Ammonolysis modified diester oil for TPE (thermoplastic elastomer) and preparation method of ammonolysis modified diester oil

Abstract

The invention provides ammonolysis modified diester oil for TPE (thermoplastic elastomer) and a preparation method of the ammonolysis modified diester oil. The ammonolysis modified diester oil comprises the following components in parts by weight: 100-120 parts of modified disubstituted diester oil; 20 to 50 parts of an ammonolysis agent; 0.1 to 0.3 part of a catalyst; wherein the modified disubstituted diester oil is obtained by carrying out ester exchange reaction on diester oil and aromatic alcohol. The modified disubstituted diester oil is obtained through ester exchange reaction of diester oil and aromatic alcohol, and two non-polar benzene ring structures are introduced into a molecular chain of the modified disubstituted diester oil, so that the compatibility of the modified disubstituted diester oil and SBS / SEBS is effectively improved, and the modified diester oil can be directly used for producing and processing TPE materials. An ammonolysis agent is added for ammonolysis reaction, so that the modified diester oil obtains amido bonds with high light and heat stability and hydrolysis resistance, and the aging resistance of the TPE material applying the diester oil can be effectively improved.

Description

Technical Field

[0001] This application relates to the field of oil technology for TPE production, and in particular to an ammonolytic modified diester oil for TPE and its preparation method. Background Technology

[0002] TPE (Thermoplastic Polystyrene) material is a novel rubber material based on thermoplastic styrene block polymers (SBS / SEBS). Due to its combination of the elasticity of thermosetting cross-linked rubbers and the processability of thermoplastic materials, it is widely used in automotive, military, and medical fields. During its production, to obtain sufficient processability (plasticity), oil needs to be added to SBS / SEBS as a processing lubricant and softener. Currently, the oils used for processing TPE materials are generally base mineral oils, such as naphthenic oils and paraffin oils. Base mineral oils have relatively good compatibility with SBS / SEBS, and adding appropriate amounts can effectively improve the ease of processing TPE materials, while also improving the material's flexibility and elongation at break. However, it can severely affect the tensile strength and aging resistance of TPE materials. Summary of the Invention

[0003] This application aims to address the technical problem that the base mineral oil used in the processing of TPE materials in the prior art seriously affects their hardness, tensile strength, and temperature resistance; it proposes an ammonolytic modified diester oil for TPE and its preparation method to effectively improve the tensile strength and aging resistance of TPE materials.

[0004] To achieve the above objectives, this application adopts the following technical solution:

[0005] An ammonolytic modified diester oil for TPE comprises the following components in parts by weight:

[0006] 100-120 parts of modified disubstituted diester oil;

[0007] 20-50 parts of ammonolysis agent;

[0008] Catalyst: 0.1–0.3 parts;

[0009] The modified disubstituted diester oil is obtained by transesterification of diester oil and aromatic alcohol.

[0010] Furthermore, the diester oil is dioctyl adipate or di(2-ethylhexyl) sebacate.

[0011] Furthermore, the aromatic alcohol is an aromatic monool that is readily soluble or soluble in water.

[0012] Furthermore, the ammonolysis agent is a primary amine or a miscible mixture of ammonia and a solvent.

[0013] Furthermore, when the ammonolysis agent is a miscible mixture of ammonia and solvent, the weight fraction is 30 to 50 parts; when the ammonolysis agent is a primary amine, the weight fraction is 20 to 40 parts.

[0014] Furthermore, when the ammonolysis agent is a primary amine, the catalyst is sodium methoxide or sodium cyanide; when the ammonolysis agent is a miscible mixture of ammonia and solvent, the catalyst is copper sulfate.

[0015] Furthermore, the primary amine is an aliphatic primary amine.

[0016] Furthermore, the solvent is ethanol.

[0017] The above-mentioned method for preparing an ammonolytic modified diester oil for TPE includes the following steps:

[0018] S1. Weigh the modified disubstituted diester oil, ammonolysis agent, and catalyst according to their weight fractions;

[0019] S2. The modified disubstituted diester oil, ammonolysis agent and catalyst are placed in a reaction vessel to carry out ammonolysis reaction;

[0020] S3. After the ammonolysis reaction is completed, wash away the residual ammonolysis agent with NaHCO3 aqueous solution and dry the water to obtain the crude product.

[0021] S4. The crude product is purified by chromatography to obtain ammonolytic modified diester oil.

[0022] Furthermore, the temperature of the ammonolysis reaction is 150℃~180℃, and the reaction time is 40min~70min.

[0023] Furthermore, the eluent used in the chromatography method is a mixture of petroleum ether and ethyl acetate prepared by mixing them in a volume ratio of 5:1.

[0024] The beneficial effects of this application are:

[0025] The modified disubstituted diester oil used in this application is obtained through a transesterification reaction between diester oil and aromatic alcohol. The introduction of two nonpolar benzene ring structures into its molecular chain effectively improves its compatibility with SBS / SEBS, allowing the modified diester oil to be directly used in the production and processing of TPE materials. Furthermore, by adding an ammonolytic agent to carry out an ammonolysis reaction, the modified diester oil acquires amide bonds with high photothermal stability and hydrolysis resistance, thereby effectively improving the aging resistance of the TPE materials in which it is applied.

[0026] The ammonolytic modified diester oil obtained after ammonolysis of this application introduces amide bonds, which can effectively improve the compatibility of the TPE material it is used with polar materials such as PA, PC, and ABS, so that the TPE material can be used directly as a bonding / coating material. Detailed Implementation

[0027] This invention provides an ammonolytic modified diester oil for TPE and its preparation method to solve the technical problem that the base mineral oil used in the processing of TPE materials in the prior art seriously affects its hardness, tensile strength and temperature resistance.

[0028] The overall concept adopted in this invention is as follows:

[0029] This invention first obtains a modified disubstituted diester oil with two nonpolar benzene rings through a transesterification reaction of diester oil and aromatic alcohol, ensuring the compatibility of the base material with SBS / SEBS, thus enabling its direct application in the production and processing of TPE materials. Then, an ammonolysis reaction is carried out by adding an ammonolytic agent to give the modified diester oil amide bonds with high photothermal stability and hydrolysis resistance, thereby effectively improving the aging resistance of the applied TPE materials. During preparation, it is best to use a slightly excess of the modified disubstituted diester oil, as follows:

[0030] An ammonolytic modified diester oil for TPE comprises the following components in parts by weight:

[0031] 100-120 parts of modified disubstituted diester oil;

[0032] 20-50 parts of ammonolysis agent;

[0033] Catalyst: 0.1–0.3 parts;

[0034] The modified disubstituted diester oil is obtained by transesterification of diester oil and aromatic alcohol. The transesterification process is as follows: diester oil, aromatic alcohol, and concentrated sulfuric acid are placed in a reaction vessel, heated to 100℃~120℃, and reacted for 6-8 hours to obtain a primary product. The aromatic alcohol and concentrated sulfuric acid in the primary product are washed away with sodium carbonate solution, and then water and fusel oil are removed by rotary evaporation to obtain the modified disubstituted diester oil. The diester oil, aromatic alcohol, and concentrated sulfuric acid are mixed in weight ratios of 100 parts, (10-30) parts, and (0.15-0.35) parts, respectively.

[0035] The diester oil is one of dioctyl adipate or di(2-ethylhexyl) sebacate. The aromatic alcohol is an aromatic monool that is readily soluble or soluble in water. For example, it can be phenylbutanol, salicylol, etc.

[0036] The ammonolysis agent is a primary amine or a miscible mixture of ammonia and a solvent. The primary amine is an aliphatic primary amine, such as dimethoxyethylamine or 2-amino-2-methyl-1-propanol. The solvent is ethanol.

[0037] When the ammonolysis agent is a primary amine, the catalyst is sodium methoxide or sodium cyanide; when the ammonolysis agent is a miscible mixture of ammonia and solvent, the catalyst is copper sulfate.

[0038] The above-mentioned method for preparing ammonolytic modified diester oil for TPE includes the following steps:

[0039] S1. Weigh the modified disubstituted diester oil, ammonolysis agent, and catalyst according to their weight fractions;

[0040] S2. The modified disubstituted diester oil, ammonolysis agent and catalyst are placed in a reaction vessel to carry out ammonolysis reaction; wherein, the temperature of the ammonolysis reaction is 150℃~180℃ and the reaction time is 40min~70min.

[0041] S3. After the ammonolysis reaction is completed, wash away the residual ammonolysis agent with NaHCO3 aqueous solution and dry the water to obtain the crude product.

[0042] S4. The crude product is purified by chromatography to obtain ammonolytic modified diester oil.

[0043] The eluent used in the chromatography method is a mixture of petroleum ether and ethyl acetate prepared by mixing them in a volume ratio of 5:1.

[0044] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of the embodiments will be described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of this application, and not all of them. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application. In the description of this application, the experimental methods, unless otherwise specified, are conventional methods; the reagents and materials, unless otherwise specified, are all commercially available.

[0045] The following disclosure provides many different implementations or examples for carrying out this application. To simplify the disclosure of this application, specific examples of components and arrangements are described below. Of course, these are merely examples and are not intended to limit the scope of this application. Those skilled in the art will recognize the application of other processes and / or the use of other materials.

[0046] Example 1

[0047] The preparation of modified disubstituted diester oil includes the following steps:

[0048] A. Weigh each component according to the following weights:

[0049] 1000g dioctyl adipate, 100g phenylbutanol, 1.5g 98wt.% concentrated sulfuric acid.

[0050] B. Weigh out dioctyl adipate, phenylbutanol and concentrated sulfuric acid and place them in a reaction vessel. Heat to 110°C and react for 6 hours to obtain the primary product.

[0051] C. After washing away the phenylbutanol and concentrated sulfuric acid from the primary product with sodium carbonate solution, water and fusel oil are removed by rotary evaporation to obtain the modified disubstituted diester oil. The rotary evaporation temperature is 90°C.

[0052] A method for preparing an ammonolytic modified diester oil for TPE includes the following steps:

[0053] S1. Weigh each component according to the following weights:

[0054] 1000g modified disubstituted diester oil, 51g ammonia, 500g 95% ethanol, and 2g anhydrous copper sulfate. The ammonia was weighed using a mass flow meter.

[0055] S2. Dissolve ammonia completely in 95% ethanol to obtain a miscible mixture (i.e., ammonolysis agent);

[0056] S3. The modified disubstituted diester oil, the miscible mixture, and anhydrous copper sulfate are placed in a reaction vessel for ammonolysis reaction. The ammonolysis reaction is carried out at a temperature of 150°C and a reaction time of 40 min.

[0057] S4. After the ammonolysis reaction is completed, wash away the residual ammonolysis agent with NaHCO3 aqueous solution and dry the water to obtain the crude product.

[0058] S5. The crude product is purified by chromatography to obtain ammonolytic modified diester oil, which is denoted as S1.

[0059] The eluent used in the chromatography method is a mixture of petroleum ether and ethyl acetate prepared by mixing them in a volume ratio of 5:1.

[0060] Example 2

[0061] The preparation of modified disubstituted diester oil includes the following steps:

[0062] A. Weigh each component according to the following weights:

[0063] 1000g di(2-ethylhexyl) sebacate, 200g salicyl alcohol, 1.5g 98wt.% concentrated sulfuric acid.

[0064] B. Weigh out di(2-ethylhexyl) sebacate, salicyl alcohol and concentrated sulfuric acid and place them in a reaction vessel. Heat to 100°C and react for 8 hours to obtain the primary product.

[0065] C. After washing away salicylates and concentrated sulfuric acid from the primary product with sodium carbonate solution, water and fusel oil are removed by rotary evaporation to obtain the modified disubstituted diester oil. The rotary evaporation temperature is 90°C.

[0066] A method for preparing an ammonolytic modified diester oil for TPE includes the following steps:

[0067] S1. Weigh each component according to the following weights:

[0068] 1000g modified disubstituted diester oil, 42g ammonia, 400g 95% ethanol, and 2g anhydrous copper sulfate. The ammonia was weighed using a mass flow meter.

[0069] S2. Dissolve ammonia completely in 95% ethanol to obtain a miscible mixture (i.e., ammonolysis agent);

[0070] S3. The modified disubstituted diester oil, the miscible mixture, and anhydrous copper sulfate are placed in a reaction vessel for ammonolysis reaction. The ammonolysis reaction is carried out at a temperature of 150°C and a reaction time of 40 min.

[0071] S4. After the ammonolysis reaction is completed, wash away the residual ammonolysis agent with NaHCO3 aqueous solution and dry the water to obtain the crude product.

[0072] S5. The crude product is purified by chromatography to obtain ammonolytic modified diester oil, which is denoted as S2.

[0073] The eluent used in the chromatography method is a mixture of petroleum ether and ethyl acetate prepared by mixing them in a volume ratio of 5:1.

[0074] Example 3

[0075] A method for preparing an ammonolytic modified diester oil for TPE includes the following steps:

[0076] S1. Weigh each component according to the following weights:

[0077] 1000g modified disubstituted diester oil, 300g dimethoxyethylamine, and 2.5g sodium methoxide. The modified disubstituted diester oil used is the same as that used in Example 1.

[0078] S2. The modified disubstituted diester oil, dimethoxyethylamine and sodium methoxide are placed in a reaction vessel for ammonolysis reaction. The ammonolysis reaction is carried out at a temperature of 180°C and a reaction time of 70 min.

[0079] S3. After the ammonolysis reaction is completed, wash away the residual ammonolysis agent with NaHCO3 aqueous solution and dry the water to obtain the crude product.

[0080] S4. The crude product is purified by chromatography to obtain ammonolytic modified diester oil, which is denoted as S3.

[0081] The eluent used in the chromatography method is a mixture of petroleum ether and ethyl acetate prepared by mixing them in a volume ratio of 5:1.

[0082] Example 4

[0083] A method for preparing an ammonolytic modified diester oil for TPE includes the following steps:

[0084] S1. Weigh each component according to the following weights:

[0085] 1000g modified disubstituted diester oil, 270g 2-amino-2-methyl-1-propanol, and 2.5g sodium methoxide. The modified disubstituted diester oil used is the same as that used in Example 1.

[0086] S2. The modified disubstituted diester oil, 2-amino-2-methyl-1-propanol and sodium methoxide are placed in a reaction vessel for ammonolysis reaction. The ammonolysis reaction is carried out at a temperature of 160°C and a reaction time of 60 min.

[0087] S3. After the ammonolysis reaction is completed, wash away the residual ammonolysis agent with NaHCO3 aqueous solution and dry the water to obtain the crude product.

[0088] S4. The crude product is purified by chromatography to obtain ammonolytic modified diester oil, which is denoted as S4.

[0089] The eluent used in the chromatography method is a mixture of petroleum ether and ethyl acetate prepared by mixing them in a volume ratio of 5:1.

[0090] Comparative Example 1

[0091] A method for preparing an ammonolyzed diester oil includes the following steps:

[0092] S1. Weigh each component according to the following weights:

[0093] 1000g diester oil, 270g 2-amino-2-methyl-1-propanol, 2.5g sodium methoxide. The diester oil used was the unmodified dioctyl adipate from Example 1.

[0094] S2. The modified disubstituted diester oil, 2-amino-2-methyl-1-propanol and sodium methoxide are placed in a reaction vessel for ammonolysis reaction. The ammonolysis reaction is carried out at a temperature of 160°C and a reaction time of 60 min.

[0095] S3. After the ammonolysis reaction is completed, wash away the residual ammonolysis agent with NaHCO3 aqueous solution and dry the water to obtain the crude product.

[0096] S4. The crude product is purified by chromatography to obtain ammonolytic modified diester oil, which is denoted as D1.

[0097] The eluent used in the chromatography method is a mixture of petroleum ether and ethyl acetate prepared by mixing them in a volume ratio of 5:1.

[0098] Comparative Example 2

[0099] The preparation of modified disubstituted diester oil includes the following steps:

[0100] A. Weigh each component according to the following weights:

[0101] 1000g dioctyl adipate, 100g phenylbutanol, 1.5g 98wt.% concentrated sulfuric acid.

[0102] B. Weigh out dioctyl adipate, phenylbutanol and concentrated sulfuric acid and place them in a reaction vessel. Heat to 110°C and react for 6 hours to obtain the primary product.

[0103] C. After washing away the phenylbutanol and concentrated sulfuric acid from the primary product with sodium carbonate solution, remove the water and fusel oil by rotary evaporation to obtain the modified disubstituted diester oil, denoted as D2. The rotary evaporation temperature used in this process is 90°C.

[0104] The difference between this comparative example and Example 1 above is that the diester oil is modified and then no longer subjected to ammonolysis, and is subsequently used directly in the production of TPE materials.

[0105] Product application trial

[0106] In order to compare the effects of the products obtained in the above embodiments and comparative examples when applied to the production of TPE materials, the products obtained in the above embodiments and comparative examples are now processed according to the following component formulation and preparation method.

[0107] The TPE material production formula includes the following components in parts by weight:

[0108]

[0109] The method for preparing TPE materials includes the following steps:

[0110] Step 1: Weigh out SBES, oil additives, PP resin and 800-mesh calcium carbonate by weight.

[0111] Step 2: Place the weighed SBES and oil additives in a high-speed mixer and mix for 5 minutes;

[0112] Step 3: Add the weighed PP and 800-mesh calcium carbonate to the high-speed mixer from Step 2 and continue mixing for 5 minutes to obtain the mixture;

[0113] Step 4: The mixture obtained in Step 3 is extruded and granulated using a twin-screw extruder to obtain the corresponding TPE product. The extrusion temperature in Step 4 is 190°C.

[0114] Product performance testing

[0115] To verify the performance of the oil products obtained in the above embodiments and comparative examples, and the performance of the TPE materials obtained through their filling applications, the oil products obtained in the above embodiments and comparative examples were subjected to tests on various properties, including thermal decomposition rate (test conditions: temperature 260℃, time 100h, gas atmosphere: air), viscosity index, and atomization. The atomization performance was tested using FAW Group's enterprise standard Q / CAM-546, while the other properties were tested using conventional testing methods in the field.

[0116] The performance test results of the oil products obtained in each embodiment and comparative example are shown in Table 1.

[0117] Table 1. Performance test results of oil products obtained from each embodiment and comparative example.

[0118]

[0119] The performance test results of the oil products obtained from the above embodiments and comparative examples show that the ammonolytic modified diester oil obtained by the method of the present invention has a significantly reduced thermal decomposition rate and a significantly increased viscosity index due to its stronger internal hydrogen bonding and intermolecular interactions. Specifically, the thermal decomposition rate of the ammonolytic modified diester oil obtained by the method of the present invention is below 11.2% under the conditions of 260℃, 100h, and an air atmosphere, with a minimum of 8.0%, and the atomization rate is below 15mg, with a minimum of 11mg.

[0120] Further analysis was conducted on the hardness, tensile strength, tensile strength decay rate after long-term heat aging (aging temperature 120℃, aging time 1000h), tensile strength decay rate after long-term damp heat aging (double 85 test, 1000h), and overmolding strength of TPE materials obtained from the above embodiments and comparative examples using oil-based filler applications. 2100, ABS is Formosa Plastics 12A1, and the test method is "VDI 2019") and other properties. The test results of various properties of TPE materials obtained by filling with oil products in each example and comparative example are shown in Table 2.

[0121] Table 2 shows the performance test results of TPE materials obtained from the application of oil products in each embodiment and comparative example.

[0122]

[0123] The performance test results of the TPE materials obtained from the above embodiments and comparative examples using oil-based products show that the ammonolytic modified diester oil obtained by the method of this invention can effectively improve the tensile strength and aging resistance of TPE materials. This is mainly due to the presence of both phenyl and amide bonds in its molecular chain, which, while maintaining high compatibility with SBS / SEBS, greatly improves its water and moisture resistance, giving SBS / SEBS products high resistance to temperature, water, and damp heat, and also giving the products good wettability to polar materials such as PC and ABS.

[0124] In the above embodiments, the descriptions of each embodiment have different focuses. For parts not described in detail in a certain embodiment, please refer to the relevant descriptions in other embodiments.

[0125] The above provides a detailed description of a method for preparing an ammonolytic modified diester oil for TPE provided in the embodiments of this application. Specific examples have been used to illustrate the principles and implementation methods of this application. The descriptions of the above embodiments are only for the purpose of helping to understand the technical solutions and core ideas of this application. Those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. These modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application.

Claims

1. An ammonolytic modified diester oil for TPE, characterized in that, The components include the following parts by weight: 100-120 parts of modified disubstituted diester oil; 20-50 parts of ammonolysis agent; Catalyst: 0.1–0.3 parts; The modified disubstituted diester oil is obtained by transesterification of diester oil and aromatic alcohol.

2. The ammonochemical modified diester oil for TPE as described in claim 1, characterized in that: The diester oil is dioctyl adipate or di(2-ethylhexyl) sebacate.

3. The ammonochemical modified diester oil for TPE as described in claim 1, characterized in that: The aromatic alcohol is an aromatic monool that is readily soluble or soluble in water.

4. The ammonolytic modified diester oil for TPE as described in claim 1, characterized in that: The ammonolysis agent is a primary amine or a miscible mixture of ammonia and a solvent.

5. The ammonochemical modified diester oil for TPE as described in claim 4, characterized in that: When the ammonolysis agent is a primary amine, the catalyst is sodium methoxide or sodium cyanide; when the ammonolysis agent is a miscible mixture of ammonia and solvent, the catalyst is copper sulfate.

6. The ammonochemical modified diester oil for TPE as described in claim 4, characterized in that: The primary amine is an aliphatic primary amine.

7. The ammonochemical modified diester oil for TPE as described in claim 4, characterized in that: The solvent is ethanol.

8. A method for preparing an ammonolytic modified diester oil for TPE as described in any one of claims 1 to 7, characterized in that, Includes the following steps: S1. Weigh the modified disubstituted diester oil, ammonolysis agent, and catalyst according to their weight fractions; S2. The modified disubstituted diester oil, ammonolysis agent and catalyst are placed in a reaction vessel to carry out ammonolysis reaction; S3. After the ammonolysis reaction is completed, wash away the residual ammonolysis agent with NaHCO3 aqueous solution and dry the water to obtain the crude product. S4. The crude product is purified by chromatography to obtain ammonolytic modified diester oil.

9. The method for preparing ammonolytically modified diester oil for TPE as described in claim 8, characterized in that: The ammonolysis reaction is carried out at a temperature of 150℃ to 180℃ for a reaction time of 40 min to 70 min.

10. The method for preparing ammonolytically modified diester oil for TPE as described in claim 8, characterized in that: The eluent used in the chromatography method is a mixture of petroleum ether and ethyl acetate prepared in a volume ratio of 5:1.

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