A polyurethane slow-rebound buffer material composition, preparation method and application thereof

Abstract

The invention relates to a polyurethane slow-rebound buffer material composition, a preparation method and an application thereof, and mainly solves the problems in the prior art that the slow-rebound buffer material hardens at low temperatures and has average tensile and tearing performance. The invention adopts a polyurethane slow-rebound buffer material composition, which is composed of component A and component B, wherein component A comprises the following components in parts by weight: polyether polyol a: 40-80 parts, polyether polyol b: 10-40 parts, polyether polyol c: 10-40 parts, foaming agent: 0.1-1.5 parts, reaction catalyst: 0.5-1.5 parts, foam stabilizer: 0.5-1.0 parts, cross-linking agent: 2-8 parts, chain extender: 2-6 parts, cell opener: 1-5 parts; component B comprises: isocyanate: 20-50 parts, polyether polyol d: 10-40 parts; the technical scheme that the weight ratio of component A to component B is 100:30-60 solves the series of problems well, and is widely used in children's toys, sports insoles, sports buffer materials, protective gear or buffer protection of electronic components.

Description

Technical Field

[0001] The invention relates to a polyurethane slow-rebound buffer material composition, a preparation method and application thereof, and belongs to the technical field of polyurethane foaming. Background Art

[0002] In high-speed sports such as skiing, motorcycles and bicycles, people are often subjected to large impacts. In order to avoid joint injuries, sportswear with protective pads is required. Protective pads fixed to vulnerable parts of the human body such as knees, elbows, shoulders, backs, etc. can greatly reduce the risk of athletes being injured. With the development of science and technology, protective pads are gradually developing in the direction of better impact resistance, thinner and more comfortable. Protective pads mainly include thick felt materials, polymer damping materials, etc. Polymer damping materials include EVA, rubber and polyurethane, etc. Polyurethane slow rebound foam itself has the functions of energy absorption, shock resistance, impact resistance and excellent high damping, and is widely used in children's toys, sports insoles, sports protective gear and buffering protection of electronic components. However, the existing technology needs to be further improved in terms of improving the damping factor of the material, fast hardness increase at low temperature and tensile tearing performance. The present invention provides a scheme with better performance, preparing a sports buffer material with high damping impact resistance, high tensile tearing strength and no obvious hardness increase at low temperature.

[0003] Chinese patent CN 109836551B discloses a polyurethane sports protective foam pad composition and its preparation method. The invention develops a polyurethane sports protective foam pad composition. The invention uses a special polyether polyol, specifically a polyether polyol obtained by ring-opening polymerization of 1,2-propylene oxide using two or more of 1,2-propylene glycol, glycerol, diethylene glycol or trimethylolpropane as a mixed initiator, and a grafted polyether polyol obtained by free radical polymerization by adding acrylonitrile monomer, styrene monomer and initiator, wherein the grafting rate is 29-31%wt. In the formulation design, this type of polyether is the main body, and there is a big problem, that is, the viscosity of the entire formulation system is too large, the equipment requirements are high, and it is not easy to produce. At the same time, when the low molecular weight and high hydroxyl value polyether is the main body, the glass transition temperature of the foam product will be relatively low, and the temperature feeling will be particularly obvious, that is, at low temperatures, the foam product will become very stiff, with only rigidity but insufficient toughness, affecting the use. In the physical property test results, the too low elongation at break is a good reflection.

[0004] Chinese patent CN 114031741A discloses a high-performance polyurethane slow-rebound protective gear composite material and a method for preparing the protective gear. The invention formula still uses a large amount of low molecular weight, high hydroxyl value polyether CHE-307, which also has the problem of hardening at low temperatures.

[0005] Chinese patent CN 113583214A discloses a slow-rebound high-damping soft polyurethane foam and its preparation method. The idea of ​​improving the damping performance of polyurethane foam in this patent is: using a combination of hyperbranched polyether polyol and hyperbranched polyester polyol to increase the internal friction between molecules in polyurethane foam after foaming, thereby improving the damping performance of polyurethane foam. However, the full text does not mention how much its performance has been improved, and lacks sufficient physical property data support. Summary of the invention

[0006] One of the technical problems to be solved by the present invention is that there is a technical problem in the prior art that the slow-rebound buffer material hardens at low temperature and has average tensile tear strength. A new polyurethane slow-rebound buffer material is provided, which has the advantages of no obvious increase in hardness at low temperature, high damping impact resistance, and high tear tensile strength. The second technical problem to be solved by the present invention is to provide a method for preparing a polyurethane slow-rebound buffer material corresponding to solving one of the problems. The third technical problem to be solved by the present invention is to provide an application of a polyurethane slow-rebound buffer material corresponding to solving one of the problems.

[0007] In order to solve one of the above technical problems, the technical solution adopted by the present invention is as follows: a polyurethane slow rebound buffer material composition, calculated by weight, comprises the following components: component A: polyether polyol a: 40-80 parts, polyether polyol b: 10-40 parts, polyether polyol c: 10-40 parts, foaming agent: 0.1-1.5 parts, reaction catalyst: 0.5-1.5 parts, foam stabilizer: 0.5-1.0 parts, crosslinking agent: 2-8 parts, chain extender: 2-6 parts, cell opener: 1-5 parts; component B :Isocyanate: 30-60 parts, polyether polyol d: 10-40 parts; the weight ratio of component A to component B is 100:30-60; wherein polyether polyol a is a polyester ether polyol with a molecular weight of 600-3000, a viscosity of 1000-2500mpa·s, a functionality of 2-4, and an ester content of 10-40%; polyether polyol b is a polyether polyol with a molecular weight of 200-3000 and at least one of propylene glycol, pentaerythritol, xylitol, sorbitol or sucrose as an initiator, The unsaturation degree is 0.01-0.2 mmol / g, and the functionality is 2-4; the polyether polyol c is a polyether polyol with a molecular weight of 3000-10000, at least one of glycerol, pentaerythritol, xylitol, sorbitol or sucrose as an initiator, and the unsaturation degree is 0.01-0.2 mmol / g, and the functionality is 2-4; the foam stabilizer is a polysiloxane-oxidized olefin block or graft copolymer; the crosslinking agent is a small molecule polyol and a polyamine compound containing two or more functional groups; the The chain extender is a non-amine small molecule alcohol compound containing two functional groups; the pore opening agent is a polyoxyalkylene-polysiloxane copolymer; the isocyanate is selected from at least one of toluene diisocyanate, crude MDI or carbodiimide modified isocyanate; the polyether polyol d is a polyether polyol with at least one of propylene glycol, pentaerythritol, xylitol, sorbitol or sucrose as an initiator, a molecular weight of 1000-6000, an unsaturation of 0.01-0.2 mmol / g, and a functionality of 2-4.

[0008] In the above technical solution, preferably, the B component further comprises a storage stabilizer, and the amount of the storage stabilizer added is 20-40×10 -6 The storage stabilizer is selected from one of phosphoric acid and benzoyl chloride. The storage stabilizer is selected from one of phosphoric acid and benzoyl chloride.

[0009] In the above technical scheme, preferably, the reaction catalyst is selected from at least one of a foaming tertiary amine catalyst, a gel tertiary amine catalyst or a balanced tertiary amine catalyst; the foam stabilizer is selected from at least one of B-8002, L-580 or HC-8240; the cross-linking agent is at least one of triethanolamine (TEA), diethanolamine (DEOA), glycerol or trimethylolpropane; the chain extender is selected from at least one of ethylene glycol (EG), diethylene glycol (DEG), 1,4-butanediol (1,4-BG), 1,3-propylene glycol (1,3-PDO), dipropylene glycol (DPG) or 1,6-hexanediol; the cell opener is selected from at least one of CHE-350D or SKC-1900; the isocyanate is selected from at least one of MDI-LL or M20S.

[0010] In the above technical scheme, preferably, the foaming tertiary amine catalyst is selected from at least one of dimethylaminoethoxyethanol, trimethylhydroxyethylethylenediamine or N,N,N'-trimethyl-N'-hydroxyethylbisaminoethyl ether; the gel tertiary amine catalyst is selected from N,N-bis(dimethylaminopropyl)isopropanolamine or N-(dimethylaminopropyl)diisopropanolamine; and the balanced tertiary amine catalyst is dimethylethanolamine.

[0011] In the above technical solution, preferably, the foaming agent is water; and the polyether polyol a is selected from CHE-214LF.

[0012] To solve the second of the above technical problems, the technical solution provided by the present invention is as follows:

[0013] A method for preparing the aforementioned polyurethane slow-rebound buffer material is characterized by comprising the following steps:

[0014] (1) Preparation of component A

[0015] Weigh 40-80 parts of polyether polyol a, 10-40 parts of polyether polyol b, 10-40 parts of polyether polyol c, 0.1-1.5 parts of foaming agent, 0.5-1.5 parts of reaction catalyst, 0.5-1.0 parts of foam stabilizer, 2-8 parts of crosslinking agent, 2-6 parts of chain extender and 1-5 parts of cell opener respectively, add them into a container in sequence, stir and mix thoroughly to obtain component A;

[0016] (2) Preparation of component B

[0017] Weigh 10-40 parts of polyether polyol d by weight, add to a reaction kettle, stir and heat to 90-100°C, dehydrate and degas under vacuum for 2-3 hours, cool, add 20-50 parts of isocyanate, heat to 80-85°C and react for 2-3 hours, detect NCO content at 18%-22%, and obtain component B;

[0018] (3) Preparation of cushioning materials

[0019] (a) Raise the mold temperature to 40-60°C and evenly spray a release agent on the inner surface of the mold;

[0020] (b) Wait for 2 to 3 minutes until the release agent solidifies into a film on the mold surface;

[0021] (c) Mix the prepared component A and component B in a ratio of 100:30-60, stir them thoroughly for 3-5 seconds at a speed of 2000-5000 rpm, and then quickly inject them into the mold and lock the mold;

[0022] (d) The mold is maintained for 6 to 10 minutes, and then the mold is opened. After the product is taken out, it is aged at room temperature for 2 to 4 days to obtain the polyurethane slow rebound cushioning material and can be put into use.

[0023] In the above technical solution, preferably, the release agent is a water-based release agent.

[0024] In the above technical solution, preferably, the release agent is 3011B.

[0025] In the above technical solution, preferably, in the preparation of the B component in step (2), a storage stabilizer is added at the same time as the isocyanate, and the amount of the storage stabilizer added is 20-40×10 -6 share.

[0026] To solve the third of the above technical problems, the technical solution provided by the present invention is as follows:

[0027] The aforementioned polyurethane slow-rebound cushioning material is used in the cushioning protection of children's toys, sports shoe insoles, sports protective gear or electronic components.

[0028] The invention provides a polyurethane slow-rebound buffer material, which is foamed by combining component A mainly composed of polyol and component B composed of self-made prepolymerized modified isocyanate. Compared with the buffer material prepared by using a large amount of low molecular weight and high hydroxyl value polyether in the prior art, it has the following characteristics: first, it has a higher glass transition temperature, and the hardness of the product does not increase significantly at low temperature, which greatly improves the problem of hardening at low temperature; second, the invention adopts a polyester ether polyol with a special structure, introduces an ester structure, greatly increases the content of polar groups in the polyol, increases the intermolecular force, and effectively improves the tensile tearing performance of the buffer material product; third, the invention does not use a polymer polyol with a high viscosity, which also makes the material have better fluidity, has low requirements for foaming equipment, and greatly improves the production yield. The prepared polyurethane slow-rebound buffer material has a tensile strength greater than 1500kPa, an elongation at break greater than 200%, a tear strength greater than 10.90N / cm, and an impact absorption rate greater than 73%, and has achieved good technical effects. DETAILED DESCRIPTION

[0029] Table 1 List of raw materials – additives

[0030]

[0031]

[0032] Table 2 Raw materials list – main raw materials

[0033]

[0034] [Example 1]

[0035] (1) Preparation of component A

[0036] In parts by weight, weigh 40 parts of CHE-214LF, 20 parts of CHE-204, 40 parts of CHE-330, 0.1 parts of water, 0.3 parts of 33LV, 0.2 parts of ZF-10, 1.0 parts of B-8002, 4 parts of DEOA, 4 parts of TEOA, 1 part of EG, 1 part of BDO; and 21 parts of pore opener SKC-1900, and add them into a container in sequence, stir and mix thoroughly to obtain component A.

[0037] (2) Preparation of component B

[0038] By weight, weigh 10 parts of CHED-28, add it to the reactor, stir and heat it to 90-100°C, dehydrate and degas under vacuum for 2-3 hours, cool it down, add 35 parts of liquefied LL and 15 parts of M20S, storage stabilizer benzoyl chloride: 20×10 -6The mixture was heated to 80-85°C for 2-3 hours, and the NCO content was detected to be 18.5%, thereby obtaining component B.

[0039] (3) High damping impact resistant polyurethane slow rebound cushioning material composition

[0040] a) Raise the mold temperature to 60°C and evenly spray the release agent 3011B on the inner surface of the mold;

[0041] b) Wait for 2 to 3 minutes until the release agent solidifies into a film on the mold surface;

[0042] c) Mix the prepared component A and component B in a ratio of 100:60, stir thoroughly for 5 seconds at a speed of 2500 rpm, quickly inject into the mold and lock the mold;

[0043] d) The mold is maintained for 7 minutes, and then the mold is opened. After the product is taken out, it is aged at room temperature for 48 hours. The polyurethane slow rebound cushioning material can be put into use. The conventional physical property test data of the prepared polyurethane slow rebound cushioning material are shown in Table 5.

[0044] [Example 2 to Example 8 and Comparative Example 1 to Comparative Example 3]

[0045] Examples 2 to 4 are carried out according to the steps of Example 1, with the only difference being the type of reaction raw materials, the type of catalyst, the raw material ratio, the reaction time, the temperature and the stirring speed, as shown in Table 3. The conventional physical property test data of the prepared polyurethane slow rebound cushioning material are shown in Table 5.

[0046] Examples 5 to 8 and Comparative Examples 1 to 3 were carried out according to the steps of Example 1, wherein the only difference between Examples 5 to 8 is the different B components, and the difference between Comparative Examples 1 to 3 is the different types of reaction raw materials, catalyst types, raw material ratios, reaction times and temperatures, as shown in Table 4. The conventional physical property test data of the prepared polyurethane slow rebound cushioning material are shown in Table 5.

[0047] Table 3 Weight parts of raw materials of each component in Examples 1 to 4

[0048]

[0049]

[0050]

[0051] Table 4 Weight percentage of raw materials of each component in Examples 5 to 8 and Comparative Examples 1 to 3

[0052]

[0053]

[0054] Table 5 Performance test data of slow rebound cushioning materials prepared in Examples 1 to 7 and Comparative Examples 1 to 3

[0055]

[0056]

[0057] Comparative Examples 1 to 2 are slow-rebound buffer materials prepared using component A and component B that has not been prepolymerized and modified in the present invention, and Comparative Example 3 is a conventional preparation route for slow-rebound buffer materials. The results show that there are two extremes in Comparative Examples 1 and 2. The tensile strength and surface hardness of Comparative Example 1 are both about 20% higher than those of other embodiments, but the elongation at break and tear strength are greatly reduced, and the lack of certain toughness will affect its service life due to frequent bending actions, and also greatly reduce the impact performance of the material. Comparative Example 2 has all the indicators of tensile strength, tear strength, elongation at break and impact coefficient. Comparative Example 3 has the situation that the tear strength, elongation at break and impact performance are all too low. However, Examples 1-8 in the present invention all perform well in comprehensive data. According to Example 3, while obtaining a higher tensile strength (1689kpa), it can also obtain a good elongation at break (279%), tear strength (10.92N / cm) and impact absorption rate (75%).

[0058] The above content introduces in detail a polyurethane slow rebound buffer material composition and preparation method provided by the present invention. The embodiments in this article illustrate the principle and implementation mode of the present invention. The introduction of the above embodiments is only for understanding the core idea of ​​the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the field of technology shall make modifications to the present invention within the protection scope of the claims without departing from the principle of the present invention.

Claims

1. A polyurethane slow-rebound cushioning material composition, comprising the following components in parts by weight: Component A: polyether polyol a: 40-80 parts, polyether polyol b: 10-40 parts, polyether polyol c: 10-40 parts, foaming agent: 0.1-1.5 parts, reaction catalyst: 0.5-1.5 parts, foam stabilizer: 0.5-1.0 parts, crosslinking agent: 2-8 parts, chain extender: 2-6 parts, cell opener: 1-5 parts; Component B: isocyanate: 30-60 parts, polyether polyol d: 10-40 parts; the weight ratio of component A to component B is 100:30-60; wherein, polyether polyol b is a polyether polyol with propylene glycol as the initiator, a molecular weight of 200-3000, and an unsaturation of 0.01-0.2 mmol / g, functionality is 2; polyether polyol c is a polyether polyol with glycerol as the initiator, a molecular weight of 3000-10000, and an unsaturation of 0.01-0.2 mmol / g, functionality is 3; the foam stabilizer is a polysiloxane-olefin oxide block or graft copolymer; the cross-linking agent is a small molecule polyol and a polyamine compound containing two or more functional groups; the chain extender is a non-amine small molecule alcohol compound containing two functional groups; the pore opening agent is a polyoxyalkylene-polysiloxane copolymer; the isocyanate is selected from at least one of toluene diisocyanate, crude MDI or carbodiimide modified isocyanate; the polyether polyol d is a polyether polyol with at least one of propylene glycol, pentaerythritol, xylitol, sorbitol or sucrose as an initiator, a molecular weight of 1000-6000, an unsaturation of 0.01-0.2mmol / g, and a functionality of 2-4; the foaming agent is water; the polyether polyol a is CHE-214LF, functionality is 2, molecular weight is 1300, viscosity is 1300, and ester content is 30%.

2. The polyurethane slow-rebound cushioning material composition according to claim 1, characterized in that: The B component also includes a storage stabilizer, and the amount of the storage stabilizer added is 20-40×10 -6 parts; the storage stabilizer is selected from one of phosphoric acid or benzoyl chloride.

3. The polyurethane slow-rebound cushioning material composition according to claim 1, characterized in that: The reaction catalyst is selected from at least one of a foaming tertiary amine catalyst, a gel tertiary amine catalyst or a balanced tertiary amine catalyst; the foam stabilizer is selected from at least one of B-8002, L-580 or HC-8240; the cross-linking agent is at least one of triethanolamine (TEA), diethanolamine (DEOA), glycerol or trimethylolpropane; the chain extender is selected from at least one of ethylene glycol (EG), diethylene glycol (DEG), 1,4-butanediol (1,4-BG), 1,3-propylene glycol (1,3-PDO), dipropylene glycol (DPG) or 1,6-hexanediol; the cell opener is selected from at least one of CHE-350D or SKC-1900; the isocyanate is selected from at least one of MDI-LL or M20S.

4. The polyurethane slow-rebound cushioning material composition according to claim 3, characterized in that: The foaming tertiary amine catalyst is selected from at least one of dimethylaminoethoxyethanol, trimethylhydroxyethylethylenediamine or N,N,N'-trimethyl-N'-hydroxyethylbisaminoethyl ether; the gel tertiary amine catalyst is selected from N,N-bis(dimethylaminopropyl)isopropanolamine or N-(dimethylaminopropyl)diisopropanolamine; and the balanced tertiary amine catalyst is dimethylethanolamine.

5. A method for preparing the polyurethane slow-rebound buffer material according to claim 1, characterized in that: The following steps are involved: (1) Preparation of component A Weigh 40-80 parts of polyether polyol a, 10-40 parts of polyether polyol b, 10-40 parts of polyether polyol c, 0.1-1.5 parts of foaming agent, 0.5-1.5 parts of reaction catalyst, 0.5-1.0 parts of foam stabilizer, 2-8 parts of crosslinking agent, 2-6 parts of chain extender and 1-5 parts of cell opener respectively, add them into a container in sequence, stir and mix thoroughly to obtain component A; (2) Preparation of component B Weigh 10-40 parts of polyether polyol d by weight, add to a reaction kettle, stir and heat to 90-100°C, dehydrate and degas under vacuum for 2-3 hours, cool, add 20-50 parts of isocyanate, heat to 80-85°C and react for 2-3 hours, detect NCO content at 18%-22%, and obtain component B; (3) Preparation of buffer materials (a) Raise the mold temperature to 40-60°C and evenly spray a release agent on the inner surface of the mold; (b) Wait for 2 to 3 minutes until the release agent solidifies into a film on the mold surface; (c) Mix the prepared component A and component B in a ratio of 100:30-60, stir them thoroughly for 3-5 seconds at a speed of 2000-5000 rpm, and then quickly inject them into the mold and lock the mold; (d) The mold is maintained for 6 to 10 minutes, and then the mold is opened. After the product is taken out, it is aged at room temperature for 2 to 4 days to obtain the polyurethane slow rebound cushioning material and can be put into use.

6. The method for preparing the polyurethane slow-rebound cushioning material according to claim 5, characterized in that: The release agent is a water-based release agent.

7. The method for preparing the polyurethane slow-rebound buffer material according to claim 6, wherein the release agent is 3011B.

8. The method for preparing the polyurethane slow-rebound cushioning material according to claim 5, characterized in that: In the preparation of component B in step (2), a storage stabilizer is added at the same time as the isocyanate. The amount of the storage stabilizer added is 20-40×10 -6 share.

9. The polyurethane slow-rebound cushioning material according to claim 1 is used in cushioning protection of children's toys, sports shoe insoles, sports protective gear or electronic components.

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