TWI386429B - A method of using inorganic titanium - PET polyester synthetic magnesium catalyst particles and Its Application - Google Patents
A method of using inorganic titanium - PET polyester synthetic magnesium catalyst particles and Its Application Download PDFInfo
- Publication number
- TWI386429B TWI386429B TW097116585A TW97116585A TWI386429B TW I386429 B TWI386429 B TW I386429B TW 097116585 A TW097116585 A TW 097116585A TW 97116585 A TW97116585 A TW 97116585A TW I386429 B TWI386429 B TW I386429B
- Authority
- TW
- Taiwan
- Prior art keywords
- titanium
- pet polyester
- catalyst
- polyester
- ppm
- Prior art date
Links
- 229920000728 polyester Polymers 0.000 title claims description 107
- 239000003054 catalyst Substances 0.000 title claims description 73
- 239000002245 particle Substances 0.000 title claims description 33
- 239000010936 titanium Substances 0.000 title claims description 33
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 32
- 229910052719 titanium Inorganic materials 0.000 title claims description 28
- 238000000034 method Methods 0.000 title claims description 19
- 239000011777 magnesium Substances 0.000 title claims description 11
- 229910052749 magnesium Inorganic materials 0.000 title claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims description 4
- 239000008187 granular material Substances 0.000 claims description 85
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 74
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 74
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 72
- 238000006116 polymerization reaction Methods 0.000 claims description 29
- 239000007787 solid Substances 0.000 claims description 28
- 238000006068 polycondensation reaction Methods 0.000 claims description 27
- 238000005886 esterification reaction Methods 0.000 claims description 25
- SXSVTGQIXJXKJR-UHFFFAOYSA-N [Mg].[Ti] Chemical compound [Mg].[Ti] SXSVTGQIXJXKJR-UHFFFAOYSA-N 0.000 claims description 24
- -1 phosphorus compound Chemical class 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000010954 inorganic particle Substances 0.000 claims description 18
- 239000001045 blue dye Substances 0.000 claims description 17
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 14
- 239000011574 phosphorus Substances 0.000 claims description 14
- 239000008188 pellet Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- 238000011049 filling Methods 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000009388 chemical precipitation Methods 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 239000005457 ice water Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 229910001200 Ferrotitanium Inorganic materials 0.000 claims 1
- 239000012760 heat stabilizer Substances 0.000 claims 1
- 229910001629 magnesium chloride Inorganic materials 0.000 claims 1
- 238000010298 pulverizing process Methods 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 29
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 16
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 12
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 12
- 238000002347 injection Methods 0.000 description 12
- 239000007924 injection Substances 0.000 description 12
- 238000007664 blowing Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 230000035484 reaction time Effects 0.000 description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000001044 red dye Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 230000032050 esterification Effects 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 230000005070 ripening Effects 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 235000013361 beverage Nutrition 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003017 thermal stabilizer Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910019440 Mg(OH) Inorganic materials 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010103 injection stretch blow moulding Methods 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910052712 strontium Inorganic materials 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 3
- 150000003609 titanium compounds Chemical class 0.000 description 3
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- OLRBYEHWZZSYQQ-VVDZMTNVSA-N (e)-4-hydroxypent-3-en-2-one;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.C\C(O)=C/C(C)=O.C\C(O)=C/C(C)=O OLRBYEHWZZSYQQ-VVDZMTNVSA-N 0.000 description 1
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- TXSFFZYXHRAMBM-UHFFFAOYSA-N benzoic acid;ethoxyethane Chemical compound CCOCC.OC(=O)C1=CC=CC=C1 TXSFFZYXHRAMBM-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- MXTOFRMIIQQSOE-UHFFFAOYSA-N butane;titanium(4+) Chemical compound [Ti+4].CCC[CH2-].CCC[CH2-].CCC[CH2-].CCC[CH2-] MXTOFRMIIQQSOE-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 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
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 210000001161 mammalian embryo Anatomy 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000002087 whitening effect Effects 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
- C08G63/78—Preparation processes
- C08G63/80—Solid-state polycondensation
-
- 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
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
- B65D1/0207—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features
-
- 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
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
-
- 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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
-
- 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
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- 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
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/87—Non-metals or inter-compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0041—Optical brightening agents, organic pigments
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1372—Randomly noninterengaged or randomly contacting fibers, filaments, particles, or flakes
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)
- Ceramic Engineering (AREA)
- Mechanical Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Description
本發明涉及一種PET聚酯粒,尤指一種含有少量藍色染料及無機粒子且使用無機的鈦-鎂觸媒合成的PET聚酯粒。
聚對苯二甲酸乙二醇酯(PET)聚酯粒的習知合成過程,通常是使用銻(Sb)觸媒為聚縮合觸媒,且使用純對苯二甲酸(PTA)與乙二醇(EG)為原料,經過第一段直接酯化反應(direct esterification)及第二段聚縮合反應(polycondensation),再於進行第二段聚縮合反應中加入銻(Sb)觸媒,或依需要,在完成第二段聚縮合反應後再附加固態聚合反應,以提高分子量後而製得。
近來,PET塑膠瓶幾乎取代了玻璃瓶及鋁罐等飲料容器。但,PET塑膠瓶充填飲料後會有微量的銻元素析出(migration)進入飲料中,而且,銻元素屬於重金屬對人類的健康會造成嚴重威脅。
為解決此問題,PET聚酯粒的合成過程,近年來已有專利文獻揭露採用有機的鈦觸媒取代銻觸媒為聚縮合觸媒,但使用有機的鈦觸媒所製得的PET聚酯粒,常有色相偏黃以及加工時容易發生裂解(thermal Degradation)產生較高含量的乙醛(acetaldehyde)及環狀寡聚合物(cyclic Oligomer)的缺點。而且,即在PET聚酯粒的聚合過程中藉添加染料也難以改善色相偏黃的缺點。
例如,美國第5,922,828號專利揭露一種有機的四丁基鈦酸酯
(tetrabutyltitanate,簡稱TBT)為鈦觸媒,搭配雙(2,4-二叔丁基苯基)季戊四醇二亞磷酸酯(bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,商品名稱為抗氧劑AT-626)為安定劑,使得所合成的聚合體的乙醛含量會較低。但,此專利未改善以鈦觸媒所製得的PET聚酯粒有色澤偏黃的缺點。
美國第6,013,756號專利揭露在PET聚酯粒的聚合過程中使用有機的四丁基鈦化合物為鈦觸媒,並且利用添加醋酸鈷達到改善PET聚酯粒色相偏黃的缺點。
美國第6,500,915號專利的實施例揭露使用有機的四丁基鈦酸酯(TBT)為鈦觸媒,搭配使用磷化合物及醋酸鎂合成PET聚酯粒。但,此專利未改善以鈦觸媒所製得的PET聚酯粒有色澤偏黃的缺點。
美國第6,593,447號專利揭露使用有機的鈦化合物與磷系化合物共同依一定比例與乙二醇調製成觸媒溶液,並加入酸酐類化合物(anhydride)在200℃以下的溫度反應製成一種聚縮合用觸媒。但,此專利未改善以鈦觸媒所製得的PET聚酯粒有色澤偏黃的缺點。
美國第6,667,383號專利揭露使用有機的四丁基鈦酸酯(TBT)為鈦觸媒,搭配使用磷酸酯及鎂化合物合成PET聚酯粒。但,此專利未改善以鈦觸媒所製得的PET聚酯粒有色澤偏黃的缺點。
美國第6,489,433號及第6,541,59號專利揭露使用有機的正四丁基鈦酸酯或有機的異四丙基鈦酸酯做為聚縮合觸媒,並添加一種磷酸酯以合成色澤良好的聚酯粒。
美國第7,094,863號及第7,129,317號專利揭露使用有機的異環氧丙烷
型鈦酸酯(titanium diisopropoxide bis(acetyl-acetonate)或有機的四丁基鈦酸酯(TBT)為聚縮合觸媒,且以這種鈦觸媒製得一種PET聚酯粒。而且,使用這種PET聚酯粒製成的PET瓶胚具有色澤偏白及透明度佳的特性,而且金屬元素含量低。當瓶胚製成熱充填瓶的時候,所製成的熱充填瓶仍能維持良好的透明度,而且在195~205℉的充填溫度下具有良好的尺寸安定性。
美國第6,451,959號專利揭露一種固態鈦化合物T,以鈦的鹵化物(titanium balide)進行水解(hydrolysis)得到水解物質(hydrolyzate),再進行脫水乾燥(Dehydro-drying)而取得。此專利揭露前述的固態鈦化合物T可結合其他化合物E,例如Be、Mg、Ca、Sr、Ba等的氫氧化合物(hydroxide);其中E/Ti的莫耳比例介於1/50~50/1,且OH/Ti之莫耳比介於0.09~4。
美國第7,300,998號專利揭露將氫氧化鎂(Mg(OH)2
)與氯化鈦(TiCl4
)加入水中製成水溶液,以氨水逐滴調整PH值至9左右,然後再以醋酸水溶液逐滴調整PH值至5左右,經過過濾及水洗後溶於乙二醇,再經離心分離出固體,此固體以40℃真空乾燥20小時後,予以磨成10~20μm粉末。此粉末再與含氫氧化鈉的乙二醇溶液調製成一種聚縮合觸媒,可以應用於合成瓶用聚酯粒,該專利揭露其製成之聚酯的固態聚合速率佳,及再生之乙醛低。但,此專利未改善所製得的PET聚酯粒有色澤偏黃的缺點。
第WO 2008/001473公開案揭露一種應用於生產聚酯的聚縮合鈦觸媒的製法,其作法係將MgCl2
水溶液與NaOH水溶液在170℃反應約半小時,經過濾、水洗製成氫氧化鎂(Mg(OH)2
)漿體水溶液。另氯化鈦(TiCl4
)水溶
液與NaOH水溶液混合,然後將此溶液逐滴加入前述Mg(OH)2
漿體溶液中,經過1小時熟成使氧化鈦(TiO2
)覆蓋在氫氧化鎂(Mg(OH)2
)粒子表面,將此漿體進行過濾,水洗及乾燥後,予以粉碎;再將此粉末與乙二醇調配成溶液注入聚縮合反應。該專利揭露所使用的聚縮合觸媒的反應速率及所製成的聚酯色相與使用三氧化二銻相當。
另外,以鈦觸媒或銻觸媒為聚縮合觸媒合成的PET聚酯粒為材質製成瓶胚後,使用鈦觸媒的瓶胚比使用銻觸媒的瓶胚需要更久的熟成時間(extended aging time of perform)才能進行吹瓶,否則使用鈦觸媒的瓶胚的尺寸安定性較差,容易產生收縮變形。而且,若未延長使用鈦觸媒的瓶胚的熟成時間,當瓶胚以熱結晶製程製成耐熱充填瓶(hot filled bottle made from heat-setted process)後,所製成的充填瓶的結晶度將偏低,並且造成使用鈦觸媒的充填瓶的耐熱充填溫度會低於使用銻觸媒的充填瓶。
本發明的主要目的在於揭示一種PET聚酯粒,含有少量藍色染料或再進一步含有無機粒子,且在聚酯的合成過程中,使用無機的鈦-鎂觸媒為聚縮合觸媒,搭配適當含量的磷系安定劑而製得,具有色相不會偏黃以及加工後再生乙醛及環狀寡聚合物含量少的特性。本發明的PET聚酯粒,適用於製成瓶胚,且可縮短瓶胚的熟成時間,以提高製瓶生產效率及減少瓶胚庫存空間。
本發明的另一主要目在於揭示一種PET聚酯粒的製法,是以純對苯二甲酸與乙二醇為原料,經過第一段直接酯化反應及第二段聚縮合反應後,
再經過進行固態聚合反應提升固有黏度至0.70dl/g以上而製得,而且,在第一段直接酯化反應結束前加入藍色染料,所注入的藍色染料含量,是基於PET聚酯粒少於3ppm;以及,在進行第二段聚縮合反應之前的任何時段,將無機的鈦-鎂觸媒及磷系化合物注入進行第一段直接酯化反應的反應槽內,且所注入的無機的鈦-鎂觸媒的含量,為基於聚對苯二甲酸乙二醇酯樹酯介於10~100ppm,其中,鈦元素含量為基於聚對苯二甲酸乙二醇酯介於5~10ppm,鈦元素對鎂元素的莫耳比介於0.005~1;所注入的磷元素化合物的磷元素含量,為基於聚對苯二甲酸乙二醇酯為5~50ppm。或者,在進行第二段聚縮合反應中再加入四氧化三鐵或硫酸鋇無機粒子,且所注入的無機粒子的含量,為基於PET聚酯粒介於20~250ppm,使得所製得的PET聚酯粒,含有少量藍色染料及有無機粒子。
本發明的PET聚酯粒,是以純對苯二甲酸(PTA)與乙二醇(EG)為原料,經過第一段直接酯化反應及第二段聚縮合反應,或依需要,再附加固態聚合反應以提高分子量和提升固有黏度至0.70dl/g以上而製得。而且,在第一段直接酯化反應結束前加入藍色染料,以及,使用無機的鈦-鎂觸媒為聚縮合觸媒及使用磷系化合物為熱安定劑,並且在進行第二段聚縮合反應之前的任何時段,將無機的鈦-鎂觸媒、磷系化合物注入反應槽內。
本發明的PET聚酯粒的另一實施例,除了加入藍色染料和使用無機的鈦-鎂觸媒為聚縮合觸媒及使用磷系化合物為熱安定劑外,並在第二段聚縮合反應加入無機粒子,使得所製得的PET聚酯粒含有無機粒子。
本發明的PET聚酯粒的具體製法,詳細說明如下:將純對苯二甲酸(PTA)與乙二醇(EG)先調製成漿體,其中EG/PTA的比例介於1.0~2.0;再將PTA漿體利用幫浦連續輸送至酯化反應槽進行第一段直接酯化反應。酯化反應的料溫介於240~270℃,較好介於250~260℃,酯化壓力介於常壓~2.0Kg/cm2
,較好介於0.01~1.0 Kg/cm2
,酯化反應時間介於3~8小時,較好介於4~6小時,酯化反應槽出口單體的轉化率(conversion rate,簡稱C值)至少92%,最好高於95%。直接酯化反應過程中形成的乙二醇及水等,經由汽化管進入蒸餾塔進行分離。自蒸餾塔底部收集的乙二醇再回流至酯化反應槽。
接著進行第二段聚縮合反應,將上述酯化反應製成的單體,以輸送幫浦連續送至預聚合槽進行預聚合反應;預聚合槽可以是一個或兩個槽體;預聚合的料溫介於260~280℃,較好介於250~260℃;預聚合反應的壓力介於10~200 mmHg。預聚合反應產生的乙二醇等氣態副產物以真空幫浦抽至冷卻器中冷凝成液態;預聚合反應的時間介於0.5~2.0小時。
上述預聚合反應後的低聚合物,以幫浦連續輸送至高度真空之主聚合槽(finisher)進一步進行聚縮合反應,提高固有黏度至至少0.50dl/g;主聚合槽可以是一個或兩個槽體,槽體內設計可以是籠式(cage type)或轉盤式(disc type),主聚合反應的料溫介於265~290℃,較好低於285℃;主聚合反應利用多段式噴射器使真空壓力低於2 mmHg,並且以主聚合反應最終聚合體的黏度回饋控制真空度。
上述主聚合反應完成後的聚合體,以聚合體幫浦連續輸送至一組噴條
板(die head),擠出之膠條以冷凍水急冷經切粒機切成非結晶性聚酯粒(amorphous chip)。
本發明所使用的無機的鈦-鎂觸媒,是由以下的化學沉澱法(chemical precipitation)或與此相當的製法合成而得:將氯化鈦(TiCl4
)溶於去離子水中,置於冰水浴中進行水解(hydrolysis)使形成水解物(hydrolyzate)之水溶液,再與氯化鎂(MgCl2
)水溶液依一定的Ti/Mg莫耳比例,在室溫下進行攪拌混合;然後將氫氧化鈉(NaOH)水溶液慢慢地加入持續攪拌的Ti-Mg混合液內,使逐漸形成含白色沉澱物之漿液,將此漿液以去離子水進行洗滌,過濾並在100℃溫度下予以真空乾燥,再進行粉碎成為1μm以下的粉末。將所製得的粉末再以乙二醇調製成觸媒溶液,即成為本發明所使用的無機的鈦-鎂觸媒。
本發明所使用的無機的鈦-鎂觸媒,粒徑小於1μm,其Ti/Mg莫耳比例介於0.005~1,最好介於0.1~0.2。在合成本發明的PET聚酯粒的過程中,本發明的無機的鈦-鎂觸媒的添加量,是基於PET聚酯粒介於10~100ppm,其中鈦元素的含量是基於PET聚酯粒介於5~10ppm;本發明的鈦-鎂觸媒與乙二醇調配成的觸媒溶液濃度是介於0.01%~15%。
本發明所使用的磷系化合物,可以選自磷酸、亞磷酸或各類磷酸酯的其中一種。在合成本發明的PET聚酯粒的過程中,本發明的磷系化合物的添加量,是基於PET聚酯粒介於5~50ppm,最好介於10~30ppm。
本發明所使用的無機粒子,選自粒徑小於1μm的四氧化三鐵(Fe3
O4
)或硫酸鋇(BaSO4
)無機粒子。在合成本發明的PET聚酯粒的過程中,本發明
的無機粒子的添加量,是基於PET聚酯粒介於20~250ppm,最好介於25~50ppm。
本發明的PET聚酯粒為避免色澤偏黃,需要添加染料來降低以Hunter色計測得的聚酯粒的色澤b值。所添加的染料可選用藍色染料,例如使用Blue 104。藍色染料的添加量,是基於PET聚酯粒少於3ppm,較好少於2ppm,最好少於1ppm。另外,爲避免以Hunter色計測得的聚酯粒的色澤a值太低外觀偏綠,必要時可以添加少量的紅色染料,但添加紅色染料會使聚酯粒的L值下降,造成外觀偏暗。
在合成PET聚酯粒的過程中,要進行固態聚合反應的設備,本發明是選用瑞士Buhler公司、義大利Sinco公司或美國Bepex公司生產的連續式固態聚合設備。所以,經過第二段聚縮合反應所製成的非結晶性聚酯粒,可經由所述的連續式固態聚合設備而提高聚酯粒的分子量,使得本發明的PET聚酯粒的固有黏度至少達到0.70dl/g,最好介於為0.72~0.86dl/g。
本發明的PET聚酯粒可以應用於採用一段式製瓶法或二段式製瓶法來製作聚酯充填瓶。採用一段式製瓶法的時候,PET聚酯粒直接以射出延伸吹瓶機在熔融溫度270~295℃的條件下將聚酯粒塑化後,經過短暫冷卻立即將瓶胚直接吹製成聚酯充填瓶。採用二段式製瓶法的時候,PET聚酯粒以射出吹瓶機在熔融溫度270~290℃的條件下製成瓶胚(preform),經過數日的熟成時間後,再以近紅外線燈管將瓶胚加熱至高於玻璃轉移溫度,並且隨即將之延伸吹脹成聚酯充填瓶。
另外,本發明的PET聚酯粒還具備以下的特點:
1.在PET聚酯粒的合成過程中,使用本發明的無機的鈦-鎂觸媒為聚縮合觸媒,當第二段聚縮合反應結束時的聚合體溫度偏高時,本發明的PET聚酯粒的色澤b值上升程度明顯低於使用有機的鈦觸媒合成的PET聚酯粒。
2.在PET聚酯粒的合成過程中,先前技術是使用有機的鈦觸媒搭配作為熱安定劑的磷酸一起使用,但有機的鈦觸媒的活性會被磷酸明顯抑制。然而,在合成本發明的PET聚酯粒的過程中,是使用無機的鈦-鎂觸媒搭配作為熱安定劑的磷酸一起使用,經過實驗結果,無機的鈦-鎂觸媒的活性卻不會被磷酸明顯抑制。因此,使用本發明的PET聚酯粒所製成的塑膠瓶,具有乙醛含量較低的特性。
3.在合成本發明的PET聚酯粒的過程中,添加相同含量的染料時,使用本發明的無機的鈦-鎂觸媒合成的PET聚酯粒的色澤明顯優於使用有機的鈦觸媒的聚酯粒。因此,本發明的PET聚酯粒的藍色染料含量可以比其他鈦觸媒添加更少,且以Hunter色計測得的聚酯粒的色澤的L值較高,以及使用本發明的PET聚酯粒所製成的塑膠瓶具有較明亮的外觀。
4.本發明的PET聚酯粒含有四氧化三鐵(Fe3
O4
)或硫酸鋇(BaSO4
)無機粒子,使得使用這種聚酯粒所製成的瓶胚的熟成時間比未添加無機粒子的瓶胚的熟成時間更短。一般使用銻觸媒的瓶胚製造之後,通常需等待5~7天才能進行吹瓶,否則所製成的塑膠瓶的尺寸安定性較差,尤其是在製作口部有熱結晶白化的熱充填瓶時,若瓶胚的熟成時間不足,熱充填瓶的口部的結晶度會較低,且會造成充填瓶用於熱充填的時候容易發生變型,以
及導致封蓋的密封性不佳,如此將嚴重縮短飲料的保存期限。然而,使用本發明的PET聚酯粒所製成的瓶胚的熟成時間卻可以縮短至5天以內,甚至能小於3天。
茲列舉以下實施例及比較例來闡明本發明的效果,但本發明的權利範圍不是僅限於實施例的範圍。
將射出製成之瓶胚,以液態氮予以冷凍粉碎成粉末,放入玻璃樣品瓶內(cell)中以橡膠封蓋(septum cap),置於150℃加熱30分鐘的環境下,以取樣針刺穿橡膠封蓋,自動抽取氣體注入氣相層析儀進行分析。
精秤PET聚酯樣品,以六氟異丙醇溶劑熔解成透明溶液,經真空過濾後將澄清濾液蒸發乾燥得到白色晶狀物即為環狀寡聚合物,再以二氧二乙稀(dioxane)溶解呈透明溶液,將此溶液注入HPLC高效能液相層析儀(High-performance Liquid Chromatography)中進行分析。
聚酯粒以射出機製成瓶胚,將瓶胚分別放置1天,2天,3天,4天,5天,6天及7天,分別以近紅外燈管照射瓶口,使得瓶口溫度達到約160℃,且經歷3分鐘使得瓶口呈現白化,將瓶胚的瓶口部白化部份剪下,利用密度梯度管法(Column Gradient Density)分析其結晶度;紀錄當瓶口結晶度超過35%時之熟成天數。
自連續式熔融態聚合生產線上的酯化反應槽,取得酯化率約88%的對苯甲酸二乙酯(BHET)單體,秤取該BHET單體10.81Kg,加入乙二醇(EG)3.23Kg,並加入磷酸6g (60ppm),加熱至190℃以上進行酯化反應,攪拌器的轉速為60rpm,酯化反應壓力約1Kg/cm2
,反應時間2小時,酯化反應完成時的料溫約240℃,酯化反應完成時酯化率高於95%;酯化反應完成後加入溶於乙二醇的無機的鈦-鎂觸媒,其中鈦/鎂之元素重量比=0.25,加入的鈦元素含量基於聚酯粒為5ppm,同時另加入溶於乙二醇的藍色染料基於聚酯粒為2.0ppm及加入溶於乙二醇的紅色染料基於聚酯粒為0.7ppm,此酯化完成的單體進行真空預聚合反應,反應壓力由760torr逐漸下降至10torr,反應溫度為240~255℃,反應時間為1小時;後續在高真空的環境下進行主聚合反應,反應壓力低於1torr,反應溫度自255℃逐步升高,聚合體的黏度亦逐步提高,當攪拌器維持相同之扭力下,轉速下降至25rpm左右,聚合體的末溫為280.7℃;聚合體經卸料急冷切成非晶態原粒,分析其固有黏度IV值為0.613dl/g,反應時間為82分鐘;將此聚酯粒放入錐形真空固聚槽進行固態聚合反應,提高其IV值至0.724 dl/g,且使用此聚酯粒進行射出吹瓶。對所製成的原粒,固態聚合粒及瓶胚進行各項檢測,其結果詳如表1所示。
如實施例1的作法,但添加1.1ppm之藍色染料,當聚合體的溫度達
到275.0℃時,將聚合體經卸料急冷切成非晶態原粒,分析其固有黏度IV值為0.538dl/g,反應時間90分鐘。將聚酯粒進行固態聚合反應提升固有黏度至0.74dl/g,且使用此聚酯粒進行射出吹瓶。對所製成的原粒,固態聚合粒及瓶胚進行各項檢測,其結果詳如表1所示。
如實施例1的作法,但添加0.9ppm之藍色染料,及0.6ppm之紅色染料,當聚合體的溫度達到281.1℃時將聚合體經卸料急冷切成非晶態原粒,分析其固有黏度IV值為0.607dl/g,反應時間81分鐘。將聚酯粒進行固態聚合反應提升固有黏度至0.73dl/g,且使用此聚酯粒進行射出吹瓶。對所製成的原粒,固態聚合粒及瓶胚進行各項檢測,其結果詳如表1所示。
如實施例3的作法,但在加入藍色及紅色染料之後,再添加四氧化三鐵(Fe3
O4
)25ppm的無機粒子,當聚合體的溫度達到280.1℃時,將聚合體經卸料急冷切成非晶態原粒,分析其固有黏度IV值為0.610dl/g,反應時間80分鐘。將聚酯粒進行固態聚合反應提升固有黏度至0.72dl/g,且使用此聚酯粒進行射出吹瓶。對所製成的原粒,固態聚合粒及瓶胚進行各項檢測,其結果詳如表1所示。
如實施例4的作法,但添加四氧化三鐵(Fe3
O4
)50ppm的無機粒子,當聚合體的溫度達到280.0℃時,將聚合體經卸料急冷切成非晶態原粒,分
析其固有黏度IV值為0.608dl/g,反應時間81分鐘。將聚酯粒進行固態聚合反應提升固有黏度至0.71dl/g,且使用此聚酯粒進行射出吹瓶。對所製成的原粒,固態聚合粒及瓶胚進行各項檢測,其結果詳如表1所示。
如實施例4的作法,但不添加紅色染料,只添加0.5ppm之藍色染料及添加四氧化三鐵(Fe3
O4
)250ppm的無機粒子,當聚合體的溫度達到279.8℃時,將聚合體經卸料急冷切成非晶態原粒,分析其固有黏度IV值為0.605dl/g,反應時間81分鐘。將聚酯粒進行固態聚合反應提升固有黏度至0.72dl/g,且使用此聚酯粒進行射出吹瓶。對所製成的原粒,固態聚合粒及瓶胚進行各項檢測,其結果詳如表1所示。
如實施例2的作法,但無機的鈦-鎂觸媒的添加量為鈦元素含量基於聚酯粒為10ppm。將聚酯粒進行固態聚合反應提升固有黏度至0.76dl/g,且使用此聚酯粒進行射出吹瓶。對所製成的原粒,固態聚合粒及瓶胚進行各項檢測,其結果詳如表1所示。
如實施例1的作法,但使用有機的四丁基鈦酸酯(tetrabutyltitanate)觸媒取代無機的鈦-鎂觸媒,以及使用磷酸三乙酯(triethyl phosphate)為安定劑。將聚酯粒進行固態聚合反應提升固有黏度至0.72dl/g,且使用此聚酯粒進行射出吹瓶。對所製成的原粒,固態聚合粒及瓶胚進行各項檢測,其結
果詳如表1所示。
如實施例2的作法,但使用有機的四丁基鈦酸酯觸媒取代無機的鈦-鎂觸媒,以及使用磷酸三乙酯為安定劑。將聚酯粒進行固態聚合反應提升固有黏度至0.72dl/g,且使用此聚酯粒進行射出吹瓶。對所製成的原粒,固態聚合粒及瓶胚進行各項檢測,其結果詳如表1所示。
如實施例2的作法,但使用有機的四丁基鈦酸酯觸媒取代無機的鈦-鎂觸媒,以及使用磷酸為安定劑。將聚酯粒進行固態聚合反應提升固有黏度至0.67dl/g,且使用此聚酯粒進行射出吹瓶。對所製成的原粒,固態聚合粒及瓶胚進行各項檢測,其結果詳如表1所示。
經過比較表1所示的實施例1-7及比較例1-3的結果後,可以得到以下結論:1.實施例1至7的PET聚酯粒,含有少量藍色染料,且在聚酯的合成過程中,使用無機的鈦-鎂觸媒為聚縮合觸媒搭配磷酸而製得,具有色相不會偏黃、透明度佳以及加工後再生乙醛(acetaldehyde)及環狀三量體(cyclic trimer)含量少的特性。
2.實施例4至6的PET聚酯粒進一步含有四氧化三鐵(Fe3
O4
)無機粒子,當使用射出延伸吹瓶機製成瓶胚的時候,確實具有較高的結晶度。因此
,使用實施例4至6的PET聚酯粒製成瓶胚時,具有可以縮短瓶胚的熟成時間、提高製瓶生產效率及減少瓶胚庫存空間的優勢。
3.實施例5的PET聚酯粒含有50ppm四氧化三鐵(Fe3
O4
)無機粒子,當使用射出延伸吹瓶機製成瓶胚的時候,僅存放2天熟成時間後就可以進行瓶胚加熱及拉伸吹瓶。
Claims (4)
- 一種PET聚酯粒,其特徵在於,含有基於PET聚酯粒介於0.5~2.0ppm的藍色染料及介於20~250ppm的四氧化三鐵或硫酸鋇無機粒子,且以純對苯二甲酸與乙二醇為原料,經過第一段直接酯化反應及第二段聚縮合反應後,再經過進行固態聚合反應提升固有黏度至0.70dl/g以上而製得,在進行第二段聚縮合反應之前的任何時段,以如下化學沉澱法:將氯化鈦溶於去離子水中,置於冰水浴中進行水解使形成水解物的水溶液,再與氯化鎂水溶液,依一定的Ti/Mg莫耳比例,在室溫下進行攪拌混合,然後將氫氧化鈉水溶液慢慢地加入持續攪拌的Ti-Mg混合液內,使逐漸形成含白色沉澱物的漿液,將此漿液以去離子水進行洗滌,過濾並在100℃下予以真空乾燥,再進行粉碎,製得粒徑小於1μm的無機的鈦-鎂粉末以乙二醇調製成觸媒溶液,及使用磷系化合物為熱穩定劑,一起注入進行第一段直接酯化反應的反應槽內,且所注入的無機的鈦-鎂觸媒的含量,為基於聚對苯二甲酸乙二醇酯樹酯介於10~100ppm,其中,鈦元素含量為基於聚對苯二甲酸乙二醇酯介於5~10ppm,鈦元素對鎂元素的莫耳比介於0.005~1;所注入的磷元素化合物的磷元素含量,為基於聚對苯二甲酸乙二醇酯為5~50ppm。
- 如申請專利範圍第1項所述的PET聚酯粒,其中,所述的四氧化三鐵或硫酸鋇無機粒子的粒徑小於1μm。
- 一種瓶胚,由申請專利範圍第1項的PET聚酯粒製成。
- 一種聚酯充填瓶,由申請專利範圍第3項的瓶胚經放置2天熟成後拉伸 吹製而成。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
TW097116585A TWI386429B (zh) | 2008-05-06 | 2008-05-06 | A method of using inorganic titanium - PET polyester synthetic magnesium catalyst particles and Its Application |
US12/222,401 US8945695B2 (en) | 2008-05-06 | 2008-08-08 | Polyethylene terephthalate resin synthesized inorganic Ti—Mg catalyst and its applications thereof |
JP2008227326A JP4944857B2 (ja) | 2008-05-06 | 2008-09-04 | 無機Ti‐Mg触媒を用いて合成されたポリエチレンテレフタレート樹脂及びその使用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
TW097116585A TWI386429B (zh) | 2008-05-06 | 2008-05-06 | A method of using inorganic titanium - PET polyester synthetic magnesium catalyst particles and Its Application |
Publications (2)
Publication Number | Publication Date |
---|---|
TW200946558A TW200946558A (en) | 2009-11-16 |
TWI386429B true TWI386429B (zh) | 2013-02-21 |
Family
ID=41267083
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW097116585A TWI386429B (zh) | 2008-05-06 | 2008-05-06 | A method of using inorganic titanium - PET polyester synthetic magnesium catalyst particles and Its Application |
Country Status (3)
Country | Link |
---|---|
US (1) | US8945695B2 (zh) |
JP (1) | JP4944857B2 (zh) |
TW (1) | TWI386429B (zh) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW201122051A (en) * | 2009-12-18 | 2011-07-01 | Nanya Plastics Corp | Polyethylene teraphthalate polyester grain without containing antimony and cobalt elements. |
CN106280293B (zh) * | 2015-06-09 | 2020-04-07 | 东丽纤维研究所(中国)有限公司 | 一种聚酯组合物及其制备方法和用途 |
TWI629294B (zh) | 2016-07-06 | 2018-07-11 | 全能材料科技股份有限公司 | 用於製造pet樹酯之觸媒系統組合物 |
TWI664186B (zh) * | 2017-10-05 | 2019-07-01 | 遠東新世紀股份有限公司 | 磷酸酯物質及其製備方法、含磷酸酯物質的聚酯樹脂及其製備方法 |
CN113024786B (zh) * | 2021-03-17 | 2022-09-09 | 浙江恒逸石化有限公司 | 一种无锑高压阳离子可染聚酯的制备方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6346070B1 (en) * | 1998-12-25 | 2002-02-12 | Mitsui Chemicals Inc | Catalyst for polyester production, process for producing polyester using the catalyst, polyester obtained by the process, and uses of the polyester |
CN1675284A (zh) * | 2002-08-05 | 2005-09-28 | 三菱化学株式会社 | 聚酯树脂及其生产方法 |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19513056B4 (de) * | 1995-04-07 | 2005-12-15 | Zimmer Ag | Titanhaltige Katalysatoren und Verfahren zur Herstellung von Polyester |
DE19518943C2 (de) | 1995-05-23 | 1999-12-09 | Inventa Fischer Gmbh | Verfahren zur Herstellung von Polyestern unter Verwendung von titanhaltigen Katalysator-Inhibitor-Kombinationen |
JPH09277473A (ja) * | 1996-04-09 | 1997-10-28 | Teijin Ltd | 金属板ラミネート用2軸延伸積層フィルム |
US5922828A (en) | 1996-09-03 | 1999-07-13 | Hoechst Celanese Corp. | Process for producing polyethylene terephthalate using a specific catalyst stabilizer system |
US6022920A (en) * | 1998-01-23 | 2000-02-08 | Eastman Chemical Company | Method for the production of clear bottles having improved reheat |
US6451959B1 (en) * | 1998-12-25 | 2002-09-17 | Mitsui Chemicals, Inc. | Catalyst for polyester production, process for producing polyester using the catalyst, polyester obtained by the process, and uses of the polyester |
TW548291B (en) | 1999-06-24 | 2003-08-21 | Teijin Ltd | Catalyst for producing a polyester and process for producing the polyester by using same |
JP2001055434A (ja) * | 1999-08-17 | 2001-02-27 | Mitsui Chemicals Inc | ポリエステル製造用触媒、この触媒を用いるポリエステルの製造方法およびこの触媒により製造されるポリエチレンテレフタレート |
AU780389B2 (en) | 1999-11-11 | 2005-03-17 | Mitsubishi Chemical Corporation | Polyester resin and its production process |
JP4393004B2 (ja) | 2001-02-06 | 2010-01-06 | 三菱化学株式会社 | ポリエステル樹脂 |
US6489433B2 (en) | 2001-02-23 | 2002-12-03 | E. I. Du Pont De Nemours And Company | Metal-containing composition and process therewith |
WO2003072633A1 (fr) | 2002-02-14 | 2003-09-04 | Mitsui Chemicals, Inc. | Resine polyester et catalyseur destine a la production de polyester, procede de production de cette resine polyester au moyen de ce catalyseur, resine polyester obtenue au moyen de ce catalyseur et recipient moule creux comprenant cette resine polyester |
JP4363101B2 (ja) * | 2002-08-05 | 2009-11-11 | 三菱化学株式会社 | ポリエステル樹脂及びその製造方法 |
DE602004025111D1 (de) | 2003-05-21 | 2010-03-04 | Wellman Inc | Langsam kristallisierende polyesterharze |
US7094863B2 (en) | 2003-05-21 | 2006-08-22 | Wellman, Inc. | Polyester preforms useful for enhanced heat-set bottles |
JP2006070101A (ja) * | 2004-08-31 | 2006-03-16 | Mitsubishi Chemicals Corp | ポリエステル樹脂および樹脂組成物ならびに延伸ブロー成形用プリフォーム及び中空容器 |
CN101107287B (zh) * | 2005-01-21 | 2011-12-21 | 三菱化学株式会社 | 聚酯制备用缩聚催化剂以及用其制造聚酯树脂的方法 |
JP5165186B2 (ja) * | 2005-03-03 | 2013-03-21 | 三菱化学株式会社 | ポリエステル樹脂及び該樹脂の製造方法 |
JP2007161958A (ja) * | 2005-12-16 | 2007-06-28 | Nippon Ester Co Ltd | ポリエステル |
-
2008
- 2008-05-06 TW TW097116585A patent/TWI386429B/zh active
- 2008-08-08 US US12/222,401 patent/US8945695B2/en active Active
- 2008-09-04 JP JP2008227326A patent/JP4944857B2/ja active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6346070B1 (en) * | 1998-12-25 | 2002-02-12 | Mitsui Chemicals Inc | Catalyst for polyester production, process for producing polyester using the catalyst, polyester obtained by the process, and uses of the polyester |
CN1675284A (zh) * | 2002-08-05 | 2005-09-28 | 三菱化学株式会社 | 聚酯树脂及其生产方法 |
Also Published As
Publication number | Publication date |
---|---|
JP4944857B2 (ja) | 2012-06-06 |
JP2009270083A (ja) | 2009-11-19 |
TW200946558A (en) | 2009-11-16 |
US20090280279A1 (en) | 2009-11-12 |
US8945695B2 (en) | 2015-02-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7129317B2 (en) | Slow-crystallizing polyester resins | |
JP5288676B2 (ja) | ポリエステル製造用触媒、ポリエステルの製造方法およびポリエステル | |
US7094863B2 (en) | Polyester preforms useful for enhanced heat-set bottles | |
TWI386429B (zh) | A method of using inorganic titanium - PET polyester synthetic magnesium catalyst particles and Its Application | |
JP2010235940A (ja) | 芳香族ポリエステル成形体 | |
JP4363101B2 (ja) | ポリエステル樹脂及びその製造方法 | |
KR20010089942A (ko) | 고내열성 폴리에스터 병용 수지제조방법 | |
JP2006241294A (ja) | ポリエステル樹脂及び該樹脂の製造方法 | |
CN101270184B (zh) | 一种使用无机的钛-镁催化剂合成的pet聚酯粒及其应用 | |
JP3960810B2 (ja) | ポリエステル樹脂の製造方法 | |
JP2001048972A (ja) | 中空成形体およびその製造方法 | |
CN102002214A (zh) | 一种不含锑及钴元素的聚对苯二甲酸乙二醇酯聚酯组合物 | |
JP2009052044A (ja) | ポリエステル組成物及びそれからなるポリエステル成形体 | |
KR100455456B1 (ko) | 적외선 흡수성이 개선된 폴리에스테르 수지 | |
US20110152419A1 (en) | Antimony-free and cobalt-free polyethylene terephthalate resin composition | |
JP2007002240A (ja) | ポリエステル延伸中空成形体及びその製造方法 | |
JP2010150488A (ja) | 耐熱容器成形用エチレンテレフタレート系ポリエステル樹脂及びこの樹脂から成るプリフォーム | |
JP4618246B2 (ja) | ポリエステル樹脂 | |
JP3427202B2 (ja) | ポリエステル樹脂組成物 | |
JP5320891B2 (ja) | ポリエステル成形体 | |
US8735482B2 (en) | Polyester resin containing tungsten—titanium carbide particles and polyester preform made therefrom | |
CN1254509C (zh) | 用于生产聚酯热充填瓶的聚酯组合物及其瓶胚 | |
JP2006188676A (ja) | ポリエステル組成物およびそれからなるポリエステル成形体 | |
US20110263812A1 (en) | Ethylene terephthalate type polyester resin for forming containers and process for producing the same | |
JPH05170882A (ja) | 共重合ポリエステルならびにそれより成る中空容器および延伸フィルム |