A rubber release agent for tire and preparation method thereof
By using rubber mold release agents with components such as quaternary ammonium salt modified polyurethane, fluoroquaternary ammonium salt and thiodecafluorooctyl trimethoxysilane, the problems of high cost and poor mold release effect in the prior art are solved, and the problem of high cost and poor mold release effect is achieved. Efficient mold release effect and cost control.
Patent Information
- Application Number
- CN202411239811.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-05
- Publication Date
- 2024-12-31
- Estimated Expiration
- 2044-09-05
AI Technical Summary
The existing rubber release agent has shortcomings in terms of cost and release effect, and it is difficult to meet the problems of complex components and high costs.
Using quaternary ammonium modified polyurethane, fluoroquaternary ammonium salt and thiodecafluorooctyl trimethoxysilane and other components, the formation of modified nano calcium carbonate and organic-inorganic complexes can reduce the agglomeration of nano calcium carbonate and improve and Compatibility of organic matter and a lubricating layer is formed on the mold surface by quaternary ammonium salt, reducing friction and adhesion, thereby achieving excellent mold release effect.
A good demolding effect is achieved, reducing friction and adhesion between the mold and the material, improving the product's component compatibility and demolding efficiency, and reducing costs.
Smart Images
Figure SMS_1
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of rubber release agents, in particular to a rubber release agent for tires and a preparation method thereof. Background Art
[0002] Rubber release agent is a commonly used additive in rubber manufacturing. It can form an isolation layer between the mold and the rubber to prevent adhesion, thereby facilitating demoulding. In the rubber industry, the use of release agents plays an important role in product quality, production efficiency and cost control. Rubber release agents can be divided into multiple types, including fluorine-based, silicone-based, wax-based, surfactant-based, etc. For example, patent CN106393512A discloses an organic fluorine compound silicone oil-based composite release agent emulsion, which only meets the characteristics of less product demoulding residue and excellent corrosion inhibition effect, but the product composition is relatively complex, the cost is high, and the demoulding effect needs to be improved. Summary of the invention
[0003] 1. Technical issues to be resolved
[0004] In view of the deficiencies in the prior art, the present invention provides a rubber release agent for tires and a preparation method thereof, which have good demoulding effect.
[0005] (II) Technical solution
[0006] To achieve the above object, the present invention provides the following technical solution: a rubber release agent for tires, comprising the following parts by weight: 6-8 parts by weight of quaternary ammonium salt modified polyurethane, 12-16 parts by weight of fluorine-containing quaternary ammonium salt, 2-5 parts by weight of tridecafluorooctyltrimethoxysilane, and 4-8 parts by weight of dipropylene glycol dimethyl ether.
[0007] Preferably, the preparation method of the quaternary ammonium salt modified polyurethane is:
[0008] (1) Add calcium carbonate to deionized water, stir to dissolve, continue to add isoleucine, react at 58-60°C for 50-72 minutes, filter after reaction, dry the filter cake in an oven at 72-85°C for 4.8-6.2 hours, and obtain isoleucine-modified calcium carbonate nanoparticles;
[0009] (2) adding isoleucine-modified calcium carbonate nanoparticles and 2,3-epoxypropyltrimethylammonium chloride to N,N-dimethylformamide solvent, stirring and mixing, reacting at 25-30° C. for 4-6 hours, and washing after reduced pressure distillation to obtain a quaternary ammonium salt-modified isoleucine-modified calcium carbonate nanoparticle chain extender;
[0010] (3) Add toluene diisocyanate and polyoxypropylene glycol into the reactor, then add dibutyltin dilaurate, introduce nitrogen protection, and carry out prepolymerization at a temperature of 74-92°C for 2.4-4 hours. Then add quaternary ammonium salt-modified isoleucine-modified calcium carbonate nanosphere chain extender to carry out chain extension reaction. After the reaction is completed, cool, wash and dry to obtain quaternary ammonium salt-modified polyurethane.
[0011] Preferably, the mass ratio of calcium carbonate to isoleucine in (1) is 1:0.78-0.82.
[0012] Preferably, the mass ratio of isoleucine-modified calcium carbonate nanospheres to 2,3-epoxypropyltrimethylammonium chloride in (2) is 1:1.4-1.6.
[0013] Preferably, the mass ratio of toluene diisocyanate, polyoxypropylene glycol, dibutyltin dilaurate and quaternary ammonium salt-modified isoleucine-modified calcium carbonate nanosphere chain extender in (3) is 1.12-1.2:1:0.04-0.042:1.8-1.9.
[0014] Preferably, the preparation method of the fluorine-containing quaternary ammonium salt is:
[0015] S1. Add phosphorus oxychloride and quaternary ammonium salt-modified isoleucine-modified calcium carbonate nanosphere chain extender to the acetonitrile solution, introduce nitrogen protection, stir and mix, control the temperature at 85-92°C, reflux for 14-28h, filter, evaporate and concentrate, and cool to room temperature to obtain intermediate 1;
[0016] S2. Dissolve the intermediate 1 and 4-fluoro-4'-hydroxybiphenyl in N,N-dimethylformamide solvent, react at 50-68°C for 6-10h, wash and dry to obtain a fluorine-containing quaternary ammonium salt.
[0017] Preferably, the mass ratio of phosphorus oxychloride to quaternary ammonium salt-modified isoleucine-modified calcium carbonate nanosphere chain extender in S1 is 1:3.2-4.5.
[0018] Preferably, the mass ratio of the intermediate 1 to 4-fluoro-4'-hydroxybiphenyl in S2 is 1:1.6-2.
[0019] Preferably, the preparation method of the rubber release agent for tire is: add quaternary ammonium salt modified polyurethane, fluorine-containing quaternary ammonium salt, and tridecafluorooctyltrimethoxysilane into a reactor, stir for 1-1.5 hours at a speed of 1000-1200 rpm, then add dipropylene glycol dimethyl ether, and continue stirring for 2-3 hours to obtain the rubber release agent for tire.
[0020] 3. Beneficial technical effects
[0021] The invention prepares a rubber release agent for tires by adding quaternary ammonium salt modified polyurethane, fluorine-containing quaternary ammonium salt and tridecafluorooctyl trimethoxysilane into a reactor, stirring, and then adding dipropylene glycol dimethyl ether and continuing stirring.
[0022] The nano calcium carbonate contained in the quaternary ammonium salt modified polyurethane of the present invention contains a large amount of hydroxyl groups, which is modified and grafted with organic matter to form an organic-inorganic composite, thereby reducing the agglomeration of the nano calcium carbonate and improving the compatibility with organic matter. The nano calcium carbonate itself has a good demoulding effect; the quaternary ammonium salt forms a lubricating layer on the surface of the tire mold, effectively reducing the friction and adhesion between the mold and the material, thereby achieving a demoulding effect; the polyurethane itself also has a good demoulding effect. Phosphorus oxychloride and quaternary ammonium salt modified isoleucine modified calcium carbonate nano microsphere chain extender are reacted to obtain an intermediate 1, which is further reacted with 4-fluoro-4'-hydroxybiphenyl to generate a fluorine-containing quaternary ammonium salt, while improving the substitution degree of the quaternary ammonium salt and the fluorine element. The fluorine element has a lower surface energy and non-stickiness, and is applied in a demoulding agent to have a good demoulding effect. DETAILED DESCRIPTION Example 1
[0023] (1) Calcium carbonate was added to deionized water, stirred to dissolve, and isoleucine was added thereto, wherein the mass ratio of calcium carbonate to isoleucine was 1:0.78, and the reaction was carried out at 58°C for 50 minutes. After the reaction, the mixture was filtered, and the filter cake was dried in an oven at 72°C for 4.8 hours. After the reaction, isoleucine-modified calcium carbonate nanoparticles were obtained.
[0024] (2) adding isoleucine-modified calcium carbonate nanospheres and 2,3-epoxypropyltrimethylammonium chloride to N,N-dimethylformamide solvent, wherein the mass ratio of isoleucine-modified calcium carbonate nanospheres to 2,3-epoxypropyltrimethylammonium chloride is 1:1.4, stirring and mixing, reacting at 25°C for 4 hours, and washing after reduced pressure distillation to obtain a quaternary ammonium salt-modified isoleucine-modified calcium carbonate nanosphere chain extender;
[0025] (3) Add toluene diisocyanate and polyoxypropylene glycol into a reactor, and then add dibutyltin dilaurate, wherein the mass ratio of toluene diisocyanate, polyoxypropylene glycol, dibutyltin dilaurate and quaternary ammonium salt-modified isoleucine-modified calcium carbonate nanosphere chain extender is 1.12:1:0.04:1.8, introduce nitrogen protection, and carry out prepolymerization at a temperature of 74°C for 2.4 hours. Then, add quaternary ammonium salt-modified isoleucine-modified calcium carbonate nanosphere chain extender to carry out chain extension reaction. After the reaction is completed, cool, wash and dry to obtain quaternary ammonium salt-modified polyurethane.
[0026] (4) Adding phosphorus oxychloride and quaternary ammonium salt-modified isoleucine-modified calcium carbonate nano-microsphere chain extender to the acetonitrile solution, wherein the mass ratio of phosphorus oxychloride to quaternary ammonium salt-modified isoleucine-modified calcium carbonate nano-microsphere chain extender is 1:3.2, introducing nitrogen protection, stirring and mixing, controlling the temperature at 85°C, reflux reaction for 14 hours, filtering, evaporating and concentrating, and cooling to room temperature to obtain intermediate 1;
[0027] (5) The intermediate 1 and 4-fluoro-4'-hydroxybiphenyl were dissolved in N,N-dimethylformamide solvent, wherein the mass ratio of the intermediate 1 to 4-fluoro-4'-hydroxybiphenyl was 1:1.6, and the mixture was reacted at 50°C for 6 hours. The mixture was washed and dried to obtain a fluorine-containing quaternary ammonium salt.
[0028] (6) 6 parts by weight of quaternary ammonium salt-modified polyurethane, 12 parts by weight of fluorine-containing quaternary ammonium salt, and 2 parts by weight of tridecafluorooctyltrimethoxysilane were added to a reactor, stirred at a speed of 1000 rpm for 1 hour, and then 4 parts by weight of dipropylene glycol dimethyl ether were added, and stirring was continued for 2 hours to obtain a rubber release agent for tires. Example 2
[0029] (1) Calcium carbonate was added to deionized water, stirred to dissolve, and isoleucine was added thereto, wherein the mass ratio of calcium carbonate to isoleucine was 1:0.82, and the reaction was carried out at 60° C. for 72 min. After the reaction was completed, the mixture was filtered, and the filter cake was dried in an oven at 85° C. for 6.2 h. After the reaction was completed, isoleucine-modified calcium carbonate nanoparticles were obtained;
[0030] (2) adding isoleucine-modified calcium carbonate nanospheres and 2,3-epoxypropyltrimethylammonium chloride to N,N-dimethylformamide solvent, wherein the mass ratio of isoleucine-modified calcium carbonate nanospheres to 2,3-epoxypropyltrimethylammonium chloride is 1:1.6, stirring and mixing, reacting at 30°C for 6 hours, and washing after reduced pressure distillation to obtain a quaternary ammonium salt-modified isoleucine-modified calcium carbonate nanosphere chain extender;
[0031] (3) Add toluene diisocyanate and polyoxypropylene glycol into a reactor, and then add dibutyltin dilaurate, wherein the mass ratio of toluene diisocyanate, polyoxypropylene glycol, dibutyltin dilaurate and quaternary ammonium salt-modified isoleucine-modified calcium carbonate nano-microsphere chain extender is 1.2:1:0.042:1.9, introduce nitrogen protection, and carry out prepolymerization at a temperature of 92°C for 4 hours. Then, add quaternary ammonium salt-modified isoleucine-modified calcium carbonate nano-microsphere chain extender to carry out chain extension reaction. After the reaction is completed, cool, wash and dry to obtain quaternary ammonium salt-modified polyurethane.
[0032] (4) Adding phosphorus oxychloride and quaternary ammonium salt-modified isoleucine-modified calcium carbonate nano-microsphere chain extender to the acetonitrile solution, wherein the mass ratio of phosphorus oxychloride to quaternary ammonium salt-modified isoleucine-modified calcium carbonate nano-microsphere chain extender is 1:4.5, introducing nitrogen protection, stirring and mixing, controlling the temperature at 92°C, reflux reaction for 28 hours, filtering, evaporating and concentrating, and cooling to room temperature to obtain intermediate 1;
[0033] (5) The intermediate 1 and 4-fluoro-4'-hydroxybiphenyl were dissolved in N,N-dimethylformamide solvent, wherein the mass ratio of the intermediate 1 to 4-fluoro-4'-hydroxybiphenyl was 1:2, and the mixture was reacted at 68°C for 10 h. The mixture was washed and dried to obtain a fluorine-containing quaternary ammonium salt.
[0034] (6) 8 parts by weight of quaternary ammonium salt-modified polyurethane, 16 parts by weight of fluorine-containing quaternary ammonium salt, and 5 parts by weight of tridecafluorooctyltrimethoxysilane were added to a reactor, and stirred at a speed of 1200 rpm for 1.5 hours. Then, 8 parts by weight of dipropylene glycol dimethyl ether was added, and stirring was continued for 3 hours to obtain a rubber release agent for tires. Example 3
[0035] (1) Calcium carbonate was added to deionized water, stirred to dissolve, and isoleucine was added thereto, wherein the mass ratio of calcium carbonate to isoleucine was 1:0.8, and the reaction was carried out at 59° C. for 61 min. After the reaction was completed, the mixture was filtered, and the filter cake was dried in an oven at 78° C. for 5.5 h. After the reaction was completed, isoleucine-modified calcium carbonate nanoparticles were obtained.
[0036] (2) adding isoleucine-modified calcium carbonate nanospheres and 2,3-epoxypropyltrimethylammonium chloride to N,N-dimethylformamide solvent, wherein the mass ratio of isoleucine-modified calcium carbonate nanospheres to 2,3-epoxypropyltrimethylammonium chloride is 1:1.5, stirring and mixing, reacting at 27°C for 5 hours, and washing after reduced pressure distillation to obtain a quaternary ammonium salt-modified isoleucine-modified calcium carbonate nanosphere chain extender;
[0037] (3) Adding toluene diisocyanate and polyoxypropylene glycol into a reactor, and then adding dibutyltin dilaurate, wherein the mass ratio of toluene diisocyanate, polyoxypropylene glycol, dibutyltin dilaurate and quaternary ammonium salt-modified isoleucine-modified calcium carbonate nano-microsphere chain extender is 1.16:1:0.041:1.85, passing nitrogen protection, and performing prepolymerization at a temperature of 83°C for 3.2 hours, and then adding quaternary ammonium salt-modified isoleucine-modified calcium carbonate nano-microsphere chain extender to perform chain extension reaction. After the reaction is completed, cooling, washing and drying are performed to obtain quaternary ammonium salt-modified polyurethane;
[0038] (4) Adding phosphorus oxychloride and quaternary ammonium salt-modified isoleucine-modified calcium carbonate nano-microsphere chain extender to the acetonitrile solution, wherein the mass ratio of phosphorus oxychloride to quaternary ammonium salt-modified isoleucine-modified calcium carbonate nano-microsphere chain extender is 1:3.8, introducing nitrogen protection, stirring and mixing, controlling the temperature at 88°C, reflux reaction for 21 hours, filtering, evaporating and concentrating, and cooling to room temperature to obtain intermediate 1;
[0039] (5) Dissolving the intermediate 1 and 4-fluoro-4'-hydroxybiphenyl in N,N-dimethylformamide solvent, wherein the mass ratio of the intermediate 1 to 4-fluoro-4'-hydroxybiphenyl is 1:1.8, reacting at 59° C. for 8 h, washing and drying to obtain a fluorine-containing quaternary ammonium salt;
[0040] (6) 7 parts by weight of quaternary ammonium salt-modified polyurethane, 14 parts by weight of fluorine-containing quaternary ammonium salt, and 3 parts by weight of tridecafluorooctyltrimethoxysilane were added to a reactor, and stirred at a speed of 1100 rpm for 1.2 hours. Then, 6 parts by weight of dipropylene glycol dimethyl ether were added, and stirring was continued for 2.5 hours to obtain a rubber release agent for tires. Example 4
[0041] (1) Calcium carbonate was added to deionized water, stirred to dissolve, and isoleucine was added thereto, wherein the mass ratio of calcium carbonate to isoleucine was 1:0.78, and the reaction was carried out at 58°C for 50 minutes. After the reaction, the mixture was filtered, and the filter cake was dried in an oven at 72°C for 4.8 hours. After the reaction, isoleucine-modified calcium carbonate nanoparticles were obtained.
[0042] (2) adding isoleucine-modified calcium carbonate nanospheres and 2,3-epoxypropyltrimethylammonium chloride to N,N-dimethylformamide solvent, wherein the mass ratio of isoleucine-modified calcium carbonate nanospheres to 2,3-epoxypropyltrimethylammonium chloride is 1:1.4, stirring and mixing, reacting at 25°C for 4 hours, and washing after reduced pressure distillation to obtain a quaternary ammonium salt-modified isoleucine-modified calcium carbonate nanosphere chain extender;
[0043] (3) Add toluene diisocyanate and polyoxypropylene glycol into a reactor, and then add dibutyltin dilaurate, wherein the mass ratio of toluene diisocyanate, polyoxypropylene glycol, dibutyltin dilaurate and quaternary ammonium salt-modified isoleucine-modified calcium carbonate nano-microsphere chain extender is 1.2:1:0.042:1.9, introduce nitrogen protection, and carry out prepolymerization at a temperature of 92°C for 4 hours. Then, add quaternary ammonium salt-modified isoleucine-modified calcium carbonate nano-microsphere chain extender to carry out chain extension reaction. After the reaction is completed, cool, wash and dry to obtain quaternary ammonium salt-modified polyurethane.
[0044] (4) Adding phosphorus oxychloride and quaternary ammonium salt-modified isoleucine-modified calcium carbonate nano-microsphere chain extender to the acetonitrile solution, wherein the mass ratio of phosphorus oxychloride to quaternary ammonium salt-modified isoleucine-modified calcium carbonate nano-microsphere chain extender is 1:4.5, introducing nitrogen protection, stirring and mixing, controlling the temperature at 92°C, reflux reaction for 28 hours, filtering, evaporating and concentrating, and cooling to room temperature to obtain intermediate 1;
[0045] (5) Dissolving the intermediate 1 and 4-fluoro-4'-hydroxybiphenyl in N,N-dimethylformamide solvent, wherein the mass ratio of the intermediate 1 to 4-fluoro-4'-hydroxybiphenyl is 1:1.8, reacting at 59° C. for 8 h, washing and drying to obtain a fluorine-containing quaternary ammonium salt;
[0046] (6) 7 parts by weight of quaternary ammonium salt-modified polyurethane, 14 parts by weight of fluorine-containing quaternary ammonium salt, and 3 parts by weight of tridecafluorooctyltrimethoxysilane were added to a reactor, and stirred at a speed of 1100 rpm for 1.2 hours. Then, 6 parts by weight of dipropylene glycol dimethyl ether were added, and stirring was continued for 2.5 hours to obtain a rubber release agent for tires.
[0047] Comparative Example 1
[0048] The difference between this comparative example and implementation 4 is that no quaternary ammonium salt-modified polyurethane is added.
[0049] Comparative Example 2
[0050] This comparative example is compared with implementation 4, the difference is that no fluorine-containing quaternary ammonium salt is added.
[0051] The rubber release agent product was applied to a metal plate with a length and width of 15x10cm, cured at 120℃ for 30min, and the friction coefficient of the release agent coating and the percentage of the rough surface area to the total coating area were tested. The test results are shown in Table 1.
[0052] Table 1: Smoothness test.
[0053]
[0054] As can be seen from Table 1, Examples 1-4 of the present invention have better smoothness than Comparative Examples 1-2. The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the contents of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is only limited by the claims and their full scope and equivalents.
Claims
1. A rubber release agent for tires, characterized in that: The invention comprises the following components by weight: 6-8 parts by weight of quaternary ammonium salt modified polyurethane, 12-16 parts by weight of fluorine-containing quaternary ammonium salt, 2-5 parts by weight of tridecafluorooctyltrimethoxysilane, and 4-8 parts by weight of dipropylene glycol dimethyl ether; The preparation method of the quaternary ammonium salt modified polyurethane is: (1) Add calcium carbonate to deionized water, stir to dissolve, continue to add isoleucine, react at 58-60°C for 50-72 minutes, filter after reaction, dry the filter cake in an oven at 72-85°C for 4.8-6.2 hours, and obtain isoleucine-modified calcium carbonate nanoparticles; (2) adding isoleucine-modified calcium carbonate nanoparticles and 2,3-epoxypropyltrimethylammonium chloride to N,N-dimethylformamide solvent, stirring and mixing, reacting at 25-30° C. for 4-6 hours, and washing after reduced pressure distillation to obtain a quaternary ammonium salt-modified isoleucine-modified calcium carbonate nanoparticle chain extender; (3) Adding toluene diisocyanate and polyoxypropylene glycol into the reactor, then adding dibutyltin dilaurate, introducing nitrogen protection, and performing prepolymerization at a temperature of 74-92° C. for 2.4-4 hours, then adding a quaternary ammonium salt-modified isoleucine-modified calcium carbonate nano-microsphere chain extender to perform a chain extension reaction, and after the reaction is completed, cooling, washing, and drying to obtain a quaternary ammonium salt-modified polyurethane; The preparation method of the fluorine-containing quaternary ammonium salt is: S1. Add phosphorus oxychloride and quaternary ammonium salt-modified isoleucine-modified calcium carbonate nanosphere chain extender to the acetonitrile solution, introduce nitrogen protection, stir and mix, control the temperature at 85-92°C, reflux for 14-28h, filter, evaporate and concentrate, and cool to room temperature to obtain intermediate 1; S2. Dissolve the intermediate 1 and 4-fluoro-4'-hydroxybiphenyl in N,N-dimethylformamide solvent, react at 50-68°C for 6-10h, wash and dry to obtain a fluorine-containing quaternary ammonium salt.
2. The tire rubber release agent according to claim 1, characterized in that The mass ratio of calcium carbonate to isoleucine in (1) is 1:0.78-0.
82.
3. The tire rubber release agent according to claim 1, characterized in that The mass ratio of isoleucine-modified calcium carbonate nanoparticles to 2,3-epoxypropyltrimethylammonium chloride in (2) is 1:1.4-1.
6.
4. The tire rubber release agent according to claim 1, characterized in that The mass ratio of toluene diisocyanate, polyoxypropylene glycol, dibutyltin dilaurate and quaternary ammonium salt-modified isoleucine-modified calcium carbonate nanosphere chain extender in (3) is 1.12-1.2:1:0.04-0.042:1.8-1.
9.
5. The tire rubber release agent according to claim 1, characterized in that: The mass ratio of phosphorus oxychloride to quaternary ammonium salt-modified isoleucine-modified calcium carbonate nano-microsphere chain extender in S1 is 1:3.2-4.
5.
6. The tire rubber release agent according to claim 1, characterized in that: The mass ratio of the intermediate 1 to 4-fluoro-4'-hydroxybiphenyl in S2 is 1:1.6-2.
7. A method for preparing a rubber release agent for tire according to any one of claims 1 to 6, characterized in that: The preparation method of the tire rubber release agent comprises the following steps: adding quaternary ammonium salt modified polyurethane, fluorine-containing quaternary ammonium salt and tridecafluorooctyltrimethoxysilane into a reactor, stirring at a rotation speed of 1000-1200 rpm for 1-1.5 hours, then adding dipropylene glycol dimethyl ether, and continuing stirring for 2-3 hours to obtain the tire rubber release agent.