Polyalkylene oxide ester polymers, their preparation and uses

Abstract

Weight average molecular weight M w A polyalkylene oxide ester polymer having a molecular weight of 500-50,000 g / mol, a polydispersity index PD of 2-6, containing 10-560 ether groups and 2-51 ester groups bonded to alkylene groups and one another, and having significantly superior biodegradability to conventional polyalkylene oxide polymers; preparation of such polyalkylene oxide ester polymer; and use thereof.

Description

[Technical field]

[0001] The present invention relates to a method for producing a polymer having a weight average molecular weight M w The present invention relates to a polyalkylene oxide ester polymer having a molecular weight of 500 to 50,000 g / mol, a polydispersity index PD of 2 to 6, containing 10 to 560 ether groups and 2 to 51 ester groups bonded to alkylene groups and each other, and having significantly superior biodegradability to conventional polyalkylene oxide polymers.

[0002] The present invention further relates to processes for preparing such polyalkylene oxide ester polymers and uses thereof. [Background technology]

[0003] Polyalkylene oxides are important polymers with a wide range of applications, among which they are used as solvents, viscosity improvers, emulsifiers, dispersants, protective colloids, plasticizers, release agents, as well as components or raw materials in the manufacture of a wide variety of polymers, such as adhesives and graft polymers. Besides various technical applications, they are also used in a wide variety of consumer products, such as cosmetics or washing and cleaning agents.

[0004] However, a certain amount of these consumer products is washed away after use, and if they are not biodegradable or are not removed at sewage treatment plants, they may eventually become microplastics in rivers and oceans. In the course of the present invention, it was found that polyalkylene oxides with molecular weights in the range of several hundred g / mol to several thousand g / mol are less biodegradable.

[0005] Efforts have already been made in various countries to ban microplastics, especially in cosmetics. Beyond the ban of these insoluble microplastics, there is an intense exchange of ideas regarding future requirements for soluble polymers used in consumer products. It is therefore highly desirable to identify more biodegradable ingredients for this type of application. Even radical-generated graft polymers with a polyethylene glycol backbone show only limited biodegradability in wastewater when the polyethylene glycol backbone has a molecular weight within the ranges mentioned above, especially when the molecular weight exceeds several thousand g / mol.

[0006] M w Low molecular weight polyethylene oxide with a molecular weight of 600 g / mol is easily biodegradable, whereas M w Polyethylene oxide with a molecular weight of 6000 g / mol shows poor biodegradability. The Safety Data Sheet for Pluriol® E 600 from BASF, revision 2.0, dated January 5, 2021, states that M w The DOC value (dissolved organic carbon) of polyethylene glycol with a molecular weight of 600 g / mol, measured according to OECD 301A, is found to be greater than 70%. w = 6000 g / mol, the Safety Data Sheet for BASF's Pluriol® E 6000 Pellet, Revision 2.0 dated 10 August 2018, states that it is only poorly biodegradable, with the CO2 production according to OECD 301B being only 10-20% of the theoretical value (60d).

[0007] Classical polyalkylene oxides contain a polymer chain of oxyalkylene groups with OH groups at both ends, but the prior art also knows polyalkylene oxides with functionalized end groups that exhibit specific properties and can be used for specific applications.

[0008] CN110498915A discloses the preparation of omega hydroxy alpha carboxy polyethylene oxide by polymerizing hydroxy compounds functionalized with ester groups, such as methyl 2,2-dimethyl-3-hydroxypropionate, with ethylene oxide to give omega hydroxy polyethylene oxide alpha ester intermediates, which are then hydrolyzed to the corresponding omega hydroxy alpha carboxy polyethylene oxide.The COOH end groups are said to serve as reaction sites with other molecules in forming modified polyethylene oxides, for example for their use in the biological or medical fields.

[0009] U.S. Patent No. 2,585,448 describes polyethylene oxide in which one or both of the OH end groups are esterified with aromatic or aliphatic carboxylic acids. The mono- and diesters are said to be useful as plasticizers.

[0010] Other documents relate to cyclic polyetheresters, usually called oxocrown ethers, which are cyclic polyalkylene oxides with at least one ester group in the ring.

[0011] JP 55-143981 A discloses the preparation of cyclic polyether esters, usually called oxocrown ethers. The oxocrown ethers described therein are cyclic esters having 2-9 ether groups and 1-2 ester groups. They are synthesized by a multi-step synthesis, starting with polyethylene oxide, which is converted to a monosodium salt of polyethylene oxide using metallic sodium, sodium bromoacetate is added while eliminating sodium bromide, and p-toluenesulfonyl chloride (also called tosyl chloride) is added as a leaving group to the resulting carboxylate group, and the ω-hydroxy-α-tosyl ester is cyclized intramolecularly while eliminating the tosyl group in the presence of a template metal ion to obtain the corresponding oxocrown ether. Oxocrown ethers are described as being used, for example, as complexing agents for alkali metal and alkaline earth metal cations in organic synthesis, separation, analysis, biochemistry and pharmaceuticals.

[0012] Y. Nakatsuji et al., Synthesis (1981) 42-44, also describes the preparation of oxo crown ethers with 3-5 ether groups and one ester group. Polyethylene oxide is reacted with metallic sodium and bromoacetic acid to give polyethylene oxide with terminal methanecarboxylate groups, which are then esterified with methanol. The resulting ω-hydroxy-α-methyl esters are then either directly cyclized by intramolecular transesterification to the corresponding oxo crown ethers, or saponified to polyethylene oxide with terminal carboxylic acid and OH groups, which are then intramolecularly cyclized by dehydration.

[0013] L. van der Mee et al., J. Polymer Sci. Part A, Polymer Chem. 44(7) (2006) 2166-2176, disclose the preparation of 2-oxa-12-crown-4-ether by conversion of triethylene glycol with tert-butyl bromoacetate with elimination of sodium bromide and cyclization of the resulting tert-butyl ester in the presence of cobalt dichloride. Furthermore, the authors report the ring-opening polymerization of the resulting 2-oxa-12-crown-4-ether and the copolymerization of 2-oxa-12-crown-4-ether and ω-pentadecanolactone in the presence of Novozym 435 as catalyst and benzyl alcohol, [ka] Units or [ka] It is disclosed that the oxocrown ethers are linear polymers containing either a mixture of units. It is stated that oxocrown ethers are very interesting monomers for the synthesis of hydrophilic polyesters.

[0014] Besides the end-group functionalized polyalkylene oxides and oxocrown ethers, linear polyalkylene oxides having functionalized groups within the oxyalkylene chain are also known in the prior art.

[0015] US 2011 / 0,207,634 discloses the preparation of polyalkylene oxides with carboxylate end groups, where the polyalkylene oxide chain can contain exactly one ester group. Polyalkylene oxides with carboxylate end groups and one ester group in the polymer chain are prepared by reacting the corresponding polyalkylene oxide starting material with OH end groups with a base in the presence of a transition metal catalyst, eliminating hydrogen. Ether carboxylates are said to be useful for mild anionic surfactants.

[0016] WO 2001 / 012,203 relates to a new class of surgical polymers useful as sterile anti-adhesion barriers for use between animal tissues, which have a first repeat unit: [ka] (In the formula, R 1 and R 2 are independently hydrogen or C 1~8 is an alkyl group, R 3 is C 2~12 an alkylene group or an oxyalkylene group having up to 2000 repeating units; and an oxyalkylene group or a divalent unit having up to 2000 repeating units: [ka] (In the formula, R 5 and a second repeating unit which is either a specific alkylene group having up to 17 carbon atoms, a specific oxyalkylene group having 3 carbon atoms and 1 oxygen atom, a specific keto unit having 3 to 7 CH2 groups and 1 keto group, or a specific alkyl ester group having 2 to 6 CH2 groups and 1 -O-CO- group.

[0017] US 6,147,168, US 6,224,894, EP 0,771,832 and EP 0,771,849 contain repeat units as defined in WO 2001 / 012,203 and additional third repeat units, in particular divalent units: [ka] (In the formula, R 30 is a divalent alkylene, arylene, or arylalkylene group) or a divalent unit: [ka] (In the formula, R 13is a specific alkylene group having up to 17 carbon atoms, a specific oxyalkylene group having 3 carbon atoms and 1 oxygen atom, a specific keto group having 3-7 CH2 groups and 1 keto group, or a specific alkyl ester group having 2-6 CH2 groups and 1 -O-CO- group, and P is an integer such that the number average molecular weight of the polymer is ensured to be less than 1,000,000.

[0018] The documents cited herein relating to linear polyalkylene oxides with functionalized groups in the oxyalkylene chain mention specific applications of such types of functionalized polyalkylene oxides, such as their use as mild anionic surfactants or for the manufacture of surgical instruments, but do not mention environmental issues, particularly the biodegradability of this type of polymer.Moreover, their synthesis requires at least two isolated components, such as dicarboxylic acids and diols, which must be prepared, isolated and purified in advance, which complicates the production.

[0019] WO 96 / 36656 deals with biodegradable polyalkylene oxide ester copolymers based on alkylene oxide units and lactone units, the lactone units being of the formula: [ka] where R' is defined as hydrogen, an alkyl group, a cycloalkyl group, an alkoxy group, or a monocyclic aromatic hydrocarbon group, and n>1, is a structural unit that is bonded to other lactone units or polyalkylene oxide units within the polyalkylene oxide ester copolymer.

[0020] European Patent Application No. 21182316.6 describes the use of polyalkylene oxide ester polymers for preparing biodegradable graft polymers by grafting polymeric side chains onto the polyalkylene oxide ester polymer, such as polymers obtained by polymerizing vinyl ester monomers and optionally other vinyl monomers. Summary of the Invention [Problem to be solved by the invention]

[0021] The aim of the present invention was to find a new class of compounds capable of replacing polyalkylene oxides, in particular polyethylene oxide, polypropylene oxide, poly-1,2-butylene oxide and polytetrahydrofuran, in their typical applications, such as the encapsulation of perfumes, or in the preparation of graft polymers for use in home care and laundry applications, and having the same or at least very similar application properties as the products based on polyalkylene oxides, but with better biodegradability. Furthermore, this new class of polymers will be easy to manufacture and therefore will be based in particular on readily available starting materials. Finally, they will be safe and durable in their applications.

[0022] A further object of the present invention was to find a process for the preparation of such novel compounds, which is easy to carry out, is based on the use of readily available starting materials, allows high yields and in particular produces the novel compounds in a purity that allows their further use without complex purification.

[0023] A further object of the present invention was to demonstrate the usefulness of this novel compound in various applications. [Means for solving the problem]

[0024] Surprisingly, the inventors have found that the weight average molecular weight M whas a molecular weight of 500 to 50,000 g / mol, a polydispersity index PD of 2 to 6, and contains 10 to 560 ether groups and 2 to 51 ester groups which are bonded to an alkylene group and each other, A) 1 to 51 of general formula (I): [ka] (In the formula, The -O- unit on the left is bonded to the -CO- unit of the adjacent unit of the polymer to form an ester unit, The -CO- unit on the right is linked to an -O- unit in an adjacent unit of the polymer to form an additional ester unit, R 1 , R 2 , R 3 , R 4 , R 5 are each independently a hydrogen atom or C 1~12 represents an alkyl group, a, b, c, d, and e each independently represent an integer of 0 or 1, and the sum of a to e is 1 to 5; X represents a polyalkylene oxide unit having 4 to 100 alkylene oxide units, which alkylene oxide units contain, independently of one another, 2 to 6 carbon atoms in a direct chain directly bonded between two -O- units, and the carbon atoms in the chain directly bonded between two -O- units each independently contain 2 hydrogen atoms or 1 hydrogen atom and 1 C 1~12 and a structural element, B) 1 to 25 of general formula (II): [ka] (In the formula, The -CO- unit on the left is bonded to the -O- unit of the adjacent unit of the polymer to form an ester unit, The -CO- unit on the right is linked to an -O- unit in an adjacent unit of the polymer to form an additional ester unit, R 7 , R 8 , R 9, R 10 , R 11 , R 13 , R 14 , R 15 , R 16 , R 17 are each independently a hydrogen atom or C 1~12 represents an alkyl group, g, h, i, j, k, m, n, o, p, and q are each independently an integer of 0 or 1, the sum of g through k is 1 to 5, and the sum of m through q is 1 to 5; Y represents a polyalkylene oxide unit having 0 to 99 alkylene oxide units, the alkylene oxide units each independently containing 2 to 6 carbon atoms in a chain directly bonded between two ether groups, the carbon atoms in the chain directly bonded between two ether groups each independently containing 2 hydrogen atoms or 1 hydrogen atom and 1 C 1~12 and a structural element, C) a number of -CO- units of the structural elements of the formulae (I) and (II) of the general formula (III): [ka] (In the formula, The -O- unit on the left is bonded to the -CO- unit of the adjacent unit of the polymer to form an ester unit, The -O- unit on the right is bonded to a -CO- unit of an adjacent unit of the polymer to form an additional ester unit, R 19 , R 20 , R 21 , R 22 , R 23 , R 24 are each independently a hydrogen atom or C 1~12 represents an alkyl group, s, t, u, v, w, and x each independently represent an integer of 0 or 1, and the sum of s to x is 2 to 6; Z represents a polyalkylene oxide unit having 0 to 100 alkylene oxide units, which alkylene oxide units contain, independently of one another, 2 to 6 carbon atoms in the chain directly bonded between the two ether groups, and the carbon atoms in the chain directly bonded between the two ether groups each independently contain 2 hydrogen atoms or 1 hydrogen atom and 1 C 1~12 and a polyalkylene oxide unit, Including, provided, however, that the total number of ester groups does not exceed the maximum number of ester groups specified for the polyalkylene oxide ester polymer; Polyalkylene oxide ester polymers have been discovered. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0025] The polyalkylene oxide ester polymer of the present invention has a weight average molecular weight M w , its polydispersity PD, its number of ether groups, its number of ester groups and the presence of at least one structural element (I).

[0026] M w takes into account the mass of each individual chain that contributes to the overall molecular weight of the polymer, taking into account that larger molecules have a higher mass than smaller ones. It is determined by liquid-solid size exclusion chromatography (SEC) and detecting the differential refractive index against a reference cell, with the units calibrated using polymers of known molecular weight. The result of this measurement is a chromatogram that shows the distribution of separated polymer molecules, from which the mass M of each polymer molecule can be determined. i and their number n i Then, based on the progression of the chromatogram curve, the general formula:

number

[0027] The performance of size exclusion chromatography (SEC) and the evaluation of its results are well known to those skilled in the art.

[0028] The weight average molecular weight M of the polyalkylene oxide ester polymer of the present invention w The weight average molecular weight M is 500 to 50,000 g / mol. w is preferably ≧750 g / mol, more preferably ≧1000 g / mol, particularly preferably ≧2000 g / mol, very particularly preferably ≧3000 g / mol, most preferably ≧4000 g / mol, and preferably ≦45000 g / mol, more preferably ≦40000 g / mol, particularly preferably ≦35000 g / mol, very particularly preferably ≦25000 g / mol, most preferably ≦15000 g / mol.

[0029] Weight average molecular weight M w Since PD is only an average molecular weight and does not provide any information regarding the distribution of the molecular weights of the individual molecules, the polyalkylene oxide ester polymers of the present invention are further defined by their polydispersity, PD.

number

number

[0030] The polydispersity PD of the polyalkylene oxide ester polymer of the present invention is from 2 to 6, preferably ≧2.5, more preferably ≧3, and preferably ≦5.

[0031] Number average molecular weight M nis preferably 250 to 20000 g / mol, more preferably ≧500 g / mol, and particularly preferably ≧1000 g / mol, more preferably ≦15000 g / mol, and particularly preferably ≦10000 g / mol.

[0032] The critical feature of the polyalkylene oxide ester polymer of the present invention that allows for surprisingly high biodegradability is the presence of ester groups in the polyalkylene oxide polymer chain. The polyalkylene oxide units that are themselves at least substantially biodegradable are linked to each other with ester groups. Since the polyalkylene oxide units themselves contain alternating ether and alkylene groups, the polyalkylene oxide ester polymer can also be described as a polymer that contains ether and ester groups linked to each other with alkylene groups. For the sake of clarity, it is noted that the term "polyalkylene oxide" does not include acetal or ketal units in which one carbon atom connects two ether groups, such as -O-CH2-O-. This is consistent with the common usage of the term polyalkylene oxide and is known to those skilled in the art.

[0033] The term "ether group" in the context of this document defines an -O- unit having carbon atoms attached to both sides thereof, which carbon atoms have, independently of one another, the oxidation number -2, -1 or 0, and which are further attached to a hydrogen atom or another carbon atom, e.g. -2 for a methyl group, -1 for an unsubstituted alkylene group, and 0 for an alpha-alkyl substituted alkylene group. Similarly, the term "ester group" defines a -CO- unit bonded on one side to a carbon atom having an oxidation number of -3, -2, -1 or 0, e.g., -3 for a methyl group, -2 for an unsubstituted alkylene group which is further bonded to another carbon atom in the polymer chain, -1 for an alpha alkyl substituted alkylene group which is further bonded to another carbon atom in the polymer chain or which is further bonded to an -O- group, and 0 for an alpha alkyl substituted alkylene group which is bonded to an -O- group, and bonded on the other side to an -O- unit which, on the other side, is in turn bonded to a carbon atom having an oxidation number of -2, -1 or 0.

[0034] The number of ether groups specified above as 10 to 560 and the number of ester groups specified above as 2 to 51 refer to individual polyalkylene oxide ester polymer molecules. w The number of ether and ester groups in a particular polyalkylene oxide ester polymer molecule, which is composed of a polyalkylene oxide ester polymer having a molecular weight of 500 to 50,000 g / mol and a polydispersity index PD of 2 to 6, shows an individual distribution depending on the polydispersity index PD. Thus, a polyalkylene oxide ester polymer usually contains polyalkylene oxide ester polymer molecules having different numbers of ester and ether groups.

[0035] The average number of ether and ester groups in the polyalkylene oxide ester polymer can be determined analytically using the knowledge of one skilled in the art. wThe polydispersity PD of the polyalkylene oxide ester polymer and the ratio of ether groups to ester groups can be determined.

[0036] The structural elements of formulae (I), (II) and (III) are characteristically linked such that a number of ester linkages are formed to form a polyalkylene oxide ester polymer containing a total number of ether and ester groups within a specified range.

[0037] The end group of the polyalkylene oxide ester polymer can be essentially any end group suitable for forming the end of such a polymer. Examples of suitable end groups are -OH, -COOH, primary, secondary or tertiary amine groups, branched or linear alkyl groups, aralkyl groups, aromatic groups, hydroxyalkyl groups, carbonyl groups, carboxyl groups, carboxylic ester groups, amide groups, urethane groups, carbamide groups, xanthic acid groups, dithiocarbamate groups or carbamate groups. However, -OH, -COOH, carboxyl groups, hydroxyalkyl groups and alkyl groups are usually preferred, especially -OH and -COOH.

[0038] As already mentioned above, the polyalkylene oxide ester polymer of the present invention comprises 1 to 51 alkyl groups of the general formula (I): [ka] (In the formula, The -O- unit on the left is bonded to the -CO- unit of the adjacent unit of the polymer to form an ester unit, The -CO- unit on the right is linked to an -O- unit in an adjacent unit of the polymer to form an additional ester unit, R 1 , R 2 , R 3 , R 4 , R 5 are each independently a hydrogen atom or C 1~12 represents an alkyl group, a, b, c, d, and e each independently represent an integer of 0 or 1, and the sum of a to e is 1 to 5; X represents a polyalkylene oxide unit having 4 to 100 alkylene oxide units, which alkylene oxide units contain, independently of one another, 2 to 6 carbon atoms in the chain directly bonded between two -O- units, and the carbon atoms in the chain directly bonded between two -O- units each independently contain 2 hydrogen atoms or 1 hydrogen atom and 1 C 1~12 The structural elements of the compound include any of the alkyl groups.

[0039] R in formula (I) 1 , R 2 , R 3 , R 4 , R 5 are each independently a hydrogen atom or C 1~12 Represents an alkyl group. The alkyl group may be linear, and may be C 3~12 In the case of alkyl, it may be linear or branched. 1~12 The alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl. 2 , R 3 , R 4 and R 5 represents a hydrogen atom, R 1 is a hydrogen atom or C 1~12 More preferably, R 1 stands for a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, particularly preferably for a hydrogen atom, methyl, ethyl, n-propyl or n-decyl, very particularly preferably for a hydrogen atom or methyl, most preferably for a hydrogen atom.

[0040] The subscripts a, b, c, d, and e each independently represent an integer of 0 or 1, and the sum of a to e is 1 to 5. Preferably, a, b, and c are 1, and d and e are 0. More preferably, a is 1, and b, c, d, and e are 0.

[0041] Particularly preferred structural elements according to formula (I) have the general formula (Ia): [ka] (In the formula, R 1 is a hydrogen atom or C 1~12 represents an alkyl group, more preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, particularly preferably a hydrogen atom, methyl, ethyl, n-propyl or n-decyl, very particularly preferably a hydrogen atom or methyl, most preferably a hydrogen atom, b and c represent integers of 0 or 1, and the sum of b to c is 0 or 2.

[0042] Further particularly preferred structural elements according to formula (Ia) are of the general formula (Ib): [ka] (In the formula, R 1 is a hydrogen atom or C 1~12 represents an alkyl group, more preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, particularly preferably a hydrogen atom, methyl, ethyl, n-propyl or n-decyl, very particularly preferably a hydrogen atom or methyl, most preferably a hydrogen atom).

[0043] The unit X in (I) represents a polyalkylene oxide unit having 4 to 100 alkylene oxide units, which independently of each other contain 2 to 6 carbon atoms in a chain directly bonded between two -O- units, which is C 2~6 Each of the carbon atoms in the chain that are directly bonded between two -O- units can be represented as an alkylene unit, and each of the carbon atoms in the chain that are directly bonded between two -O- units can be represented as an alkylene unit, and each of the carbon atoms in the chain can be represented as an alkylene unit, and each of the carbon atoms ... in the chain can be represented as an alkylene unit. 1~12 Preferred units X include any of the alkyl groups represented by the general formula (Ic): [ka] (In the formula, α is a subscript from 1 to Xn that defines the running count of each repeat unit, R 1 xα , R 2 xα , R 3 xα , R 4 xα , R 5 xα , R 6 xα are each independently a hydrogen atom or C, taking into consideration that α is the sequence number of each repeating unit. 1~12 represents an alkyl group, a xα , b xα , c xα , d xα , e xα , f xα each independently represents an integer of 0 or 1, taking into consideration that α is the sequence number of each repeating unit; xα ~f xα The sum of is 2 to 6, Xn represents an integer between 4 and 100.

[0044] For example, R 1 xα and groups such as, for example, a xαThe lower case x in the subscripts of the formulas R indicates that they are related to the unit X. The capital X in the formula Xn, which is the number of repeating units, also indicates the same. 1 xα and groups such as, for example, a xα The lower case α in the subscripts such as ##STR1## indicates that the groups and subscripts each have their own sub-number and indicates that within a polyalkylene oxide unit X, the groups and subscripts can vary from one alkylene oxide unit to another. For example, R 1 x1 The R group can be a hydrogen atom, while the R 1 x2 can be a methyl group, and so on. Similarly, and this should also be understood as an example, the subscript c of the alkylene oxide unit with sequence number 1 x1 can be 0, while the c of the alkylene oxide unit with sequence number 2 x2 can be 1, and so on.

[0045] R in formula (Ic) 1 xα , R 2 xα , R 3 xα , R 4 xα , R 5 xα , R 6 xα C in the group 1~12 The alkyl group may be linear, 3~12 In the case of alkyl, it can be linear or branched. 1~12 The alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl. 2 xα , R 3 xα , R 4 xα , R 5xα and R 6 xα represents a hydrogen atom, R 1 xα is a hydrogen atom or C 1~12 More preferably, R 1 xα stands for a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, particularly preferably for a hydrogen atom, methyl, ethyl, n-propyl or n-decyl, very particularly preferably for a hydrogen atom or methyl, most preferably for a hydrogen atom.

[0046] Subscript a xα , b xα , c xα , d xα , e xα , f xα each independently represents an integer of 0 or 1; xα ~f xα The sum of a is 2 to 6. Preferably, a xα , b xα , c xα , f xα is 1, and d xα , e xα is 0. More preferably, a xα , f xα is 1, and b xα , c xα , d xα , e xα is 0.

[0047] Particularly preferred units X have the general formula (Id): [ka] During the ceremony, R 1 xα is a hydrogen atom or C 1~12represents an alkyl group, more preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, particularly preferably a hydrogen atom, methyl, ethyl, n-propyl or n-decyl, very particularly preferably a hydrogen atom or methyl, most preferably a hydrogen atom, b xα , c xα represents an integer of 0 or 1, and the sum of b to c is 0 or 2; Xn is an integer between 4 and 100.

[0048] Further particularly preferred units X according to formula (Id) are those of the general formula (Ie): [ka] (In the formula, R 1 xα is a hydrogen atom or C 1~12 an alkyl group, more preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, particularly preferably a hydrogen atom, methyl, ethyl, n-propyl or n-decyl, very particularly preferably a hydrogen atom or methyl, most preferably a hydrogen atom, Xn is an integer between 4 and 100.

[0049] The number of repeating units Xn in formula (Ic) is an integer from 4 to 100. It is preferably ≧5, more preferably ≧8, particularly preferably ≧10, and is also preferably ≦75, more preferably ≦50.

[0050] The alkylene oxide units in the unit X are each independently selected from different groups R 1 xα ~R 6 xαIn terms of, and different subscript a xα ~f xα It is emphasized that the repeating units may be identical to the units X or may be different from each other in this respect. In this regard, in formula (Ic), the subscript xα is used based on the sequence number of each repeating unit, and the subnumber of each group is, for example, R 1 xα Specify the child number of each subscript as, for example, a xα As already mentioned, the following specification is used:

[0051] It is further emphasized that each structural element (I) in the polyalkylene oxide ester polymer, when more than one element (I) is present, may be the same as or different from the other(s).

[0052] The different moieties of the structural element (I), such as the radicals, subscripts and units X, including their general and preferred values, are as already described above. The following paragraphs relate to particular preferred combinations of these moieties.

[0053] Particularly preferred polyalkylene oxide ester polymers are R 1 represents a hydrogen atom or a methyl group; R 2 , R 3 represents a hydrogen atom, d, e are 0, a is 1, b and c each represent an integer of 0 or 1, and the sum of b to c is 0 or 2; X represents a polyalkylene oxide unit having 4 to 100 alkylene oxide units, which alkylene oxide units have, independently of one another, 2 or 4 carbon atoms in the chain directly bonded between two ether groups, and each alkylene oxide unit has, independently of one another, one of the carbon atoms located α to the -O- unit either containing 2 hydrogen atoms or containing 1 hydrogen atom and 1 methyl group, and the remaining 1 or 3 carbon atoms each containing 2 hydrogen atoms, and the number of methyl groups bonded to the α carbon atom of each -O- unit does not exceed 1, Contains a structural element (I).

[0054] This particularly relates to the respective polymers in which the structural element (I) is formed exclusively from C2-units, exclusively from C4-units or from a mixture thereof. Each C2- and C4-unit can be bonded either exclusively to hydrogen atoms or to hydrogen atoms and one methyl group. If a methyl group is present in a C2- or C4-unit, it is bonded to the carbon atom α to the -O-unit, the number of methyl groups bonded to the α carbon atom of each -O-unit not exceeding one.

[0055] This type of element is typically based on ethylene oxide monomer, propylene oxide monomer, tetrahydrofuran monomer or mixtures thereof. In the propylene oxide-based -CHCH3-CH2-O- unit and the tetrahydrofuran-based -CH2-CH2-CH2-CH2-O- unit in formula (I), it may be advantageous if the structural element (I) contains one or more C2-based units without methyl groups in the boundary region of the element (I). This can be easily achieved by first polymerizing propylene oxide or tetrahydrofuran, then stopping the addition of propylene oxide and tetrahydrofuran, respectively, and feeding ethylene oxide to complete the polymerization to obtain C2-based units at both ends. The resulting polyalkylene oxide can then be further treated as described below to form the structural unit (I) in the polyalkylene oxide ester polymer. By using the manufacturing process described herein, ethylene oxide is copolymerized with propylene oxide and tetrahydrofuran, respectively, resulting in irregular structures in which -CHCH3-CH2-O- and -CH2-CH2-CH2-CH2-O- units, respectively, alternate with -CH2-CH2-O- units in the boundary regions, resulting in indistinct transitions from -CHCH3-CH2-O- and -CH2-CH2-CH2-CH2-O- units, respectively, to -CH2-CH2-O- units. Such effects are well known in the art, and the corresponding alternating structures are sometimes called "dirty structures".

[0056] Other particularly preferred polyalkylene oxide ester polymers are R 1 represents a hydrogen atom or a methyl group; b, c, d, e are 0, a is 1, X represents a polyalkylene oxide unit having 4 to 100 alkylene oxide units, which alkylene oxide units contain, independently of one another, two carbon atoms in the chain which are directly bonded between two ether groups, and each alkylene oxide unit, independently of one another, one of the carbon atoms which is in the α position to the -O- unit either contains two hydrogen atoms or one hydrogen atom and one methyl group, and the other carbon atom contains two hydrogen atoms, and the number of methyl groups bonded to the α carbon atom of each -O- unit does not exceed one, Contains a structural element (I).

[0057] This particularly relates to the respective polymers in which the structural element (I) is formed exclusively from C2-units based on ethylene oxide and propylene oxide.

[0058] Particularly preferred are the acyclic polyalkylene oxide ester polymers A) to D) shown below, where the groups and subscripts refer to formulae (I) and (Ic).

[0059] [Table 1]

[0060] [Table 2]

[0061] [Table 3]

[0062] [Table 4]

[0063] For the polyalkylene oxide ester polymers described above as B), R 1 xα The group is preferably H, while the remaining R1 xα The group is preferably methyl. This is typically based on the preparation of this type of element starting from the polymerization of propylene oxide, copolymerizing ethylene oxide onto the end.

[0064] For the polyalkylene oxide ester polymers described above as C), the subscript b at or near the boundary between two X units xα and c xα is preferably 0, while the remaining b xα and c xα is preferably 1. This is typically based on the preparation of this type of element starting from the polymerization of 1,2-butylene oxide, copolymerized at the end with ethylene oxide.

[0065] As already mentioned above, the polyalkylene oxide ester polymer of the present invention further comprises 1 to 25 alkyl groups of the general formula (II): [ka] (In the formula, The -CO- unit on the left is bonded to the -O- unit of the adjacent unit of the polymer to form an ester unit, The -CO- unit on the right is linked to an -O- unit in an adjacent unit of the polymer to form an additional ester unit, R 7 , R 8 , R 9 , R 10 , R 11 , R 13 , R 14 , R 15 , R 16 , R 17 are each independently a hydrogen atom or C 1~12 represents an alkyl group, g, h, i, j, k, m, n, o, p, and q each independently represent an integer of 0 or 1, the sum of g to k is 1 to 5, and the sum of m to q is 1 to 5; Y represents a polyalkylene oxide unit having 0 to 99 alkylene oxide units, the alkylene oxide units each independently containing 2 to 6 carbon atoms in a chain directly bonded between two ether groups, the carbon atoms in the chain directly bonded between two ether groups each independently containing 2 hydrogen atoms or 1 hydrogen atom and 1 C 1~12 and a structural element, A number of -CO- units of the structural elements of formulae (I) and (II) of general formula (III): [ka] (In the formula, The -O- unit on the left is bonded to the -CO- unit of the adjacent unit of the polymer to form an ester unit, The -O- unit on the right is bonded to a -CO- unit of an adjacent unit of the polymer to form an additional ester unit, R 19 , R 20 , R 21 , R 22 , R 23 , R 24 are each independently a hydrogen atom or C 1~12 represents an alkyl group, s, t, u, v, w, and x each independently represent an integer of 0 or 1, and the sum of s to x is 2 to 6; Z represents a polyalkylene oxide unit having 0 to 100 alkylene oxide units, which alkylene oxide units contain, independently of one another, 2 to 6 carbon atoms in the chain directly bonded between the two ether groups, and the carbon atoms in the chain directly bonded between the two ether groups each independently contain 2 hydrogen atoms or 1 hydrogen atom and 1 C 1~12 and a polyalkylene oxide unit, Including, However, the total number of ester groups, taken together with the structural elements of formula (I), does not exceed the maximum number of ester groups specified for the polyalkylene oxide ester polymer.

[0066] Each end of the structural element (II) can be bonded, for example, to the side containing the -O- unit of the structural element (I), the structural element (III), the side containing the -O- unit of any other polyalkylene oxide, or to another structural element of the polymer that is not represented by any of the structural elements (I), (II), or (III). Needless to say, it is also possible for one end of (II) to be bonded to an end group of the polyalkylene oxide ester polymer. Similarly, each end of the structural element (III) can be bonded, for example, to the side containing the -CO- unit of the structural element (I), the structural element (II), the side containing the -CO- unit of any other polyalkylene oxide, or to another structural element of the polymer that is not represented by any of the structural elements (I), (II), or (III). Needless to say, it is also possible for one end of (III) to be bonded to an end group of the polyalkylene oxide ester polymer.

[0067] R in formula (II) 7 , R 8 , R 9 , R 10 , R 11 , R 13 , R 14 , R 15 , R 16 , R 17 The groups are each independently a hydrogen atom or a C 1~12 Represents an alkyl group. The alkyl group may be linear, and may be C 3~12 In the case of alkyl, it may be linear or branched. 1~12 The alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl. 7 , R 8 , R 9 , R 10 , R 11 , R 14 , R 15 , R 16 , R 17 represents a hydrogen atom, R 13 is a hydrogen atom or C 1~12More preferably, R 13 stands for a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, particularly preferably for a hydrogen atom, methyl, ethyl, n-propyl or n-decyl, very particularly preferably for a hydrogen atom or methyl, most preferably for a hydrogen atom.

[0068] In formula (II), the subscripts g, h, i, j, k, m, n, o, p, and q each independently represent an integer of 0 or 1, and the sum of g to k is 1 to 5, and the sum of m to q is 1 to 5. Preferably, i, j, k, m, n, and o are 1, and g, h, p, and q are 0. More preferably, k and m are 1, and g, h, i, j, n, o, p, and q are 0.

[0069] Particularly preferred structural elements according to formula (II) are of the general formula (IIa): [ka] (In the formula, R 13 is a hydrogen atom or C 1~12 represents an alkyl group, more preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, particularly preferably a hydrogen atom, methyl, ethyl, n-propyl or n-decyl, very particularly preferably a hydrogen atom or methyl, most preferably a hydrogen atom, i, j, n, and o represent integers of 0 or 1, the sum of i through j is 0 or 2, and the sum of n through o is 0 or 2.

[0070] Further particularly preferred structural elements according to formula (IIa) are those of the general formula (IIb): [ka] (In the formula, R 13 is a hydrogen atom or C 1~12 represents an alkyl group, more preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, particularly preferably a hydrogen atom, methyl, ethyl, n-propyl or n-decyl, very particularly preferably a hydrogen atom or methyl, most preferably a hydrogen atom).

[0071] The unit Y in formula (II) represents a polyalkylene oxide unit having 0 to 99 alkylene oxide units, which independently of one another contain 2 to 6 carbon atoms in a chain directly bonded between two -O- units, which is C 2~6 Each of the carbon atoms in the chain that are directly bonded between two -O- units can be represented as an alkylene unit, and each of the carbon atoms in the chain that are directly bonded between two -O- units can be represented as an alkylene unit, and each of the carbon atoms in the chain can be represented as an alkylene unit, and each of the carbon atoms ... in the chain can be represented as an alkylene unit. 1~12 The alkyl group may be any of the alkyl groups.

[0072] Preferred units Y are of the general formula (IIc): [ka] (In the formula, β represents a subscript from 1 to Yn that defines the sequence number of each repeat unit, R 7 yβ , R 8 yβ , R 9 yβ , R 10 yβ , R 11 yβ , R 12 yβ are each independently a hydrogen atom or C, taking into consideration that β is the sequence number of each repeating unit. 1~12 represents an alkyl group, g yβ , hyβ , i yβ , j yβ , k yβ , l yβ are each independently an integer of 0 or 1, taking into consideration that β is the sequence number of each repeat unit; g yβ ~l yβ The sum of is 2 to 6, Yn represents an integer from 0 to 99.

[0073] For example, R 7 yβ Groups such as, for example, g yβ The lower case y in the subscripts of the formulas R indicates that they are related to the unit Y. The same is true for the number of repeating units, Yn, as well as the capital Y. 7 yβ Groups such as, for example, g yβ The lowercase β in the subscripts such as β indicates that the group and subscript each have their own subnumber and that the group and subscript can vary from alkylene oxide unit to alkylene oxide unit within the polyalkylene oxide unit Y. For example, the alkylene oxide unit R 7 y1 The R group can be a hydrogen atom, while the R 7 y2 can be a methyl group, and so on. Similarly, and this should also be understood as an example, the subscript i of the alkylene oxide unit having sequence number 1 y1 can be 0, while the i of the alkylene oxide unit having the sequence number 2 y2 can be 1, and so on.

[0074] R in formula (IIc) 7 yβ , R 8 yβ , R 9 yβ , R 10 yβ , R 11 yβ , R 12 yβ C in the group 1~12The alkyl group may be linear and may be C 3~12 In the case of C, it can be linear or branched. 1~12 The alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl. 8 yβ , R 9 yβ , R 10 yβ , R 11 yβ , R 12 yβ represents a hydrogen atom, R 7 yβ is a hydrogen atom or C 1~12 More preferably, R 7 yβ stands for a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, particularly preferably for a hydrogen atom, methyl, ethyl, n-propyl or n-decyl, very particularly preferably for a hydrogen atom or methyl, most preferably for a hydrogen atom.

[0075] Subscript g in formula (IIc) yβ , h yβ , i yβ , j yβ , k yβ , l yβ each independently represents an integer of 0 or 1; g yβ ~l yβ The sum of g is 2 to 6. yβ , h yβ , i yβ , l yβ is 1, and j yβ , k yβ is 0. More preferably, g yβ , l yβ is 1, and h yβ , i yβ , j yβ , kyβ is 0.

[0076] Particularly preferred units Y are those of the general formula (IId): [ka] (In the formula, R 7 yβ is a hydrogen atom or C 1~12 represents an alkyl group, more preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, particularly preferably a hydrogen atom, methyl, ethyl, n-propyl or n-decyl, very particularly preferably a hydrogen atom or methyl, most preferably a hydrogen atom, h yβ , i yβ represents an integer of 0 or 1, and h yβ ~i yβ is 0 or 2, Yn is a unit of measurement that represents an integer from 0 to 99.

[0077] Further particularly preferred units Y according to formula (IId) are those of the general formula (IIe): [ka] (In the formula, R 7 yβ is a hydrogen atom or C 1~12 represents an alkyl group, more preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, particularly preferably a hydrogen atom, methyl, ethyl, n-propyl or n-decyl, very particularly preferably a hydrogen atom or methyl, most preferably a hydrogen atom, Yn is a unit of measurement that represents an integer from 0 to 99.

[0078] The number of repeating units Yn in formula (IIc) is an integer from 0 to 99. It is preferably ≧1, more preferably ≧3, particularly preferably ≧7, very particularly preferably ≧9, and is preferably ≦74, more preferably ≦49.

[0079] The alkylene oxide units in the unit Y are each independently selected from different groups R 7 yβ ~R 12 yβ In terms of, and different subscript g yβ ~l yβ It is emphasized that the repeating units Y may be identical or different from each other in this respect. In this regard, in formula (IIc), the subscript yβ is used based on the sequence number of each repeating unit, and the subnumber of each group is, for example, R 7 yβ For example, the subscript number is g yβ As already mentioned, the following specification is used:

[0080] It is further emphasized that each structural element (II) in the polyalkylene oxide ester polymer, when more than one element (II) is present, may be the same as or different from the other one or more.

[0081] R in formula (III) 19 , R 20 , R 21 , R 22 , R 23 , R 24 are each independently a hydrogen atom or C 1~12 Represents an alkyl group. The alkyl group may be linear, and may be C 3~12 In the case of alkyl, it may be linear or branched. 1~12The alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl. 19 , R 20 , R 21 , R 22 , R 23 , R 24 represents a hydrogen atom, R 19 is a hydrogen atom or C 1~12 More preferably, R 19 stands for a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, particularly preferably for a hydrogen atom, methyl, ethyl, n-propyl or n-decyl, very particularly preferably for a hydrogen atom or methyl, most preferably for a hydrogen atom.

[0082] In formula (III), the subscripts s, t, u, v, w, and x each independently represent an integer of 0 or 1, and the sum of x is 2 to 6. Preferably, s, t, u, and x are 1, and v and w are 0. More preferably, s and x are 1, and t, u, v, and w are 0.

[0083] Particularly preferred structural elements based on formula (III) have the general formula (IIIa): [ka] (In the formula, R 19 is a hydrogen atom or C 1~12represents an alkyl group, more preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, particularly preferably a hydrogen atom, methyl, ethyl, n-propyl or n-decyl, very particularly preferably a hydrogen atom or methyl, most preferably a hydrogen atom, t and u are integers of 0 or 1, and the sum of t to u is 0 or 2.

[0084] Further particularly preferred structural elements based on formula (IIIa) are of the general formula (IIIb): [ka] (In the formula, R 19 is a hydrogen atom or C 1~12 represents an alkyl group, more preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, particularly preferably a hydrogen atom, methyl, ethyl, n-propyl or n-decyl, very particularly preferably a hydrogen atom or methyl, most preferably a hydrogen atom).

[0085] The unit Z in (III) represents a polyalkylene oxide unit having 0 to 100 alkylene oxide units, which independently of each other contain 2 to 6 carbon atoms in a chain directly bonded between two -O- units, which is C 2~6 It can also be represented as an alkylene unit, where the carbon atoms in the chain that are directly bonded between two -O- units each contain, independently of each other, either two hydrogen atoms or one hydrogen atom and one C1-12 alkyl group.

[0086] Preferred units Z are of the general formula (IIIc): [ka] (In the formula, γ represents a subscript from 1 to Zn that defines the sequence number of each repeat unit, R 19 zγ , R 20 zγ , R 21 zγ , R 22 zγ , R 23 zγ , R 24 zγ are each independently a hydrogen atom or C, taking into consideration that γ is the sequence number of each repeating unit. 1~12 represents an alkyl group, · s zγ , t zγ , u zγ , v zγ , w zγ , x zγ each independently represents an integer of 0 or 1, taking into consideration that γ is the sequence number of each repeat unit; s zγ ~x zγ The sum of is 2 to 6, Zn represents an integer from 0 to 100.

[0087] For example, R 19 zγ Groups such as, for example, s zγ The lower case z in the subscripts of the formulas R, ... 19 zγ Groups such as, for example, s zγ The lowercase γ in the subscripts such as γ indicates that the group and subscript each have their own subnumber and that the group and subscript can vary from alkylene oxide unit to alkylene oxide unit within the polyalkylene oxide unit Z. For example, the alkylene oxide unit R 19 z1 The R group can be a hydrogen atom, while the R 19 z2can be a methyl group, and so on. Similarly, and this should also be understood as an example, the subscript u of the alkylene oxide unit with sequence number 1 z1 can be 0, while u of the alkylene oxide unit with sequence number 2 can be z2 can be 1, and so on.

[0088] R in formula (IIIc) 19 zγ , R 20 zγ , R 21 zγ , R 22 zγ , R 23 zγ , R 24 zγ C in the group 1~12 The alkyl group may be linear, 3~12 In the case of alkyl, it can be linear or branched. 1~12 The alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl. 20 zγ , R 21 zγ , R 22 zγ , R 23 zγ , R 24 zγ represents a hydrogen atom, and R 19 zγ is a hydrogen atom or C 1~12 More preferably, R 19 zγ stands for a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, particularly preferably for a hydrogen atom, methyl, ethyl, n-propyl or n-decyl, very particularly preferably for a hydrogen atom or methyl, most preferably for a hydrogen atom.

[0089] The subscript s in formula (IIIc) zγ , t zγ , u zγ , v zγ , w zγ , x zγ each independently represents an integer of 0 or 1; zγ ~x zγ The sum of is 2 to 6. Preferably, s zγ , t zγ , u zγ , x zγ is 1, and v zγ , w zγ is 0. More preferably, s zγ , x zγ is 1, and t zγ , u zγ , v zγ , w zγ is 0.

[0090] Particularly preferred units Z have the general formula (IIId): [ka] (In the formula, R 19 zγ is a hydrogen atom or C 1~12 represents an alkyl group, more preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, particularly preferably a hydrogen atom, methyl, ethyl, n-propyl or n-decyl, very particularly preferably a hydrogen atom or methyl, most preferably a hydrogen atom, t zγ , u zγ represents an integer of 0 or 1; t zγ ~u zγ is 0 or 2, Zn is a unit of zinc (representing an integer from 0 to 100).

[0091] Particularly preferred units Z according to formula (IIId) have the general formula (IIIe): [ka] (In the formula, R 19 zγ is a hydrogen atom or C 1~12 represents an alkyl group, more preferably a hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl, particularly preferably a hydrogen atom, methyl, ethyl, n-propyl or n-decyl, very particularly preferably a hydrogen atom or methyl, most preferably a hydrogen atom, Zn is a unit of zinc (representing an integer from 0 to 100).

[0092] The number of repeating units Zn in formula (IIIc) is an integer from 0 to 100. It is preferably ≧2, more preferably ≧4, particularly preferably ≧8, very particularly preferably ≧10, and is preferably ≦75, more preferably ≦50.

[0093] The alkylene oxide units in the unit Z are each independently selected from different groups R 19 zγ ~R 24 zγ In terms of, and different subscripts s zγ ~x zγ It is emphasized that the repeating units Z may be identical or different from each other in this respect. In this regard, in formula (IIIc), the subscript zγ is used based on the sequence number of each repeating unit, and the subnumber of each group is, for example, R 19 zγ For example, the subscript number is s zγ As already mentioned, the following specification is used:

[0094] It is further emphasized that each structural element (III) in the polyalkylene oxide ester polymer, when more than one element (III) is present, may be the same as or different from the other one or more.

[0095] The different moieties of structural elements (II) and (III), such as the groups, subscripts and units X and Y, including their general and preferred values, are as already described above. The following paragraphs relate to particular preferred combinations of these moieties.

[0096] Particularly preferably, the polyalkylene oxide ester polymer comprising the structural elements (I), (II) and (III) is R 13 , R 19 each independently represents a hydrogen atom or a methyl group, R 9 , R 10 , R 11 , R 14 , R 15 , R 20 , R 21 , R 24 represents a hydrogen atom, g, h, p, q, v, w are 0, k, m, s, and x are 1, i, j, n, o, t, and u each independently represent an integer of 0 or 1, the sum of i through j is 0 or 2, the sum of n through o is 0 or 2, and the sum of t through u is 0 or 2; Y represents a polyalkylene oxide unit having 3 to 99 alkylene oxide units and Z represents a polyalkylene oxide unit having 4 to 100 alkylene oxide units, which alkylene oxide units have, independently of one another, 2 or 4 carbon atoms in the chain directly bonded between two ether groups, and in which, independently of one another, one of the carbon atoms which is alpha to the -O- unit either contains 2 hydrogen atoms or contains 1 hydrogen atom and 1 methyl group, and the other remaining 1 or 3 carbon atoms each contain 2 hydrogen atoms, and the number of methyl groups bonded to the alpha carbon atom of each -O- unit does not exceed 1.

[0097] This particularly relates to the respective polymers in which the structural elements (II) and (III) are formed exclusively from C2-units, exclusively from C4-units or from a mixture thereof. Each C2-unit and each C4-unit can be bonded either exclusively to hydrogen atoms or to hydrogen atoms and one methyl group. If a methyl group is present in a C2-unit or a C4-unit, it is bonded to the carbon atom α to the -O-unit, the number of methyl groups bonded to the α carbon atom of each -O-unit not exceeding one.

[0098] This type of element is typically based on ethylene oxide, propylene oxide, tetrahydrofuran monomers or mixtures thereof. In the -CHCH3-CH2-O- units based on propylene oxide and -CH2-CH2-CH2-CH2-O- units based on tetrahydrofuran in formulas (II) and (III), it may be advantageous if the structural elements (II) and (III) contain one or more C2-based units without methyl groups at the boundary region of each element. This can be easily achieved by first polymerizing propylene oxide or tetrahydrofuran, then stopping the addition of propylene oxide and tetrahydrofuran, respectively, and feeding ethylene oxide to complete the polymerization to obtain C2-based units at both ends. The resulting polyalkylene oxide can then be further treated as described below to form the structural units (II) and (III) in the polyalkylene oxide ester polymer. By using the preparation process described herein, ethylene oxide is copolymerized with propylene oxide and tetrahydrofuran, respectively, resulting in irregular structures in which -CHCH3-CH2-O- and -CH2-CH2-CH2-CH2-O- units, respectively, alternate with -CH2-CH2-O- units in the boundary regions, resulting in indistinct transitions from -CHCH3-CH2-O- and -CH2-CH2-CH2-CH2-O- units, respectively, to -CH2-CH2-O- units. Such effects are well known in the art, and the corresponding alternating structures are sometimes called "impurity structures".

[0099] Other particularly preferred polyalkylene oxide ester polymers comprise structural elements (I), (II) and (III): R 13 , R 19 each independently represents a hydrogen atom or a methyl group, R 9 , R 10 , R 11 , R 14 , R 15 , R 20 , R21 , R 24 represents a hydrogen atom, g, h, i, j, n, o, p, q, t, u, v, w are 0, k, m, s, and x are 1, Y represents a polyalkylene oxide unit having 3 to 99 alkylene oxide units and Z represents a polyalkylene oxide unit having 4 to 100 alkylene oxide units, which alkylene oxide units contain, independently of one another, 2 carbon atoms in the chain directly bonded between two ether groups, and each alkylene oxide unit, independently of one another, one of the carbon atoms in the alpha position to the -O- unit either contains 2 hydrogen atoms or contains 1 hydrogen atom and 1 methyl group, the other remaining carbon atoms contain 2 hydrogen atoms, and the number of methyl groups bonded to the carbon atom in the alpha position to each -O- unit does not exceed 1.

[0100] This particularly relates to polymers in which the structural elements (II) and (III) respectively are formed exclusively from C2-units based on ethylene oxide and propylene oxide.

[0101] In particular, the weight average molecular weight M w In the case of polyalkylene oxide ester polymers with lower molecular weights, such as less than 1000 g / mol, the polymer may alternatively have cyclic structures, but overall has a non-cyclic structure.

[0102] As already mentioned above, the polyalkylene oxide ester polymer of the invention comprises 10 to 560 ether groups and 2 to 51 ester groups. For the avoidance of doubt, it is emphasized that the amounts of ether and ester groups mentioned above relate to the entire polyalkylene oxide ester polymer, including the groups present in the structural elements of formulae (I), (II) and (III). The polyalkylene oxide ester polymer preferably comprises ≧15, more preferably ≧20, particularly preferably ≧30 ether groups, and preferably ≦500, more preferably ≦400, particularly preferably ≦350 ether groups. It preferably comprises ≧3, more preferably ≧4, particularly preferably ≧5 ester groups, and preferably ≦41, more preferably ≦31, particularly preferably ≦21, very particularly preferably ≦15 ester groups.

[0103] The ratio of the number of ether groups to the number of ester groups is preferably 4 to 100, more preferably ≧5, particularly preferably ≧10, very particularly preferably ≧15, and preferably ≦75, more preferably ≦50, particularly preferably ≦40, very particularly preferably ≦35.

[0104] The polyalkylene oxide ester polymer may be formed entirely of the structural elements (I), (II) and (III) with terminal groups at both ends containing one or more further alkylene oxide elements or one or more other structural elements. Preferably, the polyalkylene oxide ester polymer contains at the end of the element a further alkylene oxide having -O- and -CO- units, which together with the -CO- and -O- units of the other elements form an ester group.

[0105] The structural elements that form an ester group with the structural elements (I), (II) and (III) or with other structural elements contain either at least one -O- or at least one -CO- unit at one end of such structural elements. In that case, the -O- and -CO- units formally form an ester unit. Such structural elements of further alkylene oxide units preferably contain either two -CO- or two -O- units at the end of such structural elements. Since an ester group formally requires one -O- and one -CO- unit, the number of structural elements with one -O- and one -CO- units at their ends will advantageously be balanced.

[0106] The number of structural elements (I) in the polyalkylene oxide ester polymer is 1 to 51, preferably ≧2, more preferably ≧3, particularly preferably ≧4, very particularly preferably ≧5, and preferably ≦41, more preferably ≦31, particularly preferably ≦21, very particularly preferably ≦15, most preferably ≦9.

[0107] The number of structural elements (II) in the polyalkylene oxide ester polymer is from 1 to 25, preferably ≧2, more preferably ≧3, particularly preferably ≧4, very particularly preferably ≧5, most preferably ≧6, and preferably ≦23, more preferably ≦22, particularly preferably ≦20, very particularly preferably ≦17. The total number of elements (I) and (II) is adapted so that the total number of ester groups does not exceed the maximum number of ester groups specified for the polyalkylene oxide ester polymer.

[0108] Since the formation of ester groups from elements (I), (II) and (III) requires an -O- unit at the end of one element and an -CO- unit at the end of another element, the total number of such -O- units and -CO- units in the elements forming the polyalkylene oxide ester polymer is preferably adjusted so that the intended amount of ester groups is formed. The potentially redundant -O- or -CO- units may be attached, for example, to the end group of the polymer or to other structural elements. Since the number of -O- and -CO- units in element (I) is already balanced, and element (II) provides only -CO- units, element (III) is preferably present in a number suitable for forming an ester bond with the -CO- units of the structural elements of formulae (I) and (II). More preferably, the ratio of the number of elements (II) to the number of elements (III) is 0.8 to 1.2, particularly preferably ≧0.9, very particularly preferably ≧0.95, and particularly preferably ≦1.1, very particularly preferably ≧1.05, most preferably 1. The extra -O- or -CO- units may, for example, be attached to end groups or other structural elements.

[0109] Since the polyalkylene oxide ester polymer of the present invention is advantageously produced by esterification of monomers, it is preferable to use monomers that are readily available. Suitable monomers are in particular monomers that already contain structural element (I), for example, monomers of element (I) that contain a hydroxy group as a precursor of the -O- unit at one end and a carboxylic acid, carboxylic acid alkyl ester or carboxylate (e.g., -COONa, etc.) group as a precursor of the -CO- unit at the other end. Even if the monomer of element (I) can be prepared in large quantities with high purity, it is easier to obtain a mixture of monomers of elements (I), (II) and (III). Thus, polyalkylene oxide ester polymers based on such mixtures contain elements (I), (II) and (III). When based on a composition of such monomer mixtures, polyalkylene oxide ester polymers in which the ratio of the number of structural elements (I) to the number of structural elements (II) is 0.5 to 8 are preferred, a ratio of 0.7 to 6 is more preferred, and a ratio of 0.85 to 4.7 is particularly preferred.

[0110] As already mentioned above, the polyalkylene oxide ester polymers of the invention can also contain, apart from the end groups, further polyalkylene oxide elements other than (I), (II) and (III) or further different structural elements. Further polyalkylene oxide elements other than (I), (II) and (III) can be, for example, elements having an alkylene unit with more than 6 carbon atoms in the chain directly bonded between two ether groups. The other structural elements can be, for example, based on diols other than structural element (III), dicarboxylic acids other than structural element (II) or alpha-hydroxy-omega carboxylic acids other than structural element (I), for example sebacic acid or terephthalic acid. In general, structural elements (I), (II) and (III) are the number-average molecular weight M of the polyalkylene oxide ester polymer. n The nature of the structural elements, and hence the composition of the polyalkylene oxide ester polymer, can be determined, for example, by hydrolysis of the ester bonds and the structural units using conventional analytical methods such as gas chromatography, HPLC, NMR and the like.

[0111] Due to the presence of end groups on both sides of the polymer, the amount of structural elements (I), (II) and (III) is usually at least equal to the number average molecular weight M of the polyalkylene oxide ester polymer, even if the polymer contains no other elements than (I), (II) and (III). n However, due to the quantitative effect that the molecular mass of the hydrogen atom is very small compared to the molecular weight of the polyalkylene oxide ester polymer, especially when -OH groups are present as end groups, a value of 100% can be achieved, taking into account the accuracy of the analytical measurement.

[0112] Although elements other than elements (I), (II) and (III) may be present in the polyalkylene oxide ester polymer, preferably only two end groups are included in addition to elements (I), (II) and (III).

[0113] Particularly preferred polyalkylene oxide ester polymers A) to D) based on structural elements (I), (II) and (III) are the following polymers, where the groups and indices relate to formulae (I), (Ic), (II), (IIc), (III) and (IIIc):

[0114] [Table 5]

[0115] [Table 6]

[0116] [Table 7]

[0117] [Table 8]

[0118] For the polyalkylene oxide ester polymers described above as B), R 2 at or near the boundaries of two of the X, Y and Z units is 1 xα , R 7 yβ and R 19 zγ The group is preferably H, while the remaining R 1 xα , R 7 yβ and R 19 zγis preferably methyl. This is typically based on the preparation of this type of element starting from the polymerization of propylene oxide, copolymerizing ethylene oxide at the end.

[0119] For the polyalkylene oxide ester polymers described above as C), R 2 is at or near the boundary between two of the X, Y and Z units. 1 xα , R 7 yβ and R 19 zγ The group is preferably H, while the remaining R 1 xα , R 7 yβ and R 19 zγ is preferably ethyl. This is typically based on the preparation of this type of element starting from the polymerization of 1,2-butylene oxide, copolymerized at the end with ethylene oxide.

[0120] The polyalkylene oxide ester polymers of the present invention are characterized by application properties that are comparable or even better than those of conventional polyalkylene oxide polymers such as polyethylene glycol, polypropylene glycol, ethylene oxide, n-butylene oxide or polytetrahydrofuran block polymers, but are more biodegradable. Typically, the biodegradability of many polymers decreases as the molecular weight increases. This is also true for conventional polyalkylene oxide polymers. For example, the weight average molecular weight M w Conventional high molecular weight polyethylene oxide polymers, which have a weight average molecular weight M of 6000 g / mol or more, are difficult to degrade naturally. Surprisingly, the polyalkylene oxide ester polymers of the present invention have a high weight average molecular weight M, e.g., in the case of polyethylene oxide polymers, of more than 10,000 g / mol. wThey nevertheless exhibit very good biodegradability, even when they have a molecular weight of 0.01 to 0.01. Nevertheless, they can easily replace conventional polyalkylene oxide polymers in their applications, such as perfume encapsulation, or in the preparation of graft polymers for use in home care and laundry applications.

[0121] Biodegradability is the ability of organic substances to be broken down into simpler substances by the action of enzymes derived from microorganisms. During this decomposition process oxygen is consumed and carbon dioxide is evolved, both of which can be measured by defined tests. Tests that are accepted worldwide are published as OECD 301 Chemicals Testing Guidelines. Depending on the specific test method, dissolved organic carbon (DOC), carbon dioxide evolution or oxygen consumption are measured over time during decomposition under standardized conditions.

[0122] Based on OECD measurements, the polyalkylene oxide ester polymers of the present invention, even those with a weight average molecular weight Mw of 20,000 g / mol, can usually be biodegraded to 70-90% within one month, whereas conventional polyalkylene oxide polymers only reach values ​​below 20% or even below 10%.

[0123] The polyalkylene oxide ester polymers of the invention can be easily prepared by esterifying the blocks of each structural element that builds the polymer, while the block to be esterified contains at least one esterifiable end group in the block if it is intended to be a terminal group of the polyalkylene oxide ester polymer, or two esterifiable end groups in the block if it is intended to be an internal group of the polyalkylene oxide ester polymer. In principle, as esterifiable end groups, basically any group that is usually known as an esterifiable group can be used. However, the esterifiable end group that will later form the -O-part of the -COO-ester group is, for example, -OH, and the esterifiable end group that will later form the -CO-part of the -COO-ester group is, for example, -COOH, -COOR, such as, for example, the -COOCH3 group (R is a hydrocarbon group having 1 to 12 C atoms) or a carboxylate, the cation of which is preferably an alkali metal, such as sodium or potassium, preferably -COOH and -COONa.

[0124] For the sake of completeness, in principle, weight average molecular weights M of more than 50,000 g / mol, for example 100,000 g / mol or even more, are also included. w It should be noted that polyalkylene oxide ester polymers having the formula: can also be readily prepared by esterifying the corresponding blocks.

[0125] In this regard, there is provided a process for preparing a polyalkylene oxide ester polymer, comprising the steps of: a) a polyalkylene oxide or a mixture of such polyalkylene oxides comprising the structural element (I) and having one primary OH and one COOH end group, b) a polyalkylene oxide or a mixture of such polyalkylene oxides, which comprises the structural element (II) and has two COOH end groups, c) a polyalkylene oxide or a mixture of such polyalkylene oxides comprising structural element (III) and having two primary OH end groups, at a temperature of 50 to 250° C. and a pressure of 0.1 kPa abs to 1 MPa abs in the presence of an esterification catalyst.

[0126] The polyalkylene oxides based on a) to c) described above in the previous paragraph can be easily synthesized. One possibility is to prepare the various polyalkylene oxides based on a) to c) described above separately and mix them in the intended mixing ratio.

[0127] Polyalkylene oxides containing the structural element (III) and having two primary OH end groups can be readily prepared by methods known to those skilled in the art.

[0128] Polyalkylene oxides containing structural element (I) and having one primary OH end group and one COOH end group can be synthesized in various ways. One possibility is to partially oxidize the corresponding polyalkylene oxide having two primary OH end groups and separate the polyalkylene oxide component having one primary OH end group and one COOH end group (called "mono-acid") from the unconverted polyalkylene oxide having two OH end groups (called "diol") and the fully oxidized polyalkylene oxide having two COOH end groups (called "di-acid"), for example by vacuum distillation. Another possibility is to synthesize a specific polyalkylene oxide having one primary OH and one COOH end group, for example by adding metallic sodium and bromoacetic acid to the polyalkylene oxide and treating the resulting sodium carboxylate end groups to the corresponding carboxylate end groups. However, both methods, although complex in terms of their process steps due to vacuum distillation and complex synthesis steps, may be feasible if polyalkylene oxide ester polymers with a high content of structural unit (I) are desired.

[0129] Polyalkylene oxides comprising structural element (II) and having two COOH end groups can be readily prepared either by fully oxidizing the corresponding polyalkylene oxide having two primary OH end groups or by partially oxidizing the corresponding polyalkylene oxide having two primary OH end groups and separating the partially oxidized polyalkylene oxide having one primary OH and one COOH end group (the "mono-acid") and the unconverted polyalkylene oxide (the "diol"), for example by vacuum distillation.

[0130] Another possible and preferred method for preparing the polyalkylene oxides based on the above-mentioned a)-c) is to directly prepare a mixture of components a)-c) by partial oxidation of the corresponding polyalkylene oxides having two primary OH end groups. Such partial oxidation is further described below. For the sake of completeness, it is mentioned that the mixture of components a)-c) can of course also be prepared by mixing the individual components.

[0131] The ester groups of the polyalkylene oxide ester polymer are usually formed by esterification of the polyalkylene oxide block having an esterifiable end group, and since one -O-containing end group such as an -OH group and one -CO-containing end group such as a -COOH group are required to obtain each ester group, it is preferable that these amounts are equal or approximately equal. However, if there is a slight excess of one type, this can be absorbed by an element other than (I), (II) and (III) that can be linked to the -O- or -CO- group. Furthermore, two end groups of the polyalkylene oxide ester polymer can also be linked to two of such groups. Based on this, the ratio of the number of OH end groups to the number of COOH end groups is preferably 0.9 to 1.1, more preferably ≧0.95, particularly preferably ≧0.98, even more particularly preferably ≧0.99, and more preferably ≦1.05, particularly preferably ≦1.02, even more particularly preferably ≦1.01.

[0132] The esterification of each polyalkylene oxide block can generally be carried out by methods known in the industry, for example, as described in U.S. Patent No. 6,310,235 or U.S. Patent No. 5,324,853. The educt is esterified in the presence of an esterification catalyst, preferably provided such that the number of OH end groups to the number of COOH end groups is within a target range.

[0133] Generally, various kinds of esterification catalysts can be used. They can be broadly divided into acidic catalysts, amphoteric catalysts and basic catalysts. Representatives of acidic catalysts include mineral acids, such as sulfuric acid and phosphoric acid, and organic sulfonic acids, such as methanesulfonic acid and p-toluenesulfonic acid, trifluoromethansulfonsaeure. Further acidic catalysts can also be acidic solids, such as zeolites, especially Ti-zeolites, various oxides, mixed metal oxides, sulfated oxides, acidic ion exchange resins, protonic heteropolyoxoanions, salts of heteropolyoxoanions, acidic clays and phosphates. Representative basic catalysts are, for example, ZnO, La2O3, ThO2, ZrO2, hydrotalcite, hydroxyapatite, alkali metal oxides, alkaline earth metal oxides, basic zeolites and solid superbases such as Verkade base or guanidine. Possible amphoteric catalysts include oxides of zinc (II), tin (II) and tin (IV). In addition, Lewis acid catalysts derived from metal cations of group 4 of the periodic table of elements, such as Ti and Zr compounds, such as Ti (VI) and Zr (IV), Lewis acid catalysts derived from metal cations of group 3 of the periodic table of elements, such as Sc (III) compounds, or Lewis acid catalysts derived from metal cations of group 5 of the periodic table of elements, such as Al (III) compounds, are also useful. However, catalysts containing metal cations of groups 12 and 15 of the periodic table of elements, such as Sn (IV), Sn (II), Zn (II) and Bi (III), are also included. The corresponding anions can usually be selected from alkoxylates, such as isopropoxylate and isobutyrate, alkanoates, aralkylcarboxylates, halogens, sulfates, organic sulfonates, such as p-toluenesulfonate or methanesulfonate, amido-methanesulfonate, trifluoromethanesulfonate or trifluoromethanesulfonimide.

[0134] The esterification catalyst is usually used in a conventional amount in the range of 0.02 to 10% by weight, preferably ≧0.05% by weight, more preferably ≧0.1% by weight, and preferably ≦5% by weight, more preferably ≦2% by weight, based on the total amount of the compound to be esterified.

[0135] The esterification can be carried out in the absence or presence of a solvent. When carried out in the presence of a solvent, it is preferred to use an organic solvent that is inert under the reaction conditions. These include, for example, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, aromatic and substituted aromatic hydrocarbons or ethers. Preferably, the solvent is selected from pentane, hexane, heptane, ligroin, petroleum ether, cyclohexane, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, dibutyl ether, tetrahydrofuran, dioxane and mixtures thereof. Suitable solvents that form an azeotrope with water are aromatic hydrocarbons, such as benzene, alkyl aromatic compounds, toluene or xylene. Suitable halogenated compounds with high boiling points are also useful.

[0136] The esterification is carried out at a temperature of 50-250°C, preferably ≧70°C, more preferably ≧80°C, and preferably ≦220°C, more preferably ≦200°C. When the esterification catalyst is an organic acid or a mineral acid, the esterification is usually carried out at a temperature in the range of 50-160°C. When the esterification catalyst is a metal-containing catalyst, the esterification is usually carried out at a temperature in the range of 80-250°C. With regard to pressure, the esterification can be carried out in a wide pressure range from vacuum to pressures above atmospheric pressure, ranging from 0.1 kPa abs to 1 MPa abs. Preferably, it is carried out at ≦0.5 MPa abs, more preferably ≦0.2 MPa abs.

[0137] The esterification can be carried out in the absence or presence of an inert gas, which is generally understood to mean a gas which, under the reaction conditions defined, does not take part in any reaction with the starting materials, reagents, solvents or resulting products involved in the reaction.

[0138] Suitable reactors for carrying out the esterification process are in principle all reactors suitable for esterification, examples of which include stirred tanks.

[0139] The esterification usually requires a reaction time of from 1 to 24 hours, more typically from 2 to 12 hours, which depends mainly on the nature of the inducer, the type and amount of catalyst and the reaction temperature.

[0140] The obtained polyalkylene oxide ester polymer is usually, but not necessarily, subjected to work-up depending on the intended purity. When work-up is performed, components other than the polyalkylene oxide ester polymer, especially esterification catalyst, are usually removed. In general, it is important for the quality of the product that the polyalkylene oxide ester polymer does not contain esterification catalyst. Heterogeneous catalysts can usually be removed by physical methods such as filtration or centrifugation. Homogeneous catalysts can usually be removed using fixed ion exchange equipment.

[0141] The molecular weight of the polyalkylene oxide ester polymer can be easily adjusted by the ratio of OH end groups to COOH end groups of the compound to be esterified. In simple terms, the more this ratio deviates from exactly 1:1, the fewer ester groups are formed in the polyalkylene oxide ester polymer. In practice, this can be done, for example, by adding a diol component or a diacid component, ideally one of the sources of this, to the reaction mixture. However, the addition of other monools or monocarboxylic acids can also serve this purpose.

[0142] The end groups of the polyalkylene oxide compounds that are not esterified with other polyalkylene oxide compounds usually form the end groups of the polyalkylene oxide ester polymers of the invention. Thus, the unesterified -OH end groups of the polyalkylene oxide compounds become the -OH end groups of the polyalkylene oxide ester polymers, and the unesterified -COOH, -COOR or -COOM end groups of the polyalkylene oxide compounds become the -COOH, -COOR or -COOM end groups of the polyalkylene oxide ester polymers (R is usually a hydrocarbon group having 1 to 12 C atoms, for example a methyl group, and M is usually an alkali metal, for example sodium or potassium).

[0143] For the sake of completeness, it is mentioned that, in addition to the blocks containing structural elements (I), (II) and (III), other elements having esterifiable end groups can also be present, especially when it is intended to prepare a polyalkylene oxide ester polymer which is also to contain such other elements. An example of such other elements is a polyalkylene oxide element having an alkylene unit with more than 6 carbon atoms in the chain directly bonded between two ether groups.

[0144] As already mentioned above, mixtures of components a)-c) containing so-called "mono-acids", "di-acids" and "diols" can be easily prepared by partial oxidation of the corresponding polyalkylene oxides ("diols") having two primary OH end groups. This allows a high degree of freedom, therefore, in the case where a polyalkylene oxide ester polymer with a higher content of structural element (I) is required, by separating at least a portion of the other components (so-called "di-acids" and "diols") to obtain a polyalkylene oxide (so-called "mono-acid") or a mixture of such polyalkylene oxides with a higher content of structural element (I) and one primary OH and one COOH end group.

[0145] In a preferred process, the mixture of components a) to c) used for the esterification is prepared by partial oxidation of the corresponding polyalkylene oxide having two primary OH end groups or a mixture of such polyalkylene oxides with oxygen in the presence of water and a heterogeneous catalyst comprising platinum, palladium or gold at temperatures between 20 and 100°C and oxygen partial pressures between 0.01 and 2 MPa abs, the oxidation reaction being stopped after the ratio of the number of OH end groups to the number of COOH end groups has reached a range of 0.9 to 1.1. For the sake of completeness, it is of course also possible to blend other polyalkylene oxides into this composition in order to adjust the ratio of OH end groups to COOH end groups, even if such partial oxidation does not achieve the intended ratio range mentioned above.

[0146] The corresponding polyalkylene oxides having two primary OH end groups used as starting materials for partial oxidation can be easily prepared by methods known in the art. The presence of primary OH groups is necessary for the oxidation of OH end groups to COOH end groups. For example, polyethylene oxide can be advantageously prepared by polymerizing ethylene oxide. Similarly, polypropylene oxide and poly-1,2-butylene oxide can be advantageously prepared by polymerizing propylene oxide and 1,2-butylene oxide, respectively, but due to the presence of a secondary OH group at one end, ethylene oxide units are usually formed in the outer region by copolymerizing ethylene oxide at the end at the end of the polymerization, while the inner region contains propylene oxide and 1,2-butylene oxide units, respectively. Furthermore, polytetrahydrofuran can be advantageously prepared by polymerizing tetrahydrofuran.

[0147] The partial oxidation process is carried out in the presence of water. Water promotes the oxidation of -OH end groups to -COOH end groups in various ways. For example, when a suspension catalyst is used, water improves its suspension in the reaction mixture and also reduces the viscosity of the reaction mixture. The content of water in the liquid phase is preferably maintained at 50-95 wt.%, preferably ≧60 wt.%, preferably ≦90 wt.%, more preferably ≦80 wt.%.

[0148] The catalyst used in the partial oxidation process is a heterogeneous catalyst containing platinum, palladium or gold as active component, preferably platinum. Usually, the active metal is fixed on a support. A variety of different materials can be used as the support. Examples include inorganic oxides, such as aluminum oxide, zirconium oxide, titanium dioxide, silicon oxide, inorganic silicates, such as aluminum silicate or charcoal. It is of course also possible to use a mixture of different supports. It is preferred to use charcoal as the support.

[0149] Preferred catalysts comprising platinum as active component generally comprise 0.1% to 10% by weight of platinum, preferably ≧0.5% by weight, more preferably ≧1% by weight, even more preferably ≧4% by weight, and preferably ≦8% by weight, more preferably ≦6% by weight, based on the total mass of the heterogeneous catalyst in each case. More preferably, heterogeneous catalysts are used which comprise 1 to 10% by weight, in particular 4 to 10% by weight, of platinum on charcoal.

[0150] The catalyst used may also contain further metals besides platinum, palladium or gold. The term "further metals" is understood to mean metals of periods 4 to 6 of groups 3 to 16 of the periodic table of the elements, starting with scandium (atomic number 21) and ending with polonium (atomic number 84). Preferably, the total content of further metals is 0 to 100% by weight, preferably 0 to 30% by weight, more preferably 0 to 10% by weight, even more preferably 0 to 1% by weight, in particular 0 to 0.1% by weight, based on the mass of platinum. In particular, the total content of cadmium, lead and bismuth is preferably 0 to 1% by weight, more preferably 0 to 0.5% by weight, particularly preferably 0 to 0.1% by weight, even more preferably 0 to 0.05% by weight, in particular 0 to 0.01% by weight, based on the mass of platinum. Thus, the catalyst is preferably prepared without the intentional addition of further metals.

[0151] The supported heterogeneous catalysts can be used in various geometric shapes and sizes, for example as powders or moldings. Powder catalysts can be operated, for example, in suspension mode. In the case of a fixed bed mode, it is preferred to use moldings, for example pellets, cylinders, hollow cylinders, spheres or extrudates or tablets. In that case, the moldings are usually fixed in the reactor by known methods. In the case of catalyst moldings, their average particle size is preferably 1 to 10 mm.

[0152] However, preferably, a catalyst in powder form is used, which is then suspended in the reactor. A filter is usually used here to hold the suspended catalyst so that it does not flow out of the reaction system. An example of a commonly used filter is the cross-flow filter.

[0153] Regardless of the geometric shape and size of the catalyst particles, the platinum is generally in the form of particles having an average diameter of 0.1 to 50 nm as measured by x-ray diffraction, although smaller or larger particles may also be present.

[0154] In the preparation of supported heterogeneous catalysts, platinum is generally applied to a support by a suitable method, such as that described in US 2020 / 017,745.

[0155] Supported heterogeneous catalysts generally have a BET surface area, measured according to DIN ISO 9277:2014-01, of ≥ 1 m 2 / g and ≦10000m 2 When carbon is used as the support, the BET surface area is preferably ≥ 500 m 2 / g and ≦10000m 2 / g range.

[0156] The preferred platinum-based catalyst is typically applied in an amount of 0.1 to 50 mg, preferably ≧1 mg and preferably ≦20 mg, of platinum per gram of polyalkylene oxide to be partially oxidized.

[0157] Since the aqueous solution of the polyalkylene oxide feedstock has a neutral pH, the pH at the start of the oxidation is usually at or near 7. As a result of the formation of COOH groups, the pH gradually decreases and thus generally reaches a value of 1 or 3 as the oxidation approaches its end.

[0158] However, the partial oxidation can also be carried out in the presence of a base such as sodium hydroxide or potassium hydroxide. The basic conditions increase the oxidation power and lead to the formation of carboxylates instead of carboxylic acids. As already mentioned above in the description of the esterification process, the carboxylates can also be used directly for the esterification.

[0159] In the absence of a basic compound, the carboxylic acid is formed directly, thereby avoiding (i) the use of additional chemicals (base and exogenous acid) and (ii) the disposal of salts formed from the base and exogenous acid.

[0160] The oxidation medium used in the partial oxidation process is molecular oxygen. The oxygen is added either in pure form or diluted with other gases, for example in the form of air or O2 / N2 mixtures. Preferably, a gaseous oxygen content of ≧90% by volume is used, more preferably ≧95% by volume, even more preferably ≧99% by volume, in particular ≧99.5% by volume. The use of very concentrated or pure oxygen makes it possible to keep the off-gas relatively small.

[0161] To facilitate the distribution of the oxygen in the reactor, it is advantageous to meter it in the form of fine bubbles, for example through a frit.

[0162] The oxygen partial pressure in the oxidation is 0.01 to 2 MPa, preferably ≧0.02 MPa, more preferably ≧0.05 MPa, and preferably ≦1 MPa, more preferably ≦0.3 MPa.

[0163] The oxidation is carried out at a temperature of 20-100°C, preferably ≧30°C, more preferably ≧40°C, and preferably ≦80°C, more preferably ≦70°C.

[0164] Reactors suitable for carrying out the partial oxidation process are in principle any reactor suitable for carrying out exothermic gas / liquid reactions. Examples include stirred tanks, trickle bed reactors and bubble column reactors. To remove the heat of reaction, the reactor is usually equipped with a cooling device. Depending on the type of reactor and the nature of the catalyst, the cooling device advantageously comprises a cooling element inside the reactor or a cooling element in an external circuit outside the reactor. For example, stirred tanks are preferably equipped with internal cooling elements, while bubble columns are more advantageously equipped with cooling elements, for example in the external circuit.

[0165] When the catalyst is in the form of moldings, it is usually fixed in the reactor in the form of a fixed bed.For this purpose, trickle bed reactors are a particularly useful option, in which case the catalyst can be introduced in the form of a bed.However, it is also possible to use catalyst moldings in stirred tank reactors.In that case, it is advantageous to fix the catalyst moldings in a partition, for example in a wire cage.

[0166] For the preferred use of powdered catalysts, the suspended form in the reaction mixture is advantageous. Reactors preferred for this purpose are, for example, stirred tanks or bubble columns. In order to prevent the settling of the powdered catalyst, it is necessary to carry out a corresponding mixing of the liquid reaction mixture. In stirred tanks, this is usually achieved by using a stirrer. In the case of bubble columns, the mixing is usually achieved via an external circuit with a transport pump. In principle, the bubble column can be operated either in the upward or downward direction with respect to the liquid circuit, but the downward direction is usually more advantageous.

[0167] The partial oxidation process can be operated semi-continuously or continuously, in either case oxygen is fed to the reactor continuously or at least intermittently to ensure the desired partial pressure, preferably continuously.

[0168] In semi-continuous operation, the reactor is initially charged with the entire aqueous reactant mixture along with the catalyst prior to starting the reaction, and no fresh reactants are added or liquid reaction mixture is withdrawn during the oxidation reaction. The reactor is not emptied until after the oxidation reaction is complete.

[0169] In continuous operation, the liquid reaction mixture is likewise present in the reactor together with the catalyst, but small amounts of liquid reactant are constantly withdrawn and a corresponding amount of aqueous reactant is provided, where if a suspended catalyst is used, the liquid reaction mixture is advantageously removed from the reactor by means of a filtering device, for example a cross-flow filter.

[0170] Since the partially oxidized polyalkylene oxide is in any case to contain polyalkylene oxides with one primary OH and one COOH end group, the oxidation reaction must be carried out in such a way that some primary OH groups remain unoxidized and others are already oxidized to COOH groups. This can be easily achieved by stopping the oxidation reaction when the desired amount of partially oxidized polyalkylene oxide is present. With the exception of low molecular weight polyalkylene oxides with molecular weights of only a few hundred g / mol, the probability of a primary OH group being oxidized to a COOH group is independent of whether the other end group of the polyalkylene oxide is already oxidized or not. At the beginning of the oxidation, polyalkylene oxides with one primary OH and one COOH end group (called "monoacids") are mainly formed. As their amount increases, the probability of the other OH group also being oxidized also increases, so that polyalkylene oxides with two COOH end groups (called "diacids") are also formed.

[0171] In the case of semi-continuous operation, the simplest way to stop further oxidation is to stop the supply of oxygen in a timely manner. At the very least, the oxygen present in the reactor will be consumed. Additional operations that can be combined with such stopping of the oxygen supply are, for example, supplying additional inert gas to replace part of the oxygen in the reactor, reducing the total pressure in the reactor so that the oxygen partial pressure naturally decreases, or cooling the reaction liquid, for example by withdrawing it from the reactor through a cooling device. However, the most effective measure is to stop the oxygen supply.

[0172] The oxidation reaction takes many hours to proceed, and the time range in which the "mono acids" are present in high concentration is long enough that the interruption of the progression of such an oxidation reaction can be controlled very easily. The time range in which the partial oxidation reaction should be stopped can be determined in various ways. Firstly, the time required for partial oxidation under defined conditions such as temperature, oxygen partial pressure, nature and amount of catalyst can be determined by preliminary tests in which the oxidation is stopped at different times and the composition of the reaction product is analyzed. The oxidation time required to obtain the desired composition can then be estimated. Another possibility for controlling the partial oxidation is to measure the amount of oxygen fed to the reactor, as an indicator of the oxygen absorbed by the oxidation. The degree of oxidation can then be calculated by the amount of OH groups present in the polyalkylene oxide derivative and the stoichiometric amount of oxidation of them to COOH groups. Another method is to take samples over time and analyze them, for example by titration and by measuring the acid number, as an indicator of the COOH groups already formed. Last but not least, physical measurements such as electrical conductivity, dielectric constant or impedance measurements can also be carried out in situ, which of course require prior calibration.

[0173] In the case of continuous operation, the degree of oxidation can be easily controlled by the residence time of the mixture in the reactor under reaction conditions.

[0174] As already mentioned above, the oxidation reaction requires a long time. The usual reaction time for partially oxidizing about 50% of OH groups is about 3 to 20 hours, preferably ≧4 hours, more preferably ≧5 hours, preferably ≦18 hours, more preferably ≦15 hours.

[0175] For the sake of completeness, it should be mentioned that in addition to the main reaction of oxidation of OH groups to COOH groups, oxidative decomposition also occurs to a lesser extent. In such oxidative decomposition, a small number of alkylene oxide units may be completely oxidized. As a result, the inner chain length of the partially oxidized alkylene oxide is inevitably slightly shorter than that of the alkylene oxide from which it was derived before the partial oxidation.

[0176] After the reaction is completed, the reaction mixture is usually removed from the reactor and separated from the catalyst. If a suspended catalyst is used, it is advisable to remove it by filtration. Alternatively, it is possible to allow the suspended catalyst to settle to the bottom of the reactor after the reaction is completed and remove the supernatant. It is also possible to separate the catalyst using centrifugation. The removed catalyst can generally be reused without further workup. The water or at least a large part of the water is usually removed by distillation, for example in a thin film evaporator. The partially oxidized polyalkylene oxide can then be used in the esterification step.

[0177] The polyalkylene oxide ester polymers of the present invention can replace conventional polyalkylene oxide polymers in a wide range of applications.

[0178] Preferred applications of the polyalkylene oxide ester polymers of the present invention include the encapsulation of perfumes and their use as building blocks to prepare block polymers.

[0179] Perfume is often encapsulated in order to reduce its vapor pressure so that the concentration released in the air is low, because high perfume concentration often makes the smell very strong, and to increase the time that perfume is released and therefore the product is fragrant.Encapsulation is often carried out by mixing perfume into a liquid, usually a molten polymer, and then solidifying this mixture.By using the polyalkylene oxide ester polymer of the present invention, even if a polymer with a lower molecular weight is used, the product can be fragrant for a longer period of time.

[0180] A block polymer is a polymer that contains blocks of different structural units, in particular different types of polymers. One important group of block polymers are polymers formed by reacting the end groups of polyalkylene oxide ester polymers with monomeric or polymeric compounds so that successive blocks of different polymer units are formed. Another important group of block polymers are graft polymers. Graft polymers are polymers that have side chains on the polymer backbone. The polymer backbone is also called the backbone. The polyalkylene oxide ester polymers of the present invention are preferably used for the preparation of this type of graft polymer. The polyalkylene oxide ester polymers of the present invention can be easily grafted with side chain forming monomers similar or identical to conventional polyalkylene oxide polymers. In particular, graft polymers prepared by grafting vinyl-based monomers such as vinyl acetate, vinyl laurate, vinyl alkylate or vinyl pyrrolidone are important graft polymers for home care products and laundry applications. Graft polymers based on the polyalkylene oxide ester polymers of the present invention are described in more detail in the European patent application already cited at the beginning.

[0181] Products containing or made with such polyalkylene oxide ester polymers are significantly more biodegradable than similar products containing or made with conventional polyalkylene oxide polymers.

[0182] The polyalkylene oxide ester polymer of the present invention is a new type of polymer that can replace polyalkylene oxides, particularly polyethylene oxide, polypropylene oxide, poly-1,2-butylene oxide and polytetrahydrofuran, in typical applications such as perfume encapsulation and in the preparation of graft polymers for home care and laundry applications, and some application properties of the polyalkylene oxide ester polymer are even improved compared to conventional polyalkylene oxides.The greatest advantage of this new type of polymer is that the biodegradability is greatly improved, which can be important for contributing to environmental protection, and in particular, this polyalkylene oxide ester polymer can easily replace conventional polyalkylene oxides in home care and laundry applications.The polyalkylene oxide ester polymer is safe and durable in its application.

[0183] Moreover, the polyalkylene oxide ester polymers of the present invention can be easily prepared in high yields in a two-step process from readily available starting materials. EXAMPLES

[0184] Measurement of K value The K value is determined by measuring the relative viscosity of a diluted polymer solution and is a relative measure of the average molecular weight. For a particular polymer, the K value tends to increase as the average molecular weight of the polymer increases. The K values ​​of the esterified mixtures were determined in a 3 wt. % NaCl solution at 23° C. and a polymer concentration of 1 wt. % polymer by the method of H. Fikentscher, described in “Cellulosechemie”, 1932, 13, 58.

[0185] M n , M w and PD determination The number average molecular weight M of the esterified mixture n , weight average molecular weight M w and polydispersity M w / M n was determined in tetrahydrofuran by size exclusion chromatography (SEC). Tetrahydrofuran containing 0.035 mol / L diethanolamine was used as mobile phase (eluent). The concentration of the esterified polymer in tetrahydrofuran was 2.0 mg / mL. After filtering (pore size 0.2 μm), 100 μL of this solution was injected into the SEC system. Four different columns (heated to 60 °C) were used for the separation (SDV precolumn, SDV 1000A, SDV 100000A, SDV 1000000A). The SEC system was operated at a flow rate of 1 mL / min. A DRI Agilent 1100 was used as the detection system. The molecular weight M was used for calibration. n Poly(ethylene glycol) (PEG) standards (PL) with concentrations ranging from 106 to 1 378 000 g / mol were used.

[0186] OECD 301B Decomposition Test Explanation Biodegradation was tested in triplicate using the OECD 301B manometric respirometry method. 30 mg / mL of the test substance is inoculated into water taken from a wastewater treatment plant in Mannheim (Germany) and incubated in closed flasks at 25°C for 28 days. The oxygen consumed during this period is measured as the pressure change in the flask using an OxiTop C (WTW). The evolved CO2 is absorbed using a NaOH solution. The amount of oxygen consumed by the microbial population during the biodegradation of the test substance is expressed as a percentage of the theoretical oxygen demand ("ThOD") after correction with a blank.

[0187] Examples 1 to 10 In Examples 1-10, polyalkylene oxides having two primary OH end groups (referred to as "diols") were oxidized to obtain mixtures containing at least two COOH end groups (referred to as "diacids") and polyalkylene oxides having one primary OH and one COOH end group (referred to as "monoacids"), and optionally a remainder polyalkylene oxide having two primary OH end groups. The mixtures were prepared as follows:

[0188] Platinum on charcoal (5.0 wt.% Pt on C, moisture content: 59.7 wt.%, 283 g, 29.2 mmol Pt) was suspended in a mixture of polyalkylene oxide containing two primary OH end groups (details see Table 1) and water (details see Table 1), heated to 52° C. and stirred at 800 rpm. While stirring the mixture, oxygen was bubbled (20 nL / h) through a glass tube equipped with a glass frit and the temperature was raised to 60° C. The oxygen supply and temperature were maintained for the time stated in Table 1, then the oxygen supply was stopped and the mixture was cooled to room temperature. The solid was separated from the liquid phase by filtration and the filter cake was washed with 500 mL of warm water. The washing water was mixed with the filtrate. Water was removed by evaporation from the liquid mixture using a thin film evaporator (total height: 87.2 cm, diameter: 3.54 cm, wiped height: 43 cm, feed rate: 4.0 mL / min, 44°C, 1.8 kPa abs, 600 rpm). The sump product from the thin film evaporator was analyzed. The hydroxyl value was measured to determine the OH group content, and the acid value was measured to determine the COOH group content. The conversion rate of polyalkylene oxide in partial oxidation was derived from this acid value.

[0189] M wFor partially oxidized mixtures based on low molecular weight polyalkylene oxides with a value of 200 g / mol, the distribution of diols, monoacids and diacids was determined by gas chromatography. To do so, 0.1 g of a dry sample of partially oxidized polyalkylene oxide was heated to 80° C. together with 1 g of N-methyl-N-(trimethylsilyl)trifluoroacetamide and maintained at this temperature for 1 hour. The resulting mixture was then analyzed by gas chromatography. For other mixtures based on polyalkylene oxides with a value of 400 g / mol or more, the distribution was calculated from the total content of OH and COOH groups, assuming that each OH group is oxidized with equal probability, regardless of whether it is part of a diol or a monoacid. The respective values ​​are shown in Table 1.

[0190] Examples 11 to 21 and 22 Examples 11-21 relate to the esterification of the oxidized polyalkylene oxide mixtures obtained according to Examples 1-10 and the determination of the biodegradability of the polyalkylene oxide ester polymers obtained thereby. Example 22 is a comparative example to determine the biodegradability of conventional polyethylene oxide ("PEG").

[0191] In Examples 11-21, 98 g of polyalkylene oxide mixture obtained by the oxidation procedure described in Examples 1-10, hereinafter referred to as inducer mixture (see Tables 2a and 2b for details), was mixed with 2 g of water with an esterification catalyst (see Tables 2a and 2b for details) and heated under reduced pressure of 1 kPa abs for the period of time described in Tables 2a and 2b, starting from 125°C and slowly increasing the temperature to 145°C.

[0192] The resulting esterified mixture was then analyzed to determine the K value, number average molar mass M n and molecular weight distribution M w was determined as described above. Biodegradability was determined by the OECD 301B degradation test described above.

[0193] The average number of ester and ether groups in the polyalkylene oxide ester polymers was estimated from the estimated average molecular weight of each polyalkylene oxide ester polymer and each polyalkylene oxide used in the preceding oxidation step. For each polyalkylene oxide ester polymer, a number average molecular weight M, which is a good indicator of the average molecular weight on a molecular scale, was calculated. n For each polyalkylene oxide used in the preceding oxidation step, the molecular average molecular weight M w The reason is that polyethylene oxide typically has a low polydispersity PD, slightly above 1, so M w and M n This is because there is only a very slight difference between the

[0194] The number of ester groups in the polyalkylene oxide ester polymer based on the use of partially oxidized polyethylene oxide (with a ratio of oxidized OH groups of about 50%) was estimated as follows: First, the number of structural units was calculated based on (1) the number average molecular weight M of the polyalkylene oxide ester polymer, taking into account two terminal groups and correcting by 18 g / mol. n (2) was estimated by dividing by the average molecular weight of the esterified structural element. The latter is the molecular average molecular weight M w From this, 18 g / mol is subtracted to account for the separation of water by esterification, and 16 g / mol is added and 2 g / mol is subtracted to account for the arithmetic average formation of one -CO- unit from the corresponding -CH2- unit per structural element. In the case of the structural element of formula (I), there is exactly one per structural element, and in the case of the combination of the structural elements of formulas (II) and (III), there are two and zero, which also average out to one. Next, 1 is subtracted from the number of structural units, taking into account that each ester group of the polyalkylene oxide ester polymer of the example connects two structural elements, thereby resulting in one more structural element than the number of ester groups.

[0195] The above estimation is specifically explained with reference to Example 12. The number average molecular weight M of the polyalkylene oxide ester polymer is n was 2400 g / mol, giving a value of 2382 g / mol. The average molecular weight of the structural elements used in the esterification was (400-4) g / mol = 396 g / mol. From this, the average number of structural units is 2382 / 396 = 6.0, and therefore the average number of ester groups is 5.0. Alternatively, this can be expressed by the formula:

number

[0196] The number of ether groups in the polyalkylene oxide ester polymer based on the use of partially oxidized polyethylene oxide (with a ratio of oxidized OH groups of about 50%) was estimated as follows. First, (1) taking into consideration that terminal groups are formally formed by the addition of one water molecule per polyethylene oxide molecule during polymerization, the molecular average molecular weight M w The number of ethylene oxide units in the polyethylene oxide used was determined by subtracting 18 g / mol from the total molecular weight of the polyethylene oxide and then dividing by 44 g / mol, which is the molecular weight of the (2) -CH2CH2-O- unit. Next, 1 is subtracted from the number of ethylene oxide units, taking into account that the number of ether groups in each polyethylene oxide is one less than the number of ethylene oxide units. The result is the average number of ether groups in the polyethylene oxide. This number is then further multiplied by the number of structural units of the polyalkylene oxide ester polymer, determined as described above.

[0197] The above estimation will be specifically explained with reference to Example 12. The molecular average molecular weight M wwas 400 g / mol, giving a value of 382 g / mol. Dividing this by 44 g / mol gives the number of -CH2CH2-O- units as 8.7, and therefore the average number of ether units in the polyethylene oxide as 7.7. Since the average number of structural units in the polyalkylene oxide ester polymer was estimated above to be 6.0, the average number of ether groups in the polyalkylene oxide ester polymer is 46. Or, the formula:

number

[0198] In the case of the examples based on the use of fully oxidized polyethylene oxide (with a proportion of oxidized OH groups of around 95-100%) and therefore requiring the addition of a diol as a second constituent, the estimation of the number of ester and ether groups was performed in a similar manner to that described above, with the main difference being the molecular average molecular weight M of the polyethylene oxide used in the calculation. w is the molecular average molecular weight M of the polyalkylene oxide used in the oxidation. w and the molecular average molecular weight M of the polyalkylene oxide used as the diol component. w This approach is based on the simplifying assumption that both structural units are evenly distributed within the polyalkylene oxide ester polymer.

[0199] This revised estimate is called M w = 600 g / mol of polyethylene oxide is almost completely oxidized, and M w A specific example will be described with reference to Example 14, which uses polyethylene oxide having a molecular weight of 1,500 g / mol. The formula for the estimation of the ester group is as follows:

number

number

[0200] The polyalkylene oxide ester polymers obtained in Examples 11 to 21 all had a weight average molecular weight M w The M ranged from 4050 to 18300 g / mol, while the biodegradability ranged from 73 to 89% of the theoretical CO2 production after 28 days. w Conventional polyethylene oxide, which has a molecular weight of M = 8720 g / mol, w This contrasts with the much poorer biodegradability measured by CO2 production within 28 days, which was only 16%, despite being well below 10,000 g / mol.

[0201] Examples 23 to 29 In Examples 23 to 29, the properties of the polyalkylene oxide ester polymers obtained in Examples 16 to 21 as fragrance carriers were investigated and compared with a conventional PEG 9000 sample.

[0202] 9 g of each polymer (see Table 3 for details) was melted at 60°C and mixed with 1 g of mint flavor mixture (boiling point: 207-228°C). The molten mixture was dropped onto a cold plate to obtain pellets weighing about 40 mg. The theoretical mint flavor content immediately after pellet preparation was 10 wt%, which was also measured by gas chromatography analysis. All the pellets were then stored together in a drying cabinet at 40°C for 12 weeks, and the mint flavor content was again measured by gas chromatography analysis. The results are shown in Table 3.

[0203] From this experiment it can be seen that the amount of mint flavor in pellets prepared with the polyalkylene oxide ester polymer of the invention is still in the range of 2.3-3.0 wt % compared to only 2.2 wt % for the conventional PEG 9000 polymer. The higher flavor retention of the polyalkylene oxide ester polymer of the invention allows either less flavor to be used for a given duration or the flavored pellets to last longer.

[0204] In addition, the biodegradability of the polyalkylene oxide ester polymer used is much better than that of the conventional PEG 9000 polymer, with the biodegradability of the polyalkylene oxide ester polymer being as high as 73-79%, while that of the conventional PEG 9000 polymer is very low at 16%.

[0205] [Table 9]

[0206] [Table 10]

[0207] [Table 11]

[0208] [Table 12]

Claims

1. The weight average molecular weight M ｗ is 500 to 50,000 g / mol, the polydispersity PD is 2 to 6, and it contains 10 to 560 ether groups and 2 to 51 ester groups that are bonded to each other with an alkylene group, and is a polyalkylene oxide ester polymer, wherein the polyalkylene oxide ester polymer is: A) 1 to 51 general formulas (I): 【Chemical Formula 1】 (In the formula, - The left - O - unit is bonded to the - CO - unit of the adjacent unit of the polymer to form an ester unit, - The right - CO - unit is bonded to the - O - unit of the adjacent unit of the polymer to form a further ester unit, - R １ 、R ２ 、R ３ 、R ４ 、R ５ are, independently of each other, a hydrogen atom or a C １～１２ alkyl group, - a, b, c, d, e are, independently of each other, an integer of 0 or 1, and the sum of a to e is 1 to 5, - X represents a polyalkylene oxide unit having 4 to 100 alkylene oxide units, and the alkylene oxide units, independently of each other, contain 2 to 6 carbon atoms in the chain directly bonded between two - O - units, and the carbon atoms in the chain directly bonded between two - O - units each contain, independently of each other, either two hydrogen atoms or one hydrogen atom and one C １～１２ alkyl group), and B) 1 to 25 general formulas (II): 【Chemical Formula 2】 (In the formula, - The left - CO - unit is bonded to the - O - unit of the adjacent unit of the polymer to form an ester unit, - The right - CO - unit is bonded to the - O - unit of the adjacent unit of the polymer to form a further ester unit, - R ７ 、R ８ 、R ９ 、R １０ 、R １１ 、R １３ 、R １４ 、R １５ 、R １６ 、R １７ are, independently of one another, a hydrogen atom or a C １～１２ alkyl group, - g, h, i, j, k, m, n, o, p, q are, independently of one another, an integer of 0 or 1, the sum of g to k is 1 to 5, and the sum of m to q is 1 to 5, - Y represents a polyalkylene oxide unit having 0 to 99 alkylene oxide units, and the alkylene oxide units each independently contain 2 to 6 carbon atoms in the chain directly connecting between two ether groups, and the carbon atoms in the chain directly connecting between two ether groups each independently contain either two hydrogen atoms or one hydrogen atom and one C １～１２ alkyl group), and C) A number of general formula (III) suitable for forming an ester bond with the -CO- unit of the structural elements of formulas (I) and (II): [Chemical Formula 3] (In the formula, - The left -O- unit is bonded to the -CO- unit of the adjacent unit of the polymer to form an ester unit, - The right -O- unit is bonded to the -CO- unit of the adjacent unit of the polymer to form a further ester unit, - R １９ 、R ２０ 、R ２１ 、R ２２ 、R ２３ 、R ２４ are, independently of one another, a hydrogen atom or a C １～１２ alkyl group, - s, t, u, v, w, x are, independently of one another, an integer of 0 or 1, and the sum of s to x is 2 to 6, - Z represents a polyalkylene oxide unit having 0 to 100 alkylene oxide units, and the alkylene oxide units each independently contain 2 to 6 carbon atoms in a chain directly bonded between two ether groups, and the carbon atoms in the chain directly bonded between two ether groups each independently contain either two hydrogen atoms or one hydrogen atom and one C １～１２ alkyl group), and a polyalkylene oxide unit; and includes However, the total number of the ester groups does not exceed the maximum number of the ester groups defined for the polyalkylene oxide ester polymer, and it is a polyalkylene oxide ester polymer.

2. - R １ represents a hydrogen atom or a methyl group, - R ２ , R ３ represents a hydrogen atom, - d and e are 0, - a is 1, - b and c represent integers of 0 or 1, and the sum of b to c is 0 or 2, - X represents a polyalkylene oxide unit having 4 to 100 alkylene oxide units, and the alkylene oxide units each independently have 2 or 4 carbon atoms in a chain directly bonded between two ether groups, and each alkylene oxide unit independently has one of the carbon atoms at the α-position relative to the -O- unit containing two hydrogen atoms or one hydrogen atom and one methyl group, and the other one or three carbon atoms each contain two hydrogen atoms, and the number of methyl groups bonded to the carbon atoms at the α-position of each -O- unit does not exceed 1, The polyalkylene oxide ester polymer according to claim 1.

3. - R １ represents a hydrogen atom or a methyl group, - b, c, d, and e are 0, - a is 1, - X represents a polyalkylene oxide unit having 4 to 100 alkylene oxide units, the alkylene oxide units each independently contain 2 carbon atoms in the chain directly bonded between two ether groups, and for each alkylene oxide unit, one of the carbon atoms at the α-position relative to the -O- unit contains either 2 hydrogen atoms or 1 hydrogen atom and 1 methyl group, the other carbon atom contains 2 hydrogen atoms, and the number of methyl groups bonded to the carbon atom at the α-position of each -O- unit does not exceed 1. The polyalkylene oxide ester polymer according to claim 1.

4. - R １３ and R １９ each independently represent a hydrogen atom or a methyl group. - R ９ and R １０ and R １１ and R １４ and R １５ and R ２０ and R ２１ and R ２４ represent hydrogen atoms. - g, h, p, q, v, w are 0. - k, m, s, x are 1. - i, j, n, o, t, u each independently represent an integer of 0 or 1, the sum of i to j is 0 or 2, the sum of n to o is 0 or 2, and the sum of t to u is 0 or 2. - Y represents a polyalkylene oxide unit having 3 to 99 alkylene oxide units, Z represents a polyalkylene oxide unit having 4 to 100 alkylene oxide units, the alkylene oxide units each independently contain 2 or 4 carbon atoms in the chain directly bonded between two ether groups, and for each alkylene oxide unit, one of the carbon atoms at the α-position relative to the -O- unit contains either 2 hydrogen atoms or 1 hydrogen atom and 1 methyl group, the other remaining 1 or 3 carbon atoms each contain 2 hydrogen atoms, and the number of methyl groups bonded to the carbon atom at the α-position of each -O- unit does not exceed 1. The polyalkylene oxide ester polymer according to claim 1.

5. ・ R １３ and R １９ each independently represent a hydrogen atom or a methyl group, ・ R ９ and R １０ and R １１ and R １４ and R １５ and R ２０ and R ２１ and R ２４ represent a hydrogen atom, ・ g, h, i, j, n, o, p, q, t, u, v, w are 0, ・ k, m, s, x are 1, ・ Y represents a polyalkylene oxide unit having 3 to 99 alkylene oxide units, Z represents a polyalkylene oxide unit having 4 to 100 alkylene oxide units, the alkylene oxide units each independently contain 2 carbon atoms in the chain directly bonded between two ether groups, each alkylene oxide unit each independently has one of the carbon atoms at the α-position relative to the -O- unit containing 2 hydrogen atoms or containing 1 hydrogen atom and 1 methyl group, and the remaining carbon atoms contain 2 hydrogen atoms, and the number of methyl groups bonded to the carbon atom at the α-position of each -O- unit does not exceed 1, The polyalkylene oxide ester polymer according to claim 1.

6. The polyalkylene oxide ester polymer according to claim 1, wherein the ratio of the number of ether groups to the number of ester groups is 4 to 100.

7. The polyalkylene oxide ester polymer according to claim 1, wherein the ratio of the number of structural element (I) to the number of structural element (II) is 0.5 to 8.

8. The polyalkylene oxide ester polymer according to claim 1, wherein the structural elements (I), (II) and (III) constitute 80 to 100% of the molecular weight of the polyalkylene oxide ester polymer.

9. A process for preparing a polyalkylene oxide ester polymer according to claim 1, comprising: a) a polyalkylene oxide or a mixture of such polyalkylene oxides, containing structural element (I) and having one primary OH and one COOH end group; b) a polyalkylene oxide or a mixture of such polyalkylene oxides, containing structural element (II) and having two COOH end groups; c) a polyalkylene oxide or a mixture of such polyalkylene oxides, containing structural element (III) and having two primary OH end groups; comprising a mixture of esterifying at a temperature of 50 to 250 °C and a pressure of 0.1 kPa abs to 1 MPa abs in the presence of an esterification catalyst.

10. The process according to claim 9, wherein the ratio of the number of OH end groups to the number of COOH end groups is 0.9 to 1.

1.

11. The mixture of components a) to c) is produced by partially oxidizing the corresponding polyalkylene oxide or a mixture of such polyalkylene oxides having two primary OH end groups with oxygen at a temperature of 20 to 100 °C and an oxygen partial pressure of 0.01 to 2 MPa abs in the presence of a heterogeneous catalyst containing water and platinum, palladium or gold, and the oxidation reaction is stopped after the ratio of the number of OH end groups to the number of COOH end groups reaches the range of 0.9 to 1.

1. The process according to claim 9.

12. Use of the polyalkylene oxide ester polymer according to claim 1 as a constituent unit for preparing a block polymer for encapsulating a fragrance, or for use in home care and laundry applications.

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