CN111138861A - Graphene-based organic silicon porous nano material and preparation method thereof - Google Patents

Graphene-based organic silicon porous nano material and preparation method thereof Download PDF

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CN111138861A
CN111138861A CN201911409608.9A CN201911409608A CN111138861A CN 111138861 A CN111138861 A CN 111138861A CN 201911409608 A CN201911409608 A CN 201911409608A CN 111138861 A CN111138861 A CN 111138861A
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graphene
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蒋璐瑶
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Suzhou Tongli Optoelectronics Co ltd
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Suzhou Tongli Optoelectronics Co ltd
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Priority to PCT/CN2020/114658 priority patent/WO2021135379A1/en
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Abstract

A graphene-based organosilicon porous nano material and a preparation method thereof are disclosed, wherein the graphene-based organosilicon porous nano material is composed of a component A and a component B in a weight ratio of 1-2:1, and the component A comprises the following raw materials in parts by weight: 10-50 parts of methyl vinyl polysiloxane; 5-20 parts of methyl hydrogenpolysiloxane; 0.1-5 parts of a chain extender; 0.1-10 parts of a release agent; 5-30 parts of graphene; 0.05-2 parts of a structural control agent; 0.05-2 parts of a silane coupling agent; 0.01-1 part of silicone-based inhibitor; 0.5-5 parts of foaming agent. The component B comprises the following raw materials in parts by weight: 10-20 parts of methyl vinyl polysiloxane; 10-30 parts of methyl vinyl MQ silicon resin; 0.1-10 parts of a release agent; 5-30 parts of graphene; 0.05-2 parts of a structural control agent; 0.01-1 part of catalyst; 0.5-5 parts of an activating agent. The graphene-based organic silicon porous nano material is light in weight, viscoelastic, fine and uniform in cross-section pores, the graphene nano film and the organic silicon material substrate are interacted, the bonding substrate is firm, and the graphene-based organic silicon porous nano material is excellent in compression resistance, impact resistance and thermal stability, and is suitable for light application scenes such as sealing shock absorption, microwave absorption, electromagnetic shielding and heat dissipation protection.

Description

Graphene-based organic silicon porous nano material and preparation method thereof
Technical Field
The invention belongs to the technical field of organic silicon materials, and relates to a graphene-based organic silicon porous nano material and a preparation method thereof.
Background
Graphene is a two-dimensional planar nano front material with excellent performance, and is prepared by the earliest discovery of Constantine NovoSchroff and Anderson Gem and microcomputer stripping, and the two-dimensional graphene is a basic composition unit of a carbonaceous material and can be curled into zero-dimensional fullerene and one-dimensional carbon nano-tubes, and can also be overlapped and stacked into three-dimensional graphite. Graphene contains the following properties: firstly, the thinnest material is found, the thickness of single-layer graphene is only 0.335nm, which is equivalent to the diameter of carbon atoms; secondly, the specific surface area is large, and the specific surface area of graphene reaches 2600m2More than g, the material is an energy storage material with excellent performance; third, the conductivity is strong, the electrons in the graphene have almost no mass, and the movement speed of the electrons greatly exceeds that of the electrons in metal conductors and other semiconductors, so that the graphene can be used as an ideal conductive material; and fourthly, the thermal conductivity is strong, the thermal conductivity of the graphene reaches more than 5000W/mk, and exceeds metal materials such as gold, silver, copper and aluminum, and the graphene can be used as an ideal heat conduction material. Compounds containing a silicon-carbon bond (Si-C) and having at least one organic group bonded to the silicon atom are referred to as organosilicon compounds, and compounds having an organic group bonded to the silicon atom through an atom of oxygen, sulfur, nitrogen or the like are also referred to as organosilicon compoundsAmong them, the polysiloxane having a siloxane bond (-Si-O-Si-) as a main chain has the largest variety and is most widely used. Graphene and silicone, a revolutionary emerging material, and a traditional material with unique properties, all play a significant role in the material industry.
In recent years, by combining the research of graphene and organic silicon and the development of products, processes and applications around graphene/organic silicon, through continuous exploration and struggle of researchers, graphene/organic silicon composite materials are layered endlessly, and the application of graphene/organic silicon composite materials is more and more extensive. However, the depth and the breadth of the application of the graphene/organic silicon in daily life of people have not reached the expectation of researchers in the field, and the main reasons are as follows: 1, a graphene/organic silicon composite material is used as a leading-edge material, and after being developed, the graphene/organic silicon composite material can be applied in a large scale only through a long-time reliability test; 2, the graphene/organic silicon composite material also has certain technical problems that a long time is needed to overcome, such as easy agglomeration of graphene due to self-generation, poor compatibility of graphene and organic silicon, structural and intrinsic defects of graphene and the like. Due to incomparable performance advantages of the graphene/organic silicon composite material, more and more scientific researchers are invested, and domestic scientific researchers are expected to make technical breakthroughs in the field, so that the application of the graphene/organic silicon composite material in different fields is widened, and the competitiveness and the influence of China in the material field are improved.
Disclosure of Invention
The invention aims to provide a graphene-based organic silicon porous nano material and a preparation method thereof.
In order to achieve the above objects and other related objects, the present invention provides the following technical solutions: a graphene-based organosilicon porous nano material is formed by mixing a component A and a component B according to the mass ratio of 1-2: 1;
the component A comprises the following raw materials in parts by weight:
Figure BDA0002349611140000021
the component B comprises the following raw materials in parts by weight:
Figure BDA0002349611140000022
the preferable technical scheme is as follows: the methylvinylpolysiloxane is at least one of the compounds corresponding to the general formulae A, B and C:
(ViMe2SiO1/2)(MeSiO3/2) a is a general formula A;
wherein Me is methyl, Vi is vinyl, a is 1-5, the kinematic viscosity of the compound conforming to the general formula A is 500-10000 centipoises at 25 ℃, and the mass fraction of the vinyl functional group is 0.01-1%;
(ViMe2SiO1/2)(Me2SiO)b(MeSiO3/2) c is a general formula B;
wherein Me is methyl, Vi is vinyl, B/c is 1-10, the kinematic viscosity of the compound conforming to the general formula B is 5000-10000 centipoises at 25 ℃, and the mass fraction of the vinyl functional group is 0.5-5%;
ViMe3SiO1/2)2(Me2SiO)d
wherein Me is methyl, Vi is vinyl, d is 50-500, the kinematic viscosity of the compound corresponding to the general formula C is 100-100000 at 25 ℃, and the mass fraction of the vinyl functional group is 0.05-2%.
The preferable technical scheme is as follows: the methyl hydrogenpolysiloxane is at least one of compounds conforming to general formulas D, E and F:
[(CH3)3SiO1/2]x[(CH3)R1SiO2/2]y[R2SiO3/2]m[SiO4/2]n is represented by the general formula D;
wherein, x is 1-5, y is 1-5, m is 1-5, n is 1-5;
[(CH3)2R1SiO1/2]x[(CH3)R2SiO2/2]y[R3SiO3/2]m[SiO4/2]n is of the general formula E;
wherein, x is 1-5, y is 1-5, m is 1-5, n is 1-5;
[(CH3)2R1SiO1/2][(CH3)2SiO2/2]x[R2SiO3/2]y is of the formula F;
wherein, x is 1-5, y is 1-5;
wherein R1, R2 and R3 respectively and independently represent gamma-glycidoxypropyl, gamma-methacryloxypropyl, gamma-mercaptopropyltriethoxy, hydrogen radical and active functional group containing hydrogen radical.
The preferable technical scheme is as follows: the chain extender is a compound conforming to the following general formula:
(HMe2SiO1/2)x(MeSiO3/2)y
wherein Me is methyl, x is 1-10, y/x is 1-5, and the kinematic viscosity is 100-10000 at 25 ℃.
The preferable technical scheme is as follows: the isolating agent is at least one of talcum powder, fullerene, carbon nano tube, fumed silica and precipitated silica.
The preferable technical scheme is as follows: the graphene is at least one of single-layer graphene, double-layer graphene and multi-layer graphene; the loose density of the graphene is 0.01-0.05g/cm3Within the range of 0.05-0.1 g/cm in tap density3。
The preferable technical scheme is as follows: the structural control agent is at least one of hydroxyl-terminated polydimethylsiloxane, diphenyl silanediol, dimethyldialkoxysilane and hexamethyldisilazane with low molar mass.
The preferable technical scheme is as follows: the silane coupling agent is a compound corresponding to the following general formula:
YRnSiX3-n
wherein Y represents a mercapto group, a long chain alkyl group, an epoxy group or a methacryloxy group, R represents an alkylene group, X represents a group capable of hydrolysis, and n is 0 or 1. The alkylene group is a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms. The group capable of hydrolysis means a group capable of being detached from the main skeleton of the compound by a hydrolysis reaction. For example: -OR, -OCOR, -O-N ═ CR2, -NR2, -NHR, and halogen, wherein R represents a substituted OR unsubstituted alkyl group having 1 to 4 carbon atoms, etc., and is preferably-OR (i.e., alkoxy group). Examples of R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, etc.; chloromethyl, etc. Among these, an alkyl group is preferable, an unsubstituted alkyl group is particularly preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, and may be a hydroxyl group formed by hydrolysis of a hydrolyzable group.
The preferable technical scheme is as follows: the silicone-based inhibitor is at least one of MVC, DVS, 3- (trimethylsilyl) propiolic alcohol, 1-ethynyl-1-cyclohexanol and 1-ethynylcyclohexanol.
The preferable technical scheme is as follows: the foaming agent is at least one of sodium bicarbonate, ammonium bicarbonate, azodicarbonamide, N-dinitrosopentamethylenetetramine, diphenylsulfonyl hydrazide ether, diazoaminobenzene, p-toluenesulfonhydrazide and azobisisobutyronitrile.
The preferable technical scheme is as follows: the knot formula of the methyl vinyl MQ silicon resin is as follows:
[(CH3)2(CH2＝CH)Si01/2]a[(CH3)3Si01/2]b[Si04/2]c
wherein [ (CH)3)2(CH2＝CH)Si01/2]a[(CH3)3Si01/2]b is M structure, [ Si0 ]4/2]c is a Q structure, the M: Q value is 0.5-1, the kinematic viscosity is 1000-100000 at 25 ℃, and the mass fraction of the vinyl functional group is 0.1% -5%.
The preferable technical scheme is as follows: the platinum catalyst is at least one of a Kanst platinum catalyst and a chloroplatinic acid-ketone, alkene, ester, alcohol, ether or polysiloxane complex platinum catalyst, wherein the concentration of platinum metal is 100-10000 ppm.
The preferable technical scheme is as follows: the activating agent is at least one of zinc oxide, magnesium oxide, alum, stearic acid, zinc acetate, urea, benzoic acid, salicylic acid, dihydric alcohol, ethylenediamine and diphenylguanidine.
In order to achieve the above objects and other related objects, the present invention provides the following technical solutions: a method for preparing an graphene-based organosilicon porous nanomaterial comprises the following steps: the method is characterized in that: comprises a preparation method of the component A and a preparation method of the component B; the preparation method of the component A comprises the following steps: dispersing a separant, graphene and a foaming agent in a mixed system consisting of methyl vinyl polysiloxane, methyl hydrogen-containing polysiloxane, a chain extender, a structural control agent, a silane coupling agent and a silicone-based inhibitor to prepare a component A;
the preparation method of the component B comprises the following steps: and dispersing the separant, the graphene and the activating agent in a mixed system consisting of methyl vinyl polysiloxane, methyl vinyl MQ silicon resin, a structural control agent and a catalyst to prepare a component B.
The preferable technical scheme is as follows: the vacuum negative pressure during dispersion is-0.08 to-0.1 Mpa, and the rotating speed of the stirring paddle is 30 to 50 r/min; the rotating speed of the dispersion disc is 800-1200 r/min.
Due to the application of the technical scheme, compared with the prior art, the invention has the advantages that:
the graphene-based organic silicon porous nano material prepared by the invention has the advantages of light weight, viscoelasticity and fine and uniform cross-section pores. The graphene nano film and the organic silicon material substrate interact, the bonding substrate is firm, and the compression resistance, impact resistance and thermal stability performance are excellent, so that the graphene nano film is suitable for light application scenes such as sealing shock absorption, microwave absorption, electromagnetic shielding and heat dissipation protection.
Detailed Description
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure.
Example 1: graphene-based organic silicon porous nano material and preparation method thereof
A graphene-based organosilicon porous nanomaterial comprises a component A and a component B in a weight ratio of 1.5:1, wherein the component A comprises the following raw materials in parts by weight: 30 parts of methyl vinyl polysiloxane; 12.5 parts of methyl hydrogenpolysiloxane; 2.55 parts of a chain extender; 5 parts of a release agent; 18 parts of graphene; 1 part of a structural control agent; 1 part of a silane coupling agent; 0.5 part of silicone-based inhibitor; 2.6 parts of foaming agent.
The component B comprises the following raw materials in parts by weight: 15 parts of methyl vinyl polysiloxane; 20 parts of methyl vinyl MQ silicon resin; 5 parts of a release agent; 18 parts of graphene; 1.02 parts of a structural control agent; 0.5 part of a catalyst; and 2.75 parts of an activating agent.
The preferable technical scheme is as follows: the methylvinylpolysiloxane is at least one of the compounds corresponding to the general formulae A, B and C:
(ViMe2SiO1/2)(MeSiO3/2) a is a general formula A;
wherein Me is methyl, Vi is vinyl, a is 1-5, the kinematic viscosity of the compound conforming to the general formula A is 500-10000 centipoises at 25 ℃, and the mass fraction of the vinyl functional group is 0.01-1%;
(ViMe2SiO1/2)(Me2SiO)b(MeSiO3/2) c is a general formula B;
wherein Me is methyl, Vi is vinyl, B/c is 1-10, the kinematic viscosity of the compound conforming to the general formula B is 5000-10000 centipoises at 25 ℃, and the mass fraction of the vinyl functional group is 0.5-5%;
ViMe3SiO1/2)2(Me2SiO)d
wherein Me is methyl, Vi is vinyl, d is 50-500, the kinematic viscosity of the compound corresponding to the general formula B is 100-100000 at 25 ℃, and the mass fraction of the vinyl functional group is 0.05-2%.
The preferable technical scheme is as follows: the methyl hydrogenpolysiloxane is at least one of compounds conforming to general formulas D, E and F:
[(CH3)3SiO1/2]x[(CH3)R1SiO2/2]y[R2SiO3/2]m[SiO4/2]n is represented by the general formula D;
wherein, x is 1-5, y is 1-5, m is 1-5, n is 1-5;
[(CH3)2R1SiO1/2]x[(CH3)R2SiO2/2]y[R3SiO3/2]m[SiO4/2]n is of the general formula E;
wherein, x is 1-5, y is 1-5, m is 1-5, n is 1-5;
[(CH3)2R1SiO1/2][(CH3)2SiO2/2]x[R2SiO3/2]y is of the formula F;
wherein, x is 1-5, y is 1-5;
wherein R1, R2 and R3 respectively and independently represent gamma-glycidoxypropyl, gamma-methacryloxypropyl, gamma-mercaptopropyltriethoxy, hydrogen radical and active functional group containing hydrogen radical.
The preferable technical scheme is as follows: the chain extender is a compound conforming to the following general formula:
(HMe2SiO1/2)x(MeSiO3/2)y
wherein Me is methyl, x is 1-10, y/x is 1-5, and the kinematic viscosity is 100-10000 at 25 ℃.
The preferable technical scheme is as follows: the isolating agent is at least one of talcum powder, fullerene, carbon nano tube, fumed silica and precipitated silica.
The preferable technical scheme is as follows: the graphene is at least one of single-layer graphene, double-layer graphene and multi-layer graphene; the loose density of the graphene is 0.01-0.05g/cm3Within the range of 0.05-0.1 g/cm in tap density3。
The preferable technical scheme is as follows: the structural control agent is at least one of hydroxyl-terminated polydimethylsiloxane, diphenyl silanediol, dimethyldialkoxysilane and hexamethyldisilazane with low molar mass.
The preferable technical scheme is as follows: the silane coupling agent is a compound corresponding to the following general formula:
YRnSiX3-n
wherein Y represents a mercapto group, a long chain alkyl group, an epoxy group or a methacryloxy group, R represents an alkylene group, X represents a group capable of hydrolysis, and n is 0 or 1. The alkylene group is a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms. The group capable of hydrolysis means a group capable of being detached from the main skeleton of the compound by a hydrolysis reaction. For example: -OR, -OCOR, -O-N ═ CR2, -NR2, -NHR, and halogen, wherein R represents a substituted OR unsubstituted alkyl group having 1 to 4 carbon atoms, etc., and is preferably-OR (i.e., alkoxy group). Examples of R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, etc.; chloromethyl, etc. Among these, an alkyl group is preferable, an unsubstituted alkyl group is particularly preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, and may be a hydroxyl group formed by hydrolysis of a hydrolyzable group.
The preferable technical scheme is as follows: the silicone-based inhibitor is at least one of MVC, DVS, 3- (trimethylsilyl) propiolic alcohol, 1-ethynyl-1-cyclohexanol and 1-ethynylcyclohexanol.
The preferable technical scheme is as follows: the foaming agent is at least one of sodium bicarbonate, ammonium bicarbonate, azodicarbonamide, N-dinitrosopentamethylenetetramine, diphenylsulfonyl hydrazide ether, diazoaminobenzene, p-toluenesulfonhydrazide and azobisisobutyronitrile.
The preferable technical scheme is as follows: the knot formula of the methyl vinyl MQ silicon resin is as follows:
[(CH3)2(CH2＝CH)Si01/2]a[(CH3)3Si01/2]b[Si04/2]c
wherein [ (CH)3)2(CH2＝CH)Si01/2]a[(CH3)3Si01/2]b is M structure, [ Si0 ]4/2]c is a Q structure, the M: Q value is 0.5-1, the kinematic viscosity is 1000-100000 at 25 ℃, and the mass fraction of the vinyl functional group is 0.1% -5%.
The preferable technical scheme is as follows: the platinum catalyst is at least one of a Kanst platinum catalyst and a chloroplatinic acid-ketone, alkene, ester, alcohol, ether or polysiloxane complex platinum catalyst, wherein the concentration of platinum metal is 100-10000 ppm.
The preferable technical scheme is as follows: the activating agent is at least one of zinc oxide, magnesium oxide, alum, stearic acid, zinc acetate, urea, benzoic acid, salicylic acid, dihydric alcohol, ethylenediamine and diphenylguanidine.
The preparation method comprises the following steps: comprises a preparation method of a component A and a preparation method of a component B, wherein the preparation method of the component A comprises the following steps: 5 parts of separant, 18 parts of graphene and 2.6 parts of foaming agent are dispersed in a mixed system of 10-50 parts of methyl vinyl polysiloxane, 12.5 parts of methyl hydrogen-containing polysiloxane, 2.55 parts of chain extender, 1 part of structural control agent, 1 part of silane coupling agent and 0.5 part of silicone-based inhibitor by high-speed stirring in batches under the conditions of vacuum negative pressure and circulating water cooling to prepare the component A.
The preparation method of the component B comprises the following steps: 5 parts of separant, 18 parts of graphene and 2.75 parts of activating agent are dispersed in a mixed system of 15 parts of methyl vinyl polysiloxane, 20 parts of methyl vinyl MQ silicon resin, 1.02 parts of structural control agent and 0.5 part of catalyst by high-speed stirring in batches under the conditions of vacuum negative pressure and circulating water cooling to prepare the component B.
The vacuum negative pressure is-0.09 MPa, and the rotating speed of the stirring paddle is 40 r/min; the rotating speed of the dispersion disc is 1000 r/min.
Example 2: graphene-based organic silicon porous nano material and preparation method thereof
A graphene-based organic silicon porous nano material is formed by mixing a component A and a component B according to the mass ratio of 1: 1;
the component A comprises the following raw materials in parts by weight:
Figure BDA0002349611140000071
the component B comprises the following raw materials in parts by weight:
Figure BDA0002349611140000081
the preferable technical scheme is as follows: the methylvinylpolysiloxane is a compound corresponding to the general formula A:
(ViMe2SiO1/2)(MeSiO3/2) a is a general formula A;
wherein Me is methyl, Vi is vinyl, a-2, the kinematic viscosity of the compound corresponding to formula A is 8000 centipoises at 25 ℃, and the mass fraction of vinyl functional groups is 0.02%.
The preferable technical scheme is as follows: the methyl hydrogenpolysiloxane is a compound conforming to a general formula D:
[(CH3)3SiO1/2]x[(CH3)R1SiO2/2]y[R2SiO3/2]m[SiO4/2]n is represented by the general formula D;
wherein x is 2, y is 1, m is 2, and n is 3;
wherein, R1 gamma-glycidoxypropyl and R2 hydrogen radical.
The preferable technical scheme is as follows: the chain extender is a compound conforming to the following general formula:
(HMe2SiO1/2)x(MeSiO3/2)y
wherein Me is methyl, x-2, and y-6 has a kinematic viscosity of 5000 at 25 ℃.
The preferable technical scheme is as follows: the separant is talcum powder.
The preferable technical scheme is as follows: the graphene is single-layer graphene; the loose density of the graphene is 0.01g/cm3Within, the tap density is 0.05g/cm3。
The preferable technical scheme is as follows: the structural control agent is diphenyl silanediol.
The preferable technical scheme is as follows: the silane coupling agent is a compound corresponding to the following general formula:
YRnSiX3-n
wherein Y represents mercapto, R represents methyl, X represents propyl, and n-1. The alkylene group is a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms. The group capable of hydrolysis means a group capable of being detached from the main skeleton of the compound by a hydrolysis reaction. For example: -OR, -OCOR, -O-N ═ CR2, -NR2, -NHR, and halogen, wherein R represents a substituted OR unsubstituted alkyl group having 1 to 4 carbon atoms, etc., and is preferably-OR (i.e., alkoxy group). Examples of R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, etc.; chloromethyl, etc. Among these, an alkyl group is preferable, an unsubstituted alkyl group is particularly preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, and may be a hydroxyl group formed by hydrolysis of a hydrolyzable group.
The preferable technical scheme is as follows: the silicone-based inhibitor is 3- (trimethylsilyl) propiolic alcohol.
The preferable technical scheme is as follows: the foaming agent is sodium bicarbonate.
The preferable technical scheme is as follows: the knot formula of the methyl vinyl MQ silicon resin is as follows:
[(CH3)2(CH2＝CH)Si01/2]a[(CH3)3Si01/2]b[Si04/2]c
wherein [ (CH)3)2(CH2＝CH)Si01/2]a[(CH3)3Si01/2]b is M structure, [ Si0 ]4/2]c is a Q structure, the M: Q value is 0.6, the kinematic viscosity is 40000 at 25 ℃, and the mass fraction of the vinyl functional group is 0.2%.
The preferable technical scheme is as follows: the platinum catalyst is a Kanst platinum catalyst and chloroplatinic acid-ketone, wherein the concentration of platinum metal is 5000 ppm.
The preferable technical scheme is as follows: the activating agent is zinc oxide.
The method for preparing the graphene-based organic silicon porous nano material comprises the following steps: the method is characterized in that: comprises a preparation method of the component A and a preparation method of the component B; the preparation method of the component A comprises the following steps: dispersing a separant, graphene and a foaming agent in a mixed system consisting of methyl vinyl polysiloxane, methyl hydrogen-containing polysiloxane, a chain extender, a structural control agent, a silane coupling agent and a silicone-based inhibitor to prepare a component A;
the preparation method of the component B comprises the following steps: and dispersing the separant, the graphene and the activating agent in a mixed system consisting of methyl vinyl polysiloxane, methyl vinyl MQ silicon resin, a structural control agent and a catalyst to prepare a component B.
When in use, the component A and the component B are mixed
The preferable technical scheme is as follows: the vacuum negative pressure during dispersion is-0.08 Mpa, and the rotating speed of the stirring paddle is 30 r/min; the rotating speed of the dispersion disc is 800 r/min.
Example 3: graphene-based organic silicon porous nano material and preparation method thereof
A graphene-based organic silicon porous nano material is formed by mixing a component A and a component B according to the mass ratio of 2: 1;
the component A comprises the following raw materials in parts by weight:
Figure BDA0002349611140000091
Figure BDA0002349611140000101
the component B comprises the following raw materials in parts by weight:
Figure BDA0002349611140000102
the preferable technical scheme is as follows: the methylvinylpolysiloxane is a compound corresponding to the general formulae A, B and C according to 1: 1:1 in mass ratio:
(ViMe2SiO1/2)(MeSiO3/2) a is a general formula A;
wherein Me is methyl, Vi is vinyl, a is 5, the kinematic viscosity of the compound conforming to the general formula A is 10000 centipoises at 25 ℃, and the mass fraction of the vinyl functional group is 1%;
(ViMe2SiO1/2)(Me2SiO)b(MeSiO3/2) c is a general formula B;
wherein Me is methyl, Vi is vinyl, B/c is 10, at 25 ℃, the kinematic viscosity of the compound conforming to the general formula B is 10000 centipoises, and the mass fraction of the vinyl functional group is 5 percent;
ViMe3SiO1/2)2(Me2SiO)d
where Me is methyl, Vi is vinyl and d is 500, the kinematic viscosity of the compound corresponding to formula B is 100000 and the mass fraction of vinyl functions is 2% at 25 ℃.
The preferable technical scheme is as follows: the methyl hydrogenpolysiloxane is a compound corresponding to a general formula D, a general formula E and a general formula F according to the formula 1: 1: 3 in mass ratio:
[(CH3)3SiO1/2]x[(CH3)R1SiO2/2]y[R2SiO3/2]m[SiO4/2]n is represented by the general formula D;
wherein x is 5, y is 5, m is 1, and n is 1;
[(CH3)2R1SiO1/2]x[(CH3)R2SiO2/2]y[R3SiO3/2]m[SiO4/2]n is of the general formula E;
wherein x is 5, y is 5, m is 1, and n is 1;
[(CH3)2R1SiO1/2][(CH3)2SiO2/2]x[R2SiO3/2]y is of the formula F;
wherein x is 1 and y is 2;
wherein R1 represents gamma-glycidoxypropyl group, R2 represents hydrogen group, and R3 represents gamma-methacryloxypropyl group.
The preferable technical scheme is as follows: the chain extender is a compound conforming to the following general formula:
(HMe2SiO1/2)x(MeSiO3/2)y
where Me is methyl, x-5, y/x-1, and has a kinematic viscosity of 5000 at 25 ℃.
The preferable technical scheme is as follows: the separant is talcum powder fumed silica according to a weight ratio of 1:1 in a mass ratio.
The preferable technical scheme is as follows: the graphene is a single-layer graphene or a double-layer graphene, and the ratio of the graphene to the double-layer graphene is 1:1 in a mass ratioAn agent; the loose density of the graphene is 0.03g/cm3Within, the tap density is 0.08g/cm3。
The preferable technical scheme is as follows: the structural control agent is low-molar-mass hydroxyl-terminated polydimethylsiloxane and diphenyl silanediol, and the weight ratio of the hydroxyl-terminated polydimethylsiloxane to the diphenyl silanediol is 1:1 in a mass ratio.
The preferable technical scheme is as follows: the silane coupling agent conforms to the general structural formula YRnSiX3-nWherein Y represents an organic functional group, R represents an alkylene group, X represents a group capable of hydrolysis, and n is 0 to 3; the functional additive of (1); n is 1 and Y is amino; the alkylene group is a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, and specifically, a methylene group in this embodiment. The group capable of hydrolysis means a group capable of being detached from the main skeleton of the compound by a hydrolysis reaction. For example: -OR, -OCOR, -O-N ═ CR2, -NR2, -NHR, and halogen, wherein R represents a substituted OR unsubstituted alkyl group having 1 to 4 carbon atoms, etc., and is preferably-OR (i.e., alkoxy group). Examples of R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, etc.; chloromethyl, etc. Among these, an alkyl group is preferable, an unsubstituted alkyl group is particularly preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, and may be a hydroxyl group formed by hydrolysis of a hydrolyzable group. This example is specifically a propyl group.
The preferable technical scheme is as follows: the silicone-based inhibitor is DVS.
The preferable technical scheme is as follows: the foaming agent is azobisisobutyronitrile.
The preferable technical scheme is as follows: the knot formula of the methyl vinyl MQ silicon resin is as follows:
[(CH3)2(CH2＝CH)Si01/2]a[(CH3)3Si01/2]b[Si04/2]c
wherein [ (CH)3)2(CH2＝CH)Si01/2]a[(CH3)3Si01/2]b is M structure, [ Si0 ]4/2]c is a Q structure, the M: Q value is 1, the kinematic viscosity is 1000-100000 at 25 ℃, and the mass fraction of the vinyl functional groupThe number was 5%.
The preferable technical scheme is as follows: the platinum catalyst is a Kanst platinum catalyst and chloroplatinic acid-ketone according to the weight ratio of 1:1, wherein the concentration of platinum metal is 10000 ppm.
The preferable technical scheme is as follows: the activating agent is alum.
The method for preparing the graphene-based organic silicon porous nano material comprises the following steps: the method is characterized in that: comprises a preparation method of the component A and a preparation method of the component B; the preparation method of the component A comprises the following steps: dispersing a separant, graphene and a foaming agent in a mixed system consisting of methyl vinyl polysiloxane, methyl hydrogen-containing polysiloxane, a chain extender, a structural control agent, a silane coupling agent and a silicone-based inhibitor to prepare a component A;
the preparation method of the component B comprises the following steps: and dispersing the separant, the graphene and the activating agent in a mixed system consisting of methyl vinyl polysiloxane, methyl vinyl MQ silicon resin, a structural control agent and a catalyst to prepare a component B.
The preferable technical scheme is as follows: the vacuum negative pressure during dispersion is-0.1 Mpa, and the rotating speed of the stirring paddle is 50 r/min; the rotating speed of the dispersion disc is 1200 r/min.
Example 4: graphene-based organic silicon porous nano material and preparation method thereof
The other embodiments are different from the embodiment 2 in that:
the preferable technical scheme is as follows: the methylvinylpolysiloxane is a compound corresponding to the general formula B:
(ViMe2SiO1/2)(Me2SiO)b(MeSiO3/2) c is a general formula B;
wherein Me is methyl, Vi is vinyl, B/c is 5, the kinematic viscosity of the compound corresponding to the general formula B is 5000-10000 centipoises at 25 ℃, and the mass fraction of the vinyl functional group is 0.5-5%.
The preferable technical scheme is as follows: the methyl hydrogenpolysiloxane is a compound conforming to a general formula E:
[(CH3)2R1SiO1/2]x[(CH3)R2SiO2/2]y[R3SiO3/2]m[SiO4/2]n is of the general formula E;
wherein x is 1, y is 1, m is 2, and n is 3;
wherein R1, R2 and R3 represent hydrogen.
The preferable technical scheme is as follows: the chain extender is a compound conforming to the following general formula:
(HMe2SiO1/2)x(MeSiO3/2)y
where Me is methyl, x-5, y-10, y/x-2, kinematic viscosity at 25 ℃ 16000.
The preferable technical scheme is as follows: the separant is talcum powder and precipitated white carbon black according to the weight ratio of 1:1 in a mass ratio.
The preferable technical scheme is as follows: the graphene is at least one of multi-layer graphene; the loose density of the graphene is 0.01-0.05g/cm3Within the range of 0.05-0.1 g/cm in tap density3。
The preferable technical scheme is as follows: the structuring control agent is diphenyl silanediol with low molar mass.
The preferable technical scheme is as follows: the silane coupling agent is a compound corresponding to the following general formula:
YRnSiX3-n
wherein Y represents mercapto, R represents butylene, X represents propyl, and n-1. The alkylene group is a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms. The group capable of hydrolysis means a group capable of being detached from the main skeleton of the compound by a hydrolysis reaction. For example: -OR, -OCOR, -O-N ═ CR2, -NR2, -NHR, and halogen, wherein R represents a substituted OR unsubstituted alkyl group having 1 to 4 carbon atoms, etc., and is preferably-OR (i.e., alkoxy group). Examples of R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, etc.; chloromethyl, etc. Among these, an alkyl group is preferable, an unsubstituted alkyl group is particularly preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, and may be a hydroxyl group formed by hydrolysis of a hydrolyzable group.
The preferable technical scheme is as follows: the silicone-based inhibitor is 1-ethynyl-1-cyclohexanol and 1-ethynylcyclohexanol according to a 1:1 in a mass ratio.
The preferable technical scheme is as follows: the foaming agent is diphenyl sulfonyl hydrazide ether and diazoaminobenzene, and the weight ratio of the foaming agent to the foaming agent is 1:1 in a mass ratio.
The preferable technical scheme is as follows: the knot formula of the methyl vinyl MQ silicon resin is as follows:
[(CH3)2(CH2＝CH)Si01/2]a[(CH3)3Si01/2]b[Si04/2]c
wherein [ (CH)3)2(CH2＝CH)Si01/2]a[(CH3)3Si01/2]b is M structure, [ Si0 ]4/2]The c is a Q structure, the M: Q value is 0.7, the kinematic viscosity is 4000 at 25 ℃, and the mass fraction of the vinyl functional group is 0.8%.
The preferable technical scheme is as follows: the platinum catalyst is a Kanst platinum catalyst, wherein the concentration of platinum metal is 80000 ppm.
The preferable technical scheme is as follows: the activating agent is zinc oxide and magnesium oxide, and the weight ratio of zinc oxide to magnesium oxide is 1:1 in a mass ratio.
Example 5: graphene-based organic silicon porous nano material and preparation method thereof
The other embodiments are different from the embodiment 3 in that:
the preferable technical scheme is as follows: the methylvinylpolysiloxane is a compound corresponding to the general formula C:
ViMe3SiO1/2)2(Me2SiO) d is represented by the general formula C;
where Me is methyl, Vi is vinyl, d-100, the kinematic viscosity of the compound corresponding to formula C is 65000 and the mass fraction of vinyl functional groups is 1.5% at 25 ℃.
The preferable technical scheme is as follows: the methyl hydrogenpolysiloxane is a compound conforming to the general formula F:
[(CH3)2R1SiO1/2][(CH3)2SiO2/2]x[R2SiO3/2]y is of the formula F;
wherein x is 5 and y is 5;
wherein R1 represents gamma-glycidoxypropyl group, R2 represents gamma-mercaptopropyltriethoxy group and R3 represents hydrogen group.
The preferable technical scheme is as follows: the chain extender is a compound conforming to the following general formula:
(HMe2SiO1/2)x(MeSiO3/2)y
where Me is methyl, x-2, y-6, y/x-3, and a kinematic viscosity of 1000 at 25 ℃.
The preferable technical scheme is as follows: the release agent is fullerene.
The preferable technical scheme is as follows: the graphene is single-layer graphene; the loose density of the graphene is 0.01g/cm3Within, the tap density is 0.05g/cm3。
The preferable technical scheme is as follows: the structural control agent is dimethyl dialkoxy silane.
The preferable technical scheme is as follows: the silane coupling agent is a compound corresponding to the following general formula:
YRnSiX3-n
wherein Y represents an epoxy group, R represents a pentylene group, X represents Cl, and n-1. The alkylene group is a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms. The group capable of hydrolysis means a group capable of being detached from the main skeleton of the compound by a hydrolysis reaction. For example: -OR, -OCOR, -O-N ═ CR2, -NR2, -NHR, and halogen, wherein R represents a substituted OR unsubstituted alkyl group having 1 to 4 carbon atoms, etc., and is preferably-OR (i.e., alkoxy group). Examples of R include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, etc.; chloromethyl, etc. Among these, an alkyl group is preferable, an unsubstituted alkyl group is particularly preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, and may be a hydroxyl group formed by hydrolysis of a hydrolyzable group.
The preferable technical scheme is as follows: the silicone-based inhibitor is MVC.
The preferable technical scheme is as follows: the foaming agent is sodium bicarbonate and ammonium bicarbonate, and the foaming agent is prepared from the following raw materials in percentage by weight of 1:1 in a mass ratio.
The preferable technical scheme is as follows: the knot formula of the methyl vinyl MQ silicon resin is as follows:
[(CH3)2(CH2＝CH)Si01/2]a[(CH3)3Si01/2]b[Si04/2]c
wherein [ (CH)3)2(CH2＝CH)Si01/2]a[(CH3)3Si01/2]b is M structure, [ Si0 ]4/2]c is a Q structure, the M: Q value is 0.5, the kinematic viscosity is 1000 at 25 ℃, and the mass fraction of the vinyl functional group is 0.1 percent.
The preferable technical scheme is as follows: the platinum catalyst is a platinum catalyst and chloroplatinic acid-ester according to the weight ratio of 1:1, wherein the concentration of platinum metal is 5000 ppm.
The preferable technical scheme is as follows: the activator is stearic acid.
The foregoing is illustrative of the preferred embodiment of the present invention and is not to be construed as limiting thereof in any way, and any modifications or variations thereof that fall within the spirit of the invention are intended to be included within the scope thereof.

Claims (15)

1. A graphene-based organosilicon porous nanomaterial is characterized in that: the paint is formed by mixing a component A and a component B according to the mass ratio of 1-2: 1;
the component A comprises the following raw materials in parts by weight:
Figure FDA0002349611130000011
the component B comprises the following raw materials in parts by weight:
Figure FDA0002349611130000012
2. the graphene-based silicone porous nanomaterial according to claim 1, characterized in that: the methylvinylpolysiloxane is at least one of the compounds corresponding to the general formulae A, B and C:
(ViMe2SiO1/2)(MeSiO3/2) a is a general formula A;
wherein Me is methyl, Vi is vinyl, a is 1-5, the kinematic viscosity of the compound conforming to the general formula A is 500-10000 centipoises at 25 ℃, and the mass fraction of the vinyl functional group is 0.01-1%;
(ViMe2SiO1/2)(Me2SiO)b(MeSiO3/2) c is a general formula B;
wherein Me is methyl, Vi is vinyl, B/c is 1-10, the kinematic viscosity of the compound conforming to the general formula B is 5000-10000 centipoises at 25 ℃, and the mass fraction of the vinyl functional group is 0.5-5%;
ViMe3SiO1/2)2(Me2SiO) d is represented by the general formula C;
wherein Me is methyl, Vi is vinyl, d is 50-500, the kinematic viscosity of the compound corresponding to the general formula C is 100-100000 at 25 ℃, and the mass fraction of the vinyl functional group is 0.05-2%.
3. The graphene-based silicone porous nanomaterial according to claim 1, characterized in that: the methyl hydrogenpolysiloxane is at least one of compounds conforming to general formulas D, E and F:
[(CH3)3SiO1/2]x[(CH3)R1SiO2/2]y[R2SiO3/2]m[SiO4/2]n is represented by the general formula D;
wherein, x is 1-5, y is 1-5, m is 1-5, n is 1-5;
[(CH3)2R1SiO1/2]x[(CH3)R2SiO2/2]y[R3SiO3/2]m[SiO4/2]n is of the general formula E;
wherein, x is 1-5, y is 1-5, m is 1-5, n is 1-5;
[(CH3)2R1SiO1/2][(CH3)2SiO2/2]x[R2SiO3/2]y is of the formula F;
wherein, x is 1-5, y is 1-5;
wherein R1, R2 and R3 respectively and independently represent gamma-glycidoxypropyl, gamma-methacryloxypropyl, gamma-mercaptopropyltriethoxy, hydrogen radical and active functional group containing hydrogen radical.
4. The graphene-based silicone porous nanomaterial according to claim 1, characterized in that: the chain extender is a compound conforming to the following general formula:
(HMe2SiO1/2)x(MeSiO3/2)y
wherein Me is methyl, x is 1-10, y/x is 1-5, and the kinematic viscosity is 100-10000 at 25 ℃.
5. The graphene-based silicone porous nanomaterial according to claim 1, characterized in that: the isolating agent is at least one of talcum powder, fullerene, carbon nano tube, fumed silica and precipitated silica.
6. The graphene-based silicone porous nanomaterial according to claim 1, characterized in that: the graphene is at least one of single-layer graphene, double-layer graphene and multi-layer graphene; the loose density of the graphene is 0.01-0.05g/cm3Within the range of 0.05-0.1 g/cm in tap density3。
7. The graphene-based silicone porous nanomaterial according to claim 1, characterized in that: the structural control agent is at least one of hydroxyl-terminated polydimethylsiloxane, diphenyl silanediol, dimethyldialkoxysilane and hexamethyldisilazane with low molar mass.
8. The graphene-based silicone porous nanomaterial according to claim 1, characterized in that: the silane coupling agent is a compound corresponding to the following general formula:
YRnSiX3-n
wherein Y represents a mercapto group, a long chain alkyl group, an epoxy group or a methacryloxy group, R represents an alkylene group, X represents a group capable of hydrolysis, and n is 0 or 1.
9. The graphene-based silicone porous nanomaterial according to claim 1, characterized in that: the silicone-based inhibitor is at least one of MVC, DVS, 3- (trimethylsilyl) propiolic alcohol, 1-ethynyl-1-cyclohexanol and 1-ethynylcyclohexanol.
10. The graphene-based silicone porous nanomaterial according to claim 1, characterized in that: the foaming agent is at least one of sodium bicarbonate, ammonium bicarbonate, azodicarbonamide, N-dinitrosopentamethylenetetramine, diphenylsulfonyl hydrazide ether, diazoaminobenzene, p-toluenesulfonhydrazide and azobisisobutyronitrile.
11. The graphene-based silicone porous nanomaterial according to claim 1, characterized in that: the knot formula of the methyl vinyl MQ silicon resin is as follows:
[(CH3)2(CH2＝CH)Si01/2]a[(CH3)3Si01/2]b[Si04/2]c
wherein [ (CH)3)2(CH2＝CH)Si01/2]a[(CH3)3Si01/2]b is M structure, [ Si0 ]4/2]c is a Q structure, the M: Q value is 0.5-1, the kinematic viscosity is 1000-100000 at 25 ℃, and the mass fraction of the vinyl functional group is 0.1% -5%.
12. The graphene-based silicone porous nanomaterial according to claim 1, characterized in that: the platinum catalyst is at least one of a Kanst platinum catalyst and a chloroplatinic acid-ketone, alkene, ester, alcohol, ether or polysiloxane complex platinum catalyst, wherein the concentration of platinum metal is 100-10000 ppm.
13. The graphene-based silicone porous nanomaterial according to claim 1, characterized in that: the activating agent is at least one of zinc oxide, magnesium oxide, alum, stearic acid, zinc acetate, urea, benzoic acid, salicylic acid, dihydric alcohol, ethylenediamine and diphenylguanidine.
14. A method of preparing the graphene-based silicone porous nanomaterial of any of claims 1-13: the method is characterized in that: comprises a preparation method of the component A and a preparation method of the component B; the preparation method of the component A comprises the following steps: dispersing a separant, graphene and a foaming agent in a mixed system consisting of methyl vinyl polysiloxane, methyl hydrogen-containing polysiloxane, a chain extender, a structural control agent, a silane coupling agent and a silicone-based inhibitor to prepare a component A;
the preparation method of the component B comprises the following steps: and dispersing the separant, the graphene and the activating agent in a mixed system consisting of methyl vinyl polysiloxane, methyl vinyl MQ silicon resin, a structural control agent and a catalyst to prepare a component B.
15. The method of claim 14, wherein: the vacuum negative pressure during dispersion is-0.08 to-0.1 Mpa, and the rotating speed of the stirring paddle is 30 to 50 r/min; the rotating speed of the dispersion disc is 800-1200 r/min.
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