method and application thereof |
| CN112876986A (en) * | 2021-01-19 | 2021-06-01 | 首都师范大学 | Organic silicon transparent flexible hard coating material and preparation method thereof |
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| CN114960036A (en) * | 2022-04-07 | 2022-08-30 | 苏州大学 | Super-hydrophobic composite membrane and preparation method thereof |
| CN115558105B (en) * | 2022-10-14 | 2023-08-18 | 浙江大学 | Method for preparing functional trapezoid silsesquioxane by mesoporous molecular sieve catalysis and product thereof |
| CN115975543A (en) * | 2022-12-15 | 2023-04-18 | 成都硅宝科技股份有限公司 | Novel water-blocking tackifier and preparation method and application thereof |
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