CN106854261A - A kind of method that emulsion and body process integration prepare ABS resin - Google Patents
A kind of method that emulsion and body process integration prepare ABS resin Download PDFInfo
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- CN106854261A CN106854261A CN201611163511.0A CN201611163511A CN106854261A CN 106854261 A CN106854261 A CN 106854261A CN 201611163511 A CN201611163511 A CN 201611163511A CN 106854261 A CN106854261 A CN 106854261A
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- Prior art keywords
- abs resin
- latex
- emulsion
- extractant
- resin preparation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F279/02—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 on to polymers of conjugated dienes
- C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/02—Polymerisation in bulk
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
Abstract
The present invention relates to a kind of method that emulsion and body process integration prepare ABS resin.Its technological process is that the butadiene graft latex that will be prepared adds flocculating agent and cationic surfactant, the graft latex is extracted with unsaturated monomer and saturated solvent, the water phase isolated after extraction is removed by methods such as centrifugation, extruding or decantations again, the graft latex after water removal is finally carried out into polymerisation in bulk into continuous bulk device and is prepared ABS resin.The problems such as it is relatively difficult that the technique mainly solves the toughening rubber kind buying that current substance law used, and expensive, with rubber of the emulsion method for needed for substance law is provided, high-impact ABS resin has been prepared while reduction production cost.
Description
Technical field
The invention belongs to synthesis of polymer material and preparation field, it is related to synthetic resin field, is related specifically to one kind
The technique that emulsion and body process integration prepare high-impact ABS resin..
Background technology
Two kinds of main methods of current industrial production ABS resin are emulsion graft polymerization blending method and continuous bulk.
Emulsion graft polymerization blending method is to prepare rubber latex by emulsion polymerization, then the latex with it is a certain amount of
Styrene, acrylonitrile grafting polymerization, cohesion, dehydration obtain ABS grafting powders；ABS grafting powders and SAN resins under certain proportion
Blending, obtains ABS resin product.The adjustment of emulsion graft polymerization blending method technical recipe very flexibly, can produce connecing for high-glue content
Branch powder product, and rubber size size and distribution momentarily controlled, but the technological process is more long and complexity, gives birth to
High cost is produced, pollution is big, a large amount of promoter effect ABS resin heat endurances remained in product.
Continuous bulk is the newest synthetic technologys of current ABS, and the concise production process is compact, pollutes small, and ABS resin is produced
Product are pure.Continuous bulk is that toughening rubber is dissolved in styrene, acrylonitrile and solvent under certain proportion, the glue after dissolving
Under liquid uniform temperature, and graft reaction is carried out in the presence of the auxiliary agent such as initiator and molecular weight regulator, then by devolatilization, make
Grain process obtains ABS resin product.But the technique is higher for toughening rubber type requirements, price also all costly, causes
Toughening rubber purchase is relatively difficult, and the ABS resin glue content of the technique productions is relatively low, and the size of rubber size and distribution are controlled
System is more difficult, so the ABS resin product impact strength and glossiness that prepare are relatively low.
Chinese patent CN1807502A discloses a kind of side for two kinds of devices being used in combination and preparing high-performance ABS resin
Method.High-impact is prepared by the heat-resisting ABS resin for preparing emulsion method and general ABS resin blending extrusion prepared by substance law high
Heat-resisting ABS resin.The particle diameter of the heat-resisting ABS resin rubber particles that emulsion polymerization is obtained is in 0.1-2.0 μm, and polymerisation in bulk is obtained
The particle diameter of the general ABS resin rubber particles for obtaining is in 2.0-6.0 μm, when the rubber particles and the rubber granule of small particle of big particle diameter
Protonatomic mass ratio is 1:1-1:When between 25, the ABS resin for preparing is blended has excellent erosion-resisting characteristics and heat resistance.But the party
Method is to be made full use of the product of two kinds of production technologies, and respective production technology does not have any change, still exists
Respective intrinsic problem.
United States Patent (USP) US4206293, US3957912 and US3950455 also disclose it is a kind of two kinds of devices are combined make
Method with ABS resin is prepared.The method is the graft rubber latex monomer that will prepare and solvent as extractant pair
It is extracted, and mechanically mutually removes the water of separation after extraction, then the graft rubber latex after water removal is carried out into body
Polymerisation prepares ABS resin.This kind of method learns from other's strong points to offset one's weaknesses two kinds of process makes full uses, reduces the life of substance law
Producing in still thering is substantial amounts of water to remain in graft latex after extract in cost, but this kind of method, directly influence the ABS for preparing
The combination property of resin is bad.
The content of the invention
It is an object of the invention to provide a kind of method for preparing ABS resin by emulsion and body process integration.The joint
The graft rubber latex water removal that technique prepares emulsion method, then the graft latex after water removal is entered into continuous bulk device,
With rubber of the emulsion method for needed for substance law is provided, production cost is reduced.At the same time, be prepared into for polymerisation in bulk by the method
To big particle diameter (2.5 μm or so) prepolymer and small particle (0.7 μm or so) graft polymers for preparing of emulsion polymerization
Mix, such that it is able to prepare the ABS resin product of high shock resistance type.
Difficult point of the invention is the removal process of graft rubber emulsion.The present invention is made using unsaturated monomer and saturated solvent
For extractant is extracted to graft latex, the water of 60%-85% in graft emulsion can be isolated.Generally for more efficiently
The water in graft emulsion is removed, cationic surfactant is first added before extraction, because preparing rubber latex and Graft Adhesive
In the emulsion polymerization of breast, typically all positively charged cation form is added from the anion surfactant with negative electrical charge
Face activating agent can be neutralized both, form a kind of hydrophobic salt for being difficult ionization, and the hydrophobic salt preferably can be dissolved in oil phase,
So allow for the graft latex in extraction process more effectively can enter into oil phase more quickly, so as to by graft emulsion
Water separated to the full extent.Water by still containing remaining 1%-4% in graft latex after said process, the portion
Point water the process such as can be heated and condensed and be removed by graft latex in prepolymerization kettle.
Oil phase after extraction generally has certain viscosity, if the viscosity of oil phase is too high, height is needed in polymerisation in bulk
The pump of efficiency is conveyed to it, and dangerous also with raising in production process；If the viscosity of oil phase is too low, right after extraction
The separation of water phase comparatively difficulty can be separated mutually, it is necessary to introduce special device to water.The viscosity of general oil phase exists
It is suitable to be in 3000cps-100000cps, but in order to follow-up polymerisation in bulk more preferably can be carried out more successfully, typically by oil
The viscosity of phase is controlled in the range of 15000-50000cps.Consumption by increasing saturated solvent in extractant of the invention, increases
The ratio of acrylonitrile in extractant, adjusts the method such as the pH of graft emulsion system and the consumption of flocculating agent and oil phase after extraction is glued
Degree is controlled.
A kind of method that the present invention prepares ABS resin for emulsion and body process integration, with following characteristics：
The flocculating agent of 1.0-5.0wt%, stirring a period of time is added to be adjusted to system pH=3 after standing in graft latex left
The right side, adds 0.5-3.5wt% cationic surfactants, and the grafting rubbers latex after treatment is added into 30-400wt% extractions
In agent, 0.5-2h is stirred in turbine stirring groove, sufficient standing is until forming the complete oil phase of layering and water phase after stirring, if extraction
Rear oil phase is taken for grume, the water phase that the method removing from extruding is isolated, if the oil phase after extraction is the liquid of flowing,
The water phase isolated is removed from decantation or the method for centrifugation.
The grafting rubbers emulsion extracted after water removal is entered into prepolymerization kettle and the process such as is heated and is condensed and remove oil phase
The water of the 1%-4wt% of middle residual, then by this graft emulsion be sent to continuous bulk polymerization reaction unit second reactor or
In 3rd reactor polymer solution out, devolatilization, cooling, extrusion prepare high shock resistance type ABS resin.
Wherein, extractant should at least include a kind of unsaturated monomer and a kind of saturated solvent.
Wherein, unsaturated monomer generally selects the mass ratio of grafted monomers styrene and acrylonitrile, styrene and acrylonitrile
80:20-0:Between 100, and the efficiency of the content water removal higher of acrylonitrile is also higher, and general acrylonitrile accounts for unsaturated monomer
The 40%-80% of quality.
Wherein, the boiling point of saturated solvent will be between 25 DEG C -250 DEG C, and boiling point is more suitable at 35 DEG C -180 DEG C, and saturation is molten
Nitrile, hydrocarbon, halogenated hydrocarbon, low carbon number carboxylate, cyclic ethers, formamide and acetamide etc. are generally selected in agent,
In experiment to select the nitriles such as propionitrile and butyronitrile as saturated solvent, the quality of saturated solvent should be not less than extractant gross mass more
8%, it is optimal typically between 10%-40%.
The invention has the advantages that：The emulsion process and bulk process that the present invention will prepare ABS resin are combined,
The emulsion device of current stopping production is made full use of, the production cost of substance law is reduced on this basis, at the same time prepared
The ABS resin product of high shock resistance type.
Specific embodiment
The present invention is further illustrated with reference to embodiment, but not limits the claims in the present invention protection domain.
The initiator K of 0.08wt%2S4O8, the molecular weight regulator tert-dodecylmercaotan mercaptan of 0.15wt%, 10.0%
Emulsifying agent disproportionated rosin acid potassium, the potassium oleate of 8.0wt%, the potassium hydroxide of 3.0wt%, the potassium carbonate of 8.0wt%, 60-75
12h is reacted at DEG C and prepares butadiene rubber latex, the butadiene latex is condensed into 0.7 μm or so of rubber size at 35 DEG C
Afterwards, connect in the redox system of 0.05wt% isopropyl benzene hydroperoxides-ferrous sulfate/glucose at 60-80 DEG C
Branch reaction, grafted monomers styrene and acrylonitrile 6:4, finally prepare butadiene graft rubber latex.
Embodiment 1
From the above-mentioned butadiene graft rubber latexs of 100g, mass ratio is 80:20、60:40、40:60 and 20:80 propylene
, used as extractant, the quality of extractant is the 150% of monomer mass, and water rem oval is carried out after extracting at room temperature for nitrile and styrene
Calculate, as a result as shown in table 1.
The test result of table 1- embodiments 1
Embodiment 2
From the above-mentioned butadiene graft rubber latexs of 100g, mass ratio is 60:40 acrylonitrile and styrene and acetonitrile is made
Be extractant, the quality of extractant is the 150% of monomer mass, the quality of acetonitrile for extractant quality 15%, 20%,
25%, water rem oval is calculated after extracting at room temperature, as a result as shown in table 2.
The test result of table 2- embodiments 2
Embodiment 3
From the above-mentioned butadiene graft rubber latexs of 100g, acrylonitrile and styrene and acetonitrile are used as extractant, extractant
Quality account for the 150% of monomer mass, wherein the mass ratio of acrylonitrile and styrene is 60:40, acetonitrile accounts for extractant quality
20wt%, adds the cationic surfactant of 0.5wt%, 1.0wt% and 1.5wt% or the flocculating agent of 1.0wt% before extraction,
Water rem oval is calculated after extracting at room temperature, as a result as shown in table 3.
The test result of table 3- embodiments 3
Embodiment 4
From the above-mentioned butadiene graft rubber latexs of 100g, acrylonitrile and styrene and acetonitrile are used as extractant, extractant
Quality account for the 150% of monomer mass, wherein the mass ratio of acrylonitrile and styrene is 60:40, acetonitrile accounts for extractant quality
20wt%, adds the cationic surfactant of 1.0wt% and the flocculating agent of 1.0wt% before extraction, will be connect after extracting at room temperature
The prepolymerization kettle that branch latex enters 80 DEG C adds the water for removing remainder, then that this graft emulsion is sent into continuous bulk polymerization is anti-
Answer in the second reactor or the 3rd reactor of device polymer solution out, carry out polymerisation in bulk, be prepared by the process
The impact strength of ABS resin is tested, as a result as shown in table 4.
The test result of table 4- embodiments 4
Above example is only exemplary embodiment of the invention, is not used in the limitation present invention, protection scope of the present invention
It is defined by the claims.Those skilled in the art are in essence of the invention and protection domain, and what the present invention was made is various
Modification or equivalent are also within the scope of the present invention.
Claims (14)
1. a kind of method that emulsion and body process integration prepare ABS resin, it is characterised in that comprise the following steps：
Step (1)：The initiator K of 0.1-0.3wt%2S4O8, the molecular weight regulator tert-dodecylmercaotan of 0.2-0.5wt%,
The emulsifying agent disproportionated rosin acid potassium of 10-15wt%, the potassium oleate of 8-12wt%, the potassium hydroxide of 3-10wt%, 8-15wt%'s
Potassium carbonate, 60-75 DEG C of emulsion polymerisation reaction 12h prepares particle diameter in 0.08 μm or so butadiene rubber latex, conversion ratio
Can reach more than 90%；Temperature is down to 35 DEG C of rubber sizes for making butadiene latex be condensed into 0.7 μm or so；Latex after cohesion
At 60-80 DEG C isopropyl benzene hydroperoxide be oxidant, ferrous sulfate is reducing agent, and glucose is the redox for helping reducing agent
Graft reaction is carried out using continuous feeding method in system and prepares butadiene graft latex, styrene, acrylonitrile are grafted monomers,
Step (2)：The flocculating agent of 1.0-5.0wt%, stirring a period of time is added to be adjusted to system pH after standing in graft latex
=3 or so, 0.5-3.5wt% cationic surfactants are added, the grafting rubbers latex after treatment is added to 30-
In 400wt% extractants, 0.5-2h is stirred in turbine stirring groove, sufficient standing is until forming the complete oil phase of layering after stirring
With water phase, then mutually removed by the water that decantation, extruding, centrifugation or other mechanical means will be isolated.
Step (3)：The grafting rubbers emulsion extracted after water removal is entered into prepolymerization kettle and the process such as heated, condensed and circulated
The water of the 1-4wt% remained in oil phase is removed, then this graft emulsion is sent to the second anti-of continuous bulk polymerization reaction unit
In answering device or the 3rd reactor polymer solution out, devolatilization, cooling, extrusion prepare the ABS resin of high-impact.
2. ABS resin preparation method according to claim 1, it is characterised in that rubber latex selects conjugated diene rubber
The mixed rubber latex of glue latex, ter-polymer rubber latex, acrylic rubber latex and the above.
3. ABS resin preparation method according to claim 1, it is characterised in that rubber latex size controlling is in 0.25-
In 2.0 μ ms.
4. ABS resin preparation method according to claim 1, it is characterised in that flocculating agent selects inorganic salts (Al2
(SO4)3、MgSO4、CaCl2Deng), acid (H2SO4、CH3COOH etc.), polymer dielectric (PEO) or other emulsion condensation agent.
5. ABS resin preparation method according to claim 1, it is characterised in that cationic surfactant selects quaternary ammonium
Salt form and heterocyclic type (such as morpholine type, pyridine type and imidazole type) cationic surfactant.
6. ABS resin preparation method according to claim 1, it is characterised in that extractant should at least include a kind of insatiable hunger
With monomer and a kind of saturated solvent.
7. extractant according to claim 6, it is characterised in that unsaturated monomer selects grafted monomers styrene and propylene
The mass ratio of nitrile, styrene and acrylonitrile is 80:20-0:Between 100, acrylonitrile accounts for the 40%-80% of unsaturated monomer quality.
8. extractant according to claim 6, it is characterised in that the boiling point of saturated solvent is satisfied between 25 DEG C -250 DEG C
With solvent from nitrile, hydrocarbon, halogenated hydrocarbon, low carbon number carboxylate, cyclic ethers, formamide and acetamide etc..
9. extractant according to claim 8, it is characterised in that the quality of saturated solvent is not less than extractant gross mass
8%.
10. ABS resin preparation method according to claim 1, it is characterised in that extraction temperature is controlled at 20 DEG C -30 DEG C.
11. ABS resin preparation methods according to claim 1, it is characterised in that the viscosity control of oil phase exists after extraction
In 3000cps-100000cps.
12. ABS resin preparation methods according to claim 1, it is characterised in that the pre-polymerization entered before continuous bulk device
The temperature of kettle is 70 DEG C -90 DEG C.
13. ABS resin preparation methods according to claim 1, it is characterised in that in Devolatilization device add condensing unit and
Receiving device reclaims unreacted monomer and solvent and is recycled as extractant, reduces production cost.
14. ABS resin preparation methods according to claim 1, it is characterised in that continuous bulk device is tubular type laminar flow
Four reactor assembly reactors, the Izod notched impact strength of the ABS resin for preparing is between 284-336J/m.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3950455A (en) * | 1972-11-11 | 1976-04-13 | Toray Industries, Inc. | Method for graft polymerization of diene polymer |
| US3957912A (en) * | 1973-12-26 | 1976-05-18 | Monsanto Company | Method for preparation of abs type resins |
| US3981944A (en) * | 1970-12-09 | 1976-09-21 | Toray Industries, Inc. | Method for producing impact resistant thermoplastic resin by continuous bulk polymerization |
| EP0009417A2 (en) * | 1978-09-27 | 1980-04-02 | Monsanto Company | A process for dewatering a grafted rubber latex |
| US4206293A (en) * | 1978-07-14 | 1980-06-03 | Monsanto Company | Method for preparing ABS type resin |
| US4513111A (en) * | 1980-01-30 | 1985-04-23 | Mitsubishi Rayon Co., Ltd. | Process for producing impact-resistant resins |
| EP0810242A3 (en) * | 1996-05-31 | 1999-02-03 | Mitsui Chemicals, Inc. | A process of producing an ABS resin, an ABS resin, and an ABS-polycarbonate resin composition making use of the same |
| CN103342864A (en) * | 2013-07-19 | 2013-10-09 | 上海锦湖日丽塑料有限公司 | Electroplating ABS (Acrylonitrile Butadiene Styrene) resin with high binding force and preparation method thereof |
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| US3950455A (en) * | 1972-11-11 | 1976-04-13 | Toray Industries, Inc. | Method for graft polymerization of diene polymer |
| US3957912A (en) * | 1973-12-26 | 1976-05-18 | Monsanto Company | Method for preparation of abs type resins |
| US4206293A (en) * | 1978-07-14 | 1980-06-03 | Monsanto Company | Method for preparing ABS type resin |
| EP0009417A2 (en) * | 1978-09-27 | 1980-04-02 | Monsanto Company | A process for dewatering a grafted rubber latex |
| US4513111A (en) * | 1980-01-30 | 1985-04-23 | Mitsubishi Rayon Co., Ltd. | Process for producing impact-resistant resins |
| EP0810242A3 (en) * | 1996-05-31 | 1999-02-03 | Mitsui Chemicals, Inc. | A process of producing an ABS resin, an ABS resin, and an ABS-polycarbonate resin composition making use of the same |
| US20150266988A1 (en) * | 2012-09-07 | 2015-09-24 | Sumitomo Rubber Industries, Ltd. | Rubber composition for tires, tire member, and pneumatic tire |
| 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 |
| CN103342864A (en) * | 2013-07-19 | 2013-10-09 | 上海锦湖日丽塑料有限公司 | Electroplating ABS (Acrylonitrile Butadiene Styrene) resin with high binding force and preparation method thereof |
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| 潘广勤: "聚丁二烯胶乳的合成", 《兰化科技》 * |
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Effective date of registration: 20180315 Address after: 124021 Hongqi Street, Shuangtaizi District, Panjin, Liaoning Applicant after: Northern Huajin Formosan Union Chemical Corporation Address before: 124021 Hongqi Street, Shuangtaizi District, Liaoning, China, No. 482, No. Applicant before: North Hua Jin Chemical Industry Group Co., Ltd |
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Application publication date: 20170616 |