CN117843937A - Modified copolyester material, preparation method and application - Google Patents
Modified copolyester material, preparation method and application Download PDFInfo
- Publication number
- CN117843937A CN117843937A CN202410053890.6A CN202410053890A CN117843937A CN 117843937 A CN117843937 A CN 117843937A CN 202410053890 A CN202410053890 A CN 202410053890A CN 117843937 A CN117843937 A CN 117843937A
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- Prior art keywords
- copolyester material
- reaction
- acid
- polycondensation
- modified copolyester
- Prior art date
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- 239000000463 material Substances 0.000 title claims abstract description 113
- 229920001634 Copolyester Polymers 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 32
- 239000000945 filler Substances 0.000 claims abstract description 25
- 239000005003 food packaging material Substances 0.000 claims abstract description 4
- 238000006068 polycondensation reaction Methods 0.000 claims description 78
- 238000005886 esterification reaction Methods 0.000 claims description 59
- 239000003054 catalyst Substances 0.000 claims description 58
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 34
- 239000002253 acid Substances 0.000 claims description 33
- 239000000126 substance Substances 0.000 claims description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 30
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 30
- 239000004970 Chain extender Substances 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 17
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- 239000005639 Lauric acid Substances 0.000 claims description 15
- 125000003367 polycyclic group Chemical group 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 125000001931 aliphatic group Chemical group 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- -1 alkane diol Chemical class 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 239000001506 calcium phosphate Substances 0.000 claims description 4
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 4
- 235000011010 calcium phosphates Nutrition 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 claims description 4
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 4
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229920000728 polyester Polymers 0.000 abstract description 14
- 230000003678 scratch resistant effect Effects 0.000 abstract description 12
- 238000001746 injection moulding Methods 0.000 abstract description 3
- 239000012770 industrial material Substances 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract description 2
- 229920006267 polyester film Polymers 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 83
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 47
- 239000000203 mixture Substances 0.000 description 31
- 239000012153 distilled water Substances 0.000 description 29
- 238000010438 heat treatment Methods 0.000 description 27
- 230000032050 esterification Effects 0.000 description 26
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 18
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 18
- 239000003381 stabilizer Substances 0.000 description 18
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 16
- 230000008859 change Effects 0.000 description 16
- 239000004246 zinc acetate Substances 0.000 description 16
- 229960000314 zinc acetate Drugs 0.000 description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 15
- 238000005266 casting Methods 0.000 description 15
- 238000001035 drying Methods 0.000 description 15
- 239000000155 melt Substances 0.000 description 15
- 239000011574 phosphorus Substances 0.000 description 15
- 229910052698 phosphorus Inorganic materials 0.000 description 15
- 229920000139 polyethylene terephthalate Polymers 0.000 description 15
- 239000005020 polyethylene terephthalate Substances 0.000 description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 14
- 230000001105 regulatory effect Effects 0.000 description 14
- 235000012239 silicon dioxide Nutrition 0.000 description 14
- 238000005809 transesterification reaction Methods 0.000 description 14
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 14
- 239000011701 zinc Substances 0.000 description 14
- 229910052725 zinc Inorganic materials 0.000 description 14
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 13
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 8
- 150000002009 diols Chemical class 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 150000003752 zinc compounds Chemical class 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 3
- 229940035437 1,3-propanediol Drugs 0.000 description 3
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 3
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 2
- 229920003232 aliphatic polyester Polymers 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001463 antimony compounds Chemical class 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229940057499 anhydrous zinc acetate Drugs 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/127—Acids containing aromatic rings
- C08G63/13—Acids containing aromatic rings containing two or more aromatic rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- 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
- C08K3/32—Phosphorus-containing 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- 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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/325—Calcium, strontium or barium phosphate
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a modified copolyester material, a preparation method and application thereof. Relates to the technical field of polyester materials. The modified copolyester material comprises filler particles and a copolyester material, wherein the structural formula of the copolyester material is as follows:
Description
Technical Field
The invention relates to the technical field of polyester materials, in particular to a modified copolyester material, a preparation method and application thereof.
Background
PET (polyethylene terephthalate) is one of five engineering plastics, and has the characteristics of good comprehensive performance, including high strength, high modulus, high hardness, high heat resistance, good creep resistance, chemical corrosion resistance, ageing resistance, recycling and the like. The modified PET material can impart more excellent properties. Conjugated systems can be formed between benzene rings and ester groups in the PET structure, so that the PET material has high rigidity, and the product tends to show high brittleness. Due to the existence of conjugated system, the short flexible chain segment (-CH) in the molecule is acted by external force 2 -CH 2 (-) and benzene rings can only move as a whole, and the rigidity exhibited by molecular chains results in a glass transition temperature of 75-85 ℃ for common PET, thereby increasing the possibility of brittle failure of the polyester. Thus, during the transportation of PET articles, scratches may be formed between articles or between the articles and the packaging container on the surface to affect the beauty, and some strong scratches may deform the surface of the material, resulting in a partial loss of performance of the articles.
Accordingly, there is a need to develop scratch resistant polyester materials. At present, the methods for improving the scratch resistance of the polyester material mainly comprise the following steps:
1. the PET material is blended with other scratch-resistant materials, and the scratch resistance of the modified alloy is improved by adding a scratch-resistant agent and a scratch-resistant modifier to the blended matrix. However, the addition of scratch resistance agents and scratch resistance modifiers increases cost, and the performance is unstable and the improvement degree is limited.
2. The coating is manufactured on the surface of PET material, and common coating processes comprise a double-sided coating photo-curing acrylate hardening coating and a spraying process. However, these processes are complex and costly, and the coating thickness is often not uniform.
3. Elastic particles are introduced into the PET material structure to toughen the PET material to improve scratch resistance. This includes a method of blending an auxiliary agent containing a shell-core copolymer, a rubber elastomer, toughened ABS, an olefin grafted glycidyl ester, and the like with PET. However, this method has a problem that the material properties are lost with time.
Based on this, there is a need to develop scratch-resistant polyester materials with better effects, which overcome the defects of the prior art, such as inherent brittleness and complicated process for improving scratch resistance of PET materials.
Disclosure of Invention
The first technical problem to be solved by the invention is as follows:
a modified copolyester material is provided.
The second technical problem to be solved by the invention is as follows:
a method for preparing the modified copolyester material is provided.
The third technical problem to be solved by the invention is:
the application of the modified copolyester material.
In order to solve the first technical problem, the invention adopts the following technical scheme:
a modified copolyester material comprising filler particles and a copolyester material, the copolyester material having the structural formula:
wherein x is greater than 0, y is greater than 0, n is greater than 0, and m is greater than 0;
x：y：n＝3.3～9.2：1：1.0～1.2；
y：m＝12.4～2019.7：1～1.5。
according to the embodiments of the present invention, one of the technical solutions has at least one of the following advantages or beneficial effects:
the invention relates to a soft scratch-resistant copolyester material, which has the characteristics of softness, good scratch resistance, easy molding, good impact resistance and the like, can be applied to the fields of industrial materials and food packaging materials, and is preferably used as a raw material of a polyester film, a polyester bottle and an injection molding product.
According to the invention, the aliphatic polyester units are randomly inserted into the aromatic PET polymer chains through a copolymerization modification method, so that the comprehensive properties of the aliphatic polyester and the PET-based aromatic polyester are combined, wherein the soft chain segments (such as m and n chain segments) and the inorganic chain extension particles in the material can endow the material with soft and smooth properties, and the scratch resistance of the material can be improved. The filler particles can be used as the stress concentration center position, a large number of stress concentration points can trigger to generate a large number of cracks, and the particles can absorb and consume a large amount of energy. The sample is impacted by external force to generate micro cracks, at the moment, the flexible groups and the chain extender are similar to rubber to cross two sides of the cracks, and the cracks further expand to stretch the elastic groups and the rigid particles, so that a large amount of energy can be absorbed, and the impact strength of plastics is improved. The invention discloses a soft scratch-resistant polyester material, which aims to fundamentally solve the problems that the traditional polyester product has large brittleness and is easy to scratch and crack in the transportation process.
According to one embodiment of the invention, x: y: n=3.44 to 9.11:1:1.0 to 1.2.
According to one embodiment of the invention, x: y: n=3.4 to 9.2:1:1.07 to 1.15.
According to one embodiment of the invention, x: y: n=3.446 to 9.104:1:1.078 to 1.150.
According to one embodiment of the invention, y: m=12.41 to 2019.66:1 to 1.5.
According to one embodiment of the invention, y: m=12.4 to 2019.6:1 to 1.2.
According to one embodiment of the invention, y: m= 12.413 to 2019.651:1 to 1.5.
According to one embodiment of the invention, the filler particles comprise at least one of silica, nano zinc oxide, calcium carbonate and calcium phosphate. The filler particles are randomly distributed in the modified copolyester material, and the blending mode can be called a sea-island structure, so that the mechanical property of the material can be improved and the scratch resistance of the surface of the material can be improved by the blending mode.
According to one embodiment of the invention, the filler particles have a particle size of 0.01-10 μm.
According to one embodiment of the invention, the filler particles have a mass of 100-500ppm of the mass of the copolyester material.
According to one embodiment of the present invention, the filler particles are added in an amount of 1 to 5g.
In order to solve the second technical problem, the invention adopts the following technical scheme:
a method of preparing the modified copolyester material comprising the steps of:
s1, mixing polycyclic dibasic acid, aliphatic dibasic acid, aromatic dibasic acid and dihydric alcohol, and carrying out esterification reaction to obtain an esterified substance;
s2, mixing the esterified substance, the polycondensation catalyst, the filler particles and the chain extender in a vacuum atmosphere, and performing polycondensation reaction to obtain the modified copolyester material.
According to the embodiments of the present invention, one of the technical solutions has at least one of the following advantages or beneficial effects:
the preparation method disclosed by the invention is simple in process, can be used for continuous, intermittent and semi-continuous equipment, and the prepared modified copolyester material is a scratch-resistant copolyester material, so that the material has good scratch resistance and good impact resistance.
In the method for preparing the modified copolyester material, the method of esterification and polycondensation is adopted to prepare the scratch-resistant copolyester material, acid and alcohol reaction monomers are firstly added into slurry, and an esterification catalyst is added for esterification, so that an esterification product is obtained. Before the polycondensation reaction, chain extender, polycondensation catalyst and filler particles are added into a reaction vessel, and then the polycondensation reaction is carried out to prepare the scratch-resistant copolyester material. The reaction is essentially a chain extension reaction of several monomers at elevated temperature and with the aid of a catalyst. The toughness and scratch resistance of the copolyester material can be controlled by designing a process route, changing the feeding proportion and type, feeding sequence and optimizing the reaction condition.
The soft chain segment and the inorganic chain extension particles in the modified copolyester material of the invention endow the material with soft and smooth performance on one hand, and improve the scratch resistance of the material on the other hand. The filler particles can act as stress concentration points, absorbing a lot of energy, thereby preventing a lot of cracks from occurring.
The invention does not need to use any solvent, and only generates non-toxic and harmless byproduct water. As the related monomers, catalysts, other auxiliary agents and copolyester finished products are nontoxic and harmless, the obtained copolyester material not only reaches the food-grade standard, but also is applicable to the aspects of polyester bottles, plates, films, injection molding shell parts, sheets and the like.
The soft scratch-resistant polyester material disclosed by the invention remarkably overcomes the defects of limitation in application caused by strong rigidity and poor low-temperature resistance of the polyester material. When the test specimen is impacted by external force, the flexible groups and the chain extender are similar to rubber to cross two sides of a crack, and the crack further expands to stretch the elastic groups and the rigid particles, so that a large amount of energy can be absorbed, and the impact strength of the plastic is improved.
According to an embodiment of the present invention, in step S1, when the polycyclic dibasic acid, the aliphatic dibasic acid, the aromatic dibasic acid, and the diol are mixed, the step of adding the esterification catalyst is further included.
According to an embodiment of the present invention, in the method for preparing the modified copolyester material, the reaction involved in the step S1 includes the following reaction formula:
according to an embodiment of the present invention, in the method for preparing the modified copolyester material, the reaction involved in the step S2 includes the following reaction formula:
according to an embodiment of the present invention, in step S1, the steps of: mixing polycyclic dibasic acid, aliphatic dibasic acid, aromatic dibasic acid, dihydric alcohol, esterification catalyst, stabilizer and antioxidant.
According to one embodiment of the present invention, the stabilizer includes at least one of phosphoric acid, polyphosphoric acid, triphenyl phosphate, and trimethyl phosphate.
According to one embodiment of the invention, the stabilizer is added in an amount of 30 to 600ppm calculated as the ratio of the total weight of the copolyester material finally produced.
According to one embodiment of the present invention, the antioxidant includes at least one of hindered phenol and aromatic amine antioxidants.
According to one embodiment of the invention, the antioxidant is added in an amount of 100-300ppm of the total mass of the copolyester material finally produced.
According to one embodiment of the present invention, the antioxidant is added in an amount of 1 to 3g.
According to an embodiment of the present invention, in step S1, the steps of: mixing polycyclic dibasic acid, aliphatic dibasic acid, dihydric alcohol and esterification catalyst, performing esterification reaction, and continuing the esterification reaction after the water yield reaches 90% -100% of theoretical value (theoretical value is used for assuming that the added acid is completely reacted, namely the corresponding water yield is calculated according to the addition amount of the acid), and then adding aromatic dibasic acid to obtain the esterified product.
According to one embodiment of the present invention, the polycyclic dibasic acid includes at least one of 1, 4-naphthalene dicarboxylic acid and 2, 6-naphthalene dicarboxylic acid.
According to one embodiment of the invention, the addition amount of the polycyclic dibasic acid is 10-20% of the mass of the finally produced copolyester material.
According to one embodiment of the invention, the aliphatic dibasic acid comprises at least one of azelaic acid and lauric acid.
According to one embodiment of the invention, the aliphatic additive amount is 10% -20% of the mass of the copolyester material finally produced.
According to one embodiment of the present invention, the aromatic dibasic acid includes at least one of terephthalic acid and isophthalic acid.
According to one embodiment of the invention, the glycol comprises a linear or branched C2-C5 alkanediol.
According to one embodiment of the invention, the dihydric alcohol comprises at least one of ethylene glycol, 1, 3-propanediol and neopentyl glycol.
According to one embodiment of the invention, the molar ratio of the dihydric alcohol to the dibasic acid is 1.1-3.0: 1 to 1.5, wherein the dibasic acid comprises at least one of aromatic dibasic acid, polycyclic dibasic acid and aliphatic dibasic acid.
According to one embodiment of the present invention, the esterification catalyst includes at least one of a zinc compound, a magnesium compound, a manganese compound, and a cobalt compound.
According to one embodiment of the invention, the esterification catalyst comprises at least one of zinc acetate, manganese acetate, cobalt acetate.
According to one embodiment of the invention, the polycondensation catalyst comprises at least one of a titanium compound, an antimony compound and a zinc compound.
According to one embodiment of the invention, the polycondensation catalyst is a compound system of two or more catalysts.
According to one embodiment of the invention, the zinc compound comprises a tetraalkoxy titanate comprising at least one of tetraethoxy titanium, tetrapropoxy titanium, tetraisopropoxy titanium, n-butyl titanate.
According to one embodiment of the present invention, the antimony compound includes at least one of antimony oxide, ethylene glycol antimony, and antimony acetate.
According to one embodiment of the invention, the zinc compound comprises at least one of zinc acetate and zinc chloride.
According to one embodiment of the invention, the total addition of the esterification catalyst and polycondensation catalyst is calculated as the ratio of the mass of central metal atoms of the catalyst to the total weight of the copolyester material finally produced.
According to one embodiment of the invention, the total addition amount of the esterification catalyst and the polycondensation catalyst is 5 to 500ppm.
According to one embodiment of the invention, the chain extender comprises at least one of trimellitic anhydride, pyromellitic anhydride, and trimethylolpropane.
According to one embodiment of the invention, the chain extender is added in an amount of 100 to 5000ppm of the total mass of the copolyester material finally produced.
In another aspect of the invention, a food packaging material is also provided. Comprising a modified copolyester material as described in the example of aspect 1 above. The application adopts all the technical schemes of the modified copolyester material, so that the modified copolyester material has at least all the beneficial effects brought by the technical schemes of the embodiment.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The words "preferably," "more preferably," and the like in the present invention refer to embodiments of the invention that may provide certain benefits in some instances. However, other embodiments may be preferred under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values for the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range description features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
The reagents, methods and apparatus employed in the present invention, unless otherwise specified, are all conventional in the art.
The modified copolyester material obtained in the embodiment comprises filler particles and a copolyester material, wherein the structural formula of the copolyester material is as follows:
in examples 1 to 4, x: y: n=3.32: 1:1.11, y: n=67.3: 1, y: n=67.3: 1, a step of;
in example 5, x: y: n=3.32: 1:1.11, y: n= 59.24:1, a step of;
in example 6, x: y: n=3.32: 1:1.111, y: n= 41.369:1, a step of;
in example 7, x: y: n=3.32: 1:1.11, y: n=67.3: 1.
example 1
The preparation method of the modified copolyester material comprises the following steps:
s1, adding 2000g of 2,6 naphthalene dicarboxylic acid, 1000g of azelaic acid, 1000g of lauric acid, 5000g of ethylene glycol, 50ppm of esterification catalyst zinc acetate (calculated according to the content of zinc element) and 50ppm of stabilizer trimethyl phosphate (calculated according to the content of phosphorus element) into a 20L reaction kettle, uniformly mixing, heating to 200 ℃, and carrying out esterification reaction under the pressure of 0.27 MPa; adding 5100g of terephthalic acid when the distilled water reaches a theoretical value, heating to 240 ℃ to continue esterification reaction, and obtaining an esterified substance mixture when the distilled water reaches the theoretical value;
s2, adding 10ppm of polycondensation catalyst germanium oxide, 30g of chain extender pyromellitic anhydride, 3g of silicon dioxide and 3g of antioxidant 1010 and 168 into the mixture of the esterified substances obtained in the S1, and performing transesterification polycondensation reaction, wherein the pressure of a reaction container is kept at micro positive pressure at first during polycondensation, then the reaction kettle is kept in a vacuum state, the vacuum degree is 90Pa, the temperature is regulated to 290 ℃, the reaction is performed for 300min, the change of melt viscosity in the reaction kettle is judged through the torque of a stirrer, and the polycondensation reaction is stopped when the torque theoretical value is reached. And then flowing the melt into a water tank through a casting belt opening, granulating through a granulator, and drying to obtain the modified copolyester material.
Example 2
Example 2 differs from example 1 in that: filler particles are different. Wherein, the filler particles in the embodiment 2 are 3g of nano zinc oxide, and the filler particles in the embodiment 1 are 3g of silicon dioxide.
Specific:
the preparation method of the modified copolyester material comprises the following steps:
s1, adding 2000g of 2,6 naphthalene dicarboxylic acid, 1000g of azelaic acid, 1000g of lauric acid, 5000g of ethylene glycol, 50ppm of esterification catalyst zinc acetate (calculated according to the content of zinc element) and 50ppm of stabilizer trimethyl phosphate (calculated according to the content of phosphorus element) into a 20L reaction kettle, uniformly mixing, heating to 200 ℃, and carrying out esterification reaction under the pressure of 0.27 MPa; adding 5100g of terephthalic acid when the distilled water reaches a theoretical value, heating to 240 ℃ to continue esterification reaction, and obtaining an esterified substance mixture when the distilled water reaches the theoretical value;
s2, adding 10ppm of polycondensation catalyst germanium oxide, 30g of chain extender pyromellitic anhydride, 3g of nano zinc oxide and 3g of antioxidant 1010 and 168 into the mixture of the esterified substances obtained in the S1, and performing transesterification polycondensation reaction, wherein the pressure of a reaction container is kept at micro positive pressure at first during polycondensation, then the reaction kettle is kept in a vacuum state, the vacuum degree is 90Pa, the temperature is regulated to 290 ℃, the reaction is performed for 300min, the change of melt viscosity in the reaction kettle is judged through the torque of a stirrer, and the polycondensation reaction is stopped when the torque theoretical value is reached. And then flowing the melt into a water tank through a casting belt opening, granulating through a granulator, and drying to obtain the modified copolyester material.
Example 3
Example 3 differs from example 1 in that: filler particles are different. Wherein, the filler particles in the example 3 are 3g of calcium carbonate, and the filler particles in the example 1 are 3g of silicon dioxide.
Specific:
the preparation method of the modified copolyester material comprises the following steps:
s1, adding 2000g of 2,6 naphthalene dicarboxylic acid, 1000g of azelaic acid, 1000g of lauric acid, 5000g of ethylene glycol, 50ppm of esterification catalyst zinc acetate (calculated according to the content of zinc element) and 50ppm of stabilizer trimethyl phosphate (calculated according to the content of phosphorus element) into a 20L reaction kettle, uniformly mixing, heating to 200 ℃, and carrying out esterification reaction under the pressure of 0.27 MPa; adding 5100g of terephthalic acid when the distilled water reaches a theoretical value, heating to 240 ℃ to continue esterification reaction, and obtaining an esterified substance mixture when the distilled water reaches the theoretical value;
s2, adding 10ppm of polycondensation catalyst germanium oxide, 30g of chain extender pyromellitic anhydride, 3g of calcium carbonate and 3g of antioxidant 1010 and 168 into the mixture of the esterified substances obtained in the S1, and performing transesterification polycondensation reaction, wherein the pressure of a reaction container is kept at micro positive pressure at first during polycondensation, then the reaction kettle is kept in a vacuum state, the vacuum degree is 90Pa, the temperature is regulated to 290 ℃, the reaction is performed for 300min, the change of melt viscosity in the reaction kettle is judged through the torque of a stirrer, and the polycondensation reaction is stopped when the torque theoretical value is reached. And then flowing the melt into a water tank through a casting belt opening, granulating through a granulator, and drying to obtain the modified copolyester material.
Example 4
Example 4 differs from example 1 in that: filler particles are different. Wherein, the filler particles in example 4 are 3g of calcium phosphate, and the filler particles in example 1 are 3g of silicon dioxide.
Specific:
the preparation method of the modified copolyester material comprises the following steps:
s1, adding 2000g of 2,6 naphthalene dicarboxylic acid, 1000g of azelaic acid, 1000g of lauric acid, 5000g of ethylene glycol, 50ppm of esterification catalyst zinc acetate (calculated according to the content of zinc element) and 50ppm of stabilizer trimethyl phosphate (calculated according to the content of phosphorus element) into a 20L reaction kettle, uniformly mixing, heating to 200 ℃, and carrying out esterification reaction under the pressure of 0.27 MPa; adding 5100g of terephthalic acid when the distilled water reaches a theoretical value, heating to 240 ℃ to continue esterification reaction, and obtaining an esterified substance mixture when the distilled water reaches the theoretical value;
s2, adding 10ppm of polycondensation catalyst germanium oxide, 30g of chain extender pyromellitic anhydride, 3g of calcium phosphate and 3g of antioxidant 1010 and 168 into the mixture of the esterified substances obtained in the S1, and performing transesterification polycondensation reaction, wherein the pressure of a reaction container is kept at micro positive pressure at first, then the reaction kettle is kept in a vacuum state, the vacuum degree is 90Pa, the temperature is regulated to 290 ℃, the reaction is performed for 300min, the change of melt viscosity in the reaction kettle is judged through the torque of a stirrer, and the polycondensation reaction is stopped when the torque theoretical value is reached. And then flowing the melt into a water tank through a casting belt opening, granulating through a granulator, and drying to obtain the modified copolyester material.
Example 5
Example 5 differs from example 1 in that: chain extenders vary. Wherein the chain extender of example 5 is trimellitic anhydride and the chain extender of example 1 is pyromellitic anhydride.
Specific:
the preparation method of the modified copolyester material comprises the following steps:
s1, adding 2000g of 2,6 naphthalene dicarboxylic acid, 1000g of azelaic acid, 1000g of lauric acid, 5000g of ethylene glycol, 50ppm of esterification catalyst zinc acetate (calculated according to the content of zinc element) and 50ppm of stabilizer trimethyl phosphate (calculated according to the content of phosphorus element) into a 20L reaction kettle, uniformly mixing, heating to 200 ℃, and carrying out esterification reaction under the pressure of 0.27 MPa; adding 5100g of terephthalic acid when the distilled water reaches a theoretical value, heating to 240 ℃ to continue esterification reaction, and obtaining an esterified substance mixture when the distilled water reaches the theoretical value;
s2, adding 10ppm of polycondensation catalyst germanium oxide, 30g of chain extender trimellitic anhydride and 3g of silicon dioxide into the mixture of the esterified substances obtained in the S1, adding 3g of antioxidant 1010 and 168 into the mixture of the esterified substances, performing transesterification polycondensation, firstly keeping the pressure of a reaction container at micro positive pressure, then keeping the reaction kettle in a vacuum state, controlling the vacuum degree to 90Pa, controlling the temperature to 290 ℃, reacting for 300min, judging the change of melt viscosity in the reaction kettle through the torque of a stirrer, and stopping the polycondensation when the torque theoretical value is reached. And then flowing the melt into a water tank through a casting belt opening, granulating through a granulator, and drying to obtain the modified copolyester material.
Example 6
Example 6 differs from example 1 in that: chain extenders vary. Wherein the chain extender of example 6 is trimethylol propane and the chain extender of example 1 is pyromellitic anhydride.
Specific:
the preparation method of the modified copolyester material comprises the following steps:
s1, adding 2000g of 2,6 naphthalene dicarboxylic acid, 1000g of azelaic acid, 1000g of lauric acid, 5000g of ethylene glycol, 50ppm of esterification catalyst zinc acetate (calculated according to the content of zinc element) and 50ppm of stabilizer trimethyl phosphate (calculated according to the content of phosphorus element) into a 20L reaction kettle, uniformly mixing, heating to 200 ℃, and carrying out esterification reaction under the pressure of 0.27 MPa; adding 5100g of terephthalic acid when the distilled water reaches a theoretical value, heating to 240 ℃ to continue esterification reaction, and obtaining an esterified substance mixture when the distilled water reaches the theoretical value;
s2, adding 10ppm of polycondensation catalyst germanium oxide, 30g of chain extender trimethylol propyl, 3g of silicon dioxide and 3g of antioxidant 1010 and 168 into the mixture of the esterified substances obtained in the S1, and performing transesterification polycondensation reaction, wherein the pressure of a reaction container is kept at micro positive pressure at first during polycondensation, then the reaction kettle is kept in a vacuum state, the vacuum degree is 90Pa, the temperature is regulated to 290 ℃, the reaction is performed for 300min, the change of melt viscosity in the reaction kettle is judged through the torque of a stirrer, and the polycondensation reaction is stopped when the torque theoretical value is reached. And then flowing the melt into a water tank through a casting belt opening, granulating through a granulator, and drying to obtain the modified copolyester material.
Example 7
Example 7 differs from example 1 in that: polycyclic dibasic acids are different. Wherein the polycyclic dibasic acids of example 7 were 1, 4-naphthalenedicarboxylic acid and 2, 6-naphthalenedicarboxylic acid, each 1000g; the polycyclic dibasic acid of example 1 was 2000g of 2,6 naphthalene dicarboxylic acid.
The preparation method of the modified copolyester material comprises the following steps:
s1, adding 1000g of 1, 4-naphthalene dicarboxylic acid, 1000g of 2, 6-naphthalene dicarboxylic acid, 1000g of azelaic acid, 1000g of lauric acid, 5000g of ethylene glycol, 50ppm of esterification catalyst zinc acetate (calculated according to the content of zinc element) and 50ppm of stabilizer trimethyl phosphate (calculated according to the content of phosphorus element) into a 20L reaction kettle, uniformly mixing, heating to 200 ℃, and carrying out esterification reaction under the pressure of 0.27 MPa; adding 5100g of terephthalic acid when the distilled water reaches a theoretical value, heating to 240 ℃ to continue esterification reaction, and obtaining an esterified substance mixture when the distilled water reaches the theoretical value;
s2, adding 10ppm of polycondensation catalyst germanium oxide, 30g of chain extender pyromellitic anhydride, 3g of silicon dioxide and 3g of antioxidant 1010 and 168 into the mixture of the esterified substances obtained in the S1, and performing transesterification polycondensation reaction, wherein the pressure of a reaction container is kept at micro positive pressure at first during polycondensation, then the reaction kettle is kept in a vacuum state, the vacuum degree is 90Pa, the temperature is regulated to 290 ℃, the reaction is performed for 300min, the change of melt viscosity in the reaction kettle is judged through the torque of a stirrer, and the polycondensation reaction is stopped when the torque theoretical value is reached. And then flowing the melt into a water tank through a casting belt opening, granulating through a granulator, and drying to obtain the modified copolyester material.
Example 8
Example 8 differs from example 1 in that: diols are different. Wherein the diol in example 8 is 1, 3-propanediol and the diol in example 1 is ethylene glycol.
Specific:
the preparation method of the modified copolyester material comprises the following steps:
s1, adding 2000g of 2,6 naphthalene dicarboxylic acid, 1000g of azelaic acid, 1000g of lauric acid, 6128g of 1, 3-propanediol, 50ppm of esterification catalyst zinc acetate (calculated according to the content of zinc element) and 50ppm of stabilizer trimethyl phosphate (calculated according to the content of phosphorus element) into a 20L reaction kettle, uniformly mixing, heating to 200 ℃, and carrying out esterification reaction under the pressure of 0.27 MPa; adding 5100g of terephthalic acid when the distilled water reaches a theoretical value, heating to 240 ℃ to continue esterification reaction, and obtaining an esterified substance mixture when the distilled water reaches the theoretical value;
s2, adding 10ppm of polycondensation catalyst germanium oxide, 30g of chain extender pyromellitic anhydride, 3g of silicon dioxide and 3g of antioxidant 1010 and 168 into the mixture of the esterified substances obtained in the S1, and performing transesterification polycondensation reaction, wherein the pressure of a reaction container is kept at micro positive pressure at first during polycondensation, then the reaction kettle is kept in a vacuum state, the vacuum degree is 90Pa, the temperature is regulated to 290 ℃, the reaction is performed for 300min, the change of melt viscosity in the reaction kettle is judged through the torque of a stirrer, and the polycondensation reaction is stopped when the torque theoretical value is reached. And then flowing the melt into a water tank through a casting belt opening, granulating through a granulator, and drying to obtain the modified copolyester material.
Example 9
Example 9 differs from example 1 in that: diols are different. Wherein the diol in example 9 is neopentyl glycol and the diol in example 1 is ethylene glycol.
Specific:
the preparation method of the modified copolyester material comprises the following steps:
s1, adding 2000g of 2,6 naphthalene dicarboxylic acid, 1000g of azelaic acid, 1000g of lauric acid, 4923g of neopentyl glycol, 50ppm of esterification catalyst zinc acetate (calculated according to the content of zinc element) and 50ppm of stabilizer trimethyl phosphate (calculated according to the content of phosphorus element) into a 20L reaction kettle, uniformly mixing, heating to 200 ℃, and carrying out esterification reaction under the pressure of 0.27 MPa; adding 5100g of terephthalic acid when the distilled water reaches a theoretical value, heating to 240 ℃ to continue esterification reaction, and obtaining an esterified substance mixture when the distilled water reaches the theoretical value;
s2, adding 10ppm of polycondensation catalyst germanium oxide, 30g of chain extender pyromellitic anhydride, 3g of silicon dioxide and 3g of antioxidant 1010 and 168 into the mixture of the esterified substances obtained in the S1, and performing transesterification polycondensation reaction, wherein the pressure of a reaction container is kept at micro positive pressure at first during polycondensation, then the reaction kettle is kept in a vacuum state, the vacuum degree is 90Pa, the temperature is regulated to 290 ℃, the reaction is performed for 300min, the change of melt viscosity in the reaction kettle is judged through the torque of a stirrer, and the polycondensation reaction is stopped when the torque theoretical value is reached. And then flowing the melt into a water tank through a casting belt opening, granulating through a granulator, and drying to obtain the modified copolyester material.
Example 10
Example 10 differs from example 1 in that: polycondensation catalysts are different. Wherein the polycondensation catalyst of example 10 is 1 in parts by weight: titanium tetrapropoxide and germanium oxide of example 1, the polycondensation catalyst of example 1 was germanium oxide.
Specific:
the preparation method of the modified copolyester material comprises the following steps:
s1, adding 2000g of 2,6 naphthalene dicarboxylic acid, 1000g of azelaic acid, 1000g of lauric acid, 5000g of ethylene glycol, 50ppm of esterification catalyst zinc acetate (calculated according to the content of zinc element) and 50ppm of stabilizer trimethyl phosphate (calculated according to the content of phosphorus element) into a 20L reaction kettle, uniformly mixing, heating to 200 ℃, and carrying out esterification reaction under the pressure of 0.27 MPa; adding 5100g of terephthalic acid when the distilled water reaches a theoretical value, heating to 240 ℃ to continue esterification reaction, and obtaining an esterified substance mixture when the distilled water reaches the theoretical value;
s2, adding 10ppm of polycondensation catalyst (tetrapropoxy titanium and germanium oxide with the weight ratio of 1:1), 30g of chain extender pyromellitic anhydride, 3g of silicon dioxide, and 3g of antioxidant 1010 and 168 into the mixture of the esterified substances obtained in the S1, and performing transesterification polycondensation reaction, wherein the pressure of a reaction container is kept at micro positive pressure at first during polycondensation, then the reaction kettle is kept in a vacuum state, the vacuum degree is 90Pa, the temperature is regulated to 290 ℃, the reaction is performed for 300min, the change of melt viscosity in the reaction kettle is judged through the torque of a stirrer, and the polycondensation reaction is stopped when the torque theoretical value is reached. And then flowing the melt into a water tank through a casting belt opening, granulating through a granulator, and drying to obtain the modified copolyester material.
Example 11
Example 11 differs from example 1 in that: polycondensation catalysts are different. Wherein the polycondensation catalyst of example 11 is 1 in parts by weight: 1 and germanium oxide, the polycondensation catalyst of example 1 being germanium oxide.
Specific:
the preparation method of the modified copolyester material comprises the following steps:
s1, adding 2000g of 2,6 naphthalene dicarboxylic acid, 1000g of azelaic acid, 1000g of lauric acid, 5000g of ethylene glycol, 50ppm of esterification catalyst zinc acetate (calculated according to the content of zinc element) and 50ppm of stabilizer trimethyl phosphate (calculated according to the content of phosphorus element) into a 20L reaction kettle, uniformly mixing, heating to 200 ℃, and carrying out esterification reaction under the pressure of 0.27 MPa; adding 5100g of terephthalic acid when the distilled water reaches a theoretical value, heating to 240 ℃ to continue esterification reaction, and obtaining an esterified substance mixture when the distilled water reaches the theoretical value;
s2, adding 10ppm of polycondensation catalyst (antimony oxide and germanium oxide in a weight ratio of 1:1), 30g of chain extender pyromellitic anhydride, 3g of silicon dioxide, and 3g of antioxidant 1010 and 168 into the mixture of the esterified substances obtained in the S1, and performing transesterification polycondensation reaction, wherein the pressure of a reaction container is kept at micro positive pressure at first during polycondensation, then the reaction kettle is kept in a vacuum state, the vacuum degree is 90Pa, the temperature is regulated to 290 ℃, the reaction is performed for 300min, the change of melt viscosity in the reaction kettle is judged through the torque of a stirrer, and the polycondensation reaction is stopped when the torque theoretical value is reached. And then flowing the melt into a water tank through a casting belt opening, granulating through a granulator, and drying to obtain the modified copolyester material.
Example 12
Example 12 differs from example 1 in that: polycondensation catalysts are different. Wherein the polycondensation catalyst of example 12 is 1 in parts by weight: 1 and germanium oxide, the polycondensation catalyst of example 1 being germanium oxide.
Specific:
the preparation method of the modified copolyester material comprises the following steps:
s1, adding 2000g of 2,6 naphthalene dicarboxylic acid, 1000g of azelaic acid, 1000g of lauric acid, 5000g of ethylene glycol, 50ppm of esterification catalyst zinc acetate (calculated according to the content of zinc element) and 50ppm of stabilizer trimethyl phosphate (calculated according to the content of phosphorus element) into a 20L reaction kettle, uniformly mixing, heating to 200 ℃, and carrying out esterification reaction under the pressure of 0.27 MPa; adding 5100g of terephthalic acid when the distilled water reaches a theoretical value, heating to 240 ℃ to continue esterification reaction, and obtaining an esterified substance mixture when the distilled water reaches the theoretical value;
s2, adding 10ppm of polycondensation catalyst (zinc chloride and germanium oxide in a weight ratio of 1:1), 30g of chain extender pyromellitic anhydride, 3g of silicon dioxide, and 3g of antioxidant 1010 and 168 into the mixture of the esterified substances obtained in the S1, and performing transesterification polycondensation reaction, wherein the pressure of a reaction container is kept at micro positive pressure at first during polycondensation, then the reaction kettle is kept in a vacuum state, the vacuum degree is 90Pa, the temperature is regulated to 290 ℃, the reaction is performed for 300min, the change of melt viscosity in the reaction kettle is judged through the torque of a stirrer, and the polycondensation reaction is stopped when the torque theoretical value is reached. And then flowing the melt into a water tank through a casting belt opening, granulating through a granulator, and drying to obtain the modified copolyester material.
Comparative example 1
The preparation method of the copolyester material comprises the following steps:
s1, adding 8100g of terephthalic acid, 4700g of ethylene glycol (72.5 mol), 50ppm of esterification catalyst anhydrous zinc acetate (calculated according to the content of zinc element) and 40ppm of stabilizer phosphoric acid (calculated according to the content of phosphorus element) into a 20L reaction kettle, uniformly mixing, heating to 230 ℃, and carrying out esterification reaction under the pressure of 0.28 MPa; stopping the reaction when the distilled water reaches a theoretical value, wherein the obtained product is an esterified compound mixture;
s2, adding 160ppm of polycondensation catalyst ethylene glycol antimony into the mixture of the esterified substances obtained in the step S1, stirring uniformly, then entering a polycondensation reaction, firstly keeping the pressure of a reaction container at micro positive pressure during polycondensation, then keeping the reaction kettle in a vacuum state, keeping the vacuum degree at 90Pa, regulating the temperature to 265 ℃, reacting for about 200min, judging the change of melt viscosity in the reaction kettle through the torque of a stirrer, and stopping the polycondensation reaction when the torque theoretical value is reached. And then the melt flows into a water tank through a casting belt opening, and after granulation by a granulator, the copolyester material is obtained after drying.
Comparative example 2
The preparation method of the copolyester material comprises the following steps:
s1, adding 1000g of azelaic acid, 1000g of lauric acid, 4300g of ethylene glycol, 50ppm of esterification catalyst zinc acetate (calculated according to the content of magnesium element) and 40ppm of stabilizer trimethyl phosphate (calculated according to the content of phosphorus element) into a 20L reaction kettle, uniformly mixing, heating to 200 ℃, and carrying out esterification reaction under the pressure of 0.24 MPa; when the distilled water reaches a theoretical value, 6600g of terephthalic acid is added, the temperature is raised to 240 ℃ to continue the esterification reaction, and when the distilled water reaches the theoretical value, an esterified compound mixture is obtained;
s2, adding 120ppm of polycondensation catalyst ethylene glycol antimony, 30g of chain extender pyromellitic anhydride, 3g of silicon dioxide and 3g of antioxidant 1010 and 168 into the mixture of the esterified substances obtained in the S1, and performing transesterification polycondensation reaction, wherein the pressure of a reaction container is kept at micro positive pressure at first, then the reaction container is kept in a vacuum state, the vacuum degree is 110Pa, the temperature is regulated to 275 ℃, the reaction is carried out for about 250 minutes, the change of melt viscosity in the reaction container is judged through the torque of a stirrer, and the polycondensation reaction is stopped when the torque theoretical value is reached. And then the melt flows into a water tank through a casting belt opening, and after granulation by a granulator, the copolyester material is obtained after drying.
Comparative example 3
The preparation method of the copolyester material comprises the following steps:
s1, adding 2000g of 2,6 naphthalene dicarboxylic acid, 5000g of ethylene glycol, 50ppm of esterification catalyst zinc acetate (calculated according to the content of zinc element) and 45ppm of stabilizer triphenyl phosphate (calculated according to the content of phosphorus element) into a 20L reaction kettle, uniformly mixing, heating to 190 ℃, and carrying out esterification reaction under the pressure of 0.29 MPa; when the distilled water reaches a theoretical value, 7000g of terephthalic acid is heated to 240 ℃ to continue esterification reaction, and when the distilled water reaches the theoretical value, the product is an esterified compound mixture;
s2, adding 150ppm of a polycondensation catalyst of n-butyl titanate, 30g of a chain extender of pyromellitic anhydride, 3g of silicon dioxide and 3g of antioxidants 1010 and 168 into the mixture of the esterified substances obtained in the S1, and performing transesterification polycondensation, wherein the pressure of a reaction container is kept at micro positive pressure at first during polycondensation, then the reaction kettle is kept in a vacuum state, the vacuum degree is 110Pa, the temperature is regulated to 280 ℃, the reaction is performed for 300min, the change of melt viscosity in the reaction kettle is judged through the torque of a stirrer, and the polycondensation is stopped when the torque theoretical value is reached. And then the melt flows into a water tank through a casting belt opening, and after granulation by a granulator, the copolyester material is obtained after drying.
Performance test:
the materials obtained in examples 1 to 7 and comparative examples 1 to 3 were subjected to performance test, and the test results are shown in Table 1.
The performance characterization of the material is mainly tested by referring to GB/T1040-2006, and the impact resistance of the material is tested according to the GB/T1043.2-2018 method. The scratch resistance of the material is mainly tested by a cross scratch test and is tested by referring to GB/T9279.1-2015: the surface of the material is meshed with fixed load and space, the color change at the scratch is measured, the scratch resistance of the material is characterized by the blushing degree represented by an DeltaL value, and the larger the DeltaL value is, the worse the scratch resistance of the material is.
TABLE 1
The foregoing is merely exemplary embodiments of the present invention and are not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention or direct or indirect application in the relevant art are intended to be included in the scope of the present invention.
Claims (10)
1. A modified copolyester material, characterized in that: the composite material comprises filler particles and a copolyester material, wherein the structural formula of the copolyester material is as follows:
wherein x is greater than 0, y is greater than 0, n is greater than 0, and m is greater than 0;
x：y：n＝3.3～9.2：1：1.0～1.2；
y：m＝12.4～2019.7：1～1.5。
2. the modified copolyester material according to claim 1, characterized in that: the filler particles include at least one of silica, nano zinc oxide, calcium carbonate, and calcium phosphate.
3. The modified copolyester material according to claim 1, characterized in that: the mass of the filler particles is 100-500ppm of the mass of the copolyester material.
4. A process for preparing a modified copolyester material according to any one of claims 1 to 3, characterized in that: the method comprises the following steps:
s1, mixing polycyclic dibasic acid, aliphatic dibasic acid, aromatic dibasic acid and dihydric alcohol, and carrying out esterification reaction to obtain an esterified substance;
s2, mixing the esterified substance, the polycondensation catalyst, the filler particles and the chain extender in a vacuum atmosphere, and performing polycondensation reaction to obtain the modified copolyester material.
5. The method according to claim 4, wherein: the polycyclic dibasic acid comprises at least one of 1, 4-naphthalene dicarboxylic acid and 2, 6-naphthalene dicarboxylic acid.
6. The method according to claim 4, wherein: the aliphatic dibasic acid includes at least one of azelaic acid and lauric acid.
7. The method according to claim 4, wherein: the aromatic dibasic acid includes at least one of terephthalic acid and isophthalic acid.
8. The method according to claim 4, wherein: the dihydric alcohol comprises a linear or branched C2-C5 alkane diol.
9. The method according to claim 4, wherein: the chain extender comprises at least one of trimellitic anhydride, pyromellitic anhydride and trimethylolpropane.
10. A food packaging material characterized in that: a modified copolyester material comprising any one of claims 1 to 3.
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