CN112851958A - Graphene in-situ polymerization semi-aromatic polyamide and preparation method thereof - Google Patents
Graphene in-situ polymerization semi-aromatic polyamide and preparation method thereof Download PDFInfo
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- CN112851958A CN112851958A CN202011629738.6A CN202011629738A CN112851958A CN 112851958 A CN112851958 A CN 112851958A CN 202011629738 A CN202011629738 A CN 202011629738A CN 112851958 A CN112851958 A CN 112851958A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 57
- 229920006012 semi-aromatic polyamide Polymers 0.000 title claims abstract description 34
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 28
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000004760 aramid Substances 0.000 claims abstract description 24
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 24
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000004985 diamines Chemical class 0.000 claims abstract description 17
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 12
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 3
- 239000006185 dispersion Substances 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 6
- -1 aliphatic diamine Chemical class 0.000 claims description 6
- 150000004984 aromatic diamines Chemical class 0.000 claims description 6
- 238000010168 coupling process Methods 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 150000003384 small molecules Chemical class 0.000 claims description 5
- 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
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical group ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical group NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 3
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- YFOOEYJGMMJJLS-UHFFFAOYSA-N 1,8-diaminonaphthalene Chemical compound C1=CC(N)=C2C(N)=CC=CC2=C1 YFOOEYJGMMJJLS-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 125000003916 ethylene diamine group Chemical group 0.000 claims description 2
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 2
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 abstract description 5
- 229920002647 polyamide Polymers 0.000 abstract description 5
- 239000000463 material Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 229920001778 nylon Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000004677 Nylon Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 230000008878 coupling Effects 0.000 description 5
- 238000005859 coupling reaction Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- OYNOCRWQLLIRON-UHFFFAOYSA-N 1-n,3-n-bis(2,2,6,6-tetramethylpiperidin-4-yl)benzene-1,3-dicarboxamide Chemical compound C1C(C)(C)NC(C)(C)CC1NC(=O)C1=CC=CC(C(=O)NC2CC(C)(C)NC(C)(C)C2)=C1 OYNOCRWQLLIRON-UHFFFAOYSA-N 0.000 description 4
- 239000005711 Benzoic acid Substances 0.000 description 4
- 235000010233 benzoic acid Nutrition 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000010345 tape casting Methods 0.000 description 4
- 238000003809 water extraction Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 229920003231 aliphatic polyamide Polymers 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 239000003733 fiber-reinforced composite Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 230000005355 Hall effect Effects 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- OLRHRIPRMRRHJI-UHFFFAOYSA-L calcium N,N-dimethylacetamide dichloride Chemical compound [Cl-].[Ca+2].CC(=O)N(C)C.[Cl-] OLRHRIPRMRRHJI-UHFFFAOYSA-L 0.000 description 1
- HIKUCVORZZXYNF-UHFFFAOYSA-L calcium;1-methylpyrrolidin-2-one;dichloride Chemical compound Cl[Ca]Cl.CN1CCCC1=O HIKUCVORZZXYNF-UHFFFAOYSA-L 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 229920006039 crystalline polyamide Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- HCOAPXXZSLSJCN-UHFFFAOYSA-M lithium;1-methylpyrrolidin-2-one;chloride Chemical compound [Li+].[Cl-].CN1CCCC1=O HCOAPXXZSLSJCN-UHFFFAOYSA-M 0.000 description 1
- YPJJABHAGGFGAM-UHFFFAOYSA-M lithium;n,n-dimethylacetamide;chloride Chemical compound [Li+].[Cl-].CN(C)C(C)=O YPJJABHAGGFGAM-UHFFFAOYSA-M 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
Images
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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/96—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from other synthetic polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2387/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
Abstract
The invention discloses graphene in-situ polymerization semi-aromatic polyamide and a preparation method thereof, and belongs to the technical field of graphene modified polyamide. The preparation method of the modified semi-aromatic polyamide comprises the steps of firstly, reacting binary acyl chloride with diamine to generate micromolecular aromatic polyamide; then putting the graphene, the small-molecular aromatic polyamide, caprolactam and the auxiliary agent into a reaction kettle, carrying out ring opening/polycondensation balance reaction, and carrying out post-treatment on a product to obtain the graphene in-situ polymerized semi-aromatic polyamide. Compared with the strength of common polyamide products, the rigidity and the strength of the product have obvious advantages, and the heat resistance is obviously improved.
Description
Technical Field
The invention belongs to the technical field of graphene modified polyamide, and particularly relates to graphene in-situ polymerized semi-aromatic polyamide and a preparation method thereof.
Background
The graphene is formed by the SP of carbon atoms2The planar two-dimensional structural material is hexagonal honeycomb-shaped and composed of hybrid tracks. In 2004, Novoselov and geom first discovered graphene materials using micromechanical lift-off methods, which are the thinnest materials known to date, with a thickness of about one carbon atom (0.34 nm). The discovery of graphene enriches the types of carbon materials: one-dimensional carbon nanotubes, two-dimensional graphene, and three-dimensional graphite, diamond, and the like.
The main properties of graphene include: the specific surface area is high and can reach 2600m2(ii)/g; the hardness is high, the Young modulus exceeds 1000GPa, and the material is the currently known hardest material; the thermal conductivity is high and can reach 5000W/mK; the charge transfer speed is high and can reach 2.5 multiplied by 105cm-2Vs, and also has some unique properties such as perfect quantum tunneling, half-integer quantum hall effect. Due to the excellent properties, graphene is widely researched and applied in the fields of electronic instruments, biomedical treatment, energy sources and the like.
Polyamide, also called nylon, is a generic name for polymers containing amide groups in the repeating units of the main chain of macromolecules. Currently, nylon which is produced and used in large quantities is mainly aliphatic nylon, and generally, aliphatic nylon has advantages of fast crystallization speed, high crystallinity, good flexibility and high mechanical strength, which makes crystalline polyamides represented by nylon 6, nylon 66, nylon 1010 and nylon 1212 have been widely used as fibers and general engineering plastics. However, these nylons generally have a use temperature of not more than 80 ℃ and, when the environmental humidity is high, they also undergo a large change in volume due to water absorption and a decrease in mechanical properties, so that they have been limited in applications in fields requiring high heat resistance and dimensional stability, such as electronic component surface mounting techniques developed in recent years and automobile engine room components requiring good heat resistance. Therefore, the market is still demanding to develop nylon materials with good heat resistance, good dimensional stability and mechanical properties.
Chinese patent 2011101452375 published 12-5-2012 discloses a semi-aromatic polyamide short fiber reinforced composite material and a preparation method thereof. The composite material disclosed by the invention comprises the following components in percentage by weight: 60-90% of resin and 10-40% of semi-aromatic polyamide short fiber. The preparation method of the composite material disclosed by the invention comprises the following steps of: premixing 60-90% of dry resin and 10-40% of semi-aromatic polyamide short fiber in a high-speed mixer with the rotation speed of 500-2000rpm for 2-10min, melting the premix through a screw extruder, extruding, cooling in a water bath, and granulating to obtain the semi-aromatic polyamide short fiber reinforced composite material. However, the semi-aromatic polyamide staple fiber of the patent technology has a large amount of addition and a high cost, and is not suitable for practical use.
Disclosure of Invention
In view of the above problems in the prior art, the present invention aims to provide an in-situ polymerized graphene semi-aromatic polyamide material, which can significantly improve the product performance when a small amount of semi-aromatic polyamide is added. The invention also aims to provide a preparation method of the composite material.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
an in-situ polymerized graphene semi-aromatic polyamide with a structural formula as follows:
wherein-NH-Graphene-NH-is amino functionalized Graphene;
R1、R2、R3is a substituent;
R1or R2Contains aryl and methylene.
A preparation method of graphene in-situ polymerized semi-aromatic polyamide comprises the steps of firstly reacting binary acyl chloride with diamine to generate micromolecular aromatic polyamide; then putting the graphene, the small-molecular aromatic polyamide, caprolactam and the auxiliary agent into a reaction kettle, carrying out ring opening and polycondensation balance reaction, and carrying out post-treatment on a product to obtain the graphene in-situ polymerized semi-aromatic polyamide.
Further, the specific method for generating the micromolecular aromatic polyamide by reacting the diacid chloride with the diamine comprises the following steps: under the protection of protective gas, firstly dissolving diamine and an acid-binding agent in a good solvent, ensuring the temperature of the system to be-10 ℃, then adding binary acyl chloride into the reaction system for reaction for 0.5-5h, and after the reaction is finished, settling out, extracting and drying to obtain small-molecule aromatic polyamide powder; the selected diacid chloride or diamine contains aryl and methylene.
Further, the molar ratio of diamine to diacid chloride is (1.05-1.5): 1.
further, the diamine is aliphatic diamine or aromatic diamine, the aliphatic diamine is ethylenediamine, pentanediamine or hexanediamine, and the aromatic diamine is p-phenylenediamine or 1, 8-diaminonaphthalene; the binary acyl chloride is aliphatic or aromatic binary acyl chloride, the aliphatic binary acyl chloride is 1, 7-pimeloyl dichloride, and the aromatic binary acyl chloride is terephthaloyl chloride or isophthaloyl dichloride; when the diamine is aliphatic diamine, the diacid chloride is aromatic diacid chloride, and when the diamine is aromatic diamine, the diacid chloride is aliphatic diacid chloride.
Further, 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.
Further, the using amount of the graphene is 0.1-5% of the total mass of the reactants, and is preferably 0.1-1%; the dosage of the small molecular aromatic polyamide is 0.01-10 percent of the total mass of reactants, and the optimal dosage is 1-5 percent.
Further, before the reactants are put into the reaction kettle, the graphene is dispersed in a mixed system of the small molecular aromatic polyamide, the caprolactam and the reaction auxiliary agent, the dispersion mode is a high-shear ultrasonic coupling technology, the ultrasonic power is 1-20kW, the shear rate is 4500-20000rpm, the dispersion time is 2-24h, and the dispersion temperature is 60-90 ℃.
Further, the ring-opening reaction conditions are 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 conditions are that the temperature is 240-255 ℃, the pressure is-0.05-0.20 MPa, and the reaction time is 3-10 h.
Further, the graphene is amino-functionalized graphene.
Compared with the prior art, the invention has the beneficial effects that: due to the addition of the micromolecular aromatic polyamide and the graphene, the rigidity and the strength of the graphene in-situ polymerized semi-aromatic polyamide product have obvious advantages compared with the strength of a common polyamide product, and the heat resistance is obviously improved.
The reaction involved in the invention is an in-situ polymerization reaction, so the addition amount of the graphene and the micromolecular aromatic polyamide is small, but the performance of the obtained product is obviously improved, and the obtained graphene in-situ polymerization semi-aromatic polyamide can be widely applied to various fields of engineering plastics, fibers, films and the like.
Drawings
FIG. 1 is a thermogravimetric analyzer TG curve of the section obtained in example 3.
Detailed Description
The invention is further described with reference to specific examples.
The graphene used in the following examples is amino-functional graphene prepared by the method described in example 1 in chinese patent 201810212266.0.
The rest raw materials are commercial industrial grade.
Example 1
Under the protection of high-purity nitrogen, firstly, dissolving 20.92g of hexamethylenediamine and 15g of acid-binding agent pyridine in 150mL of good solvent (N-methylpyrrolidone-lithium chloride system), controlling the system temperature to be-5 ℃, then adding 30.45g of isophthaloyl dichloride into the reaction system in a dropwise manner for reaction for 3h, after the reaction is finished, precipitating and extracting the reaction solution, removing unreacted substances and impurities, and drying to obtain 35g of micromolecule aromatic polyamide powder.
Dispersing 2g of graphene in a mixed system of 35g of small-molecular aromatic polyamide, 1000g of caprolactam, 1g of N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, 1g of benzoic acid and 15g of water, wherein the dispersion mode is a high-shear ultrasonic coupling technology, the ultrasonic power is 15kW, the shear rate is 8000rpm, the dispersion time is 4 hours, and the dispersion temperature is controlled at 80 ℃.
Putting the dispersed mixed system into a polymerization reaction kettle, and controlling the ring-opening reaction condition to be 260 ℃, the pressure to be 0.15-0.85 MPa and the reaction time to be 3 hours; and (3) carrying out polymerization reaction at the temperature of 245 ℃ and under the pressure of-0.05 to-0.20 MPa for 5 hours in an equilibrium reaction, and carrying out tape casting, cooling, granulating, water extraction and drying to obtain the semi-aromatic polyamide slice in which the graphene is polymerized in situ.
Example 2
Under the protection of high-purity nitrogen, 59.62g of p-phenylenediamine and 25g of acid-binding agent 2-methylpyridine are dissolved in 250mL of good solvent (dimethylacetamide-lithium chloride system), the temperature of the system is controlled to be 0 ℃, 98.53g of 1, 7-pimeloyl chloride is added into the reaction system in a dropwise manner for reaction for 4 hours, and the reaction solution is precipitated and extracted to remove unreacted substances and impurities, and then dried to obtain 120g of micromolecular aromatic polyamide powder.
Dispersing 6g of graphene in a mixed system of 100g of small-molecular aromatic polyamide, 2980g of caprolactam, 3g of N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, 3g of benzoic acid and 300g of water, wherein the dispersion mode is a high-shear ultrasonic coupling technology, the ultrasonic power is 10kW, the shear rate is 14000rpm, the dispersion time is 6h, and the dispersion temperature is controlled at 75 ℃.
Putting the dispersed mixed system into a polymerization reaction kettle, and controlling the ring-opening reaction condition to be 265 ℃, the pressure to be 0.15-0.85 MPa and the reaction time to be 3.5 h; the polymerization reaction conditions are that the temperature is 250 ℃, the pressure is-0.05 to-0.20 MPa, the equilibrium reaction time is 8 hours, and then semi-aromatic polyamide chips polymerized in situ by graphene are obtained after tape casting, cooling, grain cutting, water extraction and drying.
Example 3
Under the protection of high-purity nitrogen, 27.18g of pentamethylene diamine and acid-binding agent pyridine are dissolved in a good solvent (dimethylacetamide-calcium chloride system), the temperature of the system is controlled to be 5 ℃, 45g of terephthaloyl chloride is added into the reaction system in a dropwise adding mode for reaction for 3 hours, and after the reaction is finished, reaction liquid is poured into the reaction system and is subjected to precipitation, extraction and drying to obtain 50g of small-molecule aromatic polyamide powder.
Dispersing 2g of graphene in a mixed system of 45g of small-molecular aromatic polyamide, 200g of caprolactam, 0.2g of N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, 0.2g of benzoic acid and 10g of water, wherein the dispersion mode is a high-shear ultrasonic coupling technology, the ultrasonic power is 15kW, the shear rate is 6000rpm, the dispersion time is 6h, and the dispersion temperature is controlled at 80 ℃.
Putting the dispersed mixed system into a polymerization reaction kettle, and controlling the ring-opening reaction condition to be 255 ℃, the pressure to be 0.15-0.85 MPa and the reaction time to be 4 hours; and (3) carrying out polymerization reaction at the temperature of 255 ℃ and under the pressure of-0.05 to-0.20 MPa for 3 hours in an equilibrium reaction, and carrying out tape casting, cooling, granulating, water extraction and drying to obtain the semi-aromatic polyamide slice in which the graphene is polymerized in situ.
Example 4
Under the protection of high-purity nitrogen, 50g of ethylenediamine and acid-binding agent pyridine are dissolved in a good solvent (N-methylpyrrolidone-calcium chloride system), the temperature of the system is controlled to be-10 ℃, 112.6g of terephthaloyl chloride is added into the reaction system in a dropwise adding mode for reaction, the reaction time is 5 hours, and after the reaction is finished, reaction liquid is poured into the reaction system and is subjected to precipitation, extraction and drying to obtain 130g of small-molecule aromatic polyamide powder.
Dispersing 24g of graphene in a mixed system of 120g of small-molecule aromatic polyamide, 2252g of caprolactam, 2g of N, N' -bis (2,2,6, 6-tetramethyl-4-piperidyl) -1, 3-benzenedicarboxamide, 2g of benzoic acid and 150g of water, wherein the dispersion mode is 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 controlled at 60 ℃.
Putting the dispersed mixed system into a polymerization reaction kettle, and controlling the ring-opening reaction condition to be 275 ℃, the pressure to be 0.15-0.85 MPa and the reaction time to be 1.5 h; and (3) carrying out polymerization reaction at the temperature of 240 ℃, under the pressure of-0.05 to-0.20 MPa, carrying out equilibrium reaction for 10 hours, and carrying out tape casting, cooling, granulating, water extraction and drying to obtain the semi-aromatic polyamide slice in which the graphene is polymerized in situ.
And (4) performing injection molding on the obtained slices by using a vertical injection molding machine to obtain standard sample strips, and performing mechanical property characterization. The thermal properties of the material were characterized by a thermogravimetric analyzer TGA. And spinning the obtained slices into fibers with the specification of drawing yarns FDY70D/24f by using a melt spinning process, and performing mechanical property characterization and function detection.
TABLE 1 test results
As can be seen from Table 1, the graphene in-situ polymerized semi-aromatic polyamide prepared by the method disclosed by the invention has excellent performance, good mechanical properties, high strength and strong rigidity, and has antibacterial and far infrared properties.
FIG. 1 is a TGA curve of the thermogravimetric analyzer of the section of example 3, wherein TG and DTG curves correspond to the sample obtained in example 3, and it can be seen from the graph that the maximum weight loss temperature is 442.8 ℃, the weight loss rate is 15.11%, the residual mass at 800 ℃ is 1.14%, and the thermal stability of the material is good.
Claims (10)
1. The graphene in-situ polymerized semi-aromatic polyamide is characterized in that the structural formula is as follows:
wherein-NH-graphene NH is amino-functionalized graphene;
R1、R2、R3is a substituent;
R1or R2Contains aryl and methylene.
2. The preparation method of the graphene in-situ polymerized semi-aromatic polyamide as claimed in claim 1, characterized by firstly reacting diacid chloride with diamine to generate small-molecule aromatic polyamide; then putting the graphene, the small-molecular aromatic polyamide, caprolactam and the auxiliary agent into a reaction kettle, carrying out ring opening and polycondensation balance reaction, and carrying out post-treatment on a product to obtain the graphene in-situ polymerized semi-aromatic polyamide.
3. The method for preparing the graphene in-situ polymerized semi-aromatic polyamide as claimed in claim 2, wherein the specific method for reacting diacid chloride with diamine to generate the micromolecular aromatic polyamide comprises the following steps: under the protection of protective gas, firstly dissolving diamine and an acid-binding agent in a good solvent, ensuring the temperature of the system to be-10 ℃, then adding binary acyl chloride into the reaction system for reaction for 0.5-5h, and after the reaction is finished, carrying out precipitation, extraction and drying to obtain micromolecule aromatic polyamide; the selected diacid chloride or diamine contains aryl and methylene.
4. The method for preparing the graphene in-situ polymerized semi-aromatic polyamide as claimed in claim 2 or 3, wherein the molar ratio of diamine to diacid chloride is (1.05-1.5): 1.
5. the method for preparing graphene in-situ polymerized semi-aromatic polyamide according to claim 2 or 3, wherein the diamine is aliphatic or aromatic diamine, the aliphatic diamine is ethylenediamine, pentanediamine or hexanediamine, and the aromatic diamine is p-phenylenediamine or 1, 8-diaminonaphthalene; the binary acyl chloride is aliphatic or aromatic binary acyl chloride, the aliphatic binary acyl chloride is 1, 7-pimeloyl dichloride, and the aromatic binary acyl chloride is terephthaloyl chloride or isophthaloyl dichloride; when the diamine is aliphatic diamine, the diacid chloride is aromatic diacid chloride, and when the diamine is aromatic diamine, the diacid chloride is aliphatic diacid chloride.
6. The method for preparing graphene in-situ polymerized semi-aromatic polyamide according to claim 3, wherein 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.
7. The preparation method of the graphene in-situ polymerized semi-aromatic polyamide as claimed in claim 2, characterized in that the amount of graphene is 0.1% -5%, preferably 0.1% -1% of the total mass of reactants; the dosage of the small molecular aromatic polyamide is 0.01-10 percent of the total mass of reactants, and the optimal dosage is 1-5 percent.
8. The method for preparing the graphene in-situ polymerized semi-aromatic polyamide as claimed in claim 2, wherein the graphene is dispersed in the mixed system of the small molecular aromatic polyamide, the caprolactam and the reaction auxiliary agent before the reactants are put into the reaction kettle, the dispersion method is a high shear ultrasonic coupling technique, the ultrasonic power is 1-20kW, the shear rate is 4500-20000rpm, the dispersion time is 2-24h, and the dispersion temperature is 60-90 ℃.
9. The preparation method of the graphene in-situ polymerized semi-aromatic polyamide as claimed in claim 2, characterized in that the ring-opening reaction conditions are 255-275 ℃, 0.15-0.85 MPa, and the reaction time is 1.5-4 h; the polymerization reaction conditions are that the temperature is 240-255 ℃, the pressure is-0.05-0.20 MPa, and the reaction time is 3-10 h.
10. The method for preparing graphene in-situ polymerized semi-aromatic polyamide according to claim 2, wherein the graphene is amino functionalized graphene.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110245378A1 (en) * | 2010-03-26 | 2011-10-06 | Richard Russ | Nanomaterial-reinforced resins and related materials |
| CN104371314A (en) * | 2013-08-13 | 2015-02-25 | 骏马化纤股份有限公司 | Semi-aromatic polyamide resin prepared through graphene in-situ polymerization and preparation method thereof |
| CN106498538A (en) * | 2016-11-18 | 2017-03-15 | 株洲时代新材料科技股份有限公司 | The preparation method and applications of high-termal conductivity aromatic polyamide fibre |
| CN107541805A (en) * | 2017-09-08 | 2018-01-05 | 常州恒利宝纳米新材料科技有限公司 | A kind of graphene in-situ polymerization modified polyamide 6 preoriented yarn and preparation method thereof |
| CN108727808A (en) * | 2017-04-21 | 2018-11-02 | 山东圣泉新材料股份有限公司 | - 6 agglomerate material of polyamide, the fiber and purposes comprising it of graphene modification |
| CN109096486A (en) * | 2018-08-09 | 2018-12-28 | 成都新柯力化工科技有限公司 | A kind of railroad track fastener selfreparing nylon composite materials and preparation method |
| CN109180932A (en) * | 2018-09-25 | 2019-01-11 | 江苏扬农化工集团有限公司 | It is a kind of it is poly- between phenyl-diformyl m-xylene diamine polycondensation synthetic method |
| CN110093679A (en) * | 2019-05-14 | 2019-08-06 | 东华大学 | A kind of 66/ nylon 6 fiber of graphene modification of nylon and its preparation and application |
| CN110204707A (en) * | 2019-05-28 | 2019-09-06 | 江苏江山红化纤有限责任公司 | The preparation method of graphene in-situ polymerization modified polyamide epoxy hardener |
-
2020
- 2020-12-31 CN CN202011629738.6A patent/CN112851958A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110245378A1 (en) * | 2010-03-26 | 2011-10-06 | Richard Russ | Nanomaterial-reinforced resins and related materials |
| CN104371314A (en) * | 2013-08-13 | 2015-02-25 | 骏马化纤股份有限公司 | Semi-aromatic polyamide resin prepared through graphene in-situ polymerization and preparation method thereof |
| CN106498538A (en) * | 2016-11-18 | 2017-03-15 | 株洲时代新材料科技股份有限公司 | The preparation method and applications of high-termal conductivity aromatic polyamide fibre |
| CN108727808A (en) * | 2017-04-21 | 2018-11-02 | 山东圣泉新材料股份有限公司 | - 6 agglomerate material of polyamide, the fiber and purposes comprising it of graphene modification |
| CN107541805A (en) * | 2017-09-08 | 2018-01-05 | 常州恒利宝纳米新材料科技有限公司 | A kind of graphene in-situ polymerization modified polyamide 6 preoriented yarn and preparation method thereof |
| CN109096486A (en) * | 2018-08-09 | 2018-12-28 | 成都新柯力化工科技有限公司 | A kind of railroad track fastener selfreparing nylon composite materials and preparation method |
| CN109180932A (en) * | 2018-09-25 | 2019-01-11 | 江苏扬农化工集团有限公司 | It is a kind of it is poly- between phenyl-diformyl m-xylene diamine polycondensation synthetic method |
| CN110093679A (en) * | 2019-05-14 | 2019-08-06 | 东华大学 | A kind of 66/ nylon 6 fiber of graphene modification of nylon and its preparation and application |
| CN110204707A (en) * | 2019-05-28 | 2019-09-06 | 江苏江山红化纤有限责任公司 | The preparation method of graphene in-situ polymerization modified polyamide epoxy hardener |
Non-Patent Citations (1)
| Title |
|---|
| 彭思敏: "原位法制备两种碳材料/聚酰亚胺纳米复合薄膜", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
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