Polyether ester elastomer material as well as preparation method and application thereof

Abstract

The invention discloses a polyether ester elastomer material and a preparation method and application thereof.The elastomer material can be used for manufacturing a rail transit vehicle rail fastener base plate material, the molecular structural formula is shown in the figure 1, and the preparation method comprises the steps that S1, aromatic dibasic acid and / or ester thereof and aliphatic dihydric alcohol are heated and mixed to be uniform, and slurry is obtained; s2, carrying out esterification reaction on the slurry to obtain an esterification product; and S3, carrying out condensation polymerization on the long-chain dihydroxy polyether and the esterification product. The anti-fatigue polyether ester elastomer material has the advantages of large weight-average relative molecular weight and good anti-fatigue effect, the micro-channel reactor is adopted for reaction, the reaction degree is high, the production efficiency is high, and polyether ester resin with more excellent performance can be obtained.

Description

Technical Field

[0001] The invention relates to the field of polymer materials, and in particular to a polyether ester elastomer material and a preparation method and application thereof. Background Art

[0002] Thermoplastic polyetherester elastomer (TPEE): It is a type of block copolymer with polybutylene terephthalate (PBT) as the hard segment and polyether or polyester as the soft segment, also known as polyester thermoplastic elastomer or polyester rubber (third generation rubber).

[0003] Invention patent CN116180511A discloses a material for rail fastener pads, which is a polyurethane material. Polyurethane elastomer has certain advantages in mechanical properties, but its hot water resistance is poor and it is not suitable for use in hot and humid climate areas. Invention patent CN111171461A discloses a material for rail transit rail fastener pads, which is made of rubber. The heat resistance of rubber is insufficient and it is easy to age. Invention patent CN115401937A discloses a rail fastener pad made of vulcanized rubber. The rail fastener pad made of vulcanized rubber has excellent low temperature resistance and heat resistance, and can adapt to extreme weather in winter outdoors, but the production process of vulcanized rubber is seriously polluted. Polyether ester elastomer is a type of material with high mechanical strength, heat and cold resistance, and a wide range of operating temperatures. It can well meet the use requirements of parts in the field of rail transit and is a material with great potential, but its application in the field of rail transit is not yet widespread enough.

[0004] Vibration-damping products in the field of rail transit usually need to withstand high-intensity fatigue, which poses a higher challenge to polyetherester materials. Existing technologies for the synthesis of polyetherester elastomers are all carried out in reactors. Traditional kettle polymerizers generally use mechanical stirring to mix materials, which cannot achieve full mixing of multiple immiscible liquids, and there are problems such as material temperature gradients. As a result, the reaction efficiency is low, and polyetherester elastomers with a large weight-average molecular weight cannot be obtained, which has an adverse effect on the performance of polyetherester elastomers. Summary of the invention

[0005] The present invention provides a polyether ester elastomer material and a preparation method and application thereof, which are used to solve the technical problem that the existing materials have poor fatigue resistance and cannot meet the application requirements in the field of rail transportation.

[0006] In order to solve the above technical problems, the present invention adopts the following technical solutions: A fatigue-resistant polyether ester elastomer material, whose molecular structure is shown in formula (1); ; In the formula, A1 is an aromatic dibasic acid and / or its ester group, A2 is an aliphatic diol group, and A3 is a long-chain dihydroxy polyether group.

[0007] As a further preferred embodiment of the above technical solution, the aromatic dibasic acid and / or its ester group includes at least one group selected from terephthalic acid and its esters, furandicarboxylic acid and its esters, and thiophenedicarboxylic acid and its esters.

[0008] As a further preferred embodiment of the above technical solution, the aliphatic diol group is an aliphatic diol group having 2 to 10 carbon atoms; the aliphatic diol group having 2 to 10 carbon atoms includes at least one group selected from 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol and 1,10-decanediol.

[0009] As a further preferred embodiment of the above technical solution, the long-chain dihydroxy polyether group includes at least one group selected from polyethylene glycol, polypropylene glycol and polytetrahydrofuran; the molecular weight of the long-chain dihydroxy polyether group is 200-2000 g / mol. By using long-chain polyols with different molecular weights, polyether ester elastomer materials with different hardness can be prepared.

[0010] Based on the unified technical concept, the present invention also provides a method for preparing the above-mentioned polyether ester elastomer material, comprising the following steps: S1, heating and mixing an aromatic dibasic acid or its ester with an aliphatic diol to obtain a slurry; S2, subjecting the slurry to an esterification reaction under nitrogen protection to obtain an esterification product; S3, subjecting the long-chain dihydroxy polyether to a polycondensation reaction with the esterification product to obtain the fatigue-resistant polyether ester elastomer material.

[0011] As a further preferred embodiment of the above technical solution, the esterification reaction in step S2 and / or the polycondensation reaction in step S3 are completed under the catalytic action of a catalyst, and the catalyst includes at least one of metal element catalysts containing titanium, tin or antimony.

[0012] As a further preferred embodiment of the above technical solution, a functional additive is further added during the esterification reaction in step S2 and / or the polycondensation reaction in step S3, and the functional additive includes at least one of uracil, 2-ureido-4-pyrimidone and cytosine. The introduced pyrimidine functional additive can promote the formation of multiple hydrogen bonds between the molecular chains of the polyether ester elastomer material, thereby obtaining a polyether ester resin with excellent fatigue performance, which is suitable for use in the field of rail transportation.

[0013] As a further preferred embodiment of the above technical solution, the esterification reaction in the step S2 is carried out in a first microchannel reactor, and the polycondensation reaction in the step S3 is carried out in a second microchannel reactor, and there are microchannels in which the catalyst is fixed inside the first microchannel reactor and the second microchannel reactor. Compared with the traditional kettle reactor, the microchannel reactor has a higher mass transfer and heat transfer efficiency and can be produced continuously when using a microchannel reactor to synthesize thermoplastic polyether ester elastomer. During the reaction, the catalyst is fixed in the microchannel and does not need to be added in a fixed proportion. Since the contact area between the material and the catalyst in the microchannel is larger, the degree of reaction is higher and more sufficient. Compared with the kettle reactor, when the relative viscosity of the polymer product is close to the number average relative molecular mass, the use of a microchannel reactor can obtain more products with a larger weight average relative molecular weight.

[0014] As a further preferred embodiment of the above technical solution, the esterification reaction temperature in step S2 is 150-200° C., and the reaction time is 2-4 hours.

[0015] As a further preferred embodiment of the above technical solution, the polycondensation reaction temperature of step S3 is 220-280°C, the reaction time is 4-8h, and the vacuum degree is maintained at 50Pa or less during the reaction.

[0016] Based on the unified technical concept, the present invention also provides an application of the above-mentioned polyether ester elastomer material, which is used to make rail transit track fastener pad materials.

[0017] Compared with the prior art, the advantages of the present invention are: Compared with the traditional polyether ester elastomer material, the polyether ester elastomer material provided in the present invention has a larger weight average relative molecular mass when the relative viscosity of the resin is close to the number average relative molecular mass, which makes the material have better fatigue resistance and improves the disadvantage of the traditional polyether ester material in the field of rail transportation that the high-strength fatigue resistance is insufficient. On the other hand, the method designed by the present invention using microchannel reaction equipment and adding multi-hydrogen bond functional additives can continuously and efficiently produce fatigue-resistant resins, providing a new technical solution for the synthesis of polyether ester materials. DETAILED DESCRIPTION

[0018] The present invention is further described in detail below in conjunction with specific embodiments.

[0019] Embodiment 1: The fatigue-resistant polyether ester elastomer material of this embodiment has a molecular structure as shown in formula (1); ; In the formula, A1 is a terephthalic acid group, A2 is a butanediol group, and A3 is a polytetrahydrofuran group (molecular weight is 2000 g / mol).

[0020] The fatigue-resistant polyether ester elastomer material of this embodiment is prepared by the following method: S1. Heat and mix 2 kg of terephthalic acid, 2.2 kg of butanediol and 10 g of cytosine at 60° C. in a high-speed mixer to obtain a slurry.

[0021] S2. The slurry is transported to the first microchannel reactor by a high-pressure pump, and an esterification reaction is carried out at 160° C. for 4 hours to obtain an esterification product. A microchannel having 4.2 g of stannous octoate catalyst fixed therein exists inside the first microchannel reactor.

[0022] S3. The esterification product and 5 kg of tetrahydrofuran are introduced into a second microchannel reactor, and a polycondensation reaction is carried out at 260° C. for 6 hours to obtain the fatigue-resistant polyether ester elastomer material of this embodiment; a microchannel having 5 g of stannous octoate catalyst fixed therein is present inside the second microchannel reactor.

[0023] The fatigue-resistant polyether ester elastomer material of this embodiment was subjected to performance tests, and the results are shown in Table 1. The test methods are as follows: the hardness was tested according to the ASTM D2240 method; the tensile strength and elongation at break were tested according to the ASTM D638 method; the relative viscosity was tested according to the following method: the relative viscosity of the product with a concentration of 0.5 g / dL was measured using an Ubbelohde viscometer in a phenol solution at (25±0.01)°C; the molecular weight was determined using a Waters 1515 gel chromatography tester.

[0024] The fatigue-resistant polyetherester elastomer material of this embodiment can be used to make rail transit track fastener pad materials, which are processed into track fastener products, and the fasteners are subjected to fatigue resistance tests in accordance with TB / T 3396.4-2015.

[0025] Embodiment 2: The fatigue-resistant polyether ester elastomer material of this embodiment has a molecular structure as shown in formula (1); ; In the formula, A1 is a dimethyl furandicarboxylate group, A2 is a butanediol group, and A3 is a polytetrahydrofuran group (molecular weight is 2000 g / mol).

[0026] The fatigue-resistant polyetherester elastomer material of this embodiment is prepared by the following method: S1. Heat and mix 2.15 kg of dimethyl furandicarboxylate, 2.2 kg of butanediol and 8 g of 2-ureido-4-pyrimidone in a high-speed mixer at 60° C. to obtain a slurry.

[0027] S2. The slurry is transported to the first microchannel reactor by a high-pressure pump, and an esterification reaction is carried out at 160° C. for 4 hours to obtain an esterification product. There is a microchannel in the first microchannel reactor in which 4.2 g of stannous octoate catalyst is fixed.

[0028] S3. The esterification product and 5 kg of polytetrahydrofuran are introduced into a second microchannel reactor, and a polycondensation reaction is carried out at 240° C. for 6 hours to obtain the fatigue-resistant polyether ester elastomer material of this embodiment; a microchannel having 5 g of stannous octoate catalyst fixed therein is present inside the second microchannel reactor.

[0029] The fatigue-resistant polyether ester elastomer material of this embodiment was subjected to performance tests, and the results are shown in Table 1. The test methods are as follows: the hardness was tested according to the ASTM D2240 method; the tensile strength and elongation at break were tested according to the ASTM D638 method; the relative viscosity was tested according to the following method: the relative viscosity of the product with a concentration of 0.5 g / dL was measured using an Ubbelohde viscometer in a phenol solution at (25±0.01)°C; the molecular weight was determined using a Waters 1515 gel chromatography tester.

[0030] The fatigue-resistant polyetherester elastomer material of this embodiment can be used to make rail transit track fastener pad materials, which are processed into track fastener products, and the fasteners are subjected to fatigue resistance tests in accordance with TB / T 3396.4-2015.

[0031] Embodiment 3: The fatigue-resistant polyether ester elastomer material of this embodiment has a molecular structure as shown in formula (1); ; In the formula, A1 is a terephthalic acid group, A2 is a butanediol group, and A3 is a polytetrahydrofuran group (molecular weight is 2000 g / mol).

[0032] The fatigue-resistant polyetherester elastomer material of this embodiment is prepared by the following method: S1. Heat and mix 3 kg of terephthalic acid, 2.4 kg of butanediol and 10.8 g of uracil at 60° C. in a high-speed mixer to obtain a slurry.

[0033] S2. The slurry is transported to the first microchannel reactor by a high-pressure pump, and an esterification reaction is carried out at 160° C. for 4 hours to obtain an esterification product. A microchannel with 5.4 g of catalyst fixed therein exists inside the first microchannel reactor.

[0034] S3. The esterification product and 4.5 kg of polytetrahydrofuran are introduced into a second microchannel reactor, and a polycondensation reaction is carried out at 260° C. for 8 hours to obtain the fatigue-resistant polyether ester elastomer material of this embodiment; a microchannel with 4.5 g of catalyst fixed therein is present inside the second microchannel reactor.

[0035] The fatigue-resistant polyether ester elastomer material of this embodiment was subjected to performance tests, and the results are shown in Table 1. The test methods are as follows: the hardness was tested according to the ASTM D2240 method; the tensile strength and elongation at break were tested according to the ASTM D638 method; the relative viscosity was tested according to the following method: the relative viscosity of the product with a concentration of 0.5 g / dL was measured using an Ubbelohde viscometer in a phenol solution at (25±0.01)°C; the molecular weight was determined using a Waters 1515 gel chromatography tester.

[0036] The fatigue-resistant polyetherester elastomer material of this embodiment can be used to make rail transit track fastener pad materials, which are processed into track fastener products, and the fasteners are subjected to fatigue resistance tests in accordance with TB / T 3396.4-2015.

[0037] Embodiment 4: The fatigue-resistant polyether ester elastomer material of this embodiment has a molecular structure as shown in formula (1); ; Wherein, A1 is a terephthalic acid group, A2 is an ethylene glycol group, and A3 is a polytetrahydrofuran group (molecular weight is 1000 g / mol).

[0038] The fatigue-resistant polyetherester elastomer material of this embodiment is prepared by the following method: S1. Heat and mix 3 kg of terephthalic acid, 2 kg of ethylene glycol and 12 g of uracil at 60° C. in a high-speed mixer to obtain a slurry.

[0039] S2. The slurry is transported to the first microchannel reactor by a high-pressure pump, and an esterification reaction is carried out at 160° C. for 4 hours to obtain an esterification product. A microchannel having 5 g of stannous octoate catalyst fixed therein exists inside the first microchannel reactor.

[0040] S3. The esterification product and 7 kg of polytetrahydrofuran are introduced into a second microchannel reactor, and a polycondensation reaction is carried out at 260° C. for 8 hours to obtain the fatigue-resistant polyether ester elastomer material of this embodiment; a microchannel having 7 g of stannous octoate catalyst fixed therein is present inside the second microchannel reactor.

[0041] The fatigue-resistant polyether ester elastomer material of this embodiment was subjected to performance tests, and the results are shown in Table 1. The test methods are as follows: the hardness was tested according to the ASTM D2240 method; the tensile strength and elongation at break were tested according to the ASTM D638 method; the relative viscosity was tested according to the following method: the relative viscosity of the product with a concentration of 0.5 g / dL was measured using an Ubbelohde viscometer in a phenol solution at (25±0.01)°C; the molecular weight was determined using a Waters 1515 gel chromatography tester.

[0042] The fatigue-resistant polyetherester elastomer material of this embodiment can be used to make rail transit track fastener pad materials, which are processed into track fastener products, and the fasteners are subjected to fatigue resistance tests in accordance with TB / T 3396.4-2015.

[0043] Comparative Example 1: The difference between the preparation method of the elastomer in this comparative example and that in Example 1 is that this comparative example adopts a reactor to carry out the esterification reaction of S2 and the polycondensation reaction of S3, and other parameters and processes are consistent with those in Example 1.

[0044] Comparative Example 2: The difference between the preparation method of the elastomer in this comparative example and that in Example 1 is that the functional auxiliary agent cytosine is not added to S1 in this comparative example, and other parameters and processes are consistent with those in Example 1.

[0045] Comparative Example 3: The difference between the preparation method of the elastomer in this comparative example and that in Example 1 is that this comparative example adopts a reactor to carry out the esterification reaction of S2 and the condensation reaction of S3, and this comparative example does not add the functional auxiliary agent cytosine to S1, and other parameters and processes are consistent with those in Example 1.

[0046] Comparative Example 4: The difference between the preparation method of the elastomer in this comparative example and that in Example 2 is that this comparative example adopts a reactor to carry out the esterification reaction of S2 and the polycondensation reaction of S3, and other parameters and processes are consistent with those in Example 2.

[0047] The performance of the elastomers of the embodiments and comparative examples was tested, and the results are shown in Table 1 below (the testing method of the comparative examples is the same as that of the embodiments).

[0048] Table 1. Performance test results of the elastomers of various embodiments and comparative examples

[0049] By comparing the results of Example 1 and Comparative Example 1 in Table 1 above, it can be seen that the microchannel reactor used in the present invention can synthesize a polyether ester elastomer resin with higher viscosity and high weight average molecular weight; by comparing Example 1 and Comparative Example 2, and Comparative Example 1 and Comparative Example 2, it can be seen that the introduction of functional additives can increase the weight average relative molecular mass of the synthesized resin, and the high weight average relative molecular mass can improve the fatigue resistance of the material; by comparing Example 2 and Comparative Example 4, it can be seen that the use of a microchannel reactor can also synthesize a resin with a higher weight average relative molecular mass, and the high weight average relative molecular mass can improve the fatigue resistance of the material. The above results show that the microchannel reactor used in the present invention and the method of adding functional additives can make the weight average relative molecular mass of the resin higher while ensuring that the viscosity of the material is close to the number average relative molecular mass, and the higher weight average relative molecular mass can make the material have better fatigue resistance.

[0050] The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments. For those skilled in the art, improvements and changes obtained without departing from the technical concept of the present invention should also be regarded as the protection scope of the present invention.

Claims

1. A fatigue-resistant polyetherester elastomer material, characterized in that: Its molecular structure is shown in formula (1); ; In the formula, A1 is an aromatic dibasic acid and / or its ester group, A2 is an aliphatic diol group, and A3 is a long-chain dihydroxy polyether group.

2. The polyetherester elastomer material according to claim 1, characterized in that: The aromatic dibasic acid and / or its ester group includes at least one group selected from terephthalic acid and its ester, furandicarboxylic acid and its ester, and thiophenedicarboxylic acid and its ester.

3. The polyetherester elastomer material according to claim 1, characterized in that: The aliphatic diol group is an aliphatic diol group having 2 to 10 carbon atoms; the aliphatic diol group having 2 to 10 carbon atoms includes at least one group selected from 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol and 1,10-decanediol.

4. The polyetherester elastomer material according to claim 1, characterized in that: The long-chain dihydroxy polyether group includes at least one group selected from polyethylene glycol, polypropylene glycol and polytetrahydrofuran; the molecular weight of the long-chain dihydroxy polyether group is 200-2000 g / mol.

5. A method for preparing the polyether ester elastomer material according to any one of claims 1 to 4, characterized in that: The following steps are involved: S1, heating and mixing an aromatic dibasic acid or its ester with an aliphatic diol to obtain a slurry; S2, subjecting the slurry to an esterification reaction under nitrogen protection to obtain an esterification product; S3: subjecting the long-chain dihydroxy polyether to a polycondensation reaction with the esterification product to obtain the fatigue-resistant polyether ester elastomer material.

6. The method for preparing a polyetherester elastomer material according to claim 5, characterized in that: The esterification reaction in step S2 and / or the polycondensation reaction in step S3 are completed under the catalytic action of a catalyst, and the catalyst includes at least one of metal element catalysts containing titanium, tin or antimony.

7. The method for preparing a polyetherester elastomer material according to claim 6, characterized in that: A functional auxiliary agent is further added during the esterification reaction in step S2 and / or the polycondensation reaction in step S3, and the functional auxiliary agent includes at least one of uracil, 2-ureido-4-pyrimidone and cytosine.

8. The method for preparing a polyetherester elastomer material according to claim 7, characterized in that: The esterification reaction in step S2 is carried out in a first microchannel reactor, and the polycondensation reaction in step S3 is carried out in a second microchannel reactor. Microchannels in which the catalyst and / or functional additive are fixed exist in the first microchannel reactor and the second microchannel reactor.

9. The method for preparing a polyether ester elastomer material according to any one of claims 5 to 8, characterized in that: The esterification reaction temperature of step S2 is 150-200° C., and the reaction time is 2-4 hours.

10. The method for preparing a polyether ester elastomer material according to any one of claims 5 to 8, characterized in that: The polycondensation reaction temperature of step S3 is 220-280° C., the reaction time is 4-8 hours, and the vacuum degree is maintained at 50 Pa or less during the reaction.

11. Use of the polyether ester elastomer material according to any one of claims 1 to 4 or the polyether ester elastomer material prepared by the preparation method according to any one of claims 5 to 10, characterized in that: The polyetherester elastomer material is used for making rail transit vehicle track fastener pad material.

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