阅读说明：本技术 一种光致变色硅烷偶联剂及其制备方法和应用 (Photochromic silane coupling agent and preparation method and application thereof ) 是由 马松 马德龙 张雪 潘琳琳 王桂伦 王才鹏 王庆振 于 2021-08-25 设计创作，主要内容包括：本发明公开了一种光致变色硅烷偶联剂及其制备方法和应用,由带有双键侧链的螺吡喃和三烷氧基硅氢在催化剂作用下通过硅氢加成反应生成。本发明硅烷偶联剂通过在硅原子上增加螺吡喃分子,从而实现在改性的同时具有光致变色的作用,可作为纳米粉体或橡胶的改性剂和变色剂,反应操作简单,且与纳米粉体或橡胶的相容性好,不会降低纳米粉体或橡胶的自身性能,是一种十分理想的硅烷偶联剂。(The invention discloses a photochromic silane coupling agent and a preparation method and application thereof, which are generated by the addition reaction of spiropyran with double bond side chain and trialkoxy hydrosilane under the action of a catalyst. The silane coupling agent has the photochromic function while modifying by adding the spiropyran molecules on the silicon atoms, can be used as a modifier and a color-changing agent of nano powder or rubber, has simple reaction operation and good compatibility with the nano powder or rubber, does not reduce the self performance of the nano powder or rubber, and is an ideal silane coupling agent.)

1. A photochromic silane coupling agent characterized by having the formula:

；

wherein R is C1-C3 alkyl.

2. The photochromic silane coupling agent according to claim 1, wherein: r is ethyl.

3. The process for producing a photochromic silane coupling agent according to claim 1 or 2, wherein: the spiropyran with double bond side chain shown in formula A and trialkoxy hydrosilane shown in formula B react under the action of a catalyst to obtain the spiropyran derivative;

。

4. the method of claim 3, wherein: the catalyst is a noble metal catalyst; preferably, the catalyst is chloroplatinic acid or ruthenium chloride; preferably, the molar amount of the catalyst is 0.008 to 0.05 times, preferably 0.02 times the molar amount of compound a.

5. The method of claim 3, wherein: the molar ratio of spiropyran with double-bond side chain to trialkoxysilylhydrogen is 1: 1-1.5, preferably 1:1.

6. the method of claim 3, wherein: the reaction is carried out in the presence of an organic solvent, wherein the organic solvent is an ether solvent; preferably, the organic solvent is tetrahydrofuran, diethyl ether or dioxane.

7. The method of claim 6, wherein: the dosage of the organic solvent is 10-40 times of the total mass of the reaction raw materials.

8. The method of claim 3, wherein: the reaction temperature is 40-67 ℃, and preferably 60 ℃; the reaction time is 3-10h, preferably 6 h.

9. The method of claim 3, wherein: the reaction is carried out under the protection of inert gas.

10. Use of the photochromic silane coupling agent of claim 1 or 2 in rubber.

Technical Field

The invention relates to a photochromic silane coupling agent, a preparation method and application thereof, belonging to the technical field of silane coupling agents.

Background

The silane coupling agent has wide application fields, in particular to four fields of organic polymer composite material preparation, metal/nonmetal material protection, organic silicon modification of high molecular compounds, organic polymer/inorganic function hybrid material synthesis and the like. Although the research and development of silane coupling agents has been over 70 years, synthesis and application research has been ongoing.

Modification of an object with a silane coupling agent to improve the reactivity, stability and dispersibility of nanopowder or rubber is a common method. Silane coupling agents improve the reactivity of nanopowders and the properties of rubber to some extent, but further reactions may be required to obtain the target modification. In the research, it is found that if the nano powder or the rubber product is required to have photochromic properties, the photochromic properties are considered, the modified silane coupling agent is required to satisfy the compatibility with the nano powder or the rubber product, and the performance of the nano powder or the rubber product cannot be reduced, which is difficult. Therefore, the difficulty of designing and synthesizing the silane coupling agent which has photochromic property and can be suitable for nano powder or rubber products is large, and the silane coupling agent is not reported at present.

Disclosure of Invention

The invention provides a photochromic silane coupling agent which can be used as a coupling agent to realize surface modification of nano powder or rubber, so that the nano powder or rubber and the like have photochromic characteristics, can realize specific color change requirements, has good compatibility with the nano powder or rubber, cannot reduce the self performance of the nano powder or rubber, and has good application prospect.

The specific technical scheme of the invention is as follows:

the photochromic silane coupling agents of the present invention have the formula:

。

the photochromic silane coupling agent disclosed by the invention is coupled with nano powder or rubber and the like by hydrolyzing alkoxy in a molecule to form hydroxyl, and has a special structure, wherein R is C1-C3 alkyl, such as methyl, ethyl, propyl and isopropyl. Preferably, R is ethyl.

The photochromic silane coupling agent is generated by the reaction of spiropyran with double bond side chain shown in formula A and trialkoxy silicon hydride shown in formula B through hydrosilylation under the action of a catalyst; the reaction formula is as follows:

further, the catalyst is a noble metal catalyst, such as chloroplatinic acid, ruthenium chloride, and the like. The molar amount of the catalyst is 0.008 to 0.05 times, preferably 0.02 times the molar amount of the compound A.

Further, the spiropyran with a double-bond side chain shown in the formula A is spiropyran with an allyl side chain, and the molar ratio of the spiropyran with the double-bond side chain to trialkoxy silicon hydrogen is 1: 1-1.5, preferably 1:1.

further, the reaction is carried out in the presence of an organic solvent, which may be an ether solvent such as tetrahydrofuran, diethyl ether, dioxane, or the like. The dosage of the organic solvent is 10-40 times of the total mass of the reaction raw materials (the spiropyran with double bond side chain and trialkoxy silicon hydrogen).

Further, the reaction is carried out under the protection of gas, and the gas is nitrogen or inert gas such as argon.

Further, the preparation method comprises the following specific steps: adding spiropyran with double-bond side chain, trialkoxy silicon hydride, catalyst and organic solvent into a reaction kettle, controlling the reaction temperature under the protection of gas to carry out reaction, and finishing the reaction after a period of time to obtain the product.

Further, the reaction temperature is 40-67 ℃, and preferably 60 ℃.

Further, the reaction time is 3 to 10 hours, preferably 6 hours.

The invention also provides application of the photochromic silane coupling agent in nano powder or rubber.

The photochromic silane coupling agent is obtained by reacting the spiropyran with a double-bond side chain with trialkoxysilane, has simple preparation method, low cost and high product yield, has good photochromic characteristic, can be used as a modifier and a color-changing agent of nano powder or rubber, has simple reaction operation, has good compatibility with the nano powder or rubber, does not reduce the self performance of the nano powder or rubber, and is an ideal silane coupling agent.

Detailed Description

The invention is further illustrated by the following specific examples, which are not intended to be limiting and whose scope is indicated in the claims.

Example 1

34.8 g (0.1 mol) of spiropyran having an allyl side chain, 16.4 g (0.1 mol) of triethoxysilylhydride, 815 mg (0.002 mol) of H, were reacted in a molar ratio of 1:1 as the starting materials₂PtCl₆And adding dried THF (800 g) into a reaction kettle, controlling the reaction temperature to be 60 ℃, reacting for 6 hours under the protection of nitrogen, ending the reaction, and detecting the reaction liquid by gas chromatography and mass spectrometry to obtain the product with the purity of 92% and the yield of 90.8%.

Example 2

34.8 g (0.1 mol) of spiropyran having an allyl side chain, 16.4 g (0.1 mol) of triethoxysilylhydride, 325 mg (0.0008 mol) of H, were reacted in a molar ratio of 1:1 as the starting materials₂PtCl₆And adding dried THF (800 g) into a reaction kettle, controlling the reaction temperature to be 60 ℃, reacting for 5 hours under the protection of nitrogen, finishing the reaction, and detecting the reaction liquid by gas chromatography and mass spectrometry to obtain the product with the purity of 91.7% and the yield of 89.9%.

Example 3

34.8 g (0.1 mol) of spiropyran bearing an allyl side chain and 16.4 g (0.1 mol) of triethoxysilylhydride, 2.037g (0.005 mol) of H, were reacted in a molar ratio of 1:1 of the starting materials₂PtCl₆And adding dried THF (800 g) into a reaction kettle, controlling the reaction temperature at 60 ℃, reacting for 3 hours under the protection of nitrogen, finishing the reaction, and carrying out gas phase reaction on the reaction liquidAnd (5) detecting by chromatography and mass spectrometry, wherein the purity of the product is 93% and the yield is 91.1%.

Example 4

34.8 g (0.1 mol) of spiropyran having an allyl side chain and 19.44 g (0.12 mol) of triethoxysilylhydride, 815 mg (0.002 mol) of H were added in a molar ratio of 1:1.2 as the starting materials₂PtCl₆And adding dried THF (800 g) into a reaction kettle, controlling the reaction temperature to be 67 ℃, reacting for 6 hours under the protection of argon, ending the reaction, and detecting the reaction liquid by gas chromatography and mass spectrometry to obtain the product with the purity of 91.8% and the yield of 91%.

Example 5

34.8 g (0.1 mol) of spiropyran bearing an allyl side chain and 22.68 g of triethoxysilylhydride (0.14 mol), 815 mg (0.002 mol) of H were added in a molar ratio of 1:1.4 of the starting materials₂PtCl₆And adding dried diethyl ether (800 g) into a reaction kettle, controlling the reaction temperature to be 67 ℃, reacting for 6 hours under the protection of argon, ending the reaction, and detecting the reaction liquid by gas chromatography and mass spectrometry to obtain the product with the purity of 90.1% and the yield of 88%.

Example 6

34.8 g (0.1 mol) of spiropyran having an allyl side chain and 24.3 g (0.15 mol) of triethoxysilylhydride, 815 mg (0.002 mol) of H were added in a molar ratio of 1:1.5 as the starting materials₂PtCl₆And adding dried dioxane (800 g) into a reaction kettle, controlling the reaction temperature at 45 ℃, reacting for 10 hours under the protection of nitrogen, finishing the reaction, and detecting the reaction liquid by gas chromatography and mass spectrometry to obtain the product with the purity of 88.6% and the yield of 80.9%.

Example 7

34.8 g (0.1 mol) of spiropyran having an allyl side chain, 12.2 g of trimethoxysilylhydride (0.1 mol), 815 mg (0.002 mol) of H, were reacted in a molar ratio of 1:1 as the starting materials₂PtCl₆And adding dried THF (800 g) into a reaction kettle, controlling the reaction temperature at 60 ℃, reacting for 6 hours under the protection of nitrogen, finishing the reaction, detecting the reaction liquid by gas chromatography and mass spectrometry to obtain the product with purity of 89% and yield of 84%, and finding the product in the post-treatment processHydrolysis is very easy to occur.

Example 8

34.8 g (0.1 mol) of spiropyran having an allyl side chain, 20.6 g of tripropoxysilane (0.1 mol), 815 mg (0.002 mol) of H, were added in a molar ratio of 1:1 as the starting materials₂PtCl₆And adding dried THF (800 g) into a reaction kettle, controlling the reaction temperature to be 60 ℃, reacting for 6 hours under the protection of nitrogen, ending the reaction, and detecting the reaction liquid by gas chromatography and mass spectrometry to obtain the product with the purity of 92% and the yield of 88%.

Comparative example 1

34.8 g (0.1 mol) of spiropyran having an allyl side chain, 24.8 g (0.1 mol) of tributoxysilylhydride, 815 mg (0.002 mol) of H, were reacted in a molar ratio of 1:1 as the starting materials₂PtCl₆And adding dried THF (800 g) into a reaction kettle, controlling the reaction temperature to be 60 ℃, reacting for 6 hours under the protection of nitrogen, ending the reaction, and detecting the reaction liquid by gas chromatography and mass spectrometry to obtain the product with the purity of 56% and the yield of less than 40%.

Comparative example 2

34.8 g (0.1 mol) of spiropyran having an allyl side chain, 29.1 g (0.1 mol) of tripentoxysilicone, 815 mg (0.002 mol) of H, were reacted in a molar ratio of 1:1 as the starting materials₂PtCl₆And adding dried THF (800 g) into a reaction kettle, controlling the reaction temperature to be 60 ℃, reacting for 6 hours under the protection of nitrogen, ending the reaction, and detecting the reaction liquid by gas chromatography and mass spectrometry to obtain the raw material conversion rate of 47%.

Comparative example 3

According to the molar ratio of 1:1 of the reaction raw materials, 34.8 g (0.1 mol) of spiropyran having an allyl side chain, 33.2 g (0.1 mol) of ethoxydioctyloxyhydrosilation, 815 mg (0.002 mol) of H₂PtCl₆And adding dried THF (800 g) into a reaction kettle, controlling the reaction temperature to be 60 ℃, reacting for 6 hours under the protection of nitrogen, ending the reaction, and detecting the reaction liquid by gas chromatography and mass spectrometry to obtain the raw material conversion rate of 17%.

Comparative example 4

According to the molar ratio of the reaction raw materials 1:1, 34.8 g (0.1 mol)Spiropyran bearing an allylic side chain, 27.6 g ethoxydihexyloxysilicone (0.1 mol), 815 mg (0.002 mol) H₂PtCl₆And adding dried THF (800 g) into a reaction kettle, controlling the reaction temperature to be 60 ℃, reacting for 6 hours under the protection of nitrogen, ending the reaction, and detecting the reaction liquid by gas chromatography and mass spectrometry to obtain the raw material conversion rate of 29.5%.

Comparative example 5

According to the molar ratio of 1:1 of the reaction raw materials, 36.2 g (0.1 mol) of spiropyran having butenyl (terminal) side chain, 16.4 g of triethoxysilylhydride (0.1 mol), 815 mg (0.002 mol) of H₂PtCl₆And adding dried THF (800 g) into a reaction kettle, controlling the reaction temperature to be 60 ℃, reacting for 6 hours under the protection of nitrogen, ending the reaction, and detecting the reaction liquid by using gas chromatography and mass spectrometry to obtain the product with the raw material conversion rate of 56.5%, more unknown impurities and the yield of 39.4%.

Comparative example 6

According to the molar ratio of 1:1 of the reaction raw materials, 37.6 g (0.1 mol) of spiropyran with pentenyl (terminal) side chain, 16.4 g of triethoxysilylhydride (0.1 mol) and 815 mg (0.002 mol) of H₂PtCl₆And adding dried THF (800 g) into a reaction kettle, controlling the reaction temperature to be 60 ℃, reacting for 6 hours under the protection of nitrogen, ending the reaction, and detecting the reaction liquid by using gas chromatography and mass spectrometry to obtain the product with the raw material conversion rate of 51.7%, more unknown impurities and the yield of 13.1%.

Comparative example 7

37.6 g (0.1 mol) of spiropyran having a pentenyl (non-terminal) side chain, 16.4 g of triethoxysilylhydride (0.1 mol), 815 mg (0.002 mol) of H, were added in a molar ratio of 1:1 as the starting materials₂PtCl₆And adding dried THF (800 g) into a reaction kettle, controlling the reaction temperature to be 60 ℃, reacting for 6 hours under the protection of nitrogen, ending the reaction, and detecting the reaction liquid by using gas chromatography and mass spectrometry to obtain the product with the raw material conversion rate of 61.4%, more unknown impurities and the yield of 12.3%.

Performance verification

1. The loading amount and compatibility of the photochromic silane coupling agent prepared in the above examples and comparative examples were verified by the following method:

1.1, uniformly dispersing gas-phase silica gel in an ethanol solution under an ultrasonic condition, adding a photochromic silane coupling agent accounting for 10% of the mass of the gas-phase silica gel under magnetic stirring, continuously stirring for 30 minutes to form uniform slurry or turbid liquid, and then concentrating or performing suction filtration to obtain a solid product, namely the modified gas-phase silica gel. And (3) representing the load capacity of the photochromic silane coupling agent in the modified gas-phase silica gel by adopting a thermal weight loss method.

Load = thermogravimetric mass difference/original mass of fumed silica 100%

The results for each sample loading are shown in table 1 below:

as can be seen from the results in the above table, the products of examples 1-6 can be mixed and loaded with silica gel in the gas phase rapidly and in a short time. While other embodiments and comparative examples have less load at the same time.

1.2, observing the micro-morphology and the surface of the modified sample by using a field emission scanning electron microscope with an energy spectrum analyzer, and finding that the samples of the examples 1 to 8 and the comparative examples 1 to 2 have good compatibility with the gas phase silica gel, and the samples of the comparative examples 3 to 7 have slightly poor compatibility with the gas phase silica gel, and have slight agglomeration phenomenon.

The photochromic silane coupling agents prepared in the above examples and comparative examples were verified for their photochromic properties and mechanical properties by the following methods:

2.1, according to the method of 1.1, the gas-phase silica gel is respectively mixed and modified with the photochromic silane coupling agents prepared in the examples 1-8 and the comparative examples 1-7, so that the loading capacity of each photochromic silane coupling agent on the gas-phase silica gel is ensured to be between 5% and 6%.

2.2 sizing formula: the rubber test sizing material is prepared and mixed according to GB T6038-.

2.3 the preparation method of the sizing material comprises the following steps: dumbbell preparations were carried out according to GB/T528-1998 and GB T6038-2006.

2.4 the compound obtained above was irradiated with ultraviolet light for 60s to observe the discoloration of the compound, and the results are shown in the following table 2:

2.5 according to GB/T528-.

The results are shown in table 3 below:

the photochromic silane coupling agents prepared in examples 1-6 performed best, combining the properties of the above aspects.