CN116515290B - Antistatic glass fiber-PA double 6 composite material and preparation method thereof - Google Patents
Antistatic glass fiber-PA double 6 composite material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 239000011521 glass Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 63
- 239000003365 glass fiber Substances 0.000 claims description 44
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 42
- 229920006150 hyperbranched polyester Polymers 0.000 claims description 40
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 37
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- MLFIYYDKLNZLAO-UHFFFAOYSA-N 2-aminoethane-1,1-diol Chemical compound NCC(O)O MLFIYYDKLNZLAO-UHFFFAOYSA-N 0.000 claims description 23
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 23
- -1 amide modified carbon Chemical class 0.000 claims description 23
- 239000002041 carbon nanotube Substances 0.000 claims description 23
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 18
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 18
- 150000001408 amides Chemical class 0.000 claims description 17
- 229920006149 polyester-amide block copolymer Polymers 0.000 claims description 17
- 230000010355 oscillation Effects 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 10
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000001746 injection moulding Methods 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 9
- 238000011282 treatment Methods 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- 239000012043 crude product Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 9
- 239000004677 Nylon Substances 0.000 abstract description 2
- 229920001778 nylon Polymers 0.000 abstract description 2
- 230000004048 modification Effects 0.000 description 11
- 238000012986 modification Methods 0.000 description 11
- 229920002302 Nylon 6,6 Polymers 0.000 description 9
- 239000000203 mixture Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000002048 multi walled nanotube Substances 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
Classifications
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of nylon material preparation and discloses an antistatic glass fiber-PA double 6 composite material and a preparation method thereof.
Description
Technical Field
The invention relates to the technical field of nylon material preparation, in particular to an antistatic glass fiber-PA double 6 composite material and a preparation method thereof.
Background
The polyhexamethylene adipamide PA bis 6 is formed by polycondensation of adipic acid and hexamethylenediamine, can be used as engineering plastics, synthetic fibers and the like, has good solvent resistance and large hardness, and is widely applied to the aspects of gears, lubrication bearings, machine shells, automobile engine blades and the like; the requirements of industrial development are met at present, higher requirements are put forward on the comprehensive performance of the PA double 6, the antistatic property, the mechanical strength and the like of the PA double 6 are improved, and the modification method of the PA double 6 mainly comprises nano material filling modification, grafting monomer copolymerization modification and the like at present;
glass fiber is an inorganic nonmetallic material with excellent performance, has the advantages of good heat resistance, high strength and the like, is widely applied to filling modification of high polymer materials, for example, the literature MAH-g-POE and modification study of glass fiber on nylon 66 are disclosed, and the nylon 66 is subjected to blending modification by adopting maleic anhydride grafted ethylene-1-octene copolymer and glass fiber, so that the interface combination of PA 66 and glass fiber can be improved by adopting maleic anhydride grafted ethylene-1-octene copolymer, the compatibility of a system is enhanced, and the notch impact strength and the tensile strength of the composite material are improved;
the carbon nano tube is a novel one-dimensional carbon nano material, has excellent mechanical, electrical and chemical properties, has wide application in PA double 6 and other materials, and reports that the MWCNTs/nylon 66 composite material is prepared by respectively adding different modified multi-wall carbon nano tubes into a nylon 66 matrix in literature on research on the influence of carbon nano tube surface modification on the mechanical properties of the carbon nano tube/nylon 66 composite material, and amide groups are introduced into the surface of the MWCNTs through an acidification-ammoniation process, so that the carbon nano tube is uniformly dispersed in the nylon 66 matrix, and the tensile strength and tensile modulus of the nylon 66 composite material are improved. The invention utilizes hyperbranched polyester amide carbon nano tube with hydroxyl and carboxyl at the tail end and glass fiber to carry out surface modification, and then the PA double 6 is blended and modified, thereby passing through the antistatic property and mechanical property of the PA double 6 material.
Disclosure of Invention
(one) solving the technical problems
The invention provides an antistatic glass fiber-PA double-6 composite material and a preparation method thereof, which solve the problems of poor compatibility of glass fiber and carbon nano tubes in PA double-6, poor antistatic performance of PA double-6 material and the like.
(II) technical scheme
The preparation method of the antistatic glass fiber-PA double 6 composite material comprises the following steps:
(1) Acidifying the carbon nano tube by concentrated sulfuric acid and concentrated nitric acid, adding the acidified carbon nano tube and chopped glass fibers into N, N-dimethylformamide, dispersing for 20-40min by ultrasonic oscillation, adding hyperbranched polyester amide with hydroxyl and carboxyl at the tail end, carrying out ultrasonic oscillation treatment, filtering, and washing by deionized water to obtain the hyperbranched polyester amide modified carbon nano tube-glass fiber composite material.
(2) And (3) melting and blending the PA double-6 and hyperbranched polyester amide modified carbon nano tube-glass fiber composite material in a torque rheometer, and then processing and injecting by an injection molding machine to obtain the antistatic glass fiber-PA double-6 composite material.
Further, the dosage of the carbon nano tube and the glass fiber in the step (1) is 5-20% and 15-80% of the mass of the hyperbranched polyesteramide in sequence.
Further, the frequency of ultrasonic oscillation treatment in the step (1) is 20-30KHz, the time is 1-3h, and the temperature is 20-50 ℃.
Further, the dosage of the hyperbranched polyester amide modified carbon nano tube-glass fiber composite material in the step (2) is 10-40% of that of PA double 6.
Further, in the step (2), the melt blending temperature in the torque rheometer is 220-235 ℃; the injection temperature of the injection molding machine is 260-270 ℃.
Further, the preparation method of the hyperbranched polyesteramide comprises the following steps:
s1, dissolving 4,4 '-biphenyl ether dianhydride and ethanolamine into N, N-dimethylformamide in nitrogen atmosphere, reacting for 2-5 hours at room temperature, adding ethyl acetate and water into the solution after the reaction, standing for layering, adding anhydrous sodium sulfate into the ethyl acetate solution after extraction for drying and removing water, filtering, rotating the filtrate to remove ethyl acetate, washing the crude product with diethyl ether, and recrystallizing in ethanol to obtain the 4,4' -biphenyl (dihydroxyethylamide dicarboxylic acid) intermediate. The reaction mechanism is as follows:
s2, dissolving a 4,4' -biphenyl (dihydroxyethyl amide dicarboxylic acid) intermediate and trimethylolpropane into dimethylbenzene, dropwise adding p-toluenesulfonic acid, reacting under the protection of nitrogen, filtering the solvent, washing with ethanol, and drying to obtain hyperbranched polyesteramide with hydroxyl and carboxyl at the tail end.
Further, the amount of ethanolamine in the step S1 is 40-55% of the mass of 4,4' -biphenyl ether dianhydride.
Further, the amount of trimethylolpropane dissolved and p-toluenesulfonic acid used in step S2 is 5-8% and 7-12% of the 4,4' -biphenyl (dihydroxyethylamide dicarboxylic acid) intermediate, respectively.
Further, the reaction temperature in the step S2 is 110-130 ℃ and the reaction time is 18-36h.
(III) beneficial technical effects
1. The invention uses anhydride group of 4,4' -biphenyl ether dianhydride and amino group of ethanolamine to generate ring-opening reaction to obtain 4,4' -biphenyl (dihydroxyethyl amide dicarboxylic acid) intermediate containing dicarboxyl and bishydroxy, then uses trimethylol propane as nucleus, uses 4,4' -biphenyl (dihydroxyethyl amide dicarboxylic acid) intermediate as branching monomer, and obtains hyperbranched polyester amide with hydroxy and carboxyl at the end through esterification polycondensation reaction.
2. The terminal hydroxyl and carboxyl of hyperbranched polyester amide are used to form hydrogen bond interaction with hydroxyl and carboxyl of acidified carbon nano tube and hydroxyl on the surface of glass fiber, so that the carbon nano tube and the glass fiber are bridged by the hyperbranched polyester amide, and the hyperbranched polyester amide modified carbon nano tube-glass fiber composite material with a three-dimensional network hybridization system is obtained.
3. The hyperbranched polyester amide modified carbon nano tube-glass fiber composite material is subjected to blending modification with the PA double 6, and after the carbon nano tube and the glass fiber are subjected to hyperbranched polyester amide modification, the carbon nano tube and the PA double 6 have good compatibility and strong interface binding force, can be uniformly dispersed in a PA double 6 matrix, can effectively play a role in enhancing the carbon nano tube and the glass fiber, has obvious enhancement effect on the tensile property and the shock resistance of the PA double 6 material, and can enhance the conductivity of the PA double 6, reduce the resistivity and improve the antistatic effect.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
Example 1
(1) Preparation of 4,4' -biphenyl (dihydroxyethylamide dicarboxylic acid) intermediate: 6g of 4,4 '-biphenyl ether dianhydride and 3.3g of ethanolamine are dissolved in N, N-dimethylformamide under nitrogen atmosphere to react for 2 hours at room temperature, ethyl acetate and water are added into the solution after the reaction, the mixture is stood for layering, anhydrous sodium sulfate is added into the ethyl acetate solution after extraction to dry and remove water, the filtrate is filtered to remove ethyl acetate after filtration, the crude product is washed by diethyl ether and recrystallized in ethanol to obtain the 4,4' -biphenyl (dihydroxyethylamide dicarboxylic acid) intermediate.
(2) Preparation of hyperbranched polyesteramide: 10g of 4,4' -biphenyl (dihydroxyethylamide dicarboxylic acid) intermediate and 0.5g of trimethylolpropane are dissolved in xylene, 0.7g of p-toluenesulfonic acid is added dropwise, the reaction is carried out for 36 hours at 120 ℃ under the protection of nitrogen, the solvent is filtered, the ethanol is used for washing, and the hyperbranched polyesteramide with hydroxyl and carboxyl at the tail end is obtained after drying.
(3) Preparing a hyperbranched polyester amide modified carbon nano tube-glass fiber composite material: acidifying 1g of carbon nano tube by concentrated sulfuric acid and concentrated nitric acid, adding 3g of chopped glass fiber with the mass of hyperbranched polyester amide into N, N-dimethylformamide, dispersing for 20min by ultrasonic oscillation, adding 20g of hyperbranched polyester amide with hydroxyl and carboxyl at the tail end, carrying out ultrasonic oscillation treatment for 3h at the temperature of 30 ℃ under the ultrasonic frequency of 20KHz, filtering, and washing with deionized water to obtain the hyperbranched polyester amide modified carbon nano tube-glass fiber composite material.
(4) Preparing an antistatic glass fiber-PA double 6 composite material: and (3) melting and blending 200gPA double 6 and 20g of hyperbranched polyester amide modified carbon nano tube-glass fiber composite material in a torque rheometer at 235 ℃, and then processing and injecting by an injection molding machine at 270 ℃ to obtain the antistatic glass fiber-PA double 6 composite material.
Example 2
(1) Preparation of 4,4' -biphenyl (dihydroxyethylamide dicarboxylic acid) intermediate: 6g of 4,4 '-biphenyl ether dianhydride and 2.4g of ethanolamine are dissolved in N, N-dimethylformamide under nitrogen atmosphere to react for 2 hours at room temperature, ethyl acetate and water are added into the solution after the reaction, the mixture is stood for layering, anhydrous sodium sulfate is added into the ethyl acetate solution after extraction to dry and remove water, the filtrate is filtered to remove ethyl acetate after filtration, the crude product is washed by diethyl ether and recrystallized in ethanol to obtain the 4,4' -biphenyl (dihydroxyethylamide dicarboxylic acid) intermediate.
(2) Preparation of hyperbranched polyesteramide: 10g of 4,4' -biphenyl (dihydroxyethylamide dicarboxylic acid) intermediate and 0.8g of trimethylolpropane are dissolved in xylene, 1.2g of p-toluenesulfonic acid is added dropwise, the reaction is carried out for 24 hours at 120 ℃ under the protection of nitrogen, the solvent is filtered, the ethanol is used for washing, and the hyperbranched polyesteramide with hydroxyl and carboxyl at the tail end is obtained after drying.
(3) Preparing a hyperbranched polyester amide modified carbon nano tube-glass fiber composite material: acidifying 2g of carbon nano tube by concentrated sulfuric acid and concentrated nitric acid, adding 8g of chopped glass fiber with the mass of hyperbranched polyester amide into N, N-dimethylformamide, dispersing for 30min by ultrasonic oscillation, adding 20g of hyperbranched polyester amide with hydroxyl and carboxyl at the tail end, carrying out ultrasonic oscillation treatment for 2h at the ultrasonic frequency of 30KHz and the temperature of 40 ℃, filtering, and washing by deionized water to obtain the hyperbranched polyester amide modified carbon nano tube-glass fiber composite material.
(4) Preparing an antistatic glass fiber-PA double 6 composite material: and (3) melting and blending 200gPA double 6g and 30g of hyperbranched polyester amide modified carbon nano tube-glass fiber composite material in a torque rheometer at 235 ℃, and then processing and injecting by an injection molding machine at 270 ℃ to obtain the antistatic glass fiber-PA double 6 composite material.
Example 3
(1) Preparation of 4,4' -biphenyl (dihydroxyethylamide dicarboxylic acid) intermediate: 6g of 4,4 '-biphenyl ether dianhydride and 2.8g of ethanolamine are dissolved in N, N-dimethylformamide under nitrogen atmosphere to react for 2 hours at room temperature, ethyl acetate and water are added into the solution after the reaction, the mixture is stood for layering, anhydrous sodium sulfate is added into the ethyl acetate solution after extraction to dry and remove water, the filtrate is filtered to remove ethyl acetate after filtration, the crude product is washed by diethyl ether and recrystallized in ethanol to obtain the 4,4' -biphenyl (dihydroxyethylamide dicarboxylic acid) intermediate.
(2) Preparation of hyperbranched polyesteramide: 10g of 4,4' -biphenyl (dihydroxyethylamide dicarboxylic acid) intermediate and 0.6g of trimethylolpropane are dissolved in xylene, 1g of p-toluenesulfonic acid is added dropwise, the reaction is carried out for 18h at 130 ℃ under the protection of nitrogen, the solvent is filtered, ethanol is used for washing, and the hyperbranched polyesteramide with hydroxyl and carboxyl at the tail end is obtained after drying.
(3) Preparing a hyperbranched polyester amide modified carbon nano tube-glass fiber composite material: 4g of carbon nano tube is acidified by concentrated sulfuric acid and concentrated nitric acid, then 16g of chopped glass fiber with the mass of hyperbranched polyester amide is added into N, N-dimethylformamide, dispersion is carried out for 20min through ultrasonic oscillation, then 20g of hyperbranched polyester amide with hydroxyl and carboxyl at the tail end is added, ultrasonic oscillation treatment is carried out for 3h at the temperature of 40 ℃ under the ultrasonic frequency of 25KHz, and then the hyperbranched polyester amide modified carbon nano tube-glass fiber composite material is obtained after filtration and deionized water washing.
(4) Preparing an antistatic glass fiber-PA double 6 composite material: and (3) melting and blending 200gPA double 6 and 45g of hyperbranched polyester amide modified carbon nano tube-glass fiber composite material in a torque rheometer at 220 ℃, and then processing and injecting by an injection molding machine at 260 ℃ to obtain the antistatic glass fiber-PA double 6 composite material.
Example 4
(1) Preparation of 4,4' -biphenyl (dihydroxyethylamide dicarboxylic acid) intermediate: 6g of 4,4 '-biphenyl ether dianhydride and 3.3g of ethanolamine are dissolved in N, N-dimethylformamide under nitrogen atmosphere to react for 4 hours at room temperature, ethyl acetate and water are added into the solution after the reaction, the mixture is stood for layering, anhydrous sodium sulfate is added into the ethyl acetate solution after extraction to dry and remove water, the filtrate is filtered to remove ethyl acetate after filtration, the crude product is washed by diethyl ether and recrystallized in ethanol to obtain the 4,4' -biphenyl (dihydroxyethylamide dicarboxylic acid) intermediate.
(2) Preparation of hyperbranched polyesteramide: 10g of 4,4' -biphenyl (dihydroxyethylamide dicarboxylic acid) intermediate and 0.5g of trimethylolpropane are dissolved in xylene, 0.7g of p-toluenesulfonic acid is added dropwise, the reaction is carried out for 36 hours at 120 ℃ under the protection of nitrogen, the solvent is filtered, the ethanol is used for washing, and the hyperbranched polyesteramide with hydroxyl and carboxyl at the tail end is obtained after drying.
(3) Preparing a hyperbranched polyester amide modified carbon nano tube-glass fiber composite material: acidifying 3g of carbon nano tube by concentrated sulfuric acid and concentrated nitric acid, adding 12g of chopped glass fiber with the mass of hyperbranched polyester amide into N, N-dimethylformamide, dispersing for 20min by ultrasonic oscillation, adding 20g of hyperbranched polyester amide with hydroxyl and carboxyl at the tail end, carrying out ultrasonic oscillation treatment for 1h at the temperature of 50 ℃ under the ultrasonic frequency of 20KHz, filtering, and washing by deionized water to obtain the hyperbranched polyester amide modified carbon nano tube-glass fiber composite material.
(4) Preparing an antistatic glass fiber-PA double 6 composite material: and (3) melting and blending 200gPA double 6 and 65g of hyperbranched polyester amide modified carbon nano tube-glass fiber composite material in a torque rheometer at 220 ℃, and then processing and injecting by an injection molding machine at 270 ℃ to obtain the antistatic glass fiber-PA double 6 composite material.
Example 5
(1) Preparation of 4,4' -biphenyl (dihydroxyethylamide dicarboxylic acid) intermediate: 6g of 4,4 '-biphenyl ether dianhydride and 3g of ethanolamine are dissolved in N, N-dimethylformamide under nitrogen atmosphere to react for 2 hours at room temperature, ethyl acetate and water are added into the solution after the reaction, the mixture is stood for layering, anhydrous sodium sulfate is added into the ethyl acetate solution after extraction for drying and water removal, the filtrate is filtered and rotated to remove ethyl acetate, the crude product is washed by diethyl ether and recrystallized in ethanol to obtain the 4,4' -biphenyl (dihydroxyethylamide dicarboxylic acid) intermediate.
(2) Preparation of hyperbranched polyesteramide: 10g of 4,4' -biphenyl (dihydroxyethylamide dicarboxylic acid) intermediate and 0.8g of trimethylolpropane are dissolved in xylene, 1.2g of p-toluenesulfonic acid is added dropwise, the reaction is carried out at 110 ℃ for 36 hours under the protection of nitrogen, the solvent is filtered, the ethanol is used for washing, and the hyperbranched polyesteramide with hydroxyl and carboxyl at the tail end is obtained after drying.
(3) Preparing a hyperbranched polyester amide modified carbon nano tube-glass fiber composite material: acidifying 1g of carbon nano tube by concentrated sulfuric acid and concentrated nitric acid, adding 3g of chopped glass fiber with the mass of hyperbranched polyester amide into N, N-dimethylformamide, dispersing for 30min by ultrasonic oscillation, adding 20g of hyperbranched polyester amide with hydroxyl and carboxyl at the tail end, carrying out ultrasonic oscillation treatment for 3h at the ultrasonic frequency of 30KHz and the temperature of 20 ℃, filtering, and washing by deionized water to obtain the hyperbranched polyester amide modified carbon nano tube-glass fiber composite material.
(4) Preparing an antistatic glass fiber-PA double 6 composite material: and (3) melting and blending 200gPA double 6 and 80g of hyperbranched polyester amide modified carbon nano tube-glass fiber composite material in a torque rheometer at 225 ℃, and then processing and injecting by an injection molding machine at 270 ℃ to obtain the antistatic glass fiber-PA double 6 composite material.
Comparative example 1
(1) And (3) melting and blending 200gPA double 6g of acidified carbon nano tubes and 0.8g of chopped glass fibers in a torque rheometer at 230 ℃, and then processing and injecting by an injection molding machine at 270 ℃ to obtain the antistatic glass fiber-PA double 6 composite material.
The volume resistivity of the PA double 6 composite material is tested by a volume resistivity tester, and the test standard GB/T15662-1995. An impact tester is adopted to test the impact resistance of the PA double 6 composite material, and the test standard GB/T1843-2008; testing the tensile property of the PA double 6 composite material by adopting a universal material testing machine, wherein the test standard is GB/T1040.1-2018;
the PA bis 6 of examples 1-5 is added with hyperbranched polyesteramide modified carbon nanotube-glass fiber compositeThe material has obviously improved antistatic performance, tensile performance and impact resistance of PA double 6 material, the minimum volume resistivity is only 5.7Ω & cm, and the maximum impact strength is up to 35.8kJ/cm 2 The maximum tensile strength and elongation at break reach 182.4MPa and 8.3 percent.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (6)
1. The preparation method of the antistatic glass fiber-PA double 6 composite material is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) Acidifying a carbon nano tube by concentrated sulfuric acid and concentrated nitric acid, adding the acidified carbon nano tube and chopped glass fibers into N, N-dimethylformamide, dispersing for 20-40min by ultrasonic oscillation, adding hyperbranched polyester amide with hydroxyl and carboxyl at the tail end, performing ultrasonic oscillation treatment, filtering, and washing with deionized water to obtain the hyperbranched polyester amide modified carbon nano tube-glass fiber composite material;
(2) Melting and blending the PA double-6 and hyperbranched polyester amide modified carbon nano tube-glass fiber composite material in a torque rheometer, and then processing and injecting by an injection molding machine to obtain an antistatic glass fiber-PA double-6 composite material;
the preparation method of the hyperbranched polyesteramide comprises the following steps:
s1, dissolving 4,4' -diphenyl ether dianhydride and ethanolamine into N, N-dimethylformamide in a nitrogen atmosphere, wherein the dosage of the ethanolamine is 40-55% of the mass of the 4,4' -diphenyl ether dianhydride, reacting for 2-5 hours at room temperature, adding ethyl acetate and water into the solution after the reaction, standing for layering, adding anhydrous sodium sulfate into the ethyl acetate solution after extraction for drying and removing water, filtering, rotating the filtrate to remove the ethyl acetate, washing the crude product with diethyl ether, and recrystallizing in ethanol to obtain a 4,4' -biphenyl (dihydroxyethylamide dicarboxylic acid) intermediate;
s2, dissolving a 4,4 '-biphenyl (dihydroxyethyl amide dicarboxylic acid) intermediate and trimethylolpropane into dimethylbenzene, and dropwise adding p-toluenesulfonic acid, wherein the dosages of the trimethylolpropane solution and the p-toluenesulfonic acid are respectively 5-8% and 7-12% of the 4,4' -biphenyl (dihydroxyethyl amide dicarboxylic acid) intermediate, reacting under the protection of nitrogen, filtering the solvent, washing with ethanol, and drying to obtain the hyperbranched polyesteramide with hydroxyl and carboxyl at the tail end.
2. The method for preparing the antistatic glass fiber-PA double 6 composite material according to claim 1, wherein the method comprises the following steps: the dosage of the carbon nano tube and the glass fiber in the step (1) is 5-20% and 15-80% of the mass of the hyperbranched polyesteramide in sequence.
3. The method for preparing the antistatic glass fiber-PA double 6 composite material according to claim 1, wherein the method comprises the following steps: the frequency of ultrasonic oscillation treatment in the step (1) is 20-30KHz, the time is 1-3h, and the temperature is 20-50 ℃.
4. The method for preparing the antistatic glass fiber-PA double 6 composite material according to claim 1, wherein the method comprises the following steps: the dosage of the hyperbranched polyester amide modified carbon nano tube-glass fiber composite material in the step (2) is 10-40% of that of PA double 6.
5. The method for preparing the antistatic glass fiber-PA double 6 composite material according to claim 1, wherein the method comprises the following steps: the melt blending temperature in the transfer rheometer in the step (2) is 220-235 ℃; the injection temperature of the injection molding machine is 260-270 ℃.
6. The method for preparing the antistatic glass fiber-PA double 6 composite material according to claim 1, wherein the method comprises the following steps: the reaction temperature in the step S2 is 110-130 ℃ and the reaction time is 18-36h.
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