Environment-friendly chlorine-free high-temperature release agent as well as preparation method and application thereof

Abstract

The invention relates to an environment-friendly chlorine-free high-temperature release agent as well as a preparation method and application thereof, and belongs to the technical field of release agents. The invention provides a release agent which comprises the following components in percentage by mass: 3.5%-7% of an anti-wear reagent at extreme pressure, 0.1%-1% of a corrosion inhibitor, 0.1%-1% of an antioxidant and the balance of synthetic ester, the extreme pressure anti-wear agent is prepared from polyisobutene, tricresyl phosphate and triphenyl thiophosphate; the synthetic ester comprises at least one of trimethylolpropane trioleate, polyol ester, trimethylolpropane C18 unsaturated fatty acid diester and trimethylolpropane C18 unsaturated fatty acid triester. The release agent is compounded by the extreme pressure anti-wear agent, the corrosion inhibitor, the antioxidant and the synthetic ester, so that high-temperature wear and surface damage can be effectively prevented, the demolding efficiency is remarkably improved, the service life of a mold is remarkably prolonged, and the environment-friendly manufacturing development direction and the environment-friendly requirement are met.

Description

Technical Field

[0001] The invention belongs to the technical field of mold release agents, and in particular relates to an environmentally friendly chlorine-free high-temperature mold release agent and a preparation method and application thereof. Background Art

[0002] Traditional high-temperature mold release agents often use chlorinated paraffin, which may decompose into harmful chlorine, hydrogen chloride and other toxic substances at high temperatures, which may harm the health of operators and the environment. In addition, this type of mold release agent may volatilize harmful gases during the production process, increasing the environmental protection pressure of the enterprise, and the operators may face health risks.

[0003] Chlorine-free high-temperature release agents do not use chlorine at all, avoiding the release of harmful gases, meeting green environmental protection requirements and effectively reducing environmental pollution. The formula of chlorine-free release agents is more environmentally friendly, can reduce pollution to air and water sources, and meets the increasingly stringent environmental standards around the world.

[0004] However, the current environmentally friendly chlorine-free high-temperature release agents have disadvantages such as poor lubrication performance and high wear degree. Therefore, it is of great significance to develop high-temperature release agents with good wear resistance and corrosion resistance. Summary of the invention

[0005] The purpose of the present invention is to overcome the problems existing in the above-mentioned prior art and to provide an environmentally friendly chlorine-free high-temperature release agent and a preparation method and application thereof.

[0006] The present invention is achieved through the following technical solutions:

[0007] In a first aspect, the present invention provides an environmentally friendly chlorine-free high-temperature mold release agent, which comprises the following components by mass percentage: 3.5%-6% of an extreme pressure anti-wear agent, 0.1%-1% of a corrosion inhibitor, 0.1%-1% of an antioxidant, and the balance is a synthetic ester;

[0008] The synthetic ester includes at least one of trimethylolpropane trioleate, polyol ester, trimethylolpropane C18 unsaturated fatty acid diester, and trimethylolpropane C18 unsaturated fatty acid triester; the extreme pressure anti-wear agent includes polyisobutylene, tricresyl phosphate and triphenylthiophosphate.

[0009] The environmentally friendly chlorine-free high-temperature mold release agent of the present invention adopts extreme pressure anti-wear agent, corrosion inhibitor, antioxidant and specific synthetic ester compound, which can effectively prevent high-temperature wear and surface damage, significantly improve demoulding efficiency and mold service life, and meet the development direction of green manufacturing and environmental protection requirements. The present invention adopts polyisobutylene, tricresyl phosphate and triphenylthiophosphate as extreme pressure anti-wear agent, which can effectively reduce the friction between the metal surface and the mold material, reduce wear, improve the processing surface quality, and prevent premature wear of the mold. Polyisobutylene has good thermal stability at high temperature, forms a lubricating film under high temperature environment, can effectively reduce the friction between metal surfaces, and help improve the smoothness of the demoulding process. Tricresyl phosphate (TCP) forms a solid film by chemical reaction with the metal surface, which plays a role in preventing friction damage. Its extreme pressure performance is very strong, and the stability of the lubricating film can be maintained under high temperature and high pressure. Under extreme high temperature, tricresyl phosphate can prevent direct contact between the metal surface, reduce wear, and improve demoulding performance. In addition, it has strong antioxidant ability, which helps to extend the service life of the mold. Triphenyl thiophosphate has good anti-wear properties. It combines with the metal surface to form a chemical film with good adhesion to reduce wear and friction. Its sulfide group has good lubrication and can effectively reduce the friction coefficient. In a high temperature environment, triphenyl thiophosphate can react with the metal surface to form a protective film, effectively reducing the friction between metals and having strong high temperature resistance. The use of three ingredients in synergy can significantly improve the performance of the release agent.

[0010] Preferably, the synthetic ester comprises at least one of trimethylolpropane trioleate, polyol ester, trimethylolpropane C18 unsaturated fatty acid diester and triester.

[0011] In a specific embodiment of the present invention, trimethylolpropane trioleate, polyol ester, trimethylolpropane C18 unsaturated fatty acid diester and triester are used as synthetic esters, all of which can make the release agent have excellent high temperature resistance and lubrication properties.

[0012] Preferably, in the extreme pressure anti-wear agent, the mass ratio of the polyisobutylene, tricresyl phosphate and triphenylthiophosphate is (1.5-3): (1.5-3): (0.5-1).

[0013] More preferably, in the extreme pressure anti-wear agent, the mass ratio of the polyisobutylene, tricresyl phosphate and triphenylthiophosphate is 3:3:1.

[0014] The present invention has found that polyisobutylene, tricresol phosphate and triphenylthiophosphate in the extreme pressure anti-wear agent can better play a synergistic role under the above preferred mass ratio. Polyisobutylene reduces friction by providing lubricity; tricresol phosphate provides extreme pressure performance to prevent wear; triphenylthiophosphate further improves wear resistance and antioxidant capacity. They work together through reasonable proportions to effectively protect the mold and metal surface under high temperature conditions and prevent surface damage caused by high temperature. The extreme pressure anti-wear agent of the present invention can ensure efficient demoulding at a high temperature of more than 300°C and extend the life of the mold, and is particularly suitable for metal molding and high temperature treatment processes.

[0015] Preferably, the weight average molecular weight of the polyisobutylene is 400-680.

[0016] Preferably, the corrosion inhibitor includes at least one of 2,5-dimercapto-1,3,4-thiadiazole derivatives and NN-di(2-ethylhexyl)-methyl-1H-benzotriazole-1-methylamine.

[0017] The thiadiazole compound in the corrosion inhibitor of the present invention forms a thin adsorption film on the metal surface, which can effectively isolate the contact between the metal and the corrosive medium (such as water, acid, oxygen, etc.). In particular, the nitrogen and sulfur atoms in the thiadiazole can react with metal ions to form a stable metal-ligand complex, thereby slowing down the corrosion rate of the metal. The nitrogen, sulfur and other atoms in the thiadiazole ring have a strong electron attraction ability, which helps to form a stable chemical adsorption with the metal surface through electrostatic adsorption, further enhances its protective effect on the metal surface, and improves the corrosion resistance of the metal. Through complexation, the concentration of free metal ions on the metal surface can be reduced, and the metal is reduced from being corroded. The benzotriazole and methylamine groups of NN-di(2-ethylhexyl)-methyl-1H-benzotriazole-1-methylamine have strong polarity and affinity, and can produce adsorption with the metal surface through electrostatic action or hydrogen bonding, thereby reducing the corrosion reaction of the metal surface. The 2-ethylhexyl group is hydrophobic and can form a hydrophobic environment in the solution, further isolating the metal from contact with the corrosive factors in the aqueous solution, thereby enhancing the corrosion inhibition effect. The corrosion inhibitor of the present invention uses at least one of 2,5-dimercapto-1,3,4-thiadiazole derivatives and NN-di(2-ethylhexyl)-methyl-1H-benzotriazole-1-methylamine to effectively improve the anti-corrosion effect of the release agent, reduce wear, and increase the service life of the mold.

[0018] Preferably, the antioxidant comprises at least one of trimethylquinoline polymer, sterically hindered phenol derivatives, and 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionate.

[0019] In a second aspect, the present invention provides a method for preparing the environmentally friendly chlorine-free high-temperature release agent, comprising the following steps: uniformly stirring synthetic ester, extreme pressure anti-wear agent, corrosion inhibitor, and antioxidant to obtain the environmentally friendly chlorine-free high-temperature release agent.

[0020] The preparation method of the release agent of the invention has simple process, simple operation and can realize batch production.

[0021] Preferably, the stirring temperature is 20°C-30°C, and the stirring time is 0.5h-1.5h.

[0022] In a third aspect, the present invention provides the use of the environmentally friendly chlorine-free high-temperature release agent in the manufacture of battery pole pieces.

[0023] The release agent of the invention has excellent lubricity, extreme pressure and wear resistance, and can be used in the field of battery pole piece manufacturing.

[0024] The present invention has the following beneficial effects:

[0025] The environmentally friendly chlorine-free high-temperature release agent of the present invention has excellent high-temperature stability, can maintain effective demoulding performance at higher temperatures, is not easy to burn or decompose, and ensures that the demoulding effect is durable and reliable. And the lubrication performance is good, effectively reducing the friction between the mold and the workpiece, reducing wear, improving the smoothness of demoulding and the service life of the mold. It can also reduce corrosion, help molds and equipment to maintain a good working state, extend their service life, and reduce maintenance costs. It can be applied to molds of more different materials, such as aluminum alloys, steels, copper alloys, etc., and can adapt to different production processes (such as casting, heat treatment, plastic injection molding, etc.), and has a wider range of applicability. The release agent of the present invention has excellent lubricity, extreme pressure wear resistance and biodegradability, can effectively improve the quality of the workpiece, extend the tool life, and reduce equipment maintenance costs. It is a high-quality new environmentally friendly chlorine-free high-temperature release agent. DETAILED DESCRIPTION

[0026] To better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments. It should be understood by those skilled in the art that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0027] Unless otherwise specified, the experimental methods used in the examples are all conventional methods; the materials, reagents, etc. used, unless otherwise specified, can be obtained from commercial channels.

[0028] In the following examples and comparative examples,

[0029] The weight average molecular weight of the polyisobutylene is 400, Daelim PB400 from South Korea;

[0030] The 2,5-dimercapto-1,3,4-thiadiazole derivatives are: Vanderbilt, Cuvan 826;

[0031] The sterically hindered phenol derivative is: Rhein Chemie, RC7115;

[0032] The 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionate is: Rhein Chemie, RC7235;

[0033] The trimethylquinoline polymer is: Rhein Chemie, RC7010;

[0034] The trimethylolpropane C18 unsaturated fatty acid diester and triester are: Tecnofluid SRL, Temest H65;

[0035] The triphenylthiophosphate is: BASF, IrgalubeTPPT;

[0036] The nitrogen-containing derivative of sulfuric acid is: Shenyang Hualun Lubricant Additive Co., Ltd., T305;

[0037] The polyol ester is: Shanghai Nac Lubrication Technology Co., Ltd., PriEco 6000;

[0038] Unless otherwise specified, the components and raw materials used in the embodiments and comparative examples of the present invention are all commercially available raw materials, and the components and raw materials used in each parallel experiment are all of the same kind.

[0039] Examples 1-9

[0040] The components and contents of the environmentally friendly chlorine-free high-temperature release agents of Examples 1-9 are shown in Table 1.

[0041] The preparation method of the release agent comprises the following steps: stirring the synthetic ester, extreme pressure anti-wear agent, corrosion inhibitor and antioxidant at 25° C. for 1 hour according to the mass described in Table 1 to obtain the environmentally friendly chlorine-free high-temperature release agent.

[0042] Comparative Examples 1-5

[0043] The difference between the comparative examples and the embodiments is only in the types and proportions of components, as shown in Table 2.

[0044] Table 1 Content of each component in the environmentally friendly chlorine-free high-temperature release agent of Examples 1-9 (in mass %)

[0045]

[0046] Table 2 Content of each component in the environmentally friendly chlorine-free high-temperature release agent of Comparative Examples 1-5 (by mass%)

[0047]

[0048]

[0049] The release agents of the embodiments and comparative examples were tested for performance, and the testing method was as follows:

[0050] 1. Appearance test: visual inspection;

[0051] 2. Viscosity: GB / T265-1988 is used to test the kinematic viscosity of the high temperature release agent at 40°C;

[0052] 3. Flash point: GB / T 3536-2008 Cleveland open cup method;

[0053] 4. Acid value (mgKOH / g): GB / T 7304-2014 is used to test the acid value of high temperature release agent;

[0054] 5. Wear spot diameter: Use a four-ball friction tester according to SH / T0189-2017, with a static pressure of 40kg, to test the wear spot diameter of the release agent. The larger the wear spot diameter, the worse the lubricity of the high-temperature release agent.

[0055] 6. Average torque: refer to ASTMD5619 test standard, use Microtap teast lubricant tester TTTsystem G8 system to simulate on-site processing process for measurement, test metal plate is 316 stainless steel test plate, test depth is 12mm. The tester can select the appropriate depth range to simulate the needs of lubricant demoulding of metals of different thicknesses in actual production, which helps to evaluate the lubricity of environmentally friendly chlorine-free high-temperature demoulding agent under different thickness metal processing conditions. The smaller the average torque in the test result, the better the lubricity of environmentally friendly chlorine-free high-temperature demoulding agent.

[0056] 7. Copper corrosion test: Refer to GB / T5096-2017 Petroleum Product Copper Strip Corrosion Test Method, immerse a polished copper sheet in a certain volume of sample, heat it to the specified temperature according to the product category of the sample, and keep it for a certain time. At the end of the heating cycle, take out the copper sheet, wash it, and compare it with the copper sheet corrosion standard color plate to evaluate the discoloration of the copper sheet and determine the corrosion level.

[0057] The test results are shown in Table 3.

[0058] Table 3 Performance test results of release agents of embodiments and comparative examples

[0059]

[0060] It can be seen from Table 1 that the environmentally friendly chlorine-free high-temperature release agents of the embodiments of the present invention have excellent lubricity, extreme pressure anti-wear and corrosion resistance, among which the performance of Embodiment 1 is the best.

[0061] Compared with Example 1, the flash point of the mold release agent using other types of synthetic esters in Comparative Examples 1 and 2 is lower than 300°C, and the thermal stability is quite different from that of the synthetic esters in the examples. The synthetic esters in Comparative Examples 1 and 2 have poor high temperature resistance, and may undergo thermal cracking, oxidative degradation or polymerization under high temperature conditions, resulting in a significant decrease in lubrication performance. Esters with poor thermal stability will lose their lubrication ability under high temperature conditions, and may even cause the production of undesirable deposits, which will affect the smooth progress of the demoulding process, resulting in a decrease in the lubrication performance of the mold release agent, an increase in the diameter of the wear spot, and an increase in the average torque. In Comparative Example 3, a single nitrogen-containing derivative of sulfuric acid is used as an extreme pressure anti-wear agent, and the molecular structure is relatively simple, lacking sufficient versatility and a longer chain structure. Therefore, in a multiphase lubrication environment, when used alone, its extreme pressure and anti-wear performance are limited. Nitrogen-containing derivatives of sulfuric acid are not sufficient to provide continuous protection over a wide temperature and pressure range. The extreme pressure anti-wear agents in Comparative Examples 4 and 5 lack a certain component or two components, and cannot provide sufficient demoulding effect, especially under high pressure and high temperature environments. The wear spot diameter is significantly increased, and the lubricity and anti-wear performance are reduced. In contrast, the synergistic effect of the extreme pressure agents in the examples provides a more stable and superior demoulding effect. They not only improve lubricity, but also enhance anti-wear performance, especially under high load and harsh working conditions, and can play an excellent demoulding effect. Under high speed and heavy load conditions, the performance of the extreme pressure anti-wear agents of Comparative Examples 4 and 5 is difficult to match the synergistic effect of the extreme pressure anti-wear agents in the examples.

[0062] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. An environmentally friendly chlorine-free high-temperature release agent, characterized in that: The composition comprises the following components by mass percentage: 3.5%-7% of extreme pressure anti-wear agent, 0.1%-1% of corrosion inhibitor, 0.1%-1% of antioxidant, and the balance is synthetic ester; The synthetic ester includes at least one of trimethylolpropane trioleate, polyol ester, trimethylolpropane C18 unsaturated fatty acid diester, and trimethylolpropane C18 unsaturated fatty acid triester; the extreme pressure anti-wear agent includes polyisobutylene, tricresyl phosphate and triphenylthiophosphate.

2. The environmentally friendly chlorine-free high-temperature release agent according to claim 1, characterized in that: In the extreme pressure anti-wear agent, the mass ratio of the polyisobutylene, tricresyl phosphate and triphenylthiophosphate is (1.5-3): (1.5-3): (0.5-1).

3. The environmentally friendly chlorine-free high-temperature release agent according to claim 1 or 2, characterized in that: In the extreme pressure anti-wear agent, the mass ratio of the polyisobutylene, tricresyl phosphate and triphenylthiophosphate is 3:3:

1.

4. The environmentally friendly chlorine-free high-temperature release agent according to claim 1, characterized in that: The weight average molecular weight of the polyisobutylene is 400-680.

5. The environmentally friendly chlorine-free high-temperature release agent according to claim 1, characterized in that: The corrosion inhibitor includes at least one of 2,5-dimercapto-1,3,4-thiadiazole derivatives and NN-di(2-ethylhexyl)-methyl-1H-benzotriazole-1-methylamine.

6. The environmentally friendly chlorine-free high-temperature release agent according to claim 1, characterized in that: The antioxidant comprises at least one of trimethylquinoline polymer, sterically hindered phenol derivatives and 3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionate.

7. The method for preparing the environmentally friendly chlorine-free high-temperature release agent according to any one of claims 1 to 6, characterized in that: The method comprises the following steps: uniformly stirring synthetic ester, extreme pressure anti-wear agent, corrosion inhibitor and antioxidant to obtain the release agent.

8. The method for preparing an environmentally friendly chlorine-free high-temperature release agent according to claim 7, characterized in that: The stirring temperature is 20°C-30°C, and the stirring time is 0.5h-1.5h.

9. Use of the environmentally friendly chlorine-free high-temperature release agent according to any one of claims 1 to 6 in the manufacture of battery pole pieces.

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