CN107540792B - Ultrahigh impact-resistant ABS resin composition and preparation method thereof - Google Patents
Ultrahigh impact-resistant ABS resin composition and preparation method thereof Download PDFInfo
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Abstract
The invention provides an ABS resin composition with ultrahigh impact resistance and a preparation method thereof, wherein the ABS resin composition comprises a monomer and a diluent, and the monomer comprises the following components: styrene, acrylonitrile, butadiene rubber, a molecular weight regulator and an initiator. The preparation method comprises the following steps: adding styrene, acrylonitrile and a diluent into a reaction kettle, adding the crushed butadiene rubber until the butadiene rubber is completely dissolved, adding a molecular weight regulator and an initiator, stirring at a proper rotating speed of 60-180rpm, and reacting at 125-135 ℃ to obtain the ultrahigh impact-resistant bulk ABS resin composition. The ABS resin prepared by the invention has short reaction time and good mechanical property, and the impact strength can reach more than 550J/m and can reach more than 600J/m at most.
Description
Technical Field
The invention relates to an ultrahigh impact-resistant bulk ABS resin composition and a preparation method thereof, belonging to the technical field of synthesis and preparation of high polymer materials.
Background
ABS resin has been developed in China for more than 60 years, and the industrial production process of ABS resin at present comprises the following steps: emulsion and bulk processes. The technology for preparing the ABS resin by the emulsion method is mature in China, but the production process steps are complex, and a large amount of waste water is generated to pollute the environment; various additives in the powder of the product cannot be removed completely, and the product is not pure enough, so that the performance of the ABS resin is influenced.
The continuous bulk method for producing the ABS resin has simple process on the production process, does not generate waste water, and the ABS resin product is purer compared with the ABS resin produced by emulsion after monomer recovery and devolatilization. However, the reaction control of the bulk device is difficult, and the domestic companies for producing ABS by the continuous bulk method include Liaoning Cui Shuangxing engineering plastics company and China petrochemical Shanghai Gaoqiao division company, which all use the technology and equipment of the American Dow chemical company. At present, the impact performance of the ABS resin in the domestic market is generally low, the impact strength of the common ABS resin is 150-300J/m, and the impact strength of the high-impact ABS resin is 300-530J/m.
For example, in patent CN 105778183A applied by China Petroleum and gas Co., Ltd, the nitrile rubber latex is prepared by emulsion method according to the method provided by the patent, and the high-toughness ABS resin is prepared by melt blending SAN resin, and the impact strength can reach as high as 400J/m. Compared with the common ABS resin, the toughness of the finally prepared ABS resin is improved to a certain extent, but the improvement degree is limited.
In patent CN 104558430A applied by North China brocade chemical group Limited, four-kettle series plug flow reactor is used, and various rubbers are mixed to prepare high-toughness ABS resin, and the impact strength can reach 350J/m at most. The ABS resin is toughened by improving production process equipment and changing the composition of added rubber, and the performance of the finally prepared ABS resin is yet to be enhanced.
For example, in patent CN 102190852B granted by shanghai petrochemical institute of petrochemical engineering, ltd, china, the ABS resin produced by the bulk method is blended with MBS in a ratio of 60-99 and MBS in a ratio of 1-40, extruded and granulated to obtain a new modified ABS resin, and the impact strength is preferably only 300J/m, which needs to be further improved.
Disclosure of Invention
The invention aims to provide a method for preparing ultrahigh impact resistant ABS resin by using a reaction kettle, and the prepared ultrahigh impact resistant ABS resin has the characteristics of good impact resistance, short reaction time, short process flow, simplicity and easiness in operation. Compared with the prior high impact ABS resin technical product, the impact value is improved by more than 100J/m.
The invention is realized by the following technical scheme:
in a first aspect, the invention provides an ultrahigh impact resistance ABS resin composition, which comprises the following components in percentage by weight:
monomer (b): 60-80%;
diluent agent: 20-40%;
wherein the monomer comprises the following components in percentage by weight:
if the content of the styrene is higher than 80 percent (the content of the acrylonitrile is lower than 7 percent), the reaction time is prolonged, the reaction rate is slowed down, and the mechanical strength of the prepared ABS resin is seriously reduced. If the content of the styrene is less than 55 percent (the content of the acrylonitrile is more than 28 percent), the reaction rate of the system is too high, the viscosity of the system is very high, the stirring and heat removal are difficult, and a large amount of heat in the kettle is quickly accumulated and is easy to implode. Too much molecular weight regulator can result in too low molecular weight of SAN resin matrix and poor overall mechanical properties of ABS resin.
Preferably, the butadiene rubber is prepared by anionic solution polymerization, preferably German Langshan 550T anionic solution polymerization butadiene rubber.
Preferably, the diluent is at least one selected from the group consisting of toluene, ethylbenzene and xylene.
Preferably, the molecular weight regulator is one or two selected from n-dodecyl mercaptan and t-dodecyl mercaptan.
Preferably, the initiator is selected from one or two of di-tert-butyl peroxide and benzoyl peroxide.
In a second aspect, the invention also provides a preparation method of the above-mentioned ultrahigh impact resistance bulk ABS resin composition, which comprises the following steps:
adding styrene, acrylonitrile and a diluent into a reaction kettle, adding the crushed butadiene rubber until the butadiene rubber is completely dissolved, adding a molecular weight regulator and an initiator, stirring, and reacting at 125-135 ℃ to obtain the ultrahigh impact-resistant ABS resin composition.
Preferably, the rotation speed of the stirring is the same as 60-180 rpm.
Compared with the prior art, the invention has the following beneficial effects:
the butadiene rubber prepared by anionic solution polymerization has better dissolubility of crushed rubber particles in a mixed solution of a monomer and a solvent and has better affinity to the monomer and the solvent. In the process of dissolving the same type of domestic butadiene rubber, a part of high-crosslinked rubber is not dissolved and floats on the mixed liquid surface, which brings inconvenience to processing and synthesis. Moreover, the rubber of the high crosslinking part does not participate in the ABS polymerization reaction, and is a waste in terms of rubber utilization rate. By adjusting the dosage of polybutadiene rubber and the feeding proportion of styrene monomer and acrylonitrile monomer, the ABS resin with good impact strength can be obtained. The most important thing is that the reaction temperature used by the invention is high, ABS can stably and rapidly carry out rubber grafting, resin chain growth, resin droplet enrichment and phase inversion in a reaction kettle, and after the reaction is finished, the rubber in the ABS is induced to be partially crosslinked at high temperature, so that the toughness of the ABS resin is better. According to the method provided by the invention, when the feeding proportion is proper, and proper initiator and molecular weight regulator are added, the molecular weight of the resin phase is controlled within a proper range, almost all rubber particles used as a dispersed phase have an occlusion structure, the ABS resin has good mechanical property, and the impact strength can reach more than 550J/m and can reach more than 600J/m at most.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a TEM electron micrograph of an ultra-high impact ABS resin prepared in example 1 of the present invention;
FIG. 2 is a TEM electron micrograph of the ultra-high impact ABS resin prepared in example 2 of the present invention.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
In the ultra-high impact ABS resin of this embodiment, 10 parts of butadiene rubber, 12 parts of acrylonitrile and 88 parts of styrene are dissolved in 41 parts of xylene diluent. Simultaneously adding the mixture into a reaction kettle together with 500ppm of di-tert-butyl peroxide and 1500ppm of tert-dodecyl mercaptan, exhausting air in the reaction kettle by using nitrogen, and then starting the reaction. The reaction temperature was set at 130 ℃ and the reaction was carried out for 150 min. After the reaction is finished, vacuum devolatilization is carried out to obtain the super impact resistant ABS resin, and the monomer conversion rate is 63%.
The high impact ABS resin was compression molded using a flat vulcanization press to produce 120X 65X 3.5mm sheets. The specimens were cut into standard impact specimens according to GB1040-92 standard on a prototype, and subjected to impact testing by using a model XJV-22 Izod impact tester manufactured by Chengdi Material testing machine manufacturer according to the method of GB1843-80, and the test results are shown in Table 1.
The transmission electron micrograph of the ultra-high impact resistant ABS resin prepared in this example is shown in FIG. 1, and the formed particles with inclusions are bimodal particles, that is, the particles include two types of large particles and small particles, the particle size of the large particles is 1-20 μm, and the particle size of the small particles is 200-400 nm.
Example 2
In the ultra-high impact ABS resin of this embodiment, 10 parts of butadiene rubber, 30 parts of acrylonitrile and 70 parts of styrene are dissolved in 41 parts of xylene diluent. Simultaneously adding the mixture into a reaction kettle together with 500ppm of di-tert-butyl peroxide and 1500ppm of tert-dodecyl mercaptan, exhausting air in the reaction kettle by using nitrogen, and then starting the reaction. The reaction temperature was set at 130 ℃ and the reaction time was 120 min. After the reaction is finished, vacuum devolatilization is carried out to obtain the super impact resistant ABS resin, and the monomer conversion rate is 74%.
The high impact ABS resin was compression molded using a flat vulcanization press to produce 120X 65X 3.5mm sheets. The specimens were cut into standard impact specimens according to GB1040-92 standard on a prototype, and subjected to impact testing by using a model XJV-22 Izod impact tester manufactured by Chengdi Material testing machine manufacturer according to the method of GB1843-80, and the test results are shown in Table 1.
The transmission electron micrograph of the ultrahigh impact resistant ABS resin prepared by the embodiment is shown in FIG. 2, and is characterized in that the formed particles with inclusions are bimodal particles, namely, the particles comprise two types of large particles and small particles, the particle size of the large particles is 1.5-10 μm, and the particle size of the small particles is 200-400 nm.
Example 3
In the ultra-high impact ABS resin of this embodiment, 10 parts of butadiene rubber, 47 parts of acrylonitrile and 63 parts of styrene were dissolved in 41 parts of xylene diluent. Simultaneously adding the mixture into a reaction kettle together with 500ppm of di-tert-butyl peroxide and 1500ppm of tert-dodecyl mercaptan, exhausting air in the reaction kettle by using nitrogen, and then starting the reaction. The reaction temperature was set at 130 ℃ and the reaction was carried out for 90 min. After the reaction is finished, vacuum devolatilization is carried out to obtain the super impact resistant ABS resin, and the monomer conversion rate is 73%.
The high impact ABS resin was compression molded using a flat vulcanization press to produce 120X 65X 3.5mm sheets. The specimens were cut into standard impact specimens according to GB1040-92 standard on a prototype, and subjected to impact testing by using a model XJV-22 Izod impact tester manufactured by Chengdi Material testing machine manufacturer according to the method of GB1843-80, and the test results are shown in Table 1.
Example 4
In the ultra-high impact ABS resin of this embodiment, 8 parts of butadiene rubber, 30 parts of acrylonitrile and 70 parts of styrene are dissolved in 41 parts of xylene diluent. Simultaneously adding the mixture into a reaction kettle together with 500ppm of di-tert-butyl peroxide and 1500ppm of tert-dodecyl mercaptan, exhausting air in the reaction kettle by using nitrogen, and then starting the reaction. The reaction temperature was set at 130 ℃ and the reaction time was 120 min. After the reaction is finished, vacuum devolatilization is carried out to obtain the super impact resistant ABS resin, and the monomer conversion rate is 71%.
The high impact ABS resin was compression molded using a flat vulcanization press to produce 120X 65X 3.5mm sheets. The specimens were cut into standard impact specimens according to GB1040-92 standard on a prototype, and subjected to impact testing by using a model XJV-22 Izod impact tester manufactured by Chengdi Material testing machine manufacturer according to the method of GB1843-80, and the test results are shown in Table 1.
Example 5
In the ultra-high impact ABS resin of this embodiment, 10 parts of butadiene rubber, 30 parts of acrylonitrile and 70 parts of styrene are dissolved in 41 parts of xylene diluent. Simultaneously adding the mixture into a reaction kettle together with 500ppm of di-tert-butyl peroxide and 3000ppm of tert-dodecyl mercaptan, exhausting air in the reaction kettle by using nitrogen, and then starting the reaction. The reaction temperature was set at 130 ℃ and the reaction time was 120 min. After the reaction is finished, vacuum devolatilization is carried out to obtain the super impact resistant ABS resin, and the monomer conversion rate is 70%.
The high impact ABS resin was compression molded using a flat vulcanization press to produce 120X 65X 3.5mm sheets. The specimens were cut into standard impact specimens according to GB1040-92 standard on a prototype, and subjected to impact testing by using a model XJV-22 Izod impact tester manufactured by Chengdi Material testing machine manufacturer according to the method of GB1843-80, and the test results are shown in Table 1.
Example 6
In the ultra-high impact ABS resin of this embodiment, 10 parts of butadiene rubber, 30 parts of acrylonitrile and 70 parts of styrene are dissolved in 41 parts of xylene diluent. Simultaneously, the mixture was charged into a reaction vessel together with 500ppm of di-t-butyl peroxide and 4500ppm of t-dodecyl mercaptan, and the reaction was started after the air in the reaction vessel was purged with nitrogen. The reaction temperature was set at 130 ℃ and the reaction time was 120 min. After the reaction is finished, vacuum devolatilization is carried out to obtain the super impact resistant ABS resin, and the monomer conversion rate is 66%.
The high impact ABS resin was compression molded using a flat vulcanization press to produce 120X 65X 3.5mm sheets. The specimens were cut into standard impact specimens according to GB1040-92 standard on a prototype, and subjected to impact testing by using a model XJV-22 Izod impact tester manufactured by Chengdi Material testing machine manufacturer according to the method of GB1843-80, and the test results are shown in Table 1.
Example 7
In the ultra-high impact ABS resin of this embodiment, 10 parts of butadiene rubber, 30 parts of acrylonitrile and 70 parts of styrene are dissolved in 41 parts of xylene diluent. Simultaneously adding the mixture, 500ppm of di-tert-butyl peroxide and 6000ppm of tert-dodecyl mercaptan into the reaction kettle, exhausting air in the reaction kettle by using nitrogen, and then starting the reaction. The reaction temperature was set at 130 ℃ and the reaction was carried out for 150 min. After the reaction, the super impact resistant ABS resin is obtained by vacuum devolatilization, and the monomer conversion rate is 57%.
The high impact ABS resin was compression molded using a flat vulcanization press to produce 120X 65X 3.5mm sheets. The specimens were cut into standard impact specimens according to GB1040-92 standard on a prototype, and subjected to impact testing by using a model XJV-22 Izod impact tester manufactured by Chengdi Material testing machine manufacturer according to the method of GB1843-80, and the test results are shown in Table 1.
Comparative example 1
In the ultra-high impact ABS resin of this embodiment, 10 parts of butadiene rubber produced by shanghai high bridge, 30 parts of acrylonitrile and 70 parts of styrene are dissolved in 41 parts of xylene diluent. Simultaneously adding the mixture into a reaction kettle together with 500ppm of di-tert-butyl peroxide and 1500ppm of tert-dodecyl mercaptan, exhausting air in the reaction kettle by using nitrogen, and then starting the reaction. The reaction temperature was set at 130 ℃ and the reaction time was 120 min. After the reaction is finished, vacuum devolatilization is carried out to obtain the super impact resistant ABS resin, and the monomer conversion rate is 69%.
The high impact ABS resin was compression molded using a flat vulcanization press to produce 120X 65X 3.5mm sheets. The specimens were cut into standard impact specimens according to GB1040-92 standard on a prototype, and subjected to impact testing by using a model XJV-22 Izod impact tester manufactured by Chengdi Material testing machine manufacturer according to the method of GB1843-80, and the test results are shown in Table 1.
TABLE 1
Compared with the comparative example 1, the comparison of the example 2 shows that the impact strength is reduced by nearly 100J/m by replacing butadiene rubber used by the butadiene produced by the Shanghai bridge chemical company in the same process, but the mechanical property of the ABS resin produced by the process is still higher than that of most ABS resins in the market. The solubility of the rubber produced by domestic high-bridge companies to the monomer solvent solution is not the same as that of the rubber used in the patent, wherein the high-crosslinking rubber contained in the butadiene rubber produced by high-bridge companies is too much, and the rubber utilization rate is also influenced. Since the highly crosslinked rubber cannot be dissolved in the monomer solvent, it cannot be divided and surrounded by the resin matrix at the time of phase inversion, and rubber particles cannot be formed, which is structurally disadvantageous.
From examples 2 and 5 to 7, it is understood that the molecular weight of the resin phase gradually decreases with the increase in the amount of the molecular weight modifier, the conversion of the polymer gradually decreases within the same reaction time, and the impact strength rapidly decreases. The molecular weight of the resin matrix has great influence on the mechanical property of the ABS resin, the larger the molecular weight of the SAN matrix is, the longer the chain is, the longer the high molecular chain is more easily intertwined together, and the fracture resistance is stronger when impact collision occurs. However, the molecular weight is too high, the chains are entangled together to be unfavorable for flow property, and the production and processing are unfavorable, and at this time, a balance point needs to be found, so that the flow property of the ABS resin is improved to be favorable for processing under the condition that the impact property is not reduced seriously. Examples 2, 5, 6 and 7 explore the law of the mechanical properties and the addition of molecular weight regulators.
It is understood from examples 2 and 4 that the mechanical properties of the ultra-high impact ABS resin are drastically reduced as the amount of the rubber is reduced. The dosage of the toughening rubber plays an important role in the ultrahigh impact resistant ABS resin.
From examples 1 to 3, it is understood that as the content of acrylonitrile increases, the content of styrene decreases, the mechanical properties increase and then decrease, and the fluidity is also poor.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (3)
1. The ABS resin composition with the ultrahigh impact resistance is characterized by comprising the following components in percentage by weight:
monomer (b): 60 to 80 percent;
diluent agent: 20 to 40 percent;
wherein the monomer comprises the following components in percentage by weight:
the butadiene rubber is prepared by anionic solution polymerization; the initiator is selected from one or two of di-tert-butyl peroxide and benzoyl peroxide; the molecular weight regulator is tert-dodecyl mercaptan.
2. The ultra-high impact resistance bulk ABS resin composition according to claim 1 wherein said diluent is selected from xylene.
3. A method for preparing an ultra-high impact resistance bulk ABS resin composition according to any of claims 1-2, comprising the steps of:
adding styrene, acrylonitrile and a diluent into a reaction kettle, adding the crushed butadiene rubber until the butadiene rubber is completely dissolved, adding a molecular weight regulator and an initiator, stirring at the rotation speed of 60-180rpm, and reacting at the temperature of 80-140 ℃ to obtain the ultrahigh impact-resistant bulk ABS resin composition.
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| JP6911985B1 (en) * | 2020-08-31 | 2021-07-28 | 日本ゼオン株式会社 | Dispersant composition for electrochemical element, conductive material dispersion for electrochemical element, slurry composition for electrochemical element electrode and its manufacturing method, electrode for electrochemical element, and electrochemical element |
| CN113121757A (en) * | 2021-04-13 | 2021-07-16 | 长春工业大学 | Preparation method of high-flow transparent MABS resin with bimodal structure |
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| CN102977279A (en) * | 2012-12-21 | 2013-03-20 | 北方华锦化学工业集团有限公司 | Tubular plug flow reactor with material internal circulation and preparation method for preparing continuous bulk ABS (Acrylonitrile-Butadiene-Styrene) resin |
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| KR100671135B1 (en) * | 2004-09-08 | 2007-01-17 | 주식회사 엘지화학 | Method for Preparing Styrenic Resin Having High Impact Strength and Gloss |
| CN103030743B (en) * | 2012-12-21 | 2014-06-25 | 北方华锦化学工业集团有限公司 | Continuous pipe type flexible plug flow reactor and method for preparing mass ABS resin or SAN resin |
| CN104558430A (en) * | 2015-01-27 | 2015-04-29 | 北方华锦化学工业集团有限公司 | Method of preparing mass ABS (acrylonitrile-butadiene-styrene) resin with high impact resistance |
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| CN102977279A (en) * | 2012-12-21 | 2013-03-20 | 北方华锦化学工业集团有限公司 | Tubular plug flow reactor with material internal circulation and preparation method for preparing continuous bulk ABS (Acrylonitrile-Butadiene-Styrene) resin |
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