Jacking modifying agent for knee pad material as well as preparation method and application of bonding modifying agent

Abstract

The invention discloses a technical modification agent for a kneecap material as well as a preparation method and application of the technical modification agent. The technical modification agent for the kneecap material is prepared from the following raw materials in parts by weight: 90 to 110 parts of adipic dihydrazide, 85 to 89 parts of 3-hydroxypropionaldehyde, 41 to 44 parts of acrylic acid, 64 to 68 parts of furoic acid, 81 to 90 parts of N-hydroxyethyl maleimide and 6 to 9 parts of auxiliaries. The grafting modifier can graft and modify TPE and TPV, secondary valence bonds capable of being broken and recombined are introduced into the kneecap material, various acting forces can be generated among molecules, the internal structure and viscosity of fluid are affected, and therefore the kneecap material shows the non-Newtonian characteristic.

Description

Technical Field

[0001] The invention relates to the technical field of knee pad materials, and in particular to a grafting modifier for knee pad materials and a preparation method and application thereof. Background Art

[0002] Sports knee pads are an important sporting product that can reduce the impact of athletes through the cushioning, energy absorption, and pressure resistance of the material, thereby reducing the injuries suffered by athletes. A light, thin, and comfortable sports knee pad plays a vital role in various sports, which can reduce the occurrence of sports injuries and improve the performance and comfort of athletes. It provides protection and support for athletes.

[0003] Non-Newtonian fluid materials can be composed of a variety of different particles or molecules, and the bond energy between them is generally smaller than covalent bonds and larger than van der Waals forces, such as hydrogen bonds, disulfide bonds, ion complex bonds, etc. These secondary bond forces will affect the internal structure and viscosity of the fluid, causing it to exhibit non-Newtonian characteristics. Non-Newtonian fluid materials are soft and comfortable in normal conditions. When subjected to impact, the secondary bonds in the material break and reorganize to fully absorb the impact energy, and have good cushioning and shock absorption performance.

[0004] At present, the non-Newtonian fluid materials in existing sports protective gear technology usually use polyborosiloxane materials. The boric acid in polyborosiloxane materials is toxic and harmful to the human body. In addition, silicon-based materials have poor compatibility with many carbon-based materials, and the performance is unstable after blending, which limits the application of polyborosiloxane.

[0005] In view of this, the present invention is proposed. Summary of the invention

[0006] The purpose of the present invention is to provide a grafting modifier for knee pad materials and a preparation method and application thereof. The grafting modifier of the present invention can graft-modify TPE and TPV, introduce secondary bonds that can be broken and reorganized into the knee pad material, so that various forces can occur between molecules, affecting the internal structure and viscosity of the fluid, thereby causing it to exhibit non-Newtonian characteristics.

[0007] In order to achieve the above-mentioned purpose of the present invention, the following technical solutions are particularly adopted:

[0008] The first aspect of the present invention provides a grafting modifier for knee pad materials, wherein the grafting modifier for knee pad materials comprises the following raw materials in parts by weight:

[0009] 90-110 parts of adipic acid dihydrazide, 85-89 parts of 3-hydroxypropionaldehyde, 41-44 parts of acrylic acid, 64-68 parts of furoic acid, 81-90 parts of N-hydroxyethylmaleimide and 6-9 parts of auxiliary agent.

[0010] Preferably, the grafting modifier of the TPE knee pad material comprises the following raw materials in parts by weight:

[0011] 100 parts of adipic acid dihydrazide, 87 parts of 3-hydroxypropanal, 43 parts of acrylic acid, 66 parts of furoic acid, 86 parts of N-hydroxyethylmaleimide and 6.5 parts of auxiliary agent.

[0012] Preferably, each part of the auxiliary agent includes 1.5 to 2.5 parts of catalyst, 1.5 to 2.5 parts of inhibitor and 2 to 3 parts of water-carrying agent;

[0013] The catalyst is p-toluenesulfonic acid and / or sulfurous acid; the inhibitor is a silane coupling agent and / or titanium dioxide; and the water-carrying agent is selected from at least one of normal alkanes, heteroalkanes and cycloalkanes.

[0014] The second aspect of the present invention provides a method for preparing the grafting modifier for knee pad materials, the method comprising the following steps:

[0015] (a) dissolving adipic acid dihydrazide in an organic solvent, adding 3-hydroxypropanal to carry out a reflux reaction, and drying and removing the solvent after the reflux reaction is completed to obtain a first reaction product;

[0016] (b) mixing the first reaction product with acrylic acid and adding 0.4 to 0.6 times the total amount of an auxiliary agent to react to obtain a second reaction product;

[0017] (c) mixing the second reaction product with furfural and adding the remaining auxiliary agent to react to obtain a third reaction product;

[0018] (d) mixing the third reaction product with N-hydroxyethylmaleimide to react, thereby obtaining the grafting modifier for knee pad materials.

[0019] Preferably, in step (a), the reflux reaction temperature is 83-88° C., and the reflux reaction time is 3-5 h;

[0020] The organic solvent is selected from at least one of ethanol, isopropanol and butanone.

[0021] Preferably, in step (b), the reaction temperature is 65-80° C. and the reaction time is 80-100 min.

[0022] Preferably, in step (c), the reaction temperature is 55-70°C and the reaction time is 80-100 min;

[0023] In the step (d), the reaction temperature is 55-65° C. and the reaction time is 3-5 hours.

[0024] During preparation, the reaction temperature and time must be strictly controlled to reduce the occurrence of side reactions and improve the yield.

[0025] The third aspect of the present invention provides a use of the grafting modifier for knee pad materials in the preparation of knee pad materials.

[0026] The fourth aspect of the present invention provides a TPV knee pad material, wherein the TPV knee pad material is formed by mixing and pelletizing modified EPDM, maleic anhydride grafted PP and reinforcing carbon black;

[0027] The modified EPDM is prepared from the grafting modifier for knee pad material, EPDM and thermal initiator BPO.

[0028] The fifth aspect of the present invention provides a TPE knee pad material, wherein the TPE knee pad material is blended with modified SBS, rubber oil and polypropylene:

[0029] The modified SBS is prepared from the grafting modifier for knee pad material, SBS and thermal initiator BPO.

[0030] Compared with the prior art, the beneficial effects of the present invention include at least:

[0031] The grafting modifier of the present invention can be used to graft-modify TPE and TPV, and introduces macromolecular segments containing secondary bonds that can be broken and reorganized into the knee pad material, so that various forces can occur between molecules, affecting the internal structure and viscosity of the fluid, thereby causing it to exhibit non-Newtonian characteristics; the macromolecular segments can increase the internal friction of the material, and can convert more impact energy into frictional heat energy for consumption; the macromolecular segments contain secondary bonds, and when impacted, the secondary bonds can absorb energy to split and reorganize the secondary bonds, thereby consuming the received impact energy; the grafting modifier of the present invention contains multiple secondary bonds (two acylhydrazone bonds and one DA bond), which can greatly improve the energy absorption and shock absorption effect of the material.

[0032] The grafting modifier of the present invention can make TPE and TPV more fusible, and the application range of the modified TPE and TPV is wider; the secondary valent bonds are grafted on the main chains of TPE and TPV as side chains, and the performance is more stable after blending. DETAILED DESCRIPTION

[0033] 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.

[0034] 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.

[0035] The present application provides a grafting modifier for a knee pad material, which is used to improve the cushioning and shock absorbing properties of the knee pad material. The grafting modifier can be used for grafting and modifying commonly used knee pad materials, such as TPE and TPV. TPE is mainly blended from SBS, rubber oil and polypropylene. The raw materials of SBS mainly include styrene and butadiene. After polymerization, butadiene contains unsaturated double bonds. The grafting modifier can be grafted onto SBS through a thermal initiator or a thermal initiator, thereby improving the energy absorption and shock absorption effects of SBS. TPV is a maleic anhydride grafted PP / EPDM type dynamic vulcanized elastomer. The raw materials of EPDM are mainly ethylene, propylene and a third monomer (referring to diene). It also contains unsaturated double bonds. The grafting modifier can be grafted onto EPDM through a thermal initiator or a thermal initiator, thereby improving the energy absorption and shock absorption effects of EPDM. The grafting modifier can add macromolecular segments to the knee pad material. The macromolecular segments can increase the internal friction of the material and can convert more impact energy into frictional heat energy for consumption. The macromolecular chain segments in the grafted modifier also contain multiple secondary bonds. When impacted, the secondary bonds can absorb energy to split and reorganize the secondary bonds, thereby greatly consuming the impact energy and greatly improving the energy absorption and shock absorption effect of the material.

[0036] Example 1

[0037] This embodiment is a grafting modifier for knee pad materials, and the grafting modifier for knee pad materials includes the following raw materials in parts by weight:

[0038] 100 parts of adipic acid dihydrazide, 87 parts of 3-hydroxypropanal, 43 parts of acrylic acid, 66 parts of furoic acid, 86 parts of N-hydroxyethylmaleimide and 6.5 parts of auxiliary agent;

[0039] Each part of additives includes 2 parts of catalyst, 2 parts of inhibitor and 2.5 parts of water-carrying agent;

[0040] The catalyst is toluenesulfonic acid and sulfurous acid in equal weight; the inhibitor is a silane coupling agent; and the water-carrying agent is n-dodecane.

[0041] The preparation method of the above-mentioned grafting modifier for knee pad materials comprises the following steps:

[0042] (a) dissolving adipic acid dihydrazide in an organic solvent, adding 3-hydroxypropanal to carry out reflux reaction, drying and removing the solvent after the reflux reaction is completed to obtain a first reaction product, wherein the reflux reaction temperature is 85° C., the reflux reaction time is 4 hours, and the organic solvent is isopropanol;

[0043] (b) mixing the first reaction product with acrylic acid and adding 0.5 times the total amount of an auxiliary agent to react to obtain a second reaction product, wherein the reaction temperature is 70° C. and the reaction time is 90 min;

[0044] (c) mixing the second reaction product with furfural and adding the remaining auxiliary agent to react to obtain a third reaction product, wherein the reaction temperature is 60° C. and the reaction time is 90 min;

[0045] (d) The third reaction product is mixed with N-hydroxyethylmaleimide for reaction at a temperature of 60° C. for a reaction time of 4 hours to obtain a grafting modifier for knee pad materials.

[0046] Example 2

[0047] This embodiment is a grafting modifier for knee pad materials, and the grafting modifier for knee pad materials includes the following raw materials in parts by weight:

[0048] 100 parts of adipic acid dihydrazide, 85 parts of 3-hydroxypropionaldehyde, 41 parts of acrylic acid, 64 parts of furoic acid, 81 parts of N-hydroxyethylmaleimide and 6 parts of auxiliary agent;

[0049] Each part of additives includes 2 parts of catalyst, 2 parts of inhibitor and 2.5 parts of water-carrying agent;

[0050] The catalyst is toluenesulfonic acid and sulfurous acid in equal weight; the inhibitor is a silane coupling agent; and the water-carrying agent is n-dodecane.

[0051] The preparation method of the above-mentioned grafting modifier for knee pad materials comprises the following steps:

[0052] (a) dissolving adipic acid dihydrazide in an organic solvent, adding 3-hydroxypropanal to carry out reflux reaction, drying and removing the solvent after the reflux reaction is completed to obtain a first reaction product, wherein the reflux reaction temperature is 85° C., the reflux reaction time is 4 hours, and the organic solvent is isopropanol;

[0053] (b) mixing the first reaction product with acrylic acid and adding 0.5 times the total amount of an auxiliary agent to react to obtain a second reaction product, wherein the reaction temperature is 70° C. and the reaction time is 90 min;

[0054] (c) mixing the second reaction product with furfural and adding the remaining auxiliary agent to react to obtain a third reaction product, wherein the reaction temperature is 60° C. and the reaction time is 90 min;

[0055] (d) The third reaction product is mixed with N-hydroxyethylmaleimide for reaction at a temperature of 60° C. for a reaction time of 4 hours to obtain a grafting modifier for knee pad materials.

[0056] Example 3

[0057] This embodiment is a grafting modifier for knee pad materials, and the grafting modifier for knee pad materials includes the following raw materials in parts by weight:

[0058] 100 parts of adipic acid dihydrazide, 89 parts of 3-hydroxypropionaldehyde, 44 parts of acrylic acid, 68 parts of furoic acid, 90 parts of N-hydroxyethylmaleimide and 9 parts of auxiliary agent;

[0059] Each part of additives includes 2 parts of catalyst, 2 parts of inhibitor and 2.5 parts of water-carrying agent;

[0060] The catalyst is toluenesulfonic acid and sulfurous acid in equal weight; the inhibitor is a silane coupling agent; and the water-carrying agent is n-dodecane.

[0061] The preparation method of the above-mentioned grafting modifier for knee pad materials comprises the following steps:

[0062] (a) dissolving adipic acid dihydrazide in an organic solvent, adding 3-hydroxypropanal to carry out reflux reaction, drying and removing the solvent after the reflux reaction is completed to obtain a first reaction product, wherein the reflux reaction temperature is 85° C., the reflux reaction time is 4 hours, and the organic solvent is isopropanol;

[0063] (b) mixing the first reaction product with acrylic acid and adding 0.5 times the total amount of an auxiliary agent to react to obtain a second reaction product, wherein the reaction temperature is 70° C. and the reaction time is 90 min;

[0064] (c) mixing the second reaction product with furfural and adding the remaining auxiliary agent to react to obtain a third reaction product, wherein the reaction temperature is 60° C. and the reaction time is 90 min;

[0065] (d) The third reaction product is mixed with N-hydroxyethylmaleimide for reaction at a temperature of 60° C. for a reaction time of 4 hours to obtain a grafting modifier for knee pad materials.

[0066] Example 4

[0067] This embodiment is a TPE knee pad material, the raw materials of the TPE knee pad material include: modified SBS: 100 parts by weight; rubber oil: 80 parts by weight; polypropylene: 30 parts by weight; filler: 15 parts by weight of talcum powder; anti-aging agent: 0.6 parts by weight; stabilizer: 0.8 parts by weight. The specific preparation method is as follows:

[0068] The modified SBS, rubber oil, polypropylene and filler additives are uniformly mixed, the mixture is heated and melted and extruded through a twin-screw extruder, and the TPE knee pad material is obtained after cooling and shaping. The preparation method of the modified SBS includes: mixing 65wt% of SBS, 32wt% of the grafting modifier of Example 1 and 3wt% of the thermal initiator BPO, and heat curing at 105°C for 45 minutes to obtain the modified SBS.

[0069] Example 5

[0070] This embodiment is a TPE knee pad material, the raw materials of the TPE knee pad material include: modified SBS: 100 parts by weight; rubber oil: 80 parts by weight; polypropylene: 30 parts by weight; filler: 15 parts by weight of talcum powder; anti-aging agent: 0.6 parts by weight; stabilizer: 0.8 parts by weight. The specific preparation method is as follows:

[0071] The modified SBS, rubber oil, polypropylene and filler additives are uniformly mixed, the mixture is heated and melted and extruded through a twin-screw extruder, and the TPE knee pad material is obtained after cooling and shaping. The preparation method of the modified SBS includes: mixing 65wt% of SBS, 32wt% of the grafting modifier of Example 2 and 3wt% of the thermal initiator BPO, and heat curing at 105°C for 45 minutes to obtain the modified SBS.

[0072] Example 6

[0073] This embodiment is a TPE knee pad material, the raw materials of the TPE knee pad material include: modified SBS: 100 parts by weight; rubber oil: 80 parts by weight; polypropylene: 30 parts by weight; filler: 15 parts by weight of talcum powder; anti-aging agent: 0.6 parts by weight; stabilizer: 0.8 parts by weight. The specific preparation method is as follows:

[0074] The modified SBS, rubber oil, polypropylene and filler additives are uniformly mixed, the mixture is heated and melted and extruded through a twin-screw extruder, and the TPE knee pad material is obtained after cooling and shaping. The preparation method of the modified SBS includes: mixing 65wt% of SBS, 32wt% of the grafting modifier of Example 3 and 3wt% of the thermal initiator BPO, and heat curing at 105°C for 45 minutes to obtain the modified SBS.

[0075] Example 7

[0076] This embodiment is a TPV knee pad material, which is made by twin-screw blending and pelletizing of 70 parts of modified EPDM, 30 parts of maleic anhydride grafted PP and 15 parts of reinforcing carbon black;

[0077] The preparation method of the modified EPDM comprises: mixing 81 wt % of EPDM, 17 wt % of the grafting modifier of Example 1 and 2 wt % of the thermal initiator BPO, and performing a thermal curing treatment at 105° C. for 45 minutes to obtain the modified EPDM.

[0078] Example 8

[0079] This embodiment is a TPV knee pad material, which is made by twin-screw blending and pelletizing of 70 parts of modified EPDM, maleic anhydride grafted PP30 and 15 parts of reinforcing carbon black;

[0080] The preparation method of the modified EPDM comprises: mixing 81 wt % of EPDM, 17 wt % of the grafting modifier of Example 2 and 2 wt % of the thermal initiator BPO, and performing a thermal curing treatment at 105° C. for 45 minutes to obtain the modified EPDM.

[0081] Example 9

[0082] This embodiment is a TPV knee pad material, which is made by twin-screw blending and pelletizing of 70 parts of modified EPDM, 30 parts of maleic anhydride grafted PP and 15 parts of reinforcing carbon black;

[0083] The preparation method of the modified EPDM comprises: mixing 81 wt % of EPDM, 17 wt % of the grafting modifier of Example 3 and 3 wt % of the thermal initiator BPO, and performing a thermal curing treatment at 105° C. for 45 minutes to obtain the modified EPDM.

[0084] Comparative Example 1

[0085] This comparative example is a common TPE knee pad material, which is blended by 100 parts by weight of common SBS, 45 parts by weight of rubber oil, 30 parts by weight of polypropylene, 2 parts by weight of activated carbon as filler, 0.8 parts by weight of plasticizer, 0.6 parts by weight of anti-aging agent, 0.8 parts by weight of stabilizer and 0.8 parts by weight of colorant.

[0086] Comparative Example 2

[0087] This comparative example is a TPV kneepad material, which is prepared by twin-screw blending and pelletizing of 70 parts of common EPDM, 30 parts of maleic anhydride grafted PP and 15 parts of reinforcing carbon black.

[0088] Comparative Example 3

[0089] This comparative example is a commercially available NBR knee pad with a thickness of 25 mm.

[0090] Comparative Example 4

[0091] This comparative example is a commercially available EVA kneepad with a thickness of 25 mm.

[0092] Comparative Example 5

[0093] This comparative example is a commercially available XPE knee pad with a thickness of 25 mm.

[0094] Comparative Example 6

[0095] This comparative example is a knee pad from a competitor on the market in the UK.

[0096] Experimental example

[0097] Performance Testing

[0098] Kneepads of 220 mm*125 mm in size were prepared using the kneepad materials of Examples 4 to 9 and Comparative Examples 1 to 6, and performance tests were performed on the prepared kneepads.

[0099] Impact cushioning (knee pads): The knee pads are impact tested using the reference standard EN1621-1, and the cushioning performance of each knee pad is recorded to pass the minimum thickness and weight required for LEVEL 1 and LEVEL 2.

[0100] Impact cushioning (temperature): The reference standard EN1621-1 is used to test the cushioning performance of the knee pads at normal temperature (23°C) and low temperature (-10°C) under the parameters of LEVEL 1.

[0101] Test Results

[0102] The performance test results of the knee pads are shown in Table 1 below.

[0103] Table 1: Knee pad performance test

[0104]

[0105] According to the EN1621-1 test, to meet the LEVEL 1 (first-level knee pad standard), the impact must be less than or equal to 35kN, and to meet the LEVEL 2 (second-level knee pad standard), the impact must be less than or equal to 20kN. It can be seen from Table 1:

[0106] Compared with the comparative example, the knee pad material prepared in the embodiment of the present invention has more excellent mechanical properties. The knee pad prepared in the embodiment of the present invention has better performance than the competing knee pads, while the NBR, EVA and XPE protective gear sold on the market still cannot pass the performance test of EN1621-1 at 25mm.

[0107] 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 grafting modifier for knee pad materials, characterized in that: The grafting modifier for knee pad materials comprises the following raw materials in parts by weight: 90-110 parts of adipic acid dihydrazide, 85-89 parts of 3-hydroxypropionaldehyde, 41-44 parts of acrylic acid, 64-68 parts of furoic acid, 81-90 parts of N-hydroxyethylmaleimide and 6-9 parts of auxiliary agent.

2. The grafting modifier for knee pad materials according to claim 1, characterized in that: The grafting modifier of the TPE knee pad material includes the following raw materials in parts by weight: 100 parts of adipic acid dihydrazide, 87 parts of 3-hydroxypropanal, 43 parts of acrylic acid, 66 parts of furoic acid, 86 parts of N-hydroxyethylmaleimide and 6.5 parts of auxiliary agent.

3. The grafting modifier for knee pad materials according to claim 1 or 2, characterized in that: Each part of the auxiliary agent includes 1.5 to 2.5 parts of catalyst, 1.5 to 2.5 parts of inhibitor and 2 to 3 parts of water-carrying agent; The catalyst is p-toluenesulfonic acid and / or sulfurous acid; the inhibitor is a silane coupling agent and / or titanium dioxide; and the water-carrying agent is selected from at least one of normal alkanes, heteroalkanes and cycloalkanes.

4. The method for preparing the grafting modifier for knee pad materials according to any one of claims 1 to 3, characterized in that: The preparation method comprises the following steps: (a) dissolving adipic acid dihydrazide in an organic solvent, adding 3-hydroxypropanal to carry out a reflux reaction, and drying and removing the solvent after the reflux reaction is completed to obtain a first reaction product; (b) mixing the first reaction product with acrylic acid and adding 0.4 to 0.6 times the total amount of an auxiliary agent to react to obtain a second reaction product; (c) mixing the second reaction product with furfural and adding the remaining auxiliary agent to react to obtain a third reaction product; (d) mixing the third reaction product with N-hydroxyethylmaleimide to react, thereby obtaining the grafting modifier for knee pad materials.

5. The preparation method according to claim 4, characterized in that: In the step (a), the reflux reaction temperature is 83-88° C., and the reflux reaction time is 3-5 h; The organic solvent is selected from at least one of ethanol, isopropanol and butanone.

6. The preparation method according to claim 4, characterized in that: In the step (b), the reaction temperature is 65-80° C. and the reaction time is 80-100 min.

7. The preparation method according to claim 4, characterized in that: In the step (c), the reaction temperature is 55-70°C and the reaction time is 80-100 min; In the step (d), the reaction temperature is 55-65° C. and the reaction time is 3-5 hours.

8. Use of the grafting modifier for knee pad materials according to any one of claims 1 to 3 in the preparation of knee pad materials.

9. A TPV knee pad material, characterized in that: The TPV knee pad material is made of modified EPDM, maleic anhydride grafted PP and reinforcing carbon black blended and pelletized; The modified EPDM is prepared from the grafting modifier for knee pad materials described in any one of claims 1 to 3, EPDM and thermal initiator BPO.

10. A TPE knee pad material, characterized in that: The TPE knee pad material is blended from modified SBS, rubber oil and polypropylene: The modified SBS is prepared from the grafting modifier for knee pad materials described in any one of claims 1 to 3, SBS and a thermal initiator BPO.

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