A lubricating agent for ABS resin and preparation method thereof

Abstract

The invention relates to a lubricating auxiliary for ABS resin and a preparation method thereof, belonging to the technical field of plastic processing. The lubricating auxiliary comprises, by weight, 50 parts of a lubricating main agent, 25-35 parts of a calcium-based auxiliary agent and 15-25 parts of a dispersant; wherein the lubricating main agent is prepared by amine ester exchange between a dialkylamine and diethyl diallylmalonate to prepare an amide compound with alkyl chain modification, namely, intermediate 1; then, mercaptoethanol is subjected to click addition with double bonds in the intermediate 1 molecule to introduce a thioether structure and a terminal active primary alcohol into the intermediate 1 molecule to obtain intermediate 2; finally, single-ended epoxy silicone oil is ring-opened with an alcohol hydroxyl grafted in the intermediate 2 to introduce silicone oil chain modification to obtain the lubricating main agent; the lubricating auxiliary has both internal and external lubricity for ABS plastics and solves the problem of strength reduction of ABS products caused by lubricants.

Description

Technical Field

[0001] The invention belongs to the technical field of plastic processing, and in particular relates to a lubricating agent for ABS resin and a preparation method thereof. Background Art

[0002] ABS plastic (acrylonitrile-butadiene-styrene copolymer) has been widely used in electronic products, household appliances, automotive parts and other fields due to its excellent mechanical properties, good impact resistance and easy processing. However, in the processing of ABS plastic, due to its high melt viscosity and poor fluidity, lubricants are often needed to improve its processing performance.

[0003] Existing ABS plastic lubricants mainly include fatty acid amide, paraffin wax, polyethylene wax, etc. These lubricants can reduce melt viscosity and improve fluidity to a certain extent. However, the addition of these lubricants often leads to a decrease in the performance of ABS plastics. The main factors include the following two points. First, in order to improve the molding ability of ABS plastics, it is generally necessary to use internal lubricants and external lubricants at the same time. Too little lubrication will result in poor lubrication effect, and too much will cause a significant decrease in the strength of ABS plastics. Second, some lubricants have poor compatibility with ABS plastics, which can easily lead to agglomeration of lubricants inside the plastic, forming local defects in ABS plastics, which directly affects the mechanical strength of ABS plastics. The use of lubricants greatly limits the application of ABS plastics in certain high-performance applications. Summary of the invention

[0004] In order to solve the technical problems mentioned in the background technology, the object of the present invention is to provide a lubricating agent for ABS resin and a preparation method thereof.

[0005] The purpose of the present invention can be achieved by the following technical solutions:

[0006] A lubricating auxiliary agent for ABS resin is a composite lubricating composition, comprising, by weight, 50 parts of a lubricating main agent, 25-35 parts of a calcium-based auxiliary agent, and 15-25 parts of a dispersant.

[0007] The lubricating main agent is prepared by the following method:

[0008] Step A1: Diethyl diallylmalonate, dialkylamine and anhydrous toluene are mixed, nitrogen is introduced for protection, the temperature is raised to 55-70°C, stirring is applied at 40-60 rpm, sodium hydride is added in batches to react for 5-7 hours, and toluene is removed by rotary evaporation after the reaction is completed. The rotary evaporation substrate is washed with water and dried to obtain intermediate 1;

[0009] Further, the amount ratio of diethyl diallyl malonate, dialkylamine, sodium hydride and anhydrous toluene is 0.1 mol: 0.205-0.21 mol: 0.1-0.16 g: 80-120 mL, and under the promotion of sodium hydride, dialkylamine and diethyl diallyl malonate undergo amine ester exchange to prepare an amide compound with alkyl chain modification;

[0010] Preferably, the dialkylamine is selected from one of di-n-octylamine and di-n-decylamine.

[0011] Step A2: Mix intermediate 1, mercaptoethanol, dimethylphenylphosphine and acetone, raise the temperature to 40-50°C, apply stirring at 120-180 rpm and 150-300 W / m 2 UV irradiation, reaction for 2.5-3.5h, after the reaction, acetone was removed by rotary evaporation to obtain intermediate 2;

[0012] Furthermore, the dosage ratio of intermediate 1, mercaptoethanol, dimethylphenylphosphine and acetone is 0.1 mol: 0.2 mol: 20-30 mg: 100-150 mL. Under the promotion of dimethylphenylphosphine and initiation of ultraviolet radiation, mercaptoethanol clicks and adds to the double bond in the intermediate 1 molecule to introduce a thioether structure and a terminal active primary alcohol into the intermediate 1 molecule.

[0013] Step A3: Mix the intermediate 2, single-ended epoxy silicone oil, triethylamine and dimethylacetamide, introduce nitrogen protection, heat to 85-100°C, stir at 60-90 rpm, react for 1.5-2.2 hours, wash with water and dry after the reaction to obtain a lubricating main agent;

[0014] Furthermore, the epoxy content of intermediate 2, single-ended epoxy silicone oil, triethylamine and dimethylacetamide are used in a ratio of 0.1 mol: 0.2 mol: 15-20 mL: 120-160 mL. Under the promotion of triethylamine, the grafted alcoholic hydroxyl group in intermediate 2 is ring-opened with the single-ended epoxy silicone oil to introduce silicone oil chain modification;

[0015] Preferably, the single-ended epoxy silicone oil is selected from a small molecular weight silicone oil with a room temperature viscosity not higher than 50 mm 2 / s.

[0016] Preferably, the calcium-based adjuvant is selected from light calcium carbonate with a fineness of not less than 300 meshes.

[0017] Preferably, the dispersant is selected from a premix of polyethylene wax and microcrystalline wax.

[0018] A method for preparing a lubricating auxiliary agent for ABS resin comprises the following specific operations: mixing a lubricating main agent, a calcium-based auxiliary agent and a dispersant, kneading at a temperature of 120-130° C., and pelletizing after cooling to prepare the lubricating auxiliary agent for ABS resin.

[0019] Beneficial effects of the present invention:

[0020] The invention discloses a composite lubricating composition, which is compounded by a self-developed lubricating main agent with common light calcium carbonate, polyethylene wax and microcrystalline wax, and has both internal and external lubricity for ABS plastics. The lubricating main agent is prepared by amine ester exchange between dialkylamine and diethyl diallylmalonate to prepare an amide compound with alkyl chain modification, namely intermediate 1, and then mercaptoethanol is added to the double bond in the intermediate 1 molecule by click addition to introduce a thioether structure and a terminal active primary alcohol into the intermediate 1 molecule, so as to obtain intermediate 2, and finally single-end epoxy silicone oil is opened with the alcohol hydroxyl grafted in the intermediate 2 to introduce silicone oil chain modification, so as to obtain the lubricating main agent; the multi-branched alkyl short chain in the lubricating main agent molecule has good affinity with the macromolecule of ABS. The compatibility of the lubricating main agent makes it possible to disperse the lubricating main agent evenly in the ABS melt. The multi-branched alkyl short chain reduces the melt viscosity, while the introduced silicone chain reduces the friction between the ABS macromolecular chains and forms a lubricating effect between the melt and the processing equipment, showing good internal and external lubricity in the test. In addition, the disulfide structures introduced by mercaptoethanol in the lubricating main agent molecules form a chelating effect and form a chelating force with calcium carbonate. It is a low-stability ten-membered chelating ring, and the chelating force is extremely low in the high-temperature melt, and the effect on the lubricity of the melt is negligible. During the cooling and curing process, the chelating ring is reformed to strengthen the bonding strength of calcium carbonate in the ABS matrix and make up for the problem of decreased ABS matrix strength caused by the addition of the lubricant. DETAILED DESCRIPTION

[0021] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0022] Example 1, preparation of lubricating agent for ABS resin, the specific implementation process is as follows:

[0023] (1) Preparation of lubricating agent

[0024] Step A1: Diethyl diallyl malonate, dialkylamine and anhydrous toluene are mixed, nitrogen is introduced for protection, the temperature is raised to 70°C, stirring is applied at 60 rpm, equal amounts of sodium hydride are divided into four portions, and added at intervals of 30 minutes. After complete addition, the reaction is continued at a constant temperature, and the total reaction time of the addition of sodium hydride is controlled to be 7 hours, wherein the dialkylamine is selected from di-n-decylamine, and the amount ratio of diethyl diallyl malonate, dialkylamine, sodium hydride and anhydrous toluene is 0.1 mol: 0.21 mol: 0.16 g: 120 mL. After the reaction is completed, toluene is removed by rotary evaporation, and the rotary evaporation substrate is washed with water and dried to obtain intermediate 1.

[0025] Step A2: Mix intermediate 1, mercaptoethanol, dimethylphenylphosphine and acetone, raise the temperature to 50°C, stir at 180 rpm and heat at 300 W / m 2 The reaction was carried out under ultraviolet irradiation for 2.5 hours, wherein the usage ratio of intermediate 1, mercaptoethanol, dimethylphenylphosphine and acetone was 0.1 mol: 0.2 mol: 30 mg: 150 mL. After the reaction, acetone was removed by rotary evaporation to obtain intermediate 2.

[0026] Step A3: Take intermediate 2, single-ended epoxy silicone oil, triethylamine and dimethylacetamide, mix them, introduce nitrogen protection, heat to 100°C, stir at 90rpm, and react for 1.5h, wherein the single-ended epoxy silicone oil is selected from X-22-173BX type raw material, and the room temperature viscosity is 30mm 2 / s, the epoxy content of intermediate 2, single-ended epoxy silicone oil, triethylamine and dimethylacetamide are used in a ratio of 0.1 mol: 0.2 mol: 20 mL: 160 mL. After the reaction is completed, the mixture is washed with water and dried to obtain a lubricating main agent.

[0027] (2) Preparation of lubricating additives

[0028] Ingredients: The raw materials are calculated by weight, 50 parts of the lubricating main agent, which is self-made in this embodiment; 25 parts of the calcium-based auxiliary agent, and commercially available 325-mesh light calcium carbonate is used in the implementation process; 25 parts of the dispersant, and PE-200A polyethylene wax and 85# microcrystalline wax are premixed in a mass ratio of 2:1 in the implementation process.

[0029] Kneading molding: Mix the lubricating main agent, calcium-based auxiliary agent and dispersant, add them into a kneading machine, knead at 130°C, and cut into pellets after cooling to make a lubricating auxiliary agent for ABS resin.

[0030] Example 2, preparation of lubricating additive for ABS resin, the specific implementation process is as follows:

[0031] (1) Preparation of lubricating agent

[0032] Step A1: Diethyl diallyl malonate, dialkylamine and anhydrous toluene are mixed, nitrogen is introduced for protection, the temperature is raised to 55°C, stirring is applied at 40 rpm, equal amounts of sodium hydride are divided into four portions, and added at intervals of 30 minutes. After complete addition, the reaction is continued at a constant temperature, and the total reaction time of the addition of sodium hydride is controlled to be 5 hours, wherein the dialkylamine is selected from di-n-octylamine, and the amount ratio of diethyl diallyl malonate, dialkylamine, sodium hydride and anhydrous toluene is 0.1 mol: 0.205 mol: 0.1 g: 80 mL. After the reaction is completed, toluene is removed by rotary evaporation, and the rotary evaporation substrate is washed with water and dried to obtain intermediate 1.

[0033] Step A2: Mix intermediate 1, mercaptoethanol, dimethylphenylphosphine and acetone, raise the temperature to 40°C, stir at 120 rpm and apply 150 W / m 2 The reaction was carried out under ultraviolet irradiation for 3.5 hours, wherein the usage ratio of intermediate 1, mercaptoethanol, dimethylphenylphosphine and acetone was 0.1 mol: 0.2 mol: 20 mg: 100 mL. After the reaction, acetone was removed by rotary evaporation to obtain intermediate 2.

[0034] Step A3: Take intermediate 2, single-ended epoxy silicone oil, triethylamine and dimethylacetamide, mix them, pass nitrogen protection, heat to 85°C, stir at 60rpm, and react for 2.2h, wherein the single-ended epoxy silicone oil is selected from X-22-173BX type raw material, and the room temperature viscosity is 30mm 2 / s, the epoxy content of intermediate 2, single-ended epoxy silicone oil, and the usage ratio of triethylamine and dimethylacetamide are 0.1 mol: 0.2 mol: 15 mL: 120 mL. After the reaction, the mixture is washed with water and dried to obtain a lubricating main agent.

[0035] (2) Preparation of lubricating additives

[0036] Ingredients: The raw materials are calculated by weight, 50 parts of the lubricating main agent, which is self-made in this embodiment; 35 parts of the calcium-based auxiliary agent, and commercially available 325-mesh light calcium carbonate is used in the implementation process; 15 parts of the dispersant, and PE-200A polyethylene wax and 85# microcrystalline wax are premixed in a mass ratio of 2:1 in the implementation process.

[0037] Kneading molding: Mix the lubricating main agent, calcium-based auxiliary agent and dispersant, add them into a kneading machine, knead at 120°C, and cut into pellets after cooling to make a lubricating auxiliary agent for ABS resin.

[0038] Example 3, preparation of lubricating agent for ABS resin, the specific implementation process is as follows:

[0039] (1) Preparation of lubricating agent

[0040] Step A1: Diethyl diallyl malonate, dialkylamine and anhydrous toluene are mixed, nitrogen is introduced for protection, the temperature is raised to 60°C, stirring is applied at 40 rpm, equal amounts of sodium hydride are divided into four portions, and added at intervals of 30 minutes. After complete addition, the reaction is continued at a constant temperature, and the total reaction time of the addition of sodium hydride is controlled to be 6.5 hours, wherein the dialkylamine is selected from di-n-octylamine, and the amount ratio of diethyl diallyl malonate, dialkylamine, sodium hydride and anhydrous toluene is 0.1 mol: 0.208 mol: 0.12 g: 90 mL. After the reaction is completed, toluene is removed by rotary evaporation, and the rotary evaporation substrate is washed with water and dried to obtain intermediate 1.

[0041] Step A2: Mix intermediate 1, mercaptoethanol, dimethylphenylphosphine and acetone, raise the temperature to 45°C, stir at 180 rpm and heat at 200 W / m 2 The reaction was carried out under ultraviolet irradiation for 3.2 hours, wherein the usage ratio of intermediate 1, mercaptoethanol, dimethylphenylphosphine and acetone was 0.1 mol: 0.2 mol: 25 mg: 120 mL. After the reaction, acetone was removed by rotary evaporation to obtain intermediate 2.

[0042] Step A3: Mix the intermediate 2, single-ended epoxy silicone oil, triethylamine and dimethylacetamide, introduce nitrogen protection, heat to 90°C, stir at 60 rpm, and react for 2 hours. The single-ended epoxy silicone oil is selected from X-22-173BX raw material, and has a room temperature viscosity of 30 mm 2 / s, the epoxy content of intermediate 2, single-ended epoxy silicone oil, and the usage ratio of triethylamine and dimethylacetamide are 0.1 mol: 0.2 mol: 18 mL: 150 mL. After the reaction, the mixture is washed with water and dried to obtain a lubricating main agent.

[0043] (2) Preparation of lubricating additives

[0044] Ingredients: The raw materials are calculated by weight, 50 parts of the lubricating main agent, which is prepared in this embodiment; 30 parts of the calcium-based auxiliary agent, and commercially available 325-mesh light calcium carbonate is used in the implementation process; 20 parts of the dispersant, and PE-200A polyethylene wax and 85# microcrystalline wax are premixed in a mass ratio of 2:1 in the implementation process.

[0045] Kneading molding: Mix the lubricating main agent, calcium-based auxiliary agent and dispersant, add them into a kneading machine, knead at 120°C, and cut into pellets after cooling to make a lubricating auxiliary agent for ABS resin.

[0046] Example 4, preparing a lubricating agent for ABS resin, the specific implementation process is as follows:

[0047] (1) Preparation of lubricating agent

[0048] Step A1: Diethyl diallyl malonate, dialkylamine and anhydrous toluene are mixed, nitrogen is introduced for protection, the temperature is raised to 65°C, stirring is applied at 60 rpm, equal amounts of sodium hydride are divided into four portions, and added at intervals of 30 minutes. After complete addition, the reaction is continued at a constant temperature, and the total reaction time of the addition of sodium hydride is controlled to be 6.5 hours, wherein the dialkylamine is selected from di-n-decylamine, and the amount ratio of diethyl diallyl malonate, dialkylamine, sodium hydride and anhydrous toluene is 0.1 mol: 0.208 mol: 0.16 g: 100 mL. After the reaction is completed, toluene is removed by rotary evaporation, and the rotary evaporation substrate is washed with water and dried to obtain intermediate 1.

[0049] Step A2: Mix intermediate 1, mercaptoethanol, dimethylphenylphosphine and acetone, raise the temperature to 50°C, stir at 150 rpm and heat at 200 W / m2 The reaction was carried out under ultraviolet irradiation for 3 h, wherein the usage ratio of intermediate 1, mercaptoethanol, dimethylphenylphosphine and acetone was 0.1 mol: 0.2 mol: 30 mg: 130 mL. After the reaction, acetone was removed by rotary evaporation to obtain intermediate 2.

[0050] Step A3: Mix the intermediate 2, single-ended epoxy silicone oil, triethylamine and dimethylacetamide, introduce nitrogen protection, heat to 90°C, stir at 90 rpm, and react for 2 hours. The single-ended epoxy silicone oil is selected from X-22-173BX raw material, and has a room temperature viscosity of 30 mm 2 / s, the epoxy content of intermediate 2, single-ended epoxy silicone oil, and the usage ratio of triethylamine and dimethylacetamide are 0.1 mol: 0.2 mol: 15 mL: 140 mL. After the reaction is completed, the mixture is washed with water and dried to obtain a lubricating main agent.

[0051] (2) Preparation of lubricating additives

[0052] Ingredients: The raw materials are calculated by weight, 50 parts of the lubricating main agent, which is self-made in this embodiment; 28 parts of the calcium-based auxiliary agent, and commercially available 325-mesh light calcium carbonate is used in the implementation process; 22 parts of the dispersant, and PE-200A polyethylene wax and 85# microcrystalline wax are premixed in a mass ratio of 2:1 in the implementation process.

[0053] Kneading molding: Mix the lubricating main agent, calcium-based auxiliary agent and dispersant, add them into a kneading machine, knead at 120-130°C, and pelletize after cooling to make a lubricating auxiliary agent for ABS resin.

[0054] Comparative Example

[0055] This comparative example refers to Example 4, except that the main lubricating agent is replaced with 40 parts of ethylene bisstearamide and 10 parts of PL-215 silicone powder, and the rest is exactly the same as in the example.

[0056] In order to test the lubricating effect of lubricating additives on ABS, D-1000 ABS resin was used as the matrix, 1.5 wt% of the lubricating agent obtained above was added, and 10 wt% of light calcium carbonate was added to simulate the use of filler reinforcement in actual applications. A high-speed mixer was used to premix for 10 minutes at 800 rpm as the compound material.

[0057] According to ASTM D1238-2010 standard, the melt flow rate of the batch material was tested at 200°C and 5kgf; the batch material was placed in a Haake torque rheometer to test its plasticization state;

[0058] The batch material was placed in an injection molding machine with an injection temperature of 220°C to make a specimen. Samples were taken from the specimen and tensile tested with reference to the GB / T1040.2-2022 standard at a tensile rate of 50 mm / min. The gloss of the injection molded specimen was tested with an incident light of 60° according to the GB / T8807-1988 standard.

[0059] The specific test results are shown in the following table:

[0060]

[0061] It can be seen from the test results in the above table that the ABS material compounded with the lubricating additive of the embodiment has a high melt flow rate and a small torque during plasticization, showing good internal lubricity, a high surface gloss after injection molding, and good external lubricity, and the strength of the injection molded product is significantly better than that of the comparative example.

[0062] In the description of the specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0063] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. A lubricating agent for ABS resin, characterized in that: The components include 50 parts of lubricating agent, 25-35 parts of calcium-based auxiliary agent and 15-25 parts of dispersant according to weight. The lubricating main agent is prepared by the following method: Step A1: Diethyl diallylmalonate, dialkylamine and anhydrous toluene are mixed, nitrogen is introduced for protection, the temperature is raised to 55-70° C., and sodium hydride is added in batches with stirring for 5-7 hours. After the reaction is completed, toluene is removed by rotary evaporation, and the rotary evaporation substrate is washed with water and dried to obtain intermediate 1, wherein the dialkylamine is one of di-n-octylamine and di-n-decylamine; Step A2: Mix intermediate 1, mercaptoethanol, dimethylphenylphosphine and acetone, raise the temperature to 40-50°C, stir and apply 150-300W / m 2 UV irradiation, reaction for 2.5-3.5h, after the reaction, acetone was removed by rotary evaporation to obtain intermediate 2; Step A3: Mix the intermediate 2, single-ended epoxy silicone oil, triethylamine and dimethylacetamide, introduce nitrogen protection, heat to 85-100°C, stir and react for 1.5-2.2h, wash with water and dry after the reaction to obtain a lubricating main agent; The calcium-based auxiliary agent is light calcium carbonate with a fineness of not less than 300 meshes.

2. A lubricating agent for ABS resin according to claim 1, characterized in that: The usage ratio of diethyl diallylmalonate, dialkylamine, sodium hydride and anhydrous toluene is 0.1 mol: 0.205-0.21 mol: 0.1-0.16 g: 80-120 mL.

3. A lubricating agent for ABS resin according to claim 2, characterized in that: The usage ratio of intermediate 1, mercaptoethanol, dimethylphenylphosphine and acetone is 0.1 mol: 0.2 mol: 20-30 mg: 100-150 mL.

4. A lubricating agent for ABS resin according to claim 3, characterized in that: The intermediate 2, the epoxy content of the single-ended epoxy silicone oil, and the usage ratio of triethylamine and dimethylacetamide are 0.1 mol: 0.2 mol: 15-20 mL: 120-160 mL.

5. A lubricating agent for ABS resin according to claim 4, characterized in that: The room temperature viscosity of single-ended epoxy silicone oil is not higher than 50mm 2 / s.

6. A lubricating agent for ABS resin according to claim 1, characterized in that: The dispersant is a premix of polyethylene wax and microcrystalline wax.

7. The method for preparing a lubricating agent for ABS resin according to any one of claims 1 to 6, characterized in that: The specific operation is: mix the lubricating main agent, calcium-based auxiliary agent and dispersant, knead them at a temperature of 120-130°C, and pelletize them after cooling to make a lubricating auxiliary agent for ABS resin.

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