EP0000510B1 - Polyesters renfermant des groupes carbonates - Google Patents

Polyesters renfermant des groupes carbonates Download PDF

Info

Publication number
EP0000510B1
EP0000510B1 EP78100380A EP78100380A EP0000510B1 EP 0000510 B1 EP0000510 B1 EP 0000510B1 EP 78100380 A EP78100380 A EP 78100380A EP 78100380 A EP78100380 A EP 78100380A EP 0000510 B1 EP0000510 B1 EP 0000510B1
Authority
EP
European Patent Office
Prior art keywords
weight
hours
molecular weight
parts
diol
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.)
Expired
Application number
EP78100380A
Other languages
German (de)
English (en)
Other versions
EP0000510A1 (fr
Inventor
Christian Dr. Lindner
Carlhans Dr Süling
Herbert Dr Bartl
Dietrich Dr. Hardt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0000510A1 publication Critical patent/EP0000510A1/fr
Application granted granted Critical
Publication of EP0000510B1 publication Critical patent/EP0000510B1/fr
Expired legal-status Critical Current

Links

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
    • C08G63/64—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
    • C08G63/66—Polyesters containing oxygen in the form of ether groups

Definitions

  • the invention relates to aliphatic polyesters containing carbonate groups and a process for their production.
  • Aliphatic polyesters can be produced by condensation of diols with dicarboxylic acids or dicarboxylic acid derivatives or by polycondensation of hydroxycarboxylic acids or lactones. They usually have relatively low molecular weights of up to a few thousand and can be used as diol components in the production of polyurethanes.
  • polyester diols preferably with molecular weights Mn of 800, in particular from 1400 to about 3500
  • bifunctional carbonic acid derivatives in as equimolar amounts as possible in vacuo (below 35 torr, preferred) at 25 to 1 torr) at a temperature between 100 ° C and 300 ° C, preferably 130 to 200 ° C, polycondensed in the presence of catalysts and the resulting condensation products are distilled off.
  • Mn number average
  • Reaction products of polyhydric alcohols with polyhydric aliphatic carboxylic acids are preferably those of dihydric and optionally additionally trihydric alcohols with preferably dihydric aliphatic carboxylic acids.
  • their anhydrides or esters with lower alcohols or their mixtures can also be used.
  • the polyvalent carboxylic acids are preferably acyclic. Examples include oxalic acid, malonic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, hexahydrophthalic anhydride, glutaric anhydride.
  • the polyhydric alcohols optionally in a mixture with one another, e.g. Ethylene glycol, propylene glycol- (1,2) and - (1,3, butylene glycol- (1,4) and - (2,3), hexanediol- (1,6), octanediol- (1,8), neopentylglycol, cyclohexanedimethanol , 1,4-bis (hydroxymethylcyclohexane), 2-methyl-1,3-propanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol and dibutylene glycol in question.
  • Ethylene glycol propylene glycol- (1,2) and - (1,3, butylene glycol- (1,4) and - (2,3)
  • hexanediol- (1,6), octanediol- (1,8) neopentylglycol
  • the reaction products obtained from these carboxylic acids and alcohols are polyesters with terminal hydroxyl groups. They have molecular weights of approximately 800 to approximately 3500, they can be symbolized by the formula HO-X-OH, where X has the meaning given above.
  • the polyesters according to the invention containing carbonate groups result from these polyesters with terminal hydroxyl groups by reaction with bifunctional carbonic acid aryl esters.
  • Suitable catalysts for the reaction of the hydroxyl group-containing polyesters and the carbonic acid aryl esters are the transesterification catalysts, such as, for example, alkali metal or alkaline earth metal phenates, alkali metal or alkaline earth metal alcoholates and tertiary amines, such as, for example, triethylenediamine, morpholine, pyrrolidine, pyridine, triethylamine or zinc compounds, such as antimony trioxide and antioxidant trioxide Titanium tetrabutyl ester.
  • the transesterification catalysts such as, for example, alkali metal or alkaline earth metal phenates, alkali metal or alkaline earth metal alcoholates and tertiary amines, such as, for example, triethylenediamine, morpholine, pyrrolidine, pyridine, triethylamine or zinc compounds, such as antimony trioxide and antioxidant trioxide Titanium tetrabutyl ester.
  • the catalyst is used in amounts of 20 to 200 ppm, based on the total weight of the polycondensation components.
  • the amount of catalyst can be fallen below if the starting products contain no basic impurities when using the acidic catalysts and no acidic impurities when using the basic catalysts;
  • the smallest possible amounts of catalyst are preferred in order to avoid the product's inherent color.
  • the reaction is preferably carried out in bulk, ie in the absence of solvents.
  • solvents which are inert under the reaction conditions such as hydrocarbons, in particular aromatic hydrocarbons, can also be used.
  • the reaction time depends on the reaction temperature, the type and amount of the catalyst used and on the desired molecular weight of the polyester containing carbonate groups. In general, 2 to 48 hours, preferably 4 to 24 hours, are sufficient.
  • the resulting volatile condensation products can be removed during the reaction, by batchwise distillation, in continuous mode by fractional distillation.
  • a mixture of polyester diol and bifunctional carbonic acid aryl ester, preferably diphenyl carbonate, or a mixture of diphenyl carbonate and compounds of the formula (11) is preferably polycondensed at 110 to 170 ° C. and then at 170 ° C. and higher by adding a bifunctional carbonic acid aryl ester to the sodium phenolate as catalyst Formula (11), preferably with n> 1, with simultaneous removal of volatile condensation products by distillation, increases the viscosity of the polycondensation mixture. It proved to be advantageous to carry out the polycondensation in high-viscosity reactors such as kneaders or screw machines.
  • the polycondensation can be carried out in a known manner, e.g. can be ended by lowering the reaction temperature, destroying or removing the catalyst or by means of so-called stoppers. It has proven to be advantageous to use carboxylic acid aryl esters in the case of alcohol end groups and alcohols as stoppers in the case of aryl carbonate end groups. If bifunctional compounds are used as stoppers, it is possible to terminate the polycondensation with an increase in the average molecular weight if the dosage is precise.
  • polyesters according to the invention can be used as polymeric plasticizers or additives for other plastics, their good rubber properties, aging resistance and excellent processability in a mixture with other plastics being particularly striking. Depending on the molecular weight and chemical composition, they can also be used as adhesives, sealing materials or for coating textiles.
  • reaction mixture is dissolved after cooling 120 ° C in 1 liter of toluene, 20 parts by weight of the above polyester diol is added with thorough mixing and the toluene is then evaporated off in vacuo, slowly increasing the internal temperature of the reaction mixture to 220 ° C; at this temperature the reaction mixture is dried for 2 hours in a vacuum and careful evaporation of all volatile products.
  • the colorless rubber-like material thus formed has a Staudinger index [ 1]] , measured in THF, of 1.35.
  • the product a colorless, rubbery mass, has a Staudinger index [q], measured in THF, of 1.3.

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)

Claims (1)

1. Des polyesters porteurs de groupes carbonate, qui sont formés de motifs structuraux récurrents de formule:
Figure imgb0007
dans laquelle
X est le reste d'un produit de réaction d'un alcool aliphatique polyvalent avec un acide carboxylique aliphatique polyvalent de poids moléculaire compris entre 800 et 3500,
X' es égal à X ou est le reste d'un polyéther aliphatique de poids moléculaire compris entre 800 et 3500,
n a une valeur de 0 ou 1 à 10 et
m est un nombre supérieur à 20,

la viscosité limite dans le tétrahydrofuranne ayant une valeur de 0,8 à 2,5
Figure imgb0008
EP78100380A 1977-07-20 1978-07-12 Polyesters renfermant des groupes carbonates Expired EP0000510B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2732718 1977-07-20
DE19772732718 DE2732718A1 (de) 1977-07-20 1977-07-20 Carbonatgruppen enthaltende polyester

Publications (2)

Publication Number Publication Date
EP0000510A1 EP0000510A1 (fr) 1979-02-07
EP0000510B1 true EP0000510B1 (fr) 1980-09-03

Family

ID=6014355

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100380A Expired EP0000510B1 (fr) 1977-07-20 1978-07-12 Polyesters renfermant des groupes carbonates

Country Status (5)

Country Link
US (1) US4192940A (fr)
EP (1) EP0000510B1 (fr)
JP (1) JPS5422494A (fr)
DE (2) DE2732718A1 (fr)
IT (1) IT1106853B (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2823161A1 (de) * 1978-05-26 1979-11-29 Bayer Ag Weichgemachte vinylchloridpolymerisate
US4506045A (en) * 1982-10-02 1985-03-19 Bayer Aktiengesellschaft Cellulose ester-aliphatic polycarbonate thermoplastic moulding compositions
DE3316851A1 (de) 1983-05-07 1984-11-08 Bayer Ag, 5090 Leverkusen Polymerisierbare dentalmassen und hieraus hergestellte dentalformkoerper
DE3322667A1 (de) * 1983-06-23 1985-01-10 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung hochmolekularer polyestercarbonate
DE3932949A1 (de) * 1989-10-03 1991-04-11 Bayer Ag Elasthanfasern hoher dehnbarkeit und festigkeit und ein verfahren zu ihrer herstellung
US5654380A (en) * 1994-05-23 1997-08-05 Mitsubishi Gas Chemical Company, Inc. Aliphatic polyester carbonate and process for producing the same

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1495626B1 (de) * 1960-03-30 1971-06-09 Bayer Ag Verfahren zum herstellen von polyestern
DE1301552B (de) * 1963-06-19 1969-08-21 Teijin Ltd Verfahren zur Herstellung von linearen Polyestern
FR1401635A (fr) * 1964-06-19 1965-06-04 Teijin Ltd Procédé de préparation de polyesters essentiellement linéaires
DE1964998C3 (de) * 1969-12-24 1979-02-15 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von Polyurethanelastomeren
DE2651639A1 (de) * 1976-11-12 1978-05-24 Bayer Ag Verfahren zur herstellung von kohlensaeureestern von polyesterpolyolen
DE2712435A1 (de) * 1977-03-22 1978-09-28 Bayer Ag Verfahren zur herstellung von kohlensaeurearylestern von ueber carbonat- gruppen-verlaengerten polyesterdiolen

Also Published As

Publication number Publication date
US4192940A (en) 1980-03-11
DE2732718A1 (de) 1979-02-15
EP0000510A1 (fr) 1979-02-07
JPS5422494A (en) 1979-02-20
DE2860136D1 (en) 1980-12-11
IT7850345A0 (it) 1978-07-18
JPS6256173B2 (fr) 1987-11-24
IT1106853B (it) 1985-11-18

Similar Documents

Publication Publication Date Title
DE60202449T2 (de) Copolycarbonatdiol und daraus erhaltenes thermoplastisches polyurethan
DE68925667T2 (de) Copolyester-Diol-Polycarbonate, Verfahren zu ihrer Herstellung und deren Verwendung
DE69513159T2 (de) Verfahren zur herstellung von polycarbonaten mit hydroxylendgruppen
DE2712435C2 (fr)
DE2651639A1 (de) Verfahren zur herstellung von kohlensaeureestern von polyesterpolyolen
DE1745695A1 (de) Verfahren zur Herstellung von linearen,thermoplastischen Mischpolyestern mit Erweichungstemperaturen ueber 100 deg.C
DE102014226785A1 (de) Polycarbonatdiol enthaltende Carbonatverbindungen
DE10321149A1 (de) Ytterbium(III)acetylacetonat als Katalysator zur Herstellung von aliphatischen Oligocarbonatpolyolen
EP0000510B1 (fr) Polyesters renfermant des groupes carbonates
EP0066167B1 (fr) Procédé de préparation d'oligouréthanes contenant des groupes mercapto, leur utilisation comme liant pour des masses de revêtement ou de calfatage durcissables par oxydation ou comme additif pour des résines époxydes
EP0105399B1 (fr) Compositions de moulage thermoplastiques
EP0164667A1 (fr) Composition thermoplastique à base de polyoxyméthylène et d'un polyester mixte adipati carbonate
EP0136396B1 (fr) Utilisation de polyétherols et de polyisocyanates séléctionnés pour la préparation de matieres adhesives à base de polyurethane
DE2408149C2 (fr)
EP0005736B1 (fr) Compositions de polychlorure de vinyle plastifiées
DE102004031900A1 (de) Oligocarbonatpolyole mit endständig sekundären Hydroxylgruppen
EP0024672A1 (fr) Polycarbonates segmentés, aromatiques, thermoplastiques à haut poids moléculaire préparés par condensation d'esters d'acides gras dimérisés, leur préparation et utilisation
EP0618248B1 (fr) Polymère contenant des groupes d'esters de l'acide carboxylique et d'esters de l'acide carbonique et procédé de fabrication
DE2650533C2 (de) Kohlensäurearylester von über Carbonat-Gruppen-verlängerten Polyalkylenoxiddiolen und Verfahren zu deren Herstellung
DE2619831A1 (de) Verfahren zur herstellung von kohlensaeurearylestern von polyalkylenoxidpolyolen
EP0837893B1 (fr) Production et utilisation d'oligocarbonates liquides derives de diols dimeres
DD148957A1 (de) Verfahren zur herstellung von hochmolekularen polyetheralkoholen
EP0346717B1 (fr) Procédé de production de feuilles de PVC rigide
EP0131164B1 (fr) Procédé pour la préparation de polyestercarbonates à poids moléculaire élevé
DE1570207A1 (de) Modifizierungsmittel fuer Polymerisate

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

17P Request for examination filed
AK Designated contracting states

Designated state(s): DE FR GB NL

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): DE FR GB NL

REF Corresponds to:

Ref document number: 2860136

Country of ref document: DE

Date of ref document: 19801211

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19900621

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19900628

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19900702

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19900731

Year of fee payment: 13

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19910712

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19920201

GBPC Gb: european patent ceased through non-payment of renewal fee
NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19920331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19920401

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT