Polyalkylene oxide polymers, their preparation and use

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] This invention relates to weight-average molecular weight M w This invention relates to a polyalkylene oxide ester polymer having a molecular weight of 500 to 50,000 g / mol, a polydispersity PD of 2 to 6, and containing 10 to 560 ether groups and 2 to 51 ester groups bonded to the alkylene group, and exhibiting significantly superior biodegradability compared to conventional polyalkylene oxide polymers.

[0002] Furthermore, the present invention relates to a process for preparing such polyalkylene oxide polymers and to the use thereof. [Background technology]

[0003] Polyalkylene oxides are important polymers with a wide range of applications. Among these, they are used as solvents, viscosity improvers, emulsifiers, dispersants, protective colloids, plasticizers, and mold release agents, as well as components or raw materials in the manufacture of various polymers such as adhesives and graft polymers. Beyond these various technical applications, they are also used in a variety of consumer products, such as cosmetics and 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 can eventually become microplastics in rivers and oceans. In the course of this invention, it was found that polyalkylene oxides exhibit reduced biodegradability in the molecular weight range of several hundred g / mol to several thousand g / mol.

[0005] Efforts to ban microplastics, particularly in cosmetics, have already begun in various countries. Beyond the ban on these insoluble microplastics, there is enthusiastic discussion regarding future requirements for soluble polymers used in consumer products. Therefore, there is a strong desire to identify components with higher biodegradability for use in these types of applications. Even radical-generated graft polymers with a polyethylene glycol backbone exhibit very limited biodegradability in wastewater if the polyethylene glycol backbone has a molecular weight within the range mentioned above, especially if 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, but on the other hand, M w Polyethylene oxide with a concentration of 6000 g / mol exhibits insufficient biodegradability. According to the revised 2.0. of the safety data sheet for BASF's Pluriol® E 600, dated January 5, 2021, M w The DOC value (dissolved organic carbon) of polyethylene glycol at 600 g / mol, measured according to OECD 301A, has been confirmed to exceed 70%. In contrast, M w In the case of polyethylene glycol with a molecular weight of 6000 g / mol, BASF's Safety Data Sheet for Pluriol® E 6000 Pellet, revised version 2.0 dated August 10, 2018, states that it is only insufficiently biodegradable, and the amount of CO2 produced in accordance with OECD 301B is only 10-20% of the theoretical value (60d).

[0007] Classical polyalkylene oxides consist of polymer chains of oxyalkylene groups with OH groups at both ends. On the other hand, in the prior art, polyalkylene oxides with functionalized end groups are also known, exhibiting specific properties and usable for specific applications.

[0008] Chinese Patent Application Publication No. 110498915A discloses the preparation of omega-hydroxy-alpha-carboxypolyethylene oxide by polymerizing an ester-functionalized hydroxy compound, such as methyl 2,2-dimethyl-3-hydroxypropionate, with ethylene oxide to obtain an omega-hydroxy-polyethylene oxide alpha-ester intermediate product, which is then hydrolyzed to obtain the corresponding omega-hydroxy-alpha-carboxypolyethylene oxide. It is stated that this COOH terminal group plays a role as a reaction site with other molecules in forming modified polyethylene oxides, for example, for use in the biological or medical fields.

[0009] U.S. Patent No. 2,585,448 describes polyethylene oxides in which one or both of the OH-terminal groups are esterified with aromatic or aliphatic carboxylic acids. Mono- and diesters are described as useful as plasticizers.

[0010] Other documents typically concern cyclic polyether esters called oxocronue ethers. Oxocronue ethers are cyclic polyalkylene oxides having at least one ester group in the ring.

[0011] Japanese Patent Publication No. 55-143981 discloses the preparation of cyclic polyether esters, commonly known as oxocronuine ethers. The oxocronuine ethers described herein are cyclic esters having 2 to 9 ether groups and 1 to 2 ester groups. These are synthesized by 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 removing sodium bromide, and then 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 intramolecularly cyclized while removing the tosyl group in the presence of a template metal ion to obtain the corresponding oxocronuine ether. It is stated that oxocronuine ethers are used, for example, in organic synthesis, separation, analysis, biochemistry, and pharmaceuticals, mainly as complexing agents for alkali metal and alkaline earth metal cations.

[0012] Y. Nakatsuji et al., Synthesis (1981) 42-44 also describes the preparation of oxocrown ethers having 3 to 5 ether groups and 1 ester group. By reacting polyethylene oxide with metallic sodium and bromoacetic acid, polyethylene oxide having a methanecarboxylate group at the end is obtained, which is then esterified with methanol. The resulting ω-hydroxy-α-methyl ester is then either directly cyclized by intramolecular transesterification to the corresponding oxocrown ether, or saponified to polyethylene oxide having terminal carboxylic acid groups and OH groups, and then intramolecularly cyclized by dehydration.

[0013] In L. van der Mee et al., J. Polymer Sci. Part A, Polymer Chem. 44(7) (2006) 2166-2176, the preparation of 2-oxa-12-crown-4-ether is disclosed by converting triethylene glycol with t-butyl bromoacetate while eliminating sodium bromide, and then cyclizing the resulting t-butyl ester in the presence of cobalt dichloride. Furthermore, the authors describe the ring-opening polymerization of the obtained 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 a catalyst and benzyl alcohol. [ka] Unit or [ka] The disclosure describes a linear polymer containing any of the unit mixtures. Oxocron ethers are described as very interesting monomers for synthesizing hydrophilic polyesters.

[0014] In addition to polyalkylene oxides and oxocrown ethers with functionalized terminal groups, linear polyalkylene oxides having functionalized groups within the oxyalkylene chain are also known in the prior art.

[0015] U.S. Patent Application Publication 2011 / 0,207,634 discloses the preparation of polyalkylene oxides having carboxylate-terminated groups, the polyalkylene oxide chains of which may contain exactly one ester group. Polyalkylene oxides having carboxylate-terminated groups and one ester group in the polymer chain are prepared by reacting the corresponding polyalkylene oxide starting material having an OH-terminated group with a base while removing hydrogen in the presence of a transition metal catalyst. Ether carboxylates are said to be useful in low-irritation anionic surfactants.

[0016] International Publication No. WO 2001 / 012,203 pamphlet relates to a new type of surgical polymer useful as a sterilized adhesion prevention barrier used between animal tissues, which is the first repeating unit: [Chemical formula] (wherein R 1 and R 2 are, independently, hydrogen or a C 1~8 alkyl group, and R 3 is a C 2~12 alkylene group or an oxyalkylene group with a maximum of 2000 repeating units) and an oxyalkylene group with a maximum of 2000 repeating units or a divalent unit: [Chemical formula] (wherein R 5 is either a specific alkylene group having a maximum of 17 carbon atoms, a specific oxyalkylene group having 3 carbon atoms and 1 oxygen atom, a specific keto unit 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) of the second repeating unit, and is formed from a polyoxaester having these.

[0017] U.S. Patent No. 6,147,168, U.S. Patent No. 6,224,894, European Patent No. 0,771,832, and European Patent No. 0,771,849 disclose the repeating units defined in International Publication No. WO 2001 / 012,203 and additional third repeating units, especially divalent units: [Chemical formula] (wherein R 30 is a divalent alkylene, arylene or arylalkylene group) or divalent unit: [Chemical formula] (wherein R 13Further surgical polymers are disclosed, comprising a third repeating unit which is 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 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, where P is an integer such that the number-average molecular weight of the polymer is reliably less than 1,000,000.

[0018] The document cited here concerning linear polyalkylene oxides having functionalized groups within the oxyalkylene chain describes specific uses of such functionalized polyalkylene oxides, such as their use as mild anionic surfactants or for the manufacture of surgical instruments, but does not address environmental issues, particularly the biodegradability of this type of polymer. Furthermore, their synthesis requires at least two isolated components, such as dicarboxylic acids and diols, which must be prepared, isolated, and purified beforehand, thus complicating the manufacturing process.

[0019] International Publication No. 96 / 36656 deals with biodegradable polyalkylene oxide copolymers based on alkylene oxide units and lactone units, where the lactone unit is given by formula: [ka] (wherein R' is defined as hydrogen, alkyl group, cycloalkyl group, alkoxy group, or monocyclic aromatic hydrocarbon group, and n≧1) This is a structural unit that is bonded to other lactone units or polyalkylene oxide units within the polyalkylene oxide copolymer.

[0020] European Patent Application No. 21182316.6 describes the use of polyalkylene oxide polymers for preparing biodegradable graft polymers, which involves grafting polymer side chains onto the polyalkylene oxide polymer, such as polymers obtained by polymerizing vinyl ester monomers and optionally other vinyl monomers. [Overview of the Initiative] [Problems that the invention aims to solve]

[0021] The objective of the present invention was to find a novel type of compound that can replace polyalkylene oxides, particularly polyethylene oxide, polypropylene oxide, poly-1,2-butylene oxide, and polytetrahydrofuran, in their typical applications such as fragrance encapsulation, or in the preparation of graft polymers for use in home care and laundry applications, and that has the same or at least very similar application properties as polyalkylene oxide-based products, but with superior biodegradability. Furthermore, this novel type of polymer is easy to manufacture and therefore primarily uses readily available starting materials. Finally, it is safe and durable in its applications.

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

[0023] Furthermore, another objective 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 wThe molecular weight is 500 to 50000 g / mol, the polydispersity PD is 2 to 6, and it contains 10 to 560 ether groups and 2 to 51 ester groups bonded to the alkylene group. A) 1 to 51 general formulas (I): [ka] (In the formula, The -O- unit on the left bonded to the -CO- unit of an adjacent polymer unit to form an ester unit. The -CO- unit on the right bonded to the -O- unit of an adjacent polymer unit to form a further ester unit. · R 1 , R 2 , R 3 , R 4 , R 5 These are, independently of each other, hydrogen atoms or C 1~12 Represents an alkyl group, a, b, c, d, and e are independent integers of either 0 or 1, and the sum of a through e is between 1 and 5. • X represents a polyalkylene oxide unit having 4 to 100 alkylene oxide units, each alkylene oxide unit containing 2 to 6 carbon atoms in a direct chain directly bonded between two -O- units, and each carbon atom in the direct chain directly bonded between two -O- units independently contains either two hydrogen atoms or one hydrogen atom and one carbon atom. 1~12 Structural elements (including any alkyl group) B) 1 to 25 general formulas (II): [ka] (In the formula, The -CO- unit on the left is bonded to the -O- unit of an adjacent polymer unit to form an ester unit. The -CO- unit on the right bonded to the -O- unit of an adjacent polymer unit 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 These are, independently of each other, hydrogen atoms or C 1~12 Represents an alkyl group, g, h, i, j, k, m, n, o, p, q are mutually independent integers of 0 or 1, the sum of g to k is between 1 and 5, and the sum of m to q is between 1 and 5. • Y represents a polyalkylene oxide unit having 0 to 99 alkylene oxide units, each alkylene oxide unit independently containing 2 to 6 carbon atoms in a chain directly bonded between two ether groups, and each carbon atom in the chain directly bonded between the two ether groups independently contains either 2 hydrogen atoms or 1 hydrogen atom and 1 carbon atom. 1~12 Structural elements (including any alkyl group) C) General formula (III) for a number of structural elements of formulas (I) and (II) suitable for forming ester bonds with -CO- units: [ka] (In the formula, The -O- unit on the left bonded to the -CO- unit of an adjacent polymer unit to form an ester unit. The -O- unit on the right bonded to the -CO- unit of an adjacent unit in the polymer to form a further ester unit. · R 19 , R 20 , R 21 , R 22 , R 23 , R 24 These are, independently of each other, hydrogen atoms or C 1~12 Represents an alkyl group, • s, t, u, v, w, and x represent integers of 0 or 1 independently of each other, and the sum of s to x is between 2 and 6. • Z represents a polyalkylene oxide unit having 0 to 100 alkylene oxide units, each alkylene oxide unit containing 2 to 6 carbon atoms in a chain directly bonded between two ether groups, and each carbon atom in the chain directly bonded between the two ether groups independently contains either two hydrogen atoms or one hydrogen atom and one carbon atom. 1~12 A polyalkylene oxide unit (containing any of the alkyl groups), Includes, However, the total number of ester groups shall not exceed the maximum number of ester groups specified for polyalkylene oxide ester polymers. We discovered polyalkylene oxide polymers. [Modes for carrying out the invention]

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

[0026] M w This takes into account the mass of individual chains that contribute to the overall molecular weight of the polymer, and it is considered that larger molecules have a higher mass than smaller molecules. This is determined by performing liquid-solid size exclusion chromatography (SEC) and detecting the differential refractive index relative to a reference cell, and the units are calibrated using polymers of known molecular weight. As a result of this measurement, the distribution of separated polymer molecules is obtained as a chromatogram, from which the mass M of each polymer molecule is determined. i and the number of those n i We can then determine the following. Next, based on the changes in the chromatogram curve, we can formulate the general formula:

number

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

[0028] The weight-average molecular weight M of the polyalkylene oxide polymer of the present invention w Its weight-average molecular weight is 500-50000 g / mol. w The concentration is preferably ≥750 g / mol, more preferably ≥1000 g / mol, particularly preferably ≥2000 g / mol, particularly very preferably ≥3000 g / mol, most preferably ≥4000 g / mol, and also preferably ≤45000 g / mol, more preferably ≤40000 g / mol, particularly preferably ≤35000 g / mol, particularly very preferably ≤25000 g / mol, and most preferably ≤15000 g / mol.

[0029] Weight average molecular weight M w Since this is only an average value of molecular weight and does not provide information about the distribution of molar weights of individual molecules, the polyalkylene oxide ester polymer of the present invention is further defined by its polydispersity PD. The polydispersity PD is,

number

number

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

[0031] Number average molecular weight M nThe concentration is 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] A critically important feature of the polyalkylene oxide ester polymer of the present invention, which enables remarkably high biodegradability, is the presence of ester groups within the polyalkylene oxide polymer chain. Polyalkylene oxide units, which themselves exhibit at least considerable biodegradability, are bonded to each other with ester groups. Since the polyalkylene oxide units themselves alternately contain ether groups and alkylene groups, this polyalkylene oxide ester polymer can also be described as a polymer containing ether groups and ester groups bonded to each other with alkylene groups. For the sake of clarity, it should be noted that the term "polyalkylene oxide" does not include acetal units or ketal units in which one carbon atom links two ether groups, such as -O-CH2-O-. This is consistent with the general usage of the term polyalkylene oxide and is known to those skilled in the art.

[0033] The term "ether group" as used in this document refers to an -O- unit in which carbon atoms are bonded to both sides, and these carbon atoms have an oxidation state of -2, -1, or 0 independently of each other, and are further bonded to a hydrogen atom or another carbon atom. For example, the oxidation state is -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" refers to a -CO- unit in which one end is bonded to a carbon atom whose oxidation state is -3, -2, -1, or 0. For example, -3 for a methyl group, -2 for an unsubstituted alkylene group further bonded to other carbon atoms in the polymer chain, -1 for an alpha-alkyl-substituted alkylene group further bonded to other carbon atoms in the polymer chain or an unsubstituted alkylene group further bonded to an -O- group, and 0 for an alpha-alkyl-substituted alkylene group bonded to an -O- group, and the other end is bonded to an -O- unit, the opposite end of which is now bonded to a carbon atom whose oxidation state is -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 polymer molecules. Weight-average molecular weight M w The number of ether and ester groups in a specific polyalkylene oxide polymer molecule, composed of polyalkylene oxide polymers with a polydispersity PD of 2 to 6 and a polydispersity PD of 500 to 50,000 g / mol, exhibits individual distributions depending on the polydispersity PD. Therefore, polyalkylene oxide polymers typically contain polyalkylene oxide polymer molecules having different numbers of ester and ether groups.

[0035] The average number of ether and ester groups in a polyalkylene oxide polymer can be determined by analysis using the knowledge of those skilled in the art, based on the weight-average molecular weight M. wThis can be determined based on the polydispersity PD of the polyalkylene oxide ester polymer and the ratio of ether groups to ester groups.

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

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

[0038] As already mentioned above, the polyalkylene oxide polymer of the present invention is a general formula (I) of 1 to 51: [ka] (In the formula, The -O- unit on the left bonded to the -CO- unit of an adjacent polymer unit to form an ester unit. The -CO- unit on the right bonded to the -O- unit of an adjacent polymer unit to form a further ester unit. · R 1 , R 2 , R 3 , R 4 , R 5 These are, independently of each other, hydrogen atoms or C 1~12 Represents an alkyl group, a, b, c, d, and e are independent integers of either 0 or 1, and the sum of a through e is between 1 and 5. • X represents a polyalkylene oxide unit having 4 to 100 alkylene oxide units, each alkylene oxide unit containing 2 to 6 carbon atoms in a chain directly bonded between two -O- units, and each carbon atom in the chain directly bonded between two -O- units independently contains either two hydrogen atoms or one hydrogen atom and one carbon atom. 1~12 Includes structural elements (including any alkyl group).

[0039] R in equation (I) 1 , R 2 , R 3 , R 4 , R 5 These are, independently of each other, hydrogen atoms or C 1~12 Represents an alkyl group. The alkyl group may be a straight chain, C 3~12 In the case of alkyl groups, they may be linear or branched. Preferred C 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. Preferably, R 2 , R 3 , R 4 and R 5 represents a hydrogen atom, and R 1 is a hydrogen atom or C 1~12 Represents an alkyl group. More preferably, R 1 represents 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, particularly very preferably a hydrogen atom or methyl, most preferably a hydrogen atom.

[0040] The subscripts a, b, c, d, and e independently represent integers of 0 or 1, and the sum of a to e is between 1 and 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] A particularly preferred structural element based on formula (I) is given by 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 preferably a hydrogen atom or methyl, most preferably a hydrogen atom. b and c are elements of the formula (where b and c represent integers of 0 or 1, and the sum of b to c is 0 or 2).

[0042] A particularly preferred structural element based on formula (Ia) is general formula (Ib): [ka] (In the formula, · R 1 is a hydrogen atom or C 1~12 The element 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 preferably a hydrogen atom or methyl, and most preferably a hydrogen atom.

[0043] (I), the unit X represents a polyalkylene oxide unit having 4 to 100 alkylene oxide units, and the alkylene oxide units each independently contain 2 to 6 carbon atoms in the chain directly bonded between two -O- units, which is C 2~6 It can also be represented as an alkylene unit, and the carbon atoms in the chain directly bonded between two -O- units each independently contain either two hydrogen atoms or one hydrogen atom and one C 1~12 either an alkyl group. Preferred unit X is of the general formula (Ic): [Chemical formula] (wherein, · α represents a subscript from 1 to Xn that defines the running count of each repeating unit, · R 1 xα , R 2 xα , R 3 xα , R 4 xα , R 5 xα , R 6 xα are each independently, and considering that α is the running count of each repeating unit, a hydrogen atom or a C 1~12 alkyl group, · a xα , b xα , c xα , d xα , e xα , f xα are each independently, and considering that α is the running count of each repeating unit, represent an integer of 0 or 1, and the sum of a xα ~f xα is 2 to 6, · Xn represents an integer from 4 to 100).

[0044] For example, groups such as R 1 xα and for example a xαThe lowercase x in subscripts such as indicates that they are related to the unit X. The uppercase X in Xn, which is the number of repeating units, indicates the same thing. Furthermore, for example, R 1 xα such as and for example a xα The lowercase letter α included in subscripts such as indicates that the base and subscript each have their own sub-number, suggesting that within the polyalkylene oxide unit X, the base and subscript can change for each alkylene oxide unit. For example, the R of an alkylene oxide unit with a sequential number of 1. 1 x1 The group can be a hydrogen atom, while the R group is an alkylene oxide unit with a consecutive number of 2. 1 x2 This can be a methyl group, and so can the others. Similarly, although this should also be understood as just one example, the subscript c of the alkylene oxide unit has a sequential number of 1. x1 It can be 0, while the alkylene oxide unit c has a consecutive number of 2. x2 It can be 1, and so can the others.

[0045] R in equation (Ic) 1 xα , R 2 xα , R 3 xα , R 4 xα , R 5 xα , R 6 xα C in the base 1~12 The alkyl group may be linear, C 3~12 In the case of alkyl groups, they can be linear or branched. Preferred C 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. Preferably, R 2 xα , R 3 xα , R 4 xα , R 5xα and R 6 xα represents a hydrogen atom, and R 1 xα is a hydrogen atom or C 1~12 Represents an alkyl group. More preferably, R 1 xα represents 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, particularly very preferably a hydrogen atom or methyl, and most preferably a hydrogen atom.

[0046] subscript a xα , b xα , c xα d xα , e xα ,f xα Each represents an integer of 0 or 1, independently of the other, and a xα ~f xα The sum of 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 It is 0.

[0047] A particularly preferred unit X is given by 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 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 a unit representing integers between 4 and 100.

[0048] A more particularly preferred unit X based on formula (Id) is given by the general formula (Ie): [ka] (In the formula, · R 1 xα is a hydrogen atom or C 1~12 Alkyl, 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, particularly very preferably a hydrogen atom or methyl, most preferably a hydrogen atom. Xn is a unit representing integers between 4 and 100.

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

[0050] The alkylene oxide unit in unit X is a different group R 1 xα ~R 6 xαin this regard, and with different subscripts a xα ~f xα in this regard, it is emphasized and clearly stated that it may be the same as the unit X or may be different from each other. In this regard, in formula (Ic), based on the consecutive numbers of each repeating unit, using the subscript xα, the sub-numbers of each group are designated, for example, as R 1 xα as shown, and the sub-numbers of each subscript are already clearly stated, for example, as a xα as shown.

[0051] Furthermore, regarding each structural element (I) in the polyalkylene oxide ester polymer, when there are more than one element (I), it is emphasized and clearly stated that it may be the same as one or more of the others or may be different from one or more of the others.

[0052] The different parts of the structural element (I), for example, the group, subscript, and unit X, are as described above, including their general values and preferred values. The following paragraphs relate to specific preferred combinations of these parts.

[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, c represent an integer of 0 or 1, and the sum of b~c is 0 or 2, X represents a polyalkylene oxide unit having 4 to 100 alkylene oxide units, each alkylene oxide unit having 2 or 4 carbon atoms in a chain directly bonded between 2 ether groups, each alkylene oxide unit having one carbon atom at the α-position relative to the -O- unit containing either 2 hydrogen atoms or 1 hydrogen atom and 1 methyl group, and each of the other 1 or 3 carbon atoms containing 2 hydrogen atoms, and the number of methyl groups bonded to the α-position carbon atom of each -O- unit not exceeding 1. Includes structural element (I).

[0054] This relates in particular to polymers in which structural element (I) is formed from only C2- units, only C4- units, or a mixture thereof. Each C2- and C4- unit may be bonded to either only a hydrogen atom, or a hydrogen atom and one methyl group. If a methyl group is present in a C2- or C4- unit, it is bonded to the carbon atom at the α-position relative to the -O- unit, and the number of methyl groups bonded to the carbon atom at the α-position of each -O- unit is not greater than one.

[0055] These elements are typically based on ethylene oxide monomers, propylene oxide monomers, tetrahydrofuran monomers, or mixtures thereof. In the propylene oxide-based -CHCH3-CH2-O- units and tetrahydrofuran-based -CH2-CH2-CH2-CH2-O- units of formula (I), it may be advantageous if structural element (I) contains one or more C2-based units without methyl groups in the boundary region of 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 supplying 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 later to form structural unit (I) in the polyalkylene oxide ester polymer. By using the manufacturing process described here, ethylene oxide copolymerizes with propylene oxide and tetrahydrofuran, respectively, resulting in an irregular structure in the boundary region where -CHCH3-CH2-O- units and -CH2-CH2-CH2-CH2-O- units alternate with -CH2-CH2-O- units. As a result, the transition from -CHCH3-CH2-O- units and -CH2-CH2-CH2-CH2-O- units to -CH2-CH2-O- units may become unclear. This effect is well known in the art, and the corresponding alternating structure is sometimes called a "dirty structure."

[0056] Other particularly preferred polyalkylene oxide polymers are: · R 1 This 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, each alkylene oxide unit independently containing two carbon atoms in a chain directly bonded between two ether groups, each alkylene oxide unit independently having one carbon atom at the α-position relative to the -O- unit containing either two hydrogen atoms or one hydrogen atom and one methyl group, the other carbon atoms containing two hydrogen atoms, and the number of methyl groups bonded to the α-position carbon atom of each -O- unit not exceeding 1. Includes structural element (I).

[0057] This relates in particular to polymers in which structural element (I) is formed solely from ethylene oxide and propylene oxide-based C2 units.

[0058] The following acyclic polyalkylene oxide polymers A) to D) are particularly preferred, and their groups and subscripts relate to formulas (I) and (Ic).

[0059] [Table 1]

[0060] [Table 2]

[0061] [Table 3]

[0062] [Table 4]

[0063] Regarding the polyalkylene oxide polymers mentioned above as B), R is located at or near the boundary between the two X units. 1 xα The base is preferably H, while the remaining R in unit X1 xα The base is preferably methyl. This is typically based on the preparation of this type of element starting from the polymerization of propylene oxide and copolymerizing ethylene oxide at its terminal.

[0064] Regarding the polyalkylene oxide ester polymer described above as C), the subscripts b xα and c xα are preferably 0, while the remaining b xα and c xα in unit X are preferably 1. This is typically based on the preparation of this type of element starting from the polymerization of 1,2-butylene oxide and copolymerizing ethylene oxide at its terminal.

[0065] As already described above, the polyalkylene oxide ester polymer of the present invention further comprises 1 to 25 general formulas (II):

Chemical formula

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

[0067] R in equation (II) 7 , R 8 , R 9 , R 10 , R 11 , R 13 , R 14 , R 15 , R 16 , R 17 The groups are independent of each other, consisting of a hydrogen atom or C 1~12 Represents an alkyl group. The alkyl group may be a straight chain, C 3~12 In the case of alkyl groups, they may be linear or branched. Preferred C 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. Preferably, R 7 , R 8 , R 9 , R 10 , R 11 , R 14 , R 15 , R 16 , R 17 represents a hydrogen atom, and R 13 is a hydrogen atom or C 1~12Represents an alkyl group. More preferably, R 13 represents 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, particularly very preferably a hydrogen atom or methyl, most preferably a hydrogen atom.

[0068] In formula (II), the subscripts g, h, i, j, k, m, n, o, p, and q independently represent integers of 0 or 1, the sum of g to k is between 1 and 5, and the sum of m to q is between 1 and 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] A particularly preferred structural element based on formula (II) is given by 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 preferably a hydrogen atom or methyl, most preferably a hydrogen atom. i, j, n, and o are elements of the set (where 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] A particularly preferred structural element based on formula (IIa) is given by general formula (IIb): [ka] (In the formula, · R 13 is a hydrogen atom or C 1~12 The element 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 preferably a hydrogen atom or methyl, and most preferably a hydrogen atom.

[0071] In formula (II), unit Y represents a polyalkylene oxide unit having 0 to 99 alkylene oxide units, each alkylene oxide unit containing 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, and the carbon atoms in the chain directly bonded between the two -O- units are, independently of each other, two hydrogen atoms or one hydrogen atom and one carbon atom. 1~12 Contains any of the alkyl groups.

[0072] The preferred unit Y is given by the general formula (IIc): [ka] (In the formula, • β represents an index from 1 to Yn that defines the sequential number of each repeating unit. · R 7 yβ , R 8 yβ , R 9 yβ , R 10 yβ , R 11 yβ , R 12 yβ These are considered to be independent of each other, and taking into account that β is the consecutive number of each repeating unit, a hydrogen atom or C 1~12 Represents an alkyl group, · G yβ hyβ i yβ , j yβ , k yβ ,l yβ These represent integers 0 or 1, independent of each other and considering that β is a consecutive number of each repeating unit, and g yβ ~l yβ The sum is between 2 and 6. Yn can be represented as an integer between 0 and 99.

[0073] For example, R in equation (IIc) 7 yβ such as and for example g yβ The lowercase 'y' in subscripts such as indicates that they are related to the unit Y. The uppercase 'Y' in Yn, which is the number of repeating units, suggests the same thing. Furthermore, for example, R 7 yβ such as and for example g yβ The lowercase β in subscripts such as indicates that the group and subscript each have their own child number, showing that within the polyalkylene oxide unit Y, the group and subscript can change for each alkylene oxide unit. For example, the alkylene oxide unit R has a continuity of 1. 7 y1 The group can be a hydrogen atom, while the R group is an alkylene oxide unit with 2 consecutive units. 7 y2 It can be a methyl group, and so can the others. Similarly, although this should also be understood as just one example, the subscript i of the alkylene oxide unit has a sequential number of 1. y1 It can be 0, on the other hand, i of the alkylene oxide unit has a consecutive number of 2. y2 It can be 1, and so can the others.

[0074] R in equation (IIc) 7 yβ , R 8 yβ , R 9 yβ , R 10 yβ , R 11 yβ , R 12 yβ C in the base 1~12The alkyl group may be linear, C 3~12 In this case, it can be a straight chain or a branched chain. Preferred C 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. Preferably, R 8 yβ , R 9 yβ , R 10 yβ , R 11 yβ , R 12 yβ represents a hydrogen atom, and R 7 yβ is a hydrogen atom or C 1~12 Represents an alkyl group. More preferably, R 7 yβ represents 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, particularly very preferably a hydrogen atom or methyl, and most preferably a hydrogen atom.

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

[0076] A particularly preferred unit Y is given by 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 preferably a hydrogen atom or methyl, most preferably a hydrogen atom. h yβ i yβ h represents an integer of 0 or 1, yβ ~i yβ The sum is 0 or 2. Yn is a unit representing integers from 0 to 99.

[0077] A more particularly preferred unit Y based on formula (IId) is given by 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 preferably a hydrogen atom or methyl, most preferably a hydrogen atom. Yn is a unit representing integers from 0 to 99.

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

[0079] The alkylene oxide unit in unit Y is a different group R 7 yβ ~R 12 yβ In that respect, and different subscript g yβ ~l yβ In this regard, it is emphasized that they may be the same within unit Y, or they may be different from one another. In this regard, in equation (IIc), the subscript yβ is used based on the consecutive number of each repeating unit, and the child number of each base is, for example, R 7 yβ Specify it as shown, and the child number of each subscript is, for example, g yβ We have already explicitly stated that it should be specified as such.

[0080] Furthermore, regarding each structural element (II) in the polyalkylene oxide polymer, if there is more than one element (II), it should be emphasized that it may be identical to or different from one or more other elements (II).

[0081] R in equation (III) 19 , R 20 , R 21 , R 22 , R 23 , R 24 These are, independently of each other, hydrogen atoms or C 1~12 Represents an alkyl group. The alkyl group may be a straight chain, C 3~12 In the case of alkyl groups, they may be linear or branched. Preferred C 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. Preferably, R in formula (III) 19 , R 20 , R 21 , R 22 , R 23 , R 24 represents a hydrogen atom, and R 19 is a hydrogen atom or C 1~12 Represents an alkyl group. More preferably, R 19 represents 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, particularly very preferably a hydrogen atom or methyl, most preferably a hydrogen atom.

[0082] In equation (III), the subscripts s, t, u, v, w, and x independently represent integers of 0 or 1, and the sum of x is between 2 and 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] A particularly preferred structural element based on formula (III) is given by 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 preferably a hydrogen atom or methyl, most preferably a hydrogen atom. • t and u are elements of a matrix where t and u are integers of 0 or 1, and the sum of t and u is 0 or 2.

[0084] A more particularly preferred structural element based on formula (IIIa) is general formula (IIIb): [ka] (In the formula, · R 19 is a hydrogen atom or C 1~12 The element 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 preferably a hydrogen atom or methyl, and most preferably a hydrogen atom.

[0085] In (III), unit Z represents a polyalkylene oxide unit having 0 to 100 alkylene oxide units, and these alkylene oxide units independently 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 each carbon atom in the chain directly bonded between two -O- units independently contains either two hydrogen atoms or one hydrogen atom and one C1-12 alkyl group.

[0086] The preferred unit Z is given by the general formula (IIIc): [ka] (In the formula, • γ represents a subscript from 1 to Zn that defines the sequential number of each repeating unit. · R 19 zγ , R 20 zγ , R 21 zγ , R 22 zγ , R 23 zγ , R 24 zγ These are considered to be independent of each other, and taking into account that γ is a consecutive number in each repeating unit, a hydrogen atom or C 1~12 Represents an alkyl group, · s zγ t zγ u zγ , v zγ , w zγ , x zγ These represent integers of 0 or 1, independent of each other and considering that γ is a consecutive number of each repeating unit, and s zγ ~x zγ The sum is between 2 and 6. Zn can be represented as an integer between 0 and 100.

[0087] For example, R in equation (IIIc) 19 zγ such as and for example s zγ The lowercase letter z in subscripts such as indicates that these are related to the unit Z. The uppercase letter Z in Zn, which is the number of repeating units, also suggests the same thing. Furthermore, for example, R 19 zγ such as and for example s zγ The lowercase subscript γ indicates that the group and subscript each have their own unique sub-number, showing that within the polyalkylene oxide unit Z, the group and subscript can change for each alkylene oxide unit. For example, the alkylene oxide unit R has a continuity of 1. 19 z1 The group can be a hydrogen atom, while the R group is an alkylene oxide unit with 2 consecutive units. 19 z2This can be a methyl group, and so can the others. Similarly, although this should also be understood as an example, the subscript u of the alkylene oxide unit has a sequential number of 1. z1 It can be 0, on the other hand, the alkylene oxide unit u has a consecutive number of 2. z2 It can be 1, and so can the others.

[0088] R in equation (IIIc) 19 zγ , R 20 zγ , R 21 zγ , R 22 zγ , R 23 zγ , R 24 zγ C in the base 1~12 The alkyl group may be linear, C 3~12 In the case of alkyl groups, they can be linear or branched. Preferred C 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. Preferably, R 20 zγ , R 21 zγ , R 22 zγ , R 23 zγ , R 24 zγ represents a hydrogen atom, R 19 zγ is a hydrogen atom or C 1~12 Represents an alkyl group. More preferably, R 19 zγ represents 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, particularly very preferably a hydrogen atom or methyl, and most preferably a hydrogen atom.

[0089] Subscript s in equation (IIIc) zγ t zγ u zγ , v zγ , w zγ , x zγ Each represents an integer of 0 or 1, independently of the others. zγ ~x zγ The sum 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 It is 0.

[0090] A particularly preferred unit Z is given by 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 preferably a hydrogen atom or methyl, most preferably a hydrogen atom. · t zγ u zγ represents an integer of 0 or 1, and t zγ ~u zγ The sum is 0 or 2. Zn is a unit of integers (representing integers from 0 to 100).

[0091] A particularly preferred unit Z based on formula (IIId) is given by 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 preferably a hydrogen atom or methyl, most preferably a hydrogen atom. Zn is a unit of integers (representing integers 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, particularly very preferably ≥10, and preferably ≤75, more preferably ≤50.

[0093] The alkylene oxide unit in unit Z is a different group R 19 zγ ~R 24 zγ In that respect, and different subscripts s zγ ~x zγ In this regard, it is emphasized that they may be the same or different within unit Z. In this regard, in equation (IIIc), the subscript zγ is used to determine the child number of each unit, for example, R, based on the consecutive number of each repeating unit. 19 zγ Specify it as shown, and the child number of each subscript is, for example, s zγ We have already explicitly stated that it should be specified as such.

[0094] Furthermore, regarding each structural element (III) in the polyalkylene oxide polymer, if there is more than one element (III), it should be emphasized that it may be identical to or different from one or more of the other elements (III).

[0095] The different parts of structural elements (II) and (III), such as the base, subscript, and units X and Y, including their general and preferred values, are as already described above. The following paragraphs concern specific preferred combinations of these parts.

[0096] Particularly preferred are polyalkylene oxide polymers comprising structural elements (I), (II), and (III), · R 13 , R 19 However, each independently represents either a hydrogen atom or a methyl group. · R 9 , R 10 , R 11 , R 14 , R 15 , R 20 , R 21 , R 24 This 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 represent integers 0 or 1 independently of each other, 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, and Z represents a polyalkylene oxide unit having 4 to 100 alkylene oxide units, each alkylene oxide unit having 2 or 4 carbon atoms in a chain directly bonded between 2 ether groups, each alkylene oxide unit having 1 or 4 carbon atoms in one of the carbon atoms at the α position relative to the -O- unit, each of the remaining 1 or 3 carbon atoms each containing 2 hydrogen atoms, and the number of methyl groups bonded to the α-position carbon atom of each -O- unit not exceeding 1.

[0097] This relates in particular to polymers in which structural elements (II) and (III) are formed solely from C2-units, solely from C4-units, or from a mixture thereof. Each C2-unit and C4-unit may be bonded to either a hydrogen atom alone, or a hydrogen atom and one methyl group. If a methyl group is present in a C2-unit or C4-unit, it is bonded to the carbon atom at the α-position relative to the -O-unit, and the number of methyl groups bonded to the carbon atom at the α-position of each -O-unit is not greater than one.

[0098] These elements are typically based on ethylene oxide monomers, propylene oxide monomers, tetrahydrofuran monomers, or mixtures thereof. In the propylene oxide-based -CHCH3-CH2-O- units and tetrahydrofuran-based -CH2-CH2-CH2-CH2-O- units in formulas (II) and (III), it may be advantageous if structural elements (II) and (III) contain one or more C2-based units without methyl groups in 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 supplying ethylene oxide to complete the polymerization, thereby obtaining C2-based units at both ends. The resulting polyalkylene oxide can then be further treated as described later to form structural units (II) and (III) in the polyalkylene oxide ester polymer. By using the manufacturing process described herein, ethylene oxide copolymerizes with propylene oxide and tetrahydrofuran, respectively, resulting in an irregular structure in the boundary region where -CHCH3-CH2-O- units and -CH2-CH2-CH2-CH2-O- units alternate with -CH2-CH2-O- units. As a result, the transition from -CHCH3-CH2-O- units and -CH2-CH2-CH2-CH2-O- units to -CH2-CH2-O- units may become unclear. Such effects are well known in the art, and the corresponding alternating structure is sometimes called an "impure structure."

[0099] Other particularly preferred polyalkylene oxide polymers include structural elements (I), (II), and (III), · R 13 , R 19 These independently represent a hydrogen atom or a methyl group. · R 9 , R 10 , R 11 , R 14 , R 15 , R 20 , R21 , R 24 This 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, each alkylene oxide unit independently containing two carbon atoms in a chain directly bonded between two ether groups, each alkylene oxide unit independently having one carbon atom at the α-position relative to the -O- unit containing either two hydrogen atoms or one hydrogen atom and one methyl group, the other remaining carbon atoms containing two hydrogen atoms, and the number of methyl groups bonded to the carbon atom at the α-position of each -O- unit not exceeding 1.

[0100] This relates in particular to polymers in which structural elements (II) and (III) are formed solely from ethylene oxide and propylene oxide-based C2 units.

[0101] In particular, weight-average molecular weight M w In the case of polyalkylene oxide polymers with lower concentrations, such as less than 1000 g / mol, the polymer may have a cyclic structure instead, but overall it has an acyclic structure.

[0102] As already stated above, the polyalkylene oxide ester polymer of the present invention contains 10 to 560 ether groups and 2 to 51 ester groups. To avoid doubt, it should be emphasized that the amounts of ether groups and ester groups stated above refer to the entire polyalkylene oxide ester polymer including each group present in the structural elements of formulas (I), (II), and (III). The polyalkylene oxide ester polymer contains preferably ≥15, more preferably ≥20, particularly preferably ≥30 ether groups, and preferably ≤500, more preferably ≤400, particularly preferably ≤350 ether groups. This also contains preferably ≥3, more preferably ≥4, particularly preferably ≥5 ester groups, and preferably ≤41, more preferably ≤31, particularly preferably ≤21, and particularly very preferably ≤15 ester groups.

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

[0104] Polyalkylene oxide polymers can be formed entirely by structural elements (I), (II), and (III), as well as end groups at both ends containing one or more additional alkylene oxide elements or one or more other structural elements. Preferably, the polyalkylene oxide polymer contains additional alkylene oxides having -O- and -CO- units at the ends of its elements, which together with the -CO- and -O- units of other elements to form an ester group.

[0105] Structural elements that form an ester group together with structural elements (I), (II), and (III) or with other structural elements include at least one -O- unit or at least one -CO- unit at one terminal end of such structural element. In this case, the -O- unit and the -CO- unit formally form an ester unit. Such further alkylene oxide unit structural elements preferably include at their terminals either two -CO- units or two -O- units. Since an ester group formally requires one -O- unit and one -CO- unit, the number of structural elements having an -O- unit and one -CO- unit at their terminals is favorably 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, particularly very preferably ≥5, and preferably ≤41, more preferably ≤31, particularly preferably ≤21, particularly very preferably ≤15, and most preferably ≤9.

[0107] The number of structural elements (II) in the polyalkylene oxide ester polymer is 1 to 25, preferably ≥2, more preferably ≥3, particularly preferably ≥4, particularly very preferably ≥5, most preferably ≥6, and preferably ≤23, more preferably ≤22, particularly preferably ≤20, and particularly very 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 -O- units located at the ends of one element and -CO- units located at the ends of the other elements, the total number of such -O- 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. Any excess -O- or -CO- units may be bonded, for example, to the end groups 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 ester bonds with the -CO- units of the structural elements of formulas (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, particularly very preferably ≥0.95, and particularly preferably ≤1.1, particularly very preferably ≥1.05, and most preferably 1. Excess -O- units or -CO- units may be bonded, for example, to terminal groups or other structural elements.

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

[0110] As already stated above, the polyalkylene oxide polymer of the present invention may include, in addition to terminal groups, further polyalkylene oxide elements or even different structural elements distinct from (I), (II), and (III). Further polyalkylene oxide elements distinct from (I), (II), and (III) may, for example, be elements having alkylene units with more than six carbon atoms in a chain directly bonded between two ether groups. Other structural elements may be, for example, diols other than structural element (III), dicarboxylic acids other than structural element (II), or alpha-hydroxy-omegacarboxylic acids other than structural element (I), such as sebacic acid or terephthalic acid. In general, structural elements (I), (II), and (III) are the number-average molecular weight M of the polyalkylene oxide polymer. n It constitutes 50-100%, preferably 70-100%, more preferably 80-100%, particularly preferably 90-100%, particularly very preferably 95-100%, and most preferably 98-100%. The properties of the structural elements, and therefore the composition of the polyalkylene oxide ester polymer, can be determined, for example, by hydrolyzing the ester bonds and using conventional analytical methods such as gas chromatography, HPLC, NMR, and others of the same kind.

[0111] Because end groups are present on both sides of the polymer, even if the polymer does not contain elements other than (I), (II), and (III), the amounts of structural elements (I), (II), and (III) are usually at least the number average molecular weight M of the polyalkylene oxide polymer. n It will be slightly less than 100%. However, especially when the -OH group is present as a terminal group, 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 polymer, a value of 100% can be achieved when considering the accuracy of analytical measurements.

[0112] Other elements besides elements (I), (II), and (III) may be present in the polyalkylene oxide polymer, but preferably, elements (I), (II), and (III) plus only two terminal groups are included.

[0113] Particularly preferred polyalkylene oxide polymers A) to D) based on structural elements (I), (II), and (III) are the polymers shown below, where these groups and subscripts relate to formulas (I), (Ic), (II), (IIc), (III), and (IIIc):

[0114] [Table 5]

[0115] [Table 6]

[0116] [Table 7]

[0117] [Table 8]

[0118] Regarding the polyalkylene oxide polymers described above as B), R is located at or near the boundary between the two X, Y, and Z units. 1 xα , R 7 yβ and R 19 zγ The base is preferably H, while the remaining R in the X, Y, and Z units 1 xα , R 7 yβ and R 19 zγThe compound is preferably methyl. This is typically based on the preparation of this type of element, starting with the polymerization of propylene oxide and copolymerizing ethylene oxide at its ends.

[0119] Regarding the polyalkylene oxide polymers mentioned above as C), R is located at or near the boundary between the two X, Y, and Z units. 1 xα , R 7 yβ and R 19 zγ The base is preferably H, while the remaining R in the X, Y, and Z units 1 xα , R 7 yβ and R 19 zγ The compound is preferably ethyl. This is typically based on the preparation of this type of element, starting with the polymerization of 1,2-butylene oxide and copolymerizing ethylene oxide at its ends.

[0120] The polyalkylene oxide ester polymer of the present invention is characterized by having application properties equivalent to or even better than those of conventional polyalkylene oxide polymers such as polyethylene glycol, polypropylene glycol, ethylene oxide, n-butylene oxide, or polytetrahydrofuran block polymer, but with superior biodegradability. Generally, the biodegradability of many polymers decreases as their 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 of 6000 g / mol or more, are difficult to decompose naturally. Surprisingly, the polyalkylene oxide ester polymer of the present invention has a high weight-average molecular weight, such as over 10000 g / mol in the case of polyethylene oxide polymers. wEven with these properties, they exhibit excellent biodegradability. Nevertheless, they can easily replace conventional polyalkylene oxide polymers in their applications, such as fragrance encapsulation, or in the preparation of graft polymers for use in home care and laundry applications.

[0121] Biodegradability is the ability of organic matter to be broken down into simpler substances by the action of enzymes derived from microorganisms. This decomposition process consumes oxygen and produces carbon dioxide. Both can be measured by prescribed tests. The OECD 301 Chemical Testing Guidelines are a globally accepted set of tests. Depending on the specific test method, dissolved organic carbon (DOC), carbon dioxide production, or oxygen consumption are measured over time under standardized conditions during decomposition.

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

[0123] The polyalkylene oxide polymer of the present invention can be easily prepared by esterifying blocks of each structural element that make up the polymer. The blocks to be esterified contain at least one esterifiable end group if intended to be end groups of the polyalkylene oxide polymer, and two esterifiable end groups if intended to be inner groups of the polyalkylene oxide polymer. In principle, any group commonly known as an esterifiable group can be used as the esterifiable end group. However, the esterifiable end group that will later form the -O- portion of the -COO-ester group is, for example, -OH, and the esterifiable end group that will later form the -CO- portion of the -COO-ester group is, for example, -COOH, -COOR (where R is a hydrocarbon group having 1 to 12 C atoms), such as -COOCH3, or a carboxylate whose cation is preferably an alkali metal such as sodium or potassium, preferably -COOH and -COONa.

[0124] For completeness, as a general rule, weight-average molecular weight M exceeds 50,000 g / mol, for example, 100,000 g / mol or even more. w It should be noted that polyalkylene oxide polymers having the corresponding block can also be easily prepared by esterifying the corresponding block.

[0125] In connection with this, a process for preparing polyalkylene oxide polymers, a) A polyalkylene oxide or a mixture of such polyalkylene oxides comprising structural element (I) and having one primary OH and one COOH terminal group, b) A polyalkylene oxide or a mixture of such polyalkylene oxides containing structural element (II) and having two COOH terminal groups, c) A polyalkylene oxide or a mixture of such polyalkylene oxides comprising structural element (III) and having two primary OH-terminated groups, A process was discovered for esterification at temperatures of 50-250°C and pressures of 0.1 kPa abs-1 MPa abs in the presence of an esterification catalyst.

[0126] Polyalkylene oxides based on a) to c) described above can be easily synthesized. One possible method 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 structural element (III) and having two primary OH-terminated 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-terminated group and one COOH-terminated group can be synthesized in various ways. One possible method is to partially oxidize the corresponding polyalkylene oxide having two primary OH-terminated groups and separate the polyalkylene oxide component having one primary OH-terminated group and one COOH-terminated group (referred to as the "monoacid") from the unconverted polyalkylene oxide having two OH-terminated groups (referred to as the "diol") and the fully oxidized polyalkylene oxide having two COOH-terminated groups (referred to as the "diacid"), for example, by vacuum distillation. Another possibility is to synthesize specific polyalkylene oxides having one primary OH-terminated group and one COOH-terminated group by adding metallic sodium and bromoacetic acid to the polyalkylene oxide and treating the resulting sodium carboxylate-terminated groups to the corresponding carboxylic acid-terminated groups. However, both methods involve vacuum distillation and complex synthesis steps, making them complex in terms of process steps, but they can be viable when a polyalkylene oxide ester polymer with a high structural unit (I) content is desired.

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

[0130] Another possible preferred method for preparing polyalkylene oxides based on a) to c) described above is to directly produce a mixture of components a) to c) by partially oxidizing the corresponding polyalkylene oxide having two primary OH-terminated groups. Such partial oxidation will be further described below. For the sake of completeness of the explanation, it should be noted that a mixture of components a) to c) can also be prepared by mixing the individual components, not to mention the individual components.

[0131] The ester groups of polyalkylene oxide polymers are typically formed by esterification of polyalkylene oxide blocks having esterifiable end groups. To obtain each ester group, one -O- containing end group, such as an -OH group, and one -CO- containing end group, such as a -COOH group, are required. Therefore, it is preferable that these amounts be equal or approximately equal. However, if one type is slightly in excess, this can be absorbed into elements other than (I), (II), and (III) that can be linked to -O- or -CO- groups. Furthermore, two end groups of a polyalkylene oxide polymer can also be bonded to two 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 preferably ≥0.99, and more preferably ≤1.05, particularly preferably ≤1.02, and even more preferably ≤1.01.

[0132] The esterification of each polyalkylene oxide block can generally be carried out by industrially known methods, for example, those 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 terminal groups versus the number of COOH terminal groups falls within a target range.

[0133] Typically, various types of esterification catalysts can be used. These can be broadly classified into acidic catalysts, amphoteric catalysts, and basic catalysts. Representative acidic catalysts include mineral acids, such as sulfuric acid and phosphoric acid, and organic sulfonic acids, such as methanesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid. 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 include, for example, ZnO, La2O3, ThO2, ZrO2, hydrotalcite, hydroxyapatite, alkali metal oxides, alkaline earth metal oxides, basic zeolites, and solid superbases such as Verkade bases or guanidine. Possible amphoteric catalysts include oxides of zinc(II), tin(II), and tin(IV). Furthermore, Lewis acid catalysts derived from metal cations of Group 4 of the periodic table, such as Ti(VI) and Zr(IV) compounds, Lewis acid catalysts derived from metal cations of Group 3 of the periodic table, such as Sc(III) compounds, or Lewis acid catalysts derived from metal cations of Group 5 of the periodic table, such as Al(III) compounds, are also useful. However, catalysts containing metal cations of Groups 12 and 15 of the periodic table, such as Sn(IV), Sn(II), Zn(II), and Bi(III), are also acceptable. The corresponding anion can typically be selected from alkoxylates, such as isopropoxylates and isobutyrates, alkanoates, aralkylcarboxylates, halogens, sulfates, and organic sulfonates, such as p-toluenesulfonate or methanesulfonate, amidemethanesulfonate, trifluoromethanesulfonate, or trifluoromethanesulfonimide.

[0134] The esterification catalyst is typically used in a conventional dose ranging from 0.02 to 10% by weight, preferably ≥0.05% by weight, more preferably ≥0.1% by weight, and preferably ≤5% by weight, and more preferably ≤2% by weight, based on the total compound to be esterified.

[0135] Esterification can be carried out in the absence or presence of a solvent. When carried out in the presence of a solvent, it is preferable to use an inert organic solvent under the reaction conditions. Examples of such solvents include 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 for forming azeotropic mixtures 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] Esterification is carried out at a temperature of 50 to 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 mineral acid, esterification is usually carried out at a temperature in the range of 50 to 160°C. When the esterification catalyst is a metal-containing catalyst, esterification is usually carried out at a temperature in the range of 80 to 250°C. With respect to pressure, esterification can be carried out over a wide pressure range of 0.1 kPa abs to 1 MPa abs, from vacuum to pressures exceeding atmospheric pressure. Preferably, this is carried out at ≤0.5 MPa abs, more preferably ≤0.2 MPa abs.

[0137] Esterification can be carried out in the absence or presence of an inert gas. An inert gas is generally understood to mean a gas that does not participate in the reaction with the starting materials, reagents, solvents, or the resulting product under the given reaction conditions.

[0138] In principle, any reactor suitable for esterification is suitable for carrying out the esterification process. A stirred tank is one example.

[0139] Esterification typically requires a reaction time of 1 to 24 hours, more typically 2 to 12 hours, which depends primarily on the properties of the derivative, the type and amount of catalyst, and the reaction temperature.

[0140] The resulting polyalkylene oxide polymer is, although not essential, usually subjected to work-up depending on the intended purity. During work-up, components other than the polyalkylene oxide polymer, particularly the esterification catalyst, are typically removed. Generally, the absence of the esterification catalyst in the polyalkylene oxide polymer is important for product quality. 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 a polyalkylene oxide polymer can be easily adjusted by the ratio of OH-terminal groups to COOH-terminal groups of the compound being esterified. Simply put, the further this ratio deviates from exactly 1:1, the fewer ester groups will be formed within the polyalkylene oxide polymer. In fact, this can be achieved, for example, by adding a diol component or a diacid component, ideally one of these derivatives, to the reaction mixture. However, this objective can also be achieved by adding other monools or monocarboxylic acids.

[0142] End groups of polyalkylene oxide compounds that are not esterified with other polyalkylene oxide compounds typically form end groups of the polyalkylene oxide ester polymer of the present invention. Therefore, the unesterified -OH end groups of polyalkylene oxide compounds become the -OH end groups of the polyalkylene oxide ester polymer, and the unesterified -COOH, -COOR, or -COOM end groups of polyalkylene oxide compounds become the -COOH, -COOR, or -COOM end groups of the polyalkylene oxide ester polymer (where R is typically a hydrocarbon group having 1 to 12 carbon atoms, such as a methyl group, and M is typically an alkali metal, such as sodium or potassium).

[0143] For the sake of completeness of explanation, it should be noted that, in addition to the blocks containing structural elements (I), (II), and (III), other elements having esterifiable end groups may also be present, especially when attempting to produce polyalkylene oxide ester polymers that also include such other elements. An example of this type of other element is a polyalkylene oxide element having alkylene units with more than six carbon atoms in a chain directly bonded between two ether groups.

[0144] As already mentioned above, a mixture of components a) to c) including so-called "mono acids," "di acids," and "diols" can be easily produced by partially oxidizing the corresponding polyalkylene oxide ("diol") having two primary OH-terminated groups. In this way, if a polyalkylene oxide ester polymer containing structural element (I) in a higher content is desired, it is also possible to obtain a polyalkylene oxide (so-called "mono acid") containing structural element (I) and having one primary OH and one COOH-terminated group, or a mixture of such polyalkylene oxides, in a higher content by separating at least a portion of the other components (so-called "di acids" and "diols"), thus increasing the degree of flexibility.

[0145] In a preferred process, the mixture of components a) to c) used for esterification is produced by partially oxidizing the corresponding polyalkylene oxide having two primary OH-terminated groups, or a mixture of such polyalkylene oxides, 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 water and a heterogeneous catalyst containing platinum, palladium, or gold, where the oxidation reaction is stopped after the ratio of OH-terminated groups to COOH-terminated groups reaches a range of 0.9 to 1.1. For completeness, it should be noted that, even if the intended ratio range described above is not achieved by such partial oxidation, it is certainly possible to blend other polyalkylene oxides into this composition to adjust the ratio of OH-terminated groups to COOH-terminated groups.

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

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

[0148] The catalyst used in the partial oxidation process is a heterogeneous catalyst containing platinum, palladium, or gold, preferably platinum, as the active component. Typically, the active metal is immobilized on a support. Various 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 carbon. Needless to say, mixtures of different supports can also be used. The use of carbon as the support is preferred.

[0149] A preferred catalyst containing platinum as an active ingredient generally contains platinum in an amount of 0.1% to 10% by weight, preferably ≥0.5% by weight, more preferably ≥1% by weight, even more preferably ≥4% by weight, and preferably ≤8% by weight, and more preferably ≤6% by weight, based on the total mass of the heterogeneous catalyst in each case. More preferably, a heterogeneous catalyst containing 1 to 10% by weight, particularly 4 to 10% by weight, of platinum on carbon is used.

[0150] The catalyst used may contain additional metals in addition to platinum, palladium, or gold. The term "additional metals" is understood to mean metals from periods 4 to 6 of groups 3 to 16 of the periodic table, starting with scandium (atomic number 21) and ending with polonium (atomic number 84). Preferably, the total content of additional 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, and particularly 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, and particularly 0 to 0.01% by weight, based on the mass of platinum. Therefore, the catalyst is preferably prepared without the intentional addition of additional metals.

[0151] The supported heterogeneous catalyst can be used in various geometric shapes and sizes, for example, as a powder or molded product. The powder catalyst can be actuated, for example, in a suspension manner. In the case of a fixed-bed system, it is preferable to use molded products, such as pellets, cylinders, hollow cylinders, spheres, extruded products, or tablets. In this case, the molded products are usually fixed in the reactor by known methods. In the case of catalyst molded products, the average particle size is preferably 1 to 10 mm.

[0152] However, preferably, a catalyst in powder form is used. In this case, the powder catalyst is suspended in the reactor. To prevent it from flowing out of the reaction system, a filter is usually used to hold the suspended catalyst in place, as is done herein. An example of a commonly used filter is a cross-flow filter.

[0153] Regardless of the geometric shape and size of the catalyst particles, platinum generally exists in the form of particles with an average diameter of 0.1–50 nm as measured by X-ray diffraction. However, particles smaller or larger than this may also exist.

[0154] In the production of supported heterogeneous catalysts, platinum is generally applied to the support by preferred methods, such as those described in U.S. Patent No. 2020 / 017,745.

[0155] The supported heterogeneous catalyst generally has a BET surface area of ​​≥1 m², as measured according to DIN ISO 9277:2014-01. 2 / g and ≤10000m 2 The value is / g. When carbon is used as the support, the BET surface area is preferably ≥500m². 2 / g and ≤10000m 2 It is within the range of / g.

[0156] A preferred platinum-based catalyst is typically applied such that the amount of platinum per gram of polyalkylene oxide to be partially oxidized is 0.1 to 50 mg, preferably ≥1 mg and preferably ≤20 mg.

[0157] Since the pH of the aqueous solution of the polyalkylene oxide feedstock is neutral, the pH at the start of oxidation is usually 7 or around 7. As a result of the formation of COOH groups, the pH gradually decreases and therefore generally becomes 1 or 3 as oxidation nears its end.

[0158] However, partial oxidation can also be carried out in the presence of a base such as sodium hydroxide or potassium hydroxide. Basic conditions increase the oxidizing capacity, and a carboxylate is formed instead of the carboxylic acid. As already mentioned above in the explanation of the esterification process, carboxylates can also be used directly in esterification.

[0159] If a basic compound is not present, a carboxylic acid is formed directly. This eliminates (i) the need for additional chemicals (bases and external acids) and (ii) the need to discard salts formed from the bases and external acids.

[0160] The oxidation medium used in the partial oxidation process is molecular oxygen. Oxygen is added either in pure form or diluted with another gas, for example, in the form of air or an O2 / N2 mixture. Preferably, the gaseous oxygen content is ≥90% by volume, more preferably ≥95% by volume, even more preferably ≥99% by volume, and especially ≥99.5% by volume. Using very high concentrations or pure oxygen makes it possible to maintain relatively small amounts of off-gas.

[0161] To promote the dispersion of oxygen within the reactor, it is advantageous to meter and supply it in the form of fine bubbles, for example, by passing it through frit.

[0162] The partial pressure of oxygen during 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] Oxidation is carried out at a temperature of 20 to 100°C, preferably ≥30°C, more preferably ≥40°C, and preferably ≤80°C, more preferably ≤70°C.

[0164] In principle, any reactor suitable for carrying out a partial oxidation process is any reactor suitable for carrying out an exothermic gas / liquid reaction. Examples include stirred tanks, trickle bed reactors, and bubble tower reactors. To remove the heat of reaction, reactors are usually equipped with a cooling system. Depending on the type of reactor and the properties of the catalyst, the cooling system may be advantageously equipped with a cooling element inside the reactor or with a cooling element in an external circuit outside the reactor. For example, a stirred tank preferably has an internal cooling element, while a bubble tower is more advantageous, for example, to have a cooling element incorporated into an external circuit.

[0165] When the catalyst is in the form of a molded mass, 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 bed form. However, it is also possible to use the catalyst molded mass in a stirred-tank reactor. In that case, it is advantageous to fix the catalyst molded mass within a partition, for example, in a wire cage.

[0166] Regarding the preferred use of powdered catalysts, a suspended form in the reaction mixture is advantageous. Preferred reactors for this purpose are, for example, a stirred tank or a bubble tower. To prevent the powdered catalyst from settling, it is necessary to mix it according to the liquid reaction mixture. In a stirred tank, this is usually achieved by using a stirrer. In the case of a bubble tower, mixing is usually achieved via an external circuit equipped with a transport pump. In principle, a bubble tower can be operated in either an upward or downward direction with respect to the liquid circuit, but the downward direction is usually more advantageous.

[0167] In the partial oxidation process, semi-continuous or continuous operation is possible. In either case, oxygen is supplied to the reactor continuously or at least intermittently to ensure the desired partial pressure, but continuous supply is preferred.

[0168] In semi-continuous operation, before the reaction starts, the entire aqueous reactant mixture is first introduced into the reactor along with the catalyst. No new reactants are supplied, nor is the liquid reactant mixture removed, during the oxidation reaction. The reactor remains empty until the oxidation reaction is complete.

[0169] In continuous operation, the liquid reaction mixture is similarly present in the reactor along with the catalyst, but a small amount of liquid reactant is continuously withdrawn and a corresponding amount of aqueous reactant is supplied. If a suspended catalyst is used, the liquid reaction mixture is advantageously removed from the reactor using a filtration device, such as a cross-flow filter.

[0170] Since partially oxidized polyalkylene oxides inevitably contain one primary OH group and one COOH-terminated group, the oxidation reaction must be carried out in such a way that some primary OH groups remain unoxidized while others have already been oxidized to COOH groups. This can be easily achieved by stopping the oxidation reaction once the desired amount of partially oxidized polyalkylene oxide is present. Except for 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 other terminal groups of the polyalkylene oxide have already been oxidized. Initially, the oxidation mainly produces polyalkylene oxides with one primary OH group and one COOH-terminated group (referred to as "monoacids"). As the amount increases, the probability of the other OH group being oxidized also increases, so polyalkylene oxides with two COOH-terminated groups (referred to as "diacids") are also formed.

[0171] In the case of semi-continuous operation, the simplest way to stop further oxidation is to cut off the oxygen supply 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 cutting off the oxygen supply include, for example, supplying additional inert gas to replace some of the oxygen in the reactor, lowering the total pressure in the reactor so that the oxygen partial pressure decreases naturally, or cooling the reaction mixture by, for example, removing it from the reactor via a condenser. However, the most effective means is to cut off the oxygen supply.

[0172] Oxidation reactions take many hours to proceed, and since the time range in which "monoacids" are present at high concentrations is sufficiently long, interference with such oxidation reactions can be controlled very easily. The time range in which a partial oxidation reaction should be stopped can be determined in various ways. First, the time required for partial oxidation under specified conditions such as temperature, oxygen partial pressure, and catalyst properties and amount can be determined by preliminary tests in which oxidation is stopped at different times and the composition of the reaction products is analyzed. Then, the oxidation time required to obtain the desired composition can be estimated. Another possibility for controlling partial oxidation is to measure the amount of oxygen supplied to the reactor as an indicator of the oxygen absorbed by oxidation. Then, the degree of oxidation can be calculated from the amount of OH groups present in the polyalkylene oxide, which is the source, and the stoichiometric amount that oxidizes them to COOH groups. Another method is to take samples over time, titrate them, for example, and analyze them by measuring the acid value as an indicator of the COOH groups that have already been formed. Finally, and importantly, physical measurements such as conductivity, dielectric constant, or impedance can be performed in situ, and these must, of course, be calibrated beforehand.

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

[0174] As already mentioned above, oxidation reactions take a lot of time. The typical reaction time for partially oxidizing around 50% of the OH groups is around 3 to 20 hours, preferably ≥4 hours, more preferably ≥5 hours, preferably ≤18 hours, and more preferably ≤15 hours.

[0175] To ensure a complete explanation, it is necessary to mention that, in addition to the oxidation from the OH group to the COOH group as the main reaction, oxidative decomposition also occurs, albeit to a lesser degree. In such oxidative decomposition, a small amount of alkylene oxide units may be completely oxidized. Consequently, the inner chain length of the partially oxidized alkylene oxide is inevitably slightly shorter than that of the alkylene oxide source before partial oxidation.

[0176] After the reaction is complete, the reaction mixture is usually removed from the reactor and separated from the catalyst. If a suspension catalyst is used, it is advisable to remove it by filtration. Alternatively, the suspension catalyst can be allowed to settle at the bottom of the reactor after the reaction is complete, and the supernatant can be removed. Separation of the catalyst is also possible by centrifugation. The removed catalyst can generally be reused without further work-up. Water or at least a large portion of the water is usually removed by distillation, for example, by 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 broadly replace conventional polyalkylene oxide polymers in their applications.

[0178] Preferred applications of the polyalkylene oxide polymer of the present invention include its use as a structural unit for encapsulating fragrances and preparing block polymers.

[0179] Fragrances are often encapsulated to reduce their vapor pressure, thereby lowering the concentration released into the air, and to extend the duration of fragrance release, and thus the duration of the product's fragrance, because high fragrance concentrations often result in a very strong smell. Encapsulation is usually carried out by mixing the fragrance in a liquid, typically a molten polymer, and then solidifying the mixture. By using the polyalkylene oxide ester polymer of the present invention, it becomes possible to extend the duration of the product's fragrance even when using polymers with lower molecular weights.

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

[0181] Products containing such polyalkylene oxide polymers, or products produced using such polyalkylene oxide polymers, exhibit significantly better biodegradability than conventional products containing polyalkylene oxide polymers or similar products produced using them.

[0182] The polyalkylene oxide ester polymers of the present invention are a novel 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 fragrance encapsulation and the preparation of graft polymers for use in home care and laundry applications. Some application properties of the polyalkylene oxide ester polymers may even be improved compared to conventional polyalkylene oxides. The greatest advantage of this novel type of polymer is its significantly improved biodegradability, which can be important for contributing to environmental protection, particularly because it can easily replace conventional polyalkylene oxides in home care and laundry applications. The polyalkylene oxide ester polymers are safe and durable in their applications.

[0183] Furthermore, the polyalkylene oxide polymer of the present invention can be easily produced in high yield through a two-step process using 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 serves as a relative measure of the average molecular weight. For a given polymer, the K value tends to increase as the average molecular weight of the polymer increases. The K values ​​of esterified mixtures were determined using the method of H. Fikentscher, described in "Cellulosechemie", 1932, 13, 58, in a 3 wt% NaCl solution at 23°C, with a polymer concentration of 1 wt% polymer.

[0185] M n M w and PD decision Number average molecular weight M of the esterified mixture n , weight average molecular weight M w and polydispersity M w / M n The polymer was determined in tetrahydrofuran by size exclusion chromatography (SEC). A mobile phase (eluent) of tetrahydrofuran containing 0.035 mol / L diethanolamine was used. The concentration of the esterified polymer in tetrahydrofuran was set to 2.0 mg / mL. After filtration (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 separation (SDV pre-column, 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. Molecular weight M was used for calibration. n Poly(ethylene glycol) (PEG) standard substance (PL) with a concentration of 10⁶ to 1,378,000 g / mol was used.

[0186] Description of the OECD 301B disassembly test. Biodegradation was tested in a triple series using the OECD 301B manometric respirometry method. 30 mg / mL of the test substance was inoculated into water collected from the Mannheim (Germany) wastewater treatment plant and incubated in a sealed flask at 25°C for 28 days. The oxygen consumed during this period was measured as a pressure change in the flask using OxiTop C (WTW). The generated CO2 was absorbed using a NaOH solution. The amount of oxygen consumed by the microbial community during the biodegradation of the test substance was corrected using a blank and expressed as a percentage of the theoretical oxygen demand ("ThOD").

[0187] Examples 1-10 In Examples 1 to 10, polyalkylene oxides having two primary OH-terminated groups (referred to as "diols") were oxidized to obtain a mixture containing a polyalkylene oxide having at least two COOH-terminated groups (referred to as "diacids"), a polyalkylene oxide having one primary OH-terminated group and one COOH-terminated group (referred to as "monoacids"), and optionally the remaining polyalkylene oxide having two primary OH-terminated groups. This mixture was prepared as follows.

[0188] Platinum on carbon (5.0 wt Pt on carbon, moisture content: 59.7 wt%, 283 g, Pt 29.2 mmol) was suspended in a mixture of polyalkylene oxide containing two primary OH-terminated groups (see Table 1 for details) and water (see Table 1 for details), heated to 52°C, and stirred at 800 rpm. While stirring the mixture, oxygen was supplied through a glass tube equipped with glass frit (20 nL / h) and the temperature was raised to 60°C. The oxygen supply and temperature were maintained for the time indicated 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 filtrate cake was washed with 500 mL of warm water. The washing water was mixed with the filtrate. Water was removed from the liquid mixture by evaporation using a thin-film evaporator (total height: 87.2 cm, diameter: 3.54 cm, liquid film height (wiped height): 43 cm, feed rate: 4.0 mL / min, 44°C, 1.8 kPa abs, 600 rpm). The residual liquid (sump product) from the thin-film evaporator was analyzed. The OH group content was determined by measuring the hydroxyl value, and the COOH group content was determined by measuring the acid value. 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 molecular weight of 200 g / mol, the distribution of diols, monoacids, and diacids was measured by gas chromatography. To this end, 0.1 g of a dried sample of partially oxidized polyalkylene oxide was heated to 80°C with 1 g of N-methyl-N-(trimethylsilyl)trifluoroacetamide, and this temperature was maintained for 1 hour. The resulting mixture was then analyzed by gas chromatography. For other mixtures based on polyalkylene oxides with a molecular weight 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 part of a monoacid. The respective values ​​are shown in Table 1.

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

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

[0192] Next, the resulting esterified mixture was analyzed to determine the K value and the number-average molar mass M. n and molecular weight distribution M w The requirements were 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 polymer was estimated from the estimated average molecular weight of each polyalkylene oxide polymer and each polyalkylene oxide used in the preceding oxidation step. For each polyalkylene oxide polymer, the number-average molecular weight M was used as a good indicator of the average molecular weight at the molecular scale. n For each polyalkylene oxide used in the preceding oxidation step, the molecular average molecular weight (M) was used instead. w Polyethylene oxide can be used. The reason is that polyethylene oxide typically has a low polydispersity PD, which is slightly above 1, so M w and M n This is because the difference is very slight.

[0194] The number of ester groups in polyalkylene oxide polymers based on the use of partially oxidized polyethylene oxide (with an oxidized OH group ratio of approximately 50%) was estimated as follows: First, the number of structural units was calculated by (1) considering two terminal groups and correcting for 18 g / mol, and then determining the number-average molecular weight M of the polyalkylene oxide polymer. n This was estimated by (2) dividing by the average molecular weight of the esterified structural elements. The latter is the average molecular weight M of the polyethylene oxide used. w From this, we subtract 18 g / mol considering the separation of water by esterification, and then add 16 g / mol and subtract 2 g / mol considering that one -CO- unit is formed from the corresponding -CH2- unit per structural element by the arithmetic mean. In the case of the structural element of formula (I), there is exactly one unit per structural element, and in the case of the combination of structural elements of formulas (II) and (III), there are 2 and 0 units respectively, and on average it is still 1 unit. Next, considering that each ester group of the polyalkylene oxide ester polymer in the example links two structural elements, and that the number of structural elements is one more than the number of ester groups, we subtract 1 from the number of structural units.

[0195] The above estimation will be explained in detail with respect to Example 12. Number average molecular weight M of the polyalkylene oxide polymer n Since the molecular weight was 2400 g / mol, a value of 2382 g / mol is obtained. The average molecular weight of the structural elements used in 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 as a formula:

number

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

[0197] The above estimation will be explained in detail with respect to Example 12. The average molecular weight M of the polyethylene oxide used. wSince the concentration was 400 g / mol, a value of 382 g / mol is obtained. Dividing this by 44 g / mol, the number of -CH2CH2-O- units is 8.7, and consequently, the average number of ether units in polyethylene oxide is 7.7. Since the average number of structural units of polyalkylene oxide polymer was estimated to be 6.0 above, the average number of ether groups in polyalkylene oxide polymer is 46. Alternatively, the formula is:

number

[0198] In the example where the use of completely oxidized polyethylene oxide (referring to one in which the proportion of oxidized OH groups is around 95-100%) was required, and therefore a diol had to be added as a second component, the estimation of the number of ester and ether groups was carried out in the same manner as described above, except that the main difference was the molecular average molecular weight M of the polyethylene oxide used in the calculation. w The average molecular weight M of the polyalkylene oxide used for oxidation w and the average molecular weight M of the polyalkylene oxide used as a diol component. w This involved taking the arithmetic mean of the two. This method is based on the simplified assumption that both structural units are evenly distributed within the polyalkylene oxide polymer.

[0199] This modified estimate is M w Polyethylene oxide, which is 600 g / mol, is almost completely oxidized, and M is added as a diol component. w Example 14, which uses polyethylene oxide with a concentration of 1500 g / mol, will be described in detail. The formula for determining the ester group is as follows:

number

number

[0200] The polyalkylene oxide polymers obtained in Examples 11-21 all have a weight-average molecular weight M w While the concentration ranged from 4050 to as high as 18300 g / mol, biodegradability was measured at 73-89% of the theoretical value of CO2 production after 28 days. w Conventional polyethylene oxide, which has a concentration of 8720 g / mol, is M w This is in contrast to the biodegradability measured by CO2 generation within 28 days, which, despite values ​​well below 10,000 g / mol, shows a significantly lower value of only 16%.

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

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

[0203] This experiment shows that the amount of mint flavoring in pellets prepared using the polyalkylene oxide polymer of the present invention remains within the range of 2.3 to 3.0% by weight, while that of conventional PEG 9000 polymer is only 2.2% by weight. By allowing the polyalkylene oxide polymer of the present invention to retain a larger amount of flavoring, it becomes possible to either reduce the amount of flavoring used for a given duration or to extend the duration of the flavored pellets.

[0204] In addition, the biodegradability of the polyalkylene oxide polymer used is far superior to that of conventional PEG 9000 polymers. The biodegradability of the polyalkylene oxide polymer is high at 73-79%, while that of conventional PEG 9000 polymers is very low at 16%.

[0205] [Table 9]

[0206] [Table 10]

[0207] [Table 11]

[0208] [Table 12] The present invention encompasses the following embodiments. (Embodiment 1) Weight average molecular weight M w A polyalkylene oxide ester polymer having a molecular weight of 500 to 50000 g / mol, a polydispersity PD of 2 to 6, and containing 10 to 560 ether groups and 2 to 51 ester groups bonded to an alkylene group, wherein the polyalkylene oxide ester polymer is: A) 1 to 51 general formulas (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 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 These are, independently of each other, hydrogen atoms or C 1~12 Represents an alkyl group, · a, b, c, d, and e are independent integers, either 0 or 1, and the sum of a through e is between 1 and 5. · X represents a polyalkylene oxide unit having 4 to 100 alkylene oxide units, where each alkylene oxide unit independently contains 2 to 6 carbon atoms in a chain directly bonded between two -O- units, and each of the carbon atoms in the chain directly bonded between two -O- units independently contains either two hydrogen atoms or one hydrogen atom and one carbon atom. 1~12 Structural elements (including any alkyl group) B) 1 to 25 general formulas (II):

change

change

Claims

1. Weight average molecular weight M ｗ A polyalkylene oxide ester polymer having a concentration of 500 to 50,000 g / mol, a polydispersity PD of 2 to 6, and containing 10 to 560 ether groups and 2 to 51 ester groups bonded to an alkylene group, wherein the polyalkylene oxide ester polymer is: A) 1 to 51 general formulas (I): 【Chemistry 1】 (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 side 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 These are, independently of each other, hydrogen atoms or C １～１２ Represents an alkyl group, a, b, c, d, and e are independent integers of 0 or 1, and the sum of a through e is between 1 and 5. X represents a polyalkylene oxide unit having 4 to 100 alkylene oxide units, where each alkylene oxide unit independently contains 2 to 6 carbon atoms in a chain directly bonded between two -O- units, and each of the carbon atoms in the chain directly bonded between two -O- units independently contains either two hydrogen atoms or one hydrogen atom and one carbon atom. １～１２ Structural elements (including any alkyl group), B) 1 to 25 general formulas (II): 【Chemistry 2】 (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 side 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 、 R 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 mutually independent integers of 0 or 1, the sum of g to k is between 1 and 5, and the sum of m to q is between 1 and 5. Y represents a polyalkylene oxide unit having 0 to 99 alkylene oxide units, where each alkylene oxide unit independently contains 2 to 6 carbon atoms in a chain directly bonded between two ether groups, and each of the carbon atoms in the chain directly bonded between the two ether groups independently contains either 2 hydrogen atoms or 1 hydrogen atom and 1 carbon atom. １～１２ Structural elements (including any alkyl group), C) General formula (III) with a suitable number of -CO- units for forming ester bonds with structural elements of formulas (I) and (II): 【Transformation 3】 (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 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 These are, independently of each other, hydrogen atoms or C １～１２ Represents an alkyl group, s, t, u, v, w, and x are independent integers of 0 or 1, and the sum of s through x is between 2 and 6. Z represents a polyalkylene oxide unit having 0 to 100 alkylene oxide units, where each alkylene oxide unit independently contains 2 to 6 carbon atoms in a chain directly bonded between two ether groups, and each of the carbon atoms in the chain directly bonded between the two ether groups independently contains either 2 hydrogen atoms or 1 hydrogen atom and 1 carbon atom. １～１２ A polyalkylene oxide unit (containing any of the alkyl groups), Includes, However, the total number of ester groups in the polyalkylene oxide ester polymer does not exceed the maximum number of ester groups specified for the polyalkylene oxide ester polymer.

2. ・ R １ This represents a hydrogen atom or a methyl group, ・ R ２ , R ３ This 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, wherein each alkylene oxide unit independently has 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 either 2 hydrogen atoms or 1 hydrogen atom and 1 methyl group, and the other 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 polymer according to claim 1.

3. ・ R １ This 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, wherein each alkylene oxide unit independently contains two 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 either two hydrogen atoms or one hydrogen atom and one methyl group, and the other carbon atoms containing two hydrogen atoms, and the number of methyl groups bonded to the carbon atom at the α-position of each -O- unit does not exceed one. The polyalkylene oxide polymer according to claim 1.

4. ・ R １３ , R １９ However, each independently represents either a hydrogen atom or a methyl group. ・ R ９ , R １０ , R １１ , R １４ , R １５ , R ２０ , R ２１ , R ２４ This represents a hydrogen atom, - g, h, p, q, v, w are 0, k, m, s, x are 1, i, j, n, o, t, and u represent integers 0 or 1 independently of each other, 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, wherein each alkylene oxide unit independently contains 2 or 4 carbon atoms in a chain directly bonded between 2 ether groups, and each alkylene oxide unit independently has one of the carbon atoms at the α position relative to the -O- unit containing either 2 hydrogen atoms or 1 hydrogen atom and 1 methyl group, and the 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 polymer according to claim 1.

5. ・ R １３ , R １９ However, each independently represents either a hydrogen atom or a methyl group. ・ R ９ , R １０ , R １１ , R １４ , R １５ , R ２０ , R ２１ , R ２４ This represents 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, and Z represents a polyalkylene oxide unit having 4 to 100 alkylene oxide units, wherein each alkylene oxide unit independently contains two 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 either two hydrogen atoms or one hydrogen atom and one methyl group, and the other remaining carbon atoms containing two 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 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 polymer according to claim 1, wherein the ratio of the number of structural elements (I) to the number of structural elements (II) is 0.5 to 8.

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

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

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

1.

11. The process according to claim 9, wherein the mixture of components a) to c) is produced by partially oxidizing a corresponding polyalkylene oxide having two primary OH-terminated groups or a mixture of such polyalkylene oxides 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 water and a heterogeneous catalyst containing platinum, palladium, or gold, the oxidation reaction being stopped after the ratio of the number of OH-terminated groups to the number of COOH-terminated groups reaches a range of 0.9 to 1.

1.

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

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