Carbon dioxide-based TPU foaming resin and preparation method thereof, carbon dioxide-based TPU foaming material and preparation method thereof, and foaming product

Abstract

The invention relates to a carbon dioxide-based TPU foaming resin and a preparation method thereof, a carbon dioxide-based TPU foaming material and a preparation method thereof, and a foaming product. The carbon dioxide-based TPU foaming resin is prepared from the following raw materials in percentage by mass: 10%-90% of a carbon dioxide-based TPU elastic material, 0.5%-1% of an organic nucleating agent, 3%-5% of an inorganic nucleating agent, 0.5%-1% of a compatilizer and 3%-86% of a biodegradable material. In the raw materials of the carbon dioxide-based TPU foaming resin, the carbon dioxide-based TPU elastic material is synthesized by carbon dioxide collected in the atmospheric environment and other carbon-based materials, and carbon dioxide in the atmosphere can be effectively digested and absorbed. The combination of the components and the mass fraction range of the components are determined through a large number of tests, and the combination and the percentage range enable a carbon dioxide-based TPU foaming material formed by the carbon dioxide-based TPU foaming resin to have the full-biological negative carbon characteristic and have direct contributions to carbon reduction and carbon neutralization.

Description

Technical Field

[0001] The present invention relates to the technical field of foaming materials, and in particular to a carbon dioxide-based TPU foaming resin and a preparation method thereof, a carbon dioxide-based TPU foaming material and a preparation method thereof, and a foamed product. Background Art

[0002] Thermoplastic polyurethane (TPU) is a type of elastomer that plasticizes when heated and dissolves in solvents. It boasts excellent overall properties, including high strength, high toughness, wear resistance, and oil resistance. Its excellent processing properties make it widely used in industries such as defense, healthcare, and food. TPU foam not only shares these advantages with TPU resin but also offers advantages like lightness, softness, and high resilience, leading to its widespread application.

[0003] Green and low-carbon industrialization is bound to become a key development target in the future. However, there is currently no TPU foam material that can achieve green and low-carbon development. Summary of the Invention

[0004] Based on this, it is necessary to provide a fully bio-negative carbon dioxide-based TPU foaming resin and its preparation method, a carbon dioxide-based TPU foaming material and its preparation method and foamed products.

[0005] A carbon dioxide-based TPU foaming resin, wherein the raw materials for preparing the carbon dioxide-based TPU foaming resin include the following components by mass fraction:

[0006]

[0007]

[0008] Among the raw materials of the above-mentioned carbon dioxide-based TPU foaming resin, the carbon dioxide-based TPU elastic material is synthesized using carbon-based materials such as carbon dioxide collected from the atmospheric environment, which can effectively digest and absorb carbon dioxide in the atmosphere; the combined use of organic nucleating agents and inorganic nucleating agents in the above-mentioned mass fraction range is conducive to the simultaneous existence of homogeneous nucleation and heterogeneous nucleation in the system, which not only reduces the Gibbs free energy required to form bubble nuclei, but also increases the flexibility of the molecular chain, giving full play to the advantages of the two nucleating agents, and increasing the foaming ratio; the compatibilizer plays the role of compatibilizing various raw materials; the biodegradable material is used to improve the soft and hard ratio and other properties of the foaming material. The combination of these components and the above-mentioned mass fraction range of each component are determined through a large number of experiments. The above-mentioned combination and percentage range make the carbon dioxide-based TPU foam material formed by the carbon dioxide-based TPU foaming resin of the present invention have full bio-negative carbon characteristics, which directly contributes to carbon reduction and carbon neutrality.

[0009] In a feasible implementation, the raw materials for preparing the carbon dioxide-based TPU foaming resin include the following components, calculated by mass fraction:

[0010]

[0011] In a feasible implementation, the organic nucleating agent is a hydrazide nucleating agent.

[0012] In a feasible implementation, the inorganic nucleating agent is selected from at least one of nano-sized talc and nano-sized barium sulfate.

[0013] In a feasible implementation, the compatibilizer is an epoxy compatibilizer.

[0014] In a feasible implementation, the biodegradable material is selected from at least one of PBAT and PLA.

[0015] A method for preparing any of the above-mentioned carbon dioxide-based TPU foaming resins comprises the following steps:

[0016] The carbon dioxide-based TPU elastic material, the organic nucleating agent, the inorganic nucleating agent, the compatibilizer and the biodegradable material are uniformly mixed according to mass fractions and then extruded and granulated to obtain the carbon dioxide-based TPU foaming resin.

[0017] The preparation method of the carbon dioxide-based TPU foamed resin of the technical solution of the present invention is simple in process. The prepared carbon dioxide-based TPU foamed resin can effectively digest and absorb carbon dioxide in the atmosphere. The prepared finished product is a standard "negative carbon" material, which has a direct contribution to carbon reduction and carbon neutrality.

[0018] A method for preparing a carbon dioxide-based TPU foam material comprises the following steps:

[0019] The carbon dioxide-based TPU foaming resin is foamed and molded to obtain a carbon dioxide-based TPU foaming material.

[0020] The preparation method of the carbon dioxide-based TPU foam material of the technical solution of the present invention is simple in process. The carbon dioxide content in the prepared carbon dioxide-based TPU foam material is 10% to 40%, which can effectively digest and absorb carbon dioxide in the atmosphere and make a direct contribution to carbon reduction and carbon neutrality.

[0021] A carbon dioxide-based TPU foam material is prepared by using the above-mentioned method for preparing the carbon dioxide-based TPU foam material.

[0022] The carbon dioxide content in the carbon dioxide-based TPU foaming material of the technical solution of the present invention is 10% to 40%, which can effectively digest and absorb carbon dioxide in the atmosphere and make a direct contribution to carbon reduction and carbon neutrality.

[0023] A foamed product is prepared by using the above-mentioned carbon dioxide-based TPU foaming material.

[0024] The foamed product of the technical solution of the present invention can effectively digest and absorb carbon dioxide in the atmosphere, and has a direct contribution to carbon reduction and carbon neutrality.

[0025] In a feasible implementation, the foamed product is a yoga mat, a crawling mat or a shoe material. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 Flowchart of a method for preparing a carbon dioxide-based TPU foaming resin according to one embodiment of the present invention;

[0027] Figure 2 The present invention is a flowchart of a method for preparing a carbon dioxide-based TPU foam material according to an embodiment of the present invention. DETAILED DESCRIPTION

[0028] To make the above-mentioned objects, features, and advantages of the present invention more readily apparent, specific embodiments of the present invention are described in detail below with reference to the accompanying drawings. The following description sets forth numerous specific details to facilitate a full understanding of the present invention. However, the present invention can be implemented in many other ways than those described herein, and those skilled in the art may make similar modifications without departing from the scope of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0029] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this invention pertains. The terms used in this specification of the present invention are for the purpose of describing specific embodiments only and are not intended to limit the present invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0030] The carbon dioxide-based TPU foaming resin of one embodiment includes the following components in terms of mass fraction:

[0031]

[0032] Among the raw materials of the above-mentioned carbon dioxide-based TPU foaming resin, the carbon dioxide-based TPU elastic material is synthesized using carbon-based materials such as carbon dioxide collected from the atmospheric environment, and can effectively digest and absorb carbon dioxide in the atmosphere.

[0033] Among the raw materials of the above-mentioned carbon dioxide-based TPU foaming resin, the combined use of organic nucleating agents and inorganic nucleating agents in the above-mentioned mass fraction range is conducive to the simultaneous existence of homogeneous nucleation and heterogeneous nucleation in the system, which not only reduces the Gibbs free energy required to form bubble nuclei, but also increases the flexibility of the molecular chain, brings out the advantages of the two nucleating agents, and increases the foaming ratio.

[0034] Among the raw materials of the above-mentioned carbon dioxide-based TPU foaming resin, the compatibilizer plays the role of compatibilizing various raw materials; the biodegradable material is used for biodegradation, is environmentally friendly, and is also used to improve the properties of the foaming material, such as the softness and hardness ratio.

[0035] The combination of these components and the above-mentioned mass fraction range of each component are determined through a large number of experiments. The above-mentioned combination and percentage range make the carbon dioxide-based TPU foam material formed by the carbon dioxide-based TPU foam resin of the present invention have full bio-negative carbon characteristics, which directly contributes to carbon reduction and carbon neutrality.

[0036] On the basis of the above embodiment, the raw materials for preparing the carbon dioxide-based TPU foaming resin include the following components in terms of mass fraction:

[0037]

[0038] Based on the above embodiment, the organic nucleating agent is a hydrazide nucleating agent, which can increase the crystallization rate, optimize the cell structure of the foaming material, and improve the mechanical properties of the foaming material.

[0039] Based on the aforementioned embodiment, the inorganic nucleating agent is selected from at least one of nano-sized talc and nano-sized barium sulfate. Combining these inorganic nucleating agents with a hydrazide nucleating agent can further reduce the Gibbs free energy required to form bubble nuclei while increasing the flexibility of the molecular chain, leveraging the advantages of both nucleating agents and increasing the foaming ratio.

[0040] Based on the above embodiment, the compatibilizer is an epoxy compatibilizer. The epoxy compatibilizer can improve the compatibility of different materials, so that these materials can be better combined with each other.

[0041] Based on the above embodiment, the biodegradable material is selected from at least one of PBAT and PLA. Both PBAT (Poly (butylene adipate-co-terephthalate)) and PLA (polylactic acid) have excellent biodegradability and are important for preparing fully biobased and biodegradable foaming resins.

[0042] Among the raw materials of the carbon dioxide-based TPU foaming resin of the technical solution of the present invention, the carbon dioxide-based TPU elastic material is synthesized using carbon-based materials such as carbon dioxide collected from the atmospheric environment, which can effectively digest and absorb carbon dioxide in the atmosphere; the combined use of organic nucleating agents and inorganic nucleating agents in the above mass fraction range is conducive to the simultaneous existence of homogeneous nucleation and heterogeneous nucleation in the system, which not only reduces the Gibbs free energy required to form bubble nuclei, but also increases the flexibility of the molecular chain, giving full play to the advantages of the two nucleating agents, and increasing the foaming ratio; the compatibilizer plays the role of compatibilizing various raw materials; the biodegradable material is used to improve the soft and hard ratio and other properties of the foaming material. The combination of these components and the above mass fraction range of each component are determined through a large number of experiments. The above combination and percentage range make the carbon dioxide-based TPU foaming material formed by the carbon dioxide-based TPU foaming resin of the present invention have full bio-negative carbon characteristics, which directly contributes to carbon reduction and carbon neutrality.

[0043] See Figure 1 The method for preparing any of the above-mentioned carbon dioxide-based TPU foamed resins according to one embodiment of the present invention comprises the following steps:

[0044] S10. According to the mass fractions, the carbon dioxide-based TPU elastic material, the organic nucleating agent, the inorganic nucleating agent, the compatibilizer and the biodegradable material are uniformly mixed and then extruded and granulated to obtain a carbon dioxide-based TPU foaming resin.

[0045] In step S10, extrusion granulation can be performed by a twin-screw extruder. The prepared carbon dioxide-based TPU foam resin can be widely used in the fields of yoga mats, climbing mats, shoe materials, etc.

[0046] The preparation method of the carbon dioxide-based TPU foamed resin of the technical solution of the present invention is simple in process. The prepared carbon dioxide-based TPU foamed resin can effectively digest and absorb carbon dioxide in the atmosphere. The prepared finished product is a standard "negative carbon" material, which has a direct contribution to carbon reduction and carbon neutrality.

[0047] See Figure 2 A method for preparing a carbon dioxide-based TPU foam material according to one embodiment of the present invention comprises the following steps:

[0048] S20 , foaming and molding the carbon dioxide-based TPU foaming resin obtained in step S10 to obtain a carbon dioxide-based TPU foaming material.

[0049] In one feasible implementation, the CO2-based TPU foamed resin obtained in step S10 is foamed and then heat-set at 120°C to 150°C. Furthermore, the heat-setting temperature may be, but is not limited to, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, or 150°C. The heat-setting time may be 100 seconds to 500 seconds, depending on factors such as thickness and temperature.

[0050] Furthermore, in the method for preparing the carbon dioxide-based TPU foam material of the present invention, the foaming can be physical foaming or chemical foaming. The physical foaming step comprises: passing the carbon dioxide-based TPU foam resin obtained in step S10 into a supercritical fluid for foaming. The supercritical fluid is selected from at least one of supercritical carbon dioxide and supercritical nitrogen. The foaming temperature is 150°C to 165°C, and the pressure is above 12 MPa.

[0051] The chemical foaming process involves uniformly mixing the carbon dioxide-based TPU foaming resin obtained in step S10 with a chemical foaming agent, and then heating the mixture to decompose the chemical foaming agent and generate gas, thereby promoting foaming of the TPU polymer. The chemical foaming agent may be an azo compound, a nitroso compound, an inorganic compound, or a hydrazine.

[0052] Carbon dioxide-based TPU foaming material The carbon dioxide-based TPU foaming material prepared in step S20 is a fully bio-carbon-negative foaming elastic material, which can be widely used in yoga mats, crawling mats, shoe materials and other fields.

[0053] The preparation method of the carbon dioxide-based TPU foam material of the technical solution of the present invention is simple in process. The carbon dioxide content in the prepared carbon dioxide-based TPU foam material is 10% to 40%, which can effectively digest and absorb carbon dioxide in the atmosphere and make a direct contribution to carbon reduction and carbon neutrality.

[0054] The carbon dioxide-based TPU foam material of one embodiment is prepared by using the above-mentioned method for preparing the carbon dioxide-based TPU foam material.

[0055] The carbon dioxide content in the carbon dioxide-based TPU foaming material of the technical solution of the present invention is 10% to 40%, which can effectively digest and absorb carbon dioxide in the atmosphere and make a direct contribution to carbon reduction and carbon neutrality.

[0056] A foamed product according to one embodiment is prepared using the above-mentioned carbon dioxide-based TPU foaming material.

[0057] The foamed material can be injected into a mold or formed through other molding processes, and then solidified in the mold or in a specific shape to obtain a foamed product of the desired shape and size.

[0058] In a feasible implementation, the foamed product is a yoga mat, a crawling mat or a shoe material.

[0059] The foamed product of the technical solution of the present invention can effectively digest and absorb carbon dioxide in the atmosphere, and has a direct contribution to carbon reduction and carbon neutrality.

[0060] With reference to the above implementation contents, in order to make the technical solution of the present invention more specific, clear and easy to understand, the technical solution of the present invention is now given as an example. However, it should be noted that the content to be protected by the present invention is not limited to the following embodiments.

[0061] Example 1 to Example 6

[0062] The preparation process of the carbon dioxide-based TPU foamed resin and the carbon dioxide-based TPU foamed material of Examples 1 to 6 is as follows:

[0063] Weigh the raw materials according to Table 1, mix the carbon dioxide-based TPU elastic material, organic nucleating agent, inorganic nucleating agent, compatibilizer and biodegradable material evenly, and then extrude and granulate to obtain a carbon dioxide-based TPU foaming resin;

[0064] The obtained carbon dioxide-based TPU foaming material was introduced into supercritical carbon dioxide for foaming at a foaming pressure of 12 MPa, a foaming temperature of 150° C., and a foaming time of 2 h to obtain a carbon dioxide-based TPU foaming material.

[0065] Table 1 Raw materials of carbon dioxide-based TPU foaming resin and carbon dioxide-based TPU foaming material of Examples 1 to 6

[0066]

[0067] Notes: (1) The source of the carbon dioxide-based TPU elastic material in Examples 1 to 6 is: the manufacturer is Suzhou Kunsheng Biodegradable New Materials Co., Ltd., brand T1; (2) The copolymer of MMA and GMA is a copolymer of methyl methacrylate (MMA) and glycidyl methacrylate (GMA).

[0068] Performance testing:

[0069] (1) The carbon dioxide-based TPU foamed resins obtained in Examples 1 to 6 were tested. The test standards and test results are shown in Table 2.

[0070] Table 2 Test standards and test results of carbon dioxide-based TPU foaming resins of Examples 1 to 6

[0071]

[0072] In Table 2, “-” indicates that the value is within the standard range.

[0073] As shown in Table 2, the moisture content, tensile strength, and elongation at break of the CO2-based TPU foamed resins of Examples 1 to 6 of the present invention are all within the test standard ranges. The ash content and density have relatively small deviations from their respective standard values, indicating that the CO2-based TPU foamed resins of Examples 1 to 6 of the present invention have good overall performance and meet the relevant test standards. The CO2-based TPU foamed resins of the present invention, including CO2-based TPU elastic materials, can effectively absorb atmospheric carbon dioxide, exhibiting full bio-negative carbon properties and directly contributing to carbon reduction and carbon neutrality.

[0074] (2) The foaming ratio of the carbon dioxide-based TPU foam material obtained in Examples 1 to 6 was calculated according to the following formula to obtain Table 3.

[0075] Foaming ratio = volume after foaming / original volume;

[0076] Table 3 Foaming ratio of carbon dioxide-based TPU foam materials of Examples 1 to 6

[0077] Example Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Foaming ratio 10 15 20 16 14 15

[0078] It can be seen from Table 3 that the foaming ratios of the carbon dioxide-based TPU foam materials of Examples 1 to 6 of the present invention are between 10 and 20 times, and the foaming ratios are generally high.

[0079] The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, not all possible combinations of the technical features in the above-mentioned embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0080] The above-described embodiments merely illustrate several implementations of the present invention, and while their descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent. It should be noted that a person skilled in the art would be able to make numerous variations and improvements without departing from the spirit of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent for this invention shall be determined by the appended claims.

Claims

1. A carbon dioxide-based TPU foaming resin, characterized in that: The raw materials for preparing the carbon dioxide-based TPU foaming resin include the following components by mass fraction:

2. The carbon dioxide-based TPU foamed resin according to claim 1, characterized in that: The raw materials for preparing the carbon dioxide-based TPU foaming resin include the following components by mass fraction:

3. The carbon dioxide-based TPU foamed resin according to claim 1, characterized in that: The organic nucleating agent is a hydrazide nucleating agent; the inorganic nucleating agent is selected from at least one of nano-grade talc and nano-grade barium sulfate.

4. The carbon dioxide-based TPU foamed resin according to claim 1, characterized in that: The compatibilizer is an epoxy compatibilizer.

5. The carbon dioxide-based TPU foamed resin according to claim 1, characterized in that: The biodegradable material is selected from at least one of PBAT and PLA.

6. A method for preparing a carbon dioxide-based TPU foamed resin according to any one of claims 1 to 5, characterized in that: The steps include: According to the mass fraction, the carbon dioxide-based TPU elastic material, the organic nucleating agent, the inorganic nucleating agent, the compatibilizer and the biodegradable material are uniformly mixed and then extruded and granulated to obtain the carbon dioxide-based TPU foaming resin.

7. A method for preparing a carbon dioxide-based TPU foam material, characterized in that: The steps include: The carbon dioxide-based TPU foamed resin obtained in claim 6 is foamed and molded to obtain a carbon dioxide-based TPU foamed material.

8. A carbon dioxide-based TPU foam material, characterized in that: The carbon dioxide-based TPU foam material is prepared by the preparation method of claim 7.

9. A foamed product, characterized in that: It is prepared by using the carbon dioxide-based TPU foaming material described in claim 8.

10. The foamed product according to claim 9, characterized in that: The foamed product is a yoga mat, a crawling mat or a shoe material.

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