CN114874603B - Composite material based on polyimide nanofiber and preparation method thereof - Google Patents
Composite material based on polyimide nanofiber and preparation method thereof Download PDFInfo
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- CN114874603B CN114874603B CN202210610294.4A CN202210610294A CN114874603B CN 114874603 B CN114874603 B CN 114874603B CN 202210610294 A CN202210610294 A CN 202210610294A CN 114874603 B CN114874603 B CN 114874603B
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- 239000004642 Polyimide Substances 0.000 title claims abstract description 78
- 229920001721 polyimide Polymers 0.000 title claims abstract description 78
- 239000002121 nanofiber Substances 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title abstract description 14
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 19
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 claims abstract description 18
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 claims abstract description 18
- 239000007822 coupling agent Substances 0.000 claims abstract description 17
- 239000003365 glass fiber Substances 0.000 claims abstract description 17
- 229910052796 boron Inorganic materials 0.000 claims abstract description 16
- 239000000835 fiber Substances 0.000 claims abstract description 16
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 15
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 15
- 239000004417 polycarbonate Substances 0.000 claims abstract description 13
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 11
- NADYEWVQIJRXJM-UHFFFAOYSA-N 1,3-bis(oxiran-2-ylmethyl)-5-prop-2-enyl-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC=C)C(=O)N1CC1CO1 NADYEWVQIJRXJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920000137 polyphosphoric acid Polymers 0.000 claims abstract description 8
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims abstract description 6
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 23
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 7
- 238000002347 injection Methods 0.000 claims description 7
- 239000007924 injection Substances 0.000 claims description 7
- 238000001746 injection moulding Methods 0.000 claims description 7
- 239000003381 stabilizer Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 5
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 4
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N methyl pentane Natural products CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 2
- 238000003878 thermal aging Methods 0.000 abstract description 8
- 230000006750 UV protection Effects 0.000 abstract description 7
- 229920001971 elastomer Polymers 0.000 description 15
- 239000005060 rubber Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 11
- 230000032683 aging Effects 0.000 description 9
- 208000017899 Foot injury Diseases 0.000 description 6
- 206010061225 Limb injury Diseases 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- 230000002265 prevention Effects 0.000 description 5
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- -1 lanthanum glutamate dithiocarbamate Chemical compound 0.000 description 2
- DZBOAIYHPIPCBP-UHFFFAOYSA-L magnesium;2-methylprop-2-enoate Chemical compound [Mg+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O DZBOAIYHPIPCBP-UHFFFAOYSA-L 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- SHBZGQGJTNGCBL-UHFFFAOYSA-N 1-(oxiran-2-ylmethyl)-3-prop-2-enyl-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC=C)C(=O)NC(=O)N1CC1OC1 SHBZGQGJTNGCBL-UHFFFAOYSA-N 0.000 description 1
- QMNWYGTWTXOQTP-UHFFFAOYSA-N 1h-triazin-6-one Chemical group O=C1C=CN=NN1 QMNWYGTWTXOQTP-UHFFFAOYSA-N 0.000 description 1
- GSDOQISZWWRJRC-UHFFFAOYSA-N 2-phenyl-1h-indole-3-thiol Chemical compound N1C2=CC=CC=C2C(S)=C1C1=CC=CC=C1 GSDOQISZWWRJRC-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/016—Additives defined by their aspect ratio
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a polyimide nanofiber-based composite material which is prepared from the following raw materials in parts by weight: 50-60 parts of bisphenol A type polycarbonate, 10-20 parts of ultrahigh molecular weight polyethylene, 15-25 parts of polyimide nanofiber, 3-5 parts of glass fiber, 4-8 parts of nano boron fiber, 4-6 parts of coupling agent, 3-5 parts of amino-terminated hyperbranched polyimide, 4-6 parts of 2-acrylamido-2-methylpropanesulfonic acid, 2-3 parts of phosphorus pentoxide, 0.5-1 part of polyphosphoric acid, 1-2 parts of initiator, 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, 2-4 parts of heat stabilizer and 1-3 parts of antioxidant. The invention also discloses a preparation method of the polyimide nanofiber-based composite material. The polyimide nanofiber-based composite material disclosed by the invention has the advantages of high strength, light weight, sufficient ultraviolet resistance and thermal aging resistance, good flame retardance, heat resistance and humidity resistance and long service life.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a polyimide nanofiber-based composite material for a safety rubber boot instep arch-type framework and a preparation method thereof.
Background
The safety rubber boots are necessary protective articles which are needed to be worn in working environments of some places such as mining operation, tunnel construction, fire rescue, oil exploration and the like, and can prevent foot organs of constructors from being disabled. The ideal safety rubber boots need to have the functional characteristics of smashing prevention, kicking prevention, puncture prevention, skid prevention, moisture prevention and the like. The prior safety rubber boots usually adopt steel plates for preventing foot injury. The safety boots have the advantages of low safety coefficient, simple and rough process structure, heavy steel materials, no elasticity and buffering function, strong fatigue feeling when people wear the boots for a long time, red swelling and stink phenomenon of feet, and no ideal protection effect.
In order to solve the above problems, many studies have been carried out by researchers in the industry, and many studies have been made. The technology that a high-strength composite material is adopted to replace a steel plate as a material for the arch-type framework of the instep of the safety rubber boot attracts great attention and importance. However, due to the compatibility problem between the filler and the base material, the existing composite material for the safety rubber boot instep arch-type skeleton is easy to generate phase separation in the long-term use process to influence the performance stability and the service life, and the composite material for the safety rubber boot instep arch-type skeleton on the market also has the defects of insufficient ultraviolet resistance, flame retardance, temperature resistance, moisture resistance and strength to be further improved.
As disclosed in patent CN114230873a, a safety boot for petroleum workers is prepared from natural rubber, butadiene rubber, white carbon black, mercaptophenyl indole, lignin, polydimethyldiallyl ammonium chloride, magnesium methacrylate, lanthanum glutamate dithiocarbamate, N-phenyl-N' - (gamma-triethoxysilane) -propyl-thiourea, 1-bis (t-butylperoxy) 3, 5-trimethylcyclohexane, promoter CZ, promoter DM, rubber binder, cross-linking agent and coupling agent, wherein the coupling agent is a mixture of gamma-ammonium propyltriethoxysilane, isopropyl tri (dioctyl pyrophosphoryloxy) titanate and magnesium methacrylate; under the functional conditions of flame retardance and insulation, the high-low temperature resistance, chemical corrosion resistance, weather resistance and thermal stability of the protective boot sole are enhanced, the physical and mechanical properties and ageing resistance of the rubber boot sole are further improved, and meanwhile, the flexibility of the rubber boot sole is improved, so that the rubber boot sole has the characteristics of wear resistance and no deformation, and meanwhile, the rubber boot sole has the functions of puncture resistance and heat absorption and release. However, the strength, uv resistance and thermal aging resistance of the materials used for the safety boot still need to be further improved.
Polyimide (PI) is a compound with imide rings on a main chain, belongs to the field of high-performance engineering plastics, has excellent comprehensive performance, has good high-low temperature resistance, and products prepared from the PI, such as polyimide nanofibers, combine the advantages of PI and nanomaterials, have very high tensile strength, high-temperature resistance, ageing resistance and thermal dimensional stability under the multiple effects of surface and interface effects, small-size effects, quantum size effects, macroscopic quantum tunneling effects and the like, and have very high application prospects in the field of materials for safety rubber boot instep arch-type frameworks.
Therefore, the polyimide nanofiber-based composite material for the arch-type skeleton of the instep of the safety rubber boot, which has the advantages of high strength, light weight, ultraviolet resistance, sufficient thermal aging resistance, flame retardance, good temperature resistance and good moisture resistance and long service life, and the preparation method thereof meets the market demand, has wide market value and application prospect, and has very important significance in promoting the development of the field of the safety boot.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a polyimide nanofiber-based composite material for a safety rubber boot instep arch-type framework, which has the advantages of high strength, light weight, ultraviolet resistance, sufficient thermal aging resistance, flame retardance, good temperature resistance and good moisture resistance and long service life, and a preparation method thereof.
The invention can be realized by the following technical scheme:
The composite material based on polyimide nano fibers is prepared from the following raw materials in parts by weight: 50-60 parts of bisphenol A type polycarbonate, 10-20 parts of ultrahigh molecular weight polyethylene, 15-25 parts of polyimide nanofiber, 3-5 parts of glass fiber, 4-8 parts of nano boron fiber, 4-6 parts of coupling agent, 3-5 parts of amino-terminated hyperbranched polyimide, 4-6 parts of 2-acrylamido-2-methylpropanesulfonic acid, 2-3 parts of phosphorus pentoxide, 0.5-1 part of polyphosphoric acid, 1-2 parts of initiator, 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, 2-4 parts of heat stabilizer and 1-3 parts of antioxidant.
Preferably, the heat stabilizer is at least one of an organotin stabilizer MS181 and a heat stabilizer Mark 9306.
Preferably, the antioxidant is at least one of antioxidant 1076, antioxidant 1010 and antioxidant 168.
Preferably, the initiator is a mixture formed by mixing dicumyl peroxide and 2, 5-dimethyl-2, 5-di-tert-butyl peroxyhexane according to a mass ratio of 1 (3-5).
Preferably, the amino-terminated hyperbranched polyimide is prepared according to the method of example 1 in patent CN 107789677B.
Preferably, the coupling agent is at least one of a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH 570.
Preferably, the average diameter of the nano boron fiber is 300-500nm, and the length-diameter ratio is (15-25): 1.
Preferably, the glass fibers have an average diameter of 3 to 9 μm and an aspect ratio of (12 to 20): 1.
Preferably, the polyimide nanofibers, having an average diameter of 1500nm, are prepared as described in example 1 of CN 109666979B.
Preferably, the ultra-high molecular weight polyethylene is Takara UHMWPE ultra-high molecular weight polyethylene GUR 4170.
Preferably, the bisphenol A type polycarbonate is Japanese emperor PC, with the trade name L-1250Y and the melt flow rate of 10g/10min.
The invention also aims at providing a preparation method of the polyimide nanofiber-based composite material, which comprises the following steps: and uniformly mixing the raw materials in parts by weight to obtain a mixed material, and then performing injection molding on the mixed material in a screw type injection machine to obtain the polyimide nanofiber-based composite material.
Compared with the prior art, the invention has the beneficial effects that:
(1) The preparation method of the polyimide nanofiber-based composite material disclosed by the invention is simple and convenient to operate, easy to obtain raw materials, low in dependence on equipment and suitable for large-scale batch production.
(2) The polyimide nanofiber-based composite material disclosed by the invention has the advantages that through reasonable selection of the types and the proportions of the raw materials, the raw materials can better interact, so that the prepared material has high strength (800 kg of impact resistance), sufficient ultraviolet resistance and thermal aging resistance, good flame retardance, good temperature resistance and moisture resistance and long service life. The steel plate is not used, so that the weight of the steel plate is light (one twentieth of the weight of the steel plate), and the wearing comfort of people for a long time is good; the installation is convenient and quick, and no displacement occurs after the installation. In addition, the foot-shaped plate can be processed and molded according to human foot shapes, foot force points, bending points, comfort points and the like of China, japan, european and American countries and the like during walking and sports.
(3) According to the polyimide nanofiber-based composite material disclosed by the invention, the amino-terminated hyperbranched polyimide contains a polyimide structure, and according to a similar compatibility principle, the compatibility between polyimide nanofibers and raw materials of the polyimide nanofibers can be improved, so that the raw materials are more tightly connected, and the mechanical property and the performance stability of the composite material are further improved; the benzene ring on bisphenol A type polycarbonate can react with the sulfonic acid group on 2-acrylamide-2-methylpropanesulfonic acid; unsaturated olefinic bond on 2-acrylamido-2-methylpropanesulfonic acid can also generate copolymerization grafting reaction with 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione and ultra-high molecular weight polyethylene; the epoxy group on the 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione can also perform epoxy ring opening reaction with the amino group on the amino-terminated hyperbranched polyimide to form a multiple interpenetrating network structure, and the physical property and the property stability of the material can be effectively improved.
(4) The polyimide nanofiber-based composite material disclosed by the invention has the advantages that the polyimide nanofiber, the glass fiber and the nano boron fiber are mutually matched, so that the strength of the composite material can be effectively improved, and the material is endowed with excellent heat aging resistance, flame retardance, temperature resistance and humidity resistance; the triazinone structure is introduced into the molecular structure of the material, so that the ultraviolet resistance can be improved.
Detailed Description
In order to better understand the technical solution of the present invention, the following describes the product of the present invention in further detail with reference to examples.
Wherein the amino-terminated hyperbranched polyimide is prepared according to the method of example 1 in patent CN 107789677B; the polyimide nanofibers, having an average diameter of 1500nm, were prepared as described in example 1 of CN 109666979B; the ultra-high molecular weight polyethylene is Takara UHMWPE ultra-high molecular weight polyethylene GUR 4170; the bisphenol A type polycarbonate is Japanese emperor PC, the brand is L-1250Y, and the melt flow rate is 10g/10min
Example 1
The composite material based on polyimide nano fibers is prepared from the following raw materials in parts by weight: 50 parts of bisphenol A type polycarbonate, 10 parts of ultra-high molecular weight polyethylene, 15 parts of polyimide nanofiber, 3 parts of glass fiber, 4 parts of nano boron fiber, 4 parts of coupling agent, 3 parts of amino-terminated hyperbranched polyimide, 4 parts of 2-acrylamide-2-methylpropanesulfonic acid, 2 parts of phosphorus pentoxide, 0.5 part of polyphosphoric acid, 1 part of initiator, 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, 1 part of heat stabilizer and 1 part of antioxidant.
The heat stabilizer is an organotin stabilizer MS181; the antioxidant is antioxidant 1076; the initiator is a mixture formed by mixing dicumyl peroxide and 2, 5-dimethyl-2, 5-di-tert-butyl peroxyhexane according to a mass ratio of 1:3.
The coupling agent is a silane coupling agent KH550; the average diameter of the nano boron fiber is 300nm, and the length-diameter ratio is 15:1; the average diameter of the glass fibers is 3 μm, and the length-diameter ratio is 12:1.
The preparation method of the polyimide nanofiber-based composite material comprises the following steps: the raw materials are uniformly mixed according to parts by weight to obtain a mixed material, and then the mixed material is subjected to injection molding in a screw type injection machine to obtain the polyimide nanofiber-based composite material, wherein the instep arch-shaped framework made of the composite material has the effect of preventing foot injury.
Example 2
The composite material based on polyimide nano fibers is prepared from the following raw materials in parts by weight: 53 parts of bisphenol A type polycarbonate, 12 parts of ultra-high molecular weight polyethylene, 17 parts of polyimide nanofiber, 3.5 parts of glass fiber, 5 parts of nano boron fiber, 4.5 parts of coupling agent, 3.5 parts of amino-terminated hyperbranched polyimide, 4.5 parts of 2-acrylamido-2-methylpropanesulfonic acid, 2.3 parts of phosphorus pentoxide, 0.7 part of polyphosphoric acid, 1.2 parts of initiator, 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, 1.5 parts of heat stabilizer and 1.5 parts of antioxidant.
The heat stabilizer is a heat stabilizer Mark9306; the antioxidant is antioxidant 1010; the initiator is a mixture formed by mixing dicumyl peroxide and 2, 5-dimethyl-2, 5-di-tert-butyl peroxyhexane according to a mass ratio of 1:3.5; the coupling agent is silane coupling agent KH560; the average diameter of the nano boron fiber is 350nm, and the length-diameter ratio is 17:1; the average diameter of the glass fibers is 5 μm, and the length-diameter ratio is 14:1.
The preparation method of the polyimide nanofiber-based composite material comprises the following steps: the raw materials are uniformly mixed according to parts by weight to obtain a mixed material, and then the mixed material is subjected to injection molding in a screw type injection machine to obtain the polyimide nanofiber-based composite material, wherein the instep arch-shaped framework made of the composite material has the effect of preventing foot injury.
Example 3
The composite material based on polyimide nano fibers is prepared from the following raw materials in parts by weight: 55 parts of bisphenol A type polycarbonate, 15 parts of ultrahigh molecular weight polyethylene, 20 parts of polyimide nanofiber, 4 parts of glass fiber, 6 parts of nano boron fiber, 5 parts of coupling agent, 4 parts of amino-terminated hyperbranched polyimide, 5 parts of 2-acrylamide-2-methylpropanesulfonic acid, 2.5 parts of phosphorus pentoxide, 0.8 part of polyphosphoric acid, 1.5 parts of initiator, 2 parts of 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, 3 parts of heat stabilizer and 2 parts of antioxidant.
The heat stabilizer is an organotin stabilizer MS181; the antioxidant is antioxidant 168; the initiator is a mixture formed by mixing dicumyl peroxide and 2, 5-dimethyl-2, 5-di-tert-butyl peroxyhexane according to a mass ratio of 1:4. The coupling agent is a silane coupling agent KH570; the average diameter of the nano boron fiber is 400nm, and the length-diameter ratio is 20:1; the glass fibers had an average diameter of 6 μm and an aspect ratio of 16:1.
The preparation method of the polyimide nanofiber-based composite material comprises the following steps: the raw materials are uniformly mixed according to parts by weight to obtain a mixed material, and then the mixed material is subjected to injection molding in a screw type injection machine to obtain the polyimide nanofiber-based composite material, wherein the instep arch-shaped framework made of the composite material has the effect of preventing foot injury.
Example 4
The composite material based on polyimide nano fibers is prepared from the following raw materials in parts by weight: 58 parts of bisphenol A type polycarbonate, 19 parts of ultra-high molecular weight polyethylene, 23 parts of polyimide nanofiber, 4.5 parts of glass fiber, 7.5 parts of nano boron fiber, 5.5 parts of coupling agent, 4.5 parts of amino-terminated hyperbranched polyimide, 5.5 parts of 2-acrylamido-2-methylpropanesulfonic acid, 2.8 parts of phosphorus pentoxide, 0.9 part of polyphosphoric acid, 1.8 parts of initiator, 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, 3.5 parts of heat stabilizer and 2.5 parts of antioxidant.
The heat stabilizer is a mixture formed by mixing an organotin stabilizer MS181 and a heat stabilizer Mark9306 according to a mass ratio of 3:5; the antioxidant is a mixture formed by mixing an antioxidant 1076, an antioxidant 1010 and an antioxidant 168 according to a mass ratio of 1:3:2; the initiator is a mixture formed by mixing dicumyl peroxide and 2, 5-dimethyl-2, 5-di-tert-butyl peroxyhexane according to a mass ratio of 1:4.5.
The coupling agent is a mixture formed by mixing a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH570 according to a mass ratio of 1:1:3; the average diameter of the nano boron fiber is 450nm, and the length-diameter ratio is 23:1; the average diameter of the glass fibers is 8 μm, and the length-diameter ratio is 18:1.
The preparation method of the polyimide nanofiber-based composite material comprises the following steps: the raw materials are uniformly mixed according to parts by weight to obtain a mixed material, and then the mixed material is subjected to injection molding in a screw type injection machine to obtain the polyimide nanofiber-based composite material, wherein the instep arch-shaped framework made of the composite material has the effect of preventing foot injury.
Example 5
The composite material based on polyimide nano fibers is prepared from the following raw materials in parts by weight: 60 parts of bisphenol A type polycarbonate, 20 parts of ultrahigh molecular weight polyethylene, 25 parts of polyimide nanofiber, 5 parts of glass fiber, 8 parts of nano boron fiber, 6 parts of coupling agent, 5 parts of amino-terminated hyperbranched polyimide, 6 parts of 2-acrylamide-2-methylpropanesulfonic acid, 3 parts of phosphorus pentoxide, 1 part of polyphosphoric acid, 2 parts of initiator, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, 3 parts of heat stabilizer and 3 parts of antioxidant.
The heat stabilizer is an organotin stabilizer MS181; the antioxidant is antioxidant 1076; the initiator is a mixture formed by mixing dicumyl peroxide and 2, 5-dimethyl-2, 5-di-tert-butyl peroxyhexane according to a mass ratio of 1:5; the coupling agent is a silane coupling agent KH550; the average diameter of the nano boron fiber is 500nm, and the length-diameter ratio is 25:1; the average diameter of the glass fibers is 9 μm and the length-diameter ratio is 20:1.
The preparation method of the polyimide nanofiber-based composite material comprises the following steps: the raw materials are uniformly mixed according to parts by weight to obtain a mixed material, and then the mixed material is subjected to injection molding in a screw type injection machine to obtain the polyimide nanofiber-based composite material, wherein the instep arch-shaped framework made of the composite material has the effect of preventing foot injury.
Comparative example 1
A composite material based on polyimide nanofibers, the formulation and preparation method of which are substantially the same as those of example 1, except that glass fibers are used instead of polyimide nanofibers.
Comparative example 2
A polyimide nanofiber-based composite material was prepared in the same manner as in example 1, except that 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione was not added.
Meanwhile, in order to evaluate the specific technical effects of the polyimide nanofiber-based composite material of the present invention, performance tests were performed on the polyimide nanofiber-based composite materials of the examples and comparative examples of the present invention, and the test methods and test results are shown in table 1. Wherein, the thermal aging resistance is measured by the retention rate of tensile strength of each product after being subjected to artificial accelerated aging for 96 hours at 85 ℃, and the thermal aging resistance is better when the value is larger. Ultraviolet aging resistance: the ultraviolet aging resistance is tested by using a gallium lamp to simulate ultraviolet light, the wavelength of the ultraviolet light is 200-780nm, the peak value is 420nm, the irradiation intensity is 300 mu W/cm 2, and the tensile strength retention rate is measured after the ultraviolet light is aged for 24 hours.
TABLE 1
| Project | Tensile Strength (MPa) | Limiting oxygen index (%) | Thermal aging resistance (%) | Ultraviolet aging resistance (%) |
| Example 1 | 70 | 38 | 98.89 | 99.12 |
| Example 2 | 72 | 40 | 99.02 | 99.30 |
| Example 3 | 75 | 41 | 99.30 | 99.45 |
| Example 4 | 76 | 41 | 99.54 | 99.56 |
| Example 5 | 80 | 43 | 99.68 | 99.82 |
| Comparative example 1 | 59 | 33 | 97.32 | 98.71 |
| Comparative example 2 | 63 | 35 | 96.59 | 95.20 |
As can be seen from table 1, the polyimide nanofiber-based composite material disclosed in the examples of the present invention has higher tensile strength, more excellent flame retardancy, heat aging resistance and uv aging resistance, as a result of the synergistic effect of the various components, as compared with the comparative example product.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention in any way; those of ordinary skill in the art will readily implement the invention as described above; however, those skilled in the art should not depart from the scope of the invention, and make various changes, modifications and adaptations of the invention using the principles disclosed above; meanwhile, any equivalent changes, modifications and evolution of the above embodiments according to the essential technology of the present invention still fall within the scope of the present invention.
Claims (9)
1. The composite material based on polyimide nano fibers is characterized by being prepared from the following raw materials in parts by weight: 50-60 parts of bisphenol A type polycarbonate, 10-20 parts of ultrahigh molecular weight polyethylene, 15-25 parts of polyimide nanofiber, 3-5 parts of glass fiber, 4-8 parts of nano boron fiber, 4-6 parts of coupling agent, 3-5 parts of amino-terminated hyperbranched polyimide, 4-6 parts of 2-acrylamido-2-methylpropanesulfonic acid, 2-3 parts of phosphorus pentoxide, 0.5-1 part of polyphosphoric acid, 1-2 parts of initiator, 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, 2-4 parts of heat stabilizer and 1-3 parts of antioxidant.
2. The polyimide nanofiber-based composite according to claim 1, wherein the heat stabilizer is at least one of an organotin stabilizer MS181 and a heat stabilizer Mark 9306.
3. The polyimide nanofiber-based composite of claim 1, wherein the antioxidant is at least one of antioxidant 1076, antioxidant 1010, and antioxidant 168.
4. A polyimide nanofiber-based composite material according to claim 1, wherein the initiator is a mixture of dicumyl peroxide and 2, 5-dimethyl-2, 5-di-tert-butylperoxy hexane in a mass ratio of 1 (3-5).
5. The polyimide nanofiber-based composite according to claim 1, wherein the coupling agent is at least one of a silane coupling agent KH550, a silane coupling agent KH560, and a silane coupling agent KH 570.
6. A polyimide nanofiber based composite according to claim 1, wherein the average diameter of the nano-boron fibers is 300-500nm and the aspect ratio is (15-25): 1.
7. A composite material based on polyimide nanofibers according to claim 1, wherein said glass fibers have an average diameter of 3 to 9 μm and an aspect ratio of (12 to 20): 1; the polyimide nanofibers had an average diameter of 1500nm.
8. A polyimide nanofiber based composite according to claim 1, wherein the ultra-high molecular weight polyethylene is taken UHMWPE ultra-high molecular weight polyethylene GUR 4170.
9. A method for preparing a polyimide nanofiber based composite according to any one of claims 1 to 8, comprising the steps of: and uniformly mixing the raw materials in parts by weight to obtain a mixed material, and then performing injection molding on the mixed material in a screw type injection machine to obtain the polyimide nanofiber-based composite material.
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