Yellowing-resistant polyurethane grip material and preparation method thereof

Abstract

The invention relates to the technical field of high polymer materials, and particularly discloses an anti-yellowing polyurethane grip material and a preparation method thereof. The anti-yellowing polyurethane grip material comprises polyurethane resin and a foaming agent, and is characterized by further comprising an anti-yellowing agent. The anti-yellowing agent is prepared from an ultraviolet light absorber, a polymer of succinic acid and (4-hydroxy-2, 2, 6, 6-tetramethyl-1-piperidinol) and beta-(3, 5-di-tert-butyl-4-hydroxyphenyl) octadecanol propionate, and the anti-yellowing agent is prepared from an ultraviolet light absorber, a polymer of succinic acid and (4-hydroxy-2, 2, 6, 6-tetramethyl-1-piperidinol). According to the anti-yellowing polyurethane grip material disclosed by the invention, the anti-yellowing agent containing the ultraviolet light absorber, the polymer of the succinic acid and the (4-hydroxy-2, 2, 6, 6-tetramethyl-1-piperidinol) and the beta-(3, 5-di-tert-butyl-4-hydroxyphenyl) octadecanol propionate is added into the anti-yellowing polyurethane grip material, so that the anti-yellowing performance of the grip material is improved; therefore, the prepared anti-yellowing polyurethane grip material has relatively good anti-yellowing performance.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to a yellowing-resistant polyurethane grip material and a preparation method thereof. Background Art

[0002] Polyurethane is a type of macromolecular polymer containing carbamate groups on the main chain. Its full name is polyurethane. Due to its excellent performance, it has become a key material in many industries and is known as the "fifth largest plastic". Soft polyurethane has better stability, chemical resistance, resilience and mechanical properties than PVC foam materials, and has smaller compression deformation, so it is widely used as a grip material.

[0003] Chinese invention patent CN202011370729.X discloses a golf club grip material and its preparation method. The golf club grip material comprises the following components in parts by weight: 80-120 parts of polyurethane resin; 5-10 parts of foaming composition; 0.5-2 parts of anti-aging agent; 1-3 parts of lubricant. When the golf club grip material is used, it is attached to the golf club grip, which can make the golf club have a special and comfortable grip.

[0004] Although the golf club grip material prepared in the above patent has a good grip when used on a golf club grip, the inventor found in further research that the anti-aging agent is not well matched, resulting in poor yellowing resistance. Therefore, a polyurethane grip material with good yellowing resistance is needed. Summary of the invention

[0005] In order to overcome at least one of the technical problems existing in the prior art, the present invention provides a yellowing-resistant polyurethane grip material and a preparation method thereof.

[0006] The above technical problems to be solved by the present invention are solved by the following technical solutions:

[0007] The present invention firstly provides a yellowing-resistant polyurethane grip material, which comprises a polyurethane resin and a foaming agent, and is characterized in that it also comprises an anti-yellowing agent.

[0008] Preferably, the anti-yellowing agent comprises an ultraviolet absorber, a polymer of succinic acid and (4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol) and β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate.

[0009] The present invention provides a novel yellowing-resistant polyurethane grip material; the present invention adds an anti-yellowing agent comprising an ultraviolet absorber, a polymer of succinic acid and (4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol) and β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate octadecyl alcohol to the yellowing-resistant polyurethane grip material, so that the prepared yellowing-resistant polyurethane grip material has good yellowing resistance.

[0010] More preferably, the weight ratio of the ultraviolet absorber, succinic acid, (polymer of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol) and β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate is 3-5:1-2:1-2.

[0011] Most preferably, the weight ratio of the ultraviolet absorber, succinic acid to (polymer of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol) 2 and β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate is 4:1:1.

[0012] Preferably, the ultraviolet absorber comprises cerium dioxide and 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole.

[0013] More preferably, the weight ratio of cerium dioxide to 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole in the ultraviolet absorber is 2 to 4:1.

[0014] Most preferably, the weight ratio of cerium dioxide to 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole in the ultraviolet absorber is 3:1.

[0015] Further preferably, the cerium dioxide is modified cerium dioxide;

[0016] The modified cerium dioxide is prepared by the following method:

[0017] (1) Add the modifier to water and stir evenly to obtain a modified solution;

[0018] (2) mixing the modified liquid and cerium dioxide and stirring for 1 to 3 hours to obtain a modified mixed slurry;

[0019] (3) Drying the modified mixed slurry to obtain the modified cerium dioxide.

[0020] The inventors found in further research that the yellowing resistance of the yellowing-resistant polyurethane grip material can be further improved by replacing cerium dioxide with modified cerium dioxide obtained by the above method in the ultraviolet absorber.

[0021] In addition, the inventors also found in their research that after adding the anti-yellowing agent described in the present invention to the yellowing-resistant polyurethane grip material, the tensile strength of the yellowing-resistant polyurethane grip material was reduced, which needs to be further improved; and the inventors were surprised to find in further research that when the ultraviolet absorber is replaced by modified cerium dioxide obtained by the above method, it can further significantly improve the tensile strength of the yellowing-resistant polyurethane grip material.

[0022] Further preferably, the modifier obtained in step (1) includes dichloromethyltriethoxysilane, coconut oil fatty acid diethanolamide and sodium dodecyl diphenyl ether disulfonate.

[0023] The inventors surprisingly found in further research that the composition of the modifier of the present invention is very critical; in the ultraviolet absorber, the modified cerium dioxide obtained by modifying the modifier composed of triethoxy dichloromethyl silane, coconut oil fatty acid diethanolamide and sodium dodecyl diphenyl oxide disulfonate must be used to replace the cerium dioxide, so as to further significantly improve the tensile strength of the yellowing-resistant polyurethane grip material. However, replacing the cerium dioxide with the modified cerium dioxide obtained by modifying the modifier composed of only two of triethoxy dichloromethyl silane, coconut oil fatty acid diethanolamide and sodium dodecyl diphenyl oxide disulfonate cannot further significantly improve the tensile strength of the yellowing-resistant polyurethane grip material.

[0024] Preferably, the weight ratio of dichloromethyl triethoxysilane, coconut oil fatty acid diethanolamide and sodium dodecyl diphenyl ether disulfonate in the modifier is 1-3:2-4:1-3.

[0025] Most preferably, the weight ratio of dichloromethyltriethoxysilane, coconut oil fatty acid diethanolamide and sodium dodecyl diphenyl ether disulfonate in the modifier is 2:3:2.

[0026] Preferably, the weight ratio of the modifier to water is 1:8-12.

[0027] Most preferably, the weight ratio of modifier to water is 1:10.

[0028] Preferably, the usage ratio of the modified liquid to cerium dioxide is 2 to 4:1.

[0029] Most preferably, the ratio of the modified liquid to cerium dioxide is 3:1.

[0030] Preferably, the yellowing-resistant polyurethane grip material comprises the following components in parts by weight:

[0031] 80-120 parts of polyurethane resin; 5-10 parts of foaming agent; 1-3 parts of anti-yellowing agent.

[0032] The present invention also provides a method for preparing a yellowing-resistant polyurethane grip material, which comprises the following steps: placing polyurethane resin, a foaming agent and an anti-aging agent into a mixing device for mixing and then producing sheets to obtain the yellowing-resistant polyurethane grip material.

[0033] Beneficial effects: The present invention provides a new yellowing-resistant polyurethane grip material; the present invention adds an anti-yellowing agent comprising an ultraviolet absorber, a polymer of succinic acid and (4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol) and β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate octadecyl ester to the yellowing-resistant polyurethane grip material, so that the prepared yellowing-resistant polyurethane grip material has good yellowing resistance; further, the present invention uses modified cerium dioxide obtained by the new method of the present invention to replace cerium dioxide in the ultraviolet absorber, which can further significantly improve the tensile strength of the yellowing-resistant polyurethane grip material. DETAILED DESCRIPTION

[0034] The present invention is further explained below in conjunction with specific examples, but the examples do not limit the present invention in any form.

[0035] The polyurethane resin in the following examples is a thermoplastic polyurethane with a brand name of DP9395A produced by Bayer, Germany.

[0036] Example 1 Preparation of yellowing-resistant polyurethane grip material

[0037] Raw material weight composition: 100 parts of thermoplastic polyurethane; 8 parts of foaming agent; 2 parts of anti-yellowing agent;

[0038] The foaming agent is sodium bicarbonate;

[0039] The anti-yellowing agent is composed of an ultraviolet absorber, succinic acid and (polymer of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol) 2 and β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate octadecyl alcohol ester in a weight ratio of 4:1:1;

[0040] The ultraviolet absorber is composed of cerium dioxide and 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole in a weight ratio of 3:1.

[0041] Preparation method: put thermoplastic polyurethane, foaming agent and anti-yellowing agent into an open rubber mixer, and mix them at 150°C for 20 minutes; after mixing, flakes are produced to obtain a sheet-like anti-yellowing polyurethane grip material.

[0042] Example 2 Preparation of yellowing-resistant polyurethane grip material

[0043] Raw material weight composition: 100 parts of thermoplastic polyurethane; 8 parts of foaming agent; 2 parts of anti-yellowing agent;

[0044] The foaming agent is sodium bicarbonate;

[0045] The anti-yellowing agent is composed of an ultraviolet absorber, succinic acid and (polymer of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol) 2 and β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate octadecyl alcohol ester in a weight ratio of 4:1:1;

[0046] The ultraviolet absorber is composed of modified cerium dioxide and 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole in a weight ratio of 3:1;

[0047] The modified cerium dioxide is prepared by the following method:

[0048] (1) adding a modifier to water and stirring to obtain a modified liquid; wherein the weight ratio of the modifier to water is 1:10; the modifier is composed of dichloromethyl triethoxysilane, coconut oil fatty acid diethanolamide and sodium dodecyl diphenyl ether disulfonate in a weight ratio of 2:3:2;

[0049] (2) mixing the modified liquid and cerium dioxide and stirring for 2 hours to obtain a modified mixed slurry; wherein the amount ratio of the modified liquid to cerium dioxide is 3:1;

[0050] (3) Drying the modified mixed slurry to obtain the modified cerium dioxide.

[0051] Preparation method: put thermoplastic polyurethane, foaming agent and anti-yellowing agent into an open rubber mixer, and mix them at 150°C for 20 minutes; after mixing, flakes are produced to obtain a sheet-like anti-yellowing polyurethane grip material.

[0052] Comparative Example 1 Preparation of yellowing-resistant polyurethane grip material

[0053] Raw material weight composition: 100 parts of thermoplastic polyurethane; 8 parts of foaming agent; 2 parts of anti-yellowing agent;

[0054] The foaming agent is sodium bicarbonate;

[0055] The anti-yellowing agent is composed of an ultraviolet absorber, succinic acid and (polymer of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol) 2 and β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate octadecyl alcohol ester in a weight ratio of 4:1:1;

[0056] The ultraviolet absorber is composed of modified cerium dioxide and 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole in a weight ratio of 3:1;

[0057] The modified cerium dioxide is prepared by the following method:

[0058] (1) adding a modifier to water and stirring to obtain a modified liquid; wherein the weight ratio of the modifier to water is 1:10; the modifier is composed of dichloromethyl triethoxysilane and coconut oil fatty acid diethanolamide in a weight ratio of 2:3;

[0059] (2) mixing the modified liquid and cerium dioxide and stirring for 2 hours to obtain a modified mixed slurry; wherein the amount ratio of the modified liquid to cerium dioxide is 3:1;

[0060] (3) Drying the modified mixed slurry to obtain the modified cerium dioxide.

[0061] Preparation method: put thermoplastic polyurethane, foaming agent and anti-yellowing agent into an open rubber mixer, and mix them at 150°C for 20 minutes; after mixing, flakes are produced to obtain a sheet-like anti-yellowing polyurethane grip material.

[0062] Comparative Example 2 Preparation of yellowing-resistant polyurethane grip material

[0063] Raw material weight composition: 100 parts of thermoplastic polyurethane; 8 parts of foaming agent; 2 parts of anti-yellowing agent;

[0064] The foaming agent is sodium bicarbonate;

[0065] The anti-yellowing agent is composed of an ultraviolet absorber, succinic acid and (polymer of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol) 2 and β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate octadecyl alcohol ester in a weight ratio of 4:1:1;

[0066] The ultraviolet absorber is composed of modified cerium dioxide and 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole in a weight ratio of 3:1;

[0067] The modified cerium dioxide is prepared by the following method:

[0068] (1) adding a modifier to water and stirring to obtain a modified liquid; wherein the weight ratio of the modifier to water is 1:10; the modifier is composed of coconut oil fatty acid diethanolamide and sodium dodecyl diphenyl ether disulfonate in a weight ratio of 3:2;

[0069] (2) mixing the modified liquid and cerium dioxide and stirring for 2 hours to obtain a modified mixed slurry; wherein the amount ratio of the modified liquid to cerium dioxide is 3:1;

[0070] (3) Drying the modified mixed slurry to obtain the modified cerium dioxide.

[0071] Preparation method: put thermoplastic polyurethane, foaming agent and anti-yellowing agent into an open rubber mixer, and mix them at 150°C for 20 minutes; after mixing, flakes are produced to obtain a sheet-like anti-yellowing polyurethane grip material.

[0072] Comparative Example 3 Preparation of yellowing-resistant polyurethane grip material

[0073] Raw material weight composition: 100 parts of thermoplastic polyurethane; 8 parts of foaming agent; 2 parts of anti-yellowing agent;

[0074] The foaming agent is sodium bicarbonate;

[0075] The anti-yellowing agent is composed of an ultraviolet absorber, succinic acid and (polymer of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol) 2 and β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate octadecyl alcohol ester in a weight ratio of 4:1:1;

[0076] The ultraviolet absorber is composed of modified cerium dioxide and 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole in a weight ratio of 3:1;

[0077] The modified cerium dioxide is prepared by the following method:

[0078] (1) adding a modifier to water and stirring to obtain a modified solution; wherein the weight ratio of the modifier to water is 1:10; the modifier is composed of dichloromethyl triethoxysilane and sodium dodecyl diphenyl ether disulfonate in a weight ratio of 1:1;

[0079] (2) mixing the modified liquid and cerium dioxide and stirring for 2 hours to obtain a modified mixed slurry; wherein the amount ratio of the modified liquid to cerium dioxide is 3:1;

[0080] (3) Drying the modified mixed slurry to obtain the modified cerium dioxide.

[0081] Preparation method: put thermoplastic polyurethane, foaming agent and anti-yellowing agent into an open rubber mixer, and mix them at 150°C for 20 minutes; after mixing, flakes are produced to obtain a sheet-like anti-yellowing polyurethane grip material.

[0082] The yellowing grade of the yellowing-resistant polyurethane grip materials prepared in Examples 1 to 2 and Comparative Examples 1 to 3 was tested with reference to the method in GB250-1995; the tensile strength of the yellowing-resistant polyurethane grip materials prepared in Examples 1 to 2 and Comparative Examples 1 to 3 was tested with reference to the method in GB / T 528-2009; the test results are shown in Table 1.

[0083] Table 1. Test results of yellowing-resistant polyurethane grip material properties

[0084]

[0085]

[0086] It can be seen from the experimental results in Table 1 that the yellowing grade of the yellowing-resistant polyurethane grip material prepared in Example 1 reaches 3.9; this indicates that the present invention adds an anti-yellowing agent comprising an ultraviolet absorber, a polymer of succinic acid and (4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol) and β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate octadecyl alcohol to the yellowing-resistant polyurethane grip material, so that the prepared yellowing-resistant polyurethane grip material has good yellowing resistance.

[0087] It can be seen from the experimental results in Table 1 that the yellowing grade of the yellowing-resistant polyurethane grip material prepared in Example 2 reaches 4.5, which is further significantly improved compared with Example 1; this shows that when the ultraviolet absorber is replaced by modified cerium dioxide obtained by the method of the present invention, the yellowing resistance of the yellowing-resistant polyurethane grip material can be further improved.

[0088] It can be seen from the experimental results in Table 1 that the tensile strength of the yellowing-resistant polyurethane grip material prepared in Example 2 is much higher than that of the yellowing-resistant polyurethane grip material prepared in Example 1; this indicates that when the ultraviolet absorber is replaced by the modified cerium dioxide obtained by the method of the present invention, the tensile strength of the yellowing-resistant polyurethane grip material can be further greatly improved.

[0089] It can be seen from the experimental results in Table 1 that the tensile strength of the yellowing-resistant polyurethane grip material prepared in Comparative Examples 1 to 3 is improved compared with that in Example 1, but the improvement is not large and is much smaller than that of the yellowing-resistant polyurethane grip material prepared in Example 2. This shows that the composition of the modifier of the present invention is very critical. In the ultraviolet absorber, the modified cerium dioxide obtained by modifying the modifier composed of triethoxydichloromethylsilane, coconut oil fatty acid diethanolamide and sodium dodecyl diphenyl oxide disulfonate must be used to replace the cerium dioxide to further significantly improve the tensile strength of the yellowing-resistant polyurethane grip material. However, the use of the modified cerium dioxide obtained by modifying the modifier composed of only two of triethoxydichloromethylsilane, coconut oil fatty acid diethanolamide and sodium dodecyl diphenyl oxide disulfonate to replace the cerium dioxide does not further significantly improve the tensile strength of the yellowing-resistant polyurethane grip material.

Claims

1. A yellowing-resistant polyurethane grip material, characterized in that: The invention comprises a polyurethane resin and a foaming agent, and is characterized in that it also comprises an anti-yellowing agent.

2. The yellowing-resistant polyurethane grip material according to claim 1, characterized in that: The anti-yellowing agent comprises an ultraviolet absorber, a polymer of succinic acid and (4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol) and β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate octadecyl alcohol.

3. The yellowing-resistant polyurethane grip material according to claim 1, characterized in that: The weight ratio of the ultraviolet absorber, succinic acid, (polymer of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol) and β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate is 3-5:1-2:1-2. Most preferably, the weight ratio of the ultraviolet absorber, succinic acid to (polymer of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol) 2 and β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate is 4:1:

1.

4. The yellowing-resistant polyurethane grip material according to claim 1, characterized in that: The ultraviolet absorber comprises cerium dioxide and 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole.

5. The yellowing-resistant polyurethane grip material according to claim 4, characterized in that: The weight ratio of cerium dioxide to 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole in the ultraviolet absorber is 2 to 4:

1. Most preferably, the weight ratio of cerium dioxide to 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole in the ultraviolet absorber is 3:

1.

6. The yellowing-resistant polyurethane grip material according to claim 1, characterized in that: The cerium dioxide is modified cerium dioxide; The modified cerium dioxide is prepared by the following method: (1) Add the modifier to water and stir evenly to obtain a modified solution; (2) mixing the modified liquid and cerium dioxide and stirring for 1 to 3 hours to obtain a modified mixed slurry; (3) Drying the modified mixed slurry to obtain the modified cerium dioxide.

7. The yellowing-resistant polyurethane grip material according to claim 6, characterized in that: The modifier obtained in step (1) includes dichloromethyl triethoxysilane, coconut oil fatty acid diethanolamide and sodium dodecyl diphenyl ether disulfonate.

8. The yellowing-resistant polyurethane grip material according to claim 7, characterized in that: The weight ratio of dichloromethyl triethoxysilane, coconut oil fatty acid diethanolamide and sodium dodecyl diphenyl ether disulfonate in the modifier is 1-3:2-4:1-3. Most preferably, the weight ratio of dichloromethyltriethoxysilane, coconut oil fatty acid diethanolamide and sodium dodecyl diphenyl ether disulfonate in the modifier is 2:3:

2.

9. The yellowing-resistant polyurethane grip material according to claim 1, characterized in that: Contains the following components in parts by weight: 80-120 parts of polyurethane resin; 5-10 parts of foaming agent; 1-3 parts of anti-yellowing agent.

10. The method for preparing the yellowing-resistant polyurethane grip material according to any one of claims 1 to 9, characterized in that: The method comprises the following steps: putting polyurethane resin, foaming agent and anti-aging agent into a mixing device for mixing and then producing sheets to obtain the yellowing-resistant polyurethane grip material.

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