CN111040177A - Silicon-titanium oligomer containing bifunctional group and preparation method thereof - Google Patents
Silicon-titanium oligomer containing bifunctional group and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a silicon-titanium oligomer containing bifunctional groups and a preparation method thereof, belonging to the field of materials. Firstly, two siloxanes are cohydrolyzed to obtain silanol containing two functional groups, and then the silanol and titanate are subjected to condensation reaction to prepare the silicon-titanium oligomer containing two functional groups. The oligomer can be used for preparing sealants, adhesives, modifiers and the like, and has good application prospects in the fields of aerospace, transportation, petrochemical industry, ship manufacturing and the like.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a silicon-titanium oligomer containing bifunctional groups and a preparation method thereof.
Background
The molecular chain of the organic silicon polymer is mainly composed of Si-O bonds, and the organic silicon polymer is widely applied to various fields due to excellent performances of high and low temperature resistance, insulation, aging resistance and the like. Titanium is a metal element, which is introduced into polysiloxanes by russian researchers in the last 60 th century to obtain a silicon-titanium polymer with excellent properties. The research shows that the organic silicon titanium polymer has better heat resistance, solvent resistance, adhesion and higher strength. Can be applied to the fields of aerospace, transportation, ship manufacturing, petrochemical industry and the like. Early russian researchers used chlorosilane to react with titanate in a basic system to obtain silicon titanium polymers, but at lower yields. The subsequent synthesis of silicon-titanium polymers with different structures, in particular with different substituents on the silicon atom, has attracted considerable attention. Various organic silicon or semi-organic semi-inorganic polymers are generated by hybridizing titanium-containing compounds with silane and hydroxysilane. The silicon-titanium polymer can be used as a coupling agent, a catalyst, a polymer modifier, a ceramic precursor and the like. However, so far, literature reports that a silicon-titanium polymer containing terminal hydroxyl is mainly synthesized, so that subsequent curing and modification reactions are single, and the improvement of heat resistance is limited. Therefore, the silicon-titanium oligomer containing the bifunctional group is designed and synthesized by the patent, can be subjected to condensation reaction and addition reaction, and is beneficial to subsequent curing and modification reaction, so that the performance of the silicon-titanium polymer is improved.
Disclosure of Invention
The invention provides a silicon-titanium oligomer containing bifunctional groups and a preparation method thereof. Firstly, two siloxanes are used for cohydrolysis and de-ethoxylation to obtain silanol containing two functional groups, and then the silanol and titanate are subjected to condensation reaction to prepare the silicon-titanium oligomer containing two functional groups. The oligomer can be used for preparing sealants, adhesives, modifiers and the like, and has good application prospects in the fields of aerospace, transportation, petrochemical industry, ship manufacturing and the like.
The invention provides a silicon-titanium oligomer containing bifunctional groups, which has a structure shown as a general formula I:
wherein R is1Is C1-C18A linear or branched alkyl or cycloalkyl group of (a); r3Is H atom or C1-C16The linear alkyl group of (1); r5Is C4A linear or branched alkyl group of (a); x is 4 to 9, y is 10 to x, and z is (x + y)/2 to 20.
The invention also provides a preparation method of the silicon-titanium oligomer containing the bifunctional group, which comprises the following steps:
(1) and (3) carrying out co-hydrolysis reaction: dissolving siloxane a and siloxane b in an organic solvent, and stirring to obtain a silane mixed solution; mixing an organic solvent, water and an inorganic acid to obtain a mixed solvent, and then dropwise adding a silane mixed solution into the mixed solvent under a stirring state to perform a cohydrolysis reaction; washing the product with water for 3-5 times to neutrality after the reaction is finished, drying the product with anhydrous calcium chloride, and finally drying the product in a vacuum drying oven at the temperature of 50 ℃ for 3 hours to constant weight to obtain colorless viscous liquid, namely cohydrolysis silanol c;
(2) condensation reaction: respectively dissolving a compound d and the cohydrolyzed silanol c obtained in the step (1) in a dry organic solvent, dropwise adding a compound d solution into a cohydrolyzed silanol c solution at room temperature, continuously stirring while dropwise adding, raising the reaction temperature after dropwise adding is finished, carrying out condensation reaction, and keeping the whole reaction process in a reduced pressure distillation state; removing the solvent from the product after the reaction, and drying the product for 3 hours in a vacuum drying oven at the temperature of 60 ℃ to constant weight to obtain light yellow viscous liquid, namely the silicon-titanium oligomer containing the bifunctional group;
further, R in the siloxane a1Is C1-C18A linear or branched alkyl or cycloalkyl group of (a); r2Is C1-C5Linear or branched alkyl groups of (a). Preferably, R1Is C6-C8Straight-chain alkyl radicals of, e.g., - (CH)2)5CH3、-(CH2)7CH3；R2Is C1-C2Straight-chain alkyl radicals of, e.g. -CH3、-CH2CH3. Specific examples are: n-octyltrimethoxysilane, n-octyltriethoxysilane, preferably n-octyltriethoxysilane. R in the siloxane b3Is H atom or C1-C16Straight chain alkyl group of；R4Is C1-C5Linear or branched alkyl groups of (a). Preferably, R3Is H atom, C1-C2Straight-chain alkyl radicals of, e.g. -CH3、-CH2CH3；R4Is C1-C2Straight-chain alkyl radicals of, e.g. -CH3、-CH2CH3. Specific examples are: vinyltrimethoxysilane, vinyltriethoxysilane, preferably vinyltriethoxysilane.
Further, the molar ratio of the siloxane a to the siloxane b in the step (1) is 4-9:6-1, preferably 7-8: 3-2.
Further, the organic solvent in step (1) is diethyl ether, petroleum ether, methanol, ethanol, propanol or isopropanol, preferably diethyl ether.
Further, the molar ratio of water to organic solvent in step (1) is 1-10:1, preferably 1-3: 1.
Further, the inorganic acid in the step (1) is hydrochloric acid or sulfuric acid, preferably hydrochloric acid. The inorganic acid has a concentration of 10-30%, preferably 10%, and is added in an amount of 0.5-10 ml.
Further, the conditions of the cohydrolysis reaction in the step (1) are as follows: the dropping speed is 0.01-2.0ml/s, preferably 0.1-0.2 ml/s; the stirring speed is 100-10000rpm, preferably 1000-2000 rpm; the reaction temperature is 10-60 ℃, preferably 25-34 ℃; the reaction time is from 1 to 48 hours, preferably from 18 to 36 hours.
Further, R in the compound d in the step (2)5Is C1-C8Linear or branched alkyl of, preferably, R5Is C4Linear or branched alkyl groups of (a). Specific examples are: tetrabutyl titanate and tetraisobutyl titanate, preferably tetrabutyl titanate.
Further, the mol ratio of the cohydrolyzed silanol c and the compound d in the step (2) is 2-20: 1, preferably 8: 1.
further, the organic solvent in the step (2) is benzene, toluene, xylene, n-hexane, cyclohexane or tetrahydrofuran, preferably toluene or benzene.
Further, after the dropwise addition in the step (2) is completed, raising the reaction temperature to perform a condensation reaction; the conditions of the condensation reaction are as follows: the dropping speed is 0.01-2.0ml/s, preferably 0.1-0.2 ml/s; the stirring speed is 100-10000rpm, preferably 1000-2000 rpm; the reaction temperature is 10-80 ℃, preferably 45-55 ℃; the reaction time is 0.5 to 12 hours, preferably 1.5 to 3 hours.
The invention has the beneficial effects that the silicon-titanium oligomer containing two functional groups is prepared by using two silanes as raw materials through cohydrolysis and direct synthesis. The oligomer can be subjected to condensation reaction and addition reaction, and overcomes the defect that the oligomer contains a silicon-titanium oligomer with a functional group so as to meet different performance requirements. The prepared oligomer can be used for sealing agents, adhesives, modifiers and the like, and can improve the heat resistance of polymers such as liquid fluororubber, epoxy resin, polyurethane and the like if the oligomer is used as a polymer modifier. The silicon-titanium oligomer has the advantages of simple preparation process, more raw material sources and easy industrialization.
Drawings
FIG. 1 is an IR spectrum of n-octylsilanol and n-octyltitanosilicate oligomer in comparative example 1.
FIG. 2 is a thermogravimetric plot of n-octylsilanol and n-octyltitanosilicate oligomers in comparative example 3.
FIG. 3 is an IR spectrum of cohydrolyzed silanol and cohydrolyzed titanosilicate oligomer of example 1.
FIG. 4 is a graph of the thermogravimetric curves of cohydrolyzed silanol and cohydrolyzed titanosilicate oligomers in example 1.
FIG. 5 is a comparison of the weight loss on heating of n-octylsilicontitanium oligomer of comparative example 3 and cohydrolyzed silicontitanium oligomer of example 1.
Detailed Description
The following non-limiting examples will allow one of ordinary skill in the art to more fully understand the present invention, but are not intended to limit the invention in any way.
Comparative example 1
(1) Hydrolysis of n-octyl triethoxy siloxane: taking a 250ml three-mouth round-bottom flask as a reaction container, weighing 0.50mol of n-octyl triethoxysilane, dissolving in 10ml of diethyl ether, and uniformly stirring to obtain a silane solution; 1.5mol of distilled water was mixed with 1.0mol of diethyl ether to obtain a mixed solvent, and 2.5ml of 10% hydrochloric acid was added dropwise. The siloxane solution was then added dropwise to a mixed solvent of distilled water and ether using a constant pressure funnel. The dropping speed was controlled to 0.1ml/s, the rotation speed of the stirring shaft was controlled to 1000rpm, the reaction temperature was 50 ℃ and the reaction time was 5 hours. And (3) after the reaction is finished, washing the product for 3-5 times to be neutral, drying the product by using anhydrous calcium chloride, and finally drying the product in a vacuum drying oven at the temperature of 50 ℃ for 3 hours to constant weight to obtain colorless viscous liquid, namely the silanol.
(2) Condensation of silanol with tetrabutyl titanate: taking a 250ml three-mouth round-bottom flask as a reaction container, dissolving 1mol of tetrabutyl titanate in 5ml of dry toluene, weighing 4mol of silanol obtained in the step (1) and dissolving in 10ml of dry toluene, dropwise adding tetrabutyl titanate solution into the silanol solution by using a constant-pressure funnel at room temperature under stirring for condensation reaction, controlling the dropwise adding speed to be 0.1ml/s, after the tetrabutyl titanate solution is completely dropwise added into the silanol solution, increasing the reaction temperature to 45 ℃, controlling the reaction time to be 1.5 hours, and keeping the whole reaction process in a reduced pressure distillation state. After the reaction, the product was subjected to rotary evaporation at 75 ℃ for 1.5 hours to remove the solvent. And drying the product in a vacuum drying oven at the temperature of 60 ℃ for 3 hours to constant weight to obtain light yellow viscous liquid, namely the silicon-titanium oligomer.
As shown in FIG. 1, the infrared analysis results of n-octylsilicon titanium oligomer were as follows: 925cm-1(Si-O-Ti)，3229cm-1(Si-OH),780cm-1(Ti-O-Ti)。
Comparative examples 2 to 5
The preparation process of comparative example 1 was followed except that the molar ratio of silanol to tetrabutyl titanate was varied, and the specific ratios and results are shown in Table 1.
TABLE 1
TGA (thermogravimetric analysis) tests of comparative examples 1-5 show that the heat resistance of the product is best at a molar ratio of silanol to tetrabutyl titanate of 10:1 (the heat resistance of the product is expressed as 800 ℃), as shown in FIG. 2, the initial decomposition temperature is up to 448 ℃ and the 800 ℃ residue is up to about 39%.
Example 1
(1) Co-hydrolysis: taking a 250ml three-mouth round-bottom flask as a reaction container, respectively weighing 0.8mol of n-octyl triethoxysilane and 0.2mol of vinyl triethoxysilane, dissolving in 20ml of diethyl ether, and stirring to obtain a silane solution; 2mol of distilled water was mixed with 1.0mol of diethyl ether to obtain a mixed solvent, and 5ml of 10% hydrochloric acid was added dropwise. Then, the silane solution was added dropwise to a mixed solvent of distilled water and ether using a constant pressure funnel. The dropping speed was controlled to 0.1ml/s, the rotation speed of the stirring shaft was controlled to 1000rpm, the reaction temperature was 25 ℃ and the reaction time was 18 hours. And (3) after the reaction is finished, washing the product for 3-5 times to be neutral, drying the product by using anhydrous calcium chloride, and finally drying the product in a vacuum drying oven for 3 hours to constant weight at the temperature of 50 ℃ to obtain colorless viscous liquid, namely co-hydrolyzed n-octyl vinyl silanol.
(2) Condensation of silanol with tetrabutyl titanate: taking a 250ml three-mouth round-bottom flask as a reaction container, dissolving 1mol of tetrabutyl titanate in 10ml of dry toluene, weighing 8mol of silanol obtained in the step (1) and dissolving in 20ml of dry toluene, dropwise adding tetrabutyl titanate solution into the silanol solution by using a constant-pressure funnel at room temperature under stirring for condensation reaction, controlling the dropwise adding speed to be 0.1ml/s, after the tetrabutyl titanate solution is completely dropwise added into the silanol solution, increasing the reaction temperature to 45 ℃, controlling the reaction time to be 1.5 hours, and keeping the whole reaction process in a reduced pressure distillation state. After the reaction was completed, the solvent was removed by rotary evaporation at 75 ℃ for 1.5 hours. And drying the product in a vacuum box at the temperature of 60 ℃ for 3 hours to constant weight to obtain light yellow viscous liquid, namely the silicon-titanium oligomer.
The yield of the product was 91%, the initial decomposition temperature was 468 ℃ and the residual rate at 800 ℃ was 44% (FIG. 4).
As shown in FIG. 3, the results of infrared analysis of the cohydrolyzed silicon-titanium oligomer were as follows: 925cm-1(Si-O-Ti)，3229cm-1(Si-OH),780cm-1(Ti-O-Ti)，1560cm-1(C＝C)。
Examples 2 to 5
The preparation process according to example 1 was followed, except that the ratio of n-octyltriethoxysilane to vinyltriethoxysilane was varied, and the specific ratios and results are shown in Table 2.
TABLE 2
Examples 6 to 9
The preparation method according to example 1 was followed, except that the ratio of distilled water to organic solvent in the first cohydrolysis reaction was varied, and the specific ratio and results are shown in Table 3.
TABLE 3
Examples 10 to 13
The preparation process according to example 1 was carried out, except that the amount of the inorganic acid (hydrochloric acid) used in the first cohydrolysis reaction was varied, and the specific amounts and results are shown in Table 4.
TABLE 4
Examples 14 to 18
The preparation process according to example 1 was carried out, except that the reaction time in the first cohydrolysis reaction was varied, and the specific time and results are shown in Table 5.
TABLE 5
Examples 19 to 21
The preparation process according to example 1 was followed, except that the ratio of n-octylvinylsilol to tetrabutyl titanate was varied, and the specific ratios and results are shown in Table 6.
TABLE 6
Examples 22 to 24
The preparation process according to example 1 was carried out, except that the organic solvent used in the second condensation reaction was different, and the specific solvents and results are shown in Table 7.
TABLE 7
Examples 25 to 27
The production process according to example 1 was carried out, except that the reaction temperature in the second condensation reaction was varied, and the specific temperature and results are shown in Table 8.
TABLE 8
Examples 28 to 31
The preparation process according to example 1 was carried out, except that the reaction time in the second condensation reaction was varied, and the specific time and results are shown in Table 9.
TABLE 9
TGA tests performed on the prepared samples showed that the initial decomposition temperature of the product prepared according to the present invention could reach above 435 ℃, wherein the heat resistance of the product obtained in example 1 was the best, and the initial decomposition temperature was up to 468 ℃, and the residual rate at 800 ℃ was up to about 44% (see fig. 4).
Compared with comparative examples 1-5, the silicon-titanium oligomer obtained in examples 1-31 has obviously improved residual rate at 800 ℃. It was demonstrated that the introduction of vinyl groups into the silicon-titanium oligomer by the cohydrolysis method can improve its heat resistance (see fig. 2 and 5).
The results show that the silicon-titanium oligomer containing the bifunctional groups has simple preparation process, high yield and good heat resistance, is higher than common organic matters and even heat-resistant polymers, and can carry out condensation reaction and addition reaction. Therefore, the oligomer can be used as a high-temperature-resistant sealant, an adhesive, a modifier and the like, and has good application prospects in the fields of aerospace, transportation, petrochemical industry, ship manufacturing and the like.
The embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. The bifunctional silicon-titanium oligomer is characterized in that the structure of the silicon-titanium oligomer is shown as the general formula I:
wherein R is1Is C1-C18A linear or branched alkyl or cycloalkyl group of (a); r3Is H atom or C1-C16The linear alkyl group of (1); r5Is C4A linear or branched alkyl group of (a); x is 4 to 9, y is 10 to x, and z is (x + y)/2 to 20.
2. The method of preparing a bifunctional silicon-titanium oligomer of claim 1, comprising the steps of:
(1) and (3) carrying out co-hydrolysis reaction: dissolving siloxane a and siloxane b in an organic solvent, and stirring to obtain a silane mixed solution; mixing an organic solvent, water and an inorganic acid to obtain a mixed solvent, and then dropwise adding a silane mixed solution into the mixed solvent under a stirring state to perform a cohydrolysis reaction; after the reaction is finished, washing the product to be neutral by water, and drying to constant weight to obtain cohydrolysis silanol c;
(2) condensation reaction: respectively dissolving a compound d and the cohydrolyzed silanol c obtained in the step (1) in a dry organic solvent, dropwise adding a compound d solution into a cohydrolyzed silanol c solution at room temperature, continuously stirring while dropwise adding, raising the reaction temperature after dropwise adding is finished, carrying out condensation reaction, and keeping the whole reaction process in a reduced pressure distillation state; removing the solvent from the product after the reaction, and drying to obtain a silicon-titanium oligomer containing bifunctional groups;
3. the method according to claim 2, wherein R in said siloxane a is2Is C1-C5A linear or branched alkyl group of (a); r in siloxane b4Is C1-C5Linear or branched alkyl groups of (a).
4. The method according to claim 2, wherein the molar ratio of siloxane a to siloxane b in step (1) is 4 to 9: 6-1.
5. The method according to claim 2, wherein the organic solvent in step (1) is diethyl ether, petroleum ether, methanol, ethanol, propanol or isopropanol; the mol ratio of water to organic solvent in the step (1) is 1-10: 1.
6. the production method according to claim 2, wherein the inorganic acid in the step (1) is hydrochloric acid or sulfuric acid; the inorganic acid has a concentration of 10-30% and is added in an amount of 0.5-10 ml.
7. The method according to claim 2, wherein the conditions of the cohydrolysis reaction in the step (1) are as follows: the dropping speed is 0.01-2.0ml/s, the stirring speed is 100-10000rpm, the reaction temperature is 10-60 ℃, and the reaction time is 1-48 hours.
8. The method according to claim 2, wherein the molar ratio of cohydrolyzed silanol c to compound d in step (2) is 2 to 20: 1.
9. the method according to claim 2, wherein the organic solvent in the step (2) is benzene, toluene, xylene, n-hexane, cyclohexane or tetrahydrofuran.
10. The production method according to claim 2, wherein after completion of the dropwise addition in the step (2), the condensation reaction is carried out by raising the reaction temperature; the conditions of the condensation reaction are as follows: the dropping speed is 0.01-2.0ml/s, the stirring speed is 100-10000rpm, the reaction temperature is 10-80 ℃, and the reaction time is 0.5-12 hours.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5663845A (en) * | 1979-10-26 | 1981-05-30 | Nippon Kogaku Kk <Nikon> | Inorganic substance product having surface layer rendered hydrophilic and its manufacture |
| US5548050A (en) * | 1994-02-25 | 1996-08-20 | Dow Cornings Asia, Ltd. | Method for the preparation of organic solvent-soluble polytitanosiloxanes |
| CN103408763A (en) * | 2013-04-08 | 2013-11-27 | 北京化工大学 | Method for preparing silicon-titanium polymers |
| CN104774334A (en) * | 2015-03-08 | 2015-07-15 | 北京化工大学 | Preparation method for silicon-titanium polymer capable of being used as additive |
| CN105399956A (en) * | 2015-11-25 | 2016-03-16 | 烟台德邦先进硅材料有限公司 | High-temperature-resistant high-refractive-index Ti-containing organic silicon resin and preparation method thereof |
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- 2019-12-25 CN CN201911354956.0A patent/CN111040177A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5663845A (en) * | 1979-10-26 | 1981-05-30 | Nippon Kogaku Kk <Nikon> | Inorganic substance product having surface layer rendered hydrophilic and its manufacture |
| US5548050A (en) * | 1994-02-25 | 1996-08-20 | Dow Cornings Asia, Ltd. | Method for the preparation of organic solvent-soluble polytitanosiloxanes |
| CN103408763A (en) * | 2013-04-08 | 2013-11-27 | 北京化工大学 | Method for preparing silicon-titanium polymers |
| CN104774334A (en) * | 2015-03-08 | 2015-07-15 | 北京化工大学 | Preparation method for silicon-titanium polymer capable of being used as additive |
| CN105399956A (en) * | 2015-11-25 | 2016-03-16 | 烟台德邦先进硅材料有限公司 | High-temperature-resistant high-refractive-index Ti-containing organic silicon resin and preparation method thereof |
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