CN117304683A - Polyamide material with high fluidity, high rigidity and high toughness and preparation method thereof - Google Patents
Polyamide material with high fluidity, high rigidity and high toughness and preparation method thereof Download PDFInfo
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- CN117304683A CN117304683A CN202311182791.XA CN202311182791A CN117304683A CN 117304683 A CN117304683 A CN 117304683A CN 202311182791 A CN202311182791 A CN 202311182791A CN 117304683 A CN117304683 A CN 117304683A
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 82
- 229920002647 polyamide Polymers 0.000 title claims abstract description 82
- 239000000463 material Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 98
- 239000004917 carbon fiber Substances 0.000 claims abstract description 98
- 229920000642 polymer Polymers 0.000 claims abstract description 38
- 239000003607 modifier Substances 0.000 claims abstract description 34
- 239000012745 toughening agent Substances 0.000 claims abstract description 27
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- FBRJYBGLCHWYOE-UHFFFAOYSA-N 2-(trifluoromethyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(F)(F)F FBRJYBGLCHWYOE-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 92
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 79
- 238000006243 chemical reaction Methods 0.000 claims description 65
- 239000000243 solution Substances 0.000 claims description 55
- 239000000203 mixture Substances 0.000 claims description 46
- 238000001035 drying Methods 0.000 claims description 45
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 238000002156 mixing Methods 0.000 claims description 35
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000002244 precipitate Substances 0.000 claims description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- 229920001610 polycaprolactone Polymers 0.000 claims description 21
- 239000004632 polycaprolactone Substances 0.000 claims description 21
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000001291 vacuum drying Methods 0.000 claims description 18
- 239000012065 filter cake Substances 0.000 claims description 17
- 238000001746 injection moulding Methods 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 16
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 15
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 239000003963 antioxidant agent Substances 0.000 claims description 14
- 230000003078 antioxidant effect Effects 0.000 claims description 14
- 238000007664 blowing Methods 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 238000009830 intercalation Methods 0.000 claims description 14
- 230000002687 intercalation Effects 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 9
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 8
- 229920002943 EPDM rubber Polymers 0.000 claims description 8
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 8
- 235000013539 calcium stearate Nutrition 0.000 claims description 8
- 239000008116 calcium stearate Substances 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- 235000019359 magnesium stearate Nutrition 0.000 claims description 8
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 8
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 239000012286 potassium permanganate Substances 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- SWKPKONEIZGROQ-UHFFFAOYSA-N 4-trifluoromethylbenzoic acid Chemical compound OC(=O)C1=CC=C(C(F)(F)F)C=C1 SWKPKONEIZGROQ-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- 239000008187 granular material Substances 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 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
- 150000001721 carbon Chemical class 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims 1
- 239000004677 Nylon Substances 0.000 abstract description 48
- 229920001778 nylon Polymers 0.000 abstract description 48
- 230000000052 comparative effect Effects 0.000 description 9
- 229920003023 plastic Polymers 0.000 description 8
- 239000004033 plastic Substances 0.000 description 8
- 229920006351 engineering plastic Polymers 0.000 description 6
- 229920002302 Nylon 6,6 Polymers 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 230000004001 molecular interaction Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000010998 test method Methods 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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention relates to the technical field of polyamide materials, in particular to a polyamide material with high fluidity, high rigidity and high toughness and a preparation method thereof. A polyamide material with high fluidity, high rigidity and high toughness and a preparation method thereof comprise the following steps: preparing an intermediate I by polyamide-amine polymers; preparing a flow modifier; preparing a toughening agent; oxidizing carbon fibers; modifying carbon fibers; the polyamide material with high fluidity, high rigidity and high toughness is prepared. According to the invention, the flow modifier is prepared, and the nylon is added into the nylon during nylon production to enable the nylon to have high fluidity, wherein the polyamide-amine polymer enables the flow modifier to have good affinity with the polyamide, so that the polyamide-amine polymer can be better combined with the nylon, and the trifluoromethyl benzoic acid polymer enables the flow modifier to have good flow modifying capability, so that the polyamide material has high fluidity, and can be molded more quickly during production, so that the aim of saving production cost is achieved.
Description
Technical Field
The invention relates to the field of polyamide materials, in particular to a polyamide material with high fluidity, high rigidity and high toughness and a preparation method thereof.
Background
The polyamide can also be called nylon, is a high polymer formed by macromolecular main chains, and each main chain has an amide group on a repeating unit, and can be prepared by ring-opening polymerization of lactam or polycondensation of diamine and diacid, and is the plastic with the largest yield and the largest application and variety in general engineering plastics.
The molecular interaction force between the nylon molecules is large, and hydrogen bonds can be formed, so that the nylon has high melting point and mechanical property, and methylene or aryl groups are also present in the chemical structure of the nylon, so that the nylon also has certain toughness and rigidity, therefore, the nylon engineering plastic mostly has good toughness, heat resistance and mechanical property, and also has good oil resistance, wear resistance and molding processability.
The nylon has the comprehensive characteristics that other plastics do not have, but the toughness and the rigidity of the nylon are often opposite, for example, polyamide PA66 has the highest rigidity and the worst toughness, so that the nylon is easy to break and cannot be widely applied to different scenes, and in addition, the lower flowability of the nylon generally causes the lower forming speed during production, thereby influencing the production efficiency.
In order to solve the technical difficulties, the invention researches a polyamide material with high fluidity, high rigidity and high toughness, which does not lose the rigidity of the material while increasing the toughness, and has the characteristic of high fluidity, and a preparation method thereof.
Disclosure of Invention
In order to solve the technical defects, the invention researches a polyamide material with high fluidity, high rigidity and high toughness, which does not lose the rigidity of the material while increasing the toughness, and has the characteristic of high fluidity, and a preparation method thereof.
A polyamide material with high fluidity, high rigidity and high toughness and a preparation method thereof specifically comprise the following steps:
s1: preparation of intermediate I by Polyamide-amine Polymer
Adding ethylenediamine and a methanol solvent into a three-neck flask for reaction, adding methyl acrylate for reaction, distilling under reduced pressure to obtain a polyamide-amine polymer, adding the polyamide-amine polymer, hydroxybenzaldehyde and ethanol into a round-bottom flask, introducing nitrogen into the round-bottom flask, carrying out oil bath reaction, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide for reaction, distilling the obtained solution, and drying in vacuum to obtain an intermediate I;
s2: preparation of flow modifier
Intermediate I, trifluoromethyl benzoic acid and CH 2 Cl 2 Mixing, loading into a three-neck flask, sequentially adding N, N-dicyclohexylcarbodiimide and 4-dimethylaminopyridine into CH 2 Cl 2 In (2), the resulting solution was stirred by adding to a three-necked flask, then the reaction was poured onto filter paper, and the filtrate was mixed with Na 2 CO 3 Mixing the solution with saturated NaCl solution, distilling, and drying to obtain a flow modifier;
s3: preparation of toughening agent
Mixing maleic anhydride, ethylene-octene copolymer, ethylene propylene diene monomer, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, styrene and antioxidant 1010, stirring, adding into a multifunctional torque rheometer, melting and mixing, adding the mixture into a three-neck flask containing dimethylbenzene, heating for reflux, dissolving, stirring, standing, vacuum filtering, mixing the obtained white flocculent precipitate with zinc stearate, magnesium stearate and calcium stearate, stirring, adding into the multifunctional torque rheometer, and melting and blending to obtain a toughening agent;
s4: oxidized carbon fiber
Adding carbon fibers into concentrated nitric acid, stirring, adding potassium permanganate powder, stirring to obtain carbon fiber intercalation compound, loading the obtained carbon fiber intercalation compound into a flask, adding deionized water, heating for reaction, adding deionized water and hydrogen peroxide, stirring, filtering, washing a filter cake, and drying to obtain oxidized carbon fibers;
s5: modification of carbon fibers
Mixing oxidized carbon fiber and polycaprolactone, placing the mixture into a three-necked flask for ultrasonic treatment, heating, adding stannous octoate, introducing nitrogen, stirring, standing, adding dichloromethane, placing into a centrifuge for centrifugation for three times, filtering the obtained solution, and vacuum drying the product to obtain modified carbon fiber;
s6: preparation of polyamide materials with high fluidity, high rigidity and high toughness
Mixing an antioxidant, polyamide, a prepared flow modifier and a toughening agent in proportion, putting the mixture into an extruder, adding modified carbon fibers at a side feeding position of the extruder, starting the extruder to obtain carbon fiber reinforced polyamide particles, putting the carbon fiber reinforced polyamide particles into an electrothermal blowing drying oven for blowing drying, and then adding the carbon fiber reinforced polyamide particles into an injection molding machine to obtain the polyamide material with high fluidity, high rigidity and high toughness.
Further, step S1 prepares intermediate I from a polyamide-amine polymer, comprising the steps of:
s1.1: adding 8-10 parts of ethylenediamine and 30-35 parts of methanol solvent into a three-neck flask, stirring for 15-20 minutes at 25-27 ℃, dripping 75-80 parts of methyl acrylate into the three-neck flask by using a dropping funnel, standing for reaction for 20-24 hours, placing the obtained reactant into a rotary evaporator, adjusting the temperature to 50-53 ℃ and the vacuum degree to 0.1-0.15MPa, and performing reduced pressure distillation for 20-25 minutes to obtain a polyamide-amine polymer for later use;
S1.2: 17-20 parts of polyamideAmine-amine polymer, 4.8-5.2 parts of 4-hydroxybenzaldehyde and 200-210 parts of ethanol are sequentially added into a round-bottomed flask of 350-400 parts, and 300-350cm is introduced into the flask 3 Nitrogen, then placing the flask into an oil bath, heating to 50-55 ℃, reacting for 6-8 hours, adding 16-20 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide into the flask, further reacting for 14-16 hours at room temperature, placing the obtained solution into a rotary evaporator, distilling for 20-25 minutes at 50-55 ℃, placing the residual solid into a vacuum drying box at 70-75 ℃ and drying for 12-14 hours to obtain an intermediate I for later use.
Further, step S2 of preparing a flow modifier, specifically comprising the steps of:
s2.1: adding 12-15 parts of intermediate I and 6-8 parts of p-trifluoromethyl benzoic acid into a mixture containing 80-100 parts of CH 2 Cl 2 In a three-neck flask, 4 to 5 parts of N, N-dicyclohexylcarbodiimide and 0.5 to 0.6 part of 4-dimethylaminopyridine are sequentially added with 18 to 20 parts of CH 2 Cl 2 Stirring the solution in a flask for 10-15 minutes, and adding the obtained solution into a three-neck flask through a constant-pressure dropping funnel;
s2.2: placing the three-neck flask at 30-32deg.C, standing for 27-30 hr, pouring the reactant on filter paper, mixing filtrate with 50-55 parts Na 2 CO 3 Mixing and stirring the solution and 50-55 parts of saturated NaCl solution for 10-15 minutes, pouring the obtained solution into a rotary evaporator, distilling for 15-20 minutes at 55-60 ℃, placing the obtained product into a vacuum drying box, and drying for 15-17 hours at the temperature of 70-75 ℃ to obtain the flow modifier.
Further, step S3 is preparation of a toughening agent, and specifically includes the following steps:
s3.1: 1.6-1.8 parts of maleic anhydride is dried for 20-30 minutes and then ground for 10-15 minutes to obtain maleic anhydride fine powder, 50-70 parts of ethylene-octene copolymer, 30-50 parts of ethylene propylene diene monomer, 0.03-0.04 part of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, 2.5-2.8 parts of styrene and 10100.5-0.7 part of antioxidant are mixed, stirred for 15-20 minutes, and then added into a multifunctional torque rheometer, the temperature is regulated to 175-180 ℃, the rotating speed is 45-50rpm, and the mixture is obtained after full melt mixing for 4-5;
s3.2: adding the mixed material into a three-neck flask containing dimethylbenzene, heating and refluxing at constant temperature for 45-60 minutes by using a heating sleeve, pouring the obtained hot solution into a beaker containing 1/2-3/4 acetone rapidly after the mixed material is completely dissolved, stirring for 20-25 minutes, standing for 30-40 minutes to generate white flocculent precipitate, then placing into a vacuum suction filter for vacuum suction filtration for 30-35 minutes to obtain white flocculent precipitate, and drying the white flocculent precipitate in a vacuum drying oven at 50-60 ℃ for 25-30 minutes to obtain white solid;
S3.3: zinc stearate, magnesium stearate, calcium stearate were mixed at 1: (1-1.2): mixing (1-1.5) by mass ratio, putting into a vacuum drying oven for drying for 10-15 minutes, and then mixing with white solid in a ratio of (1-1.5): 1, stirring for 15-20 minutes, then adding the mixture into a multifunctional torque rheometer, regulating the temperature to 125-130 ℃, and carrying out melt blending for 20-25 minutes at the rotating speed of 45-50rpm to obtain the toughening agent.
Further, the step S4 of oxidizing the carbon fiber specifically includes the following steps:
s4.1: placing 60-65 parts of concentrated nitric acid into a reaction container, adding 4-6 parts of carbon fibers, standing for 5-6 minutes, adding 4-6 parts of carbon fibers, stirring for 30-40 minutes, slowly adding potassium permanganate powder into the reaction container for 1-1.5 hours, and after the adding is completed, placing the flask at the temperature of 0-1 ℃ and stirring for 1-2 hours to obtain a carbon fiber intercalation compound;
s4.2: putting the obtained carbon fiber intercalation compound into a flask, adding 100-120 parts of deionized water, heating to 70-80 ℃, reacting for 25-30 minutes, adding 180-200 parts of deionized water and 20-25 parts of hydrogen peroxide, stirring for 15-20 minutes, putting the obtained solution into a filter for filtering to obtain a filter cake, washing the filter cake with 32-35w/v of dilute hydrochloric acid for several times, and putting the washed filter cake into a dryer for drying at 55-60 ℃ for 30-35 minutes to obtain oxidized carbon fibers for later use.
Further, the step S5 is carbon fiber modification, and specifically includes the following steps:
s5.1: charging 8-10 parts of oxidized carbon fiber and 4-6 parts of polycaprolactone into three necksUltrasonic treating the flask for 1-1.5 hr, adding stannous octoate 0.002-0.003 parts at 100-110deg.C, and placing the obtained mixture in N 2 Stirring for 24-26 hours under the atmosphere, and then standing for 4-6 hours;
s5.2: adding dichloromethane, centrifuging at 10000-11000 r/min for 10-15 min, repeating for three times, passing the obtained solution through polytetrafluoroethylene membrane, and drying the product in vacuum drier at 40-45deg.C for 3-4 hr to obtain modified carbon fiber.
Further, step S6 prepares a polyamide material with high fluidity, high rigidity and high toughness, specifically comprising the steps of:
s6.1: the flow modifier prepared in the step S2, the toughening agent prepared in the step S3, the antioxidant and the polyamide particles are mixed according to the following ratio of 1: (0.8-1): (0.03:0.04): mixing (18-20) in a mass ratio, and stirring for 15-20 minutes to obtain a mixture;
s6.2: putting the mixture into a double-screw extruder, adding the modified carbon fiber prepared in the step S5 at the side feeding position of the extruder, starting the extruder, adjusting the extrusion temperature to 265-285 ℃, and adjusting the screw speed to 250-350rpm to prepare carbon fiber reinforced polyamide material particles;
S6.3: putting the prepared carbon fiber reinforced polyamide material granules into an electrothermal blowing drying oven, drying for 8-10 hours at 100-110 ℃ in a blowing mode, then adding into an injection molding machine, adjusting the injection molding temperature to 265-285 ℃ and the injection molding pressure to 8-10Mpa, and preparing the polyamide material with high fluidity, rigidity and toughness.
Further, a pressure sensor is arranged at the bottom of the reaction container in the step S4.1, a timer is further arranged on the wall of the reaction container cup, an automatic valve and a stirring rod are arranged at the mouth of the reaction container, the pressure sensor can control the closing of the automatic valve and the rotation of the stirring rod, the timer can control the opening of the automatic valve, concentrated nitric acid is firstly taken to be placed in the reaction container, the pressure sensor is opened, when carbon fibers are thrown in, the pressure sensor senses that the pressure increase sends out a signal, the control module receives the signal to close the automatic valve, at the moment, the timer starts timing, when the time passes 5-6 minutes, the timer sends out a signal, the control module receives the signal to open the automatic valve, the timer stops timing, at the moment, the carbon fibers are thrown into the reaction container again, the pressure sensor senses that the pressure is increased again, the control module controls the automatic valve to close, and controls the stirring rod to start stirring in the reaction container, at the moment, the timer sends out a signal when the time passes 30-40 minutes, the control module controls the stirring rod to stop stirring, and the automatic valve is controlled to open.
Further, the antioxidant used in step S6.1 is N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine.
A polyamide material with high fluidity and high rigidity and high toughness is prepared by a preparation method of the polyamide material with high fluidity and high rigidity and high toughness.
The beneficial effects are that: 1. according to the invention, the flow modifier is prepared, and the nylon is added into the nylon during nylon production to enable the nylon to have high fluidity, wherein the polyamide-amine polymer enables the flow modifier to have good affinity with the polyamide, so that the polyamide-amine polymer can be better combined with the nylon, and the trifluoromethyl benzoic acid polymer enables the flow modifier to have good flow modifying capability, so that the polyamide material has high fluidity, and can be molded more quickly during production, so that the aim of saving production cost is achieved.
2. According to the invention, the mixed maleic anhydride, ethylene-octene copolymer, ethylene propylene diene monomer, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, styrene and antioxidant 1010 are prepared into white solid by a melting method, the obtained white solid is melted and blended with zinc stearate, magnesium stearate and calcium stearate, the toughening agent is obtained by reaction, and the toughening agent is added during nylon production, so that the toughness of nylon can be obviously improved, and the fatigue resistance, tensile strength and compressive strength of the nylon are improved.
3. According to the invention, the carbon fiber is modified, so that the carbon fiber is not lost in rigidity, and meanwhile, certain toughness is increased, the carbon fiber is firstly oxidized to enable the carbon fiber to be grafted with polycaprolactone, and the carbon fiber grafted with polycaprolactone is added during nylon production, so that the toughness of nylon is not lost while the rigidity of nylon is enhanced.
Drawings
FIG. 1 is a flow chart of a process for preparing a polyamide material having high flowability, high rigidity and high toughness according to an embodiment of the present invention.
FIG. 2 is a table diagram showing the comparison of the hardness, impact strength and viscosity of the polyamide material and nylon 66 in comparative example 1 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Examples
A polyamide material with high fluidity, high rigidity and high toughness and a preparation method thereof are shown in figure 1, and specifically comprise the following steps:
S1: preparation of intermediate I by Polyamide-amine Polymer
S1.1: adding 8 parts of 0.15mol of ethylenediamine and 30 parts of methanol solvent into a three-neck flask, stirring for 18 minutes at 25 ℃, dripping 75 parts of methyl acrylate into the three-neck flask by using a dropping funnel, standing for 20 hours to enable reactants of ethylenediamine and methanol to fully react with the methyl acrylate, placing the obtained reactants into a rotary evaporator, adjusting the temperature to 50 ℃ and the vacuum degree to 0.1MPa, performing reduced pressure distillation for 22 minutes, removing excessive raw materials of methyl acrylate and methanol to obtain a polyamide-amine polymer, wherein the polyamide-amine polymer enables a flow modifier to have good affinity with polyamide, so that the polyamide-amine polymer can be better combined with nylon for later use;
s1.2: 18 parts of 0.02mol of a polyamide-amine polymer, 4.8 parts of 0.04mol of 4-hydroxybenzaldehyde and 200 parts of ethanol are successively introduced into a 350-part round-bottomed flask, and 320cm of the flask is charged 3 Nitrogen, then put the flask into an oil bath, heat up to 50 ℃, react for 6 hours, then 18 parts of 0.04mol of 9, 10-dihydro-9-oxa-10-phosphorus are addedThe phenanthrene-10-oxide was added to the flask and reacted further at room temperature for 14 hours, the resulting solution was put in a rotary evaporator and distilled at 50 ℃ for 20 minutes, and the residual solid was dried in a vacuum oven at 70 ℃ for 12 hours to give intermediate i for use.
S2: preparation of flow modifier
S2.1: the polymer of the intermediate I with the concentration of 0.005mol and the p-trifluoromethyl benzoic acid with the concentration of 6 parts with the concentration of 0.01mol ensure that the flow modifier has good flow modifying capability, so that the polyamide material can obtain high fluidity, and can be molded and added with 90 parts of CH more quickly during production 2 Cl 2 In a three-necked flask of (2), 4 parts of 0.01mol of N, N-dicyclohexylcarbodiimide and 0.5 part of 0.0025mol of 4-dimethylaminopyridine were successively charged with 18 parts of CH 2 Cl 2 Stirring the solution in a flask for 10 minutes, and adding the obtained solution into a three-neck flask through a constant-pressure dropping funnel;
s2.2: the three-necked flask was allowed to stand at 30℃for 27 hours, an esterification reaction was carried out in the flask, then the reaction product was poured onto a filter paper, the precipitate was filtered off, and the filtrate was reacted with 50 parts of Na 2 CO 3 The solution and 50 parts of saturated NaCl solution were mixed and stirred for 10 minutes, then the resulting solution was poured into a rotary evaporator, distilled at 55℃for 15 minutes, and the resulting product was placed in a vacuum oven and dried at a temperature of 70℃for 15 hours to obtain a flow modifier.
S3: preparation of toughening agent
S3.1: 1.6 parts of maleic anhydride is dried for 25 minutes and then ground for 12 minutes to obtain maleic anhydride fine powder, the maleic anhydride fine powder is mixed with 55 parts of ethylene-octene copolymer, 35 parts of ethylene propylene diene monomer, 0.03 part of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, 2.5 parts of styrene and 10100.5 parts of antioxidant, stirred for 15 minutes, then the mixture is added into a multifunctional torque rheometer, the temperature is regulated to 175 ℃ and the rotating speed is 45rpm, and the mixture is obtained after the mixture is fully melted and mixed for 4 minutes by a melting method which is simple to operate and quick to react;
S3.2: adding the mixed material into a three-neck flask containing dimethylbenzene, heating and refluxing the mixed material at a constant temperature for 45 minutes by using a heating sleeve until the dimethylbenzene is not over 1/2 of the mixed material, pouring the obtained hot solution into a beaker containing 1/2 of acetone rapidly after the mixed material is completely dissolved, stirring for 20 minutes, standing for 30 minutes until white flocculent precipitate appears, then placing the white flocculent precipitate into a vacuum suction filter for vacuum suction filtration for 30 minutes to obtain white flocculent precipitate, and drying the white flocculent precipitate in a vacuum drying oven at 50 ℃ for 25 minutes to obtain white solid;
s3.3: zinc stearate, magnesium stearate, calcium stearate were mixed at 1:1:1, and then placing the mixture into a vacuum drying oven for drying for 12 minutes, and mixing the mixture with white solid according to the mass ratio of 1:1, stirring for 15 minutes, then adding the mixture into a multifunctional torque rheometer, regulating the temperature to 125 ℃, and carrying out melt blending for 20 minutes at the rotating speed of 45rpm to obtain the toughening agent, wherein the toughening agent is added during nylon production, so that the toughness of the nylon can be obviously improved, and the fatigue resistance, the tensile resistance and the compressive strength of the nylon are improved.
S4: oxidized carbon fiber
S4.1: 60 parts of concentrated nitric acid is taken and placed in a reaction vessel, 4 parts of carbon fiber is added, the mixture is kept stand for 5 minutes, then 4 parts of carbon fiber is added, stirring is carried out for 30 minutes, then potassium permanganate powder is slowly added into the reaction vessel for 1 hour, and after the addition is completed, the flask is placed at the temperature of 0 ℃ and stirred for 1 hour, thus obtaining a carbon fiber intercalation compound;
S4.2: putting the obtained carbon fiber intercalation compound into a flask, adding 100 parts of deionized water, heating to 70 ℃, reacting for 25 minutes, adding 180 parts of deionized water and 20 parts of 30% hydrogen peroxide, stirring for 15 minutes, putting the obtained solution into a filter, filtering to obtain a filter cake, washing the filter cake with 32w/v dilute hydrochloric acid for several times, putting the washed filter cake into a dryer, and drying at 55 ℃ for 30 minutes to obtain oxidized carbon fibers, so that polycaprolactone can be grafted for later use.
S5: modification of carbon fibers
S5.1: 8 parts of oxidized carbon fiber and 4 parts of polycaprolactone are placed in a three-necked flask and sonicated for 1 hour, then 0.002 parts of stannous octoate is added at 100 ℃ as a catalyst to allow the oxidized carbon fiber and polycaprolactone to react more rapidly, and the resulting mixture is placed in a flaskN 2 Stirring for 24 hours under the atmosphere, and then standing for 4 hours to cool the reaction system to the room temperature, so that the subsequent reaction is convenient to carry out;
s5.2: adding dichloromethane to disperse the pre-product, centrifuging at 10000 r/min for 10 min, repeating for three times, passing the obtained solution through polytetrafluoroethylene film, filtering out unreacted polycaprolactone, oxidized carbon fiber and free polycaprolactone which is not grafted to the surface of the oxidized carbon fiber, finally drying the product in a vacuum dryer at 40 ℃ for 3 hours to obtain modified carbon fiber, adding the modified carbon fiber during nylon production, enhancing the rigidity of nylon, and preventing the toughness of nylon from being lost for later use.
S6: preparation of polyamide materials with high fluidity, high rigidity and high toughness
S6.1: the flow modifier prepared in the step S2, the toughening agent prepared in the step S3 and the antioxidant are prepared from polyamide particles purchased by Tongshan God horse engineering plastics Limited company according to the proportion of 1:0.8:0.03:18, stirring for 15 minutes to obtain a mixture;
s6.2: putting the mixture into a double-screw extruder purchased by Nanjing chemical industry equipment, namely a side feeding part of the extruder, adding the modified carbon fiber prepared in the step S5, starting the extruder, adjusting the extrusion temperature to 265 ℃, and adjusting the screw rotation speed to 300rpm to prepare carbon fiber reinforced polyamide material particles;
s6.3: putting the prepared carbon fiber reinforced polyamide material granules into an electrothermal blowing drying oven purchased by Shandong Zibo instrument factory, drying for 8 hours at 100 ℃ in a blowing mode, then adding the materials into an injection molding machine, adjusting the injection molding temperature to 270 ℃ and the injection molding pressure to 8Mpa, and preparing the polyamide material with high fluidity, high rigidity and high toughness.
S4.1, a pressure sensor is arranged at the bottom of the reaction container, a timer is further arranged on the wall of the reaction container, an automatic valve and a stirring rod are arranged at the opening of the reaction container, the pressure sensor can control the closing of the automatic valve and the rotation of the stirring rod, the timer can control the opening of the automatic valve, concentrated nitric acid is firstly placed in the reaction container, the pressure sensor is opened, when carbon fibers are thrown into the reaction container, the pressure sensor senses the pressure increase to send out a signal, the control module receives the signal to close the automatic valve, the timer starts timing, when the time passes 5-6 minutes, the timer sends out the signal to control the module to receive the signal to open the automatic valve, the timer stops timing, when the carbon fibers are thrown into the reaction container again, the pressure sensor senses the pressure increase again to send out the signal, the control module controls the automatic valve to close, and controls the stirring rod to start stirring in the reaction container, when the timer starts timing, the timer sends out a signal when the time passes 30-40 minutes, the control module controls the stirring rod to stop stirring, and the automatic valve is controlled to open, and volatilization of concentrated nitric acid is effectively prevented when stirring.
Examples
A polyamide material with high fluidity, high rigidity and high toughness and a preparation method thereof are shown in figure 1, and specifically comprise the following steps:
s1: preparation of intermediate I by Polyamide-amine Polymer
S1.1: adding 10 parts of ethylenediamine and 35 parts of methanol solvent into a three-neck flask, stirring for 18 minutes at 25 ℃, dripping 80 parts of methyl acrylate into the three-neck flask by using a dropping funnel, standing for 20 hours to enable reactants of ethylenediamine and methanol to fully react with the methyl acrylate, placing the obtained reactants into a rotary evaporator, adjusting the temperature to 50 ℃ and the vacuum degree to 0.1MPa, carrying out reduced pressure distillation for 22 minutes, removing excessive raw materials of methyl acrylate and methanol to obtain a polyamide-amine polymer, wherein the polyamide-amine polymer enables a flow modifier to have good affinity with polyamide, so that the polyamide-amine polymer can be better combined with nylon for later use;
s1.2: 20 parts of 0.02mol of a polyamide-amine polymer, 5 parts of 0.04mol of 4-hydroxybenzaldehyde and 210 parts of ethanol are successively introduced into a 400-part round-bottomed flask, and 350cm of the flask is charged 3 Nitrogen, then placing the flask into an oil bath, heating to 50 ℃, reacting for 6 hours, adding 20 parts of 0.04mol of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide into the flask, further reacting for 14 hours at room temperature, placing the obtained solution into a rotary evaporator, distilling for 20 minutes at 50 ℃, and placing the residual solid into a vacuum drying oven at 70 DEG C Intermediate I is obtained after 12 hours of drying for standby.
S2: preparation of flow modifier
S2.1: the polymer of 15 parts of 0.005mol of intermediate I and 8 parts of 0.01mol of p-trifluoromethyl benzoic acid ensures that the flow modifier has good flow modifying capability, can ensure that the polyamide material has high fluidity, and can be molded and added with 100 parts of CH more quickly during production 2 Cl 2 In a three-necked flask of (2), 5 parts of 0.01mol of N, N-dicyclohexylcarbodiimide and 0.6 part of 0.0025mol of 4-dimethylaminopyridine were successively charged with 20 parts of CH 2 Cl 2 Stirring the solution in a flask for 10 minutes, and adding the obtained solution into a three-neck flask through a constant-pressure dropping funnel;
s2.2: the three-necked flask was allowed to stand at 30℃for 27 hours, an esterification reaction was carried out in the flask, then the reaction product was poured onto a filter paper, the precipitate was filtered off, and the filtrate was reacted with 55 parts of Na 2 CO 3 The solution and 55 parts of saturated NaCl solution were mixed and stirred for 10 minutes, then the resulting solution was poured into a rotary evaporator, distilled at 55℃for 15 minutes, and the resulting product was placed in a vacuum oven and dried at a temperature of 70℃for 15 hours to obtain a flow modifier.
S3: preparation of toughening agent
S3.1: 1.8 parts of maleic anhydride is dried for 25 minutes and then ground for 12 minutes to obtain maleic anhydride fine powder, the maleic anhydride fine powder is mixed with 65 parts of ethylene-octene copolymer, 45 parts of ethylene propylene diene monomer, 0.04 part of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, 2.8 parts of styrene and 10100.7 parts of antioxidant, stirred for 15 minutes, then the mixture is added into a multifunctional torque rheometer, the temperature is regulated to 175 ℃ and the rotating speed is 45rpm, and the mixture is obtained after the mixture is fully melted and mixed for 4 minutes by a melting method which is simple to operate and quick to react;
S3.2: adding the mixed material into a three-neck flask containing dimethylbenzene, wherein the dimethylbenzene is not over 1/2 of the mixed material, heating and refluxing for 45 minutes at constant temperature by using a heating sleeve, pouring the obtained hot solution into a beaker containing 3/4 acetone rapidly after the mixed material is completely dissolved, stirring for 20 minutes, standing for 30 minutes to generate white flocculent precipitate, then placing into a vacuum suction filter for vacuum suction filtration for 30 minutes to obtain white flocculent precipitate, and drying the white flocculent precipitate in a vacuum drying oven at 50 ℃ for 25 minutes to obtain white solid;
s3.3: zinc stearate, magnesium stearate, calcium stearate were mixed at 1:1.2:1.5, and then put into a vacuum drying oven to be dried for 12 minutes, and then the mixture is mixed with white solid according to the mass ratio of 1:1.5, stirring for 15 minutes, then adding the mixture into a multifunctional torque rheometer, regulating the temperature to 125 ℃, the rotating speed to 45rpm, and carrying out melt blending for 20 minutes to obtain the toughening agent, wherein the toughening agent is added during nylon production, so that the toughness of the nylon can be obviously improved, and the fatigue resistance, the tensile resistance and the compressive strength of the nylon are improved.
S4: oxidized carbon fiber
S4.1: placing 65 parts of concentrated nitric acid into a reaction container, adding 6 parts of carbon fibers, standing for 5 minutes, adding 6 parts of carbon fibers again, stirring for 30 minutes, then slowly adding potassium permanganate powder into the reaction container for 1 hour, and stirring the flask at the temperature of 0 ℃ for 1 hour after the addition is completed to obtain a carbon fiber intercalation compound;
S4.2: putting the obtained carbon fiber intercalation compound into a flask, adding 120 parts of deionized water, heating to 70 ℃, reacting for 25 minutes, adding 200 parts of deionized water and 25 parts of hydrogen peroxide with the content of 30%, stirring for 15 minutes, putting the obtained solution into a filter, filtering to obtain a filter cake, washing the filter cake with 35w/v dilute hydrochloric acid for several times, putting the washed filter cake into a dryer, and drying at 55 ℃ for 30 minutes to obtain oxidized carbon fibers, so that polycaprolactone can be grafted for later use.
S5: modification of carbon fibers
S5.1: 10 parts of oxidized carbon fiber and 6 parts of polycaprolactone are put into a three-necked flask, ultrasonic treatment is carried out for 1 hour, then 0.003 part of stannous octoate is added at the temperature of 100 ℃ again, and the oxidized carbon fiber and the polycaprolactone are reacted more rapidly as a catalyst, and the obtained mixture is put into N 2 Stirring for 24 hours under the atmosphere, and then standing for 4 hours to cool the reaction system to the room temperature, so that the subsequent reaction is convenient to carry out;
s5.2: adding dichloromethane to disperse the pre-product, centrifuging at 10000 r/min for 10 min, repeating for three times, passing the obtained solution through polytetrafluoroethylene film, filtering out unreacted polycaprolactone, oxidized carbon fiber and free polycaprolactone which is not grafted to the surface of the oxidized carbon fiber, finally drying the product in a vacuum dryer at 40 ℃ for 3 hours to obtain modified carbon fiber, adding the modified carbon fiber during nylon production, enhancing the rigidity of nylon, and preventing the toughness of nylon from being lost for later use.
S6: preparation of polyamide materials with high fluidity, high rigidity and high toughness
S6.1: the flow modifier prepared in the step S2, the toughening agent prepared in the step S3 and the antioxidant are prepared from polyamide particles purchased by Tongshan God horse engineering plastics Limited company according to the proportion of 1:1:0.04:20, and stirring for 15 minutes to obtain a mixture;
s6.2: putting the mixture into a double-screw extruder purchased by Nanjing chemical industry equipment, namely a side feeding part of the extruder, adding the modified carbon fiber prepared in the step S5, starting the extruder, adjusting the extrusion temperature to 265 ℃, and adjusting the screw rotation speed to 300rpm to prepare carbon fiber reinforced polyamide material particles;
s6.3: putting the prepared carbon fiber reinforced polyamide material granules into an electrothermal blowing drying oven purchased by Shandong Zibo instrument factory, drying for 8 hours at 100 ℃ in a blowing mode, then adding the materials into an injection molding machine, adjusting the injection molding temperature to 270 ℃ and the injection molding pressure to 8Mpa, and preparing the polyamide material with high fluidity, high rigidity and high toughness.
S4.1, a pressure sensor is arranged at the bottom of the reaction container, a timer is further arranged on the wall of the reaction container, an automatic valve and a stirring rod are arranged at the opening of the reaction container, the pressure sensor can control the closing of the automatic valve and the rotation of the stirring rod, the timer can control the opening of the automatic valve, concentrated nitric acid is firstly placed in the reaction container, the pressure sensor is opened, when carbon fibers are thrown into the reaction container, the pressure sensor senses the pressure increase to send out a signal, the control module receives the signal to close the automatic valve, the timer starts timing, when the time passes 5-6 minutes, the timer sends out the signal to control the module to receive the signal to open the automatic valve, the timer stops timing, when the carbon fibers are thrown into the reaction container again, the pressure sensor senses the pressure increase again to send out the signal, the control module controls the automatic valve to close, and controls the stirring rod to start stirring in the reaction container, when the timer starts timing, the timer sends out a signal when the time passes 30-40 minutes, the control module controls the stirring rod to stop stirring, and the automatic valve is controlled to open, and volatilization of concentrated nitric acid is effectively prevented when stirring.
Examples
A polyamide material with high fluidity, high rigidity and high toughness and a preparation method thereof are shown in figure 1, and specifically comprise the following steps:
s1: preparation of intermediate I by Polyamide-amine Polymer
S1.1: adding 8 parts of 0.15mol of ethylenediamine and 30 parts of methanol solvent into a three-neck flask, stirring for 20 minutes at 27 ℃, dripping 75 parts of methyl acrylate into the three-neck flask by using a dropping funnel, standing for 24 hours to enable reactants of ethylenediamine and methanol to fully react with the methyl acrylate, placing the obtained reactants into a rotary evaporator, adjusting the temperature to 53 ℃ and the vacuum degree to be 0.15MPa, and carrying out reduced pressure distillation for 25 minutes to remove excessive raw materials of methyl acrylate and methanol, thereby obtaining a polyamide-amine polymer, wherein the polyamide-amine polymer enables a flow modifier to have good affinity with polyamide, so that the polyamide-amine polymer can be better combined with nylon for standby;
s1.2: 18 parts of 0.02mol of a polyamide-amine polymer, 4.8 parts of 0.04mol of 4-hydroxybenzaldehyde and 200 parts of ethanol are successively introduced into a 350-part round-bottomed flask, and 320cm of the flask is charged 3 Nitrogen, then put the flask into an oil bath, raise the temperature to 55 ℃ for reaction for 8 hours, then add 18 parts of 0.04mol of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide into the flask, react for 16 hours at room temperature, put the obtained solution into a rotary evaporator for distillation at 55 ℃ for 25 minutes, and put the residual solid into a vacuum drying oven at 75 ℃ for drying for 14 hours to obtain an intermediate I for standby.
S2: preparation of flow modifier
S2.1: 12 parts of 0.005mol of the middleThe polymer of the body I and 6 parts of 0.01mol of p-trifluoromethyl benzoic acid ensures that the flow modifier has good flow modifying capability, can ensure that the polyamide material has high fluidity, and can be molded and added with 90 parts of CH more quickly during production 2 Cl 2 In a three-necked flask of (2), 4 parts of 0.01mol of N, N-dicyclohexylcarbodiimide and 0.5 part of 0.0025mol of 4-dimethylaminopyridine were successively charged with 18 parts of CH 2 Cl 2 Stirring the solution in a flask for 15 minutes, and adding the obtained solution into a three-neck flask through a constant-pressure dropping funnel;
s2.2: the three-necked flask was allowed to stand at 32℃for 30 hours, an esterification reaction was carried out in the flask, then the reaction product was poured onto a filter paper, the precipitate was filtered off, and the filtrate was reacted with 50 parts of Na 2 CO 3 The solution and 50 parts of saturated NaCl solution were mixed and stirred for 15 minutes, then the resulting solution was poured into a rotary evaporator, distilled at 60℃for 20 minutes, and the resulting product was placed in a vacuum oven and dried at 75℃for 17 hours to obtain a flow modifier.
S3: preparation of toughening agent
S3.1: 1.6 parts of maleic anhydride is dried for 30 minutes and then ground for 15 minutes to obtain maleic anhydride fine powder, the maleic anhydride fine powder is mixed with 55 parts of ethylene-octene copolymer, 35 parts of ethylene propylene diene monomer, 0.03 part of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, 2.5 parts of styrene and 10100.5 parts of antioxidant, and stirred for 20 minutes, then the mixture is added into a multifunctional torque rheometer, the temperature is adjusted to 180 ℃, the rotating speed is 50rpm, and the mixture is obtained after the mixture is fully melted and mixed for 5 minutes by a melting method which is simple to operate and quick to react;
S3.2: adding the mixed material into a three-neck flask containing dimethylbenzene, heating and refluxing the mixed material at a constant temperature for 45 minutes by using a heating sleeve until the dimethylbenzene is not over 1/2 of the mixed material, pouring the obtained hot solution into a beaker containing 1/2 of acetone rapidly after the mixed material is completely dissolved, stirring for 25 minutes, standing for 40 minutes until white flocculent precipitate appears, then placing the white flocculent precipitate into a vacuum suction filter for vacuum suction filtration for 35 minutes to obtain white flocculent precipitate, and drying the white flocculent precipitate in a vacuum drying oven at a temperature of 60 ℃ for 30 minutes to obtain white solid;
s3.3: zinc stearate, magnesium stearate, calcium stearate were mixed at 1:1:1, and then placing the mixture into a vacuum drying oven for drying for 15 minutes, and mixing the mixture with white solid according to the mass ratio of 1:1, stirring for 20 minutes, then adding the mixture into a multifunctional torque rheometer, regulating the temperature to 130 ℃, and carrying out melt blending for 25 minutes at the rotating speed of 50rpm to obtain the toughening agent, wherein the toughening agent is added during nylon production, so that the toughness of the nylon can be obviously improved, and the fatigue resistance, the tensile resistance and the compressive strength of the nylon are improved.
S4: oxidized carbon fiber
S4.1: 60 parts of concentrated nitric acid is taken and placed in a reaction vessel, 4 parts of carbon fiber is added, the mixture is kept stand for 6 minutes, then 4 parts of carbon fiber is added, stirring is carried out for 40 minutes, then potassium permanganate powder is slowly added into the reaction vessel for 1.5 hours, and after the addition is completed, the flask is placed at the temperature of 1 ℃ and stirred for 2 hours, thus obtaining a carbon fiber intercalation compound;
S4.2: putting the obtained carbon fiber intercalation compound into a flask, adding 100 parts of deionized water, heating to 80 ℃, reacting for 30 minutes, adding 180 parts of deionized water and 20 parts of 30% hydrogen peroxide, stirring for 20 minutes, putting the obtained solution into a filter, filtering to obtain a filter cake, washing the filter cake with 32w/v dilute hydrochloric acid for several times, putting the washed filter cake into a dryer, and drying at 60 ℃ for 35 minutes to obtain oxidized carbon fibers, so that polycaprolactone can be grafted for later use.
S5: modification of carbon fibers
S5.1: 8 parts of oxidized carbon fiber and 4 parts of polycaprolactone are placed in a three-necked flask and sonicated for 1.5 hours, then 0.002 parts of stannous octoate is added at 110 ℃ as a catalyst to allow the oxidized carbon fiber and polycaprolactone to react more rapidly, and the resulting mixture is placed in N 2 Stirring for 26 hours under the atmosphere, and then standing for 6 hours, so that the reaction system is cooled to room temperature, and the subsequent reaction is facilitated;
s5.2: adding dichloromethane to disperse the pre-product, centrifuging at 11000 r/min for 15 min, repeating for three times, passing the obtained solution through a polytetrafluoroethylene film, filtering out unreacted polycaprolactone, oxidized carbon fiber and free polycaprolactone which is not grafted to the surface of the oxidized carbon fiber, finally, placing the product into a vacuum dryer, and drying for 4 hours in a vacuum environment at 45 ℃ to obtain modified carbon fiber, wherein the modified carbon fiber is added during nylon production, so that the toughness of nylon is not lost while the rigidity of nylon is enhanced, and the nylon is ready for use.
S6: preparation of polyamide materials with high fluidity, high rigidity and high toughness
S6.1: the flow modifier prepared in the step S2, the toughening agent prepared in the step S3 and the antioxidant are prepared from polyamide particles purchased by Tongshan God horse engineering plastics Limited company according to the proportion of 1:0.8:0.03:18, stirring for 20 minutes to obtain a mixture;
s6.2: putting the mixture into a double-screw extruder purchased by Nanjing chemical industry equipment, namely a side feeding part of the extruder, adding the modified carbon fiber prepared in the step S5, starting the extruder, adjusting the extrusion temperature to 285 ℃, and adjusting the screw speed to 325rpm to prepare carbon fiber reinforced polyamide material particles;
s6.3: putting the prepared carbon fiber reinforced polyamide material granules into an electrothermal blowing drying oven purchased by Shandong Zibo instrument factory, drying for 10 hours at 110 ℃ in a blowing mode, then adding into an injection molding machine, adjusting the injection molding temperature to 285 ℃ and the injection molding pressure to 10Mpa, and preparing the polyamide material with high fluidity, high rigidity and high toughness.
S4.1, a pressure sensor is arranged at the bottom of the reaction container, a timer is further arranged on the wall of the reaction container, an automatic valve and a stirring rod are arranged at the opening of the reaction container, the pressure sensor can control the closing of the automatic valve and the rotation of the stirring rod, the timer can control the opening of the automatic valve, concentrated nitric acid is firstly placed in the reaction container, the pressure sensor is opened, when carbon fibers are thrown into the reaction container, the pressure sensor senses the pressure increase to send out a signal, the control module receives the signal to close the automatic valve, the timer starts timing, when the time passes 5-6 minutes, the timer sends out the signal to control the module to receive the signal to open the automatic valve, the timer stops timing, when the carbon fibers are thrown into the reaction container again, the pressure sensor senses the pressure increase again to send out the signal, the control module controls the automatic valve to close, and controls the stirring rod to start stirring in the reaction container, when the timer starts timing, the timer sends out a signal when the time passes 30-40 minutes, the control module controls the stirring rod to stop stirring, and the automatic valve is controlled to open, and volatilization of concentrated nitric acid is effectively prevented when stirring.
Comparative example 1 differs from example 1 in that comparative example 1 is a commercially available nylon 66, specifically nylon 66 sold by Tongshan God Massa engineering plastics Co., ltd, and is designated as comparative example 1.
The polyamide materials obtained in example 1, example 2 and example 3 and comparative example 1 were each 100g in mass and 5cm in shape and size 3 The square body of the (C) is tested twice by adopting the method for testing the indentation hardness of the rubber pocket durometer according to the national standard GB/T531-1999, and the method is used for testing the hardness according to the standard environment for the state adjustment and experiment of the plastic sample according to the national standard GB/T2918-1998, the hardness can reflect the rigidity of the plastic, the higher the hardness is, the higher the rigidity is, the polyamide materials prepared in the example 1, the example 2 and the example 3 and the comparative example 1 are taken to have the mass of 100g, and the shape and the size are 5cm 3 The square body of the plastic is tested for impact strength twice by adopting a 'Chinese national standard GB/T1043-93 rigid plastic simply supported beam impact test method', data are recorded, the impact strength of the plastic can reflect the toughness of the plastic, the higher the impact strength is, the higher the toughness reflected by the higher the impact strength is, the polyamide materials prepared in the examples 1, 2 and 3 with the mass of 100g and the comparative example 1 are melted, the viscosity is tested by the 'Chinese national standard GB/T265-liquid viscosity test method', the data are recorded, the viscosity can reflect the flowability of fluid, the smaller the viscosity is, the better the flowability is, the data are tabulated, and referring to FIG. 2, the hardness of the examples 1, 2 and 3 is almost the same as the toughness of the comparative example 1 with the highest hardness on the market, but the toughness and the flowability are far higher than those of the comparative example 1, and the process flow in the examples is proved to be capable of obtaining the polyamide material with high flowability and high rigidity.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (10)
1. The preparation method of the polyamide material with high fluidity, high rigidity and high toughness is characterized by comprising the following steps:
s1: preparation of intermediate I by Polyamide-amine Polymer
Adding ethylenediamine and a methanol solvent into a three-neck flask for reaction, adding methyl acrylate for reaction, distilling under reduced pressure to obtain a polyamide-amine polymer, adding the polyamide-amine polymer, hydroxybenzaldehyde and ethanol into a round-bottom flask, introducing nitrogen into the round-bottom flask, carrying out oil bath reaction, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide for reaction, distilling the obtained solution, and drying in vacuum to obtain an intermediate I;
s2: preparation of flow modifier
Intermediate I, trifluoromethyl benzoic acid and CH 2 Cl 2 Mixing, loading into a three-neck flask, sequentially adding N, N-dicyclohexylcarbodiimide and 4-dimethylaminopyridine into CH 2 Cl 2 In (2), the resulting solution was stirred by adding to a three-necked flask, then the reaction was poured onto filter paper, and the filtrate was mixed with Na 2 CO 3 Mixing the solution with saturated NaCl solution, distilling, and drying to obtain a flow modifier;
s3: preparation of toughening agent
Mixing maleic anhydride, ethylene-octene copolymer, ethylene propylene diene monomer, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, styrene and antioxidant 1010, stirring, adding into a multifunctional torque rheometer, melting and mixing, adding the mixture into a three-neck flask containing dimethylbenzene, heating for reflux, dissolving, stirring, standing, vacuum filtering, mixing the obtained white flocculent precipitate with zinc stearate, magnesium stearate and calcium stearate, stirring, adding into the multifunctional torque rheometer, and melting and blending to obtain a toughening agent;
s4: oxidized carbon fiber
Adding carbon fibers into concentrated nitric acid, stirring, adding potassium permanganate powder, stirring to obtain carbon fiber intercalation compound, loading the obtained carbon fiber intercalation compound into a flask, adding deionized water, heating for reaction, adding deionized water and hydrogen peroxide, stirring, filtering, washing a filter cake, and drying to obtain oxidized carbon fibers;
S5: modification of carbon fibers
Mixing oxidized carbon fiber and polycaprolactone, placing the mixture into a three-necked flask for ultrasonic treatment, heating, adding stannous octoate, introducing nitrogen, stirring, standing, adding dichloromethane, placing into a centrifuge for centrifugation for three times, filtering the obtained solution, and vacuum drying the product to obtain modified carbon fiber;
s6: preparation of polyamide materials with high fluidity, high rigidity and high toughness
Mixing an antioxidant, polyamide, a prepared flow modifier and a toughening agent in proportion, putting the mixture into an extruder, adding modified carbon fibers at a side feeding position of the extruder, starting the extruder to obtain carbon fiber reinforced polyamide particles, putting the carbon fiber reinforced polyamide particles into an electrothermal blowing drying oven for blowing drying, and then adding the carbon fiber reinforced polyamide particles into an injection molding machine to obtain the polyamide material with high fluidity, high rigidity and high toughness.
2. The method for preparing a polyamide material with high fluidity, high rigidity and high toughness according to claim 1, wherein step S1 prepares intermediate i by polyamide-amine polymer, comprising the following steps:
s1.1: adding 8-10 parts of ethylenediamine and 30-35 parts of methanol solvent into a three-neck flask, stirring for 15-20 minutes at 25-27 ℃, dripping 75-80 parts of methyl acrylate into the three-neck flask by using a dropping funnel, standing for reaction for 20-24 hours, placing the obtained reactant into a rotary evaporator, adjusting the temperature to 50-53 ℃ and the vacuum degree to 0.1-0.15MPa, and performing reduced pressure distillation for 20-25 minutes to obtain a polyamide-amine polymer for later use;
S1.2: 17 to 20 parts of polyamide-amine polymer and 4.8 to 5.2 parts of 4Sequentially adding hydroxybenzaldehyde and 200-210 parts of ethanol into a 350-400 parts round-bottomed flask, and introducing 300-350cm into the flask 3 Nitrogen, then placing the flask into an oil bath, heating to 50-55 ℃, reacting for 6-8 hours, adding 16-20 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide into the flask, further reacting for 14-16 hours at room temperature, placing the obtained solution into a rotary evaporator, distilling for 20-25 minutes at 50-55 ℃, placing the residual solid into a vacuum drying box at 70-75 ℃ and drying for 12-14 hours to obtain an intermediate I for later use.
3. The method for preparing a polyamide material with high fluidity, high rigidity and high toughness according to claim 1, wherein the step S2 of preparing the flow modifier comprises the following steps:
s2.1: adding 12-15 parts of intermediate I and 6-8 parts of p-trifluoromethyl benzoic acid into a mixture containing 80-100 parts of CH 2 Cl 2 In a three-neck flask, 4 to 5 parts of N, N-dicyclohexylcarbodiimide and 0.5 to 0.6 part of 4-dimethylaminopyridine are sequentially added with 18 to 20 parts of CH 2 Cl 2 Stirring the solution in a flask for 10-15 minutes, and adding the obtained solution into a three-neck flask through a constant-pressure dropping funnel;
S2.2: placing the three-neck flask at 30-32deg.C, standing for 27-30 hr, pouring the reactant on filter paper, mixing filtrate with 50-55 parts Na 2 CO 3 Mixing and stirring the solution and 50-55 parts of saturated NaCl solution for 10-15 minutes, pouring the obtained solution into a rotary evaporator, distilling for 15-20 minutes at 55-60 ℃, placing the obtained product into a vacuum drying box, and drying for 15-17 hours at the temperature of 70-75 ℃ to obtain the flow modifier.
4. The method for preparing the polyamide material with high fluidity, high rigidity and high toughness according to claim 1, wherein the preparation of the toughening agent in the step S3 specifically comprises the following steps:
s3.1: 1.6-1.8 parts of maleic anhydride is dried for 20-30 minutes and then ground for 10-15 minutes to obtain maleic anhydride fine powder, 50-70 parts of ethylene-octene copolymer, 30-50 parts of ethylene propylene diene monomer, 0.03-0.04 part of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, 2.5-2.8 parts of styrene and 10100.5-0.7 part of antioxidant are mixed, stirred for 15-20 minutes, and then added into a multifunctional torque rheometer, the temperature is regulated to 175-180 ℃, the rotating speed is 45-50rpm, and the mixture is obtained after full melt mixing for 4-5 minutes;
S3.2: adding the mixed material into a three-neck flask containing dimethylbenzene, heating and refluxing at constant temperature for 45-60 minutes by using a heating sleeve, pouring the obtained hot solution into a beaker containing 1/2-3/4 acetone rapidly after the mixed material is completely dissolved, stirring for 20-25 minutes, standing for 30-40 minutes to generate white flocculent precipitate, then placing into a vacuum suction filter for vacuum suction filtration for 30-35 minutes to obtain white flocculent precipitate, and drying the white flocculent precipitate in a vacuum drying oven at 50-60 ℃ for 25-30 minutes to obtain white solid;
s3.3: zinc stearate, magnesium stearate, calcium stearate were mixed at 1: (1-1.2): mixing (1-1.5) by mass ratio, putting into a vacuum drying oven for drying for 10-15 minutes, and then mixing with white solid in a ratio of (1-1.5): 1, stirring for 15-20 minutes, then adding the mixture into a multifunctional torque rheometer, regulating the temperature to 125-130 ℃, and carrying out melt blending for 20-25 minutes at the rotating speed of 45-50rpm to obtain the toughening agent.
5. The method for preparing the polyamide material with high fluidity, high rigidity and high toughness according to claim 1, wherein the step S4 of oxidizing the carbon fiber comprises the following steps:
s4.1: placing 60-65 parts of concentrated nitric acid into a reaction container, adding 4-6 parts of carbon fibers, standing for 5-6 minutes, adding 4-6 parts of carbon fibers, stirring for 30-40 minutes, slowly adding potassium permanganate powder into the reaction container for 1-1.5 hours, and after the adding is completed, placing the flask at the temperature of 0-1 ℃ and stirring for 1-2 hours to obtain a carbon fiber intercalation compound;
S4.2: putting the obtained carbon fiber intercalation compound into a flask, adding 100-120 parts of deionized water, heating to 70-80 ℃, reacting for 25-30 minutes, adding 180-200 parts of deionized water and 20-25 parts of hydrogen peroxide, stirring for 15-20 minutes, putting the obtained solution into a filter for filtering to obtain a filter cake, washing the filter cake with 32-35w/v of dilute hydrochloric acid for several times, and putting the washed filter cake into a dryer for drying at 55-60 ℃ for 30-35 minutes to obtain oxidized carbon fibers for later use.
6. The method for preparing the polyamide material with high fluidity, high rigidity and high toughness according to claim 1, wherein the modification of the carbon fiber in the step S5 comprises the following steps:
s5.1: filling 8-10 parts of oxidized carbon fiber and 4-6 parts of polycaprolactone into a three-necked flask, carrying out ultrasonic treatment for 1-1.5 hours, then adding 0.002-0.003 parts of stannous octoate at 100-110 ℃, and placing the obtained mixture into N 2 Stirring for 24-26 hours under the atmosphere, and then standing for 4-6 hours;
s5.2: adding dichloromethane, centrifuging at 10000-11000 r/min for 10-15 min, repeating for three times, passing the obtained solution through polytetrafluoroethylene membrane, and drying the product in vacuum drier at 40-45deg.C for 3-4 hr to obtain modified carbon fiber.
7. The method for preparing a polyamide material with high fluidity, high rigidity and high toughness according to claim 1, wherein the step S6 is to prepare the polyamide material with high fluidity, high rigidity and high toughness, and specifically comprises the following steps:
s6.1: the flow modifier prepared in the step S2, the toughening agent prepared in the step S3, the antioxidant and the polyamide particles are mixed according to the following ratio of 1: (0.8-1): (0.03:0.04): mixing (18-20) in a mass ratio, and stirring for 15-20 minutes to obtain a mixture;
s6.2: putting the mixture into a double-screw extruder, adding the modified carbon fiber prepared in the step S5 at the side feeding position of the extruder, starting the extruder, adjusting the extrusion temperature to 265-285 ℃ and adjusting the screw N 2 Preparing carbon fiber reinforced polyamide material particles at 250-350 rpm;
s6.3: putting the prepared carbon fiber reinforced polyamide material granules into an electrothermal blowing drying oven, drying for 8-10 hours at 100-110 ℃ in a blowing mode, then adding into an injection molding machine, adjusting the injection molding temperature to 265-285 ℃ and the injection molding pressure to 8-10Mpa, and preparing the polyamide material with high fluidity, rigidity and toughness.
8. The preparation method of the polyamide material with high fluidity and high rigidity and high toughness according to claim 5, wherein a pressure sensor is arranged at the bottom of the reaction container in the step S4.1, a timer is further arranged on the reaction container, an automatic valve and a stirring rod are arranged at the mouth of the reaction container, the pressure sensor can control the closing of the automatic valve and the rotation of the stirring rod, the timer can control the opening of the automatic valve, concentrated nitric acid is firstly placed in the reaction container, the pressure sensor is opened, when carbon fibers are thrown in, the pressure sensor senses the pressure increase to send out a signal, the control module receives the signal to close the automatic valve, at the moment, the timer starts to count time, when the time passes for 5-6 minutes, the timer sends out the signal to receive the signal to open the automatic valve, the timer stops counting, at the moment, the pressure sensor senses the carbon fibers are thrown in the reaction container again to increase to send out the signal, the control module controls the automatic valve to close, and controls the stirring rod to start stirring the reaction container, at the moment, and when the timer starts to count time for 30-40 minutes, the timer sends out the signal, the control the stirring rod to stop stirring and controls the automatic valve to open.
9. The method for producing a polyamide material having high flowability, high rigidity and high toughness according to claim 7, wherein the antioxidant used in step S6.1 is N, N' -bis- (3, 5-di-t-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine.
10. Polyamide material with high flowability, high rigidity and high toughness, characterized in that it is obtained by a process for the preparation of a polyamide material with high flowability, high rigidity and high toughness according to any of the preceding claims 1-9.
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