CN118185301B - Poly (imide-amide) reinforced modified polyamide 6 and preparation process thereof - Google Patents
Poly (imide-amide) reinforced modified polyamide 6 and preparation process thereof Download PDFInfo
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- 229920002292 Nylon 6 Polymers 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 20
- -1 (iminobenzoic acid) anilide Chemical compound 0.000 claims description 19
- 239000012948 isocyanate Substances 0.000 claims description 19
- 150000002513 isocyanates Chemical class 0.000 claims description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims description 14
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- 238000001746 injection moulding Methods 0.000 claims description 10
- XJUZRXYOEPSWMB-UHFFFAOYSA-N Chloromethyl methyl ether Chemical compound COCCl XJUZRXYOEPSWMB-UHFFFAOYSA-N 0.000 claims description 9
- 229940061627 chloromethyl methyl ether Drugs 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 8
- 239000011592 zinc chloride Substances 0.000 claims description 8
- 235000005074 zinc chloride Nutrition 0.000 claims description 8
- 238000005660 chlorination reaction Methods 0.000 claims description 7
- 238000006722 reduction reaction Methods 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 150000001540 azides Chemical class 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- XPAQFJJCWGSXGJ-UHFFFAOYSA-N 4-amino-n-(4-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC=C(N)C=C1 XPAQFJJCWGSXGJ-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- ZVSKZLHKADLHSD-UHFFFAOYSA-N benzanilide Chemical compound C=1C=CC=CC=1C(=O)NC1=CC=CC=C1 ZVSKZLHKADLHSD-UHFFFAOYSA-N 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims 1
- 239000004952 Polyamide Substances 0.000 abstract description 12
- 229920002647 polyamide Polymers 0.000 abstract description 12
- 230000002787 reinforcement Effects 0.000 abstract description 10
- 239000002131 composite material Substances 0.000 abstract description 9
- 150000008430 aromatic amides Chemical class 0.000 abstract description 7
- 238000005452 bending Methods 0.000 abstract description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract description 5
- 150000001408 amides Chemical class 0.000 abstract description 4
- 125000003277 amino group Chemical group 0.000 abstract description 4
- 239000000155 melt Substances 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 239000000463 material Substances 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 8
- 238000005979 thermal decomposition reaction Methods 0.000 description 7
- 150000003949 imides Chemical class 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000006268 reductive amination reaction Methods 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 150000003931 anilides Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to the technical field of polyamide and polyamide, and discloses a poly (imide-amide) reinforced modified polyamide 6 and a preparation process thereof. In the melt blending process, the amino groups of the ammoniated poly (imide-amide) react with the isocyanate groups of the montmorillonite to enable the molecular chains of the poly (imide-amide) to be grafted on the surface of the montmorillonite, and the two form the organic-inorganic composite reinforcement. The aromatic amide and alkylamide structure contained in the poly (imide-amide) has good interfacial force and compatibility with the amide structural unit of the polyamide 6, and improves the heat resistance, tensile strength, impact strength and bending property of the polyamide 6.
Description
Technical Field
The invention relates to the technical field of polyamide and polyamide, in particular to poly (imide-amide) reinforced modified polyamide 6 and a preparation process thereof.
Background
Nylon is a polyamide material containing amide structural units, wherein polyamide 6 has excellent comprehensive performance, high yield and wide application range, can be made into plastics, fibers and the like, and has important application in engineering materials, packaging materials, textiles and the like. However, polyamide 6 has problems such as poor rigidity and strength, low heat resistance, and limited application range. Therefore, reinforcement modification of polyamide 6 is required. Patent CN107082881B discloses that the use of semi-aromatic polyimide for modifying nylon polyamide material can improve the electrical insulation performance, bending strength and other properties of nylon polyamide material. However, the heat resistance of the nylon polyamide material is not improved well.
Montmorillonite as silicate natural mineral has rich reserve, low cost and easy obtaining, and has wide application in filling modification of polyamide, polystyrene, phenolic resin and other polymer materials, and certain improvement effect on mechanical, blocking and other performances of the materials. However, montmorillonite layers contain a large amount of inorganic ions, which show oleophobicity, and have poor compatibility with polymer matrix and poor dispersibility; the invention enhances and modifies the polyamide 6 by the poly (imide-amide) and the montmorillonite, and improves the mechanical strength, high temperature resistance and other performances of the polyamide 6.
Disclosure of Invention
The invention solves the technical problems that: the polyamide 6 is enhanced and modified by utilizing a poly (imide-amide) and montmorillonite, so that the mechanical strength, high temperature resistance and other performances of the polyamide 6 are improved.
The technical scheme provided by the invention is as follows:
A poly (imide-amide) reinforced modified polyamide 6 comprises 100 parts by weight of polyamide 6, 5-30 parts by weight of ammoniated poly (imide-amide), 0.5-5 parts by weight of isocyanate montmorillonite and 0.4-0.8 part by weight of antioxidant.
The preparation process of the ammoniated poly (imide-amide) comprises the following steps:
(1) Introducing nitrogen into the reaction kettle, adding 4,4' -bis (imidobenzoic acid) benzanilide and 1, 6-hexamethylenediamine, performing polymerization reaction, and discharging under pressure to obtain the poly (imido-amide).
(2) Introducing nitrogen into a reaction bottle, adding chloroform and poly (imide-amide), stirring, adding zinc chloride and chloromethyl methyl ether, performing chlorination reaction at 50-60 ℃ for 3-6h, adding methanol for precipitation, filtering, washing with water and ethanol in sequence, and drying to obtain chlorinated poly (imide-amide).
(3) Adding N, N-dimethylformamide and poly (imide-amide) chloride into a reaction bottle, stirring, adding sodium azide, performing an azide reaction at a temperature of 100-120 ℃ for 6-18h, adding water for precipitation, filtering, washing with water and ethanol sequentially, drying a product, adding into tetrahydrofuran, stirring, adding an elemental zinc and ammonium chloride aqueous solution, performing a reduction reaction at a temperature of 15-30 ℃ for 2-6h, removing tetrahydrofuran by rotary evaporation, washing with dilute hydrochloric acid, water and ethanol sequentially, and drying to obtain the ammoniated poly (imide-amide).
Wherein the molar amount of 4,4' -bis (iminobenzoic acid) anilide in (1) is 95 to 110% of the molar amount of 1, 6-hexamethylenediamine.
Wherein, the polymerization reaction in the step (1) is firstly carried out for 3-4 hours at the temperature of 210-220 ℃ under the pressure of 1.5-2 MPa; then the reaction is carried out for 2 to 3 hours at the temperature of 230 to 240 ℃ under normal pressure.
Wherein the mass of zinc chloride and chloromethyl methyl ether in the step (2) is 12-30% and 36-90% of the mass of poly (imide-amide).
Wherein the mass of sodium azide in (3) is 10-25% of the mass of the chlorinated poly (imide-amide).
Wherein, the preparation process of the 4,4' -bis (iminobenzoic acid) benzanilide comprises the following steps:
adding glacial acetic acid, trimellitic anhydride and 4,4 '-diaminobenzanilide into a reaction bottle, condensing and refluxing at 130-140 ℃ for reaction for 12-18h, cooling, adding water for precipitation, filtering, washing with water, and recrystallizing the product with ethanol to obtain 4,4' -bis (iminobenzoic acid) benzanilide.
Wherein the mole amount of the trimellitic anhydride is 200-220% of that of the 4,4' -diaminobenzil anilide.
Wherein, the preparation process of the poly (imide-amide) reinforced modified polyamide 6 comprises the following steps: extruding 100 parts by weight of polyamide 6, 5-30 parts by weight of ammoniated poly (imide-amide), 0.5-5 parts by weight of isocyanate montmorillonite and 0.4-0.8 part by weight of antioxidant in a double screw extruder, wherein the temperature of each section is 200-240 ℃; and then water-cooling, granulating and injection molding to obtain the poly (imide-amide) reinforced modified polyamide 6.
The invention has the technical effects that: the invention uses trimellitic anhydride and 4,4 '-diaminobenzene anilide to carry out imide cyclization reaction to obtain 4,4' -di (imidobenzoic acid) benzene anilide monomer, and then carries out melt polymerization reaction with 1, 6-hexamethylenediamine to obtain poly (imido-amide) containing imide ring, aromatic amide and alkylamide structural units; through chloridizing reaction, azidating reaction and reductive amination reaction of chloromethyl methyl ether, rich amino groups are introduced into the molecular main chain of poly (imide-amide) to obtain novel aminated poly (imide-amide).
According to the invention, ammoniated poly (imide-amide), isocyanate montmorillonite and polyamide 6 are melt blended to obtain poly (imide-amide) reinforced modified polyamide 6. In the melt blending process, amino rich in the main chain of the ammoniated poly (imide-amide) molecule reacts with the isocyanate group of montmorillonite to enable the poly (imide-amide) molecule chain to be grafted on the surface of montmorillonite, and the amino rich in the main chain of the ammoniated poly (imide-amide) molecule reacts with the isocyanate group of montmorillonite to form an organic-inorganic composite reinforcement. The aromatic amide and alkylamide structure contained in the poly (imide-amide) has good interfacial force and compatibility with the amide structural unit of the polyamide 6, improves the compatibility between the organic-inorganic composite reinforcement of the poly (imide-amide) -montmorillonite and the polyamide 6, has excellent dispersion in a polyamide 6 matrix, ensures that the montmorillonite plays a better reinforcing and modifying role, and improves the tensile strength, the impact strength and the bending property of the polyamide 6.
The poly (imide-amide) contains a rigid imide ring and an aromatic amide structure, has good high temperature resistance and high mechanical structure stability, and is chemically bonded with the isocyanate montmorillonite to form an organic-inorganic composite reinforcement, so that the heat resistance of the polyamide 6 is improved, and the higher thermal decomposition temperature is shown. Greatly improves the tensile strength, impact strength and bending property of the polyamide 6 material.
Drawings
FIG. 1 is a reaction scheme for 4,4' -bis (iminobenzoic acid) anilide.
FIG. 2 is a reaction scheme of poly (imide-amide).
FIG. 3 is a reaction mechanism diagram of an aminated poly (imide-amide).
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The preparation process of the isocyanate montmorillonite comprises the following steps:
Adding 0.5g of sodium montmorillonite into 30mL of toluene solvent, dispersing, adding 0.4g of toluene-2, -4-diisocyanate, introducing nitrogen, reacting at 80 ℃ for 2 hours, cooling, filtering and washing to obtain the isocyanate montmorillonite.
Example 1
70ML of glacial acetic acid, 20mmol of trimellitic anhydride and 10mmol of 4,4 '-diaminobenzil anilide are added into a reaction bottle, reflux-condensation reaction is carried out for 18h at the temperature of 140 ℃, cooling is carried out, water is added for precipitation, water washing is carried out after filtration, and the product is recrystallized by ethanol to obtain 4,4' -bis (iminobenzoic acid) benzil anilide.
Introducing nitrogen into a reaction kettle, adding 44mmol of 4,4' -bis (iminobenzoic acid) benzanilide and 40 mmoles of 1, 6-hexamethylenediamine, and carrying out polymerization reaction for 4 hours at 220 ℃ under the pressure of 1.5 MPa; then, the polymerization reaction is carried out for 3 hours at the temperature of 235 ℃ under normal pressure, and the poly (imide-amide) is obtained after the pressurization and the discharge.
The reaction flask was purged with nitrogen, 300mL of chloroform and 30g of poly (imide-amide) were added, followed by stirring, 3.6g of zinc chloride and 10.8g of chloromethyl methyl ether were added, chlorination was carried out at 50℃for 6 hours, methanol was added to precipitate, filtration was carried out, washing with water and ethanol was carried out in sequence, and drying was carried out to obtain chlorinated poly (imide-amide).
300ML of N, N-dimethylformamide and 30g of poly (imide-amide) chloride are added into a reaction bottle, 3g of sodium azide is added after stirring, the reaction is carried out at the temperature of 110 ℃ for 18 hours, water is added for precipitation, filtration is carried out, water and ethanol are sequentially used for washing, the product is dried and then added into tetrahydrofuran, 10.2g of elemental zinc and an aqueous solution containing 18.6g of ammonium chloride are added after stirring, the reduction reaction is carried out at the temperature of 30 ℃ for 4 hours, the tetrahydrofuran is removed by rotary evaporation, dilute hydrochloric acid, water and ethanol are sequentially used for washing, and drying is carried out, thus obtaining the ammoniated poly (imide-amide).
Extruding 1000g of polyamide 6, 50g of ammoniated poly (imide-amide), 5g of isocyanate montmorillonite and 8g of antioxidant 1076 in a double screw extruder, wherein the temperature of each section is 200 ℃, 225 ℃, 240 ℃ and 230 ℃; and then water-cooling, granulating and injection molding to obtain the poly (imide-amide) reinforced modified polyamide 6.
Example 2
50ML of glacial acetic acid, 22mmol of trimellitic anhydride and 10mmol of 4,4 '-diaminobenzil anilide are added into a reaction bottle, reflux-condensation reaction is carried out for 18h at the temperature of 130 ℃, cooling is carried out, water is added for precipitation, water washing is carried out after filtration, and the product is recrystallized by ethanol to obtain 4,4' -bis (iminobenzoic acid) benzil anilide.
Introducing nitrogen into a reaction kettle, adding 40mmol of 4,4' -bis (iminobenzoic acid) benzanilide and 40mmol of 1, 6-hexamethylenediamine, and carrying out polymerization reaction for 3 hours at 220 ℃ under the pressure of 1.5 MPa; then, the polymerization reaction is carried out for 2 hours at the temperature of 240 ℃ under normal pressure, and the poly (imide-amide) is obtained after the pressurized discharge.
The reaction flask was purged with nitrogen, 500mL of chloroform and 30g of poly (imide-amide) were added, followed by stirring, 6.4g of zinc chloride and 18.6g of chloromethyl methyl ether were added, chlorination was carried out at 60℃for 4 hours, methanol was added to precipitate, filtration was carried out, washing with water and ethanol was carried out in sequence, and drying was carried out to obtain chlorinated poly (imide-amide).
400ML of N, N-dimethylformamide and 30g of chlorinated poly (imide-amide) are added into a reaction bottle, 5.8g of sodium azide is added after stirring, the reaction is carried out at 120 ℃ for 6 hours, water is added for precipitation, filtration is carried out, water and ethanol are sequentially used for washing, the product is dried and then added into tetrahydrofuran, 12.6g of elemental zinc and an aqueous solution containing 32.5g of ammonium chloride are added after stirring, the reduction reaction is carried out at 30 ℃ for 2 hours, the tetrahydrofuran is removed by rotary evaporation, dilute hydrochloric acid, water and ethanol are sequentially used for washing, and drying is carried out, thus obtaining the ammoniated poly (imide-amide).
Extruding 1000g of polyamide 6, 180g of ammoniated poly (imide-amide), 30g of isocyanate montmorillonite and 4g of antioxidant 1076 in a double screw extruder, wherein the temperature of each section is 200 ℃, 225 ℃, 240 ℃ and 230 ℃; and then water-cooling, granulating and injection molding to obtain the poly (imide-amide) reinforced modified polyamide 6.
Example 3
80ML of glacial acetic acid, 22mmol of trimellitic anhydride and 10mmol of 4,4 '-diaminobenzil anilide are added into a reaction bottle, the mixture is condensed and refluxed at the temperature of 140 ℃ for 12 hours, the mixture is cooled, water is added for precipitation, the mixture is filtered and washed, and the product is recrystallized by ethanol to obtain 4,4' -bis (iminobenzoic acid) benzil anilide.
Introducing nitrogen into a reaction kettle, adding 38mmol of 4,4' -bis (iminobenzoic acid) benzanilide and 40 mmoles of 1, 6-hexamethylenediamine, and carrying out polymerization reaction for 4 hours at the temperature of 210 ℃ under the pressure of 2 MPa; then, the polymerization reaction is carried out for 3 hours at the temperature of 230 ℃ under normal pressure, and the poly (imide-amide) is obtained after the pressurization and the discharge.
Introducing nitrogen into a reaction bottle, adding 500mL of chloroform and 30g of poly (imide-amide), stirring, adding 9g of zinc chloride and 27g of chloromethyl methyl ether, carrying out chlorination reaction at 60 ℃ for 3h, adding methanol for precipitation, filtering, washing with water and ethanol in sequence, and drying to obtain the chlorinated poly (imide-amide).
400ML of N, N-dimethylformamide and 30g of chlorinated poly (imide-amide) are added into a reaction bottle, 7.5g of sodium azide is added after stirring, the reaction is carried out at the temperature of 100 ℃ for 18 hours, water is added for precipitation, filtration is carried out, water and ethanol are sequentially used for washing, the product is dried and then added into tetrahydrofuran, 25g of elemental zinc and an aqueous solution containing 46.8g of ammonium chloride are added after stirring, the reduction reaction is carried out at the temperature of 15 ℃ for 6 hours, the tetrahydrofuran is removed by rotary evaporation, dilute hydrochloric acid, water and ethanol are sequentially used for washing, and drying is carried out, thus obtaining the ammoniated poly (imide-amide).
Extruding 1000g of polyamide 6, 300g of ammoniated poly (imide-amide), 50g of isocyanate montmorillonite and 4g of antioxidant 1076 in a double screw extruder, wherein the temperature of each section is 200 ℃, 225 ℃, 240 ℃ and 230 ℃; and then water-cooling, granulating and injection molding to obtain the poly (imide-amide) reinforced modified polyamide 6.
Comparative example 1 differs from example 1 mainly in that no aminated poly (imide-amide) and isocyanate-based montmorillonite were added.
Extruding 1000g of polyamide 6 and 8g of antioxidant 1076 in a double screw extruder, wherein the temperature of each section is 200 ℃, 225 ℃, 240 ℃ and 230 ℃; and then water-cooling, granulating and injection molding to obtain the polyamide 6 material.
Comparative example 2 differs from example 1 mainly in that no ammoniated poly (imide-amide) and isocyanate-based montmorillonite were added, and ordinary sodium-based montmorillonite was added.
1000G of polyamide 6, 5g of sodium montmorillonite and 8g of antioxidant 1076 in parts by weight are extruded in a double screw extruder, and the temperature of each section is 200 ℃, 225 ℃, 240 ℃ and 230 ℃; and then water-cooling, granulating and injection molding to obtain the polyamide 6 material.
Comparative example 3 differs from example 1 mainly in that no aminated poly (imide-amide) was added.
1000G of polyamide 6, 5g of isocyanate montmorillonite and 8g of antioxidant 1076 in parts by weight are extruded in a double screw extruder, and the temperature of each section is 200 ℃, 225 ℃, 240 ℃ and 230 ℃; and then water-cooling, granulating and injection molding to obtain the polyamide 6 material.
Comparative example 4 differs from example 1 mainly in that no ammoniated poly (imide-amide) was added, and poly (imide-amide) was added.
Extruding 1000g of polyamide 6, 50g of poly (imide-amide), 5g of isocyanate montmorillonite and 8g of antioxidant 1076 in a double screw extruder, wherein the temperature of each section is 200 ℃, 225 ℃, 240 ℃ and 230 ℃; and then water-cooling, granulating and injection molding to obtain the polyamide 6 material.
Comparative example 5 differs from example 1 mainly in that no aminated poly (imide-amide) was added and chlorinated poly (imide-amide) was added.
Extruding 1000g of polyamide 6, 50g of chlorinated poly (imide-amide), 5g of isocyanate montmorillonite and 8g of antioxidant 1076 in a double screw extruder, wherein the temperature of each section is 200 ℃, 225 ℃, 240 ℃ and 230 ℃; and then water-cooling, granulating and injection molding to obtain the polyamide 6 material.
Thermal performance test: the temperature rising rate of the TG thermogravimetric analyzer is 10 ℃/min under the nitrogen atmosphere, and the test temperature is 25-800 ℃.
TABLE 1 thermal performance test of Polyamide materials
T 5% is the 5% mass loss temperature; t 50% is the 50% mass loss temperature.
Mechanical property test: the tensile strength, impact strength and flexural properties of the polyamides were tested according to GB/T1040.1-2006, GB/T1843-2008, GB/T9341-2008.
TABLE 2 mechanical testing of Polyamide materials
In each example, 4' -bis (iminobenzoic acid) anilide and 1, 6-hexamethylenediamine were subjected to melt polymerization to obtain a poly (imide-amide) containing imide ring, aromatic amide and alkylamide structural units; and then the novel ammoniated poly (imide-amide) is obtained through the chlorination reaction, the azide reaction and the reductive amination reaction of chloromethyl methyl ether.
The ammoniated poly (imide-amide) is melt blended with isocyanate montmorillonite and polyamide 6 to obtain poly (imide-amide) reinforced modified polyamide 6. In the melt blending process, rich amino groups of an ammoniated poly (imide-amide) molecular main chain react with isocyanate groups of montmorillonite to enable the poly (imide-amide) molecular chain to be grafted on the surface of montmorillonite, and the two are formed into an organic-inorganic composite reinforcement; the aromatic amide and alkylamide structure contained in the poly (imide-amide) has good interfacial force and compatibility with the amide structural unit of the polyamide 6, improves the compatibility between the organic-inorganic composite reinforcement of the poly (imide-amide) -montmorillonite and the polyamide 6, and has excellent dispersion in a polyamide 6 matrix. The montmorillonite plays a better role in enhancing and modifying, and improves the tensile strength, impact strength and bending property of the polyamide 6.
The poly (imide-amide) contains a rigid imide ring and an aromatic amide structure, has good high temperature resistance and high mechanical structure stability, and is chemically bonded with the isocyanate montmorillonite to form an organic-inorganic composite reinforcement, so that the heat resistance of the polyamide 6 is improved, and the higher thermal decomposition temperature is shown. Greatly improves the tensile strength, impact strength and bending property of the polyamide 6 material.
Comparative example 1 is a pure polyamide 6 material with lower thermal decomposition temperature and mechanical strength.
Comparative example 2 only added common sodium montmorillonite, poor compatibility with polyamide 6, poor dispersibility, small improvement of mechanical strength of polyamide 6, and reduced thermal decomposition temperature and impact strength.
In comparative example 3, only isocyanate group montmorillonite is added, and after the montmorillonite is organically modified, the compatibility of the polyamide 6 is improved, and the mechanical properties such as tensile strength and the like of the polyamide 6 material are obviously improved. However, no aminated poly (imide-amide) was added and no organic-inorganic composite reinforcement was formed, which had mechanical strength and thermal decomposition temperature lower than the examples.
Comparative example 4a poly (imide-amide) and an isocyanate-based montmorillonite were added; comparative example 5 chlorinated poly (imide-amide) and isocyanate-montmorillonite were added. The main chain of the poly (imide-amide) molecules of the two compounds does not contain rich amino groups, so that the poly (imide-amide) molecules are difficult to react with the isocyanate of montmorillonite, and the organic-inorganic composite reinforcement is difficult to form through chemical bonding, and the mechanical strength and the thermal decomposition temperature are lower than those of each embodiment. However, the poly (imide-amide) has good compatibility with the polyamide 6, can play a certain role in reinforcing and modifying, and has higher mechanical strength and thermal decomposition temperature than those of comparative example 3.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (10)
1. A poly (imide-amide) reinforced modified polyamide 6, characterized by comprising 100 parts by weight of polyamide 6, 5-30 parts by weight of ammoniated poly (imide-amide), 0.5-5 parts by weight of isocyanate montmorillonite, and 0.4-0.8 parts by weight of antioxidant;
the preparation process of the ammoniated poly (imide-amide) comprises the following steps:
(1) Introducing nitrogen into a reaction kettle, adding 4,4' -bis (imidobenzoic acid) benzanilide and 1, 6-hexamethylenediamine, performing polymerization reaction, and discharging under pressure to obtain poly (imido-amide);
(2) Introducing nitrogen into a reaction bottle, adding chloroform and poly (imide-amide), stirring, adding zinc chloride and chloromethyl methyl ether, performing chlorination reaction, performing precipitation, filtering, washing and drying to obtain chlorinated poly (imide-amide);
(3) Adding N, N-dimethylformamide and poly (imide-amide) chloride into a reaction bottle, stirring, adding sodium azide, performing an azide reaction, performing precipitation, filtering, washing, drying a product, adding into tetrahydrofuran, stirring, adding elemental zinc and an ammonium chloride aqueous solution, performing a reduction reaction, performing rotary evaporation, washing, and drying to obtain the ammoniated poly (imide-amide).
2. The poly (imide-amide) reinforced modified polyamide 6 of claim 1 wherein the molar amount of 4,4' -bis (iminobenzoic acid) anilide in (1) is 95 to 110% of the molar amount of 1, 6-hexamethylenediamine.
3. The poly (imide-amide) reinforced modified polyamide 6 of claim 1 wherein the polymerization reaction in (1) is first conducted at a pressure of 1.5-2MPa and a temperature of 210-220 ℃ for 3-4 hours; then the reaction is carried out for 2 to 3 hours at the temperature of 230 to 240 ℃ under normal pressure.
4. The poly (imide-amide) reinforced modified polyamide 6 of claim 1 wherein the mass of zinc chloride, chloromethyl methyl ether in (2) is 12-30%, 36-90% of the mass of poly (imide-amide).
5. The poly (imide-amide) reinforced modified polyamide 6 of claim 1 wherein the chlorination reaction in (2) is controlled at a temperature of 50-60 ℃ for a period of 3-6 hours.
6. The poly (imide-amide) reinforced modified polyamide 6 of claim 1 wherein the mass of sodium azide in (3) is 10-25% of the mass of the chlorinated poly (imide-amide).
7. The poly (imide-amide) reinforced modified polyamide 6 of claim 1 wherein the azide reaction in (3) is controlled at a temperature of 100-120 ℃ for a period of 6-18 hours; the temperature of the reduction reaction is controlled to be 15-30 ℃ and the time is controlled to be 2-6h.
8. The poly (imide-amide) reinforced modified polyamide 6 of claim 1 wherein the process for the preparation of 4,4' -bis (iminobenzoic acid) anilide is:
Adding glacial acetic acid, trimellitic anhydride and 4,4 '-diaminobenzanilide into a reaction bottle, condensing and refluxing at 130-140 ℃ for reaction for 12-18h, cooling, precipitating, filtering, washing, and recrystallizing to obtain 4,4' -bis (iminobenzoic acid) benzanilide.
9. The poly (imide-amide) reinforced modified polyamide 6 of claim 8 wherein the molar amount of trimellitic anhydride is 200-220% of the molar amount of 4,4' -diaminobenzanilide.
10. A process for the preparation of a poly (imide-amide) reinforced modified polyamide 6 as claimed in any one of claims 1 to 9, wherein 100 parts by weight of polyamide 6, 5 to 30 parts by weight of ammoniated poly (imide-amide), 0.5 to 5 parts by weight of isocyanatomontmorillonite, 0.4 to 0.8 parts by weight of antioxidant are extruded in a twin screw extruder, each at a temperature of 200 to 240 ℃; and then water-cooling, granulating and injection molding to obtain the poly (imide-amide) reinforced modified polyamide 6.
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| CN112262124A (en) * | 2018-06-28 | 2021-01-22 | 株式会社德山 | Process for producing alpha-azidoaniline derivative or alpha, alpha' -diazide derivative |
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| CN101081928A (en) * | 2007-06-29 | 2007-12-05 | 浙江工业大学 | Preparation method of polyamide/nano montmorillonite masterbatch |
| CN112262124A (en) * | 2018-06-28 | 2021-01-22 | 株式会社德山 | Process for producing alpha-azidoaniline derivative or alpha, alpha' -diazide derivative |
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