阅读说明：本技术 一种凹凸棒石/氧化石墨烯复合材料及其制备方法和作为高分子材料助剂的用途 (Attapulgite/graphene oxide composite material, preparation method thereof and application of attapulgite/graphene oxide composite material as high polymer material auxiliary agent ) 是由 张哲� 张元硕 潘昊 靳亚娥 孙江波 曹一康 *** 于 2019-10-17 设计创作，主要内容包括：本发明公开了一种凹凸棒石/氧化石墨烯复合材料,该凹凸棒石/氧化石墨烯复合材料主要由硅烷偶联剂改性的凹凸棒石与含磷化合物改性的氧化石墨烯反应得到。与现有凹凸棒、氧化石墨烯作为高分子材料助剂相比,本发明凹凸棒石/氧化石墨烯复合材料可作为高分子材料多功能助剂,能够很好地提高高分子材料的各种性能,使高分子材料具有更高的力学性能和阻燃性,燃烧时具有更低的烟密度和毒性,具有良好的市场应用前景。(The invention discloses an attapulgite/graphene oxide composite material which is mainly obtained by reacting attapulgite modified by a silane coupling agent and graphene oxide modified by a phosphorus-containing compound. Compared with the existing attapulgite and graphene oxide used as polymer material additives, the attapulgite/graphene oxide composite material can be used as a polymer material multifunctional additive, can well improve various performances of a polymer material, enables the polymer material to have higher mechanical properties and flame retardance, has lower smoke density and toxicity during combustion, and has good market application prospect.)

1. The attapulgite/graphene oxide composite material is mainly obtained by reacting attapulgite modified by a silane coupling agent and graphene oxide modified by a phosphorus-containing compound.

2. The attapulgite/graphene oxide composite material according to claim 1, wherein: the mass ratio of the attapulgite modified by the silane coupling agent to the graphene oxide modified by the phosphorus-containing compound is 1: 0.5-1: 1.

3. The attapulgite/graphene oxide composite material according to claim 1 or 2, wherein: the structural formula of the phosphorus-containing compound is as follows:

4. The attapulgite/graphene oxide composite material according to claim 3, wherein: the phosphorus-containing compound is aminomethylphosphonic acid.

5. The attapulgite/graphene oxide composite material according to claim 1, wherein: the silane coupling agent is a polyamino silane coupling agent containing more than 2N, and preferably N- (2-aminoethyl) -3-aminopropyltrimethoxysilane.

6. The preparation method of the attapulgite/graphene oxide composite material of any one of claims 1 to 5, comprising the following steps:

and (3) carrying out reflux reaction on the attapulgite modified by the silane coupling agent and the graphene oxide modified by the phosphorus-containing compound in a solvent to obtain the attapulgite/graphene oxide composite material.

7. The method of claim 6, wherein: the silane coupling agent modified attapulgite is obtained by reflux reaction of the silane coupling agent and the attapulgite in water, and the using amount of the silane coupling agent is 2-10% of the mass of the attapulgite.

8. The method of claim 6, wherein: the phosphorus-containing compound modified graphene oxide is obtained by carrying out reflux reaction on a phosphorus-containing compound and graphene oxide in a solvent, wherein the amount of the phosphorus-containing compound is 10-25% of the mass of the graphene oxide.

9. Use of the attapulgite/graphene oxide composite material of any one of claims 1 to 5 as a polymer material additive.

10. A polymer composite material, which comprises a polymer material used as a matrix and the attapulgite/graphene oxide composite material used as an auxiliary agent according to any one of claims 1 to 5, wherein the attapulgite/graphene oxide composite material preferably comprises 0.5 to 2 percent of the polymer material by mass.

Technical Field

The invention relates to an attapulgite/graphene oxide composite material and application of the composite material as a multifunctional auxiliary agent in a high polymer material.

Background

With the development of the technology, a single material cannot meet the development requirements of the advanced technical field, and therefore, the novel composite material draws extensive attention of the scientific and technological field and becomes a research hotspot in the material research field. The composite material can play the advantages of various materials, avoid the defects thereof and fully utilize and save resources, so the scientific and technological field researches the composite material as a novel material.

Composite materials, ceramic, high polymer, metal, and four major materials, have been one of the signs for measuring the industrial level of composite materials in a country or region, and are the source of competitive advantages for national safety and national economy.

Among the composite materials, polymer materials have been widely used in various fields as an important branch. As the name suggests, the polymer composite material is a new material developed on the basis of polymer materials. The pure high polymer material has many defects in the using process, such as inconsistent rigidity and toughness, poor aging resistance, easy combustion, poor thermal stability, poor antistatic property, large smoke amount during combustion, easy falling during combustion, easy secondary fire accidents and the like. The addition of various functional additives to the polymer material is one of the effective ways to improve the above properties of the polymer material.

CN105906964A discloses a flame-retardant polymer composite material, which adopts graphene nanoplatelets as a condensed phase flame retardant to reduce the heat release rate and smoke density of the polymer.

CN106046683A discloses a low-smoke flame-retardant polymer composite material, which takes a hybrid of oxidized graphene surface loaded with metal ions as a smoke-suppressing synergist.

CN109897273A discloses a composite flame retardant graft-modified EVA foam material, which adopts a modified DOPO/graphene oxide composite material as a composite flame retardant.

CN102010585A discloses a preparation method of an efficient and environment-friendly composite flame retardant, which is obtained by sequentially coating nanoscale attapulgite with an inorganic flame retardant and a halogen-free phosphate flame retardant.

CN106117604A discloses a preparation method of an adsorption type attapulgite-based flame retardant material, which takes adsorption type attapulgite as a core body and is obtained by intercalating and stripping montmorillonite in the adsorption type attapulgite clay through melamine-formaldehyde resin polymerization reaction.

CN102304237A discloses a halogen-free smoke-suppressing flame retardant, which is prepared by mixing graphite oxide, palygorskite clay and sodium bicarbonate in a mass ratio of 1:1: 0.5-1: 10: 5.

"preparation of graphene oxide assisted dispersion attapulgite nano-composite and application thereof in polymer modification" [ D ], university of Anhui, in 2016 (3 months), discloses preparation of graphene oxide assisted dispersion attapulgite by using graphene oxide as an assisted dispersion carrier and KH550 modified attapulgite as an acceptor in an electrostatic assembly manner.

Although the above prior art discloses that graphene, graphene oxide and attapulgite are added into a polymer composite material to improve the flame retardant property or mechanical property of the polymer material, the functions are relatively single and the properties are still to be improved.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide the attapulgite/graphene oxide composite material which can be used as a high polymer material multifunctional auxiliary agent to improve the mechanical property and the flame retardance of a high polymer material and reduce the smoke density and the toxicity during combustion.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

the attapulgite/graphene oxide composite material is mainly obtained by reacting attapulgite modified by a silane coupling agent and graphene oxide modified by a phosphorus-containing compound.

Preferably, the mass ratio of the attapulgite modified by the silane coupling agent to the graphene oxide modified by the phosphorus-containing compound is 1: 0.5-1: 1.

Preferably, the phosphorus-containing compound has the structural formula:

R¹、R²and R³Each independently is an alkoxy, aryloxy, hydroxy, hydroxyalkyl, or aminoalkyl group.

Preferably, the phosphorus-containing compound is aminomethylphosphonic acid.

Preferably, the silane coupling agent is a polyamino silane coupling agent containing more than 2N, preferably N- (2-aminoethyl) -3-aminopropyltrimethoxysilane.

The preparation method of the attapulgite/graphene oxide composite material comprises the following steps:

and (3) carrying out reflux reaction on the attapulgite modified by the silane coupling agent and the graphene oxide modified by the phosphorus-containing compound in a solvent to obtain the attapulgite/graphene oxide composite material.

Preferably, the silane coupling agent modified attapulgite is obtained by reflux reaction of the silane coupling agent and the attapulgite in water, and the using amount of the silane coupling agent is 2-10% of the mass of the attapulgite.

Preferably, the phosphorus-containing compound modified graphene oxide is obtained by a reflux reaction of a phosphorus-containing compound and graphene oxide in a solvent, and the amount of the phosphorus-containing compound is 10-25% of the mass of the graphene oxide.

The attapulgite/graphene oxide composite material is used as a high polymer material additive.

A polymer composite material, which comprises a polymer material used as a matrix and the attapulgite/graphene oxide composite material as claimed in any one of claims 1 to 5 used as an auxiliary agent.

Preferably, the content of the attapulgite/graphene oxide composite material is 0.5-2% by mass.

Compared with the existing attapulgite and graphene oxide used as polymer material additives, the attapulgite/graphene oxide composite material has good versatility, can well improve various performances of polymer materials under the condition of adding 1%, has higher mechanical properties and flame retardance, has lower smoke density and toxicity during combustion, and has good market application prospect.

Drawings

FIG. 1 is an ATT-O infrared spectrum;

FIG. 2 is an ATT-P-GO infrared spectrum;

FIG. 3 is an ATT-P-GO scanning electron microscope and EDS elemental analysis chart;

FIG. 4 is an ATT-P-GO transmission electron micrograph;

FIG. 5 is an XRD test curve of ATT-P-GO.

Detailed Description

The present invention will be described in further detail with reference to examples.

The attapulgite/graphene oxide composite material is mainly obtained by reacting attapulgite modified by a silane coupling agent and graphene oxide modified by a phosphorus-containing compound.

In some embodiments of the invention, the mass ratio of the silane coupling agent modified attapulgite to the phosphorus compound modified graphene oxide is 1: 0.5-1: 1, such as 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1: 1.

In some embodiments of the present invention, the phosphorus-containing compound has the formula:R¹、R²and R³Each independently is alkoxy, aryloxy, hydroxy, hydroxyalkyl orAn aminoalkyl group.

The above alkoxy group is C1-6 alkoxy group, such as methoxy, ethoxy, propoxy, butoxy, pentoxy, and hexoxy.

The above aryloxy group is, for example, phenoxy, p-tert-butylphenoxy, p-aminophenoxy, p-hydroxyphenyloxy.

The hydroxyalkyl group is a hydroxyalkyl group having 1-6 carbon atoms, such as hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, and hydroxyhexyl, preferably a hydroxyalkyl group having 1-3 carbon atoms.

The aminoalkyl group is an aminoalkyl group having 1 to 6 carbon atoms, such as aminomethyl, aminoethyl, aminopropyl, aminobutyl, aminopentyl, aminohexyl, preferably an aminoalkyl group having 1 to 3 carbon atoms.

In some embodiments of the invention, the phosphorus-containing compound is aminomethylphosphonic acid, 2-aminoethylphosphonic acid, or tris (hydroxymethyl) phosphonium oxide.

The silane coupling agent is a polyamino silane coupling agent containing 2 or more N, such as N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, A-1120, and A-1130.

The preparation method of the attapulgite/graphene oxide composite material comprises the following steps:

and (3) carrying out reflux reaction on the attapulgite modified by the silane coupling agent and the graphene oxide modified by the phosphorus-containing compound in a solvent to obtain the attapulgite/graphene oxide composite material. The reflux reaction time is 10-15 hours.

In some embodiments of the present invention, the silane coupling agent modified attapulgite can be obtained by reflux reaction of the silane coupling agent and attapulgite in water, and the amount of the silane coupling agent is 2% to 10% of the mass of the attapulgite, such as 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%. The reflux reaction time is 12-48 hours.

In some embodiments of the present invention, the phosphorus-containing compound modified graphene oxide may be obtained by a reflux reaction of a phosphorus-containing compound and graphene oxide in a solvent, and the amount of the phosphorus-containing compound is 10% to 25% of the mass of the graphene oxide, such as 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%. The reflux reaction time is 2-5 hours.

The solvent may be selected from N, N-dimethylformamide and/or water.