CN114874603A - 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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- CN114874603A CN114874603A CN202210610294.4A CN202210610294A CN114874603A CN 114874603 A CN114874603 A CN 114874603A CN 202210610294 A CN202210610294 A CN 202210610294A CN 114874603 A CN114874603 A CN 114874603A
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- 239000004642 Polyimide Substances 0.000 title claims abstract description 80
- 229920001721 polyimide Polymers 0.000 title claims abstract description 80
- 239000002121 nanofiber Substances 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 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
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052796 boron Inorganic materials 0.000 claims abstract description 16
- 239000000835 fiber Substances 0.000 claims abstract description 16
- 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
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 claims abstract description 12
- 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 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
- ZKVGXVGEPRBBQV-UHFFFAOYSA-N CN1C(NC(N(C1=O)CC=C)=O)=O.C1CO1 Chemical compound CN1C(NC(N(C1=O)CC=C)=O)=O.C1CO1 ZKVGXVGEPRBBQV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920000137 polyphosphoric acid Polymers 0.000 claims abstract description 8
- 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 13
- 238000000034 method Methods 0.000 claims description 9
- 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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- 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 3
- 239000000155 melt Substances 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 230000006750 UV protection Effects 0.000 abstract description 7
- 238000003878 thermal aging Methods 0.000 abstract description 6
- 229920001971 elastomer Polymers 0.000 description 14
- 239000005060 rubber Substances 0.000 description 14
- 230000032683 aging Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N methyl pentane Natural products CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 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
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 230000002265 prevention Effects 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 210000001142 back Anatomy 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- -1 lanthanum dithio-glutamate 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
- 230000008569 process Effects 0.000 description 2
- 230000004224 protection Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 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 description 1
- QMNWYGTWTXOQTP-UHFFFAOYSA-N 1h-triazin-6-one Chemical group O=C1C=CN=NN1 QMNWYGTWTXOQTP-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- OXGOEZHUKDEEKS-UHFFFAOYSA-N 3-tert-butylperoxy-1,1,5-trimethylcyclohexane Chemical compound CC1CC(OOC(C)(C)C)CC(C)(C)C1 OXGOEZHUKDEEKS-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- 239000007983 Tris buffer Substances 0.000 description 1
- UMHKOAYRTRADAT-UHFFFAOYSA-N [hydroxy(octoxy)phosphoryl] octyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OP(O)(=O)OCCCCCCCC UMHKOAYRTRADAT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003277 amino group Chemical group 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
- 239000000872 buffer Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- HGAZMNJKRQFZKS-UHFFFAOYSA-N chloroethene;ethenyl acetate Chemical group ClC=C.CC(=O)OC=C HGAZMNJKRQFZKS-UHFFFAOYSA-N 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
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 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
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 125000005462 imide group Chemical group 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 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
- 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
- 230000036314 physical performance Effects 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000000126 substance Substances 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
- 125000001544 thienyl group Chemical group 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 composite material based on polyimide nano fibers, which is prepared from the following raw materials in parts by weight: 50-60 parts of bisphenol A polycarbonate, 10-20 parts of ultrahigh molecular weight polyethylene, 15-25 parts of polyimide nano fiber, 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-acrylamide-2-methylpropanesulfonic acid, 2-3 parts of phosphorus pentoxide, 0.5-1 part of polyphosphoric acid, 1-2 parts of initiator, 1, 3-bis (ethylene oxide methyl) -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 composite material based on the polyimide nano-fibers. The composite material based on the polyimide nano fibers has the advantages of high strength, light weight, ultraviolet resistance, sufficient thermal aging resistance, flame retardance, temperature resistance, good moisture resistance and long service life.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a composite material based on polyimide nanofibers and used for a safety rubber boot instep arch-shaped framework and a preparation method thereof.
Background
The safety rubber boots are necessary protective articles which need to be worn in the working environments of some places such as mine operation, tunnel construction, fire rescue, oil exploration and the like, and can prevent the foot organs of constructors from being damaged. The ideal safety rubber boots need to have the functions of smashing prevention, kicking prevention, puncture prevention, skid prevention, moisture prevention and the like. The safety rubber boots used at present usually adopt steel plates in order to prevent the foot surface from being injured by crashing. The safety factor of the safety boots is lower, the process structure is simple and rough, the used steel material is heavy, the elasticity and the buffer function are not provided, the fatigue feeling is stronger when a person wears the safety boots for a long time, the feet are red, swollen and smelly, and the ideal protection effect cannot be achieved.
In order to solve the above problems, researchers in the industry have performed a lot of work and have achieved many research results. The technology of adopting high-strength composite materials to replace steel plates as the materials for the instep arch type framework of the safety rubber boot attracts wide attention and high attention of people. However, the existing composite material for the safety rubber boot instep arch type framework is easy to phase separate in the long-term use process due to the compatibility problem between the filler and the base material, so that the performance stability and the service life are influenced, and the composite material for the safety rubber boot instep arch type framework on the market also has the defects of insufficient ultraviolet resistance, flame retardance, temperature resistance, moisture resistance and strength which are required to be further improved.
For example, patent CN114230873A discloses a safety protective boot for petroleum workers, which comprises raw materials, by weight, of natural rubber, butadiene rubber, white carbon black, thiophenyl thiolindole, lignin, polydimethyldiallylammonium chloride, magnesium methacrylate, lanthanum dithio-glutamate, N-phenyl-N' - (γ -triethoxysilane) -propyl-thiourea, 1-bis (t-butylperoxy) 3,3, 5-trimethylcyclohexane, accelerator CZ, accelerator DM, rubber binder, crosslinking agent, and coupling agent, wherein the coupling agent is a mixture of γ -ammoniumpropyltriethoxysilane, isopropyl tris (dioctylpyrophosphate) titanate and magnesium methacrylate; under the condition of meeting the flame-retardant and insulating functional conditions, the high and low temperature resistance, the chemical corrosion resistance, the weather resistance and the thermal stability of the boot sole of the protective boot are enhanced, the physical and mechanical properties and the aging resistance of the outsole of the rubber boot are further improved, and meanwhile, the flexibility of the outsole of the rubber boot is improved, so that the outsole of the rubber boot has the characteristics of wear resistance and no deformation, and has the functions of puncture resistance and heat absorption and release. However, the strength, uv resistance and thermal aging resistance of the material used for the safety boots still need to be further improved.
Polyimide (PI) is a compound with imide rings on the main chain, belongs to the field of high-performance engineering plastics, has excellent comprehensive performance and good high and low temperature resistance, is a product prepared from PI, such as polyimide nanofiber, combines the advantages of PI and nano materials, has very high tensile strength, high temperature resistance, aging resistance and thermal dimensional stability under the action of multiple effects such as surface and interface effect, small-size effect, quantum-size effect, macroscopic quantum tunneling effect and the like, and has very high application prospect in the field of materials for safety rubber boot arch-shaped frameworks.
Therefore, the polyimide nanofiber-based composite material for the instep arch type framework of the safety rubber boot, which has the advantages of high strength, light weight, sufficient ultraviolet resistance and thermal aging resistance, good flame retardance, temperature resistance and moisture resistance and long service life, and the preparation method thereof are developed, meet market demands, have wide market values and application prospects, and have very important significance in promoting the development of the field of safety boots.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a polyimide nanofiber-based composite material for a dorsum arch framework of a safety rubber boot, which has the advantages of high strength, light weight, ultraviolet resistance, sufficient thermal aging resistance, good flame retardance, temperature resistance and 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 the polyimide nanofiber is prepared from the following raw materials in parts by weight: 50-60 parts of bisphenol A polycarbonate, 10-20 parts of ultrahigh molecular weight polyethylene, 15-25 parts of polyimide nano fiber, 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-acrylamide-2-methylpropanesulfonic acid, 2-3 parts of phosphorus pentoxide, 0.5-1 part of polyphosphoric acid, 1-2 parts of initiator, 1, 3-bis (ethylene oxide methyl) -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 organic tin 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 peroxy hexane 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 average diameter of the glass fiber is 3-9 μm, and the length-diameter ratio is (12-20): 1.
Preferably, the polyimide nanofibers have an average diameter of 1500nm and are prepared according to the method of example 1 in patent CN 109666979B.
Preferably, the ultra-high molecular weight polyethylene is tygon UHMWPE ultra-high molecular weight polyethylene GUR 4170.
Preferably, the bisphenol A polycarbonate is Japanese imperial PC with a designation of L-1250Y and a melt flow rate of 10g/10 min.
Another object of the present invention is to provide a method for preparing the polyimide nanofiber-based composite material, comprising the following steps: 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, the raw materials are easy to obtain, the dependence on equipment is small, and the polyimide nanofiber-based composite material is 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 with each other, so that the prepared material has the advantages of high strength (impact resistance of 800kg), sufficient ultraviolet resistance and thermal aging resistance, good flame retardance, temperature resistance and humidity resistance and long service life. Because the steel plate is not used, the weight of the shoe is light (one twentieth of the weight of the steel plate), and the shoe is comfortable for people to wear for a long time; the installation is convenient and quick, and the displacement does not occur after the installation. In addition, the foot shape of Chinese, Japan, Europe and America and other countries and foot force applying points, bending points, comfort points and the like during walking exercise can be processed and molded according to ergonomics.
(3) According to the composite material based on the polyimide nanofiber, the hyperbranched polyimide with the amino end capping contains a polyimide structure, and according to the similar compatibility principle, the compatibility between the polyimide nanofiber and the raw materials can be improved, so that the raw materials are connected more tightly, and the mechanical property and the performance stability of the composite material are improved; benzene rings on the bisphenol A polycarbonate can chemically react with sulfonic groups on the 2-acrylamide-2-methylpropanesulfonic acid; unsaturated ethylenic bond on 2-acrylamide-2-methylpropanesulfonic acid can also generate copolymerization grafting reaction with 1, 3-bis (ethylene oxide methyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione and ultrahigh molecular weight polyethylene; epoxy groups on the 1, 3-bis (ethylene oxide methyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione can also perform an epoxy ring-opening reaction with amino groups on the amino-terminated hyperbranched polyimide to form a multiple interpenetrating network structure, and the physical properties and performance stability of the material can be effectively improved.
(4) According to the polyimide nanofiber-based composite material disclosed by the invention, the polyimide nanofibers, the glass fibers and the nano boron fibers 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 molecular structure of the material is introduced with a triazinone structure, so that the ultraviolet resistance can be improved.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the following provides a detailed description of the product of the present invention with reference to the examples.
Wherein the amino-terminated hyperbranched polyimide is prepared according to the method of example 1 in patent CN 107789677B; the average diameter of the polyimide nano fiber is 1500nm, and the polyimide nano fiber is prepared by the method of example 1 in patent CN 109666979B; the ultra-high molecular weight polyethylene is American Tycona UHMWPE ultra-high molecular weight polyethylene GUR 4170; the bisphenol A polycarbonate is Japanese emperor PC with the trademark of L-1250Y, and the melt flow rate is 10g/10min
Example 1
A composite material based on polyimide nanofibers is prepared from the following raw materials in parts by weight: 50 parts of bisphenol A polycarbonate, 10 parts of ultra-high molecular weight polyethylene, 15 parts of polyimide nano fiber, 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 (ethylene oxide methyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, 2 parts of heat stabilizer and 1 part of antioxidant.
The heat stabilizer is an organic tin stabilizer MS 181; the antioxidant is an antioxidant 1076; the initiator is a mixture formed by mixing dicumyl peroxide and 2, 5-dimethyl-2, 5-di-tert-butyl peroxy hexane according to a mass ratio of 1:3.
The coupling agent is a silane coupling agent KH 550; the average diameter of the nano boron fiber is 300nm, and the length-diameter ratio is 15: 1; the average diameter of the glass fiber is 3 μm, and the length-diameter ratio is 12: 1.
A preparation method of the composite material based on the polyimide nano-fibers comprises the following steps: the preparation method comprises the steps of 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 a composite material based on the polyimide nanofiber, wherein the instep arch-shaped framework made of the composite material has the effect of preventing feet from being injured by smashing.
Example 2
A composite material based on polyimide nanofibers is prepared from the following raw materials in parts by weight: 53 parts of bisphenol A polycarbonate, 12 parts of ultra-high molecular weight polyethylene, 17 parts of polyimide nano fiber, 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-acrylamide-2-methylpropanesulfonic acid, 2.3 parts of phosphorus pentoxide, 0.7 part of polyphosphoric acid, 1.2 parts of initiator, 1, 3-bis (epoxy ethyl methyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, 2.5 parts of heat stabilizer and 1.5 parts of antioxidant.
The heat stabilizer is a heat stabilizer Mark 9306; the antioxidant is 1010; the initiator is a mixture formed by mixing dicumyl peroxide and 2, 5-dimethyl-2, 5-di-tert-butyl peroxy hexane according to a mass ratio of 1: 3.5; the coupling agent is a silane coupling agent KH 560; the average diameter of the nano boron fiber is 350nm, and the length-diameter ratio is 17: 1; the glass fiber has an average diameter of 5 μm and an aspect ratio of 14: 1.
A preparation method of the composite material based on the polyimide nano-fibers comprises the following steps: the preparation method comprises the steps of 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 a composite material based on the polyimide nanofiber, wherein the instep arch-shaped framework made of the composite material has the effect of preventing feet from being injured by smashing.
Example 3
A composite material based on polyimide nanofibers is prepared from the following raw materials in parts by weight: 55 parts of bisphenol A polycarbonate, 15 parts of ultra-high molecular weight polyethylene, 20 parts of polyimide nano fiber, 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, 1, 3-bis (ethylene oxide methyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, 2 parts of heat stabilizer and 2 parts of antioxidant.
The heat stabilizer is an organic tin stabilizer MS 181; the antioxidant is antioxidant 168; the initiator is a mixture formed by mixing dicumyl peroxide and 2, 5-dimethyl-2, 5-di-tert-butyl peroxy hexane according to a mass ratio of 1:4. The coupling agent is a silane coupling agent KH 570; the average diameter of the nano boron fiber is 400nm, and the length-diameter ratio is 20: 1; the average diameter of the glass fiber is 6 μm, and the length-diameter ratio is 16: 1.
A preparation method of the composite material based on the polyimide nano-fibers comprises the following steps: the preparation method comprises the steps of 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 a composite material based on the polyimide nanofiber, wherein the instep arch-shaped framework made of the composite material has the effect of preventing feet from being injured by smashing.
Example 4
A composite material based on polyimide nanofibers is prepared from the following raw materials in parts by weight: 58 parts of bisphenol A polycarbonate, 19 parts of ultra-high molecular weight polyethylene, 23 parts of polyimide nano fiber, 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-acrylamide-2-methylpropanesulfonic acid, 2.8 parts of phosphorus pentoxide, 0.9 part of polyphosphoric acid, 1.8 parts of initiator, 1, 3-bis (ethylene oxide methyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, 2.5 parts of heat stabilizer and 2.5 parts of antioxidant.
The heat stabilizer is a mixture formed by mixing an organic tin stabilizer MS181 and a heat stabilizer Mark9306 according to the 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 the 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 peroxy hexane 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 the 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 fiber is 8 μm, and the length-diameter ratio is 18: 1.
A preparation method of the composite material based on the polyimide nano-fibers comprises the following steps: the preparation method comprises the steps of uniformly mixing the raw materials in parts by weight to obtain a mixed material, and then carrying out injection molding on the mixed material in a screw type injection machine to obtain the composite material based on the polyimide nanofiber, wherein the dorsum arch-shaped framework made of the composite material has the effect of preventing feet from being injured by smashing.
Example 5
A composite material based on polyimide nanofibers is prepared from the following raw materials in parts by weight: 60 parts of bisphenol A polycarbonate, 20 parts of ultra-high molecular weight polyethylene, 25 parts of polyimide nano fiber, 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 parts of 1, 3-bis (ethylene oxide methyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, 4 parts of heat stabilizer and 3 parts of antioxidant.
The heat stabilizer is an organic tin stabilizer MS 181; the antioxidant is an antioxidant 1076; the initiator is a mixture formed by mixing dicumyl peroxide and 2, 5-dimethyl-2, 5-di-tert-butyl peroxy hexane according to a mass ratio of 1: 5; the coupling agent is a silane coupling agent KH 550; the average diameter of the nano boron fiber is 500nm, and the length-diameter ratio is 25: 1; the glass fiber has an average diameter of 9 μm and an aspect ratio of 20: 1.
A preparation method of the composite material based on the polyimide nano-fibers comprises the following steps: the preparation method comprises the steps of 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 a composite material based on the polyimide nanofiber, wherein the instep arch-shaped framework made of the composite material has the effect of preventing feet from being injured by smashing.
Comparative example 1
A composite material based on polyimide nanofibers, whose formulation and preparation method are substantially the same as those of example 1, except that glass fibers are used instead of the polyimide nanofibers.
Comparative example 2
A polyimide nanofiber-based composite material having a formulation and preparation method substantially the same as those of 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 according to the present invention, performance tests, test methods, and test results of the polyimide nanofiber based composite materials according to the examples and comparative examples of the present invention were performed as shown in table 1. Wherein, the heat aging resistance is measured by the retention rate of tensile strength after the products of each example are placed at 85 ℃ for 96 hours of artificial accelerated aging, and the larger the value is, the better the heat aging resistance is. 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, and the irradiation intensity is 300 mu W/cm 2 Measured as tensile strength retention after 24 hours of UV light aging.
TABLE 1
| Item | Tensile Strength (MPa) | Limiting oxygen index (%) | Heat 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 composite material based on polyimide nanofibers disclosed in the examples of the present invention has higher tensile strength, more excellent flame retardancy, thermal aging resistance and ultraviolet aging resistance as compared to the comparative example product, which is a result of the synergistic effect of the various components.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner; those of ordinary skill in the art can readily practice the present invention as described herein; however, those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention; meanwhile, any changes, modifications, and evolutions of the equivalent changes of the above embodiments according to the actual techniques of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. The composite material based on the polyimide nanofiber is characterized by being prepared from the following raw materials in parts by weight: 50-60 parts of bisphenol A polycarbonate, 10-20 parts of ultrahigh molecular weight polyethylene, 15-25 parts of polyimide nano fiber, 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-acrylamide-2-methylpropanesulfonic acid, 2-3 parts of phosphorus pentoxide, 0.5-1 part of polyphosphoric acid, 1-2 parts of initiator, 1, 3-bis (ethylene oxide methyl) -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 material as claimed in claim 1, wherein said heat stabilizer is at least one of organic tin stabilizer MS181 and heat stabilizer Mark 9306.
3. The polyimide nanofiber based composite according to claim 1, wherein the antioxidant is at least one of antioxidant 1076, antioxidant 1010 and antioxidant 168.
4. The polyimide nanofiber-based composite material according to claim 1, wherein the initiator is a mixture formed by mixing dicumyl peroxide and 2, 5-dimethyl-2, 5-di-tert-butylperoxyhexane in a mass ratio of 1 (3-5).
5. The polyimide nanofiber based composite material 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. The polyimide nanofiber based composite as claimed in claim 1, wherein the average diameter of said nano boron fiber is 300-500nm, and the aspect ratio is (15-25): 1.
7. The polyimide nanofiber based composite material according to claim 1, wherein the glass fibers have an average diameter of 3 to 9 μm and an aspect ratio (12-20): 1; the average diameter of the polyimide nanofibers was 1500 nm.
8. The polyimide nanofiber based composite of claim 1, wherein said ultra high molecular weight polyethylene is tycona UHMWPE ultra high molecular weight polyethylene, GUR 4170.
9. The polyimide nanofiber based composite material according to claim 1, wherein the bisphenol a polycarbonate is teijin PC, brand L-1250Y, and the melt flow rate is 10g/10 min.
10. A method for preparing a polyimide nanofiber based composite according to any one of claims 1 to 9, comprising the steps of: 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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| CN115678276A (en) * | 2022-12-14 | 2023-02-03 | 宁波东鑫高强度螺帽有限公司 | Fastener for composite material |
| CN116135923A (en) * | 2023-02-28 | 2023-05-19 | 广东联塑科技实业有限公司 | Polyvinyl chloride material and preparation method and application thereof |
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