GB819640A - Improvements in the manufacture of esters - Google Patents

Improvements in the manufacture of esters

Info

Publication number
GB819640A
GB819640A GB32433/55A GB3243355A GB819640A GB 819640 A GB819640 A GB 819640A GB 32433/55 A GB32433/55 A GB 32433/55A GB 3243355 A GB3243355 A GB 3243355A GB 819640 A GB819640 A GB 819640A
Authority
GB
United Kingdom
Prior art keywords
catalyst
lanthanum
ethylene glycol
acid
dimethyl
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
GB32433/55A
Inventor
Robert Morris Cavanaugh
Jane Bowen Dempster
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.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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
Priority to DEP14949A priority Critical patent/DE1002751B/en
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to GB32433/55A priority patent/GB819640A/en
Publication of GB819640A publication Critical patent/GB819640A/en
Expired legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/03Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/08Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78Preparation processes
    • C08G63/82Preparation processes characterised by the catalyst used
    • C08G63/84Boron, aluminium, gallium, indium, thallium, rare-earth metals, or compounds thereof

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

Polyesters are obtained by reacting at least one glycol having from 2 to 10 carbon atoms per molecule with at least one polycarboxylic acid or lower alkyl (C1-C4) ester thereof in the presence of a lanthanum-containing material other than lanthanum oxide as catalyst. The process is particularly suitable for the manufacture of polymeric ethylene glycol terephthalate from ethylene glycol and dimethyl terephthalate but blends of glycols, e.g. of ethylene glycol with diethylene glycol or pentaglycol (2,2-dimethyl-1,3-propanediol) may also be used as may the specified glycols alone. Mixtures of polycarboxylic acids, e.g. of terephthalic acid with isophthalic, sebacic, azelaic, suberic and adipic acid in the form of their lower alkyl esters may also be used as may the specified acids or their lower alkyl esters alone. Several forms of lanthanum may be used as catalyst, lanthanum in metallic form or a compound of lanthanum containing a radical of a weak acid or a radical of a volatile acid being particularly suitable. An additional esterification or transesterification catalyst such as materials containing antimony, germanium (e.g. GeO2), cerium (e.g. CeO2), calcium (e.g. Ca(OH)2), silicon (e.g. elemental silicon), cobalt, manganese, zinc or magnesium may also be present. The catalyst should preferably be appreciably soluble in the reaction medium either initially or during the course of the reaction and the amount of catalyst (calculated as the element) should preferably be between 0.001 mol. per cent and 0.07 mol. per cent of the polycarboxylic acid or its ester. In an example for the production of polymeric ethylene glycol terephthalate the monomer is first formed from dimethyl terephthalate and an excess of ethylene glycol in the presence of the lanthanum-containing catalyst the vapours distilling over being not allowed to exceed 70-75 DEG C. and suitable pot temperatures being 150-230 DEG C., e.g. 160-225 DEG C. The resulting monomer is polymerized in a tube provided with a side arm for distillation purposes and a capillary extending to the bottom of the tube through which pure dry nitrogen gas is introduced. A flask is connected to the side arm to collect the distillate, this flask being provided with a vacuum pump connection. Polymerization is effected by heating for several hours at 230-290 DEG C., e.g. at 265 DEG C., at 0.5 mm. Hg. pressure, and a table is given to show the results obtained when the polymerization is effected at 275 DEG C. using the formate, acetate, trifluoro-acetate, nitrate, phthalate, chloride, benzoate, benzene sulphonate, sulphate, and oxalate of lanthanum respectively as catalyst, the formate, trifluoroacetate, phthalate and benzoate being used in admixture with Sb2O3 as auxiliary catalyst and the chloride being used alone and in admixture with Sb2O3. The results obtained in a comparative example using lead oxide as catalyst are also tabulated. The results show that the lanthanum-containing catalysts generally give an improved reaction rate and a less-coloured product than is obtained when lead oxide is used and that the lanthanum salts of non-volatile strong acids (the oxalate, sulphate and benzene sulphonate) have only a low degree of catalytic activity. The Sb2O3 used as auxiliary catalyst is added after the first alcoholysis stage is completed and before the polymerization stage is begun. Other specified reactions in which the lanthanum-containing material may be used as catalyst are the ester-exchange reactions between (1) ethylene glycol and dimethyl sebacate; ethylene glycol and a 50-30 mixture of dimethyl terephthalate and dimethyl sebacate; (3) diethylene glycol and dimethyl terephthalate; (4) a 90-10 mixture of ethylene glycol and pentaglycol and dimethyl terephthalate; (5) ethylene glycol and isophthalic acid; and (6) ethylene glycol and terephthalic acid. Other specified esters which may be used are diethyl and dibutyl terephthalates. Specification 769,220 is referred to.ALSO:Esters of polycarboxylic acids are obtained by reacting at least one glycol having from 2 to 10 carbon atoms per molecule with at least one polycarboxylic acid or lower alkyl (C1-C4) ester thereof in the presence of a lanthanum-containing material other than lanthanum oxide as catalyst. The process is applicable to the production of monomeric and polymeric esters and is particularly suitable for the manufacture of monomeric and polymeric ethylene glycol terephthalate from ethylene glycol and dimethyl terephthalate but blends of glycols, e.g. of ethylene glycol with diethylene glycol or pentaglycol (2,2-dimethyl-1,3-propanediol) may also be used as may the specified glycols alone. Mixtures of polycarboxylic acids, e.g. of terephthalic acid with isophthalic, sebacic, azelaic, suberic and adipic acid in the form of their lower alkyl esters may also be used as may the specified acids or their lower alkyl esters alone. Several forms of lanthanum may be used as catalyst, lanthanum in metallic form or a compound of lanthanum containing a radical of a weak acid or a radical of a volatile acid being particularly suitable. An additional esterification or transesterification catalyst such as materials containing antimony, germanium (e.g. GeO2), cerium (e.g. CeO2), calcium (e.g. Ca(OH)2), silicon (e.g. elemental silicon), cobalt, manganese, zinc or magnesium may also be present. The catalyst should preferably be appreciably soluble in the reaction medium either initially or during the course of the reaction and the amount of catalyst (calculated as the element) should preferably be between 0.001 mol. per cent and 0.07 mol. per cent of the polycarboxylic acid or its ester. In an example for the production of monomeric ethylene glycol terephthalate from dimethyl terephthalate and an excess of ethylene glycol in the presence of the lanthanum-containing catalyst the vapours distilling over are not allowed to exceed 70-75 DEG C. and suitable pot temperatures are 150-230 DEG C., e.g. 160-225 DEG C. The resulting monomer may be polymerized in a tube provided with a side arm for distillation purposes and a capillary extending to the bottom of the tube through which pure dry nitrogen gas is introduced. A flask is connected to the side arm to collect the distillate, this flask being provided with a vacuum pump connection. Polymerization is effected by heating for several hours at 230-290 DEG C., e.g. at 265 DEG or 275 DEG C., at 0.5 mm. Hg pressure, and a table is given to show the results obtained when the polymerization is effected at 275 DEG C. using the formate, acetate, trifluoroacetate, nitrate, phthalate, chloride, benzoate, benzene sulphonate, sulphate, and oxalate of lanthanum respectively as catalyst, the formate, trifluoroacetate, phthalate and benzoate being used in admixture with Sb2O3 as auxiliary catalyst and the chloride being used alone and in admixture with Sb2O3. The results obtained in a comparative example using lead oxide as catalyst are also tabulated. The results show that the lanthanum-containing catalysts generally give an improved reaction rate and a less coloured product than is obtained when lead oxide is used and that the lanthanum salts of non-volatile strong acids (the oxalate, sulphate and benzene sulphonate) have only a low degree of catalytic activity. The Sb2O3 used as auxiliary catalyst is added after the first alcoholysis stage is completed and before the polymerization stage is begun. Other specified reactions in which the lanthanum-containing material may be used as catalyst are the ester-exchange reactions between (1) ethylene glycol and dimethyl sebacate, (2) ethylene glycol and a 50-30 mixture of dimethyl terephthalate and dimethyl sebacate, (3) diethylene glycol and dimethyl terephthalate, (4) a 90-10 mixture of ethylene glycol and pentaglycol and dimethyl terephthalate, (5) ethylene glycol and isophthalic acid, and (6) ethylene glycol and terephthalic acid. Other specified esters which may be used are diethyl and dibutyl terephthalates. Specification 769,220, [Group IV (a)], is referred to.
GB32433/55A 1954-11-15 1955-11-14 Improvements in the manufacture of esters Expired GB819640A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DEP14949A DE1002751B (en) 1954-11-15 1955-10-08 Process for the preparation of monomeric and polymeric polycarboxylic acid glycol esters
GB32433/55A GB819640A (en) 1954-11-15 1955-11-14 Improvements in the manufacture of esters

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US1138419XA 1954-11-15 1954-11-15
GB32433/55A GB819640A (en) 1954-11-15 1955-11-14 Improvements in the manufacture of esters

Publications (1)

Publication Number Publication Date
GB819640A true GB819640A (en) 1959-09-09

Family

ID=26261373

Family Applications (1)

Application Number Title Priority Date Filing Date
GB32433/55A Expired GB819640A (en) 1954-11-15 1955-11-14 Improvements in the manufacture of esters

Country Status (2)

Country Link
DE (1) DE1002751B (en)
GB (1) GB819640A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3060223A (en) * 1960-03-17 1962-10-23 Standard Oil Co Preparation of dihydroxyethyl terephthalate
CN101328261B (en) * 2008-07-29 2011-01-12 南京工业大学 Preparation of high molecular weight poly(butylene succinate)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1168888B (en) * 1958-12-27 1964-04-30 Kemijska Ind Zajednica Process for the production of bis-hydroxyethyl terephthalate
BE630421A (en) * 1962-03-31

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3060223A (en) * 1960-03-17 1962-10-23 Standard Oil Co Preparation of dihydroxyethyl terephthalate
CN101328261B (en) * 2008-07-29 2011-01-12 南京工业大学 Preparation of high molecular weight poly(butylene succinate)

Also Published As

Publication number Publication date
DE1002751B (en) 1957-02-21

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