High-strength wear-resistant polyurethane elastomer and preparation method thereof

Abstract

The invention relates to the technical field of high polymer materials, in particular to a high-strength wear-resistant polyurethane elastomer and a preparation method thereof. The high-strength wear-resistant polyurethane elastomer is prepared from the following raw materials in parts by weight; 30 to 70 parts of polyol; 15 to 30 parts of isocyanate; 1-10 parts of modified nano potassium aluminum silicate; 10-30 parts of a chain extender; 0.5-2 parts of a light stabilizer; 0.5 to 2 parts of an antioxidant; 0.5-2 parts of an ultraviolet absorbent; 0.01 to 0.5 part of a catalyst; the modified nano potassium aluminum silicate is prepared by modifying nano potassium aluminum silicate with a silane coupling agent. The specific modified nano potassium aluminum silicate is applied to manufacturing of a polyurethane material, and the modified nano potassium aluminum silicate remarkably improves the strength, hardness and elongation at break of polyurethane. And meanwhile, the modified nano potassium aluminum silicate can be well matched with other components in a specific ratio, so that the mechanical property of the polyurethane elastomer is further improved.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and particularly relates to a high-strength and wear-resistant polyurethane elastomer and a preparation method thereof. Background Art

[0002] The physical and chemical properties of polyurethane depend on the types and proportions of raw materials during synthesis. Generally speaking, the types of raw materials, such as the number of functional groups, molecular structure, and molecular weight within each reactant molecule, determine the characteristics of the final polyurethane material and how it will form. Although polyurethane has excellent properties, for extremely special operating conditions, many drawbacks will still be exposed, and its strength, toughness, and wear resistance are poor.

[0003] Currently, mainly through molecular modification design, chemical cross-linking methods are used to increase the connection points between molecules, improve the cross-linking density between polyurethane molecules, and form a more stable network structure, thereby enhancing its wear resistance and mechanical strength. Or by adding inorganic fillers (such as carbon black, silica, molybdenum disulfide, etc.) to polyurethane, its hardness, wear resistance, and thermal stability can be significantly improved. However, methods such as chemical cross-linking and fillers will affect the mechanical properties of the material and reduce mechanical properties such as the elongation at break of the material. Summary of the Invention

[0004] In view of this, the technical problem to be solved by the present invention is to provide a high-strength and wear-resistant polyurethane elastomer and a preparation method thereof. The high-strength and wear-resistant polyurethane elastomer provided by the present invention has excellent strength, toughness, and wear resistance.

[0005] The present invention provides a high-strength and wear-resistant polyurethane elastomer, which is prepared from raw materials including the following components in parts by weight;

[0006]

[0007]

[0008] The modified nano-potassium aluminosilicate is obtained by modifying nano-potassium aluminosilicate with a silane coupling agent.

[0009] Preferably, the mass ratio of the nano-potassium aluminosilicate to the silane coupling agent is 10 - 40:10 - 30.

[0010] Preferably, the preparation method of the modified nano-potassium aluminosilicate includes the following steps:

[0011] Mix the nano-potassium aluminosilicate with an ethanol solution of the silane coupling agent and react under ultrasonic conditions to obtain the modified nano-potassium aluminosilicate.

[0012] Preferably, the polyol includes polyether polyol or polyester polyol;

[0013] The weight-average molecular weight of the polyol is 1,000 to 3,000.

[0014] Preferably, the isocyanate includes at least one of toluene diisocyanate, diphenylmethane diisocyanate, dimethylbiphenyl diisocyanate, naphthalene-1,5-diisocyanate, p-phenylene diisocyanate, toluene diisocyanate, and hexamethylene diisocyanate trimer.

[0015] Preferably, the chain extender includes at least one of 1,4-butanediol, 1,6-hexanediol, and 3,3'-dichloro-4,4'-diaminodiphenylmethane;

[0016] The light stabilizer includes triphenyl phosphite;

[0017] The antioxidant includes antioxidant 1135;

[0018] The ultraviolet absorber includes UV-531;

[0019] The catalyst includes dibutyltin dilaurate and / or stannous zincate.

[0020] The present invention also provides a method for preparing the high-strength and wear-resistant polyurethane elastomer described above, comprising the following steps:

[0021] A) Under the condition of a protective gas, the polyol and the isocyanate are stirred and reacted to obtain a prepolymer;

[0022] B) The prepolymer is mixed with modified nano-potassium aluminosilicate and stirred and reacted to obtain a mixed prepolymer;

[0023] C) The mixed prepolymer, chain extender, light stabilizer, antioxidant, ultraviolet absorber, and catalyst are stirred and mixed evenly, vulcanized and molded, and after curing, a high-strength and wear-resistant polyurethane elastomer is obtained.

[0024] Preferably, in step A), the protective gas is nitrogen;

[0025] The temperature of the stirring reaction is 75 to 85 °C; the time is 2 to 3 h.

[0026] Preferably, in step B), the temperature of the stirring reaction is 70 to 90 °C; the time is 0.3 to 0.7 h.

[0027] Preferably, in step C), the temperature of the vulcanization molding is 115 to 125 °C, and the time is 1 to 2 h;

[0028] The temperature of the curing is 100 to 120 °C, and the time is 22 to 26 h.

[0029] The present invention provides a high-strength and wear-resistant polyurethane elastomer, which is prepared from raw materials including the following components in parts by weight: 30-70 parts of polyol; 15-30 parts of isocyanate; 1-10 parts of modified nano-potassium aluminosilicate; 10-30 parts of chain extender; 0.5-2 parts of light stabilizer; 0.5-2 parts of antioxidant; 0.5-2 parts of ultraviolet absorber; 0.01-0.5 parts of catalyst; the modified nano-potassium aluminosilicate is prepared by modifying nano-potassium aluminosilicate with a silane coupling agent. The present invention applies a specific modified nano-potassium aluminosilicate to the manufacture of polyurethane materials. After modification, amino groups exist on the surface of the nano-potassium aluminosilicate, which react with the isocyanate groups in the polyurethane to form ureido groups, increasing the degree of hydrogen bonding and microphase separation inside the system, and significantly improving the physical properties of the polyurethane such as strength, hardness, and elongation at break. At the same time, the modified nano-potassium aluminosilicate can cooperate well with other components in a specific ratio, further improving the mechanical properties of the polyurethane elastomer, such as strength, toughness, and wear resistance. Detailed Embodiments

[0030] Next, the technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0031] The present invention provides a high-strength and wear-resistant polyurethane elastomer, which is prepared from raw materials including the following components in parts by weight:

[0032]

[0033] The modified nano-potassium aluminosilicate is prepared by modifying nano-potassium aluminosilicate with a silane coupling agent.

[0034] In some embodiments of the present invention, the mass ratio of the nano-potassium aluminosilicate to the silane coupling agent is 10-40:10-30, such as 20:20.

[0035] In some embodiments of the present invention, the preparation method of the modified nano-potassium aluminosilicate includes the following steps:

[0036] Mix the nano-potassium aluminosilicate with an ethanol solution of the silane coupling agent and react under ultrasonic conditions to obtain the modified nano-potassium aluminosilicate.

[0037] The ethanol solution of the silane coupling agent is prepared by dissolving the silane coupling agent in absolute ethanol; specifically, it includes: stirring and mixing the silane coupling agent and absolute ethanol for 0.5 to 1.5 h (such as 1 h) to obtain the ethanol solution of the silane coupling agent. The mass ratio of the silane coupling agent to absolute ethanol is 10 to 30:20 to 50, such as 20:30.

[0038] The temperature of the reaction is room temperature; the time is 0.5 to 1.5 h, such as 1 h.

[0039] The frequency of the ultrasonic wave is 20 to 40 kHz, such as 40 kHz.

[0040] After the reaction, it further includes: washing with absolute ethanol and drying. The drying temperature is 115 to 125 °C, such as 120 °C; the time is 1.5 to 2.5 h, such as 2 h. The drying can be carried out in an oven.

[0041] In some embodiments of the present invention, the polyol is polyether polyol or polyester polyol. The polyether polyol can be polytetrahydrofuran diol. The weight-average molecular weight of the polyol is 1000 to 3000, such as 1000. The weight fraction of the polyol is 45 to 55 parts, such as 50.6 parts, 50.1 parts, 48.2 parts.

[0042] In some embodiments of the present invention, the isocyanate is at least one of toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), dimethylbiphenyl diisocyanate (TODI), naphthalene-1,5-diisocyanate (NDI), p-phenylene diisocyanate (PPDI), toluene diisocyanate (TDI), and hexamethylene diisocyanate trimer. The weight fraction of the isocyanate is 20 to 25 parts, such as 22.7 parts, 21.7 parts, 21.1 parts.

[0043] In some embodiments of the present invention, the weight fraction of the modified nano-potassium aluminosilicate is 3 parts, 5 parts, 8 parts.

[0044] In some embodiments of the present invention, the chain extender is at least one of 1,4-butanediol (BDO), 1,6-hexanediol (HDO), and 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA). The weight fraction of the chain extender is 15 to 25 parts, such as 20.6 parts, 20.1 parts, 19.6 parts.

[0045] In some embodiments of the present invention, the light stabilizer is triphenyl phosphite. The weight fraction of the light stabilizer is 0.8 to 1.2 parts, such as 1 part.

[0046] In some embodiments of the present invention, the antioxidant is antioxidant 1135. The weight parts of the antioxidant are 0.8 to 1.2 parts, such as 1 part.

[0047] In some embodiments of the present invention, the ultraviolet absorber is UV-531. The weight parts of the ultraviolet absorber are 0.8 to 1.2 parts, such as 1 part.

[0048] In some embodiments of the present invention, the catalyst is dibutyltin dilaurate and / or stannous zincate. The weight parts of the catalyst are 0.05 to 0.15 parts, such as 0.1 part.

[0049] The present invention also provides a method for preparing the high-strength and wear-resistant polyurethane elastomer described above, comprising the following steps:

[0050] A) Under the condition of a protective gas, polyol and isocyanate are stirred and reacted to obtain a prepolymer;

[0051] B) The prepolymer is mixed with modified nano-potassium aluminosilicate and stirred and reacted to obtain a mixed prepolymer;

[0052] C) The mixed prepolymer, chain extender, light stabilizer, antioxidant, ultraviolet absorber and catalyst are stirred and mixed evenly, vulcanized and molded, and after curing, a high-strength and wear-resistant polyurethane elastomer is obtained.

[0053] Regarding step A):

[0054] Under the condition of a protective gas, polyol and isocyanate are stirred and reacted to obtain a prepolymer.

[0055] In some embodiments of the present invention, the protective gas is nitrogen.

[0056] In some embodiments of the present invention, before stirring and reacting polyol and isocyanate, it further includes:

[0057] Stir the polyol to remove water.

[0058] The temperature of the water removal by stirring is 110 to 120 °C, such as 120 °C; the time is 2 to 3 h, such as 2 h. The water removal by stirring is carried out under the condition of a protective gas. The protective gas can be nitrogen.

[0059] After the vacuum water removal, it further includes: cooling. The cooling can be natural cooling. The temperature after cooling is 55 to 65 °C, such as 60 °C.

[0060] In some embodiments of the present invention, the temperature of the stirring reaction is 75 to 85 °C, such as 75 °C; the time is 2 to 3 h, such as 2 h.

[0061] Regarding step B):

[0062] Mix the prepolymer with modified potassium aluminosilicate nanometer, and stir and react to obtain a mixed prepolymer.

[0063] In some embodiments of the present invention, the temperature of the stirring reaction is 70-90 °C, such as 80 °C; the time is 0.3-0.7 h, such as 0.5 h.

[0064] Regarding step C):

[0065] Stir and mix the mixed prepolymer, chain extender, light stabilizer, antioxidant, ultraviolet absorber and catalyst, and perform vulcanization molding. After curing, a high-strength and wear-resistant polyurethane elastomer is obtained.

[0066] In some embodiments of the present invention, the temperature of the vulcanization molding is 115-125 °C, such as 120 °C; the time is 1-2 h, such as 1 h. The vulcanization molding is carried out in a flat vulcanizer. The vulcanization molding is carried out in a mold. After the vulcanization molding, it further includes: demolding.

[0067] In some embodiments of the present invention, the temperature of the curing is 100-120 °C, such as 100 °C; the time is 22-26 h, such as 24 h.

[0068] The present invention has no special restrictions on the sources of the raw materials used above, and they can be generally commercially available.

[0069] In order to further illustrate the present invention, the following is a detailed description of a high-strength and wear-resistant polyurethane elastomer and its preparation method provided by the present invention in combination with examples, but it should not be understood as a limitation on the protection scope of the present invention.

[0070] Example 1

[0071] 1) Under nitrogen protection, 50.6 parts by weight of polytetrahydrofuran diol (weight average molecular weight 1000) was stirred to remove water at 120 °C for 2 h, and then naturally cooled to 60 °C; 22.7 parts by weight of isocyanate (TDI) was added, and the mixture was stirred and reacted at 75 °C for 2 h under nitrogen protection to obtain a prepolymer.

[0072] 2) Preparation of modified potassium aluminosilicate nanometer:

[0073] Dissolve the silane coupling agent (KH550) in absolute ethanol, and stir and mix for 1 h to obtain an ethanol solution of the silane coupling agent;

[0074] Add potassium aluminosilicate nanometer to the ethanol solution of the silane coupling agent, react at room temperature and under ultrasonic conditions (ultrasonic frequency is 40 kHz) for 1 h, wash with absolute ethanol, and then dry in an oven at 120 °C for 2 h to obtain modified potassium aluminosilicate nanometer;

[0075] The mass ratio of the potassium aluminosilicate nanometer and the silane coupling agent is 20:20;

[0076] The mass ratio of the silane coupling agent and absolute ethanol is 20:30.

[0077] Preparation of the mixed prepolymer:

[0078] Add 3 parts by weight of the modified potassium aluminosilicate nanometer to the prepolymer, and after stirring and reacting at 80 °C for 0.5 h, a mixed prepolymer is obtained.

[0079] 3) Stir evenly the mixed prepolymer, 20.6 parts by weight of the chain extender 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA), 1 part by weight of the light stabilizer triphenyl phosphite, 1 part by weight of the antioxidant 1135, 1 part by weight of the UV absorber UV-531, and 0.1 part by weight of the catalyst dibutyltin dilaurate, pour it into a mold, vulcanize and mold at 120 °C in a flat vulcanizer for 1 h, demold, and then post-cure in an oven at 100 °C for 24 h. Take out the specimen to obtain a high-strength and wear-resistant polyurethane elastomer, and perform performance tests after placing it at room temperature for 7 days. The performance test results are shown in Table 1.

[0080] Example 2

[0081] 1) Under nitrogen protection, stir and dehydrate 50.1 parts by weight of polytetrahydrofuran diol (weight average molecular weight 1000) at 120 °C for 2 h, and then naturally cool to 60 °C; add 21.7 parts by weight of isocyanate (TDI), and stir and react at 75 °C for 2 h under nitrogen protection to obtain a prepolymer.

[0082] 2) Preparation of the modified potassium aluminosilicate nanometer: the same as in Example 1;

[0083] Preparation of the mixed prepolymer:

[0084] Add 5 parts by weight of the modified potassium aluminosilicate nanometer to the prepolymer, and after stirring and reacting at 80 °C for 0.5 h, a mixed prepolymer is obtained.

[0085] 3) Stir evenly the mixed prepolymer, 20.1 parts by weight of the chain extender 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA), 1 part by weight of the light stabilizer triphenyl phosphite, 1 part by weight of the antioxidant 1135, 1 part by weight of the UV absorber UV-531, and 0.1 part by weight of the catalyst dibutyltin dilaurate, pour it into a mold, vulcanize and mold at 120 °C in a flat vulcanizer for 1 h, demold, and then post-cure in an oven at 100 °C for 24 h. Take out the specimen to obtain a high-strength and wear-resistant polyurethane elastomer, and perform performance tests after placing it at room temperature for 7 days. The performance test results are shown in Table 1.

[0086] Example 3

[0087] 1) Under nitrogen protection, 48.2 parts by weight of polytetrahydrofuran diol (weight average molecular weight 1000) was stirred to remove water at 120 °C for 2 h, and then naturally cooled to 60 °C; 21.1 parts by weight of isocyanate (TDI) was added, and the mixture was stirred and reacted at 75 °C for 2 h under nitrogen protection to obtain a prepolymer.

[0088] 2) Preparation of modified nano-potassium aluminosilicate: The same as in Example 1;

[0089] Preparation of the mixed prepolymer:

[0090] 8 parts by weight of modified nano-potassium aluminosilicate was added to the prepolymer, and the mixture was stirred and reacted at 80 °C for 0.5 h to obtain a mixed prepolymer.

[0091] 3) The mixed prepolymer, 19.6 parts by weight of chain extender 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA), 1 part by weight of light stabilizer triphenyl phosphite, 1 part by weight of antioxidant 1135, 1 part by weight of UV-531 ultraviolet absorber, and 0.1 part by weight of catalyst dibutyltin dilaurate were stirred evenly, poured into a mold, vulcanized and molded at 120 °C for 1 h in a flat vulcanizer. After demolding, it was post-cured in an oven at 100 °C for 24 h. The specimen was taken out to obtain a high-strength and wear-resistant polyurethane elastomer, and the performance test was carried out after being placed at room temperature for 7 days. The performance test results are shown in Table 1.

[0092] Comparative Example 1

[0093] 1) Under nitrogen protection, 52.9 parts by weight of polytetrahydrofuran diol (weight average molecular weight 1000) was stirred to remove water at 120 °C for 2 h, and then naturally cooled to 60 °C; 22.9 parts by weight of isocyanate (TDI) was added, and the mixture was stirred and reacted at 75 °C for 2 h under nitrogen protection to obtain a prepolymer.

[0094] 2) The prepolymer, 21.1 parts by weight of chain extender 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA), 1 part by weight of light stabilizer triphenyl phosphite, 1 part by weight of antioxidant 1135, 1 part by weight of UV-531 ultraviolet absorber, and 0.1 part by weight of catalyst dibutyltin dilaurate were stirred evenly, poured into a mold, vulcanized and molded at 120 °C for 1 h in a flat vulcanizer. After demolding, it was post-cured in an oven at 100 °C for 24 h. The specimen was taken out to obtain a polyurethane elastomer, and the performance test was carried out after being placed at room temperature for 7 days. The performance test results are shown in Table 1.

[0095] In the performance test, the tensile test instrument was an Instron testing machine, model instro5960; the Akron abrasion test was carried out using an Akron abrasion tester, model GT-7012-A.

[0096] Table 1 Performance test results of the polyurethane elastomers of Examples 1 to 3 and Comparative Example 1

[0097]

[0098] The description of the above embodiments is only used to help understand the method and its core idea of the present invention. Various modifications to these embodiments will be obvious to those skilled in the art. The general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to these embodiments shown herein, but rather should be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A high-strength and wear-resistant polyurethane elastomer prepared from raw materials comprising the following components in parts by weight; The modified nano-potassium aluminum silicate is prepared by modifying nano-potassium aluminum silicate with a silane coupling agent.

2. The high-strength and wear-resistant polyurethane elastomer according to claim 1, characterized in that: The mass ratio of the nano-potassium aluminum silicate to the silane coupling agent is 10-40:10-30.

3. The high-strength and wear-resistant polyurethane elastomer according to claim 1, characterized in that: The preparation method of the modified nano-potassium aluminum silicate comprises the following steps: The modified nano potassium aluminum silicate is prepared by mixing nano potassium aluminum silicate with an ethanol solution of a silane coupling agent and reacting them under ultrasonic conditions.

4. The high-strength and wear-resistant polyurethane elastomer according to claim 1, characterized in that: The polyol includes polyether polyol or polyester polyol; The weight average molecular weight of the polyol is 1000-3000.

5. The high-strength and wear-resistant polyurethane elastomer according to claim 1, characterized in that: The isocyanate includes at least one of toluene diisocyanate, diphenylmethane diisocyanate, dimethylbiphenyl diisocyanate, naphthalene-1,5 diisocyanate, p-phenylene diisocyanate, toluene diisocyanate and hexamethylene diisocyanate trimer.

6. The high-strength and wear-resistant polyurethane elastomer according to claim 1, characterized in that: The chain extender includes at least one of 1,4-butanediol, 1,6-hexanediol and 3,3'-dichloro-4,4'-diaminodiphenylmethane; The light stabilizer includes triphenyl phosphite; The antioxidant includes antioxidant 1135; The ultraviolet absorber includes UV-531; The catalyst includes dibutyltin dilaurate and / or stannous zincate.

7. A method for preparing the high-strength and wear-resistant polyurethane elastomer according to any one of claims 1 to 6, comprising the following steps: A) under the condition of protective gas, stirring and reacting polyol and isocyanate to obtain a prepolymer; B) mixing the prepolymer with modified nano-potassium aluminum silicate, stirring and reacting to obtain a mixed prepolymer; C) stirring and mixing the mixed prepolymer, chain extender, light stabilizer, antioxidant, ultraviolet absorber and catalyst, vulcanizing and molding, and aging to obtain a high-strength and wear-resistant polyurethane elastomer.

8. The preparation method according to claim 7, characterized in that: In step A), the protective gas is nitrogen; The stirring reaction is carried out at a temperature of 75 to 85° C. and for 2 to 3 hours.

9. The preparation method according to claim 7, characterized in that: In step B), the stirring reaction temperature is 70-90° C. and the time is 0.3-0.7 h.

10. The preparation method according to claim 7, characterized in that: In step C), the vulcanization molding temperature is 115-125°C and the time is 1-2h; The aging temperature is 100-120° C. and the aging time is 22-26 hours.

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