CN113388244A - Thermoplastic polyurethane elastomer composite material with interface self-repairing function and preparation method thereof - Google Patents
Thermoplastic polyurethane elastomer composite material with interface self-repairing function and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a thermoplastic polyurethane elastomer composite material with an interface self-repairing function, which comprises the following components in percentage by weight: (a)100 parts by weight of a thermoplastic polyurethane elastomer; (b)1-150 parts by weight of an inorganic substance treated with a surface treatment agent, wherein the surface treatment agent is a surface treatment agent prepared from a silane coupling agent and a disulfide, and the composite material can automatically repair the interface damage between the base material and the inorganic substance under normal temperature or heating conditions, thereby recovering or partially recovering the mechanical properties of the composite material.
Description
Technical Field
The invention relates to a polymer composite material with an interface self-repairing function and a preparation method thereof, in particular to a thermoplastic polyurethane elastomer composite material with an interface self-repairing function and a preparation method thereof.
Background
In polymer composites, the interfacial layer between the polymer and the mineral plays a crucial role in the mechanical properties of the composite, the main function of which is to transfer the load between the two materials. Under dynamic loading or impact, polymer composites tend to develop stress concentrations due to base material cracking or fissuring at the interface layers and in the vicinity thereof, leading to premature material failure. These cracks or fissures are generally unpredictable and difficult to detect, and their repair costs are relatively high, so how to avoid and repair them is a hot topic in the field of composite materials.
Self-healing techniques for polymeric materials have made significant progress over the past decade to extend the useful life of the material. Researchers have implemented self-repair of polymers through molecular chain diffusion, light-induced reactions, reactive end groups, reversible chemical bonds, ionomers, embedding microcapsules, and many other approaches. Among them, techniques of inducing polymerization of monomers by light or catalyst have been successfully applied to polymer composites. Patent US20150291745 pre-embeds dicyclopentadiene microcapsule bodies and Grubbs catalyst into polyethylene/nanofiller composite, and repairs cracks of the composite by catalyzing dicyclopentadiene polymerization with the Grubbs catalyst; patent US10167398 fills a repairing agent into a carbon nanotube and then closes both ends of the carbon nanotube, and mixes a catalyst into a polymer matrix to prepare a polymer/carbon nanotube composite material having a self-repairing function. Patent US9701797 introduces a polymer layer containing reversible chemical bonds between the polymer matrix and the carbon fibers, with which the polymer layer confers self-healing properties to the polymer/carbon fiber composite. However, the active monomer or repairing agent with the repairing function is usually volatile organic compound, and inevitably escapes into the air in the self-repairing process, thereby posing great threat to human health; the in-situ polymerization on the surface of inorganic substances such as carbon fiber has strict requirements on process conditions, treatment environment, surface active groups of the inorganic substances and the purity of the inorganic substances, and has poor universality on inorganic substances such as industrial-grade fillers and reinforcing fibers.
The patent is inspired by self-repairing technology, and aims to develop a thermoplastic polyurethane elastomer composite material with an interface having a self-repairing function and a preparation method thereof.
Disclosure of Invention
The invention provides a thermoplastic polyurethane elastomer composite material with an interface self-repairing function, which can automatically repair a damaged interface layer between a base material and an inorganic substance under normal temperature or heating condition so as to recover or partially recover the mechanical property of the composite material; organic monomer volatilization does not exist in the self-repairing process of the composite material, and the composite material has high environmental protection property and high safety; the preparation method of the composite material has no special requirements on site environment, inorganic matter purity and inorganic matter form, and is suitable for various TPU/inorganic matter composite materials.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a thermoplastic polyurethane elastomer composite with interfacial self-healing functionality comprising:
(a)100 parts by weight of a thermoplastic polyurethane elastomer; (b)1 to 150 parts by weight, preferably 10 to 100 parts by weight of an inorganic substance treated with a surface treatment agent.
The thermoplastic polyurethane elastomer (TPU) may be a conventional TPU, such as at least one selected from polyester, polyether, polycarbonate, polycaprolactone-type TPU.
The molecular chain of the TPU consists of a soft segment and a hard segment, wherein the hard segment is obtained by reacting diisocyanate and a chain extender, and the diisocyanate is at least one of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI), p-phenylene diisocyanate (PPDI), isophorone diisocyanate (IPDI), 1, 5-Naphthalene Diisocyanate (NDI), Xylylene Diisocyanate (XDI) and dimethylbiphenyl diisocyanate (TODI);
the chain extender is micromolecule diamine and/or micromolecule dihydric alcohol, wherein the micromolecule diamine is preferably at least one of 3,3 '-dichloro-4, 4' -diaminodiphenylmethane, 3, 5-diamino isobutyl p-chlorobenzoate, diethyl toluene diamine and 3, 5-dimethyl sulfur toluene diamine; the small molecular dihydric alcohol is preferably at least one of 1, 4-butanediol, ethylene glycol, propylene glycol, methyl propylene glycol, diethylene glycol, 1, 4-cyclohexanediol and neopentyl glycol;
the soft segment is selected from at least one of polyether polyol, polyester polyol, polycaprolactone polyol and polycarbonate polyol;
the polyether polyol is preferably at least one of polypropylene oxide polyol, polytetrahydrofuran polyol and polyether polyol copolymer;
the polyester polyol is preferably at least one of polyethylene adipate polyol, polypropylene adipate polyol, polybutylene adipate polyol, polyhexamethylene adipate polyol, polyethylene adipate glycol polyol, polybutylene adipate polyol and dimethyl polypropylene adipate polyol, and more preferably at least one of polyethylene adipate polyol and polypropylene adipate polyol;
the polycaprolactone polyol is prepared by ring-opening polymerization of epsilon-caprolactone monomers;
the polycarbonate polyol is preferably at least one of polyethylene carbonate polyol, polybutylene carbonate polyol and hexamethylene carbonate polyol.
The amounts of the components of the TPU and the preparation process are well known in the art and are not described in detail.
The inorganic substance is preferably at least one of graphite, expanded graphite, carbon fiber, carbon black, boron nitride, aluminum nitride, silicon boron nitride, aluminum oxide, magnesium oxide, titanium oxide, zinc oxide, silicon carbide, glass fiber, glass microsphere, glass powder, wollastonite, montmorillonite, calcium carbonate, kaolin, talc, mica, metal powder, metal fiber, magnesium hydroxide and aluminum hydroxide, and more preferably at least one of glass powder, glass microsphere, glass fiber, silicon carbide, silicon nitride, magnesium hydroxide and aluminum hydroxide.
The surface of the inorganic substance is not treated with any kind of coupling agent before being treated with the surface treating agent according to the present invention.
The surface treating agent is a surface treating agent prepared from a silane coupling agent and disulfide.
The silane coupling agent is selected from at least one of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane, 3- (2, 3-epoxypropoxy) propyl triethoxy silane, 3-isocyanate propyl trimethoxy silane and 3-isocyanate propyl triethoxy silane; preferably, the silane coupling agent is a mixture of 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane in a molar ratio of 1: 1-2.
The disulfide is at least one selected from bis (2-hydroxyethyl) disulfide, 2 ' -diaminodiphenyl disulfide, 4 ' -dihydroxydiphenyl disulfide and 3,3' -dihydroxydiphenyl disulfide; preferably, the disulfide is a mixture of bis (2-hydroxyethyl) disulfide and 4, 4' -diaminodiphenyl disulfide in a molar ratio of 1: 2-3.
The surface treating agent contains urethane groups or urea groups which have good compatibility with TPU base materials, and can improve the interface acting force through intermolecular hydrogen bonds and urea groups formed by the isocyanate groups and residual TPU isocyanate groups.
The diphenyl disulfide structure in the molecular structure of the surface treating agent has higher self-repairing capability.
The preparation method of the thermoplastic polyurethane elastomer composite material with the interface self-repairing function can be divided into three steps.
The first step of the preparation method of the thermoplastic polyurethane elastomer composite material with the interface self-repairing function is to prepare a surface treating agent.
The method for preparing the surface treating agent comprises the following steps: heating an inert gas such as disulfide protected by nitrogen to a reaction temperature, dropwise adding a silane coupling agent into the disulfide which is continuously stirred and is protected by the inert gas such as nitrogen, continuously stirring for a plurality of minutes after the dropwise adding of the silane coupling agent is finished, and finally cooling the product to room temperature to obtain the surface treating agent.
In the method for producing the surface treatment agent, the molar ratio of the silane coupling agent to the disulfide is preferably 1.0 to 2.0, more preferably 1.05 to 1.20;
the reaction temperature is preferably 30-100 ℃, and more preferably 50-90 ℃;
the time for continuing stirring after the completion of the dropwise addition of the silane coupling agent is preferably 30 to 100min, and more preferably 60 to 90 min.
The second step of the preparation method of the thermoplastic polyurethane elastomer composite material with the interface self-repairing function is to treat inorganic matters by using a surface treatment agent.
The method for treating inorganic substances comprises the following steps: preparing alcohol-water solution from alcohol and deionized water, adding acid to adjust pH to 3.5-5.5, adding surface treating agent while stirring, hydrolyzing for 1-30min to obtain hydrolysate of the surface treating agent, spraying the hydrolysate onto the surface of inorganic matter, stirring in a high-speed mixer for 10-30min, or immersing the inorganic matter into the hydrolysate for 1-30min, and drying the hydrolysate sprayed with the surface treating agent or the inorganic matter impregnated with the hydrolysate of the surface treating agent at 80-120 deg.C for 30-120min to obtain the inorganic matter treated with the surface treating agent.
In the method for treating inorganic matters, the alcohol is selected from methanol, ethanol and isopropanol, preferably ethanol;
the acid is selected from formic acid, acetic acid, oxalic acid, malonic acid, methanolic acid, glycolic acid, benzoic acid, phenylacetic acid, preferably acetic acid;
the weight ratio of the surface treating agent to the alcohol to the deionized water is 15-25:65-75:6-10, and the preferred weight ratio is 20:72: 8;
the hydrolysate of the surface treating agent is prepared for use, and the storage time of the hydrolysate is less than 1 hour.
The third step of the preparation method of the thermoplastic polyurethane elastomer composite material with the interface self-repairing function is melt mixing granulation.
The melt mixing granulation is a conventional operation in the art, and the preferred steps are as follows: and uniformly mixing the inorganic substance treated by the surface treatment agent and the thermoplastic polyurethane elastomer by using a mixing device, then feeding or independently metering and feeding, and finally melting and mixing by using an extruder, an internal mixer or an open mill to obtain the composite material.
The repairing method of the thermoplastic polyurethane elastomer composite material with the interface self-repairing function can restore the damaged composite material to the original shape or shape, and then self-repair is carried out under the condition of 20-100 ℃/12-72 h.
The thermoplastic polyurethane elastomer composite material with the interface self-repairing function does not comprise the repairing between two fracture surfaces after the material is completely fractured in the repairing category.
The invention has the beneficial effects that:
1. the surface treating agent contains the same urethane group or carbamido group as the TPU matrix material, and can form stronger interface action with the matrix material through intermolecular hydrogen bond and carbamido group.
2. The preparation method of the thermoplastic polyurethane elastomer composite material has no special requirements on site environment, inorganic matter purity and form, and is suitable for most TPU/inorganic matter composite materials.
3. The thermoplastic polyurethane elastomer composite material prepared by the invention realizes self-repair by forming disulfide bonds through the re-reaction of sulfydryl, and organic monomer volatilization does not exist in the self-repair process, so the environment-friendly property and the high safety are realized.
4. The thermoplastic polyurethane elastomer composite material can automatically repair the interface damage between the base material and the inorganic substance under the normal temperature or the heating condition, thereby recovering or partially recovering the mechanical property of the composite material.
The specific implementation mode is as follows:
the invention will be further illustrated by the following specific examples, which are not to be construed as limiting the invention; the terminology used herein is for the purpose of describing particular aspects only and is not intended to limit the scope of the present invention. Efforts have been made to ensure accuracy with respect to numbers, but some errors and deviations should be accounted for. Unless otherwise indicated, parts are parts by mass and pressure is at or near atmospheric pressure.
In the examples, the raw material sources are as follows:
TPU: polyester type TPU, WHT-1185, Vanhua chemical group Ltd
Glass microspheres: s60HS, 3M Co
Magnesium hydroxide: star Beida chemical Material Co Ltd
Silicon carbide: 3M Co Ltd
4, 4' -diaminodiphenyl disulfide: jianshun chemical engineering and technology Co Ltd
Bis (2-hydroxyethyl) disulfide: bailingwei Tech Co Ltd
3-isocyanatopropyltrimethoxysilane: silong 9907M, Stylon materials science & technology Ltd
3-isocyanatopropyltriethoxysilane: silong 9907E, Stylon materials science & technology Ltd
In examples 1 to 5, the surface-treated inorganic substance was mixed with TPU in the weight ratio shown in Table 1 below.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| TPU | 100 | 100 | 100 | 100 | 100 |
| Surface treated glass microspheres | 10 | - | - | 10 | 10 |
| Surface treated silicon carbide | - | 60 | - | - | - |
| Surface treated magnesium hydroxide | - | - | 100 | - | - |
In comparative examples 1-4, the surface treated inorganic and untreated inorganic were mixed with TPU in the weight ratios shown in Table 2 below.
TABLE 2
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| TPU | 100 | 100 | 100 | 100 |
| Surface treated glass microspheres | - | - | - | 10 |
| Glass microspheres | 10 | - | - | |
| Silicon carbide | - | 60 | - | |
| Magnesium hydroxide | - | - | 100 |
Example 1
Heating nitrogen-protected 4,4 '-diaminodiphenyl disulfide to 80 ℃, then dropwise adding nitrogen-protected silane coupling agent 3-isocyanatopropyltriethoxysilane into continuously stirred 4, 4' -diaminodiphenyl disulfide (the molar ratio of the silane coupling agent to the disulfide is 1.01:1), continuously stirring for 60min after finishing dropwise adding the silane coupling agent, and finally cooling the product to room temperature to obtain the surface treatment agent.
Respectively weighing absolute ethyl alcohol, deionized water and a surface treating agent according to a mass ratio of 72:8:20, preparing an alcohol-water solution from the absolute ethyl alcohol and the deionized water, adding acetic acid to adjust the pH value to 4.5, adding the surface treating agent while stirring, hydrolyzing for 5min to obtain a hydrolysate of the surface treating agent, spraying the hydrolysate on the surface of the glass microsphere, stirring for 20min at normal temperature of 200r/min in a high-speed mixer, and drying the glass microsphere for 30min at 120 ℃ to obtain the surface treated glass microsphere.
Mixing TPU and the glass microspheres subjected to surface treatment uniformly at normal temperature for 5min at a speed of 200r/min by using a high-speed mixer, and finally carrying out melt mixing by using a double-screw extruder to prepare the composite material, wherein the temperature is set as follows: the conveying section is 180 ℃, the melting section is 190 ℃, the homogenizing section is 195 ℃ and the head is 190 ℃.
Example 2
Heating nitrogen-protected 4,4 '-diaminodiphenyl disulfide to 80 ℃, then dropwise adding nitrogen-protected silane coupling agent 3-isocyanatopropyl trimethoxy silane into continuously stirred 4, 4' -diaminodiphenyl disulfide (the molar ratio of the silane coupling agent to the disulfide is 1.05:1), continuously stirring for 80min after finishing dropwise adding the silane coupling agent, and finally cooling the product to room temperature to obtain the surface treating agent.
The hydrolysate of the surface treatment agent was prepared according to the method of example 1, by immersing silicon carbide in the hydrolysate of the surface treatment agent for 20min, and then drying at 80 ℃ for 120min to obtain surface-treated silicon carbide;
a composite material was obtained by mixing a thermoplastic polyurethane elastomer with the treated silicon carbide in the same manner as in example 1.
Example 3
Heating nitrogen-protected 4,4 '-diaminodiphenyl disulfide to 90 ℃, then dropwise adding nitrogen-protected silane coupling agent 3-isocyanatopropyltriethoxysilane into continuously stirred 4, 4' -diaminodiphenyl disulfide (the molar ratio of the silane coupling agent to the disulfide is 1.1:1), continuously stirring for 30min after finishing dropwise adding the silane coupling agent, and finally cooling the product to room temperature to obtain the surface treatment agent.
The hydrolysate of the surface treatment agent is prepared according to the method of the embodiment 1, the hydrolysate of the surface treatment agent is sprayed on the surface of magnesium hydroxide and stirred for 30min at the normal temperature of 100r/min in a high-speed mixer, and then the magnesium hydroxide with the surface treatment is obtained after curing for 90min at the temperature of 100 ℃;
TPU and treated magnesium hydroxide were combined in the same manner as in example 1 to produce a composite material.
Example 4
Firstly heating a mixture of bis (2-hydroxyethyl) disulfide and 4, 4' -diaminodiphenyl disulfide with a molar ratio of 1:2 under nitrogen protection to 60 ℃, then dropwise adding 3-isocyanatopropyl trimethoxy silane under nitrogen protection into the continuously stirred disulfide mixture (the molar ratio of the silane coupling agent to the disulfide is 1.05:1), continuously stirring for 90min after the dropwise adding of the silane coupling agent is finished, and finally cooling the product to room temperature to obtain the surface treating agent.
The hydrolysate of the surface treatment agent is prepared according to the method of the embodiment 1, the hydrolysate of the surface treatment agent is sprayed on the surface of the glass microsphere and is stirred for 20min at normal temperature of 200r/min in a high-speed mixer, and then the glass microsphere with the surface treatment is obtained after being solidified for 120min at 80 ℃;
a composite material was prepared by mixing the thermoplastic polyurethane elastomer and the treated glass microspheres in the same manner as in example 1.
Example 5
Firstly, heating a mixture of bis (2-hydroxyethyl) disulfide and 4, 4' -diaminodiphenyl disulfide with a molar ratio of 1:3 under nitrogen protection to 70 ℃, then dropwise adding a mixture of 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane with a molar ratio of 1:2 under nitrogen protection to the continuously stirred disulfide mixture (the molar ratio of the silane coupling agent to the disulfide is 1.05:1), continuously stirring for 60min after the dropwise adding of the silane coupling agent is finished, and finally cooling the product to room temperature to obtain the surface treating agent.
The hydrolysate of the surface treatment agent is prepared according to the method of the embodiment 1, the hydrolysate of the surface treatment agent is sprayed on the surface of the glass microsphere and is stirred for 20min at normal temperature of 200r/min in a high-speed mixer, and then the glass microsphere with the surface treatment is obtained after being solidified for 120min at 80 ℃;
a composite was prepared by combining TPU with the treated glass microspheres in the same manner as in example 1.
Comparative example 1
Mixing TPU and glass microspheres uniformly at normal temperature for 5min at a speed of 200r/min by using a high-speed mixer, and finally melting and mixing by using a double-screw extruder to prepare the composite material, wherein the temperature is set as follows: the conveying section is 180 ℃, the melting section is 190 ℃, the homogenizing section is 195 ℃ and the head is 190 ℃.
Comparative example 2
TPU and silicon carbide were combined in the same manner as in comparative example 1 to produce a composite material.
Comparative example 3
TPU and magnesium hydroxide were used to prepare a composite material in the same manner as in comparative example 1.
Comparative example 4
2- ((3-triethoxysilane) propyl) disulfide) pyridine was prepared according to the preparation method reported in "Synthesis of silane coupling agent containing cleavable disulfide bond and multifunctional linking arm", gan bin ". Hydrolyzing 2- ((3-triethoxysilane) propyl) disulfide) pyridine according to the method described in example 1, spraying the hydrolysate on the surface of the glass microsphere, stirring at normal temperature of 200r/min for 20min in a high-speed mixer, and drying at 80 ℃ for 120min to obtain the surface-treated glass microsphere;
a composite was prepared by combining TPU with the treated glass microspheres in the same manner as in example 1.
The composite materials obtained in the above examples and comparative examples were injection molded into test specimens, cured at 80 ℃ for 16 hours, allowed to stand in a standard laboratory for 24 hours, then subjected to performance testing and 100 bending tests, and then the bent specimens were placed at 15 × 20cm2Between two parallel iron plates, a weight of 2Kg is placed on the upper iron plate, and then the upper iron plate is placed at 80 ℃ for repairing for 24 hours, and the maximumAnd testing the performance of the sample before bending, after bending and after repairing.
Repair rate (%) - (T)2-T1)/(T0-T1)*100％
Wherein, T0Representing the original property, T1Indicates the Performance before repair, T2Indicating the performance after repair.
Tensile strength was measured according to ASTM D412 with a jig moving speed of 500 mm/min;
tear strength was tested according to ASTM D624 with a jig moving speed of 500 mm/min;
the notched impact strength was tested according to ASTM D256, with pre-treatment conditions of-10 ℃/24 h.
Examples 1-5 the results of the performance tests are given in table 3 below:
TABLE 3
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Tensile Strength before bending (MPa) | 18.6 | 16.0 | 13.7 | 17.9 | 17.3 |
| Tensile Strength after bending (MPa) | 16.5 | 13.8 | 9.9 | 14.1 | 14.4 |
| Post repair tensile Strength (MPa) | 17.4 | 14.9 | 11.4 | 16.2 | 16.2 |
| Tensile Strength repair Rate (%) | 43 | 50 | 39 | 55 | 62 |
| Tear Strength before bending (N/mm) | 52 | 47 | 43 | 49 | 47 |
| Tear Strength after bending (N/mm) | 45 | 41 | 36 | 36 | 38 |
| Tear Strength after repair (N/mm) | 49 | 45 | 39 | 44 | 43 |
| Tear Strength repair Rate (%) | 57 | 67 | 43 | 62 | 56 |
| Notched impact Strength before bending (J/m) | 63 | 56 | 52 | 57 | 58 |
| Notched impact Strength after bending (J/m) | 54 | 46 | 41 | 48 | 46 |
| Notched impact Strength after repair (J/m) | 58 | 51 | 47 | 52 | 53 |
| Impact ofStrength repair Rate (%) | 44 | 50 | 55 | 44 | 58 |
Comparative examples 1-4 the results of the performance tests are given in table 4 below:
TABLE 4
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Tensile Strength before bending (MPa) | 15.3 | 12.1 | 10.0 | 16.5 |
| Tensile Strength after bending (MPa) | 13.3 | 10.6 | 6.7 | 14.8 |
| Post repair tensile Strength (MPa) | 13.5 | 10.9 | 6.9 | 15.3 |
| Tensile Strength repair Rate (%) | 10 | 20 | 6 | 29 |
| Tear Strength before bending (N/mm) | 46 | 41 | 37 | 50 |
| Tear Strength after bending (N/mm) | 39 | 32 | 25 | 37 |
| Tear Strength after repair (N/mm) | 40 | 33 | 25 | 40 |
| Tear Strength repair Rate (%) | 14 | 11 | 0 | 23 |
| Notched impact Strength before bending (J/m) | 61 | 50 | 46 | 57 |
| Notched impact Strength after bending (J/m) | 50 | 41 | 34 | 45 |
| Notched impact Strength after repair (J/m) | 51 | 43 | 35 | 49 |
| Impact Strength repair Rate (%) | 9 | 22 | 8 | 33 |
As can be seen by comparing examples 1-5 and comparative examples 1-3 of the invention, the performance of the composite material of the examples is obviously improved compared with the repair rate of the corresponding proportion by adopting the method of the invention under the premise of the same inorganic matter type and content, wherein the tensile strength is repaired by 39-62%, the tear strength is repaired by 43-67%, and the impact strength is repaired by 44-58%. Comparing example 5 with comparative example 4, it can be seen that the performance of the composite material prepared by the method is higher than the repair efficiency of the prior art under the premise of the same inorganic matter type and content, wherein the tensile strength repair rate is improved by 33 percent compared with the prior art, the tear strength repair is improved by 33 percent, and the impact strength repair is improved by 25 percent.
Claims (10)
1. A thermoplastic polyurethane elastomer composite with interfacial self-healing functionality comprising:
(a)100 parts by weight of a thermoplastic polyurethane elastomer;
(b)1 to 150 parts by weight, preferably 10 to 100 parts by weight, of an inorganic substance treated with a surface treatment agent;
the surface treating agent is a surface treating agent prepared from a silane coupling agent and a disulfide.
2. The composite material according to claim 1, wherein the surface treatment agent is prepared by a process comprising: heating the disulfide protected with inert gas to a reaction temperature of 30 to 100 ℃, preferably 50 to 90 ℃, then slowly adding the silane coupling agent to the disulfide protected with inert gas under continuous stirring, continuing stirring after the end of the addition, and finally cooling to room temperature to obtain the surface treating agent.
3. The composite material according to claim 1 or 2, wherein the silane coupling agent is at least one selected from the group consisting of 3- (2, 3-glycidoxy) propyltrimethoxysilane, 3- (2, 3-glycidoxy) propyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane; preferably, the silane coupling agent is a mixture of 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane in a molar ratio of 1: 1-2.
4. Composite according to any of claims 1 to 3, characterized in that the disulfide is selected from at least one of bis (2-hydroxyethyl) disulfide, 2 ' -diaminodiphenyl disulfide, 4 ' -dihydroxydiphenyl disulfide, 3' -dihydroxydiphenyl disulfide; preferably, the disulfide is a mixture of bis (2-hydroxyethyl) disulfide and 4, 4' -diaminodiphenyl disulfide in a molar ratio of 1: 2-3.
5. Composite according to any of claims 1 to 4, characterized in that the molar ratio of silane coupling agent to disulfide is between 1.0 and 2.0, preferably between 1.05 and 1.20.
6. Composite according to any one of claims 1 to 5, characterized in that the inorganic substance is selected from at least one of graphite, expanded graphite, carbon fibers, carbon black, boron nitride, aluminum nitride, silicon boron nitride, aluminum oxide, magnesium oxide, titanium oxide, zinc oxide, silicon carbide, glass fibers, glass microspheres, glass powder, wollastonite, montmorillonite, calcium carbonate, kaolin, talc, mica, metal powder, metal fibers, magnesium hydroxide, aluminum hydroxide, preferably at least one of glass powder, glass microspheres, glass fibers, silicon carbide, silicon nitride, magnesium hydroxide, aluminum hydroxide.
7. The composite material according to any one of claims 1 to 6, wherein the inorganic substance treated with the surface treatment agent is prepared by: preparing alcohol-water solution from alcohol and deionized water, adding acid to regulate pH to 3.5-5.5, adding surface treating agent while stirring, hydrolyzing to obtain hydrolysate of the surface treating agent, spraying the hydrolysate onto the surface of inorganic matter, stirring, or soaking the inorganic matter in the hydrolysate, and drying the hydrolysate or the inorganic matter soaked with the hydrolysate.
8. Composite material according to claim 7, characterized in that the alcohol is selected from methanol, ethanol, isopropanol, preferably ethanol; the acid is selected from formic acid, acetic acid, oxalic acid, malonic acid, methanolic acid, glycolic acid, benzoic acid, phenylacetic acid, preferably acetic acid; the weight ratio of the surface treating agent to the alcohol to the deionized water is 15-25:65-75:6-10, and the preferred weight ratio is 20:72: 8.
9. The composite material according to claim 7 or 8, wherein the hydrolysis time is 1-30min after the surface treatment agent is added; the drying condition is drying at 80-120 deg.C for 30-120 min.
10. A method of making the composite material of any one of claims 1-9, comprising: the inorganic matter treated by the surface treating agent and the thermoplastic polyurethane elastomer are uniformly mixed by a mixing device and then fed, or are separately metered and fed, and finally the composite material is prepared by melting and mixing.
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