CN111574549A - Silane coupling agent containing double bonds and preparation method thereof - Google Patents

Silane coupling agent containing double bonds and preparation method thereof Download PDF

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CN111574549A
CN111574549A CN202010556376.6A CN202010556376A CN111574549A CN 111574549 A CN111574549 A CN 111574549A CN 202010556376 A CN202010556376 A CN 202010556376A CN 111574549 A CN111574549 A CN 111574549A
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silane coupling
coupling agent
double bonds
chlorosilane
containing double
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籍建亚
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02Silicon compounds
    • C07F7/08Compounds having one or more C—Si linkages
    • C07F7/18Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804Compounds having Si-O-C linkages
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02Silicon compounds
    • C07F7/08Compounds having one or more C—Si linkages
    • C07F7/18Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804Compounds having Si-O-C linkages
    • C07F7/1872Preparation; Treatments not provided for in C07F7/20
    • C07F7/188Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes

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Abstract

The invention discloses a silane coupling agent containing double bonds and a preparation method thereof; the silane coupling agent containing double bonds is prepared by reacting chlorosilane and alkyne under the catalysis of graphene oxide supported diimine palladium catalyst to generate chlorosilane containing double bonds, and carrying out alcoholysis on the obtained chlorosilane containing double bonds under an acidic condition to obtain the silane coupling agent containing double bonds; the preparation method of the silane coupling agent containing double bonds is safe and nontoxic, simple and convenient to operate, high in yield and capable of recycling the catalyst; meanwhile, the silane coupling agent containing double bonds can be bonded with various inorganic materials, and when the polymer material is prepared, the double bonds can generate crosslinking reaction with the polymer to prepare various functional materials.

Description

Silane coupling agent containing double bonds and preparation method thereof
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a double-bond-containing silane coupling agent and a preparation method thereof.
Background
The development of silane coupling agents began with the improvement of the properties of glass fiber reinforced resin matrix composites. With the development of science, silane coupling agents are mainly applied to four fields of preparation of organic polymer composite materials, protection of metal materials, modification of high molecular polymers, synthesis of organic polymer/inorganic functional hybrid materials and the like, the silane coupling agents are already the most widely applied coupling agents, and the silane coupling agents are widely applied because the silane coupling agents have special molecular structures, wherein the silane coupling agents have groups capable of being combined with inorganic materials (such as glass, metal and the like) and groups capable of being combined with organic materials (such as synthetic resin and the like).
CN100436522C discloses a silane coupling agent containing double bonds and a preparation method thereof, wherein mercapto-hydrocarbon silane reacts with unsaturated acyl chloride to obtain the silane coupling agent containing unsaturated double bonds on a straight chain. Son Thanh Phan et al utilize tetrakis (triphenylphosphine) palladium to catalyze the reaction of chlorosilanes with alkynes substituted with different substituents to produce chlorosilanes with cycloalkene substituents (Son Thanh Phan, Weon Chem Lim, Joon Soo Han, Bok Ryul Yoo, and Il NanJung. organometallics 2004,23, 169.). However, the used tetrakis (triphenylphosphine) palladium catalyst is expensive, sensitive to air, complex in reaction operation, high in toxicity and not friendly to environment, and the N ^ N bidentate ligand is a ligand with low toxicity, so that the invention prepares the cycloolefin substituent substituted silane coupling agent by using the supported diimine palladium catalyst.
Disclosure of Invention
The invention aims to provide a double bond-containing silane coupling agent.
The invention also aims to provide a preparation method of the double bond-containing silane coupling agent.
The above purpose of the invention is realized by the following technical scheme:
a double bond-containing silane coupling agent has a structural formula shown as the following formula (I):
Figure BDA0002544452750000021
wherein R is1Is H, SiCl3、SiMeCl2,R2Is H, CH3,R3Is H, CH3
The reaction process and preparation method of the double bond-containing silane coupling agent are as follows:
Figure BDA0002544452750000022
1. adding chlorosilane into a reaction flask with a branch mouth, N2Under protection, adding a reaction solvent, introducing an alkyne gas reaction package into a branched flask, adding an organic solvent supported diimine palladium catalyst, heating to 80-110 ℃, reacting for 2-8 hours, dotting a plate to track the reaction progress, filtering the catalyst out of the reaction system after the reaction is finished, washing filter residues with absolute ethyl alcohol and acetone, drying, concentrating the filtrate, and performing column chromatography on the concentrated solution to obtain chlorosilane containing double bonds.
Wherein, the reaction solvent is benzene, toluene, dichloromethane, hexane and cyclohexane.
Preferably, the supported diimine palladium catalyst is a graphene oxide supported diimine palladium catalyst.
2.N2Under protection, adding chlorosilane containing double bonds into a flask with a branch mouth, adding a certain amount of ethanol and toluene, heating to 110 ℃, reacting for 2-5 hours, and adding a proper amount of Na2CO3Neutralizing excessive hydrochloric acid, filtering, concentrating the filtrate, and performing column chromatography on the concentrated solution to obtain the silane coupling agent containing double bonds.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the preparation method of the double-bond-containing silane coupling agent is safe and nontoxic, is simple and convenient to operate, has high yield, and can recycle the catalyst.
(2) The silane coupling agent containing double bonds prepared by the invention can be bonded with various inorganic materials at the same time, and when a polymer material is prepared, the double bonds can generate crosslinking reaction with the polymer to prepare various functional materials.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of a double bond-containing silane coupling agent 4cb prepared by the invention.
FIG. 2 is a nuclear magnetic hydrogen spectrum of the silane coupling agent 4bc containing double bonds prepared by the invention.
Detailed Description
Example 1
This example provides a double bond-containing chlorosilane 3aa, which was synthesized as follows.
Chlorosilane 1a (1.07g, 5.0mmol) was added to a reaction 100mL branched flask, N2Adding 50mL of toluene under protection, connecting a branched flask into a reaction bag containing alkyne 2a, adding 0.02g of graphene oxide supported diimine palladium catalyst dissolved in toluene, heating to 110 ℃, reacting for 4 hours, dotting and tracking the degree of reaction, filtering the catalyst out of the reaction system after the reaction is finished, washing filter residues with absolute ethyl alcohol and acetone, drying, concentrating the filtrate, and carrying out column chromatography on the concentrated solution to obtain the double-bond-containing catalystChlorosilane 3aa1.14g of (g) was obtained at a yield of 95%.
Example 2
This example provides a method for synthesizing chlorosilane 3ab containing double bonds as follows.
Following the synthesis procedure of example 1, alkyne 2a was replaced with alkyne 2b to give double bond-containing chlorosilane 3ab1.06g, 79% yield.
Example 3
This example provides a method for synthesizing chlorosilane 3ac containing double bonds, as follows.
Following the synthesis procedure of example 1, alkyne 2a was replaced with alkyne 2c to give double bond-containing chlorosilane 3ac1.11g in 87% yield.
Example 4
This example provides a chlorosilane 3ba containing double bonds, which was synthesized as follows.
According to the synthesis method of example 1, chlorosilane 1b was used instead of chlorosilane 1a, and double bond-containing chlorosilane 3ba1.08g was obtained in 58% yield.
Example 5
This example provides a chlorosilane 3bb containing a double bond, which was synthesized as follows.
According to the synthesis method of example 1, chlorosilane 1b was used instead of chlorosilane 1a, and alkyne 2b was used instead of alkyne 2a, to obtain 1.29g of double bond-containing chlorosilane 3bb in 64% yield.
Example 6
This example provides a double bond-containing chlorosilane 3bc synthesized as follows.
According to the synthesis method of example 1, chlorosilane 1b was used instead of chlorosilane 1a, and alkyne 2c was used instead of alkyne 2a, to obtain 1.26g of double bond-containing chlorosilane 3bc with a yield of 65%.
Example 7
This example provides a double bond-containing chlorosilane 3ca, which was synthesized as follows.
According to the synthesis method of example 1, chlorosilane 1c was used instead of chlorosilane 1a, and double bond-containing chlorosilane 3ca1.70g was obtained in a yield of 96%.
Example 8
This example provides a double bond-containing chlorosilane 3cb, which was synthesized as follows.
According to the synthesis method of example 1, chlorosilane 1c was used instead of chlorosilane 1a, and alkyne 2b was used instead of alkyne 2a, to obtain 1.55g of double bond-containing chlorosilane 3cb, in 81% yield.
Example 9
This example provides 3cc of a double bond-containing chlorosilane, which was synthesized as follows.
According to the synthesis method of example 1, chlorosilane 1c was used instead of chlorosilane 1a, and alkyne 2c was used instead of alkyne 2a, to obtain 1.38g of double bond-containing chlorosilane 3cc in a yield of 75%.
Example 10
This example provides a silane coupling agent 4aa containing double bonds, and the synthesis method is as follows.
N2Under protection, adding chlorosilane 3aa (1.19g, 5.0mmol) containing double bonds into a 100mL flask with a branch, adding ethanol (0.23g, 5.0mmol) and 40mL of methylbenzene, heating to 110 ℃, reacting for 4 hours, dotting and tracking the degree of reaction, and adding a proper amount of Na after the reaction is finished2CO3Neutralizing excessive hydrochloric acid, filtering, concentrating the filtrate, and performing column chromatography on the concentrated solution to obtain the silane coupling agent containing double bonds 4aa 1.24g, wherein the yield is 87%.
Example 11
This example provides a silane coupling agent 4ab containing double bonds, which is synthesized as follows.
Following the synthesis procedure of example 10, alkyne 3aa was replaced with alkyne 3ab to give double bond-containing chlorosilane 4ab1.30g, 83% yield.
Example 12
This example provides a silane coupling agent 4ac containing double bonds, and the synthesis method is as follows.
Following the synthesis procedure of example 10, alkyne 3aa was replaced with alkyne 3ac to give double bond-containing chlorosilane 4ac1.25g, 84% yield.
Example 13
This example provides a silane coupling agent 4ba containing double bonds, which is synthesized as follows.
Following the synthesis procedure of example 10, substituting alkyne 3aa with alkyne 3ba, chlorosilane 4ba1.59g containing double bonds was obtained in 76% yield.
Example 14
This example provides a silane coupling agent 4bb containing double bonds, which is synthesized as follows.
Following the synthesis procedure of example 10, alkyne 3bb was substituted for alkyne 3aa to afford double bond-containing chlorosilane 4bb1.56g in 70% yield.
Example 15
This example provides a silane coupling agent 4bc containing double bonds, and its synthesis method is as follows.
Following the synthetic procedure of example 10, alkyne 3bc was substituted for alkyne 3aa to afford double bond-containing chlorosilane 4bc1.53g in 71% yield.
Example 16
This example provides a silane coupling agent 4ca containing double bonds, which is synthesized as follows.
Following the synthesis procedure of example 10, alkyne 3ca was substituted for alkyne 3aa to afford double bond-containing chlorosilane 4ca1.59g, 80% yield.
Example 17
This example provides a double bond-containing silane coupling agent 4cb, which was synthesized as follows.
Following the synthesis procedure of example 10, alkyne 3cb was used in place of alkyne 3aa to afford double bond-containing chlorosilane 4cb1.59g, 75% yield.
Example 18
This example provides 4cc of a double bond-containing silane coupling agent, which was synthesized as follows.
Following the synthesis procedure of example 10, substituting alkyne 3aa with alkyne 3cc, chlorosilane 4cc1.60g containing double bond was obtained in 78% yield.
Example 19
The graphene oxide supported diimine palladium catalyst used in example 1 is filtered out from the reaction system, washed by absolute ethyl alcohol and acetone, dried, reused for the reaction of chlorosilane 1a and alkyne 2a, and recycled five times to obtain the silane coupling agent containing double bonds with yields of 94%, 92%, 89%, 85% and 80%, respectively. According to the yield of the reaction, the graphene oxide supported diimine palladium catalyst has high catalytic efficiency in catalyzing chlorosilane and alkyne, and can be recycled.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents and are included in the scope of the present invention.

Claims (5)

1. The double bond-containing silane coupling agent is characterized in that the structural formula of the double bond-containing silane coupling agent is shown as the following formula (I):
Figure FDA0002544452740000011
wherein R is1Is H, SiCl3、SiMeCl2,R2Is H, CH3,R3Is H, CH3
2. The method for producing a double bond-containing silane coupling agent according to claim 1, characterized by comprising the steps of:
(1)N2under protection, supported diimine palladium is used as a catalyst, chlorosilane is dissolved in an organic solvent and reacts with alkyne, the temperature is raised to 80-110 ℃, and after the reaction is carried out for 2-8 hours, the chlorosilane containing double bonds is obtained, and the structural formula of the chlorosilane is shown as (II);
Figure FDA0002544452740000012
wherein R is1Is H, SiCl3、SiMeCl2,R2Is H, CH3,R3Is H, CH3
(2)N2Under protection, adding chlorosilane containing double bonds into a flask with a branch mouth, and adding a certain amount of BAfter the alcohol and the toluene are mixed, the temperature is raised to 110 ℃, the reaction is carried out for 2 to 5 hours, and a proper amount of Na is added2CO3Neutralizing excessive hydrochloric acid, and purifying the product to obtain a double-bond-containing silane coupling agent with a structural formula shown in (I);
Figure FDA0002544452740000013
wherein R is1Is H, SiCl3、SiMeCl2,R2Is H, CH3,R3Is H, CH3
3. The method for preparing a double bond-containing silane coupling agent according to claim 2, wherein in the step (1), the supported diimine palladium catalyst is a graphene oxide supported diimine palladium catalyst.
4. The method for preparing a silane coupling agent containing a double bond according to claim 2, wherein in the step (1), the reaction solvent is benzene, toluene, dichloromethane, hexane, cyclohexane.
5. The silane coupling agent containing double bonds as claimed in claim 1, wherein said silane coupling agent containing double bonds is used in the preparation of antibacterial materials.
CN202010556376.6A 2020-06-17 2020-06-17 Silane coupling agent containing double bonds and preparation method thereof Pending CN111574549A (en)

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