CN113861411A - High-stability nylon polymer and preparation method thereof - Google Patents
High-stability nylon polymer and preparation method thereof Download PDFInfo
- Publication number
- CN113861411A CN113861411A CN202111351444.6A CN202111351444A CN113861411A CN 113861411 A CN113861411 A CN 113861411A CN 202111351444 A CN202111351444 A CN 202111351444A CN 113861411 A CN113861411 A CN 113861411A
- Authority
- CN
- China
- Prior art keywords
- nylon
- polymer
- salt
- stability
- salt solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001778 nylon Polymers 0.000 title claims abstract description 119
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000004677 Nylon Substances 0.000 claims abstract description 82
- 229920006118 nylon 56 Polymers 0.000 claims abstract description 59
- 229920000642 polymer Polymers 0.000 claims abstract description 33
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 32
- 239000004611 light stabiliser Substances 0.000 claims abstract description 32
- 150000001412 amines Chemical class 0.000 claims abstract description 31
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 31
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 24
- 239000012266 salt solution Substances 0.000 claims abstract description 24
- 150000003839 salts Chemical class 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000003381 stabilizer Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 229920006141 Polyamide 5X Polymers 0.000 claims abstract description 8
- 238000001704 evaporation Methods 0.000 claims abstract description 7
- 230000008020 evaporation Effects 0.000 claims abstract description 7
- 229920005989 resin Polymers 0.000 claims abstract description 7
- 239000011347 resin Substances 0.000 claims abstract description 7
- -1 3, 5-di-t-butyl-4-hydroxyphenyl Chemical group 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 12
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 claims description 12
- 239000000155 melt Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- FTVFPPFZRRKJIH-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-amine Chemical compound CC1(C)CC(N)CC(C)(C)N1 FTVFPPFZRRKJIH-UHFFFAOYSA-N 0.000 claims description 8
- MFNFHZVOHDNCDN-UHFFFAOYSA-N 4,6-bis[(2,2,6,6-tetramethylpiperidin-3-yl)amino]benzene-1,3-dicarboxamide Chemical compound CC1(NC(CCC1NC1=CC(=C(C=C1C(=O)N)C(=O)N)NC1C(NC(CC1)(C)C)(C)C)(C)C)C MFNFHZVOHDNCDN-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 4
- 239000002028 Biomass Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical group OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- ACVXGYXDJXAWGY-UHFFFAOYSA-N 2-hydroxyethyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=CC(CCC(=O)OCCO)=CC(C(C)(C)C)=C1O ACVXGYXDJXAWGY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- ZEUVPBIKPGDABT-UHFFFAOYSA-N n'-(2-ethoxyphenyl)-n-(4-ethylphenyl)oxamide Chemical compound CCOC1=CC=CC=C1NC(=O)C(=O)NC1=CC=C(CC)C=C1 ZEUVPBIKPGDABT-UHFFFAOYSA-N 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002530 phenolic antioxidant Substances 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 15
- 238000009987 spinning Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 8
- 238000012545 processing Methods 0.000 abstract description 8
- 238000004043 dyeing Methods 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 23
- 239000004952 Polyamide Substances 0.000 description 17
- 229920002647 polyamide Polymers 0.000 description 17
- 230000032683 aging Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 238000004383 yellowing Methods 0.000 description 12
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 8
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000001361 adipic acid Substances 0.000 description 5
- 229920006122 polyamide resin Polymers 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 229920006021 bio-based polyamide Polymers 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical class 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 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920006052 Chinlon® Polymers 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 241001589086 Bellapiscis medius Species 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920000572 Nylon 6/12 Polymers 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920013724 bio-based polymer Polymers 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010036 direct spinning Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229920006119 nylon 10T Polymers 0.000 description 1
- 239000008041 oiling agent Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000013520 petroleum-based product Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229920006012 semi-aromatic polyamide Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the technical field of high molecular materials, and discloses a high-stability nylon polymer which comprises a bio-based nylon 5X polymer, wherein the raw materials of the bio-based nylon 5X polymer comprise nylon 5X salt and a stabilizer composition, and the stabilizer composition comprises a hindered phenol antioxidant and a hindered amine light stabilizer. And a preparation method of the nylon polymer is disclosed. According to the invention, the hindered phenol antioxidant and the hindered amine light stabilizer are added in nylon polymerization, so that the nylon achieves the ideal effects of high light and heat stability in the using process, and the nylon has excellent effects on overcoming spinnability, dyeing property and the like when the bio-based nylon is used for spinning fibers; the preparation process adopts a method of polymerizing the concentrated polyamide 5X salt solution, the polymerization process is divided into two steps of pre-polymerization and post-polymerization, flash evaporation is carried out between the two steps of polymerization, and the obtained nylon 5X resin slice is not degraded and gelatinized under the high-temperature processing condition and still keeps good fluidity.
Description
Technical Field
The invention belongs to the technical field of high molecular materials, and relates to a high-stability nylon polymer and a preparation method thereof.
Background
Since the first polyamide (PA, commonly called nylon) product appeared in 1938, the development of the polyamide has been going on for nearly 80 years, and the variety is various. The polyamide has good comprehensive performance, specific strength higher than that of metal, good mechanical performance, heat resistance, abrasion resistance, chemical resistance, flame retardance and self-lubrication, easy processing and low friction factor, is suitable for filling, reinforcing and modifying glass fiber and other materials, and is widely applied to the aspects of automobiles, electronic and electric products, packaging, machinery, sports and leisure goods, daily necessities and the like.
With the gradual decrease of petroleum resources, the search for alternatives to petroleum has been a global problem. Bio-based polymers and their fibers derived from renewable resources have acquired unprecedented opportunities for development. The important point of the research of the bio-based polyamide is the renewable research of the raw materials, and the problem of 'nipping neck' of the international raw materials in the traditional petroleum-based products is solved. With the increasing market demand and the continuous emergence of new technologies, the bio-based polyamide technology and products show diversified development.
The polyamide material is easily degraded under the conditions of light, heat, oxygen and impurities, so that the polyamide material is aged and yellowed. The main reason for this is that in the thermal process, the polyamides are subject to oxidative degradation, which reduces their molecular mass. In this process, the amide bond in the polyamide is easily cleaved due to low dissociation energy. Meanwhile, the amide group is also oxidized by oxygen to form a chromophore containing a carbon-nitrogen double bond, resulting in yellowing. The polyamide structure is easy to absorb water and is easy to hydrolyze at high temperature, so that the structure is damaged, and the performance of the material is reduced. In addition, the polyamide linkages also age to varying degrees under different wavelengths of light. Under the illumination of specific wavelength, the polyamide may generate a free radical reaction process, so that amide bond is cracked or a photooxidation crosslinking reaction is generated, the product is aged, and the material performance is reduced. For the above reasons, the stability of polyamides has been a focus of research in the industrial field.
The nylon 56 is used as a bio-based polyamide material, and the main raw materials of the nylon 56 are pentanediamine and adipic acid, wherein the pentanediamine is prepared by biological fermentation, and the source of the pentanediamine is plant raw materials such as corn starch and the like. The high-stability nylon 56 polymer raw material is a very key quality guarantee for developing downstream applications of nylon 56 such as textile fibers or engineering plastics.
The patent "nylon fiber and its preparation method (201710193878.8)" discloses a preparation method of nylon fiber, which comprises directly spinning after polymerization of raw materials containing 1, 5-pentanediamine and adipic acid. The patent "a nylon fiber (201310060413.4)" discloses a nylon fiber, the raw material of which comprises nylon resin prepared from pentanediamine and aliphatic dibasic acid, wherein at least one of the pentanediamine and the aliphatic dibasic acid is prepared by biological method, and also comprises polyamide 56 fiber. However, polyamide 56 is easily degraded under high temperature conditions, and gel is easily generated under high temperature conditions similarly to polyamide 66, which has great influence on the stability of industrial long-term production and the quality of products. According to the literature data available at present, the melting point of polyamide 56 is generally 250-255 ℃, and the spinning temperature is generally 280-290 ℃ in order to maintain the spinning stability (the physical properties and spinnability of nylon 56 are ascertained [ J ], polyester industry, 2014, 27 (1): 38-39; preparation and characterization of novel nylon 56 fiber [ D ], Donghua university, 2014.). However, when the temperature reaches 275 ℃, the polyamide 56 starts to degrade and gel, and the processing temperature is not suitable to exceed 275 ℃ for a long time in order to ensure the production stability and the product quality, but the good fluidity of the melt of the polyamide 56 cannot be ensured because the melting point of the polyamide 56 is 250-255 ℃ and the processing temperature below 275 ℃.
The patent 'polyamide resin' (application No. 200780017406.9) provides a polyamide resin with excellent retention thermal stability and high biomass ratio, nylon 56 salt generated by the reaction of pentanediamine and adipic acid is polymerized with caprolactam with the addition ratio of 3% -25%, and phosphite is used as a heat stabilizer. The patent 'a heat-resistant modified chinlon 56 polymer and a preparation method thereof' (application number 201610428381.2) adopts modified montmorillonite such as alkylamine salt or alkyl ammonium phosphate salt and the like as a heat-resistant agent to improve the heat resistance of chinlon 56. The patent "a polyamide resin with yellowing resistance and a preparation method thereof" (application No. 201811473696.4) relates to a polyamide resin with good yellowing resistance and a preparation method thereof, which effectively inhibits the generation of impurities in a pentamethylenediamine-adipic acid nylon salt by adding an anti-yellowing agent and an antioxidant and using oxygen removal operation treatment, and simultaneously can improve the yellowing resistance of the polyamide resin under high temperature and illumination conditions.
These methods can significantly improve the thermal stability of bio-based nylon, but have two problems: 1) the heat-resistant agent of the bio-based nylon has the problem of saturated use and failure in a long-term use state; 2) the anti-yellowing agent or antioxidant (hypophosphite, phosphite or copper ions and the like) may react with titanium dioxide, which is a delustering agent for textile fibers, to cause coagulation of the titanium dioxide, thereby affecting the spinnability of the bio-based nylon resin.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, one aspect of the present invention relates to a high stability nylon polymer.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high-stability nylon polymer comprises a bio-based nylon 5X polymer, wherein the raw material of the bio-based nylon 5X polymer comprises a nylon 5X salt and a stabilizer composition, and the stabilizer composition comprises a hindered phenol antioxidant and a hindered amine light stabilizer.
Preferably, the raw materials of the bio-based nylon 5X polymer comprise, by weight, 90-100 parts of nylon 5X salt, 0.1-5 parts of hindered phenol antioxidants and 0.1-5 parts of hindered amine light stabilizers.
More preferably, the content of the hindered phenol antioxidant and the hindered amine light stabilizer is 0.3-2 parts.
The raw material of the nylon 5X salt comprises pentamethylene diamine from biological substances, the pentamethylene diamine and dibasic acid are subjected to neutralization reaction to obtain the nylon 5X salt, and the dibasic acid can also be dibasic acid from biological substances.
Preferably, the nylon 5X is selected from one or more of nylon 54, nylon 56, nylon 59, nylon 510, nylon 511, nylon 512, nylon 513, nylon 514, nylon 516, and the like.
Further preferably, the nylon 5X is selected from one or more of nylon 56, nylon 510, nylon 511, nylon 512, nylon 514 and nylon 516.
In a preferred embodiment of the present invention, the nylon polymer further comprises other nylon resins such as: nylon 6, nylon 66, nylon 69, nylon 610, nylon 612, nylon 1010, nylon 11, nylon 12, nylon 1012, nylon 1212 and nylon 46, semi-aromatic polyamides such as nylon 6T, nylon 9T, nylon 10T, and the like.
The hindered phenol antioxidant is any one or combination of more than two of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, ethylene glycol (beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate), triethylene glycol bis-3- (3-di-tert-butyl-4-hydroxyphenyl) propionate) and N, N' -bis- (2- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy.
The hindered amine light stabilizer (containing amide energy groups) is any one or the combination of more than two of 4-amino-2, 2, 6, 6-tetramethylpiperidine, bis (2, 2, 6, 6-tetramethyl-3-piperidylamino) -isophthalamide, N- (2-ethoxyphenyl) -N '- (4-ethylphenyl) -ethanediamide and N- (5- (1, 1) dimethylethyl) -2-ethoxyphenyl) -N' - (2-ethylphenyl) ethanediamide.
Preferably, the hindered phenol antioxidant is pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
Preferably, the hindered amine light stabilizer is 4-amino-2, 2, 6, 6-tetramethylpiperidine and/or bis (2, 2, 6, 6-tetramethyl-3-piperidinylamino) -isophthalamide; particularly preferably, the hindered amine light stabilizer is 4-amino-2, 2, 6, 6-tetramethylpiperidine.
Preferably, the bio-based nylon 5X polymer further comprises any auxiliary agent which does not impair the effect of the present invention. Such adjuvants include, but are not limited to: plasticizers, antistatic agents, flame retardants, catalysts, molecular weight regulators, hydrolysis resistance agents, fluorescent agents, dyes, inorganic powders such as inorganic pigments, delustering agents, nucleating agents, and anti-ultraviolet agents, and the like, any of which may be added alone or in any combination.
The person skilled in the art will be able to understand the usual choice of the abovementioned auxiliaries and can obtain them commercially. For example, the nucleating agents include, but are not limited to, the following listed adjuvants: inorganic powder such as silica, talc, barium sulfate, and montmorillonite, and metal oxide such as zinc oxide and titanium dioxide; the inorganic powder comprises the following additives: carbon black, titanium dioxide, barium sulfate, magnesium sulfate, calcium carbonate, zinc oxide, montmorillonite, kaolin, glass fiber, glass micro-beads, carbon fiber, graphene, carbon nano-tubes, mica and other inorganic functional powder.
In another aspect, the present invention relates to a method for preparing the high stability nylon polymer, comprising the following steps:
1) under the protection of nitrogen, pentanediamine and dibasic acid in stoichiometric ratio react in water at room temperature to prepare a nylon 5X salt solution; or directly and uniformly mixing nylon 5X salt and water to prepare a nylon 5X salt solution, wherein the mass concentration of the nylon 5X salt solution is 40-70%, and the pH value is 6.0-10.0;
2) adding the hindered phenol antioxidant and the hindered amine light stabilizer into a nylon 5X salt solution according to a proportion, and uniformly stirring; heating the nylon 5X salt solution to a boiling point for concentration, wherein the concentration of the concentrated polyamide 5X salt solution is 65-95%;
3) feeding the concentrated polyamide 5X salt solution obtained in the step 2) into a continuous polymerization pre-polymerizer, controlling the reaction temperature to be 200-270 ℃, the pressure to be 1.0-3.0 MPa, and the reaction time to be 1-4 hours;
4) flashing, reducing the pressure of a reaction system to 0.0-0.1 Pa, and the flashing temperature is 260-300 ℃;
5) feeding the melt obtained after flash evaporation into a post-polymerizer, controlling the temperature to be 260-300 ℃, the pressure to be 0.0pa to-0.1 Mpa, and the post-polymerization residence time to be 20-60 minutes to obtain a nylon 5X polymer final polymerization melt;
if the flatting agent is added, the prepared TiO2 and water suspension can be added in any step of the steps 1) to 5);
6) and 5) carrying out bracing and dicing on the melt obtained in the step 5) to obtain nylon 5X resin slices.
Preferably, in the step 1), the molar ratio of the pentamethylene diamine to the dibasic acid is 1-1.05: 1.
Preferably, in the step 1), the concentration of the nylon 5X salt solution is 50-65%, and the pH value is 7.0-9.0.
Preferably, in the step 2), the concentration of the polyamide 5X salt solution after concentration is 75 to 90%.
Preferably, in the step 3), the reaction temperature is controlled to be 220-250 ℃, the pressure is 1.5-2.5 MPa, and the reaction time is 2-3 hours.
Preferably, in the step 4), the flash evaporation temperature is 275-285 ℃.
Preferably, in the step 5), the temperature is controlled to be 270-290 ℃, and the post-polymerization residence time is 30-40 minutes.
Further, semi-dull chip, TiO2The addition amount of (B) is 0.3 part; the addition amount of the full-dull slice TiO2 is 1.0-2.0 parts.
The preparation method of the high-stability nylon polymer can adopt a continuous process and can also adopt an intermittent process.
In the high-stability nylon polymer, any auxiliary agent which does not damage the effect of the invention can be added in the whole production process of polymerization, namely the process of adding monomer raw materials into polymer final polymerization molding (granulating or melt direct spinning and the like).
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the hindered phenol antioxidant and the hindered amine light stabilizer are added in nylon polymerization (especially bio-based nylon 56 polymerization), and the two auxiliaries can continuously capture free radicals generated by light and heat effects in the nylon polymer and continuously regenerate with each other, so that the nylon can achieve ideal effects of high light and heat stability in the using process, is long-acting, and has excellent effects on overcoming spinnability, dyeing property and the like when the bio-based nylon is used for spinning fibers.
(2) In the preparation process of the high-stability nylon polymer, a method for polymerizing the concentrated polyamide 5X salt solution is adopted, the polymerization process is divided into two steps of pre-polymerization and post-polymerization, flash evaporation is carried out in the middle of the two steps of polymerization, and the obtained nylon 5X resin slice can not be degraded and gelated under the high-temperature processing condition of over 280 ℃, and still can keep good fluidity.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
In the following examples, the resulting nylon viscosity is characterized by the relative viscosity of a 98% concentrated sulfuric acid test.
Example 1
A high-stability nylon polymer comprises a bio-based nylon 56 polymer, wherein the raw material of the bio-based nylon 56 polymer comprises a nylon 56 salt and a stabilizer composition, and the stabilizer composition comprises a hindered phenol antioxidant and a hindered amine light stabilizer.
The bio-based nylon 56 polymer raw material comprises, by weight, 98 parts of nylon 56 salt, 1 part of hindered phenol antioxidant and 1 part of hindered amine light stabilizer.
The hindered phenol antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and the hindered amine light stabilizer is 4-amino-2, 2, 6, 6-tetramethylpiperidine.
The preparation method of the high-stability nylon polymer comprises the following steps:
1) under the protection of nitrogen with the purity of more than 99%, the molar ratio of the pentanediamine to the adipic acid is 1.03: 1 neutralizing in desalted water to obtain nylon 56 salt with the pH value of 7.5;
2) adding 98 parts of nylon 56 salt solution into 1 part of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and 1 part of 4-amino-2, 2, 6, 6-tetramethylpiperidine, and uniformly stirring; concentrating the nylon 56 salt solution under the conditions of 0.15MPa of pressure and 150 ℃ to reach the polymer concentration of 85 percent;
3) feeding 85% nylon 56 salt solution into a pre-polymerizer, wherein the pressure is 1.7MPa, the temperature is divided into three sections, the temperature is 220 ℃, 235 ℃ and 250 ℃, the pre-polymerization time is 3 hours in total, and the reaction time is about 1 hour at each section of temperature;
4) flashing the polymer, reducing the pressure to 0.0Pa, and enabling the temperature of the polymer system to reach 275 ℃;
5) the melt enters a post-polymerizer, the temperature is maintained at 280 ℃, the pressure is normal, and the reaction time is 20 minutes, so that a final polymer is obtained;
6) and cooling the melt in circulating water at 2 ℃, and granulating and forming.
The resulting nylon 56 was determined to have a relative viscosity of 2.4 and a melting point of 252 ℃. After the 180 ℃ oven aging test for 30min and the ultraviolet aging test for 120 hours, no obvious yellowing is observed.
Example 2
A high-stability nylon polymer comprises a bio-based nylon 56 polymer, wherein the raw material of the bio-based nylon 56 polymer comprises a nylon 56 salt and a stabilizer composition, and the stabilizer composition comprises a hindered phenol antioxidant and a hindered amine light stabilizer.
The bio-based nylon 56 polymer raw material comprises, by weight, 98.2 parts of nylon 56 salt, 0.5 part of hindered phenol antioxidant and 1 part of hindered amine light stabilizer. The hindered phenol antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and the hindered amine light stabilizer is 4-amino-2, 2, 6, 6-tetramethylpiperidine.
The preparation method of the high-stability nylon polymer is the same as that of the example 1, except that:
the prepared suspension of TiO2 and water was added at the rear stage of the front polymerizer in a proportion of 0.3 part.
The relative viscosity of the obtained nylon 56 is 2.5, the melting point is 252 ℃, and the content of TiO2 is 0.3 percent. After the 180 ℃ oven aging test for 30min and the ultraviolet aging test for 120 hours, no obvious yellowing is observed.
Example 3
Example 3 differs from example 2 in that:
(1) adding 96.4 parts of nylon 56 salt solution in the step 2);
(2) the prepared suspension of TiO2 and water was added after flash evaporation and before the post-polymerization reactor at a rate of 1.6 parts.
The relative viscosity of the obtained nylon 56 is 2.6, the melting point is 252 ℃, and the content of TiO2 is 1.6 percent. After the 180 ℃ oven aging test for 30min and the ultraviolet aging test for 120 hours, no obvious yellowing is observed.
Example 4
A high-stability nylon polymer comprises a bio-based nylon 56 polymer, wherein the raw material of the bio-based nylon 56 polymer comprises a nylon 56 salt and a stabilizer composition, and the stabilizer composition comprises a hindered phenol antioxidant and a hindered amine light stabilizer.
The bio-based nylon 56 polymer raw material comprises 99 parts by weight of nylon 56 salt, 0.5 part by weight of hindered phenol antioxidant and 0.5 part by weight of hindered amine light stabilizer. The hindered phenol antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, the hindered amine light stabilizer is bis (2, 2, 6, 6-tetramethyl-3-piperidylamino) -isophthalamide, and the bis (2, 2, 6, 6-tetramethyl-3-piperidylamino) -isophthalamide is also called S-EED (a product of Kelaien company), and is a multifunctional stabilizer suitable for nylon. Research shows that the S-EED can stabilize the pressure of the nylon melt, stabilize the processing process and reduce filament breakage during fiber spinning; meanwhile, the S-EED is highly compatible with nylon and can be bonded with nylon molecules together, so that the stability of the S-EED on the nylon exceeds the limit of the traditional light stabilizer. Generally, S-EED is used alone in polymers, and has a remarkable effect in the initial stage of use of nylon, but is liable to be dissipated during processing to cause a reduction in the long-term stability. Researches show that when the S-EED and the hindered phenol antioxidant are compounded for use, the compound has good synergistic effect and long-acting effect, can obviously improve the light and heat stability of nylon, and has the characteristic of remarkably preventing nylon from aging.
The procedure for preparing the above high stability nylon polymer was the same as in example 2.
The relative viscosity of the obtained nylon 56 is 2.7, the melting point is 252 ℃, and the content of TiO2 is 0.3 percent. After the 180 ℃ oven aging test for 30min and the ultraviolet aging test for 120 hours, no obvious yellowing is observed.
Example 5
A high-stability nylon polymer comprises a bio-based nylon 510 polymer, wherein the raw material of the bio-based nylon 510 polymer comprises a nylon 510 salt and a stabilizer composition, and the stabilizer composition comprises a hindered phenol antioxidant and a hindered amine light stabilizer.
The bio-based nylon 510 polymer raw material comprises, by weight, 99.4 parts of nylon 510 salt, 0.3 part of hindered phenol antioxidant and 0.3 part of hindered amine light stabilizer. The hindered phenol antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and the hindered amine light stabilizer is bis (2, 2, 6, 6-tetramethyl-3-piperidinylamino) -isophthalamide.
The procedure for preparing the above high stability nylon polymer was the same as in example 2.
The resulting nylon 510 had a relative viscosity of 2.8 and a melting point of 215 ℃ as determined. After the 180 ℃ oven aging test for 30min and the ultraviolet aging test for 120 hours, no obvious yellowing is observed.
Example 6
A high-stability nylon polymer comprises a bio-based nylon 512 polymer, wherein the raw material of the bio-based nylon 512 polymer comprises a nylon 512 salt and a stabilizer composition, and the stabilizer composition comprises a hindered phenol antioxidant and a hindered amine light stabilizer.
The bio-based nylon 512 polymer raw material comprises, by weight, 99.4 parts of nylon 510 salt, 0.3 part of hindered phenol antioxidant and 0.3 part of hindered amine light stabilizer. The hindered phenol antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and the hindered amine light stabilizer is bis (2, 2, 6, 6-tetramethyl-3-piperidinylamino) -isophthalamide.
The procedure for preparing the above high stability nylon polymer was the same as in example 1.
The resulting nylon 512 was determined to have a relative viscosity of 2.7 and a melting point of 210 ℃. After the 180 ℃ oven aging test for 30min and the ultraviolet aging test for 120 hours, no obvious yellowing is observed.
Example 7
The nylon 56 obtained in the embodiment 1-5 is spun, and the method comprises the following steps:
1) drying the nylon 56 slices; and (3) a drying process: continuous nitrogen drying at the dew point of-40 ℃; the oxygen content in the nitrogen is less than 3 ppm; the drying temperature is 72 ℃; drying time is 18 hours; the dry slices contained 600ppm water;
2) spinning the slices obtained after drying in the step 1), extruding and melting the nylon 56 slices by a screw, spraying the melt from a spinning pipeline, a spinning box, a metering pump, a spinning pack and a spinneret plate to obtain melt trickle, cooling and blowing the melt trickle to solidify into fibers, and oiling and winding the fibers to obtain the nylon 56 filaments. The spinning process comprises the following steps: the rotating speed of the screw is 70 r/min; the screw is generally provided with 6 zones, the first three: especially, the heating power of the second area and the third area is larger, the slicing is changed into a melt state from a solid state and the rapid temperature rise is mainly completed in the first three areas, and the temperature of each area of the screw is as follows in sequence: 250 ℃ in the first region, 288 ℃ in the second region, 285 ℃ in the third region, 283 ℃ in the fourth region, 283 ℃ in the fifth region and 283 ℃ in the sixth region; the temperature of a spinning box body is 283 ℃; cooling and solidifying the melt thin flow into fibers by side air blowing, wherein the cooling air speed is 0.6 m/min; the wind temperature is 21 ℃, and the wind pressure is 400 Pa; the oiling amount is controlled by the supply amount of an oiling agent pump, and the oiling amount of the pre-oriented yarn POY is 0.3 percent; POY spinning speed is 4350 m/min; POY specification 33dtex/24f, breaking strength 3.0cn/dtex, and elongation at break 75%.
The POY is subjected to stretching false-twist texturing to obtain DTY, and the DTY process of the false-twist textured yarn comprises the following steps: the drafting temperature is 200 ℃; the drafting multiple is 1.2; the speed of the drawing roller is 550 m/min; the twisting is divided into S twisting or Z twisting, and the twisting tension is 30 cN; untwisting tension of 30 cN; the ratio D/Y of the surface speed of the friction disc to the speed of the filament leaving the false twister is 1.5; the network wind pressure is 1.0 bar; the diameter of the nozzle is 1.0 mm; the heat setting temperature is 200 ℃; the winding speed was 500 m/min.
In the processing process, the degradation and gelation phenomena are avoided, and the good fluidity is always kept.
The DTY breaking strength is about 3.8cn/dtex, the elongation at break is about 28 percent, and the moisture regain is 5-5.5 percent. The DTY fiber is placed in an oven at 180 ℃ for 30min, the fiber does not yellow, the breaking strength is detected to be 3.7 cn/dtex, and the elongation at break is 26%; the fiber is not yellowed after being irradiated by an ultraviolet lamp for 120 hours, and the breaking strength and the breaking elongation of the fiber are detected to be 3.8cn/dtex and 27 percent.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (10)
1. The high-stability nylon polymer is characterized by comprising a bio-based nylon 5X polymer, wherein the raw material of the bio-based nylon 5X polymer comprises a nylon 5X salt and a stabilizer composition, and the stabilizer composition comprises a hindered phenol antioxidant and a hindered amine light stabilizer.
2. The high-stability nylon polymer according to claim 1, wherein the bio-based nylon 5X polymer raw material comprises 90-100 parts by weight of nylon 5X salt, 0.1-5 parts by weight of hindered phenol antioxidant, and 0.1-5 parts by weight of hindered amine light stabilizer.
3. The high stability nylon polymer of claim 2, wherein the hindered phenol antioxidant and the hindered amine light stabilizer are both 0.3-2 parts.
4. The high stability nylon polymer of claim 1, wherein the raw material of the nylon 5X salt comprises pentane diamine derived from biomass, and the pentane diamine and the dibasic acid undergo a neutralization reaction to obtain the nylon 5X salt, and the dibasic acid can also be a dibasic acid derived from biomass.
5. The high stability nylon polymer of claim 1, wherein the nylon 5X is selected from one or more of nylon 54, nylon 56, nylon 59, nylon 510, nylon 511, nylon 512, nylon 513, nylon 514, nylon 516, etc.
6. The highly stable nylon polymer according to claim 1, wherein the hindered phenol-based antioxidant is any one or a combination of two or more of tetrakis [ β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], ethylene glycol (β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate), triethylene glycol bis-3- (3-di-t-butyl-4-hydroxyphenyl) propionate) and N, N' -bis- (2- (3, 5-di-t-butyl-4-hydroxyphenyl) propionyloxy; the hindered amine light stabilizer (containing amide energy groups) is any one or the combination of more than two of 4-amino-2, 2, 6, 6-tetramethylpiperidine, bis (2, 2, 6, 6-tetramethyl-3-piperidylamino) -isophthalamide, N- (2-ethoxyphenyl) -N '- (4-ethylphenyl) -ethanediamide and N- (5- (1, 1) dimethylethyl) -2-ethoxyphenyl) -N' - (2-ethylphenyl) ethanediamide.
7. The highly stable nylon polymer of claim 6, wherein the hindered phenolic antioxidant is pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
8. The high stability nylon polymer of claim 6, wherein the hindered amine light stabilizer is 4-amino-2, 2, 6, 6-tetramethylpiperidine and/or bis (2, 2, 6, 6-tetramethyl-3-piperidinylamino) -isophthalamide.
9. A method for preparing the high-stability nylon polymer as defined in any one of claims 1 to 8, comprising the steps of:
1) under the protection of nitrogen, pentanediamine and dibasic acid in stoichiometric ratio react in water at room temperature to prepare a nylon 5X salt solution; or directly and uniformly mixing nylon 5X salt and water to prepare a nylon 5X salt solution, wherein the mass concentration of the nylon 5X salt solution is 40-70%, and the pH value is 6.0-10.0;
2) adding the hindered phenol antioxidant and the hindered amine light stabilizer into a nylon 5X salt solution according to a proportion, and uniformly stirring; heating the nylon 5X salt solution to a boiling point for concentration, wherein the concentration of the concentrated polyamide 5X salt solution is 65-95%;
3) feeding the concentrated polyamide 5X salt solution obtained in the step 2) into a continuous polymerization pre-polymerizer, controlling the reaction temperature to be 200-270 ℃, the pressure to be 1.0-3.0 MPa, and the reaction time to be 1-4 hours;
4) flashing, reducing the pressure of a reaction system to 0.0Pa, and enabling the flashing temperature to be 260-300 ℃;
5) feeding the melt obtained after flash evaporation into a post-polymerizer, controlling the temperature to be 260-300 ℃, the pressure to be 0.0pa to-0.1 Mpa, and the post-polymerization residence time to be 20-60 minutes to obtain a nylon 5X polymer final polymerization melt;
if the flatting agent is added, adding the prepared TiO in any one step of the steps 1) to 5)2A suspension with water;
6) and 5) carrying out bracing and dicing on the melt obtained in the step 5) to obtain nylon 5X resin slices.
10. The method for preparing the high-stability nylon polymer according to claim 9, wherein in the step 1), the mole ratio of the pentanediamine to the dibasic acid is 1-1.05: 1, the concentration of the nylon 5X salt solution is 50-65%, and the pH value is 7.0-9.0; in the step 2), the concentration of the concentrated polyamide 5X salt solution is 75-90%; in the step 3), the reaction temperature is controlled to be 220-250 ℃, the pressure is 1.5-2.5 MPa, and the reaction time is 2-3 hours; in the step 4), the flash evaporation temperature is 275-285 ℃; in the step 5), the temperature is controlled to be 270-290 ℃, and the post-polymerization residence time is 30-40 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111351444.6A CN113861411A (en) | 2021-11-16 | 2021-11-16 | High-stability nylon polymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111351444.6A CN113861411A (en) | 2021-11-16 | 2021-11-16 | High-stability nylon polymer and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113861411A true CN113861411A (en) | 2021-12-31 |
Family
ID=78984720
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111351444.6A Pending CN113861411A (en) | 2021-11-16 | 2021-11-16 | High-stability nylon polymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113861411A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114369962A (en) * | 2022-01-04 | 2022-04-19 | 上海普弗门化工新材料科技有限公司 | Disperse dye dyeing method for bio-based nylon 56 fabric |
| CN115286786A (en) * | 2022-04-01 | 2022-11-04 | 温州邦鹿化工有限公司 | Nylon-56 continuous polymerization method and polymerization reactor |
| CN117364274A (en) * | 2023-10-07 | 2024-01-09 | 青岛康威化纤有限公司 | Full-biology-based high-strength nylon 510 fiber and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103146189A (en) * | 2013-02-26 | 2013-06-12 | 上海凯赛生物技术研发中心有限公司 | Nylon modified plastic |
| CN109401301A (en) * | 2018-10-22 | 2019-03-01 | 滁州吉胜新材料科技有限公司 | Weather-proof enhancing nylon 56 of one kind and preparation method thereof |
| CN110028784A (en) * | 2018-01-12 | 2019-07-19 | 天津利安隆新材料股份有限公司 | Light stabilizer combination for nylon |
| CN110117832A (en) * | 2013-10-28 | 2019-08-13 | 上海凯赛生物技术研发中心有限公司 | Nylon fiber and preparation method thereof |
-
2021
- 2021-11-16 CN CN202111351444.6A patent/CN113861411A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103146189A (en) * | 2013-02-26 | 2013-06-12 | 上海凯赛生物技术研发中心有限公司 | Nylon modified plastic |
| CN110117832A (en) * | 2013-10-28 | 2019-08-13 | 上海凯赛生物技术研发中心有限公司 | Nylon fiber and preparation method thereof |
| CN110028784A (en) * | 2018-01-12 | 2019-07-19 | 天津利安隆新材料股份有限公司 | Light stabilizer combination for nylon |
| CN109401301A (en) * | 2018-10-22 | 2019-03-01 | 滁州吉胜新材料科技有限公司 | Weather-proof enhancing nylon 56 of one kind and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114369962A (en) * | 2022-01-04 | 2022-04-19 | 上海普弗门化工新材料科技有限公司 | Disperse dye dyeing method for bio-based nylon 56 fabric |
| CN114369962B (en) * | 2022-01-04 | 2024-03-08 | 上海普弗门化工新材料科技有限公司 | Dyeing method of bio-based nylon 56 fabric disperse dye |
| CN115286786A (en) * | 2022-04-01 | 2022-11-04 | 温州邦鹿化工有限公司 | Nylon-56 continuous polymerization method and polymerization reactor |
| CN117364274A (en) * | 2023-10-07 | 2024-01-09 | 青岛康威化纤有限公司 | Full-biology-based high-strength nylon 510 fiber and preparation method and application thereof |
| CN117364274B (en) * | 2023-10-07 | 2024-03-15 | 青岛康威化纤有限公司 | Full-biology-based high-strength nylon 510 fiber and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113861411A (en) | High-stability nylon polymer and preparation method thereof | |
| JP3228977B2 (en) | Carbodiimide-modified polyester fiber and method for producing the same | |
| KR20220101647A (en) | Polyamide 5X industrial yarn, manufacturing method thereof and use thereof | |
| US6818293B1 (en) | Stabilized polyester fibers and films | |
| JP6250685B2 (en) | Polyamide compositions and processes | |
| US12000065B2 (en) | Method for preparing PET/PTT parallel complex filament with high self-crimpiness | |
| TWI519687B (en) | Dull polyamide 56 fiber and method for manufacturing the same | |
| NZ284802A (en) | Use of 4-amino-2,2,6,6-tetramethyl piperidine derivatives in a process for producing inherently light- and heat-stabilised polyamides | |
| US3078248A (en) | Process of extruding fibers from a molten polyamide containing a phosphorous compound | |
| CN109402764B (en) | High-strength low-elongation polyamide 6 staple fiber and preparation method thereof | |
| EP1709220B1 (en) | Polyamide composition comprising optical brightener, yarns made therefrom and process for heat setting such yarns | |
| CN103526325B (en) | Water-repellent creep-resistant polyester fully drawn yarn (FDY) fiber and preparation method thereof | |
| CN114045562B (en) | High-stability bio-based polyamide 56 fiber and preparation process thereof | |
| KR102401622B1 (en) | Semi-aromatic polyamide fibers and method for producing the same | |
| US3296216A (en) | Nylon composition having enhanced dyeability | |
| WO1995033088A1 (en) | Polyhexamethyleneadipamide fiber and process for producing the fiber | |
| CN103204989A (en) | Method for preparing nylon 6 for fibers from hindered amine prepolymerization unit | |
| US5925300A (en) | Process of making a shaped article from nylon polymer | |
| CN111876840B (en) | Preparation method of high-fluidity polyamide 56 fiber | |
| US4076696A (en) | Extrusion of polypyrrolidone | |
| JP2013155460A (en) | Polyamide fiber and method for producing the same | |
| US3536804A (en) | Process for producing polyxyleneadipamide fibers | |
| FR3008984A1 (en) | ARTICLES OBTAINED FROM POLYMERIC COMPOSITION, PROCESS FOR PREPARATION AND USES | |
| CN103556291B (en) | A kind of creep resistant resistant to hydrolysis polyester FDY fiber and preparation method thereof | |
| CN116876102B (en) | Wear-resistant PET monofilament and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211231 |