A high-impact and high-vibration-resistant abs resin and a preparation method thereof

Abstract

This invention proposes a bulk polymer-modified high-vibration-resistance and high-impact ABS resin and its preparation method. The method involves mixing and dissolving toughening rubber, solvent, monomers acrylonitrile, acrylate monomers, and styrene monomer to form a raw rubber solution. The raw rubber solution, vibration-damping reinforcing agent, initiator, and chain transfer agent are then fed into four plug flow reactors connected in series for continuous bulk polymerization. The polymerized material is then extruded for devolatilization and granulation to obtain the high-vibration-resistance and high-impact ABS resin. This invention enhances molecular chain flexibility and compatibility by adding monomeric acrylate elastomers and vibration-damping reinforcing agents during continuous bulk polymerization without adding any mechanical performance additives. Simultaneously, it adjusts the monomer composition, controls the polymerization temperature and stirring rate, and adjusts the rubber particle size and the degree of crosslinking of the product. This ensures the mechanical properties of the product while improving the damping performance of the resin and thus enhancing the vibration resistance of the ABS resin.

Description

Technical Field

[0001] This invention belongs to the field of polymer material preparation technology, specifically relating to a bulk high vibration and high impact ABS resin and its preparation method. Background Technology

[0002] Vibration-resistant ABS resin is a special resin developed based on general-purpose ABS resin. Through production or modification optimization, ABS resins with excellent damping and impact resistance are prepared. This material can effectively absorb and dissipate mechanical vibration energy, reduce resonance amplitude, and can be widely used in industrial scenarios requiring vibration reduction and noise reduction, such as automotive parts, electronic device housings, and building materials.

[0003] Currently, the main method for preparing vibration-resistant ABS resin is blending modification, which improves its vibration resistance by adding modifiers. Common modifiers include elastomers (such as TPU and SBS), nanofillers (such as nanoclay and carbon nanotubes), and toughening agents (such as MBS and EVA). In addition, designing a core-shell structure for ABS resin using an emulsion method to prepare vibration-resistant ABS resin is also a common method. Currently, there is a lack of technology for preparing vibration-resistant ABS resin using a bulk method. Existing methods for improving the vibration resistance of ABS resin mainly involve blending with other fillers, such as Chinese patent application CN10109851981A, which improves the micro-vibration elastic energy absorption capacity of modified ABS materials by adding hollow microspheres, SBS resin, sepiolite, polyamide resin, and oily tackifiers, thereby improving the shock resistance of the material after it is used to make battery casings. However, the addition of additives inevitably leads to a decrease in the mechanical properties of the resin. Summary of the Invention

[0004] (a) Technical problems to be solved This invention proposes a bulk high vibration and impact ABS resin and its preparation method to solve the technical problem of how to prepare ABS resin with excellent vibration resistance and impact resistance by bulk method without adding any mechanical performance additives.

[0005] (II) Technical Solution To address the aforementioned technical problems, this invention proposes a method for preparing bulk high-vibration-resistance and high-impact ABS resin. This method involves mixing and dissolving toughening rubber, solvent, acrylonitrile monomer, acrylate elastomer monomer, and styrene monomer to form a raw rubber solution. The raw rubber solution, vibration-enhancing agent, initiator, and chain transfer agent are then fed into four plug flow reactors connected in series for continuous bulk polymerization. The polymerized material is then fed into an extruder for devolatilization and granulation to obtain the high-vibration-resistance and high-impact ABS resin.

[0006] Further, based on mass fractions, 8%~13% toughening rubber, 13%~25% solvent, 12%~23% monomer acrylonitrile, 3%~12% monomer acrylate elastomer, and 45%~60% monomer styrene are mixed and dissolved at 25~40°C to form a raw rubber solution; the raw rubber solution, 1%~3% vibration-damping agent, 0.02%~0.06% initiator, and 0.2%~0.6% chain transfer agent are transported to four plug flow reactors connected in series for continuous bulk polymerization reaction.

[0007] Furthermore, the toughening rubber is butadiene rubber.

[0008] Furthermore, the solvent is toluene, ethylbenzene, xylene, or a mixture thereof.

[0009] Furthermore, the initiator is 1,1-di-tert-butylperoxycyclohexane; the chain transfer agent is n-dodecyl mercaptan.

[0010] Furthermore, the vibration-enhancing agent is one of N-phenylmaleimide, N,N-methylenediphenylbismaleimide, and N-methylphthalimide.

[0011] Furthermore, the monomeric acrylate elastomer is one of methyl acrylate, ethyl acrylate, and methyl methacrylate.

[0012] Furthermore, the polymerization temperature of the first plug flow reactor is 92℃~101℃, the polymerization temperature of the second plug flow reactor is 103℃~110℃, the polymerization temperature of the third plug flow reactor is 114℃~128℃, and the polymerization temperature of the fourth plug flow reactor is 132℃~160℃.

[0013] Furthermore, the stirring speed of each plug flow reactor is 8~25 rpm.

[0014] Furthermore, this invention also proposes a high vibration-resistant and high impact-resistant ABS resin, which is prepared by the above method. The high vibration-resistant and high impact-resistant ABS resin has a loss factor tanδ > 0.1 and an impact strength > 18 KJ / m. 2 .

[0015] (III) Beneficial Effects This invention proposes a bulk high-vibration-resistance and high-impact ABS resin and its preparation method. Toughening rubber, solvent, monomers acrylonitrile, acrylate monomers, and styrene monomer are mixed and dissolved to form a raw rubber solution. The raw rubber solution, vibration-damping reinforcing agent, initiator, and chain transfer agent are fed into four plug flow reactors connected in series for continuous bulk polymerization. The polymerized material is then fed into an extruder for devolatilization and granulation to obtain the high-vibration-resistance and high-impact ABS resin. This invention, without adding any mechanical performance additives, enhances molecular chain flexibility and compatibility by adding monomeric acrylate elastomers and vibration-damping reinforcing agents during continuous bulk polymerization. Simultaneously, it adjusts the monomer composition, controls the polymerization temperature and stirring rate, and adjusts the rubber particle size and the degree of crosslinking of the product. This ensures the product's mechanical properties while improving the resin's damping performance and vibration resistance. The resulting high-vibration-resistance and high-impact ABS resin can be applied to vibration reduction and noise reduction applications, such as in the automotive, electronics, and construction industries. Detailed Implementation

[0016] To make the objectives, contents, and advantages of the present invention clearer, the specific embodiments of the present invention will be described in further detail below with reference to examples.

[0017] Example 1 According to mass fractions, 9.2% polybutadiene rubber, 50.8% styrene, 14.5% acrylonitrile, 6% methyl acrylate, and 16.0% ethylbenzene were added to a sol-gel reactor and stirred at 30°C until a homogeneous, lump-free raw rubber solution was obtained. The prepared raw rubber solution was then sequentially transferred to the first, second, third, and fourth plug flow reactors. The reaction temperatures in the upper, middle, and lower zones of the first, second, third, and fourth reactors were controlled at 94.2°C, 98.0°C, 100.6°C, 102.3°C, 105.4°C, 108.1°C, 116.0°C, 120.7°C, 125.9°C, 137.9°C, 145.0°C, and 153.2°C, respectively. The stirring of the four reactors was controlled. The stirring speeds were 8, 12, 12, and 15 rpm. During the polymerization process, 0.04% of 1,1-di-tert-butylcyclohexane peroxide and 0.16% of n-dodecyl mercaptan were added at the inlet of the first plug flow reactor; 0.2% of n-dodecyl mercaptan and 1.5% of N-phenylmaleic acid ester were added at the inlet of the third plug flow reactor; 0.2% of n-dodecyl mercaptan was added at the inlet of the fourth plug flow reactor; and 1.4% ethylbenzene was added at the inlet of the fourth plug flow reactor. The material entered the vacuum devolatilization system from the outlet of the fourth plug flow reactor to recover the unreacted monomers and solvents in the mixture. The melt was extruded and granulated to obtain the ABS resin product.

[0018] Example 2 According to mass fractions, 9.2% polybutadiene rubber, 50.8% styrene, 14.5% acrylonitrile, 6% methyl acrylate, and 15.0% ethylbenzene were added to a sol-gel reactor and stirred at 30°C until a homogeneous, lump-free raw rubber solution was obtained. The prepared raw rubber solution was then sequentially transferred to the first, second, third, and fourth plug flow reactors. The reaction temperatures in the upper, middle, and lower zones of the first, second, third, and fourth reactors were controlled at 94.2°C, 98.0°C, 100.6°C, 102.3°C, 105.4°C, 108.1°C, 116.0°C, 120.7°C, 125.9°C, 137.9°C, 145.0°C, and 153.2°C, respectively. The stirring of the four reactors was controlled. The stirring speeds were 8, 12, 12, and 15 rpm. During the polymerization process, 0.04% of 1,1-di-tert-butylcyclohexane peroxide and 0.16% of n-dodecyl mercaptan were added at the inlet of the first plug flow reactor; 0.2% of n-dodecyl mercaptan and 2.5% of N-phenylmaleimide were added at the inlet of the second plug flow reactor; 0.2% of n-dodecyl mercaptan was added at the inlet of the third plug flow reactor; and 1.4% ethylbenzene was added at the inlet of the fourth plug flow reactor. The material entered the vacuum devolatilization system from the outlet of the fourth plug flow reactor to recover the unreacted monomers and solvents in the mixture. The melt was extruded and granulated to obtain the ABS resin product.

[0019] Example 3 According to mass fractions, 9.2% polybutadiene rubber, 50.8% styrene, 14.5% acrylonitrile, 6% methyl acrylate, and 16.0% ethylbenzene were added to a sol-gel reactor and stirred at 30°C until a homogeneous, lump-free raw rubber solution was obtained. The prepared raw rubber solution was then sequentially transferred to the first, second, third, and fourth plug flow reactors. The reaction temperatures in the upper, middle, and lower zones of the first, second, third, and fourth reactors were controlled at 94.2°C, 98.0°C, 100.6°C, 102.3°C, 105.4°C, 108.1°C, 116.0°C, 120.7°C, 125.9°C, 137.9°C, 145.0°C, and 153.2°C, respectively. The stirring of the four reactors was controlled. The stirring speeds were 8, 15, 12, and 15 rpm. During the polymerization process, 0.04% of 1,1-di-tert-butylcyclohexane peroxide and 0.16% of n-dodecyl mercaptan were added at the inlet of the first plug flow reactor; 0.2% of n-dodecyl mercaptan and 1.5% of N-phenylmaleic acid ester were added at the inlet of the third plug flow reactor; 0.2% of n-dodecyl mercaptan was added at the inlet of the fourth plug flow reactor; and 1.4% ethylbenzene was added at the inlet of the fourth plug flow reactor. The material entered the vacuum devolatilization system from the outlet of the fourth plug flow reactor to recover the unreacted monomers and solvents in the mixture. The melt was extruded and granulated to obtain the ABS resin product.

[0020] Example 4 According to mass fractions, 9.2% polybutadiene rubber, 50.8% styrene, 14.5% acrylonitrile, 6% methyl acrylate, and 16.0% ethylbenzene were added to a sol-gel reactor and stirred at 30°C until a homogeneous, lump-free raw rubber solution was obtained. The prepared raw rubber solution was then sequentially transferred to the first, second, third, and fourth plug flow reactors. The reaction temperatures in the upper, middle, and lower zones of the first, second, third, and fourth reactors were controlled at 94.2°C, 98.0°C, 100.6°C, 102.3°C, 105.4°C, 108.1°C, 116.0°C, 120.7°C, 125.9°C, 137.9°C, 145.0°C, and 153.2°C, respectively. The stirring of the four reactors was controlled. The stirring speeds were 8, 18, 12, and 15 rpm. During the polymerization process, 0.04% of 1,1-di-tert-butylcyclohexane peroxide and 0.16% of n-dodecyl mercaptan were added at the inlet of the first plug flow reactor; 0.2% of n-dodecyl mercaptan and 1.5% of N-phenylmaleimide were added at the inlet of the second plug flow reactor; 0.2% of n-dodecyl mercaptan was added at the inlet of the third plug flow reactor; and 1.4% ethylbenzene was added at the inlet of the fourth plug flow reactor. The material entered the vacuum devolatilization system from the outlet of the fourth plug flow reactor to recover the unreacted monomers and solvents in the mixture. The melt was extruded and granulated to obtain the ABS resin product.

[0021] Example 5 According to mass fractions, 9.2% polybutadiene rubber, 50.8% styrene, 14.5% acrylonitrile, 6% methyl acrylate, and 16.0% ethylbenzene were added to a sol-gel reactor and stirred at 30°C until a homogeneous, lump-free raw rubber solution was obtained. The prepared raw rubber solution was then sequentially transferred to the first, second, third, and fourth plug flow reactors. The reaction temperatures in the upper, middle, and lower zones of the first, second, third, and fourth reactors were controlled at 94.2°C, 98.0°C, 100.6°C, 102.3°C, 105.4°C, 108.1°C, 116.0°C, 120.7°C, 125.9°C, and 135°C, respectively. The four reactors were set at 0.9℃, 143.0℃, and 151.2℃, with stirring speeds of 8, 15, 12, and 15 rpm, respectively. During polymerization, 0.04% of 1,1-di-tert-butylcyclohexane peroxide and 0.16% of n-dodecyl mercaptan were added at the inlet of the first plug flow reactor; 0.2% of n-dodecyl mercaptan and 1.5% of N-phenylmaleic acid amide were added at the inlet of the second plug flow reactor; 0.2% of n-dodecyl mercaptan was added at the inlet of the third plug flow reactor; and 1.4% of ethylbenzene was added at the inlet of the fourth plug flow reactor. The material entered the vacuum devolatilization system from the outlet of the fourth plug flow reactor to recover unreacted monomers and solvents from the mixture. The melt was extruded and granulated to obtain ABS resin products.

[0022] Example 6 According to mass fractions, 9.2% polybutadiene rubber, 50.8% styrene, 14.5% acrylonitrile, 6% methyl acrylate, and 16.0% ethylbenzene were added to a sol-gel reactor and stirred at 30°C until a homogeneous, lump-free raw rubber solution was obtained. The prepared raw rubber solution was then sequentially transferred to the first, second, third, and fourth plug flow reactors. The reaction temperatures in the upper, middle, and lower zones of the first, second, third, and fourth reactors were controlled at 94.2°C, 98.0°C, 100.6°C, 102.3°C, 105.4°C, 108.1°C, 116.0°C, 120.7°C, 125.9°C, and 133°C, respectively. The four reactors were set at 0.9℃, 141.0℃, and 149.2℃, with stirring speeds of 8, 15, 12, and 15 rpm, respectively. During polymerization, 0.04% of 1,1-di-tert-butylcyclohexane peroxide and 0.16% of n-dodecyl mercaptan were added at the inlet of the first plug flow reactor; 0.2% of n-dodecyl mercaptan and 1.5% of N-phenylmaleic acid amide were added at the inlet of the second plug flow reactor; 0.2% of n-dodecyl mercaptan was added at the inlet of the third plug flow reactor; and 1.4% ethylbenzene was added at the inlet of the fourth plug flow reactor. The material entered the vacuum devolatilization system from the outlet of the fourth plug flow reactor to recover unreacted monomers and solvents from the mixture. The melt was extruded and granulated to obtain ABS resin products.

[0023] Comparative Example 1 According to mass fractions, 9.2% polybutadiene rubber, 50.8% styrene, 14.5% acrylonitrile, and 23.5% ethylbenzene were added to a sol-gel reactor and stirred at 30°C until a homogeneous, lump-free raw rubber solution was obtained. The prepared raw rubber solution was then sequentially transferred to the first, second, third, and fourth plug flow reactors. The reaction temperatures in the upper, middle, and lower zones of the first, second, third, and fourth reactors were controlled at 94.2°C, 98.0°C, and 100°C, respectively. The polymerization temperatures were 0.6℃, 102.3℃, 105.4℃, 108.1℃, 116.0℃, 120.7℃, 125.9℃, 137.9℃, 145.0℃, and 153.2℃, with stirring speeds of 8, 12, 12, and 15 rpm for the four reactors, respectively. During polymerization, 0.04% of 1,1-di-tert-butylcyclohexane peroxide and 0.16% of n-dodecyl mercaptan were added at the inlet of the first plug flow reactor; 0.2% of n-dodecyl mercaptan was added at the inlet of the second plug flow reactor; 0.2% of n-dodecyl mercaptan was added at the inlet of the third plug flow reactor; and 1.4% ethylbenzene was added at the inlet of the fourth plug flow reactor. The material entered the vacuum devolatilization system from the outlet of the fourth plug flow reactor to recover unreacted monomers and solvents from the mixture. The melt was extruded and granulated to obtain ABS resin products.

[0024] Comparative Example 2 According to mass fractions, 9.2% polybutadiene rubber, 50.8% styrene, 14.5% acrylonitrile, 4% methyl acrylate, and 19.5% ethylbenzene were added to a sol-gel reactor and stirred at 30°C until a homogeneous, lump-free raw rubber solution was obtained. The prepared raw rubber solution was then sequentially transferred to the first, second, third, and fourth plug flow reactors. The reaction temperatures in the upper, middle, and lower zones of the first, second, third, and fourth reactors were controlled at 94.2°C, 98.0°C, 100.6°C, 102.3°C, 105.4°C, 108.1°C, 116.0°C, 120.7°C, 125.9°C, 137.9°C, 145.0°C, and 153.2°C, respectively. The stirring speeds of the four reactors were 8, 12, 12, and 15 rpm, respectively. During the polymerization process, 0.04% of 1,1-di-tert-butylcyclohexane peroxide and 0.16% of n-dodecyl mercaptan were added at the inlet of the first plug flow reactor; 0.2% of n-dodecyl mercaptan was added at the inlet of the second plug flow reactor; 0.2% of n-dodecyl mercaptan was added at the inlet of the third plug flow reactor; and 1.4% ethylbenzene was added at the inlet of the fourth plug flow reactor. The material entered the vacuum devolatilization system from the outlet of the fourth plug flow reactor to recover the unreacted monomers and solvents in the mixture. The melt was extruded and granulated to obtain the ABS resin product.

[0025] Comparative Example 3 According to mass fractions, 9.2% polybutadiene rubber, 50.8% styrene, 14.5% acrylonitrile, 6% methyl acrylate, and 17.5% ethylbenzene were added to a sol-gel reactor and stirred at 30°C until a homogeneous, lump-free raw rubber solution was obtained. The prepared raw rubber solution was then sequentially transferred to the first, second, third, and fourth plug flow reactors. The reaction temperatures in the upper, middle, and lower zones of the first, second, third, and fourth reactors were controlled at 94.2°C, 98.0°C, 100.6°C, 102.3°C, 105.4°C, 108.1°C, 116.0°C, 120.7°C, 125.9°C, 137.9°C, 145.0°C, and 153.2°C, respectively. The stirring speeds of the four reactors were 8, 12, 12, and 15 rpm, respectively. During the polymerization process, 0.04% of 1,1-di-tert-butylcyclohexane peroxide and 0.16% of n-dodecyl mercaptan were added at the inlet of the first plug flow reactor; 0.2% of n-dodecyl mercaptan was added at the inlet of the second plug flow reactor; 0.2% of n-dodecyl mercaptan was added at the inlet of the third plug flow reactor; and 1.4% ethylbenzene was added at the inlet of the fourth plug flow reactor. The material entered the vacuum devolatilization system from the outlet of the fourth plug flow reactor to recover the unreacted monomers and solvents in the mixture. The melt was extruded and granulated to obtain the ABS resin product.

[0026] Comparative Example 4 According to mass fractions, 9.2% polybutadiene rubber, 50.8% styrene, 14.5% acrylonitrile, 8% methyl acrylate, and 15.5% ethylbenzene were added to a sol-gel reactor and stirred at 30°C until a homogeneous, lump-free raw rubber solution was obtained. The prepared raw rubber solution was then sequentially transferred to the first, second, third, and fourth plug flow reactors. The reaction temperatures in the upper, middle, and lower zones of the first, second, third, and fourth reactors were controlled at 94.2°C, 98.0°C, 100.6°C, 102.3°C, 105.4°C, 108.1°C, 116.0°C, 120.7°C, 125.9°C, 137.9°C, 145.0°C, and 153.2°C, respectively. The stirring speeds of the four reactors were 8, 12, 12, and 15 rpm, respectively. During the polymerization process, 0.04% of 1,1-di-tert-butylcyclohexane peroxide and 0.16% of n-dodecyl mercaptan were added at the inlet of the first plug flow reactor; 0.2% of n-dodecyl mercaptan was added at the inlet of the second plug flow reactor; 0.2% of n-dodecyl mercaptan was added at the inlet of the third plug flow reactor; and 1.4% ethylbenzene was added at the inlet of the fourth plug flow reactor. The material entered the vacuum devolatilization system from the outlet of the fourth plug flow reactor to recover the unreacted monomers and solvents in the mixture. The melt was extruded and granulated to obtain the ABS resin product.

[0027] Table 1. Formulations and related parameters of ABS resins for comparative examples and embodiments.

[0028] The vibration resistance and mechanical properties of the bulk ABS resins in the examples and comparative examples were tested (Table 2). The test data shows that introducing the fourth monomer, methyl acrylate, increases the resin's flexibility, thereby increasing the product's impact resistance, but it also reduces the product's impact resistance. By introducing N-phenylmaleimide, adjusting the stirring rate of the second reaction and the temperature of the fourth reaction, and controlling the particle size and structure of the product, both vibration resistance and high impact resistance can be ensured.

[0029] Table 2. Relevant Tests of ABS Resin in Comparative Examples and Examples

[0030] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the technical principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing ABS resin with high vibration and impact resistance, characterized in that, The method for preparing the high vibration-resistant and high impact-resistant ABS resin is as follows: toughening rubber, solvent, monomer acrylonitrile, monomer acrylate elastomer and monomer styrene are mixed and dissolved to form a raw rubber solution; the raw rubber solution, vibration-resistant reinforcing agent, initiator and chain transfer agent are transported to four plug flow reactors connected in series for continuous bulk polymerization reaction; the polymerized material is fed into an extruder for devolatilization and granulation to obtain high vibration-resistant and high impact-resistant ABS resin.

2. The method for preparing high vibration-resistant and high impact-resistant ABS resin as described in claim 1, characterized in that, Based on mass fractions, 8%~13% toughening rubber, 13%~25% solvent, 12%~23% monomer acrylonitrile, 3%~12% monomer acrylate elastomer, and 45%~60% monomer styrene are mixed and dissolved at 25~40℃ to form a raw rubber solution. The raw rubber solution, 1%~3% vibration-damping agent, 0.02%~0.06% initiator, and 0.2%~0.6% chain transfer agent are transported to four plug flow reactors connected in series for continuous bulk polymerization.

3. The method for preparing high vibration-resistant and high impact-resistant ABS resin as described in claim 1, characterized in that, The toughening rubber is butadiene rubber.

4. The method for preparing high vibration-resistant and high impact-resistant ABS resin as described in claim 1, characterized in that, The solvent is toluene, ethylbenzene, xylene, or a mixture thereof.

5. The method for preparing high vibration-resistant and high impact-resistant ABS resin as described in claim 1, characterized in that, The initiator is 1,1-di-tert-butylperoxycyclohexane; the chain transfer agent is n-dodecyl mercaptan.

6. The method for preparing high vibration-resistant and high impact-resistant ABS resin as described in claim 1, characterized in that, The vibration-enhancing agent is one of N-phenylmaleimide, N,N-methylenediphenylbismaleimide, and N-methylphthalimide.

7. The method for preparing high vibration-resistant and high impact-resistant ABS resin as described in claim 1, characterized in that, The monomeric acrylate elastomer is one of methyl acrylate, ethyl acrylate, and methyl methacrylate.

8. The method for preparing high vibration-resistant and high impact-resistant ABS resin as described in claim 1, characterized in that, The polymerization temperature of the first plug flow reactor is 92℃~101℃, the polymerization temperature of the second plug flow reactor is 103℃~110℃, the polymerization temperature of the third plug flow reactor is 114℃~128℃, and the polymerization temperature of the fourth plug flow reactor is 132℃~160℃.

9. The method for preparing high vibration-resistant and high impact-resistant ABS resin as described in claim 1, characterized in that, The stirring speed of each plug flow reactor is 8~25 rpm.

10. A high vibration-resistant and high impact-resistant ABS resin, characterized in that, The high vibration-resistant and high impact-resistant ABS resin is prepared by the method according to any one of claims 1 to 9, wherein the loss factor tanδ of the high vibration-resistant and high impact-resistant ABS resin is >0.1 and the impact strength is >18KJ / m. 2 .

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