A yellowing-resistant polyurethane grip material and a method for preparing the same

Abstract

The application relates to the technical field of high polymer materials, and particularly discloses a yellowing-resistant polyurethane handle material and a preparation method thereof. The yellowing-resistant polyurethane handle material comprises a polyurethane resin and a foaming agent, and is characterized by further comprising a yellowing-resistant agent. The yellowing-resistant agent comprises an ultraviolet 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) propionate octadecanol ester. The yellowing-resistant polyurethane handle material prepared by adding the yellowing-resistant agent containing the ultraviolet absorber, the polymer of succinic acid and (4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol) and the beta-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate octadecanol ester has good yellowing resistance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high molecular materials, in particular to a yellowing-resistant polyurethane handle material and a preparation method thereof. BACKGROUND

[0002] Polyurethane is a kind of macromolecular polymer containing urethane groups in the main chain, and its full name is polyurethane. Because of its excellent performance, it has become a key material in many industries and is known as the "fifth plastic". Soft polyurethane has better stability, chemical resistance, resilience and mechanical properties than PVC foaming material, and has smaller compression deformation, so it is widely used as a handle material.

[0003] Chinese invention patent CN202011370729.X discloses a golf club handle material and a preparation method thereof. The golf club handle material is prepared from the following components by weight: polyurethane resin 80-120 parts; foaming composition 5-10 parts; anti-aging agent 0.5-2 parts; lubricant 1-3 parts. The golf club handle material is used to stick on the golf club handle, so that the golf club has a special comfortable grip feeling.

[0004] Although the golf club handle material prepared in the above-mentioned patent has good grip feeling when used on the golf club handle, the inventors found in further research that the anti-aging agent is not well matched, which makes the yellowing resistance performance poor. Therefore, it is necessary to provide a polyurethane handle material with good yellowing resistance. SUMMARY

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

[0006] The above technical problems solved by the present application are solved by the following technical solutions:

[0007] The present application first provides a yellowing-resistant polyurethane handle material, which comprises polyurethane resin and foaming agent, characterized in that it further comprises a yellowing-resistant agent.

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

[0009] The application provides a novel yellowing-resistant polyurethane handle material; the yellowing-resistant polyurethane handle material is prepared by adding a yellowing-resistant agent containing an ultraviolet 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) propionic acid octadecyl ester, so that the prepared yellowing-resistant polyurethane handle material has good yellowing resistance.

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

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

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

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

[0014] Most preferably, the weight ratio of cerium dioxide and 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) adding a modifier to water, stirring to obtain a modified liquid;

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

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

[0020] The inventors have found in further research that, when the ultraviolet absorber is replaced by the modified cerium dioxide prepared by the above method, the yellowing resistance of the yellowing-resistant polyurethane handle material can be further improved.

[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, and further improvement is needed; and the inventors were surprisingly found 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] Further research by the inventors surprisingly revealed that the composition of the modifiers in the present invention is crucial; in order to significantly improve the tensile strength of the yellowing-resistant polyurethane grip material, replacing ceria with a modified ceria obtained by simultaneously modifying the UV absorber with a modifier consisting of triethoxydichloromethylsilane, coconut oil fatty acid diethanolamide, and sodium dodecyl diphenyl oxide disulfonate was essential. However, replacing ceria with a modified ceria obtained by modifying the UV absorber with only two of the three modifiers did not significantly improve the tensile strength of the yellowing-resistant polyurethane grip material.

[0024] Preferably, the weight ratio of dichloromethyltriethoxysilane, 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 ratio of the modified liquid to cerium dioxide is 2 to 4:1.

[0029] Most preferably, the ratio of the modified liquid to the 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 application further provides a preparation method of the yellowing-resistant polyurethane handle material, which comprises the following steps: placing polyurethane resin, a foaming agent and an anti-aging agent into a mixing device for mixing and sheeting to obtain the yellowing-resistant polyurethane handle material.

[0033] Beneficial effects: the application provides a brand-new yellowing-resistant polyurethane handle material; the application adds a yellowing-resistant 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) propyl octadecyl alcohol ester into the yellowing-resistant polyurethane handle material, so that the yellowing-resistant polyurethane handle material prepared has good yellowing resistance; further, the application uses modified cerium dioxide obtained by a brand-new method of the application to replace cerium dioxide as the ultraviolet absorber, which can further greatly improve the tensile strength of the yellowing-resistant polyurethane handle material. DETAILED DESCRIPTION

[0034] The application will be further explained in combination with specific embodiments, but the embodiments do not limit the application in any form.

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

[0036] Preparation of the yellowing-resistant polyurethane handle material in Example 1

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

[0038] The foaming agent is sodium bicarbonate;

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

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

[0041] Preparation method: placing the thermoplastic polyurethane, the foaming agent and the yellowing-resistant agent into an open type rubber mixing machine, mixing at 150℃ for 20 min; sheeting after the mixing is completed to obtain the sheet-shaped yellowing-resistant polyurethane handle material.

[0042] Preparation of the yellowing-resistant polyurethane handle material in Example 2

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

[0044] the foaming agent is sodium bicarbonate;

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

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

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

[0048] (1) add the modifier to water and stir uniformly 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 with a weight ratio of 2:3:2;

[0049] (2) mix and stir the modified liquid and cerium dioxide for 2h to obtain a modified mixed slurry; wherein the use amount ratio of the modified liquid to cerium dioxide is 3:1;

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

[0051] Preparation method: put the thermoplastic polyurethane, foaming agent and anti-yellowing agent into an open type rubber mixing machine, mix at 150℃ for 20min; after mixing, take out the sheet to obtain the sheet-shaped anti-yellowing polyurethane handle material.

[0052] Preparation of the anti-yellowing polyurethane handle material of comparative example 1

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

[0054] the foaming agent is sodium bicarbonate;

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

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

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

[0058] (1) adding a modifier into water, 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 with a weight ratio of 2:3;

[0059] (2) mixing and stirring the modified liquid and cerium dioxide for 2h to obtain a modified mixed slurry; wherein the usage 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: placing the thermoplastic polyurethane, foaming agent and yellowing-resistant agent into an open type rubber mixing machine, mixing at 150℃ for 20min; after the mixing is completed, sheeting is performed to obtain a sheet-shaped yellowing-resistant polyurethane handle material.

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

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

[0064] The foaming agent is sodium bicarbonate;

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

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

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

[0068] (1) adding a modifier into water, 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 with a weight ratio of 2:3;

[0069] (2) mixing and stirring the modified liquid and cerium dioxide for 2h to obtain a modified mixed slurry; wherein the usage 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: the thermoplastic polyurethane, foaming agent and yellowing resistant agent were put into an open type rubber mixing machine, mixed at 150℃ for 20 min; after mixing, the sheet was taken out, and the sheet-shaped yellowing resistant polyurethane handle material was obtained.

[0072] Preparation of the yellowing resistant polyurethane handle material of the comparative example 3

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

[0074] The foaming agent is sodium bicarbonate;

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

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

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

[0078] (1) the modifier is added to water, and stirred 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 sodium dodecyl diphenyl ether disulfonate with a weight ratio of 1:1;

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

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

[0081] Preparation method: the thermoplastic polyurethane, foaming agent and yellowing resistant agent were put into an open type rubber mixing machine, mixed at 150℃ for 20 min; after mixing, the sheet was taken out, and the sheet-shaped yellowing resistant polyurethane handle material was obtained.

[0082] The yellowing grade of the yellowing resistant polyurethane handle material prepared in examples 1-2 and comparative examples 1-3 was tested according to the method in GB 250-1995; the tensile strength of the yellowing resistant polyurethane handle material prepared in examples 1-2 and comparative examples 1-3 was tested according to the method in GB / T 528-2009; the test results are shown in table 1.

[0083] Table 1. Test results of the properties of the yellowing resistant polyurethane handle material

[0084]

[0085]

[0086] As can be seen from the experimental results in Table 1, the yellowing grade of the yellowing-resistant polyurethane handle material prepared in Example 1 reaches 3.9; this shows that, by adding the yellowing-resistant agent containing the ultraviolet absorber, the polymer of succinic acid and (4-hydroxy-2, 2, 6, 6-tetramethyl-1-piperidinol), and β-(3, 5-di-tert-butyl-4-hydroxyphenyl) propyl octadecyl ester into the yellowing-resistant polyurethane handle material, the yellowing-resistant polyurethane handle material prepared has better yellowing resistance.

[0087] As can be seen from the experimental results in Table 1, the yellowing grade of the yellowing-resistant polyurethane handle material prepared in Example 2 reaches 4.5, which is further significantly improved compared with Example 1; this shows that, by replacing the cerium dioxide with the modified cerium dioxide modified by the method of the present application, the yellowing resistance of the yellowing-resistant polyurethane handle material can be further improved.

[0088] As can be seen from the experimental results in Table 1, the tensile strength of the yellowing-resistant polyurethane handle material prepared in Example 2 is significantly higher than that of the yellowing-resistant polyurethane handle material prepared in Example 1; this shows that, by replacing the cerium dioxide with the modified cerium dioxide modified by the method of the present application, the tensile strength of the yellowing-resistant polyurethane handle material can be further significantly improved.

[0089] As can be seen from the experimental results in Table 1, the tensile strength of the yellowing-resistant polyurethane handle material prepared in Comparative Examples 1-3 is improved compared with Example 1, but the improvement is not large, and is much smaller than that of the yellowing-resistant polyurethane handle material prepared in Example 2; this shows that the composition of the modifier of the present application is very critical; in the ultraviolet absorber, the modified cerium dioxide modified by the modifier composed of dichloromethyl triethoxysilane, coconut oil fatty acid diethanolamide, and sodium dodecyl diphenyl ether disulfonate and then replacing the cerium dioxide can further significantly improve the tensile strength of the yellowing-resistant polyurethane handle material. However, the modified cerium dioxide modified by the modifier composed of any two of dichloromethyl triethoxysilane, coconut oil fatty acid diethanolamide, and sodium dodecyl diphenyl ether disulfonate and then replacing the cerium dioxide cannot further significantly improve the tensile strength of the yellowing-resistant polyurethane handle 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; 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, and the ultraviolet absorber comprises cerium dioxide and 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole; 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 the modified solution; (2) Mixing and stirring the modified liquid and cerium dioxide for 1 to 3 hours to obtain a modified mixed slurry; (3) drying the modified mixed slurry to obtain the modified cerium dioxide; The modifier obtained in step (1) includes dichloromethyl triethoxysilane, coconut oil fatty acid diethanolamide and sodium dodecyl diphenyl ether disulfonate.

2. The yellowing-resistant polyurethane grip material according to claim 1, characterized in that: The weight ratio of the ultraviolet absorber, the polymer of succinic acid and 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.

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

1.

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

1.

5. The yellowing-resistant polyurethane grip material according to claim 1, characterized in that: 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 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.

7. The yellowing-resistant polyurethane grip material according to claim 6, characterized in that: The weight ratio of dichloromethyltriethoxysilane, coconut oil fatty acid diethanolamide and sodium dodecyl diphenyl ether disulfonate in the modifier is 2:3:

2.

8. 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.

9. The method for preparing the yellowing-resistant polyurethane grip material according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: putting polyurethane resin, foaming agent and anti-yellowing agent into a mixing device, mixing and then producing sheets to obtain the anti-yellowing polyurethane grip material.

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