CN116554463A - Preparation method of high-toughness copolyamide 6/66 - Google Patents
Preparation method of high-toughness copolyamide 6/66 Download PDFInfo
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- CN116554463A CN116554463A CN202310598585.0A CN202310598585A CN116554463A CN 116554463 A CN116554463 A CN 116554463A CN 202310598585 A CN202310598585 A CN 202310598585A CN 116554463 A CN116554463 A CN 116554463A
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- 229920000577 Nylon 6/66 Polymers 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims abstract description 52
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 50
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 45
- 229920002302 Nylon 6,6 Polymers 0.000 claims abstract description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 150000003839 salts Chemical class 0.000 claims abstract description 33
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000001361 adipic acid Substances 0.000 claims abstract description 25
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 23
- 239000003381 stabilizer Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000005266 casting Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 229920001577 copolymer Polymers 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 18
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 12
- 229920002292 Nylon 6 Polymers 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 230000001681 protective effect Effects 0.000 claims description 10
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 9
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 9
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 9
- 239000005711 Benzoic acid Substances 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 235000010233 benzoic acid Nutrition 0.000 claims description 6
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 6
- 238000007792 addition Methods 0.000 claims description 4
- 239000013522 chelant Substances 0.000 claims description 4
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 claims description 3
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 3
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229960002684 aminocaproic acid Drugs 0.000 claims description 3
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 3
- 229940076286 cupric acetate Drugs 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 3
- FLFJVPPJGJSHMF-UHFFFAOYSA-L manganese hypophosphite Chemical compound [Mn+2].[O-]P=O.[O-]P=O FLFJVPPJGJSHMF-UHFFFAOYSA-L 0.000 claims description 3
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 229910001380 potassium hypophosphite Inorganic materials 0.000 claims description 3
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 claims description 3
- 239000011241 protective layer Substances 0.000 claims description 3
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 claims description 3
- 239000005749 Copper compound Substances 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 claims description 2
- 150000001880 copper compounds Chemical class 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- -1 halide modified copper Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 9
- 238000006386 neutralization reaction Methods 0.000 description 7
- 230000010355 oscillation Effects 0.000 description 7
- 239000004952 Polyamide Substances 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZKXBDPZAQUNPOY-UHFFFAOYSA-N 1-azaniumylhexylazanium;hexanedioate Chemical compound CCCCCC(N)N.OC(=O)CCCCC(O)=O ZKXBDPZAQUNPOY-UHFFFAOYSA-N 0.000 description 1
- UFFRSDWQMJYQNE-UHFFFAOYSA-N 6-azaniumylhexylazanium;hexanedioate Chemical compound [NH3+]CCCCCC[NH3+].[O-]C(=O)CCCCC([O-])=O UFFRSDWQMJYQNE-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
Abstract
The invention discloses a preparation method of high-toughness copolyamide 6/66, which is characterized by comprising the following steps: (1) Respectively dissolving hexamethylenediamine and adipic acid in ethanol according to the molar ratio of 0.90-1.05, stirring and mixing at the temperature of 60-100 ℃ for reaction, filtering, washing with alcohol, and drying to obtain nylon 66 salt; (2) Adding 0.2-1 part of catalyst, 0.1-0.5 part of stabilizer and 0.1-0.8 part of heat-resistant agent into 30-80 parts of deionized water according to parts by weight, and uniformly stirring to obtain an auxiliary agent; (3) 10 to 90 weight parts of nylon 66 salt, 10 to 90 weight parts of caprolactam and 0 to 5 weight parts of monomer are added into an auxiliary agent, the mixture is added into a polymerization reaction kettle, vacuumizing and nitrogen introducing are carried out for polycondensation reaction, and the high-toughness copolyamide 6/66 is obtained after cooling, belt casting, granulating and drying, and has the advantages of obviously improving the elongation at break and the notch impact strength.
Description
Technical Field
The invention relates to the technical field of polyamide, in particular to a preparation method of modified high-toughness copolyamide 6/66.
Background
Polyamide (PA) is called nylon, and is widely used in engineering plastics, chemical fibers and material fields because of its excellent performance and outstanding lightweight advantages. Among them, polyamide 66 and polyamide 6 are the most productive and most widely used varieties of nylon products at present due to their excellent mechanical properties, abrasion resistance, good self-lubricity, and stability to chemical agents. However, PA6 also has the problems of small elastic modulus, poor dimensional stability of the product, poor impact resistance of the product in a dry state and at low temperature, poor rigidity and heat resistance under strong external force and heating conditions, and the like. In contrast, PA66 has higher strength than PA6 and better heat resistance, oil resistance, and water absorption, but PA6 has better elongation at break and impact strength than PA66, and also has better processing flowability.
In the studies reported in the literature for the preparation of copolyamide 6/66 (synthetic fiber industry, 2017,40 (30): 31-34), the authors prepared copolyamide PA6/66 by adding a ring-opening agent at normal pressure, but at normal pressure, the PA66 salt was easily decomposed at 250℃to partially volatilize hexamethylenediamine, thereby changing the ratio of caprolactam to hexamethylenediamine adipate, and the resulting copolyamide 6/66 had low elongation at break, low notched impact strength and poor toughness. 1-7, the authors adopt high-temperature high-pressure polymerization, and adopt adipic acid hexanediamine salt and caprolactam as raw materials to prepare the PA6/66 with a full range of series proportions, but the elongation at break of the copolymer is improved, but the tensile strength is obviously reduced, so that the use reliability of the copolymer is affected. Patent application CN111441099a discloses a method for preparing copolyamide 6/66 by two-stage polymerization under medium-low pressure and normal pressure, but is limited by the control of reaction conditions and the difference of ring-opener monomers, and the notch impact strength of the prepared copolymer is still low. In the prior art, although a great deal of research has been focused on compounding nylon 66 salts with other salt species, different modified copolymers were obtained by means of pressurized copolymerization. However, due to the difference of comonomer selection, the difference of polymerization temperature and polymerization pressure and the lack of heat resistance of the poly-stabilizer, the prepared copolymer has low notch impact strength and poor toughness.
Disclosure of Invention
The invention aims to provide a preparation method of high-toughness copolyamide 6/66 with obviously improved elongation at break and notch impact strength.
The technical scheme adopted for solving the technical problems is as follows: a method for preparing high-toughness copolyamide 6/66, which comprises the following steps:
(1) Respectively dissolving hexamethylenediamine and adipic acid in ethanol according to the molar ratio of 0.90-1.05, stirring and mixing at the temperature of 60-100 ℃ for reaction, filtering reactants, washing with alcohol, and drying to obtain nylon 66 salt;
(2) Adding 0.2-1 part of catalyst, 0.1-0.5 part of stabilizer and 0.1-0.8 part of heat-resistant agent into 30-80 parts of deionized water according to parts by weight, and uniformly stirring at normal temperature to obtain an auxiliary agent;
(3) Adding 10-90 parts by weight of nylon 66 salt, 10-90 parts by weight of caprolactam and 0-5 parts by weight of monomer in the step (1) into the auxiliary agent uniformly mixed in the step (2), adding the mixture into a polymerization reaction kettle, vacuumizing, introducing nitrogen to remove air in the reactor, controlling the heating temperature to 220-240 ℃ under the protection of nitrogen, controlling the polymerization pressure to 1.5-3.0 MPa, gradually deflating to normal pressure after polycondensation reaction for 1-6 h, gradually raising the temperature to 260-280 ℃, vacuumizing the polymerization reaction kettle, continuing polymerizing for 0.5-2 h under the vacuum degree of 50kPa, extruding the polymer by using protective gas, and cooling, casting, granulating and drying to obtain the high-toughness copolyamide 6/66.
Further, the catalyst in the step (2) is one or more of phosphoric acid, sodium hypophosphite, sodium phosphite, phenylphosphoric acid, potassium hypophosphite and manganese hypophosphite. The solid phase polymerization rate can be increased by using a phosphorus-containing catalyst.
Further, the stabilizer in the step (2) is bis (2, 6-tetramethyl-3-piperidylamino) -isophthalamide. The stabilizer is added in the polymerization process to bond the stabilizer molecule to the polymer chain, so that the light resistance, oxidation resistance and aging resistance of the copolymer can be improved.
Further, the heat resistant agent in the step (2) is a metal copper compound/halide modified copper master batch taking nylon 6 or nylon 66 prepolymer as a carrier. The addition of the copper master batch can form a six-membered ring halogen chelate taking copper ions as the center in the polymerization process, and the chelate has the function of a heat-resistant protective layer, thereby being beneficial to improving the use temperature of the copolymer.
Further, the copper master batch is cuprous iodide/potassium bromide or cupric acetate/potassium iodide.
Further, the monomer in the step (3) is 6-aminocaproic acid, benzoic acid, terephthalic acid, isophthalic acid, 2-naphthoic acid, p-xylylenediamine, m-xylylenediamine, or aliphatic, aromatic, aliphatic, aromatic dibasic acid or diamine containing more than 6 carbons.
Compared with the prior art, the invention has the advantages that: according to the preparation method of the high-toughness copolyamide 6/66, the introduction of the comonomer reduces the molecular chain regularity of the copolyamide, reduces the intermolecular acting force and improves the elongation at break and the notch impact strength of the copolymer. The modified high-toughness copolymer has an elongation at break of 120.4% at maximum and a notched impact strength of 27.6 kJ.m 2 The modified polyamide is obviously higher than pure PA66 and pure PA6, which shows that the modified polyamide can improve the processability of the copolymer and effectively improve the toughness of the copolymer, and can be used for preparing plastic products with good processability.
In summary, the preparation method of the high-toughness copolyamide 6/66 provided by the invention carries out in-situ melt polymerization on nylon 66 salt, caprolactam and modified monomers, and can enhance the toughness of the polymer, reduce the rigidity and enhance the plasticity by a copolymerization modification mode, so that the processability of the polymer is improved, the high-toughness polyamide 6/66 has higher elongation at break and notch impact strength, the processability of the copolymer can be improved, the toughness of the copolymer can be effectively improved, and the high-toughness polyamide 6/66 can be used for preparing plastic products with good processability.
Detailed Description
The present invention is described in further detail below with reference to examples.
1. Detailed description of the preferred embodiments
Example 1
A method for preparing high-toughness copolyamide 6/66, which comprises the following steps:
(1) Respectively dissolving 580g of hexamethylenediamine and 730g of adipic acid in 500mL of ethanol, carrying out ultrasonic oscillation at 60 ℃ for 0.5h, slowly adding the hexamethylenediamine solution into the adipic acid solution, carrying out neutralization reaction on the hexamethylenediamine and the adipic acid in the alcohol solution to generate nylon 66 salt, separating out, filtering, washing with alcohol to obtain nylon 66 salt, and drying for later use;
(2) Adding 10g of sodium hypophosphite, 3g of stabilizer and 6g of copper master batch into 800g of deionized water, and uniformly stirring at normal temperature; (3) Adding 900g of nylon 66 salt, 300g of caprolactam and 24g of benzoic acid in the step (1) into the auxiliary agent uniformly mixed in the step (2), adding into a polymerization reaction kettle, vacuumizing, introducing nitrogen to remove air in the reactor, heating to 220-240 ℃ under the protection of nitrogen, polycondensing under the condition that the polymerization pressure is controlled to be 1.8-2.0 MPa for 2 hours, gradually deflating to normal pressure, gradually raising the temperature to 260-280 ℃, vacuumizing the system at the temperature, continuing polymerizing for 0.75 hours under the vacuum degree of about 50kPa, extruding the polymer by using protective gas, and cooling, casting, granulating and drying to obtain the copolyamide 6/66.
Example 2
A method for preparing high-toughness copolyamide 6/66, which comprises the following steps:
(1) Respectively dissolving 580g of hexamethylenediamine and 730g of adipic acid in 500mL of ethanol, carrying out ultrasonic oscillation at 60 ℃ for 0.5h, slowly adding the hexamethylenediamine solution into the adipic acid solution, carrying out neutralization reaction on the hexamethylenediamine and the adipic acid in the alcohol solution to generate nylon 66 salt, separating out, filtering, washing with alcohol to obtain nylon 66 salt, and drying for later use;
(2) Adding 10g of sodium hypophosphite, 3g of stabilizer and 6g of copper master batch into 800g of deionized water, and uniformly stirring at normal temperature; (3) 600g of nylon 66 salt, 600g of caprolactam and 24g of benzoic acid in the step (1) are added into the auxiliary agent uniformly mixed in the step (2), the mixture is added into a polymerization reaction kettle, vacuumizing is carried out, nitrogen is introduced to remove air in the reactor, heating is carried out to 220-240 ℃ under the protection of nitrogen, polycondensation is carried out for 2 hours under the condition that the polymerization pressure is controlled to be 1.8-2.0 MPa, then the mixture is gradually deflated to normal pressure, and the temperature is gradually increased to 260-280 ℃. The system was evacuated at this temperature and polymerization was continued for 0.75 hours at a vacuum of about 50kPa, and then the polymer was extruded with a shielding gas, and after cooling, tape casting, pelleting and drying, copolyamide 6/66 was obtained.
Example 3
A method for preparing high-toughness copolyamide 6/66, which comprises the following steps:
(1) Respectively dissolving 580g of hexamethylenediamine and 730g of adipic acid in 500mL of ethanol, carrying out ultrasonic oscillation at 60 ℃ for 0.5h, slowly adding the hexamethylenediamine solution into the adipic acid solution, carrying out neutralization reaction on the hexamethylenediamine and the adipic acid in the alcohol solution to generate nylon 66 salt, separating out, filtering, washing with alcohol to obtain nylon 66 salt, and drying for later use;
(2) Adding 10g of sodium hypophosphite, 3g of stabilizer and 6g of copper master batch into 800g of deionized water, and uniformly stirring at normal temperature; (3) Adding 300g of nylon 66 salt, 900g of caprolactam and 24g of benzoic acid in the step (1) into the auxiliary agent uniformly mixed in the step (2), adding into a polymerization reaction kettle, vacuumizing, introducing nitrogen to remove air in the reactor, heating to 220-240 ℃ under the protection of nitrogen, polycondensing for 2 hours under the condition that the polymerization pressure is controlled to be 1.8-2.0 MPa, then gradually deflating to normal pressure, and gradually raising the temperature to 260-280 ℃. The system was evacuated at this temperature, and polymerization was continued for 0.75 hours at a vacuum of about 50 kPa. The polymer is then extruded with a protective gas, cooled, cast, pelletized and dried to give copolyamide 6/66.
Example 4
A method for preparing high-toughness copolyamide 6/66, which comprises the following steps:
(1) Respectively dissolving 580g of hexamethylenediamine and 730g of adipic acid in 500mL of ethanol, carrying out ultrasonic oscillation at 60 ℃ for 0.5h, slowly adding the hexamethylenediamine solution into the adipic acid solution, carrying out neutralization reaction on the hexamethylenediamine and the adipic acid in the alcohol solution to generate nylon 66 salt, separating out, filtering, washing with alcohol to obtain nylon 66 salt, and drying for later use;
(2) Adding 10g of sodium hypophosphite, 3g of stabilizer and 6g of copper master batch into 800g of deionized water, and uniformly stirring at normal temperature; (3) 600g of nylon 66 salt, 600g of caprolactam and 48g of benzoic acid in the step (1) are added into the auxiliary agent uniformly mixed in the step (2), the mixture is added into a polymerization reaction kettle, vacuumizing is carried out, nitrogen is introduced to remove air in the reactor, heating is carried out to 220-240 ℃ under the protection of nitrogen, polycondensation is carried out for 2 hours under the condition that the polymerization pressure is controlled to be 1.8-2.0 MPa, then the mixture is gradually deflated to normal pressure, and the temperature is gradually increased to 260-280 ℃. The system was evacuated at this temperature, and polymerization was continued for 0.75 hours at a vacuum of about 50 kPa. The polymer is then extruded with a protective gas, cooled, cast, pelletized and dried to give copolyamide 6/66.
Example 5
A method for preparing high-toughness copolyamide 6/66, which comprises the following steps:
(1) Respectively dissolving 580g of hexamethylenediamine and 730g of adipic acid in 500mL of ethanol, carrying out ultrasonic oscillation at 60 ℃ for 0.5h, slowly adding the hexamethylenediamine solution into the adipic acid solution, carrying out neutralization reaction on the hexamethylenediamine and the adipic acid in the alcohol solution to generate nylon 66 salt, separating out, filtering, washing with alcohol to obtain nylon 66 salt, and drying for later use;
(2) Adding 10g of sodium hypophosphite, 3g of stabilizer and 6g of copper master batch into 800g of deionized water, and uniformly stirring at normal temperature; (3) 600g of nylon 66 salt, 600g of caprolactam and 24g of 6-aminocaproic acid in the step (1) are added into the auxiliary agent uniformly mixed in the step (2), the mixture is added into a polymerization reaction kettle, vacuumizing is carried out, nitrogen is introduced to remove air in the reactor, heating is carried out to 220-240 ℃ under the protection of nitrogen, the polymerization pressure is controlled to be 1.8-2.0 MPa, polycondensation is carried out for 2 hours, then the mixture is gradually deflated to normal pressure, the temperature is gradually increased to 260-280 ℃, vacuumizing is carried out on the system at the temperature, polymerization is continued for 0.75 hours under the vacuum degree of about 50kPa, and then the polymer is extruded by using protective gas, and the copolyamide 6/66 is obtained after cooling, casting, granulating and drying.
Example 6
A method for preparing high-toughness copolyamide 6/66, which comprises the following steps:
(1) Respectively dissolving 580g of hexamethylenediamine and 730g of adipic acid in 500mL of ethanol, carrying out ultrasonic oscillation at 60 ℃ for 0.5h, slowly adding the hexamethylenediamine solution into the adipic acid solution, carrying out neutralization reaction on the hexamethylenediamine and the adipic acid in the alcohol solution to generate nylon 66 salt, separating out, filtering, washing with alcohol to obtain nylon 66 salt, and drying for later use;
(2) Adding 10g of sodium hypophosphite, 3g of stabilizer and 6g of copper master batch into 800g of deionized water, and uniformly stirring at normal temperature; (3) 600g of nylon 66 salt, 600g of caprolactam and 24g of terephthalic acid in the step (1) are added into the auxiliary agent uniformly mixed in the step (2), the mixture is added into a polymerization reaction kettle, vacuumizing is carried out, nitrogen is introduced to remove air in the reactor, the mixture is heated to 220-240 ℃ under the protection of nitrogen, the polymerization pressure is controlled to be 1.8-2.0 MPa, the mixture is polycondensed for 2 hours, then the mixture is gradually deflated to normal pressure, and the temperature is gradually increased to 260-280 ℃. The system was evacuated at this temperature, and polymerization was continued for 0.75 hours at a vacuum of about 50 kPa. The polymer is then extruded with a protective gas, cooled, cast, pelletized and dried to give copolyamide 6/66.
Example 8
A method for preparing high-toughness copolyamide 6/66, which comprises the following steps:
(1) Respectively dissolving 580g of hexamethylenediamine and 730g of adipic acid in 500mL of ethanol, carrying out ultrasonic oscillation at 60 ℃ for 0.5h, slowly adding the hexamethylenediamine solution into the adipic acid solution, carrying out neutralization reaction on the hexamethylenediamine and the adipic acid in the alcohol solution to generate nylon 66 salt, separating out, filtering, washing with alcohol to obtain nylon 66 salt, and drying for later use;
(2) Adding 10g of sodium hypophosphite, 3g of stabilizer and 6g of copper master batch into 800g of deionized water, and uniformly stirring at normal temperature; (3) 600g of nylon 66 salt, 600g of caprolactam and 24g of 2-naphthoic acid in the step (1) are added into the auxiliary agent uniformly mixed in the step (2), the mixture is added into a polymerization reaction kettle, vacuumizing is carried out, nitrogen is introduced to remove air in the reactor, heating is carried out to 220-240 ℃ under the protection of the nitrogen, the polymerization pressure is controlled to be 1.8-2.0 MPa, polycondensation is carried out for 2 hours, then the mixture is gradually deflated to normal pressure, the temperature is gradually increased to 260-280 ℃, vacuumizing is carried out on the system at the temperature, polymerization is continued for 0.75 hours under the vacuum degree of about 50kPa, and then the polymer is extruded by using protective gas, and the copolyamide 6/66 is obtained after cooling, belt casting, granulating and drying.
In the above embodiment, the stabilizer is bis (2, 6-tetramethyl-3-piperidylamino) -isophthalamide, and the copper master batch is cuprous iodide/potassium bromide or cupric acetate/potassium iodide. In addition to the above examples, the molar ratio of hexamethylenediamine to adipic acid in step (1) may be any value within the range of 0.90 to 1.05, and the reaction temperature may be any value within the range of 60 to 100 ℃; the catalyst in the step (2) is any value in 0.2 to 1 part and is one of phosphoric acid, sodium phosphite, phenylphosphoric acid, potassium hypophosphite and manganese hypophosphite, the stabilizer is any value in 0.1 to 0.5 part, the heat resistant agent is any value in 0.1 to 0.8 part, and the deionized water is any value in 30 to 80 parts; in the step (3), the nylon 66 salt is any value in 10-90 parts, the caprolactam is any value in 10-90 parts, the monomer is any value in 0-5 parts, the heating temperature is any value in 220-240 ℃, the polymerization pressure is any value in 1.5-3.0 MPa, the polycondensation reaction is any value in 1-6 h, and the temperature is gradually increased to any value in 260-280 ℃. The monomer may be isophthalic acid, m-xylylenediamine, or an aliphatic, aromatic, aliphatic having a side chain, aromatic dibasic acid having a side chain, or diamine having 6 or more carbons.
2. Analysis of experimental results
Comparative example 1
The difference with the above example 1 is that 1200g of nylon 66 salt is added into the assistant uniformly mixed in the step (2) in the step (3), and then added into a polymerization reaction kettle, and the mixture is vacuumized, introduced with nitrogen to remove air in the reactor, heated to 220-240 ℃ under the protection of nitrogen, polycondensed for 2 hours under the condition that the polymerization pressure is controlled to 1.8-2.0 MPa, then gradually deflated to normal pressure, the temperature is gradually raised to 260-280 ℃, the system is vacuumized at the temperature, and polymerization is continued for 0.75 hours under the vacuum degree of about 50kPa, and then the polymer is extruded by using a protective gas, cooled, cast, pelletized and dried to obtain the polyamide 66.
Comparative example 2
The difference with the above example 1 is that step (1) is omitted, and step (3) is adjusted to add 1200g of caprolactam into the uniformly mixed auxiliary agent, add into the polymerization reactor, vacuumize, introduce nitrogen to remove air in the reactor, heat to 220-240 ℃ under the protection of nitrogen, polycondense for 2 hours under the condition that the polymerization pressure is controlled to 1.8-2.0 MPa, then gradually deflate to normal pressure, and gradually raise the temperature to 260-280 ℃. The system was evacuated at this temperature, and polymerization was continued for 0.75 hours at a vacuum of about 50 kPa. The polymer is then pressed out with a protective gas, cooled, cast, pelletized and dried to give polyamide 6.
Comparative example 3
The difference is that the heat-resistant agent is omitted in the step (2) as in the above example 1.
To further investigate the properties of the modified copolyamide, the properties of the copolymers prepared in examples 1 to 7 and comparative examples 1 to 3 were examined and the results are recorded in Table 1 below.
TABLE 1 Properties of the copolymers prepared in examples 1-7 and comparative examples 1-3
TABLE 1 Properties of the copolymers prepared in examples 1-7 and comparative examples 1-3
Test conditions: injection molding the copolymer according to GB/T2406.2-2009 standard;
the tensile properties were determined according to GB/T1040-2018 at a tensile rate of 50 mm/min;
the bending performance is measured according to GB/T9341-2008 standard under the bending rate of 2 mm/min;
measuring elongation at break according to GB/T3923-2013 standard under the condition that the thickness of a spline is 4 mm;
the impact strength was measured according to GB/T1843-2008 at a spline thickness of 4 mm.
As can be seen from the data of comparative examples 1 and 2 in the table, the modified high toughness copolyamide 6/66 of the present invention showed a tendency to decrease in melting temperature, crystallinity, tensile and flexural properties, but in contrast, the elongation at break and notched impact strength of the copolymer were significantly increased, as compared to nylon 66 and nylon 6. This shows that the introduction of benzene ring in copolymerization modification can increase the bond energy of the main chain of molecular chain, so that more energy is absorbed when the molecular chain breaks; meanwhile, the steric hindrance of the benzene ring is large, so that the molecular chains are not easy to slide mutually, when the spline is broken, the probability of breaking the chemical bond is increased, more impact energy can be absorbed, and the notch impact strength is increased. In comparative examples 2 and 4, the elongation at break and impact properties of the copolymer decreased with increasing amount of the modifying comonomer, indicating that the introduction of excess monomer increased the rigidity of the molecular chain, decreased deformation under load, and increased brittleness of the material, which was detrimental to improving processability of the copolymer. Furthermore, the data of comparative example 3 show that the addition of copper master batch helps to form a heat resistant protective layer, increasing the service temperature of the copolymer. By the modification method, the elongation at break and the notch impact strength of the copolymer can be improved, the toughness is enhanced, and the preparation of plastic products with good processability is facilitated.
The above description is not intended to limit the invention, nor is the invention limited to the examples described above. Variations, modifications, additions, or substitutions will occur to those skilled in the art and are therefore within the spirit and scope of the invention.
Claims (6)
1. The preparation method of the high-toughness copolyamide 6/66 is characterized by comprising the following steps:
(1) Respectively dissolving hexamethylenediamine and adipic acid in ethanol according to the molar ratio of 0.90-1.05, stirring and mixing at the temperature of 60-100 ℃ for reaction, filtering reactants, washing with alcohol, and drying to obtain nylon 66 salt;
(2) Adding 0.2-1 part of catalyst, 0.1-0.5 part of stabilizer and 0.1-0.8 part of heat-resistant agent into 30-80 parts of deionized water according to parts by weight, and uniformly stirring at normal temperature to obtain an auxiliary agent;
(3) Adding 10-90 parts by weight of nylon 66 salt, 10-90 parts by weight of caprolactam and 0-5 parts by weight of monomer in the step (1) into the auxiliary agent uniformly mixed in the step (2), adding the mixture into a polymerization reaction kettle, vacuumizing, introducing nitrogen to remove air in the reactor, controlling the heating temperature to 220-240 ℃ under the protection of nitrogen, controlling the polymerization pressure to 1.5-3.0 MPa, gradually deflating to normal pressure after polycondensation reaction for 1-6 h, gradually raising the temperature to 260-280 ℃, vacuumizing the polymerization reaction kettle, continuing polymerizing for 0.5-2 h under the vacuum degree of 50kPa, extruding the polymer by using protective gas, and cooling, casting, granulating and drying to obtain the high-toughness copolyamide 6/66.
2. The method for preparing the high-toughness copolyamide 6/66 according to claim 1, wherein the method comprises the following steps: the catalyst in the step (2) is one or more of phosphoric acid, sodium hypophosphite, sodium phosphite, phenylphosphoric acid, potassium hypophosphite and manganese hypophosphite. The solid phase polymerization rate can be increased by using a phosphorus-containing catalyst.
3. The method for preparing the high-toughness copolyamide 6/66 according to claim 1, wherein the method comprises the following steps: the stabilizer in the step (2) is bis (2, 6-tetramethyl-3-piperidylamino) -isophthalamide. The stabilizer is added in the polymerization process to bond the stabilizer molecule to the polymer chain, so that the light resistance, oxidation resistance and aging resistance of the copolymer can be improved.
4. The method for preparing the high-toughness copolyamide 6/66 according to claim 1, wherein the method comprises the following steps: the heat resistant agent in the step (2) is a metal copper compound/halide modified copper master batch taking nylon 6 or nylon 66 prepolymer as a carrier. The addition of the copper master batch can form a six-membered ring halogen chelate taking copper ions as the center in the polymerization process, and the chelate has the function of a heat-resistant protective layer, thereby being beneficial to improving the use temperature of the copolymer.
5. The method for preparing high-toughness copolyamide 6/66 according to claim 4, wherein: the copper master batch is cuprous iodide/potassium bromide or cupric acetate/potassium iodide.
6. The method for preparing the high-toughness copolyamide 6/66 according to claim 1, wherein the method comprises the following steps: the monomer in the step (3) is 6-aminocaproic acid, benzoic acid, terephthalic acid, isophthalic acid, 2-naphthoic acid, p-xylylenediamine, m-xylylenediamine or aliphatic, aromatic, aliphatic containing side chains and aromatic dibasic acid or diamine containing more than 6 carbons.
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