CN113980190A - Preparation process of anti-impact bulk ABS resin - Google Patents
Preparation process of anti-impact bulk ABS resin Download PDFInfo
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- CN113980190A CN113980190A CN202111307517.1A CN202111307517A CN113980190A CN 113980190 A CN113980190 A CN 113980190A CN 202111307517 A CN202111307517 A CN 202111307517A CN 113980190 A CN113980190 A CN 113980190A
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- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
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Abstract
The invention belongs to the field of high polymer materials, and particularly relates to a preparation process of an anti-impact ABS resin in a bulk method. The impact resistance of the product can reach more than 28 KJ/square meter, and the product has impact resistance.
Description
Technical Field
The invention belongs to the field of preparation of high polymer materials, and particularly relates to a preparation process of an ABS resin by a medium impact bulk method.
Background
By utilizing the production process of the body ABS device, high-impact ABS resin products with high added values are developed, foreign monopoly is broken, the upgrading of the body ABS products is promoted, the profitability of the ABS device is improved, and the current situations of few types and poor performance of the body ABS device products are solved.
Acrylonitrile-butadiene-styrene (ABS) plastics generally refer to graft copolymers of polybutadiene rubber with the monomers styrene and acrylonitrile, but in addition to free styrene-acrylonitrile copolymers (SAN) resulting from the copolymerization of the monomers styrene and acrylonitrile, such mixtures being generally referred to in the industry as ABS. ABS produced by a continuous bulk method has the characteristics of pure ground color, good colorability, low residual monomer rate and good compatibility with other resins.
The medium impact ABS is well-sold in the market, has very wide application, can be used as a base material of a modified material, and is used for producing shells of household appliances, automotive interiors, electroplated parts and the like.
Disclosure of Invention
The invention provides a preparation method for preparing middle impact resistant ABS resin aiming at the characteristics and market demands of the existing ABS resin.
In order to realize the purpose of the invention, the invention provides a preparation process of an impact-resistant ABS resin in a bulk method, which comprises the following steps:
(1) mixing and dissolving the cut rubber, the solvent, the acrylonitrile and the styrene sol in a kettle until the raw rubber solution is uniform and has no rubber block;
the rubber is composite rubber, preferably two of 565T and 97B, 565T and 1322, 565T and 490, 565T and N210, 700A and 720AX, and 30AF and 720 AX;
(2) the dissolved crude rubber solution, the initiator, the chain transfer agent and the silicone oil are sent to four plug flow reactors connected in series by a conveying device to carry out continuous bulk polymerization reaction;
(3) and (3) devolatilizing, extruding and granulating the polymerized material to prepare the middle impact resistant ABS resin.
The rubber content in the raw rubber solution in the step (1) is 10-15% of the raw rubber solution; butyl acrylate with the mass content of 1-2% is added into the raw glue solution.
And (3) increasing the addition of the sealed mineral oil of the stirrer of the third reactor in the step (2), and adding trace mineral oil into the reaction kettle.
And (3) in the step (2), adjusting the temperature of the fourth reactor, and reducing the temperatures of the tenth zone and the eleventh zone by 6 ℃ respectively.
The impact strength of the prepared ABS resin reaches 28 KJ/square meter.
The invention has the beneficial effects that:
the high-viscosity rubber is selected in the process formula, the rubber particle size in the prepared bulk ABS resin is larger, and the glossiness of the product is effectively reduced;
(1) the rubber containing vinyl 1 and 2 with high structure can improve the grafting rate, and meanwhile, the compatibility of a rubber phase and a continuous phase is improved by proper rubber proportion, so that the impact property of the product is improved;
(2) the addition of a proper amount of butyl acrylate in the glue solution can improve the activity of the grafting reaction, but the addition is not excessive, otherwise the compatibility between two phases is poor, and the impact strength is reduced;
(3) the addition of a small amount of mineral oil plays a role of a compatilizer, greatly promotes the compatibility between two phases, promotes the dispersion of rubber, and improves the interface bonding strength, so the impact strength is improved; but when the addition amount is larger, the concentration of free radicals can be diluted, the reaction activity is reduced, and the product performance can be greatly reduced;
(4) when the material enters the fourth reactor, the material already enters the final stage of reaction, and the excessive high crosslinking degree can be avoided by properly reducing the reaction temperature, so that the impact property of the product is ensured;
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited thereto.
The ABS resin products of the above examples had melt indices determined according to ASTM D1228, tensile strengths determined according to ASTM D638, impact strengths determined according to ASTM D256, flexural strengths determined according to ASTM D790, and gloss degrees determined according to GB 8807-88.
Detailed description of the preferred embodiment 1
6.9kg of 565T rubber, 13.78kg of 97B rubber, 100kg of styrene and 28.6kg of ethylbenzene mixture were added to the compounding tank, and stirred and dissolved for 12 hours at normal temperature, and then 32kg of acrylonitrile and 3kg of butyl acrylate were added and stirred and dispersed for 12 hours.
Introducing the reaction liquid in the liquid preparation tank into a first reactor for graft polymerization reaction, wherein the main feeding amount of the reactor is 4.5kg/h, the rotating speed of the first reactor is 100rpm, the reaction temperatures of the three intervals are respectively controlled at 95 ℃, 96 ℃ and 98 ℃, and 0.38kg/h of chain transfer agent is added into an outlet pipeline of the first reactor;
continuously introducing the reaction liquid into a second reactor for phase transition reaction, wherein the rotating speed of the second reactor is 80rpm, the reaction temperatures of the three intervals are respectively controlled at 101 ℃, 106 ℃ and 107 ℃, and 0.045kg/h of acrylonitrile is supplemented behind the second reactor;
introducing the reaction liquid into a third reactor, wherein the rotating speed of a stirring paddle of the third reactor is 100rpm, the reaction temperatures of the three intervals are controlled at 120 ℃, 124 ℃ and 132 ℃, and the addition amount of the sealed mineral oil of the stirrer of the third reactor is 3.76 kg;
the reaction solution continues to react in a fourth reactor, the rotating speed of a stirring paddle of the fourth reactor is 80rpm, and the reaction temperatures of three intervals are respectively controlled at 138 ℃, 150 ℃ and 137 ℃;
after the polymerization reaction is finished, the reaction materials are devolatilized, extruded and granulated to obtain the middle impact resistant ABS resin.
Specific example 2
6.6kg of 565T rubber, 16.0kg of 97B rubber, 100kg of styrene and 28.6kg of ethylbenzene are added into the liquid preparation tank, stirred and dissolved for 12 hours at normal temperature, and then 32kg of acrylonitrile and 3kg of butyl acrylate are added and stirred and dispersed for 12 hours.
Introducing the reaction liquid in the liquid preparation tank into a first reactor for graft polymerization reaction, wherein the main feeding amount of the reactor is 4.5kg/h, the rotating speed of the first reactor is 100rpm, the reaction temperatures of the three intervals are respectively controlled at 95 ℃, 96 ℃ and 98 ℃, and 0.38kg/h of chain transfer agent is added into an outlet pipeline of the first reactor;
continuously introducing the reaction liquid into a second reactor for phase transition reaction, wherein the rotating speed of the second reactor is 80rpm, the reaction temperatures of the three intervals are respectively controlled at 101 ℃, 106 ℃ and 107 ℃, and 0.045kg/h of acrylonitrile is supplemented behind the second reactor;
introducing the reaction liquid into a third reactor, wherein the rotating speed of a stirring paddle of the third reactor is 100rpm, the reaction temperatures of the three intervals are controlled at 120 ℃, 124 ℃ and 132 ℃, and the addition amount of the sealed mineral oil of the stirrer of the third reactor is 3.76 kg;
the reaction solution continues to react in a fourth reactor, the rotating speed of a stirring paddle of the fourth reactor is 80rpm, and the reaction temperatures of three intervals are respectively controlled at 138 ℃, 150 ℃ and 137 ℃;
after the polymerization reaction is finished, the reaction materials are devolatilized, extruded and granulated to obtain the middle impact resistant ABS resin.
Specific example 3
The liquid preparation tank was charged with a mixture of 565T rubber (6.9 kg), 97B rubber (13.78 kg), styrene (100 kg) and ethylbenzene (28.6 kg), and the mixture was dissolved under stirring at room temperature for 12 hours, and then, acrylonitrile (32 kg) and butyl acrylate (3.76 kg) were added and the mixture was further dispersed under stirring for 12 hours.
Introducing the reaction liquid in the liquid preparation tank into a first reactor for graft polymerization reaction, wherein the main feeding amount of the reactor is 4.5kg/h, the rotating speed of the first reactor is 100rpm, the reaction temperatures of the three intervals are respectively controlled at 95 ℃, 96 ℃ and 98 ℃, and 0.38kg/h of chain transfer agent is added into an outlet pipeline of the first reactor;
continuously introducing the reaction liquid into a second reactor for phase transition reaction, wherein the rotating speed of the second reactor is 80rpm, the reaction temperatures of the three intervals are respectively controlled at 101 ℃, 106 ℃ and 107 ℃, and 0.045kg/h of acrylonitrile is supplemented behind the second reactor;
introducing the reaction liquid into a third reactor, wherein the rotating speed of a stirring paddle of the third reactor is 100rpm, the reaction temperatures of the three intervals are controlled at 120 ℃, 124 ℃ and 132 ℃, and the addition amount of the sealed mineral oil of the stirrer of the third reactor is 3.76 kg;
the reaction solution continues to react in a fourth reactor, the rotating speed of a stirring paddle of the fourth reactor is 80rpm, and the reaction temperatures of three intervals are respectively controlled at 138 ℃, 150 ℃ and 137 ℃;
after the polymerization reaction is finished, the reaction materials are devolatilized, extruded and granulated to obtain the middle impact resistant ABS resin.
Specific example 4
6.9kg of 565T rubber, 13.78kg of 97B rubber, 100kg of styrene and 28.6kg of ethylbenzene mixture were added to the compounding tank, and stirred and dissolved for 12 hours at normal temperature, and then 32kg of acrylonitrile and 3kg of butyl acrylate were added and stirred and dispersed for 12 hours.
Introducing the reaction liquid in the liquid preparation tank into a first reactor for graft polymerization reaction, wherein the main feeding amount of the reactor is 4.5kg/h, the rotating speed of the first reactor is 100rpm, the reaction temperatures of the three intervals are respectively controlled at 95 ℃, 96 ℃ and 98 ℃, and 0.38kg/h of chain transfer agent is added into an outlet pipeline of the first reactor;
continuously introducing the reaction liquid into a second reactor for phase transition reaction, wherein the rotating speed of the second reactor is 80rpm, the reaction temperatures of the three intervals are respectively controlled at 101 ℃, 106 ℃ and 107 ℃, and 0.045kg/h of acrylonitrile is supplemented behind the second reactor;
introducing the reaction liquid into a third reactor, wherein the rotating speed of a stirring paddle of the third reactor is 100rpm, the reaction temperatures of the three intervals are controlled at 120 ℃, 124 ℃ and 132 ℃ respectively, and the addition amount of the sealed mineral oil of the stirrer of the third reactor is 5.64 kg;
the reaction solution continues to react in a fourth reactor, the rotating speed of a stirring paddle of the fourth reactor is 80rpm, and the reaction temperatures of three intervals are respectively controlled at 138 ℃, 150 ℃ and 137 ℃;
after the polymerization reaction is finished, the reaction materials are devolatilized, extruded and granulated to obtain the middle impact resistant ABS resin.
Specific example 5
6.9kg of 565T rubber, 13.78kg of 97B rubber, 100kg of styrene and 28.6kg of ethylbenzene mixture were added to the compounding tank, and stirred and dissolved for 12 hours at normal temperature, and then 32kg of acrylonitrile and 3kg of butyl acrylate were added and stirred and dispersed for 12 hours.
Introducing the reaction liquid in the liquid preparation tank into a first reactor for graft polymerization reaction, wherein the main feeding amount of the reactor is 4.5kg/h, the rotating speed of the first reactor is 100rpm, the reaction temperatures of the three intervals are respectively controlled at 95 ℃, 96 ℃ and 98 ℃, and 0.38kg/h of chain transfer agent is added into an outlet pipeline of the first reactor;
continuously introducing the reaction liquid into a second reactor for phase transition reaction, wherein the rotating speed of the second reactor is 80rpm, the reaction temperatures of the three intervals are respectively controlled at 101 ℃, 106 ℃ and 107 ℃, and 0.045kg/h of acrylonitrile is supplemented behind the second reactor;
introducing the reaction liquid into a third reactor, wherein the rotating speed of a stirring paddle of the third reactor is 100rpm, the reaction temperatures of the three intervals are controlled at 120 ℃, 124 ℃ and 132 ℃, and the addition amount of the sealed mineral oil of the stirrer of the third reactor is 3.76 kg;
the reaction solution continues to react in a fourth reactor, the rotating speed of a stirring paddle of the fourth reactor is 80rpm, and the reaction temperatures of three intervals are respectively controlled at 144 ℃, 156 ℃ and 137 ℃;
after the polymerization reaction is finished, the reaction materials are devolatilized, extruded and granulated to obtain the middle impact resistant ABS resin.
The performance of the test products was analyzed using the corresponding astm d standard as shown in table 1.
TABLE 1 analytical results of examples 1 to 6
The ABS resin products of the above examples had melt indices determined according to ASTM D1228, tensile strengths determined according to ASTM D638, impact strengths determined according to ASTM D256, flexural strengths determined according to ASTM D790, and gloss degrees determined according to GB 8807-88.
As can be seen from the above examples, the ABS resin prepared by the method of the present invention has excellent other mechanical properties while having low gloss and high flow.
It can be seen from comparison of examples 1 and 2 that the change in the rubber ratio can affect the compatibility between the continuous phase and the rubber phase, and thus the impact properties of the product, and it is found from comparison of examples 1 and 3 that the addition of a large amount of butyl acrylate can also cause the melt index of the product to decrease rapidly, and also affect the compatibility between the two phases, reducing the impact of the product; as can be seen from comparison of examples 1 and 4, increasing the amount of mineral oil added dilutes the concentration of free radicals, reduces reactivity, and decreases product impact properties; by comparing examples 1 and 5, it was found that increasing the temperature in the tenth and eleventh zones of the fourth reactor resulted in too high a degree of crosslinking and a rapid decrease in the impact properties of the product.
Claims (2)
1. A preparation process of an anti-impact bulk ABS resin is characterized by comprising the following steps:
(1) mixing the following raw materials: mixing and dissolving the cut rubber, the solvent, the acrylonitrile, the butyl acrylate and the styrene in a sol kettle until the raw glue solution is uniform and has no glue block;
(2) the dissolved crude rubber solution, the initiator, the chain transfer agent and the silicone oil are sent to four plug flow reactors connected in series by a conveying device to carry out continuous bulk polymerization reaction;
(3) devolatilizing the polymerized material, extruding and granulating to prepare the middle impact resistant ABS resin;
the rubber used in step (1) is any two of 565T and 97B, 565T and 1322, 565T and 490, 565T and N210, 700A and 720AX, or 30AF and 720 AX; the rubber content is 10-15% of the mass fraction of the base glue solution, and the butyl acrylate is 1-2% of the mass fraction of the base glue solution.
2. The process for preparing a medium impact bulk ABS resin according to claim 1, wherein the tenth and eleventh zones of the fourth plug flow reactor are each reduced in temperature by 6 ℃.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5470915A (en) * | 1993-06-28 | 1995-11-28 | Miwon Petrochemical Corporation | ABS resins having impact resistance and low-gloss properties and processes for preparing them |
| KR20050044174A (en) * | 2003-11-07 | 2005-05-12 | 주식회사 엘지화학 | Method for preparing acrylonitrile-butadiene-styrene 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 |
| CN105482045A (en) * | 2015-12-14 | 2016-04-13 | 北方华锦化学工业集团有限公司 | Method for preparing heat-resistant bulk ABS resin |
| CN111057190A (en) * | 2019-12-11 | 2020-04-24 | 北方华锦化学工业股份有限公司 | Preparation method of high-gloss bulk ABS resin |
| CN111499813A (en) * | 2020-04-09 | 2020-08-07 | 北方华锦化学工业股份有限公司 | Method for preparing high-flow AES resin by adopting continuous bulk method |
-
2021
- 2021-11-05 CN CN202111307517.1A patent/CN113980190A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5470915A (en) * | 1993-06-28 | 1995-11-28 | Miwon Petrochemical Corporation | ABS resins having impact resistance and low-gloss properties and processes for preparing them |
| KR20050044174A (en) * | 2003-11-07 | 2005-05-12 | 주식회사 엘지화학 | Method for preparing acrylonitrile-butadiene-styrene 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 |
| CN105482045A (en) * | 2015-12-14 | 2016-04-13 | 北方华锦化学工业集团有限公司 | Method for preparing heat-resistant bulk ABS resin |
| CN111057190A (en) * | 2019-12-11 | 2020-04-24 | 北方华锦化学工业股份有限公司 | Preparation method of high-gloss bulk ABS resin |
| CN111499813A (en) * | 2020-04-09 | 2020-08-07 | 北方华锦化学工业股份有限公司 | Method for preparing high-flow AES resin by adopting continuous bulk method |
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