Elastomer polymer material, preparation method thereof and tough elastic yarn

Abstract

The invention provides an elastomer polymer material, a preparation method thereof and a tough elastic yarn. The elastomer polymer material is prepared from the following raw materials: a polyolefin elastomer POE, a thermoplastic polyester elastomer TPEE and a bridging agent. According to the elastomer polymer material provided by the invention, the polyolefin elastomer POE, the thermoplastic polyester elastomer TPEE and the bridging agent are synergistically compounded, so that the elastomer polymer material has a relatively high melting point and a net structure; the tough and elastic yarn prepared from the tough and elastic yarn has the characteristics that the elasticity is good, the boiling water shrinkage rate is not lower than 45%, and the breaking tensile strength is not lower than 3.2 cN / dTex, and the tough and elastic yarn fabric is not broken in the subsequent 180 DEG C ironing processing environment.

Description

Technical Field

[0001] This invention belongs to the field of yarn technology, and relates to an elastomer polymer material, its preparation method, and a resilient elastic yarn. Background Technology

[0002] Polyolefin elastomer (POE) is a random copolymer polymerized from ethylene and α-olefins (1-butene, 1-hexene, 1-octene, etc.) under the action of a metallocene catalyst. It possesses excellent weather resistance and chemical resistance, as well as good transparency and flexibility. It exhibits good compatibility with polyolefins and combines the high elasticity of rubber with the easy processability of plastics, making it an ideal spinning material. Elastic fabrics obtained from POE are less expensive, lighter, consume less energy, and are more environmentally friendly. However, because the melting point of POE is generally below 130℃, the yarn will melt and break easily at processing temperatures above 180℃, limiting its application in the spinning field. Therefore, modifying POE to increase its melting point and developing high-melting-point POE spinning materials for use in footwear fabrics has become a key development topic in the textile industry, possessing significant research value and broad commercial prospects. Summary of the Invention

[0003] To address the shortcomings of existing technologies, the present invention aims to provide an elastomeric polymer material, its preparation method, and a resilient elastic yarn. Specifically, addressing the deficiency that the melting point of current polyolefin elastomer POE is generally below 130°C, the present invention uses a thermoplastic polyester elastomer TPEE with a melting point of approximately 180°C to 220°C to blend with it. By introducing a high-melting-point (greater than 180°C) elastomeric polymer, the melting point of the POE material is increased, while maintaining the inherent lightweight and flexible properties of POE, and also ensuring good compatibility between the two elastomers.

[0004] The elastomeric polymer material provided by this invention has excellent mechanical properties and heat resistance due to its special network structure. This ensures that the elastic yarn fabric made from it will not break when exposed to high temperatures of 180°C during subsequent ironing and finishing processes. It is also lightweight, soft, and has high shrinkage properties.

[0005] To achieve this objective, the present invention adopts the following technical solution:

[0006] In a first aspect, the present invention provides an elastomeric polymer material, wherein the raw materials for preparing the elastomeric polymer material include polyolefin elastomer POE, thermoplastic polyester elastomer TPEE, and crosslinking agent.

[0007] The elastomeric polymer material provided by this invention, through the synergistic compounding of three components—polyolefin elastomer POE, thermoplastic polyester elastomer TPEE, and crosslinking agent—gains a high melting point and a network structure. The elastic yarn prepared from it has the characteristics of good elasticity, boiling water shrinkage rate of not less than 45%, and tensile strength at break of not less than 3.2 cN / dTex. Furthermore, the elastic yarn fabric does not break during subsequent 180°C ironing processing.

[0008] POE is a non-polar polyolefin material, while TPEE is a polar polyester material. The two have extremely poor compatibility, and directly blending them will result in a "plastic island structure". This invention introduces a crosslinking agent into the system, which can transform the isolated "island-like structures" into a more continuous network structure, giving the material superior mechanical properties and heat resistance.

[0009] Preferably, the thermoplastic polyester elastomer TPEE has a melting point of 180℃~220℃, for example, it can be 180℃, 181℃, 182℃, 183℃, 184℃, 185℃, 186℃, 187℃, 188℃, 189℃, 190℃, 191℃, 192℃, 193℃, 194℃, 195℃, 196℃, 197℃, 198℃, 199℃, 200℃, 201℃. The specific point values ​​included in the range are as follows: 202℃, 203℃, 204℃, 205℃, 206℃, 207℃, 208℃, 209℃, 210℃, 211℃, 212℃, 213℃, 214℃, 215℃, 216℃, 217℃, 218℃, 219℃, 220℃, etc., as well as the specific point values ​​between the above-mentioned point values. Due to space limitations and for the sake of brevity, this invention will not exhaustively list the specific point values ​​included in the range.

[0010] Preferably, the crosslinking agent comprises dicumyl peroxide (DCP).

[0011] Preferably, based on the total weight of the polyolefin elastomer POE and the thermoplastic polyester elastomer TPEE as 100%, the content of the polyolefin elastomer POE is 35% to 65%, for example, it can be 35%, 36%, 38%, 40%, 42%, 44%, 45%, 46%, 48%, 50%, 52%, 54%, 55%, 56%, 58%, 60%, 62%, 64%, 65%, etc., and specific values ​​between the above points. Due to space limitations and for the sake of brevity, this invention... The present invention will not exhaustively list the specific values ​​included in the range. The content of the thermoplastic polyester elastomer TPEE is 35% to 65%, for example, it can be 35%, 36%, 38%, 40%, 42%, 44%, 45%, 46%, 48%, 50%, 52%, 54%, 55%, 56%, 58%, 60%, 62%, 64%, 65%, etc., as well as the specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0012] Preferably, based on the total weight of the polyolefin elastomer POE and the thermoplastic polyester elastomer TPEE as 100%, the content of the polyolefin elastomer POE is 50%~60%, for example, it can be 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, etc., and specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range. The content of the thermoplastic polyester elastomer TPEE is 40%~50%, for example, it can be 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, etc., and specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0013] Preferably, the content of the crosslinking agent is 0.5% to 2% of the sum of the weights of the polyolefin elastomer POE and the thermoplastic polyester elastomer TPEE. For example, it can be 0.5%, 0.6%, 0.8%, 1%, 1.2%, 1.3%, 1.5%, 1.6%, 1.8%, 2%, etc., as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0014] Preferably, the raw materials for preparing the elastomeric polymer material further include UV absorbers and / or antioxidants.

[0015] Preferably, the content of the UV absorber is 0.1% to 2% of the sum of the weights of the polyolefin elastomer POE and the thermoplastic polyester elastomer TPEE. For example, it can be 0.1%, 0.2%, 0.3%, 0.5%, 0.6%, 0.8%, 1%, 1.2%, 1.3%, 1.5%, 1.6%, 1.8%, 2%, etc., as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0016] Preferably, the antioxidant content is 0.1% to 2% of the sum of the weights of the polyolefin elastomer POE and the thermoplastic polyester elastomer TPEE, for example, it can be 0.1%, 0.2%, 0.3%, 0.5%, 0.6%, 0.8%, 1%, 1.2%, 1.3%, 1.5%, 1.6%, 1.8%, 2%, etc., as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0017] Preferably, the melting point of the elastomeric polymer material is not lower than 165°C, for example, it can be 165°C, 168°C, 170°C, 172°C, 173°C, 175°C, 178°C, 180°C, 183°C, 185°C, 188°C, 190°C, 193°C, 200°C, etc., as well as specific values ​​between the above points. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0018] In a second aspect, the present invention provides a method for preparing an elastomeric polymer material as described in the first aspect, the method comprising the following steps:

[0019] Polyolefin elastomer POE, thermoplastic polyester elastomer TPEE, crosslinking agent, optional UV absorber, and optional antioxidant are mixed, melt-sheared, and extruded to obtain the elastomer polymer material.

[0020] Preferably, the melt shearing is performed in a twin-screw extruder.

[0021] Preferably, the melting shearing temperature is 200~220℃, such as 200℃, 205℃, 210℃, 215℃, 220℃, etc.

[0022] Thirdly, the present invention provides a resilient elastic yarn, which is prepared from the elastomeric polymer material described in the first aspect.

[0023] Preferably, the elastic yarn is prepared by the following method:

[0024] The elastomeric polymer material is melted, drawn and shaped through a spinneret to obtain the elastic yarn.

[0025] Preferably, the boiling water shrinkage rate of the elastic yarn is not less than 45%, such as 45%, 46%, 48%, 50%, 55%, 60%, 65%, etc.

[0026] Preferably, the tensile strength at break of the elastic yarn is not less than 3.2 cN / dTex, such as 3.2 cN / dTex, 3.5 cN / dTex, 3.8 cN / dTex, 4.0 cN / dTex, 4.5 cN / dTex, etc.

[0027] Fourthly, the present invention provides an application of the elastic yarn as described in the third aspect in shoe material fabrics.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] The elastomeric polymer material provided by this invention, through the synergistic compounding of three components—polyolefin elastomer POE, thermoplastic polyester elastomer TPEE, and crosslinking agent—gains a high melting point and a network structure. The elastic yarn prepared from it has the characteristics of good elasticity, boiling water shrinkage rate of not less than 45%, and tensile strength at break of not less than 3.2 cN / dTex. Furthermore, the elastic yarn fabric does not break during subsequent 180°C ironing processing. Attached Figure Description

[0030] Figure 1 The flowchart shows the preparation method of the elastomeric polymer material provided in Example 1.

[0031] Figure 2 A flowchart illustrating the preparation method of the elastic yarn provided in Application Example 1. Detailed Implementation

[0032] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0033] Unless otherwise specified, some of the raw material information used in the following embodiments and comparative examples of the present invention is as follows:

[0034] Polyolefin elastomer (POE): Mitsui EP1013 (Japan);

[0035] Thermoplastic polyester elastomer TPEE: TX506.

[0036] Example 1

[0037] This embodiment provides an elastomeric polymer material, the raw materials for preparing the elastomeric polymer material comprising the following components by weight:

[0038] 60 parts of polyolefin elastomer POE;

[0039] 40 parts of thermoplastic polyester elastomer TPEE;

[0040] 0.5 parts of crosslinking agent;

[0041] 0.5 parts of UV absorber;

[0042] Antioxidant 0.5 parts;

[0043] Among them, the crosslinking agent is DCP, the UV absorber is UV234, and the antioxidant is antioxidant 1010.

[0044] The method for preparing the elastomeric polymer material includes the following steps:

[0045] The polyolefin elastomer POE, thermoplastic polyester elastomer TPEE, crosslinking agent, UV absorber, and antioxidant are mixed in the specified amounts and then melt-sheared and extruded through a twin-screw extruder at 210°C to obtain the elastomer polymer material.

[0046] The flowchart of the preparation method of the elastomer polymer material provided in this embodiment is as follows: Figure 1 As shown.

[0047] Example 2

[0048] This embodiment provides an elastomeric polymer material, the raw materials for preparing the elastomeric polymer material comprising the following components by weight:

[0049] 60 parts of polyolefin elastomer POE;

[0050] 40 parts of thermoplastic polyester elastomer TPEE;

[0051] One part of bridging agent;

[0052] 0.5 parts of UV absorber;

[0053] Antioxidant 0.5 parts;

[0054] Among them, the crosslinking agent is DCP, the UV absorber is UV234, and the antioxidant is antioxidant 1010.

[0055] The preparation method is the same as in Example 1.

[0056] Example 3

[0057] This embodiment provides an elastomeric polymer material, the raw materials for preparing the elastomeric polymer material comprising the following components by weight:

[0058] 60 parts of polyolefin elastomer POE;

[0059] 40 parts of thermoplastic polyester elastomer TPEE;

[0060] Two parts of bridging agent;

[0061] 0.5 parts of UV absorber;

[0062] Antioxidant 0.5 parts;

[0063] Among them, the crosslinking agent is DCP, the UV absorber is UV234, and the antioxidant is antioxidant 1010.

[0064] The preparation method is the same as in Example 1.

[0065] Example 4

[0066] This embodiment provides an elastomeric polymer material, the raw materials for preparing the elastomeric polymer material comprising the following components by weight:

[0067] 50 parts of polyolefin elastomer POE;

[0068] 50 parts of thermoplastic polyester elastomer TPEE;

[0069] One part of bridging agent;

[0070] 0.5 parts of UV absorber;

[0071] Antioxidant 0.5 parts;

[0072] Among them, the crosslinking agent is DCP, the UV absorber is UV234, and the antioxidant is antioxidant 1010.

[0073] The preparation method is the same as in Example 1.

[0074] Example 5

[0075] This embodiment provides an elastomeric polymer material, the raw materials for preparing the elastomeric polymer material comprising the following components by weight:

[0076] 40 parts of polyolefin elastomer POE;

[0077] 60 parts of thermoplastic polyester elastomer TPEE;

[0078] One part of bridging agent;

[0079] 0.5 parts of UV absorber;

[0080] Antioxidant 0.5 parts;

[0081] Among them, the crosslinking agent is DCP, the UV absorber is UV234, and the antioxidant is antioxidant 1010.

[0082] The preparation method is the same as in Example 1.

[0083] Comparative Example 1

[0084] This comparative example provides an elastomeric polymer material, the raw materials for preparing the elastomeric polymer material comprising, by weight, the following components:

[0085] 100 parts of polyolefin elastomer POE;

[0086] One part of bridging agent;

[0087] 0.5 parts of UV absorber;

[0088] Antioxidant 0.5 parts;

[0089] Among them, the crosslinking agent is DCP, the UV absorber is UV234, and the antioxidant is antioxidant 1010.

[0090] The method for preparing the elastomeric polymer material includes the following steps:

[0091] The polyolefin elastomer POE, crosslinking agent, UV absorber, and antioxidant are mixed in the prescribed amounts and then melt-sheared and extruded through a twin-screw extruder at 210°C to obtain the elastomer polymer material.

[0092] Comparative Example 2

[0093] The only difference between this comparative example and Example 2 is that the raw materials for preparing the elastomeric polymer material do not include crosslinking agents.

[0094] Comparative Example 3

[0095] The only difference between this comparative example and Example 2 is that the thermoplastic polyester elastomer TPEE is replaced with an equal weight proportion of polyamide thermoplastic elastomer TPAE (UBESTA XPA, Ube Industries, Inc., Japan).

[0096] Comparative Example 4

[0097] The only difference between this comparative example and Example 2 is that the crosslinking agent (DCP) is replaced with an equal weight proportion of isocyanate crosslinking agent (TAIC, triallyl isocyanurate).

[0098] Application Example 1

[0099] This application example provides a resilient elastic yarn, which is prepared from the elastomeric polymer material provided in Example 1. The specific preparation method includes the following steps:

[0100] The elastomeric polymer material provided in Example 1 is melted, drawn and shaped through a spinneret to obtain the elastic yarn.

[0101] The flowchart of the preparation method of the elastic yarn provided in this application example is as follows: Figure 2 As shown.

[0102] Application Example 2-5, Comparison with Application Example 1-4

[0103] The only difference from Application Example 1 is that the elastomeric polymer material provided in Example 1 is replaced with the elastomeric polymer materials provided in Examples 2-5 and Comparative Examples 1-4, respectively.

[0104] The performance of the elastomeric polymer materials, application examples, and comparative application examples provided in the embodiments and comparative examples of the present invention was tested using the following methods:

[0105] (1) Melting point of elastomeric polymer materials: Tested in accordance with GB / T 14190-2017;

[0106] (2) Tensile strength at break of elastic yarn: Tested in accordance with GB / T 3916-2013;

[0107] (3) Whether the elastic yarn breaks under the high temperature 180℃ ironing process: Observe under a microscope whether the elastic yarn breaks under the high temperature 180℃ ironing process.

[0108] The performance test results are shown in Table 1.

[0109] Table 1

[0110]

[0111] As shown in Table 1, in Examples 1, 2, and 3, the addition of thermoplastic polyester elastomer (TPEE) increased the melting point of the elastomer polymer material to 165°C. Furthermore, as the amount of crosslinking agent increased from 0.5 parts to 2 parts, the microstructure of the elastomer polymer was most clearly defined at a dosage of 1.0 part, indicating the best degree of crosslinking. When the elastomer polymer material was used for spinning, the resulting elastic yarn exhibited better mechanical properties than those in Examples 1 and 3, with a tensile strength at break reaching 4.5 cN / dTex, a boiling water shrinkage rate of not less than 45%, and no breakage even during subsequent high-temperature (180°C) ironing processes.

[0112] In Examples 4 and 5, with the optimal crosslinking agent dosage remaining unchanged, the melting point of the elastomeric polymer material increases accordingly with the increase of TPEE dosage, and the elastomeric polymer material exhibits obvious rubber elasticity. However, this increases the difficulty of spinning and the cost.

[0113] In Examples 1 to 5, the addition of UV absorbers and antioxidants ensures that the resulting elastic yarn has good weather resistance and anti-phenolic yellowing effects.

[0114] Compared to the polyolefin elastomer POE, the melting point of the elastomer polymer provided in Comparative Example 1 did not change significantly.

[0115] Compared with Example 2, the tensile strength at break and the boiling water shrinkage of the elastomeric polymers provided in Comparative Examples 2-4 were significantly reduced, and thread breakage occurred during the spinning process.

[0116] The applicant declares that this invention illustrates the elastomeric polymer material, its preparation method, and the elastic yarn through the above embodiments. However, this invention is not limited to the above embodiments, meaning that this invention does not necessarily rely on the above embodiments for implementation. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of the raw materials used, additions of auxiliary components, and selection of specific methods all fall within the protection and disclosure scope of this invention.

Claims

1. An elastomeric polymer material, characterized in that, The raw materials for preparing the elastomeric polymer material include polyolefin elastomer POE, thermoplastic polyester elastomer TPEE, and crosslinking agent.

2. The elastomeric polymer material according to claim 1, characterized in that, The melting point of the thermoplastic polyester elastomer TPEE is 180℃~220℃.

3. The elastomeric polymer material according to claim 1 or 2, characterized in that, The bridging agent includes dicumyl peroxide.

4. The elastomeric polymer material according to any one of claims 1-3, characterized in that, Based on the total weight of the polyolefin elastomer POE and the thermoplastic polyester elastomer TPEE as 100%, the content of the polyolefin elastomer POE is 35%~65%, and the content of the thermoplastic polyester elastomer TPEE is 35%~65%. Preferably, based on the total weight of the polyolefin elastomer POE and the thermoplastic polyester elastomer TPEE as 100%, the content of the polyolefin elastomer POE is 50%~60%, and the content of the thermoplastic polyester elastomer TPEE is 40%~50%.

5. The elastomeric polymer material according to any one of claims 1-4, characterized in that, The crosslinking agent content is 0.5% to 2% of the sum of the weights of the polyolefin elastomer POE and the thermoplastic polyester elastomer TPEE.

6. The elastomeric polymer material according to any one of claims 1-5, characterized in that, The raw materials for preparing the elastomer polymer material also include UV absorbers and / or antioxidants; Preferably, the content of the UV absorber is 0.1% to 2% of the sum of the weights of the polyolefin elastomer POE and the thermoplastic polyester elastomer TPEE; Preferably, the antioxidant content is 0.1% to 2% of the sum of the weights of the polyolefin elastomer POE and the thermoplastic polyester elastomer TPEE.

7. The elastomeric polymer material according to any one of claims 1-6, characterized in that, The melting point of the elastomeric polymer material is not lower than 165°C.

8. A method for preparing an elastomeric polymer material as described in any one of claims 1-7, characterized in that, The preparation method includes the following steps: Polyolefin elastomer POE, thermoplastic polyester elastomer TPEE, crosslinking agent, optional UV absorber, and optional antioxidant are mixed, melt-sheared, and extruded to obtain the elastomer polymer material.

9. The preparation method according to claim 8, characterized in that, The melt shearing is performed in a twin-screw extruder; Preferably, the temperature of the melt shearing is 200~220℃.

10. A type of resilient elastic yarn, characterized in that, The elastic yarn is prepared from the elastopolymer material according to any one of claims 1-7; Preferably, the elastic yarn is prepared by the following method: The elastomeric polymer material is melted, drawn and shaped through a spinneret to obtain the elastic yarn; Preferably, the boiling water shrinkage rate of the elastic yarn is not less than 45%; Preferably, the tensile strength at break of the elastic yarn is not less than 3.2 cN / dTex.

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