Thermoplastic elastomer as well as preparation method and application thereof
By controlling the ratio of ethylene, cycloolefin and α-olefin by terpolymerization, thermoplastic elastomers with good strength and toughness are prepared, solving the problem of limited application of thermoplastic elastomers under high temperature conditions in the prior art.
Patent Information
- Application Number
- CN202510020735.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-07
- Publication Date
- 2025-07-08
AI Technical Summary
The existing thermoplastic elastomers are limited in application under high temperature conditions, and there are problems of poor creep resistance and insufficient strength.
The thermoplastic elastomer was prepared by terpolymerization. By controlling the molar content and proportion of ethylene, cyclic olefins and α-olefins in the soft and hard segment structures, thermoplastic elastomers with high strength and good toughness were prepared.
The application of thermoplastic elastomers under high temperature conditions has been realized, and the creep resistance and strength have been improved.
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Figure CN120271738A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of polymer materials, and particularly relates to a thermoplastic elastomer, a preparation method thereof, and an application thereof. Background Art
[0002] Thermoplastic elastomer (TPE) is a polymer material that combines the elasticity of rubber and the thermoplasticity of plastic. It has the elasticity of rubber at room temperature and can be plasticized and molded at high temperature. It is the third generation of rubber after natural rubber and synthetic rubber. Due to its unique properties, TPE has been widely used in various fields, including but not limited to shoe materials, automobiles, household appliances, electronic products, medical devices, etc. There are many types of TPE, including styrene-based TPE, olefin-based TPE, engineering plastics, diene-based TPE, vinyl chloride-based TPE, etc.
[0003] Among them, polyolefin elastomers (POE for short) are a class of polymer materials with rubber characteristics and thermoplastic processing properties. Common polyolefin elastomers mainly include the following types:
[0004] 1. Random copolymer types: ethylene / α-olefin random copolymers (such as ethylene-1-octene copolymer), ethylene-propylene copolymers (EPM), and ethylene-propylene-diene rubbers (EPDM).
[0005] 2. Block copolymer types: ethylene / α-olefin block copolymers (OBC), polystyrene-based elastomers (SBS, SEBS, SIS, SEPS). Olefin block copolymer (OBC) is synthesized by chain shuttling polymerization technology, including crystalline ethylene-octene segments (hard segments) with low comonomer content and high melting temperature, and amorphous ethylene-octene segments (soft segments) with high comonomer content and low glass transition temperature.
[0006] 3. Comb-shaped polyolefin elastomer (CPOE) is prepared by first homopolymerizing ethylene to prepare a crystalline PE macromonomer (PE-M) with a double bond at the end, and then synthesizing CPOE by terpolymerizing ethylene / 1-octene / PE-M. In the existing technology, the commercialized POE has its application at high temperature limited due to the insertion of α-olefin destroying the crystalline structure. The disadvantage of random copolymers is poor creep resistance, while the olefin block copolymer OBC has insufficient strength, and SBS cannot withstand high temperatures exceeding 80°C. Precise control of the length and number of long branches is required during the preparation of comb-shaped polyolefin elastomers. Due to the special process, there are some challenges in commercial production and application. Another type is cycloolefin block copolymer obtained by chain shuttling copolymerization of ethylene and norbornene. Its heat resistance is very good, but its elasticity and elongation at break need to be further improved.
[0007] Therefore, it is necessary to provide a thermoplastic elastomer and its preparation method and application, so that the thermoplastic elastomer has high strength and good toughness. Summary of the Invention
[0008] The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. For this purpose, the present invention provides a thermoplastic elastomer and its preparation method and application, so that the thermoplastic elastomer has high strength and good toughness.
[0009] The first aspect of the present invention provides a thermoplastic elastomer.
[0010] Specifically, a thermoplastic elastomer includes a soft segment structure and a hard segment structure;
[0011] Both the soft segment structure and the hard segment structure are composed of an ethylene structure, a cycloolefin structure, and an α-olefin structure, and the molar contents of the ethylene structure, the cycloolefin structure, and the α-olefin structure in the soft segment structure and the hard segment structure are different;
[0012] The molar content of the α-olefin structure in the thermoplastic elastomer does not exceed 5%.
[0013] Preferably, the ratio of the soft segment structure in the thermoplastic elastomer is 10-90%;
[0014] The ratio of the hard segment structure in the thermoplastic elastomer is 10-90%.
[0015] More preferably, the ratio of the soft segment structure in the thermoplastic elastomer is 50-90%; the ratio of the hard segment structure in the thermoplastic elastomer is 10-50%.
[0016] Even more preferably, the ratio of the soft segment structure in the thermoplastic elastomer is 80%; the ratio of the hard segment structure in the thermoplastic elastomer is 20%.
[0017] Preferably, the ratio of α-olefin to cycloolefin in the soft segment structure is 10-30%.
[0018] More preferably, the ratio of α-olefin to cycloolefin in the soft segment structure is 10-20%.
[0019] Even more preferably, the ratio of α-olefin to cycloolefin in the soft segment structure is 13-17%.
[0020] Preferably, the ratio of α-olefin to cycloolefin in the hard segment structure is 20-90%.
[0021] More preferably, the ratio of α-olefin to cycloolefin in the hard segment structure is 20-60%.
[0022] More preferably, the ratio of α-olefin to cycloolefin in the hard segment structure is 42-47%.
[0023] Preferably, by molar content, the thermoplastic elastomer comprises 65-85% of ethylene structure, 10-30% of cycloolefin structure, and 0.1-5% of α-olefin structure.
[0024] Preferably, by molar content, the thermoplastic elastomer comprises 65-70% of ethylene structure, 25-30% of cycloolefin structure, and 3-5% of α-olefin structure.
[0025] Preferably, the cycloolefin structure comprises at least one of cyclopentene, cyclohexene, cycloheptene, cyclooctene, norbornene, ethylidene norbornene, dicyclopentadiene.
[0026] Preferably, the α-olefin structure comprises at least one of 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene.
[0027] The second aspect of the present invention provides a preparation method of a thermoplastic elastomer.
[0028] Specifically, it includes the following steps:
[0029] First, mix the solvent, cycloolefin, and α-olefin, introduce ethylene gas and start mixing, then add trimethylaluminoxane and diethylzinc, and finally add the catalyst, react to obtain the thermoplastic elastomer.
[0030] Preferably, the reaction temperature is 10-30°C, and the reaction time is 1-5 h.
[0031] Preferably, the molar ratio of trimethylaluminoxane to the catalyst is 800-1000:1.
[0032] More preferably, the molar ratio of trimethylaluminoxane to the catalyst is 900-1000:1.
[0033] Even more preferably, the molar ratio of trimethylaluminoxane to the catalyst is 1000:1.
[0034] Preferably, the solvent includes toluene.
[0035] Preferably, the inlet pressure of the ethylene gas is 1-10 atm.
[0036] More preferably, the inlet pressure of the ethylene gas is 1-5 atm.
[0037] Even more preferably, the inlet pressure of the ethylene gas is 1 atm.
[0038] Preferably, the catalyst is FI-1 catalyst and FI-2 catalyst;
[0039] Among them, the structural formula of the FI-1 catalyst is The FI-1 catalyst has a lower comonomer insertion rate;
[0040] The structural formula of the FI-2 catalyst is The FI-2 catalyst has a higher comonomer insertion rate.
[0041] Further preferably, the molar ratio of FI-1 to FI-2 is 1 to 7:1.
[0042] The third aspect of the present invention provides an application of a thermoplastic elastomer in shoe materials, automobiles, household appliances, electronic products, and medical devices.
[0043] Compared with the prior art, the beneficial effects of the present invention are as follows:
[0044] The present invention performs terpolymerization with three monomers and realizes chain shuttling to prepare a thermoplastic elastomer, thereby having good creep resistance. By controlling the distribution of the three monomers in the two hard and soft segments, better strength and toughness are achieved. Description of the Drawings
[0045] Figure 1 It is a toughness result diagram of the thermoplastic elastomer prepared in Examples 1 to 3 of the present invention;
[0046] Figure 2 It is a toughness result diagram of the thermoplastic elastomer prepared in Example 3 and Comparative Example 1 of the present invention;
[0047] Figure 3 It is a toughness result diagram of the thermoplastic elastomer prepared in Example 3 and Comparative Example 2 of the present invention. Detailed Embodiments
[0048] In order to make those skilled in the art more clearly understand the technical solutions described in the present invention, the following examples are listed for illustration. It should be noted that the following examples do not limit the protection scope required by the present invention.
[0049] In the following examples, the raw materials, reagents or devices used can be obtained from conventional commercial channels or can be obtained by existing known methods without special instructions.
[0050] Example 1
[0051] A thermoplastic elastomer and its preparation method.
[0052] Thermoplastic elastomer: It includes a soft segment structure and a hard segment structure; among them, the ratio of the soft segment structure in the thermoplastic elastomer is 80%, and the ratio of the hard segment structure in the thermoplastic elastomer is 20%. The ratio of α-olefin to cycloolefin in the soft segment structure is 13%. The ratio of α-olefin to cycloolefin in the hard segment structure is 42%. By molar content, the thermoplastic elastomer in Example 1 contains 70% ethylene structure, 25% norbornene structure, and 5% 1-octene structure.
[0053] Preparation method:
[0054] First, add 460 mL of toluene, 10.5 g of norbornene, and 35 mL of 0.4 M 1-octene to the reaction kettle, introduce ethylene gas (1 atm) and start stirring (rotation speed 300 r / min), then add 19 mL of trimethylaluminoxane MAO and 2.5 mL of 5 mM diethylzinc Et2Zn. At the same time, dissolve the FI catalyst (the FI catalyst is 0.037 g of FI-1 catalyst and 0.007 g of FI-2 catalyst) with 15 mL of trimethylaluminoxane MAO. The molar ratio of MAO to the FI catalyst is 1000:1. Then add the dissolved FI catalyst to the reaction kettle, increase the rotation speed to 600 r / min. After reacting for 1 h, add the reaction solution to 800 mL of ethanol for precipitation, wash it with ethanol multiple times and then dry it to obtain the thermoplastic elastomer. The reaction equation of the thermoplastic elastomer prepared in Example 1 of the present invention is as follows:
[0055] Example 2
[0056] A thermoplastic elastomer and its preparation method.
[0057] Thermoplastic elastomer: It includes a soft segment structure and a hard segment structure; among them, the ratio of the soft segment structure in the thermoplastic elastomer is 80%, and the ratio of the hard segment structure in the thermoplastic elastomer is 20%. The ratio of α-olefin to cycloolefin in the soft segment structure is 15%. The ratio of α-olefin to cycloolefin in the hard segment structure is 45%. By molar content, the thermoplastic elastomer in Example 2 contains 67% ethylene structure, 28% norbornene structure, and 5% 1-octene structure.
[0058] Preparation method:
[0059] The difference from Example 1 is that the addition amount of norbornene is 16 g.
[0060] Example 3
[0061] A thermoplastic elastomer and its preparation method.
[0062] Thermoplastic elastomer: It includes a soft segment structure and a hard segment structure; among them, the ratio of the soft segment structure in the thermoplastic elastomer is 80%, and the ratio of the hard segment structure in the thermoplastic elastomer is 20%. The ratio of α-olefin to cycloolefin in the soft segment structure is 17%. The ratio of α-olefin to cycloolefin in the hard segment structure is 47%. By molar content, the thermoplastic elastomer in Example 3 contains 65% ethylene structure, 30% norbornene structure, and 5% 1-octene structure.
[0063] Preparation method:
[0064] The difference from Example 1 is that the addition amount of norbornene is 21 g.
[0065] Comparative Example 1
[0066] A thermoplastic elastomer and its preparation method.
[0067] Thermoplastic elastomer: It includes a soft segment structure and a hard segment structure; among them, the ratio of the soft segment structure in the thermoplastic elastomer is 80%, and the ratio of the hard segment structure in the thermoplastic elastomer is 20%. The ratio of cycloolefin in the soft segment structure is 17%. The ratio of cycloolefin in the hard segment structure is 47%. By molar content, the thermoplastic elastomer in Comparative Example 1 contains 70% ethylene structure and 30% norbornene structure.
[0068] Preparation method:
[0069] First, add 500 mL of toluene and 21 g of norbornene to the reaction kettle, introduce ethylene gas (1 atm) and start stirring (rotation speed 300 r / min), then add 18 mL of trimethylaluminoxane MAO and 2.5 mL of 5 mM diethylzinc Et2Zn. At the same time, dissolve the FI catalyst (the FI catalyst is 0.028 g of FI-1 catalyst and 0.007 g of FI-2 catalyst) with 15 mL of trimethylaluminoxane MAO. The molar ratio of MAO to the FI catalyst is 1000:1. Then add the dissolved FI catalyst to the reaction kettle, increase the rotation speed to 600 r / min. After reacting for 1 h, add the reaction solution to 800 mL of ethanol for precipitation, wash it with ethanol multiple times and then dry it to obtain the thermoplastic elastomer.
[0070] Comparative Example 2
[0071] A thermoplastic elastomer and its preparation method.
[0072] Thermoplastic elastomer: It includes a soft segment structure and a hard segment structure; among them, the ratio of the soft segment structure in the thermoplastic elastomer is 80%, and the ratio of the hard segment structure in the thermoplastic elastomer is 20%. The ratio of α-olefin to cycloolefin in the soft segment structure is 17%. The ratio of α-olefin to cycloolefin in the hard segment structure is 47%. By molar content, the thermoplastic elastomer in Comparative Example 2 contains 60% ethylene structure, 30% norbornene structure, and 10% 1-octene structure.
[0073] Preparation method:
[0074] First, add 315 mL of toluene, 21 g of norbornene, and 175 mL of 0.4 M 1-octene to the reaction kettle, introduce ethylene gas (1 atm) and start stirring (rotation speed 300 r / min). Then add 19 mL of trimethylaluminoxane MAO and 2.5 mL of 5 mM diethylzinc Et2Zn. At the same time, dissolve the FI catalyst (the FI catalyst is 0.037 g of FI-1 catalyst and 0.007 g of FI-2 catalyst) with 15 mL of trimethylaluminoxane MAO. The molar ratio of MAO to the FI catalyst is 1000:1. Then add the dissolved FI catalyst to the reaction kettle, increase the rotation speed to 600 r / min. After reacting for 1 h, add the reaction solution to 800 mL of ethanol for precipitation, wash it with ethanol multiple times and then dry it to obtain the thermoplastic elastomer.
[0075] As Figure 1 shown, it is a process schematic diagram of the thermoplastic elastomer prepared by the present invention. As Figure 2 shown, among the thermoplastic elastomers prepared in Examples 1 to 3, as the concentration of norbornene increases, the toughness gradually decreases. This is because the increase in the content of norbornene increases the glass transition temperature (Tg) of the soft segment, reduces the chain segment movement ability, and thus leads to a decrease in strain. At the same time, due to the increase in the concentration of norbornene, the polymer crystallization ability decreases, resulting in a decrease in the modulus of the elastomer.
[0076] As Figure 2 shown, Example 3 has better toughness compared to Comparative Example 1. This is because in chain shuttling terpolymerization, the amount of the third monomer 1-octene added can adjust the Tg of the soft segment and the hard segment compared to chain shuttling binary copolymerization. Example 3 added more 1-octene than Comparative Example 4, reducing the Tg of the soft segment and the hard segment, improving the movement ability of the soft segment, and thus achieving an increase in toughness.
[0077] As Figure 3 shown, the toughness of Comparative Example 2 increases compared to Example 3. This is because as the concentration of 1-octene increases, the Tg of the soft segment gradually decreases, the chain segment movement ability improves, and the toughness increases accordingly. However, the breaking strength decreases because the Tg of the hard segment decreases significantly, resulting in a decrease in the strength of the hard segment and thus a decrease in the breaking strength.
[0078] The above has described in detail the preferred specific embodiments of the present invention. It should be understood that those of ordinary skill in the art can make many modifications and variations based on the concept of the present invention without creative work. Therefore, any technical solutions obtained by those skilled in the art in the technical field of the present invention through logical analysis, reasoning, or limited experiments based on the concept of the present invention on the basis of the prior art, such as any modifications, equivalent replacements, improvements, etc., should be within the protection scope determined by the claims.
Claims
1. A thermoplastic elastomer, characterized in that, It includes a soft segment structure and a hard segment structure; Both the soft segment structure and the hard segment structure are composed of an ethylene structure, a cycloolefin structure and an α-olefin structure, and the molar contents of the ethylene structure, the cycloolefin structure and the α-olefin structure in the soft segment structure and the hard segment structure are different; The molar content of the α-olefin structure in the thermoplastic elastomer does not exceed 5%.
2. The thermoplastic elastomer according to claim 1, wherein The ratio of the soft segment structure in the thermoplastic elastomer is 10-90%; The ratio of the hard segment structure in the thermoplastic elastomer is 10-90%.
3. The thermoplastic elastomer according to claim 1, characterized in that, The ratio of α-olefin to cycloolefin in the soft segment structure is 10-30%.
4. The thermoplastic elastomer according to claim 1, characterized in that, The ratio of α-olefin to cycloolefin in the hard segment structure is 20-90%.
5. The thermoplastic elastomer according to claim 1, characterized in that, By molar content, the thermoplastic elastomer includes 65-85% of an ethylene structure, 10-30% of a cycloolefin structure, and 0.1-5% of an α-olefin structure.
6. The thermoplastic elastomer according to claim 1, characterized in that, The cycloolefin structure includes at least one of cyclopentene, cyclohexene, cycloheptene, cyclooctene, norbornene, ethylidene norbornene, dicyclopentadiene.
7. The thermoplastic elastomer according to claim 1, wherein The α-olefin structure includes at least one of 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene.
8. The method for preparing the thermoplastic elastomer according to any one of claims 1 to 7, characterized in that, It includes the following steps: First, mix the solvent, cycloolefin and α-olefin, introduce ethylene gas and start mixing, then add trimethylaluminoxane and diethylzinc, and finally add a catalyst and react to obtain the thermoplastic elastomer.
9. The preparation method according to claim 8, characterized in that, The molar ratio of the trimethylaluminoxane to the catalyst is 800-1000:
1.
10. Application of the thermoplastic elastomer according to any one of claims 1 to 7 in shoe materials, automobiles, household appliances, electronic products, and medical devices.