CN104387416A - Silane-based vulcanized metal compound and preparation method thereof - Google Patents
Silane-based vulcanized metal compound and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of organic compounds, and provides a silane-based vulcanized metal compound. The structural general formula is shown in the specification, in the formula, M is one of Zn, Cu and Fe, each of R1 and R2 is one of ethyl or propyl independently, and each of R3, R4, R5, R6, R7 and R8 is independently selected from one of H, methyl and ethyl. The silane-based vulcanized metal compound has effects of a dispersing agent, a reinforcing agent and a vulcanizing activator, and can have a vulcanizing activation function in a vulcanizing process of a sizing material; besides, the compatibility of an inorganic filler and rubber macromolecules can be improved, the dispersity of the inorganic filler can be improved, and the function of the reinforcing agent can be realized when an R of an end group is hydrogen; meanwhile, the compatibility of the silane-based vulcanized metal compound and the rubber macromolecules can be also promoted by the organic groups R1 and R2, and the processability and mechanical property of the sizing material can be improved.
Description
Technical field
The invention belongs to organic compound field, be specifically related to a kind of siliceous organic compound additive and preparation thereof.
Background technology
White carbon black is a kind of important reinforced filling in rubber industry, and within 1992, a large amount of white carbon black is used for passenger car tire tread glue by company of French Michelin, has manufactured 1st generation energy-conserving and environment-protective tire, has become " green tire ".The rolling resistance of green tire reduces about 20% than conventional tyre, and have that heat-dissipating is low, anti tear and the good feature of anti-slippery.But because white carbon black particle diameter is little, easily flies upward and assemble, not easily disperseing in rubber, because which limit the application of white carbon black.
The performance of the dispersiveness of white carbon black and other performances just must be used with silane coupling agent, can say that silane coupling agent is a kind of New-type adjuvant grown up after white carbon black becomes rubber reinforcing filler, white carbon black filler can organically combine with rubber molecule by silane coupling agent effectively, improve processing characteristics and the mechanical property of rubber item, typically commercially available Si69 and Si75.Use silane coupling agent to improve the dispersiveness of white carbon black as dispersion agent, solve the affinity of white carbon black and sizing material, improve the processing characteristics of sizing material, improve the stress at definite elongation of sizing material, tensile strength, tear strength and wear resistance.Meanwhile, sulfur-bearing one type of silane coupling agent (as Si69, Si75), as containing sulfur donor, can participate in the crosslinking reaction of rubber, both can play the effect of coupling agent in the sizing material course of processing, can play again the effect of vulcanization activator.
Sulphur is unsaturated rubber, vulcanizing agent as the most frequently used in natural rubber (NR), cis-1,4-polybutadiene rubber (BR) and styrene-butadiene rubber(SBR) (SBR).Crosslinking reaction between natural rubber and sulphur be unable to do without the activation of zinc oxide, zinc oxide generates Zinic stearas with stearic acid generation chemical reaction in sulfuration early stage, coordinative activity presoma is formed with the sulfur-bearing of vulcanization accelerator or nitrogen-containing functional group, the insertion open loop of catalysis sulfur molecule, thus the reactive hydrogen atom dehydrogenation chemically crosslinked of the double bond caused in sulphur atom and unsaturated rubber molecular chain and allylic; Phase zinc oxide remains in rubber after curing, and comprehensive utilization, does not bring pollution to environment.Along with the arrival in low-carbon economy epoch, zinc pollution obtains more and more higher attention, and the substitute products of exploitation zinc oxide are subject to rubber processing aids field and more and more pay attention to.
The domestic vulcanization activator product in order to alternative zinc oxide mainly contains nano zine oxide, organic zinc etc. at present.Nano zine oxide, due to nano zine oxide, to have the little and specific surface area of particle diameter large, Zn content increased, can play reduced training, but the reunion tendency of nano zine oxide in pure state and rubber must be solved could real its effect of performance.Organic zinc compound, as products such as two methylterephthalic acid two zinc, zinc acrylate resins, organic composition is introduced in structure, decrease Zn content in organic zinc compound (being down to 40%, 30%, 25% even 20% from original 80%), organic zinc is compared with common zinc oxide has Zn content and heavy metal content is low, density is low, the feature that anti ageing property is good.Organic zinc can improve the cross-linking density of sizing material, and the intensity of Reinforced Rubber, surely controls sulfidation, does not reduce rubber physical performance, also can improve its tensile strength and elongation at break, can increase substantially the heat aging property of rubber.Meanwhile, organic zinc shows better environment-friendly type, and the minimizing of zinc element can alleviate the pollution of heavy metal to environment.
Summary of the invention
For the weak point that this area exists, the object of the invention is to propose a kind of silylation metal sulphide compound integrating coupling agent, strengthening agent and vulcanization activator.Silylation metal sulphide compound provided by the invention, both can play activation in rubber vulcanization process, improves rubber vulcanization speed; The consistency of mineral filler and rubber macromolecule can be improved again as strengthening agent, coupling agent, improve the dispersing property of mineral filler (as white carbon black), improve processing characteristics and the mechanical property of sizing material.
Another object of the present invention is the preparation method proposing described silylation metal sulphide compound.
Realizing above-mentioned purpose technical scheme of the present invention is:
A kind of silylation metal sulphide compound, its general structure is:
In formula, M is the one in Zn, Cu, Fe, R
1, R
2be ethyl or propyl group independently of each other, R
3, R
4, R
5, R
6, R
7, R
8be selected from the one in H, methyl, ethyl independently of each other.
Prepare a method for described silylation metal sulphide compound, comprise the following steps:
Step 1. takes sulfuric silane and is dissolved in organic solvent A,
Described sulfuric silane is selected from 3-mercaptopropyi Trimethoxy silane, 3-Mercaptopropyltriethoxysilane, 2-mercaptoethyl triethoxyl silane, mercapto methyl Trimethoxy silane, mercapto methyl triethoxyl silane, two (propyl-triethoxysilicane) disulphide, two (triethoxyl silane propyl group) trisulphide, two (propyl-triethoxysilicane) tetrasulfide, two (triethoxyl silane methyl) disulphide, two (triethoxyl silane methyl) trisulphide, one or more mixtures in two (triethoxyl silane methyl) tetrasulfide,
Step 2. takes fatty acid metal salt and is dissolved in organic solvent B, and described fatty acid metal salt general molecular formula is R'-COOM, R' is hydrogen or alkyl, and M is the one in Zn, Cu, Fe;
The solution of step 2 gained is added drop-wise in the solution of step 1 gained by step 3., stirred at reflux condition reaction 1 ~ 6h,
Step 4. stops stirring, and naturally cools to room temperature,
Step 5. suction filtration, washing, oven dry.
Further, in described step 1, the mass percentage concentration of sulfuric silane solution is 5 ~ 30%.
Wherein, in described step 2, the mass percentage concentration of fatty acid metal salts solution is 5 ~ 20%.
Preferably, in described step 2, described fatty acid metal salt general molecular formula is R'-COOM, and wherein R' is the alkyl of hydrogen or C1-C10, and M is Zn or Cu.
Wherein, described fatty acid metal salt is selected from the one in zinc formate, zinc acetate, zinc propionate, zinc butyrate, isocaprylic acid zinc, neutralized verdigris.
Wherein, in described step 1 and step 2, organic solvent A and organic solvent B are selected from one or more the mixture in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, the trimethyl carbinol, hexalin, ether, positive propyl ether, n-butyl ether, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane, acetone, butanone independently of each other.
Further, the filtrate that organic solvent A and organic solvent B are filtered after directly can using step 5 washing or suction filtration is discharged.Save solvent, decrease exhaust emission.
Wherein, the ratio dripping solution in step 3 is the mol ratio of sulfuric silane and fatty acid metal salt is 0.8:1 ~ 2.3:1.
Wherein, in described step 5, wash with one or more in ethanol, methyl alcohol, acetone, n-propyl alcohol, Virahol, propyl carbinol.
Wherein, in described step 5, the temperature of oven dry is preferably 40-80 DEG C.
Beneficial effect of the present invention is:
Compared with prior art, silylation metal sulphide compound provided by the invention has the effect of dispersion agent, strengthening agent and vulcanization activator concurrently, S-M-S on the one hand in molecular formula can play sulfuration activation in rubber vulcanization process, improves rubber vulcanization speed; On the other hand, the silyl group of compound end group can improve the consistency of mineral filler and rubber macromolecule, improves the dispersing property of mineral filler (as white carbon black), when the R of end group is hydrogen, the effect of strengthening agent can be played, simultaneously organic group R
1and R
2also the consistency of silylation metal sulphide compound and rubber macromolecule be can promote, processing characteristics and the mechanical property of sizing material improved, as tensile property, tear resistance and wear resistance etc.
Preparation method's technique of silylation metal sulphide compound provided by the invention is simple, raw material is easy to get, energy consumption is low, filtrate in reaction process after filtering and washing can reuse, as reaction solution or cleaning solvent, reduce the pollution to environment, reproducible, meet the developing direction of safety, green, environmental protection, there is great development prospect.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of the silylation zinc sulphide that embodiment 1 obtains.
Embodiment
Below in conjunction with drawings and Examples, the specific embodiment of the present invention is described in further detail.
Embodiment 1
Taking 8.0g zinc acetate joins in 60g methyl alcohol, forms zinc acetate/methanol solution, pour in dropping funnel for subsequent use by this solution after stirring and dissolving;
Whipping appts is equipped with in employing, the 250mL four-hole boiling flask of temperature regulating device and reflux condensate device is as reaction vessel, 15.0g 3-Mercaptopropyltriethoxysilane is added in container, then 50g ethanol is added, after stirring and dissolving, drip the zinc acetate/methanol solution in dropping funnel while stirring, drip zinc acetate/methanol solution, be warming up to stirred at reflux condition reaction, stop stirring after reaction 3h, a large amount of throw out is had to generate in solution, after above-mentioned reaction solution is naturally cooled to room temperature, carry out suction filtration, and with the solid matter that methanol wash obtains, filtrate is filtered to isolate after washing, solid after washing is placed in 45 DEG C of baking ovens and is dried to constant weight, obtain silylation zinc sulphide.
Embodiment 2
Taking 7.5g zinc acetate joins in 50g methyl alcohol, forms zinc acetate/methanol solution, pour in dropping funnel for subsequent use by this solution after stirring and dissolving;
Whipping appts is equipped with in employing, the 250mL four-hole boiling flask of temperature regulating device and reflux condensate device is as reaction vessel, 15.0g 3-mercaptopropyi Trimethoxy silane is added in container, then 35g methyl alcohol is added, after stirring and dissolving, drip the zinc acetate/methanol solution in dropping funnel while stirring, drip zinc acetate/methanol solution, be warming up to stirred at reflux condition reaction, stop stirring after reaction 1h, after naturally cooling to room temperature, above-mentioned solution is carried out suction filtration, with the solid matter that methanol wash obtains, after washing, suction filtration isolates filtrate, solid after washing is placed in 45 DEG C of baking ovens and is dried to constant weight, obtain silylation zinc sulphide.
Embodiment 3
Taking 6.8g zinc acetate joins in 50g methyl alcohol, forms zinc acetate/methanol solution, pour in dropping funnel for subsequent use by this solution after stirring and dissolving;
Whipping appts is equipped with in employing, the 250mL four-hole boiling flask of temperature regulating device and reflux condensate device is as reaction vessel, 13.5g 2-mercaptoethyl triethoxyl silane is added in container, then 100g ethanol is added, after stirring and dissolving, drip the zinc acetate/methanol solution in dropping funnel while stirring, drip zinc acetate/methanol solution, be warming up to stirred at reflux condition reaction, stirring reaction 6h, a large amount of throw out is had to generate in solution, stop stirring, after naturally cooling to room temperature, above-mentioned solution is carried out suction filtration, with the solid matter that washing with alcohol obtains, filtrate is filtered to isolate after washing, solid after washing is placed in 45 DEG C of baking ovens and is dried to constant weight, obtain silylation zinc sulphide.
Embodiment 4
Taking 10.5g isocaprylic acid zinc joins in 50g methyl alcohol, forms isocaprylic acid zinc/methanol solution, pour in dropping funnel for subsequent use by this solution after stirring and dissolving;
Whipping appts is equipped with in employing, the 250mL four-hole boiling flask of temperature regulating device and reflux condensate device is as reaction vessel, 15.0g 3-Mercaptopropyltriethoxysilane is added in container, then 100g ethanol is added, after stirring and dissolving, drip the isocaprylic acid zinc/methanol solution in dropping funnel while stirring, drip isocaprylic acid zinc/methanol solution, be warming up to stirred at reflux condition reaction, a large amount of throw out is had to generate in reaction process in solution, stop stirring after reaction 6h, after naturally cooling to room temperature, above-mentioned solution is carried out suction filtration, with the solid matter that washing with alcohol obtains, filtrate is filtered to isolate after washing, solid after washing is placed in 45 DEG C of baking ovens and is dried to constant weight, obtain silylation zinc sulphide.
Embodiment 5
Taking 8.0g zinc acetate joins in 50g methyl alcohol, forms zinc acetate/methanol solution, pour in dropping funnel for subsequent use by this solution after stirring and dissolving;
Whipping appts is equipped with in employing, the 250mL four-hole boiling flask of temperature regulating device and reflux condensate device is as reaction vessel, two (triethoxyl silane propyl group) tetrasulfide of 19.5g is added in container, then 80g ethanol is added, after stirring and dissolving, drip the zinc acetate/methanol solution in dropping funnel while stirring, drip zinc acetate/methanol solution, be warming up to stirred at reflux condition reaction, a large amount of throw out is had to generate in solution after reaction 5h, stop stirring, after naturally cooling to room temperature, above-mentioned solution is carried out suction filtration, with the solid matter that washing with alcohol obtains, filtrate is filtered to isolate after washing, solid after washing is placed in 45 DEG C of baking ovens and is dried to constant weight, obtain silylation zinc sulphide.
Embodiment 6
Taking 10.0g zinc naphthenate joins in 50g acetone, forms zinc naphthenate/acetone soln, pour in dropping funnel for subsequent use by this solution after stirring and dissolving;
Whipping appts is equipped with in employing, the 250mL four-hole boiling flask of temperature regulating device and reflux condensate device is as reaction vessel, 15.0g 3-Mercaptopropyltriethoxysilane is added in container, then 50g ethanol is added, after stirring and dissolving, drip the zinc naphthenate/acetone soln in dropping funnel while stirring, drip zinc naphthenate/acetone soln, be warming up to stirred at reflux condition reaction, a large amount of throw out is had to generate in solution, stop stirring after reaction 3h, after naturally cooling to room temperature, above-mentioned solution is carried out suction filtration, with the solid matter that washing with acetone obtains, after washing, suction filtration isolates filtrate, solid after washing is placed in 45 DEG C of baking ovens and is dried to constant weight, obtain silylation zinc sulphide.
Embodiment 7
Taking 7.2g neutralized verdigris joins in 50g ethanol, forms neutralized verdigris/ethanolic soln, pour in dropping funnel for subsequent use by this solution after stirring and dissolving;
Whipping appts is equipped with in employing, the 250mL four-hole boiling flask of temperature regulating device and reflux condensate device is as reaction vessel, 17.0g 3-Mercaptopropyltriethoxysilane is added in container, then 80g ethanol is added, after stirring and dissolving, drip the neutralized verdigris/ethanolic soln in dropping funnel while stirring, after dripping neutralized verdigris solution, be warming up to stirred at reflux condition reaction, stop stirring after reaction 5h, after above-mentioned solution is naturally cooled to room temperature, carry out suction filtration, and with the solid matter that washing with alcohol obtains, filtrate is filtered to isolate after washing, solid after washing is placed in 45 DEG C of baking ovens and is dried to constant weight, obtain silylation cupric sulfide.
Embodiment 8
With the filtrate (methanol/ethanol mixed solvent) after embodiment 1 filtering and washing for reaction solvent, prepare silylation zinc sulfide compounds.
Take 6.5g zinc acetate to join in 90g methanol/ethanol mixed solvent, form zinc acetate/alcoholic solution after stirring and dissolving, this solution is poured in dropping funnel for subsequent use;
Whipping appts is equipped with in employing, the 250mL four-hole boiling flask of temperature regulating device and reflux condensate device is as reaction vessel, 15.0g 3-Mercaptopropyltriethoxysilane is added in container, then 50g methanol/ethanol mixed solvent is added, after stirring and dissolving, drip the zinc acetate/alcoholic solution in dropping funnel while stirring, drip and be warming up to stirred at reflux condition reaction, a large amount of throw out is had to generate in solution after reaction 5h, stop stirring, after naturally cooling to room temperature, above-mentioned solution is carried out suction filtration, with the solid matter that methanol wash obtains, solid after washing is placed in 45 DEG C of baking ovens and is dried to constant weight, obtain silylation zinc sulphide.
Experimental example 1: examination of infrared spectrum:
Adopt NICOLET 6700FT-IR infrared spectrometer (America NI COLET company) test, test analysis is carried out to embodiment 1 ~ 8 products therefrom.Wherein, the silylation zinc sulphide that embodiment 1 obtains carries out analyzing (Fig. 1):
3423cm
-1near be the stretching vibration peak of-OH in Si-OH;
2974cm
-1neighbouring is-CH
3symmetrical stretching vibration peak;
2841cm
-1and be-CH near 2928cm-1
2-symmetric and anti-symmetric stretching vibration peak;
1251cm
-1near be the stretching vibration peak of Si-C;
It is the stretching vibration peak of Si-O in 960 ~ 1200cm-1 region.
Also there is above-mentioned diffraction peak in the IR spectrogram that embodiment 2 ~ 8 obtains product, illustrate in embodiment 1 ~ 8 and obtain in product containing Si-OH ,-CH in corresponding region
2-, the group such as Si-O (Si-O-Si), be consistent with the structural formula of target product.In addition, adopt the filtrate after washing and filtering to prepare the IR spectrogram of product as reaction solution in embodiment 8 consistent with the IR spectrogram that embodiment 1 obtains product, illustrate that experimental repeatability is good using filtrate again as reaction solvent synthesizing silane base sulfide.
Experimental example 2: constituent content is tested
Employing GB4497-84 testing example 1 ~ 8 obtains the sulphur content in silylation sulfide sample;
Employing ASTM D297-93 testing example 1 ~ 8 obtains the dioxide-containing silica in silylation sulfide sample, converses wherein silicone content;
GB/T 4500-2003 testing example 1 ~ 8 is adopted to obtain Zn content in silylation sulfide sample;
Constituent content test result is as shown in table 1.
The constituent content test result of table 1. embodiment 1 ~ 8 silylation sulfide sample
| Constituent content | S(％) | Zn(％) | SiO 2(％) | Si(％) |
| Embodiment 1 | 11.4 | 11.6 | 23.4 | 10.9 |
| Embodiment 2 | 13.1 | 14.5 | 27.1 | 12.6 |
| Embodiment 3 | 12.0 | 12.6 | 23.2 | 10.8 |
| Embodiment 4 | 11.2 | 10.9 | 21.6 | 10.1 |
| Embodiment 5 | 12.0 | 10.2 | 23.2 | 10.8 |
| Embodiment 6 | 10.9 | 11.2 | 20.9 | 9.8 |
| Embodiment 7 | 11.6 | — | 22.3 | 10.4 |
| Embodiment 8 | 9.20 | 12.7 | 27.07 | 12.6 |
In conjunction with ultimate analysis and spectrum test, determine that product that the preparation method that the present invention proposes obtains is the compound of structural formula (I).
The performance test of experimental example 3. sample in sizing material
The silylation sulfide obtained for embodiment 1 tests its performance in rubber, its test formulations table and test result as follows, wherein formula 1 is blank, add Si69 (two (triethoxyl silane propyl group) tetrasulfide) as a comparison case in formula 2, in formula 3, add embodiment 1 silylation zinc sulphide processed; Add embodiment 7 silylation cupric sulfide processed in formula 4, other each compositions are with formula 3.
The basic formula table of table 2. rubber
The preparation of sample
According to formula 1-4, with 1.6 liters of Bambury Banbury mixeies, by other compound beyond rubber, carbon black and sulphur and vulcanization accelerator 6 minutes, to obtain master batch, then use opening rubber mixing machine in master batch, mix vulcanization accelerator and sulphur, thus acquisition rubber combination, the sulfuration 60 minutes at the temperature of 150 DEG C of often kind of rubber combination obtained like this, thus obtain vulcanized rubber.
Test its processing characteristics, curability and physicals to four vulcanized rubbers obtained by above-mentioned formula and preparation method, test result is as shown in table 3:
Table 3. performance formula test result
As can be seen from Table 3, silylation zinc sulphide (formula 3) or silylation cupric sulfide (formula 4) is added in formula, the curing time (T90) of sizing material is shorter, vulcanization rate is faster, to illustrate that in sulfidation silylation zinc sulphide or silylation cupric sulfide serve and well activate promoter action, time of scorch (Ts5) slightly shortens simultaneously; Fill a prescription 3 maximum torques (MH) and tensile modulus higher, illustrate and add that the hardness of sizing material after silylation zinc sulphide or silylation cupric sulfide is higher, cross-linking density is larger, match with tensile strength at yield, tear strength and hardness (Shao A) result.
According to GB/T 6030-2006, adopt U.S. Tai Pu company Dispergrader+100 carbon black dispersion instrument to test the dispersing property of white carbon black in above-mentioned four formulas, its test result is in table 4.
The dispersed detected result of table 4. white carbon black in master batch
List the dispersancy data of white carbon black in four corresponding sizing materials of formula in table 4, wherein X represents white carbon black dispersion grade in sizing material, and X value is larger, and dispersion higher grade, illustrates that the dispersion state of sample is better.As can be seen from Table 4, after adding silylation zinc sulphide or silylation cupric sulfide in formula, the dispersing property of white carbon black in sizing material significantly improves.In addition, because silylation metal sulphide has higher sulfurate activity, the dispersing property of white carbon black in sizing material is made to compare formula 2 slightly well.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the technology of the present invention principle; can also make some improvement and replacement, these improve and replace and also should be considered as protection scope of the present invention.
Claims (10)
1. a silylation metal sulphide compound, is characterized in that, general structure is:
In formula, M is the one in Zn, Cu, Fe, R
1, R
2be ethyl or propyl group independently of each other, R
3, R
4, R
5, R
6, R
7, R
8be selected from the one in H, methyl, ethyl independently of each other.
2. prepare a method for silylation metal sulphide compound according to claim 1, it is characterized in that, comprise the following steps:
Step 1. takes sulfuric silane and is dissolved in organic solvent A,
Described sulfuric silane is selected from 3-mercaptopropyi Trimethoxy silane, 3-Mercaptopropyltriethoxysilane, 2-mercaptoethyl triethoxyl silane, mercapto methyl Trimethoxy silane, mercapto methyl triethoxyl silane, two (propyl-triethoxysilicane) disulphide, two (triethoxyl silane propyl group) trisulphide, two (propyl-triethoxysilicane) tetrasulfide, two (triethoxyl silane methyl) disulphide, two (triethoxyl silane methyl) trisulphide, one or more mixtures in two (triethoxyl silane methyl) tetrasulfide,
Step 2. takes fatty acid metal salt and is dissolved in organic solvent B, and described fatty acid metal salt general molecular formula is R'-COOM, R' is hydrogen or alkyl, and M is the one in Zn, Cu, Fe;
The solution of step 2 gained is added drop-wise in the solution of step 1 gained by step 3., stirred at reflux condition reaction 1 ~ 6h,
Step 4. stops stirring, and naturally cools to room temperature,
Step 5. suction filtration, washing, oven dry.
3. method according to claim 2, is characterized in that, in described step 1, the mass percentage concentration of sulfuric silane solution is 5 ~ 30%.
4. method according to claim 2, is characterized in that, in described step 2, the mass percentage concentration of fatty acid metal salts solution is 5 ~ 20%.
5. method according to claim 2, is characterized in that, in described step 2, described fatty acid metal salt general molecular formula is R'-COOM, and wherein R' is the alkyl of hydrogen or C1-C10, and M is Zn or Cu.
6. method according to claim 5, is characterized in that, described fatty acid metal salt is selected from the one in zinc formate, zinc acetate, zinc propionate, zinc butyrate, isocaprylic acid zinc, neutralized verdigris.
7. according to the arbitrary described method of claim 2-5, it is characterized in that, in described step 1 and step 2, organic solvent A and organic solvent B are selected from one or more the mixture in methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, the trimethyl carbinol, hexalin, ether, positive propyl ether, n-butyl ether, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane, acetone, butanone independently of each other.
8. according to the arbitrary described method of claim 2-5, it is characterized in that, the ratio dripping solution in step 3 is the mol ratio of sulfuric silane and fatty acid metal salt is 0.8:1 ~ 2.3:1.
9., according to the arbitrary described method of claim 2-5, it is characterized in that, in described step 5, wash with one or more in ethanol, methyl alcohol, acetone, n-propyl alcohol, Virahol, propyl carbinol.
10., according to the arbitrary described method of claim 2-5, it is characterized in that, the temperature of drying in described step 5 is 40-80 DEG C.
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