TWI629294B - 用於製造pet樹酯之觸媒系統組合物 - Google Patents
用於製造pet樹酯之觸媒系統組合物 Download PDFInfo
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- TWI629294B TWI629294B TW105121387A TW105121387A TWI629294B TW I629294 B TWI629294 B TW I629294B TW 105121387 A TW105121387 A TW 105121387A TW 105121387 A TW105121387 A TW 105121387A TW I629294 B TWI629294 B TW I629294B
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- pet resin
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- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 229920005989 resin Polymers 0.000 title claims abstract description 55
- 239000011347 resin Substances 0.000 title claims abstract description 55
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 14
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 12
- 239000000460 chlorine Substances 0.000 claims abstract description 12
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 6
- 239000010937 tungsten Substances 0.000 claims abstract description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- VPXSRGLTQINCRV-UHFFFAOYSA-N dicesium;dioxido(dioxo)tungsten Chemical compound [Cs+].[Cs+].[O-][W]([O-])(=O)=O VPXSRGLTQINCRV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 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 claims description 12
- 239000002245 particle Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 6
- XJIOYWPYHPACDT-UHFFFAOYSA-N [W+4].[O-2].[Y+3] Chemical compound [W+4].[O-2].[Y+3] XJIOYWPYHPACDT-UHFFFAOYSA-N 0.000 claims description 5
- BTAFASHNLKDBSO-UHFFFAOYSA-N [W+4].[O-2].[Ce+3] Chemical compound [W+4].[O-2].[Ce+3] BTAFASHNLKDBSO-UHFFFAOYSA-N 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims 2
- 229920000139 polyethylene terephthalate Polymers 0.000 abstract description 80
- 239000005020 polyethylene terephthalate Substances 0.000 abstract description 80
- 238000000034 method Methods 0.000 abstract description 28
- 238000006116 polymerization reaction Methods 0.000 abstract description 26
- 230000008569 process Effects 0.000 abstract description 24
- 239000007787 solid Substances 0.000 abstract description 16
- -1 polyethylene terephthalate Polymers 0.000 abstract description 9
- YQAGSWNDWCUORB-UHFFFAOYSA-N [W+4].[O-2].[Sr+2].[O-2].[O-2] Chemical compound [W+4].[O-2].[Sr+2].[O-2].[O-2] YQAGSWNDWCUORB-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004383 yellowing Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 13
- 229910052719 titanium Inorganic materials 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 239000008187 granular material Substances 0.000 description 9
- 238000007664 blowing Methods 0.000 description 7
- 238000006482 condensation reaction Methods 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 229910052797 bismuth Inorganic materials 0.000 description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229920002799 BoPET Polymers 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 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 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- RITRBMFNWDNZNB-UHFFFAOYSA-N oxotungsten;yttrium Chemical compound [Y].[W]=O RITRBMFNWDNZNB-UHFFFAOYSA-N 0.000 description 3
- RUDFQVOCFDJEEF-UHFFFAOYSA-N oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- SXSVTGQIXJXKJR-UHFFFAOYSA-N [Mg].[Ti] Chemical compound [Mg].[Ti] SXSVTGQIXJXKJR-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004262 Ethyl gallate Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PADGHIGYUIHZRI-UHFFFAOYSA-N [Ti].[Zn].[Ru] Chemical compound [Ti].[Zn].[Ru] PADGHIGYUIHZRI-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- VNRRSGPRRULRLF-UHFFFAOYSA-N oxotungsten;ruthenium Chemical compound [Ru].[W]=O VNRRSGPRRULRLF-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
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- 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
-
- 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
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
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- 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
- C08K3/10—Metal compounds
- C08K3/105—Compounds containing metals of Groups 1 to 3 or of Groups 11 to 13 of the Periodic Table
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
- B01J31/0212—Alkoxylates
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- 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
- C08G2390/00—Containers
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- 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
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- 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
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- 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
- C08K2003/2258—Oxides; Hydroxides of metals of tungsten
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- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/54—Inorganic substances
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- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
本發明有關於一種用於製造聚對苯二甲酸乙二酯(polyethylene terephthalate，PET)樹酯之觸媒系統組合物，觸媒系統組合物係包含聚縮合(polycondensation)反應觸媒，以及如化學式CsxWO3-yCly所示之氧化銫鎢(Cesium tungsten oxide)，其中Cs為銫，Cl為氯，W為鎢，O為氧，0<x1，0y
Description
本發明係有關於一種觸媒系統組合物，尤其係指一種可用以提高聚對苯二甲酸乙二酯(polyethylene terephthalate，縮寫PET)樹酯製程中的固態聚合速率，縮短其製程時間，並改善PET樹酯具有顏色偏黃之問題的觸媒系統組合物。
聚對苯二甲酸乙二酯(PET)樹酯為常見用於製造包裝容器的聚酯聚合物，以此製成的容器，不僅具有良好的強度，亦具有透明性佳與耐化學性之優點。PET樹酯的習知製法依序包括酯化反應(esterification)、縮合反應(condensation)與固態聚合反應(solid-state polymerization)等三個階段。
現有的製法當中，常以重金屬銻(Sb)作為縮合反應的觸媒(catalyst)，例如美國專利公開US 20090035502 A1號「適用於製造巴氏殺菌容器之聚合物組合物(Polymeric composition suitable for manufacturing pasteurizable containers)」，即揭示合成瓶用的PET與PEN共聚物(copolymer)組成物包含10~100ppm三氧化鎢(tungsten trioxide)(粒徑2~20um)，其中三氧化鎢為再加熱(reheat)添加劑，觸媒可以是銻(Sb)或鈦(Ti)或鍺(Ge)化合物；以及美國專利公告US 8901271 B2號「聚對苯二甲酸乙酯之製備方法(Process
for making polyethylene terephthalate)」，係揭示使用鈦-鋅-銻觸媒聚合系統進行縮合反應。可見利用銻(Sb)金屬為觸媒作為縮合反應的應用相當廣泛。然而，使用銻(Sb)當作縮合反應的觸媒具有多項問題，例如溶液造成環境汙染，且縮合反應速率慢需要較高含量，因此成本較高。
為解決上述問題，現有製法亦有提出以鈦(Ti)取代銻(Sb)當縮合反應的觸媒以避免銻(Sb)之使用，如中華民國專利公告第TWI386430(B)號「一種不含銻重金屬的PET樹脂及其所製成PET聚酯纖維」與美國專利公告第US 8945695 B2號「一種使用無機的鈦-鎂觸媒合成的PET聚酯粒及其應用(Polyethylene terephthalate resin synthesized inorganic Ti-Mg catalyst and its applications thereof)」，即分別揭示利用鈦元素對鎂元素的莫耳比介於0.01~0.2或0.005~0.25之無機鈦-鎂催化劑取代銻觸媒，藉以製成不含銻重金屬的PET樹酯之方法。另，美國專利公告第US6593447 B1號「用於製備聚酯觸媒及其製備方法(Catalyst for polyester production and process for producing polyester with the same)」，則揭示使用有機的鈦化合物(titanium compound)與磷化合物(phosphorus compound)共同以莫耳比1：1至1：4之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℃以下反應製成用於聚縮合作用之觸媒。
上述利用鈦(Ti)觸媒取代銻(Sb)觸媒當縮合反應的方法，雖然具有縮合反應(condensation)速率快，且所製成的PET樹酯不含重金屬的優點，但目前使用鈦(Ti)觸媒製造PET樹酯時，仍然具有固態聚合(solid-state polymerization)速率較慢，製程時間長，與PET樹酯顏色偏黃的問題。
再者，將PET樹酯製成如瓶子的容器時，需先將聚合物切
成酯粒，再用射出模製技術使酯粒形成瓶胚(parison)，然後再以紅外線(infrared radiation)加熱使此PET瓶胚達玻璃轉化點以上的特定溫度，最後將PET瓶胚拉伸吹塑成所需形狀之瓶子。因此，倘若能提升PET樹酯本身於吸收紅外光的能力，將能使PET樹酯在吹瓶製造時加速瓶胚的加熱軟化，進而減少製程所需耗費的時間。舉例而言，中國專利公告CN 102153839 B號「一種含碳化鎢鈦粒子的聚酯樹酯及由其製成的聚酯瓶胚」，即揭示在銻觸媒聚合系統中加入會吸收紅外線的碳化鎢鈦(titanium-containing tungsten carbide)，以加速瓶胚的加熱軟化與溫度均勻性之方法。
爰此，如何研發更佳的PET樹酯製程以增加PET樹酯固態聚合的速率，縮短製程時間，並改善PET樹酯顏色黃化等缺失，乃成為發明人所思及之方向。
今，發明人即是鑑於上述現有PET樹酯製程於實際實施使用時仍具有多處缺失，於是乃藉由其豐富專業知識及多年之實務經驗所輔佐，而加以改善，並據此研創出本發明。
本發明主要目的為提供一種觸媒系統組合物，其可用以提高聚對苯二甲酸乙二酯(PET)樹酯製程中的固態聚合速率，縮短其製程時間，並改善PET樹酯具有顏色偏黃之問題的觸媒系統組合物。
為了達到上述實施目的，本發明一種用於製造PET樹酯之觸媒系統組合物，其包含：(a)聚縮合(polycondensation)反應觸媒，以及(b)如式(I)所示氧化銫鎢(Cesium tungsten oxide)：CsxWO3-yCly 式(I)，其中Cs為銫，Cl為氯，W為鎢，O為氧，0<x1，0y0.5；較佳而言，氧化銫鎢對聚縮合反應觸媒之重量比係0.005~40。
再者，本發明亦提供一種利用如上述之觸媒系統組合物製造
而成的PET樹酯，係包含相對於PET樹酯含量為2~80ppm的氧化銫鎢。
於本發明之一實施例中，氧化銫鎢為粒徑2~1000奈米之粉體。
於本發明之一實施例中，聚縮合反應觸媒為包含鈦(Ti)或銻(Sb)其中至少一種之化合物；較佳而言，可例如選用鈦酸四丁酯(Tetrabutyl titanate)。
據此，利用本發明提供之觸媒系統組合物用於製造PET樹酯，可增加PET樹酯固態聚合的速率，縮短製程時間，並改善PET樹酯顏色偏黃之問題。此外，由於氧化銫鎢具有吸收紅外光的能力，故將此利用觸媒系統組合物製造而得的PET樹酯應用於紅外光加熱的吹瓶製造時，可加速瓶胚的加熱軟化，因而大幅縮短製程所需耗費的時間。
第一圖：本發明固態聚合完成後的PET酯粒外觀比較圖。
第二圖：本發明PET膜之紫外光/可見光/近紅外光(UV/VIS/IR)穿透光譜圖。
本發明之目的及其結構功能上的優點，將依據以下圖面所示之結構，配合具體實施例予以說明，俾使審查委員能對本發明有更深入且具體之瞭解。
本發明一種用於製造PET樹酯之觸媒系統組合物，其包含：(a)聚縮合(polycondensation)反應觸媒，以及(b)如式(I)所示氧化銫鎢(Cesium tungsten oxide)：CsxWO3-yCly 式(I)，其中Cs為銫，Cl為氯，W為鎢，O為氧，0<x1，0y0.5；較
佳而言，聚縮合反應觸媒可例如為包含鈦(Ti)或銻(Sb)其中至少一種之化合物，如鈦酸四丁酯(Tetrabutyl titanate)；氧化銫鎢可例如為粒徑2~1000奈米之粉體。
另，本發明亦提供一種利用如上述之觸媒系統組合物製造而成的PET樹酯；較佳而言，觸媒系統組合物所具有氧化銫鎢對聚縮合反應觸媒之重量比可例如為0.005~40。
藉此，利用上述觸媒系統組合物用於製造PET樹酯，氧化銫鎢之含量相對於PET樹酯為2~80ppm；觸媒系統組合物不僅可解決現有PET樹酯製程中固態聚合速率較慢、製程時間長以及容易黃化的問題，並且氧化銫鎢可使PET樹酯具有吸收紅外光的功能，因此將PET樹酯應用於紅外光加熱的吹瓶製程時，可加速瓶胚的加熱軟化，縮短製程時間。
此外，藉由下述具體實施例，可進一步證明本發明可實際應用之範圍，但不意欲以任何形式限制本發明之範圍。
本發明提供一種新穎製造PET樹酯的觸媒系統組合物，包含：(a)聚縮合反應觸媒，與(b)2~80ppm氧化銫鎢，其含量為相對於PET樹酯，且氧化銫鎢對聚縮合反應觸媒的重量比例介於0.005~40；藉此觸媒系統組合物可加速固態聚合時間，所製造的PET樹酯具紅外光吸收的功能並改善黃化問題。
具體而言地，本案提供三個實施例製成不同的PET樹酯予以比較，分別為比較例及實施例1與實施例2。比較例及實施例1與實施例2所使用的鈦觸媒為鈦酸四丁酯(Tetrabutyl titanate)，添加比例皆為相對於PET樹酯重量20ppm，不同之處在於，實施例1中的觸媒，除鈦酸四丁酯外，亦包含相對於PET樹酯重量10ppm的氧化銫鎢，實施例2中的觸媒，除鈦酸四丁酯外，則包含相對於PET樹酯重量50ppm的氧化銫鎢；其餘聚合反應控制條件皆相同，
諸如在真空下進行聚合反應，以用來攪拌聚合產物的攪拌機之扭力(torque)值來決定聚合反應程度。一般來說隨著聚合程度增加，攪拌機的扭力值也會隨著增加，因此設定比較例與實施例的聚合終點條件都是依據攪拌機之扭力值達到一固定值之後再下料。
〔比較例〕
秤取400g對苯二甲酸雙羥乙酯(bis-2-hydroxy-ethylterephthalate，以下簡稱BHET)單體與20g乙二醇(ethylene glycol)置於反應器中，再加入0.056g鈦酸四丁酯(簡稱TBT)觸媒(鈦含量為理論PET重量之20ppm)與0.03g磷酸(磷含量為理論PET重量之24.5ppm)；反應溫度為260℃，反應10分鐘後抽真空使真空度逐漸降為60mmHg，時間約30分鐘；然後升溫至280℃，使真空度進一步降至1torr(約等同於1mmHg)，持續反應至攪拌器顯示的扭力值大約達到一固定值之後下料。隨後進行固態聚合步驟如下，秤取50-100g之聚合後PET產物，置於真空高溫爐中，反應溫度由室溫升至215℃歷時約1小時，到達215℃時恆溫6小時，隨後降至室溫。再以奧斯瓦黏度計(Ostwald viscometer)量測固態聚合前、後產物的本質黏度(Inherent viscosity)。
〔製備例〕
觸媒系統組合物的製作：首先將全能材料公司的氧化銫鎢粉體加入乙二醇(ethylene glycol)中配製成8.8wt%之溶液，並加入相對於粉體重量為91wt%之高分子型分散劑，利用0.5mm釔鋯珠研磨分散得到奈米分散液體，粒徑大小經由雷射粒徑分析儀測得為91.8nm。再將此分散液與鈦酸四丁酯(TBT)觸媒(鈦含量為理論PET重量之20ppm)以所需濃度混合產生本發明觸媒系統組合物，其中氧化銫鎢與聚縮合反應觸媒之重量比係介於0.005~40。
〔實施例1〕
秤取400g之BHET單體與20g乙二醇(ethylene glycol)置於反應器中，再加入包含0.056g TBT觸媒(鈦含量為理論PET重量之20ppm)與0.084g之氧化銫鎢奈米分散液體(氧化銫鎢含量為理論PET重量之10ppm)的觸媒系統組合物，另外加入0.03g磷酸(磷含量為理論PET重量之24.5ppm)；反應溫度為260℃，反應10分鐘後抽真空使真空度逐漸降為60mmHg，時間約30分鐘；然後升溫至280℃，使真空度進一步降至1torr(約等同於1mmHg)，持續反應至攪拌器顯示的扭力值大約達到一固定值之後下料。隨後進行固態聚合步驟如下，秤取50-100g之聚合後PET產物，置於真空高溫爐中，反應溫度由室溫升至215℃歷時約1小時，到達215℃時恆溫6小時，隨後降至室溫。再以奧斯瓦黏度計(Ostwald viscometer)量測固態聚合前、後產物的本質黏度(Inherent viscosity)。
〔實施例2〕
秤取400g之BHET單體與20g乙二醇(ethylene glycol)置於反應器中，再加入包含0.056g TBT觸媒(鈦含量為理論PET重量之20ppm)，0.420g之氧化銫鎢奈米分散液體(氧化銫鎢含量為理論PET重量之50ppm)的觸媒系統組合物，另外加入0.03g磷酸(磷含量為理論PET重量之24.5ppm)；反應溫度為260℃，反應10分鐘後抽真空使真空度逐漸降為60mmHg，時間約30分鐘；然後升溫至280℃，使真空度進一步降至1torr(約等同於1mmHg)，持續反應至攪拌器顯示的扭力值大約達到一固定值之後下料。隨後進行固態聚合步驟如下，秤取50-100g之聚合後PET產物，置於真空高溫爐中，反應溫度由室溫升至215℃歷時約1小時，到達215℃時恆溫6小時，隨後降至室溫。再以奧斯瓦黏度計(Ostwald viscometer)量測固態聚合前、後產物的本質黏度(Inherent viscosity)。
本質黏度量測方式係參考ISO 1628試驗標準：塑膠-利用毛細管黏度劑(capillary viscometers)測定稀釋溶液中聚合物的黏度(Determination of the viscosity of polymers in dilute solution)，在此，以奧斯瓦黏度計(Ostwald viscometer)進行量測，詳細量測方式如下：
i.樣品的配置：濃度0.3g/dL，精秤0.0300g的樣本(sample)溶於10ml的溶劑(solvent)中，該溶劑為苯酚(phenol)/三氯乙烯(1,1,2,2-trichloroethylene,TCE)=6/4，上述可容許之誤差為0.0001g。配置好之樣品於約80℃下加熱溶解，全溶後靜置於室溫冷卻即可。
ii.恆溫水槽設定30℃，至少恆溫1小時後才開始操作。
iii.利用空白組(Blank)實驗求得t0：取10ml的溶劑(phenol/TCE=6/4)注入黏度計，置於恆溫水槽中恆溫5分鐘，重複測定3次誤差不可大於0.3秒，若誤差太大則需重測。
iv.取樣本溶液10ml注入黏度計中，置於恆溫水槽中恆溫5分鐘，重複測定3次誤差不可大於0.3秒，取平均值即可得到t。
v.將t0和t帶入公式即可求得本質黏度(inherent viscosity，簡稱IV)；黏度之公式如下述。
上述比較例及實施例1與實施例2樣品間的本質黏度變化量記錄結果如表一所示。由表一可知，在固態聚合前、後實施例1的本質黏度(IV)差異(0.20dL/g)與實施例2的本質黏度(IV)差異(0.18dL/g)明顯較比較例(0.12dL/g)提高。
表一
取固態聚合完成的PET酯粒，置於白紙上拍攝外觀如第一圖。由第一圖相互比較可發現，比較例僅含有鈦觸媒的PET酯粒其顏色黃化程度較實施例1與實施例2的PET酯粒明顯。
為了進一步驗證，取各比較例與實施例的PET酯粒，以250℃熱壓成厚度0.5mm的PET膜，並以分光光度計(HUNTER LAB UNIVERSAL COLAR QUEST XE)量測色座標，參考ASTM E313：根據儀器測定的色座標計算黃色和白色指數的標準實施規程(Standard Practice for Calculating Yellowness and Whiteness Indices from Instrumentally Measured Color Coordinates)，其黃度指數(Yellowness Index，簡稱Y.I.)結果列於表二。由表二可知隨著氧化銫鎢含量增加，PET膜的黃度指數有逐漸下降的趨勢，此結果與第一圖外觀照片中實施例2的PET酯粒相對於比較例的PET酯粒較為不黃之現象，可相互映證。
第二圖為上述將PET酯粒熱壓成PET膜之樣品，以紫外光/可見光/近紅外光(UV/VIS/IR)光譜儀(SHIMAZU UV3600)進行量測
之穿透率(transmittance，T)圖，並以ISO 9050進行可見光穿透率(Tvis)與紅外線穿透率(Tir)計算列於表二。由表二可以發現在相近的可見光穿透率(Tvis約82%)下，實施例1添加10ppm氧化銫鎢多吸收0.4%的紅外光，實施例2中添加50ppm氧化銫鎢則可多吸收5.3%的紅外光。由此可證明本發明之觸媒系統組合物具紅外光(波長大於780nm之光線)吸收的功能，推測此功能對於PET後段吹瓶製程具有加速瓶胚的加熱軟化之效果。
進一步地具體測試，將加熱照光實驗作為簡易模擬PET吹瓶製程時之條件，觀察實施例2中添加50ppm氧化銫鎢的樣品是否於照光後溫度會較高。由於鹵素燈較易取得且其發光波長分佈與一般應用於吹瓶製程的加熱光源相近，因此取250W鹵素燈，距離樣品8.5公分連續照射10分鐘，並記錄照射前後樣品表面的溫度差異，其結果列於表二中。由10分鐘的溫差結果可以發現，實施例2添加50ppm氧化銫鎢(△T為60.8℃)比沒添加任何氧化銫鎢的比較例(△T為51.4℃)升溫多達9.4℃，由此可證明本發明之觸媒系統組合物具紅外光(波長大於780nm之光線)吸收的功能，應用於紅外光加熱的吹瓶製程時，可加速瓶胚的加熱軟化，縮短製程時間，增加產速。
由上述之實施說明可知，本發明與現有技術相較之下，本發明具有以下優點：
1.本發明提供之觸媒系統組合物用於製造PET樹酯，可解決現有PET樹酯製程具有固態聚合速率低、製程時間長，以及PET樹酯顏色黃化之問題。
2.本發明之觸媒系統組合物包含具有吸收紅外光能力的氧化銫鎢，故將利用此觸媒系統組合物製造所得的PET樹酯，進一步應用於紅外光加熱的吹瓶製造時，可加速瓶胚的加熱軟化，因而大幅縮短製程所需耗費的時間。
綜上所述，本發明之用於製造PET樹酯之觸媒系統組合物，的確能藉由上述所揭露之實施例，達到所預期之使用功效，且本發明亦未曾公開於申請前，誠已完全符合專利法之規定與要求。爰依法提出發明專利之申請，懇請惠予審查，並賜准專利，則實感德便。
惟，上述所揭之圖示及說明，僅為本發明之較佳實施例，非為限定本發明之保護範圍；大凡熟悉該項技藝之人士，其所依本發明之特徵範疇，所作之其它等效變化或修飾，皆應視為不脫離本發明之設計範疇。
Claims (6)
- 一種用於製造PET樹酯之觸媒系統組合物，其包含：(a)聚縮合(polycondensation)反應觸媒，為鈦酸四丁酯(Tetrabutyl titanate)，以及(b)如式(I)所示氧化銫鎢(Cesium tungsten oxide)：CsxWO3-yCly 式(I)，其中Cs為銫，Cl為氯，W為鎢，O為氧，0<x1，0y0.5，且其中該氧化銫鎢對該聚縮合反應觸媒之重量比係0.005~40。
- 如申請專利範圍第1項所述之觸媒系統組合物，其中該氧化銫鎢之含量相對於該PET樹酯為2~80ppm。
- 如申請專利範圍第1項所述之觸媒系統組合物，其中該氧化銫鎢為粒徑2~1000奈米之粉體。
- 一種利用如申請專利範圍第1項所述之觸媒系統組合物製造而成的PET樹酯，係包含2~80ppm氧化銫鎢。
- 如申請專利範圍第4項所述之PET樹酯，其中該觸媒系統組合物所具有氧化銫鎢對該聚縮合反應觸媒之重量比係0.005~40。
- 如申請專利範圍第4項所述之PET樹酯，其中該氧化銫鎢為粒徑2~1000奈米之粉體。
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| TW105121387A TWI629294B (zh) | 2016-07-06 | 2016-07-06 | 用於製造pet樹酯之觸媒系統組合物 |
| US15/437,747 US10351666B2 (en) | 2016-07-06 | 2017-02-21 | Catalytic composition for preparing PET resin |
| DE102017104054.4A DE102017104054B4 (de) | 2016-07-06 | 2017-02-27 | Katalysatorsystemzusammensetzung zur Herstellung von PET-Harzen |
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| TW105121387A TWI629294B (zh) | 2016-07-06 | 2016-07-06 | 用於製造pet樹酯之觸媒系統組合物 |
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| TW201802140A TW201802140A (zh) | 2018-01-16 |
| TWI629294B true TWI629294B (zh) | 2018-07-11 |
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| US9776379B2 (en) | 2014-04-29 | 2017-10-03 | Pleotint, L.L.C. | Absorbing solar control interlayers |
| CN110606946B (zh) * | 2019-09-30 | 2021-06-29 | 常州大学盱眙凹土研发中心 | 一种绿色钛系聚酯催化剂的制备方法及应用 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TW200530132A (en) * | 2003-10-20 | 2005-09-16 | Sumitomo Metal Mining Co | Infrared shielding material microparticle dispersion, infrared shield, process for producing infrared shielding material microparticle, and infrared shielding material microparticle |
| TW201237061A (en) * | 2011-03-07 | 2012-09-16 | Nanya Plastics Corp | Polyester resin containing tungsten-titanium carbide particles and polyester bottle preform made therefrom |
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| US5453479A (en) * | 1993-07-12 | 1995-09-26 | General Electric Company | Polyesterification catalyst |
| TW548291B (en) | 1999-06-24 | 2003-08-21 | Teijin Ltd | Catalyst for producing a polyester and process for producing the polyester by using same |
| US20090035502A1 (en) | 2007-07-31 | 2009-02-05 | Kulkarni Sanjay Tammaji | Polymeric composition suitable for manufacturing pasteurizable containers |
| TWI386429B (zh) | 2008-05-06 | 2013-02-21 | Nanya Plastics Corp | A method of using inorganic titanium - PET polyester synthetic magnesium catalyst particles and Its Application |
| TWI386430B (zh) | 2008-12-04 | 2013-02-21 | Nanya Plastics Corp | Which does not contain heavy metal antimony PET resin and the PET polyester fibers |
| EP2287225A1 (en) | 2009-08-20 | 2011-02-23 | Saudi Basic Industries Corporation | Process for making polyethylene terephthalate |
| ITRM20100228A1 (it) * | 2010-05-10 | 2011-11-10 | Bayer Materialscience Ag | Composizione polimerica con caratteristiche di assorbimento del calore e migliorate caratteristiche di colore. |
| CN102153839B (zh) | 2011-03-15 | 2012-09-19 | 南亚塑胶工业股份有限公司 | 一种含碳化钨钛粒子的聚酯树脂及由其制成的聚酯瓶胚 |
| KR101354261B1 (ko) * | 2012-11-01 | 2014-02-05 | (주) 나노비젼텍 | 복합기능성 폴리에스터 섬유의 제조방법 및 그에 의해서 제조된 복합기능성 폴리에스터 섬유 |
| TWI503346B (zh) * | 2014-06-11 | 2015-10-11 | Zirco Applied Materials Co Ltd | 近紅外光屏蔽膜及近紅外光屏蔽膜之製造方法 |
| WO2017130492A1 (ja) * | 2016-01-28 | 2017-08-03 | 住友金属鉱山株式会社 | ポリカーボネート樹脂組成物、熱線遮蔽成形体および熱線遮蔽積層体 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200530132A (en) * | 2003-10-20 | 2005-09-16 | Sumitomo Metal Mining Co | Infrared shielding material microparticle dispersion, infrared shield, process for producing infrared shielding material microparticle, and infrared shielding material microparticle |
| TW201237061A (en) * | 2011-03-07 | 2012-09-16 | Nanya Plastics Corp | Polyester resin containing tungsten-titanium carbide particles and polyester bottle preform made therefrom |
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| Publication number | Publication date |
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| US20180009939A1 (en) | 2018-01-11 |
| DE102017104054B4 (de) | 2019-01-10 |
| US10351666B2 (en) | 2019-07-16 |
| TW201802140A (zh) | 2018-01-16 |
| DE102017104054A1 (de) | 2018-01-11 |
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