阅读说明：本技术 一种改性氧化石墨烯材料及其制备方法和应用 (Modified graphene oxide material and preparation method and application thereof ) 是由 王政芳 李善吉 温华文 于 2021-08-27 设计创作，主要内容包括：本发明公开了一种改性氧化石墨烯材料及其制备方法和应用,所述改性氧化石墨烯由包括如下的原料反应得到：非离子型环氧乳化剂、氨基官能化氧化石墨烯；所述非离子型环氧乳化剂由含以下组分的原料聚合得到：丙烯酸酯单体、甲基丙烯酸酯单体、烯丙基聚醚、甲基丙烯酸缩水甘油酯。改性氧化石墨烯材料中同时含有环氧基、聚醚长链、聚丙烯酸酯链段和石墨烯结构,使得改性氧化石墨烯具有优异的水性和较强的乳化能力,且环氧基团与环氧树脂具有较好的相容性,从而提高了氧化石墨烯在环氧树脂中的分散性。(The invention discloses a modified graphene oxide material and a preparation method and application thereof, wherein the modified graphene oxide material is obtained by reacting the following raw materials: a non-ionic epoxy emulsifier, amino-functionalized graphene oxide; the nonionic epoxy emulsifier is obtained by polymerizing raw materials containing the following components: acrylate monomer, methacrylate monomer, allyl polyether and glycidyl methacrylate. The modified graphene oxide material simultaneously contains an epoxy group, a polyether long chain, a polyacrylate chain segment and a graphene structure, so that the modified graphene oxide has excellent water-based property and strong emulsifying capacity, and the epoxy group and the epoxy resin have good compatibility, thereby improving the dispersibility of the graphene oxide in the epoxy resin.)

1. A modified graphene oxide material is characterized in that: the modified graphene oxide is obtained by reacting the following raw materials: a non-ionic epoxy emulsifier, amino-functionalized graphene oxide; the nonionic epoxy emulsifier is obtained by polymerizing raw materials containing the following components: acrylate monomer and/or methacrylate monomer, allyl polyether, glycidyl methacrylate.

2. The modified graphene oxide material of claim 1, wherein: the mass ratio of the amino-functionalized graphene oxide to the nonionic epoxy emulsifier is 5-20: 100.

3. the modified graphene oxide material of claim 1, wherein: the raw materials for preparing the non-ionic epoxy emulsifier also comprise an initiator;

preferably, the nonionic epoxy emulsifier comprises the following preparation raw materials in parts by mass:

10-30 parts of acrylate monomer and/or methacrylate monomer

20-50 parts of allyl polyether

5-30 parts of glycidyl methacrylate

0.2-5 parts of an initiator.

4. The modified graphene oxide material according to any one of claims 1 to 3, wherein: the acrylate monomer comprises one or a mixture of more than one of methyl acrylate, ethyl acrylate, butyl acrylate and isobutyl acrylate; preferably, the methacrylate monomer is one or a mixture of more than one of methyl methacrylate, ethyl methacrylate, butyl methacrylate and isobutyl methacrylate.

5. The modified graphene oxide material according to any one of claims 1 to 3, wherein: the amino-functionalized graphene oxide is a reaction product of an aminosilane coupling agent and graphene oxide; preferably, the mass ratio of the aminosilane coupling agent to the graphene oxide is (1-5): 1.

6. the modified graphene oxide material of claim 5, wherein: the modified graphene oxide material has the following structural formula:

wherein R is₁is-CH₃Or H, R₂Is C_1～4The straight chain or branched chain-containing alkane of (1), m, n, x, y and z are independently integers between 1 and 100,represents a chain segment between Si and amino in the amino silane coupling agent; wherein R is₁is-CH₃Or H, R₂Is C_1～4The straight chain or branched chain-containing alkane of (1), m, n, x, y and z are independently integers of 1-100.

7. The method for preparing the modified graphene oxide material according to any one of claims 1 to 6, wherein: the method comprises the following steps:

mixing a nonionic epoxy emulsifier with amino-functionalized graphene oxide, and reacting to obtain the modified graphene oxide material.

8. An epoxy resin emulsion, characterized in that: the epoxy resin emulsion contains the modified graphene oxide material according to any one of claims 1 to 6; preferably, the epoxy resin emulsion contains an epoxy resin, a solvent and a modified graphene oxide material.

9. The process for producing an epoxy resin emulsion according to claim 8, wherein: the method comprises the following steps: and dispersing epoxy resin and the modified graphene oxide material in a solvent for an emulsification reaction to obtain an epoxy resin emulsion.

10. Use of the epoxy resin emulsion according to claim 8 for the preparation of epoxy anticorrosive coatings.

Technical Field

The invention relates to the technical field of emulsifiers, and particularly relates to a modified graphene oxide material and a preparation method and application thereof.

Background

The epoxy resin anticorrosive paint has the characteristics of good adhesive force, excellent chemical resistance, high hardness, chemical corrosion resistance, excellent friction performance, stability in solvent, salt mist resistance, alkali corrosion resistance, low cost and the like, and is suitable for steel structure protection in common corrosion and severe corrosion environments, such as light and heavy anticorrosive fields of road fences, ships, offshore platforms and the like. The traditional solvent-based epoxy anticorrosive paint is gradually replaced by more efficient, nontoxic and environment-friendly water-based heavy anticorrosive paint, which is a necessary trend. The main task of the water-based treatment in the field of epoxy resin heavy-duty anticorrosive paint is to perform water-based treatment on the epoxy resin which is a film-forming substance of the paint, and at present, the water-based treatment on the epoxy resin mainly comprises the following three ways: emulsifier adding method, chemical modifying method and curing agent emulsifying method.

Graphene has high thermal and chemical stability and can form a physical barrier layer between a metal surface and an active medium, thereby effectively blocking molecules such as water and oxygen from passing through. The graphene has the advantages of large specific surface area, excellent conductivity, ultrahigh strength, toughness, shielding property and the like, so that the graphene has potential application prospects in anticorrosive coatings. However, the poor dispersion performance of graphene in epoxy resin matrix seriously hinders the application of graphene oxide in epoxy anticorrosive coatings.

Disclosure of Invention

The present invention is directed to solving at least one of the problems of the prior art. Therefore, the modified graphene oxide material provided by the invention can be uniformly dispersed in epoxy resin, so that the corrosion resistance of the epoxy resin coating is improved.

Meanwhile, the invention also provides a preparation method and application of the modified graphene oxide material.

Specifically, the invention adopts the following technical scheme:

the first aspect of the present invention provides a modified graphene oxide material, wherein the modified graphene oxide material is obtained by reacting the following raw materials: a non-ionic epoxy emulsifier, amino-functionalized graphene oxide; the nonionic epoxy emulsifier is obtained by polymerizing raw materials containing the following components: acrylate monomer and/or methacrylate monomer, allyl polyether, glycidyl methacrylate.

The modified graphene oxide material according to the first aspect of the present invention has at least the following beneficial effects:

acrylate monomer and/or methacrylate monomer, allyl polyether, glycidyl methacrylate and the like are polymerized to form the nonionic epoxy emulsifier with polyacrylate chain segments, polyether long chains and epoxy groups, and the epoxy groups in the nonionic emulsifier are connected with the amino groups in the amino-functionalized graphene oxide, so that the graphene oxide can be connected to the nonionic epoxy emulsifier in the form of chemical bonds. The modified graphene oxide material simultaneously contains epoxy groups (the epoxy groups in the nonionic emulsifier can not completely react, and a part of the epoxy groups, polyether long chains, polyacrylate chain segments and a graphene structure are reserved in the modified graphene oxide material), so that the modified graphene oxide material has excellent water-based property and strong emulsifying capacity, and the epoxy groups and the epoxy resin have good compatibility, thereby improving the dispersibility of the graphene oxide in the epoxy resin.

In some embodiments of the invention, the mass ratio of the amino-functionalized graphene oxide to the nonionic epoxy emulsifier is 5-20: 100.

in some embodiments of the present invention, the raw materials for preparing the nonionic epoxy emulsifier further comprise an initiator.

In some embodiments of the present invention, the nonionic epoxy emulsifier comprises the following preparation raw materials in parts by mass:

10-30 parts of acrylate monomer and/or methacrylate monomer

20-50 parts of allyl polyether

5-30 parts of glycidyl methacrylate

0.2-5 parts of an initiator.

In some embodiments of the present invention, the raw material for preparing the nonionic epoxy emulsifier further comprises 50 to 100 parts of a solvent.

In some embodiments of the invention, the acrylate monomer comprises one or a mixture of more than one of methyl acrylate, ethyl acrylate, butyl acrylate, and isobutyl acrylate. The methacrylate monomer is one or a mixture of more than one of methyl methacrylate, ethyl methacrylate, butyl methacrylate and isobutyl methacrylate.

In some embodiments of the present invention, the initiator is an azo-based initiator, including at least one of azobisisobutyronitrile and azobisisoheptonitrile.

In some embodiments of the present invention, the solvent comprises at least one of benzene, toluene, and butanone.

In some embodiments of the invention, the amino-functionalized graphene oxide is the reaction product of an aminosilane coupling agent and graphene oxide. And (3) reacting Si-OH in the aminosilane coupling agent with functional groups such as hydroxyl, carboxyl and the like of the graphene oxide, so as to perform amino functionalization on the graphene oxide.

In some embodiments of the invention, the mass ratio of the aminosilane coupling agent to the graphene oxide is (1-5): 1.

in some embodiments of the invention, the aminosilane coupling agent comprises at least one of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, N-aminoethyl-gamma-aminopropylmethyldimethoxysilane, N-aminoethyl-gamma-aminopropyltriethoxysilane, N-aminoethyl-gamma-aminopropylmethyldiethoxysilane.

In some embodiments of the present invention, the amino-functionalized graphene oxide is prepared by mixing an aminosilane coupling agent with graphene oxide and reacting to obtain the amino-functionalized graphene oxide. The reaction temperature is 30-80 ℃, and the reaction time is 1-5 h.

In some embodiments of the present invention, the modified graphene oxide material has the following structural formula:

wherein R is₁is-CH₃Or H, R₂Is C_1～4The straight chain or branched chain-containing alkane of (1), m, n, x, y and z are independently integers between 1 and 100,represents a segment between Si and an amino group in an aminosilane coupling agent. In the structural formula, the epoxy groups remaining in the nonionic epoxy emulsifier are not shown.

In some embodiments of the present invention, when the aminosilane coupling agent comprises gamma-aminopropyltriethoxysilane and/or gamma-aminopropyltrimethoxysilane, the modified graphene oxide material has the following structural formula:

wherein R is₁is-CH₃Or H, R₂Is C_1～4The straight chain or branched chain-containing alkane is shown in the specification, and m, n, x, y and z are integers of 1-100 independently.

The second aspect of the present invention provides a preparation method of the modified graphene oxide material, including the following steps:

mixing a nonionic epoxy emulsifier with amino-functionalized graphene oxide, and reacting to obtain the modified graphene oxide material.

In some embodiments of the present invention, the reaction temperature of the nonionic epoxy emulsifier and the amino-functionalized graphene oxide is 10 to 50 ℃, preferably 20 to 30 ℃; the reaction time is 0.5-3 h.

In some embodiments of the present invention, the reaction of the nonionic epoxy emulsifier and the amino-functionalized graphene oxide further includes a step of removing the solvent, for example, the solvent can be removed by evaporation at 80 to 120 ℃ for 0.5 to 1 hour.

The third aspect of the present invention provides an epoxy resin emulsion containing the above-described modified graphene oxide material.

The fourth aspect of the present invention provides a method for preparing the epoxy resin emulsion, comprising the steps of: and dispersing epoxy resin and the modified graphene oxide material in a solvent for an emulsification reaction to obtain an epoxy resin emulsion.

The invention also provides an application of the epoxy resin emulsion in preparing epoxy anticorrosive paint.

In some embodiments of the present invention, the raw materials for preparing the epoxy anticorrosive paint comprise: epoxy resin emulsion, curing agent, filler and auxiliary agent. The curing agent, the filler and the auxiliary agent can be selected according to actual conditions, and are not limited. As an example, for example, one or more of a polyamide-based curing agent, a fatty amine-based curing agent, and a phenol-aldehyde amine-based curing agent may be used as the curing agent. The auxiliary agent comprises a defoaming agent, a dispersing agent, a flatting agent and the like, wherein the defoaming agent comprises a mineral oil defoaming agent, a polysiloxane defoaming agent and the like; the dispersing agent comprises polyacrylate, acrylate, sodium polycarboxylate, sodium carboxylate and the like; the leveling agent includes a cellulose dispersant, a siloxane dispersant, and the like. The proportion of the epoxy resin emulsion, the curing agent, the filler and the auxiliary agent can be adjusted according to the actual situation.

Compared with the prior art, the invention has the following beneficial effects:

according to the invention, reactive amino is modified on the surface of graphene oxide, acrylate monomers and/or methacrylate monomers, allyl polyether, glycidyl methacrylate and the like are polymerized to form a nonionic epoxy emulsifier with a polyacrylate chain segment and a polyether long chain, and the amino is reacted with the nonionic epoxy emulsifier to realize chemical connection of the graphene oxide and the nonionic epoxy emulsifier, so that the modified graphene oxide material is obtained.

The modified graphene oxide material simultaneously contains an epoxy group, a polyether long chain, a polyacrylate chain segment and a graphene structure, so that the modified graphene oxide has excellent water-based property and strong emulsifying capacity, and the epoxy group has good compatibility with epoxy resin, thereby improving the dispersibility of the graphene oxide in the epoxy resin.

Meanwhile, when the coating is prepared by using the emulsion formed by the modified graphene oxide material and the epoxy resin and the curing agent together, in the curing stage, the epoxy group in the modified graphene oxide material participates in the curing film-forming process, so that the modified graphene oxide material is prevented from being separated out in the coating to form a stable coating; the flexible polyether long chain in the modified graphene oxide material forms a flexible micro-area in the coating, so that the flexibility of the coating is improved; the polyacrylate chain segment and the epoxy resin form a cross-linked network structure, so that the toughness of the coating can be further improved, and the brittleness of the coating can be reduced.

Detailed Description

The technical solution of the present invention is further described below with reference to specific examples. The starting materials used in the following examples, unless otherwise specified, are available from conventional commercial sources; the processes used, unless otherwise specified, are conventional in the art.

Example 1

(1) Preparation of amino-functionalized graphene oxide

5g of gamma-aminopropyltriethoxysilane, 5g N-aminoethyl-gamma-aminopropyltrimethoxysilane and 10g of graphene oxide are reacted at 50 ℃ for 5 hours to obtain amino-functionalized graphene oxide.

(2) Preparation of nonionic epoxy emulsifier

80g of toluene, 10g of methyl acrylate, 5g of ethyl acrylate, 10g of butyl methacrylate, 5g of isobutyl methacrylate, 30g of allyl polyether and 20g of glycidyl methacrylate are mixed uniformly, 0.2g of initiator azobisisobutyronitrile is added, and the mixture is reacted at 110 ℃ for 3 hours to obtain the nonionic epoxy emulsifier.

(3) Preparation of modified graphene oxide material and epoxy resin emulsion

And (3) reacting 10g of the amino-functionalized graphene oxide prepared in the step (1) with 100g of the nonionic epoxy emulsifier prepared in the step (2) under the action of ultrasound for 0.8h, and performing rotary evaporation at 110 ℃ for 0.8h to remove the solvent, thereby obtaining the modified graphene oxide material.

Then, 100g of water and 50g of bisphenol A epoxy resin E epoxy resin were added to obtain an epoxy resin emulsion.

The solid content of the obtained epoxy resin emulsion is 52%, and the epoxy resin emulsion does not deteriorate (does not have layering, particle aggregation and sedimentation) after being stored for 6 months at normal temperature.

Example 2

(1) Preparation of amino-functionalized graphene oxide

15g of gamma-aminopropyltrimethoxysilane, 5g N-aminoethyl-gamma-aminopropylmethyldimethoxysilane and 10g of graphene oxide were reacted at 30 ℃ for 3 hours to obtain amino-functionalized graphene oxide.

(2) Preparation of nonionic epoxy emulsifier

40g of toluene, 10g of benzene, 5g of methyl acrylate, 5g of butyl acrylate, 5g of methyl methacrylate, 5g of ethyl methacrylate, 30g of allyl polyether and 10g of glycidyl methacrylate were mixed uniformly, 0.2g of azobisisoheptonitrile and 0.3g of azobisisobutyronitrile were added, and a reaction was carried out at 120 ℃ for 5 hours to obtain a nonionic epoxy emulsifier.

(3) Preparation of modified graphene oxide material and epoxy resin emulsion

And (3) reacting 20g of the amino-functionalized graphene oxide prepared in the step (1) with 100g of the nonionic epoxy emulsifier prepared in the step (2) under the action of ultrasound for 1h, and performing rotary evaporation at 120 ℃ for 0.5h to remove the solvent to obtain the modified graphene oxide material.

Then, 50g of water and 50g of bisphenol F type epoxy resin were added, and an emulsion reaction was carried out in an emulsifying machine to obtain an epoxy resin emulsion.

The solid content of the obtained epoxy resin emulsion is 70%, and the epoxy resin emulsion does not deteriorate (does not have layering, particle aggregation and sedimentation) after being stored for 6 months at normal temperature.

Example 3

(1) Preparation of amino-functionalized graphene oxide

Reacting 15g N-aminoethyl-gamma-aminopropyltriethoxysilane, 10g N-aminoethyl-gamma-aminopropylmethyldiethoxysilane and 10g graphene oxide at 60 ℃ for 2 hours to obtain amino-functionalized graphene oxide.

(2) Preparation of nonionic epoxy emulsifier

100g of butanone, 5g of methyl acrylate, 5g of isobutyl acrylate, 3g of ethyl methacrylate, 2g of butyl methacrylate, 50g of allyl polyether and 5g of glycidyl methacrylate are mixed uniformly, 0.5g of azobisisobutyronitrile and 0.3g of azobisisoheptonitrile are added, and the mixture is reacted at 80 ℃ for 8 hours to obtain the nonionic epoxy emulsifier.

(3) Preparation of modified graphene oxide material and epoxy resin emulsion

And (3) reacting 15g of the amino-functionalized graphene oxide prepared in the step (1) with 100g of the nonionic epoxy emulsifier prepared in the step (2) under the action of ultrasound for 2h, and rotationally evaporating at 80 ℃ for 1h to remove the solvent to obtain the modified graphene oxide material.

Then, 60g of water and 50g of bisphenol A epoxy resin E51 were added to carry out an emulsification reaction in an emulsifier to obtain an epoxy resin emulsion.

The solid content of the obtained epoxy resin emulsion is 64%, and the emulsion does not deteriorate (no layering, no particle aggregation and no sedimentation) after being stored for 6 months at normal temperature.

Example 4

(1) Preparation of amino-functionalized graphene oxide

Reacting 50g of gamma-aminopropyltriethoxysilane with 10g of graphene oxide at 60 ℃ for 1 hour to obtain amino-functionalized graphene oxide.

(2) Preparation of nonionic epoxy emulsifier

Uniformly mixing 80g of butanone serving as a solvent, 5g of methyl acrylate, 5g of methyl (meth) acrylate monomer, 25g of allyl polyether and 30g of glycidyl methacrylate, adding 2g of initiator, and reacting at 80 ℃ for 5 hours to obtain the nonionic epoxy emulsifier.

(3) Preparation of modified graphene oxide material and epoxy resin emulsion

And (3) reacting 5g of the amino-functionalized graphene oxide prepared in the step (1) with 100g of the nonionic epoxy emulsifier prepared in the step (2) under the action of ultrasound for 0.5h, and performing rotary evaporation at 80 ℃ for 0.8h to remove the solvent, thereby obtaining the modified graphene oxide material.

Then, 80g of water and 50g of bisphenol A epoxy resin E54 were added to carry out an emulsion reaction in an emulsifying machine, thereby obtaining an epoxy resin emulsion.

The solid content of the obtained epoxy resin emulsion is 55%, and the epoxy resin emulsion does not deteriorate (does not have layering, particle aggregation and sedimentation) after being stored for 6 months at normal temperature.

Example 5

(1) Preparation of amino-functionalized graphene oxide

20g of gamma-aminopropyltrimethoxysilane, 20g N-aminoethyl-gamma-aminopropyltrimethoxysilane and 10g of graphene oxide were reacted at 80 ℃ for 3 hours to obtain amino-functionalized graphene oxide.

(2) Preparation of nonionic epoxy emulsifier

100g of butanone 5g of ethyl acrylate monomer, 5g of isobutyl (meth) acrylate monomer, 40g of allyl polyether and 30g of glycidyl methacrylate are mixed uniformly, 5g of initiator is added, and reaction is carried out at 80 ℃ for 7 hours to obtain the nonionic epoxy emulsifier.

(3) Preparation of modified graphene oxide material and epoxy resin emulsion

And (3) reacting 12g of amino-functionalized graphene oxide prepared in the step (1) with 100g of nonionic epoxy emulsifier prepared in the step (2) under the action of ultrasound for 3h, and rotationally evaporating at 80 ℃ for 1h to remove the solvent to obtain the modified graphene oxide material.

Then, 80g of water and 50g of epoxy resin were added to carry out an emulsification reaction in an emulsifier to obtain an epoxy resin emulsion.

The solid content of the obtained epoxy resin emulsion is 57%, and the epoxy resin emulsion does not deteriorate (does not have layering, particle aggregation and sedimentation) after being stored for 6 months at normal temperature.

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 thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.