Photocuring composite material, preparation method and sports ware

Abstract

The invention discloses a light-cured composite material, a preparation method and a sports protector. The light-cured composite material comprises the following raw materials in parts by weight: 90-110 parts of a polyurethane prepolymer, 45-60 parts of a reaction monomer, 3-5 parts of a catalyst, 0.8-1.2 parts of a polymerization inhibitor and 0.8-1.2 parts of a water-carrying agent, the reaction monomer is acrylic acid hydroxyl ester containing an acylhydrazone bond; acylhydrazone bonds and secondary valence bonds are introduced into the light-cured composite material, so that the light-cured composite material has partial characteristics of non-Newtonian fluid, and the shock absorption and energy absorption effects of the light-cured composite material are improved; in addition, the light-cured composite material disclosed by the invention is good in curing performance, good in flexibility after curing and excellent in buffering and damping performance.

Description

Technical Field

[0001] The invention relates to the technical field of sports protective gear materials, and in particular to a light-cured composite material and a preparation method thereof, and a sports protective gear. Background Art

[0002] Sports protective gear is an important sporting product that can reduce the impact force on athletes' bodies through the cushioning, energy absorption, and pressure resistance of materials, thereby reducing injuries to athletes. They play a vital role in various sports, reducing the occurrence of sports injuries, improving athletes' performance and comfort, and providing protection and support for athletes.

[0003] With the development of technology, the precision of 3D printing technology is getting higher and higher, and more and more fields are using 3D printing technology to meet people's personalized needs. However, the existing 3D printed protective gear products used in the field of sports protection have poor buffering performance. Most of them use the compression deformation of the 3D lattice structure to perform elastic buffering like a spring. This kind of protective gear that buffers by extending the impact time cannot absorb some higher impact forces. This is because the existing 3D printing material - light-cured resin has poor impact absorption capacity, and the buffering capacity is greatly affected by thickness. It is impossible to pass the CE standards with high impact absorption requirements such as EN1621 while ensuring lightness and comfort, which limits the development of 3D printing technology in the field of protective gear under high-speed impact such as skiing, motorcycles, roller skating, military and police.

[0004] In view of this, the present invention is proposed. Summary of the invention

[0005] The purpose of the present invention is to provide a photocurable composite material, a preparation method and a sports protective gear. The photocurable composite material of the present invention introduces secondary bonds so that the photocurable composite material has partial non-Newtonian fluid properties, thereby improving the shock absorption and energy absorption effects of the photocurable composite material.

[0006] In order to achieve the above-mentioned purpose of the present invention, the following technical solutions are particularly adopted:

[0007] A first aspect of the present invention provides a photocurable composite material, wherein the photocurable composite material comprises the following raw materials in parts by weight:

[0008] 90-110 parts of polyurethane prepolymer, 45-60 parts of reactive monomer, 3-5 parts of catalyst, 0.8-1.2 parts of polymerization inhibitor and 0.8-1.2 parts of water-carrying agent;

[0009] The reactive monomer is an acrylic acid hydroxy ester containing an acylhydrazone bond.

[0010] Preferably, the polyurethane prepolymer comprises a hard segment and a soft segment, and the mass ratio of the hard segment to the soft segment is 1:(0.2-0.25).

[0011] Preferably, the hard segment comprises toluene diisocyanate;

[0012] The soft segment comprises terminal hydroxyl polybutadiene-acrylonitrile and polyethylene glycol adipate in a mass ratio of 1: (0.8-1.2).

[0013] Preferably, the polyurethane prepolymer is prepared by the following method:

[0014] The terminal hydroxyl polybutadiene-acrylonitrile and polyethylene glycol propylene glycol adipate are mixed uniformly, water is removed, toluene diisocyanate is added, and then reacted at 80-85° C. to obtain the polyurethane prepolymer.

[0015] Preferably, the acrylic acid hydroxyester containing an acylhydrazone bond is prepared from acrylic acid, 3-hydroxypropanal and adipic acid dihydrazide;

[0016] The molar ratio of acrylic acid, 3-hydroxypropanal and adipic acid dihydrazide is 1:(1.8-2.2):(0.8-1.2).

[0017] Preferably, the acrylic acid hydroxyester containing an acylhydrazone bond is prepared by the following method:

[0018] Adipic acid dihydrazide is dissolved in an organic solvent, 3-hydroxypropanal is added dropwise for reaction, and then dried to obtain a diol containing an acylhydrazone bond; the diol containing an acylhydrazone bond is reacted with acrylic acid to obtain the acrylic acid hydroxy ester containing an acylhydrazone bond. The alcohol hydroxyl group in the obtained acrylic acid hydroxy ester is a primary alcohol, which has a greater reactivity with an isocyanate group, and the reactivity of the isocyanate group with a primary alcohol is greater than that with a secondary alcohol and much greater than that with a tertiary alcohol.

[0019] Preferably, the catalyst is a mixture of toluenesulfonic acid and sulfurous acid in equal amounts;

[0020] The polymerization inhibitor is a silane coupling agent and / or titanium dioxide;

[0021] The water-carrying agent is normal alkane, cycloalkane or heteroalkane.

[0022] A second aspect of the present invention provides a method for preparing the photocurable composite material, the method comprising the following steps:

[0023] The polyurethane prepolymer is preheated, and then a reaction monomer is added, and then a catalyst, a polymerization inhibitor and a water-carrying agent are added dropwise, and then a temperature-raising reaction is carried out to obtain the light-curing composite material.

[0024] Preferably, the preheating temperature is 50-55°C; the heating reaction temperature is 70-75°C, and the reaction time is 90-100 min.

[0025] In the preparation method of the present invention, a polyurethane prepolymer containing -NCO semi-terminated is firstly reacted to generate, and then an acrylic acid hydroxyl ester containing an acylhydrazone bond is added thereto to introduce a double bond that can be photocured. The oligomer obtained by the reaction has a narrow relative molecular weight distribution, and the acrylic acid hydroxyl ester has a short residence time in the reactor, which avoids the long-term thermal polymerization of the double bond and can effectively ensure the photo-initiated polymerization of the polyurethane acrylate in the later stage. However, a slightly larger amount of hydroxyalkyl acrylate needs to be added, which increases the possibility of small molecules remaining inside. During the preparation, the reaction temperature and time need to be strictly controlled to reduce the occurrence of side reactions and improve the yield.

[0026] A third aspect of the present invention provides a sports protective gear, wherein the material of the sports protective gear is the photocurable composite material.

[0027] Compared with the prior art, the beneficial effects of the present invention include at least:

[0028] The photocurable composite material of the present invention introduces an acylhydrazone secondary bond, so that the photocurable composite material has some non-Newtonian fluid properties, and the shock absorption and energy absorption effects of the photocurable composite material are improved; in addition, the photocurable composite material of the present invention has good curing performance, good flexibility after curing, and excellent buffering and shock absorption performance. DETAILED DESCRIPTION

[0029] The following embodiments of the technical solution of the present invention are described in detail in conjunction with the embodiments. The following embodiments are only used to more clearly illustrate the technical solution of the present invention, and are therefore only used as examples, and cannot be used to limit the protection scope of the present invention.

[0030] It should be noted that, unless otherwise specified, the technical terms or scientific terms used in this application should have the common meanings understood by those skilled in the art to which the present invention belongs.

[0031] 3D printed protective gear in related technologies usually uses a buffer structure as support, similar to the principle of a spring, and improves the buffering performance of the printed product through compression deformation. However, the compression and support function of the protective gear has its limits, that is, similar to a spring being compressed to its limit, the shock-absorbing and buffering performance of the protective gear will be greatly reduced, and it cannot reliably protect the wearer. Therefore, the printed protective gear in the prior art can only meet the shock-absorbing and buffering requirements of smaller impacts, and cannot cope with the shock-absorbing and buffering requirements of higher impacts, and has poor safety.

[0032] The embodiment of the present application provides a light-curing composite material that can be applied to 3D printing. Through molecular structure design, the light-curing composite material itself has high air permeability and high cushioning and shock absorption performance. The protective gear does not need to rely too much on the cushioning structure, has higher comfort and safety, and can better meet the personalized design of the protective gear.

[0033] The present application will be further described below in conjunction with specific embodiments.

[0034] Example 1

[0035] This embodiment is a photocurable composite material, which includes the following raw materials in parts by weight:

[0036] 100 parts of polyurethane prepolymer, 50 parts of reactive monomer, 4 parts of catalyst, 1 part of polymerization inhibitor and 1 part of water-carrying agent;

[0037] The polyurethane prepolymer is prepared by the following method:

[0038] 10 parts by weight of hydroxy-terminated polybutadiene-acrylonitrile and 10 parts by weight of polyethylene glycol propylene glycol adipate were mixed evenly, and then water was removed, and then 80 parts by weight of toluene diisocyanate was added, and the mixture was reacted at a temperature of 82° C. to obtain a polyurethane prepolymer;

[0039] The reaction monomer is prepared by the following method:

[0040] Adipic acid dihydrazide is dissolved in ethanol and added dropwise to 3-hydroxypropanal, reacted fully at room temperature, and dried to obtain a diol containing an acylhydrazone bond; the diol containing an acylhydrazone bond is reacted with acrylic acid at 48°C for 90 minutes to obtain an acrylic acid hydroxy ester containing an acylhydrazone bond, wherein the molar ratio of acrylic acid, 3-hydroxypropanal and adipic acid dihydrazide is 1:2:1.

[0041] The catalyst is a mixture of equal masses of toluenesulfonic acid and sulfurous acid;

[0042] The polymerization inhibitor is a silane coupling agent;

[0043] The water-carrying agent is n-dodecane.

[0044] The preparation method of the above-mentioned light-curable composite material comprises the following steps:

[0045] The polyurethane prepolymer was preheated to 52° C., and then the reaction monomer was added. Then, the catalyst, the polymerization inhibitor and the water-carrying agent were added dropwise, and then the temperature was raised to 72° C. and reacted for 95 minutes to obtain a light-cured composite material.

[0046] Example 2

[0047] This embodiment is a photocurable composite material, which includes the following raw materials in parts by weight:

[0048] 90 parts of polyurethane prepolymer, 45 parts of reactive monomer, 3 parts of catalyst, 0.8 parts of polymerization inhibitor and 0.8 parts of water-carrying agent;

[0049] The polyurethane prepolymer is prepared by the following method:

[0050] 10 parts by weight of hydroxy-terminated polybutadiene-acrylonitrile and 10 parts by weight of polyethylene glycol propylene glycol adipate were mixed evenly, and then water was removed, and then 80 parts by weight of toluene diisocyanate was added, and the mixture was reacted at a temperature of 82° C. to obtain a polyurethane prepolymer;

[0051] The reaction monomer is prepared by the following method:

[0052] Adipic acid dihydrazide is dissolved in ethanol and added dropwise to 3-hydroxypropanal, reacted fully at room temperature, and dried to obtain a diol containing an acylhydrazone bond; the diol containing an acylhydrazone bond is reacted with acrylic acid at 45°C for 95 minutes to obtain an acrylic acid hydroxy ester containing an acylhydrazone bond, wherein the molar ratio of acrylic acid, 3-hydroxypropanal and adipic acid dihydrazide is 1:1.8:0.8.

[0053] The catalyst is a mixture of equal masses of toluenesulfonic acid and sulfurous acid;

[0054] The polymerization inhibitor is a silane coupling agent;

[0055] The water-carrying agent is n-dodecane.

[0056] The preparation method of the above-mentioned light-curable composite material comprises the following steps:

[0057] The polyurethane prepolymer was preheated to 50° C., and then the reaction monomer was added. Then, the catalyst, the polymerization inhibitor and the water-carrying agent were added dropwise, and then the temperature was raised to 70° C. and reacted for 100 minutes to obtain a light-cured composite material.

[0058] Example 3

[0059] This embodiment is a photocurable composite material, which includes the following raw materials in parts by weight:

[0060] 110 parts of polyurethane prepolymer, 60 parts of reactive monomer, 5 parts of catalyst, 1.2 parts of inhibitor and 1.2 parts of water-carrying agent;

[0061] The polyurethane prepolymer is prepared by the following method:

[0062] 10 parts by weight of hydroxy-terminated polybutadiene-acrylonitrile and 10 parts by weight of polyethylene glycol propylene glycol adipate were mixed evenly, and then water was removed, and then 80 parts by weight of toluene diisocyanate was added, and the mixture was reacted at a temperature of 82° C. to obtain a polyurethane prepolymer;

[0063] The reaction monomer is prepared by the following method:

[0064] Adipic acid dihydrazide is dissolved in ethanol and added dropwise to 3-hydroxypropanal, reacted fully at room temperature, and dried to obtain a diol containing an acylhydrazone bond; the diol containing an acylhydrazone bond is reacted with acrylic acid at 50°C for 85 minutes to obtain an acrylic acid hydroxy ester containing an acylhydrazone bond, wherein the molar ratio of acrylic acid, 3-hydroxypropanal and adipic acid dihydrazide is 1:2.2:1.2.

[0065] The catalyst is a mixture of equal masses of toluenesulfonic acid and sulfurous acid;

[0066] The polymerization inhibitor is a silane coupling agent;

[0067] The water-carrying agent is n-dodecane.

[0068] The preparation method of the above-mentioned light-curable composite material comprises the following steps:

[0069] The polyurethane prepolymer was preheated to 55°C, and then the reaction monomer was added. Then, the catalyst, the polymerization inhibitor and the water-carrying agent were added dropwise, and then the temperature was raised to 75°C for reaction for 90 minutes to obtain a light-cured composite material.

[0070] Comparative Example 1

[0071] This comparative example is a photocurable composite material, which includes the following raw materials in parts by weight:

[0072] 100 parts of polyurethane prepolymer, 30 parts of reactive monomer, 4 parts of catalyst, 1 part of inhibitor and 1 part of water-carrying agent;

[0073] The polyurethane prepolymer is prepared by the following method:

[0074] 10 parts by weight of hydroxy-terminated polybutadiene-acrylonitrile and 10 parts by weight of polyethylene glycol propylene glycol adipate were mixed evenly, and then water was removed, and then 80 parts by weight of toluene diisocyanate was added, and the mixture was reacted at a temperature of 82° C. to obtain a polyurethane prepolymer;

[0075] The reaction monomer is prepared by the following method:

[0076] Adipic acid dihydrazide is dissolved in ethanol and added dropwise to 3-hydroxypropanal, reacted fully at room temperature, and dried to obtain a diol containing an acylhydrazone bond; the diol containing an acylhydrazone bond is reacted with acrylic acid at 48°C for 90 minutes to obtain an acrylic acid hydroxy ester containing an acylhydrazone bond, wherein the molar ratio of acrylic acid, 3-hydroxypropanal and adipic acid dihydrazide is 1:2:1.

[0077] The catalyst is a mixture of equal masses of toluenesulfonic acid and sulfurous acid;

[0078] The polymerization inhibitor is a silane coupling agent;

[0079] The water-carrying agent is n-dodecane.

[0080] The preparation method of the above-mentioned light-curable composite material comprises the following steps:

[0081] The polyurethane prepolymer was preheated to 52° C., and then the reaction monomer was added. Then, the catalyst, the polymerization inhibitor and the water-carrying agent were added dropwise, and then the temperature was raised to 72° C. and reacted for 95 minutes to obtain a light-cured composite material.

[0082] Comparative Example 2

[0083] This comparative example is a commercially available light-cured composite material (3D printing material from CARBON, USA).

[0084] Experimental example

[0085] Performance Testing

[0086] The photocurable composite materials of Examples 1 to 3 and Comparative Examples 1 to 2 were used to prepare knee pads with a size of 220 mm*125 mm, and the performance of the prepared knee pads was tested.

[0087] Impact cushioning (knee pads): The protective gear is impact tested using the reference standard EN1621-1, and the cushioning performance of each protective gear is recorded to pass the minimum thickness and weight required for LEVEL 1 and LEVEL 2.

[0088] Impact cushioning (temperature): The reference standard EN1621-1 is used to test the cushioning performance of the knee pads at room temperature (23°C) and low temperature (-10°C) when passing the LEVEL 1 and LEVEL 2 tests. Test results

[0089] The performance test results of the protective gear are shown in Tables 1 and 2 below.

[0090] Table 1: Knee pad performance test LEVEL 1

[0091]

[0092] Table 2: Knee pad performance test LEVEL 2

[0093]

[0094]

[0095] From Table 1 and Table 2, we can see that:

[0096] According to the EN1621-1 test, to meet LEVEL 1 (first-level knee pad standard) requires an average impact test value of less than or equal to 35kN, and to meet LEVEL 2 (second-level knee pad standard) requires an average impact test value of less than or equal to 20kN. Compared with the comparative example, the photocurable composite material prepared in the embodiment of the present invention has better mechanical properties, which is significantly better than the photocurable material in the prior art, and the existing commercially available photocurable materials still cannot pass the LEVEL 2 impact test at 25mm.

[0097] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein by equivalents. These modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present invention, and they should all be included in the scope of the claims and specification of the present invention.

Claims

1. A photocurable composite material, characterized in that: The photocurable composite material comprises the following raw materials in parts by weight: 90-110 parts of polyurethane prepolymer, 45-60 parts of reactive monomer, 3-5 parts of catalyst, 0.8-1.2 parts of polymerization inhibitor and 0.8-1.2 parts of water-carrying agent; The reactive monomer is an acrylic acid hydroxy ester containing an acylhydrazone bond.

2. The light-curable composite material according to claim 1, characterized in that: The polyurethane prepolymer comprises a hard segment and a soft segment, and the mass ratio of the hard segment to the soft segment is 1:(0.2-0.25).

3. The light-curable composite material according to claim 2, characterized in that: The hard segment includes toluene diisocyanate; The soft segment comprises terminal hydroxyl polybutadiene-acrylonitrile and polyethylene glycol adipate in a mass ratio of 1: (0.8-1.2).

4. The light-curable composite material according to claim 1, characterized in that: The polyurethane prepolymer is prepared by the following method: The terminal hydroxyl polybutadiene-acrylonitrile and polyethylene glycol propylene glycol adipate are mixed uniformly, water is removed, toluene diisocyanate is added, and then reacted at 80-85° C. to obtain the polyurethane prepolymer.

5. The light-curable composite material according to claim 1, characterized in that: The acrylic acid hydroxy ester containing an acylhydrazone bond is prepared from acrylic acid, 3-hydroxypropanal and adipic acid dihydrazide; The molar ratio of acrylic acid, 3-hydroxypropanal and adipic acid dihydrazide is 1:(1.8-2.2):(0.8-1.2).

6. The light-curable composite material according to claim 5, characterized in that: The acrylic acid hydroxy ester containing acylhydrazone bond is prepared by the following method: Adipic acid dihydrazide is dissolved in an organic solvent, 3-hydroxypropanal is added dropwise for reaction, and then dried to obtain a diol containing an acylhydrazone bond; the diol containing an acylhydrazone bond is reacted with acrylic acid to obtain the acrylic acid hydroxy ester containing an acylhydrazone bond.

7. The light-curable composite material according to claim 1, characterized in that: The catalyst is a mixture of toluenesulfonic acid and sulfurous acid of equal mass; The polymerization inhibitor is a silane coupling agent and / or titanium dioxide; The water-carrying agent is normal alkane, cycloalkane or heteroalkane.

8. The method for preparing the photocurable composite material according to any one of claims 1 to 7, characterized in that: The preparation method comprises the following steps: The polyurethane prepolymer is preheated, and then a reaction monomer is added, and then a catalyst, a polymerization inhibitor and a water-carrying agent are added dropwise, and then a temperature-raising reaction is carried out to obtain the light-curing composite material.

9. The preparation method according to claim 8, characterized in that: The preheating temperature is 50-55°C; the heating reaction temperature is 70-75°C, and the reaction time is 90-100 minutes.

10. A sports protective gear, characterized in that: The material of the sports protective gear is the light-cured composite material described in any one of claims 1 to 7.

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