CN100453572C - High rubber content MBS emulsion after-treatment technology - Google Patents
High rubber content MBS emulsion after-treatment technology Download PDFInfo
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- CN100453572C CN100453572C CNB2006100422812A CN200610042281A CN100453572C CN 100453572 C CN100453572 C CN 100453572C CN B2006100422812 A CNB2006100422812 A CN B2006100422812A CN 200610042281 A CN200610042281 A CN 200610042281A CN 100453572 C CN100453572 C CN 100453572C
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Abstract
The invention relates to a process of post treating MBS emulsion containing high amount of rubber. Said MBS emulsion containing high amount of rubber is emulsion polymerized to get MBS emulsion with rubber concentration being 40-80% and solid concentration being 20-60%. It is characterized in that the MBs emulsion is dried by pressure type spray dryer to get MBS resin powder. The inlet temperature of drying tower is controlled between 120- 200 Deg. C, and the pressure of transfer pump is controlled between 2.0- 5.0 Mpa. The invention is characterized by short process, high productivity, high bulk density of powder, no addition of coagulating agent, saving of a large amount of industrial desalinization water, saving complicate post treatment device, no industrial wastewater and great lowered production cost.
Description
Technical field
The present invention relates to the MBS emulsion after-treatment technology of high rubber content.
Background technology
As everyone knows, MBS resin (methyl methacrylate-butadiene-styrene terpolymer) is-kind contain " nucleocapsid " structural polymer of rubber phase, mainly be the toughening modifying that is used for polyvinyl chloride (PVC).Because it is many more that the MBS resin contains rubber phase, good more to the toughening effect of PVC, so the rubber content of general MBS resin can not be lower than 40% (mass percent, below all with).But because rubber content is high more, its second-order transition temperature is low more, is easy to generate the adhesion conglomeration in drying process more, so its aftertreatment technology is the difficult problem of puzzlement preparation MBS production of resins producer always, also is the focus of always studying.The multi-step emulsion polymerization of the most of employing of synthetic method both at home and abroad, and then process cohesion-centrifugal-exsiccant prepared MBS resin (as patent documentation: CN95110434, CN1198758, JP63135404, JP63254636 etc.) at present.The main technique flow process is: by vinylbenzene, divinyl and needed reagent and additive in polymerization, carry out the first step polymerization, obtained styrene-butadiene latex.And then add monomer and reagent and additive in polymerization such as vinylbenzene, methyl methacrylate successively, and carry out repeatedly graft polymerization, obtain the MBS emulsion of solid content 20～40% (mass percent, below all with).Add de-salted water then, flocculation agent carries out many stills and condenses continuously, goes into centrifuge dewatering and washing through overcooling is laggard again, the MBS resin after centrifugal is moisture about 25～40%, adopts conveying belt to send into gas flow tube and a sulfuration bed drying obtains the MBS rosin products.Therefore MBS resin polymerization technique flow process complexity not only, and the aftertreatment technology that is prepared into dry powder difficulty especially.Prior art exists in various degree all that technical process is long, operation easier is big, and the MBS resinous powder particles form of formation is irregular, flowing property is bad; Problem such as the wide and bulk density of size-grade distribution is little.And because of agglomeration process needs a large amount of de-salted waters, flocculation agent and dispersion agent etc.; The waste water that contains flocculation agent, dispersion agent and MBS fine-powder in a large number that is produced also will could discharge after repeatedly handling, so production cost is very high.
The content of invention
Technical problem to be solved by this invention is to improve the MBS emulsion after-treatment technology, and shortened process improves product yield and quality product, does not produce trade effluent, reduces production costs.
The MBS emulsion after-treatment technology of high rubber content of the present invention, the MBS emulsion of described high rubber content be adopt rubber quality content that emulsion polymerisation process obtains 40～80%, solid content is in the MBS of 20～60% scopes emulsion, it is characterized in that the MBS emulsion obtains the MBS toner by press spray drying tower convection drying, the temperature in of drying tower is controlled at 120～200 ℃ scope, and the pressure-controlling of transferpump is between 2.0～5.0Mpa.
The present invention does not change original MBS emulsion polymerization technique, has just changed MBS emulsion post processing mode, obtains MBS resin dry powder by simple mode.
The temperature in of press spray drying tower of the present invention is controlled at 120～200 ℃ scope.If be lower than 120 ℃, the moisture in the emulsion can fully not evaporate; When surpassing 200 ℃, can cohere on the spray-drying tower wall, form and deceive yellow point, even can catch fire and smolder because of the softening temperature that surpasses the MBS resin.Only temperature in is between 150～170 ℃.The pressure-controlling of transferpump is at 2.0～5.0Mpa.Pressure is little, and throughput is not enough; Pressure is excessive, and toner is thin, and the dust of generation is many.Can produce breakdown of emulsion when serious.The pressure of transferpump preferably is controlled at the scope of 3.0～4.0Mpa.
The present invention is fit to the high rubber content MBS emulsion that the employing emulsion polymerisation process obtains.If emulsion solid content is less than 20%, energy consumption for drying is big, and product fugitive constituent height does not reach the quality index requirement; If emulsion solid content is greater than 60%, the emulsion viscosity height is difficult to control and difficulty of transportation when dry in the building-up process.So the MBS emulsion solid content when dry is preferably between the 30-50%, rubber content is 50～70%.
The MBS resin mainly is methyl methacrylate-butadiene-styrene terpolymer; Also can be the possible vinylaromatic monomers of copolymerization, the monomeric multiple copolymer of unsaturated fatty acids alkyl esters to be arranged with above three kinds of monomers.Wherein: vinylaromatic monomers and unsaturated fatty acids alkyl esters monomer refer to: vinyl toluene, Jia Jibingxisuanyizhi, butyl methacrylate, methyl acrylate, ethyl propenoate, butyl acrylate, ethylacrylic acid methyl esters, ETHYL HEXYL ACRYLATE, butylacrylic acid methyl esters etc. many can with the monomer of above three kinds of monomer copolymerizations.
Advantage of the present invention:
The MBS emulsion of the high rubber content that polymerization is obtained directly obtains the MBS toner by press spray moisture eliminator drying.Technical process is short, the product yield height; Powder morphology is good and bulk density is high; Do not add any flocculation agent; Save a large amount of industrial de-salted waters; Saved complicated finishing apparatus; Do not produce trade effluent etc., greatly reduce production cost.
Embodiment
The present invention will be described below in conjunction with embodiment, but obviously, the present invention is not limited by embodiment.
Embodiment 1: at first a certain proportion of deionized water is joined in the pressure polymerisation still, add quantitative vinylbenzene, divinyl and needed reagent and additive in polymerization more successively, carry out the first step polymerization, under 50～70 ℃, finished, obtained styrene-butadiene latex through 8～12 hours.In styrene-butadiene latex, add monomer and needed graft polymerization auxiliary agents such as quantitative vinylbenzene, methyl methacrylate then again, still under above temperature, carry out repeatedly graft polymerization, through just obtain after 4～8 hours rubber content 60% (in mass percent, down with), the MBS emulsion of solid content 40% (in mass percent, down with).
Is this emulsion that 160 ℃, the pressure-controlling of transferpump carry out drying during at 3.0Mpa in the spray-drying tower temperature in, and the MBS toner performance that obtains sees Table 1.
Embodiment 2: polymerization process is with embodiment 1.Is this emulsion that 180 ℃, the pressure-controlling of transferpump carry out drying during at 3.0Mpa in the spray-drying tower temperature in, and the MBS toner performance that obtains sees Table 1.
Embodiment 3: polymerization process is with embodiment 1.Is this emulsion that 140 ℃, the pressure-controlling of transferpump carry out drying during at 3.5Mpa in the spray-drying tower temperature in, and the MBS toner performance that obtains sees Table 1.
Embodiment 4: polymerization process is with embodiment 1.Is this emulsion that 160 ℃, the pressure-controlling of transferpump carry out drying during at 3.5Mpa in the spray-drying tower temperature in, and the MBS toner performance that obtains sees Table 1.
Embodiment 5: polymerization process is with embodiment 1, but MBS emulsion solid content 42%.Is this emulsion that 180 ℃, the pressure-controlling of transferpump carry out drying during at 3.0Mpa in the spray-drying tower temperature in, and the MBS toner performance that obtains sees Table 1.
Embodiment 6: polymerization process is with embodiment 1.Is this emulsion that 120 ℃, the pressure-controlling of transferpump carry out drying during at 4.0Mpa in the spray-drying tower temperature in, and the MBS toner performance that obtains sees Table 1.
Embodiment 7: polymerization process is with embodiment 1.Is this emulsion that 200 ℃, the pressure-controlling of transferpump carry out drying during at 3.0Mpa in the spray-drying tower temperature in, and the MBS toner performance that obtains sees Table 1.
Comparative example 1: polymerization process is with embodiment 1.Is this emulsion that 110 ℃, the pressure-controlling of transferpump carry out drying during at 4.0Mpa in the spray-drying tower temperature in, and the MBS toner performance that obtains sees Table 1.
Comparative example 2: polymerization process is with embodiment 1.Is this emulsion that 210 ℃, the pressure-controlling of transferpump carry out drying during at 3.0Mpa in the spray-drying tower temperature in, and the MBS toner performance that obtains sees Table 1.
Comparative example 3: polymerization process is with embodiment 1.This emulsion through traditional acid cure poly--MBS toner performance that centrifugal washing-fluidised bed drying obtains sees Table 1.
Table 1: the MBS resin property that spraying drying obtains relatively
| Numbering | Outward appearance | Fugitive constituent, % | Bulk density, g/cm 3 | Size-grade distribution (40～180 order), % | Flowability, s | The salable product yield, % |
| Embodiment 1 | The white spherical particle | 0.82 | 0.45 | 96.5 | 6 | 98.8 |
| Embodiment 2 | The white spherical particle | 0.75 | 0.43 | 97.6 | 6 | 98.6 |
| Embodiment 3 | The white spherical particle | 0.96 | 0.42 | 96.3 | 7 | 97.4 |
| Embodiment 4 | The white spherical particle | 0.98 | 0.44 | 95.8 | 6 | 98.5 |
| Embodiment 5 | The white spherical particle | 0.74 | 0.42 | 96.5 | 7 | 97.7 |
| Embodiment 6 | The white spherical particle | 1.04 | 0.42 | 97.8 | 7 | 97.2 |
| Embodiment 7 | The same, a little stain and sticking wall arranged | 0.36 | 0.44 | 95.7 | 7 | 94.8 |
| Comparative example 1 | The white spherical particle | 2.45 | 0.41 | 97.8 | 9 | 95.5 |
| Comparative example 2 | The same, more stain and sticking wall arranged | 0.26 | 0.42 | 95.7 | 7 | 93.6 |
| Comparative example 3 | White random powder, dust is big | 0.45 | 0.32 | 78.8 | Do not flow | 90.8 |
Just performance is good for sheet material, film and the plate produced after MBS resin that employing the inventive method obtains and the PVC blend, and product all reaches the quality standard of national regulation, the results are shown in Table 2.
Table 2:MBS resin toughening PVC product performance relatively
| Numbering | Shock strength (KJ/cm) | Transparency (%) | Mist degree (%) |
| The product that utilizes the present invention to obtain | 7.65 | 88.4 | 5.2 |
| Domestic like product (utilizing the cohesion desiccating method) | 7.23 | 87.8 | 5.0 |
| External like product (utilizing the cohesion desiccating method) | 7.85 | 88.8 | 5.6 |
| Testing standard | GB1843-1980 | GB2410-1980 | GB2410-1980 |
Claims (3)
1, a kind of MBS emulsion after-treatment technology of high rubber content, the MBS emulsion of described high rubber content be adopt rubber quality content that emulsion polymerisation process obtains 40～80%, solid content is in the MBS of 20～60% scopes emulsion, wherein said MBS is methyl methacrylate-butadiene-styrene terpolymer, it is characterized in that the MBS emulsion obtains the MBS toner by press spray drying tower convection drying, the temperature in of drying tower is controlled at 120～200 ℃ scope, and the pressure-controlling of transferpump is between 2.0～5.0Mpa.
2, aftertreatment technology according to claim 1 is characterized in that the temperature in of drying tower is controlled at 150～170 ℃ scope, and the pressure-controlling of transferpump is between 3.0～4.0Mpa.
3, aftertreatment technology according to claim 1, the rubber quality content that it is characterized in that described MBS emulsion 50～70%, solid content is 30～50%.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100422812A CN100453572C (en) | 2006-01-24 | 2006-01-24 | High rubber content MBS emulsion after-treatment technology |
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| CNB2006100422812A CN100453572C (en) | 2006-01-24 | 2006-01-24 | High rubber content MBS emulsion after-treatment technology |
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| CN101007859A CN101007859A (en) | 2007-08-01 |
| CN100453572C true CN100453572C (en) | 2009-01-21 |
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| CN102675493B (en) * | 2012-06-11 | 2014-03-12 | 淄博东大弘方化工有限公司 | Post treatment process of MBS (methacrylate-butadiene-styrene) resin emulsion |
| CN105131307A (en) * | 2015-09-11 | 2015-12-09 | 怡维怡橡胶研究院有限公司 | Continuous preparation method for rubber masterbatch and rubber masterbatch prepared by method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034552A (en) * | 1988-01-27 | 1989-08-09 | 齐鲁石油化工公司研究院 | Divinyl, vinylbenzene, methyl methacrylate copolymer method for making |
| JP2000302814A (en) * | 1999-04-22 | 2000-10-31 | Asahi Chem Ind Co Ltd | Less impure styrene resin for use in food |
| CN1731057A (en) * | 2005-09-05 | 2006-02-08 | 吉化集团公司 | Method and apparatus for drying copolymer of methyl methacrylate-styrene-butadiene |
-
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- 2006-01-24 CN CNB2006100422812A patent/CN100453572C/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034552A (en) * | 1988-01-27 | 1989-08-09 | 齐鲁石油化工公司研究院 | Divinyl, vinylbenzene, methyl methacrylate copolymer method for making |
| JP2000302814A (en) * | 1999-04-22 | 2000-10-31 | Asahi Chem Ind Co Ltd | Less impure styrene resin for use in food |
| CN1731057A (en) * | 2005-09-05 | 2006-02-08 | 吉化集团公司 | Method and apparatus for drying copolymer of methyl methacrylate-styrene-butadiene |
Non-Patent Citations (2)
| Title |
|---|
| CN 1 034 552 A 1989.08.09 |
| CN 1 731 057 A 2006.02.08 |
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Effective date of registration: 20160525 Address after: 262600, Dongcheng Road, Dongcheng County, Shandong, Linqu (Yulin shop village) Patentee after: Weifang Donglin Chemical Co., Ltd. Address before: Zhu Taiwan Industrial Zone Linzi District 255432 Shandong city of Zibo province Shandong shuntianli Plastic Co. Ltd Patentee before: Lu Xiao Patentee before: Lu Yubin |
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Effective date of registration: 20190423 Address after: 262600 No. 3130 Panlongshan Road, Longshan High-tech Industrial Park, Linqu County, Shandong Province Patentee after: SHANDONG DONGLIN NEW MATERIALS CO., LTD. Address before: 262600 Yuqian Road, Dongcheng Street, Linqu County, Shandong Province (Yulin Dian Village) Patentee before: Weifang Donglin Chemical Co., Ltd. |