WO2015135948A1 - Method for producing polyacetal-polyesters from cyclic anhydrides and aldehydes - Google Patents

Abstract

The invention relates to a method for producing polyacetal-polyesters by reacting cyclic anhydrides with aldehydes, characterised in that the reaction of aldehydes with cyclic anhydrides is carried out in the presence of a catalyst and an open-chained monoanhydride as a chain regulator. The invention also relates to polyacetal-polyester which can be obtained according to the claimed method, and to the use thereof as thermoplasts or polymer additives, and for producing elastomers and duromers.

Description

 Process for the preparation of polyacetal polyesters from cyclic anhydrides and aldehydes

The present invention relates to a process for the preparation of polyacetal polyesters by reaction of cyclic anhydrides with aldehydes, characterized in that the reaction of aldehydes with cyclic anhydrides in the presence of a catalyst and an open-chain monoanhydride is carried out as a chain regulator. The present invention also relates to polyacetal polyesters, which are obtainable by a process according to the invention, and their use as thermoplastics or polymer additives, and for the production of elastomers and duromers. Polyacetal polyesters are interesting for applications in the polyoxymethylene (POM) and polyester sectors. The incorporation of ester units leads to increased chemical and thermal stability of the polymer chains compared to polyoxymethylene (POM) homopolymers. Furthermore, physical properties such as melting point, glass transition temperature, melt viscosity, etc., can be specifically adjusted by the choice of the cyclic anhydride and the aldehyde and via the monomer ratio of aldehyde and cyclic anhydride.

Angew. Chem. 1962 (74), 248 discloses the reaction of open-chain monoanhydrides, especially acetic anhydride, with trioxane as a formaldehyde trimer in the presence of a catalyst to give low molecular weight oligooxymethylene diacetates having 1 to 3 oxymethylene units. The resulting products contain oxymethylene ester groups exclusively as oxy methylene acetate end groups and have no internal ester linkages along the polymer chain. The use of cyclic anhydrides as comonomer is not described.

US 3378527 discloses a process for the preparation of ester-ether-acetal random copolymers which are obtained by reaction of epoxides or oxetanes with cyclic carboxylic acid anhydrides and aldehydes and optionally a polymerization initiator. The disclosed process can be carried out without a catalyst according to the disclosure text. Copolymers containing as comonomers exclusively aldehydes and carboxylic acid anhydrides (ie obtained in the absence of epoxides or oxetanes) are not disclosed. Furthermore, open-chain monocarboxylic acid anhydrides are not used in the context of the disclosure.

US 3232906 discloses a process for the preparation of polyoxymethylene polymers. Here, formaldehyde is polymerized in the presence of a stannous (II) carboxylate. Further, a carboxylic acid anhydride is provided as an acylating reagent, and acetic anhydride is mentioned as an open-chain monoanhydride. As cyclic anhydrides maleic anhydride and succinic anhydride are mentioned. However, the combination of an open-chain monoaldehyde and a cyclic anhydride is not disclosed. "

 - 2 -

US 3687898 discloses end capping of polyoxymethylene polymers by anhydrides in the presence of Lewis acid catalysts. In this case, no units based on anhydrides are contained in the polymer chain. Furthermore, no cyclic anhydrides are disclosed.

US Pat. No. 3,428,590 discloses the preparation of trioxane copolymers, it being possible to use cyclic anhydrides as reaction accelerators. For open-chain anhydrides, such as biepsielsweise acetic anhydride, this technical effect according to the application is not achieved.

US 3719637 relates to the polymerization of tetraoxane in the presence of a carboxylic acid anhydride and a polymerization initiator. The application discloses a list of anhydrides, among which cyclic and open chain monoanhydrides occur. However, a combination of cyclic and open-chain anhydrides is not disclosed.

US 3900411 discloses lubricant compositions with alkenyl succinic acid polyol acetals or ketals wherein the alkenyl group contains at least 30 carbon atoms. In this application, no open-chain monoanhydrides are described.

It is apparent from the prior art that no process is known, according to which polyester polyesters are obtained, which consist of a random or regular sequence of one or more acetal units with diester units. Furthermore, according to the prior art, no method is known by which said polyacetal polyesters having a defined molecular weight can be obtained.

The present invention has set itself the task of providing such a method. Surprisingly, it has been found that by reaction of cyclic anhydrides and aldehydes in the presence of suitable catalysts, e.g. Bronsted acids or Lewis acids, and an open-chain monoanhydride thermally stable polyacetal polyester having a decomposition temperature> 130 ° C can be obtained. It has furthermore been found that the open-chain monoanhydride acts as a chain regulator and thus the molecular weight of the polyacetal polyesters can be controlled via the relative mole fraction of the open-chain monoanhydride in the reaction mixture.

The invention therefore provides a process for the preparation of polyacetal polyesters by reaction of cyclic anhydrides with aldehydes in the presence of a catalyst, characterized in that the reaction is carried out in the presence of an open-chain monoanhydride.

By the method according to the invention polyacetal polyesters are obtained, which were previously not accessible by known methods. The obtained polyacetal polyester offer compared to pure polyacetals such as polyoxymethylene (POM) or paraformaldehyde the advantage that the physical properties, such as glass transition temperature, melting point, viscosity on the choice of cyclic anhydrides and aldehydes, on the incorporation ratio of cyclic anhydrides and aldehydes, as well as the Molecular weight can be adjusted specifically.

The polyacetal polyesters according to the invention are prepared by copolymerization of aldehydes and cyclic anhydrides in the presence of a catalyst, wherein the copolymerization is carried out at least temporarily in the presence of an open-chain monoanhydride. The role of the open-chain monoanhydride is to limit, as a chain regulator, the chain length of the polyacetal polyester chains formed during the copolymerization reaction, and thus to achieve control of the number average molecular weight. Without wishing to be bound by theory, it is believed that this occurs by the introduction of carboxylate terminal groups -OC (O) R ³ which are unreactive under the present reaction conditions. By means of a suitable molar ratio of open-chain monoanhydride to cyclic anhydride and aldehyde, it is thus possible to set a theoretical number-average target molecular weight MWth such that polyacetal polyesters having a defined molecular weight can be obtained.

The theoretical number-average molecular weight MWth can be determined in this case as the ratio of the total mass of monomers used (aldehyde and cyclic anhydride) and chain regulator (open-chain monoanhydride) to the molar amount of open-chain monoanhydride used. The actual number average molecular weight may vary within certain limits from the theoretical number average molecular weight MW _th and depends on the reaction conditions and the type of monomers used, the chain regulator used and the catalyst used.

The linking of one or more contiguous acetal units via diester units resulting from the cyclic anhydrides, as well as the incorporation of the open-chain monoanhydride in the form of an ester end group, further leads to a stabilization of the polymer structure relative to polyacetal homopolymers.

Polyacetal polyesters according to the invention include compounds of the general formula (I),

which contain an alternating sequence of mono- or polyacetal sections -O- (CHR ¹ -O) _m - and carbonic acid diester units -O-C (O) -R ² -C (O) -O-, where the mono- or polyacetal sections or polyacetal _Λ

 - 4 -

Sections and the die-ester units are each directly linked via a common oxygen atom, m and x are integers, m is an integer> 1 and different m in different sections - (CHR'-C m- different values x can be an integer> 1 and different x in different compounds of the general formula (I) can assume different values,

R ^{1 is} hydrogen or a saturated or unsaturated, linear or branched C ¹ - to C 20 -alkyl, aryl, alkylaryl or arylalkyl radical which optionally contains further heteroatoms such as oxygen, nitrogen, sulfur, phosphorus, silicon, fluorine, chlorine, bromine, Contains iodine, and different R ^{1 may} differ in different units -CHR'-O- within a compound of general formula (I),

R ^{2 is} a chain of 2, 3 or 4 carbon atoms, wherein the carbon atoms in the chain R ² are linked to each other via single or double bonds or a bridging oxygen or sulfur atom, or R ² part an aromatic or cycloaliphatic mono-, bi- or polycyclic ring system, and the carbon atoms in R ² or in the R ² -containing aromatic or cycloaliphatic ring system independently of one another can carry one or more substituents which are selected from the group

R ⁴ , alkenyl = CR ⁴ ₂ , ether -OR ⁴ , thioether -SR ⁴ , amino -NR ⁴ ₂ , phosphino-PR ⁴ ₂ , silyl -SiR ⁴ ₃ , carboxyl -C0 ₂ H, carboxylate -C0 ₂ \ ester - C0 ₂ R ^4, -S0 ₃ H sulfonic acid, sulfonate -S0 ₃ ^", sulfonic fonsäureester -SO3R ^4, fluorine, chlorine, bromine, iodine, nitrile -CN, nitro -NO 2, wherein R ⁴ in all cases, the analogous meaning has as R ¹ , may differ from R ¹ , and different substituents R ^{4 may} differ within a chain R ² and / or may be linked together such that they each other and / or with R ^{2 is} a mono-, bi- or polycyclic Ring system, and different R ^{2 may} differ in different diester units -O-C (O) -R ² -C (O) -O- within a compound of general formula (I),

R ^{3 has} the analogous meaning as R ¹ , wherein R ^{3 may be} identical to R ¹ or different from R ¹ and different R ^{3 may} differ within a compound of general formula (I). Polyacetal polyesters according to the invention also include mixtures of two or more compounds of general formula (I) in any composition.

In addition to compounds of the formula (I), the polyacetal-polyester compounds according to the invention include compounds or mixtures of two or more compounds of the general formula (II)

with a, in which in comparison to compounds of general formula (I) in addition to or in place of polyacetal portions -0- (CHR ¹ -0) _m - also polyoxyalkylene polyacetal portions -0 [(CHR ¹ 0) _a (( CR _^'2) oO) _b] i- are present, where a and b are each an integer independently of one another> 0 and within a How-derholungseinheit [(CHR ¹ 0) _a ^((CR' ₂₎ oO) _b], the Sum of a + b> 1,

1 and x are independently an integer> 1, o = 2, 3 or 4, different a, b, 1 and o in different repeat units [(CHR ¹ 0) _a ((CR 2) oO) b] i can assume different values within a compound of the formula (II), x can assume different values in different compounds of the general formula (II),

R ¹ and R ^{2 have} the abovementioned meaning,

R ^{3 has} the analogous meaning as R ¹ , wherein R ^{3 may be} R ¹ or different from R ¹ and different R ^{3 may} differ within a compound of general formula (I), and R 'has an analogous meaning as R ¹ where R 'may be R ¹ or different from R ¹ and different R' within a repeating unit ((CR'2) o-0) and in different repeating units ((CR'2) o-0) b within a compound of Formula (II) may be different and R 'is preferably hydrogen or a methyl group.

Polyacetal polyesters according to the invention also include mixtures of one or more polyacetal polyesters of the general formula (I) with one or more polyoxyalkylene polyacetal polyesters of the general formula (II) and / or with other compounds. _r

 - 6 -

Other compounds which may be present in the polyacetal polyesters according to the invention in admixture with compounds of the general formula (I) and / or compounds of the general formula (II) are, for example, mono-, di-, tri- or oligooxymethylene-dicarboxylates R ³ C (0) -O- (CHR ¹ -O) _k -C (O) R ³ , where k is an integer from 1 to 100 and R ¹ and R ^{3 have} the abovementioned meaning. These compounds may arise, for example, from the reaction of aldehydes with open-chain monoanhydrides without the participation of a cyclic anhydride.

The polyacetal polyesters of the invention according to the general formulas (I) and (II) usually contain end groups ester groups -O-C (O) R ³ , wherein the ester end groups via a common oxygen atom directly with a mono- or polyacetal Section -0- (CHR ¹ - 0) _m - or a polyoxyalkylene-polyacetal section -0 [(CHR ¹ 0) _a ((CR ^' 2) oO) b] i-linked. The presence of compounds in which with respect to compounds of formula (I) and / or compounds of formula (II) individual ester end groups -0-C (O) R ³ against other end groups such as carboxylic acid groups -0-C (0 ) -R ² -C (O) -OH, hemiacetal groups -O-CHR'-OH (wherein R ¹ and R ^{2 have} the meaning given above), formyl groups -CH = 0 or methoxy groups -OCH 3 exchanged are, wherein the respective end group via a common oxygen atom with a mono or polyacetal section -0- (CHR ¹ -0) _m -, a polyoxyalkylene polyacetal section -0 [(CHR ¹ 0) _a ((CR ^' ₂ ) oO) _b ] i or a diester unit -O-C (0) -R ² -C (O) -O- is linked and the enumeration of the end groups is not considered complete, is not excluded.

Therefore, the other compounds which may be present in the polyacetal polyesters according to the invention in admixture with compounds of general formula (I) and / or compounds of general formula (II) also include compounds in which compared to compounds of formula (I) and / or compounds of the formula (II) individual ester end groups -O-C (O) R ³ against other end groups such as carboxylic acid groups -0-C (0) -R ² - C (0) -OH, hemiacetal groups -O-CHR'-OH (wherein R ¹ and R ^{2 have} the meaning given above), formyl groups -CH = 0 or methoxy groups -OCH 3 are exchanged, this list is not to be considered as complete.

The polyacetal polyesters of the invention generally have a number average molecular weight> 232 g / mol. Number average molecular weight can be determined by gel permeation chromatography (GPC) or by average molecular weight by 'H NMR spectroscopy, as explained in the description of the methods.

Cyclic anhydrides in the context of the invention are compounds of the general formula (III)

wherein R has the meaning given above.

Examples of compounds of formula (III) are succinic anhydride, maleic anhydride, phthalic anhydride, 1, 2-cyclohexanedicarboxylic anhydride, diphenic anhydride, phthalic anhydride tetrahydrophthalic, methyltetrahydrophthalic, Norbomendisäureanhydrid and their chlorination products, glutaric anhydride, diglycolic anhydride, 1,8-naphthalic anhydride, dodecenylsuccinic anhydride, tetradecenylsuccinic anhydride, hexadecenyl succinic anhydride, octadecenylsuccinic anhydride, 3- and 4-nitrophthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, itaconic anhydride, dimethylmaleic anhydride, allylnorbornendioic anhydride, 3-methylfuran-2,5-dione, 3-methyldihydrofuran-2,5-dione, dihydro-2H-pyran-2 , 6 (3H) -dione, 1,4-dioxane-2,6-dione, 2H-pyran-2,4,6 (3H, 5H) -trione, 3-ethyl-dihydrofuran-2,5-dione, 3-methoxy-dihydrofuran -2,5-dione, 3- (prop-2-en-1-yl) dihydrofuran-2,5-dione, N- (2,5-dioxotetrahydrofuran-3-yl) formamide d, 3 [(2E) -but-2-en-1-yl] dihydrofuran-2,5-dione, phenylsuccinic anhydride, 2-phenylsuccinic anhydride, (+) - diacetyl-L-tartaric anhydride, dibenzoyl-L-tartaric anhydride, 2-

Acetoxysuccinic anhydride, 3-methylglutaric anhydride, 2,2-dimethylglutaric anhydride, 3,3-dimethylglutaric anhydride, hexafluoroglutaric anhydride, 3-butyldihydrofuran-2,5-dione, 3- (2-methyl-2-propenyl) -dihydro-2,5-butanedione, Thiodiglycolic anhydride, nonenyldihydrofuran-2,5-dione, d-aconitic anhydride, 1,8-naphthalenedicarboxylic anhydride, 2,3-

Pyridinedicarboxylic acid anhydride, camphorsanhydride, 3,3 ', 4,4'-

Benzophenonetetracarboxylic dianhydride, 1, 2,4-benzoyltricarboxylic anhydride chloride. Preferred compounds of the general formula (III) are succinic anhydride, glutaric anhydride, phthalic anhydride, maleic anhydride and itaconic anhydride.

Cyclic anhydrides according to the invention also comprise mixtures of two or more cyclic anhydrides of the general formula (III) in any desired composition.

Use can be made according to the invention of monomeric aldehydes of the general formula (IV) and / or their aldehyde equivalents of the general formula (V) and (VI)

(IV) (V) (VI) wherein R ^{1 has} the meaning given above, c is 1 or 2, y is an integer> 1 and Z is hydrogen, a linear or branched, saturated or unsaturated C 1 to C 20 alkyl or acyl radical , In connection with compounds of the general formula (IV), the adjective "monomeric" merely serves to distinguish between cyclized or polymerized aldehydes (general formulas (V) and (VII)) and makes no statement about the constitution of the radical R ¹ for compounds of the general formula (IV), the monomeric aldehydes are formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde and their higher homologs, acrolein, crotonaldehyde and their higher homologs, methacrolein, furfural, trifluoroacetaldehyde, trichloroacetaldehyde Preferred compounds of the general formula IV are formaldehyde , Acetaldehyde, acrolein, crotonaldehyde, methacrolein, furfural, particularly preferred is formaldehyde.

Examples of aldehyde-equivalent compounds of the general formula (V) are 1,3,5-trioxane, 1,3,5,7-tetraoxane, paraldehyde (acetaldehyde trimer). Preferred compounds of the general formula (V) are 1,3,5-trioxane and 1,3,5,7-tetraoxane, more preferably 1,3,5-trioxane. Aldehyde-equivalent compounds of the general formula (V) are cyclic trimers or tetamers of compounds of the general formula (IV). A compound of formula (V) with c = 1 is therefore considered to be a triple aldehyde (ie corresponding to three monomeric aldehyde units), a compound of formula (V) where c = 2 is a quadruple aldehyde (corresponding to four monomeric aldehyde units). Examples of aldehyde-equivalent compounds of the general formula (VI) are formaldehyde hydrate (R ¹ = H, Z = H, y = 1, eg aqueous formaldehyde solution), paraformaldehyde (R ¹ = H, Z = H or Me, typically y = 8 to 100) or polyoxymethylene (R ¹ = H, typically Z = - COCH 3, H, -C 2 H 4 -OH and y> 100). A preferred compound of general formula (VI) is paraformaldehyde. Aldehyde-equivalent compounds of the formula (VI) are hydrates, oligomers or polymers of compounds of the formula IV. A compound of the formula (VI) having an average number of repeating units is therefore considered as a y-fold aldehyde (ie corresponding to monomeric aldehyde units) ,

In addition to monomeric aldehydes and their aldehyde equivalents of the general formula (IV), (V), (VI), aldehydes in the context of the invention also include aldehyde-equivalent compounds of the general formula (VII),

wherein R ¹ and R 'have the abovementioned meaning, different R' can differ within a compound of formula (VII) and d is an integer from 1 to 3.

Examples of compounds of formula (VII) are 1,3-dioxolane, 4-methyl-l, 3-dioxolane, 4,5-dimethyl-l, 3-dioxolane, 1,3-dioxane, 5-methyl-l, 3 Dioxane, 5,5-dimethyl-1,3-dioxane, 4,6-dimethyl-1,3-dioxane, 1,3-dioxepane. Preferred compounds of formula (VII) are 1,3-dioxolane and 1,3-dioxepane.

Compounds of formula (VII) contain a monomeric aldehyde moiety CHR'-O adjacent to an alkylene oxide equivalent (CR'2) d + 10 and are referred to as oxyalkylene-acetal group - [(CR'2) d + iO] CHR ¹ 0- built into the polyacetal polyesters of the invention.

Monomeric aldehydes or their aldehyde equivalents within the meaning of the invention also comprise mixtures of two or more aldehydes and / or their aldehyde equivalents of the general formulas (IV), (V), (VI) and / or (VII) in any desired composition, mixtures of aldehydes and / or their aldehyde equivalents of the general formula (IV), (V) and / or (VI) are preferred. In the context of the present invention, for reasons of linguistic simplification, the term "aldehyde" is used in summary both for monomeric aldehydes and for their aldehyde equivalents.

Open-chain monoanhydrides in the context of the invention are compounds of the general formula

(VIII), o

R '(VIII) where R has the meaning given above and different R within a compound of formula (VIII) may differ and different R ^{3 are} not directly linked within a compound of formula (VIII).

Examples of open-chain monoanhydrides of the general formula (VIII) are acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride, isovalerinic anhydride and their branched and / or higher homologs, anhydrides of saturated or mono- or polyunsaturated C 8 to C 20 fatty acids, such as pelargonic anhydride, capric anhydride , Lauric anhydride, myristic anhydride, palmitic anhydride, margaric anhydride, Stearic anhydride, Arachinsäureanhydrid, Undecylensäureanhydrid, Palmitoleinsäureanhydrid, Petroselinsäureanhydrid, oleic anhydride, Elaidinsäureanhydrid, Vaccensäureanhydrid, Cadoleinsäureanhydrid, Icosensäureanhydrid, linoleic, a-Linolensäureanhydrid, Calendualsäureanhydrid, Arachidonsäureanhydrid, aromatic anhydrides such as benzoic, or substituted benzoic anhydrides, α, β-unsaturated anhydrides such as acrylic anhydride, methacrylic , Crotonsäureanhydrid or 2-ethyl-3-propylacrylic anhydride and their higher linear or branched homologues. Preferred open-chain monoanhydrides of the formula (VIII) are acetic anhydride, benzoic anhydride, acrylic anhydride, methacrylic anhydride, crotonic anhydride, particular preference is given to acetic anhydride, benzoic anhydride and methacrylic anhydride.

In addition to open-chain monoanhydrides of the general formula (VIII), compounds of the general formula IX

can be used, wherein R ² and R ^{3 have} the meaning given above, k is an integer> 1, and different R ³ can differ within a compound of formula IX and different R ³ within a compound of formula IX are not directly with each other are linked.

Compounds of the general formula IX can be obtained from the reaction of open-chain monoanhydrides of the formula (VIII) with cyclic anhydrides of the formula (II) and be formed proportionally in the reaction mixture or prepared separately and used in the copolymerization with aldehydes and cyclic anhydrides.

Open-chain monoanhydrides according to the invention also comprise mixtures of two or more open-chain monoanhydrides of the general formulas VIII and / or IX in any desired composition. In principle, the process according to the invention can also be carried out in the presence of a further comonomer. As further comonomers, for example, all oxygen-containing cyclic compounds, in particular cyclic ethers, such as e.g. Epoxies, oxetane, THF, dioxane are used.

A catalyst in the context of the invention is a compound or a combination of two or more compounds which are not identical to the aldehydes / or anhydrides used, and whose presence in the reaction mixture results in that from the reaction between aldehyde and cyclic anhydride in the presence of an open-chain monoanhydride according to the invention polyacetal polyesters emerge. Examples of catalysts in the context of the invention are Bronsted acids, such as trifluoromethanesulfonic acid or perchloric acid and / or Lewis acids, such as metal triflates. The copolymerization can be carried out in the presence or absence of a solvent. Suitable solvents are aprotic organic solvents such as, for example, linear or branched alkanes or alkane mixtures, toluene, the various xylene isomers or mixtures thereof, mesitylene, one or more halogenated aromatics or alkanes such as chlorobenzene, the various dichlorobenzene isomers, dichloromethane, Chloroform or the various di-, tri- and tetrachloroethane isomers, open-chain or cyclic ethers such as

Tetrahydrofuran (THF) or methyl tert-butyl ether (MTBE), open-chain or cyclic esters, e.g. Ethyl acetate, propyl acetate or butyl acetate, 1,4-dioxane, acetonitrile, N, N-dimethylformamide (DMF), N, N-dimethylacetamide, dimethylsulfoxide (DMSO), cyclic carbonates, e.g. Ethylene carbonate or propylene carbonate, N-methylpyrrolidone (NMP), sulfolane, tetramethylurea, N, N'-dimethylethyleneurea or mixtures thereof with each other in any composition. The use of liquid or supercritical carbon dioxide as a solvent in pure substance or as a mixture with one of the abovementioned solvents is also possible. Preferred solvents are linear or branched alkanes or alkane mixtures, toluene, the various xylene isomers or mixtures thereof, mesitylene, mono- or polychlorinated aromatics or alkanes, e.g. Chlorobenzene, the various dichlorobenzene isomers, dichloromethane, chloroform or the various di-, tri- and tetrachloroethane isomers, open-chain esters such as e.g. Ethyl acetate, propyl acetate or butyl acetate, cyclic carbonates, e.g. Ethylene carbonate or propylene carbonate, N-methylpyrrolidone (ΝΜΡ), sulfolane, tetramethylurea, N, N'-dimethylethyleneurea or mixtures thereof with each other and / or with other solvents, as well as liquid or supercritical carbon dioxide.

Also preferred is the reaction in the absence of solvents. Particularly preferred are dichloromethane and the absence of solvents.

The copolymerization can be carried out in a batch process, in a semi-batch process or in a continuous process. The copolymerization takes place when the components aldehyde, cyclic anhydride and catalyst, optionally in the presence of a solvent, are in contact with each other at a temperature sufficient to initiate the copolymerization. The copolymerization reaction is carried out at least temporarily in the presence of an open-chain monoanhydride.

Regardless of the procedure, it is advisable that the aldehyde and catalyst are not contacted in the absence of a cyclic anhydride at a temperature sufficient to initiate homopolymerization of the aldehyde. Otherwise "

 There is the possibility that aldehyde homopolymers may be formed, which may need to be separated from the polyacetal polyesters, and that the aldehyde so reacted is no longer available for copolymerization with cyclic anhydrides in the presence of an open-chain monoanhydride. Furthermore, it is advisable that aldehyde, catalyst and open chain monoanhydride are not contacted in the absence of a cyclic anhydride at a temperature sufficient to initiate a reaction of the open chain monoanhydride with aldehyde. Otherwise, there is the possibility that reinforced mono-, di-, tri- or polyoxymethylene-diacetates are formed which do not contain any diester units derived from the cyclic anhydride, and thus are not polyacetal polyesters according to the invention. Although the presence of mono-, di-, tri-, or polyoxymethylene diacetates is not explicitly excluded in the polyacetal polyesters of this invention, increased formation of these compounds results in a reduction of the average molecular weight and a deterioration in product properties. Suitable reaction temperatures for the preparation of the polyacetal polyesters according to the invention are typically in a range from -78 to 250 ° C, preferably from -20 to 120 ° C and more preferably from 0 to 100 ° C. When choosing the reaction temperature, the type and boiling point of the solvent, the aldehyde, the cyclic anhydride, the open-chain monoanhydride and the catalyst must be taken into account. At a reaction temperature above the boiling point of one or more of these components, it is advisable to carry out the copolymerization under reflux or in a closed system (for example an autoclave) in order to avoid the partial or complete loss of one or more of these components by evaporation. Furthermore, the type of catalyst to be considered in the choice of the reaction temperature. The temperature must be chosen so that the catalyst has sufficient activity for the copolymerization reaction. The copolymerization should continue to be carried out at temperatures which are below the decomposition temperature of the polyacetal polyester to be produced. The decomposition temperature can be determined by means of thermogravimetric analysis (TGA), as explained in the description of the methods. Embodiments of the method according to the invention are described below. They can be combined with each other as long as the opposite does not result from the context.

In one embodiment of the process according to the invention, the catalyst is a Bronsted acid or a Lewis acid. Bronsted acids in the sense of the invention are protic acids which are able to reversibly cleave off one or more protons and to transfer them intermediately or in the long term to reaction partners with lone pairs of electrons. Examples of Bronsted acid catalysts are Bronsted inorganic acids such as perchloric acid, sulfuric acid, phosphoric acid, hydrogen fluoride or hydrofluoric acid, hydrogen chloride or hydrochloric acid, hydrobromic or hydrobromic acid, hydrogen iodide or hydriodic acid, hexafluoroantimonic acid, tetrafluoroboric acid, or organic Bronsted acids, such as for example, carboxylic acids such as formic acid, acetic acid, propionic acid or higher homologs, trifluoroacetic acid, trichloroacetic acid, or sulfonic acids such as trifluoromethanesulfonic acid, toluenesulfonic acid, methanesulfonic acid. The Bronsted acids are preferably used in pure form or as a concentrated aqueous solution. However, depending on the available forms of administration of the respective Bronsted acid, use in admixture with other solvents or in other dilution stages, as well as the presence of further substances mixed with the Bronsted acid, are not excluded. Bronsted acids within the meaning of the invention also refer to mixtures of two or more Bronsted acids in any desired composition.

Preferred Bronsted acids are strong Bronsted acids with a pK _a <2.8. Examples of strong Bronsted acids are trifluoromethanesulfonic acid (pKa = -12), hydrogen iodide or hydriodic acid (pKa = -9.3), hydrogen bromide or hydrobromic acid (pKa = -8.7), perchloric acid (pKa = -8) , Hydrochloric acid or hydrochloric acid (pKa = -6.3), sulfuric acid (pKa = -3 in the first dissociation stage). Preferred strong Bronsted acids are trifluoromethanesulfonic acid and perchloric acid.

It is further preferred if the strong Bronsted acid is not a strongly oxidizing or decomposing Bronsted acid, such as nitric acid.

Lewis acids within the meaning of the invention are characterized in that they contain at least one metal atom coordinatively unsaturated under reaction conditions selected from the group of scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, niobium, tantalum, molybdenum, tungsten, rhenium , Iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, boron, aluminum, gallium, indium, tallium, tin, lead, antimony, bismuth or the series of lanthanides , Thus, the Lewis acidic catalyst can be a free or a complexed metal ion.

Nucleophilic binding partners can bind to the coordinatively unsaturated Lewis acid center. The coordinatively unsaturated Lewis acidic center may already be present in the compound used as a catalyst or forms in the reaction mixture, for example by cleavage of a weakly bound nucleophilic binding partner, after cleavage from the _Λ

 - 14 -

Lewis acidic catalyst can form a stable electronically neutral or negatively charged compound. Examples of weakly bound nucleophilic binding partners which can form a stable electronically neutral or negative charged compound after cleavage from the Lewis acid catalyst are halides such as fluoride, chloride, bromide or iodide, cyanide, cyanate, isocyanate, azide, carbon monoxide, Carbon dioxide, nitrogen, or organic compounds containing either nitrogen, oxygen, phosphorus or sulfur atoms and / or isolated or conjugated double bond systems with which they can form bonds to the metal atom. Examples of these are organic nitriles such as acetonitrile, ethers such as tetrahydrofuran or diethyl ether, thioethers such as dimethyl sulfide, alkenes such as ethene, cyclooctaene or cyclooctadiene, linear or branched saturated or mono- or polyunsaturated Cl to C20 -Alcoholates, linear or branched saturated or mono- or polyunsaturated, optionally fluorinated C 1 - to C 20 -carboxylates, linear or branched saturated or mono- or polyunsaturated, optionally fluorinated C 1 - to C 20 -sulfonates, primary, secondary or tertiary Cl- to C 20 -amines, N-alkyl- or N-arylalkylideneamines, N-alkyl- or N-arylbenzylideneamines, trialkylphosphines, triarylphosphines or mixed alkylarylphosphines, trialkylphosphites, triarylphosphites or mixed alkylarylphosphites, trialkylphosphine oxides, triarylphosphine oxides or mixed alkylarylphosphine oxides, unsubstituted or or multiply substituted Ace tylacetonate, unsubstituted or mono- or polysubstituted, l, 3-arylpropan-l, 3-dionates, unsubstituted or mono- or polysubstituted cyclopentadienyl anions, unsubstituted or mono- or polysubstituted benzene derivatives.

Bonding partners which can form a stable electronically neutral or negatively charged compound after cleavage from the Lewis acidic catalyst are also binding partners which have additional nitrogen, oxygen, phosphorus and / or sulfur atoms and / or double bonds. with which they are bound to the metal atom, and remain bound to the metal atom after removal of a bond to the metal atom via at least one further bond. Examples of these are bisphosphines such as 1,2-bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, 1, 4-

Bis (diphenylphosphino) butane, diols such as 1, 2-ethanediol, 1,2- or 1,3-propanediol, 2,3-butanediol, diamines such as 1,2-ethylenediamine, 1,2-cyclohexylenediamine, 1 , 2-diaminobenzene or toluene, or salen compounds derived by reaction with aldehydes of diamines such as 1,2-ethylenediamine, 1,2-cyclohexylenediamine or 1,2-diaminobenzene, 1,5-cyclooctadiene or 1,3, 5.7-cyclooctatetraene.

The Lewis acids can be used in pure form or dissolved in a suitable solvent. Lewis acids within the meaning of the invention also refer to mixtures of two or more Lewis acids in any composition. Preference is given to soft Lewis acids which contain at least one metal atom selected from the series scandium, yttrium, lanthanum, zirconium, hafnium, niobium, tantalum, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, copper, silver , Gold, zinc, gallium, indium, tallium, tin, antimony, bismuth or the group of lanthanides. Preferred soft Lewis acids are compounds containing at least one metal atom selected from the group consisting of scandium, yttrium, lanthanum, zinc, gallium, tin, antimony, bismuth or an element of the lanthanide series.

Particularly preferred soft Lewis acids are scandium triflate, yttrium triflate, lanthanum triflate, tin triflate, tin trifluoroacetate, bismuth triflate, bismuth trifluoroacetate. In a specific embodiment, the catalyst is a mixture of one or more Bronsted acids and one or more Lewis acids.

In one embodiment, the molar amount of catalyst used based on the total amount of the anhydrides used (cyclic anhydride and open-chain monoanhydride) from 0.001 mol% to 100 mol%, preferably 0.01 mol% to 10 mol%, particularly preferably 0.1 mol % to 10 mol% and most preferably 0.5 mol% to 2 mol%.

In one embodiment of the process according to the invention, the aldehyde is formaldehyde, the term "formaldehyde", unless particularly (eg as monomeric formaldehyde) characterized, both monomeric formaldehyde of the general formula (IV) with R ¹ = H and cyclic formaldehyde - Oligomers of the general formula (V) with R ¹ = H and formaldehyde hydrate or formaldehyde-0 / zgowere and formaldehyde o / jwere the general formula (VI) with R ¹ = H.

Formaldehyde can be used in the solid, liquid or gaseous state, optionally as a mixture with inert gases such as nitrogen or argon or as a mixture with gaseous, supercritical or liquid carbon dioxide, or as a solution. Formaldehyde solutions may be aqueous formaldehyde solutions having a formaldehyde content between 1% by weight and 37% by weight, which may optionally contain up to 15% by weight of methanol as stabilizer. Alternatively, solutions of formaldehyde in polar organic solvents such as methanol or higher monohydric or polyhydric alcohols, 1,4-dioxane, acetonitrile, N, N-dimethylformamide (DMF), N, N-dimethylacetamide, dimethylsulfoxide (DMSO), cyclic carbo - Naten, for example, ethylene carbonate or propylene carbonate, N-methylpyrrolidone (ΝΜΡ), sulfolane, tetramethylurea, N, N'-dimethylethyleneurea, in mono- or polychlorinated aromatics or alkanes, such as chlorobenzene, the various dichlorobenzene isomers, dichloromethane, chloroform or the various di-, tri- and tetrachloroethane isomers or in another of the solvents listed above as suitable for the copolymerization reaction, and in _{1 r}

 - lo mixtures of the same with each other, be used with water and / or other solvents. The presence of other substances in solution is also included. Preference is given to the use of formaldehyde in the form of 1,3,5-trioxane in chlorinated solvents such as dichloromethane or in the absence of solvents. Also preferred is the use of mixtures of monomeric formaldehyde with argon, nitrogen or carbon dioxide.

Also preferred is the use of solutions of formaldehyde in aprotic polar organic solvents, e.g. 1,4-dioxane, acetonitrile, N, N-dimethylformamide (DMF), N, N-dimethylacetamide, dimethyl sulfoxide (DMSO), cyclic carbonates, e.g. Ethylene carbonate or propylene carbonate, N-methylpyrrolidone (ΝΜΡ), sulfolane, tetramethylurea, Ν, Ν'-dimethylethyleneurea or mixtures thereof with one another, and / or other solvents.

Monomeric formaldehyde can also be generated in situ from a suitable source of formaldehyde. As a source of formaldehyde, substances may be used which contain chemically bound formaldehyde, usually in the form of oxymethylene groups, and which are capable, under suitable conditions, of releasing formaldehyde. Suitable conditions for the release may be e.g. elevated temperatures and / or the use of catalysts and / or the presence of acids, bases or other reagents that lead to the release of monomeric formaldehyde include. Preferred formaldehyde sources are 1,3,5-trioxane, paraformaldehyde, high molecular weight polyoxymethylene (POM), dimethylacetal, 1,3-dioxolane, 1,3-dioxane and / or 1,3-dioxepane, more preferably 1,3, 5-trioxane and paraformaldehyde.

In a further embodiment, the copolymerization of aldehydes with cyclic anhydrides in the presence of a catalyst and an open-chain monoanhydride is further carried out in the presence of a further comonomer. Suitable further comonomers are in principle all oxygen-containing cyclic compounds, in particular cyclic ethers. Examples of cyclic ethers are epoxides such as e.g. Ethylene oxide, propylene oxide or styrene oxide, oxetanes, tetrahydrofuran, 1,4-dioxane. Preferred further comonomers are epoxides and oxetanes, particularly preferred other comonomers are ethylene oxide and propylene oxide. The other comonomers are incorporated with ring opening in the polyacetal polyesters according to the invention. When using cyclic ethers as further comonomers, polyacetal polyesters of the general formula (II) can be obtained.

In a preferred embodiment, formaldehyde is used in the form of cyclic or open-chain oligomers or polymers of the general formula (V) or (VI), where R ^{1 is} hydrogen. Preferred cyclic formaldehyde oligomers of the general formula (V) are 1,3,5-trioxane and 1,3,5,7-tetraoxane, preferred open-chain oligomers or polymers of the general formula Paraformaldehyde and polyoxymethylene are particularly preferred in my formula (VI); 1,3,5-trioxane and 1,3,5,7-tetraoxane are particularly preferred.

The cyclic or open-chain formaldehyde oligomers or polymers of the general formula (V) or (VI) can be used in pure form or dissolved or suspended in a suitable solvent of the abovementioned choice.

In a further embodiment of the process according to the invention, the aldehyde comprises compounds of the general formula (VII) where R ^{1 is} hydrogen. The compounds of general formula (VII) thus contain oxymethylene groups and are to be regarded as formaldehyde equivalents. Preferred compounds of the general formula (VII) are 1,3-dioxolane, 1,3-dioxane and 1,3-dioxepane.

In a specific embodiment, the aldehyde is a mixture of one or more compounds of general formula (V) and one or more compounds of general formula (VII). The mixtures preferably contain compounds of the general formula (V) and the general formula (VII) in which R ^{1 is} hydrogen. The mixtures particularly preferably contain 1,3,5-trioxane and / or 1,3,5,7-tetraoxane and also 1,3-dioxolane and / or 1,3-dioxane and / or 1,3-dioxepane.

The mixtures of compounds of the general formulas (V) and (VII) can be used in any desired composition. The mixtures preferably contain compounds of the general formula (V) and compounds of the general formula (VI) in a molar ratio of from 1:10 to 10: 1, more preferably from 1: 3 to 5: 1, very particularly preferably from 1 : 1 to 3: 1.

In a further embodiment, at least one unsaturated cyclic anhydride is used. Unsaturated cyclic anhydrides in the context of the invention are compounds of the general formula (III) where R ² contains at least one C =C double bond within the meaning given above, this C =C double bond not being part of an aromatic ring system. The C =C double bond may in this case be part of the chain R ² and / or part of a substituent contained in the chain R ² .

Examples of unsaturated cyclic anhydrides are maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, norbornene diacetic anhydride, dodecenylsuccinic anhydride, tetradecenylsuccinic anhydride, hexadecenylsuccinic anhydride, octadecenylsuccinic anhydride, itaconic anhydride, dimethylmaleic anhydride, allylnorbornendioic anhydride, 3-methylfuran-2,5-dione,

Nonenyldihydrofuran-2,5-dione, d-acetic acid anhydride. Preferred unsaturated cyclic anhydrides are maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic acid anhydride, norbornene diacetic anhydride, dodecenylsuccinic anhydride, tetradecenylsuccinic anhydride, hexadecenylsuccinic anhydride, octadecenylsuccinic anhydride, itaconic anhydride, dimethylmaleic anhydride, allylnorbornendioic anhydride, particularly preferred are maleic anhydride and itaconic anhydride. In a specific embodiment, the cyclic anhydride is a mixture of at least one unsaturated cyclic anhydride and at least one further cyclic anhydride, which is not an unsaturated cyclic anhydride and therefore a saturated cyclic anhydride. Mixtures are preferably used, in which the unsaturated cyclic anhydride is selected from the group hydrophthalic anhydride, tetrahydrophthalic anhydride, Methyltetra-, Norbornendisäureanhydrid, Dodecenylbemsteinsäureanhydrid, tetra- decenylsuccinic anhydride, hexadecenylsuccinic, Octadecenylbernstein- anhydride is selected itaconic anhydride, dimethyl maleic anhydride, and the saturated cyclic anhydride Allylnorbornendisäureanhydrid from the group of succinic anhydride, glutaric anhydride, 1,2-cyclohexanedicarboxylic anhydride, diglycolic anhydride. Particular preference is given to using mixtures in which the unsaturated cyclic anhydride is maleic anhydride and / or itaconic anhydride and the saturated cyclic anhydride is succinic anhydride and / or glutaric anhydride.

By using unsaturated cyclic anhydrides unsaturated polyacetal polyesters can be obtained which contain reactive C = C double bonds which, after reaction with thiols or under the influence of ultraviolet radiation or free-radical initiators such as organic peroxides, optionally with the addition of further unsaturated compounds such For example, styrene, acrylic acid or acrylic acid esters, can be connected to three-dimensional networks. The products thus obtained are particularly suitable for applications in the field of elastomers and thermosets. The ratio between unsaturated cyclic anhydrides and saturated cyclic

Anhydrides are freely selectable. However, it is preferred if the quantitative ratio between unsaturated cyclic anhydride and saturated cyclic anhydride is chosen such that in the resulting polyacetal polyester a double bond content of 0.5 to 15 wt .-%, preferably 1 to 10 wt .-%, particularly preferably from 2 to 5 wt .-%. The double bond content denotes the proportion by weight of the double bond-containing C = C units contained in the polyacetal polyester (with a molar mass of 24 g / mol) of the total weight of the polyacetal polyester.

In a further embodiment, at least one unsaturated open-chain monoanhydride is used. Unsaturated open-chain monoanhydrides in the context of the invention are compounds of the general formula (VIII) where R ^{3 has} the meanings given above at least contains a C = C double bond, this C = C double bond is not part of an aromatic ring system.

Examples of unsaturated open-chain monoanhydrides of the general formula (VIII) are anhydrides of mono- or polyunsaturated C 8 to C 20 fatty acids, such as e.g. Undecylenic anhydride, palmitoleic anhydride, petroselinic anhydride, oleic anhydride, elaidic anhydride, vaccenic anhydride, cadolinic anhydride, icosenoic anhydride, linoleic anhydride, α-linolenic anhydride, calendic anhydride, arachidonic anhydride, α, β-unsaturated anhydrides, e.g. Acrylic acid anhydride, methacrylic anhydride, crotonic anhydride or 2-ethyl-3-propylacrylic anhydride and their higher linear or branched homologues. Preferred unsaturated open-chain monoanhydrides are acrylic anhydride, methacrylic anhydride, crotonic anhydride or 2-ethyl-3-propylacrylic anhydride, particularly preferred are acrylic anhydride, crotonic anhydride and methacrylic anhydride.

In a preferred embodiment, the open-chain monoanhydride is an unsaturated open-chain monoanhydride or a mixture of two or more unsaturated open-chain monoanhydrides.

The use of unsaturated open-chain monoanhydrides polyacetal polyesters are obtained with unsaturated end groups containing C = C double bonds. These can be connected to three-dimensional networks after reaction with thiols or under the influence of ultraviolet radiation or radical initiators such as organic peroxides, optionally with the addition of further unsaturated compounds such as styrene, acrylic acid or acrylic acid esters. The products thus obtained are particularly suitable for applications in the field of elastomers and thermosets.

In one embodiment of the method according to the invention, this is carried out in a batch process. In the batch process, all components, ie aldehyde, cyclic anhydride, open-chain monoanhydride, catalyst and optionally solvent, are brought into contact with each other at the beginning of the reaction. This can be done by presenting a mixture of cyclic anhydride, open-chain monoanhydride and catalyst (optionally in the presence of a solvent) and then adding the aldehyde (optionally dissolved in a solvent). Alternatively, a mixture of cyclic anhydride, open chain monoanhydride and aldehyde (optionally in the presence of a solvent) may be charged and then the catalyst (optionally dissolved or suspended in a solvent) may be added. Furthermore, cyclic anhydride and aldehyde (optionally in the presence of a solvent) are introduced and then a mixture of open-chain _2Q

Monoanhydride and catalyst (optionally dissolved or suspended in a solvent) are added.

The reaction is initiated when at least one anhydride (open chain monoanhydride or cyclic anhydride), aldehyde and catalyst are contacted. In order to avoid homopolymerization of the aldehyde, it is advantageous if aldehyde and catalyst are brought into contact only in the presence of an anhydride. Furthermore, it is advantageous if the aldehyde, catalyst and open-chain monoanhydride are brought into contact only in the presence of the cyclic anhydride in order to suppress as far as possible the formation of low molecular weight products which result from open-chain monoanhydride and aldehyde without incorporation of cyclic anhydride.

In a further embodiment of the method according to the invention, this is carried out in a semi-batch process. When carried out in the semi-batch process, one or more of the components aldehyde, cyclic anhydride, open-chain monoanhydride and catalyst, if appropriate in the presence of a solvent, are introduced into the reactor, and the remaining components are metered in during the reaction. It is also possible for one or more components initially to introduce a subset and then to meter in the remaining amount together with the remaining components during the reaction.

In a special embodiment of the semi-batch process, catalyst, if appropriate dissolved in a suitable solvent, is introduced into the reactor and the reactor is brought to the desired reaction temperature. Then aldehyde, cyclic anhydride and open-chain monoanhydride are added. In principle, it is also possible to initially introduce only a partial amount of the catalyst at the beginning of the reaction and to meter in the remainder of the catalyst during the reaction. The metered addition of the components can be carried out in a mixture, together with a suitable solvent, or as a separate metered addition of the individual components, if appropriate dissolved in a suitable solvent, it being possible to choose the metering rate independently for each component. Furthermore, a partial amount of the respective individual components can be introduced analogously to a batch process in the reactor and the reaction can be initiated by adding the catalyst. The residual amounts of the respective individual components can then be metered in during the course of the reaction. In an alternative embodiment of the semi-batch process, cyclic anhydride and catalyst, if appropriate dissolved in a suitable solvent, are introduced into the reactor and aldehyde and open-chain monoanhydride are metered in as a mixture or as individual components, if appropriate dissolved in a suitable solvent. It is in principle also possible to initially introduce only a partial amount of the catalyst at the beginning of the reaction and to meter in the remainder of the catalyst during the reaction, it being advisable not to use the catalyst in the reaction _

 - 21 -

To meter mixture with aldehyde and open-chain monoanhydride. Furthermore, it is possible in this embodiment, initially present at the beginning of the reaction, only a subset of the cyclic anhydride and to meter in the remaining amount in the course of the reaction, either in admixture with open-chain monoanhydride and / or aldehyde or as a single component. In a further embodiment of the semi-batch process, a mixture of cyclic anhydride and open-chain monoanhydride, optionally dissolved in a suitable solvent and optionally in admixture with catalyst, is introduced into the reactor and aldehyde, optionally dissolved in a suitable solvent, is metered in during the reaction , It is also possible initially to introduce a partial amount of cyclic anhydride and open-chain monohydric anhydride and meter in the respective residual amount during the reaction, either mixed with one another and / or aldehyde, or as individual components. Furthermore, it is possible to initially introduce only a partial amount of the catalyst and to meter in the remaining amount during the reaction, it being advisable if the catalyst is not added in admixture with aldehyde and an anhydride. In a further embodiment of the semi-batch process, aldehyde, optionally dissolved in a suitable solvent, is introduced into the reactor, and cyclic anhydride, open-chain monoanhydride and catalyst in mixture or as individual components, optionally dissolved in a suitable solvent, are added to the reaction.

In a further embodiment of the method according to the invention this is carried out in a continuous process.

In one embodiment of the continuous process, a polyacetal polyester is first prepared by a batch or semi-batch process. Subsequently, the reaction is continuously metered in the components aldehyde, cyclic anhydride and open-chain monoanhydride and optionally catalyst and solvent. When the maximum fill level of the reactor is reached, a partial amount of the reaction mixture is withdrawn continuously, while the components aldehyde, cyclic anhydride, open-chain monoanhydride and catalyst and, if appropriate, solvent are metered in continuously. The components can be metered in as a mixture of two or more components and / or as individual components, it being advisable for the catalyst and aldehyde to come into contact with each other only in the reactor.

In one embodiment of the process according to the invention, the ratio of the amount of aldehyde used to the total amount of anhydrides (cyclic anhydride and open-chain monoanhydride) is between 1: 1 and 10: 1, preferably between 1: 1 and 6: 1, more preferably between 1: 1 and 3: 1. This ratio determines the average theoretical ""

 - 22 -

Number of m _th of acetal units within all polyacetal polyacetal contained in the polyacetal sections -0- (CHR ¹ -0) _m - (see formula (I)), wherein the average number of acetals found in a polyacetal polyester obtained Units within all polyacetal sections contained -0- (CHR ¹ -0) _m - may differ from m _t h and depends on the reaction conditions and the type of monomers used, the chain regulator used and the catalyst used. Typically, vc is in a range of 40% to 150% of _mt h, preferably in a range of 50%> to 125% of _mth and more preferably in a range of 60%) to 105% of _mt h and all more preferably in a range of 70% to 100% of mth, where vc can be determined, for example, by 'H-NMR spectroscopy, as described in the experimental part.

The precise setting of vc can be determined experimentally for a given polyacetal polyester (ie the combination of certain aldehydes with certain cyclic and open chain monoanhydrides) by systematic adjustment of the reaction parameters, the type and amount of catalyst and the molar ratio of the monomers (cyclic anhydride and aldehyde ) to one another and to the open-chain monoanhydride used.

In a further embodiment of the process according to the invention, the molar ratio of the amounts of cyclic anhydride used to open-chain monoanhydride (chain regulator) is between 1: 1 and 15,500: 1, preferably between 2: 1 and 1550: 1 and more preferably between 10: 1 and 100 The ratio of cyclic anhydride to open-chain monoanhydride can be used to set the theoretical number-average molecular weight MWth for a given ratio of the amount of aldehyde used to the total amount of anhydride used (open-chain monoanhydride and cyclic anhydride).

The theoretical number-average molecular weight MWth denotes the ratio of the total mass of monomers used (aldehyde and cyclic anhydride) and chain regulator (open-chain monoanhydride) to the molar amount of open-chain monoanhydride used. The actual number average molecular weight may differ from the theoretical number average molecular weight MW _th and depends on the reaction conditions and the type of monomers used, the chain regulator used and the catalyst used.

In one embodiment of the process according to the invention, the theoretical number average molecular weight MWth is in a range from> 232 g / mol to <2,000,000 g / mol, preferably from> 260 g / mol to <200,000 g / mol, particularly preferably> 1,000 g / mol to <25,000 g / mol. ""

 - 23 -

In a further embodiment, the number average molecular weight actually achieved ranges from 50 to 150% of the theoretical number average molecular weight MWth, preferably from 70% to 130% and more preferably from 80% to 110%) of the theoretical MW, the actual number average molecular weight being determined by gel permeation chromatography (GPC) or as average molecular weight by 'H-NMR spectroscopy, as described in the methods.

Accurate adjustment of the number average molecular weight actually achieved for a particular polyacetal polyester (ie the combination of certain aldehydes with certain cyclic and open chain monoanhydrides) can be achieved experimentally by systematic adjustment of the reaction parameters, the type and amount of catalyst and the molar ratio of the monomers (Cyclic anhydride and aldehyde) to each other and to the open-chain monoanhydride used.

The invention further relates to a process according to the invention obtainable polyacetal polyester.

-0 [(CHR ¹ 0) and / or polyoxyalkylene polyacetal portions _a ((CR ^'2) - In one embodiment of the invention, the polyacetal polyester polyacetal polyester polyacetal sections contain -0- (CHR ¹ -0) _m oO) b] i-, where R ^{1 is} hydrogen and R ', a, b, 1, m and o have the abovementioned meaning. In a preferred embodiment of the SEN erfindungsgemä- polyacetal polyester R ¹ is -0- in all contained polyacetal portions (CHR ¹ -0) _m - and / or polyoxyalkylene polyacetal portions -0 [(CHR ¹ 0) _a (( CR ^' 2) oO) b] i- hydrogen. In a preferred embodiment, the polyacetal polyesters therefore include oxymethylene units-O- (CH 2 -O) _m - as polyacetal sections. In a particularly preferred embodiment, R 'in the polyoxyalkylene polyacetal portions -0 [(CHR ¹ 0) _a ^((CR' ₂₎ oO) _b] i- also hydrogen. In a most preferred embodiment of the polyacetal polyesters of the invention, the polyacetal polyesters contain polyacetal moieties -O- (CHR ¹ -O) _m - where R ^{1 is} hydrogen and no polyoxyalkylene polyacetal moieties -0 [(CHR ¹ 0) _a ((CR ^' ₂ ) oO) _b ] i-.

In a further embodiment of the polyacetal polyesters according to the invention, the average number n of acetal units -CHR'-O- in polyacetal sections present between two ester units is -0- (CHR ¹ -0) _m -1 to 6, preferably 1.2 to 4, more preferably 1.8 to 3. The average number of nuvo of acetal units present between two ester units can be determined, for example, by 'H-NMR spectroscopic analysis of the incorporation ratio of aldehyde: anhydride in the product, as described in the experimental part. " _Λ

 - 24 -

In a further embodiment of the polyacetal polyesters according to the invention, these have a number-average molecular weight of> 232 g / mol to <2,000,000 g / mol, preferably from> 260 g / mol to <200,000 g / mol and particularly preferably> 388 g / mol to <25 000 g / mol. The number average molecular weight can be determined by gel permeation chromatography (GPC) or by the average molecular weight by 'H-NMR spectroscopy, as explained in the description of the methods.

In a further embodiment of the polyacetal polyesters according to the invention, these have a decomposition temperature Td> 130 ° C., preferably> 140 ° C. and particularly preferably> 180 ° C. The determination of the decomposition temperature by thermogravimetric analysis (TGA) is described in the experimental part.

In a further embodiment of the polyacetal polyesters according to the invention, the polyacetal polyesters are unsaturated polyacetal polyesters. Unsaturated polyacetal polyesters contain C = C double bonds which are not part of an aromatic ring system. These C =C double bonds can, for example, be converted into three-dimensional networks after reaction with thiols or under the influence of ultraviolet radiation or free-radical initiators such as organic peroxides, optionally with the addition of further unsaturated compounds such as styrene, acrylic acid or acrylic acid esters. The products thus obtained are particularly suitable for applications in the field of elastomers and thermosets. Unsaturated polyacetal polyesters can be obtained by a process according to the invention by using unsaturated cyclic anhydrides and / or unsaturated open-chain monoanhydrides and / or unsaturated aldehydes.

In one embodiment of the unsaturated polyacetal polyesters according to the invention, these have a double bond content of from 0.5 to 15% by weight, preferably from 1 to 10% by weight, particularly preferably from 2 to 5% by weight. The double bond content refers to the proportion by weight of the double bond-containing C = C units contained in the polyacetal polyester (with a molar mass of 24 g / mol) of the total weight of the unsaturated polyacetal polyester.

Polyacetal polyesters are of interest for applications as thermoplastics or polymer additives, for example in the polyoxymethylene (POM) or polyester sector. Furthermore, polyacetal polyesters are of interest for applications such as plasticizers, detergent and cleaner formulations, emulsion paints, drilling fluids, fuel additives, ionic and nonionic surfactants, lubricants, process chemicals for the paper or textile production or cosmetic formulations.

Therefore, the invention further relates to the use of polyacetal polyesters as thermoplastics or polymer additives, in particular as a plasticizer, in washing and ^

Detergent formulations, emulsion paints, drilling fluids, as fuel additives, in ionic and nonionic surfactants, lubricants, as process chemicals for paper or textile production or in cosmetic formulations.

Unsaturated polyacetal polyesters can be connected to three-dimensional networks after reaction with thiols or under the influence of ultraviolet radiation or free-radical initiators such as organic peroxides, optionally with the addition of other unsaturated compounds such as styrene, acrylic acid or acrylic acid esters. The products thus obtained are particularly suitable for applications in the field of elastomers and thermosets.

Therefore, the invention further relates to the use of unsaturated polyacetal polyesters as feedstocks for elastomers and duromers.

_

 - 26 -

Examples

The invention will be explained in more detail with reference to the following figures and examples, but without being limited thereto.

Aldehydes used: 1,3,5-trioxane [110-88-3]: Aldrich, catalog no. T81108,> 99%

Methacrolein [78-85-3]: Aldrich, catalog no. 133035.95%

Furfural [98-01-1]: Aldrich, catalog no. 185914, 99%

Paraldehyde [123-63-7]: Aldrich, catalog no. 76260,> 97%

Cyclic anhydrides used: succinic anhydride [108-30-5]: Aldrich, catalog no. 239690,> 99%

Glutaric anhydride [108-55-4]: Aldrich, catalog no. G3806, 95%

Itaconic Acid Anhydride [2170-03-8]: Acros Organics, catalog no. 412940250, 98%

Used open-chain monoanhydrides:

Acetic anhydride [108-24-7]: Aldrich, catalog no. 320102,> 99% benzoic anhydride [93-97-0]: Aldrich, catalog no. AB109129, 98% methacrylic anhydride [760-93-0]: Aldrich, cat. No. 276685, 94% Catalysts used:

Trifluoromethanesulfonic acid [1493-13-6]: Aldrich, catalog no. 347817, 99% bismuth (III) triflate [88189-03-1]: Aldrich, cat. No. 633305 Solvents used: dichloromethane [75-09-2]:

As reaction solvent: Aldrich, catalog no. 270997,> 99.8% (contains 50 - 150 ppm amylene, <8 ppm water)

For refurbishment: Aldrich, catalog no. 443484, 99.5% purity (includes 50 ppm amylene) "

 - 27 -

Chloroform [67-66-2]: Aldrich, catalog no. 3485,> 99.8% (HPLC grade)

Acetone [67-64-1]: Aldrich, catalog no. 650501,> 99.9% dimethyl formate [68-12-2]: Aldrich, catalog no. D4551,> 99% dimethyl sulfoxide [67-68-5], Aldrich, catalog no. D4540,> 99.5% tetrahydrofuran [109-99-9], Fluka, catalog no. 87371,> 99.5% methanol [67-56-1], Aldrich, catalog no. 34860,> 99.9% l, l, l, 3,3,3-hexafluoro-2-propanol [920-66-1], Aldrich, cat. No. 105228,> 99% Reactors used: Reactor 1: Double-walled glass reactor with an internal reactor volume of 100 mL. The interior of the reactor had the following connections: a neck of NS29 glass, fitted with a reflux condenser connected via the top opening to an argon line and a bubble counter for pressure equalization, a neck with GL18 fitting fitted with a PTFE-coated thermocouple (Pt100 external probe 8981016) was inserted into the reactor interior so as to reach the reaction mixture, a neck with GL18 fitting for the addition and withdrawal of reagents and a Schlenk connection with stopcock connected to an argon line. The outer jacket had two connections with a GL 14 screw connection, via which the heat transfer medium was supplied and removed. The reactor was heated via the outer jacket with a mixture of 30 vol.% Ethylene glycol in water as Wärmeträgerme- dium. The temperature of the heat transfer medium was carried out with a thermostat CF41 Julabo. The temperature control was carried out via the internal temperature of the reactor with the help of there extending into the thermocouple. The mixing of the reaction mixture was carried out with a PTFE-coated magnetic stirrer.

Reactor 2: Autoclave made of stainless steel with an internal volume of 200 mL. The reactor was equipped with a thermocouple, a manometer, a Premex stirrer with gas inlet stirrer, a rupture disk (maximum pressure 293 bar at 20 ° C), a gas inlet with shut-off valve and an additional hole in the reactor head with blanking plug (access 1) for addition and removal of Reagents equipped. The connection of the thermocouple, the manometer, the bursting disc and the supply lines to the reactor was made via swagelock screw connections. The reactor was heated by a heating jacket. The temperature was controlled by means of the thermocouple via the internal reactor temperature, the thermocouple was mounted so that it reached into the reaction mixture. The control of the temperature and the stirring speed was carried out with control units from Horst. Description of the methods:

The theoretical number-average molecular weight MWth was determined according to the following formula: m Aid + m _oA + m zA

MW _t , where mAid denotes the total mass of aldehydes used, nioA denotes the total mass of open-chain monoanhydrides used, m _Z A denotes the total mass of cyclic anhydrides used and rioA denotes the total amount of open-chain monoanhydrides used.

Gel Permeation Chromatography (GPC): Measurements were made on the 1200 Series (G1310A Iso Pump, G1329A ALS, G1316A TCC, G1362A RID, G1365D MWD) from Agilent, detection via RID; Eluent: chloroform (HPLC grade), flow rate 1.0 ml / min; Column combination: PSS SDV precolumn 8x50 mm (5 μιη), 2x PSS SDV linear S 8x300 ml (5 μιη).

Polystyrene samples of known molecular mass from "PSS Polymer Standards Service" were used for the calibration and the software package "PSS WinGPC Unity" was used as the measurement recording and evaluation software. The GPC chromatograms were recorded on the basis of DIN 55672-1 using chloroform instead of tetrahydrofuran as the eluent.

'H NMR Spectroscopy: Measurements were taken on the AV400 (400 MHz) instrument from Broker; the chemical shifts were calibrated relative to trimethylsilane as an internal standard (δ = 0.00 ppm) or to the solvent signal (CDCb, δ = 7.26 ppm); s = singlet, m = multiplet, bs = widened singlet, kb = complex region. The indication of the size of the surface integrals of the signals is relative to one another.

The determination of n vc (average number of acetal units between two ester units) was carried out by determining the incorporation ratio aldehyde: anhydride according to the following equation:

_ _ ^N Ald A _ALD IP _MD

mAVG ^{~ ~} . 1 I '

n ₀ A + n _zA AIPOA + AI PZA where nAid stands for the amount of aldehyde units which have been incorporated into the product as acetal units (in the case of formaldehyde or 1,3,5-trioxane, ie oxymethylene units -CH 2 O-), AAM for the area integral (or the sum of all surface integrals) of these units in the 'H-NMR spectrum, _AW for the number of hydrogen atoms contained in this unit (in the case of formaldehyde or 1,3,5-trioxane, ie pAid = 2), noA for the amount of substance open-chain monoanhydride incorporated in the product in the form of acyl groups (two acyl groups being formed from each molecule of an open-chain monoanhydride), A ₀ A represents the area integral (or the sum of all surface integrals) of the acyl-group-containing open-chain monoanhydrides in the 'H' NMR spectrum, p ₀ A for the number of hydrogen atoms in a molecule of the incorporated open-chain monoanhydride (ie p ₀ A = 6 for acetic anhydride, p ₀ A = 10 for benzoic anhydride, p ₀ A = 10 for methacrylic anhydride), n _Z A for the amount of diester unit cyclic anhydride, A _ZA for the area integral (or the sum of all area integrals) of the cyclic anhydrides incorporated in the form of diester units, and p _Z A for the number the hydrogen atoms in a molecule of the incorporated cyclic anhydride (ie p _Z A = 4 for succinic anhydride, p _Z A = 6 for glutaric anhydride, p _Z A = 4 for itaconic anhydride).

The determination of the average molecular weight MWAVG was carried out according to the following equation:

wherein AAW, PAW, A ₀ A, POA, A _Z A, p _Z A have the abovementioned meaning, and MAW represents the molar mass of the incorporated in the form of acetal units aldehyde (ie MAW = 30.03 g / mol for formaldehyde or 1,3,5-trioxane), M ₀ A for the molar mass of the incorporated in the form of acyl groups open-chain monoanhydride (ie M ₀ A = 102.09 g / mol for acetic anhydride, M ₀ A = 226.23 g / mol for benzoic anhydride, M ₀ A = 154.15 g / mol for methacrylic anhydride) and M _Z A for the molar mass of the incorporated in the form of diester units cyclic anhydride (ie M _Z A = 100.07 g / mol for Succinic anhydride, M _Z A = 114.10 g / mol for glutaric anhydride and M _Z A = 112.08 for itaconic anhydride).

¹³ C NMR Spectroscopy: Measurements were taken on the Bruker AV400 (100 MHz) instrument; the chemical shifts were calibrated relative to trimethylsilane as an internal standard (δ = 0.00 ppm) or to the solvent signal (CDCl3, δ = 77.16 ppm); APT (attached proton test): CFh, C _qua rt: positive signal (+); CH, CH3: negative signal (-); HMBC: Hetero multiple bond correlation; HSQC: heteronuclear single-quantum correlation. _3Q

Infrared (IR) spectroscopy: Measurements were taken on Bruker's Alpha-P FT-IR spectrometer; the measurements were made in pure substance; Signal intensities: vs = very strong, s = strong, m = medium, w = weak, vw = very weak; b = broadened band.

TGA (thermogravimetric analyzes) were carried out with the device TGA / DSC 1 from Mettler Toledo. Between 6 and 20 mg of the sample to be measured were heated from 25 ° C. to 600 ° C. at a heating rate of 10 K / min and the relative weight loss as a function of the temperature was determined. The evaluation software used was STARe SW 11.00. Unless otherwise stated, a tangential evaluation method was used to determine the different decomposition stages. The decomposition temperature Td is the "midpoint" of the first decomposition step.

The determination of the glass transition temperature was carried out by DSC (differential scanning calorimetry) on a DSC 1 STARe from Mettler Toledo. The sample was measured at a heating rate of 10 K / min over four heating cycles from -80 ° C to + 100 ° C. The glass transition temperature T _g was given for the second heating rate. Carrying out the experiments

Protocol 1: Preparation of Polyacetal Polyesters in Reactor 1 (Open System with Pressure Equilibrium)

In the heated reactor 1, 80 mL of dichloromethane were placed under an argon atmosphere. Aldehyde, cyclic anhydride and open chain monoanhydride were then added while stirring in argon countercurrent. Subsequently, catalyst (1 mol% based on the total amount of the anhydrides used) was added with stirring in an argon countercurrent catalyst. The resulting reaction mixture was heated under reflux to 40 ° C internal temperature and stirred for 12 hours under reflux at 40 ° C and 48 h at 25 ° C (at a stirring speed of 300 U / min). Subsequently, the resulting reaction mixture was poured into 100 mL of saturated aqueous sodium carbonate solution. The organic phase was separated and the aqueous phase extracted three times with 100 mL dichloromethane. The organic fractions were combined and the volatiles removed under reduced pressure. The distillation residue was dried for 16 hours at 2 × 10 ^-3 bar.

Regulation 2: Preparation of polyacetal polyesters in reactor 2 (closed system without pressure equalization)

Reactor 2 was charged with cyclic anhydride and optionally with catalyst. The reactor was closed and exposed to 3 bar argon four times and relaxed against atmospheric pressure. In a heated Schlenk tube was under argon atmosphere aldehyde in 20 mL dissolved dry dichloromethane. The resulting solution was transferred to Reactor 2 via a syringe via Access 1 against an argon stream. Subsequently, the Schlenk tube was rinsed with 20 mL of dry dichloromethane and the rinse solution was also transferred via a syringe via access 1 against an argon stream in reactor 2. Subsequently, in the same Schlenk tube under argon atmosphere, open-chain monoanhydride was dissolved in 20 mL of dry dichloromethane. If no catalyst was initially charged in reactor 2, then catalyst was added to the solution of the open-chain monoanhydride. The resulting solution was transferred to Reactor 2 via a syringe via Access 1 against an argon stream. Subsequently, the Schlenk tube was rinsed with 20 mL of dry dichloromethane and the rinse solution was also transferred via a syringe via access 1 against an argon stream in reactor 2. In the next step, access 1 was shut off, the reactor charged with 3 bar argon and the gas inlet valve closed. The reaction mixture was heated with stirring at 800 U / min to 100 ° C and stirred after reaching the temperature for a further 18 h at this temperature. Then the heater was turned off. After the internal temperature had dropped to 30 ° C, the reactor was depressurized. After opening the reactor, the reactor contents were filtered through a paper filter into a round bottom flask containing sodium acetate and a magnetic stir bar. Reactor 2 was rinsed twice with 20 ml of dichloromethane, the filter residue was washed with the respective rinse solution, and the washings were combined with the filtrate. Subsequently, the resulting mixture was stirred at 300 rpm for 45 minutes. Subsequently, the mixture was filtered through a paper filter. The round bottom flask was rinsed twice with 20 mL dichloromethane, the filter residue washed with the respective rinse solution and the washings combined with the filtrate. After removal of the volatiles under reduced pressure, the distillation residue was dried for 1 hour at 2 ^× 10 ^-3 bar.

Example 1: formaldehyde / B-type anhydride copolymer (polyacetal polyester) obtained according to procedure 1 using acetic anhydride as a chain regulator and trifluoromethanesulfonic acid as catalyst, ratio open-chain monoanhydride: cyclic anhydride = 1: 1 0.

According to protocol 1, 50 μM trifluoromethanesulfonic acid, 5.34 g trioxane (corresponding to 177 mmol formaldehyde), 5.50 g (55 mmol) succinic anhydride and 0.55 g (5.4 mmol) acetic anhydride were used. After drying in vacuo, 7.76 g of a yellow viscous oil were obtained. A fraction (0.97 g) of the product was taken up in 50 mL dichloromethane and filtered through a paper filter. After removing the volatiles of the filtrate under reduced pressure, 0.69 g of a yellow oil was obtained.

The theoretical number average target molecular weight was MWth = 2109 g / mol. ""

 - 32 -

By gel permeation chromatography (GPC) against polystyrene standards with chloroform as the eluent, a number average molecular weight M _n = 2091 g / mol and a polydispersity index PDI = 1.99 were determined.

By differential scanning calorimetry (DSC), a glass transition temperature T _g = -28.5 ° C was determined.

IR: v = 2975 (vw, v [CH ₂ ]), 1737 (s, v [C = 0]), 1559 (w), 1411 (w), 1359 (w), 1319 (vw), 1207 (vw ), 1115 (s), 1078 (vw), 909 (vs), 835 (vw), 805 (vw), 661 (vw) cm ^"1 .

'Η-ΝΜΡν (400 MHz, CDCl ₃ ): δ = 2.10 (m, 3.000 H, C (O) CH ₃ ), 2.69 (m, 20.9449 H, C (O) CH ₂ CH ₂ C (0)), 4.89 (m, 9.0759 H, CH ₂ 0-CH ₂ 0-CH ₂ 0), 5.37 (m, 17.2049 H, C (0) 0-CH ₂ 0 - CH ₂ 0), 5.76 (m, 2.6836 H, C (O) O-CH ₂ O-C (0)) ppm.

According to 1 H-NMR spectroscopy, the ratio is CH ₃ CO: C (O) CH ₂ CH ₂ C (O): CH ₂ O = 2: 10.48: 28.96.

Thus, IHAVG ⁼ 2.52.

The average molecular weight is MWAVG = 2019 g / mol. ¹³ C-APT NMR (125 MHz, CDCl 3): δ = 28.7 (+, C (O) CH ₂ CH ₂ C (0)), 28.9 (+, C (0) CH ₂ CH ₂ C (0)),

79.4 (+, CH ₂ O), 79.5 (+, CH ₂ O), 85.9 (+, CH ₂ O), 87.1 (+, CH ₂ O), 89.3 (+, CH ₂ 0), 90.8 (+, CH ₂ 0),

92.5 (+, CH ₂ 0), 171.6 (+, C = 0) ppm.

Remote coupling of a ¹³ C NMR signal at 171.6 ppm (C = 0) to an 'H NMR signal at 5.76 ppm and an' H NMR signal at 5, was determined by HMBC NMR spectroscopy. 37 ppm were observed, which were assigned to oxymethylene groups. This demonstrates beyond any doubt that the ester groups resulting from the anhydrides are bound to oxymethylene groups.

Furthermore, the following remote couplings between oxymethylene groups (assignment of the ¹³ C NMR signals to the corresponding 'H NMR signals by HSQC NMR spectroscopy) were observed by HMBC spectroscopy: ¹³ C NMR /' H NMR remote coupling to ¹ H-NMR / ¹³ C-NMR

85.9 ppm / 5.37 ppm 4.89 ppm / 89.3-92.5 ppm

87.1 ppm / 5.37 ppm 5.37 ppm / 87.1 ppm

90.8 ppm / 4.89 ppm 4.89 ppm / 90.8 ppm; 5.37 ppm / 87.1 ppm

92.5 ppm / 4.89 ppm 5.37 ppm / 87.1 ppm ""

 - 33 -

This demonstrates beyond any doubt that bonds of the oxymethylene groups bonded to ester groups at 85.9 and 87.1 ppm ( ¹³ C-NMR signal) and 5.37 ppm ('H-NMR signal) lead to further oxymethylene groups consist.

Thus, the structure of the polyacetal polyester of the invention is proven beyond doubt. By thermogravimetric analysis (TGA), a decomposition temperature Td = 218 ° C was determined.

EXAMPLE 2 Fumaricdehyde / B is obtained according to procedure 1 using acetic anhydride as chain regulator and trifluoromethanesulfonic acid as catalyst, ratio open-chain monoanhydride: cyclic anhydride = 1: 100.

According to protocol 1, 50 μM trifluoromethanesulfonic acid, 5.34 g trioxane (corresponding to 177 mmol formaldehyde), 5.55 g (55 mmol) succinic anhydride and 0.05 mL (0.054 g, 0.53 mmol) acetic anhydride were used. After drying in vacuo, 8.19 g of a yellow viscous oil were obtained. A fraction (0.43 g) of the product was taken up in 50 mL dichloromethane and filtered through a paper filter. Removal of the volatile constituents of the filtrate under reduced pressure gave 0.27 g of a yellow oil.

The theoretical number average target molecular weight was MWth = 20649 g / mol.

The product is soluble in chloroform.

No glass transition temperature was observed by differential scanning calorimetry (DSC). IR: v = 2982 (vw, v [CH ₂ ]), 2927 (vw, v [CH ₃ ]), 1735 (s, v [C = 0]), 1464 (vw), 1410 (w), 1358 ( w), 1319 (vw), 1238 (vw), 1205 (vw), 1155 (vw), 1116 (s), 1077 (vw), 917 (vs), 836 (vw), 803 (vw), 553 ( vw) cm ^"1 .

'H-NMR (400 MHz, CDC1 _3): δ = 2.11 (m, 3.000 H, C (0) CH _3), 2.69 (m, H 201.3750, C (0) CH ₂ CH ₂ C (0)), 4.90 (m, 47.8427 H, CH ₂ 0-CH ₂ 0-CH ₂ 0), 5.36 (m, H 146.3479, C (0) 0- _CH2 0 -CH ₂ O), 5.77 (m, 25.46255 H, C (O) O-CH ₂ O-C (0)) ppm.

According to 1 H-NMR spectroscopy, the ratio is CH ₃ CO: C (O) CH ₂ CH ₂ C (0): CH ₂ O = 2: 100.69: 219.65.

This is n vo

The average molecular weight is MWAVG = 16774 g / mol. " _Λ

 - 34 -

¹³ C-APT NMR (125 MHz, CDCl ₃ ): δ = 28.7 (+, C (O) CH ₂ CH ₂ C (0)), 28.9 (+, C (0) CH ₂ CH ₂ C (0)), 79.5 (+, CH ₂ O), 85.9 (+, CH ₂ O), 87.1 (+, CH ₂ O), 90.8 (+, CH ₂ O), 92.5 (+, CH ₂ O), 171.6 (+, C = 0) ppm.

By thermogravimetric analysis (TGA), a decomposition temperature Td = 217 ° C was determined.

comparison

Table 1: Molecular weight control by adjusting the ratio of open-chain monoanhydride: cyclic anhydride in the preparation of polyacetal polyesters. ^a

 a Obtained using Procedure 1 with trifluoromethanesulfonic acid as catalyst; Aldehyde = trioxane, cyclic anhydride = succinic anhydride, open-chain monoanhydride logo CNRS logo INIST

Acetic anhydride, molar ratio of aldehyde: total anhydride = 3: 1

Examples 1 and 2 according to the invention show that polyacetal polyesters of the invention are obtainable by a process according to the invention by reacting an aldehyde (trioxane) with a cyclic anhydride (succinic anhydride) in the presence of a catalyst (trifluoromethanesulfonic acid) and an open-chain monoanhydride (acetic anhydride) as a chain regulator are.

Comparison of Examples 1 and 2 of the present invention shows that by changing the molar ratio of open-chain monoanhydride to cyclic anhydride while maintaining the molar ratio of aldehyde to total anhydride under otherwise similar reaction conditions, products having different average molecular weight MWAVG, the average molecular weight obtained MWAVG is in the range of 50% to 150% of the theoretical number average molecular weight. The function of the open-chain monoanhydride as a chain regulator is thus proved beyond doubt. "

 - 35 -

Example 3: Formaldehyde / B-type anhydride copolymer (polyacetal polyester) obtained according to procedure 2 using acetic anhydride as a chain regulator and trifluoromethanesulfonic acid as catalyst

According to procedure 2, 5.50 g (55 mmol) of succinic anhydride were initially introduced in reactor 2 and successively 5.34 g (59 mmol) of trioxane (corresponding to 177 mmol of formaldehyde), 0.55 g (5.4 mmol) of acetic anhydride and 50 μΕ Trifluoromethanesulfonic added. After drying in vacuo, 10.75 g of an amber oily suspension were obtained. A fraction (2.33 g) of the product was taken up in 100 mL dichloromethane and filtered through a paper filter. Removal of the volatiles of the filtrate under reduced pressure gave 1.85 g of an amber oil.

The product is soluble in chloroform.

A glass transition temperature T _g = -39.5 ° C was determined by differential scanning calorimetry (DSC).

IR: v = 2982 (vw, v [CH ₂ ]), 2926 (vw, v [CH ₃ ]), 1863 (vw, v [C = 0]), 1784 (w, v [C = 0]), 1736 (s, v [C = 0]), 1460 (vw), 1411 (w), 1361 (w), 1319 (vw), 1206 (vw), 1116 (s), 1079 (vw), 1046 (w ), 904 (vs), 835 (vw), 735 (vw), 606 (vw), 561 (vw) cm ^"1 .

'H-NMR (400 MHz, CDC1 _3): δ = 2.09 (m, 3.000 H, C (0) CH _3), 2.69 (m, 18.0341 H, C (0) CH ₂ CH ₂ C (0)), 2.99 (s, 5.1749 H, C (0) CH ₂ CH ₂ C (0), succinic anhydrides), 3.68 (s, 0.7834 H), 4.91 (m , 7.3470 H, CH ₂ 0-CH ₂ 0-CH ₂ 0), 5.14 (s, 0.3365 H, 3 x CH ₂ 0, trioxane), 5.35 (m, 10.3368 H, C (0) 0-CH ₂ 0-CH ₂ 0), 5.75 (m, 3.4860 H, C (0) 0-CH ₂ 0-C (0)) ppm.

According to 1 H-NMR spectroscopy, the ratio is CH ₃ CO: C (O) CH ₂ CH ₂ C (0): CH ₂ O = 2: 9.02: 21.17.

Thus n vc = 2.11.

The average molecular weight is MWAVG = 1640 g / mol. ¹³ C-APT NMR (125 MHz, CDCl 3): δ = 20.8 (-, C (O) CH ₃ ), 28.5 (+, C (O) CH ₂ CH ₂ C (0)), 28 , 6 (+,

C (O) CH ₂ CH ₂ C (O)), 28.7 (+, C (O) CH ₂ CH ₂ C (O)), 28.9 (+, C (O) CH ₂ CH ₂ C ( 0)), 29.4 (+, C (O) CH ₂ CH ₂ C (O)), 78.5 (+, CH ₂ O), 79.4 (+, CH ₂ O), 79.5 ( +, CH ₂ O), 85.9 (+, CH ₂ O), 87.1 (+, CH ₂ O), 87.1 (+, CH ₂ O), 89.3 (+, CH ₂ O) , 90.8 (+, CH ₂ O), 92.4 (+, CH ₂ O), 171.1 (+, C = 0), 171.6 (+, C = 0), 171.7 (+ , C = 0) ppm.

By thermogravimetric analysis (TGA), a decomposition temperature Td = 146 ° C was determined. ""

 - 36 -

EXAMPLE 4 (Comparative Example) Reaction of trioxane with acetic anhydride according to procedure 2 in the absence of a cyclic anhydride using trifluoromethanesulfonic acid as catalyst

In reactor 2, in the absence of a cyclic anhydride according to procedure 2, 5.35 g (59 mmol) of trioxane (corresponding to 177 mmol of formaldehyde) and a mixture of 6.07 g (60 mmol) of acetic anhydride and 50 μM of trifluoromethanesulfonic acid were added. After removing the volatiles under reduced pressure, 9.56 g of a low-viscosity liquid were obtained. On drying in vacuo was omitted.

The product is soluble in chloroform. 'H-NMR (400 MHz, CDC1 _3): δ = 2.07 (m, 3.000 H, C (0) CH _3), 4.87 (m, 0.5923 H, CH ₂ 0-CH ₂ 0-

((S, 0.4117 H, 3 x CH ₂ 0, trioxane), 5.30 (m, 1.0879 H, C 0) _CH2 0), 5.11 0 0 CH _{2-CH 2} 0) , 5.68 (s, 0.4897 H, C (0) 0-CH ₂ 0-C (0)) ppm.

According to 'H-NMR spectroscopy the ratio is CH ₃ CO: CH ₂ 0 = 2: 2,11.

Thus n vc = 2.11. The average molecular weight is MWAVG = 165.5 g / mol.

¹³ C-APT NMR (125 MHz, CDCl 3): δ = 20.7 (-, CH ₃ C (0)), 20.9 (-, CH ₃ C (0)), 21.0 (-, CH ₃ C (0)), 79.2 (+, CH ₂ O), 85.5 (+, CH ₂ O), 85.6 (+, CH ₂ O), 86.9 (+, CH ₂ O) , 89.2 (+, CH ₂ O), 89.2 (+, CH ₂ O), 89.2 (+, CH ₂ O), 90.7 (+, CH ₂ O), 90.8 (+ , CH ₂ O), 92.4 (+, CH ₂ O), 93.6 (+, CH ₂ O, trioxane), 169.8 (+, C = 0) ppm. EXAMPLE 5 (Comparative Example): Formaldehyde / B ernstoic acid ester copolymer obtained according to procedure 2 in the absence of an open-chain monoanhydride as a chain regulator using trifluoromethanesulfonic acid as catalyst

In accordance with protocol 2, 5.51 g (55 mmol) of succinic anhydride were initially introduced in reactor 2, and 5.34 g (59 mmol) of trioxane (corresponding to 177 mmol of formaldehyde) and 50 μM of trifluoromethanesulfonic acid were successively added. After drying in vacuo, 10.13 g of a brown solid were obtained. A fraction (0.97 g) of the product was taken up in 100 mL dichloromethane and filtered through a paper filter. Removal of the volatiles of the filtrate under reduced pressure gave 0.56 g of a brown solid. Thus, only 57.7% by weight of the product was found in the filtrate, while 42.3% by weight of the product was obtained as an insoluble solid. The soluble fraction was analyzed as follows:

By differential scanning calorimetry (DSC), a glass transition temperature T _g = -32.5 ° C was determined.

IR: v = 2980 (vw, v [CH ₂ ]), 2932 (vw, v [CH ₂ ]), 1734 (s, v [C = 0]), 1682 (vw), 1416 (w), 1360 ( w), 1316 (vw), 1197 (vw), 1156 (vw), 1115 (s), 1025 (w), 908 (vs), 835 (vw), 802 (vw), 735 (vw), 606

(vw) cm ^"1 .

'H-NMR (400 MHz, CDC1 _3): δ = 1.23 (m, 28.8106 H), 2.10 (m, 3.000 H, C (0) _CH3), 2.69 (m, 347 , 0078 H, C (0) CH ₂ CH ₂ C (0)), 3.00 (s, 4.8116 H, C (0) CH ₂ CH ₂ C (0), succinic anhydrides), 3.69 (s , 33.1471 H), 4.14 (m, 12.3523 H), 4.89 (m, 72.9132 H, CH ₂ 0-CH ₂ 0-CH ₂ 0), 5.15 (s, 8 , 7264 H, 3 x CH ₂ 0, trioxane), 5.37 (m, H 144.2745, C (0) 0-CH ₂ 0-CH ₂ 0), 5.76 (m, 59.8011 H,

C (0) 0 -CH ₂ 0-C (0)) ppm.

According to 'H-NMR spectroscopy, mwo = 1.60.

A determination of the average molecular weight by 'H-NMR spectroscopy is not possible. ¹³ C-APT NMR (125 MHz, CDCl 3): δ = 28.6 (+, C (O) CH ₂ CH ₂ C (0)), 28.7 (+, C (0) CH ₂ CH ₂ C (0)),

28.9 (+, C (O) CH ₂ CH ₂ C (O)), 29.1 (+, C (O) CH ₂ CH ₂ C (O)), 29.4 (+, C (0) CH ₂ CH ₂ C (O)), 52.1 (-), 78.6 (+, CH ₂ O), 79.5 (+, CH ₂ O), 85.9 (+, CH ₂ O), 87.1 (+, CH ₂ O), 90.8 (+, CH ₂ O), 171.1 (+, C = 0), 171.6 (+, C = 0).

By thermogravimetric analysis (TGA), a decomposition temperature Td = 95 ° C was determined.

comparison

Table 2: Preparation of polyacetal polyesters ^a in the presence or absence of cyclic anhydrides and open-chain monoanhydrides.

Example Presence Insoluble fraction MWAVG T _d open-chain cyclic [wt%] [g / mol] [° C] monoanhydride anhydride

3 yes yes 20,6 1640 146

4 (cf.) Yes no 0 166 n.b.

5 (no.) No yes 42.3 nb 95 ^a Obtained using Procedure 2 with trifluoromethanesulfonic acid as catalyst; Aldehyde = trioxane, cyclic anhydride = succinic anhydride, open chain monoanhydride = acetic anhydride, aldehyde molar ratio: total anhydride = 3: 1; nb = not determinable. Example 3 according to the invention demonstrates that polyacetal polyesters according to the invention are obtained by reacting an aldehyde (trioxane) with a cyclic anhydride (succinic anhydride) in the presence of a catalyst (trifluoromethanesulfonic acid) and an open-chain monoanhydride (acetic anhydride).

Comparison of example 4 (comparative example) with inventive example 3 shows that polyacetyl polyesters according to the invention are not obtained when under the same conditions trioxane as aldehyde in the presence of trifluoromethanesulfonic acid as catalyst and acetic anhydride as open chain monoanhydride but in the absence of a cyclic anhydride reacts (according to the prior art, Angew Chem 1962 (74), 248). Instead, low molecular weight products are obtained with a molecular weight <232 g / mol. Comparison of Example 5 (Comparative) with Example 3 of this invention shows that the reaction of trioxane as aldehyde with succinic anhydride as the open chain monoanhydride in the presence of trifluoromethanesulfonic acid as a catalyst but in the absence of an open chain monoanhydride under otherwise similar conditions greatly enhances products insoluble solid fraction, which is presumably due to the formation of high molecular weight products and / or polyacetal polyester-deviating structure (eg polyoxymethylene). Further, in the absence of open-chain monoanhydrides, a thermally unstable product having a decomposition temperature of 95 ° C was obtained. It was thus shown that, in the absence of open-chain monoanhydrides, no thermally stable polyacetal polyesters according to the invention with a defined molecular weight distribution are obtained.

Example 6 (comparative example): Thermal stability of polyoxymethylene homopolymers

The thermal stability of paraformaldehyde as a representative of oligomeric polyoxymethylene homopolymers was investigated by thermogravimetric analysis (TGA). It was determined a decomposition temperature T _d = 129 ° C. ^

comparison

Table 3: Thermal stability of polyacetal polyesters compared to polyoxymethylene homopolymers.

Example product T _d

[° C]

1 trioxane / succinic anhydride copolymer 218

6 (See) paraformaldehyde (formaldehyde homopolymer) 129

The comparison of Example 1 to Example 6 (Comparative Example) shows that polyacetal polyesters according to the invention in which the acetal units are derived from formaldehyde have increased thermal stability over formaldehyde homopolymers.

Example 7: Formaldehyde / B A-type (polyacetal-polyester) copolymer obtained according to procedure 1 using bismuth (III) triflate as a catalyst

According to procedure 1, 402.1 mg bismuth (III) triflate, 5.34 g trioxane (corresponding to 177 mmol formaldehyde), 5.51 g (55 mmol) succinic anhydride and 0.55 g (5.4 mmol) acetic anhydride were used. After drying in vacuo, 7.55 g of a yellow viscous oil were obtained. A fraction (0.95 g) of the product was taken up in 50 mL dichloromethane and filtered through a paper filter. Removal of the volatiles of the filtrate under reduced pressure gave 0.63 g of a yellow oil.

The product is soluble in chloroform.

By gel permeation chromatography (GPC) against polystyrene standards with chloroform as the eluent, a number average molecular weight M _n = 1987 g / mol and a polydispersity index PDI = 1.52 were determined.

By differential scanning calorimetry (DSC), a glass transition temperature T _g = -25.3 ° C was determined.

IR: v = 2982 (vw, v [CH ₂ ]), 2930 (vw, v [CH ₃ ]), 1737 (s, v [C = 0]), 1461 (w), 1410 (w), 1359 ( w), 1319 (vw), 1205 (vw), 1119 (s), 1076 (vw), 1021 (vw), 931 (vs), 835 (vw), 803 (vw), 606 (vw), 556 ( vw) cm ^"1 . _

 - 40 -

'H-NMR (400 MHz, CDC1 _3): δ = 2.11 (m, 3.000 H, C (0) CH _3), 2.69 (m, 18.4659 H, C (0) CH ₂ CH ₂ C (0)), 4.91 (m, 2.0817 H, CH ₂ 0-CH ₂ 0-CH ₂ 0), 5.35 (m, 13.4495 H, C (0) 0-CH ₂ 0 - CH ₂ 0), 5.76 (m, 3.0719 H, C (0) 0 -CH ₂ 0-C (0)) ppm.

According to 1 H NMR spectroscopy, the ratio is CH ₃ CO: C (O) CH ₂ CH ₂ C (0): CH ₂ O = 2: 9, 23: 18.60.

Thus n vc = 1.82.

The average molecular weight is MWAVG = 1584 g / mol.

¹³ C-APT NMR (125 MHz, CDCl 3): δ = 21.0 (-, C (O) CH ₃ ), 28.4 (+, C (O) CH ₂ CH ₂ C (0)), 28 , 7 (+, C (O) CH ₂ CH ₂ C (0)), 79.4 (+, CH ₂ O), 79.5 (+, CH ₂ O), 85.9 (+, CH ₂ O ), 86.9 (+, CH ₂ O), 87.1 (+, CH ₂ O), 87.2 (+, CH ₂ O), 90.8 (+, CH ₂ O), 92.4 ( +, CH ₂ O), 171.4 (+, C = 0), 171.6 (+, C = 0) ppm.

By thermogravimetric analysis (TGA), a decomposition temperature of 220 ° C was determined.

EXAMPLE 8 (Comparative Example) Reaction of trioxane with succinic anhydride according to procedure 2 using acetic anhydride as chain regulator in the absence of a catalyst

In accordance with protocol 2, 5.51 g (55 mmol) of succinic anhydride were initially charged in reactor 2, and 5.34 g (59 mmol) of trioxane (corresponding to 177 mmol of formaldehyde) and 0.56 g (5.5 mmol) of acetic anhydride were successively added. After removal of the volatiles, 8.85 g of a colorless crystalline solid were obtained. The product is soluble in chloroform.

'H-NMR (400 MHz, CDCl3): δ = 2.08 (s, 0.2582 H, C (0) _CH3, sodium acetate), 2.20 (s, 0.5696 H, C (0) CH ₃ , acetic anhydride), 3.00 (s, 4 H, C (O) CH ₂ CH ₂ C (0), succinic anhydride), 5.14 (s, 7.2957 H, CH ₂ O-CH ₂ O-CH ₂ 0, trioxane) ppm.

¹³ C-APT NMR (125 MHz, CDCl 3): δ = 22.2 (-, C (O) CH ₃ , acetic anhydride, 28.5 (+, C (O) CH ₂ CH ₂ C (0), succinic anhydride ), 93.7 (+, CH ₂ O, trioxane), 170.9 (+, C = O, succinic anhydride) ppm.

According to NMR spectroscopy, a mixture of the starting materials trioxane, succinic anhydride and acetic anhydride was obtained. Thus, no conversion to polyacetal polyesters of the invention took place. _Λ

 - 41 -

comparison

Table 4: Variation of the catalyst in the preparation of polyacetal polyesters ^a

 a aldehyde = trioxane, cyclic anhydride = succinic anhydride, open chain monoanhydride = acetic anhydride, aldehyde molar ratio: total anhydride = 3: 1; molar ratio open-chain monoanhydride: cyclic anhydride = 1: 10.

Examples 1, 7 and 3 according to the invention show that both Bronsted acids (trifluoromethanesulfonic acid, CF 3 SO 3 H) and Lewis acids (bismuth (III) triflate, Bi ⁱⁿ (OTf) 3) serve as catalysts for the preparation of polyacetal polyesters are suitable.

The comparison of Example 8 (Comparative) with Example 3 shows that under otherwise similar conditions no polyacetal polyesters are obtained when no catalyst is present in the reaction mixture. Thus, the necessity of a catalyst for the preparation of polyacetal polyester of the invention has been proven beyond doubt.

EXAMPLE 9 Formaldehyde / glutaric anhydride copolymer (polyacetal polyester) obtained according to procedure 2 using acetic anhydride as chain regulator and trifluoromethanesulfonic acid as catalyst

According to procedure 2, 6.16 g (54 mmol) of glutaric anhydride were initially charged in reactor 2 and successively 5.34 g (59 mmol) of trioxane (corresponding to 177 mmol of formaldehyde) and a mixture of 0.55 g (5.4 mmol) of acetic anhydride and 50 μΕ trifluoromethanesulfonic used. After drying in vacuo, 11.11 g of an amber-colored suspension were obtained. A fraction (1.16 g) of the product was taken up in 100 mL dichloromethane and filtered through a paper filter. Removal of the volatiles of the filtrate under reduced pressure gave 0.89 g of a brown solid.

The product is soluble in chloroform. A glass transition temperature T _g = -48.5 ° C was determined by differential scanning calorimetry (DSC).

IR: v = 2977 (vw, v [CH ₂ ]), 2947 (vw, v [CH ₃ ]), 1737 (s, v [C = 0]), 1706 (w, v [C = 0]), 1454 (vw), 1414 (w), 1369 (vw), 1316 (vw), 1281 (vw), 1117 (s), 1052 (vw), 978 (vw), 925 (vs), 785 (vw), 736 (vw), 603 (vw), 523 (vw), 460 (vw) cm.

'H-NMR (400 MHz, CDC1 _3): δ = 1.95 (quint, 14.518 H, 7.16 Hz C (0) CH ₂ CH ₂ H ₂ C (0)), 2.09 (m, 3,000 H, C (0) CH _3), 2.45 (m, 29.0559 H, C (0) CH ₂ CH ₂ H ₂ C (0)), 3.66 (s, H 0.6338), 4 89 (m, 4.2660 H, CH ₂ 0-CH ₂ 0-CH ₂ 0), 5.15 (s, 1.1258 H, 3 x CH ₂ 0, trioxane), 5.36 (m, 9 . 6645 H, C (0) 0- 0 CH _{2-CH 2} 0), 5.74 (m, 5.9513 H, C (0) 0-CH ₂ 0-C (0)) ppm. According to 'H-NMR spectroscopy, the ratio is CH ₃ CO: C (O) CH ₂ CH ₂ C (O): CH ₂ O = 2: 14.52: 19.88.

Thus n vc = 1.28.

The average molecular weight is MWAVG = 2356 g / mol.

¹³ C-APT NMR (125 MHz, CDCl 3): δ = 19.5 (+, C (O) CH ₂ CH ₂ CH ₂ C (0)), 19.5 (+, C (0) CH ₂ CH ₂ CH ₂ C (0)), 20.8 (-, C (O) CH ₃ ), 32.7 (+, C (O) CH ₂ CH ₂ CH ₂ C (O)), 32.9 (+ , C (O) CH ₂ CH ₂ CH ₂ C (O)), 33.0 (+, C (O) CH ₂ CH ₂ CH ₂ C (O)), 33.1 (+, C (O) CH ₂ CH ₂ CH ₂ C (0)), 79.3 (+, CH ₂ O), 85.7 (+, CH ₂ O), 87.0 (+, CH ₂ O), 87.3 (+, CH ₂ O), 89.1 (+, CH ₂ O), 90.9 (+, CH ₂ O), 92.4 (+, CH ₂ O), 171.7 (+, C = 0), 178 , 9 (+, C = 0) ppm.

Remote coupling of a ¹³ C NMR signal at 171.7 ppm (C = 0) to an 'H NMR signal at 5.74 ppm and a' H NMR signal at 5, was determined by HMBC NMR spectroscopy. 36 ppm observed which oxymethylene groups were assigned. This demonstrates beyond any doubt that the ester groups resulting from the anhydrides are bound to oxymethylene groups.

Furthermore, the following remote coupling between oxymethylene groups (assignment of the ¹³ C NMR signals to the corresponding 'H NMR signals by HSQC NMR spectroscopy) was observed by HMBC spectroscopy:

¹³ C-NMR / 'H-NMR Remote coupling to ¹ H-NMR / ¹³ C-NMR

85.7 ppm / 5.36 ppm 4.89 ppm / 89.1-92.4 ppm

87.0 ppm / 5.36 ppm 5.36 ppm / 87.0 ppm

89.1 ppm / 4.89 ppm 4.89 ppm / 89.1 ppm , "

 - 43 -

90.9 ppm / 4.89 ppm 4.89 ppm / 90.9 ppm; 5.36 ppm / 85.7 ppm 92.4 ppm / 4.89 ppm 5.36 ppm / 87.3 ppm

This demonstrates beyond any doubt that bonds between the oxymethyl groups bound to ester fragments at 85.7 and 87.0 ppm ( ¹³ C-NMR signal) and 5.36 ppm ('H-NMR signal) lead to further oxymethylene Grappen exist.

Thus, the structure of the polyacetal polyester of the invention is proven beyond doubt.

Example 1 0: Formaldehyde / Itaconic Acid Anhydride Copolymer (polyacetal polyester obtained according to procedure 2 using acetic anhydride as chain regulator and bismuth (III triflate as catalyst) In accordance with procedure 2, 6.05 g (54 mmol) were added to reactor 2. Itaconic anhydride and 0.354 g

(0.54 mmol) of bismuth (III) triflate and successively added 5.34 g (59 mmol) of trioxane (corresponding to 177 mmol of formaldehyde) and 0.55 g (5.4 mmol) of acetic anhydride. After removal of the volatiles, 10.83 g of an amber oil was obtained.

The product is soluble in chloroform. 'H-NMR (400 MHz, CDC1 _3): δ = 2.08 (m, 3.000 H, C (0) CH _3), 3.36 (m, 6.3545 H,

C (0) CH ₂ C (= CH ₂ ) C (0)), 3.60 (t, 2.6714 H, J = 2.56 Hz C (0) CH ₂ C (= CH ₂ ) C (0 ), itaconic anhydride), 3.67 (s, 1.3946 H), 4.86 (m, 5.3049 H, CH ₂ 0-CH ₂ 0-CH ₂ 0), 5.12 (s, 7.0287 H, 3 x CH ₂ O, trioxane), 5.24 (s, 0.9418 H, CH ₂ Cl ₂ ) 5.35 (m, 6.3376 H, C (O) O-CH ₂ O-CH ₂ 0), 5.71 (m, 0.8019 H, C (O) O-CH ₂ O-C (O)), 5.80 (m, 3.6384 H, C (O) CH ₂ C (= CH (H)) C (O) & C (O) O-CH ₂ O-C (O)), 5.90 (m, 1.5847 H, C (O) CH ₂ C (= CH (H) ) C (0) (itaconic anhydride) & C (0) 0-CH ₂ 0-C (0)), 6,41 (m, 3,3182 H, C (0) CH ₂ C (= CH (H)) C (0)), 6.48 (t, 1.1.3179 H, J = 2.76 Hz C (0) CH ₂ C (= CH (H)) C (0) (itaconic anhydride) ppm.

According to 1 H NMR spectroscopy, the ratio is CH ₃ CO: C (O) CH ₂ C (= CH ₂ ) C (0): CH ₂ O = 2: 6.64: 12.23. Thus n vo = 1.60.

The average molecular weight is MWAVG = 1214 g / mol.

¹³ C-APT NMR (125 MHz, CDCl 3): δ = 20.8 (-, C (O) CH ₃ ), 33.7 (+, C (O) CH ₂ C (= CH ₂ ) C (0 ), Itaconic anhydride), 37.1 (+, C (O) CH ₂ C (= CH ₂ ) C (O)), 37.2 (+, C (O) CH ₂ C (= CH ₂ ) C (0 ), 37.3 (+, C (O) CH ₂ C (= CH ₂ ) C (O)), 37.4 (+, C (O) CH ₂ C (= CH ₂ ) C (0)) , 38.2 (+, C (O) CH ₂ C (= CH ₂ ) C (O)), 38.3 (+, C (O) CH ₂ C (= CH ₂ ) C (O)), 79 , 9 (+, CH ₂ O), 86.0 (+, CH ₂ O), 86.9 (+, CH ₂ O), 87.1 (+, CH ₂ O), 89.3 (+, CH ₂ O), 90.8 (+, CH ₂ O), 92.3 (+, CH ₂ O), 93.6 (+, trioxanes), 126.6 (+, C (O) CH ₂ C (= CH ₂ ) C (0), itaconic anhydride), 130.5 (+, C (O) CH ₂ C (= CH ₂ ) C (O)), 130.9 (+, C (0) CH ₂ C (= CH ₂ ) C (0)), 131.0 (+, C (O) CH ₂ C (= CH ₂ ) C (O)), 131.3 (+, C (0) CH ₂ C (= CH ₂ ) C (0)), 132.9 (+, C (O) CH ₂ C (= CH ₂ ) C (O)), 164.7 (+, C = O, itaconic anhydride), 168, 0 (+, C = 0), 171.0 (+, C = 0), 176.2 (+, C = 0) ppm. By HMBC NMR spectroscopy remote coupling of a ¹³ C NMR signal at 171.0 ppm

(C = 0) to a 'H-NMR signal at 5.80 ppm and a' H-NMR signal at 5.35 ppm and a ¹³ C-NMR signal at 168.0 ppm (C = 0) observed an 'H NMR signal at 5.80 ppm and a' H NMR signal at 5.35 ppm assigned to oxymethylene groups. This demonstrates beyond any doubt that the ester groups resulting from the anhydrides are bonded to oxyme- thylene groups.

Furthermore, the following remote coupling between oxymethylene groups (assignment of the ¹³ C NMR signals to the corresponding 'H NMR signals by HSQC NMR spectroscopy) was observed by HMBC spectroscopy:

¹³ C-NMR / 'H-NMR Remote coupling to ¹ H-NMR / ¹³ C-NMR 86.0 ppm / 5.35 ppm 4.89 ppm / 89.3-92.3 ppm

86.9 ppm / 5.35 ppm 5.35 ppm / 86.9 ppm

87.1 ppm / 5.35 ppm 5.35 ppm / 87.1 ppm

89.3 ppm / 4.86 ppm 4.86 ppm / 89.3 ppm

90.8 ppm / 4.86 ppm 4.86 ppm / 90.8 ppm; 5.35 ppm / 86.0 ppm 92.5 ppm / 4.86 ppm 5.37 ppm / 86.9 ppm

This demonstrates beyond any doubt that bonds of the oxymethylene groups bonded to ester groups at 86.0 ppm ( ¹³ C NMR signal) and 5.37 ppm ('H NMR signal) result in further oxymethylene groups.

Furthermore, two 'H NMR signals at 5.80 ppm and 6.41 ppm could be assigned to an unsaturated system via coupling to ¹³ C NMR signals at 130.5 - 132.9 ppm by HSQC spectroscopy. It was shown by HMBC spectroscopy that these 'H-NMR signals couple to a ¹³ C NMR signal at 168.0 and 171.0 ppm (C = 0), respectively. In addition, the coupling of these two 'H NMR signals at 5.80 ppm and 6.41 ppm to ¹³ C NMR signals was observed between 37.1 and 38.3 ppm. These showed a coupling to a 'H NMR signal at 3.36 ppm in the HSQC spectrum. By ¹³ C-APT NMR spectroscopy was the corresponding _Λ

 - 45 -

Group identified as CH2 group. This demonstrates beyond any doubt that itaconic anhydride was incorporated into the polymer chain to obtain the double bond.

Thus, the structure of the polyacetal polyester of the invention is proven beyond doubt.

By thermogravimetric analysis (TGA), a decomposition temperature of 195 ° C was determined.

EXAMPLE 1 1: formaldehyde / B-type acid anhydride copolymer (polyacetal polyester) obtained according to procedure 2 using benzoic anhydride as chain regulator and bismuth (III) triflate as catalyst

In accordance with protocol 2, 5.54 g (55 mmol) of succinic anhydride and 0.361 g (0.55 mmol) of bismuth (III) triflate were initially charged in reactor 2 and 5.47 g (61 mmol) of trioxane (corresponding to 183 mmol of formaldehyde) and 1 , 25 g (5.5 mol) of benzoic anhydride added. After drying in vacuo, 11.27 g of an amber-colored oil were obtained. A fraction (1.04 g) of the product was taken up in 100 mL dichloromethane and filtered through a paper filter. After removing the volatiles of the filtrate under reduced pressure, 0.78 g of a brown solid was obtained.

The product is soluble in chloroform.

By differential scanning calorimetry (DSC), a glass transition temperature T _g = -34.5 ° C was determined.

IR: v = 2981 (vw, v [CH ₂ ]), 2925 (vw, v [CH ₃ ]), 1735 (s, v [C = 0]), 1411 (vw), 1360 (w), 1317 ( vw), 1270 (vw), 1206 (vw), 1156 (vw), 1117 (s), 1048 (vw), 1023 (w), 906 (vs), 837 (vw), 734 (vw), 715 ( vw), 560 (vw) cm ^"1 .

'H-NMR (400 MHz, CDC1 _3): δ = 2.09 (m, 0.2255 H, C (0) CH _3), 2.68 (m, 16.7043 H, C (0) CH ₂ CH ₂ C (0)), 2.99 (s, 0.8996 H, C (0) CH ₂ CH ₂ C (0), succinic anhydrides), 3.68 (m, 1.6423 H), 4.89 (m, 5.8486 H, CH ₂ 0-CH ₂ 0-CH ₂ 0), 5.15 (s, 0.6912 H, 3 x CH ₂ 0, trioxane), 5.33 (m, 7.7810 H, C (0) 0-CH ₂ 0-CH ₂ 0), 5.47 (s, 0.3686 H, C (0) 0-CH ₂ 0-CH ₂ 0) 5.52 (m, 0, 1630 H, C (0) 0-CH ₂ 0-CH ₂ 0) 5.60 (m, 0.9369 H, C (0) 0-CH ₂ 0-CH ₂ 0), 5.75 (m, 2 , 4191 H, C (0) 0-CH ₂ 0- C (O)), 6.00 (m, 0.5527 H, C (0) 0-CH ₂ 0-C (0)), 6.24 (s, 0.0389 H, C (0) 0-CH ₂ 0-C (0)) 7.45 (1, 9444 H, 2 x CH _arm, meta position),)), 7.59 (1.000 H , CH _arm , para position),)), 8.06 (2.0844 H, 2 x CHarm, ortho position) ppm. According to 1 H NMR spectroscopy, the ratio PhCO: C (O) CH ₂ CH ₂ C (0): CH ₂ O = 2: 8.35 18.11. Thus, n vo = 1.94.

The average molecular weight is MWAVG = 1606 g / mol.

¹³ C-APT NMR (125 MHz, CDCl ₃ ): δ = 28.4 (+, C (0) CH ₂ CH ₂ C (0)), 28.5 (+, C (0) CH ₂ CH ₂ C (0)), 28.5 (+, C (O) CH ₂ CH ₂ C (O)), 28.6 (+, C (O) CH ₂ CH ₂ C (O)), 28.7 ( +, C (O) CH ₂ CH ₂ C (O)), 28.7 (+, C (O) CH ₂ CH ₂ C (O)), 29.0 (+, C (O) CH ₂ CH ₂ C (0)), 29.0 (+, C (O) CH ₂ CH ₂ C (O)), 29.3 (+, C (O) CH ₂ CH ₂ C (O)), 29.9 ( +, C (O) CH ₂ CH ₂ C (O)), 31.6 (+, C (O) CH ₂ CH ₂ C (O)), 51.9 (-) 78.4 (+, CH ₂ 0), 79.4 (+, CH ₂ O), 79.8 (+, CH ₂ O), 85.7 (+, CH ₂ O), 86.1 (+, CH ₂ O), 87.0 (+, CH ₂ O), 87.2 (+, CH ₂ O), 87.4 (+, CH ₂ O), 89.3 (+, CH ₂ O), 90.7 (+, CH ₂ O) ), 92.3 (+, CH ₂ O), 93.5 (+, trioxane), 128.4 (-, CH _am ), 128.5 (-, CH ₂ ), 129.8 (-, CI) , 129.8 (-, CH ™), 130.0 (- CI), 130.1 (-, CH _am), 133.5 (-, CH ^), 133.6 (-, CH ™) 133.8 (-, CH ™), 170.8 (+, C = 0), 171.0 (+, C = 0), 171.5 (+, C = 0), 171.6 (+, C = 0) ppm.

By HMBC NMR spectroscopy, remote coupling of a 'H NMR signal at 6.00 ppm to a ¹³ C NMR signal at 171.6 ppm (C = 0, succinic acid ester) and a ¹³ C NMR signal was observed at 165.0 ppm (C = 0, benzoic acid ester). The ¹³ C NMR signal at 171.6 ppm (C = O, succinic acid ester) also showed couplings to 'H NMR signals at 5.75 and 5.33 ppm, while the ¹³ C NMR signal at 165, 0 ppm (C = 0, benzoic acid ester) showed a further coupling to a 'H-NMR signal at 5.60 ppm. The signals at 5.33, 5.60, 5.75 and 6.00 ppm were assigned to oxymethylene groups. This demonstrates beyond any doubt that the ester groups resulting from the anhydrides are bound to oxymethylene groups. Furthermore, the following remote coupling between oxymethylene groups (assignment of the ¹³ C NMR signals to the corresponding 'H NMR signals by HSQC NMR spectroscopy) was observed by HMBC spectroscopy:

¹³ C-NMR / 'H-NMR Remote coupling to ¹ H-NMR / ¹³ C-NMR 85.7 ppm / 5.33 ppm 4.89 ppm / 89.2-92.3 ppm 86.1 ppm / 5.60 ppm 4.89 ppm / 89.2-92.3 ppm 87.0 ppm / 5.33 ppm 5.33 ppm / 87.0 ppm

87.2 ppm / 5.52 ppm 4.89 ppm / 89.2-92.3 ppm 87.4 ppm / 5.60 ppm 4.89 ppm / 89.2-92.3 ppm

89.3 ppm / 4.89 ppm 4.89 ppm / 90.7 ppm 90.7 ppm / 4.89 ppm 4.89 ppm / 89.3 ppm; 5.33 ppm / 85.7 ppm 92.3 ppm / 4.89 ppm 5.33 ppm / 85.7 ppm

This demonstrates beyond any doubt that bonds of the oxymethylene groups bonded to ester groups at 85.7 and 87.0 ppm ( ¹³ C-NMR signal) and 5.37 ppm ('H-NMR signal) lead to further oxymethylene groups. Groups exist. Furthermore, it was shown that oxymethylene groups with a ¹³ C-NMR signal of 86.1 ppm ('H NMR signal 5.60 ppm) and a ¹³ C NMR signal of 87.2 ppm (' H-NMR signal 5.52 ppm) are bound to ester groups and other oxymethylene groups.

Thus, the structure of the polyacetal polyester of the invention is proven beyond doubt.

Example 12: Formaldehyde / B-type tartaric anhydride copolymer (polyacetal polyester) obtained according to procedure 2 using methacrylic anhydride as chain regulator and bismuth (III) triflate as catalyst

In accordance with protocol 2, 5.46 g (54 mmol) of succinic anhydride and 0.361 g (0.55 mmol) of bismuth (III) triflate were initially charged in reactor 2 and 5.35 g (59 mmol) of trioxane (corresponding to 177 mmol of formaldehyde) and 0 were successively added , 84 g (5.4 mmol) of methacrylic anhydride added. After removal of the volatiles, 6.38 g of an amber oil was obtained.

The product is soluble in chloroform.

'H-NMR (400 MHz, CDC1 _3): δ = 1.92 (m, 3.0000 H, C (0) C (= CH ₂₎ CH _3), 2.67 (m, 18.6218 H, C (0) CH ₂ CH ₂ C (0)), 2.99 (s, 7.9469 H, C (0) CH ₂ CH ₂ C (0), succinic anhydrides), 3.68 (m, .6508 H), 4.89 (m, 8.5419 H, CH ₂ 0-CH ₂ 0-CH ₂ 0), 5.13 (s, 4.7348 H, 3 x CH ₂ 0, trioxane), 5.37 (m, 9.9196 H, C (0) 0-CH ₂ 0-CH ₂ 0), 5.63 (m, 1.0325 H, C (0) C (= C (H) H) CH ₃₎ , 5.74 (m, 2.8609 H,

C (0) 0-CH ₂ 0-C (0)), 5.80 (m, 0.7628 H, C (0) 0-CH ₂ 0-C (0)), 6.17 (m, 1 , 0554 H, C (0) C (= C (H) H) CH ₃₎ ppm.

According to ₁ H-NMR spectroscopy, the ratio H ₃ CC (= CH ₂ ) CO: C (0) CH ₂ CH ₂ C (0): CH ₂ 0 = 2: 9.31: 22.09. Thus n vc = 2.14.

The average molecular weight is MWAVG = 1749 g / mol.

¹³ C-APT NMR (125 MHz, CDCl ₃ ): δ = 17.9 (-, C (O) C (= CH ₂ ) CH ₃ ), 18.1 (-, C (0) C (= CH ₂ ) CH ₃ ), 18.2 (-, C (O) C (= CH ₂ ) CH ₃ ), 28.5 (+, C (O) CH ₂ CH ₂ C (O)), 28.6 ( +, C (O) CH ₂ CH ₂ C (O)), 28.9 (+, C (O) CH ₂ CH ₂ C (O)), 29.4 (+, C (O) CH ₂ CH ₂ C (0)), 30.0 (+, C (O) CH ₂ CH ₂ C (O)), 31.7 (+, C (O) CH ₂ CH ₂ C (O)), 78.5 ( +, CH ₂ O), 79.8 (+, CH ₂ O), 85.8 (+, CH ₂ O), 87.0 (+, CH ₂ O), 87.2 (+, CH ₂ O) , 88.8 (+, CH ₂ O), 89.3 (+, CH ₂ O), 90.7 (+, CH ₂ O), 92.3 (+, CH ₂ O), 93.7 (+ , Trioxane), 98.0 _

 - 48 -

(+, CH ₂ O), 127.0 (+, C (O) C (= CH ₂ ) CH ₃ ), 127.7 (+, C (O) C (= CH ₂ ) CH ₃ ), 127, 9 (+, C (0) C (= CH ₂ ) CH - 3), 171.0 (+, C = 0), 171.7 (+, C = 0) ppm.

Remote coupling of a ¹³ C NMR signal at 165.3 ppm (C = 0) to an 'H NMR signal at 5.80 ppm and to an' H NMR signal at 5 was reported by HMBC NMR spectroscopy , 37 ppm, and a remote coupling of a ¹³ C NMR signal at 171.0 ppm (C = 0) to a 'H NMR signal

5.74 ppm and to a 'H NMR signal at 5.37 ppm. The signals at 5.80 ppm, 5.74 ppm and 5.37 ppm were assigned to oxymethylene groups. This demonstrates beyond any doubt that the ester groups resulting from the anhydrides are bound to oxymethylene groups.

Furthermore, the following remote couplings between oxymethylene groups were assigned by HMBC spectroscopy (assignment of the ¹³ C NMR signals to the corresponding 1 H NMR signals by HSQC).

NMR spectroscopy):

¹³ C NMR / 'H NMR Remote coupling to ¹ H NMR / ¹³ C NMR 85.8 ppm / 5.37 ppm 4.89 ppm / 89.3-92.3 ppm 88.8 ppm / 5.37 ppm 4.89 ppm / 89.3-92.3 ppm 87.0 ppm / 5.37 ppm 5.37 ppm / 87.0 ppm

87.2 ppm / 5.37 ppm 5.37 ppm / 87.2 ppm

89.3 ppm / 4.89 ppm 4.89 ppm / 90.7 ppm; 5.37 ppm / 85.8 ppm

90.7 ppm / 4.89 ppm 4.89 ppm / 89.3 ppm; 5.37 ppm / 87.1 ppm

92.3 ppm / 4.89 ppm 5.37 ppm / 86.8 ppm This demonstrates beyond any doubt that bonds of the ester groups bound oxymethylene groups at 85.9 and 87.1 ppm ( ¹³ C NMR signal) and5 , 37 ppm ('H NMR signal) to further oxymethylene groups exist.

Furthermore, by HSQC spectroscopy, two 'H NMR signals at 5.63 ppm and 6.17 ppm were coupled via coupling to ¹³ C NMR signals at 127.0 and between 127.7 and 127.9 ppm of an unsaturated system be assigned. HMBC spectroscopy has been shown to couple these 'H NMR signals to ¹³ C NMR signals at 166.2 and 165.3 ppm (C = 0), respectively. In addition, coupling of these two 'H NMR signals at 5.63 ppm and 6.17 ppm to ¹³ C NMR signals in the range of 17.9 to 18.2 ppm was observed. The signals between 17.9 and 18.2 ppm in the HSQC spectrum show coupling to a 1 H NMR signal at 1.92 ppm, which was identified as methyl by ¹³ C-APT and HSQC NMR spectroscopy , This is proven beyond any doubt that the reaction was carried out to obtain the methacrylic group and methacrylic anhydride was incorporated as a chain regulator.

The structure of the polyacetal polyester of the invention is thus proved beyond doubt.

Comparison Table 5: Preparation of polyacetal polyesters ²¹ using various cyclic and open chain monoanhydrides.

 hydride = 3: 1, catalyst = trifluoromethanesulfonic acid (Ex. 3, 9) or bismuth (III) triflate (Ex. 10-12). Examples 3, 9 and 10 according to the invention show that various cyclic anhydrides can be used for the preparation of polyacetal polyesters according to the invention. These include cyclic anhydrides with a 5-ring structure (succinic anhydride, example 3 and itaconic anhydride, example 10) as well as cyclic anhydrides with a 6-ring structure (glutaric anhydride, example 9). Example 10 further demonstrates that by using cyclic anhydrides with unsaturated double bond systems, unsaturated polyacetal polyesters are obtained.

Examples 3, 11 and 12 according to the invention show that various open-chain monoanhydrides can be used as chain regulators for the preparation of polyacetal polyesters according to the invention. These include aliphatic (acetic anhydride, Example 3), aromatic (benzoic anhydride, Example 11) and unsaturated open-chain monoanhydrides (methacrylic anhydride, Example 12). Example 12 further shows that unsaturated polyacetal polyesters are obtained by using unsaturated open-chain monoanhydrides. _5Q

Example 1 3j formaldehyde / B, 8-carboxylic acid anhydride / itaconic anhydride

Terpolymer (polyacetal-polyester) obtained according to procedure 2 using methacrylic anhydride as chain regulator and bismuth (III) triflate as catalyst According to procedure 2 in reactor 2 was 3.03 g (27 mmol) succinic anhydride, 2.71 g (27 mmol) itaconic anhydride and 0.358 g (0.55 mmol) of bismuth (III) triflate and successively added 5.32 g (59 mmol) of trioxane (corresponding to 177 mmol of formaldehyde) and 0.88 g (5.7 mmol) of methacrylic anhydride. After drying in vacuo, 11.14 g of an amber-colored oil were obtained. The product is soluble in chloroform.

By differential scanning calorimetry (DSC), a glass transition temperature T _g = -39.3 ° C was determined.

IR: v = 2980 (vw, v [CH ₂ ]), 2929 (vw, v [CH ₃ ]), 1849 (vw, v [C = 0]), 1725 (s, v [C = 0]), 1639 (vw, v [C = 0]), 1410 (vw), 1361 (w), 1307 (vw), 1273 (vw), 1197 (vw), 1 159 (vw), 1 114 (s), 1048 (vw), 985 (w), 896 (vs), 803 (vw), 736 (vw), 637 (vw), 584 (vw) cm ^"1 .

'H-NMR (400 MHz, CDC1 _3): δ = 1.91 (m, 3.0000 H, C (0) C (= CH ₂₎ CH _3), 2.06 (m, 0.7554 H, C (0) _CH3), 2.66 (m, 11.0050 H, C (0) CH ₂ CH ₂ C (0)), 2.97 (s, 2.3572 H, C (0) CH ₂ CH ₂ C (0), succinic anhydrides), 3.36 (m, 4.1362 H, C (O) CH ₂ C (= CH ₂ ) C (O)), 3.60 (t, 2.3532 H, J = 2.50 Hz C (0) CH ₂ C (= CH ₂ ) C (0), itaconic anhydride), 3.66 (s, 1.4553 H), 4.86 (m, 8.3804 H, CH 0- ₂ CH ₂ 0-CH ₂ 0), 5.11 (s, 7.6244 H, 3 x CH ₂ 0, trioxane), 5.37 (m, 10.8915 H, C (0) 0-CH ₂ 0 -CH ₂ 0),

5.64 (m, 1.0820 H, C (0) C (= C (H) H) CH _3), 5.73 (m, 1.5952 H, C (0) 0-CH ₂ 0-C (0)), 5.80 (m, 2.8117 H, C (O) CH ₂ C (= CH (H)) C (O) & C (0) 0-CH ₂ O-C (0)) , 5.90 (m, 1.4552 H, C (0) CH ₂ C (= CH (H)) C (0) (itaconic anhydride) & C (0) 0-CH ₂ 0-C (0)), 6.17 (m, 1.0204 H, C (0) C (= C (H) H) CH _3), 6.41 (m, 2.1608 H, C (0) CH ₂ C (= CH ( H)) C (0)), 6.50 (t, 1.0742 H, J = 2.72 Hz C (0) CH ₂ C (= CH (H)) C (0) (itaconic anhydride) ppm.

According to 'H-NMR spectroscopy, the ratio H ₃ CC (= CH ₂ ) CO: C (0) CH ₂ C (= CH ₂ ) C (0): C (0) CH ₂ CH ₂ C (0): CH ₂ O = 2: 5.50: 4.14: 29.90.

Thus n vo = 2.75.

The average molecular weight is MWAVG = 2152 g / mol. ¹³ C-APT NMR (125 MHz, CDCl ₃ ): δ = 17.9 (-, C (O) C (= CH ₂ ) CH ₃ ), 18.1 (-, C (0) C (= CH ₂ ) CH ₃ ),

28.4 (+, C (O) CH ₂ CH ₂ C (O)), 28.6 (+, C (O) CH ₂ CH ₂ C (O)), 28.8 (+, C (0) CH ₂ CH ₂ C (O)), 29.3 (+, C (O) CH ₂ CH ₂ C (O)), 30.8 (+, C (O) CH ₂ CH ₂ C (O)), 33.6 (+, C (O) CH ₂ C (= CH ₂ ) C (O), itaconic acid anhydride) hydride), 37.2 (+, C (O) CH ₂ C (= CH ₂ ) C (O)), 37.3 (+, C (O) CH ₂ C (= CH ₂ ) C (0)) , 38.2 (+, C (O) CH ₂ C (= CH ₂ ) C (0)), 79.4 (+, CH ₂ O), 79.7 (+, CH ₂ O), 85.8 (+, CH ₂ O), 85.9 (+, CH ₂ O), 86.2 (+, CH ₂ O), 89.3 (+, CH ₂ O), 90.7 (+, CH ₂ O) ), 92.5 (+, CH ₂ O), 93.6 (+, trioxanes), 126.1 (+, C (O) CH ₂ C (= CH ₂ ) C (O), itaconic anhydride), 126, 5 (+, C (O) C (= CH ₂ ) CH ₃ ), 127.0 (+, C (O) C (= CH ₂ ) CH ₃ ), 127.6 (+, C (0) C ( = CH ₂ ) CH ₃ ), 127.9 (+, C (O) C (= CH ₂ ) CH ₃ ), 130.5 (+, C (O) CH ₂ C (= CH ₂ ) C (0) ), 131.2 (+, C (O) CH ₂ C (= CH ₂ ) C (O)), 132.9 (+, C (O) CH ₂ C (= CH ₂ ) C (O)), 171.0 (+, C = 0), 171.6 (+, C = 0) ppm.

By thermogravimetric analysis (TGA), a decomposition temperature Td = 200 ° C was determined.

comparison

Table 6: Preparation of polyacetal polyesters ^a using two cyclic and one open chain monoanhydride.

Example open-chain monoanhydride cyclic anhydrides MWAVG

 [G / mol]

3 (cf) acetic anhydride B, anhydride 1640

 13 methacrylic anhydride itaconic anhydride & 2152

 B is anhydride

a Obtained according to procedure 2, aldehyde = trioxane, molar ratio of aldehyde: total amount of anhydride = 3: 1, catalyst = trifluoromethanesulfonic acid (Ex. 3) or bismuth (III) triflate (Ex. 13).

Example 13 according to the invention shows that mixtures of cyclic anhydrides can be used for the preparation of polyacetal polyesters according to the invention, while terpolymers are obtained. Furthermore, it was shown in Example 13 that cyclic and open-chain unsaturated anhydrides can be used to obtain their double bonds.

EXAMPLE 14 Formaldehyde / B AQUA (polyacetal)

Polyester) obtained according to protocol 2 using acetic anhydride as Kettenre gulator and trifluoromethanesulfonic acid as a catalyst

In accordance with protocol 2, 5.41 g (54 mmol) of succinic anhydride were initially charged in reactor 2 and successively 16.06 g (178 mmol) of trioxane (corresponding to 534 mmol of formaldehyde) and a mixture of 0.67 g (6.5 mmol) of acetic anhydride and 50 μΕ trifluoromethanesulfonic acid used. After drying in vacuo, 8.87 g of an amber-colored oil were obtained. The product is soluble in chloroform.

By differential scanning calorimetry (DSC), a glass transition temperature T _g = -56.6 ° C was determined.

IR: v = 2982 (vw, v [CH ₂ ]), 2921 (vw, v [CH ₃ ]), 1785 (vw, v [C = 0]), 1735 (s, v [C = 0]), 1470 (vw), 1410 (vw), 1362 (vw), 1210 (vw), 1156 (vw), 1111 (s), 1050 (vw), 904 (vs), 838 (vw), 634 (vw),

581 (vw) cm.

'Η-ΝΜΡν (400 MHz, CDCl ₃ ): δ = 2.08 (m, 3.000 H, C (O) CH ₃ ), 2.66 (m, 14.645 H, C (O) CH ₂ CH ₂ C ( 0)), 2.99 (s, 1.656 H, C (0) CH ₂ CH ₂ C (0), succinic anhydrides), 3.68 (s, 4.356 H), 4.88 (m, 14.473 H, CH ₂ 0-CH ₂ O-CH ₂ O), 5.13 (s, 18, 501 H, 3 x CH ₂ O, trioxane), 5.34 (m, 10.850 H, C (O) O-CH ₂ O-CH ₂ 0), 5.75 (m, 1.332 H, C (O) O-CH ₂ O-C (0)) ppm.

According to 1 H-NMR spectroscopy, the ratio is CH ₃ CO: C (O) CH ₂ CH ₂ C (O): CH ₂ O = 2: 7.32: 26.65.

Thus, n vo = 3.20.

The average molecular weight is MWAVG = 1635 g / mol. ¹³ C-APT NMR (125 MHz, CDCl 3): δ = 20.7 (-, C (O) CH ₃ ), 28.5 (+, C (O) CH ₂ CH ₂ C (0)), 28 , 6 (+,

C (O) CH ₂ CH ₂ C (O)), 28.7 (+, C (O) CH ₂ CH ₂ C (O)), 28.9 (+, C (O) CH ₂ CH ₂ C ( 0)), 29.1 (+, C (O) CH ₂ CH ₂ C (0)), 52.0 (-), 79.5 (+, CH ₂ O), 85.3 (+, CH ₂ 0), 85.6 (+, CH ₂ O), 85.9 (+, CH ₂ O), 87.1 (+, CH ₂ O), 89.3 (+, CH ₂ O), 90.8 (+, CH ₂ O), 92.4 (+, CH ₂ O), 93.7 (+, trioxane), 171.7 (+, C = 0) ppm. By thermogravimetric analysis (TGA), a decomposition temperature Td = 202 ° C was determined.

EXAMPLE 1 5: Formaldehyde / B 8-C 8-tri-anhydride copolymer (polyacetal polyester) obtained according to procedure 1 using acetic anhydride as chain regulator and trifluoromethanesulfonic acid as catalyst In accordance with procedure 1, 30 μΕ trifluoromethanesulfonic acid, 8.29 g (92 mmol) of trioxane ( corresponding to 276 mmol of formaldehyde), 2.71 g (27 mmol) of succinic anhydride and 0.56 g (5.4 mmol) of acetic anhydride. Upon contact with water, a colorless precipitate formed, which was filtered off. After drying in vacuo, 5.01 g of a colorless solid were obtained. "

 - 53 -

The product is insoluble in chloroform, acetone, dichloromethane, dimethylformate, dimethyl sulphoxide, water, methanol, tetrahydrofuran and hexafluoroisopropanol.

IR: v = 2973 (vw, v [CH ₂ ]), 2952 (vw, v [CH ₂ ]), 2923 (vw, v [CH ₃ ]), 1741 (m, v [C = 0]), 1666 (vw), 1626 (vw), 1554 (s), 1436 (w), 1406 (w), 1369 (w), 1221 (w), 1111 (s), 910 (vs), 833 (vw), 805 (vw), 703 (vw), 660 (m) 581 (vw) cm.

By thermogravimetric analysis (TGA), a decomposition temperature Td = 230 ° C was determined.

comparison

The comparison of the infrared spectrum of the insoluble product from Example 15 with the infrared spectrum of the product from Example 1 shows a broad agreement. From a lower intensity of the carbonyl band of the spectrum of the product from Example 15 compared to the spectrum of the product from Example 1, it can be seen that the average polyacetal segment length in the product from Example 15 is greater than in the product from Example 1.

Table 7: Control of the average polyacetal segment length by adjusting the ratio of aldehydes: sum of all anhydrides used in the preparation of polyacetal polyesters. ^a

 a Obtained using Procedure 2 with trifluoromethanesulfonic acid as catalyst; Aldehyde = trioxane, cyclic anhydride = succinic anhydride, open chain monoanhydride = acetic anhydride, cyclic to open chain anhydride ratio = 10: 1

The comparison of Examples 3 and 14 according to the invention shows that, by changing the molar ratio of aldehydes: sum of all anhydrides used while retaining the molar ratio of cyclic to open-chain anhydrides under otherwise identical reaction conditions, products having different average polyacetal segment lengths are obtained. The ability to control the polyacetal segment length by adjusting the ratio of aldehydes: sum of all anhydrides used is thus proved beyond doubt. _Λ

 - 54 -

EXAMPLE 1 6: Formaldehyde / methacrolein / succinic anhydride terpolymer (polyacetal polyester obtained according to procedure 2 using acetic anhydride as chain regulator and bismuth (III triflate as catalyst.

In accordance with protocol 2, 5.42 g (54 mmol) of succinic anhydride and 0.355 g (0.54 mmol) of bismuth (III) triflate were initially charged in reactor 2 and 3.99 g (44 mmol) of trioxane (corresponding to 133 mmol of formaldehyde) and 0 were successively added , 99 g of methacrolein (14 mmol), and 0.56 g (5.5 mmol) of acetic anhydride added. After drying in vacuo, 8.55 g of a dark amber oil were obtained.

The product is soluble in chloroform. By differential scanning calorimetry (DSC), a glass transition temperature T _g determined = -45.0 ° C.

IR: v = 2932 (vw, v [CH ₂ ]), 2860 (vw, v [CH ₃ ]), 1864 (vw, v [C = 0]), 1783 (m, v [C = 0]), 1733 (s, v [C = 0]), 1459 (vw), 1421 (w), 1364 (w), 1205 (vw), 1158 (m), 1120 (m), 1046 (w), 982 (vw ), 904 (vs), 814 (vw), 735 (vw), 665 (vw), 639 (vw), 561 (vw) cm ^-1 . 'H NMR (400 MHz, CDCl ₃ ): δ = 0 , 83 (m, 1.7771 H, CH ₃ ), 1.00 (m, 0.8680 H), 1.08 (m,

0.3723 H), 1.17 (m, .7961 H), 2.07 (m, 3.0000 H, C (0) CH _3), 2.67 (m, 13.1621 H, C ( 0) CH ₂ CH ₂ C (0)), 2.99 (s, 4.4746 H, C (O) CH ₂ CH ₂ C (0), succinic anhydrides), 3.42 (d, 1.3864 H, J = 11.2 Hz, -O-CH (-O -) - C (H) H-O-), 3.67 (m, 0.7275 H), 3.82 (d, 1.1372 H, J = 11.2 Hz, -0-CH (-O -) - C (H) H-O-), 4.23 (m, 1.6429 H), 4.65 (m, 0.6463 H, -0-CH (-O -) - C (H) H-O-), 4.72 (m, 0.4870 H, -O-CH (-O -) - C (H) H-O-) , 4.91 (m, 2.6080 H, CH ₂ 0-CH ₂ 0-CH ₂ 0), 5.11 (s, 2.4681 H,

3 CH ₂ 0, trioxane), 5.35 (m, 5.7398 H, C (0) 0-CH ₂ 0-CH ₂ 0), 5.52 (m, 0.3106 H, C (0) 0 -CH ₂ O-C (O)), 5.73 (m, 2.6704 H, C (O) O-CH ₂ O-C (O)), 8.08 (m, 0.3575 H, C (O) H) ppm.

According to 1 H-NMR spectroscopy, the ratio C (O) CH ₃ : C (O) CH ₂ CH ₂ C (O): CH ₂ O: HC (0) -C (H) H-0-: -0 -CH (-O-) -C (H) H-0- = 2: 6.58: 11.33: 0.72: 2.11. Thus n vc = 1, 49.

The average molecular weight is MWAVG = 1299 g / mol.

¹³ C-APT NMR (125 MHz, CDCl 3): δ = 17.7 (-, -O-CH (-O-) C (= CH ₂ ) CH ₃ ), 18.3 (-, - 0-CH (-O-) C (= CH ₂ ) CH ₃ ), 20.8 (-, C (O) CH ₃ ), 28.5 (+, C (O) CH ₂ CH ₂ C (O)), 28 , 6 (+, C (0) CH ₂ CH ₂ C (0)), 28.8 (+, C (0) CH ₂ CH ₂ C (0)), 28.9 (+, C (0) CH ₂ CH ₂ C (0)), 29.4 (+, C (O) CH ₂ CH ₂ C (O)), 34.5 (+, C (O) CH ₂ CH ₂ C (0)), 67 , 11 (+, CH ₂ ), 72,8 (+, - O-CH (-O -) - C (H) H-O-), 72,9 (+, - 0-CH (-O-) -C (H) H-O-), 78.5 (+, CH ₂ O), 79.4 (+, CH ₂ O), 79.5 (+, CH ₂ O), 85.9 (+, CH ₂ O), 87.1 (+, CH ₂ O), 90.8 (+, CH ₂ O), 93.7 (+, trioxanes), 94.1 (+, CH ₂ O), 94.2 (+, - O-CH (-O -) - C (H) H-O-) , 171.0 (+, C = 0), 171.1 (+, C = 0) ppm.

Remote coupling of a ¹³ C NMR signal at 171.0 ppm (C = 0) to a 1 H NMR signal at 5.73 ppm as well as a ¹³ C NMR remote coupling was reported by HMBC NMR spectroscopy at 171.1 ppm (C = 0) to a 'H NMR signal at 5.35 ppm. The signals at 5.73 ppm and 5.35 ppm were assigned to oxymethylene groups. This demonstrates beyond any doubt that the ester groups resulting from the anhydrides are bound to oxymethylene groups.

Furthermore, the following remote coupling between oxymethylene groups (assignment of the ¹³ C NMR signals to the corresponding 'H NMR signals by HSQC NMR spectroscopy) was observed by HMBC spectroscopy:

¹³ C-NMR / 'H-NMR Remote coupling to ¹ H-NMR / ¹³ C-NMR

85.9 ppm / 5.35 ppm 4.91 ppm / 90.8-94.1 ppm

87.1 ppm / 5.35 ppm 5.35 ppm / 87.1 ppm

90.8 ppm / 4.91 ppm 4.91 ppm / 90.8 ppm; 5.35 ppm / 85.9 ppm 94.1 ppm / 4.91 ppm 5.35 ppm / 85.9 ppm

This demonstrates beyond any doubt that bonds of the oxymethylene groups bonded to ester groups at 85.9 and 87.1 ppm ( ¹³ C-NMR signal) and 5.35 ppm ('H-NMR signal) to further oxymethylene groups exist.

Furthermore, two signals, 1 H NMR signals at 4.65 and 4.72 ppm, respectively, were assigned to a ¹³ C NMR signal at 94.2 ppm by HSQC spectroscopy and were identified as the acetal units of the incorporated methacrolein , HMBC spectroscopy has been shown to couple these 'H NMR signals to ¹³ C NMR signals at 94.1 ppm. This shows that methacrolein was incorporated into the polyacetal chain via the aldehyde function. In addition, coupling of these two signals' H NMR signals at 4.65 and 4.72 ppm, respectively, to a ¹³ C NMR signal at 72.8 ppm was observed. This signal shows in the HSQC spectrum a coupling to two Dupplets at 3.42 and 3.82 ppm, which, with their J couplings of 11.2 Hz each, as' H-NMR signals of two electronically non-equivalent protons of a CH2- Group were identified. Furthermore, in the HMBC spectrum, remote coupling of Ή-NMR signals at 0.83 and 4.91 ppm, respectively, to a ¹³ C NMR signal at 72.8 ppm was observed, using ¹³ C-APT and NMR spectroscopy HSQC-NMR spectroscopy as methyl group or

Oxymethylene group were identified. This shows that in addition to incorporation via its aldehyde function, methacrolein can also undergo an addition reaction via the double bond into the poly _r

 - 56 - acetal chain can be installed. This is proven beyond any doubt that the reaction was carried out to obtain the methacrylic group and methacrylic anhydride was incorporated as a chain regulator.

The structure of the polyacetal polyester of the invention is thus proved beyond doubt. By thermogravimetric analysis (TGA), a decomposition temperature Td = 197 ° C was determined.

Example 1 7: Formaldehyde / furfural / B serious anhydride terpolymer (polyacetal polyester) obtained according to procedure 2 using acetic anhydride as chain regulator and bismuth (III) triflate as catalyst. According to procedure 2, 5.40 g (54 mmol) of succinic anhydride and 0.354 g (0.54 mmol) of bismuth (III) triflate were initially charged in reactor 2 and successively 2.66 g (30 mmol) of trioxane (corresponding to 90 mmol of formaldehyde) and 2 , 85 g (30 mmol) of furfural, and 0.55 g (5.4 mol) of acetic anhydride added. The product was separated as a solid by filtration. After drying in vacuo, 5.86 g of a black-silvery powder were obtained. The product is insoluble in chloroform, acetone, dichloromethane, dimethylformate, dimethyl sulphoxide, water, methanol, tetrahydrofuran and hexafluoroisopropanol.

IR: v = 2927 (vw, v [CH _3]), 2732 (vw), 2619 (w), 2530 (w), 1722 (vw, v [C = 0]), 1679 (s, v [C = 0]), 1410 (s), 1306 (s), 1197 (s), 1175 (w), 1028 (vw), 907 (vs), 891 (vw), 801 (m), 637 (vs), 582 (m), 544 (w) cm ^"1. The IR spectrum confirms the incorporation of furfural into the terpolymer obtained from trioxane, succinic anhydride and furfural.

By thermogravimetric analysis (TGA), a decomposition temperature Td = 225 ° C was determined.

Example 8: Formaldehyde / acetaldehyde / B-type tartaric acid terpolymers (polyacetal polyesters) are obtained according to procedure 2 using acetic anhydride as chain regulator and bismuth (III) triflate as catalyst.

In accordance with protocol 2, 5.40 g (54 mmol) of succinic anhydride were initially charged in reactor 2 and a mixture of 2.66 g (30 mmol) of trioxane (corresponding to 90 mmol of formaldehyde) and 3.90 g (30 mmol) of paraldehyde (corresponding to 90 mmol acetaldehyde), and a mixture of 0.55 g (5.4 mmol) of acetic anhydride and 50 μΕ Trifluormethansulfonsäure used. It was separated 5.65 g of an insoluble solid. The filtrate continued to decrease Rule 2 worked up. After drying in vacuo 4.65 g of a highly viscous oil were obtained.

The product is insoluble in chloroform, acetone, dichloromethane, dimethylformate, dimethyl sulphoxide, water, methanol, tetrahydrofuran and hexafluoroisopropanol.

IR: v = 2933 (vw, v [CH ₂ ]), 2867 (vw, v [CH ₃ ]), 1722 (s, v [C = 0]), 1685 (vw, v [C = 0]), 1453 (w), 1381 (w), 1232 (w), 1157 (s), 1071 (w), 1029 (vs), 925 (s), 733 (vw), 701 (vw), 637 (vw), 604 (vw), 584 (vw) cm ^"1 .

The IR spectrum confirms the incorporation of acetaldehyde into the terpolymer obtained from trioxane, succinic anhydride and paraldehyde.

By thermogravimetric analysis (TGA), a decomposition temperature Td = 228 ° C was determined.

comparison

Table 8: Use of aldehyde mixtures in the synthesis of polyacetal polyesters.

Example Aldehyde mixture used / ratio T _d / ° C

 3 trioxanes: - / 1: - 146

 16 trioxanes: methacrolein / 1: 0.32 197

 17 trioxanes: furfural / 1: 1 225

 18 trioxanes: paraldehyde / 1: 1 228

a Obtained using procedure 2 with trifluoromethanesulfonic acid or bismuth triflate as catalyst; cyclic anhydride = succinic anhydride, open chain monoanhydride = acetic anhydride, cyclic to open chain anhydride ratio = 10: 1

The comparison of Examples 16 to 18 according to the invention with Example 3 shows that mixtures of different aldehydes can be used. Furthermore, the comparison of the decomposition temperatures of the products obtained shows that the use of an additional aldehyde leads to an increase in the decomposition temperature of the polyacetal polyesters.

Claims

claims

1. A process for the preparation of polyacetal polyesters by reaction of cyclic anhydrides with aldehydes in the presence of a catalyst, characterized in that the reaction is carried out in the presence of an open-chain monoanhydride.

2. The method according to claim 1, wherein the catalyst is a Bronsted acid and / or a Lewis acid.

3. The method according to claim 1 or 2, wherein as aldehyde 1, 3,5-trioxane, paraformaldehyde, high molecular weight polyoxymethylene (POM), dimethyl acetal, 1, 3-dioxolane, 1, 3-dioxane 1, 3-dioxepane or a mixture of two or more of the aforementioned aldehydes is used.

4. The method according to one or more of claims 1 to 3, wherein at least one unsaturated cyclic anhydride is used as the cyclic anhydride.

5. The method according to one or more of claims 1 to 4, wherein at least one unsaturated open-chain monoanhydride is used as the open-chain monoanhydride.

6. The method according to one or more of claims 1 to 5, wherein the ratio of the amount of substance used to aldehyde to the sum of the amounts used of cyclic anhydrides and open-chain monoanhydrides between 1: 1 and 10: 1.

7. Polyacetal polyester obtainable by a process according to one or more of claims 1 to 6.

A polyacetal polyester according to claim 7, wherein the polyacetal polyesters have a number average molecular weight of 232 g / mol to 2,000,000 g / mol.

9. A polyacetal polyester according to claim 7 or 8, wherein the polyacetal polyester include oxymethylene units as polyacetal portions.

10. A polyacetal polyester according to one or more of claims 7 to 9, wherein the average number n vc of acetal units between two ester units is 1 to 6.

1 1. polyacetal polyester according to one or more of claims 7 to 10, wherein these have a decomposition temperature T _d > 130 ° C.

12. polyacetal polyester according to one or more of claims 7 to 11, wherein the poly-acetal-polyester C = C double bonds which are not part of an aromatic ring system.

13. Use of polyacetal polyesters according to one or more of claims 7 to 12 as thermoplastics and / or polymer additives.

14. Use of polyacetal polyesters according to claim 12 for the preparation of elastomers or duromers.

15. polyacetal polyester of the general formula (I),

(I) which contain an alternating sequence of mono- or polyacetal sections -O- (CHR ¹ -0) _m - and carboxylic acid diester units -O-C (0) -R ² -C (O) -O-, wherein the mono- or polyacetal segments and the diester units are each directly linked via a common oxygen atom, or

Polyacetal polyester of the general formula (II),

(Π) which an alternating sequence of polyoxyalkylene polyacetal portions -0 [(CHR ¹ 0) _a ((CR _^'2) oO) _b] i- and carbonic acid diester units -0-C (0) ^-R2 -C (0) - O-, wherein the polyoxyalkylene polyacetal sections and the diester units are each directly linked together via a common oxygen atom, wherein

1, m and x are integers, m is an integer> 1 and different m in different sections - (CHR ¹ - 0) _m - can assume different values, x is an integer> 1 and different x in different compounds of general formula (I) and / or compounds of the general formula (II) can assume different values, a and b independently of one another in each case stand for an integer> 0 and within a repeating unit [(CHR ¹ 0) _a ((CR ^' ₂ ) oO) _b ] the sum of a + b is> 1, o = 2, 3 or 4, different a, b, 1 and o in different recurring units [(CHR ¹ 0) _a ((CR ^'2) oO) b] i within a compound of formula (II) can take different values

R ^{1 is} hydrogen or a saturated or unsaturated, linear or branched C ¹ - to C 20 -alkyl, aryl, alkylaryl or arylalkyl radical which optionally contains further heteroatoms such as oxygen, nitrogen, sulfur, phosphorus, silicon, fluorine, chlorine, bromine, Contains iodine, and different R ^{1 may} differ in different units -CHR'-O- within a compound of general formula (I),

R ^{2 is} a chain of 2, 3 or 4 carbon atoms, wherein the carbon atoms in the chain R ² are linked to each other via single or double bonds or a bridging oxygen or sulfur atom, or R ² part an aromatic or cycloaliphatic mono-, bi- or polycyclic ring system, and the carbon atoms in R ² or in the R ² -containing aromatic or cycloaliphatic ring system independently of one another can carry one or more substituents which are selected from the group

R ⁴ , alkenyl = CR ⁴ ₂ , ether -OR ⁴ , thioether -SR ⁴ , amino -NR ⁴ ₂ , phosphino-PR ⁴ ₂ , silyl -SiR ⁴ ₃ , carboxyl -C0 ₂ H, carboxylate -C0 ₂ \ ester - C0 ₂ R ^4, -S0 ₃ H sulfonic acid, sulfonate -S0 ₃ ^", sulfonic fonsäureester -SO3R ^4, fluorine, chlorine, bromine, iodine, nitrile -CN, nitro -NO 2, wherein R ⁴ in all cases, the analogous meaning has as R ¹ , may differ from R ¹ , and different substituents R ^{4 may} differ within a chain R ² and / or may be linked together such that they each other and / or with R ^{2 is} a mono-, bi- or polycyclic Ring system, and different R ^{2 may} differ in different diester units -O-C (O) -R ² -C (O) -O- within a compound of general formula (I), R ^{3 has} the analogous meaning as R ¹ , wherein R ^{3 may be} R ¹ or different from R ¹ and different R ^{3 may} differ within a compound of general formula (I),

R 'has an analogous meaning to R ¹ , where R' may be R ¹ or different from R ¹ and different R 'within a repeating unit ((CR'2) o-0) and in different repeating units ((CR'2) o-0) b may be different within a compound of formula (II).