CN118530570A - High-weather-resistance master batch for color polyester and preparation method and application thereof - Google Patents
High-weather-resistance master batch for color polyester and preparation method and application thereof Download PDFInfo
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- CN118530570A CN118530570A CN202411008311.2A CN202411008311A CN118530570A CN 118530570 A CN118530570 A CN 118530570A CN 202411008311 A CN202411008311 A CN 202411008311A CN 118530570 A CN118530570 A CN 118530570A
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- Prior art keywords
- polyester
- color
- master batch
- triazine
- bis
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- 229920000728 polyester Polymers 0.000 title claims abstract description 259
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 82
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 82
- 239000000835 fiber Substances 0.000 claims abstract description 74
- 150000001875 compounds Chemical class 0.000 claims abstract description 57
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000004645 polyester resin Substances 0.000 claims abstract description 37
- 229920001225 polyester resin Polymers 0.000 claims abstract description 37
- 239000003381 stabilizer Substances 0.000 claims abstract description 34
- 239000004611 light stabiliser Substances 0.000 claims abstract description 32
- 150000001412 amines Chemical class 0.000 claims abstract description 28
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims abstract description 24
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000002516 radical scavenger Substances 0.000 claims abstract description 13
- 229940123457 Free radical scavenger Drugs 0.000 claims abstract description 12
- 239000002270 dispersing agent Substances 0.000 claims abstract description 11
- 238000001125 extrusion Methods 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 42
- -1 3, 5-di-tert-butyl-4-hydroxyphenyl Chemical group 0.000 claims description 28
- 239000003960 organic solvent Substances 0.000 claims description 26
- 239000003463 adsorbent Substances 0.000 claims description 21
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims description 10
- 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 claims description 8
- VGIJZDWQVCXVNL-UHFFFAOYSA-N 3-butoxyphenol Chemical compound CCCCOC1=CC=CC(O)=C1 VGIJZDWQVCXVNL-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910021485 fumed silica Inorganic materials 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 7
- CYHYIIFODCKQNP-UHFFFAOYSA-N 5,7-ditert-butyl-3-(3,4-dimethylphenyl)-3h-1-benzofuran-2-one Chemical group C1=C(C)C(C)=CC=C1C1C(C=C(C=C2C(C)(C)C)C(C)(C)C)=C2OC1=O CYHYIIFODCKQNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- ZSSVCEUEVMALRD-UHFFFAOYSA-N 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)phenol Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C1=NC(C=2C(=CC(C)=CC=2)C)=NC(C=2C(=CC(C)=CC=2)C)=N1 ZSSVCEUEVMALRD-UHFFFAOYSA-N 0.000 claims description 4
- RXFCIXRFAJRBSG-UHFFFAOYSA-N 3,2,3-tetramine Chemical compound NCCCNCCNCCCN RXFCIXRFAJRBSG-UHFFFAOYSA-N 0.000 claims description 4
- WBWXVCMXGYSMQA-UHFFFAOYSA-N 3,9-bis[2,4-bis(2-phenylpropan-2-yl)phenoxy]-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C=1C=C(OP2OCC3(CO2)COP(OC=2C(=CC(=CC=2)C(C)(C)C=2C=CC=CC=2)C(C)(C)C=2C=CC=CC=2)OC3)C(C(C)(C)C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 WBWXVCMXGYSMQA-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- BGHBLQKNCVRIKV-UHFFFAOYSA-N OP(O)OP(O)O.OCC(CO)(CO)CO.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O BGHBLQKNCVRIKV-UHFFFAOYSA-N 0.000 claims description 4
- 239000007983 Tris buffer Substances 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- FRVPQJVZFCJNCO-UHFFFAOYSA-N morpholine;2,4,6-trichloro-1,3,5-triazine Chemical compound C1COCCN1.ClC1=NC(Cl)=NC(Cl)=N1 FRVPQJVZFCJNCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- 125000001821 azanediyl group Chemical group [H]N(*)* 0.000 claims description 3
- 229920001303 methylated polymer Polymers 0.000 claims description 3
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 239000002861 polymer material Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 43
- 230000008569 process Effects 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 25
- 239000000463 material Substances 0.000 description 19
- 239000000126 substance Substances 0.000 description 19
- 239000000203 mixture Substances 0.000 description 17
- 230000002829 reductive effect Effects 0.000 description 17
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 16
- 238000012545 processing Methods 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 239000002250 absorbent Substances 0.000 description 15
- 230000002745 absorbent Effects 0.000 description 15
- 230000015556 catabolic process Effects 0.000 description 15
- 238000006731 degradation reaction Methods 0.000 description 15
- 230000000694 effects Effects 0.000 description 15
- 150000003254 radicals Chemical class 0.000 description 15
- 239000006229 carbon black Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000049 pigment Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000003086 colorant Substances 0.000 description 11
- 229920000139 polyethylene terephthalate Polymers 0.000 description 11
- 239000005020 polyethylene terephthalate Substances 0.000 description 11
- 230000032683 aging Effects 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 229910021645 metal ion Inorganic materials 0.000 description 9
- 239000001038 titanium pigment Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000001023 inorganic pigment Substances 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 206010051246 Photodermatosis Diseases 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000012752 auxiliary agent Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000004595 color masterbatch Substances 0.000 description 6
- 230000007774 longterm Effects 0.000 description 6
- 238000010791 quenching Methods 0.000 description 6
- HCILJBJJZALOAL-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n'-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl]propanehydrazide Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 HCILJBJJZALOAL-UHFFFAOYSA-N 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 229960003742 phenol Drugs 0.000 description 5
- 230000008845 photoaging Effects 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- 150000003852 triazoles Chemical class 0.000 description 5
- 238000004804 winding Methods 0.000 description 5
- 125000002393 azetidinyl group Chemical group 0.000 description 4
- 229940060799 clarus Drugs 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000012860 organic pigment Substances 0.000 description 4
- 125000003431 oxalo group Chemical group 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- JLZIIHMTTRXXIN-UHFFFAOYSA-N 2-(2-hydroxy-4-methoxybenzoyl)benzoic acid Chemical group OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1C(O)=O JLZIIHMTTRXXIN-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000005496 eutectics Effects 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical compound NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 239000006084 composite stabilizer Substances 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000002074 melt spinning Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- 238000002211 ultraviolet spectrum Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000000655 anti-hydrolysis Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- WAKMOVBCOYGSDK-UHFFFAOYSA-N phenol;triazine Chemical compound C1=CN=NN=C1.OC1=CC=CC=C1 WAKMOVBCOYGSDK-UHFFFAOYSA-N 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 230000000176 photostabilization Effects 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- 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
- D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents
-
- 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
- D01F6/92—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 polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention belongs to the technical field of high polymer materials, and relates to a high weather-resistant master batch for color polyester, and a preparation method and application thereof. The high weather-resistant master batch for the color polyester comprises polyester resin, a compound stabilizer and a dispersing agent; the intrinsic viscosity of the polyester resin is 0.95 to 1.05dl/g, and the content of carboxyl end groups is less than or equal to 15mol/t; the compound stabilizer comprises a compound antioxidant and a compound light stabilizer in parts by weight; the compound antioxidant comprises a main antioxidant, an auxiliary antioxidant and a free radical scavenger; the compound light stabilizer comprises a triazine ultraviolet absorber and a triazine hindered amine; the preparation method comprises the steps of mixing the components, performing melt extrusion, bracing and granulating to obtain the high weather-resistant master batch for the color polyester; the polyester fiber is prepared by using the high weather-resistant master batch for the color polyester. The color polyester product (polyester fiber) prepared by the high weather-resistant master batch for the color polyester has good weather resistance.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and relates to a high weather-resistant master batch for color polyester, and a preparation method and application thereof.
Background
Polyester materials represented by polyethylene terephthalate (PET) are engineering plastics with excellent performance and wide application. PET as a crystalline saturated polyester resin, its high crystallinity, rigid group containing a large amount of benzene rings, and inert chemical structure, together impart good fatigue resistance, abrasion resistance, chemical resistance to PET materials while maintaining high transparency. In addition, the PET material has excellent fiber forming property, is easy to process into high-strength fiber, has excellent film forming property, and can form a film with high transparency and stable performance. These characteristics, coupled with their low cost, make PET one of the most productive varieties in chemical fibers.
However, the high crystallinity and rigid structure of PET also lead to low dyeing efficiency, severe pollution and huge pressure on environmental protection. The color master batch method is used for carrying out the stock solution coloring, so that the use amount of dye can be reduced to a certain extent, and the pollution in the dyeing process is reduced, and therefore, the color polyester product is increasingly used for carrying out the stock solution coloring.
At present, high weatherability is difficult to achieve for stock-colored polyester products. The main reasons are as follows:
1. Polyester stock coloring is a high-concentration colorant dispersion obtained by melt-mixing an excessive amount of colorant with polyester, and therefore, the colorant and the polyester undergo deterioration in performance during heat processing.
2. The esterification reaction is a reversible reaction, and ester bonds of the polyester material are hydrolyzed in the processing and long-term use processes, so that the main chain of the polymer is broken to generate carboxyl-terminated and hydroxyl-terminated products, and the hydrolysis products are further oxidized under the actions of light, heat, water and gas in the environment, so that the appearance color of the polyester product is greatly influenced.
3. PET is severely affected by photo-irradiation aging, carbonyl groups in the PET can be damaged by sunlight irradiation, and the carbonyl groups are broken to cause photo-degradation or crosslinking reaction of the PET, and the PET can further influence the distribution of crystalline phase and amorphous phase of the polyester product, so that the crystallinity is improved to cause the material to become brittle.
4. The metal ions in the catalyst remaining during the polyester synthesis and the metal ions remaining during the purification of the colorant catalyze the accelerated photoaging process.
Currently, the conventional means for improving the weather resistance of common polyester products are as follows:
1. improving the hydrolysis resistance: the carboxyl end substances generated in the hydrolysis process are neutralized by adding carbodiimide or some alkaline substances, so that further hydrolysis of ester bonds is inhibited, and the ageing resistance of the polyester product is improved.
2. Using the extinction effect: by adding high-refractive index inorganic powder such as titanium white, strong light reflection is formed on the surface of the fiber after the irradiation of sunlight, so that the photo-aging influence of the polyester is reduced.
3. Adding a light stabilization auxiliary agent: the photo-stabilization auxiliary agent represented by ultraviolet absorbent is added, and the processes in photo-oxidation chain reaction are interrupted by means of high-energy ray absorption, free radical capturing, quenching and the like, so that the photo-aging is slowed down.
4. And adding an antioxidant.
However, although the means for improving the weather resistance is widely applied to common polyester products, the method for performing the anti-aging treatment only on the polymer per se has remarkable limitations and has relatively limited effect due to the complex and various components of the color polyester products. For example, when an alkali substance is used for inhibiting hydrolysis, alkali is also a catalyst for esterification reaction, so that the anti-hydrolysis agent has the defect of low addition limit, and meanwhile, most of pigment dyes used for color polyester products are sensitive to pH value, and the alkali substance can change the color of the dyes and even react mutually, so that the use risk in the color polyester products is high. The titanium white content in the extinction yarn is high, the covering power is strong, and the color development of the colorant in the color polyester product is obviously affected. The scheme of the light stabilizer adopted in the current market is not formulated aiming at the characteristics of the color polyester product, so that the addition amount of the universal light stabilizer is large, the effect is general, the deep ground color exists, and the actual use is influenced. In addition, in practical production, many colored high weather-resistant products contain carbon black for adjusting colors such as hue or configuration gray, black and the like, however, carbon black particles have large specific surface area, a certain amount of organic substances and heavy metal ions are often adsorbed on the surfaces, the adsorbed substances can generate free radicals to a certain extent, the free radicals are one of main factors for initiating thermal degradation of polyester, and meanwhile, the heavy metal ions in the carbon black can accelerate the aging of polyester under the synergistic effect of the light absorption effect of the carbon black, so that the light gray polyester product is difficult to realize high weather-resistant level.
Therefore, aiming at the composition and structural characteristics of the color polyester product, the high weather-resistant master batch for the color polyester and the preparation method thereof are researched to solve the problems, and have very important significance.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a high weather-resistant master batch for color polyester, and a preparation method and application thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the high weather-resistant master batch for the color polyester comprises, by weight, 65-70 parts of polyester resin, 30-34.5 parts of a compound stabilizer and 0.1-0.5 part of a dispersing agent (such as Tegomer P121);
The polyester resin is special polyester with high viscosity and low carboxyl end group content, the intrinsic viscosity of the polyester resin is 0.95-1.05dl/g, the carboxyl end group content is less than or equal to 15mol/t, and the ash content is less than or equal to 0.01wt%;
the compound stabilizer comprises 30-40 parts of compound antioxidant and 55-65 parts of compound light stabilizer by weight;
The compound antioxidant comprises a main antioxidant, an auxiliary antioxidant and a free radical scavenger;
The compound light stabilizer comprises a triazine ultraviolet absorber and a triazine hindered amine.
The special polyester with high viscosity and low carboxyl end group content is selected, so that the polyester degradation in the hot processing process during the preparation of the polyester master batch can be reduced, the influence caused by the viscosity reduction due to screw shearing can be reduced, the physical properties of the weather-resistant master batch are kept close to those of the conventional polyester chips, and the adverse effect caused by using an alkaline hydrolysis resistance agent is avoided.
At present, when an antioxidant is selected, the main purpose of the main flow technology is to inhibit the thermal degradation of polyester in the thermal processing process and protect the color of the polyester; therefore, a single antioxidant (e.g., hindered phenol) is often employed, or a primary antioxidant is used in combination with a secondary antioxidant (e.g., hindered phenol + phosphite). However, in colored polyester products, particularly colored polyester master batches, the color pigment is relatively large, and therefore thermal protection of the colorant is not negligible. In addition, thermal degradation of the polymer is exacerbated by the catalytic action of the colorant, which makes it difficult to fully exhibit the properties of highly weatherable colorants using the additives of the prior art routes to provide poor protection.
The compound antioxidant comprises a main antioxidant, an auxiliary antioxidant and a free radical capturing agent, and can synergistically and further inhibit the performance degradation of the polyester master batch in the hot processing process. The present invention aims to maintain the stability of the polyester material intermediate products at various stages in the chain reaction of thermal cracking to free radicals or oxidation to peroxides, and to minimize thermal degradation aging during processing. The free radical capturing agent is used as a first-stage protection to quench alkyl free radicals at the initial stage of thermal degradation chain reaction to terminate aging reaction, the main antioxidant is used as a second-stage protection to quench hydroxyl free radicals and peroxy free radicals generated by the reaction of the alkyl free radicals with oxygen/water to generate quinoid products, the auxiliary antioxidant can reduce the quinoid products generated by the main antioxidant to reduce the pollution to the whole color of the product, and the main antioxidant can play roles again.
Because of the wide variety of polyester articles and the relatively complex photoaging process, currently mainstream technology generally employs a single spectrum ultraviolet absorber for basic protection when selecting photoaging additives. For example, the commonly used triazole ultraviolet absorbent has absorption capacity in the whole ultraviolet spectrum range, and the triazole ultraviolet absorbent competes with polyester products to absorb high-energy ultraviolet rays and convert the high-energy ultraviolet rays into heat for dissipation, so that the effect of protecting high polymer materials is achieved. However, since the five-membered ring structure of the triazole-based ultraviolet absorber has poor long-term stability, the absorption performance of the polyester product is gradually reduced after the polyester product is irradiated for a high period of time, resulting in a reduced protective effect. In a few cases, the protection is carried out by combining an ultraviolet absorber with a hydrophobic hindered amine (such as UV 5050H) containing long carbon chains; when the protective effect of the ultraviolet absorbent is ineffective or insufficient, the combination can effectively terminate the aging chain reaction by quenching free radicals generated under the action of polyester light; because of the incompatibility of the long carbon chain and the polyester, the method reduces the contact between the alkaline group in the hindered amine and the polyester, thereby reducing the potential influence on ester bond breakage; however, this incompatibility also results in poor dispersibility of the long carbon chain hindered amine in the polyester article. Both of the above solutions are not suitable for color highly weatherable polyester articles.
The composite light stabilizer comprises a triazine ultraviolet absorber and a triazine hindered amine. The triazine group can realize long-term protection due to the high stability of the triazine group, thereby meeting the product requirement of long-term use of the colorful high-weather-resistant polyester. The triazine hindered amine is high-molecular-weight low-alkalinity hindered amine, has low reactivity with ester bonds and good migration resistance, can not be separated out in the polyester processing process, does not promote the degradation of the polyester, and does not damage the strength of polyester products; therefore, under the condition of low addition amount, the triazine ultraviolet absorbent can provide good weather-proof protection for polyester products and color colorants at the same time, further reduce the influence of auxiliary agents on colors and reduce the occurrence of color fouling. The triazine hindered amine is also in general dispersibility in polyester when being used independently, but the composite light stabilizer also contains a triazine ultraviolet absorbent, so that the triazine ultraviolet absorbent and the triazine hindered amine have better compatibility and can mutually play a role in dispersing, further are uniformly distributed in a polyester product, and further realize a synergistic protection effect in the polymer so as to fully show the anti-photoaging effect of the auxiliary agent on the color polyester product.
As a preferable technical scheme:
The master batch for the color polyester has high weather resistance, and the main antioxidant is more than one of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) -N' - [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] propionyl hydrazine and bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] [ oxalyl bis (azanediyl) ] bis (ethane-2, 1-diyl) ester.
The preferred main antioxidant is different from the conventional hindered phenol auxiliary agents (such as pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) commonly used by polyester, and has a oxamide or hydrazide structure besides the hindered phenol group which can stabilize peroxy radical products, and the structure has a plurality of continuous metal ion coordination sites which can chelate metal ions, so that the catalytic activity of the metal ions introduced in each link is effectively reduced according to the composition characteristics of the color polyester product, and the aging influence of residual metal ions on the color polyester product is reduced. In the colored polyester product containing carbon black, the preferred primary antioxidant is used as a free radical scavenger, which can effectively neutralize the free radical substances (hydroxyl free radicals) adsorbed by the carbon black and can chelate metal ions in the carbon black.
The auxiliary antioxidant is more than one of tri (2, 4-di-tert-butyl) phenyl phosphite, bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite, 3, 9-bis (2, 4-dicumylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane.
The high weather-resistant master batch for the color polyester has the advantage that the free radical scavenger is 5, 7-di-tert-butyl-3- (3, 4-dimethylphenyl) benzofuran-2 (3H) -one.
The high weather-resistant master batch for the color polyester is characterized in that the triazine ultraviolet absorbent is more than one of 2, 4-bis (2, 4-xylyl) -6- (2-hydroxy-4-n-octyloxyphenyl) -1,3, 5-triazine, 2- (4, 6-diphenyl-1, 3, 5-triazine-2) -5-n-hexyloxyphenol, 2, 4-bis (4-biphenyl) -6- (2, 4-dihydroxy) phenyl-1, 3, 5-triazine, 2, 4-bis [2,2' -bis (5-butoxyphenyl) ] -6- (2, 4-dibutoxybenzene) -1,3, 5-triazine and 2,4, 6-tris (4 ' -butoxy-2 ' -hydroxyphenyl) -triazine, and the triazine ultraviolet absorbent can be a long-wave absorbent or a short-wave absorbent, and the long-wave absorbent and the absorbent can be combined to realize full coverage of the whole ultraviolet region, improve the absorption efficiency and further improve the protection effect.
The prior art mainly applies 2, 4-bis [2,2' -bis (5-butoxyphenol) ] -6- (2, 4-dibutoxybenzene) -1,3, 5-triazine, 2,4, 6-tris (4 ' -butoxy-2 ' -hydroxyphenyl) -triazine to optical barrier films and not to polyesters.
The high weather-resistant master batch for the color polyester is prepared from poly [ N, N '-bis (2, 6-tetramethyl-4-piperidinyl) -1, 6-hexamethylenediamine-CO-2, 4-dichloro-6-morpholine-1, 3, 5-triazine ], N, methylated polymers of N' -bis (2, 6-tetramethyl-4-piperidinyl) -1, 6-hexamethylenediamine and morpholine-2, 4, 6-trichloro-1, 3, 5-triazine, reaction products of N, N '' -1, 2-ethanediylbis (1, 3-propanediamine) with cyclohexane and N-butyl-2, 6-tetramethyl-4-piperidylamine-2, 4, 6-trichloro-1, 3, 5-triazine peroxide.
The prior art does not apply the methylated polymers of poly [ N, N '-bis (2, 6-tetramethyl-4-piperidinyl) -1, 6-hexamethylenediamine-CO-2, 4-dichloro-6-morpholin-1, 3, 5-triazine ], N' -bis (2, 6-tetramethyl-4-piperidinyl) -1, 6-hexamethylenediamine with morpholin-2, 4, 6-trichloro-1, 3, 5-triazine to polyesters, the reaction product of N, N '' -1, 2-ethanediylbis (1, 3-propanediamine) with cyclohexane and N-butyl-2, 6-tetramethyl-4-piperidylamine-2, 4, 6-trichloro-1, 3, 5-triazine peroxide is generally used as flame retardant.
The high weather-resistant master batch for the color polyester comprises 3-5 parts by weight of an adsorbent.
The high weather-resistant master batch for the color polyester is characterized in that the adsorbent is fumed silica, preferably high specific surface area fumed silica, and the BET specific surface area is more than or equal to 350m 2/g.
The preparation process of the high weather-resistant master batch for the color polyester and the compound stabilizer comprises the following steps: mixing the compound antioxidant, the compound light stabilizer, the adsorbent and the organic solvent (such as dichloromethane), stirring uniformly, and removing the organic solvent to obtain the compound stabilizer, wherein the mass of the organic solvent is 0.1-0.5 times of the total mass of the compound antioxidant, the compound light stabilizer and the adsorbent.
According to the invention, the components of the compound stabilizer are mixed with the organic solvent, so that the pre-dispersion of the compound stabilizer can be realized, and the stability of the compound stabilizer in the subsequent processing process is improved; in order to enhance the pre-dispersion effect, chemical substances with similar structures and polarities are selected to form the compound stabilizer as much as possible. In the pulping process, part of the compound stabilizer can be dissolved in the organic solvent, so that all components of the compound stabilizer reach a eutectic state, and the protection synergistic effect of the compound stabilizer on the color polyester product in the processing and using processes is improved; the fumed silica with high specific surface area is used as a preferable adsorbent, and can effectively adsorb the eutectic compound stabilizer, so that the effect of the compound stabilizer on improving weather resistance in the master batch is further enhanced.
The high weather-resistant master batch for the color polyester has the intrinsic viscosity of 0.5710-0.6381dl/g.
The invention also provides a method for preparing the high weather-resistant master batch for the color polyester, which comprises the steps of uniformly mixing the components according to the proportion, then carrying out melt extrusion, bracing and granulating to obtain the high weather-resistant master batch for the color polyester.
The invention also provides application of the high weather-resistant master batch for color polyester, which is used for preparing polyester fibers, and the addition amount of the high weather-resistant master batch is 0.1-10wt%.
The beneficial effects are that:
The invention selects the special polyester with high viscosity and low carboxyl end group content, reduces the degradation of polyester in the hot processing process when manufacturing the polyester master batch, ensures that the physical properties of the obtained weather-proof master batch are close to those of the conventional polyester chips, and avoids the adverse effect of using an alkaline hydrolysis resistance agent.
The compound antioxidant comprises a main antioxidant, an auxiliary antioxidant and a free radical capturing agent, can synergistically inhibit performance degradation in the hot processing process of polyester master batches, and can furthest reduce thermal degradation aging.
The composite light stabilizer comprises a triazine ultraviolet absorber and triazine hindered amine, has high stability of triazine groups, can protect for a long time, and meets the long-term use requirement of color high-weather-resistance polyester. The triazine ultraviolet absorber and the triazine hindered amine have good compatibility, can be uniformly distributed in the polyester product, and realize synergistic protection.
The color polyester product (polyester fiber) prepared by the high weather-resistant master batch for the color polyester has good weather resistance.
Drawings
FIG. 1 is a graph showing the ultraviolet absorbance of different triazine ultraviolet absorbers according to the present invention; in the figure, "1164" is 2, 4-bis (2, 4-xylyl) -6- (2-hydroxy-4-n-octyloxyphenyl) -1,3, 5-triazine, "1577" is 2- (4, 6-diphenyl-1, 3, 5-triazine-2) -5-n-hexyloxyphenol, "1600" is 2, 4-bis (4-biphenyl) -6- (2, 4-dihydroxy) phenyl-1, 3, 5-triazine, "460" is 2, 4-bis [2,2' -bis (5-butoxyphenol) ] -6- (2, 4-dibutoxybenzene) -1,3, 5-triazine, "3480" is 2,4, 6-tris (4 ' -butoxy-2 ' -hydroxyphenyl) -triazine;
FIG. 2 is a graph showing the ultraviolet absorbance of combinations of different triazine ultraviolet absorbers in the present invention.
Detailed Description
The application is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
The following are test methods for the relevant performance indicators in each of the examples and comparative examples:
intrinsic viscosity: the test was performed according to GB/T14190-2017 standard.
Δe, color card grade: the test was performed according to AATCC16.3 standard.
Ultraviolet spectrum test: a triazine ultraviolet absorber (single product or a combination of various single products) was dissolved in chloroform to obtain a chloroform solution having a concentration of 10mg/L, which was used as a test sample, and chloroform was used as a reference sample, and an ultraviolet-visible light absorbance curve of 280 to 400nm was measured.
Example 1
The preparation method of the high weather-resistant master batch for the color polyester comprises the following specific steps:
(1) Preparing raw materials;
Composite antioxidant: the main antioxidant is a mixture of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) -N' - [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] propionyl hydrazine and bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] [ oxalylbis (azetidinyl) ] bis (ethane-2, 1-diyl) ester with a mass ratio of 5:7.33:1, the auxiliary antioxidant is 3, 9-bis (2, 4-dicumylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane, and the free radical scavenger is 5, 7-di-tert-butyl-3- (3, 4-dimethylphenyl) benzofuran-2 (3H) -one;
composite light stabilizer: the ultraviolet absorber is a mixture of 2, 4-bis (4-biphenyl) -6- (2, 4-dihydroxyl) phenyl-1, 3, 5-triazine and 2,4, 6-tris (4 '-butoxy-2' -hydroxyphenyl) -triazine with the mass ratio of 1.75:1 and triazine hindered amine, wherein the triazine hindered amine is a reaction product of N, N '' -1, 2-ethanediylbis (1, 3-propanediamine) and cyclohexane and N-butyl-2, 6-tetramethyl-4-piperidylamine-2, 4, 6-trichloro-1, 3, 5-triazine peroxide (manufacturer is Basiff company, model number Flamestab NOR 116,116);
an adsorbent: fumed silica, manufacturer is cabot corporation, model CLARUS 3160;
Organic solvent: dichloromethane;
Polyester resin: the manufacturer is Jiangsu Soxhlet obtained new material group Co., ltd, the variety is light type tackifying polyester slices, the intrinsic viscosity is 0.95-1.05dl/g, and the carboxyl end content is less than or equal to 15mol/t;
dispersing agent: tegomer P121, manufacturer is a winning industry group;
(2) Preparing a compound stabilizer;
According to parts by weight, mixing 40 parts of composite antioxidant, 55 parts of composite light stabilizer, 5 parts of adsorbent and organic solvent, uniformly stirring, and removing the organic solvent to obtain a compound stabilizer; wherein, the addition amount of the organic solvent is 0.1 times of the total mass of the composite antioxidant, the composite light stabilizer and the adsorbent;
(3) Preparing high weather-resistant master batches for color polyester;
According to the parts by weight, uniformly mixing 69.5 parts of polyester resin, 30 parts of compound stabilizer and 0.5 part of dispersing agent, putting into a double-screw extruder for melt extrusion, bracing and granulating to obtain high weather-resistant master batch for color polyester; wherein, the temperature of the first area of the double-screw extruder is 220 ℃, the temperature of the second area is 275 ℃, the temperature of the third area is 275 ℃, the temperature of the fourth area is 270 ℃, the temperature of the fifth area is 220 ℃, the temperature of the sixth area is 220 ℃, the temperature of the seventh area is 240 ℃, and the temperature of the eighth area is 260 ℃; the rotational speed of the twin-screw extruder was 300r/min.
The final color polyester has an intrinsic viscosity of 0.6310dl/g.
The preparation method of the color polyester fiber comprises the following specific processes: according to parts by weight, 1 part of the high weather-resistant master batch for color polyester prepared in the embodiment, 10 parts of polyester color master batch (composed of polyester resin and PB15:3; the manufacturer of the polyester resin is Jiangsu Soxhlet New Material group Co., ltd., the variety is a light-type tackifying polyester slice, the intrinsic viscosity is 0.95-1.05dl/g, the content of carboxyl end groups is less than or equal to 15mol/t, the content of PB15:3 is 0.5 wt%) and 89 parts of light polyester slice (the manufacturer is China petrochemical chemical fiber Co., ltd., model SB 500) are uniformly mixed and then melt-spun (the temperature is 285 ℃, the winding speed is 2800 r/min) to obtain the color polyester fiber with the specification of 100d/48 f.
The preparation method of the color semi-gloss polyester fiber comprises the following specific processes: 1 part of the high weather-resistant master batch for the color polyester prepared in the embodiment, 10 parts of the color polyester master batch (consisting of polyester resin and pigment; the manufacturer of the polyester resin is Jiangsu Soxhlet New Material group Co., ltd, the variety is a light-type tackifying polyester slice, the intrinsic viscosity is 0.95-1.05dl/g, and the carboxyl end group content is less than or equal to 15mol/t; the pigment is organic pigment or inorganic pigment, when the pigment is organic pigment, the content of the organic pigment is 0.5wt%, when the pigment is inorganic pigment, the content of the inorganic pigment is 5wt%, the organic pigment is PB15:3, PG7, PY147, PY150, PR122 or PR202, the inorganic pigment is PY119, PY184, PB29 or PR 101), 5 parts of titanium pigment master batch (consisting of polyester resin and titanium pigment, the manufacturer of the polyester resin is Jiangsu Suo Li New material group Co., ltd., the variety is a light type tackifying polyester slice, the intrinsic viscosity is 0.95-1.05dl/g, the content of carboxyl end is less than or equal to 15mol/t, the manufacturer of the titanium pigment is Shandong good group, the model is SA-50, the particle size is 240-320nm, the content is 5 wt%) and 84 parts of light polyester slice (the manufacturer is China petrochemical chemical fiber Limited Co., model SB 500) are evenly mixed, then melt spun (temperature is 285 ℃, winding speed 2800 r/min), the polyester semi-fiber with 100d/48f specification is obtained, the polyester semi-gloss data is recorded in a color test chart, and the color test is shown as the color chart is 1 after the test is carried out, the color test is carried out on the semi-finished, and the color test chart is shown in 500 h.
TABLE 1
| Colored semi-gloss polyester fiber | Pigment | 100h △E | 200h △E | 300h △E | 400h △E | 500h △E | 500H color chart grade |
| 1 | PB15:3 | 0.23 | 0.91 | 1.78 | 1.83 | 2.27 | 4 |
| 2 | PG7 | 0.16 | 0.42 | 0.54 | 0.69 | 0.97 | 4.5 |
| 3 | PY147 | 0.29 | 0.32 | 0.86 | 0.96 | 1.35 | 4.5 |
| 4 | PY119 | 0.42 | 0.51 | 0.64 | 0.65 | 0.68 | 4.5 |
| 5 | PY150 | 0.85 | 0.87 | 0.92 | 0.95 | 0.98 | 4.5 |
| 6 | PY184 | 1.14 | 1.17 | 1.27 | 1.33 | 1.43 | 4.5 |
| 7 | PR122 | 1.79 | 1.93 | 2.10 | 2.17 | 2.22 | 4 |
| 8 | PB29 | 0.87 | 1.28 | 1.46 | 1.69 | 1.88 | 4 |
| 9 | PR202 | 1.14 | 1.43 | 1.73 | 1.91 | 2.08 | 4 |
| 10 | PR101 | 0.17 | 0.24 | 0.29 | 0.38 | 0.44 | 4.5 |
As can be seen from table 1, after the high weather-resistant master batch for color polyester, the color polyester master batch, the titanium pigment master batch and the glossy polyester chips are mixed, the color semi-gloss polyester fiber obtained through melt spinning shows good weather resistance after being subjected to irradiation for 100-500 hours; the delta E of each colored semi-gloss polyester fiber after 500h irradiation is kept below 2.27, and the color card grade is above grade 4;
Under the same conditions, if the color polyester prepared in the embodiment is replaced by a high weather-resistant master batch with equal quality of a bright polyester chip (the manufacturer is China petrochemical chemical fiber Limited liability company, the model is SB 500), the delta E and the color card grade of each color semi-bright polyester fiber after 100-500 h irradiation are shown in Table 2:
TABLE 2
| Colored semi-gloss polyester fiber | Pigment | 100h △E | 200h △E | 300h △E | 400h △E | 500h △E | 500H color chart grade |
| 1 | PB15:3 | 1.40 | 2.57 | 4.16 | 5.42 | 6.88 | 2 |
| 2 | PG7 | 0.48 | 0.90 | 1.79 | 2.27 | 3.06 | 3.5 |
| 3 | PY147 | 1.35 | 2.12 | 3.34 | 5.19 | 6.23 | 2.5 |
| 4 | PY119 | 0.52 | 0.86 | 1.83 | 2.60 | 3.87 | 3 |
| 5 | PY150 | 0.80 | 1.01 | 1.67 | 2.11 | 2.91 | 3.5 |
| 6 | PY184 | 1.49 | 1.71 | 2.19 | 2.53 | 3.05 | 3.5 |
| 7 | PR122 | 2.62 | 4.01 | 6.73 | 7.64 | 9.01 | 2 |
| 8 | PB29 | 1.52 | 2.68 | 3.15 | 3.80 | 4.57 | 3 |
| 9 | PR202 | 1.89 | 2.99 | 3.75 | 4.34 | 4.93 | 2.5 |
| 10 | PR101 | 0.61 | 1.10 | 1.62 | 2.07 | 2.56 | 3.5 |
As can be seen from Table 2, the ΔE of each colored semi-gloss polyester fiber after 500h irradiation is above 2.56, the color card grade is below 3.5, and the weather resistance of each colored semi-gloss polyester fiber is obviously deteriorated compared with Table 1, which fully proves the effectiveness of the high weather-resistant master batch for colored polyester prepared by the embodiment in improving the weather resistance of the colored semi-gloss polyester fiber prepared by using a stock solution coloring method.
The preparation method of the color semi-gloss polyester fiber comprises the following specific processes: 1 part of the high weather-resistant master batch for color polyester prepared in the embodiment, and 1 part of the carbon black master batch (consisting of polyester resin and carbon black; the polyester resin manufacturer is Jiangsu cable force new material group limited company, the type is a light type tackifying polyester chip, the intrinsic viscosity is 0.95-1.05dl/g, the carboxyl end content is less than or equal to 15mol/t, the carbon black powder manufacturer is European Hindu corporation, the model is AROSPERSE, the primary particle diameter is 19nm, the content is 1wt%, 5 parts of titanium pigment master batch (composed of polyester resin and titanium pigment, the polyester resin manufacturer is Jiangsu cable force new material group limited company, the type is a light type tackifying polyester chip, the intrinsic viscosity is 0.95-1.05dl/g, the carboxyl end content is less than or equal to 15mol/t, the titanium pigment manufacturer is Shandong good group, the model is SA-50, the particle diameter is 240-320nm, the content is 5wt%, 10 parts of color polyester color master batch (composed of polyester resin and pigment), the polyester resin manufacturer is Jiangsu cable force new material group limited company, the type is light type tackifying polyester chip, the intrinsic viscosity is 0.95-1.05 dl/mol, the carboxyl end content is 15mol/t, the inorganic pigment content is 5wt%, the inorganic pigment is PR (PR 5% of 5) is 5m, the melt-state of 5 or equal to 500 m, the inorganic pigment is PR (PR) is 5m 100) after the fiber is mixed with the dye of a light type PR (PR) fiber is 5m 100 m, the average fiber is equal to or equal to 500 m 100 m), the delta E and color card grade of various colored semi-gloss polyester fibers after being irradiated for 100-500 hours are tested, and data recorded in the test process are shown in table 3:
TABLE 3 Table 3
| Colored semi-gloss polyester fiber | Pigment | 100h △E | 200h △E | 300h △E | 400h △E | 500h △E | 500H color chart grade |
| 1 | PR122 | 1.12 | 1.27 | 1.40 | 1.48 | 1.55 | 4 |
| 2 | PR101 | 0.23 | 0.36 | 0.49 | 0.58 | 0.86 | 4.5 |
| 3 | PR202 | 0.85 | 1.62 | 2.05 | 2.31 | 2.69 | 3.5 |
| 4 | PB15:3 | 0.90 | 1.09 | 1.27 | 1.84 | 1.94 | 4 |
| 5 | PB29 | 0.80 | 1.90 | 2.08 | 2.75 | 2.95 | 3.5 |
As can be seen from table 3, the high weather-resistant master batch for color polyester prepared in this example, after being mixed with color polyester master batch, titanium pigment master batch, carbon black master batch and glossy polyester chips, all exhibited good weather resistance after being subjected to irradiation for 100-500 hours; even if carbon black is added, delta E of each colored semi-gloss polyester fiber after 500h irradiation is kept below 2.95, and the color card grade is above 3.5 grade;
under the same conditions, if the color polyester prepared in the embodiment is replaced by a high weather-resistant master batch with equal quality of a bright polyester chip (the manufacturer is China petrochemical chemical fiber Limited liability company, the model is SB 500), the delta E and the color card grade of each color semi-bright polyester fiber after 100-500 h irradiation are shown in Table 4:
TABLE 4 Table 4
| Colored semi-gloss polyester fiber | Pigment | 100h △E | 200h △E | 300h △E | 400h △E | 500h △E | 500H color chart grade |
| 1 | PR122 | 3.71 | 5.24 | 7.83 | 9.85 | 11.51 | 1.5 |
| 2 | PR101 | 1.16 | 1.65 | 2.17 | 2.94 | 4.63 | 3 |
| 3 | PR202 | 2.47 | 3.28 | 4.36 | 5.10 | 6.31 | 2.5 |
| 4 | PB15:3 | 3.27 | 4.65 | 5.22 | 5.93 | 7.70 | 2 |
| 5 | PB29 | 2.91 | 3.42 | 4.08 | 4.73 | 6.24 | 2.5 |
As can be seen from Table 4, the ΔE of each color semi-gloss polyester fiber after 500h irradiation is above 4.63, the color card grade is below 3, and the weather resistance of each color semi-gloss polyester fiber is obviously deteriorated compared with Table 3, which fully proves the effectiveness of the high weather resistance master batch for color polyester prepared by the embodiment in improving the weather resistance of the color semi-gloss polyester fiber added with carbon black in the preparation process.
Comparative example 1
A process for preparing a masterbatch, which is substantially the same as in example 1, except that: the manufacturer of the polyester resin is China petrochemical and chemical industry Limited company with the brand SB500 (the intrinsic viscosity of the polyester resin is 0.6750dl/g, and the carboxyl end group content is 24 mol/t).
A process for the preparation of colored polyester fibers, substantially the same as in example 1, except that: the high weatherability master batch for the color polyester was replaced with the master batch of comparative example 1.
Comparative example 2
A process for preparing a masterbatch, which is substantially the same as in example 1, except that: the triazine ultraviolet absorber (a mixture of 2, 4-bis (4-biphenyl) -6- (2, 4-dihydroxy) phenyl-1, 3, 5-triazine and 2,4, 6-tris (4 '-butoxy-2' -hydroxyphenyl) -triazine in a mass ratio of 1:1.5) was replaced with an equal mass of triazole ultraviolet absorber (UV 360, manufacturer basf).
A process for the preparation of colored polyester fibers, substantially the same as in example 1, except that: the color polyester was replaced with the high weatherability master batch of comparative example 2.
The color polyester fibers of example 1, comparative example 1 and comparative example 2 were tested for Δe after 100 to 500 hours of irradiation, and the data recorded during the test are shown in table 5:
TABLE 5
| 100h △E | 200h △E | 300h △E | 400h △E | 500h △E | 500H color chart grade | |
| Example 1 | 0.89 | 1.11 | 1.41 | 1.52 | 1.64 | 4 |
| Comparative example 1 | 0.80 | 0.88 | 1.46 | 2.00 | 2.51 | 3.5 |
| Comparative example 2 | 1.26 | 2.05 | 2.95 | 3.05 | 3.49 | 3 |
As can be seen from table 1, the color polyester fibers of comparative example 1 and comparative example 2 each have a Δe after 500h irradiation that is greater than that of example 1, and the color chip scale is lower than that of example 1 because the polyester resin used in comparative example 1 has too low viscosity and too high carboxyl end group content, and polyester degradation is aggravated during the thermal processing process for producing polyester master batches, and the viscosity is further lowered by screw shearing, resulting in significant differences in physical properties of the obtained master batches and conventional polyester chips, and reduced weather resistance; the triazole ultraviolet absorbent adopted in the comparative example 2 has a five-membered ring structure, the long-term stability is poor, the absorption performance of the polyester product is gradually reduced after the polyester product is irradiated for a long time, the protection effect is weakened, and the weather resistance of the polyester product is reduced.
Example 2
The preparation method of the high weather-resistant master batch for the color polyester is basically the same as that of the embodiment 1, and the only difference is that: the main antioxidant in the composite antioxidant is bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] [ oxalyl bis (azanediyl) ] bis (ethane-2, 1-diyl) ester (the mass ratio of the main antioxidant in the composite antioxidant is the same as that in example 1).
The final color polyester has an intrinsic viscosity of 0.6242dl/g.
A process for the preparation of colored polyester fibers, substantially the same as in example 1, except that: the high weather-resistant master batch for the color polyester is prepared by the embodiment.
The delta E of the finally prepared color polyester fiber after 500h irradiation is 1.72, and the color card grade after 500h irradiation is 4 grade.
Example 3
The preparation method of the high weather-resistant master batch for the color polyester is basically the same as that of the embodiment 1, and the only difference is that: the main antioxidant in the composite antioxidant is hindered phenol auxiliary agent (tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester) commonly used in traditional polyester, and the mass ratio of the main antioxidant in the composite antioxidant is the same as that of example 1.
The final color polyester has an intrinsic viscosity of 0.6381dl/g.
A process for the preparation of colored polyester fibers, substantially the same as in example 1, except that: the high weather-resistant master batch for the color polyester is prepared by the embodiment.
The delta E of the finally prepared color polyester fiber after 500h irradiation is 2.35, and the color card grade after 500h irradiation is 4 grade.
Compared with example 1, the Δe of the colored polyester fiber after 500h irradiation is larger, because the main antioxidant in the composite antioxidant adopted in example 3 does not have an oxamide or hydrazide structure, the prepared high weather-resistant master batch for colored polyester has relatively weak effect on resisting metal ion catalytic aging, and residual metal ions are easier to catalyze degradation of polyester molecular chains under long-time irradiation conditions, so that the Δe of the colored polyester fiber is increased, and the color card grade is reduced.
Example 4
The preparation method of the high weather-resistant master batch for the color polyester is basically the same as that of the embodiment 1, and the only difference is that: and (2) directly and uniformly mixing 40 parts of composite antioxidant, 55 parts of composite light stabilizer and 5 parts of adsorbent without adding an organic solvent to obtain the composite stabilizer.
The final color polyester has an intrinsic viscosity of 0.6279dl/g.
A process for the preparation of colored polyester fibers, substantially the same as in example 1, except that: the high weather-resistant master batch for the color polyester is prepared by the embodiment.
The delta E of the finally prepared color polyester fiber after 500h irradiation is 2.68, and the color card grade after 500h irradiation is 3.5 grade.
Compared with example 1, the Δe of the color polyester fiber after 500h irradiation is larger in example 4, because the example 4 does not mix the components of the compound stabilizer with the organic solvent to realize pre-dispersion, which results in uneven distribution of the components in the subsequent processing process, and the compound stabilizer cannot be fully dissolved in the organic solvent to achieve the eutectic state in the pulping process, thereby weakening the synergistic protection effect of the compound stabilizer on the color polyester product in the processing and using processes.
Example 5
The preparation method of the high weather-resistant master batch for the color polyester is basically the same as that of the embodiment 1, and the only difference is that: the auxiliary antioxidant in the composite antioxidant is a mixture of 3, 9-bis (2, 4-dicumylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane and bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite with the mass ratio of 1:1 (the mass ratio of the auxiliary antioxidant in the composite antioxidant is the same as that of the example 1).
The final color polyester has an intrinsic viscosity of 0.6074dl/g.
A process for the preparation of colored polyester fibers, substantially the same as in example 1, except that: the high weather-resistant master batch for the color polyester is prepared by the embodiment.
The delta E of the finally prepared color polyester fiber after 500h irradiation is 2.06, and the color card grade after 500h irradiation is 4 grade.
Example 6
The preparation method of the high weather-resistant master batch for the color polyester is basically the same as that of the embodiment 1, and the only difference is that: the triazine ultraviolet absorber in the compound light stabilizer was 2, 4-bis (4-biphenyl) -6- (2, 4-dihydroxy) phenyl-1, 3, 5-triazine (the mass ratio of the triazine ultraviolet absorber in the compound light stabilizer was the same as in example 1).
The final color polyester has an intrinsic viscosity of 0.6326dl/g.
A process for the preparation of colored polyester fibers, substantially the same as in example 1, except that: the high weather-resistant master batch for the color polyester is prepared by the embodiment.
The delta E of the finally prepared color polyester fiber after 500h irradiation is 1.82, and the color card grade after 500h irradiation is 4 grade.
Example 7
The preparation method of the high weather-resistant master batch for the color polyester comprises the following specific steps:
(1) Preparing raw materials;
Composite antioxidant: the main antioxidant is a mixture of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) -N' - [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] propionyl hydrazine and bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] [ oxalylbis (azetidinyl) ] bis (ethane-2, 1-diyl) ester, the auxiliary antioxidant is bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite, and the free radical scavenger is 5, 7-di-tert-butyl-3- (3, 4-dimethylphenyl) benzofuran-2 (3H) -one, wherein the mass ratio of the main antioxidant to the auxiliary antioxidant is 5.6:5.4:1;
Composite light stabilizer: the ultraviolet absorber is a mixture of 2- (4, 6-diphenyl-1, 3, 5-triazine-2) -5-N-hexyloxyphenol, 2, 4-bis [2,2 '-bis (5-butoxyphenol) ] -6- (2, 4-dibutoxybenzene) -1,3, 5-triazine and 2,4, 6-tris (4' -butoxy-2 '-hydroxyphenyl) -triazine, wherein the mass ratio of the ultraviolet absorber to the hindered amine is 2.28:1.72:1, and the hindered amine is a mixture of N, N' -bis (2, 6-tetramethyl-4-piperidinyl) -1, 6-hexamethylenediamine and morpholine-2, 4, 6-trichloro-1, 3, 5-triazine (the manufacturer is Cyasorb UV-3529);
an adsorbent: fumed silica, manufacturer is cabot corporation, model CLARUS 3160;
Organic solvent: dichloromethane;
Polyester resin: the manufacturer is Jiangsu Soxhlet obtained new material group Co., ltd, the variety is light type tackifying polyester slices, the intrinsic viscosity is 0.95-1.05dl/g, and the carboxyl end content is less than or equal to 15mol/t;
dispersing agent: tegomer P121, manufacturer is a winning industry group;
(2) Preparing a compound stabilizer;
mixing 30 parts of a composite antioxidant, 65 parts of a composite light stabilizer, 5 parts of an adsorbent and an organic solvent according to parts by weight, uniformly stirring, and removing the organic solvent to obtain a compound stabilizer; wherein, the addition amount of the organic solvent is 0.3 times of the total mass of the composite antioxidant, the composite light stabilizer and the adsorbent;
(3) Preparing high weather-resistant master batches for color polyester;
According to the parts by weight, uniformly mixing 65 parts of polyester resin, 34.5 parts of compound stabilizer and 0.5 part of dispersing agent, putting into a double-screw extruder for melt extrusion, bracing and granulating to obtain high weather-resistant master batch for color polyester; wherein, the temperature of the first area of the double-screw extruder is 220 ℃, the temperature of the second area is 275 ℃, the temperature of the third area is 275 ℃, the temperature of the fourth area is 270 ℃, the temperature of the fifth area is 220 ℃, the temperature of the sixth area is 220 ℃, the temperature of the seventh area is 240 ℃, and the temperature of the eighth area is 260 ℃; the rotational speed of the twin-screw extruder was 300r/min.
The final color polyester has an intrinsic viscosity of 0.5710dl/g.
The preparation method of the color polyester fiber comprises the following specific processes: according to parts by weight, 1 part of the high weather-resistant master batch for color polyester prepared in the embodiment, 10 parts of polyester color master batch (composed of polyester resin and PB15:3; the manufacturer of the polyester resin is Jiangsu Soxhlet New Material group Co., ltd., the variety is a light-type tackifying polyester slice, the intrinsic viscosity is 0.95-1.05dl/g, the content of carboxyl end groups is less than or equal to 15mol/t, the content of PB15:3 is 0.5 wt%) and 89 parts of light polyester slice (the manufacturer is China petrochemical chemical fiber Co., ltd., model SB 500) are uniformly mixed and then melt-spun (the temperature is 285 ℃, the winding speed is 2800 r/min) to obtain the color polyester fiber with the specification of 100d/48 f.
Example 8
The preparation method of the high weather-resistant master batch for the color polyester comprises the following specific steps:
(1) Preparing raw materials;
Composite antioxidant: the main antioxidant is a mixture of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) -N' - [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] propionyl hydrazine and bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] [ oxalyl bis (azetidinyl) ] bis (ethane-2, 1-diyl) ester with a mass ratio of 5:6:1, the auxiliary antioxidant is phenyl tris (2, 4-di-tert-butyl) phosphite, and the free radical scavenger is 5, 7-di-tert-butyl-3- (3, 4-dimethylphenyl) benzofuran-2 (3H) -one;
Composite light stabilizer: the ultraviolet absorber is a mixture of 2, 4-bis (2, 4-xylyl) -6- (2-hydroxy-4-N-octyloxyphenyl) -1,3, 5-triazine, 2, 4-bis (4-biphenyl) -6- (2, 4-dihydroxy) phenyl-1, 3, 5-triazine and 2, 4-bis [2,2 '-bis (5-butoxyphenol) ] -6- (2, 4-dibutoxybenzene) -1,3, 5-triazine, wherein the mass ratio of the triazine ultraviolet absorber to the triazine hindered amine is 1:1:1.3, the triazine hindered amine is poly [ N, N' -bis (2, 6-tetramethyl-4-piperidinyl) -1, 6-hexamethylenediamine-CO-2, 4-dichloro-6-morpholin-1, 3, 5-triazine ] (the manufacturer is Cyasorb UV-3346, CAS model No. 82451-48-7);
an adsorbent: fumed silica, manufacturer is cabot corporation, model CLARUS 3160;
Organic solvent: dichloromethane;
Polyester resin: the manufacturer is Jiangsu Soxhlet obtained new material group Co., ltd, the variety is light type tackifying polyester slices, the intrinsic viscosity is 0.95-1.05dl/g, and the carboxyl end content is less than or equal to 15mol/t;
dispersing agent: tegomer P121, manufacturer is a winning industry group;
(2) Preparing a compound stabilizer;
according to the weight parts, mixing 36 parts of composite antioxidant, 60 parts of composite light stabilizer, 4 parts of adsorbent and organic solvent, uniformly stirring, and removing the organic solvent to obtain a compound stabilizer; wherein, the addition amount of the organic solvent is 0.5 times of the total mass of the composite antioxidant, the composite light stabilizer and the adsorbent;
(3) Preparing high weather-resistant master batches for color polyester;
According to the weight portions, 67.5 portions of polyester resin, 32 portions of compound stabilizer and 0.5 portion of dispersing agent are evenly mixed and then put into a double-screw extruder for melt extrusion, bracing and granulating, thus obtaining the high weather-resistant master batch for the color polyester; wherein, the temperature of the first area of the double-screw extruder is 220 ℃, the temperature of the second area is 275 ℃, the temperature of the third area is 275 ℃, the temperature of the fourth area is 270 ℃, the temperature of the fifth area is 220 ℃, the temperature of the sixth area is 220 ℃, the temperature of the seventh area is 240 ℃, and the temperature of the eighth area is 260 ℃; the rotational speed of the twin-screw extruder was 300r/min.
The final color polyester has an intrinsic viscosity of 0.6027dl/g.
The preparation method of the color polyester fiber comprises the following specific processes: according to parts by weight, 1 part of the high weather-resistant master batch for color polyester prepared in the embodiment, 10 parts of polyester color master batch (composed of polyester resin and PB15:3; the manufacturer of the polyester resin is Jiangsu Soxhlet New Material group Co., ltd., the variety is a light-type tackifying polyester slice, the intrinsic viscosity is 0.95-1.05dl/g, the content of carboxyl end groups is less than or equal to 15mol/t, the content of PB15:3 is 0.5 wt%) and 89 parts of light polyester slice (the manufacturer is China petrochemical chemical fiber Co., ltd., model SB 500) are uniformly mixed and then melt-spun (the temperature is 285 ℃, the winding speed is 2800 r/min) to obtain the color polyester fiber with the specification of 100d/48 f.
The color polyester fibers of example 7 and example 8 were tested for ΔE after 100-500 h irradiation, and the data recorded during the test are shown in Table 6:
TABLE 6
| Colored polyester fiber | 100h △E | 200h △E | 300h △E | 400h △E | 500h △E | 500H color chart grade |
| Example 7 | 0.93 | 1.33 | 1.82 | 1.95 | 2.14 | 4 |
| Example 8 | 0.88 | 1.56 | 2.16 | 2.31 | 2.43 | 4 |
Comparative example 3
A process for preparing a masterbatch, substantially as described in example 7, with the only differences: the composite antioxidant has no free radical scavenger (the mass ratio of the main antioxidant and the auxiliary antioxidant is the same as that of the example 7).
A process for preparing colored polyester fibers, substantially the same as in example 7, except that: the high weatherability master batch for the color polyester was replaced with the master batch of comparative example 3.
The delta E of the finally prepared color polyester fiber after 500h irradiation is 2.71, and the color card grade after 500h irradiation is 3.5 grade.
Compared with the comparative example 3 and the example 7, the ΔE of the colored polyester fiber is increased, and the color card grade is reduced, because the composite antioxidant adopted in the comparative example 3 is free of a free radical scavenger, the polyester master batch cannot effectively quench alkyl free radicals at the initial stage of thermal degradation chain reaction, so that the aging reaction cannot be terminated in time, the performance of the master batch is deteriorated in the thermal processing process, the ΔE of the finally prepared colored polyester fiber is increased, and the color card grade is reduced, which indicates that the weather resistance of the finally prepared colored polyester fiber is poor.
Comparative example 4
A process for preparing a masterbatch, substantially as described in example 7, with the only differences: the composite antioxidant has no main antioxidant (the mass ratio of the auxiliary antioxidant to the free radical scavenger is the same as that of the example 7).
A process for preparing colored polyester fibers, substantially the same as in example 7, except that: the high weatherability master batch for the color polyester was replaced with the master batch of comparative example 4.
The delta E of the finally prepared color polyester fiber after 500h irradiation is 2.68, and the color card grade after 500h irradiation is 3.5 grade.
Compared with the comparative example 4 and the example 7, the delta E of the color polyester fiber is increased, and the color card grade is reduced, because the composite antioxidant adopted in the comparative example 4 is free of a main antioxidant, so that the polyester master batch cannot effectively quench hydroxyl radicals and peroxy radicals generated by the reaction of alkyl radicals and oxygen/water in the thermal degradation chain reaction process, and further the performance of the master batch is deteriorated in the thermal processing process, and the delta E of the finally prepared color polyester fiber is increased, and the color card grade is reduced, so that the weather resistance is poor.
Comparative example 5
A process for preparing a masterbatch, substantially as described in example 7, with the only differences: the mass ratio of the triazine hindered amine in the compound light stabilizer to the compound light stabilizer is the same as that in example 7, except that the triazine hindered amine in the compound light stabilizer is replaced by a hydrophobic hindered amine (UV 5050H, manufacturer is Basoff company) containing a long carbon chain.
A process for preparing colored polyester fibers, substantially the same as in example 7, except that: the high weatherability master batch for the color polyester was replaced with the master batch of comparative example 5.
The delta E of the finally prepared color polyester fiber after 500h irradiation is 3.82, and the color card grade after 500h irradiation is 3 grade.
The comparative example 5 has an increased Δe and a decreased color chip scale compared with example 7 because the hindered amine used in comparative example 5 is a hydrophobic type hindered amine having a long carbon chain, and the long carbon chain has poor compatibility with polyester, resulting in poor dispersibility of the long carbon chain hindered amine in polyester products, which significantly affects the Δe and color chip scale of the finally produced colored polyester fiber, and has poor weather resistance.
Example 9
The preparation method of the high weather-resistant master batch for the color polyester comprises the following specific steps:
(1) Preparing raw materials;
Composite antioxidant: the main antioxidant is a mixture of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) -N' - [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] propionyl hydrazine and bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] [ oxalyl bis (azetidinyl) ] bis (ethane-2, 1-diyl) ester with a mass ratio of 5:6:1, the auxiliary antioxidant is phenyl tris (2, 4-di-tert-butyl) phosphite, and the free radical scavenger is 5, 7-di-tert-butyl-3- (3, 4-dimethylphenyl) benzofuran-2 (3H) -one;
Composite light stabilizer: the ultraviolet absorber is a mixture of 2, 4-bis (2, 4-xylyl) -6- (2-hydroxy-4-N-octyloxyphenyl) -1,3, 5-triazine, 2, 4-bis (4-biphenyl) -6- (2, 4-dihydroxy) phenyl-1, 3, 5-triazine and 2, 4-bis [2,2 '-bis (5-butoxyphenol) ] -6- (2, 4-dibutoxybenzene) -1,3, 5-triazine, wherein the mass ratio of the triazine ultraviolet absorber to the triazine hindered amine is 1:1:1.3, the triazine hindered amine is poly [ N, N' -bis (2, 6-tetramethyl-4-piperidinyl) -1, 6-hexamethylenediamine-CO-2, 4-dichloro-6-morpholin-1, 3, 5-triazine ] (the manufacturer is Cyasorb UV-3346, CAS model No. 82451-48-7);
an adsorbent: fumed silica, manufacturer is cabot corporation, model CLARUS 3160;
Organic solvent: dichloromethane;
Polyester resin: the manufacturer is Jiangsu Soxhlet obtained new material group Co., ltd, the variety is light type tackifying polyester slices, the intrinsic viscosity is 0.95-1.05dl/g, and the carboxyl end content is less than or equal to 15mol/t;
dispersing agent: tegomer P121, manufacturer is a winning industry group;
(2) Preparing a compound stabilizer;
According to parts by weight, mixing 33 parts of a composite antioxidant, 64 parts of a composite light stabilizer, 3 parts of an adsorbent and an organic solvent, uniformly stirring, and removing the organic solvent to obtain a composite stabilizer; wherein, the addition amount of the organic solvent is 0.3 times of the total mass of the composite antioxidant, the composite light stabilizer and the adsorbent;
(3) Preparing high weather-resistant master batches for color polyester;
According to the parts by weight, uniformly mixing 69.9 parts of polyester resin, 30 parts of compound stabilizer and 0.1 part of dispersing agent, putting into a double-screw extruder for melt extrusion, bracing and granulating to obtain high weather-resistant master batch for color polyester; wherein, the temperature of the first area of the double-screw extruder is 220 ℃, the temperature of the second area is 275 ℃, the temperature of the third area is 275 ℃, the temperature of the fourth area is 270 ℃, the temperature of the fifth area is 220 ℃, the temperature of the sixth area is 220 ℃, the temperature of the seventh area is 240 ℃, and the temperature of the eighth area is 260 ℃; the rotational speed of the twin-screw extruder was 300r/min.
The final color polyester has an intrinsic viscosity of 0.6245dl/g.
The preparation method of the color polyester fiber comprises the following specific processes: according to parts by weight, 10 parts of the high weather-resistant master batch for color polyester, 10 parts of polyester color master batch (composed of polyester resin and PB15:3, wherein the manufacturer of the polyester resin is Jiangsu Soxhlet New Material group Co., ltd.) is a light type tackifying polyester slice, the intrinsic viscosity is 0.95-1.05dl/g, the content of carboxyl end groups is less than or equal to 15mol/t, the content of PB15:3 is 0.5 wt%) and 80 parts of light polyester slice (the manufacturer is China petrochemical chemical fiber Co., ltd., model SB 500) are uniformly mixed, and then melt spinning (the temperature is 285 ℃, the winding speed is 2800 r/min) is carried out, so that the color polyester fiber with the specification of 100d/48f is obtained.
The delta E of the finally prepared color polyester fiber after 500h irradiation is 1.93, and the color card grade after 500h irradiation is 4 grade.
Five triazine ultraviolet absorbers selected by the invention: the absorbance of (2, 4-bis (2, 4-xylyl) -6- (2-hydroxy-4-n-octyloxyphenyl) -1,3, 5-triazine, 2- (4, 6-diphenyl-1, 3, 5-triazine-2) -5-n-hexyloxyphenol, 2, 4-bis (4-biphenyl) -6- (2, 4-dihydroxy) phenyl-1, 3, 5-triazine, 2, 4-bis [2,2' -bis (5-butoxyphenol) ] -6- (2, 4-dibutoxybenzene) -1,3, 5-triazine, 2,4, 6-tris (4 ' -butoxy-2 ' -hydroxyphenyl) -triazine) at 280-400 nm is shown in FIG. 1;
the triazine ultraviolet absorber combination selected in example 1-5 (a mixture of 2, 4-bis (4-biphenyl) -6- (2, 4-dihydroxy) -1,3, 5-triazine and 2,4, 6-tris (4 '-butoxy-2' -hydroxyphenyl) -triazine in a mass ratio of 1:1.5), the triazine ultraviolet absorber combination selected in example 7 (a mixture of 2- (4, 6-diphenyl-1, 3, 5-triazine-2) -5-n-hexyloxyphenol, 2, 4-bis [2,2 '-bis (5-butoxyphenol) ] -6- (2, 4-dibutoxybenzene) -1,3, 5-triazine and 2,4, 6-tris (4' -butoxy-2 '-hydroxyphenyl) -triazine in a mass ratio of 1:1:3, 2-bis (2, 4-hydroxy) -6- (2, 6-diphenyl) -2-5-triazine and 2,4, 6-tris (4' -hydroxybenzene) -triazine in a mixture of 2, 4-bis [2, 4 '-hydroxybenzene) -2, 4-bis [2, 4' -bis [2, 5-butoxyphenyl ] -2, 4-bis [2, 4-bis (4-hydroxybenzene) -triazine ] with the absorbance at 1:1:1:3:2.2; as can be seen from FIG. 2, the different triazine ultraviolet absorbent combinations selected by the invention have high ultraviolet absorption efficiency, and the combinations cover the whole ultraviolet region, so that not only can carbonyl groups in polyester be effectively protected from being damaged by rays close to 300nm wave bands in sunlight, but also the long wave part of the ultraviolet region can be pertinently protected by being attached to the distribution trend of the solar spectrum, thereby realizing the comprehensive and effective protection of various pigments.
Claims (10)
1. The high weather-resistant master batch for the color polyester is characterized by comprising, by weight, 65-70 parts of polyester resin, 30-34.5 parts of compound stabilizer and 0.1-0.5 part of dispersing agent;
The intrinsic viscosity of the polyester resin is 0.95 to 1.05dl/g, and the content of carboxyl end groups is less than or equal to 15mol/t;
the compound stabilizer comprises 30-40 parts of compound antioxidant and 55-65 parts of compound light stabilizer by weight;
The compound antioxidant comprises a main antioxidant, an auxiliary antioxidant and a free radical scavenger;
The compound light stabilizer comprises a triazine ultraviolet absorber and a triazine hindered amine.
2. The high weather resistant master batch for color polyester according to claim 1, wherein the main antioxidant is one or more of 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) -N' - [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazide, bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] [ oxalylbis (azanediyl) ] bis (ethane-2, 1-diyl) ester.
3. The high weather resistant master batch for color polyester according to claim 1, wherein the auxiliary antioxidant is more than one of phenyl tris (2, 4-di-t-butyl) phosphite, bis (2, 4-di-t-butylphenol) pentaerythritol diphosphite, 3, 9-bis (2, 4-dicumylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane.
4. The high weather resistant masterbatch for colored polyesters according to claim 1, characterized in that the radical scavenger is 5, 7-di-tert-butyl-3- (3, 4-dimethylphenyl) benzofuran-2 (3H) -one.
5. The high weather resistant masterbatch for color polyester according to claim 1, wherein the triazine ultraviolet absorber is one or more of 2, 4-bis (2, 4-xylyl) -6- (2-hydroxy-4-n-octyloxyphenyl) -1,3, 5-triazine, 2- (4, 6-diphenyl-1, 3, 5-triazine-2) -5-n-hexyloxyphenol, 2, 4-bis (4-biphenyl) -6- (2, 4-dihydroxy) phenyl-1, 3, 5-triazine, 2, 4-bis [2,2' -bis (5-butoxyphenol) ] -6- (2, 4-dibutoxybenzene) -1,3, 5-triazine, and 2,4, 6-tris (4 ' -butoxy-2 ' -hydroxyphenyl) -triazine.
6. The high weather resistant master batch for color polyester according to claim 1, wherein the triazine hindered amine is poly [ N, N '-bis (2, 6-tetramethyl-4-piperidinyl) -1, 6-hexamethylenediamine-CO-2, 4-dichloro-6-morpholin-1, 3, 5-triazine ], N, methylated polymers of N' -bis (2, 6-tetramethyl-4-piperidinyl) -1, 6-hexamethylenediamine and morpholine-2, 4, 6-trichloro-1, 3, 5-triazine, reaction products of N, N '' -1, 2-ethanediylbis (1, 3-propanediamine) with cyclohexane and N-butyl-2, 6-tetramethyl-4-piperidylamine-2, 4, 6-trichloro-1, 3, 5-triazine peroxide.
7. The high weather-resistant master batch for colored polyester according to claim 1, wherein the compound stabilizer further comprises 3-5 parts of adsorbent by weight; the adsorbent is fumed silica.
8. The high weather resistant master batch for color polyester according to claim 7, wherein the preparation process of the compound stabilizer is as follows: and mixing the composite antioxidant, the composite light stabilizer, the adsorbent and the organic solvent, uniformly stirring, and removing the organic solvent to obtain the compound stabilizer.
9. The method for preparing the high weather-resistant master batch for the color polyester according to any one of claims 1 to 8, which is characterized in that the high weather-resistant master batch for the color polyester is obtained by uniformly mixing the components according to the proportion, and then carrying out melt extrusion, bracing and granulating.
10. The use of a high weathering master batch for color polyesters according to any of claims 1 to 8, characterized in that it is used for the preparation of polyester fibers in an amount of 0.1 to 10% by weight.
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| CN101906244A (en) * | 2010-08-12 | 2010-12-08 | 东莞市信诺橡塑工业有限公司 | Polycarbonate composition and preparation method thereof |
| CN102492269A (en) * | 2011-12-06 | 2012-06-13 | 宁波长阳科技有限公司 | Weather-resistant white master batch, weather-resistant polyester material and preparation methods of weather-resistant white master batch and weather-resistant polyester material |
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| CN112679854A (en) * | 2020-12-28 | 2021-04-20 | 浙江普利特新材料有限公司 | High-heat-resistance and high-weather-resistance polypropylene composition and preparation method thereof |
| CN115625870A (en) * | 2022-11-30 | 2023-01-20 | 江苏康辉新材料科技有限公司 | Super-weather-resistant white polyester film and preparation method thereof |
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| CN101906244A (en) * | 2010-08-12 | 2010-12-08 | 东莞市信诺橡塑工业有限公司 | Polycarbonate composition and preparation method thereof |
| CN102492269A (en) * | 2011-12-06 | 2012-06-13 | 宁波长阳科技有限公司 | Weather-resistant white master batch, weather-resistant polyester material and preparation methods of weather-resistant white master batch and weather-resistant polyester material |
| CN111286161A (en) * | 2020-02-24 | 2020-06-16 | 营口康辉石化有限公司 | Ultraviolet-resistant polyester film |
| CN111675885A (en) * | 2020-06-22 | 2020-09-18 | 宿迁联宏新材料有限公司 | PET (polyethylene terephthalate) light aging resistant and weather resistant master batch and preparation method thereof |
| CN112679854A (en) * | 2020-12-28 | 2021-04-20 | 浙江普利特新材料有限公司 | High-heat-resistance and high-weather-resistance polypropylene composition and preparation method thereof |
| CN115625870A (en) * | 2022-11-30 | 2023-01-20 | 江苏康辉新材料科技有限公司 | Super-weather-resistant white polyester film and preparation method thereof |
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