CN-121991367-A - Hyperbranched ionic liquid for manufacturing carbon fiber composite material and preparation method thereof

CN121991367ACN 121991367 ACN121991367 ACN 121991367ACN-121991367-A

Abstract

The invention discloses a hyperbranched ionic liquid for manufacturing a carbon fiber composite material and a manufacturing method thereof, and by means of the hyperbranched ionic liquid provided by the invention, a degradable and recyclable carbon fiber composite material can be prepared, the interface bonding strength of the carbon fiber composite material is improved, and the technical problems of difficulty in improving and recycling the performance of the carbon fiber reinforced epoxy resin composite material are synchronously solved. The hyperbranched ionic liquid provided by the invention has the advantages of simple preparation process and easily available raw materials, is particularly suitable for industrial production, and provides a new solution for the green sustainable development of carbon fiber composite materials.

Inventors

ZHANG JUNHANG
MENG YANLIANG
DING KEJIA
DONG WEIHAO
HUANG ANMIN
Jiang Qinggeng
YANG HAIYANG
YAO DINGYANG
ZHANG DAOHONG

Assignees

中南民族大学

Dates

Publication Date: 20260508
Application Date: 20251231

Claims (10)

1. The hyperbranched ionic liquid for manufacturing the carbon fiber composite material is characterized in that the hyperbranched ionic liquid is obtained by a thiol-terminated hyperbranched polymer containing a hexahydro-s-triazine structure and allyl ionic liquid through a thiol-olefin clicking reaction, the number average molecular weight of the hyperbranched ionic liquid is 2000-23000g/mol, and the structural formula of the thiol-terminated hyperbranched polymer containing the hexahydro-s-triazine structure is shown as formula (1), formula (2), formula (3) or formula (4): A formula (1), A formula (2), A formula (3), Formula (4); wherein R1 is of the structure R2 is one or more of the following structures: 、、、、。
2. the hyperbranched ionic liquid for manufacturing the carbon fiber composite material according to claim 1, wherein the hyperbranched ionic liquid is prepared from a mercapto-terminated hyperbranched polymer containing a hexahydro-s-triazine structure, an allyl ionic liquid and a photoinitiator through a thiol-olefin click reaction under ultraviolet irradiation, the molar ratio of the mercapto-terminated hyperbranched polymer containing the hexahydro-s-triazine structure to the allyl ionic liquid is 1:1, and the mass ratio of the mercapto-terminated hyperbranched polymer containing the hexahydro-s-triazine structure to the photoinitiator is 100 (0.1-2.0).
3. The hyperbranched ionic liquid for manufacturing the carbon fiber composite material according to claim 2, wherein the allyl ionic liquid is one or more of 1-allyl-3-methylimidazole chloride, 1-allyl-3-methylimidazole bromide, 1-allyl-3-methylimidazole tetrafluoroborate, 1-allyl-3-methylimidazole hexafluorophosphate, 1-allyl-3-methylimidazole bistrifluoromethanesulfonimide salt, and the photoinitiator is one or more of 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone, 1-hydroxycyclohexylphenyl ketone, benzoyl isopropanol, 1-hydroxy-1-methylethyl phenyl ketone and (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide.
4. A hyperbranched ionic liquid for the manufacture of carbon fiber composites according to any one of claims 1 to 3 wherein the end mercapto hyperbranched polymer comprising hexahydro-s-triazine structure is obtained by reacting trimercapto-hexahydro-s-triazine with diisocyanate monomer, said trimercapto-hexahydro-s-triazine and isocyanate monomer being in a mass ratio of 100 (30-59).
5. A method of manufacturing a hyperbranched ionic liquid for manufacturing a carbon fiber composite according to claims 1 to 4, comprising the steps of: (1) Uniformly mixing a sulfhydryl-terminated hyperbranched polymer containing a hexahydro-s-triazine structure, an allyl ionic liquid and a photoinitiator, wherein the mol ratio of the sulfhydryl-terminated hyperbranched polymer containing the hexahydro-s-triazine structure to the allyl ionic liquid is 1:1, and the mass ratio of the sulfhydryl-terminated hyperbranched polymer containing the hexahydro-s-triazine structure to the photoinitiator is 100 (0.1-2.0); (2) And carrying out thiol-olefin click reaction for 5-10min under ultraviolet irradiation to obtain the hyperbranched ionic liquid.
6. The method for preparing the hyperbranched ionic liquid for preparing the carbon fiber composite material according to claim 5, wherein the preparation method of the mercapto-terminated hyperbranched polymer containing the hexahydro-s-triazine structure comprises the following steps of uniformly mixing trimercapto-s-triazine, diisocyanate monomer and solvent, stirring and reacting for 1-2h at 0-20 ℃ to obtain the mercapto-terminated hyperbranched polymer containing the hexahydro-s-triazine structure, wherein the diisocyanate monomer is one of hexamethylene diisocyanate, isophorone diisocyanate, 4' -methylenebis (phenyl isocyanate) and toluene diisocyanate, the solvent is one of tetrahydrofuran, acetone, N-dimethylformamide and chloroform, the mass ratio of the trimercapto-hexahydro-s-triazine to the isocyanate monomer is 100 (30-59), and the mass ratio of the trimercapto-hexahydro-s-triazine monomer to the solvent is 1 (5-20).
7. The hyperbranched ionic liquid according to claims 1 to 4, or the hyperbranched ionic liquid prepared by the method according to claims 5 to 6, for use in the manufacture of carbon fiber composites, characterized in that it comprises the following steps: A. Uniformly mixing hyperbranched ionic liquid, bisphenol A epoxy resin and a curing agent to obtain hyperbranched ionic mixed liquid; B. and (3) fully soaking the carbon fiber cloth in the hyperbranched ion mixed liquid, and then placing the carbon fiber cloth in a die for lamination and thermal curing to obtain the carbon fiber reinforced composite material.
8. The method for using the hyperbranched ionic liquid in manufacturing the carbon fiber composite material according to claim 7, wherein the mass ratio of the bisphenol A type epoxy resin to the hyperbranched ionic liquid to the curing agent is 100 (0.1-10): 10-30.
9. The method for using the hyperbranched ionic liquid in manufacturing the carbon fiber composite material according to claim 7 or 8, further comprising the step C of degrading the carbon fiber reinforced composite material obtained in the step B in a tetrahydrofuran solution of 0.1-2.0mol/L phosphoric acid, and washing the carbon fiber cloth obtained by degradation with ethanol to obtain the recyclable carbon fiber cloth.
10. The method of using the hyperbranched ionic liquid according to claim 9 in manufacturing a carbon fiber composite material, wherein the recyclable carbon fiber cloth obtained in the step C can replace the carbon fiber cloth obtained in the step B, and the carbon fiber reinforced composite material which can be recycled is obtained by laminating and thermally curing the carbon fiber cloth obtained in the step B by adopting the manufacturing method of the step B.

Description

Hyperbranched ionic liquid for manufacturing carbon fiber composite material and preparation method thereof Technical Field The invention belongs to the technical field of carbon fiber composite materials, and particularly relates to hyperbranched ionic liquid for manufacturing a carbon fiber composite material and a preparation method thereof. Background The light high-strength carbon fiber reinforced epoxy resin composite material (CFRP) is an advantage material for realizing economic structural transformation, energy conservation and emission reduction and green development, and has the characteristics of high strength, light weight, easy manufacture, heat resistance, corrosion resistance and the like. The lightweight high-strength CFRP has great development potential in the fields of wind power blades, new energy automobiles and the like, and can effectively solve the problem that the density, strength, modulus and fatigue resistance of a long blade material are difficult to balance in a large wind power environment and the problem that the automobile mileage is low in a battery system. The hyperbranched polymer has a large number of cavity structures inside and a large number of end groups, so the hyperbranched polymer has higher reactivity. Because the hyperbranched polymer has less intermolecular winding, the hyperbranched polymer is not easy to crystallize, has the characteristics of good hydrodynamic property, unique viscosity behavior, easy film formation and the like, and has been used for reinforcing and toughening bisphenol A epoxy resin. However, CFRP forms a three-dimensional irreversible cross-linked network structure in the curing process, so that the recycling and reprocessing of CFRP are difficult, and the waste of CFRP is accumulated in a large amount, so that the CFRP occupies a large amount of land and pollutes the environment, and becomes an important obstacle for sustainable development of carbon fiber composite materials. Meanwhile, the interface bonding strength is also a key factor influencing the comprehensive mechanical property of the carbon fiber reinforced epoxy resin composite material, improves the surface inertia of the carbon fiber, and improves the bonding strength of the carbon fiber reinforced epoxy resin composite material and has important research significance and value. Disclosure of Invention In order to solve the technical problems, the invention provides the hyperbranched ionic liquid for manufacturing the carbon fiber composite material and the preparation method thereof, and by means of the hyperbranched ionic liquid, the degradable and recyclable carbon fiber composite material can be prepared, the interface bonding strength of the carbon fiber composite material is improved, and the technical problems of difficult interface enhancement and recovery of the carbon fiber reinforced epoxy resin composite material are synchronously solved. In order to achieve the purpose of the invention, the first aspect of the invention provides a hyperbranched ionic liquid for manufacturing a carbon fiber composite material, wherein the hyperbranched ionic liquid is obtained by a thiol-terminated hyperbranched polymer containing a hexahydro-s-triazine structure and an allyl ionic liquid through a thiol-olefin click reaction, the number average molecular weight of the hyperbranched ionic liquid is 2000-23000g/mol, and the structural formula of the thiol-terminated hyperbranched polymer containing the hexahydro-s-triazine structure is formula (1), formula (2), formula (3) or formula (4): A formula (1), A formula (2), A formula (3),Formula (4); Wherein R1 has the structure of R2 is one or more of the following structures:、、、、。 Further, the hyperbranched ionic liquid is prepared from a sulfhydryl-terminated hyperbranched polymer containing a hexahydro-s-triazine structure, allyl ionic liquid and a photoinitiator through a mercaptan-olefin clicking reaction under ultraviolet irradiation, wherein the mol ratio of the sulfhydryl-terminated hyperbranched polymer containing the hexahydro-s-triazine structure to the allyl ionic liquid is 1:1, and the mass ratio of the sulfhydryl-terminated hyperbranched polymer containing the hexahydro-s-triazine structure to the photoinitiator is 100 (0.1-2.0). Further, the allyl ionic liquid is one or more of 1-allyl-3-methylimidazole chlorine salt, 1-allyl-3-methylimidazole bromine salt, 1-allyl-3-methylimidazole tetrafluoroborate, 1-allyl-3-methylimidazole hexafluorophosphate and 1-allyl-3-methylimidazole bis-trifluoromethanesulfonyl imide salt, and the photoinitiator is one or more of 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-acetone, 1-hydroxycyclohexyl phenyl ketone, benzoyl isopropanol, 1-hydroxy-1-methylethyl phenyl ketone and (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide. Furthermore, the end mercapto hyperbranched polymer containing the hexahydro-s-triazine structure is obtained by reacting trimercapto-hexahydro-s-triazine and di