Polyurethane composite material, preparation method thereof and cold-resistant protective equipment

Abstract

The invention relates to the technical field of high-molecular polymers, in particular to a polyurethane composite material, a preparation method thereof and cold-resistant protective equipment. The polyurethane composite material is prepared from the following raw materials: polysiloxane of which a blocking group comprises sulfydryl, a first crosslinking agent containing alkenyl, a photoinitiator, polyether polyol, a second crosslinking agent, cyclodextrin containing amino and / or hydroxyl, isocyanate, a catalyst and a solvent. The polyurethane composite material disclosed by the invention has wide-temperature-range high impact resistance and wide-temperature-range flexibility, and meets the requirements of protective equipment for high and cold sports such as skiing and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high molecular polymers, in particular to a polyurethane composite material, a preparation method thereof and cold-resistant protective equipment. BACKGROUND

[0002] With the vigorous development of global outdoor sports, the market demand for sports protective equipment continues to grow, and the product types are increasingly diversified, covering motorcycle riding clothes, skiing clothes, equestrian protective vests, roller skating protective equipment, and professional sports protective equipment such as American football, soccer, and basketball.

[0003] Polyurethane (PU) materials have become the core material of protective equipment due to their excellent softness, comfort, and impact energy absorption capacity in room temperature environments. However, the material has a significant temperature sensitivity defect: for example, in low-temperature scenarios (such as skiing and high-altitude riding), the hardness of PU rises sharply, resulting in a sharp drop in comfort, and the deterioration of flexibility also leads to a significant attenuation of damping performance, which not only causes the protective equipment to lose its protective function, but also causes the material itself to be easily damaged due to brittleness.

[0004] Some polyurethane elastomers reported so far can have high damping performance in a wide temperature range, but they do not consider the softness and comfort of the material, and cannot overcome the problem of hardness rising at low temperatures. Therefore, developing polyurethane materials with both wide-temperature-range flexibility and wide-temperature-range impact resistance has become a technical bottleneck that needs to be broken through in the field of sports protection. SUMMARY

[0005] Based on this, the first aspect of the present application provides a polyurethane composite material, and the technical scheme is as follows:

[0006] A polyurethane composite material, the raw materials of which include polysiloxane with a capping group containing a mercapto group, a first crosslinking agent containing an alkenyl group, a photoinitiator, a polyether polyol, a second crosslinking agent, cyclodextrin containing an amine group and / or a hydroxyl group, isocyanate, a catalyst, and a solvent.

[0007] The second aspect of the present application provides a preparation method of a polyurethane composite material, and the technical scheme is as follows:

[0008] A preparation method of a polyurethane composite material, comprising the following steps:

[0009] Mixing polysiloxane with a capping group containing a mercapto group, a first crosslinking agent containing an alkenyl group, a photoinitiator, a polyether polyol, a second crosslinking agent, isocyanate, and a solvent to obtain a solution;

[0010] Irradiating with ultraviolet light to cause a mercapto-alkene click reaction to obtain an intermediate product;

[0011] The intermediate product is added with cyclodextrin containing amine group and / or hydroxyl group and a catalyst, a cross-linking reaction occurs, and a polyurethane composite material is obtained.

[0012] The third aspect of the present application provides a cold-resistant protective equipment, the material of which comprises the polyurethane composite material as described above.

[0013] Compared with the traditional scheme, the present application has the following beneficial effects:

[0014] The raw materials of the polyurethane composite material of the present application can construct a unique structure of polyurethane and polysiloxane interpenetrating network through thiol-ene click reaction and cross-linking reaction. The interpenetrating network improves the compatibility of the two systems, better utilizes the advantages of each component, effectively combines the high mechanical strength of polyurethane and the low-temperature flexibility of polysiloxane, significantly reduces the glass transition temperature of the composite material, and still maintains flexibility in outdoor severe cold conditions, ensuring wear comfort. At the same time, by introducing cyclodextrin containing amine group and / or hydroxyl group, hydrogen bonds can be formed with the urethane groups in the polyurethane chain segment to enhance the network, improve the impact resistance, and make the composite material have high energy absorption efficiency and good damping performance in a wide temperature range, with excellent energy absorption and buffering characteristics. The polyurethane composite material of the present application has good low-temperature adaptability, can solve the problem of protective failure caused by low-temperature embrittlement of traditional materials, and still maintains good impact resistance and flexibility in severe cold environments, and has wide-temperature-range high impact resistance and wide-temperature-range softness, meeting the needs of skiing, cycling and other high-cold sports protective equipment, and can be expanded to the industrial buffering field as a high-performance damping material, meeting the diversified protection and damping needs. DETAILED DESCRIPTION

[0015] The present application will be further described in detail below in conjunction with specific embodiments. The present application can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present application more thorough and comprehensive.

[0016] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present application belongs. The terms used in the specification of the present application are only for the purpose of describing specific embodiments and are not intended to limit the present application.

[0017] Unless otherwise stated or contradictory, the terms or phrases used herein have the following meanings:

[0018] In the present application, "multiple", "various", "multiple times", "multiple" and the like are used, and unless otherwise specified, it means greater than or equal to 2 in quantity. For example, "one or more" means one or more than two.

[0019] In the present application, the terms "first", "second", "third", "fourth" and the like in the "first aspect", "second aspect", "third aspect", "fourth aspect" and the like are only used for description purposes, and cannot be understood as indicating or implying relative importance or quantity, nor can it be understood as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first", "second", "third", "fourth" and the like only serve the purpose of non-exhaustive enumeration description, and should be understood as not constituting a closed limitation on the quantity.

[0020] The first aspect of the present application provides a polyurethane composite material. In one embodiment, the raw materials of the polyurethane composite material include: a polysiloxane capped with a thiol group, a first cross-linking agent containing an alkenyl group, a photoinitiator, a polyether polyol, a second cross-linking agent, a cyclodextrin containing an amine group and / or a hydroxyl group, an isocyanate, a catalyst and a solvent.

[0021] Optionally, the polysiloxane capped with a thiol group is selected from a mercaptopropyl-capped polysiloxane. Polydimethylsiloxane (PDMS) can maintain its elasticity and stability within a wide temperature range, has a low glass transition temperature, and optionally, the polysiloxane capped with a thiol group is selected from a polydimethylsiloxane capped with a thiol group. Optionally, the polysiloxane capped with a thiol group is selected from a mercaptopropyl-capped polydimethylsiloxane.

[0022] Optionally, the weight average molecular weight of the polysiloxane capped with a thiol group is 1000 Da to 10000 Da.

[0023] Optionally, the first cross-linking agent containing an alkenyl group includes a first cross-linking agent containing an allyl group. Optionally, the number of allyl groups in the first cross-linking agent is at least 3. Preferably, the number of allyl groups in the first cross-linking agent is 3. Optionally, the first cross-linking agent containing an alkenyl group includes one or more of methyltriallylsilane, triallylmethoxysilane and triallyl(phenyl)silane. Preferably, it is methyltriallylsilane.

[0024] Optionally, the weight fraction of the polysiloxane capped with a thiol group is 30 to 80 parts, and the weight fraction of the first cross-linking agent containing an alkenyl group is 1 to 10 parts. Adjusting the weight fraction of the polysiloxane capped with a thiol group and the first cross-linking agent containing an alkenyl group can optimize the impact energy attenuation performance of the polyurethane composite material in a low temperature environment. Optionally, the weight fraction of the polysiloxane capped with a thiol group is 40 to 70 parts, and the weight fraction of the first cross-linking agent containing an alkenyl group is 4 to 8 parts. Optionally, the weight fraction of the polysiloxane capped with a thiol group is 40 to 60 parts, and the weight fraction of the first cross-linking agent containing an alkenyl group is 4 to 6 parts.

[0025] The polysiloxane with a capping group including a mercapto group and the first cross-linking agent including an alkenyl group can undergo a mercenyl group-alkenyl group click reaction in the presence of a photoinitiator by ultraviolet light irradiation. Optionally, the photoinitiator includes one or more of benzoin dimethyl ether (DMPA), 2,4,6-trimethylbenzoylphenyl phosphinate, and (2,4,6-trimethylbenzoyl)diphenylphosphine oxide. Preferably, the photoinitiator is DMPA. Optionally, the photoinitiator is in a weight fraction of 0.05 to 3 parts. Understandably, the weight fraction is relative to the weight fraction of the polysiloxane with a capping group including a mercapto group, i.e., when the raw materials of the polyurethane composite include 30 to 80 parts of the polysiloxane with a capping group including a mercapto group, the weight fraction of the photoinitiator is 0.05 to 3 parts. Optionally, the weight fraction of the photoinitiator is 0.5 to 2 parts.

[0026] The polyether polyol is a main raw material for cross-linking to form a polyurethane network. Optionally, the weight average molecular weight of the polyether polyol is 1000 Da to 7000 Da. Optionally, the functionality of the polyether polyol is 2 to 4. Optionally, the starter of the polyether polyol includes glycerol. Optionally, the weight fraction of the polyether polyol is 30 to 80 parts. Understandably, the weight fraction is relative to the weight fraction of the polysiloxane with a capping group including a mercapto group, i.e., when the raw materials of the polyurethane composite include 30 to 80 parts of the polysiloxane with a capping group including a mercapto group, the weight fraction of the polyether polyol is 30 to 80 parts. Optionally, the weight fraction of the polyether polyol is 30 to 60 parts. Optionally, the weight fraction of the polyether polyol is 40 to 60 parts.

[0027] The addition of the cyclodextrin including an amine group and / or a hydroxyl group can introduce the cyclodextrin on the polyurethane side chain, which further forms a hydrogen bond with the urethane group in the polyurethane segment, and is beneficial to improve the damping performance and impact resistance of the material. Preferably, the cyclodextrin including an amine group. Optionally, the cyclodextrin including an amine group includes hexanediamine-cyclodextrin (CD-NH2). Optionally, the weight fraction of the cyclodextrin including an amine group and / or a hydroxyl group is 1 to 15 parts. Understandably, the weight fraction is relative to the weight fraction of the polysiloxane with a capping group including a mercapto group, i.e., when the raw materials of the polyurethane composite include 30 to 80 parts of the polysiloxane with a capping group including a mercapto group, the weight fraction of the cyclodextrin including an amine group and / or a hydroxyl group is 1 to 15 parts. Optionally, the weight fraction of the cyclodextrin including an amine group and / or a hydroxyl group is 1 to 10 parts.

[0028] Optionally, the second cross-linking agent includes one or more of an alcohol compound having a functionality of 2 to 4 and an amine compound having a functionality of 2 to 4. Preferably, one or more of an alcohol compound having a functionality of 3 and an amine compound having a functionality of 3. Optionally, the second cross-linking agent includes one or more of diethanolamine, triethanolamine, and glycerol. Optionally, the second cross-linking agent is in a weight amount of 1 to 5 parts. It is understood that the above weight amount is with respect to the weight amount of the polysiloxane having a terminal group including a mercapto group, i.e., when the raw material of the polyurethane composite includes 30 to 80 parts of the polysiloxane having a terminal group including a mercapto group, the second cross-linking agent is in a weight amount of 1 to 5 parts. Optionally, the second cross-linking agent is in a weight amount of 1 to 3 parts.

[0029] Optionally, the isocyanate includes one or more of a urethane-modified diphenylmethane diisocyanate (MDI), a polymeric diphenylmethane diisocyanate (polymeric MDI), 4,4-diphenylmethane diisocyanate (4,4-MDI) MDI, 2,4-diphenylmethane diisocyanate (2,4-MDI), a carbodiimide-modified toluene diisocyanate (TDI), and isophorone diisocyanate (IPDI). Preferably, the urethane-modified MDI. Optionally, the isocyanate is in a weight amount of 30 to 60 parts. It is understood that the above weight amount is with respect to the weight amount of the polysiloxane having a terminal group including a mercapto group, i.e., when the raw material of the polyurethane composite includes 30 to 80 parts of the polysiloxane having a terminal group including a mercapto group, the isocyanate is in a weight amount of 30 to 60 parts. Optionally, the isocyanate is in a weight amount of 40 to 60 parts.

[0030] Optionally, the catalyst includes one or more of an amine catalyst, an organotin compound catalyst, and an organobismuth compound catalyst. Preferably, the amine catalyst. Optionally, the catalyst is in a weight amount of 0.05 to 3 parts. It is understood that the above weight amount is with respect to the weight amount of the polysiloxane having a terminal group including a mercapto group, i.e., when the raw material of the polyurethane composite includes 30 to 80 parts of the polysiloxane having a terminal group including a mercapto group, the catalyst is in a weight amount of 0.05 to 3 parts. Optionally, the catalyst is in a weight amount of 0.5 to 2 parts.

[0031] Optionally, the solvent includes one or more of tetrahydrofuran, N,N-dimethylformamide (DMF), and ethyl acetate. Preferably, the DMF. Optionally, the solvent is in a weight amount of 20 to 50 parts. It is understood that the above weight amount is with respect to the weight amount of the polysiloxane having a terminal group including a mercapto group, i.e., when the raw material of the polyurethane composite includes 30 to 80 parts of the polysiloxane having a terminal group including a mercapto group, the solvent is in a weight amount of 20 to 50 parts. Optionally, the solvent is in a weight amount of 20 to 30 parts.

[0032] In some embodiments, the polyurethane composite comprises the following raw materials by weight:

[0033] mercapto propyl terminated polydimethylsiloxane 30-80 parts, allyl containing first crosslinking agent 1-10 parts, photoinitiator 0.05-3 parts, polyether polyol 30-80 parts, second crosslinking agent 1-5 parts, hexanediamine-cyclodextrin 1-15 parts, isocyanate 30-60 parts, catalyst 0.05-3 parts, and solvent 20-50 parts.

[0034] In some embodiments, the polyurethane composite comprises the following raw materials by weight:

[0035] mercapto propyl terminated polydimethylsiloxane 30-80 parts, allyl containing first crosslinking agent 1-10 parts, photoinitiator 0.05-3 parts, polyether polyol 30-80 parts, second crosslinking agent 1-5 parts, hexanediamine-cyclodextrin 1-15 parts, isocyanate 30-60 parts, catalyst 0.05-3 parts, and solvent 20-50 parts.

[0036] The raw materials of the polyurethane composite of the present embodiment can construct a unique structure of polyurethane and polysiloxane interpenetrating network through mercapto-ene click reaction and crosslinking reaction. The interpenetrating network improves the compatibility of the two systems, better utilizes the advantages of each component, effectively combines the high mechanical strength of polyurethane and the low temperature flexibility of polysiloxane, significantly reduces the glass transition temperature of the composite, and still maintains flexibility in outdoor severe cold conditions, ensuring wear comfort. At the same time, by introducing cyclodextrin containing amine and / or hydroxyl groups, hydrogen bonds can be formed with the urethane groups in the polyurethane segment to enhance the network, improve the impact resistance, and make the composite have high energy absorption efficiency in a wide temperature range, good damping performance, and excellent energy absorption and buffering characteristics. The polyurethane composite of the present application has good low temperature adaptability, can solve the problem of protection failure caused by low temperature embrittlement of traditional materials, and still maintains good impact resistance and flexibility in severe cold environments, has wide temperature range high impact resistance and wide temperature range softness, meets the demand of skiing, cycling and other high-cold sports protective equipment, and can be expanded to industrial damping field as high-performance damping material to meet diversified protection and damping needs.

[0037] The second aspect of the present application provides a preparation method of a polyurethane composite, and the technical scheme is as follows:

[0038] A preparation method of a polyurethane composite, comprising the following steps:

[0039] mixing the polysiloxane with a capped group containing mercapto, the first crosslinking agent containing allyl, the photoinitiator, the polyether polyol, the second crosslinking agent, the isocyanate, and the solvent to obtain a solution;

[0040] irradiating the solution with ultraviolet light to cause a mercapto-ene click reaction and obtain an intermediate product;

[0041] A cyclodextrin containing amine and / or hydroxyl groups and a catalyst are added to the intermediate product to conduct a crosslinking reaction, thereby obtaining a polyurethane composite material.

[0042] Optionally, the temperature of the mixed end-capping groups, including thiol-based polysiloxanes, alkenyl-based first crosslinking agents, photoinitiators, polyether polyols, second crosslinking agents, isocyanates, and solvents, is 15°C to 20°C.

[0043] Optionally, the wavelength of the ultraviolet light irradiation is 320 nm to 400 nm. Optionally, the ambient temperature of the solution during ultraviolet light irradiation is 15 °C to 20 °C. Optionally, the duration of ultraviolet light irradiation is 20 min to 40 min.

[0044] Optionally, the ambient temperature for the crosslinking reaction is 60℃~80℃. Optionally, the reaction time is 1.5h~2.5h.

[0045] Understandably, after cross-linking, the resulting liquid is cured to obtain a polyurethane composite material.

[0046] The above preparation method incorporates a click reaction method for thiolene, which is simple and easy to implement.

[0047] A third aspect of this application provides a cold-resistant protective equipment. In one embodiment, the material of the cold-resistant protective equipment includes the polyurethane composite material described above.

[0048] The cold-resistant protective equipment of this embodiment combines high impact resistance over a wide temperature range with softness over a wide temperature range.

[0049] The following description is further illustrated with specific embodiments and comparative examples. The grades and manufacturers of the raw materials involved in the following embodiments and comparative examples are shown in Table 1. Unless otherwise specified, the processes involved in the following embodiments and comparative examples are conventional choices made by those skilled in the art.

[0050] Table 1

[0051]

[0052] Example 1

[0053] This embodiment provides a protective gear made of polyurethane composite material and its preparation method, the steps of which are as follows:

[0054] Step 1: According to the weight proportions shown in Table 2, add mercaptopropyl-terminated polydimethylsiloxane, methyltriallylsilane, and benzoin dimethyl ether into the reaction vessel and stir. Then, add WANOL sequentially. ® F3128, Diethanolamine, Wannatate ®8611 and DMF were mechanically stirred for 30 minutes under nitrogen protection and at 18°C ​​to obtain a homogeneous solution.

[0055] Step 2: Maintain the ambient temperature of the solution at 18℃, and irradiate the solution with ultraviolet light (UVA) (360nm) for 30 minutes to promote the click reaction of mercaptoene, thereby forming a PDMS network and obtaining the intermediate product.

[0056] Step 3: Raise the ambient temperature of the intermediate product to 70°C, and add WANALYST sequentially. ® KC100 and hexamethylenediamine-cyclodextrin are cross-linked to form a PU network by being kept at a constant temperature for 2 hours. The resulting liquid is poured into the mold of the protective gear and cured in a vacuum oven at 80°C for 12 hours. The protective gear is then demolded to obtain a PU composite material made of PDMS and PU interpenetrating network.

[0057] Table 2

[0058]

[0059] Examples 2-6

[0060] Referring to the raw materials and weight parts in Table 2 and the protective gear made of polyurethane composite material in Example 1 and its preparation method, polyurethane composite materials of Examples 2-6 were prepared.

[0061] Comparative Examples 1-4

[0062] Referring to the raw materials and weight parts in Table 2 and the protective gear made of polyurethane composite material in Example 1 and its preparation method, polyurethane composite materials of Comparative Examples 1-4 were prepared.

[0063] The hardness and impact resistance of the protective gear from the above embodiments and comparative examples were tested at both room temperature and low temperature. The room temperature test condition was 24.7℃, and the low temperature test condition was -18℃. For the low temperature test, the protective gear was placed at -18℃ for 24 hours before the test. The impact resistance test method followed the specifications and test procedures of EN / BSEN1621-1:2012, Clause 5.4, with an impact energy of 50J. The test results for each embodiment and comparative example are shown in Table 3.

[0064] Table 3

[0065]

[0066] As shown in Table 3:

[0067] (1) The protective gear materials in each embodiment have good flexibility and good damping and buffering characteristics at room temperature and low temperature, indicating that the polyurethane composite material is resistant to low temperature and exhibits excellent flexibility and high impact resistance over a wide temperature range.

[0068] (2) In Examples 1 and 2, by adjusting the weight proportions of mercaptopropyl-terminated polydimethylsiloxane and methyltriallylsilane, the impact energy attenuation performance in low-temperature environments can be precisely optimized while maintaining the flexibility and comfort of the protective gear material. In Examples 1 and 5, the addition of triallyl methoxysilane and the addition of methyltriallylsilane have little impact on the performance of the material.

[0069] (3) Compared to Comparative Example 3, the addition of hexamethylenediamine-cyclodextrin in Comparative Example 1 can adjust the impact attenuation performance of the protective gear material at room temperature and low temperature. Compared to Comparative Example 2, the addition of hexamethylenediamine-cyclodextrin in Examples 1, 3, and 4 resulted in better damping characteristics and improved impact resistance of the protective gear material at both room temperature and low temperature. In Examples 1, 3, and 4, the impact force test values ​​showed a systematic downward trend as the amount of hexamethylenediamine-cyclodextrin increased, indicating that the better the damping of the protective gear material, the better its impact resistance. In Examples 1 and 6, the addition of mono-(6-triethylenetetramine-6-deoxy)-β-cyclodextrin and the addition of hexamethylenediamine-cyclodextrin had little effect on the performance of the material.

[0070] (4) Compared with Comparative Example 1, the addition of polydimethylsiloxane in Comparative Example 4 has almost no improvement on the flexibility of the protective gear material at low temperature, and may even reduce the damping performance of the material at room temperature. However, the addition of mercaptopropyl-terminated polydimethylsiloxane in Example 4 improves the flexibility of the protective gear material at low temperature, and it has good damping performance at both room temperature and low temperature, and good impact resistance.

[0071] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above 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.

[0072] The embodiments described above are merely illustrative of several implementation methods of this application, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this patent application should be determined by the appended claims.

Claims

1. A polyurethane composite material, characterized in that, Its raw materials include: polysiloxanes with end-capping groups including thiol groups, a first crosslinking agent containing alkenyl groups, a photoinitiator, a polyether polyol, a second crosslinking agent, cyclodextrin containing amino groups and / or hydroxyl groups, isocyanates, catalysts, and solvents.

2. The polyurethane composite material according to claim 1, characterized in that, The polysiloxane with a thiol-terminated group is selected from mercaptopropyl-terminated polysiloxanes; optionally, the polysiloxane with a thiol-terminated group is selected from polydimethylsiloxane with a thiol-terminated group; optionally, the polysiloxane with a thiol-terminated group is selected from polydimethylsiloxane with a thiol-terminated group.

3. The polyurethane composite material according to claim 2, characterized in that, The weight-average molecular weight of the polysiloxanes whose end-capping groups include thiol groups is 1000 Da to 10000 Da.

4. The polyurethane composite material according to claim 1, characterized in that, The alkenyl-containing first crosslinking agent includes an allyl-containing first crosslinking agent; optionally, the number of allyl groups in the first crosslinking agent is at least 3; optionally, the alkenyl-containing first crosslinking agent includes one or more of methyltriallylsilane, triallylmethoxysilane and triallyl(phenyl)silane.

5. The polyurethane composite material according to claim 1, characterized in that, The polysiloxane with thiol-containing end-capping groups comprises 30-80 parts by weight, and the first crosslinking agent containing alkenyl groups comprises 1-10 parts by weight; optionally, the polysiloxane with thiol-containing end-capping groups comprises 40-70 parts by weight, and the first crosslinking agent containing alkenyl groups comprises 4-8 parts by weight; optionally, the polysiloxane with thiol-containing end-capping groups comprises 40-60 parts by weight, and the first crosslinking agent containing alkenyl groups comprises 4-6 parts by weight.

6. The polyurethane composite material according to claim 1, characterized in that, The cyclodextrin containing amino and / or hydroxyl groups satisfies at least one of the following conditions: (1) The amine-containing cyclodextrin includes hexamethylenediamine-cyclodextrin; (2) The cyclodextrin containing amino groups and / or hydroxyl groups is 1 to 15 parts by weight; optionally, the cyclodextrin containing amino groups and / or hydroxyl groups is 1 to 10 parts by weight.

7. The polyurethane composite material according to any one of claims 1 to 6, characterized in that, The polyether polyol satisfies at least one of the following conditions: (1) The weight-average molecular weight of the polyether polyol is 1000 Da to 7000 Da; (2) The functionality of the polyether polyol is 2 to 4; (3) The initiator of the polyether polyol includes glycerol; (4) The polyether polyol is 30 to 80 parts by weight; optionally, the polyether polyol is 30 to 60 parts by weight; optionally, the polyether polyol is 40 to 60 parts by weight.

8. The polyurethane composite material according to any one of claims 1 to 6, characterized in that, Includes at least one of the following features: (1) The photoinitiator includes one or more of benzoin dimethyl ether, ethyl 2,4,6-trimethylbenzoylphenylphosphonate and (2,4,6-trimethylbenzoyl)diphenylphosphine oxide; (2) The photoinitiator is 0.05 to 3 parts by weight; optionally, the photoinitiator is 0.5 to 2 parts by weight. (3) The second crosslinking agent includes one or more of alcohols with a functionality of 2 to 4 and amines with a functionality of 2 to 4; optionally, the second crosslinking agent includes one or more of diethanolamine, triethanolamine and glycerol; (4) The second crosslinking agent is 1 to 5 parts by weight; optionally, the second crosslinking agent is 1 to 3 parts by weight. (5) The isocyanate includes one or more of urethane-modified MDI, polymeric MDI, 4,4-MDI, 2,4-MDI, carbodiimide-modified TDI, and IPDI; (6) The isocyanate is in the form of 30 to 60 parts by weight; optionally, the isocyanate is in the form of 40 to 60 parts by weight. (7) The catalyst includes one or more of amine catalysts, organotin compound catalysts, and organobismuth compound catalysts; (8) The catalyst is 0.05 to 3 parts by weight; optionally, the catalyst is 0.5 to 2 parts by weight. (9) The solvent includes one or more of tetrahydrofuran, N,N-dimethylformamide and ethyl acetate; (10) The solvent is 20 to 50 parts by weight; optionally, the solvent is 20 to 30 parts by weight.

9. A method for preparing a polyurethane composite material, characterized in that, Includes the following steps: A solution is obtained by mixing a polysiloxane with thiol-containing end-capping groups, a first crosslinking agent containing alkenyl groups, a photoinitiator, a polyether polyol, a second crosslinking agent, an isocyanate, and a solvent; Irradiation with ultraviolet light causes a click reaction of mercaptoene to produce an intermediate product; A cyclodextrin containing amine and / or hydroxyl groups and a catalyst are added to the intermediate product to induce a crosslinking reaction and prepare a polyurethane composite material.

10. A cold-resistant protective equipment, characterized in that, Its material includes the polyurethane composite material as described in any one of claims 1 to 8.

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