Modified polyether esters, methods of making and using the same, elastomer additives, and elastomers

Abstract

This invention relates to the field of polymer materials, and discloses a modified polyether ester, its preparation method and application, an elastomer additive, and an elastomer. The modified polyether ester contains structural unit A as shown in formula (I) and structural unit B as shown in formula (II), where R1 is an alkylene group having 2-10 carbon atoms, m is an integer from 5-100, n is an integer from 10-125, and R2 is hydrogen or an alkyl group having 1-5 carbon atoms; the terminal carboxyl group content of the modified polyether ester is not higher than 5 mol / t. This modified polyether ester can efficiently load elastomer additives, resulting in high activity stability of the elastomer additives, thereby improving the modification effect of the elastomer additives on the elastomer, and enabling the multiple reuse of elastomer products. Formula (I), Formula (II).

Description

Technical Field

[0001] This invention relates to the field of polymer materials, specifically to a modified polyether ester, a method for preparing a modified polyether ester, an application of a modified polyether ester, an elastomer additive, and an elastomer. Background Technology

[0002] Polyether ester elastomers (TPEEs) combine the excellent properties of rubber and engineering plastics, exhibiting high strength, creep resistance, impact resistance, and excellent high and low temperature performance. They are widely used in automotive engine intake manifolds, CVJ dust covers, and other applications. However, conventional TPEEs have relatively low melt strength, which cannot meet the requirements of extruded and blow-molded parts. CN101492542A describes a method for obtaining high molecular weight polyether ester copolymers through solid-state polymerization. This method requires a relatively long solid-state polymerization period to achieve high melt viscosity, and the prolonged solid-state polymerization leads to a decrease in the material's mechanical properties and a higher color value.

[0003] Adding multifunctional chain extenders is a solution for obtaining products with low melt index. Commonly used chain extenders mainly include epoxy multifunctional polymers, polyisocyanates, or oxazoline functional chain extenders. The function of chain extenders is to reduce the melt index and increase melt strength through coupling or branching reactions of their active functional groups with other polymers, thus significantly improving the physical properties of the product. If the number of active functional groups on a single chain extender molecule is too small, it will not function as a chain extender; if the number of active functional groups is too large, gelation may occur during chain extension, affecting physical properties.

[0004] CN103788584A describes a method for reducing the melt index of polyether ester elastomers by adding isocyanate and extruding the mixture. CN1281658C provides a method for preparing blow-molding grade polyether ester elastomers by directly adding chain extenders such as polyisocyanate and epoxy resin, followed by twin-screw reactive extrusion to produce polyether ester elastomers with a melt index less than 3. These methods involve directly blending chain extenders with polyether ester elastomers and then extruding them. However, this process can lead to uneven dispersion, resulting in significant fluctuations in the melt index of the prepared material, a tendency to form gels, and the generation of small particles during part manufacturing, affecting product performance. Furthermore, polyisocyanates are toxic, produce a strong odor at high concentrations, and create a poor operating environment.

[0005] The thermoplastic polyester elastomer resin composition and molded articles containing the composition provided in CN104520379A involve preparing blow-molding grade polyether ester elastomers by separately thickening TPEE and PBT and then blending them with a chain extender. This process is complex, has a high melt index, and results in poor sag of the preform during extrusion blow molding, making it prone to stretching and deformation under gravity. Furthermore, the increased melt viscosity after thickening TPEE and PBT makes it difficult to mix the two materials evenly during blending, leading to poor product dimensional stability.

[0006] In addition, after conventional chain extension, the melt index of polyether ester elastomers decreases significantly when reused after a single application, resulting in low utilization rate and high cost because defective products and scraps cannot be reused multiple times. Summary of the Invention

[0007] The purpose of this invention is to overcome the problems of unsatisfactory chain extension effect of chain extenders on elastomers in the prior art, resulting in poor stability and low recycling rate of elastomer products. This invention provides a modified polyether ester, its preparation method and application, an elastomer additive, and an elastomer. This modified polyether ester can efficiently load elastomer additives and ensure high activity stability of the elastomer additives, thereby improving the modification effect of the elastomer additives on the elastomer. It enables multiple reuses of the elastomer product; even after 10 reuses, the melt index is <3.0 g / 10 min, and it still meets the blow molding performance requirements.

[0008] To achieve the above objectives, a first aspect of the present invention provides a modified polyether ester containing structural unit A of formula (I) and structural unit B of formula (II). Formula (I), Equation (II), Wherein, R1 is an alkylene group having 2-10 carbon atoms, m is an integer from 5 to 100, n is an integer from 10 to 125, and R2 is hydrogen or an alkyl group having 1-5 carbon atoms; the content of terminal carboxyl groups in this modified polyether ester is not higher than 5 mol / t.

[0009] The second aspect of the present invention provides a method for preparing a modified polyether ester, the method comprising: performing a polymerization reaction on a dicarboxylic acid (ester), a diol, and a diol having the structure shown in formula (I), and performing a modification reaction on the product of the polymerization reaction with a modifier having the structure shown in formula (II) to form a modified polyether ester with a terminal carboxyl group content not exceeding 5 mol / t. Formula (I), Equation (II), Wherein, R1 is an alkylene group having 2-10 carbon atoms, m is an integer from 5 to 100, n is an integer from 10 to 125, and R2 is hydrogen or an alkyl group having 1-5 carbon atoms.

[0010] A third aspect of the present invention provides a modified polyether ester prepared by the method described above.

[0011] The fourth aspect of the present invention provides the use of the modified polyether ester as described above in the preparation of elastomers, preferably in the preparation of polyether ester elastomers.

[0012] A fifth aspect of the present invention provides an elastomer additive containing the modified polyether ester as described above.

[0013] The sixth aspect of the present invention provides a polyether ester elastomer containing a polyether ester base material and elastomer additives as described above.

[0014] Through the above technical solution, the modified polyether ester provided by this invention is based on specific modified structural units A and B, and the content of terminal carboxyl groups in the modified polyether ester is controlled to be no higher than 5 mol / t. This results in a modified polyether ester that not only has a low melting point but also forms a slightly cross-linked structure, improving melt strength. This modified polyether ester can support high concentrations of elastomer additives, exhibits high reactivity and good dispersibility, and maintains the stability of the elastomer additives' activity, thereby enhancing the modification effect of the elastomer additives on the elastomer. While ensuring good processing performance of the elastomer product, it also allows for multiple reuses of the elastomer product. Furthermore, this modified polyether ester has high crystallinity, preventing material blockage at the feed port during blending with elastomers, facilitating processing, and is easy to cool, resulting in good molding performance. Detailed Implementation

[0015] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0016] A first aspect of the present invention provides a modified polyether ester comprising structural unit A of formula (I) and structural unit B of formula (II). Formula (I), Equation (II), Wherein, R1 is an alkylene group having 2-10 carbon atoms, m is an integer from 5 to 100, n is an integer from 10 to 125, and R2 is an alkyl group having 1-5 carbon atoms; the content of terminal carboxyl groups in this modified polyether ester is not higher than 5 mol / t.

[0017] During the research and development process, the inventors of this invention discovered that the chain extender exhibits significant uneven dispersion when blended with the polyester matrix during the preparation of polyester elastomers. This results in large fluctuations in the melt index of the prepared polyester elastomers, a tendency to gel, and a significant impact on product performance. Furthermore, the chain extender has poor stability in elastomer applications and subsequent processing, which also leads to a significant decrease in the melt index during the use of the elastomers, making it difficult to achieve multiple reuses.

[0018] Based on this, the inventors developed a modified polyether ester containing specific modified structural units A and B, and controlled the end carboxyl group content of the modified polyether ester to no more than 5 mol / t. This results in a modified polyether ester with a low melting point and a slightly cross-linked internal structure, leading to high melt strength. This allows the modified polyether ester to support high concentrations of chain extenders while maintaining the stability of the chain extender's activity, high reactivity, and good dispersibility, thereby enhancing the modification effect of the chain extender on the elastomer. While ensuring good processing performance of the elastomer product, it also enables multiple reuses of the elastomer product. Furthermore, the modified polyether ester has high crystallinity, preventing material blockage at the feed port during blending with elastomers, facilitating processing, and allowing for easy cooling and good molding results. When used to load chain extenders to prepare elastomer additives, no reaction occurs between the chain extender and the modified polyether ester, and the chain extender's activity is not lost.

[0019] The inventors were even more surprised to discover that the modified polyether ester could also be loaded with high concentrations of other elastomer additives (such as antioxidants, antistatic agents, UV stabilizers and flame retardants) in addition to chain extenders, achieving the effects of maintaining stable additive activity, high additive reactivity and good dispersibility, and thus serving as a universal carrier for elastomer additives.

[0020] In this invention, R1 is an alkylene group having 2-10 carbon atoms, such as ethylene, n-propylene, 1-methylethylene, n-butylene, 1,2-dimethylethylene, 1,1-dimethylethylene, 2,2-dimethylethylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, 2-ethyl-n-hexylene, n-nonane, n-decylene, etc.; preferably an alkylene group having 2-6 carbon atoms, more preferably n-butylene. R2 is hydrogen or an alkyl group having 1-5 carbon atoms, such as hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, n-pentyl, 2-methylbutyl, 3-methylbutyl, etc. R2 is preferably hydrogen, methyl, or ethyl, more preferably hydrogen.

[0021] In this invention, m can be an integer from 5 to 100, preferably 10 to 30; furthermore, in a preferred embodiment, the degree of polymerization n of the structural unit B is 80 to 125. The inventors have found that this preferred embodiment facilitates the formation of a more stable and abundant loading structure within the modified polyether ester, achieving high-concentration loading of the elastomer additive and improving its dispersibility and activity.

[0022] In this invention, structural unit A and structural unit B can be... 13 C nuclear magnetic resonance spectrum, 1 The contents of structural unit A and structural unit B can be calculated based on the integrated areas of the corresponding characteristic peaks obtained by nuclear magnetic resonance spectroscopy or infrared spectroscopy, and then their weight ratio can be obtained through the ratio. Preferably, the weight ratio of structural unit A to structural unit B in the modified polyether ester is 1-15:1.

[0023] In this invention, the end carboxyl group content of the modified polyether ester was determined according to the national standard GB / T14190-2017 "Test Method for Fiber Grade Polyester (PET) Chips".

[0024] According to the present invention, preferably, the modified polyether ester further comprises structural unit C represented by formula (III) and structural unit D represented by formula (IV). (III) (IV); Wherein, R3 is absent or is an aliphatic alkylene group having 1-8 carbon atoms, specifically it may be absent or may be methylene, ethylene, n-propylene, 1-methylethylene, n-butylene, 1,2-dimethylethylene, 1,1-dimethylethylene, 2,2-dimethylethylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, 2-ethyl-n-hexylene, etc.; more preferably, R3 is absent or is an aliphatic alkylene group having 1-4 carbon atoms. R4 is an aliphatic alkylene group having 2-10 carbon atoms, specifically ethylene, n-propylene, 1-methylethylene, n-butylene, 1,2-dimethylethylene, 1,1-dimethylethylene, 2,2-dimethylethylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, 2-ethyl-n-hexylene, n-nonane, n-decylene, etc.; more preferably, R4 is an aliphatic alkylene group having 2-6 carbon atoms. The inventors have found that, under this preferred embodiment, it is beneficial to improve the activity and dispersibility of the supported elastomer additive, and enhance the activity stability of the elastomer additive.

[0025] In this invention, structural unit C and structural unit D can be... 13 C nuclear magnetic resonance spectrum, 1The contents of structural units C and D can be calculated based on the integrated areas of the corresponding characteristic peaks obtained by nuclear magnetic resonance spectroscopy or infrared spectroscopy, and then their weight ratio can be obtained through the ratio. Preferably, the molar ratio of structural unit C to structural unit D is 1:2.4-5.3. The inventors have found that under this preferred embodiment, it is beneficial to improve its loading capacity and enhance the activity stability of the elastomer additive.

[0026] According to the present invention, preferably, the modified polyether ester also contains titanium, wherein the content of titanium is 130-260 ppm. The content of titanium in the modified polyether ester can be detected by elemental analysis.

[0027] The second aspect of the present invention provides a method for preparing a modified polyether ester, the method comprising: performing a polymerization reaction on a dicarboxylic acid (ester), a diol, and a diol having the structure shown in formula (I), and performing a modification reaction on the product of the polymerization reaction with a modifier having the structure shown in formula (II) to form a modified polyether ester with a terminal carboxyl group content not exceeding 5 mol / t. Formula (I), Equation (II), Wherein, R1 is an alkylene group having 2-10 carbon atoms, m is an integer from 5 to 100, n is an integer from 10 to 125, and R2 is hydrogen or an alkyl group having 1-5 carbon atoms.

[0028] The modified polyether ester preparation method provided by this invention, through the control of the dosage ratio of each raw material and the reaction conditions, forms a modified polyether ester with a terminal carboxyl group content of no more than 5 mol / t. It uses fewer modified monomers, and the resulting modified polyether ester has high crystallinity (high melting enthalpy). During the blending preparation process, there will be no problem of material sticking and blocking at the feed port. It has good processing performance, is easy to cool, and has good molding properties. The modifier with the structure shown in formula (II) can cause slight cross-linking of the product of the first reaction, improve the melt strength of the obtained modified polyether ester, and is beneficial for the preparation of elastomer additives containing high concentrations of additives.

[0029] In this invention, R1 is an alkylene group having 2-10 carbon atoms, such as ethylene, n-propylene, 1-methylethylene, n-butylene, 1,2-dimethylethylene, 1,1-dimethylethylene, 2,2-dimethylethylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, 2-ethyl-n-hexylene, n-nonane, n-decylene, etc.; preferably an alkylene group having 2-6 carbon atoms. Correspondingly, the diol having the structure shown in formula (I) can be polyethylene glycol, polypropylene glycol, polytetrahydrofuran glycol (PTMEG), polypentylene glycol, polyhexane glycol, etc. More preferably, R1 is an alkylene group having 2-6 carbon atoms, and even more preferably n-butylene, that is, the diol having the structure shown in formula (I) is polytetrahydrofuran glycol (PTMEG).

[0030] In this invention, m can be an integer from 5 to 100, preferably from 10 to 30. For example, the number-average molecular weight (Mn) of polytetrahydrofuran diol (PTMEG) is 600-3000 g / mol, preferably 1000-2000 g / mol.

[0031] In this invention, R2 is hydrogen or an alkyl group having 1-5 carbon atoms. R2 can be hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, n-pentyl, 2-methylbutyl, 3-methylbutyl, etc. R2 is preferably hydrogen, methyl, or ethyl, and more preferably hydrogen. In this case, the modifier having the structure shown in formula (II) is poly(1,3,5-triisopropyl-phenylene-2,4-azodiimide) (CAS: 29963-44-8).

[0032] In this invention, the degree of polymerization n of the structure shown in formula (II) in the modifier is 10-125, more preferably 80-125. Exemplarily, the number-average molecular weight (Mn) of poly(1,3,5-triisopropyl-phenylene-2,4-azodiimide) is 3000-30000 g / mol, preferably 20000-30000 g / mol.

[0033] In this invention, the dicarboxylic acid (ester) refers to a dicarboxylic acid and / or a dicarboxylic acid ester. The ratio of the dicarboxylic acid (ester) to the diol can vary within a wide range. Preferably, the molar ratio of the diol to the diacid (ester) is 2.4-5.3:1, and the weight ratio of the diol having the structure shown in formula (I), the diacid (ester), and the modifier having the structure shown in formula (II) is 1-15:10-20:1. More preferably, the weight ratio of the diol having the structure shown in formula (I) to the diacid (ester) is 0.125-0.625:1.

[0034] According to the present invention, preferably, the dicarboxylic acid (ester) contains structural unit C represented by formula (III), and the diol contains structural unit D represented by formula (IV). (III) (IV).

[0035] In this invention, R3 is absent or is an aliphatic alkylene group having 1-8 carbon atoms. Specifically, it may be absent, or it may be methylene, ethylene, n-propylene, 1-methylethylene, n-butylene, 1,2-dimethylethylene, 1,1-dimethylethylene, 2,2-dimethylethylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, 2-ethyl-n-hexylene, etc. More preferably, R3 is absent or is an aliphatic alkylene group having 1-4 carbon atoms. Correspondingly, the dicarboxylic acid (ester) may be one or more of oxalic acid (ester), malonic acid (ester), methyloxalic acid (ester), succinic acid (ester), 1,2-dimethyloxalic acid (ester), 1,1-dimethyloxalic acid (ester), glutaric acid (ester), and adipic acid (ester), and is more preferably succinic acid (ester).

[0036] In this invention, R4 is an aliphatic alkylene group having 2-10 carbon atoms, specifically ethylene, n-propylene, 1-methylethylene, n-butylene, 1,2-dimethylethylene, 1,1-dimethylethylene, 2,2-dimethylethylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, 2-ethyl-n-hexylene, n-nonane, n-decylene, etc.; more preferably, R4 is an aliphatic alkylene group having 2-6 carbon atoms. Accordingly, the diol may be ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,6-hexanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, etc., and is more preferably 1,4-butanediol.

[0037] In this invention, the polymerization reaction is carried out in the presence of a catalyst. Preferably, the polymerization reaction is carried out in the presence of a titanium-based catalyst; the titanium-based catalyst may be selected from titanate esters and / or titanium glycolate, and the titanate ester may be tetrabutyl titanate, tetraethyl titanate, or tetraisopropyl titanate. The amount of the titanium-based catalyst is preferably used in a weight ratio of 1.5-3.6:1000 to the diacid monomer.

[0038] Furthermore, the polymerization process preferably includes sequential esterification and / or transesterification reactions, prepolymerization, and polycondensation reactions. More preferably, the conditions for the esterification and / or transesterification reactions include: a temperature of 160-200°C, more preferably 180-200°C; an absolute reaction pressure of 90-110 kPa; and a time of 1-3 h, more preferably 2-3 h. The conditions for the prepolymerization and polycondensation reactions include: a temperature of 210-250°C, more preferably 220-240°C; an absolute reaction pressure of 0-100 Pa, more preferably 0-50 Pa; and a time of 1-3 h, more preferably 1.5-2.5 h.

[0039] According to the present invention, preferably, the conditions for the modification reaction include: a temperature of 160-180°C, an absolute reaction pressure of 90-110 kPa, and a time of 30-60 min.

[0040] According to a particularly preferred embodiment of the present invention, the method for preparing modified polyether ester includes: A dicarboxylic acid (ester), a diol, a diol having the structure shown in formula (I), and a titanium catalyst are mixed and first subjected to esterification and / or transesterification reactions, followed by prepolymerization and polycondensation reactions to obtain a polymer product; the polymer product is then subjected to a modification reaction with a modifier having the structure shown in formula (II) to form a modified polyether ester with a terminal carboxyl group content of no more than 5 mol / t. The dicarboxylic acid (ester) contains structural unit C as shown in formula (III), and the diol contains structural unit D as shown in formula (IV). Formula (I), Equation (II), (III) (IV); Wherein, R1 is an alkylene group having 2-6 carbon atoms, m is 10-30, R2 is hydrogen, methyl or ethyl, R3 is absent or is an aliphatic alkylene group having 1-4 carbon atoms, and R4 is an aliphatic alkylene group having 2-6 carbon atoms; the degree of polymerization n of the structure shown in formula (II) in the modifier is preferably 10-125. The molar ratio of the diol to the diacid (ester) is 2.4-5.3:1, and the weight ratio of the diol having the structure shown in formula (I), the diacid (ester), and the modifier having the structure shown in formula (II) is 1-15:10-20:1; the first reaction is carried out in the presence of a titanium catalyst, and the weight ratio of the titanium catalyst to the diacid monomer is 1.5-3.6:1000; the conditions for esterification and / or transesterification reactions include: a temperature of 180℃-200℃, an absolute pressure of atmospheric pressure, and a time of 2-3h; the conditions for the prepolymerization and polycondensation reactions include: a temperature of 220-240℃, an absolute pressure of 0-50Pa, and a time of 1.5-2.5h; the conditions for the modification reaction include: a temperature of 160-200℃ and a time of 30-60min.

[0041] A third aspect of this invention provides a modified polyether ester prepared by the method described above. This modified polyether ester can support high concentrations of various additives such as chain extenders, antioxidants, antistatic agents, UV stabilizers, and flame retardants, maintaining stable additive activity, high additive reactivity, and good dispersibility. Therefore, it can be used as a carrier for elastomer additives in elastomer processing, effectively enhancing the modification effect of additives on elastomers. While ensuring good processing performance of the elastomer product, it also allows for multiple reuses of the elastomer product. Specifically, the modified polyether ester has a terminal carboxyl group content of 1-5 mol / t, a melting point of 80-110℃, and a melting enthalpy of 45-60 J / g.

[0042] Based on this, a fourth aspect of the present invention provides the use of the modified polyether ester as described above in the preparation of elastomers.

[0043] In this invention, the elastomer can be any conventional elastomer, such as polyester elastomers, polyolefin elastomers, etc.; preferably, it is a polyether ester elastomer. The modified polyether ester provided by this invention can improve the compatibility of its loaded additives with conventional polyether esters. In subsequent applications, the additives are more uniformly dispersed, no compatibilizer needs to be added, and the material has better mechanical properties.

[0044] A fifth aspect of the present invention provides an elastomer additive containing the modified polyether ester as described above.

[0045] According to the present invention, preferably, the content of the modified polyether ester in the elastomer additive is 30-60 wt%.

[0046] According to the present invention, preferably, the elastomer additive further comprises an elastomer auxiliary agent selected from at least one of chain extenders, antioxidants, antistatic agents, UV stabilizers, and flame retardants; more preferably, the elastomer auxiliary agent is a chain extender and / or an antioxidant. Even more preferably, the elastomer auxiliary agent is both a chain extender and an antioxidant, giving the elastomer additive the dual function of chain extension and improved aging resistance of the material, and, under the action of the modified polyether ester, a high epoxy equivalent retention rate in the additive.

[0047] According to the present invention, in order to enhance the synergistic effect between the modified polyether ester and the elastomer additive and improve the activity stability of the elastomer additive, preferably, based on the weight of the elastomer additive, the content of the chain extender is 22-32 wt% and the content of the antioxidant is 18-35 wt%.

[0048] According to the present invention, preferably, the chain extender is an epoxy chain extender, more preferably an epoxy chain extender containing glycidyl acrylate units; for example, chain extender ADR4468 and chain extender KL4370.

[0049] According to the present invention, preferably, the antioxidant contains a hindered phenolic primary antioxidant and a phosphite secondary antioxidant. The hindered phenolic primary antioxidant is preferably selected from at least one of N,N'-(hexane-1,6-diyl)bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide] (abbreviated as: Antioxidant 1098), pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (abbreviated as: Antioxidant 1010), and 2,4,6-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)trimethylbenzene (abbreviated as: Antioxidant 330). The phosphite secondary antioxidant is preferably tris[2,4-di-tert-butylphenyl] phosphite (abbreviated as: Antioxidant 168). The ratio of the hindered phenolic primary antioxidant to the phosphite secondary antioxidant can be a conventional ratio.

[0050] The sixth aspect of the present invention provides a polyether ester elastomer containing a polyether ester base material and elastomer additives as described above.

[0051] The polyether ester elastomer provided by this invention, based on the use of elastomer additives containing modified polyether esters, makes the processing easier to control precisely. Defective elastomers and scraps can be reused multiple times without changing their mechanical properties, effectively reducing the cost of elastomer products. It also features excellent performance, including resistance to deformation and multiple reuse. Preferably, the polyether ester elastomer has a melt index <1.1 g / 10 min and an epoxy equivalent of 10-90 kg / mol.

[0052] According to the present invention, the amount of elastomeric additive in the polyether ester elastomer can be determined according to the characteristics required for processing the elastomer product and the corresponding additive category. Preferably, the content of the elastomeric additive is 1.6-5.9 wt% based on the weight of the polyether ester elastomer.

[0053] According to the present invention, the polyether ester base material can be a conventional polyether ester base material. Preferably, the melt index of the polyether ester base material is 5-10 kg / mol, which is beneficial to improving the modification effect of elastomer additives on polyether ester elastomers and resulting in polyether ester elastomers with better mechanical properties.

[0054] According to the present invention, preferably, the polyether ester base material contains structural unit E of formula (V), structural unit F of formula (VI), and structural unit G of formula (VII). (V), Formula (VI), (VII) Ar is an aromatic alkylene group having 6-20 carbon atoms, R' is an alkylene group having 2-10 carbon atoms, p is an integer from 5 to 100, and R'' is selected from aliphatic alkylene groups having 2-10 carbon atoms.

[0055] In this invention, Ar is an aromatic alkylene group having 6-20 carbon atoms, which may have a benzene ring, a naphthalene ring, or an anthracene ring. Accordingly, the monomer with the structure shown in formula (V) may be one or more of terephthalic acid (ester), isophthalic acid (ester), phthalic acid (ester), 2,6-naphthalenedicarboxylic acid (ester), 1,5-naphthalenedicarboxylic acid (ester), 2,7-naphthalenedicarboxylic acid (ester), 4,4'-biphenylenedicarboxylic acid (ester), and 3,4'-biphenylenedicarboxylic acid (ester), more preferably one or more of terephthalic acid (ester), isophthalic acid (ester), and phthalic acid (ester), and even more preferably terephthalic acid (ester).

[0056] In this invention, R' is an alkylene group having 2-10 carbon atoms, such as ethylene, n-propylene, 1-methylethylene, n-butylene, 1,2-dimethylethylene, 1,1-dimethylethylene, 2,2-dimethylethylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, 2-ethyl-n-hexylene, n-nonane, n-decylene, etc., preferably an alkylene group having 2-6 carbon atoms; correspondingly, the monomer having the structure shown in formula (VI) can be polyethylene glycol, polypropylene glycol, polytetrahydrofuran glycol (PTMEG), polypentylene glycol, polyhexane glycol, etc. R' is further preferably n-butylene, and the corresponding monomer is polytetrahydrofuran glycol (PTMEG).

[0057] According to the present invention, preferably, p can be an integer from 5 to 100, and more preferably, p is from 10 to 30. For example, the number-average molecular weight (Mn) of polytetrahydrofuran diol (PTMEG) is 600-3000 g / mol, preferably 1000-2000 g / mol.

[0058] In this invention, R'' is selected from aliphatic alkylene groups having 2-10 carbon atoms, specifically ethylene, n-propylene, 1-methylethylene, n-butylene, 1,2-dimethylethylene, 1,1-dimethylethylene, 2,2-dimethylethylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, 2-ethyl-n-hexylene, n-nonane, n-decylene, etc.; more preferably, R'' is an aliphatic alkylene group having 2-6 carbon atoms, and correspondingly, monomers having the structure shown in formula (VII) can be... Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,6-hexanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, etc., are preferred, with 1,4-butanediol being even more preferred.

[0059] According to the present invention, preferably, the molar ratio of structural unit G to structural unit E in the polyether ester base material is 2.3-3.1:1, and the weight ratio of structural unit F to structural unit E is 0.3-1.8:1.

[0060] In this invention, the polyether ester base material can be obtained using conventional preparation processes. Exemplarily, the preparation process includes: performing esterification and / or transesterification reaction I and polycondensation reaction I using monomers having the structure shown in formula (V), monomers having the structure shown in formula (VI), and monomers having the structure shown in formula (VII), followed by mixing with the elastomer additive. More preferably, the mixing process includes: extruding the mixed material at a temperature of 210-250°C and cooling it. Preferably, the esterification and / or transesterification reaction I and polycondensation reaction I are carried out in the presence of a titanium-based catalyst; the titanium-based catalyst can be selected from at least one of titanium glycolate, titanate, and nano-titanium dioxide, and the titanate can be tetraethyl titanate, tetraisopropyl titanate, or tetrabutyl titanate. The amount of the titanium-based catalyst is preferably in a weight ratio of 1.6-5.3:1000 to the monomer having the structure shown in formula (V).

[0061] More preferably, the conditions for the esterification and / or transesterification reaction I include: a temperature of 210-230℃; an absolute reaction pressure of 90-110 kPa; and a time of 2-4 h; the conditions for the polycondensation reaction I include: a temperature of 240-260℃; an absolute reaction pressure of <100 Pa; and a time of 1-3 h. Specifically, polyether ester base materials with different melt indices can be obtained by controlling the reaction time of the polycondensation reaction I.

[0062] The present invention will be described in detail below through embodiments.

[0063] In the following examples, the epoxy equivalent of the samples was determined according to the method in the national standard GB / T 4612-2008 "Determination of Epoxy Equivalent of Epoxy Compounds in Plastics".

[0064] The end carboxyl group content of the samples was determined according to the national standard GB / T14190-2017 "Test Method for Fiber Grade Polyester (PET) Chips"; The melt flow index of the sample was measured as follows: First, the sample granules were dried at 110℃ for 4~6h. Then, the melt flow rate of the sample was measured using a melt flow indexer at 230℃ and under a load of 2.16kg, in accordance with GB / T 3682-2000 "Determination of melt mass flow rate and melt volume flow rate of thermoplastic plastics".

[0065] The melting enthalpy of the sample was measured according to the melting point test method in the national standard GB / T14190-2017 "Test Method for Fiber Grade Polyester (PET) Chips".

[0066] The tensile strength and elongation at break of the samples were measured as follows: First, the samples were dried at 110℃ for 4-6 hours and then injection molded into standard specimens in an injection molding machine; then, the injection molded specimens were placed in a constant temperature and humidity chamber and placed at 23℃ and (50±10)% relative humidity for more than 24 hours; the tensile strength of the specimens was tested using a universal testing machine according to GB / T 528-2009 "Determination of Tensile Properties of Plastics" (tensile speed of 50 mm / min).

[0067] The evaluation method for the appearance of the strips is as follows: visual inspection, take five strips of 10cm in length and check whether the surface is rough, whether there is gel, and whether the cut is layered; touch to check whether the surface of the strip is smooth, without bumps, impurities, etc.

[0068] Unless otherwise specified, atmospheric pressure is 101 kPa.

[0069] Example 1-1 2.4 kg of succinic acid, 6 kg of 1,4-butanediol (BDO), 1.5 kg of polytetrahydrofurandiol (PTMEG, purchased from BASF, product model PolyTHF1000, Mn 1000 g / mol), and 6 g of tetraethyl titanate were added to a reactor. Esterification was first carried out at 190°C and atmospheric pressure for 3 hours, followed by polycondensation at 240°C and 50 Pa for 2.5 hours. The polymer product was obtained and then blended with 125g of poly(1,3,5-triisopropyl-phenylene-2,4-azodiimide) (CAS: 29963-44-8, purchased from Shanghai Puzhan Industrial Co., Ltd., product model S9000, Mn 25000-30000g / mol). The blend was melt-extruded by a twin-screw extruder at a temperature of 160℃ (for about 1 hour), cooled, and pelletized to obtain modified polyether ester.

[0070] Examples 1-2 3.2 kg of succinic acid, 6 kg of 1,4-butanediol (BDO), 400 g of polytetrahydrofuran (PTMEG, purchased from BASF, product model PolyTHF1000, Mn 1000 g / mol), and 4.8 g of titanium glycol were added to a reactor. Esterification was first carried out at 200℃ and atmospheric pressure for 2 hours, followed by polycondensation at 240℃ and 40 Pa for 1.5 hours to obtain the polymer product. The polymer product was then mixed with 315 g of poly(1,3,5-triisopropyl-phenylene-2,4-azodiimide) (CAS: 29963-44-8, purchased from Shanghai Puzhan Industrial Co., Ltd., product model Stabaxol). P400 and Mn (20000 g / mol) were blended, and the blend was melt-extruded (for about 30 min) by a twin-screw extruder at 180℃, cooled, and pelletized to obtain modified polyether ester.

[0071] Examples 1-3 1.8 kg of succinic acid, 6 kg of 1,4-butanediol (BDO), 960 g of polytetrahydrofuran (PTMEG, purchased from BASF, product model PolyTHF2000, Mn 2000 g / mol), and 6 g of tetrabutyl titanate were added to a reactor. Esterification was first carried out at 180℃ and atmospheric pressure for 3 hours, followed by polycondensation at 240℃ and an absolute pressure of 30 Pa for 2 hours to obtain the polymerized product. The polymer product was blended with 120g of poly(1,3,5-triisopropyl-phenylene-2,4-azodiimide) (CAS: 29963-44-8, purchased from Shanghai Puzhan Industrial Co., Ltd., product model S9000, Mn 25000-30000g / mol). The blend was melt-extruded by a twin-screw extruder at 180℃ (for about 30 min), cooled, and pelletized to obtain the modified polyether ester.

[0072] Examples 1-4 Modified polyether esters were prepared according to the methods in Examples 1-3, except that 1.8 kg of succinic acid was replaced with 2.23 kg of adipic acid, the amount of polytetrahydrofuran was replaced with 1.19 kg, the amount of poly(1,3,5-triisopropyl-phenylene-2,4-azodiimide) was replaced with 148 g, and the amount of tetrabutyl titanate was replaced with 8 g.

[0073] Examples 1-5 Modified polyether esters were prepared according to the methods in Examples 1-3, except that 1.8 kg of succinic acid was replaced with 1.5 g of malonic acid, the amount of polytetrahydrofuran was replaced with 848 g, the amount of poly(1,3,5-triisopropyl-phenylene-2,4-azodiimide) was replaced with 106 g, and the amount of tetrabutyl titanate was replaced with 5.7 g.

[0074] Examples 1-6 Modified polyether esters were prepared according to the methods of Examples 1-3, except that 6 kg of 1,4-butanediol was replaced with 5.07 kg of 1,3-propanediol.

[0075] Examples 1-7 Modified polyether esters were prepared according to the methods in Examples 1-3, except that polytetrahydrofuran was replaced with an equal weight of polyethylene glycol (purchased from Jiangsu Haian Petrochemical Plant, product model PEG-2000, Mn 2000 g / mol).

[0076] Examples 1-8 Modified polyether esters were prepared according to the methods in Examples 1-3, except that polytetrahydrofuran with Mn of 1000 g / mol was replaced with an equal weight of polytetrahydrofuran with Mn of 650 g / mol (PTMEG, purchased from BASF, product model PolyTHFG650, Mn of 650 g / mol).

[0077] Examples 1-9 1.8 kg of succinic acid, 6 kg of 1,4-butanediol (BDO), 960 g of polytetrahydrofuran (PTMEG, purchased from BASF, product model PolyTHF2000, Mn 2000 g / mol), and 6 g of tetrabutyl titanate were added to a reactor. Esterification was first carried out at 180℃ and atmospheric pressure for 3 hours, followed by polycondensation at 240℃ and an absolute pressure of 30 Pa for 2 hours to obtain the polymerized product. The polymer product was blended with 120g of poly(1,3,5-triisopropyl-phenylene-2,4-azodiimide) (CAS: 29963-44-8, purchased from Shanghai Puzhan Industrial Co., Ltd., product model S9000, Mn 25000-30000g / mol). The blend was melt-extruded using a twin-screw extruder at 200℃ (for about 2 hours), cooled, and pelletized to obtain the modified polyether ester.

[0078] Examples 1-10 Modified polyether esters were prepared according to the methods of Examples 1-3, except that the amount of 1,4-butanediol (BDO) was replaced with 3 kg.

[0079] Examples 1-11 Modified polyether esters were prepared according to the methods of Examples 1-3, except that the amount of polytetrahydrofuran (PTMEG) was replaced with 2.4 kg.

[0080] Examples 1-12 Modified polyether esters were prepared according to the methods of Examples 1-3, except that the amount of poly(1,3,5-triisopropyl-phenylene-2,4-azodiimide) was replaced with 80g.

[0081] Examples 1-13 Modified polyether esters were prepared according to the methods in Examples 1-3, except that the amount of tetrabutyl titanate was replaced with 10g.

[0082] Example 2-1 The modified polyether esters obtained in Examples 1-1 to 1-13 were dried at 60°C for 10 hours. 1.65 kg of each was then mixed with 1.6 kg of epoxy chain extender ADR4468 (epoxy equivalent of 285 g / mol, purchased from BASF) and 1.75 kg of antioxidant (composed of 1.5 kg of antioxidant 1098 and 0.25 kg of antioxidant 168, purchased from Lianyungang and Lianyungang respectively) in a high-speed mixer. The mixture was then extruded at 100°C using a twin-screw extruder, cooled, and pelletized to obtain the elastomer additive.

[0083] Example 2-2 The modified polyether esters obtained in Examples 1-2 were dried at 60°C for 10 hours. 3 kg of each ester was then taken and mixed with 1.1 kg of epoxy chain extender ADR4468 (epoxy equivalent of 285 g / mol, purchased from BASF) and 0.9 kg of antioxidant (composed of 0.8 kg of antioxidant 1010 and 0.1 kg of antioxidant 168, purchased from Lianyungang and Lianyungang respectively) in a high-speed mixer until homogeneous. The mixture was then extruded at 130°C using a twin-screw extruder, cooled, and pelletized to obtain the elastomer additive.

[0084] Example 2-3 The modified polyether ester obtained in Example 1-1 was dried at 60°C for 10 hours. 1.7 kg of the dried product was then mixed with 0.8 kg of epoxy chain extender ADR4468 (epoxy equivalent of 285 g / mol, purchased from BASF) and 2.5 kg of antioxidant (composed of 2.2 kg of antioxidant 1098 and 0.3 kg of antioxidant 168, purchased from Lianyungang Pharmaceutical Co., Ltd.) in a high-speed mixer. The mixture was then extruded at 100°C using a twin-screw extruder, cooled, and pelletized to obtain the elastomer additive.

[0085] Example 3-1 2.64 kg of terephthalic acid, 4 kg of 1,4-butanediol (BDO), 1.5 kg of polytetrahydrofurandiol (PTMEG, purchased from BASF, product model PolyTHF1000, Mn 1000 g / mol), and 5 g of tetrabutyl titanate were added to a reactor. The mixture was first esterified at 210-230°C and atmospheric pressure for 3 hours, and then polycondensed at 240-260°C and absolute pressure <100 Pa for 1 hour to obtain a polyether ester elastomer base material with a melt index of 10 g / 10 min (tested at 230°C and 2.16 kg). 4705 g of the polyether ester elastomer base material was blended with 295 g of the elastomer additives prepared in Examples 2-1 to 2-3, and then extruded, cooled, and pelletized by a twin-screw extruder at 230°C to obtain TPEE elastomer.

[0086] Example 3-2 2.64 kg of terephthalic acid, 4 kg of 1,4-butanediol (BDO), 1.5 kg of polytetrahydrofurandiol (PTMEG, purchased from BASF, product model PolyTHF1000, Mn 1000 g / mol), and 5 g of tetrabutyl titanate were added to a reactor. Esterification was first carried out at 210-230℃ and atmospheric pressure for 3 hours, followed by polycondensation at 240-260℃ and reaction pressure <100 Pa for 2 hours, yielding a polyether ester elastomer base material with a melt index of 5 g / 10 min (tested at 230℃ and 2.16 kg). 4920 g of the polyether ester elastomer base material was blended with 80 g of the elastomer additives corresponding to Examples 1-2 in Example 2-1, and then extruded, cooled, and pelletized using a twin-screw extruder at 230℃ to obtain TPEE elastomer.

[0087] Example 3-3 2.64 kg of terephthalic acid, 4 kg of 1,4-butanediol (BDO), 1.5 kg of polytetrahydrofurandiol (PTMEG, purchased from BASF, product model PolyTHF1000, Mn 1000 g / mol), and 5 g of tetrabutyl titanate were added to a reactor. Esterification was first carried out at 210-230℃ and atmospheric pressure for 3 hours, followed by polycondensation at 240-260℃ and reaction pressure <100 Pa for 2 hours, yielding a polyether ester elastomer base material with a melt index of 5 g / 10 min (tested at 230℃ and 2.16 kg). 4800 g of the polyether ester elastomer base material was blended with 200 g of the elastomer additive corresponding to Example 1-1 in Example 2-1, and then extruded by a twin-screw extruder at 230℃, cooled, and pelletized to obtain TPEE elastomer.

[0088] Examples 3-4 TPEE elastomers were prepared according to the method of Example 3-2, except that the amount of polyether ester elastomer base material was replaced with 4680g, and the amount of elastomer additives corresponding to Example 1-2 in Example 2-1 was replaced with 320g.

[0089] Comparative Example 1 2.4 kg of succinic acid, 6 kg of 1,4-butanediol (BDO), 1.5 kg of polytetrahydrofuran (PTMEG, purchased from BASF, product model PolyTHF1000, Mn 1000 g / mol), and 6 g of tetrabutyl titanate were added to a reactor. The reaction was first carried out at 190℃ and atmospheric pressure for 3 h, followed by polycondensation at 240℃ and 50 Pa for 2.5 h to obtain a polymer with a melting point of 80℃, a melting enthalpy of 45 J / g, and a terminal carboxyl group content of 25 mol / t. 95g of the polymerization product was mixed evenly with 7g of poly(1,3,5-triisopropyl-phenylene-2,4-azodiimide) (CAS: 29963-44-8, purchased from Shanghai Puzhan Industrial Co., Ltd., product model S9000, Mn 25000-30000g / mol), 92g of epoxy chain extender ADR4468 (epoxy equivalent 285g / mol, purchased from Lianlong Company), 101g of antioxidant (composed of 87g antioxidant 1098 and 14g antioxidant 168, antioxidant 1098 and antioxidant 168 purchased from Lianlong Company), and 4705g of polyether ester elastomer base material with a melt index of 10g / 10min (230℃, 2.16kg test) prepared by the method provided in Example 3-1 in a high-speed mixer. The mixture was then extruded by a twin-screw extruder at 230℃ to form TPEE elastomer.

[0090] Comparative Example 2 2.4 kg of succinic acid, 6 kg of 1,4-butanediol (BDO), 1.5 kg of polytetrahydrofuran (PTMEG, purchased from BASF, product model PolyTHF1000, Mn 1000 g / mol), and 6 g of tetrabutyl titanate were added to a reactor. The reaction was first carried out at 190℃ and atmospheric pressure for 3 h, and then polycondensation was carried out at 240℃ and 50 Pa for 2.5 h to obtain a polyether ester with a melting point of 80℃, a melting enthalpy of 45 J / g, and a terminal carboxyl group content of 25 mol / t. 1.65 kg of polyether ester was dried at 60°C for 10 h, and then mixed with 1.6 kg of epoxy chain extender 4468 (epoxy equivalent of 285 g / mol) and 1.75 kg of antioxidant (composed of 1.5 kg of antioxidant 1098 and 0.25 kg of antioxidant 168, which were purchased from Lianlong Company) in a high-speed mixer. The mixture was then extruded at 100°C by a twin-screw extruder, cooled, and pelletized to obtain an elastomer additive. 2.64 kg of terephthalic acid, 4 kg of 1,4-butanediol (BDO), 1.5 kg of polytetrahydrofurandiol (PTMEG, purchased from BASF, product model PolyTHF1000, Mn 1000 g / mol), and 6 g of tetrabutyl titanate were added to a reactor. Esterification was first carried out at 210-230℃ and atmospheric pressure for 3 hours, followed by polycondensation at 240-260℃ and reaction pressure <100 Pa for 1 hour, yielding a polyether ester elastomer base material with a melt index of 10 g / 10 min (tested at 230℃ and 2.16 kg). 4705 g of the polyether ester elastomer base material was blended with 295 g of elastomer additives, and then extruded using a twin-screw extruder at 230℃, cooled, and pelletized to obtain TPEE elastomer.

[0091] Comparative Example 3 1.65 kg of EVA elastomer with a melting point of 80℃ was mixed with 1.6 kg of epoxy chain extender 4468 (epoxy equivalent of 285 g / mol) and 1.75 kg of antioxidant (composed of 1.5 kg of antioxidant 1098 and 0.25 kg of antioxidant 168, which were purchased from Lianlong Company) in a high-speed mixer. The mixture was then extruded at 100℃ by a twin-screw extruder, cooled, and pelletized to obtain an elastomer additive. 2.64 kg of terephthalic acid, 4 kg of 1,4-butanediol (BDO), 1.5 kg of polytetrahydrofurandiol (PTMEG, purchased from BASF, product model PolyTHF1000, Mn 1000 g / mol), and 6 g of tetrabutyl titanate were added to a reactor. Esterification was first carried out at 210-230℃ and atmospheric pressure for 3 hours, followed by polycondensation at 240-260℃ and reaction pressure <100 Pa for 1 hour, yielding a polyether ester elastomer base material with a melt index of 10 g / 10 min (tested at 230℃ and 2.16 kg). 4705 g of the polyether ester elastomer base material was then uniformly mixed with 295 g of elastomer additives, and subsequently extruded using a twin-screw extruder at 230℃, cooled, and pelletized to obtain TPEE elastomer.

[0092] Comparative Example 4 2.4 kg of succinic acid, 1 kg of adipic acid, 6 kg of 1,4-butanediol (BDO), and 6 g of tetrabutyl titanate were added to a reactor. The mixture was first esterified at 190℃ and atmospheric pressure for 3 hours, followed by polycondensation at 240℃ and 50 Pa for 2.5 hours to obtain a copolyester polymer with a terminal carboxyl group content of 38 mol / t. This polymer was then blended with 125 g of poly(1,3,5-triisopropyl-phenylene-2,4-azodiimide) (CAS: 29963-44-8, purchased from Shanghai Puzhan Industrial Co., Ltd., product model S9000, Mn 25000-30000 g / mol). The blend was melt-extruded, cooled, and pelletized using a twin-screw extruder to obtain a modified polyester copolyester. After drying the modified polyether ester composition at 60°C for 10 hours, 1.65 kg of the composition was taken and mixed with 1.6 kg of epoxy chain extender 4468 (epoxy equivalent of 285 g / mol) and 1.75 kg of antioxidant (composed of 1.5 kg of antioxidant 1098 and 0.25 kg of antioxidant 168, which were purchased from Lianlong Company). The mixture was then thoroughly mixed in a high-speed mixer and subjected to twin-screw extrusion at 100°C, cooling, and pelletizing to obtain the elastomer additive. 2.64 kg of terephthalic acid, 4 kg of 1,4-butanediol (BDO), 1.5 kg of polytetrahydrofurandiol (PTMEG, purchased from BASF, product model PolyTHF1000, Mn 1000 g / mol), and 6 g of tetrabutyl titanate were added to a reactor. The mixture was first esterified at 210-230℃ and atmospheric pressure for 3 hours, and then polycondensed at 240-260℃ and absolute pressure <100 Pa for 1 hour to obtain a polyether ester elastomer base material with a melt index of 10 g / 10 min (tested at 230℃ and 2.16 kg). 4705 g of the polyether ester elastomer base material was blended with 295 g of elastomer additives and then extruded by a twin-screw extruder at 230℃, cooled, and pelletized to obtain TPEE elastomer.

[0093] Comparative Example 5 TPEE elastomers were prepared according to the method of Comparative Example 1, except that 125g of poly(1,3,5-triisopropyl-phenylene-2,4-azodiimide) was not added.

[0094] Comparative Example 6 Modified polyether esters were prepared according to the methods in Examples 1-3, except that poly(1,3,5-triisopropyl-phenylene-2,4-azodiimide) with a Mn of 30000 g / mol was replaced with an equal weight of monomer 1,3,5-triisopropyl-phenylene-2,4-azodiimide (purchased from Shanghai Puzhan Industrial Co., Ltd., product model Stabaxol-1).

[0095] The modified polyether ester was used to prepare TPEE elastomer according to the method in Example 3-1.

[0096] Test Example 1 The content of terminal carboxyl groups, melting point and enthalpy of melting of the polymerization products during the preparation of modified polyether esters in Examples 1-1 to 1-13, Comparative Example 4 and Comparative Example 6, as well as the weight ratio of structural unit A to structural unit B, the molar ratio of structural unit C to structural unit D, the content of titanium and the content of terminal carboxyl groups in the modified polyether esters were tested. The test results are shown in Table 1.

[0097] Table 1

[0098] Test Example 2 The epoxy equivalent of the elastomer additives prepared in Examples 2-1 to 2-3 was tested, and the melt enthalpy, melt index (230℃, g / 10min), epoxy equivalent, tensile strength, elongation at break, melt index (230℃, g / 10min) after 10 reuses, appearance of the strip and processing performance of the TPEE elastomers prepared in Examples 3-1 to 3-4 were tested. Table 2 shows the epoxy equivalent of the elastomer additives used in Examples 2-1 to 2-3 and the corresponding TPEE elastomer properties prepared in Example 3-1. Table 3 shows the properties of the corresponding additives and elastomers in Examples 3-2 to 3-4 and Comparative Examples 1 to 6.

[0099] Table 2

[0100] Table 3

[0101] As can be seen from the results in Table 2, the weight ratio of structural unit A to structural unit B in the modified polyether esters provided in Examples 1-1 to 1-3 is 1-15:1, while the weight ratio of structural unit A to structural unit B in the modified polyether esters provided in Examples 1-11 is 20.1:1, which is outside the range of 1-15:1. The melt index stability of the elastomers loaded with chain extenders obtained in Examples 1-1 to 1-3 after 10 reuses in elastomer products is higher than that of Examples 1-11. This indicates that controlling the weight ratio of structural unit A to structural unit B in the modified polyether ester to 1-15:1 can further improve the activity and dispersibility of the elastomer additives loaded on the modified polyether esters, and enhance the activity stability of the elastomer additives.

[0102] Furthermore, compared to Examples 1-1 to 1-3, the molar ratio of structural unit C to structural unit D in the modified polyether ester provided in Examples 1-10 is not in the range of 1:2.4-5.3; the weight ratio of diacid (ester) to modifier having the structure shown in Formula (II) in the modified polyether ester provided in Examples 1-12 is not in the range of 10-20:1; and the content of Ti element in the modified polyether ester provided in Examples 1-12 is not in the range of 130-260ppm. As can be seen from the melt index after the elastomer product is reused 10 times, the proportion or amount of each structural unit or element in the modified polyether ester is controlled within a specific range, which can further improve the activity and dispersibility of the elastomer additive loaded on the modified polyether ester and enhance the activity stability of the elastomer additive.

[0103] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A modified polyether ester, characterized in that, The modified polyether ester contains structural unit A as shown in formula (I) and structural unit B as shown in formula (II). Equation (I), Equation (II), Wherein, R1 is an alkylene group having 2-10 carbon atoms, m is an integer from 5 to 100, n is an integer from 10 to 125, and R2 is hydrogen or an alkyl group having 1-5 carbon atoms; The content of terminal carboxyl groups in this modified polyether ester is no higher than 5 mol / t.

2. The modified polyether ester according to claim 1, characterized in that, The weight ratio of structural unit A to structural unit B in this modified polyether ester is 1-15:

1.

3. The modified polyether ester according to claim 1 or 2, characterized in that, R1 is an alkylene group having 2-6 carbon atoms, and R2 is hydrogen, methyl, or ethyl. Preferably, m is 10-30 and n is 80-125.

4. The modified polyether ester according to claim 1 or 2, characterized in that, The modified polyether ester also contains structural unit C as shown in formula (III) and structural unit D as shown in formula (IV). (III), (IV); Wherein, R3 is absent or is an aliphatic alkylene group having 1-8 carbon atoms, and R4 is an aliphatic alkylene group having 2-10 carbon atoms; Preferably, the molar ratio of structural unit C to structural unit D is 1:2.4-5.3; Preferably, the modified polyether ester also contains titanium, wherein the content of titanium is 130-260 ppm.

5. A method for preparing a modified polyether ester, characterized in that, The method includes: polymerizing a dicarboxylic acid (ester), a diol, and a diol having the structure shown in formula (I), and modifying the product of the polymerization reaction with a modifier having the structure shown in formula (II) to form a modified polyether ester with a terminal carboxyl group content of not more than 5 mol / t. Equation (I), Equation (II), Wherein, R1 is an alkylene group having 2-10 carbon atoms, m is an integer from 5 to 100, n is an integer from 10 to 125, and R2 is hydrogen or an alkyl group having 1-5 carbon atoms.

6. The preparation method according to claim 5, characterized in that, R1 is an alkylene group having 2-6 carbon atoms, and R2 is hydrogen, methyl, or ethyl. Preferably, m is 10-30 and n is 80-125; Preferably, the molar ratio of the diol to the diacid (ester) is 2.4-5.3:1, and the weight ratio of the diol having the structure shown in formula (I), the diacid (ester), and the modifier having the structure shown in formula (II) is 1-15:10-20:

1. Preferably, the dicarboxylic acid (ester) contains structural unit C represented by formula (III), and the diol contains structural unit D represented by formula (IV). (III), (IV)) R3 is absent or is an aliphatic alkylene group having 1-8 carbon atoms, and R4 is an aliphatic alkylene group having 2-10 carbon atoms.

7. The preparation method according to claim 5 or 6, characterized in that, The polymerization reaction is carried out in the presence of a titanium-based catalyst; Preferably, the weight ratio of the titanium-based catalyst to the dicarboxylic acid monomer is 1.5-3.6:1000; Preferably, the polymerization reaction includes sequential esterification and / or transesterification, pre-condensation and polycondensation reactions; Preferably, the conditions for the modification reaction include: a temperature of 160-200℃, an absolute reaction pressure of 90-110 kPa, and a time of 30-60 min.

8. The modified polyether ester prepared by the method according to any one of claims 5 to 7.

9. The modified polyether ester according to claim 8, characterized in that, The modified polyether ester has a terminal carboxyl group content of 1-5 mol / t, a melting point of 80-110℃, and a melting enthalpy of 45-60 J / g.

10. The use of the modified polyether ester according to any one of claims 1 to 4 and 8 to 9 in the preparation of elastomers, preferably in the preparation of polyether ester elastomers.

11. An elastomer additive, characterized in that, The elastomer additive contains the modified polyether ester as described in any one of claims 1 to 4 and 8 to 9.

12. The elastomer additive according to claim 11, characterized in that, The modified polyether ester in this elastomer additive contains 30-60 wt%; Preferably, the elastomer additive further contains an elastomer auxiliary agent selected from at least one of chain extenders, antioxidants, antistatic agents, UV stabilizers, and flame retardants; Preferably, the elastomer additive is a chain extender and an antioxidant, wherein, based on the weight of the elastomer additive, the content of the chain extender is 22-32 wt%, and the content of the antioxidant is 18-35 wt%. Preferably, the chain extender is an epoxy chain extender, more preferably an epoxy chain extender containing glycidyl acrylate units; The antioxidant contains a hindered phenolic primary antioxidant and a phosphite secondary antioxidant. The hindered phenolic primary antioxidant is preferably selected from at least one of N,N'-(hexane-1,6-diyl)bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and 2,4,6-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)trimethylbenzene. The phosphite secondary antioxidant is preferably tris[2,4-di-tert-butylphenyl] phosphite.

13. A polyether ester elastomer, characterized in that, The polyether ester elastomer contains a polyether ester base and the elastomer additives as described in claim 11 or 12.

14. The polyether ester elastomer according to claim 13, characterized in that, The melt index of this polyether ester elastomer is <1.1 g / 10 min, and the epoxy equivalent is 10-90 kg / mol; Preferably, the content of the elastomer additive is 1.6-5.9 wt%, based on the weight of the polyether ester elastomer; Preferably, the melt index of the polyether ester base material is 5-10 kg / mol.

15. The polyether ester elastomer according to claim 13 or 14, characterized in that, The polyether ester base material contains structural unit E as shown in formula (V), structural unit F as shown in formula (VI), and structural unit G as shown in formula (VII). (V) Formula (VI), (VII), Ar is an aromatic alkylene group having 6-20 carbon atoms, R' is an alkylene group having 2-10 carbon atoms, p is an integer from 5 to 100, and R'' is an aliphatic alkylene group having 2-10 carbon atoms. Preferably, the molar ratio of structural unit G to structural unit E in the polyether ester base material is 2.3-3.1:1, and the weight ratio of structural unit F to structural unit E is 0.3-1.8:1.

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