A sheet extrusion grade ABS resin and preparation method thereof

Abstract

The present invention belongs to the technical field of polymer material preparation, and discloses a sheet extrusion grade ABS resin and a preparation method thereof. The raw materials for preparing the ABS resin include the following components by mass: 10 to 12.5 parts of rubber, 14 to 17 parts of acrylonitrile, 45 to 60 parts of styrene, and 12 to 14 parts of ethylbenzene; the Mooney viscosity of the rubber is 35 to 65 ML (1+4) 100°C, the viscosity of the styrene solution is 800 to 1500 CPS, and the viscosity of the 25% toluene solution is 400 to 1000 mPa·S; the rubber in the rubber glue at least includes low cis-butyl rubber, the vinyl structure content of the rubber is ≥8%, the weight average molecular weight is greater than 200,000, the number average molecular weight is greater than 100,000, and the molecular weight distribution is 1.2 to 3.0. The impact resistance of the ABS resin is greater than 20KJ / m 2 , melt mass flow rate (MFR) is 6-12g / 10min, Vicat softening point temperature is ≥98.5℃, and tensile yield strength is ≥38MPa.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer material preparation, and discloses a sheet extrusion-grade ABS resin and a preparation method thereof. Background Art

[0002] ABS resin is a two-phase three-component copolymer mixture composed of acrylonitrile, butadiene and styrene. It has good mechanical properties and molding processing properties and is one of the five major engineering resins. ABS resin is widely used in the fields of automobiles, electronic appliances and building materials. It is one of the important manufacturing raw materials for automobile dashboards, body panels, interior trim panels, refrigerators, televisions, washing machines, pipes, sanitary ware and other products.

[0003] As ABS resin products develop towards functionalization, refinement and differentiation, various special materials have been developed to gradually replace the original general materials to meet the needs of different levels and users. Sheet extrusion grade ABS resin is a special ABS resin material with excellent performance, large usage and high technical content, and has high added value. According to market research, sheet extrusion grade ABS resin is mainly used in refrigerators, air conditioners and other home appliances as well as automotive interiors, and has broad market prospects and application value.

[0004] Therefore, it is necessary to develop a sheet extrusion grade ABS resin and a preparation method thereof, so that it has the characteristics of high impact, high heat resistance, excellent processing performance, etc. Summary of the invention

[0005] The idea of ​​the present invention is to provide a sheet extrusion grade ABS resin and a preparation method thereof by selecting suitable preparation raw materials, under the coordinated control of factors such as feed amount, polymerization temperature, initiator, chain transfer agent, stirring speed, etc., after devolatilization, extrusion and granulation.

[0006] In a first aspect, the present invention provides a sheet extrusion grade ABS resin, wherein the raw materials for preparing the resin include the following components by weight: 10 to 12.5 parts of rubber, 14 to 17 parts of acrylonitrile, 45 to 60 parts of styrene, and 12 to 14 parts of ethylbenzene; the Mooney viscosity of the rubber is 35 to 65 ML (1+4) 100°C, the viscosity of the styrene solution is 800 to 1500 CPS, and the viscosity of the 25% toluene solution is 400 to 1000 mPa·S; the rubber includes at least low cis-butyl rubber, the vinyl structure content of the rubber is ≥8%, the weight average molecular weight is greater than 200,000, the number average molecular weight is greater than 100,000, and the molecular weight distribution is 1.2 to 3.0.

[0007] Preferably, the rubber further comprises butadiene rubber and styrene-butadiene rubber other than low-cis butadiene rubber.

[0008] Preferably, the Mooney viscosity of the rubber is 40-55ML(1+4)100°C, the styrene solution viscosity is 1000-1200CPS, the toluene solution viscosity is 600-800mPa·S, the vinyl structure content is ≥10.5%, the weight average molecular weight is greater than 240,000, the number average molecular weight is greater than 120,000, and the molecular weight distribution is 1.5-3.0.

[0009] In a second aspect, the present invention discloses a method for preparing the sheet extrusion grade ABS resin according to the first aspect, which specifically comprises the following steps:

[0010] S1: Add styrene, rubber, ethylbenzene, and acrylonitrile into a liquid preparation tank according to the mass parts of the raw materials prepared as described in the first aspect, dissolve them in the liquid preparation tank until they are uniform, obtain ABS raw rubber solution, and transport it to a feed storage tank by a rubber pump;

[0011] S2: The glue in the glue storage tank is transported to the first reactor of four plug flow tubular reactors connected in series through a feed pump, and an initiator is added to the first reactor to initiate a polymerization reaction, and an auxiliary agent is added to adjust the polymerization reaction to obtain a first polymer;

[0012] S3: the first polymer continues to undergo polymerization reaction through the second, third and fourth reactors in sequence, and auxiliary agents are added to the second, third and fourth reactors respectively to adjust the polymerization reaction, thereby obtaining an ABS melt;

[0013] S4: The ABS melt is input into an extruder, and the extruder is provided with a first vacuum pump and a second vacuum pump. The ABS melt is devolatilized, extruded, blown dry, and pelletized to obtain ABS particles;

[0014] Each reactor described in steps S2 and S3 is divided into three temperature zones: upper, middle and lower. The four reactors have a total of 12 temperature zones. The temperature of each temperature zone can be controlled individually, and the temperature is 95-180°C. A stirring paddle is provided in the reactor, and the rotation speed is 5-250rpm.

[0015] Preferably, the initiator includes 1,1-bis(tert-butylperoxy)cyclohexane, and the concentration in the reaction system is 50 to 500 ppm.

[0016] Furthermore, the concentration of the 1,1-bis(tert-butylperoxy)cyclohexane in the reaction system is 50 to 300 ppm.

[0017] Preferably, the auxiliary agent includes a chain transfer agent, and the chain transfer agent includes at least one of mercaptoethanol, dodecyl mercaptan, α-methylstyrene linear dimer, 2,4-diphenyl-4-methyl-1-pentene, and molecular weight regulator AMSD, and the concentration in the reaction system is 5 to 1000 ppm; the solvent of the chain transfer agent is ethylbenzene.

[0018] Furthermore, the auxiliary agent also includes ethylbenzene solution.

[0019] Further, the initiator is a 1.1% 1,1-bis(tert-butylperoxy)cyclohexane ethylbenzene solution;

[0020] The auxiliary agents added to the first, second, third and fourth reactors are: 1.07% n-dodecyl mercaptan ethylbenzene solution, 0.37% n-dodecyl mercaptan ethylbenzene solution, 1.68% n-dodecyl mercaptan and 0.8% antioxidant ethylbenzene solution, and pure ethylbenzene solution.

[0021] Preferably, the upper temperature zone of each reactor is connected to an auxiliary agent feed box, and the upper temperature zone of the first reactor is also connected to an initiator feed box; the initiator addition point and auxiliary agent addition point are respectively in the upper temperature zone of each reactor.

[0022] Beneficial effects achieved by the present invention:

[0023] A sheet extrusion grade ABS resin was prepared, and the impact resistance of the ABS resin was greater than 20KJ / m 2 , melt mass flow rate (MFR) is 6-12g / 10min, Vicat softening point temperature is ≥98.5℃, and tensile yield strength is ≥38MPa. DETAILED DESCRIPTION

[0024] In order to make the purpose, technical solutions and advantages of the present invention more clear, the present invention is further described in detail in conjunction with the following examples.

[0025] It should be noted that the present invention is not limited to the following examples. The methods are conventional methods unless otherwise specified. The raw materials can be obtained from public commercial channels unless otherwise specified.

[0026] Unless defined otherwise, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

[0027] Example

[0028] In order to better illustrate the product of the present invention and its production method, specific embodiments 1 to 3 are described below.

[0029] 1) Rubber uses low-cis-butadiene BR-1 rubber (LANXESS 565T), low-cis-butadiene BR-2 rubber (Denasol 97B), SSBR rubber (Styrene-butadiene rubber Denasol S1322);

[0030] 2) The initiator is 1,1-bis(tert-butylperoxy)cyclohexane;

[0031] 3) The chain transfer agent is n-dodecyl mercaptan;

[0032] 4) Prepare initiators and additives of corresponding concentrations:

[0033] Initiator: 1.1% initiator ethylbenzene solution;

[0034] Auxiliary agent 1: 1.07% chain transfer agent ethylbenzene solution;

[0035] Auxiliary agent 2: 0.37% chain transfer agent ethylbenzene solution;

[0036] Auxiliary agent 3: 1.68% chain transfer agent, 0.8% antioxidant 1010 ethylbenzene solution;

[0037] Additive 4: pure ethylbenzene.

[0038] Embodiment 1:

[0039] A) Glue ratio

[0040] Table 1 Example 1 Glue ratio

[0041]

[0042] B) Feed rate

[0043] Table 2 Feed rates of Example 1

[0044]

[0045] C) Temperature and stirring control of each temperature zone of the reactor

[0046] Table 3 Example 1 Temperature and stirring control

[0047]

[0048] Embodiment 2:

[0049] A) Glue ratio

[0050] Table 4 Example 2 Glue Proportion

[0051]

[0052] B) Feed rate

[0053] Table 5 Feed rates of Example 2

[0054]

[0055] C) Temperature and stirring control of each temperature zone of the reactor

[0056] Table 6 Example 2 Temperature and stirring control

[0057]

[0058]

[0059] Embodiment 3:

[0060] A) Glue ratio

[0061] Table 7 Example 3 Glue Proportions

[0062]

[0063] B) Feed rate

[0064] Table 8 Feed rates of Example 3

[0065]

[0066] C) Temperature and stirring control of each temperature zone of the reactor

[0067] Table 9 Example 3 Temperature and stirring control

[0068]

[0069] Effects of the embodiments

[0070] Table 10 Summary of performance tests of Examples 1 to 3

[0071]

Claims

1. A sheet extrusion grade ABS resin, characterized in that: The raw materials include the following components by weight: 10-12.5 parts of rubber, 14-17 parts of acrylonitrile, 45-60 parts of styrene, and 12-14 parts of ethylbenzene; the rubber is low-cis-butyl rubber LANXESS 565T or low-cis-butyl rubber Dynasol 97B; The preparation method comprises the following steps: S1: Add styrene, rubber, ethylbenzene and acrylonitrile into a liquid preparation tank according to the mass parts of the above-mentioned raw materials, dissolve them in the liquid preparation tank until they are uniform, obtain ABS raw rubber liquid, and transport it to a feed storage tank by a rubber liquid pump; S2: The glue in the glue storage tank is transported to the first reactor of four plug flow tubular reactors connected in series through a feed pump, and an initiator is added to the first reactor to initiate a polymerization reaction, and an auxiliary agent is added to adjust the polymerization reaction to obtain a first polymer; S3: the first polymer continues to undergo polymerization reaction through the second, third and fourth reactors in sequence, and auxiliary agents are added to the second, third and fourth reactors respectively to adjust the polymerization reaction, thereby obtaining an ABS melt; S4: The ABS melt is input into an extruder, and is subjected to devolatilization, extrusion, drying, and pelletization to obtain ABS particles; Each reactor described in steps S2 and S3 is divided into three temperature zones: upper, middle and lower. The four reactors have a total of 12 temperature zones. The temperature of each temperature zone can be controlled individually. A stirring paddle is provided in the reactor. The temperature zones and stirring speeds of the reactors are as follows: The upper, middle and lower temperature zones of the first reactor are 106~112℃, 110~117℃, 114~122℃, respectively, and the stirring speed is 200~250rpm; the upper, middle and lower temperature zones of the second reactor are 123~127℃, 128~134℃, 137~142℃, respectively, and the stirring speed is 200~250 rpm; the upper, middle and lower temperature zones of the third reactor are 143~147℃, 150~154℃, 158~162℃, respectively, and the stirring speed is 80rpm; the upper, middle and lower temperature zones of the fourth reactor are 163~170℃, 160~167℃, 160~167℃, respectively, and the stirring speed is 30rpm.

2. The ABS resin according to claim 1, characterized in that The rubber also includes styrene-butadiene rubber.

3. The ABS resin according to claim 1, characterized in that The initiator includes 1,1-bis(tert-butylperoxy)cyclohexane, and the concentration in the reaction system is 50-500 ppm.

4. The ABS resin according to claim 3, characterized in that The concentration of the 1,1-bis(tert-butylperoxy)cyclohexane in the reaction system is 50-300 ppm.

5. The ABS resin according to claim 4, characterized in that The auxiliary agent includes a chain transfer agent; the chain transfer agent includes at least one of mercaptoethanol, dodecyl mercaptan, α-methylstyrene linear dimer, 2,4-diphenyl-4-methyl-1-pentene, and molecular weight regulator AMSD, and the concentration of the chain transfer agent in the reaction system is 5-1000 ppm; the solvent of the chain transfer agent is ethylbenzene.

6. The ABS resin according to claim 5, characterized in that The auxiliary agent also includes ethylbenzene solution.

7. The preparation method according to claim 1, characterized in that: The upper temperature zone of each reactor is connected to an auxiliary agent feed box, and the upper temperature zone of the first reactor is also connected to an initiator feed box; the initiator addition point and the auxiliary agent addition point are respectively located in the upper temperature zone of each reactor.

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