CN114395215A - Sulfone ether epoxy adhesive and UHMWPE fiber reinforced bulletproof composite material and preparation method thereof - Google Patents

Abstract

The invention relates to a sulfone ether epoxy adhesive and UHMWPE fiber reinforced bulletproof composite material and a preparation method thereof. The invention has the advantages of excellent comprehensive performance, outstanding bulletproof performance, simple process, environmental protection, no organic solvent and suitability for large-scale production.

Description

Sulfone ether epoxy adhesive and UHMWPE fiber reinforced bulletproof composite material and preparation method thereof

Technical Field

The invention belongs to the field of bulletproof materials, and particularly relates to a sulfone ether epoxy adhesive and UHMWPE fiber reinforced bulletproof composite material and a preparation method thereof.

Background

The high-performance fibers used in the bullet-proof field at present mainly comprise glass fibers, carbon fibers, aramid fibers, high-strength high-modulus polyethylene fibers and the like, and the resins mainly comprise epoxy resins, polyurethane resins, polyethylene resins and the like.

After being developed in the eighties of the twentieth century, the high-strength and high-modulus polyethylene fiber (UHMWPE) has always occupied a leading position in the field of bulletproof, and the molecular formula of the high-strength and high-modulus polyethylene fiber is- (CH) - (-)₂—CH₂) n, compared with the conventional HDPE fiber, the UHMWPE fiber has ultrahigh molecular weight of more than 150 ten thousand, molecular chains of the UHMWPE fiber have extremely high orientation degree of more than 95 percent, and crystallinity of more than 85 percent, and the molecular chains are fully stretched and arranged tightly mainly because the fiber passes through the drawing force of more than dozens of times during preparation. The density of the high-strength high-modulus polyethylene fiber is only 0.97g/cm³Is the lightest fiber in high-performance fibers, has the highest tensile strength in all commercial fibers at present and is 1.5 times of aramid fibers. The wear resistance and impact resistance of the high-strength high-modulus polyethylene fiber are in the front in engineering plastics, the mortar abrasion index of the high-strength high-modulus polyethylene fiber is only 1/7 of carbon steel and 1/10 of PVC, the impact resistance of the high-strength high-modulus polyethylene fiber is dozens of times of that of PBTP plastics and more than 5 times of that of ABS plastics, and the fiber has higher chemical stability and low-temperature resistance, so that the high-strength high-modulus polyethylene fiber is high in usability in the field of bulletproof composite materials.

However, the surface of the high-strength high-modulus polyethylene fiber has no polar group, and due to the extremely high orientation and crystallinity, a layer of weak interface is arranged in the fiber, so that the interface bonding effect of the fiber and resin is poor, and the intermolecular acting force on a high molecular chain is weak, so that the heat resistance is extremely low, and the performance of the fiber is greatly reduced after the temperature is over 100 ℃. Therefore, in the field of high-strength high-modulus polyethylene fiber reinforced resin matrix composite materials, the problem is mainly solved from the aspect of fiber modification and resin layer, which is the research direction of many researchers at present. Moon et al oxygen plasma treatment of UHMWPE fibers to create light spots on the fiber surfaceMicro pits are formed by etching, so that the mechanical locking force between the fibers and the matrix resin is enhanced, the interface bonding effect is further increased, and the composite material with good effect is prepared. Intrater et al, also surface-etched UHMWPE fibers by oxygen plasma, found that many tiny depressions were created in the amorphous areas of the fiber surface, greatly increasing the adhesion between the fiber and the resin, while active groups were also found on the fiber surface. Ar for Rhee et al⁺The UHMWPE fiber is modified by the ionic radiation, so that C-O double bonds and C-O groups are generated on the surface of the fiber, the hydrophilicity of the fiber is increased, and the mechanical property of the modified high-strength high-modulus polyethylene fiber reinforced vinyl ester resin matrix composite material is improved by 22%. Herba seu radix Cayratiae AgNO₃And K₂S₂O₈The prepared modified solution leads carboxylate radicals to be introduced to the surface of the UHMWPE fiber, and then leads epoxy groups to be introduced to the UHMWPE fiber through esterification reaction, so as to prepare the modified high-strength high-modulus polyethylene fiber, and the result proves that the longitudinal tensile strength of the composite material prepared from the UHMWPE fiber with the introduced carboxylate radicals is improved by 35%, the transverse tensile strength is improved by 23%, while the longitudinal tensile strength of the UHMWPE fiber composite material with the introduced epoxy groups is improved by 85%, and the transverse tensile strength is improved by 74%.

Epoxy resins have many excellent properties: (1) good adhesion properties: the adhesive has high bonding strength and wide bonding surface, has very high bonding strength with a plurality of metals (such as iron, steel, copper, aluminum, metal alloy and the like) or non-metal materials (such as glass, ceramics, wood, plastics and the like), and has the strength of some materials even exceeding the strength of the bonded materials, thereby being one of the main components of the structural adhesive for a plurality of stressed structural members; (2) good processability: the flexibility of the epoxy resin formula, the processing technology and the diversity of product performance are the most prominent among high polymer materials; (3) good stability: the curing of the epoxy resin mainly depends on ring-opening addition polymerization of epoxy groups, so that low molecular substances are not generated in the curing process, the curing shrinkage is one of the lowest varieties in the thermosetting resin, generally 1% -2%, and if proper fillers are selected, the shrinkage can be reduced to about 0.2%; the main chain of the cured epoxy resin is an ether bond, a benzene ring and a three-dimensional crosslinking structure, so that the cured epoxy resin has excellent acid and alkali resistance.

Therefore, epoxy resins are widely used in various fields of national economy: the trace of the product can be seen in the daily life of people, whether the product is in the high and new technical field or the general technical field, whether the product is in the national defense military industry or the civil industry.

Many reports have been made on the synthetic production of epoxy resins, and many reports have been made on the production methods of glycidyl amine type epoxy resins in addition to bisphenol a type epoxy resins and phenol type epoxy resins.

Yu Xinhai et al [ Chinese invention patent: a preparation method of glycidyl amine type multifunctional epoxy resin is disclosed in CN100465206C, 2009-03-04, and is mainly characterized in that an aromatic amine compound and epichlorohydrin are subjected to ring opening reaction to produce tetrachloropropanol, and then cyclization is carried out under an alkaline condition to obtain the multifunctional epoxy resin.

Although the epoxy resin has very excellent properties, the epoxy resin has some disadvantages, such as high brittleness of the cured product and poor impact resistance, and cannot meet the use requirements of high impact resistance fields.

Polysulfone and polyethersulfone are amorphous thermoplastic novel special engineering plastics with sulfone group, ether bond and aromatic nucleus, and sulfur atom in the sulfone group is in the highest oxidation state, so that the oxidation resistance, mechanical property and thermal stability are better, and the existence of ether bond provides certain toughness. In addition, polysulfone and polyethersulfone are non-toxic, chemically resistant, and inherently flame retardant. Therefore, the polysulfone and the polyether sulfone are widely applied to the fields of electronic and electric appliances, automobile machinery, aerospace and the like.

Pasteur based on polysulfone/polyethersulfone Ultrason S and Ultrason E products have good dimensional stability, water resistance and oil resistance at high temperature, can continuously work at 190 ℃, can resist temperature in short term as high as 390 ℃, and has the capacity of being expanded from 3000t/a to 5000 t/a. Passion corporation has also newly introduced a polyether sulfone (PES) Ultrason brand of a specialized formulation for the production of food ware required to withstand microwave oven heating and high temperature boiling.

The UDEL resin developed by Solvay high Performance Polymer U.S. corporation is an amorphous sulfone polymer and has several desirable properties, such as hydrolysis resistance, thermal stability, retention of mechanical properties at high temperatures, clarity and transparency.

The Solvay company has also introduced two optimum materials for highly reflective automotive headlamps. One is polysulfone UdelLTG-2000 grade, which can be used at temperatures up to 175 ℃ and is more temperature resistant than most high temperature PC and PC/Polyetherimide (PEI) alloys; one is polyethersulfone RadelLTG-3000, particularly suited for use at 205 ℃ temperatures, which has higher temperature resistance than many PEI grades, with 50% improvement in impact resistance and a 33% increase in melt flow rate. The company has also introduced a new polysulfone product, under the trade name EpiSpire HTS-2600, which can replace metallic materials. The new material has high heat resistance, the glass transition temperature is 265 ℃, and the thermal deformation temperature is 255 ℃. Meanwhile, the insulating property and the internal flame resistance are good. EpiSpire HTS-2600 has very good mechanical properties (tensile strength of 79MPa, chemical resistance, and acid and alkali resistance. more importantly, this new material has very high dimensional control and dimensional stability during injection molding and extrusion.

Although the polysulfone or polyethersulfone resin has the excellent properties, in the process of molding the resin-based composite material, the polysulfone or polyethersulfone resin has poor wettability to the fiber reinforced material due to high viscosity, so that the comprehensive properties of the composite material cannot achieve ideal effects.

Disclosure of Invention

The invention aims to solve the technical problem of providing the sulfone ether epoxy adhesive and UHMWPE fiber reinforced bulletproof composite material and the preparation method thereof, and the composite material has the advantages of superior comprehensive performance, outstanding bulletproof performance, simple process, environmental friendliness, no organic solvent and suitability for large-scale production.

The invention provides a reinforced bulletproof composite material of a sulfone ether epoxy adhesive and UHMWPE fibers, which comprises the sulfone ether epoxy adhesive and the UHMWPE fibers with the volume ratio of 1: 5-25; the sulfone ether epoxy adhesive is composed of sulfone ether epoxy resin, other epoxy resin, a chain extender, a curing agent, an accelerator and a reactive diluent in a mass ratio of 10:10-100:0.1-20:10-100:0.1-10: 10-40.

The molecular structure general formula of the sulfone ether epoxy adhesive is as follows:

wherein m is an integer of 0-6; -Q-is a divalent residue of a dihydric phenol.

The dihydric phenol is selected from one or more of hydroquinone, resorcinol, o-methyl hydroquinone, 2-tert-butyl hydroquinone, 2, 5-di-tert-butyl hydroquinone, 2, 5-dimethyl hydroquinone, bisphenol A, bisphenol S, bisphenol F, bisphenol AF, biphenol, tetramethyl bisphenol A, tetramethyl bisphenol S, tetramethyl bisphenol AF, tetramethyl bisphenol F and tetramethyl biphenol.

The other epoxy resin is selected from one or a mixture of more of bisphenol A epoxy resin E-51, SRTEM-80 epoxy resin, SRTEM-50 epoxy resin, bisphenol A epoxy resin E-44, bisphenol S epoxy resin, bisphenol F epoxy resin, ES216 epoxy resin, ECC202 epoxy resin, o-cresol novolac epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, glycidyl ether epoxy resin, alicyclic epoxy resin, hydrogenated bisphenol A epoxy resin and aliphatic epoxy resin; wherein the glycidyl amine epoxy resin is selected from N, N-diglycidyl aniline epoxy resin, N, N-diglycidyl o-toluidine, N, N-diglycidyl p-toluidine epoxy resin, N, N-diglycidyl o-ethylaniline epoxy resin, N, N, N ', N' -tetraglycidyl p-phenylenediamine epoxy resin, N, N, N ', N' -tetraglycidyl m-phenylenediamine epoxy resin, N, N, N ', N' -tetraglycidyl o-phenylenediamine epoxy resin, N, N, N ', N' -tetraglycidyl-4, 4 '-diaminodiphenyl ether epoxy resin, N, N, N', N '-tetraglycidyl-4, 4' -diaminodiphenyl methane epoxy resin, N, N, n ', N ' -tetraglycidyl-4, 4' -diaminodiphenyl sulfone epoxy resin, N, N, N ', N ' -tetraglycidyl-3, 3' -dimethyl-4, 4' -diaminodiphenyl methane epoxy resin, N, N, N ', N ', O-pentaglycidyl-4, 4' -diamino-4 "-hydroxytriphenylmethane epoxy resin, N, N, O-triglycidyl-4-aminophenol epoxy resin, N, N, N ', N ' -tetraglycidyl-4, 4' -diaminodiphenyl ether epoxy resin, N, N, N ', N ' -tetraglycidyl-1, 4-bis (4-aminophenoxy) benzene epoxy resin, N, N, n ', N' -tetraglycidyl-2, 2-bis [4- (4-aminophenoxy) phenyl ] propane epoxy resin, N, N, N ', N' -tetraglycidyl-1, 3-bis (4-aminophenoxy) benzene epoxy resin, N, N, N ', N' -tetraglycidyl-3, 3 '-diaminodiphenylsulfone epoxy resin, N, N, N', N '-tetraglycidyl-3, 3' -dimethoxy-4, 4 '-diaminobiphenyl epoxy resin, N, N, N', N '-tetraglycidyl-3, 3' -diaminodiphenylether epoxy resin, N, N, N ', N' -tetraglycidyl-2, 2-bis [4- (3-aminophenoxy) phenyl ] propane epoxy resin, and their use, N, N, N ', N ' -tetraglycidyl-2, 2-bis [4- (3-aminophenoxy) phenyl ] hexafluoropropane epoxy resin, N, N, N ', N ' -tetraglycidyl-3, 4' -diaminodiphenyl ether epoxy resin, N, N, N ', N ' -tetraglycidyl-3, 3' -diaminodiphenyl ether epoxy resin, N, N, N ', N ' -tetraglycidyl-1, 4-bis (3-aminophenoxy) benzene epoxy resin, N, N, N ', N ' -tetraglycidyl-2, 6-bis (4-aminophenoxy) benzonitrile epoxy resin, N, N, N ', N ' -tetraglycidyl-2, 6-bis (3-aminophenoxy) benzonitrile epoxy resin, N, N ', N ' -tetraglycidyl-1, N, N ', N ' -tetraglycidyl-1, N ' -tetraglycidyl-3, 6-2, N, N, 2, N, N, N, 2, N, N, N, n, N, N ', N' -tetraglycidyl-2, 6-bis (4-aminophenoxy) tolylene epoxy resin, N, N, N ', N' -tetraglycidyl-2, 6-bis (4-aminophenoxy) benzotrifluoride epoxy resin, N, N, N ', N' -tetraglycidyl-2, 5-bis (4-aminophenoxy) tolylene epoxy resin, N, N, N ', N' -tetraglycidyl-2, 5-bis (4-aminophenoxy) tert-butylbenzene epoxy resin, N, N, N ', N' -tetraglycidyl-2, 5-di-tert-butyl-1, 4-bis (4-aminophenoxy) benzene epoxy resin, N, N, N ', N' -tetraglycidyl-4, 4' -bis (4-aminophenoxy) benzophenone epoxy resin, N, N, N ', N ' -tetraglycidyl-4, 4' -bis (4-aminophenoxy) diphenylsulfone epoxy resin, N, N, N ', N ' -tetraglycidyl-4, 4' -bis (3-aminophenoxy) benzophenone epoxy resin, N, N, N ', N ' -tetraglycidyl-4, 4' -bis (3-aminophenoxy) diphenylsulfone epoxy resin, N, N, N ', N ' -tetraglycidyl-1, 4-bis (2-trifluoromethyl-4-aminophenoxy) benzene epoxy resin, N, N, N ', N ' -tetraglycidyl-1, 3-bis (2-trifluoromethyl-4-aminophenoxy) benzene epoxy resin, N, N, N ', N ' -tetraglycidyl-4, N, N, N ' -tetraglycidyl-4-bis (3-amino-phenoxy) benzene epoxy resin, N, N ', N ' -tetraglycidyl-4, N ' -tetraglycidyl-bis (2-amino-phenoxy) benzene epoxy resin, N, N ' -tetraglycidyl-4, N, N, N, or N, N, or a mixture of, N, N, N ', N' -tetraglycidyl-2, 2-bis [4- (2-trifluoromethyl-4-aminophenoxy) phenyl ] propane epoxy resin, N, N, N ', N' -tetraglycidyl-2, 2-bis [4- (2-trifluoromethyl-4-aminophenoxy) phenyl ] hexafluoropropane epoxy resin, N, N, N ', N' -tetraglycidyl-2, 5-bis (2-trifluoromethyl-4-aminophenoxy) toluene epoxy resin, N, N, N ', N' -tetraglycidyl-2, 5-bis (2-trifluoromethyl-4-aminophenoxy) tert-butyl benzene epoxy resin, N, N, N ', N' -tetraglycidyl-2, 5-di-tert-butyl-1, 4-bis (2-trifluoromethyl-4-aminophenoxy) benzene epoxy resin, N, N, N ', N ' -tetraglycidyl-4, 4' -bis (2-trifluoromethyl-4-aminophenoxy) diphenylsulfone epoxy resin, N, N, N ', N ' -tetraglycidyl-4, 4' -bis (2-trifluoromethyl-4-aminophenoxy) -3,3',5,5' -tetramethyldiphenylsulfone epoxy resin, N, N, N ', N ' -tetraglycidyl-4, 4' -bis (2-trifluoromethyl-4-aminophenoxy) biphenyl epoxy resin, N, N, N ', N ' -tetraglycidyl-4, 4' -bis (2-trifluoromethyl-4-aminophenoxy) -3,3',5,5' -tetramethylbiphenyl epoxy resin, N, N, N ', N ' -tetraglycidyl-4, 4' -bis (2-trifluoromethyl-4-aminophenoxy) diphenyl ether epoxy resin, N, N, N ', N ' -tetraglycidyl-4, 4' -bis (3-aminophenoxy) diphenyl sulfide epoxy resin, and mixtures thereof, N, N, N ', N ' -tetraglycidyl-4, 4' -bis (4-aminophenoxy) diphenyl sulfide epoxy resin, N, N, N ', N ' -tetraglycidyl-4, 4' -bis (4-aminophenoxy) -3,3',5,5' -tetramethylbiphenyl epoxy resin, N, N, N ', N ' -tetraglycidyl-4, 4' -bis (3-aminophenoxy) -3,3',5,5' -tetramethylbiphenyl epoxy resin, N, N, N ', N ' -tetraglycidyl-2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane epoxy resin, N, N, N ', N ' -tetraglycidyl-1, one or more of 3-bis (3-aminophenoxy) benzene epoxy resin and N, N, N ', N' -tetraglycidyl-1, 3-bis (4-aminophenoxy) benzene epoxy resin.

The chain extender is selected from 2, 2-bis [4- (2, 4-diaminophenoxy) phenyl ] hexafluoropropane, 2-bis [4- (2, 4-diaminophenoxy) phenyl ] propane, 4-bis (2, 4-diaminophenoxy) diphenylsulfone, SD-248, 4-bis (2, 4-diaminophenoxy) diphenylether, 4-bis (2, 4-diaminophenoxy) diphenylsulfide, 4-bis (2, 4-diaminophenoxy) diphenylmethane, 1, 4-bis (2, 4-diaminophenoxy) benzene, 1, 3-bis (2, 4-diaminophenoxy) benzene, polyetheramine, 4-bis (2, 4-diaminophenoxy) biphenyl, 4, one or two of 4-bis (2, 4-diaminophenoxy) -3,3',5,5' -tetramethylbiphenyl.

The curing agent is selected from hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, dodecenylsuccinic anhydride, methyl hexahydrophthalic anhydride, methyl nadic anhydride, eleostearic anhydride, 80-anhydride obtained by reacting dicyclopentadiene with maleic anhydride, polyetheramine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine, polyethylene polyamine, anhydride obtained by reacting limonene with maleic anhydride, liquid anhydride obtained by reacting turpentine with maleic anhydride, pyromellitic dianhydride, 3', 4,4' -tetracarboxylbiphenyl dianhydride, 3', 4,4' -tetracarboxydiphenyl ether dianhydride, 3', 4,4' -tetracarboxydiphenylsulfenyl sulfone dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 4,4 '-bis (3, 4-dicarboxyphenoxy) diphenyl ether dianhydride, 4' -bis (3, 4-dicarboxyphenoxy) benzophenone dianhydride, 4 '-bis (3, 4-dicarboxyphenoxy) diphenylmethane dianhydride, 4' -bis (3, 4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4 '-bis (3, 4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4' -bis (3, 4-dicarboxyphenoxy) biphenyl dianhydride, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] hexafluoropropane dianhydride, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride, 1, 4-bis (3, 4-dicarboxyphenoxy) benzene dianhydride, 1, 3-bis (3, 4-dicarboxyphenoxy) benzene dianhydride, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 4 '-diaminodiphenyl ether, 3' -diaminodiphenyl ether, 4 '-diaminodiphenylmethane, 3' -dimethyl-4, 4 '-diaminodiphenylmethane, 4' -diaminobiphenyl, 3 '-dimethyl-4, 4' -diaminobiphenyl, 2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, 4 '-diaminobenzophenone, 4' -diaminodiphenyl sulfone, 3 '-diaminodiphenyl sulfone, 3,4' -diaminodiphenyl sulfone, 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2-bis [4- (3-aminophenoxy) phenyl ] propane, 2-bis [4- (3-aminophenoxy) phenyl ] hexafluoropropane, 4 '-bis (4-aminophenoxy) benzophenone, 4' -bis (3-aminophenoxy) benzophenone, 4 '-bis (4-aminophenoxy) diphenylsulfone, 4' -bis (3-aminophenoxy) diphenylsulfone, 1, 3-bis (3-aminophenoxy) benzene, 1, 4-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 2-bis [4- (2-trifluoromethyl-4-aminophenoxy) phenyl ] propane, 2-bis [4- (2-trifluoromethyl-4-aminophenoxy) phenyl ] hexafluoropropane, 4' -bis (2-trifluoromethyl-4-aminophenoxy) benzophenone, 4' -bis (2-trifluoromethyl-4-aminophenoxy) diphenylsulfone, 4' -bis (4-aminophenoxy) diphenylsulfide, 4' -bis (3-aminophenoxy) diphenylsulfide, 4' -bis (2-trifluoromethyl-4-aminophenoxy) diphenylsulfide, 4' -bis (4-aminophenoxy) biphenyl, 2-bis [ 4-trifluoromethyl-4-aminophenoxy ] phenyl ] propane, 2-bis [4- (2-trifluoromethyl-4-aminophenoxy) phenyl ] propane, 4, 2-bis [4- (2-trifluoromethyl-4-aminophenoxy) phenyl ] hexafluoropropane, 4' -bis (4-aminophenoxy) diphenylsulfide, 4-bis (4-aminophenoxy) biphenyl, 4-bis (4-aminophenoxy) biphenyl, 4-aminophenoxy) biphenyl, 4, or a mixture of benzene, 4, and a mixture of two, 4, 2,4, 2, or a mixture of, a mixture of two, a mixture of two, a mixture of two, a mixture of two or a mixture of two or a mixture of two or a mixture, 4,4' -bis (3-aminophenoxy) biphenyl, 4' -bis (2-trifluoromethyl-4-aminophenoxy) biphenyl, 1, 3-bis (2-trifluoromethyl-4-aminophenoxy) benzene, 1, 4-bis (2-trifluoromethyl-4-aminophenoxy) benzene, 2- (4-aminophenyl) -5-aminobenzimidazole, 1, 4-cyclohexyldiamine, menthanediamine, 3' -dimethyl-4, 4' -diaminodicyclohexylmethane, 4' -diaminodicyclohexylmethane.

The accelerant is one or more selected from aluminum acetylacetonate, zinc acetylacetonate, 2-ethyl-4-methylimidazole, 2-methylimidazole, imidazole and derivatives thereof, N-dimethyl-p-methylaniline, lead benzoate, metal organic compounds, DMP-30, benzyl dimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, DBU and 1, 8-diazabicyclo [5.4.0] undecene-7.

The reactive diluent is selected from one or more of hydrogenated bisphenol A epoxy resin, resorcinol diglycidyl ether epoxy resin, CE-793, 3, 4-epoxy cyclohexanoic acid-3 ', 4' -epoxy cyclohexanemethyl ester, 3, 4-epoxy-6-methyl cyclohexanoic acid-3 ', 4' -epoxy-6 ' -methyl cyclohexanemethyl ester and dipentene dioxide.

The invention provides a preparation method of a sulfone ether epoxy adhesive and UHMWPE fiber reinforced bulletproof composite material, which comprises the following steps:

(1) at room temperature, putting the sulfone ether epoxy resin, other epoxy resins and a chain extender into a reactor according to the proportion, stirring and mixing, heating to 80-100 ℃, carrying out copolymerization chain extension reaction for 0.5-1.0 hour, cooling to below 60 ℃ after completion, adding an active diluent, stirring and dissolving to form a homogeneous phase, adding a curing agent and an accelerator, and stirring and mixing uniformly to obtain the sulfone ether epoxy adhesive;

(2) and (2) coating the sulfone ether epoxy adhesive in the step (1) on the surface of UHMWPE fiber on a UD machine to prepare the UD cloth with the adhesive, cutting, superposing, heating, molding and forming to obtain the UHMWPE fiber reinforced bulletproof composite material.

The heating compression molding temperature range in the step (2) is 80-110 ℃, and the pressure range is 0.1-10 MPa.

Advantageous effects

(1) The sulfone ether epoxy adhesive disclosed by the invention is environment-friendly, free of organic solvent and excellent in adhesive property.

(2) The sulfone ether epoxy adhesive has low curing temperature and wide bonding surface, and can bond metal, ceramic, glass, carbon fiber, aramid fiber, high-strength high-modulus polyethylene fiber and the like.

(3) The sulfone ether epoxy UHMWPE fiber reinforced bulletproof composite material has the advantages of superior comprehensive performance, outstanding bulletproof performance and simple process, and is suitable for large-scale production.

Drawings

FIG. 1 is a general molecular structural formula of the sulfone ether epoxy resin of the present invention.

Fig. 2 is a schematic illustration of a single fiber pull-out test for the ballistic resistant composite material of the present invention.

Figure 3 is a photograph of a ballistic resistant composite material of example 5 of the present invention before gunshot.

Fig. 4 is a photograph of the bullet-resistant face and the bullet-resistant face after gunshot of the ballistic composite of example 5 of the invention.

Detailed Description

The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.

Example 1

Putting 68.4 g (0.3 mol) of bisphenol A, 57.4 g (0.2 mol) of 4,4' -dichlorodiphenyl sulfone (DCDS), 1520.0 g of N-methyl-2-pyrrolidone (NMP), 152.0 g of toluene and 41.4 g (0.3 mol) of potassium carbonate into a reaction kettle, heating, refluxing and water-splitting at 100-200 ℃ for 5 hours, recovering the toluene (recycling), cooling to below 60 ℃, adding 277.5 g (3.0 mol) of Epoxy Chloropropane (ECH), continuously heating, refluxing for 5 hours, filtering to remove salt after the reaction is finished, decompressing and concentrating, recovering the organic solvent and the excessive epoxy chloropropane, recycling, quickly precipitating the concentrated mother liquor in 3344 g of water, filtering, washing for 2-5 times by deionized water, and drying in vacuum at 25-180 ℃ for 2 hours to obtain 121.4 g of a solid product (the theoretical yield is 122.4 g), namely the long-chain hydroxyl-free sulfone ether epoxy resin, the yield was recorded as R-1 and was 99.2%. [ R-1 in example 1 of Chinese invention patent 202111390032.3 ]

At room temperature, 10.0 g of sulfone ether epoxy resin R-1, 20.0 g of bisphenol A epoxy resin E-51, 30.0 g of ES216 epoxy resin, 50.0 g of SRTEM-80 epoxy resin (Zhejiang ruiyun new materials science and technology Co., Ltd.), 10.0 g of SD-248 (Zhejiang ruiyun new materials science and technology Co., Ltd.) and 10.0 g of chain extender of 1, 4-bis (2, 4-diaminophenoxy) benzene are put into a reactor, stirred and mixed, heated to 80 ℃ to 100 ℃, subjected to copolymerization chain extension reaction for 1.0 hour, cooled to below 60 ℃, added with 10.0 g of CE-793 active diluent (Zhejiang ruiyun cloud new materials Co., Ltd.) and stirred and dissolved to be homogeneous, added with 100.0 g of methyl tetrahydrophthalic anhydride and 0.1 g of 2-ethyl-4-methylimidazole, stirred and mixed uniformly to obtain 240.1 g of sulfone ether epoxy adhesive, denoted SEA-1.

Example 2

At room temperature, 10.0 g of sulfone ether epoxy resin R-1, 10.0 g of bisphenol A epoxy resin E-51, 5.0 g of N, N, N ', N ' -tetraglycidyl-4, 4' -diaminodiphenylmethane epoxy resin, 5.0 g of SRTEM-80 epoxy resin (Zhejiang Yiyun New materials science and technology Co., Ltd.), 2.0 g of SD-248 (Zhejiang Yiyun New materials science and technology Co., Ltd.) and 8.0 g of a chain extender of 2, 2-bis [4- (2, 4-diaminophenoxy) phenyl ] hexafluoropropane are placed into a reactor, stirred and mixed, heated to 80-100 ℃ for copolymerization chain extension reaction for 1.0 hour, cooled to below 60 ℃ after completion, 10.0 g of CE-793 (Zhejiang Yiyun science and technology Co., Ltd.) and 30.0 g of a reactive diluent of resorcinol diglycidyl ether epoxy resin are added, stirred and dissolved to form a homogeneous phase, 10.0 grams of methylhexahydrophthalic anhydride and 20.0 grams of methylnadic anhydride curing agent, 2.0 grams of 2,4, 6-tris (dimethylaminomethyl) phenol and 3.0 grams of N, N-dimethyl-p-methylaniline accelerator were added and mixed well with stirring to give 115.0 grams of the sulfone ether epoxy adhesive, designated SEA-2.

Example 3

Putting 33.6 g (0.1 mol) of bisphenol AF, 12.4 g (0.1 mol) of o-methyl hydroquinone, 28.7 g (0.1 mol) of 4,4' -dichlorodiphenyl sulfone (DCDS), 500 g of N-methyl-2-pyrrolidone (NMP), 80.5 g of toluene and 41.4 g (0.3 mol) of potassium carbonate into a reaction kettle, heating, refluxing and reacting for 10 hours at 100-200 ℃, recovering the toluene (recycling), cooling to below 60 ℃, adding 740.0 g (1.6 mol) of Epoxy Chloropropane (ECH), continuing heating and refluxing for 8 hours, filtering to remove salt after the reaction is finished, decompressing and concentrating, recovering the organic solvent and the excessive epoxy chloropropane, recycling, quickly precipitating the concentrated mother solution in 3483 g of water, filtering, washing for 2-5 times by deionized water, drying for 8 hours at the temperature of 25-180 ℃ in vacuum to obtain 59.8 g of solid product (the theoretical yield is 60.1 g), the long-chain hydroxyl-free sulfone ether epoxy resin is recorded as R-3, and the yield is 99.5%. [ R-3 in example 3 of Chinese invention patent 202111390032.3 ]

At room temperature, 10.0 g of sulfone ether epoxy resin R-3, 10.0 g of SRTEM-50 epoxy resin (Zhejiang Yinyun New Material science and technology Co., Ltd.) and 0.1 g of chain extender of 1, 3-bis (2, 4-diaminophenoxy) benzene are put into a reactor, stirred and mixed, heated to 80-100 ℃ for copolymerization chain extension reaction for 0.5 hour, after the copolymerization chain extension reaction is completed, cooled to below 60 ℃, 35.0 g of CE-793 active diluent (Zhejiang Yinyun New Material science and technology Co., Ltd.) is added, stirred and dissolved to be homogeneous, 10.0 g of methyl tetrahydrophthalic anhydride curing agent, 5.0 g of 2-ethyl-4-methylimidazole and 5.0 g of accelerator of 1, 8-diazabicyclo [5.4.0] undecene-7 are added, stirred and mixed uniformly, and 75.1 g of sulfone ether epoxy adhesive is obtained, and is recorded as SEA-3.

Example 4

(1) Tensile shear strength test:

the appropriate amount of sulfone ether epoxy adhesives of examples 1-3, namely SEA-1, SEA-2 and SEA-3, were taken and applied evenly on standard stainless steel test pieces, respectively, and after being left for 15 minutes at room temperature, the pieces were superposed, clamped and placed in a forced air oven for curing: heating to 60 ℃ from room temperature, keeping the temperature for reaction for 0.5 hour, continuing to heat to 90 ℃, keeping the temperature for reaction for 0.5 hour, continuing to heat to 100 ℃, keeping the temperature for reaction for 0.5 hour, and naturally cooling to room temperature.

The tensile shear strength (. sigma.) was measured at room temperature (25 ℃ C.) and at high temperature (120 ℃ C.) using an electron tensile machine, and the results are shown in Table 1.

(2) Single fiber pull out test

In order to test the interfacial performance of UHMWPE and the sulfone ether epoxy adhesive, a single fiber is embedded in the adhesive, the embedding depth has a critical value Lc, the extraction force is increased along with the increase of the embedding depth when the embedding depth is below Lc, and after the embedding depth exceeds Lc, the shearing stress born by the fiber reaches the limit, and the extraction force cannot be increased when the depth is continuously increased. Generally, Lc is within 1mm, so the present invention sets the embedding depth L to 1.2mm, as shown in FIG. 2.

When an XQ-1A instrument is used for testing, one section embedded with resin is fixed on a chuck, and the other end of the section is used for clamping fibers by the chuck. The shear strength calculation formula of the sample is as follows: τ ═ F_lAnd/pi dL. Wherein, F_lThe withdrawal force is in cN; r is the fiber diameter in μm; l is the embedding depth in mm.

The single fiber extraction test results of the UHMWPE fibers of SEA-1, SEA-2, SEA-3 are shown in table 1, wherein the UHMWPE fibers were purchased from new material science and technology ltd, enging, zui, zhejiang, and the fiber surfaces were subjected to special surface treatment; and (3) a curing process: heating to 60 ℃ from room temperature, keeping the temperature for reaction for 0.5 hour, continuing to heat to 90 ℃, keeping the temperature for reaction for 0.5 hour, continuing to heat to 100 ℃, keeping the temperature for reaction for 0.5 hour, and naturally cooling to room temperature.

TABLE 1 adhesion Properties of sulfone Ether epoxy Adhesives

Sample (I)	SEA-1	SEA-2	SEA-3
				σ(MPa/25℃)	29.6	30.3	29.7
σ(MPa/120℃)	29.1	30.2	29.5
				τ(MPa/25℃)	2.42	2.57	2.38

Example 5

Taking a proper amount of the sulfone ether epoxy adhesive in the embodiment 1, namely SEA-1, coating the sulfone ether epoxy adhesive on the surface of UHMWPE fibers on a UD machine, controlling the volume ratio of the sulfone ether epoxy adhesive to the UHMWPE fibers to be 1: 10, preparing the glued UD cloth, cutting, superposing, heating, compression molding, wherein the temperature range is 80-110 ℃; the pressure intensity is 0.1 MPa-10 MPa, and the UHMWPE fiber reinforced bulletproof composite material plate (thickness 10mm) is obtained and is marked as FD-1. And (3) carrying out live-action shooting by adopting a 54 pistol, wherein the bullet is a 51-type pistol bullet with the caliber of 7.62mm, the mass of the whole bullet is 10.4g, the total length of the bullet is 34.4-34.8 mm, the shooting speed is 435m/s, the depression depth is 23.5mm, the composite material is not punctured, and the target plate absorption energy is 541.2J through calculation. The physical diagrams before and after the gunshot are shown in fig. 3 and 4.

Taking a proper amount of the sulfone ether epoxy adhesive in the embodiment 2, namely SEA-2, coating the sulfone ether epoxy adhesive on the surface of UHMWPE fibers on a UD machine, controlling the volume ratio of the sulfone ether epoxy adhesive to the UHMWPE fibers to be 1: 25, preparing the glued UD cloth, cutting, superposing, heating, compression molding, wherein the temperature range is 80-110 ℃; the pressure intensity is 0.1 MPa-10 MPa, and the UHMWPE fiber reinforced bulletproof composite material plate (the thickness is 10mm) is obtained and is marked as FD-2. And (3) carrying out live-action shooting by adopting a 54 pistol, wherein the bullet is a 51-type pistol bullet with the caliber of 7.62mm, the mass of the whole bullet is 10.4g, the total length of the bullet is 34.4-34.8 mm, the shooting speed is 435m/s, the depression depth is 22.3mm, the composite material is not punctured, and the target plate absorption energy is 550.3J through calculation.

Taking a proper amount of the sulfone ether epoxy adhesive in the embodiment 3, namely SEA-3, coating the sulfone ether epoxy adhesive on the surface of UHMWPE fibers on a UD machine, controlling the volume ratio of the sulfone ether epoxy adhesive to the UHMWPE fibers to be 1:5, preparing the glued UD cloth, cutting, superposing, heating, compression molding, wherein the temperature range is 80-110 ℃; the pressure intensity is 0.1 MPa-10 MPa, and the UHMWPE fiber reinforced bulletproof composite material plate (the thickness is 10mm) is obtained and is marked as FD-3. And (3) carrying out live-action shooting by adopting a 54 pistol, wherein the bullet is a 51-type pistol bullet with the caliber of 7.62mm, the mass of the whole bullet is 10.4g, the total length of the bullet is 34.4-34.8 mm, the shooting speed is 435m/s, the depression depth is 24.6mm, the composite material is not punctured, and the target plate absorption energy is 537.3J through calculation.

Claims (10)

1. A reinforced bulletproof composite material of a sulfone ether epoxy adhesive and UHMWPE fiber is characterized in that: comprises a sulfone ether epoxy adhesive and UHMWPE fiber with the volume ratio of 1: 5-25; the sulfone ether epoxy adhesive is composed of sulfone ether epoxy resin, other epoxy resin, a chain extender, a curing agent, an accelerator and a reactive diluent in a mass ratio of 10:10-100:0.1-20:10-100:0.1-10: 10-40.

2. The composite material of claim 1, wherein: the molecular structure general formula of the sulfone ether epoxy adhesive is as follows:

wherein m is an integer of 0-6; -Q-is a divalent residue of a dihydric phenol.

3. The composite material of claim 2, wherein: the dihydric phenol is selected from one or more of hydroquinone, resorcinol, o-methyl hydroquinone, 2-tert-butyl hydroquinone, 2, 5-di-tert-butyl hydroquinone, 2, 5-dimethyl hydroquinone, bisphenol A, bisphenol S, bisphenol F, bisphenol AF, biphenol, tetramethyl bisphenol A, tetramethyl bisphenol S, tetramethyl bisphenol AF, tetramethyl bisphenol F and tetramethyl biphenol.

4. The composite material of claim 1, wherein: the other epoxy resin is selected from one or a mixture of more of bisphenol A epoxy resin E-51, SRTEM-80 epoxy resin, SRTEM-50 epoxy resin, bisphenol A epoxy resin E-44, bisphenol S epoxy resin, bisphenol F epoxy resin, ES216 epoxy resin, ECC202 epoxy resin, o-cresol novolac epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, glycidyl ether epoxy resin, alicyclic epoxy resin, hydrogenated bisphenol A epoxy resin and aliphatic epoxy resin; wherein the glycidyl amine epoxy resin is selected from N, N-diglycidyl aniline epoxy resin, N, N-diglycidyl o-toluidine, N, N-diglycidyl p-toluidine epoxy resin, N, N-diglycidyl o-ethylaniline epoxy resin, N, N, N ', N' -tetraglycidyl p-phenylenediamine epoxy resin, N, N, N ', N' -tetraglycidyl m-phenylenediamine epoxy resin, N, N, N ', N' -tetraglycidyl o-phenylenediamine epoxy resin, N, N, N ', N' -tetraglycidyl-4, 4 '-diaminodiphenyl ether epoxy resin, N, N, N', N '-tetraglycidyl-4, 4' -diaminodiphenyl methane epoxy resin, N, N, n ', N ' -tetraglycidyl-4, 4' -diaminodiphenyl sulfone epoxy resin, N, N, N ', N ' -tetraglycidyl-3, 3' -dimethyl-4, 4' -diaminodiphenyl methane epoxy resin, N, N, N ', N ', O-pentaglycidyl-4, 4' -diamino-4 "-hydroxytriphenylmethane epoxy resin, N, N, O-triglycidyl-4-aminophenol epoxy resin, N, N, N ', N ' -tetraglycidyl-4, 4' -diaminodiphenyl ether epoxy resin, N, N, N ', N ' -tetraglycidyl-1, 4-bis (4-aminophenoxy) benzene epoxy resin, N, N, n ', N' -tetraglycidyl-2, 2-bis [4- (4-aminophenoxy) phenyl ] propane epoxy resin, N, N, N ', N' -tetraglycidyl-1, 3-bis (4-aminophenoxy) benzene epoxy resin, N, N, N ', N' -tetraglycidyl-3, 3 '-diaminodiphenylsulfone epoxy resin, N, N, N', N '-tetraglycidyl-3, 3' -dimethoxy-4, 4 '-diaminobiphenyl epoxy resin, N, N, N', N '-tetraglycidyl-3, 3' -diaminodiphenylether epoxy resin, N, N, N ', N' -tetraglycidyl-2, 2-bis [4- (3-aminophenoxy) phenyl ] propane epoxy resin, and their use, N, N, N ', N ' -tetraglycidyl-2, 2-bis [4- (3-aminophenoxy) phenyl ] hexafluoropropane epoxy resin, N, N, N ', N ' -tetraglycidyl-3, 4' -diaminodiphenyl ether epoxy resin, N, N, N ', N ' -tetraglycidyl-3, 3' -diaminodiphenyl ether epoxy resin, N, N, N ', N ' -tetraglycidyl-1, 4-bis (3-aminophenoxy) benzene epoxy resin, N, N, N ', N ' -tetraglycidyl-2, 6-bis (4-aminophenoxy) benzonitrile epoxy resin, N, N, N ', N ' -tetraglycidyl-2, 6-bis (3-aminophenoxy) benzonitrile epoxy resin, N, N ', N ' -tetraglycidyl-1, N, N ', N ' -tetraglycidyl-1, N ' -tetraglycidyl-3, 6-2, N, N, 2, N, N, N, 2, N, N, N, n, N, N ', N' -tetraglycidyl-2, 6-bis (4-aminophenoxy) tolylene epoxy resin, N, N, N ', N' -tetraglycidyl-2, 6-bis (4-aminophenoxy) benzotrifluoride epoxy resin, N, N, N ', N' -tetraglycidyl-2, 5-bis (4-aminophenoxy) tolylene epoxy resin, N, N, N ', N' -tetraglycidyl-2, 5-bis (4-aminophenoxy) tert-butylbenzene epoxy resin, N, N, N ', N' -tetraglycidyl-2, 5-di-tert-butyl-1, 4-bis (4-aminophenoxy) benzene epoxy resin, N, N, N ', N' -tetraglycidyl-4, 4' -bis (4-aminophenoxy) benzophenone epoxy resin, N, N, N ', N ' -tetraglycidyl-4, 4' -bis (4-aminophenoxy) diphenylsulfone epoxy resin, N, N, N ', N ' -tetraglycidyl-4, 4' -bis (3-aminophenoxy) benzophenone epoxy resin, N, N, N ', N ' -tetraglycidyl-4, 4' -bis (3-aminophenoxy) diphenylsulfone epoxy resin, N, N, N ', N ' -tetraglycidyl-1, 4-bis (2-trifluoromethyl-4-aminophenoxy) benzene epoxy resin, N, N, N ', N ' -tetraglycidyl-1, 3-bis (2-trifluoromethyl-4-aminophenoxy) benzene epoxy resin, N, N, N ', N ' -tetraglycidyl-4, N, N, N ' -tetraglycidyl-4-bis (3-amino-phenoxy) benzene epoxy resin, N, N ', N ' -tetraglycidyl-4, N ' -tetraglycidyl-bis (2-amino-phenoxy) benzene epoxy resin, N, N ' -tetraglycidyl-4, N, N, N, or N, N, or a mixture of, N, N, N ', N' -tetraglycidyl-2, 2-bis [4- (2-trifluoromethyl-4-aminophenoxy) phenyl ] propane epoxy resin, N, N, N ', N' -tetraglycidyl-2, 2-bis [4- (2-trifluoromethyl-4-aminophenoxy) phenyl ] hexafluoropropane epoxy resin, N, N, N ', N' -tetraglycidyl-2, 5-bis (2-trifluoromethyl-4-aminophenoxy) toluene epoxy resin, N, N, N ', N' -tetraglycidyl-2, 5-bis (2-trifluoromethyl-4-aminophenoxy) tert-butyl benzene epoxy resin, N, N, N ', N' -tetraglycidyl-2, 5-di-tert-butyl-1, 4-bis (2-trifluoromethyl-4-aminophenoxy) benzene epoxy resin, N, N, N ', N ' -tetraglycidyl-4, 4' -bis (2-trifluoromethyl-4-aminophenoxy) diphenylsulfone epoxy resin, N, N, N ', N ' -tetraglycidyl-4, 4' -bis (2-trifluoromethyl-4-aminophenoxy) -3,3',5,5' -tetramethyldiphenylsulfone epoxy resin, N, N, N ', N ' -tetraglycidyl-4, 4' -bis (2-trifluoromethyl-4-aminophenoxy) biphenyl epoxy resin, N, N, N ', N ' -tetraglycidyl-4, 4' -bis (2-trifluoromethyl-4-aminophenoxy) -3,3',5,5' -tetramethylbiphenyl epoxy resin, N, N, N ', N ' -tetraglycidyl-4, 4' -bis (2-trifluoromethyl-4-aminophenoxy) diphenyl ether epoxy resin, N, N, N ', N ' -tetraglycidyl-4, 4' -bis (3-aminophenoxy) diphenyl sulfide epoxy resin, and mixtures thereof, N, N, N ', N ' -tetraglycidyl-4, 4' -bis (4-aminophenoxy) diphenyl sulfide epoxy resin, N, N, N ', N ' -tetraglycidyl-4, 4' -bis (4-aminophenoxy) -3,3',5,5' -tetramethylbiphenyl epoxy resin, N, N, N ', N ' -tetraglycidyl-4, 4' -bis (3-aminophenoxy) -3,3',5,5' -tetramethylbiphenyl epoxy resin, N, N, N ', N ' -tetraglycidyl-2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane epoxy resin, N, N, N ', N ' -tetraglycidyl-1, one or more of 3-bis (3-aminophenoxy) benzene epoxy resin and N, N, N ', N' -tetraglycidyl-1, 3-bis (4-aminophenoxy) benzene epoxy resin.

5. The composite material of claim 1, wherein: the chain extender is selected from 2, 2-bis [4- (2, 4-diaminophenoxy) phenyl ] hexafluoropropane, 2-bis [4- (2, 4-diaminophenoxy) phenyl ] propane, 4-bis (2, 4-diaminophenoxy) diphenylsulfone, SD-248, 4-bis (2, 4-diaminophenoxy) diphenylether, 4-bis (2, 4-diaminophenoxy) diphenylsulfide, 4-bis (2, 4-diaminophenoxy) diphenylmethane, 1, 4-bis (2, 4-diaminophenoxy) benzene, 1, 3-bis (2, 4-diaminophenoxy) benzene, polyetheramine, 4-bis (2, 4-diaminophenoxy) biphenyl, 4, one or two of 4-bis (2, 4-diaminophenoxy) -3,3',5,5' -tetramethylbiphenyl.

6. The composite material of claim 1, wherein: the curing agent is selected from hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, dodecenylsuccinic anhydride, methyl hexahydrophthalic anhydride, methyl nadic anhydride, eleostearic anhydride, 80-anhydride obtained by reacting dicyclopentadiene with maleic anhydride, polyetheramine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine, polyethylene polyamine, anhydride obtained by reacting limonene with maleic anhydride, liquid anhydride obtained by reacting turpentine with maleic anhydride, pyromellitic dianhydride, 3', 4,4' -tetracarboxylbiphenyl dianhydride, 3', 4,4' -tetracarboxydiphenyl ether dianhydride, 3', 4,4' -tetracarboxydiphenylsulfenyl sulfone dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 4,4 '-bis (3, 4-dicarboxyphenoxy) diphenyl ether dianhydride, 4' -bis (3, 4-dicarboxyphenoxy) benzophenone dianhydride, 4 '-bis (3, 4-dicarboxyphenoxy) diphenylmethane dianhydride, 4' -bis (3, 4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4 '-bis (3, 4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4' -bis (3, 4-dicarboxyphenoxy) biphenyl dianhydride, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] hexafluoropropane dianhydride, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride, 1, 4-bis (3, 4-dicarboxyphenoxy) benzene dianhydride, 1, 3-bis (3, 4-dicarboxyphenoxy) benzene dianhydride, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 4 '-diaminodiphenyl ether, 3' -diaminodiphenyl ether, 4 '-diaminodiphenylmethane, 3' -dimethyl-4, 4 '-diaminodiphenylmethane, 4' -diaminobiphenyl, 3 '-dimethyl-4, 4' -diaminobiphenyl, 2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl, 4 '-diaminobenzophenone, 4' -diaminodiphenyl sulfone, 3 '-diaminodiphenyl sulfone, 3,4' -diaminodiphenyl sulfone, 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2-bis [4- (3-aminophenoxy) phenyl ] propane, 2-bis [4- (3-aminophenoxy) phenyl ] hexafluoropropane, 4 '-bis (4-aminophenoxy) benzophenone, 4' -bis (3-aminophenoxy) benzophenone, 4 '-bis (4-aminophenoxy) diphenylsulfone, 4' -bis (3-aminophenoxy) diphenylsulfone, 1, 3-bis (3-aminophenoxy) benzene, 1, 4-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 2-bis [4- (2-trifluoromethyl-4-aminophenoxy) phenyl ] propane, 2-bis [4- (2-trifluoromethyl-4-aminophenoxy) phenyl ] hexafluoropropane, 4' -bis (2-trifluoromethyl-4-aminophenoxy) benzophenone, 4' -bis (2-trifluoromethyl-4-aminophenoxy) diphenylsulfone, 4' -bis (4-aminophenoxy) diphenylsulfide, 4' -bis (3-aminophenoxy) diphenylsulfide, 4' -bis (2-trifluoromethyl-4-aminophenoxy) diphenylsulfide, 4' -bis (4-aminophenoxy) biphenyl, 2-bis [ 4-trifluoromethyl-4-aminophenoxy ] phenyl ] propane, 2-bis [4- (2-trifluoromethyl-4-aminophenoxy) phenyl ] propane, 4, 2-bis [4- (2-trifluoromethyl-4-aminophenoxy) phenyl ] hexafluoropropane, 4' -bis (4-aminophenoxy) diphenylsulfide, 4-bis (4-aminophenoxy) biphenyl, 4-bis (4-aminophenoxy) biphenyl, 4-aminophenoxy) biphenyl, 4, or a mixture of benzene, 4, and a mixture of two, 4, 2,4, 2, or a mixture of, a mixture of two, a mixture of two, a mixture of two, a mixture of two or a mixture of two or a mixture of two or a mixture, 4,4' -bis (3-aminophenoxy) biphenyl, 4' -bis (2-trifluoromethyl-4-aminophenoxy) biphenyl, 1, 3-bis (2-trifluoromethyl-4-aminophenoxy) benzene, 1, 4-bis (2-trifluoromethyl-4-aminophenoxy) benzene, 2- (4-aminophenyl) -5-aminobenzimidazole, 1, 4-cyclohexyldiamine, menthanediamine, 3' -dimethyl-4, 4' -diaminodicyclohexylmethane, 4' -diaminodicyclohexylmethane.

7. The composite material of claim 1, wherein: the accelerant is one or more selected from aluminum acetylacetonate, zinc acetylacetonate, 2-ethyl-4-methylimidazole, 2-methylimidazole, imidazole and derivatives thereof, N-dimethyl-p-methylaniline, lead benzoate, metal organic compounds, DMP-30, benzyl dimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, DBU and 1, 8-diazabicyclo [5.4.0] undecene-7.

8. The composite material of claim 1, wherein: the reactive diluent is selected from one or more of hydrogenated bisphenol A epoxy resin, resorcinol diglycidyl ether epoxy resin, CE-793, 3, 4-epoxy cyclohexanoic acid-3 ', 4' -epoxy cyclohexanemethyl ester, 3, 4-epoxy-6-methyl cyclohexanoic acid-3 ', 4' -epoxy-6 ' -methyl cyclohexanemethyl ester and dipentene dioxide.

9. A process for the preparation of a sulfone ether epoxy adhesive and UHMWPE fiber reinforced ballistic composite of claim 1 comprising the steps of:

(1) at room temperature, putting the sulfone ether epoxy resin, other epoxy resins and a chain extender into a reactor according to the proportion, stirring and mixing, heating to 80-100 ℃, carrying out copolymerization chain extension reaction for 0.5-1.0 hour, cooling to below 60 ℃ after completion, adding an active diluent, stirring and dissolving to form a homogeneous phase, adding a curing agent and an accelerator, and stirring and mixing uniformly to obtain the sulfone ether epoxy adhesive;

(2) and (2) coating the sulfone ether epoxy adhesive in the step (1) on the surface of UHMWPE fiber on a UD machine to prepare the UD cloth with the adhesive, cutting, superposing, heating, molding and forming to obtain the UHMWPE fiber reinforced bulletproof composite material.

10. The method of claim 9, wherein: the heating compression molding temperature range in the step (2) is 80-110 ℃, and the pressure range is 0.1-10 MPa.

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