AT201854B - Process for the production of polyesters - Google Patents

Description

  

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  Process for the production of polyesters
The invention relates to lactone polyesters which can be used as plasticizers and as intermediates in the manufacture of elastomers and foams.



   It has been discovered that lactones can be polymerized to polyesters of very different and easily manageable molecular weights in the presence or absence of an ester interchange catalyst. The polyesters obtained in this way are characterized by the presence of recurring lactone residues and, at least initially, by one or more terminal hydroxyl groups. They are particularly useful as intermediates for the reaction with diisocyanates for the production of elastomers and foams, especially if at least a considerable part of the lactone radicals is substituted; in addition, they are very useful as plasticizers for vinyl halide and other resins.



   The lactone polyesters prepared in accordance with this invention include polyesters of individual unsubstituted and substituted lactones, mixed polyesters of various substituted lactones, and mixed polyesters of substituted and unsubstituted lactones, and mixtures thereof.



   Any lactone or any mixture of lactones containing at least six carbon atoms in the ring and represented by the general formula can be used as the starting material
 EMI1.1
 are represented in which n is at least 4, at least n + 2 R are hydrogen and the other R are substituents, u. between hydrogen, alkyl, cycloalkyl or alkoxy radicals or radicals of single ring aromatic hydrocarbons. Lactones which have a larger number of substituents on the ring with the exception of hydrogen, and lactones with five or fewer hydrocarbon atoms in the ring are regarded as unsuitable for the purposes of the invention because their polymers tend to regress to the monomers, particularly at elevated temperatures.



   In the context of the invention, preference is given to c-caprolactones of the general formula
 EMI1.2
 used in which at least 6 R are hydrogen and the remaining R hydrogen or alkyl, cycloalkyl or alkoxy radicals or radicals of single-ring aromatic hydrocarbons, none of the substituents containing more than about twelve carbon atoms and the substituents on a lactone ring not more than about twelve carbon atoms in total exhibit. Unsubstituted caprolactone, in which all R's are hydrogen, is derived from 6-oxyhexanoic acid. Substituted e-caprolactones

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 and mixtures thereof are obtained when a corresponding substituted cyclohexanone is reacted with an oxidizing agent such as peracetic acid.

   The cyclohexanones can be obtained from substituted phenols or by other synthetic methods.



   The substituted E-caprolactones which are most suitable for the purposes of the invention include the various monoalkyl-e-caprolactones, e.g. B. monomethyl, monoethyl, monopropyl, monoisopropyl, etc. to monododecyl-E-caprolactone, also dialkyl-e-caprolactones, in which the two alkyl groups are substituted on the same or different carbon atoms, but not both on the # -Carbon atom; Trialkyl - # - caprolactones in which two or three carbon atoms of the lactone ring are substituted, provided the e-carbon atom is not disubstituted;

   Alkoxy-e-caprolactones such as methoxy- and ethoxy-# -caprolactone and cycloalkyl, aryl and aralkyl-e-caprolactones, such as cyclohexyl-, phenyl- and benzyl-e-caprolactone.



   Lactones with more than 6 carbon atoms in the ring, e.g. B. # -onantholactone and # -caprylolactone can also be polymerized by the process of the invention.
 EMI2.1
 Position of polyurethanes are to be used, it is generally preferred to use mixtures of substituted and unsubstituted lactones in order to achieve the best aging resistance. If, on the other hand, the lactone polyesters are to be used as plasticizers, the best results are obtained with polyesters made from monomethyl-substituted lactones and with mixed polyesters of unsubstituted and monomethyl-substituted lactones.

   In general, the choice of the lactone or lactone mixture used as starting material is unlimited, provided that the tendency of highly substituted lactones to regress to the monomeric forms, which exists particularly at higher temperatures, is taken into account.



   According to the process of the invention, the polymerization of the lactone is initiated by reaction with one or more compounds which have at least one reactive constituent which, with or without the support of a catalyst, is able to open the lactone ring and without the formation of water of condensation in the form of an open chain to attach to itself. Compounds which are suitable for initiating the polymerization and are hereinafter referred to as introduction compounds include monofunctional introduction compounds such as alcohols and amines, and polyfunctional introduction compounds such as polyols, polyamines, amino alcohols and vinyl polymers, and also amides, sulfonamides, hydrazones, semicarbazones, oximes, polycarboxylic acids, oxycarboxylic acids and aminocarboxylic acids.



   The alcohols suitable as monofunctional introductory compounds include primary, secondary and tertiary aliphatic alcohols such as methanol, ethanol, propanol, isopropanol, 1-butanol,
 EMI2.2
 and cycloaliphatic alcohols such as cyclohexanol and trimethylcyclohexanol.



   The amines suitable as monofunctional introductory compounds include primary and secondary aliphatic amines such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-butyl Amyl-, n-hexyl- and 2-ethylhexylamine and the corresponding dialkylamines; aromatic amines such as aniline, orthotoluidine, metatoluidine and diphenylamine;

   cycloaliphatic amines such as cyclohexyl- and dicyclohexylamine and heterocyclic amines such as pyrrolidine, piperidine and morpholine.
 EMI2.3
 
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    (CH2) nOH, 4,4'-methylenebiscyclohexanol
 EMI3.1
 4,4'-isopropylidenebiscyclohexanol
 EMI3.2
 various xylenediols
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 EMI3.4
 
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 EMI3.7
 phenethyl alcohol and various phenylene diethanols
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 various phenylenedipropanols
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 and various heterocyclic diols such as 1,4-piperazine diethanol
 EMI4.1
 
Other suitable diols are polyoxyalkylated derivatives of difunctional compounds having two reactive hydrogen atoms.

   These difunctional compounds can contain primary or secondary hydroxyls, phenolic hydroxyls, primary or secondary amino groups, amido, hydrazino, guadino, ureido, mercapto, sulfino, sulfonamide or carboxyl groups. They are available by
 EMI4.2
 (CHz) ethanol; dibasic acids such as maleic, succinic, glutamine, adipic, pimelic, sebacic, phthalic, tetrahydrophthalic and hexahydrophthalic acid; phosphorous acid; aliphatic, aromatic and cycloaliphatic primary monoamines such as methylamine, ethylamine, propylamine, butylamine, aniline, cyclohexylamine;

   secondary diamines such as N, N'-dimethylethylenediamine and amino alcohols containing a secondary amino group, such as N-methylethanolamine, reacts with alkylene oxides such as ethylene oxide, propylene oxide, 1-butylene oxide, 2-butylene oxide, isobutylene oxide, butadiene monoxide, styrene oxide and mixtures of these monoepoxides.



   The polyoxyalkylated derivatives suitable for the purposes of the invention can be prepared, for example, by reacting 1,4-butanediol with ethylene oxide:
 EMI4.3
 where x + y = 1 - 40.



   Polymers of monoepoxides which are obtained by polymerization using catalysts such as the oxonium salts of hydrogen halides are also suitable as bifunctional introductory compounds; metallic or non-metallic halides, the etherates of which form oxonium complexes, electrophilic metallic or non-metallic halides in the presence of hydrogen halides, acyl halides; or the anhydrides of inorganic and organic acids; and inorganic acids or their anhydrides, the anions of which have a low polarization tendency, are available.



  After the polymerization reaction has been carried out, polymers containing terminal hydroxyl groups can be obtained by treating these products with alkaline reagents. The monoepoxies suitable for the production of such polymers. include tetrahydrofuran, trimethylene oxide, propylene oxide, ethylene oxide, and mixtures thereof.



   The higher-functional alcohols suitable for initiating the polymerization of lactones by the process according to the invention include triols such as glycerol, trimethylolpropane, 1,2,4-butanetriol and 1,2,6-hexanetriol. N-triethanolamine and N-triisopropanolamine; various tetrols such as erythritol, pentaerythritol, N, N, N ', N'-tetrakis (2-oxyethyl) ethylene diamine
 EMI4.4
 and N, N. N '. N'-tetrakis (2-oxypropyl) ethylenediamine
 EMI4.5
 

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 Pentoles; Hexols such as dipentaerythritol and sorbitol; Alkyl glycosides and carbohydrates such as glucose, sucrose, starch and cellulose.



   The polyoxyalkylated derivatives of polyfunctional compounds are also used as polyols
 EMI5.1
 
 EMI5.2
 
 EMI5.3
 



   In addition to the polyoxyalkylated derivatives of trimethylolpropane, those of the following compounds are also suitable: glycerol, 1, 2, 4-butanetriol, 1, 2, 6-hexanetriol, erythritol, pentaerythritol, sorbitol, methyl glycosides, glucose, sucrose, diamines of the general formula H. N (CH,) NH, where n = 2 - 10, 2- (methylamino) ethylamine, various phenylene and toluene diamines, benzidine,
 EMI5.4
 of the general formula HO (CH) nNH, where n = 2-10, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polycarboxylic acids such as citric acid, aconitic acid
 EMI5.5
 Mellitic acid
 EMI5.6
 and pyromellitic acid
 EMI5.7
 and polyfunctional inorganic acids such as phosphoric acid.



   The difunctional amino alcohols which are suitable for initiating the polymerization of lactones include the aliphatic amino alcohols of the general formula HO (CH2) nNH2, where n = 2-10, N-methylethanolamine
 EMI5.8
 Isopropanolamine
 EMI5.9
 N-methylisopropanolamine
 EMI5.10
 

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 aromatic amino alcohols such as para-amino-phenethyl alcohol
 EMI6.1
 and para-amino-?

  -methylbenzyl alcohol
 EMI6.2
 and various cycloaliphatic amino alcohols such as 4-amino-cyclohexanol
 EMI6.3
 
The higher-functional amino compounds with a total of at least three hydroxyl and primary or secondary amino groups suitable for the process according to the invention include diethanolamine, diisopropanolamine, 2- (2-aminoethylamino) ethanol HNCHC -NH-CUCELOH, 2-amino-2- (oxymethyl) -1 , 3-propanediol
 EMI6.4
 
Suitable diamines include the aliphatic diamines of the general formula R "NH (CH2) nNH2 and disecondary diamines of the general formula R" NH (CH,) nNHR ", where n = 1-10 and R" is an alkyl, aryl, aralkyl or is cycloalkyl;

   aromatic diamines such as metaphenylenediamine, paraphenylenediamine, toluene-2,4-diamine, toluene-2,6-diamine, 1,5-naphthalenediamine.



    1,8-naphthalenediamine, metaxylylenediamine, paraxylylenediamine, benzidine, 3,3'-dimethyl-4 ,. 4'-biphenyldiamine, 3, 3'-dimethoxy-4,4'-biphenyldiamine, 3,3'-dichloro-4,4'-biphenyldiamine, 4,4'-methylenedianiline, 4,4'-ethylenedianiline, 2,3, 5,6-tetramethylparaphenylenediamine, 2,5-fluorenediamine and 2,7-fluorenediamine;

   cycloaliphatic diamines such as 1,4-cyclohexanediamine, 4,4'-methylenebiscyclohexylamine and 4,4'-isopropylidenebiscyclohexylamine and heterocyclic amines such as piperazine, 2,5-dimethylpiperazine and 1,4-bis (3-aminopropyl) piperazine
 EMI6.5
 
Examples of higher functional polyamines which can be used in the process according to the invention are diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, tripropylene

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 tetramine, tetrapropylenepentamine, 1, 2, 5-benzene triamine, toluene-2, 4, 6-triamine and 4, 4 ', 4 "-methylidyntrianiline
 EMI7.1
 
 EMI7.2
 
 EMI7.3
 
 EMI7.4
    Interaction R2 is H or an alkyl.



   Lactones are also capable of reacting with and polymerizing on vinyl polymers which contain reactive hydrogen atoms in side groups along the polymer molecule, particularly in hydroxyl and primary and secondary amino groups. Such vinyl polymers are e.g. B. obtainable by the copolymerization of ethylene and vinyl acetate with subsequent saponification of the acetate groups, with polymers of the following formula
 EMI7.5
 can be obtained.



   Other suitable vinyl polymers are polyvinyl alcohol and copolymers obtainable by interpolymerizing a vinyl monomer such as ethylene with other vinyl monomers which contain primary or secondary hydroxyl or amino groups or other groups with reactive hydrogen atoms. The vinyl monomers with which such copolymers can be obtained include, for. B.

   Orth, meta and para aminostyrene

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 EMI8.1
 
 EMI8.2
 
 EMI8.3
 
 EMI8.4
 
 EMI8.5
 
 EMI8.6
 
 EMI8.7
 
 EMI8.8
 
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 EMI8.10
 
 EMI8.11
 
 EMI8.12
 
 EMI8.13
 
 EMI8.14
 
 EMI8.15
 

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 Citric acid, hemimellitic acid, trimellitic acid, pyromellitic acid, 1, 2, 3, 4-butanetetracarboxylic acid HOOC - # - CH2COOH
COOH COOH
Suitable oxy- and aminocarboxylic acids include 2-oxypropionic acid, 6-oxycaproic acid, 11-oxyundecanoic acid, salicylic acid, paraoxybenzoic acid, ß-alanine, 6-aminocaproic acid, 7-amino
 EMI9.1
 
It is believed that the initiator compound opens the lactone ring to form an ester or amide with one or more terminal groups,

   which are suitable for opening further lactone rings and thus for the addition of an ever increasing amount of lactone to the molecule.



  For example, it is assumed that the polymerization of e-caprolactone initiated with an amino alcohol proceeds primarily as follows:
 EMI9.2
 
 EMI9.3
 matic or heterocyclic aromatic radical and a = b i-c.



   Similarly, a monoamine opens a series of lactone rings and attaches them to itself, as in the equation
 EMI9.4
 is shown. A dicarboxylic acid takes part in the polymerization of lactones roughly as follows:
 EMI9.5
 where x has the average value a / 2.



   From these equations it can be seen that the lactone polyesters produced according to this embodiment of the process according to the invention are expediently represented by the general formula
 EMI9.6
 can be represented in which L is an essentially linear term with the general formula
 EMI9.7
 means in which n is at least 4 and at least n + 2 R are hydrogen and the other R are substituents consisting of hydrogen or alkyl, cycloalkyl or alkoxy radicals or radicals of single ring aromatic hydrocarbons, the total number of carbon atoms in the substituents on a given radical does not exceed about twelve. The subscript x has the average value 2 and is preferably so large that the total molecular weight of the polyester is about 1500 or more.

   The number of present in the final polyester

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 linear groups is highly dependent on the molar ratio between lactone and the initiator compound. R 'is the organic radical from the initiator compound and y is a number equal to the functionality of the initiator compound; H. at least 1. Y means -O -, - NH-,
 EMI10.1
 
 EMI10.2
 



   In order to initiate and maintain the polymerization of the lactone, the lactone and the initiating compound are preferably heated to a temperature between about 1300 and 2000 ° C. so that a suitable reaction rate with minimal decomposition is obtained. However, the temperature can be much lower and needs e.g. B. to be only about 500 C, but this is at the expense of the reaction rate. The temperature can also be considerably higher, i.e. H. up to about 300 ° C., but great care must be taken at these higher temperatures, because above 2500 ° C. losses can easily occur as a result of decomposition or undesired side reactions.

   In general, it is therefore possible to work in a temperature range from 50 to 3000 ° C., but work is preferably carried out in a narrower range from about 130 to 200 ° C.



   To accelerate the reaction, the polymerization is preferably carried out with the aid of a catalyst, e.g. B. with a basic or neutral ester exchange catalyst carried out. Catalysts suitable for this purpose include metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, barium, strontium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic and cerium, as well as their Alkoxides. In addition, such as catalysts. B. the carbonates of alkali and alkaline earth metals, zinc borate, lead borate, zinc oxide, lead silicate, lead arsenate, black lead, lead carbonate, antimony trioxide, germanium dioxide, cerium dioxide, cobalt acetate and aluminum isopropoxide are suitable.

   The catalyst can be used in concentrations from about 0.001 to 0.50/0, preferably from 0.01 to 0.2ufo, based on the weight of the starting lactone.



   In the polymerization of the more difficult to polymerize lactones, such as. B. e-methyl-e-caprolactone and the various dimethyl-e-caprolactone without excessive discoloration of the polyester, zinc borate, lead borate, zinc oxide, black lead and especially organic titanium compounds are used because of their particularly high effectiveness.



   Because of their ability to promote the formation of practically colorless polyesters in a short time, titanates with the general formula are particularly used as catalysts
 EMI10.3
 is used in which X is an alkyl, aryl or aralkyl radical, those alkyl titanates in which
 EMI10.4
 Particularly noteworthy titanates in accelerating the reaction and producing practically colorless polyesters are tetraisopropyl titanate and tetrabutyl titanate.



   The duration of the polymerization is between a few minutes to about a week, depending on the lactone or lactone mixture selected, the initiating compound, the reaction temperature and, if appropriate, the catalyst. In order to obtain a better colored product, the reaction is preferably carried out in the absence of oxygen. For this purpose you can z. B. work in a partial vacuum or in the presence of an inert gas such as nitrogen, which is passed through the reaction mixture. After the polymerization has been completed, any unreacted monomer present can be removed by applying a vacuum at an elevated temperature, e.g. B. a vacuum of 1 to 5 mm Hg at 120-1600 C, can be eliminated.



   The polymerization products or polyesters obtained according to the invention generally have molecular weights above 1500, preferably in the range from about 1500 to about 7000, but are also

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 Molecular weights below or considerably above this range can be achieved if this is desired. The polyesters also have reactive terminal hydroxyl or carboxyl groups, the number of which depends on the functionality of the lead compound. They are characterized by the presence of rows of interconnected substantially linear members composed of carbon, hydrogen and oxygen.

   The linked links are open lactone residues each with a terminal oxy group at one end, a carbonyl group at the other end, an intermediate chain of at least 5 carbon atoms and at least one hydrogen substituent on the carbon atom of the intermediate chain connected to the terminal oxy group. The oxy group of one lactone radical is connected to the carbonyl group of an adjacent lactone radical in the series and the oxy group of the last lactone radical in the series is, unless a polycarboxylic acid was used as an introductory compound, connected to a hydrogen to a terminal hydroxyl group at one end of the series.



   The polyesters obtained with polyfunctional lead-in compounds and having two or more reactive groups are suitable for reaction with isocyanates to form polyurethanes of high molecular weight and better properties, which can be foamed or unfoamed as desired, produced as elastomers or in rigid form, and can be used as coating material are.



  The elastomeric products are characterized by a particularly high flexibility at low temperatures and by an unlimited shelf life without premature hardening, especially when they are made from mixed polyesters of two or more lactones. In addition, the polyesters obtained according to the invention, including those with only one reactive terminal group, are excluded.
 EMI11.1
 Polyvinyl butyral and polyvinyl chloride are particularly suitable when the polyesters are esterified in a known manner in order to make the terminal hydroxyl or carboxyl groups insoluble and thus to improve their resistance to extraction with water from resins with which they are combined.



   As plasticizers, the lactones obtained according to the invention have the unique advantage, not previously achieved in the development of plasticizers, that they have excellent behavior at low temperatures, in particular ensuring high flexibility of the resins even at freezing temperatures with low volatility and high resistance to extraction Combine water and oil. They are available as easily pourable liquids and can therefore be easily manipulated and mixed compared to the viscous, non-pourable plasticizers available up to now. At the same time, the plasticizers obtained according to the invention are non-toxic and lightfast.



   The production of plasticizers by the process of the invention has a number of particular advantages. A unique advantage that is extremely important for the use of polyesters as intermediates in the production of polyurethanes is that, with the catalysts used and without catalysts, the polyesters are formed with reactive end groups that are not in any substantial degree due to ester groups, chlorine or the like . are blocked. Another important advantage is that no water of condensation is formed and therefore no drying is required before the reaction with a diisocyanate.

   In addition, the method according to the invention has the advantage that it enables precise control of the average molecular weight of the polyester and favors the formation of an essentially homogeneous polyester in which the molecular weights of essentially all individual molecules essentially come very close to the average molecular weight. This regulation takes place through a choice of the molar ratio between lactone and introductory compound, which is easily made by the person skilled in the art. If it is z.

   B. it is desired to obtain a polyester in which the average molecular weight is about 20 times as large as the molecular weight of the starting lactone or lactone mixture, then the ratio of the lactone or lactone mixture to the initiating compound in the polymerization is selected to be about 20: 1, because it is to be expected that, on average, approximately the same number of lactones will attach to each molecule of the introductory compound and that there will be an average of 20 lactone molecules per molecule of the introductory compound.



   A simple method of determining the molecular weight of the polyester is to determine the average number of carboxyl and hydroxyl groups present in a given amount of the polyester. The acid number (mg KOH per g polyester, with phenolphthalein as an indicator) is a measure of the number of terminal carboxyl groups present in a polyester. The hydroxyl number, which is a measure of the terminal hydroxyl groups and expressed in mg KOH per g polyester

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 can be determined by adding pyridine and acetic anhydride to the polyester and titrating the acetic acid formed with KOH, as described in Ind. Eng. Chem., Anal. Ed., On pp. 541-549 in volume 16 and on p. 394 in volume 17.

   The sum of the acid or carboxyl number and the hydroxyl number is called the reactivity number. This indicates the average number of terminal groups present in the polyester and is therefore also a measure of the number of molecules present in the mass and the degree of polymerization. A polyester with long chain molecules will have a relatively low reactivity number, while a polyester with short chain molecules will have a relatively high reactivity number.



   If the polyesters are intended for use as intermediate products in the production of polyurethane elastomers, foams or coating materials, a mixture of substituted and unsubstituted lactones and a polyfunctional introductory compound which does not contain any carboxylic acid groups are preferably used. The quantity ratio between lactone and lead compound should be chosen so that polyester is formed with the lowest possible carboxyl number, which should definitely not be higher than 10, and a hydroxyl number between about 40 and about 60, so that the average molecular weight of the polyester is roughly in the range from 1900 to 2800.

   This molecular weight range is preferred because linearly stretched polyester-polyurethane diisocyanate chains of optimal length are obtained and the formation of an elastomer is favored, which has optimal properties with regard to a low embrittlement temperature and high tensile strength and age-hardening resistance. It goes without saying, however, that the molecular weights can also be considerably below or above this range, u. between down to about 300 (corresponding to the hydroxyl number 374), if a higher rigidity is desired, and up to 5000 or even 7000; corresponding to the hydroxyl number 16) when high elasticity is more important than high tensile strength.



   If the polyesters are intended for use as intermediates in the production of foamed polyurethane elastomers, carboxylic acid groups, preferably polyfunctional introduction compounds containing polycarboxylic acids, can be used in proportions to the lactones such that polyesters are formed which have terminal carboxylic acids and a molecular weight between about 500 and own about 9000.



   If the polyesters are to be used as plasticizers, the lead compound can be mono- or polyfunctional and the identity of the functional groups of the lead compound is not particularly critical. The molecular weight can be between about 1,500 and about 9,000, but molecular weights of up to 20,000 and above can readily be used when using reactive vinyl polymers as initiator compounds. Optimal plasticizer properties, in particular a lower viscosity and minimal discoloration, are obtained with polyesters which have molecular weights between about 2000 and about 4009 and were obtained from monomethyl-substituted lactones and mixtures thereof with unsubstituted lactones using glycols as introductory compounds.

   The lactone polyesters are in themselves very suitable as plasticizers, especially for vinyl resins, but in this respect they can easily be improved by acylating or esterifying their reactive terminal groups in order to increase the resistance to extraction with water. Terminal carboxylic acid groups can in a known manner by reaction with higher boiling alcohols, for. B. 2-ethyl-l-
 EMI12.1
 ether, be esterified. Terminal hydroxyl groups can readily be esterified by reaction with acids such as acetic and ethylhexanoic acid, preferably in the form of their anhydrides.



   The advantages and the usefulness of the process according to the invention and the products that can be achieved therewith emerge further from the detailed examples below, in which preferred embodiments, examples of the invention, are described. The hydroxyl and carboxyl numbers mentioned in the examples were determined according to the method described in Ind. Eng. Chem., Anal. Ed., Vol. 17, p. 394 (1945).



   Example 1: 193 g of e-caprolactone and 7.5 g of 3-aminopropanol were heated to 240-2600 ° C. for 24 hours under a stream of nitrogen. The polymer obtained was a waxy solid substance. When the molecular weight was determined in boiling toluene, values of about 1630 were obtained.
 EMI12.2
 heated. The polymer obtained was a waxy solid substance. When the molecular weight was determined in boiling toluene, values of about 2870 were obtained.

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   Example 3: 184 g of e-caprolactone and 16 g of pimelic acid were heated to 240-280 ° C. for 32 hours. The polymer obtained was a waxy solid substance. The titration of the terminal carboxyl groups gave a molecular weight of 1550 for the polymer.



     Example 4: 221 g of γ-methyl-e-caprolactone and 7.1 g of ethylene glycol were heated to 150-180 for 48 hours under flowing nitrogen together with 0.005 g of potassium carbonate. The polymer obtained was a slightly yellowish viscous liquid with the hydroxyl number 54.1 and the carboxyl number 0.1.



     Example 5: 100 g of a mixture of ss, ss', 6-trimethyl-e-caprolactone and ss, 6, 5'-trimethyl-e-caprolactone and 3.2 g of ethylene glycol, together with 0.1 g of sodium heated to 1800 C for 36 hours under a stream of nitrogen. The product was then de-iced under a vacuum of 3 mm Hg at a temperature of 108 to 1600 ° C. The polymer was a viscous liquid with a hydroxyl number of 69.



   Example 6 100 g of the lactone mixture according to Example 5, 57 g of e-caprolactone and 3.9 g of ethylene glycol were heated to 1700 ° C. for five hours under nitrogen together with 0.07 g of tetrabutyl titanate. A reddish-brown liquid with a hydroxyl number of 47.2, a carboxyl number of 0.95 and a molecular weight of 2280 was obtained as the product.



     Example 7: 100 g of the lactone mixture according to Example 5 and 3, 2 g of ethylene glycol were heated together with 0.1 g of antimony trioxide for 72 hours at 175-1800 ° C. under nitrogen. The product was de-iced under a vacuum of 3 mm Hg at 120-1600 ° C. The polymer was a brown, viscous liquid with a hydroxyl number of 60.4.



     Example 8: 140 g of a mixture of β-methyl-, γ-methyl- and 6-methyl-e-caprolactone and 3.7 g ethylene glycol were heated to 170-1800 ° C. for 86 hours under nitrogen together with 0.01 g calcium . A viscous yellow liquid with the hydroxyl number 49.8 and the carboxyl number 1.0 was obtained as the polymer.



     Example 9: 200 g of e-caprolactone and 6.2 g of ethylene glycol were heated to 1700 ° C. for 40 hours under nitrogen. The polymer obtained was a waxy solid substance with a hydroxyl number of 54.4 and a carboxyl number of 1.0.



   In the examples given below, the various initiating compounds, lactones and catalysts were mixed together in various amounts and heated to a controlled temperature of 1700 C while a gentle stream of nitrogen was passed through the mixture to keep air and moisture away, thereby discolouring the polyester Oxygen was prevented. After the polymerization, the refractive index was measured at 300 ° C. and the reaction was considered complete when the refractive index became constant. The catalysts used in each case, the amounts used, the polymerization time and the hydroxyl and carboxyl numbers and color of the polyesters obtained are indicated.



   Example 10:
Lactone 85 g cc and e-methyl-e-caprolactone and
245 g of ss-, γ- and 5-methyl-e-caprolactone
Introductory compound 9, 15 g of ethylene glycol
Catalyst 0.20 g calcium methoxide
Reaction time 20 hours
Hydroxyl number 47.2
Carboxyl number 1.9
Viscosity low
Color yellow.



   Example 11:
Lactones 120 g e-caprolactone and 120 g ss-, y- and 6-methyl-e-caprolactone
Introductory connection 90 g polyethylene glycol (average molecular weight 600)
Catalyst 0.20 g zinc borate
Response time 3.0 hours
Hydroxyl number 47.5
Carboxyl number 1, 4
Viscosity low
Color yellow.

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  Example 12: Lactones 100 g of E: -caprolactone and 250 g of ss-, γ- and 6-methyl-e-caprolactone introductory compound 85 g of polypropylene glycol (average molecular weight 425) catalyst 0.1 g of tetraisopropyl titanate reaction time 1.0 hour hydroxyl number 51.4 carboxyl number 0.6 viscosity low color light yellow.



  Example 13: Lactones 80 g of α - and # -methyl - # - caprolactone and
160 g of ss-, y- and 6-methyl-e-caprolactone introductory compound 205 g of polypropylene glycol (average molecular weight 1025) catalyst 0.1 g of tetrabutyl titanate reaction time 6.0 hours hydroxyl number 51.6 carboxyl number 0.6 color yellow.



  Example 14: Lactones 30 g of E-caprolactone and 70 g of ss-, γ- and 6-methyl-E-caprolactone introductory compound 4.6 g of p-xylene-a-a'-diol catalyst 0.05 g of black lead reaction time 2.0 Hours hydroxyl number 33, 5 carboxyl number 1, 1 color light brown.



  Example 15: Lactones 539 g # -caprolactone and 602 ss- and 6-methyl-e-caprolactone Introductory compound 31 g ethylene glycol catalyst 0.55 g calcium methoxide reaction time 24 hours hydroxyl number 48.4 carboxyl number 0.3 molecular weight 2280 color yellow.



  Example 16: Lactone 100 ss- and # -methyl - # - caprolactone
 EMI14.1
 Reaction time 1.25 hours hydroxyl number 46.7 carboxyl number 0.7 viscosity low color light brown.



  Example 17: Lactone 100 ss- and # -methyl - # - caprolactone lead compound 7, 9 g 4,4'-methylenedianiline catalyst 0.05 g black lead reaction time 16 hours hydroxyl number 40, 1 carboxyl number 1.0 viscosity high color light brown.

 <Desc / Clms Page number 15>

 
 EMI15.1
 Introductory compound 6, 1 g benzidine catalyst 0.05 g zinc borate reaction time 4 hours hydroxyl number 30, 6 carboxyl number 1, 3 viscosity- color waxy brown solid substance.



  Example 19: Lactones 90 g of a- and e-methyl-e-caprolactone and
260 g ss-, y- and 6-methyl-e-caprolacion initial compound 7.85 g 1,2,6-hexanetriol catalyst 0.075 g tetrabutyl titanate reaction time 20 hours hydroxyl number 24.4 carboxyl number 0.6 viscosity medium color yellow.



  Example 20:
 EMI15.2
 Catalyst 0.1 g zinc borate.



  Reaction time 17 hours hydroxyl number 38, 2
Carboxyl number 1, 4 viscosity medium color light yellow.



  Example 21: Lactones 100 g ss- and 6-methyl-e-caprolactone introductory compound 3.0 g N, N, N ', N'-tetrakis- (2-oxypropyl) ethylenediamine catalyst 0.03 g tetrabutyl titanate reaction time 17 hours hydroxyl number 19 , 9 carboxyl number 1, 0 viscosity high - color light brown.



  Example 22: Lactones 100α- and # -methyl- # -caprolactone and 250 g of ss-, γ- and 6-methyl-e-caprolactone Introductory compound 12, 0 g of diethylenetriamine, catalyst 0, 10 g of tetrabutyl titanate, reaction time 4 hours, hydroxyl number 50, 4 carboxyl number 2, 6 viscosity medium color yellow.



  Example 23: Lactones 100 g β- and # -methyl - # - caprolactone initial compound 2.0 g tetraethylene pentamine catalyst 0.05 g zinc borate reaction time 18 hours hydroxyl number 23.3 carboxyl number 2.6 viscosity high color brown.

 <Desc / Clms Page number 16>

 



  Example 24: Lactones 400 g of a mixture of dimethyl, ethyl, trimethyl, methyl ethyl and propyl caprolactone (made from a mixture boiling at 224-2290 ° C)
Xylenol fraction) Introductory compound 8, 45 g of ethylene glycol catalyst 0.2 g of tetrabutyl titanate reaction time 22, 5 hours hydroxyl number 36, 4 carboxyl number 1, 9 viscosity medium color reddish brown.



  Example 25:
 EMI16.1
 
Catalyst without
Response time 72 hours
Hydroxyl number 37, 3
Carboxyl number 0.3
Molecular weight 2950
Color yellow.



   Example 26:
Lactones 150 g of a mixture of cx-, 0-, y-, 6- and e-methyl-e-caprolactone (made from o-, m- and p-cresol) and 150 g of e-caprolactone
Introductory compound 11, 6 g aniline
Catalyst 0.15 g of tetraisopropyl titanate
Response time 18.5 hours
Hydroxyl number 22
Carboxyl number 0.3
Molecular weight 2480
Color pale brown.



   Example 27:
Lactone 150g e-caprolactone and 150 g of a mixture of dimethyl-e-caprolactones (produced from a xylenol fraction boiling at 212.5-219 C)
Introductory compound 57.6 g of di-2-ethylhexylamine
Catalyst 0 ', 15 g of black lead
Response time 24 hours
Hydroxyl number 35, la
Carboxyl number 1.6
Molecular weight 1465
Color yellow.



   The molecular weights of the products obtained according to Examples 10-27 were in the range from about 2,000 to 10,000. The molecular weight of each product can be determined using the hydroxyl and
 EMI16.2
 
 EMI16.3
 
 EMI16.4
 
 EMI16.5
 
 EMI16.6
 

 <Desc / Clms Page number 17>

 



   In most of the examples in which a brown color is indicated, lead-in compounds of technical quality were used, from which it can be seen that the brown color is not due to decomposition of the lactones during the polymerization but rather to impurities contained in the lead-in compound. Exceptions to this have been observed with the use of strongly basic ester exchange catalysts, which probably lead to some decomposition of the lactones on prolonged heating.



   Various typical substituted e-caprolactones were polymerized by heating them to different temperatures without a catalyst or with a catalyst in the typical concentrations given in the table below and an amount of ethylene glycol, which had been calculated with a view to achieving an average molecular weight of 2200 were. The concentrations are given in percent by weight based on the lactone. The procedure for each polymerization was such that the catalysts were added after the reactants had reached the specified temperature. To follow the progress of the reaction and to determine the polymerization time, the refractive index was determined, which becomes constant when the polymerization is complete.
 EMI17.1
 
<tb>
<tb>



  Concentration <SEP> of the <SEP> Temperature <SEP> Time,
<tb> c-Caprolactone <SEP> catalyst <SEP> catalyst, <SEP>% <SEP> C <SEP> hours
<tb> Mixture <SEP> of
<tb> α - <SEP> and <SEP> # -Methyl- <SEP> without <SEP> - <SEP> 170 <SEP> 102
<tb> "<SEP> tetrabutyl titanate <SEP> 0.1 <SEP>" <SEP> 1, <SEP> 75
<tb> 0, <SEP> 05 <SEP> "<SEP> 1.75
<tb> 0, <SEP> 01 <SEP> "<SEP> 2
<tb> 0, <SEP> 1 <SEP> 150 <SEP> 2, <SEP> 75 <SEP>
<tb> 0, <SEP> n <SEP> 0, <SEP> 05 <SEP> 11 <SEP> 5, <SEP> 25 <SEP>
<tb> 0, <SEP> 01 <SEP> "<SEP> 7.75
<tb> 0, <SEP> 1 <SEP> 130 <SEP> 7.75
<tb> 0.05 <SEP> "<SEP> 19
<tb> 0, <SEP> n <SEP> 0, <SEP> 01 .. <SEP> 16 <SEP>
<tb> ss <SEP>, <SEP> # -Dimethyl- <SEP> without <SEP> - <SEP> 170 <SEP> 102
<tb> "<SEP> tetraisopropyl titanate <SEP> 0, <SEP> 05 <SEP> tir <SEP> 0, <SEP> 5
<tb> Y <SEP> -Methyl- <SEP> without <SEP> - <SEP> It <SEP> 70 <SEP>
<tb> ..

   <SEP> Tetraisopropyl titanate <SEP> 0, <SEP> 05 <SEP> "<SEP> 0. <SEP> 25
<tb> Mixture <SEP> of
<tb> ss- <SEP> and <SEP> # -Methyl- <SEP> without <SEP> "<SEP>" <SEP> 29
<tb> "Tetraisopropyl titanate <SEP> 0, <SEP> 05 <SEP>" <SEP> 0, <SEP> 5
<tb> Mixture <SEP> of
<tb> α and <SEP> # -Methyl- <SEP> zinc borate <SEP> 0.1 <SEP> "<SEP> 7.75
<tb> ei <SEP> fI <SEP> 0, <SEP> 05 <SEP> tI <SEP> 10 <SEP>
<tb> 0, <SEP> 01 <SEP> "<SEP> 19
<tb> 0, <SEP> 05 <SEP> 150 <SEP> 23.5
<tb> 0, <SEP> 05 <SEP> 130 <SEP> 47
<tb> ss, <SEP> 6-dimethyl- "0, <SEP> 05 <SEP> 170 <SEP> 3.75
<tb> y-methyl- "0, <SEP> 05" 2 <SEP>
<tb> Mixture <SEP> of
<tb> ss- <SEP> and <SEP> # -Methyl- <SEP> "<SEP> 0.05 <SEP>" <SEP> 3.75
<tb> Mixture <SEP> of
<tb>?

  - <SEP> and <SEP> # -Methyl- <SEP> black lead <SEP> 0.1 <SEP> 170 <SEP> 7, <SEP> 25 <SEP>
<tb> er <SEP> 0, <SEP> 05 <SEP> It <SEP> 10 <SEP>
<tb> 0, <SEP> 01 <SEP> "<SEP> 19
<tb> 0, <SEP> 05 <SEP> 150 <SEP> 40
<tb> 0, <SEP> 05 <SEP> 130 <SEP> 59
<tb> Lead borate <SEP> 0, <SEP> 1 <SEP> 170 <SEP> 10.5
<tb> B, <SEP> # -Dimethyl- <SEP> black lead <SEP> 0.05 <SEP> 130 <SEP> 1.25
<tb> γ-methyl- <SEP> "<SEP> 0, <SEP> 05 <SEP> 170 <SEP> 1, <SEP> 75
<tb> Mixture <SEP> of
<tb> ss- <SEP> and <SEP> # -Methyl- <SEP> "<SEP> 0.05 <SEP>" <SEP> 1.25
<tb> Mixture <SEP> of
<tb>?

  - <SEP> and <SEP> # -Methyl- <SEP> aluminum isopropoxide <SEP> 0.1 <SEP> "<SEP> 46
<tb>
 

 <Desc / Clms Page number 18>

 
The values given in this table show the particular effectiveness of the preferred catalysts in accelerating the polymerization of the more difficultly polymerizable lactones.



   According to the embodiments of the invention cited in the above description and examples, the lactone rings are opened and connected directly to one another. In the context of the invention, however, lactone polyesters can also be produced in which the lactone radicals do not necessarily have to be directly connected to one another. This is z. B. easily caused that lactone mixtures with combinations of lead compounds, such as. B. dibasic acids and glycols, diamines and amino alcohols, are reacted.

   As an example of this type of reaction and the polyesters obtained with it, the reaction of one mole of adipic acid, one mole of γ-methylcaprolactone and slightly more than one mole of ethylene glycol, which gives a polyester which has the general formula
 EMI18.1
 has, terminal hydroxyl and in which the acid, lactone and glycol residues are distributed randomly and not necessarily as indicated above. The changes in structure and distribution that can be achieved with this measure are readily apparent from the fact that the lactone can react with both the acid and the glycol.



   Polyesters produced according to this embodiment of the invention are also suitable as plasticizers, especially if the reactive terminal groups are esterified, and as intermediates for the production of polyurethane resins and coating compositions. Glycols, diamines or amino alcohols are preferably used in a slight excess over the molar amount of the dicarboxylic acid used, so that a polyester is obtained which has predominantly terminal hydroxyl or amino groups and which is produced by the reaction of the dibasic acid with the hydroxyl or amino groups of the glycols, diamines or water of condensation formed is removed from amino alcohols.

   Optimal plasticizer properties can be achieved with esterified polyesters that have molecular weights between about 2000 and 4000 and have been produced from mixtures of monomethyl and unsubstituted lactones. Preferred embodiments of this embodiment of the invention are evident from the additional examples below.



   Example 28: 730 g of adipic acid, 570 g of e-caprolactone and 357 g of ethylene glycol were heated to 1600 ° C. under nitrogen until no more water of condensation passed over. The reactants were then held at an elevated temperature of 180 to 1900 C for a further 72 hours. The mixture was then subjected to a vacuum of 3 mm at 1200 ° C. for 6 hours. A pale brown, viscous polyester with a hydroxyl number of 40 and a carboxyl number of 1.4 was obtained.



    Example 29: 636 g of a mixture of 13 parts of glutamic acid and 37 parts of glutamic acid anhydride, 570 g of e-caprolactone and 357 g of ethylene glycol were heated to 1600 ° C. under nitrogen until no more water of condensation passed over. The reactants were then held at 1800 ° C. for a further 60 hours and then subjected to a vacuum of 3 mm at the same temperature for three hours. The polyester thus obtained was a viscous yellow liquid with a hydroxyl number of 46 and a carboxyl number of 2.7.



    Example 30: 584 g of adipic acid, 512 g of a mixture of ss-, γ- and 6-methyl-e-caprolactone and 298 g of ethylene glycol were heated to 1600 ° C. under nitrogen until no more water of condensation passed over. The reactants were then kept at an elevated temperature of 1800 C for a further 24 hours and then exposed to a vacuum of 20 mm at 180-2000 C for 3.5 hours in order to remove a small excess of ethylene glycol. The polymer thus obtained was a water-white, viscous liquid with a hydroxyl number of 49.5 and a carboxyl number of 1.9.



    Example 31: 592 g of phthalic anhydride, 456 g of e-caprolactone and 298 g of ethylene glycol were heated to 1600 ° C. under nitrogen until no more water of condensation passed over. The reactants were then kept at the same temperature for a further 24 hours and then exposed to a vacuum of 20 mm, still at the same temperature, for 3.5 hours. The polymer thus obtained was a very viscous yellow liquid with a hydroxyl number of 48.6 and a carboxyl number of 1.2.



     Example 32: 664 g of isophthalic acid, 456 g of e-caprolactone and 318 g of ethylene glycol were heated to 1800 ° C. for 6 days under nitrogen. Then the reactants were placed under vacuum for 4 hours

 <Desc / Clms Page number 19>

 
 EMI19.1
 a rubbery semi-solid substance with hydroxyl number 45.9 and carboxyl number 0.3.



   The polyesters of Examples 15, 20, 22, 24, 25, 26 and 30 were acetylated by reacting them for 4-5 hours at 1000 ° C. with four times the amount of acetic anhydride theoretically required due to their hydroxyl content. Excess acetic anhydride and acetic acid were then removed under vacuum. Finally, the acetylated polyesters were passed over a falling film evaporator at 170-180 C under a vacuum of 1 to 5 mm in order to remove small residual amounts of volatile substances.



   The remaining products were then tested for their suitability as plasticizers by triturating them for 5 minutes at 1580 ° C. on a laboratory two-roll mill with a 96: 4 vinyl chloride-vinyl acetate copolymer and 0.50/0 dibutylin maleate as stabilizer. The clear, flexible sheets obtained in this way were shaped into test specimens at 1580.degree.



   In the table immediately below, the effectiveness is the concentration of the plasticizer based on the total weight of resin and plasticizer, which results in an elastomer which is applied at 24.50 C under a load of 70.3 kg / cm2 (with a constant increase in 74 seconds ) has an elongation of 1000/0; the elongation is the increase in length when the test specimen at 24.50 C breaks; the flex temperature (flex temperature) TF and T4 indicate the pliability, where TF and T4 are those points on a temperature-stiffness curve which correspond to a stiffness modulus of 94.9 kg / mm and 70.3 kg / mm 2, respectively.

   The rigidity was determined with the aid of a Clash & Berg torsional rigidity tester according to the method according to ASTM D1043-51 (Ind. Eng. CLem., No. 34 [1942], p. 1218). The embrittlement temperature is a measure of the suppleness at low temperatures and is carried out by means of an impact test according to the method according to ASTM D746-52T; the percentage of water and oil extraction is the percentage weight loss of 0.1 mm films immersed for 10 days at 25 C in distilled water and refined mineral oil, respectively;

   The Duremeter "A" hardness is a measure of the resistance to the penetration of a needle with a frustoconical tip into a test piece of 6.35 mm according to the method of ASTM D676-49T; the SPI volatility is the percentage weight loss of films from 0.1 to 0.15 mm after contact with activated carbon granules at 700 ° C. for 24 hours according to the method according to ASTM D1203-52T; and exudation is a measure of the excretion of the plasticizer on aging for 2 weeks at room temperature. The values given in the table under "Effectiveness" apply to resin which contains the "effective" percentage of plasticizer.
 EMI19.2
 
<tb>
<tb>



  Example <SEP> No. <SEP> 15 <SEP> 20 <SEP> 22 <SEP> 24 <SEP> 25 <SEP> 26 <SEP> 30
<tb> Molecular weight <SEP> 2350 <SEP> 7900 <SEP> 3100 <SEP> 2900 <SEP> 3000 <SEP> 2525 <SEP> 2100
<tb> viscosity,
<tb> Centipoise, <SEP> at <SEP> 200 <SEP> C <SEP> 4780 <SEP> 41600 <SEP> 20920 <SEP> 37760 <SEP> 7790 <SEP> 18800 <SEP> 10940
<tb> viscosity,
<tb> Centipoise, <SEP> at <SEP> 500 <SEP> C <SEP> 1020 <SEP> 5480 <SEP> 2584 <SEP> 2368 <SEP> 1432 <SEP> 5170 <SEP> 1848
<tb> Effectiveness, <SEP>% <SEP> 39, <SEP> 9 <SEP> 40, <SEP> 9 <SEP> 44, <SEP> 4 <SEP> 45, <SEP> 6 <SEP> 41, <SEP> 0 <SEP> 43, <SEP> 2 <SEP> 42, <SEP> 6 <SEP>
<tb> Tensile strength, <SEP> kg / mmz <SEP> 1.68 <SEP> 1.60 <SEP> 1.48 <SEP> 1.51 <SEP> 1.70 <SEP> 1.66 <SEP> 1.65
<tb> elongation, <SEP>% <SEP> 360 <SEP> 345 <SEP> 345 <SEP> 340 <SEP> 350 <SEP> 365 <SEP> 345
<tb> stiffness modulus,
<tb> according to <SEP> ASTM, <SEP> kg / cm2 <SEP> 42,

  2 <SEP> 58.0 <SEP> 42.2 <SEP> 40.1 <SEP> 42.2 <SEP> 51 <SEP> 49, <SEP> 2 <SEP>
<tb> TF, <SEP> C <SEP> -17 <SEP> -16 <SEP> -13 <SEP> -14 <SEP> -19 <SEP> -14 <SEP> -21
<tb> T4, <SEP> C <SEP> 0 <SEP> 5 <SEP> 1 <SEP> 3 <SEP> -1 <SEP> 2 <SEP> -3
<tb> Embrittlement temperature, <SEP> 0 <SEP> C-20 <SEP> -21-18 <SEP> -12-22 <SEP> -22-24 <SEP>
<tb> Extraction <SEP> in <SEP>% <SEP> with <SEP> oil <SEP> 0.8 <SEP> 0.1 <SEP> nil <SEP> 3.2 <SEP> 0.8 <SEP > 0.3 <SEP> 1.0
<tb> water-0, <SEP> 2 <SEP> 0, <SEP> 1 <SEP> 0, <SEP> 5 <SEP> 0, <SEP> 2 <SEP> 0, <SEP> 1 <SEP> 0, <SEP> 5 <SEP> 1, <SEP> 5 <SEP>
<tb> Shore hardness "A" 63 <SEP> 65 <SEP> 58 <SEP> 60 <SEP> 66 <SEP> 60 <SEP> 61
<tb> SPI volatility loss <SEP> 0.3 <SEP> 0.2 <SEP> 0.1 <SEP> 0.4 <SEP> 0.5 <SEP> 0.4 <SEP> 0,

  4th
<tb> Sweating <SEP> nothing <SEP> nothing <SEP> nothing <SEP> nothing <SEP> nothing <SEP> nothing <SEP> nothing
<tb>
 
A person skilled in the art will recognize after reading the description that various modifications of the method are possible, all of which are intended to fall within the scope of the patent claims.

 

Claims (1)

PATENT CLAIMS: 1. A method for producing a polyester, characterized in that a lactone with at least 6 carbon atoms in the ring is heated to a temperature in the range from 50 to 3000 C together with an organic compound which has at least one reactive hydrogen atom. 2. The method according to claim 1, characterized by the use of a lactone mixture. 3. The method according to claim 1 or 2, characterized in that the lactone and the organic compound are heated in the presence of an ester exchange catalyst. 4. The method according to claim 3, characterized in that an organic titanium compound or an oxide or borate of lead or zinc is used as the catalyst. 5. The method according to any one of claims 1 to 4, characterized in that the lactone has the general formula EMI20.1 has, in which n is at least 4, at least n + 2 R is hydrogen and the remaining R are hydrogen or an alkyl, cycloalkyl or alkoxy radical or a radical of a single ring aromatic hydrocarbon. 6. The method according to any one of claims 1 to 5, characterized in that a polyol, polyamine, amino alcohol, a polybasic acid, an oxycarboxylic acid or an aminocarboxylic acid is used as the organic compound. 7. The method according to any one of claims 1 to 6, characterized in that the lactone is reacted with a dicarboxylic acid and a glycol, diamine or amino alcohol which is used in a molar excess based on the dicarboxylic acid.