CN114855300B - Inorganic fiber reinforced thermoplastic polyurethane composite material and preparation method thereof - Google Patents
Inorganic fiber reinforced thermoplastic polyurethane composite material and preparation method thereof Download PDFInfo
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- CN114855300B CN114855300B CN202210465284.6A CN202210465284A CN114855300B CN 114855300 B CN114855300 B CN 114855300B CN 202210465284 A CN202210465284 A CN 202210465284A CN 114855300 B CN114855300 B CN 114855300B
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- 239000012784 inorganic fiber Substances 0.000 title claims abstract description 148
- 239000002131 composite material Substances 0.000 title claims abstract description 107
- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 57
- 239000004433 Thermoplastic polyurethane Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229920002635 polyurethane Polymers 0.000 claims abstract description 55
- 239000004814 polyurethane Substances 0.000 claims abstract description 55
- 239000002105 nanoparticle Substances 0.000 claims abstract description 53
- 238000009987 spinning Methods 0.000 claims abstract description 37
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 36
- 239000007822 coupling agent Substances 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 14
- 230000004048 modification Effects 0.000 claims abstract description 12
- 238000012986 modification Methods 0.000 claims abstract description 12
- 238000002166 wet spinning Methods 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 104
- 239000000835 fiber Substances 0.000 claims description 89
- 239000010453 quartz Substances 0.000 claims description 56
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 9
- 239000004917 carbon fiber Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 4
- 230000001112 coagulating effect Effects 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 3
- 229920002748 Basalt fiber Polymers 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- XOTCJLJXDBVZBQ-UHFFFAOYSA-N CO[SiH](OC)OC.CCCOC(=O)C(C)=C Chemical compound CO[SiH](OC)OC.CCCOC(=O)C(C)=C XOTCJLJXDBVZBQ-UHFFFAOYSA-N 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 11
- 239000000243 solution Substances 0.000 description 34
- 239000000377 silicon dioxide Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 230000006872 improvement Effects 0.000 description 8
- 238000011056 performance test Methods 0.000 description 6
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 230000003746 surface roughness Effects 0.000 description 5
- 238000011010 flushing procedure Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 229920006306 polyurethane fiber Polymers 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000009998 heat setting Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000011043 treated quartz Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention provides an inorganic fiber reinforced thermoplastic polyurethane composite material and a preparation method thereof. The preparation method of the composite material comprises the following steps: firstly, putting nano particles and inorganic fibers into a solution containing a coupling agent, and carrying out surface modification on the inorganic fibers; then placing polyurethane resin particles and surface modified inorganic fibers in a binary solvent system to obtain a blending spinning solution formed by the inorganic fibers and the polyurethane resin; finally, through wet spinning, the spinning fine flow is solidified, drawn and hot pressed to obtain the inorganic fiber reinforced thermoplastic polyurethane composite material. The invention utilizes the special structure of polyurethane in binary solvent and the special structure of inorganic fiber modified by nano particles to form a ternary bonding structure among nano particles, inorganic fiber and polyurethane molecules; and a stable micro-nano interface layer is constructed between the polyurethane matrix and the inorganic fiber, so that the mechanical property of the composite material is improved.
Description
Technical Field
The invention relates to the technical field of composite material preparation, in particular to an inorganic fiber reinforced thermoplastic polyurethane composite material and a preparation method thereof.
Background
Polyurethane resin is a synthetic material between rubber and plastic, has a series of excellent properties such as high mechanical strength, high wear resistance and high elasticity, and is widely applied to textile reinforced thermoplastic resin composite materials. The inorganic fiber material is usually selected as the reinforcing phase, mainly because the inorganic fiber material has better environmental stability and rigidity and can increase the strength of the composite material. However, both the inorganic fiber material and the polyurethane resin are chemically inert and have a large difference in surface structures, so that it is difficult to bond the two together and form a stable interface layer.
At present, polyurethane resin matrix materials or inorganic fiber materials are subjected to modification treatment to enhance the interface bonding performance, so that the polyurethane resin matrix materials or the inorganic fiber materials are combined to achieve the aim of enhancing the mechanical properties. The modification treatment method is generally divided into the following steps: (1) Carrying out surface etching on polyurethane resin or inorganic fiber by plasma and other methods, and introducing active groups while improving the surface roughness so as to combine the polyurethane resin and the inorganic fiber; (2) The polyurethane resin or the inorganic fiber surface is chemically modified to improve the surface activity, so that the polyurethane resin or the inorganic fiber surface is combined. Both modification methods can damage the surface structure of the material, thereby affecting the performance of the material and further affecting the performance of the composite material prepared by the two methods.
The patent with the application number of CN201510696768.1 discloses a preparation method of a modified carbon fiber reinforced thermoplastic polyurethane composite material, which comprises the steps of firstly immersing carbon fibers in sulfuric acid solution electrolyte, electrifying to carry out electrochemical grafting modification treatment, then carrying out melt blending on the modified carbon fibers and TPU resin and other raw materials through a double screw extruder, and carrying out hot press molding to obtain the carbon fiber reinforced TPU composite material. The method has the following defects: the electrochemical treatment damages the surface structure of the carbon fiber, and simultaneously exposes the disordered structure inside the carbon fiber, so that the tensile strength of the carbon fiber is reduced, and the performance of the composite material is affected. Therefore, on the premise of not damaging the surface structures of the polyurethane resin and the inorganic fibers, the inorganic fiber reinforced polyurethane composite material with good interface performance is difficult to combine the polyurethane resin and the inorganic fiber, and particularly, the micron-sized inorganic fibers and the polyurethane fibers are compounded to obtain the high-performance composite material.
In view of the foregoing, there is a need for an improved inorganic fiber reinforced thermoplastic polyurethane composite and method of making the same that addresses the above-mentioned problems.
Disclosure of Invention
The invention aims to provide an inorganic fiber reinforced thermoplastic polyurethane composite material and a preparation method thereof, wherein nano particles are uniformly bonded on the surface of inorganic fibers by using a coupling agent, so that the activity and the surface roughness of the inorganic fibers are improved; and then placing polyurethane resin particles and surface-modified inorganic fibers in a binary solvent system to obtain a blending spinning solution formed by the inorganic fibers and the polyurethane resin, and then obtaining a composite material through wet spinning, wherein polyurethane forms a network structure which is mutually extruded in a crimping shape in the binary solvent, and according to the special structures of the polyurethane and the modified inorganic fibers, active groups (such as hydroxyl groups and the like) on the surfaces of the inorganic fibers and the nano particles are bonded with nitrogen atoms and oxygen atoms at proper sites in polyurethane molecular chains through hydrogen so as to form a stable ternary bonding structure of the inorganic fibers, the nano particles and the polyurethane molecules, and a stable micro-nano interface layer is constructed between a polyurethane matrix and the inorganic fibers, so that the interface acting force of the inorganic fibers and the polyurethane matrix material and the performance of the composite material are enhanced.
In order to achieve the above object, the present invention provides a method for preparing an inorganic fiber reinforced thermoplastic polyurethane composite material, comprising the steps of:
S1, inorganic fiber surface modification: adding a coupling agent into absolute ethyl alcohol, uniformly mixing, adding acetic acid to hydrolyze the coupling agent, then adding nano particles and inorganic fibers, reacting for 0.5-6h, washing, and drying to obtain the surface modified inorganic fibers;
s2, preparing spinning solution: uniformly mixing toluene and N, N-dimethylformamide according to a certain mass ratio to obtain a binary solvent; adding polyurethane resin particles with a preset proportion and the surface modified inorganic fibers prepared in the step S1 into the binary solvent, performing ultrasonic dispersion for 5-10min, and performing vacuum defoaming after mechanical stirring at 20-30 ℃ to obtain an inorganic fiber polyurethane composite spinning solution;
S3, spinning and post-treatment: and (2) adding the inorganic fiber polyurethane composite spinning solution obtained in the step (S2) into a wet spinning machine to spin at a certain spinning speed, drawing after spinning trickles come out of a coagulating bath, and carrying out high-temperature setting and drying after the fibers are completely formed to obtain the inorganic fiber reinforced thermoplastic polyurethane composite material.
As a further improvement of the present invention, in step S1, the inorganic fibers have a length of 1 to 15mm and a diameter of 5 to 15. Mu.m.
As a further improvement of the present invention, in step S1, the inorganic fiber includes one of quartz fiber, carbon fiber, basalt fiber, or silicon carbide fiber; the nano particles comprise one or more of carbon nano tubes, graphene, nano zinc oxide and nano titanium dioxide; the coupling agent comprises one of gamma-aminopropyl triethoxysilane, gamma-glycidyl ether propyl trimethoxysilane, gamma-propyl methacrylate trimethoxysilane, gamma-mercaptopropyl triethoxysilane or gamma-mercaptopropyl trimethoxysilane.
As a further improvement of the invention, in the step S2, the mass ratio of toluene to N, N dimethylformamide in the binary solvent is 20 percent to 80 percent to 40 percent to 60 percent; the mass ratio of the polyurethane resin particles to the surface modified inorganic fibers is (10% -30%) (0.1% -40%).
As a further improvement of the present invention, the mass ratio of the polyurethane resin particles to the surface-modified inorganic fibers is (20% -30%) (0.5% -30%).
As a further improvement of the invention, in the step S1, the mass ratio of the anhydrous ethanol to the coupling agent is (90% -99.5%) (0.5% -10%), the nano particles account for 0.1% -5% of the total mass of the anhydrous ethanol and the coupling agent, and the inorganic fibers account for 1% -50% of the total mass of the anhydrous ethanol and the coupling agent.
As a further improvement of the present invention, in step S3, the spinning speed is 2 to 4mm/min; the multiple of the drafting treatment is 1-5 times; the high-temperature setting temperature is 80-120 ℃, and the treatment time is 200-300s.
As a further improvement of the invention, in step S1, acetic acid is added to bring the pH of the solution to 4.5-6.5; the washing is carried out by using absolute ethyl alcohol; the drying is carried out for 0.5-1.5h at 90-110 ℃.
As a further improvement of the present invention, the inorganic fiber needs to be cleaned on the surface before the surface modification treatment, and the specific steps are as follows:
placing the inorganic fiber into deionized water solution of acetone according to a bath ratio of 1 (1.5-5), soaking for 10-60min at 25-30 ℃, washing with deionized water, and drying at 90-110 ℃ for 0.5-1.5h; the mass ratio of the acetone to the deionized water is (5% -20%) (80% -95%).
The invention also provides an inorganic fiber reinforced thermoplastic polyurethane composite material, which is prepared by adopting the preparation method of the inorganic fiber reinforced thermoplastic polyurethane composite material.
The beneficial effects of the invention are as follows:
(1) According to the preparation method of the inorganic fiber reinforced thermoplastic polyurethane composite material, firstly, the nano particles and the inorganic fibers are added into a solution containing a coupling agent, and the addition of the coupling agent not only improves the dispersibility of the nano particles in the solution, but also enables the nano particles to be uniformly bonded on the surface of the inorganic fibers with the micron-sized diameter; and then placing polyurethane resin particles and surface modified inorganic fibers in a binary solvent system to obtain a blend spinning solution formed by the inorganic fibers and the polyurethane resin, and obtaining the composite material through wet spinning. The surface of the inorganic fiber is modified by utilizing the nano particles, so that the surface roughness of the inorganic fiber is increased, the surface activity of the inorganic fiber is increased, the inorganic fiber is easily combined with polyurethane molecules, and the inorganic fiber with the micron-sized diameter is uniformly dispersed in the spinning solution due to the existence of the coupling agent and the nano particles; in the dissolving process of the binary solvent, the self-adjusting and arranging time of polyurethane molecular chains is prolonged, the arrangement mode of the polyurethane molecular chains in the binary solvent is regulated and controlled, the linear molecular chains are changed into a network structure which is mutually extruded in a spiral manner, and the polyurethane molecular chains of the network structure and the nano particle modified inorganic fibers are more easily combined with each other; in the process, active groups (such as hydroxyl groups and the like) on the surfaces of inorganic fibers uniformly dispersed in the spinning solution and nano particles bonded on the inorganic fibers are bonded with nitrogen atoms and oxygen atoms at proper sites in polyurethane molecular chains of a network structure through hydrogen bonding to form a stable ternary bonding structure of bonding between the nano particles, the inorganic fibers and the polyurethane molecules, wherein the ternary bonding structure is strong in stability, so that the inorganic fibers and the polyurethane are firmly combined, the interface acting force is enhanced, a stable micro-nano interface layer is constructed between a polyurethane matrix and the inorganic fibers, and the finally prepared composite material is excellent in performance. In addition, the wet spinning process does not damage a stable three-dimensional bonding structure, so that the interface acting force of the inorganic fiber and the polyurethane matrix material and the performance of the composite material are not affected.
(2) According to the invention, the inorganic fibers are modified by using the nano particles and the coupling agent, and under the premise of not damaging the surface structure of the inorganic fibers, the polyurethane resin and the modified inorganic fibers form a stable interface bonding effect by utilizing the synergistic effect of the nano particles and the coupling agent, so that the mechanical property of the inorganic fiber reinforced thermoplastic polyurethane composite material is improved.
(3) The preparation method provided by the invention has the advantages of simple process, controllable parameters and simplicity in operation, can realize industrial production, and has remarkable feasibility.
Drawings
FIG. 1 is a flow chart of the preparation of the inorganic fiber reinforced thermoplastic polyurethane composite material of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
It should be noted that, in order to avoid obscuring the present invention due to unnecessary details, only structures and/or processing steps closely related to aspects of the present invention are shown in the drawings, and other details not greatly related to the present invention are omitted.
In addition, it should be further noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
As shown in the preparation flow chart of fig. 1, the invention provides a preparation method of an inorganic fiber reinforced thermoplastic polyurethane composite material, which comprises the following steps:
S1, inorganic fiber surface modification:
in order to avoid damage in the transportation process, the surface of the commercially available inorganic fiber contains a large amount of impregnating compound, and in order to effectively modify the surface of the inorganic fiber subsequently, the surface of the inorganic fiber needs to be cleaned, and the specific operation is as follows: uniformly mixing acetone and deionized water (80% -95%) according to the mass ratio of (5% -20%), so as to obtain a deionized water solution of the acetone; placing inorganic fibers in deionized water solution of acetone according to a bath ratio of 1 (1.5-5), soaking for 10-60min at 25-30 ℃, continuously flushing with deionized water, and drying at 90-110 ℃ for 0.5-1.5h to obtain the inorganic fibers with clean surfaces.
Adding a coupling agent into absolute ethyl alcohol, uniformly mixing, adding a certain amount of acetic acid, adjusting the pH value of the solution to 4.5-6.5, adding nano particles and inorganic fibers into the solution after the coupling agent is hydrolyzed, reacting for 0.5-6h, continuously flushing the solution by using absolute ethyl alcohol, and drying at 90-110 ℃ for 0.5-1.5h to obtain the surface modified inorganic fibers.
Wherein, the mass ratio of the absolute ethyl alcohol to the coupling agent is (90% -99.5%) (0.5% -10%), the nano particles account for 0.1% -5% of the total mass of the absolute ethyl alcohol and the coupling agent, and the inorganic fibers account for 1% -50% of the total mass of the absolute ethyl alcohol and the coupling agent.
Specifically, the inorganic fibers have a length of 1 to 15mm and a diameter of 5 to 15 μm. The inorganic fiber comprises one of quartz fiber, carbon fiber, basalt fiber or silicon carbide fiber; the nano particles comprise one or more of carbon nano tubes, graphene, nano zinc oxide and nano titanium dioxide; the coupling agent comprises one of gamma-aminopropyl triethoxysilane (KH 550), gamma-glycidyl ether propyl trimethoxysilane (KH 560), gamma-propyl methacrylate trimethoxysilane (KH 570), gamma-mercaptopropyl triethoxysilane (KH 580) or gamma-mercaptopropyl trimethoxysilane (KH 590).
In the process, the silane coupling agent is firstly spread on the surface of the nano particle, alkoxy at one end of the molecule of the silane coupling agent is hydrolyzed to generate silicon hydroxyl, the silicon hydroxyl and the hydroxyl on the surface of the nano particle form hydrogen bond, and then hydrolysis condensation reaction is carried out, so that one end of the silane coupling agent is bonded with the nano particle. The other end of the silane coupling agent is chemically bonded with the surface of the inorganic fiber (containing active groups such as hydroxyl) or is adhered to the inorganic fiber through hydrogen bonds and the like. The addition of the silane coupling agent avoids the agglomeration of the nano particles and uniformly bonds the nano particles on the surface of the inorganic fiber.
S2, preparing spinning solution:
And uniformly mixing toluene and N, N-dimethylformamide according to a certain mass ratio, and mechanically stirring for 5-10min to obtain the binary solvent. Adding polyurethane resin particles and surface modified inorganic fibers in a preset proportion into the obtained binary solvent, performing ultrasonic dispersion for 5-10min, mechanically stirring for 1-2h at 20-30 ℃ to completely dissolve the polyurethane resin particles, obtaining a uniform and stable mixed solution, and then performing vacuum defoaming treatment on the mixed solution to obtain the inorganic fiber polyurethane composite spinning solution, wherein the temperature of mechanical stirring and vacuum defoaming is preferably 25-30 ℃.
Wherein, the mass ratio of toluene to N, N-dimethylformamide is 20 percent to 80 percent to 40 percent to 60 percent, preferably 30 percent to 70 percent. The mass ratio of the polyurethane resin particles to the surface modified inorganic fibers is (10% -30%), preferably (20% -30%), and the balance is a binary solvent.
In the process, when polyurethane is dissolved in a binary solvent, the solvent system prolongs the self-adjustment and arrangement time of polyurethane molecular chains, regulates and controls the arrangement mode of the polyurethane molecular chains in the binary solvent, so that the linear molecular chains are changed into a network structure which is extruded mutually in a spiral manner, and at the moment, active groups (such as hydroxyl groups and the like) on the surfaces of inorganic fibers and nanoparticles are bonded with nitrogen atoms and oxygen atoms at proper sites in the polyurethane molecular chains of the network structure through hydrogen, so that a stable ternary bonding structure of bonding every two of the nanoparticles, the inorganic fibers and the polyurethane molecules is formed. The ternary bonding structure has stronger stability, so that the combination of the inorganic fiber and polyurethane is firmer, and the performance of the finally prepared composite material is better.
S3, spinning and post-treatment:
And (3) adding the inorganic fiber polyurethane composite spinning solution obtained in the step (S2) into a wet spinning machine self-made in a laboratory for spinning, drawing after spinning trickles come out of a coagulating bath, and adopting high-temperature setting and drying after the fibers are completely formed to obtain the inorganic fiber reinforced thermoplastic polyurethane composite material.
Wherein, the spinning speed is 2-4mm/min; the multiple of the drafting treatment is 1-5 times; the high-temperature setting temperature is 80-120 ℃, and the treatment time is 200-300s.
In the process, after the spinning fine flow is subjected to solidification, drafting and high-temperature heat setting treatment, a high-stability ternary bonding structure formed by the nano particles, the inorganic fibers and polyurethane molecules is not damaged, so that the interface acting force of the inorganic fibers and the polyurethane matrix material and the mechanical property of the composite material are excellent.
The invention also provides an inorganic fiber reinforced thermoplastic polyurethane composite material, which is prepared by adopting the preparation method of the inorganic fiber reinforced thermoplastic polyurethane composite material.
The invention is described in detail below by means of several examples:
example 1
A preparation method of a quartz fiber reinforced thermoplastic polyurethane composite material comprises the following steps:
S1, modifying the surface of quartz fiber:
Uniformly mixing acetone and deionized water according to the mass ratio of 10% to 90%, so as to obtain a deionized water solution of the acetone; and placing the quartz fiber in deionized water solution of acetone according to a bath ratio of 1:3, soaking for 30min at 28 ℃, continuously flushing with deionized water, and drying at 100 ℃ for 1h to obtain the quartz fiber with a clean surface.
Adding KH550 into absolute ethyl alcohol, uniformly mixing, adding a certain amount of acetic acid, regulating the pH value of the solution to 6, adding carbon nano tubes and quartz fibers with the length of 1mm and the diameter of 7 mu m into the solution after the coupling agent is hydrolyzed, reacting for 3 hours, continuously flushing the solution by using absolute ethyl alcohol, and drying the solution at 100 ℃ for 1 hour to obtain the surface modified quartz fibers.
Wherein, the mass ratio of the absolute ethyl alcohol to the coupling agent is 90 percent to 5 percent, the nano particles account for 2.5 percent of the total mass of the absolute ethyl alcohol and the coupling agent, and the quartz fiber accounts for 25 percent of the total mass of the absolute ethyl alcohol and the coupling agent.
S2, preparing spinning solution:
and (3) uniformly mixing toluene and N, N-dimethylformamide according to the mass ratio of 30% to 70% of toluene and N, N-dimethylformamide, and mechanically stirring for 8min to obtain the binary solvent. Adding 27g of polyurethane resin particles and 0.3g of surface modified quartz fiber into the obtained binary solvent, performing ultrasonic dispersion for 5-10min, mechanically stirring for 1.5h at 28 ℃ to completely dissolve the polyurethane resin particles, obtaining a uniform and stable mixed solution, and then performing vacuum defoaming treatment on the mixed solution to obtain the quartz fiber polyurethane composite spinning solution.
S3, spinning and post-treatment:
and (3) adding the quartz fiber polyurethane composite spinning solution obtained in the step (S2) into a wet spinning machine for spinning, drawing after spinning trickles come out of a coagulating bath, and carrying out high-temperature setting and drying after the fibers are completely formed to obtain the quartz fiber reinforced thermoplastic polyurethane composite material.
Wherein, the spinning speed is 3mm/min; the multiple of the drafting treatment is 1 time; the high-temperature heat setting temperature is 100 ℃, and the treatment time is 250s.
Examples 2 to 7
The difference between the preparation method of the silica fiber reinforced thermoplastic polyurethane composite material and the embodiment 1 is that in the step S2, the addition amount of the silica fiber is different, and the other steps are substantially the same as those in the embodiment 1, and are not described herein.
The silica fiber reinforced thermoplastic polyurethane composites (hereinafter referred to simply as composites) prepared in examples 1 to 7 were subjected to performance test, and the results are shown in table 1:
TABLE 1 Properties related to the composite materials prepared in examples 1-7
As is clear from Table 1, as the amount of the silica fiber added increases, the Young's modulus and the breaking strength of the prepared silica fiber-reinforced thermoplastic polyurethane composite material are both increased and the breaking strain is decreased. The rigidity of the quartz fiber is high, the rigidity and the strength of the composite material can be improved after the quartz fiber is added into elastic polyurethane resin, and meanwhile, the nano particles, the quartz fiber and polyurethane molecules form a ternary bonding structure, so that a stable micro-nano interface layer is constructed between a polyurethane matrix and the quartz fiber, and the strength of the composite material is improved; however, as the number of quartz fibers increases, the quartz fibers accumulate in the polyurethane resin to different extents, which is unfavorable for the formation of a ternary bonding structure, and thus the fracture strain of the composite material is reduced. It can also be seen from table 1 that the change in interfacial shear strength between the quartz fiber and the polyurethane resin was small with the increase in the amount of quartz fiber added, which indicates that it was maintained at 4.89 to 5.43N: (1) The change of the addition amount of the quartz fiber basically does not influence the stable ternary bonding structure of bonding between the nano particles, the quartz fiber and polyurethane molecules; (2) The interface binding force of the quartz fiber and the polyurethane resin is strong overall.
Examples 8 to 10
The difference between the preparation method of the inorganic fiber reinforced thermoplastic polyurethane composite material and the embodiment 1 is that in the step S1, the inorganic fibers are different (the length and fineness are the same), and the other inorganic fibers are substantially the same as the embodiment 1, and are not described herein.
The inorganic fiber reinforced thermoplastic polyurethane composites (hereinafter referred to simply as composites) prepared in examples 8 to 10 were subjected to performance test, and the results are shown in table 2:
TABLE 2 Properties related to the composite materials prepared in examples 8-10
As can be seen from Table 2, the inorganic fiber reinforced thermoplastic polyurethane composite materials prepared by blending and compounding different inorganic fibers and polyurethane have certain differences in Young's modulus, breaking strength, breaking strain and interfacial shear strength. This is mainly because the different inorganic fibers differ in their own stiffness; on the other hand, the surface groups and the structures are different, so that ternary bonding structures formed by bonding the nano particles, the inorganic fibers and the polyurethane molecules are different, and the stability of the micro-nano interface layer constructed between the polyurethane matrix and the inorganic fibers is different, so that the bonding strength of the inorganic fibers and the polyurethane is different, and the performances of the finally obtained composite material are different. This illustrates that the properties of the composite material are related to the basic properties of the inorganic fibers.
Examples 11 to 15
The difference between the preparation method of the silica fiber reinforced thermoplastic polyurethane composite material and the embodiment 1 is that in the step S2, the length of the silica fiber is different, and the other steps are substantially the same as those in the embodiment 1, and are not described herein.
The silica fiber reinforced thermoplastic polyurethane composites (hereinafter referred to simply as composites) prepared in examples 11 to 15 were subjected to performance test, and the results are shown in table 3:
TABLE 3 Properties related to the composite materials prepared in examples 11-15
As shown in Table 3, with the increase of the length of the quartz fiber, the Young's modulus, breaking strength and breaking strain of the prepared quartz fiber reinforced thermoplastic polyurethane composite material are improved to a certain extent, because on one hand, the rigidity of the quartz fiber is stronger; on the other hand, when the filling amount of the quartz fiber is the same, the volume fraction of the quartz fiber is reduced along with the length increase of the quartz fiber, the aggregation of the quartz fiber in polyurethane resin is reduced, the ternary bonding structure formed by the nano particles, the quartz fiber and polyurethane molecules is more uniformly distributed, and when the composite material is subjected to external stretching, the breaking strength and the breaking strain of the composite material are both increased. It can also be seen from table 3 that as the length of the silica fiber increases, the interfacial bonding strength between the silica fiber and the polyurethane resin is substantially unchanged, mainly because the surface group and structure of the silica fiber are not changed although the length of the silica fiber is changed, and the ternary bonding structure formed by the nanoparticle, the silica fiber and the polyurethane molecule is unchanged, so that the interfacial shear strength is substantially unchanged.
When the length of the quartz fiber reaches a certain value, the performance of the prepared quartz fiber reinforced thermoplastic polyurethane composite material is weakened along with the increase of the length of the fiber. This is mainly because when the length of the quartz fiber is too long, the quartz fiber is unevenly dispersed in the composite material and is easily entangled together, and a ternary bonding structure is not easily formed, thereby affecting the performance of the composite material.
Examples 16 to 20
The difference between the preparation method of the silica fiber reinforced thermoplastic polyurethane composite material and the embodiment 1 is that in the step S2, the diameter of the silica fiber is different, and the other steps are substantially the same as those in the embodiment 1, and are not described herein.
The silica fiber reinforced thermoplastic polyurethane composites (hereinafter referred to simply as composites) prepared in examples 16 to 20 were subjected to performance test, and the results are shown in table 4:
TABLE 4 Properties related to the composite materials prepared in examples 16-20
As can be seen from Table 4, the Young's modulus of the reinforced thermoplastic polyurethane composite material prepared was not greatly changed (i.e., the rigidity was not substantially changed) with the increase of the diameter of the quartz fiber, but the mechanical properties of the composite material were optimal when the breaking strength and the breaking strain were continuously increased and the fiber diameter was 5. Mu.m. The change of the breaking strength and the breaking strain is mainly due to the fact that the ternary bonding structure generated by the nano particles, the quartz fiber and the polyurethane molecules is stable along with the increase of the diameter of the quartz fiber, so that the breaking strength and the breaking strain of the composite material are increased. Along with the increase of the diameter of the quartz fiber, the interface bonding strength between the quartz fiber and the polyurethane resin is basically unchanged, which further indicates that the structure formed by the nano particles, the quartz fiber and the polyurethane molecules is stable and basically kept unchanged.
When the diameter of the quartz fiber reaches a certain value, the performance of the prepared quartz fiber reinforced thermoplastic polyurethane composite material can be weakened along with the further increase of the diameter of the quartz fiber.
Examples 21 to 23
The difference between the preparation method of the silica fiber reinforced thermoplastic polyurethane composite material and the embodiment 1 is that in the step S1, the types of the nanoparticles used are different, and the other types are substantially the same as those in the embodiment 1, and are not described herein.
The silica fiber reinforced thermoplastic polyurethane composites (hereinafter referred to simply as composites) prepared in examples 21 to 23 were subjected to performance test, and the results are shown in table 5:
TABLE 5 Properties related to the composite materials prepared in examples 21-23
As can be seen from table 5, the use of different nanoparticle treated quartz fibers to obtain composites with different interfacial properties, the mechanical properties of which are closely related to the properties of the nanoparticles used, wherein the carbon nanotubes treated can give composites with optimal mechanical properties.
Comparative example 1
A method for preparing a silica fiber reinforced thermoplastic polyurethane composite material, which is different from example 1 in that the solvent is pure N, N dimethylformamide, and the other steps are the same as in example 1.
Comparative example 2
A preparation method of a quartz fiber reinforced thermoplastic polyurethane composite material, which is different from example 1 in that no nanoparticle is added in comparative example 2, and the other is the same as example 1.
Comparative example 3
A polyurethane fiber was prepared in the same manner as in example 1, except that the nanoparticles and the quartz fiber were not added as in example 1, which was different from example 3.
Comparative example 4
A preparation method of a quartz fiber reinforced thermoplastic polyurethane composite material, compared with example 1, the difference of comparative example 1 is that before the surface modification of quartz fiber, plasma treatment is used to destroy the surface structure of quartz fiber, otherwise the same as example 1.
The quartz fiber reinforced thermoplastic polyurethane composite materials and polyurethane fibers (hereinafter simply referred to as materials) prepared in comparative examples 1 to 3 were subjected to performance test, and the results are shown in table 6:
TABLE 6 Material related Properties prepared by comparative examples 1-3
As can be seen from table 6, the composite material prepared in (1) comparative example 1 is significantly inferior to that of example 1, mainly because the pure solvent rapidly precipitates and cures the polyurethane segment during the molding process, the linear polyurethane does not sufficiently react with the nanoparticle and the silica fiber, and the three are not easily formed into a ternary bonding structure, so that the interfacial bonding force between the silica fiber and the polyurethane is weak, thereby affecting the performance thereof. (2) The properties of the composite material prepared in comparative example 2 are also significantly inferior to those of example 1, mainly because the quartz fiber is not modified with nanoparticles first, and the surface activity and surface roughness are low; secondly, the existence of the coupling agent and the nano particles is avoided, and the dispersibility of the quartz fiber with the micron-sized diameter in the spinning solution is poor; polyurethane with a network structure which is extruded with each other in a spiral shape can be bonded with a small amount of quartz fiber surface, and meanwhile, the bonding strength and the bonding structure formed are not as stable as those of a ternary bonding structure, so that the performance of the polyurethane is poor. (3) As can be seen from the data of comparative example 3, the addition of quartz fibers significantly enhanced the properties of the composite. (4) As can be seen from the data of comparative example 4, the plasma treatment is performed before the modification of the silica fiber, and although this can increase the surface activity of the silica fiber, the original structure of the silica fiber is destroyed, the performance is affected, and thus the performance of the prepared composite material is poor.
In summary, according to the inorganic fiber reinforced thermoplastic polyurethane composite material and the preparation method thereof provided by the invention, the surface of the inorganic fiber is modified by the nano particles, so that the surface roughness of the inorganic fiber is increased, the surface activity of the inorganic fiber is also increased, and the inorganic fiber with the micron-sized diameter is uniformly dispersed in the spinning solution due to the existence of the coupling agent and the nano particles; then, a binary solvent system is utilized, the self-adjusting and arranging time of polyurethane molecular chains is prolonged, the arrangement mode of the polyurethane molecular chains in the binary solvent is regulated and controlled, and the linear molecular chains are changed into a network structure which is mutually extruded in a spiral manner, so that a stable ternary bonding structure of bonding between nano particles, inorganic fibers and polyurethane molecules in pairs is formed; a stable micro-nano interface layer is constructed between the polyurethane matrix and the inorganic fiber, so that the performance of the finally prepared composite material is better; on the premise of not damaging the surface structure of the inorganic fiber, the synergistic effect of the nano particles and the coupling agent is utilized to form a stable interface bonding effect between the polyurethane resin and the modified inorganic fiber, so that the mechanical property of the inorganic fiber reinforced thermoplastic polyurethane composite material is improved.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention.
Claims (9)
1. A preparation method of an inorganic fiber reinforced thermoplastic polyurethane composite material is characterized in that: the method comprises the following steps:
s1, inorganic fiber surface modification: adding a coupling agent into absolute ethyl alcohol, uniformly mixing, adding acetic acid to hydrolyze the coupling agent, then adding nano particles and inorganic fibers, reacting for 0.5-6h, washing, and drying to obtain the surface modified inorganic fibers; the length of the inorganic fiber is 1-15mm, and the diameter is 5-15 mu m; the inorganic fiber accounts for 1-50% of the total mass of the anhydrous ethanol and the coupling agent; the inorganic fiber comprises one of quartz fiber, carbon fiber, basalt fiber or silicon carbide fiber; the nano particles comprise one or more of carbon nano tubes, graphene, nano zinc oxide and nano titanium dioxide;
s2, preparing spinning solution: uniformly mixing toluene and N, N-dimethylformamide according to a certain mass ratio to obtain a binary solvent; adding polyurethane resin particles with a preset proportion and the surface modified inorganic fibers prepared in the step S1 into the binary solvent, performing ultrasonic dispersion for 5-10min, and performing vacuum defoaming after mechanical stirring at 20-30 ℃ to obtain an inorganic fiber polyurethane composite spinning solution;
S3, spinning and post-treatment: and (2) adding the inorganic fiber polyurethane composite spinning solution obtained in the step (S2) into a wet spinning machine to spin at a certain spinning speed, drawing after spinning trickles come out of a coagulating bath, and carrying out high-temperature setting and drying after the fibers are completely formed to obtain the inorganic fiber reinforced thermoplastic polyurethane composite material.
2. The method for preparing an inorganic fiber reinforced thermoplastic polyurethane composite according to claim 1, wherein: in step S1, the coupling agent includes one of γ -aminopropyl triethoxysilane, γ -glycidyl ether propyl trimethoxysilane, γ -propyl methacrylate trimethoxysilane, γ -mercaptopropyl triethoxysilane, or γ -mercaptopropyl trimethoxysilane.
3. The method for preparing an inorganic fiber reinforced thermoplastic polyurethane composite according to claim 1, wherein: in the step S2, the mass ratio of toluene to N, N dimethylformamide in the binary solvent is 20 percent to 80 percent to 40 percent to 60 percent; the mass ratio of the polyurethane resin particles to the surface modified inorganic fibers is (10% -30%) (0.1% -40%).
4. The method for preparing an inorganic fiber reinforced thermoplastic polyurethane composite according to claim 3, wherein: the mass ratio of the polyurethane resin particles to the surface modified inorganic fibers is (20% -30%) (0.5% -30%).
5. The method for preparing an inorganic fiber reinforced thermoplastic polyurethane composite according to claim 1, wherein: in the step S1, the mass ratio of the anhydrous ethanol to the coupling agent is (90% -99.5%) (0.5% -10%), and the nano particles account for 0.1% -5% of the total mass of the anhydrous ethanol and the coupling agent.
6. The method for preparing an inorganic fiber reinforced thermoplastic polyurethane composite according to claim 1, wherein: in the step S3, the spinning speed is 2-4mm/min; the multiple of the drafting treatment is 1-5 times; the high-temperature setting temperature is 80-120 ℃, and the treatment time is 200-300s.
7. The method for preparing an inorganic fiber reinforced thermoplastic polyurethane composite according to claim 1, wherein: in step S1, acetic acid is added to make the pH of the solution to be 4.5-6.5; the washing is carried out by using absolute ethyl alcohol; the drying is carried out for 0.5-1.5h at 90-110 ℃.
8. The method for preparing an inorganic fiber reinforced thermoplastic polyurethane composite according to claim 1, wherein: before the surface modification treatment, the inorganic fiber needs to be cleaned on the surface, and the specific steps are as follows:
placing the inorganic fiber into deionized water solution of acetone according to a bath ratio of 1 (1.5-5), soaking for 10-60min at 25-30 ℃, washing with deionized water, and drying at 90-110 ℃ for 0.5-1.5h; the mass ratio of the acetone to the deionized water is (5% -20%) (80% -95%).
9. An inorganic fiber reinforced thermoplastic polyurethane composite, characterized in that: the inorganic fiber reinforced thermoplastic polyurethane composite material is prepared by the preparation method of the inorganic fiber reinforced thermoplastic polyurethane composite material in any one of claims 1-8.
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