DE1495607B1 - Verfahren zur Herstellung von linearen Polyestern - Google Patents
Verfahren zur Herstellung von linearen PolyesternInfo
- Publication number
- DE1495607B1 DE1495607B1 DE19641495607 DE1495607A DE1495607B1 DE 1495607 B1 DE1495607 B1 DE 1495607B1 DE 19641495607 DE19641495607 DE 19641495607 DE 1495607 A DE1495607 A DE 1495607A DE 1495607 B1 DE1495607 B1 DE 1495607B1
- Authority
- DE
- Germany
- Prior art keywords
- bisphenol
- production
- general formula
- linear polyesters
- phenol
- 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.)
- Pending
Links
- 229920000728 polyester Polymers 0.000 title claims description 8
- 238000000034 method Methods 0.000 title claims description 6
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 229930185605 Bisphenol Natural products 0.000 claims description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 6
- -1 aromatic dicarboxylic acids Chemical class 0.000 claims description 4
- 125000002619 bicyclic group Chemical group 0.000 claims description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 230000031709 bromination Effects 0.000 claims description 2
- 238000005893 bromination reaction Methods 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000003367 polycyclic group Chemical group 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VNPMJHSEIXCUAL-UHFFFAOYSA-N 2,6-dibromo-4-[3-(3,5-dibromo-4-hydroxyphenyl)-3-bicyclo[2.2.1]heptanyl]phenol Chemical compound C1=C(Br)C(O)=C(Br)C=C1C1(C=2C=C(Br)C(O)=C(Br)C=2)C(C2)CCC2C1 VNPMJHSEIXCUAL-UHFFFAOYSA-N 0.000 description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- KPMKEVXVVHNIEY-RITPCOANSA-N norcamphor Chemical compound C1C[C@@H]2C(=O)C[C@H]1C2 KPMKEVXVVHNIEY-RITPCOANSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- FEVDZMGLXHFFKN-UHFFFAOYSA-N 2,6-dichloro-4-[3-(3,5-dichloro-4-hydroxyphenyl)-3-bicyclo[2.2.1]heptanyl]phenol Chemical compound C1=C(Cl)C(O)=C(Cl)C=C1C1(C=2C=C(Cl)C(O)=C(Cl)C=2)C(C2)CCC2C1 FEVDZMGLXHFFKN-UHFFFAOYSA-N 0.000 description 1
- HOLHYSJJBXSLMV-UHFFFAOYSA-N 2,6-dichlorophenol Chemical compound OC1=C(Cl)C=CC=C1Cl HOLHYSJJBXSLMV-UHFFFAOYSA-N 0.000 description 1
- RBWZNZOIVJUVRB-UHFFFAOYSA-N 4-[3-(4-hydroxyphenyl)-3-bicyclo[2.2.1]heptanyl]phenol Chemical class C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C(C2)CCC2C1 RBWZNZOIVJUVRB-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- PWAXUOGZOSVGBO-UHFFFAOYSA-N adipoyl chloride Chemical compound ClC(=O)CCCCC(Cl)=O PWAXUOGZOSVGBO-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- KPMKEVXVVHNIEY-UHFFFAOYSA-N norcamphor Chemical compound C1CC2C(=O)CC1C2 KPMKEVXVVHNIEY-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000002904 solvent Substances 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/04—Aromatic polycarbonates
- C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
-
- 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
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic 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
- C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
-
- 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
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
-
- 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
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—Dicarboxylic acids and dihydroxy compounds
-
- 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
-
- 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
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)
Description
Gegenstand der Patentanmeldung P13 00 267.0-44 ist ein Verfahren zur Herstellung von linearen Polyestern,
insbesondere Polycarbonaten, mit einer Eigenviskosität
von wenigstens 0,4, durch Umsetzung von Estern aliphatischen eycloaliphatischer oder aromatischer
Dicarbonsäuren oder von Phosgen oder einem Bischlorameisensäureester eines Diols mit einem Bisphenol, das dadurch gekennzeichnet ist, daß man ein
Bisphenol der allgemeinen Formel
HO
OH
verwendet, worinR" ein Wasserstoffatom, ein Halogenatom
und/oder eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen bedeutet und X einen geminal-zweiwertigen
Rest eines gesättigten, polycyclischen, mindestens ein bicyclisches Ringglied mit Brückenbindung
enthaltenden Ringsystems darstellt.
Der geminal-zweiwertige Rest kann aus einem der folgenden Glieder bestehen, worin R und R' Wasserstoffatome,
Halogenatome und/oder Alkylgruppen mit 1 bis 4 Kohlenstoffatomen und R1, R2 sowie R1'
Wasserstoffatome, Halogenatome, Alkylgruppen mit 1 bis 4 Kohlenstoffatomen oder Arylgruppen bedeuten:
R
R-
R-
CH
-CH
--CH
Bisphenole, die in den 2- und 6-Stellungen der Phenolkerne durch Halogenatome substituiert sind,
lassen sich dadurch herstellen, daß man bei der Herstellung der Bisphenole, bei der ein ein bicyclisches
Ringglied aufweisendes Keton mit einem Phenol kondensiert wird, ein halogeniertes Phenol verwendet.
So läßt sich beispielsweise durch Kondensation von Norcampher mit 2,6-Dichlorphenol das 4,4'-(2-Norcamphanyliden)-bis-(2,6-dichlorphenol)
herstellen.
Nach der Patentanmeldung P13 00 267.0-44 lassen
sich Bisdichlorphenole, welche in den 2- und 6-Stellungen der Phenolkerne Chloratome aufweisen, auch
durch Chlorierung der Bisphenole in Äthylenchlorid, Tetrachloräthan, Essigsäure oder einem anderen
Lösungsmittel herstellen.
Die Erfindung betrifft nun ein Verfahren zur Herstellung von linearen Polyestern, insbesondere Polycarbonaten,
mit einer Eigenviskosität von mindestens 0,4 durch Umsetzung von Estern aliphatischer, cycloaliphatischer
oder aromatischer Dicarbonsäuren oder von Phosgen oder einem Bischlorameisensäureester
eines Diols mit einem Bisphenol der allgemeinen Formel
HO
Die zur Durchführung des Verfahrens der Erfindung verwendeten Bisdibromphenole können wie folgt
hergestellt werden:
A. Herstellung von 4,4'-(2-Norbornyliden)-bis-(2,6-dibromphenol)
Eine 0,50 Mol Norcampher (2-Norbornanon), 2 Mol Phenol, 125 g konzentrierte Salzsäure und 2,5 g
/J-Mercaptopropionsäure enthaltende Mischung wurde 48 Stunden gerührt. Danach wurden 200 ml Benzol
zugesetzt und weitergerührt, um das überschüssige Phenol zu lösen, worauf die Mischung von dem als
Rückstand verbleibenden Reaktionsprodukt abfiltriert wurde. Es wurde mit Benzol gewaschen, mit Wasser
verrührt, um Spuren anhaftender Säure zu entfernen, und dann getrocknet. Die Ausbeute an rohem Produkt
betrug 80 bis 95%- Das Rohprodukt wurde dann aus wasserhaltiger Essigsäure, verdünntem Alkohol
oder aus Äthylendichlorid umkristallisiert. Aus wasserhaltiger Essigsäure oder verdünntem Alkohol kristallisierte
das unsubstituierte 4,4'-(2-Norbornyliden)-bisphenol als Hydrat aus.
1 Mol des Bisphenols wurde in 500 ml Methanol gelöst. Bei Raumtemperatur wurden 4 Mol Brom
zugesetzt. Nach Umkristallisation aus wäßriger Essigsäure wurde das 4,4'-(2-Norbornyliden)-bis-[2,6-dibromphenol]
mit einem Schmelzpunkt von 180 bis 181° C erhalten.
Das folgende Beispiel soll das Verfahren der Erfindung näher veranschaulichen:
In einen 500 ml fassenden Dreihalskolben wurden 300 ml Methylenchlorid, 50 ml trockenes Pyridin und
0,10 Mol 4,4' - (2 - Norbornyliden) - bis - (2,6 - dibromphenol),
hergestellt wie unter A beschrieben, gegeben.
Die Mischung wurde mittels eines Wasserbades auf einer Temperatur von 25 bis 300C gehalten. Unter
Rühren wurden langsam 0,10 Mol Adipoylchlorid zugegeben. Die Mischung wurde dann in Wasser
gegossen. Zur Verdünnung der gebildeten organischen Schicht wurde weiteres Methylenchlorid zugegeben.
Der pH-Wert der Mischung wurde durch Zugabe von HCl auf 1,5 eingestellt. Die Methylenchloridschicht
wurde mit Wasser gewaschen, worauf der gebildete Polyester durch Eingießen in Hexan unter Rühren
ausgefällt wurde.
Der Polyester besaß eine nach der Gleichung
OH
R"
worin R" ein Halogenatom darstellt und X die Bedeutung eines geminal-zweiwertigen Restes eines gesättigten,
polycyclischen, mindestens ein bicyclisches Ringglied mit Brückenbindung enthaltenden Ringsystems
besitzt, nach der Patentanmeldung P13 00 267.0-44, dadurch gekennzeichnet, daß man das Brombisphenol
verwendet, das durch direkte Bromierung eines Bisphenols der allgemeinen Formel
HO-
OH
worin X die angegebene Bedeutung besitzt, erhalten worden ist.
{r\r = Verhältnis der Viskosität einer etwa 0,25gewichtsprozentigen
Lösung des Polyesters in einem zu 60 Gewichtsprozent aus Phenol und 40 Gewichtsprozent
aus Tetrachloräthan bestehenden Lösungsmittelgemisch zur Viskosität des Lösungsmittelgemisches
; C = Konzentration des Polyesters in Gramm pro 100 ml Lösung) bestimmte Viskosität von 0,48.
Eine aus einer Methylenchloridlösung gegossene Folie besaß eine Festigkeit von 738 kg/cm2 und eine
Dehnung von 10%· Die Folie verlöschte nach Entfernung
aus der Flamme eines Bunsenbrenners.
Claims (1)
- Patentanspruch :Verfahren zur Herstellung von linearen Polyestern, insbesondere Polycarbonaten, mit einer Eigenviskosität von mindestens 0,4, durch Umsetzung von Estern aliphatischer, cycloaliphatischeroder aromatischer Dicarbonsäuren oder von Phosgen oder einem Bischlorameisensäureester eines Diols mit einem Bisphenol der allgemeinen FormelR" R"HOOHR"worin R" ein Halogenatom darstellt und X die Bedeutung eines geminal-zweiwertigen Restes einesgesättigten, polycyclischen, mindestens ein bicyclisches Ringglied mit Brückenbindung enthaltenden Ringsystems besitzt, nach Patentanmeldung P 13OO267.0-44, dadurch gekennzeichnet, daß man das Brombisphenol verwendet, das durch direkte Bromierung eines Bisphenols der allgemeinen FormelHOOHworin X die angegebene Bedeutung besitzt, erhalten worden ist.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13798061A | 1961-09-14 | 1961-09-14 | |
| US292139A US3317466A (en) | 1961-09-14 | 1963-07-01 | Three-dimensional polycyclic bisphenol polycarbonates and polyesters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1495607B1 true DE1495607B1 (de) | 1970-05-14 |
Family
ID=34915277
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19641495607 Pending DE1495607B1 (de) | 1961-09-14 | 1964-06-30 | Verfahren zur Herstellung von linearen Polyestern |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US3317466A (de) |
| DE (1) | DE1495607B1 (de) |
Families Citing this family (85)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3461097A (en) * | 1964-02-24 | 1969-08-12 | Union Carbide Corp | Polycarbonates of the bisphenol of dicyclopentadiene |
| US3420894A (en) * | 1965-02-26 | 1969-01-07 | Allied Chem | Process for the preparation of bisphenols |
| US3480585A (en) * | 1965-03-31 | 1969-11-25 | Allied Chem | Polycarbonate resins |
| US3527734A (en) * | 1965-06-07 | 1970-09-08 | Union Carbide Corp | Preparation of cylobutanediol polycarbonates by direct phosgenation |
| US3449298A (en) * | 1965-10-23 | 1969-06-10 | Union Carbide Corp | Norbornanediol condensation polymers |
| US3634089A (en) * | 1969-04-04 | 1972-01-11 | Eastman Kodak Co | Film-forming polyester compositions |
| US3856526A (en) * | 1973-08-06 | 1974-12-24 | Eastman Kodak Co | Protective layer for photothermographic elements |
| US3856527A (en) * | 1973-08-06 | 1974-12-24 | Eastman Kodak Co | Protective layer for photothermographic elements |
| US4081277A (en) * | 1976-10-08 | 1978-03-28 | Eastman Kodak Company | Method for making a solid-state color imaging device having an integral color filter and the device |
| US4097230A (en) * | 1976-10-08 | 1978-06-27 | Eastman Kodak Company | Method for transferring heat-transferable dyes |
| US5037947A (en) * | 1988-12-23 | 1991-08-06 | Eastman Kodak Company | Copolyesters from 4,4'-biphenyldicarboxylic acid, 1,6-hexanediol and 1,4-butanediol |
| US5037946A (en) * | 1988-12-23 | 1991-08-06 | Eastman Kodak Company | Copolyesters from 4,4'-biphenyldicarboxylic acid, 1,6-hexanediol and ethylene glycol |
| US4956448A (en) * | 1988-12-23 | 1990-09-11 | Eastman Kodak Company | Copolyesters from 4,4'-biphenyldicarboxylic acid, 1,4-cyclohexanedimethanol, and 1,4-butanediol |
| US5057595A (en) * | 1988-12-23 | 1991-10-15 | Eastman Kodak Company | Copolyesters from 4,4'-biphenyldicarboxylic acid, 1,4-cyclohexanedimethanol and ethylene glycol |
| US4973654A (en) * | 1988-12-23 | 1990-11-27 | Eastman Kodak Company | Copolyesters from 4,4'-biphenyldicarboxylic acid, 1,6-hexanediol and ethylene glycol |
| US5011878A (en) * | 1988-12-23 | 1991-04-30 | Eastman Kodak Company | Copolyesters from 4,4'-biphenyldicarboxylic acid, 1,4-cyclohexanedimethanol, and 1,4-butanediol |
| US5011877A (en) * | 1988-12-23 | 1991-04-30 | Eastman Kodak Company | Copolyesters from 4,4'-biphenyldicarboxylic acid, 1,4-cyclohexanedimethanol and 1,6-hexanediol |
| US4914179A (en) * | 1988-12-23 | 1990-04-03 | Eastman Kodak Company | Copolyesters from 4,4'-biphenyldicarboxylic acid, 1,4-cyclohexanedimethanol and ethylene glycol |
| US4916205A (en) * | 1988-12-23 | 1990-04-10 | Eastman Kodak Company | Copolyesters from 4,4'-biphenyldicarboxylic acid, 1,6-hexanediol and 1,4-butanediol |
| US4959450A (en) * | 1988-12-23 | 1990-09-25 | Eastman Kodak Company | Copolyesters from 4,4'biphenyldicarboxylic acid, 1,4-cyclohexanedimethanol and 1,6-hexanediol |
| US5017727A (en) * | 1990-07-10 | 1991-05-21 | Copolymer Rubber & Chemical Corporation | Polymerizable antioxidant composition |
| US5157164A (en) * | 1990-07-10 | 1992-10-20 | Copolymer Rubber & Chemical Corp. | Polymerizable antioxidant composition |
| US5202392A (en) * | 1991-08-22 | 1993-04-13 | Eastman Kodak Company | Blend of a polyester and a polycarbonate |
| US5202393A (en) * | 1991-08-22 | 1993-04-13 | Eastman Kodak Company | Blend of a polyester and a polycarbonate |
| US5194520A (en) * | 1991-08-22 | 1993-03-16 | Eastman Kodak Company | Blend of a polyester and a polycarbonate |
| US5194521A (en) * | 1991-08-22 | 1993-03-16 | Eastman Kodak Company | Blend of a polyester and a polycarbonate |
| US5194574A (en) * | 1991-11-04 | 1993-03-16 | Eastman Kodak Company | Thermally stable polyesters containing trans-4,4'-stilbenedicarboxylic acid |
| JPH11506487A (ja) * | 1995-06-02 | 1999-06-08 | イーストマン ケミカル カンパニー | 加水分解安定性の改良された２，６−ナフタレンジカルボン酸のポリエステル |
| US5962622A (en) * | 1996-12-28 | 1999-10-05 | Eastman Chemical Company | Process for preparing the polycarbonate of 2,2,4,4-tetramethyl-1,3-cyclobutanediol |
| US5955565A (en) * | 1996-12-28 | 1999-09-21 | Eastman Chemical Company | Polyesters from terephthalic acid, 2,2,4,4-tetramethyl-1,3-cyclobutanediol and ethylene glycol |
| EP0850971A3 (de) * | 1996-12-28 | 1999-02-24 | Eastman Chemical Company | Verfahren zur Deaktivierung von Katalysatorrückständen in Polycarbonaten |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2515906A (en) * | 1947-12-22 | 1950-07-18 | Gulf Research Development Co | Bis (hydroxyphenyl) compounds |
| US2732406A (en) * | 1952-03-11 | 1956-01-24 | New asymmetric diphenylol methanes | |
| US2761879A (en) * | 1955-03-14 | 1956-09-04 | Shell Dev | Halo-substituted bicyclic aldehydes |
| US3033822A (en) * | 1959-06-29 | 1962-05-08 | Eastman Kodak Co | Linear polyesters of 1, 4-cyclohexane-dimethanol and hydroxycarboxylic acids |
| US2991273A (en) * | 1956-07-07 | 1961-07-04 | Bayer Ag | Process for manufacture of vacuum moulded parts of high molecular weight thermoplastic polycarbonates |
| US3075949A (en) * | 1959-12-11 | 1963-01-29 | Eastman Kodak Co | Linear polyethers of bis (hydroxymethyl) durene and diphenols |
| US3251803A (en) * | 1961-09-14 | 1966-05-17 | Eastman Kodak Co | Linear condensation polymers containing urethane and carbonate units |
-
1963
- 1963-07-01 US US292139A patent/US3317466A/en not_active Expired - Lifetime
-
1964
- 1964-06-30 DE DE19641495607 patent/DE1495607B1/de active Pending
Non-Patent Citations (1)
| Title |
|---|
| None * |
Also Published As
| Publication number | Publication date |
|---|---|
| US3317466A (en) | 1967-05-02 |
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