CN116120543A - Preparation method of flame-retardant graphene polyamide 6 composite material - Google Patents
Preparation method of flame-retardant graphene polyamide 6 composite material Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 62
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229920002292 Nylon 6 Polymers 0.000 title claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 48
- BPBDZXFJDMJLIB-UHFFFAOYSA-N 2-phenylpropane-1,3-diol Chemical compound OCC(CO)C1=CC=CC=C1 BPBDZXFJDMJLIB-UHFFFAOYSA-N 0.000 claims abstract description 34
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000004952 Polyamide Substances 0.000 claims abstract description 24
- 229920002647 polyamide Polymers 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 20
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims abstract description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 3
- 238000006467 substitution reaction Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 230000008878 coupling Effects 0.000 claims description 7
- 238000010168 coupling process Methods 0.000 claims description 7
- 238000005859 coupling reaction Methods 0.000 claims description 7
- 238000007142 ring opening reaction Methods 0.000 claims description 7
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 6
- 150000001263 acyl chlorides Chemical class 0.000 claims description 6
- 239000004760 aramid Substances 0.000 claims description 6
- 229920003235 aromatic polyamide Polymers 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 4
- 150000001408 amides Chemical group 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 230000003712 anti-aging effect Effects 0.000 claims description 2
- 239000002216 antistatic agent Substances 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000012760 heat stabilizer Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 11
- 239000011159 matrix material Substances 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000002981 blocking agent Substances 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 10
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 10
- 239000012295 chemical reaction liquid Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000008096 xylene Substances 0.000 description 6
- 239000005711 Benzoic acid Substances 0.000 description 5
- 235000010233 benzoic acid Nutrition 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- HIKUCVORZZXYNF-UHFFFAOYSA-L calcium;1-methylpyrrolidin-2-one;dichloride Chemical compound Cl[Ca]Cl.CN1CCCC1=O HIKUCVORZZXYNF-UHFFFAOYSA-L 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000012796 inorganic flame retardant Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
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- 239000002341 toxic gas Substances 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/04—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
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- Life Sciences & Earth Sciences (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the technical field of preparation of polyamide, and particularly relates to a preparation method of a flame-retardant graphene polyamide 6 composite material. According to the invention, graphene, small molecular polyamide, 2-phenyl-1, 3-propylene glycol phosphoric anhydride, ethylenediamine, oxalic acid and caprolactam are mixed, an auxiliary agent and a solvent are added for ring opening polymerization, and substitution reaction of 2-phenyl-1, 3-propylene glycol phosphoric anhydride and ethylenediamine is carried out simultaneously, so that the flame-retardant graphene polyamide 6 composite material is obtained. The 2-phenyl-1, 3-propanediol phosphoric anhydride and ethylenediamine are utilized to react to generate the flame retardant, the flame retardant is generated during polymerization, the dispersibility of the flame retardant in the polyamide 6 material is improved, the 2-phenyl-1, 3-propanediol phosphoric anhydride can be used as a blocking agent to participate in the polymerization reaction, the compatibility of the flame retardant and a polymer matrix is better, the stability of the flame retardant in the polyamide 6 is improved, the migration condition of the flame retardant is reduced, and the strength performance of the composite material is improved.
Description
Technical Field
The invention belongs to the technical field of preparation of polyamide, and particularly relates to a preparation method of a flame-retardant graphene polyamide 6 composite material.
Background
The polyamide is commonly called nylon, has the characteristics of multiple varieties, large yield and wide application, and is one of five engineering plastics. The polyamide 6 is the variety with the largest usage amount in the polyamide, has excellent performances of high mechanical strength, wear resistance, oil resistance, weak acid resistance, alkali resistance and the like, and can be processed into plastics, fibers and films, but the limiting oxygen index of the polyamide 6 is only about 21 percent, and the molten drop phenomenon is serious during combustion, so that the application of the polyamide 6 is severely limited. Therefore, flame retardant and anti-dripping modification of polyamide 6 is of great importance.
The flame retardant suitable for polyamide 6 mainly comprises halogen-based, nitrogen-based, inorganic and phosphorus-based flame retardants, and different flame retardants have great differences in flame retardant mechanism, flame retardant efficiency and influence on material performance. The halogen flame retardant has the most wide application, the greatest use amount and the best flame retardant effect, but releases a large amount of smoke and toxic gas when the halogen flame retardant burns, and has great harm to the environment and human body. Inorganic flame retardants are widely used in the flame-retardant field due to the advantages of good thermal stability, low volatility, low corrosiveness, almost no toxicity and the like, but generally require higher addition amounts to achieve better flame-retardant effects. Compared with halogen flame retardants and inorganic flame retardants, nitrogen flame retardants have the advantages of good stability, environmental friendliness and the like, but most of nitrogen flame retardants are introduced into polyamide in a physical form, and have the problems of large addition amount and easy precipitation. The phosphorus flame retardant has the advantages of good thermal stability, difficult volatilization, no generation of corrosive gas, lasting flame retardant time, low toxicity and the like, and has wide application in the field of flame retardant polyamide in recent years, but is mainly added into polyamide 6 in a physical addition mode at present.
The preparation methods commonly used at present for the flame retardant polyamide 6 are a blending method and a polymerization method, wherein the polymerization method also comprises a copolymerization method and an in-situ polymerization method. The blending method has simple processing technology, high addition amount of the flame retardant, uneven dispersion and easy precipitation, and has great influence on the mechanical properties of the materials. The copolymerization flame-retardant modification is an important mode of flame-retardant modification, the research on preparing the flame-retardant polyamide by a copolymerization method is less, the copolymerization method has a complex flame-retardant process, and the mechanical property of the polyamide is greatly reduced when the addition amount is large. The in-situ polymerization method is to introduce the flame retardant into the polymer during the synthesis process to disperse between matrix molecular chains, so that the degradation caused by secondary processing of the blending method can be effectively avoided, but the required addition amount for achieving the flame retardant purpose is also larger, and the flame retardant is easy to separate out.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of a flame-retardant graphene polyamide 6 composite material.
A preparation method of a flame-retardant graphene polyamide 6 composite material comprises the following steps:
s1: mixing ethylenediamine and binary acyl chloride for reaction to generate small molecular polyamide;
s2: 2-phenyl-1, 3-propanediol reacts with phosphorus oxychloride and then is hydrolyzed to obtain 2-phenyl-1, 3-propanediol phosphoric anhydride;
s3: mixing graphene, small molecular polyamide, 2-phenyl-1, 3-propylene glycol phosphoric anhydride, ethylenediamine, oxalic acid and caprolactam, adding an auxiliary agent and a solvent, performing ring opening polymerization reaction, and simultaneously performing substitution reaction of the 2-phenyl-1, 3-propylene glycol phosphoric anhydride and ethylenediamine to obtain the flame-retardant graphene polyamide 6 composite material.
Preferably, S1 is specifically: dissolving ethylenediamine and an acid binding agent in a good solvent under the atmosphere of nitrogen, adding binary acyl chloride at 0-10 ℃ for reaction for 1-2h, and obtaining micromolecular aromatic polyamide through precipitation, extraction and drying after the reaction is finished; the mol ratio of the ethylenediamine to the dibasic acyl chloride is (1.05-1.3): 1.
preferably, the good solvent is an amide solvent-salt system, wherein the amide solvent is N-methylpyrrolidone or dimethylacetamide, and the salt is lithium chloride or calcium chloride; the acid binding agent is pyridine or 2-methylpyridine.
Preferably, S2 is specifically as follows: mixing 2-phenyl-1, 3-propanediol with dichloroethane solvent under nitrogen atmosphere, heating to 50-60 ℃, adding phosphorus oxychloride, heating to 80-85 ℃ and reacting for 2-3 hours; cooling to 0-2 ℃ after the reaction is finished, and adding deionized water and diethyl ether mixed solution; then heating to 40-45 ℃ for reaction for 3-4 hours, and purifying to obtain the 2-phenyl-1, 3-propanediol phosphoric anhydride.
Preferably, the molar ratio of the 2-phenyl-1, 3-propanediol, the phosphorus oxychloride to the deionized water is 1:1:0.5.
preferably, the purification specifically comprises concentration, cooling crystallization, filtration and recrystallization.
Preferably, the ring-opening reaction condition in S3 is that the temperature is 255-275 ℃, the pressure is 0.15-0.85 MPa, and the reaction time is 1.5-4 h; the polymerization reaction condition is that the temperature is 240-255 ℃, the pressure is minus 0.05-minus 0.20MPa, and the reaction time is 3-10 h.
Preferably, the graphene consumption in S3 accounts for 0.1% -1% of the total mass of the reactants in S3; the consumption of the small molecular polyamide accounts for 3% -5%; the dosage of the 2-phenyl-1, 3-propylene glycol phosphoric anhydride accounts for 0.5 to 1.2 percent.
Preferably, the solvent in S3 is xylene; the auxiliary agent consists of one or more of an antioxidant, an anti-aging agent, a heat stabilizer, an antistatic agent and the like.
Preferably, the mixing mode in the step S3 adopts a high-shear ultrasonic coupling technology, the ultrasonic power is 1-20kW, the shear rate is 4500-20000rpm, the dispersing time is 2-24h, and the dispersing temperature is 60-90 ℃.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, ethylenediamine is not only used as a reaction substrate of polyamide 6, but also is a reaction raw material for synthesizing the flame retardant, 2-phenyl-1, 3-propanediol phosphoric anhydride is used for reacting with ethylenediamine to generate the flame retardant, and the flame retardant is generated during polymerization, so that the dispersibility of the flame retardant in the polyamide 6 material is improved, and the 2-phenyl-1, 3-propanediol phosphoric anhydride can be used as a blocking agent to participate in the polymerization reaction, so that the compatibility of the flame retardant and a polymer matrix is better, the stability of the flame retardant in the polyamide 6 is improved, and the migration condition of the flame retardant is reduced. And by adding the small molecular polyamide, the uniformity of the polyamide 6 composite material chain segment is improved, and the strength performance of the composite material is improved.
Detailed Description
The invention is further described below in connection with specific embodiments.
In the invention, graphene is graphene oxide, and the graphene oxide in the following embodiment is purchased from the science and technology Co., ltd, of sixth element material, and is model SE2430W-N.
Example 1
Under the protection of high-purity nitrogen, 50g of ethylenediamine and an acid binding agent pyridine are firstly dissolved in a good solvent (N-methylpyrrolidone-calcium chloride system), the temperature of the system is controlled to be 5 ℃, then 150g of terephthaloyl chloride is added into a reaction system in a dropwise manner for reaction for 2 hours, and after the reaction is finished, the reaction solution is subjected to precipitation, extraction and drying to obtain 154g of small molecular aromatic polyamide powder.
0.20mol of 2-phenyl-1, 3-propanediol was added to 200mL of dichloroethane, nitrogen was introduced and the temperature was raised to 60℃with stirring, and 0.2mol of POCl was started to be added dropwise 3 The dropwise addition was completed for about 1.5 hours. Continuously introducing nitrogen, slowly heating to 80 ℃, and maintaining the reaction for 2.5h. After cooling the reaction liquid to 0-2 ℃ by using ice bath, slowly dropwise adding a mixed liquid of 0.10mol of deionized water and 5mL of diethyl ether, removing the ice bath after the dropwise adding is completed for about 0.5h, and gradually heating the reaction liquid to 40 ℃ for reaction for 4h. Concentrating the reaction solution, removing the solvent, naturally cooling, crystallizing, and recrystallizing the filtered crude product with dichloromethane to obtain 24.32g of colorless flaky crystals, namely 2-phenyl-1, 3-propanediol phosphoric anhydride.
7.5 g of graphene, 60g of small molecular polyamide, 15 g of 2-phenyl-1, 3-propanediol phosphoric anhydride, 270 g of ethylenediamine, 500 g of terephthalic acid, 530 g of caprolactam, 5g of benzoic acid, 100 g of xylene and 5g of antioxidant are mixed, and dispersed by a high-shear ultrasonic coupling technology, wherein the ultrasonic power is 20kW, the shear rate is 4500rpm, the dispersing time is 24 hours, and the dispersing temperature is 60 ℃. After the dispersion is completed, adding the mixture into a polymerization reaction kettle, controlling the ring-opening reaction condition to be 265 ℃ and the pressure to be 0.60MPa, and reacting for 3 hours; the polymerization reaction condition is that the temperature is 250 ℃, the pressure is-0.10 MPa, and the equilibrium reaction time is 7 hours, thus obtaining the polyamide 6 composite material.
Example 2
Under the protection of high-purity nitrogen, 50g of ethylenediamine and an acid binding agent pyridine are firstly dissolved in a good solvent (N-methylpyrrolidone-calcium chloride system), the temperature of the system is controlled to be 0 ℃, then 130g of terephthaloyl chloride is added into a reaction system in a dropwise manner for reaction for 1.8 hours, and after the reaction is finished, the reaction solution is subjected to precipitation, extraction and drying to obtain 135g of small-molecule aromatic polyamide powder.
0.20mol of 2-phenyl-1, 3-propanediol was added to 200mL of dichloroethane, nitrogen was introduced and the temperature was raised to 55℃with stirring, and 0.2mol of POCl was started to be added dropwise 3 The dropwise addition was completed for about 1.5 hours. Continuously introducing nitrogen, slowly heating to 85 ℃, and maintaining the reaction for 3h. After cooling the reaction liquid to 0-2 ℃ by using ice bath, slowly dropwise adding a mixed liquid of 0.10mol of deionized water and 5mL of diethyl ether, removing the ice bath after the dropwise adding is completed for about 0.5h, and gradually heating the reaction liquid to 45 ℃ for reaction for 3h. Concentrating the reaction solution, removing the solvent, naturally cooling, crystallizing, and recrystallizing the filtered crude product with dichloromethane to obtain 24.32g of colorless flaky crystals, namely 2-phenyl-1, 3-propanediol phosphoric anhydride.
1.5 g of graphene, 45 g of small molecular polyamide, 7.5 g of 2-phenyl-1, 3-propanediol phosphoric anhydride, 270 g of ethylenediamine, 500 g of terephthalic acid, 530 g of caprolactam, 5g of benzoic acid, 100 g of xylene and 5g of antioxidant are mixed, and dispersed by a high-shear ultrasonic coupling technology, wherein the ultrasonic power is 10kW, the shearing rate is 10000rpm, the dispersing time is 12 hours, and the dispersing temperature is 90 ℃. After the dispersion is completed, adding the mixture into a polymerization reaction kettle, and controlling the ring-opening reaction condition to be at the temperature of 275 ℃ and the pressure of 0.85MPa, wherein the reaction time is 1.5h; the polymerization reaction condition is that the temperature is 255 ℃, the pressure is-0.20 MPa, and the equilibrium reaction time is 3 hours, thus obtaining the polyamide 6 composite material.
Example 3
Under the protection of high-purity nitrogen, 50g of ethylenediamine and an acid binding agent pyridine are firstly dissolved in a good solvent (N-methylpyrrolidone-calcium chloride system), the temperature of the system is controlled to be 10 ℃, then 160g of terephthaloyl chloride is added into a reaction system in a dropwise manner for reaction for 1.5 hours, and after the reaction is finished, 160g of small-molecule aromatic polyamide powder is obtained after the reaction solution is subjected to precipitation, extraction and drying.
0.20mol of 2-phenyl-1, 3-propanediol was added to 200mL of dichloroethane, nitrogen was introduced and the temperature was raised to 50℃with stirring, and 0.2mol of POCl was started to be added dropwise 3 The dropwise addition was completed for about 1.5 hours. Continuously introducing nitrogen and slowly heating to 83 DEG CThe reaction was maintained for 2h. After cooling the reaction liquid to 0-2 ℃ by using ice bath, slowly dropwise adding a mixed liquid of 0.10mol of deionized water and 5mL of diethyl ether, removing the ice bath after the dropwise adding is completed for about 0.5h, and gradually heating the reaction liquid to 42 ℃ for reaction for 3.5h. Concentrating the reaction solution, removing the solvent, naturally cooling, crystallizing, and recrystallizing the filtered crude product with dichloromethane to obtain 24.32g of colorless flaky crystals, namely 2-phenyl-1, 3-propanediol phosphoric anhydride.
15 g of graphene, 75 g of small molecular polyamide, 18 g of 2-phenyl-1, 3-propanediol phosphoric anhydride, 270 g of ethylenediamine, 500 g of terephthalic acid, 530 g of caprolactam, 5g of benzoic acid, 100 g of xylene and 5g of antioxidant are mixed, dispersed by a high shear ultrasonic coupling technology, the ultrasonic power is 1kW, the shear rate is 20000rpm, the dispersion time is 2 hours, and the dispersion temperature is 70 ℃. After the dispersion is completed, adding the mixture into a polymerization reaction kettle, controlling the ring-opening reaction condition to be 255 ℃, and controlling the pressure to be 0.15MPa, wherein the reaction time is 4 hours; the polymerization reaction condition is that the temperature is 240 ℃, the pressure is-0.05 MPa, and the equilibrium reaction time is 10 hours, thus obtaining the polyamide 6 composite material.
Comparative example 1
0.20mol of 2-phenyl-1, 3-propanediol was added to 200mL of dichloroethane, nitrogen was introduced and the temperature was raised to 60℃with stirring, and 0.2mol of POCl was started to be added dropwise 3 The dropwise addition was completed for about 1.5 hours. Continuously introducing nitrogen, slowly heating to 80 ℃, and maintaining the reaction for 2.5h. After cooling the reaction liquid to 0-2 ℃ by using ice bath, slowly dropwise adding a mixed liquid of 0.10mol of deionized water and 5mL of diethyl ether, removing the ice bath after the dropwise adding is completed for about 0.5h, and gradually heating the reaction liquid to 40 ℃ for reaction for 4h. Concentrating the reaction solution, removing the solvent, naturally cooling, crystallizing, and recrystallizing the filtered crude product with dichloromethane to obtain 24.32g of colorless flaky crystals, namely 2-phenyl-1, 3-propanediol phosphoric anhydride.
7.5 g of graphene, 15 g of 2-phenyl-1, 3-propanediol phosphoric anhydride, 270 g of ethylenediamine, 500 g of terephthalic acid, 530 g of caprolactam, 5g of benzoic acid, 100 g of xylene and 5g of antioxidant are mixed, dispersed by a high shear ultrasonic coupling technology, the ultrasonic power is 20kW, the shear rate is 4500rpm, the dispersion time is 24h, and the dispersion temperature is 60 ℃. After the dispersion is completed, adding the mixture into a polymerization reaction kettle, controlling the ring-opening reaction condition to be 265 ℃ and the pressure to be 0.60MPa, and reacting for 3 hours; the polymerization reaction condition is that the temperature is 250 ℃, the pressure is-0.10 MPa, and the equilibrium reaction time is 7 hours, thus obtaining the polyamide 6 composite material.
Comparative example 2
Under the protection of high-purity nitrogen, 50g of ethylenediamine and an acid binding agent pyridine are firstly dissolved in a good solvent (N-methylpyrrolidone-calcium chloride system), the temperature of the system is controlled to be 5 ℃, then 150g of terephthaloyl chloride is added into a reaction system in a dropwise manner for reaction for 2 hours, and after the reaction is finished, the reaction solution is subjected to precipitation, extraction and drying to obtain 154g of small molecular aromatic polyamide powder.
7.5 g of graphene, 60g of small molecular polyamide, 270 g of ethylenediamine, 500 g of terephthalic acid, 530 g of caprolactam, 5g of benzoic acid, 100 g of xylene and 5g of antioxidant are mixed, and dispersed by a high-shear ultrasonic coupling technology, wherein the ultrasonic power is 20kW, the shear rate is 4500rpm, the dispersion time is 24 hours, and the dispersion temperature is 60 ℃. After the dispersion is completed, adding the mixture into a polymerization reaction kettle, controlling the ring-opening reaction condition to be 265 ℃ and the pressure to be 0.60MPa, and reacting for 3 hours; the polymerization reaction condition is that the temperature is 250 ℃, the pressure is-0.10 MPa, and the equilibrium reaction time is 7 hours, thus obtaining the polyamide 6 composite material.
The polyamide 6 composites obtained in examples 1-3 and comparative examples 1, 2 were subjected to limiting oxygen index, melting point and strength performance tests, the test results being shown in Table 1; limiting oxygen index test is referred to GB/T2406.2-2009.
TABLE 1 Polyamide 6 composite Performance test results
As can be seen from the data in Table 1, the flame retardant properties and the strength properties of the polyamide 6 material obtained in comparative example 1 were lower than those of the polyamide 6 material obtained in examples 1 to 3, and the flame retardant properties and the strength properties of the polyamide 6 material obtained in comparative example 2 were also inferior to those of the polyamide 6 material obtained in examples 1 to 3. The method shows that the effect on the performance improvement of the polyamide 6 material is small by simply adding small molecular polyamide or simply through the copolymerization reaction of the flame retardant and the polyamide, and the synergistic effect of the small molecular polyamide and the polyamide leads the polyamide 6 material to have excellent flame retardant property and good strength property.
The above detailed description is illustrative of the present application and is not intended to be limiting, since modifications may be made to the embodiments by those skilled in the art without the inventive contribution from the reader's specification, as long as they are within the scope of the claims of the present application.
Claims (10)
1. A preparation method of a flame-retardant graphene polyamide 6 composite material is characterized by comprising the following steps of: the method comprises the following steps:
s1: mixing ethylenediamine and binary acyl chloride for reaction to generate small molecular polyamide;
s2: 2-phenyl-1, 3-propanediol reacts with phosphorus oxychloride and then is hydrolyzed to obtain 2-phenyl-1, 3-propanediol phosphoric anhydride;
s3: mixing graphene, small molecular polyamide, 2-phenyl-1, 3-propylene glycol phosphoric anhydride, ethylenediamine, oxalic acid and caprolactam, adding an auxiliary agent and a solvent, performing ring opening polymerization reaction, and simultaneously performing substitution reaction of the 2-phenyl-1, 3-propylene glycol phosphoric anhydride and ethylenediamine to obtain the flame-retardant graphene polyamide 6 composite material.
2. The method for preparing the flame-retardant graphene polyamide 6 composite material according to claim 1, which is characterized in that: s1 specifically comprises the following steps: dissolving ethylenediamine and an acid binding agent in a good solvent under the atmosphere of nitrogen, adding binary acyl chloride at 0-10 ℃ for reaction for 1-2h, and obtaining micromolecular aromatic polyamide through precipitation, extraction and drying after the reaction is finished; the mol ratio of the ethylenediamine to the dibasic acyl chloride is (1.05-1.3): 1.
3. the method for preparing the flame-retardant graphene polyamide 6 composite material according to claim 2, which is characterized in that: the good solvent is an amide solvent-salt system, wherein the amide solvent is N-methylpyrrolidone or dimethylacetamide, and the salt is lithium chloride or calcium chloride; the acid binding agent is pyridine or 2-methylpyridine.
4. The method for preparing the flame-retardant graphene polyamide 6 composite material according to claim 1, which is characterized in that: s2 is specifically as follows: mixing 2-phenyl-1, 3-propanediol with dichloroethane solvent under nitrogen atmosphere, heating to 50-60 ℃, adding phosphorus oxychloride, heating to 80-85 ℃ and reacting for 2-3 hours; cooling to 0-2 ℃ after the reaction is finished, and adding deionized water and diethyl ether mixed solution; then heating to 40-45 ℃ for reaction for 3-4 hours, and purifying to obtain the 2-phenyl-1, 3-propanediol phosphoric anhydride.
5. The method for preparing the flame-retardant graphene polyamide 6 composite material according to claim 4, which is characterized in that: the molar ratio of the 2-phenyl-1, 3-propanediol to the phosphorus oxychloride to the deionized water is 1:1:0.5.
6. the method for preparing the flame-retardant graphene polyamide 6 composite material according to claim 4, which is characterized in that: the purification comprises concentration, cooling crystallization, filtration and recrystallization.
7. The method for preparing the flame-retardant graphene polyamide 6 composite material according to claim 1, which is characterized in that: the ring-opening reaction condition in S3 is that the temperature is 255-275 ℃, the pressure is 0.15-0.85 MPa, and the reaction time is 1.5-4 h; the polymerization reaction condition is that the temperature is 240-255 ℃, the pressure is minus 0.05-minus 0.20MPa, and the reaction time is 3-10 h.
8. The method for preparing the flame-retardant graphene polyamide 6 composite material according to claim 1, which is characterized in that: the graphene consumption in the S3 accounts for 0.1% -1% of the total mass of the reactants in the S3; the consumption of the small molecular polyamide accounts for 3% -5%; the dosage of the 2-phenyl-1, 3-propylene glycol phosphoric anhydride accounts for 0.5 to 1.2 percent.
9. The method for preparing the flame-retardant graphene polyamide 6 composite material according to claim 1, which is characterized in that: the solvent in S3 is dimethylbenzene; the auxiliary agent consists of one or more of an antioxidant, an anti-aging agent, a heat stabilizer, an antistatic agent and the like.
10. The method for preparing the flame-retardant graphene polyamide 6 composite material according to claim 1, which is characterized in that: the mixing mode in the step S3 adopts a high-shear ultrasonic coupling technology, the ultrasonic power is 1-20kW, the shear rate is 4500-20000rpm, the dispersing time is 2-24h, and the dispersing temperature is 60-90 ℃.
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