CN109180718B - Preparation method of peroxide silane coupling agent - Google Patents
Preparation method of peroxide silane coupling agent Download PDFInfo
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- CN109180718B CN109180718B CN201810990461.6A CN201810990461A CN109180718B CN 109180718 B CN109180718 B CN 109180718B CN 201810990461 A CN201810990461 A CN 201810990461A CN 109180718 B CN109180718 B CN 109180718B
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Abstract
The invention provides a preparation method of a peroxide silane coupling agent, which comprises the steps of mixing 1, 1-di-tert-butyl peroxide-4-hydroxycyclohexane, tetramethoxysilane, titanium tetrachloride and an aprotic solvent, adding diisopropylcarbodiimide at the temperature of 0-5 ℃, and controlling the reaction temperature to be 25-50 ℃ after the diisopropylcarbodiimide is added to obtain the peroxide silane coupling agent. The adding process of the diisopropylcarbodiimide is controlled to be between 0 and 5 ℃, so that the reaction of the intermediate in the transition state and the 1, 1-tert-butyl peroxide-4-hydroxycyclohexane can be promoted, the probability of generating a byproduct by self rearrangement of the intermediate in the transition state is reduced, the occurrence of side reactions can be greatly reduced, the reaction yield is improved, and the yield is 90 to 96 percent by calculation.
Description
Technical Field
The invention belongs to the technical field of preparation of silane coupling agents, and particularly relates to a preparation method of a peroxide silane coupling agent.
Background
The coupling agent is used as a bridge for improving the interface between inorganic materials and organic materials, and the application range of the coupling agent is wider and wider. Wherein, the silane coupling agent is the one with the largest dosage and the largest variety at present. The silane coupling agent is an organosilicon monomer with more than two different reactive groups in the molecule, and can be chemically bonded with organic and inorganic materials to increase the adhesion of the two materials. The structural general formula of the silane coupling agent is RSiX3Wherein X represents an alkoxy group capable of hydrolysis, such as halogen, alkoxy group, acyloxy group, etc., and R represents a reactive functional group having affinity or reactivity with a polymer molecule, such as oxy group, mercapto group, vinyl group, epoxy group, amide group, aminopropyl group, etc. In recent years, silane coupling agents have been the hot spot of research and development because they have achieved good results in modifying polymer matrices by using a combination of inorganic particle modification and graft polymer modification.
In order to graft-polymerize a high polymer on the surface of an inorganic material, the inorganic material is usually surface-treated with a coupling agent containing vinyl and epoxy groups, unsaturated carbon-carbon double bonds or epoxy groups are introduced, and then an initiator is added to initiate polymerization of the high polymer. The coupling agent is utilized to coat the inorganic particles, and the polymer is grafted on the surface of the inorganic particles, so that the compatibility of the inorganic particles and a polymer matrix is greatly improved, and the comprehensive performance of the inorganic particles is also improved.
For example, the prior art discloses a preparation method of a peroxide silane coupling agent, which specifically comprises the following steps of mixing 1, 1-di-tert-butyl peroxide-4-hydroxycyclohexane and tetramethoxysilane, adding the mixture into a reaction kettle, adding toluene serving as a solvent, stirring and reacting for 3-48 hours at the temperature of-10 ℃ to 50 ℃, and separating and purifying a product to obtain the peroxide silane coupling agent 1, 1-di-tert-butyl peroxide-4-hydroxycyclohexyl trimethoxysilane. The coupling agent prepared by the preparation method has one end with a hydrolyzable methoxy group and the other end with a peroxy group capable of initiating polymerization, and can be used in the combined reaction of inorganic particle surface modification and graft polymer, but the yield of the silane coupling agent in the technology is to be further improved. In view of this, it is an urgent technical problem for those skilled in the art to improve the existing preparation method of the peroxide silane coupling agent to increase the reaction yield.
Disclosure of Invention
The invention aims to overcome the defect of low yield of the existing preparation method of the peroxide silane coupling agent, and further provides a preparation method of the peroxide silane coupling agent.
The technical scheme adopted by the invention for solving the technical problems is as follows:
in a first aspect of the present invention, there is provided a method for preparing a peroxidic silane coupling agent, comprising the steps of:
(1) mixing 1, 1-di-tert-butyl peroxide-4-hydroxycyclohexane, tetramethoxysilane, titanium tetrachloride and an aprotic solvent;
(2) controlling the temperature to be 0-5 ℃, and adding diisopropylcarbodiimide into the mixture in the step (1);
(3) and (3) after the step (2) is finished, controlling the temperature to be 25-50 ℃, and filtering to obtain the peroxide silane coupling agent.
In the preparation method of the peroxide silane coupling agent, the molar ratio of the 1, 1-di-tert-butyl peroxide-4-hydroxycyclohexane to the tetramethoxysilane, the titanium tetrachloride and the diisopropylcarbodiimide is 1 (0.2-5.0): (0.01-0.05): 0.5-1, preferably 1:2.5:0.02: 0.8.
The aprotic solvent is CHCl3、CH2Cl2Or CCl4One or more of (a).
In the step (2), the method further comprises dissolving the diisopropylcarbodiimide in the aprotic solvent, and adding dropwise the solution into the mixture in the step (1) while stirring.
In the step (1), the preparation method of the 1, 1-di-tert-butyl peroxide-4-hydroxycyclohexane comprises the following steps:
mixing tert-butyl hydroperoxide with 4-hydroxycyclohexanone, controlling the temperature to be-10-20 ℃, adding concentrated sulfuric acid while stirring, continuing to stir and react for 4-10 h, preferably 5-8 h at the temperature of-10-20 ℃ after dropwise addition, washing, filtering and drying the obtained product to obtain the 1, 1-tert-butyl-4-hydroxycyclohexane.
The molar ratio of the tert-butyl hydroperoxide to the 4-hydroxycyclohexanone is 1: (2-10), preferably 1: (5-8).
Preferably, the concentration of the concentrated sulfuric acid is 98 wt%, the ratio of the mass part of the tert-butyl hydroperoxide to the volume part of the concentrated sulfuric acid is (10-20): 1, preferably (12-18): 1, and the relationship between the mass part and the volume part is g/m L.
In the above method for preparing a peroxidic silane coupling agent, the step (3) further comprises a step of purifying the obtained peroxidic silane coupling agent, which comprises:
washing the prepared peroxide silane coupling agent with the aprotic solvent, dissolving a filter cake in a mixed solvent with the volume ratio of acetone to water being (1-3) - (1-2), preferably 2:1.5, cooling for crystallization, and filtering to obtain the purified peroxide silane coupling agent.
In a second aspect of the present invention, there is provided a peroxide silane coupling agent prepared by the above-mentioned method for preparing a peroxide silane coupling agent.
The technical scheme of the invention has the following advantages:
1. the preparation method of the peroxide silane coupling agent comprises the steps of mixing 1, 1-di-tert-butyl peroxide-4-hydroxycyclohexane, tetramethoxysilane, titanium tetrachloride and an aprotic solvent, adding diisopropylcarbodiimide at the temperature of 0-5 ℃, and controlling the reaction temperature to be 25-50 ℃ after the diisopropylcarbodiimide is added to obtain the peroxide silane coupling agent. In the invention, diisopropylcarbodiimide is added at the temperature of 0-5 ℃ in the presence of titanium tetrachloride, so that the diisopropylcarbodiimide and tetramethoxysilane can form a transition intermediate, the intermediate in the transition state reacts with 1, 1-di-tert-butyl peroxide-4-hydroxycyclohexane in the system to obtain the required peroxide silane coupling agent, the adding process of the diisopropylcarbodiimide is controlled between 0-5 ℃, can promote the reaction between the intermediate in the transition state and the 1, 1-di-tert-butyl peroxide-4-hydroxycyclohexane, reduce the probability of generating byproducts by the self-rearrangement of the intermediate in the transition state, thereby greatly reducing the progress of side reactions, therefore, the method is also beneficial to improving the reaction yield, and the yield is 90-96% by calculation.
2. The preparation method of the peroxide silane coupling agent further comprises the step of purifying the peroxide silane coupling agent obtained through the reaction, namely filtering the reaction liquid obtained after the reaction is finished, washing a filter cake with the aprotic solvent, dissolving the filter cake into a mixed solvent with the volume ratio of acetone to water being (1-3) to (1-2), cooling and crystallizing, filtering to obtain the purified peroxide silane coupling agent, and purifying to improve the purity of the product peroxide silane coupling agent.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort belong to the protection scope of the present invention. Furthermore, the technical features mentioned in the different embodiments of the invention described below can be combined with each other as long as they do not conflict with each other.
Example 1
The preparation method of the peroxide silane coupling agent provided by the embodiment comprises the following steps:
(1) preparation of 1, 1-di-tert-butyl peroxide-4-hydroxycyclohexane
Mixing 10g of tert-butyl hydroperoxide and 4-hydroxycyclohexanone according to the molar ratio of 1:2, putting the mixture into a reaction stirring kettle, controlling the reaction temperature to be 20 ℃, adding concentrated sulfuric acid with the concentration of 98 wt% to be 1m L while stirring, continuing stirring and reacting for 4 hours at the temperature of 20 ℃ after the dropwise adding is finished, washing, filtering and drying the obtained product in vacuum to obtain the 1, 1-tert-butyl-4-hydroxycyclohexane dioxide, wherein the H spectrogram is shown as follows:1H NMR(600MHz,CDCl3,TMS):3.81(t,1H,COH)，2.14(s,1H,CH)， 1.81(m,4H,CHCH2CH2)，1.67(s,4H,CHCH2CH2)，1.24(t,18H,CCH3)；
(2) preparation of peroxide silane coupling agent
1mol of 1, 1-di-tert-butyl peroxide-4-hydroxycyclohexane obtained in step (1), 5mol of tetramethoxysilane and 0.01mol of titanium tetrachloride are mixed, and 100m of L CHCl is added3Forming a reaction system, controlling the temperature of the reaction system to be 0 ℃, adding 1mol of diisopropylcarbodiimide at the temperature, controlling the temperature to be 50 ℃ after the completion of the addition, reacting for 10 hours, and filtering to obtain a peroxide silane coupling agent 1, 1-di-tert-butyl peroxide-4-hydroxycyclohexyl trimethoxy silane; the yield of the example is calculated to be 90%;
(3) refining
The peroxide silane coupling agent 1, 1-di-tert-butyl peroxide-4-hydroxycyclohexyl trimethoxysilane prepared above is used with CHCl3Washing, dissolving the filter cake in a mixed solvent with the volume ratio of acetone to water being 1:2, cooling and crystallizing,filtering to obtain the purified peroxide silane coupling agent.
The purity of 1, 1-di-tert-butyl-4-hydroxycyclohexyl trimethoxysilane obtained in this example was 96% as determined by HP L C.
The structural formula of 1, 1-di-tert-butyl peroxide-4-hydroxycyclohexyl trimethoxy silane prepared in this example is as follows:
its H spectrum is as follows:1H NMR(600MHz,CDCl3,TMS):3.58(t,9H,OCH3)，2. 13(s,1H,CH)，1.81(m,4H,CHCH2CH2)，1.67(s,4H,CHCH2CH2)，1.24(t,18H,C CH3)。
example 2
The preparation method of the peroxide silane coupling agent provided by the embodiment comprises the following steps:
(1) preparation of 1, 1-di-tert-butyl peroxide-4-hydroxycyclohexane
Mixing 10g of tert-butyl hydroperoxide and 4-hydroxycyclohexanone according to the molar ratio of 1:10, putting the mixture into a reaction stirring kettle, controlling the reaction temperature to be-10 ℃, adding 0.5m L of concentrated sulfuric acid with the concentration of 98 wt% while stirring, continuing to stir and react for 10 hours at the temperature of-10 ℃ after the dropwise addition is finished, and washing, filtering and vacuum drying the obtained product to obtain 1, 1-di-tert-butyl hydroperoxide-4-hydroxycyclohexane;
(2) preparation of peroxide silane coupling agent
1mol of 1, 1-di-tert-butyl peroxide-4-hydroxycyclohexane prepared in the step (1), 0.2mol of tetramethoxysilane and 0.05mol of titanium tetrachloride are mixed, and 100m of L CH is added2Cl2And CCl4In which CH2Cl2And CCl4The volume ratio of the components is 1:1 to form a reaction system, then the temperature of the reaction system is controlled to be 5 ℃, 0.5mol of diisopropylcarbodiimide is added at the temperature, after the addition is finished, the temperature is controlled to be 25 ℃, the reaction is carried out for 8 hours, and the filtration is carried out to obtain the peroxide silane coupling agent 1, 1-di-tert-butyl peroxide4-hydroxycyclohexyl trimethoxysilane; the yield of the example is calculated to be 95%;
(3) refining
The silane peroxide coupling agent 1, 1-di-tert-butyl peroxide-4-hydroxycyclohexyl trimethoxysilane prepared by the method is used as CH2Cl2Washing, dissolving the filter cake in a mixed solvent with the volume ratio of acetone to water being 3:1, cooling for crystallization, and filtering to obtain the purified peroxide silane coupling agent.
The purity of 1, 1-di-tert-butyl-4-hydroxycyclohexyl trimethoxysilane obtained in this example was 94% as determined by HP L C.
Example 3
The preparation method of the peroxide silane coupling agent provided by the embodiment comprises the following steps:
(1) preparation of 1, 1-di-tert-butyl peroxide-4-hydroxycyclohexane
Mixing 10g of tert-butyl hydroperoxide and 4-hydroxycyclohexanone according to the molar ratio of 1:5, putting the mixture into a reaction stirring kettle, controlling the reaction temperature to be 0 ℃, adding 0.8m L of concentrated sulfuric acid with the concentration of 98 wt% while stirring, continuing to stir and react for 5 hours at the temperature of 0 ℃ after the dropwise addition is finished, and washing, filtering and drying the obtained product in vacuum to prepare 1, 1-tert-butyl hydroperoxide-4-hydroxycyclohexane;
(2) preparation of peroxide silane coupling agent
1mol of 1, 1-di-tert-butyl peroxide-4-hydroxycyclohexane prepared in the step (1), 2.5mol of tetramethoxysilane and 0.02mol of titanium tetrachloride are mixed, and 100m of L CH is added2Cl2Forming a reaction system, controlling the temperature of the reaction system to be 3 ℃, adding 0.8mol of diisopropylcarbodiimide at the temperature, controlling the temperature to be 30 ℃ after the addition is finished, reacting for 9.5h, and filtering to obtain a peroxide silane coupling agent 1, 1-di-tert-butyl peroxide-4-hydroxycyclohexyl trimethoxy silane; the yield of the example is calculated to be 96%;
(3) refining
The silane peroxide coupling agent 1, 1-di-tert-butyl peroxide-4-hydroxycyclohexyl trimethoxysilane prepared by the method is used as CH2Cl2Washing, dissolving the filter cake in a mixed solvent with the volume ratio of acetone to water being 2:1.5, cooling for crystallization, and filtering to obtain the purified peroxide silane coupling agent.
The purity of 1, 1-di-tert-butyl-4-hydroxycyclohexyl trimethoxysilane obtained in this example was 95% as determined by HP L C.
Example 4
The preparation method of the peroxide silane coupling agent provided by the embodiment comprises the following steps:
(1) preparation of 1, 1-di-tert-butyl peroxide-4-hydroxycyclohexane
Mixing 10g of tert-butyl hydroperoxide and 4-hydroxycyclohexanone according to the molar ratio of 1:8, putting the mixture into a reaction stirring kettle, controlling the reaction temperature to be 5 ℃, adding 0.5m L concentrated sulfuric acid with the concentration of 98 wt% while stirring, continuing to stir and react for 8 hours at the temperature of 5 ℃ after the dropwise addition is finished, and washing, filtering and drying the obtained product in vacuum to prepare 1, 1-tert-butyl hydroperoxide-4-hydroxycyclohexane;
(2) preparation of peroxide silane coupling agent
1mol of 1, 1-di-tert-butyl peroxide-4-hydroxycyclohexane obtained in step (1), 0.9mol of tetramethoxysilane and 0.04mol of titanium tetrachloride are mixed, and 100m of L CH is added2Cl2Forming a reaction system, controlling the temperature of the reaction system to be 1 ℃, adding 0.6mol of diisopropylcarbodiimide at the temperature, controlling the temperature to be 40 ℃ after the addition is finished, reacting for 9.5h, and filtering to obtain a peroxide silane coupling agent 1, 1-di-tert-butyl peroxide-4-hydroxycyclohexyl trimethoxy silane; the yield of this example was calculated to be 91%;
(3) refining
The silane peroxide coupling agent 1, 1-di-tert-butyl peroxide-4-hydroxycyclohexyl trimethoxysilane prepared by the method is used as CH2Cl2Washing, dissolving the filter cake in a mixed solvent with the volume ratio of acetone to water being 1.5:1, cooling for crystallization, and filtering to obtain the purified peroxide silane coupling agent.
The purity of 1, 1-di-tert-butyl-4-hydroxycyclohexyl trimethoxysilane obtained in this example was 96% as determined by HP L C.
Example 5
The preparation method of the peroxide silane coupling agent provided by the embodiment comprises the following steps:
(1) preparation of 1, 1-di-tert-butyl peroxide-4-hydroxycyclohexane
Mixing 10g of tert-butyl hydroperoxide and 4-hydroxycyclohexanone according to the molar ratio of 1:6, putting the mixture into a reaction stirring kettle, controlling the reaction temperature to be 15 ℃, adding 0.5m L concentrated sulfuric acid with the concentration of 98 wt% while stirring, continuing to stir and react for 7 hours at the temperature of 15 ℃ after the dropwise addition is finished, and washing, filtering and drying the obtained product in vacuum to prepare 1, 1-tert-butyl hydroperoxide-4-hydroxycyclohexane;
(2) preparation of peroxide silane coupling agent
1mol of 1, 1-di-tert-butyl peroxide-4-hydroxycyclohexane obtained in step (1), 0.2mol of tetramethoxysilane and 0.01mol of titanium tetrachloride are mixed, and 130m of L CH is added2Cl2Forming a reaction system, controlling the temperature of the reaction system to be 1 ℃, adding 0.5mol of diisopropylcarbodiimide at the temperature, controlling the temperature to be 45 ℃ after the addition is finished, reacting for 9.5h, and filtering to obtain a peroxide silane coupling agent 1, 1-di-tert-butyl peroxide-4-hydroxycyclohexyl trimethoxy silane; the yield of this example was calculated to be 92%;
(3) refining
The silane peroxide coupling agent 1, 1-di-tert-butyl peroxide-4-hydroxycyclohexyl trimethoxysilane prepared by the method is used as CH2Cl2Washing, dissolving the filter cake in a mixed solvent with the volume ratio of acetone to water being 1:1, cooling and crystallizing, and filtering to obtain the purified peroxide silane coupling agent.
The purity of 1, 1-di-tert-butyl-4-hydroxycyclohexyl trimethoxysilane obtained in this example was 96% as determined by HP L C.
Comparative example 1
1, 1-di-tert-butyl peroxide-4-hydroxycyclohexane and tetramethoxysilane are mixed according to a molar ratio of 1: 1.2 adding the mixture into a reaction kettle, stirring and reacting for 10 hours at the temperature of 10 ℃, and separating and purifying the product to obtain the peroxy silane coupling agent 1, 1-di-tert-butyl peroxide-4-hydroxycyclohexyl trimethoxy silane. The yield of the peroxy silane coupling agent obtained in this comparative example was calculated to be 66%.
The purity of the peroxy silane coupling agent prepared in this comparative example was 79% as determined by HP L C.
Experimental example 1
1, 1-di-tert-butyl peroxide-4-hydroxycyclohexyl trimethoxy silane prepared in the embodiment 1 of the invention and nano TiO2Adding the mixture into dimethyl sulfoxide according to the mass ratio of 1:20, mixing and stirring for 10min, then adding acrylonitrile, heating to 70 ℃, stirring and polymerizing for 6h to obtain high polymer modified nano TiO2. The grafting efficiency was 37%.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. All embodiments need not be, and cannot be, given poor exemplification here. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (8)
1. A method for preparing a peroxide silane coupling agent is characterized by comprising the following steps:
(1) mixing 1, 1-di-tert-butyl peroxide-4-hydroxycyclohexane, tetramethoxysilane, titanium tetrachloride and an aprotic solvent;
(2) controlling the temperature to be 0-5 ℃, and adding diisopropylcarbodiimide into the mixture in the step (1);
(3) after the step (2) is finished, controlling the temperature to be 25-50 ℃, and filtering to obtain a peroxide silane coupling agent;
the molar ratio of the 1, 1-di-tert-butyl peroxide-4-hydroxycyclohexane to the tetramethoxysilane, the titanium tetrachloride and the diisopropylcarbodiimide is 1 (0.2-5.0): 0.01-0.05): 0.5-1.
2. According toThe process for producing a peroxidic silane coupling agent according to claim 1, characterized in that the aprotic solvent is CHCl3、CH2Cl2Or CCl4One or more of (a).
3. The method for preparing a peroxidic silane coupling agent according to claim 1, characterized in that in step (2), diisopropylcarbodiimide is dissolved in the aprotic solvent and added dropwise to the mixture of step (1) under stirring.
4. The method for producing a peroxidic silane coupling agent according to claim 1, wherein in the step (1), the method for producing 1, 1-di-tert-butyl-4-hydroxycyclohexane comprises the steps of:
mixing tert-butyl hydroperoxide with 4-hydroxycyclohexanone, controlling the temperature to be-10-20 ℃, adding concentrated sulfuric acid while stirring, continuing to stir at-10-20 ℃ for reaction for 4-10 hours after the dropwise addition is finished, and washing, filtering and drying the obtained product to obtain the 1, 1-tert-butyl hydroperoxide-4-hydroxycyclohexane.
5. The process for producing a peroxidic silane coupling agent according to claim 4, characterized in that the molar ratio of tert-butanol hydroperoxide to 4-hydroxycyclohexanone is 1: (2-10).
6. The method for producing a peroxidic silane coupling agent according to claim 4 or 5, characterized in that the concentration of concentrated sulfuric acid is 98% by weight.
7. The method according to claim 6, wherein the ratio of the mass part of t-butyl hydroperoxide to the volume part of concentrated sulfuric acid is (10-20): 1;
the relationship between the parts by mass and the parts by volume is g/m L.
8. The method for producing a peroxidic silane coupling agent according to claim 1, wherein the step (3) further comprises a step of purifying the produced peroxidic silane coupling agent, which comprises:
and washing the prepared peroxide silane coupling agent with the aprotic solvent, dissolving a filter cake in a mixed solvent with the volume ratio of acetone to water being (1-3) to (1-2), cooling, crystallizing and filtering to obtain the purified peroxide silane coupling agent.
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Address after: Yinhe street, Ningjin economic and Technological Development Zone, Dezhou City, Shandong Province 253000 Patentee after: Shandong Yuanhe New Material Technology Co.,Ltd. Address before: 253400 Yinhe street, Ningjin Economic Development Zone, Dezhou City, Shandong Province Patentee before: SHANDONG NINGJIN HAORUN TECHNOLOGY Co.,Ltd. |