EP1379585A1 - Verfahren zur herstellung von optisch aufgehelltem polyester - Google Patents
Verfahren zur herstellung von optisch aufgehelltem polyesterInfo
- Publication number
- EP1379585A1 EP1379585A1 EP02730021A EP02730021A EP1379585A1 EP 1379585 A1 EP1379585 A1 EP 1379585A1 EP 02730021 A EP02730021 A EP 02730021A EP 02730021 A EP02730021 A EP 02730021A EP 1379585 A1 EP1379585 A1 EP 1379585A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polyester
- alkyl
- esterification
- production
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 17
- 229920000728 polyester Polymers 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title abstract description 9
- 230000003287 optical effect Effects 0.000 claims abstract description 23
- 230000032050 esterification Effects 0.000 claims abstract description 11
- 238000005886 esterification reaction Methods 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 6
- 229920005862 polyol Polymers 0.000 claims abstract description 4
- 150000003077 polyols Chemical class 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- -1 phenylene, thiophenylene Chemical group 0.000 claims description 3
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims description 2
- 125000004957 naphthylene group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 1
- 239000002202 Polyethylene glycol Substances 0.000 claims 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 claims 1
- 229920001223 polyethylene glycol Polymers 0.000 claims 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims 1
- 150000007513 acids Chemical class 0.000 abstract description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 27
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 12
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- CARJPEPCULYFFP-UHFFFAOYSA-N 5-Sulfo-1,3-benzenedicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(S(O)(=O)=O)=C1 CARJPEPCULYFFP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 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
-
- 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
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
- C08K5/353—Five-membered rings
Definitions
- polyester e.g. synthesis based on dimethyl terephthalate (DMT) and ethylene glycol.
- DMT dimethyl terephthalate
- methanol is first distilled off in a transesterification reaction with an excess of ethylene glycol and then the excess glycol is reduced and condensed in vacuo.
- the polymer can be produced by reaction from free terephthalic acid (TPA) and ethylene glycol.
- TPA free terephthalic acid
- the terephthalic acid is first esterified with an excess of ethylene glycol under pressure at about 260 ° C., and this excess is then removed in vacuo and the reaction mass is condensed.
- Recycled processes for the production of polyester material are also known. Large areas of application for polyester in terms of volume are the production of polyester fibers and the use as a food container, e.g. in bottle form and in the form of films of all kinds.
- optical brighteners are added to the polymer at different times to produce brightened polyester.
- the majority of fiber manufacturers therefore add the optical brightener as an active substance in the polycondensation stage or as a masterbatch to the polyester mass.
- the addition of optical brighteners in the transesterification phase is also known. It is generally unknown
- optical brighteners that can be used without decomposition in the esterification phase.
- thermal and acid-stable optical brighteners on the one hand increase the reproducibility and predictability of the product properties and, on the other hand, they are technically considerably easier to apply because there is no need for complex lock systems for the subsequent application of the active ingredient.
- Recycled processes in particular benefit from thermal and acid-stable optical brighteners.
- Technically significant optical brighteners for polyesters are based on the basic structure 2,2 '- (1,2-ethylenediyl-4,1-phenylene) -bisbenzoxazole, which can be substituted in different ways.
- optical brighteners in the form of a dispersion in glycol in polyester production at the stage of transesterification of DMT with glycol.
- this product class for the direct esterification of TPA with glycol, since in the presence of acids the effects of chemical decomposition are considerably restricted.
- This brightener class can therefore only be applied after the esterification is almost complete or complete. It has now surprisingly been found that this problem can be solved by using optical brighteners whose structure is free from one or more open-chain ethylenic double bonds.
- the invention relates to a process for the production of optically brightened polyester by esterification of an aliphatic and / or aromatic polycarboxylic acid, preferably dicarboxylic acid, and a polyol, preferably diol, characterized in that the esterification is carried out in the presence of an optical brightener, the structure of which is free of one or more open chain ethylenic double bonds.
- polyesters such as, for example, terephthalic acid, isophthalic acid, 5-sulfoisophthalic acid, naphthalenedicarboxylic acid and ethylene glycol, propylene glycol, butylene glycol-1,2, butylene glycol, are suitable for the preparation of the polyester -1, 4, glycerin, pentaerythritol.
- the preferred polyester is polyethylene terephthalate (PET).
- optical brighteners are compounds of the formulas 1 to 4.
- R 1 to R 8 independently of one another are hydrogen, C 1 -C 0 -alkyl or groups of the formula -COOR 9 , where Rg is hydrogen, CrC 20 -alkyl or phenyl, or R 1 to R 8 represent a group of the formula -SO 2 R- ⁇ o, where Rio is hydrogen,
- A means naphthylene, phenylene, thiophenylene or biphenylene.
- optical brighteners are added to the synthesis before the esterification.
- the esterification and condensation then take place in accordance with the processes which are customary and known in the production of polyester: in the same way, these optical brighteners can also be used in recycled processes for recycling PET, the optical brightener preferably being added to the glycol.
- optical brighteners without olefinic double bonds (according to the invention)
- optical brighteners without an open-chain ethylenic double bond are more stable compared to optical brighteners which contain such a double bond.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10114696 | 2001-03-23 | ||
| DE10114696A DE10114696A1 (de) | 2001-03-23 | 2001-03-23 | Verfahren zur Herstellung von optisch aufgehelltem Polyester |
| PCT/EP2002/002956 WO2002077088A1 (de) | 2001-03-23 | 2002-03-16 | Verfahren zur herstellung von optisch aufgehelltem polyester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1379585A1 true EP1379585A1 (de) | 2004-01-14 |
Family
ID=7679009
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP02730021A Withdrawn EP1379585A1 (de) | 2001-03-23 | 2002-03-16 | Verfahren zur herstellung von optisch aufgehelltem polyester |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20050101703A1 (enExample) |
| EP (1) | EP1379585A1 (enExample) |
| JP (1) | JP2004526842A (enExample) |
| DE (1) | DE10114696A1 (enExample) |
| WO (1) | WO2002077088A1 (enExample) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102004005837B3 (de) * | 2004-02-06 | 2005-04-14 | Clariant Gmbh | Granulierte nichtionische und wasserunlösliche optische Aufheller |
| US20060041039A1 (en) * | 2004-08-20 | 2006-02-23 | Gyorgyi Fenyvesi | Fluorescent poly(alkylene terephthalate) compositions |
| WO2006041523A1 (en) * | 2004-10-08 | 2006-04-20 | E.I. Dupont De Nemours And Company | Fluorescent poly(alkylene terephthalate) compositions |
| ATE434083T1 (de) * | 2006-01-26 | 2009-07-15 | Clariant Finance Bvi Ltd | Verfahren zur herstellung von optisch aufgehelltem papier |
| EP2546319A1 (en) * | 2011-07-13 | 2013-01-16 | Koninklijke Philips Electronics N.V. | High efficiency plastic light conversion components by incorporation of phosphor in a polymer by adding to monomers before polymerisation |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3993659A (en) * | 1971-08-10 | 1976-11-23 | Ciba-Geigy Corporation | Bis-benzoxazolyl-naphthalenes as optical brighteners |
| US5989453A (en) * | 1990-05-11 | 1999-11-23 | Societe Nouvelle De Chimie Industrielle S.A. | Process for the manufacture of pigments, especially fluorescent pigments |
| ES2101826T3 (es) * | 1991-11-04 | 1997-07-16 | Chimie Ind Sa Soc Nouv | Procedimiento para la preparacion de pigmentos, especialmente, pigmentos fluorescentes. |
-
2001
- 2001-03-23 DE DE10114696A patent/DE10114696A1/de not_active Withdrawn
-
2002
- 2002-03-16 WO PCT/EP2002/002956 patent/WO2002077088A1/de not_active Ceased
- 2002-03-16 JP JP2002576542A patent/JP2004526842A/ja active Pending
- 2002-03-16 US US10/471,951 patent/US20050101703A1/en not_active Abandoned
- 2002-03-16 EP EP02730021A patent/EP1379585A1/de not_active Withdrawn
Non-Patent Citations (1)
| Title |
|---|
| See references of WO02077088A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| US20050101703A1 (en) | 2005-05-12 |
| WO2002077088A1 (de) | 2002-10-03 |
| JP2004526842A (ja) | 2004-09-02 |
| DE10114696A1 (de) | 2002-11-07 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
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| 17P | Request for examination filed |
Effective date: 20031023 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR |
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| AX | Request for extension of the european patent |
Extension state: AL LT LV MK RO SI |
|
| RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: CLARIANT PRODUKTE (DEUTSCHLAND) GMBH |
|
| 17Q | First examination report despatched |
Effective date: 20060717 |
|
| GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN |
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| 18W | Application withdrawn |
Effective date: 20090212 |