Low-density high-elasticity bouncy ball material and preparation method thereof

Abstract

The invention discloses a low-density high-elasticity bouncy ball material and a preparation method thereof. Raw materials of the material comprise a component A and a component B, the component A comprises polyether polyol, a foaming agent, a catalyst and silicone oil; the component B is modified isocyanate; the mass ratio of the component A to the component B is 100: (30-40); the content of oxyethylidene in the polyether polyol chain segment in the component A is 20-80 wt%, and the content of oxybutylidene in the polyether polyol chain segment in the component A is 20-80 wt%; the component B is isocyanate group-terminated modified isocyanate prepared by reacting polyether polyol with isocyanate, and the polyether polyol is selected from polyether polyol with the average functionality of 3-6 and the molecular weight of 100-1000. The structure of polyether polyol in the component A is improved, and isocyanate in the component B is modified, so that the prepared bouncy ball material has high elasticity under low density.

Description

Technical Field

[0001] The invention belongs to the technical field of polyurethane, and particularly relates to a low-density high-elastic bouncy ball material and a preparation method thereof. Background Art

[0002] Compared with traditional rubber and other elastic balls, polyurethane elastic balls have the advantages of high production efficiency, low overall cost, and a wide range of application scenarios.

[0003] Patent CN 102786661 A discloses a high-elastic micro-foamed bouncy ball composition that can be molded in one step, wherein the polyether polyol is selected from one or a mixture of two or more of polypropylene oxide ether polyol, propylene oxide-ethylene oxide copolyether polyol, polyethylene glycol or polytetramethylene oxide ether polyol. Although a bouncy ball with a rebound of 80-85% can be prepared, the following problems exist: (1) The product density is relatively high, with a density greater than 500 kg / m 3 And the cost of raw material polytetramethylene ether is high.

[0004] Patent CN 102618019 A discloses a polyurethane reaction ball, wherein the polyether polyol al is prepared by the reaction of ethylene oxide or by the reaction of ethylene oxide and propylene oxide, and has a number average molecular weight of 3000-6000, an ethylene oxide content of 50-99 wt%, and an average functionality of 2.1-4. The rebound of this solution will be significantly reduced at low density (180 kg / m 3 , free fall rebound is 67%).

[0005] In summary, it is difficult for the polyurethane elastic ball in the prior art to achieve high resilience performance at low density. Summary of the invention

[0006] Purpose of the invention: The first purpose of the present invention is to provide a bouncy ball material that takes both density and resilience into consideration and can achieve good resilience at low density; the second purpose of the present invention is to provide a method for preparing the bouncy ball material.

[0007] The raw materials of the low-density high-elastic elastic ball material of the present invention include component A and component B; component A includes polyether polyol, foaming agent, catalyst and silicone oil; component B is modified isocyanate; the mass ratio of component A to component B is 100:30-40;

[0008] The polyether polyol chain segments in component A contain 20 to 80 wt% oxyethylene and 20 to 80 wt% oxybutylene;

[0009] The B component is a modified isocyanate terminated with isocyanate groups obtained by reacting a polyether polyol with an isocyanate, and the polyether polyol is selected from polyether polyols with an average functionality of 3 to 6 and a molecular weight of 100 to 1000.

[0010] Preferably, the polyether polyol in the component A is selected from polyether polyols having an average functionality of 3 to 6 and a molecular weight of 3,000 to 10,000.

[0011] Preferably, the component A comprises, by weight, 85 to 100 parts of polyether polyol, 0.1 to 5 parts of foaming agent, 0.5 to 1.0 parts of catalyst, and 0.2 to 0.5 parts of silicone oil.

[0012] Preferably, the foaming agent in the component A is selected from one or more of water, ethylene dichloride or pentafluoropropane.

[0013] Preferably, the catalyst in the A component is selected from one or more of triethylenediamine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, stannous octoate, and bis(dimethylaminoethyl) ether.

[0014] Preferably, the silicone oil in component A is selected from one or more of Evonik's B-8715, B-8734, B-8738, B-8742, and B-8747.

[0015] Preferably, the isocyanate content in the B component is 18% to 23%.

[0016] Preferably, the isocyanate in the component B is selected from one or more of 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and carbodiimide-modified isocyanate.

[0017] The method for preparing the bouncy ball composition of the present invention comprises the following steps:

[0018] (1) Mix the materials of component A;

[0019] (2) heating the isocyanate to dissolve the solid, adding the polyether polyol, and heating the polyether polyol to react with the isocyanate to obtain the modified isocyanate of component B;

[0020] (3) The component A mixed in step (1) and the modified isocyanate component B prepared in step (2) are mixed uniformly at 15 to 30° C., and then poured into a mold at 40 to 60° C., vented, and opened after 2 to 3 minutes to obtain the bouncy ball material.

[0021] Preferably, the overall density of the elastic ball product is 150-400 kg / m 3 The rebound rate is 80-85%.

[0022] Preferably, the reaction temperature of the polyether polyol and isocyanate is 75-80° C., and the reaction time is 1.5-2 h.

[0023] Invention mechanism: In the elastic ball material of the present invention, the polyether polyol of component A has higher activity and higher molecular flexibility than the polyether polyol in the existing elastic ball material due to the presence of primary hydroxyl groups and the block distribution of butylene structure, so that the product density is lower and the maturation cycle and product molding cycle are shorter; the polyether polyol of this structure is liquid above minus 10°C, and there is no problem of clogging equipment pipelines, etc., and it is suitable for ordinary foaming machines. In component B, a polyether polyol with a high cross-linking density is used, and the polyether polyol with an average functionality of 3 to 6 and a molecular weight of 100 to 1000 is modified with isocyanate, which can give the product higher rigidity. Component A and component B are combined to obtain an elastic ball product with higher resilience at low density.

[0024] Beneficial effects: Compared with the prior art, the present invention has the following advantages: (1) By improving the structure of the polyether polyol in component A and modifying the isocyanate in component B, the prepared elastic ball material has high elasticity at low density; (2) The material cost is low, the product density is low, and the overall cost is low; (3) The A / B material can be foamed at room temperature, the operation is simple, and it is suitable for ordinary foaming machines; (4) The aging cycle is short, the exhaust can be done in the middle, and the compatibility with the color printing film is high; (5) The product molding cycle is short; (6) The preparation method is simple and easy to industrialize. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is the infrared spectrum of the elastic ball material prepared in Example 1;

[0026] Figure 2 This is a picture of the elastic ball product prepared in Example 1. DETAILED DESCRIPTION

[0027] The present invention is further described below in conjunction with specific embodiments.

[0028] Example 1

[0029] The preparation method of the elastic ball material of the present invention comprises the following steps:

[0030] (1) Calculated by weight percentage, 100 parts of a polyether polyol (a product of Changhua Chemical) having an average functionality of 3, a molecular weight of 10,000, an oxyethylene content of 80 wt % and an oxybutylene content of 20 wt % in the chain segment, 0.2 parts of water as a foaming agent, 0.8 parts of triethylenediamine as a catalyst, and 0.4 parts of silicone oil B-8715 (a product of Evonik) were added into a container and mixed thoroughly to obtain component A;

[0031] (2) Calculated by mass percentage, 75 parts of 4,4'-diphenylmethane diisocyanate (Lupranate MS, BASF product) were added to a reaction container, the temperature was raised to 60°C, and after half an hour, 25 parts of polypropylene oxide polyether polyol with an average functionality of 3 and a molecular weight of 300 were added, the temperature was raised to 80°C, and the reaction was carried out for 2 hours to obtain a component B with an isocyanate content of 18%;

[0032] (3) Control the temperature of components A and B at 15-30°C, with the ratio of component A to component B being 100 / 30. Pour component A into a container according to the measurement, and then pour component B into the container containing component A according to the measurement. Stir for 5 seconds at a disperser speed of 3000 rpm, pour into a mold at a mold temperature of 40-60°C, shake the mold, and pierce the mold exhaust port with a fine needle to release air midway. Take it out after 2-3 minutes to obtain the bouncy ball material.

[0033] Example 2

[0034] The preparation method of the elastic ball material of the present invention comprises the following steps:

[0035] (1) Calculated by weight percentage, 100 parts of a polyether polyol (a product of Changhua Chemical) having an average functionality of 6, a molecular weight of 3000, an oxyethylene content of 20 wt% and an oxybutylene content of 80% in the chain segment, 0.3 parts of water as a foaming agent, 0.8 parts of triethylenediamine as a catalyst, and 0.4 parts of silicone oil B-8734 (a product of Evonik) were added into a container and mixed thoroughly to obtain component A;

[0036] (2) Calculated by mass percentage, 79 parts of carbodiimide modified isocyanate (Cosmonate LL, Wanhua Chemical product) were added to the reaction container, the temperature was raised to 60° C., and after half an hour, 21 parts of polypropylene oxide polyether polyol with an average functionality of 3 and a molecular weight of 600 were added, the temperature was raised to 80° C., and the reaction was carried out for 2 hours to obtain a component B with an isocyanate content of 20%;

[0037] (3) Control the temperature of components A and B at 15-30°C, with the ratio of component A to component B being 100 / 35. Pour component A into a container according to the measurement, and then pour component B into the container containing component A according to the measurement. Stir for 5 seconds at a disperser speed of 3000 rpm, pour into a mold at a mold temperature of 40-60°C, shake the mold, and pierce the mold exhaust port with a fine needle to release air midway. Take it out after 2-3 minutes to obtain the bouncy ball material.

[0038] Example 3

[0039] The preparation method of the elastic ball material of the present invention comprises the following steps:

[0040] (1) Calculated by weight percentage, 100 parts of a polyether polyol (a product of Changhua Chemical) having an average functionality of 4, a molecular weight of 6000, an oxyethylene content of 50 wt % and an oxybutylene content of 40 wt % in the chain segment, 0.2 parts of water as a foaming agent, 0.8 parts of tetramethylpropylenediamine as a catalyst, and 0.4 parts of silicone oil B-8715 (a product of Evonik) were added into a container and mixed thoroughly to obtain component A;

[0041] (2) Calculated by mass percentage, 40 parts of 4,4'-diphenylmethane diisocyanate (Lupranate MS, a product of BASF) and 40 parts of carbodiimide modified isocyanate (Cosmonate LL, a product of Wanhua Chemical) were added to a reaction container, the temperature was raised to 60°C, and after half an hour, 20 parts of polypropylene oxide polyether with an average functionality of 3 and a molecular weight of 900 were added, the temperature was raised to 80°C, and the reaction was carried out for 2 hours to obtain a component B with an isocyanate content of 23%;

[0042] (3) Control the temperature of components A and B at 15-30°C, with the ratio of component A to component B being 100 / 38. Pour component A into a container according to the measurement, and then pour component B into the container containing component A according to the measurement. Stir for 5 seconds at a disperser speed of 3000 rpm, pour into a mold at a mold temperature of 40-60°C, shake the mold, and pierce the mold exhaust port with a fine needle to release air midway. Take it out after 2-3 minutes to obtain the bouncy ball material.

[0043] Example 4

[0044] The preparation method of the elastic ball material of the present invention comprises the following steps:

[0045] (1) Calculated by weight percentage, 100 parts of a polyether polyol (a product of Changhua Chemical) having an average functionality of 3, a molecular weight of 6000, an oxyethylene content of 35 wt % and an oxybutylene content of 45 wt % in the chain segment, 0.2 parts of water as a foaming agent, 0.8 parts of pentamethyldiethylenetriamine as a catalyst, and 0.4 parts of silicone oil B-8715 (a product of Evonik) were added into a container and mixed thoroughly to prepare component A;

[0046] (2) Calculated by mass percentage, 39 parts of 2,4'-diphenylmethane diisocyanate and 39 parts of 4,4'-diphenylmethane diisocyanate (Lupranate MIPS, BASF product) were added to a reaction container, the temperature was raised to 60° C., and after half an hour, 22 parts of polypropylene oxide polyether polyol with an average functionality of 6 and a molecular weight of 600 were added, the temperature was raised to 80° C., and the reaction was carried out for 2 hours to obtain a component B with an isocyanate content of 23%;

[0047] (3) Control the temperature of components A and B at 15-30°C, with the ratio of component A to component B being 100 / 38. Pour component A into a container according to the measurement, and then pour component B into the container containing component A according to the measurement. Stir for 5 seconds at a disperser speed of 3000 rpm, pour into a mold at a mold temperature of 40-60°C, shake the mold, and pierce the mold exhaust port with a fine needle to release air midway. Take it out after 2-3 minutes to obtain the bouncy ball material.

[0048] Example 5

[0049] The preparation method of the elastic ball material of the present invention comprises the following steps:

[0050] (1) Calculated by weight percentage, 100 parts of a polyether polyol (a product of Changhua Chemical) having an average functionality of 6, a molecular weight of 8000, an oxyethylene content of 25 wt% and an oxybutylene content of 65% in the chain segment, 5 parts of a blowing agent, 0.8 parts of a catalyst, and 0.4 parts of a silicone oil B-8747 (a product of Evonik) were added into a container and mixed thoroughly to obtain component A;

[0051] (2) Calculated by mass percentage, 78 parts of 4,4'-diphenylmethane diisocyanate (Lupranate MS, BASF product) were added to a reaction container, the temperature was raised to 60° C., and after half an hour, 22 parts of polypropylene oxide polyether polyol with an average functionality of 3 and a molecular weight of 600 were added, the temperature was raised to 80° C., and the reaction was carried out for 2 hours to obtain a component B with an isocyanate content of 23%;

[0052] (3) Control the temperature of components A and B at 15-30°C, with the ratio of component A to component B being 100 / 38. Pour component A into a container according to the measurement, and then pour component B into the container containing component A according to the measurement. Stir for 5 seconds at a disperser speed of 3000 rpm, pour into a mold at a mold temperature of 40-60°C, shake the mold, and pierce the mold exhaust port with a fine needle to release air midway. Take it out after 2-3 minutes to obtain the bouncy ball material.

[0053] Comparative Example 1

[0054] Reference is made to Comparative Example 1 of patent CN 102786661 A.

[0055] Comparative Example 2

[0056] Based on Example 1, the polyether polyol in component A is replaced by a polyether polyol (product of Changhua Chemical) with an average functionality of 3, a molecular weight of 10,000, an oxyethylene content of 80 wt% and an oxypropylene content of 20% in the chain segment, and the other conditions remain unchanged.

[0057] Comparative Example 3

[0058] On the basis of Example 1, the polyether polyol in component B was replaced with a polyether polyol having an average functionality of 3 and a molecular weight of 6000, and the other conditions remained unchanged.

[0059] Structural characterization

[0060] The infrared structural characterization of the elastic ball material prepared in Example 1 is as follows Figure 1 As shown in the figure, it can be seen that the characteristic peak of polyether ether bond appears at 1108.4cm-1, and the characteristic peak of isocyanate group appears at 2274.58cm-1.

[0061] Performance Test:

[0062] The density, 2-meter free fall rebound rate, and mold opening time of the elastic balls prepared in Examples 1 to 5 and Comparative Examples 1 to 3 were tested. The test method is as follows:

[0063] Density of elastic ball: GB / T 6343-1995

[0064] 2m free fall rebound rate: GB / T 6670-2008

[0065] Mold opening time: The stopwatch starts when the mold is completely closed and stops when the mold is opened.

[0066] Table 1 Performance indexes of polyurethane elastic balls prepared in Examples 1 to 5 and Comparative Examples 1 to 3

[0067]

[0068]

[0069] It can be seen from Table 1 that the resilience of the elastic ball materials prepared in Examples 1 to 5 fluctuates less with the change of density, has better elasticity, and has a short mold opening time.

[0070] In Comparative Example 1, under the same raw material system, the elasticity decays significantly with the decrease of density.

[0071] The rebound performance of Comparative Example 2 is not good compared with Example 1. This is because the absence of an oxygen-free butylene structure leads to a weakening of the flexibility of the chain segments and a decrease in elasticity.

[0072] The rebound performance of Comparative Example 3 is poor compared with that of Example 1. This is because the molecular weight of the polyether polyol in component B is too large, resulting in a decrease in crosslinking density and elasticity.

Claims

1. A low-density high-elastic bouncy ball material, characterized in that: The raw materials of the material include component A and component B; component A includes polyether polyol, foaming agent, catalyst and silicone oil; component B is modified isocyanate; the mass ratio of component A to component B is 100:30-40; The polyether polyol chain segments in component A contain 20 to 80 wt% oxyethylene and 20 to 80 wt% oxybutylene; The B component is a modified isocyanate terminated with isocyanate groups obtained by reacting a polyether polyol with an isocyanate, and the polyether polyol is selected from polyether polyols with an average functionality of 3 to 6 and a molecular weight of 100 to 1000.

2. The low-density high-elastic elastic ball material according to claim 1, characterized in that: The polyether polyol in the component A is selected from polyether polyols having an average functionality of 3 to 6 and a molecular weight of 3,000 to 10,000.

3. The low-density high-elastic elastic ball material according to claim 1, characterized in that: The component A comprises, by weight, 85 to 100 parts of polyether polyol, 0.1 to 5 parts of foaming agent, 0.5 to 1.0 parts of catalyst and 0.2 to 0.5 parts of silicone oil.

4. The low-density high-elastic elastic ball material according to claim 1, characterized in that: The isocyanate content in the B component is 18% to 23%.

5. The low-density high-elastic elastic ball material according to claim 1, characterized in that: The foaming agent in the component A is selected from one or more of water, ethylene dichloride or pentafluoropropane.

6. The low-density high-elastic elastic ball material according to claim 1, characterized in that: The catalyst in the A component is selected from one or more of triethylenediamine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, stannous octoate, and bis(dimethylaminoethyl)ether.

7. The low-density high-elastic elastic ball material according to claim 1, characterized in that: The isocyanate in the B component is selected from one or more of 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and carbodiimide-modified isocyanate.

8. A method for preparing the low-density high-elastic bouncy ball material according to any one of claims 1 to 7, characterized in that: The following steps are involved: (1) Mix the materials of component A; (2) heating the isocyanate until the solid is dissolved, adding the polyether polyol, and heating the polyether polyol to react with the isocyanate to obtain a modified isocyanate of component B; (3) The component A mixed in step (1) and the modified isocyanate component B prepared in step (2) are mixed uniformly at 15 to 30° C., and then poured into a mold at 40 to 60° C., vented, and opened after 2 to 3 minutes to obtain the bouncy ball material.

9. The method for preparing a low-density high-elastic elastic ball material according to claim 8, characterized in that: The overall density of the elastic ball material is 150-400 kg / m 3 The rebound rate is 80-85%.

10. The method for preparing a low-density high-elastic elastic ball material according to claim 8, characterized in that: The reaction temperature of the polyether polyol and isocyanate is 75-85° C., and the reaction time is 1.5-2 hours.

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