CN117285818A - Polyamide composition and application thereof to high-strength transparent polyamide monofilament - Google Patents
Polyamide composition and application thereof to high-strength transparent polyamide monofilament Download PDFInfo
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- CN117285818A CN117285818A CN202311374195.1A CN202311374195A CN117285818A CN 117285818 A CN117285818 A CN 117285818A CN 202311374195 A CN202311374195 A CN 202311374195A CN 117285818 A CN117285818 A CN 117285818A
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- polyamide
- polyamide composition
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 240
- 229920002647 polyamide Polymers 0.000 title claims abstract description 240
- 239000000203 mixture Substances 0.000 title claims abstract description 94
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 59
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 58
- 229920005989 resin Polymers 0.000 claims abstract description 56
- 239000011347 resin Substances 0.000 claims abstract description 56
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229920001778 nylon Polymers 0.000 claims abstract description 24
- 239000004677 Nylon Substances 0.000 claims abstract description 23
- 229920006027 ternary co-polymer Polymers 0.000 claims abstract description 21
- 229920000577 Nylon 6/66 Polymers 0.000 claims description 32
- TZYHIGCKINZLPD-UHFFFAOYSA-N azepan-2-one;hexane-1,6-diamine;hexanedioic acid Chemical compound NCCCCCCN.O=C1CCCCCN1.OC(=O)CCCCC(O)=O TZYHIGCKINZLPD-UHFFFAOYSA-N 0.000 claims description 30
- 238000002844 melting Methods 0.000 claims description 23
- 230000008018 melting Effects 0.000 claims description 23
- 229920001897 terpolymer Polymers 0.000 claims description 20
- 150000001408 amides Chemical class 0.000 claims description 16
- 229920002292 Nylon 6 Polymers 0.000 claims description 12
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 6
- -1 PA69 Polymers 0.000 claims description 4
- 229920006018 co-polyamide Polymers 0.000 claims 1
- 230000007774 longterm Effects 0.000 abstract description 7
- 238000005470 impregnation Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 24
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 22
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 22
- 239000000835 fiber Substances 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 235000011037 adipic acid Nutrition 0.000 description 12
- 239000001361 adipic acid Substances 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 230000007423 decrease Effects 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000002791 soaking Methods 0.000 description 10
- 238000004090 dissolution Methods 0.000 description 9
- 230000002829 reductive effect Effects 0.000 description 9
- 238000009835 boiling Methods 0.000 description 8
- 238000007599 discharging Methods 0.000 description 8
- 230000000379 polymerizing effect Effects 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 7
- 238000007654 immersion Methods 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 6
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000004594 Masterbatch (MB) Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920006017 homo-polyamide Polymers 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000009987 spinning Methods 0.000 description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 4
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000009998 heat setting Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000011179 visual inspection Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 2
- 241000519995 Stachys sylvatica Species 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 1
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 229920006097 Ultramide® Polymers 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- BEIOEBMXPVYLRY-UHFFFAOYSA-N [4-[4-bis(2,4-ditert-butylphenoxy)phosphanylphenyl]phenyl]-bis(2,4-ditert-butylphenoxy)phosphane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(C=1C=CC(=CC=1)C=1C=CC(=CC=1)P(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C BEIOEBMXPVYLRY-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical group OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 1
- 239000004209 oxidized polyethylene wax Substances 0.000 description 1
- 235000013873 oxidized polyethylene wax Nutrition 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- 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
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
Abstract
The invention relates to a polyamide composition and application thereof on high-strength transparent polyamide monofilaments, wherein the polyamide composition comprises, by weight, 100 parts of nylon resin, 1.5-10 parts of polyethylene glycol with average molecular weight of 200-1000 and 1-10 parts of water; the transparent polyamide composition used in water environment comprises, by weight, 100 parts of copolymerized nylon resin, 1.5-10 parts of polyethylene glycol with average molecular weight of 200-1000 and 1.8-30 parts of ternary copolymer polyamide with alcohol solubility; transparent polyamide compositions for use in aqueous environments are used to prepare polyamide monofilaments. The polyamide composition of the invention can maintain higher breaking strength in a wet state; the mechanical strength of the transparent polyamide composition used in the water environment can be maintained at a higher level in the water environment after long-term impregnation; the polyamide monofilament prepared by the transparent polyamide composition has the characteristics of high tensile strength, high transparency and the like.
Description
Technical Field
The invention belongs to the technical field of polyamide products, and relates to a polyamide composition and application thereof to high-strength transparent polyamide monofilaments.
Background
Polyamide is a generic name of a high molecular polymer containing an amide bond (-CO-NH-) and is called nylon, and nylon 6 (polycaprolactam) and nylon 66 (polyhexamethylene diamine adipic acid) are the largest two polyamides used for injection molding, spinning, films, monofilaments and other purposes.
When polyamide monofilaments are used for deep sea fishing lines, the diameter of the monofilaments is usually 1.0mm or more, and high tensile strength at break, high transparency and the like are required. The high strength is favorable for winding and knotting the fishing line, and the high transparency ensures that the fishing line is not seen by the fish during fishing.
When high tensile break strength, high transparency, etc. are required for the monofilament, it is preferable to use a copolyamide as the main component of the monofilament, that is, to mix two or more monomers capable of forming a homopolyamide together to synthesize a polyamide. A typical example is a copolyamide prepared by polymerization of caprolactam, hexamethylenediamine and adipic acid monomers, abbreviated as Nylon 6/66. Nylon 6/66 is commonly used commercially as a raw material for industrial monofilaments. Nylon 6/66 is more disordered than nylon 6 and nylon 66 in that the amide bond in the molecular chain has less hydrogen bond formation capability than nylon 6 and nylon 66, the crystallization rate is lower than that of two homopolyamides under the same condition, and under the same process condition, compared with two homopolyamides of nylon 6 and nylon 66, nylon 6/66 has better and higher transparency. Meanwhile, due to the reduction of the crystallization rate, the drawing ratio can be higher than that of nylon 6 when preparing monofilaments, so that the monofilaments have higher tensile breaking strength.
The molecular structure of polyamide contains a large amount of amide groups, is a high molecular material with very strong polarity, can easily absorb water in the environment to influence mechanical strength, and after the polyamide monofilament is soaked in water (simulating the application environment of a fishing line), the dry polyamide can absorb water to become wet polyamide, and water molecules are very effective plasticizers for the polyamide, so that acting force among high molecular chains is reduced, and therefore, the elongation percentage of the wet polyamide is high, but the tensile breaking strength is low.
In order to solve the above-mentioned problems, CN115161797a provides a polyamide fiber and the use of a polyamide composition in textile industry; the polyamide fiber is prepared by melt spinning a polyamide composition, wherein the polyamide composition comprises polyamide 66, metal salt and an acid binding agent, and the polyamide composition has better water absorption capacity and faster water absorption rate and can still maintain better mechanical properties after water absorption through modifying the polyamide. However, the addition of metal salts such as calcium chloride and acid binding agents such as calcium stearate in this patent results in a complete opacity of the yarn produced.
Therefore, it is of great importance to study a polyamide composition and its use on high-strength transparent polyamide filaments to solve the above-mentioned problems.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a polyamide composition and application thereof to high-strength transparent polyamide monofilaments.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a polyamide composition comprises, by weight, 100 parts of nylon resin, 1.5-10 parts of polyethylene glycol and 1-10 parts of water; the number average molecular weight of the polyethylene glycol is 200-1000;
nylon resin (PA) and polyethylene glycol (PEG) are mixed and spun to obtain polyamide monofilament, and then the polyamide monofilament is placed in a constant temperature and humidity box with the temperature of 75 ℃ and the humidity of 95% to absorb moisture, so that the water content of the polyamide monofilament is equal to the water content of a polyamide composition, and the breaking strength of the polyamide monofilament with the specific water content is 5.6-6.9 cN/dtex.
As a preferable technical scheme:
in one polyamide composition as described above, the nylon resin is a nylon 6 resin, a nylon 66 resin or a nylon 6/66 resin.
In the polyamide composition, the melting point of the nylon 6/66 resin is 180-215 ℃ and the relative viscosity (RV value) is 2.7-4.5.
A polyamide composition as described above has a higher strength than prior art nylons at the same moisture content.
The invention also provides a transparent polyamide composition used in water environment, which comprises, by weight, 100 parts of copolymerized nylon resin, 1.5-10 parts of polyethylene glycol and 1.8-30 parts of ternary copolymer polyamide with alcohol solubility; the number average molecular weight of the polyethylene glycol is 200-1000; wherein, when the polyethylene glycol is added in a proportion of less than 1.5 parts, the strength improvement effect is not obvious, and when the polyethylene glycol is added in a proportion of over 10 parts, the breaking strength of the prepared monofilament is reduced; when the added part of the ternary polymerization polyamide with alcohol solubility is more than 30 parts, the prepared polyamide monofilament has lower breaking strength; when Mn of polyethylene glycol is less than 200, polyethylene glycol is relatively easy to separate when soaked in water, and when Mn of polyethylene glycol is more than 1000, polyethylene glycol is poor in compatibility with a nylon resin, the transparency of the prepared monofilament is reduced, and the appearance of the monofilament is provided with opaque white spots.
As a preferable technical scheme:
the transparent polyamide composition used in the water environment is characterized in that the copolymerized nylon resin is nylon 6/66 resin; the melting point of the nylon 6/66 resin is 180-215 ℃, and the relative viscosity (RV value) is 2.7-4.5; as noted in the literature (J.Appl.Pol.Sci.1970, 14, 2133-2143), the melting point of nylon 6/66 resin is a manifestation of inter-molecular hydrogen bond density and hydrogen bond strength, and nylon 6/66 resin has a lower melting point than nylon 6 resin in a certain monomer ratio range because copolyamide has a weaker molecular chain regularity than the corresponding homopolyamide. When the melting point of the nylon 6/66 resin is lower than 180 ℃, the hydrogen bond density among molecular chains is too low, the breaking strength of the prepared polyamide monofilament is lower, when the melting point of the nylon 6/66 resin is higher than 215 ℃, the molecular chain regularity is too high, the crystallization rate is faster, and the transparency of the prepared monofilament is reduced;
the relative viscosity of the nylon 6/66 resin affects the dry fiber strength of the polyamide composition, which further decreases after moisture absorption; when the RV value is lower than 2.7, the entanglement of the polymer molecular chain is insufficient, the polymer molecular chain is easy to break under the action of external force, and the prepared monofilament has lower breaking strength; RV values higher than 4.5 lead to processing difficulties due to too high viscosity.
A transparent polyamide composition for use in an aqueous environment as described above, the terpolymer polyamide having alcohol solubility having a relative viscosity (RV value) of 2.4 to 4.0; the relative viscosity of the terpolymer polyamide with alcohol solubility affects the dry fiber strength of the composition, which further decreases after moisture absorption; too low a relative viscosity results in too low a strength and too high a relative viscosity results in a polyamide that is difficult to melt process.
The transparent polyamide composition used in the water environment has the mass ratio of the alcohol-soluble ternary copolymer polyamide to the polyethylene glycol of more than 1.2; when the mass ratio of the alcohol-soluble ternary polymerization polyamide to the polyethylene glycol is higher than 1.2, more ternary polymerization polyamide can help provide stable dispersion of the polyethylene glycol in a matrix, and the mechanical strength of the fiber prepared from the polyamide composition under the condition of long-term immersion water environment can be maintained at a higher level, so that the polyamide composition is very beneficial to fishing line and other applications.
The transparent polyamide composition used under the water environment comprises a first amide structural unit, a second amide structural unit and a third amide structural unit, wherein the first amide structural unit is a PA6 structural unit, the second amide structural unit is a PA66 structural unit, and the third amide structural unit is one of PA610, PA69, PA12, PA612 and PA11 structural units; alcohol solubility can be achieved by adjusting certain proportions of the PA6 building blocks.
The invention also provides the use of a transparent polyamide composition for use in an aqueous environment as defined in any one of the preceding claims for the preparation of polyamide filaments.
The polyamide monofilament prepared from the transparent polyamide composition has the characteristics of high strength, transparency and high wet strength, the polyamide monofilament can keep stable mechanical properties in a long-term soaking environment, the initial wet fiber strength of the polyamide monofilament is 6.1-6.9 cN/dtex, the retention rate of the wet strength after soaking for one month is not lower than 71% compared with the initial wet fiber strength, and the strength retention rate is not lower than 61% compared with the dry polyamide monofilament strength.
The principle of the invention:
according to the research in the prior art, polyethylene glycol is found to be useful in some non-aqueous fields, such as films, as plasticizers for dry polyamides are disclosed which are capable of effectively reducing the modulus of the polyamide, making the product softer and advantageous for the winding process. When used as plasticizers, it is often desirable to select polyethylene glycols of low molecular weight, the smaller the molecular weight, the better the intermolecular lubrication. The inventors have unexpectedly found that polyethylene glycol dispersed in a polyamide composition can help to inhibit the strength of the polyamide composition from decreasing after the polyamide composition is soaked in water into a wet resin, and analyzed that the polyethylene glycol is added to provide more hydrogen to form hydrogen bonds with the nylon resin, so that water molecules which originally form hydrogen bonds with the nylon resin are replaced to a certain extent;
the PEG-containing polyamide monofilaments immersed in water for a short period of time exhibit excellent mechanical strength, further extending the immersion time, and the mechanical strength of the PEG-containing polyamide monofilaments is reduced again, which is related to migration and precipitation of PEG upon immersion in water. When the terpolymer polyamide having alcohol solubility was further incorporated in the components, it was found that the composition after long soaking did not produce a significant decrease in mechanical properties. This is related to the compatibility between the components, nylon 6/66 resin is poorly alcohol soluble, whereas PEG is soluble in water, so that the compatibility of PEG is more similar to water than nylon 6/66 resin, and when the alcohol-soluble terpolymer polyamide is introduced, PEG is affinitized with it, whereas the terpolymer polyamide is affinitized with nylon 6/66 resin, inhibiting migration and precipitation of PEG.
The beneficial effects are that:
(1) The polyamide composition has higher strength compared with nylon in the prior art under the condition of the same water content;
(2) The transparent polyamide composition used in the water environment can maintain the mechanical strength at a higher level in the water environment after being immersed for a long time;
(3) When the transparent polyamide composition used in the water environment is applied to the preparation of polyamide monofilaments, the prepared polyamide monofilaments have the characteristics of high tensile strength, high transparency and the like, and are particularly suitable for application of fishing lines.
Detailed Description
The invention is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
The partial substances used in the embodiment of the invention are as follows, and the similar substances are distinguished by different numbers:
(1) Nylon 6/66: produced by Jiangsu Huafeng2440D, with a melting point of 193 ℃, rv=4.0, noted A1;
(2) Nylon 6/66: produced by Jiangsu Huafeng2533D, melting point 189 ℃, rv=3.3, noted A2;
(3) Nylon 6/66: ultramid C40LX, produced by Basoff, has a melting point of 190 ℃, RV=4.0, denoted A3;
(4) Triethylene glycol: a national drug reagent, wherein Mn is 150;
(5) Polyethylene glycol: a national drug reagent;
(6) PA6/66/610 terpolymer amide: dupont 8061, rv=2.8, melting point=160 ℃, denoted B0;
(7) Terpolymer polyamide B1 having alcohol solubility: in a 29L high-pressure polymerization kettle, 5800g of caprolactam, 3013g of hexamethylenediamine, 2883g of adipic acid, 1252g of sebacic acid and 5000g of deionized water are added, and nitrogen is introduced for replacement for 3 times; gradually heating to 250 ℃ and maintaining the pressure at 0.3MPa for 3 hours; gradually reducing the pressure to normal pressure, keeping the temperature in the kettle at 255 ℃, polymerizing for 2 hours at normal pressure, then reducing the pressure to-0.04 MPa, and keeping the negative pressure for 20 minutes; pressurizing to 0.1MPa by introducing nitrogen, discharging and granulating to obtain slices; extracting the prepared slice in boiling water at 100 ℃ for 16 hours, and finally drying to obtain the ternary copolymer polyamide B1 with alcohol solubility; the final prepared ternary copolymer polyamide B1 with alcohol solubility has a relative viscosity of 2.68 and a melting point of 165 ℃; dissolving 10wt% of resin in methanol at 55 ℃, sealing and placing the solution in an environment at 23 ℃ after complete dissolution, and observing that the solution is still clear and transparent after 24 hours;
(8) Terpolymer polyamide B2 having alcohol solubility: in a 29L high-pressure polymerization kettle, 6050g of caprolactam, 2000g of hexamethylenediamine, 1379g of adipic acid, 1572g of sebacic acid and 5000g of deionized water are added, and nitrogen is introduced for replacement for 3 times; gradually heating to 250 ℃ and maintaining the pressure at 0.3MPa for 3 hours; gradually reducing the pressure to normal pressure, keeping the temperature in the kettle at 255 ℃, polymerizing for 2 hours at normal pressure, then reducing the pressure to-0.04 MPa, and keeping the negative pressure for 20 minutes; pressurizing to 0.1MPa by introducing nitrogen, discharging and granulating to obtain slices; extracting the prepared slice in boiling water at 100 ℃ for 16 hours, and finally drying to obtain the ternary copolymer polyamide B2 with alcohol solubility; the final prepared ternary copolymer polyamide B2 with alcohol solubility has a relative viscosity of 2.80 and a melting point of 155 ℃; dissolving 10wt% of resin in methanol at 55 ℃, sealing and placing the solution in an environment at 23 ℃ after complete dissolution, and observing that the solution is still clear and transparent after 24 hours;
(9) Terpolymer polyamide B4 having alcohol solubility: in a 29L high-pressure polymerization kettle, 5000g of caprolactam, 3091g of hexamethylenediamine, 2088g of adipic acid, 2320g of azelaic acid and 5000g of deionized water are added, and nitrogen is introduced for replacement for 3 times; gradually heating to 250 ℃ in the kettle, and maintaining the pressure for 3 hours under the pressure of 0.3 MPa; gradually reducing the pressure to normal pressure, keeping the temperature in the kettle at 255 ℃, polymerizing for 2 hours at normal pressure, then reducing the pressure to-0.04 MPa, and keeping the negative pressure for 20 minutes; pressurizing to 0.1MPa by introducing nitrogen, discharging and granulating to obtain slices, extracting the prepared slices in boiling water at 100 ℃ for 16 hours, and finally drying to obtain the ternary copolymer polyamide B4 with alcohol solubility; the final prepared ternary copolymer polyamide with alcohol solubility has a relative viscosity of 2.72 and a melting point of 131 ℃; dissolving 10wt% of B4 resin in methanol at 55 ℃, sealing and placing in an environment at 23 ℃ after complete dissolution, and observing that the solution is still clear and transparent after 24 hours;
(10) Terpolymer polyamide B6 having alcohol solubility: in a 29L high-pressure polymerization kettle, 5050g of caprolactam, 2020g of hexamethylenediamine, 1688g of adipic acid, 1341g of lauryldiacid and 5000g of deionized water are added, and nitrogen is introduced for replacement for 3 times; gradually heating to 250 ℃ in the kettle, and keeping the pressure for 3 hours under the pressure of 0.3 MPa; gradually reducing the pressure to normal pressure, keeping the temperature in the kettle at 255 ℃, polymerizing for 2 hours at normal pressure, then reducing the pressure to-0.04 MPa, and keeping the negative pressure for 20 minutes; pressurizing to 0.1MPa by introducing nitrogen, discharging and granulating to obtain slices; extracting the prepared slice in boiling water at 100 ℃ for 16 hours, and finally drying to obtain the ternary copolymer polyamide B6 with alcohol solubility; the final prepared ternary copolymer polyamide B6 with alcohol solubility has a relative viscosity of 2.72 and a melting point of 141 ℃; dissolving 10wt% of resin in methanol at 55 ℃, sealing and placing the solution in an environment at 23 ℃ after complete dissolution, and observing that the solution is still clear and transparent after 24 hours;
(11) Terpolymer polyamide B7 having alcohol solubility: in a 29L high-pressure polymerization kettle, 5050g of caprolactam, 1630g of hexamethylenediamine, 2050g of adipic acid, 1300g of laurolactam and 5000g of deionized water are added, and nitrogen is introduced for replacement for 3 times; gradually heating to 250 ℃ in the kettle, and keeping the pressure for 3 hours under the pressure of 0.3 MPa; gradually reducing the pressure to normal pressure, keeping the temperature in the kettle at 255 ℃, polymerizing for 2 hours at normal pressure, then reducing the pressure to-0.04 MPa, and keeping the negative pressure for 20 minutes. Pressurizing to 0.1MPa by introducing nitrogen, discharging and granulating to obtain slices; extracting the prepared slice in boiling water at 100 ℃ for 16 hours, and drying to prepare the ternary copolymer polyamide B7 with alcohol solubility; the final prepared terpolymer polyamide B7 having alcohol solubility had a relative viscosity of 2.66, melting point=121 ℃; dissolving 10wt% of resin in methanol at 55 ℃, sealing and placing the solution in an environment at 23 ℃ after complete dissolution, and observing that the solution is still clear and transparent after 24 hours;
(12) Terpolymer polyamide B8 having alcohol solubility: in a 29L high-pressure polymerization kettle, 5050g of caprolactam, 1630g of hexamethylenediamine, 2050g of adipic acid, 1300g of 11-aminoundecanoic acid and 5000g of deionized water are added, and nitrogen is introduced for replacement for 3 times; gradually heating to 250 ℃ in the kettle, and keeping the pressure for 3 hours under the pressure of 0.3 MPa; gradually reducing the pressure to normal pressure, keeping the temperature in the kettle at 255 ℃, polymerizing for 2 hours at normal pressure, then reducing the pressure to-0.04 MPa, and keeping the negative pressure for 20 minutes. Pressurizing to 0.1MPa by introducing nitrogen, discharging and granulating to obtain slices; extracting the prepared slice in boiling water at 100 ℃ for 16 hours, and drying to prepare the ternary copolymer polyamide B8 with alcohol solubility; the final prepared ternary copolymer polyamide B8 with alcohol solubility has a relative viscosity of 2.72 and a melting point of 126 ℃; dissolving 10wt% of resin in methanol at 55 ℃, sealing and placing the solution in an environment at 23 ℃ after complete dissolution, and observing that the solution is still clear and transparent after 24 hours;
(13) Terpolymer polyamide B3 which is not alcohol-soluble: in a 29L high-pressure polymerization kettle, 3410g of caprolactam, 3140g of hexamethylenediamine, 2640g of adipic acid, 1810.6g of sebacic acid and 5000g of deionized water are added, and nitrogen is introduced for replacement for 3 times; gradually heating to 250 ℃ in the kettle, and maintaining the pressure for 3 hours under the pressure of 0.3 MPa; gradually reducing the pressure to normal pressure, keeping the temperature in the kettle at 255 ℃, polymerizing for 2 hours at normal pressure, then reducing the pressure to-0.04 MPa, and keeping the negative pressure for 20 minutes; pressurizing to 0.1MPa by introducing nitrogen, discharging and granulating to obtain slices; extracting the prepared slice in boiling water at 100 ℃ for 16 hours, and drying to obtain ternary copolymer polyamide B3 without alcohol solubility; the final prepared ternary copolymer polyamide B3 without alcohol solubility has a relative viscosity of 2.83 and a melting point of 166 ℃; dissolving 10wt% of resin in methanol at 55 ℃, sealing and placing in an environment at 23 ℃ after complete dissolution, and observing that the solution is milky colloid after 24 hours;
(14) Preparation of the terpolymer polyamide B5 having no alcohol solubility: in a 29L high-pressure polymerization kettle, 9000g of caprolactam, 927.5g of hexamethylenediamine, 6.6.7g of adipic acid, 695.7g of azelaic acid and 5000g of deionized water are added, and nitrogen is introduced for replacement for 3 times; gradually heating to 250 ℃ in the kettle, and maintaining the pressure for 3 hours under the pressure of 0.3 MPa; gradually reducing the pressure to normal pressure, keeping the temperature in the kettle at 255 ℃, polymerizing for 2 hours at normal pressure, then reducing the pressure to-0.04 MPa, and keeping the negative pressure for 20 minutes; pressurizing to 0.1MPa by introducing nitrogen, discharging and granulating to obtain slices; extracting the prepared slice in boiling water at 100 ℃ for 16 hours, and drying to obtain ternary copolymer polyamide B5 without alcohol solubility; the final prepared ternary copolymer polyamide B5 without alcohol solubility has a relative viscosity of 2.72 and a melting point of 131 ℃; 10wt% of the resin was dissolved in methanol at 55℃and the solution was sealed in an atmosphere at 23℃after complete dissolution, and the solution was observed to be milky white in color after 24 hours.
The test method related by the invention comprises the following steps:
(1) Relative viscosity (RV value): the polyamide is tested in 96wt% strength aqueous sulfuric acid solution, the concentration c=0.01 g/ml in sulfuric acid, the test temperature being 25 ℃;
(2) Melting point: determined by DSC, procedure was first round: constant temperature of 40-280 ℃, 10 ℃/min and 3min, and the second circle: 280-40 ℃, 10 ℃/min, and the third turn: 40-280 ℃ and 10 ℃/min; taking the peak temperature of the third circle as the melting point;
(3) Breaking strength and modulus: the breaking strength and modulus of a sample of the polyamide composition were determined and the breaking strength and modulus of the monofilaments were tested according to the method of GB/T14344-2008; wiping off surface water before testing the strength in a wet state, and then testing;
(4) Characterization of transparency: the transparency of the polyamide composition sample was evaluated by visual inspection, and very good represents complete transparency by visual inspection, and o represents translucency by visual inspection and a haze feeling; x represents opacity.
The term "nylon 6/66" refers to a binary copolyamide made by copolymerizing caprolactam, hexamethylenediamine and adipic acid monomers; the term "nylon 6/66/12" refers to a terpolymer amide made by copolymerizing caprolactam, hexamethylenediamine, adipic acid, and dodecalactam monomers; the nomenclature of the other copolyamides follows the above law.
The term "polyethylene glycol" is a generic term for ethylene glycol polymers containing alpha, omega-double terminal hydroxyl groups.
The term "dry strength" refers to the tensile break strength measured in the state of a sample at a water content of 0.2wt% or less in the filaments.
The term "initial wet strength" refers to the tensile break strength measured in the sample state after immersing the filaments in deionized water at 23 ℃ for 72 hours after preparation, which is a condition commonly used for conditioning polyamide filaments.
The term "wet strength after one month of soaking" refers to the tensile break strength measured in the sample state after 1 month of soaking the monofilament in deionized water at 23 ℃ after preparation, which is a condition that simulates the effect of long term aqueous environment use on the performance of the composition.
The term "alcohol-soluble" refers to a polyamide that is 10wt% dissolved in methanol and remains a clear solution after standing at 23 ℃ for 24 hours, as reflected in the dissolution capacity in small molecule alcohols.
The term "strength retention" polyamide generally results in a decrease in strength after moisture absorption, strength retention being the percentage of wet strength to dry strength after one month of soaking.
The process for preparing polyamide filaments is known in the art and generally comprises two steps: (1) preparing master batches: and (3) carrying out melt mixing on the ternary copolymer polyamide with alcohol solubility and polyethylene glycol in a screw extruder or a kneader, and cooling, granulating and drying to obtain master batch with high concentration polyethylene glycol. (2) Spinning: the master batch and nylon 6/66 resin are compounded according to a proportion and then melt-spun into monofilaments. Conventional typical processes are generally divided into 5 steps of extrusion, cooling, first drawing, second drawing and heat setting. The extrusion temperature is generally between 200 and 280 ℃. The cooling is generally carried out by water, and the cooling temperature is generally between 0 and 50 ℃. The first draft temperature is typically between 60 and 120℃and the draft ratio is typically between 2.0 and 5.0. The second draft temperature is typically between 150 and 280℃and the draft ratio is typically 1.0 to 3.0. The heat setting temperature is generally between 150 and 280℃and the draft ratio is generally between 0.9 and 1.0, such processes being well known in the polyamide industry monofilament industry. Some spinning aids, such as lubricants, antioxidants, uv stabilizers, etc., are typically added during the spinning of polyamide filaments. Wherein the lubricant is one or more of oleamide, erucamide, stearic acid amide, ethylene Bis Stearamide (EBS), oxidized polyethylene wax, zinc stearate, calcium stearate, magnesium stearate and the like. Wherein the antioxidant is selected from hindered phenols, phosphites, thioether antioxidants such as antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant 626, antioxidant PEPQ, antioxidant 245, antioxidant 1098, antioxidant 9228, and antioxidants of phosphate, phosphite and hypophosphite. The light stabilizer is selected from light stabilizers such as benzophenone, benzotriazole, triazine, hindered amine and the like, and is commercially available for application to plastics,commonly known as Basiff GermanyAnd->And the like, and the market marks are equal. But also include other spin aids, which are not described in detail herein, and such aids and uses are well known in the polyamide industry monofilament industry.
The present invention will now be explained using one of the schemes, and the polyamide monofilaments prepared by this process are used in the examples and comparative examples of the present invention, only for convenience in describing the present invention and simplifying the description, and are not necessarily prepared according to this procedure, and thus should not be construed as limiting the present invention; the method comprises the following steps:
in a double-screw extruder with the diameter of 35mm, at the melt temperature of 200 ℃, adopting ternary copolyamide with alcohol solubility as carrier resin, adding polyethylene glycol through a liquid metering pump, melting, mixing, bracing, granulating, and drying to prepare polyethylene glycol master batch. Nylon 6/66 resin, polyethylene glycol master batch, 0.1wt% of lubricant EBS (national medicine reagent) and 0.1wt% of antioxidant 1010 (Basoff) are uniformly mixed by a high-speed mixer. Mixing, pouring into a hopper of a single screw extruder with the diameter of 25mm, and setting the temperature from a feeding end to a machine head of the single screw extruder to 240 ℃, 255 ℃ and 250 ℃; cooling with cooling water at 15 deg.c; then, after the first drafting with the drafting multiplying power of 4.2, heating by adopting steam at 100 ℃; through the second drafting with the drafting multiplying power of 1.2, the hot air with the temperature of 250 ℃ is adopted for heating; then hot air at 230 ℃ is used for heat setting, and the draft ratio is 0.95; finally, polyamide monofilaments with a diameter of 2.0mm were obtained.
Examples 1 to 5
A polyamide composition comprises, by weight, 100 parts of nylon resin, 1.5 to 10 parts of polyethylene glycol having an average molecular weight of 200 to 1000, and 1 to 10 parts of water.
Nylon resin and polyethylene glycol in the polyamide composition are used for preparing polyamide monofilaments, the polyamide monofilaments are placed in a constant temperature and humidity box with the temperature of 75 ℃ and the humidity of 95% for moisture absorption, so that the moisture content of the polyamide monofilaments is equal to that of the polyamide composition, the breaking strength of the polyamide monofilaments with the adjusted moisture content is measured, and specific data are shown in table 1:
TABLE 1
Comparative example 1
A polyamide composition substantially as in example 1, except that PEG200 was absent.
Comparative example 2
A polyamide composition substantially as in example 2, except that PEG400 was absent.
Comparative example 3
A polyamide composition substantially as in example 5 except that PEG1000 was absent.
Comparative example 4
A polyamide composition substantially as in example 5, except that PEG1000 was replaced with PEG1200 of equal mass.
Comparative example 5
A polyamide composition substantially as in example 5, except that PEG1000 was replaced with equal mass of triethylene glycol.
Comparative example 6
A polyamide composition substantially as in example 5, except that PEG1000 was replaced with PEG2000 of equal mass. The nylon resins of comparative examples 1 to 6 were used with polyethylene glycol to prepare polyamide monofilaments, and the polyamide monofilaments were then placed in a constant temperature and humidity cabinet at 75 ℃ and 95% humidity to absorb moisture, so that the water content of the polyamide monofilaments was equal to that of the polyamide composition, and the breaking strength was measured, and specific data are shown in table 2:
TABLE 2
In combination with the data of comparative examples 1 to 6, it was found that the addition of polyethylene glycol of a certain molecular weight to polyamide compositions having a moisture content of 1 to 10 parts can increase the strength value of the polyamide, because the polyethylene glycol dispersed in the polyamide can help suppress the influence of moisture on the strength of the polyamide. The inventor speculates that because polyethylene glycol is added, more hydrogen and nylon are provided to form hydrogen bonds, water molecules which originally form hydrogen bonds with nylon are replaced to a certain extent, when the composition is in a wet environment, the polyethylene glycol reduces the density of the hydrogen bonds formed by the water penetrating into polyamide monofilaments, and the polyethylene glycol is an oligomer with a certain molecular weight, and has the increase of Van der Waals force caused by entanglement of molecular chains compared with the hydrogen bonds formed by water and nylon resin, so that the mechanical property of the nylon resin is not seriously influenced, and the prepared polyamide monofilaments have higher breaking strength in a wet state.
Examples 6 to 26
A transparent polyamide composition used in water environment comprises, by weight, 100 parts of copolymerized nylon resin, 1.5-10 parts of polyethylene glycol with average molecular weight of 200-1000 and 1.8-30 parts of ternary copolymer polyamide with alcohol solubility.
The transparent polyamide composition used in water environment is used for preparing polyamide monofilaments, the prepared polyamide monofilaments can keep stable mechanical properties in a long-term soaking environment, the initial wet fiber strength of the polyamide monofilaments is 6.1-6.9 cN/dtex, and the wet strength after soaking for one month is 4.5-5.8 cN/dtex. Specific data are shown in Table 3:
TABLE 3 Table 3
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Comparative example 7
A transparent polyamide composition was substantially the same as in example 6 except that 200 to 100 parts of PEG of equal mass was directly added to nylon 6/66 resin, i.e., the polyamide composition did not contain a terpolymer amide B1 having alcohol solubility.
The transparent polyamide composition is used for preparing polyamide monofilaments, and the initial wet state fiber strength of the prepared polyamide monofilaments is 6.2cN/dtex; the wet strength of the polyamide monofilament after being soaked in water for 1 month is 2.7cN/dtex; sample transparency.
Comparative example 8
A transparent polyamide composition was substantially the same as in example 10 except that the alcohol-soluble ternary copolyamide B1 was replaced with an equal mass of the alcohol-insoluble ternary copolyamide B3.
The transparent polyamide composition is used for preparing polyamide monofilaments, and the initial wet state fiber strength of the prepared polyamide monofilaments is 6.3cN/dtex; the wet strength of the polyamide monofilament after being soaked in water for 1 month is 2.7cN/dtex; sample transparency.
Comparative example 9
A transparent polyamide composition was substantially the same as in example 15 except that PEG400 to 100 parts of nylon 6/66 resin of equal mass was directly added, i.e., the polyamide composition did not contain a terpolymer amide B1 having alcohol solubility.
The transparent polyamide composition is used for preparing polyamide monofilaments, and the initial wet state fiber strength of the prepared polyamide monofilaments is 6cN/dtex; the wet strength of the polyamide monofilament after being soaked in water for 1 month is 2.6cN/dtex; sample transparency.
Comparative example 10
A transparent polyamide composition was substantially the same as in example 15, except that the alcohol-soluble ternary copolyamide B4 was replaced with an equal mass of the alcohol-insoluble ternary copolyamide B5.
The transparent polyamide composition is used for preparing polyamide monofilaments, and the initial wet state fiber strength of the prepared polyamide monofilaments is 6.5cN/dtex; the wet strength of the polyamide monofilament after being soaked in water for 1 month is 2.8cN/dtex; sample transparency.
As is clear from comparative examples 7 to 10, the wet strength of the polyamide monofilament formed by the composition system without the addition of the alcohol-soluble ternary copolyamide or without the addition of the ternary copolyamide is remarkably reduced after soaking for 1 month, because the alcohol-soluble ternary copolyamide in the system can help to promote the compatibility of PEG in the matrix and inhibit the PEG from diffusing into water, so that the PEG is stably dispersed in the matrix, and further, the polyamide composition still has stable strength after long-term soaking.
Comparative example 11
A transparent polyamide composition was substantially the same as in example 6 except that the same mass of the alcohol-soluble ternary copolyamide B1 was directly added to 100 parts of nylon 6/66 resin, i.e., the polyamide composition did not contain polyethylene glycol.
The transparent polyamide composition is used for preparing polyamide monofilaments, and the initial wet state fiber strength of the prepared polyamide monofilaments is 5.3cN/dtex; the wet strength of the polyamide monofilament after being soaked in water for 1 month is 2.0cN/dtex; sample transparency.
Comparing comparative example 11 with example 6, it was found that the decrease in wet strength of the polyamide filaments after 1 month of immersion in water was significant because the polyethylene glycol in the system was a key aid to improve the breaking strength of the wet polyamide fibers, and the alcohol-soluble ternary copolyamide had no effect on the retention of breaking strength of the polyamide filaments in the composition system without polyethylene glycol.
Comparative example 12
A transparent polyamide composition was substantially the same as in example 6 except that the part of the ternary copolyamide B1 having alcohol solubility was 1.5 parts.
The transparent polyamide composition is used for preparing polyamide monofilaments, and the initial wet state fiber strength of the prepared polyamide monofilaments is 6.3cN/dtex; the wet strength of the polyamide monofilament after being soaked in water for 1 month is 3.1cN/dtex; sample transparency.
Comparing comparative example 12 with example 6, it was found that the decrease in wet strength of the polyamide monofilament after 1 month of immersion in water was remarkable because the improvement in wet strength in a long-term water environment was not remarkable when the content of the alcohol-soluble ternary copolyamide in the system was less than 1.8 parts.
Comparative example 13
A transparent polyamide composition was substantially the same as in example 6 except that the part of the ternary copolyamide B1 having alcohol solubility was 35 parts.
The transparent polyamide composition is used for preparing polyamide monofilaments, and the initial wet state fiber strength of the prepared polyamide monofilaments is 5.5cN/dtex; the wet strength of the polyamide monofilament after being soaked in water for 1 month is 3.7cN/dtex; sample transparency.
Comparing comparative example 13 with example 6, it can be seen that the wet strength of the polyamide monofilament is significantly reduced because the content of the alcohol-soluble ternary copolyamide in the system is too high, which in turn results in a decrease in the breaking strength of the polyamide monofilament.
Comparative example 14
A transparent polyamide composition substantially as in example 6, except that the PEG200 was 1 part.
The transparent polyamide composition is used for preparing polyamide monofilaments, and the initial wet state fiber strength of the prepared polyamide monofilaments is 5.6cN/dtex; the wet strength of the polyamide monofilament after being soaked in water for 1 month is 3.6cN/dtex; sample transparency.
Comparing comparative example 14 with example 6, it was found that the decrease in wet strength of the polyamide monofilament was remarkable because the polyethylene glycol content in the system was less than 1.5 parts, and the effect of improving the strength of the polyamide monofilament was not remarkable.
Comparative example 15
A transparent polyamide composition substantially as in example 6, except that the PEG200 was 15 parts.
The transparent polyamide composition is used for preparing polyamide monofilaments, and the initial wet state fiber strength of the prepared polyamide monofilaments is 5.1cN/dtex; the wet strength of the polyamide monofilament after being soaked in water for 1 month is 3.5cN/dtex; sample transparency.
Comparing comparative example 15 with example 6, it can be seen that the wet strength of the polyamide filaments is significantly reduced because the polyethylene glycol content in the system is too high, which in turn results in a decrease in the breaking strength of the polyamide filaments.
Comparative example 16
A transparent polyamide composition substantially as in example 6, except that PEG200 was replaced with equal mass of triethylene glycol.
The transparent polyamide composition is used for preparing polyamide monofilaments, and the initial wet state fiber strength of the prepared polyamide monofilaments is 5.5cN/dtex; the wet strength of the polyamide monofilament after being soaked in water for 1 month is 2.1cN/dtex; sample transparency.
Comparing comparative example 16 with example 6, it was found that the decrease in wet strength of the polyamide monofilament was remarkable because triethylene glycol was relatively easily detached even in the polyamide composition containing the alcohol-soluble ternary copolyamide upon immersion in water, resulting in not high initial wet fiber strength of the polyamide monofilament nor high wet strength after immersion for 1 month.
Comparative example 17
A polyamide composition substantially as in example 6, except that PEG1200 was used in place of PEG200.
The polyamide composition was used to prepare polyamide monofilaments and the sample was transparent.
Comparing comparative example 17 with example 6, it can be seen that the polyamide monofilament has reduced transparency and an opaque white spot in appearance, because the polyethylene glycol becomes too poorly compatible with the PA6/66 component.
Claims (9)
1. A polyamide composition characterized in that: comprises 100 parts of nylon resin, 1.5-10 parts of polyethylene glycol and 1-10 parts of water according to parts by weight; the number average molecular weight of the polyethylene glycol is 200-1000.
2. A polyamide composition according to claim 1, wherein the nylon resin is a nylon 6 resin, a nylon 66 resin or a nylon 6/66 resin.
3. A polyamide composition according to claim 2, wherein the nylon 6/66 resin has a melting point of 180-215 ℃ and a relative viscosity of 2.7-4.5.
4. A transparent polyamide composition for use in an aqueous environment, characterized by: comprises 100 parts of copolymerized nylon resin, 1.5-10 parts of polyethylene glycol and 1.8-30 parts of ternary copolymer polyamide with alcohol solubility by weight; the number average molecular weight of the polyethylene glycol is 200-1000.
5. A transparent polyamide composition for use in an aqueous environment according to claim 4, wherein the co-polyamide resin is a nylon 6/66 resin; the melting point of nylon 6/66 resin is 180-215 deg.C and the relative viscosity is 2.7-4.5.
6. A transparent polyamide composition for use in an aqueous environment according to claim 4, wherein the terpolymer polyamide having alcohol solubility has a relative viscosity of from 2.4 to 4.0.
7. The transparent polyamide composition for use in an aqueous environment according to claim 4, wherein the mass ratio of the alcohol-soluble terpolymer polyamide to the polyethylene glycol is greater than 1.2.
8. The transparent polyamide composition for use in an aqueous environment of claim 4, wherein the alcohol-soluble, ternary polyamide is comprised of a first amide building block, a second amide building block, and a third amide building block, the first amide building block being a PA6 building block, the second amide building block being a PA66 building block, the third amide building block being one of a PA610, PA69, PA12, PA612, and PA11 building block.
9. Use of a transparent polyamide composition for use in an aqueous environment according to any one of claims 4 to 8, characterized in that: for the preparation of polyamide monofilaments.
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