High-gloss high-flowing abs resin and its preparation method

Abstract

The application relates to the technical field of high-molecular compounds, and particularly discloses a high-gloss and high-flow ABS resin and a preparation method thereof. The raw materials of the high-gloss and high-flow ABS resin include the following components in mass parts: toughening rubber 8-15 parts, styrene 45-70 parts, acrylonitrile 10-25 parts, solvent 10-25 parts, silicon oil 0.01-0.05 part, acrylate 0.5-5 parts, high-gloss additive 0.2-1.5 parts, initiator 0.01-0.1 part, chain transfer agent 0.1-0.5 part and antioxidant 0.02-0.25 part. The high-gloss and high-flow ABS resin and the preparation method thereof can produce high-gloss ABS while maintaining high flowability, and the melt index reaches more than 30 g / 10 min, and the processing performance is good.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high molecular compounds, and specifically discloses a high-gloss high-flow ABS resin and a preparation method thereof. BACKGROUND

[0002] ABS resin is a short name of acrylonitrile-butadiene-styrene terpolymer, and is a thermoplastic high polymer material with high strength, good toughness, excellent processing performance and high chemical stability, and is widely used in the fields of household appliances, automobiles, mechanical manufacturing, office supplies and the like. The high-gloss ABS resin is one of high-performance special material products, has high gloss and good processing flowability, and the products made of the high-gloss ABS resin also have good surface gloss, are widely used in the fields of high-grade household appliances, industrial electrical equipment, cosmetic shells, consumer goods, various toys, teaching aids and sports and health products, and are favored by consumers. The high-gloss ABS resin is one of the development hotspots of high-performance ABS resin special materials at present, and has a broad application prospect. The gloss of the high-gloss ABS resin is directly related to the rubber content, rubber particle size and matrix resin flowability, and the ABS resin with less rubber content, small rubber particle size and good matrix resin flowability has good gloss. However, the rubber content, rubber particle size and matrix resin flowability are closely related to the mechanical properties and processing performance of the ABS resin, and therefore, it is very important to balance the relationship among the gloss, processing flowability and mechanical properties.

[0003] The synthesis methods of the high-gloss ABS resin mainly include a blending extrusion modification method, an emulsion grafting-body SAN blending method and a continuous body polymerization method. The blending extrusion modification method mainly melts and blends ABS resin, small particle size rubber grafting powder, SAN resin, high-gloss additives, dispersion lubricants and PMMA high-gloss resin to improve the rubber content, rubber particle size and flow dispersion of the ABS matrix resin, and finally achieve the purpose of high gloss of the ABS resin.

[0004] The process of the emulsion grafting-body SAN blending method for producing the high-gloss ABS resin generally includes polybutadiene latex synthesis, body SAN resin production, ABS grafting powder production, blending granulation and post-treatment, and the rubber particles of the emulsion ABS resin are formed by grafting styrene and acrylonitrile after butadiene monomer emulsion polymerization, have less internal inclusion, small rubber particle size, and are usually 0.1-0.4 μm, and the product has high gloss.

[0005] ABS continuous bulk polymerization process usually uses multiple reactors in series for polymerization, the process generally includes cutting rubber, rubber solution preparation, rubber grafting, free SAN polymerization, phase inversion of the system to produce rubber particles, moderate crosslinking of rubber particles, ABS product devolatilization, and granulation. The mainstream ABS bulk process production technology includes Dow Chemical's four-reactor series plug flow polymerization process, Monsanto's two-reactor series process, Mitsui East Pressure Company's four-reactor series plug flow polymerization process, and Zhonghua International's five-reactor series process. Since the rubber particles of the continuous bulk ABS resin are produced by phase inversion of the grafted rubber phase and the free SAN phase system, the rubber particles are generally larger, usually 0.6-10 μm, so the gloss of the ABS resin produced by the bulk method is usually lower. Through the optimization and compounding of low viscosity non-crosslinked rubber, the process control of rubber content and particle size, the control of the molecular weight and distribution of the base resin, and the introduction of acrylate fourth monomers, the gloss of the bulk ABS resin is greatly improved, so the continuous bulk method has become a mainstream production process for producing high-gloss ABS resin.

[0006] Currently, the four-reactor series plug flow reactor technology has the following specific process: non-crosslinked toughening rubber is dissolved in monomers and a small amount of solvent by stirring to form a rubber solution, the rubber solution is heated to 85°C by a preheater after complete dissolution, and then enters the first reactor for rubber grafting reaction in a plug flow manner. The phase inversion process is completed when the volume of the free SAN phase exceeds that of the grafted rubber phase in the second reactor, and the SAN phase polymerization and grafted rubber phase crosslinking reaction are further completed in the third and fourth reactors. After removing the unreacted monomers, oligomers and solvents through a two-stage devolatilization system, the ABS resin production process is completed.

[0007] The high-gloss ABS resin produced by the existing continuous bulk process technology has the technical problem that the gloss cannot reach the generally higher than 90% of the high-gloss ABS resin produced by blending modification and emulsion method. The melt index of the high-gloss ABS resin produced by the bulk process technology is generally below 30 g / 10 min, and the processing fluidity needs to be further improved. SUMMARY

[0008] The technical solutions adopted by the present application are as follows:

[0009] In a first aspect, the present application provides a method for preparing a high-gloss high-flow ABS resin. The raw materials for the high-gloss high-flow ABS resin include the following components by mass:

[0010] Toughening rubber 8-15 parts

[0011] Styrene 45-70 parts

[0012] Acrylonitrile 10-25 parts

[0013] Solvent 10-25 parts

[0014] Silicone oil 0.01-0.05 parts

[0015] Acrylate 0.5-5 parts

[0016] High gloss aid 0.2-1.5 parts

[0017] Initiator 0.01-0.1 parts

[0018] Chain transfer agent 0.1-0.5 parts

[0019] Antioxidant 0.02-0.25 parts

[0020] The toughening rubber is a mixed rubber of non-crosslinked low-cis polybutadiene rubber and non-crosslinked styrene-butadiene rubber, and the mixing mass ratio is 1:2-2:1; the 5% styrene solution viscosity of the non-crosslinked low-cis polybutadiene rubber is ≤30 cp, and the vinyl content is 8%-15%; the 5% styrene solution viscosity of the non-crosslinked styrene-butadiene rubber is ≤30 cp, and the vinyl content is 9%-15%;

[0021] The solvent is any one of ethylbenzene, toluene, xylene;

[0022] The silicone oil is a linear polysiloxane product in liquid state at room temperature, and the viscosity is required to be 50-2000 cs;

[0023] The acrylate is any one of methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, and ethyl methacrylate;

[0024] The high gloss aid is any one of ethylene bis-stearamide EBS, pentaerythritol stearate PETS, polyethylene wax, liquid paraffin, or a commercially available composite high gloss aid;

[0025] The initiator is 1,1 di-t-butyl peroxide cyclohexane;

[0026] The chain transfer agent is one of n-dodecyl mercaptan or tertiary dodecyl mercaptan;

[0027] The antioxidant is a hindered phenolic antioxidant;

[0028] The preparation is performed using a four-kettle series connection plug flow reactor process, and the specific process is as follows:

[0029] S1: The toughening rubber is cut into pieces, and styrene, acrylonitrile, solvent, and acrylate are dissolved into a uniform, stable, and visually glue-free original glue solution in a sol gel kettle according to the mass ratio, and stirring is given at the same time, and cooling water is supplied to the sol gel kettle jacket to ensure that the temperature of the original glue solution is ≤35℃;

[0030] S2: the dissolved raw glue solution, initiator and chain transfer agent are sent into the first, second, third and fourth flat flow reactors in sequence by conveying equipment for continuous bulk polymerization, wherein the raw glue solution is introduced from a glue tank, the initiator and chain transfer agent are added from the first flat flow reactor feed pipeline respectively; the antioxidant, silicone oil and high gloss aid are introduced from the third reactor inlet respectively;

[0031] S3: the polymerized material is sent into a granulation unit through a two-stage devolatilization system to remove unreacted monomers and solvents, and then high gloss and high flow ABS resin is obtained after cooling and pelletizing;

[0032] The first flat flow reactor is controlled at a temperature of 100-115℃ and a stirring speed of 15-25rpm; the second flat flow reactor is controlled at a temperature of 115-125℃ and a stirring speed of 25-40rpm; the third flat flow reactor is controlled at a temperature of 125-140℃ and a stirring speed of 5-15rpm; the fourth flat flow reactor is controlled at a temperature of 140-175℃ and a stirring speed of 0.5-5rpm; the temperature of the subsequent two-stage devolatilization device is controlled at 220-245℃, and the vacuum degree is required to be ≤-0.095Mpa; the extrusion die temperature of the granulation unit is controlled at 210-230℃, and the extrusion speed is matched with the pelletizing speed.

[0033] Preferably, the flat flow reactors in the four-cascade flat flow reactor process are all provided with upper, middle and lower three zones.

[0034] Preferably, the styrene is polymerization-grade styrene with a purity of ≥99.8%.

[0035] Preferably, the acrylonitrile is polymerization-grade acrylonitrile with a purity of ≥99.5%.

[0036] Preferably, in step S1, the toughening rubber is cut into pieces with a size of ≤1.5cm×1.5cm×1.5cm.

[0037] Preferably, in step S2, the initiator and chain transfer agent are respectively configured (prepared) into uniform solutions with a mass concentration of 5%-25%.

[0038] Preferably, in step S2, the antioxidant, silicone oil and high gloss aid are respectively prepared into uniform solutions with a mass concentration of 5%-30%.

[0039] In the second aspect, the application provides a high gloss and high flow ABS resin prepared by the method of the first aspect.

[0040] The application has the following beneficial effects:

[0041] The high-gloss high-flow ABS resin and the preparation method thereof can produce high-gloss ABS while maintaining high flowability, and the melt index is greater than or equal to 30 g / 10 min, and good processing performance is achieved. DETAILED DESCRIPTION

[0042] In order to make the purpose, technical scheme and advantages of the present application more clear and explicit, the present application is further described in detail in combination with the following examples. It should be noted that the present application is not limited to the following examples.

[0043] Example 1

[0044] The high-gloss high-flow ABS resin prepared by the continuous bulk method in the example is composed of the following raw materials in mass ratio:

[0045] Toughening rubber: 8 parts by mass

[0046] Styrene: 70 parts by mass

[0047] Acrylonitrile: 10 parts by mass

[0048] Solvent: 11.16 parts by mass

[0049] Silicone oil: 0.01 parts by mass

[0050] Acrylate: 0.5 parts by mass

[0051] High-gloss aid: 0.2 parts by mass

[0052] Initiator: 0.01 parts by mass

[0053] Chain transfer agent: 0.1 parts by mass

[0054] Antioxidant: 0.02 parts by mass

[0055] The toughening rubber is a mixed rubber of non-crosslinked low-cis polybutadiene rubber and non-crosslinked styrene-butadiene rubber, and the mass ratio of the mixed rubber is 1:2, wherein the 5% styrene solution viscosity of the non-crosslinked low-cis polybutadiene rubber is 30 cp, and the vinyl content is 8%; the 5% styrene solution viscosity of the non-crosslinked styrene-butadiene rubber is 30 cp, and the vinyl content is 9%;

[0056] The styrene is polymerization-grade styrene with purity greater than or equal to 99.8%;

[0057] The acrylonitrile is polymerization-grade acrylonitrile with purity greater than or equal to 99.5%;

[0058] The solvent is ethylbenzene with purity greater than or equal to 99.8%;

[0059] The silicone oil is polymethylsiloxane with viscosity of 50 cs;

[0060] The acrylate is methyl acrylate, purity ≥ 99.9%;

[0061] The high gloss aid is ethylene bis stearamide EBS;

[0062] The initiator is 1,1 di-t-butyl peroxide cyclohexane;

[0063] The chain transfer agent is n-dodecyl mercaptan;

[0064] The antioxidant is hindered phenolic antioxidant 1076;

[0065] The device used is a four-kettle series push-flow reactor and its supporting equipment patented by the United States Dow Chemical Company; the specific reaction process is as follows:

[0066] The toughening rubber is cut into pieces with a size of ≤1.5 cm×1.5 cm×1.5 cm, and is dissolved into a uniform and stable raw glue solution without visible glue blocks in a sol gel kettle according to the formula proportion of styrene, acrylonitrile, solvent and acrylate. Slow stirring is given while dissolving, and cooling water is introduced into the sol gel kettle jacket to ensure that the temperature of the raw glue solution is ≤35℃;

[0067] The dissolved raw glue solution, initiator and chain transfer agent are sequentially sent into the first, second, third and fourth push-flow reactors by conveying equipment for continuous bulk polymerization, wherein the raw glue solution is introduced from a glue solution tank, the initiator and chain transfer agent are respectively added from the first push-flow reactor feed pipeline from an additive tank, and the initiator and chain transfer agent are respectively prepared into a 5% uniform solution with solvent ethylbenzene;

[0068] The antioxidant, silicone oil and high gloss aid are respectively prepared into a 5% uniform solution with solvent ethylbenzene and introduced from the inlet of the third reactor;

[0069] The polymerized material is removed from the unreacted monomer and solvent by a two-stage devolatilization system, and then is sent into a granulation unit by conveying equipment, and after cooling and granulation, the bulk high-gloss and high-flow ABS resin is obtained.

[0070] The temperature of the first push-flow reactor is controlled at 100℃, 105℃ and 110℃ in the upper, middle and lower three zones, and the stirring speed is controlled at 15 rpm; the temperature of the second push-flow reactor is controlled at 115℃, 117℃ and 119℃, and the stirring speed is controlled at 25 rpm; the temperature of the third push-flow reactor is controlled at 125℃, 130℃ and 135℃, and the stirring speed is controlled at 5 rpm; the temperature of the fourth push-flow reactor is controlled at 140℃, 145℃ and 150℃, and the stirring speed is controlled at 0.5 rpm; the temperature of the subsequent two-stage devolatilization device is controlled at 220℃ and 225℃, the vacuum degree is controlled at -0.095 Mpa, the extrusion die temperature is controlled at 210℃, and the extrusion speed and the cutting speed are matched.

[0071] Example 2

[0072] The high-gloss, high-flow ABS resin produced by continuous bulk polymerization in this example was prepared from the following raw materials in the indicated amounts by mass:

[0073] Toughening rubber: 15 parts by mass

[0074] Styrene: 45 parts by mass

[0075] Acrylonitrile: 20 parts by mass

[0076] Solvent: 12.6 parts by mass

[0077] Silicone oil: 0.05 parts by mass

[0078] Acrylate ester: 5 parts by mass

[0079] High-gloss aid: 1.5 parts by mass

[0080] Initiator: 0.1 parts by mass

[0081] Chain transfer agent: 0.5 parts by mass

[0082] Antioxidant: 0.25 parts by mass

[0083] The toughening rubber was a mixed rubber of non-crosslinked low-cis polybutadiene rubber and non-crosslinked styrene-butadiene rubber in a mass ratio of 2:1, wherein the non-crosslinked low-cis polybutadiene rubber had a 5% styrene solution viscosity of 25 cp and a vinyl content of 15%; the non-crosslinked styrene-butadiene rubber had a 5% styrene solution viscosity of 20 cp and a vinyl content of 15%;

[0084] The styrene was polymerization-grade styrene having a purity of ≥ 99.8%;

[0085] The acrylonitrile was polymerization-grade acrylonitrile having a purity of ≥ 99.5%;

[0086] The solvent was xylene having a purity of ≥ 99.8%;

[0087] The silicone oil was a polyether polysiloxane product having a viscosity of 2000 cs;

[0088] The acrylate ester was butyl acrylate having a purity of ≥ 99.9%;

[0089] The high-gloss aid was polyethylene wax;

[0090] The initiator was 1,1 di-t-butyl peroxide cyclohexane;

[0091] The chain transfer agent was tertiary dodecyl mercaptan;

[0092] The antioxidant was hindered phenolic antioxidant 1010;

[0093] The equipment used is a four-tandem plug flow reactor and its associated equipment, licensed from Dow Chemical Company, USA; the specific reaction process is as follows:

[0094] Toughened rubber is cut into pieces ≤1.5cm×1.5cm×1.5cm and dissolved in a sol-gel kettle with styrene, acrylonitrile, solvent and acrylate in the formula ratio to form a homogeneous, stable raw rubber solution without visible rubber lumps. Slow stirring is given while dissolving and cooling water is circulated through the jacket of the sol-gel kettle to ensure that the temperature of the raw rubber solution is ≤35℃.

[0095] The dissolved raw rubber solution, initiator, and chain transfer agent are sequentially fed into the first, second, third, and fourth plug flow reactors by conveying equipment for continuous bulk polymerization. The raw rubber solution is introduced from the rubber solution tank, and the initiator and chain transfer agent are added from the feed line of the first plug flow reactor by the auxiliary agent tank. The initiator and chain transfer agent are prepared into a 25% homogeneous solution by solvent xylene.

[0096] Antioxidant, silicone oil, and high-gloss additive are each prepared into a 30% homogeneous solution using xylene as solvent, and then introduced into the inlet of the third reactor.

[0097] After polymerization, the material is passed through a two-stage devolatilization system to remove unreacted monomers and solvents, and then conveyed to the granulation unit. After cooling and pelletizing, the bulk high-gloss, high-flow ABS resin is obtained.

[0098] The temperatures of the first plug flow reactor (upper, middle, and lower zones) are controlled at 105℃, 110℃, and 115℃, with a stirring speed of 25 rpm; the temperatures of the second plug flow reactor are controlled at 117℃, 121℃, and 125℃, with a stirring speed of 40 rpm; the temperatures of the third plug flow reactor are controlled at 130℃, 135℃, and 140℃, with a stirring speed of 15 rpm; the temperatures of the fourth plug flow reactor are controlled at 145℃, 160℃, and 175℃, with a stirring speed of 5 rpm; the temperatures of the subsequent two-stage devolatilization units are controlled at 240℃ and 245℃, the vacuum degree is controlled at -0.099 MPa, the extrusion die temperature is controlled at 230℃, and the extrusion speed is matched with the pelletizing speed.

[0099] Test Results

[0100] The performance test results of the examples and comparative examples are shown in Table 1 below, wherein comparative example 1 is a high-gloss ABS resin synthesized by a commercial blending modification method, comparative example 2 is a high-gloss ABS resin synthesized by a commercial emulsion method, and comparative example 3 is a high-gloss ABS resin synthesized by a commercial continuous bulk method. The high-gloss ABS resin synthesized by the commercial blending modification method of comparative example 1 has a rubber content of 17.02%, an acrylonitrile content of 19.20%, a styrene content of 53.87%, a high-gloss blending component of polymethyl methacrylate (PMMA) with a content of 9.91%, a rubber particle size of 0.592 μm, a number average molecular weight of 48944, and a molecular weight distribution of 3.05; the high-gloss ABS resin synthesized by the commercial emulsion method of comparative example 2 has a rubber content of 14.20%, an acrylonitrile content of 21.57%, a styrene content of 64.23%, a rubber particle size of 0.355 μm, a number average molecular weight of 37424, and a molecular weight distribution of 3.43; and the high-gloss ABS resin synthesized by the commercial continuous bulk method of comparative example 3 has a rubber content of 13.31%, an acrylonitrile content of 18.85%, a styrene content of 67.84%, a rubber particle size of 0.792 μm, a number average molecular weight of 60397, and a molecular weight distribution of 2.90.

[0101] Table 1 test results

[0102]

[0103] The above only describes the preferred embodiments of the present application, and it should be noted that those of ordinary skill in the art can make several improvements and modifications without departing from the technical principles of the present application, and these improvements and modifications should also be considered within the protection scope of the present application.

Claims

1. A method for preparing a high-gloss, high-flow ABS resin, characterized in that, The raw materials for the high-gloss, high-flow ABS resin include the following components in parts by weight: 8-15 parts of toughened rubber 45-70 parts of styrene 10-25 parts acrylonitrile Solvent 10-25 parts Silicone oil 0.01~0.05 parts 0.5 to 5 parts acrylate 0.2-1.5 parts of high-gloss additive Initiator 0.01~0.1 parts Chain transfer agent 0.1~0.5 parts Antioxidant 0.02~0.25 parts; The toughening rubber is a mixture of non-crosslinked low-cis polybutadiene rubber and non-crosslinked styrene-butadiene rubber, with a mixing mass ratio of 1:2 to 2:1; the viscosity of the 5% styrene solution of the non-crosslinked low-cis polybutadiene rubber is ≤30cp, and the vinyl content is 8% to 15%; the viscosity of the 5% styrene solution of the non-crosslinked styrene-butadiene rubber is ≤30cp, and the vinyl content is 9% to 15%. The solvent is any one of ethylbenzene, toluene, and xylene; The silicone oil is a linear polysiloxane product that is liquid at room temperature, with a viscosity requirement of 50~2000cs; The acrylate is any one of methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, and ethyl methacrylate; The high-gloss additive is any one of ethylene bis-stearamide (EBS), pentaerythritol stearate (PETS), polyethylene wax, liquid paraffin, or commercially available composite high-gloss additives. The initiator is 1,1-di-tert-butylcyclohexane peroxide; The chain transfer agent is one of n-dodecyl mercaptan or tert-dodecyl mercaptan; The antioxidant is a hindered phenolic antioxidant; The preparation was carried out using a four-reactor series plug flow reactor process, as described below: S1: Cut the toughened rubber into small pieces and dissolve it in a sol-gel kettle with styrene, acrylonitrile, solvent and acrylate in the mass ratio described above to form a homogeneous, stable raw rubber solution without visible rubber lumps. Stirring is carried out while dissolving, and cooling water is circulated through the jacket of the sol-gel kettle to ensure that the temperature of the raw rubber solution is ≤35℃. S2: The dissolved raw resin solution, initiator, and chain transfer agent are sequentially fed into the first, second, third, and fourth plug flow reactors by a conveying device for continuous bulk polymerization. The raw resin solution is introduced from the resin solution tank, and the initiator and chain transfer agent are added from the feed line of the first plug flow reactor. The antioxidant, silicone oil, and high-gloss additive are introduced from the inlet of the third reactor. S3: The polymerized material is passed through a two-stage devolatilization system to remove unreacted monomers and solvents, and then sent to the granulation unit by a conveying device. After cooling and pelletizing, the bulk high-gloss, high-flow ABS resin is obtained. The temperature of the first plug flow reactor is controlled at 100-115℃, and the stirring speed is controlled at 15-25 rpm; the temperature of the second plug flow reactor is controlled at 115-125℃, and the stirring speed is controlled at 25-40 rpm; the temperature of the third plug flow reactor is controlled at 125-140℃, and the stirring speed is controlled at 5-15 rpm; the temperature of the fourth plug flow reactor is controlled at 140-175℃, and the stirring speed is controlled at 0.5-5 rpm; the temperature of the subsequent two-stage devolatilization unit is controlled at 220~245℃, and the vacuum degree is required to be ≤-0.095Mpa; the temperature of the extrusion die of the granulation unit is controlled at 210~230℃, and the extrusion speed is matched with the pelletizing speed.

2. The method for preparing high-gloss, high-flow ABS resin according to claim 1, characterized in that, The four-reactor series plug flow reactor process is equipped with three zones: upper, middle, and lower.

3. The method for preparing high-gloss, high-flow ABS resin according to claim 1, characterized in that, The styrene is polymer-grade styrene with a purity of ≥99.8%.

4. The method for preparing high-gloss, high-flow ABS resin according to claim 1, characterized in that, The acrylonitrile is polymer-grade acrylonitrile with a purity of ≥99.5%.

5. The method for preparing high-gloss, high-flow ABS resin according to claim 1, characterized in that, In step S1, the toughened rubber is cut into pieces ≤1.5cm×1.5cm×1.5cm.

6. The method for preparing high-gloss, high-flow ABS resin according to claim 1, characterized in that, In step S2, the initiator and chain transfer agent are respectively prepared into homogeneous solutions with a mass concentration of 5% to 25%.

7. The method for preparing high-gloss, high-flow ABS resin according to claim 1, characterized in that, In step S2, the antioxidant, silicone oil, and high-gloss additive are respectively prepared into a homogeneous solution with a mass concentration of 5% to 30%.

8. A high-gloss, high-flow ABS resin, characterized in that, Prepared using the method described in any one of claims 1 to 7.

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