CN85101585A - Chemistry/steam stripped - Google Patents
Chemistry/steam stripped Download PDFInfo
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- CN85101585A CN85101585A CN 85101585 CN85101585A CN85101585A CN 85101585 A CN85101585 A CN 85101585A CN 85101585 CN85101585 CN 85101585 CN 85101585 A CN85101585 A CN 85101585A CN 85101585 A CN85101585 A CN 85101585A
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Abstract
Chemistry/steam stripped can remove residual monomer from the emulsion of polymkeric substance, even emulsion remains under certain pressure and temperature condition, so that make the vapor pressure of vapor pressure at room temperature less than emulsion, and constantly add free-radical initiator in treating processes.
Description
The invention relates to the residual monomer in the emulsion of polymkeric substance is reduced to minimum.
As everyone knows, emulsion polymerization systems can be used to produce many kinds of polymkeric substance, comprises elastomeric styrene butadiene polymkeric substance and acrylonitrile polymer.The method of industrial use wishes the residual monomer amount in the emulsion is reduced to minimum.From the viewpoint of environment, the invention describes and make odorous or have the monomeric exposed amount of the hydro carbons that has a strong impact on to reduce to minimum health.From economic point of view, the free monomer of saving 1 to 0.5% can be saved very big expense to factory.The existing method that reduces residual monomer in the emulsion was both time-consuming, and production efficiency is low again.And these methods have increased energy expenditure, and then have increased expense.
Wish to find a kind of reduce residual monomer content in the emulsion fast with the method for consuming little energy.Preferably wish to find a kind of method, make most of residual monomer carry out polymerization rather than attempt to remove with physical method.
Paper " Monomer Remonal from Latex " by S.M.Eng-lund, Chemical Engineering Progress, Aug1981Pg.55 discusses some problems that industry faced.In emulsion, remove remaining hydro carbons monomer and be subjected to emulsion and fresh fluid steam, be generally the restriction of the contact velocity of steam.Emulsion contacts with quite a large amount of steam like this, guarantees fully to remove monomer.This may cause many different problems as foaming, the instability effect of emulsion or emulsion degraded.
The B.F.Goodrich difference has been developed many methods, removes remaining acrylonitrile monemer from aqueous polymerization emulsion.United States Patent (USP) 4,251,412(issued Feb.17,1981), a kind of method is disclosed, add stoichiometric amine and ACN and do in order to reduce the remaining vinyl cyanide in the emulsion.U.S.P4,272,425(issued June 9,1981) a kind of method that reduces acrylonitrile content in the emulsion is disclosed, after the conversion of monomer 90%, in excessive free acid ACN, add additional catalyzer and comonomer.U.S.P. 4,278,582(issuea July 14,1981) a kind of method that reduces residual acrylonitrile content in the emulsion is disclosed, be to add ammonia, aqua ammonia, benzenethiol, H
2S or basic metal or alkaline earth metal carbonate, phosphoric acid salt and silicate.
The present invention is different with above technology, does not plan to add in emulsion other monomer.
The additive method that reduces residual monomer is intended to spray into fluid, normally steam or rare gas element, and/or under reduced pressure make emulsion pass through a device.
The invention provides and handle one or more kind monomer methods, at least monomer 80%(weight) is poly-complete, comprise and make above-mentioned emulsion to certain temperature and pressure condition, be the vapour pressure of the vapour pressure of water under the room temperature environment less than water in the emulsion, significantly do not degrade or unsettled emulsion, at least import the free radical generating agent of about 0.01 part of weight in the emulsion polymer of per 100 parts of weight, processing unit per hour, residual monomer content is not more than 0.05%(weight in emulsion).
As being used for this specification sheets, the term free radical generating agent is the keying action that self comprises a kind of free-radical initiator and/or can produce two or more pharmaceutical chemicalss of radical, as superoxide and reductive agent.If two or more pharmaceutical chemicalss is used for free radical generating agent, the consumption of reagent is with reference to total add-on of all reagent.
The present invention can use following monomer:
C
8-12Vi-ny l aromatic monomers promptly can not be substituted or can be by C
1-4Alkyl or chain triacontanol base or chlorine or bromine atom replace;
C
4-8Conjugated diene;
C
3-9Ethylenically unsaturated carboxylic acids;
C
3-9Alkene unsaturated aldehyde;
C
3-9The amide derivatives of ethylenic unsaturated acid promptly can not be substituted or can be by C in the presence of nitrogen-atoms
1-4Alkyl, alkanol or chain triacontanol base further replace;
C
3-9The C of ethylenically unsaturated carboxylic acids
1-8Alkyl or chain triacontanol ester, wherein alkyl and chain triacontanol base can be side chain or straight chain;
C
1-9The C of saturated carboxylic acid
2-8Alkenyl or chain triacontanol ester, wherein alkenyl or chain triacontanol base can be side chain or straight chain;
C
2-8Olefinically unsaturated nitriles; With vinyl or vinylidene chlorine.
Method of the present invention is suitable for the homopolymer or the multipolymer of wide region.Present method can be used for handling polyvinyl chloride emulsion, C
1-9The saturated carboxylic acid vinyl acetate is as vinyl-acetic ester and alkene terpolymer, as vinylacetic acid vinyl acetate, polystyrene, butadiene styrene polymer, promptly contain at least one other monomer's butadiene styrene polymer and contain the polymkeric substance of vinyl cyanide.
Present method is specially adapted to may be dissolved in the one or more monomers in the polymkeric substance.In these cases, proceed to handle, the residual monomer content in being dissolved in polymkeric substance is not more than the 0.05%(weight of emulsion) till.
Present method is preferably used in the emulsion of the polymkeric substance that is generated by polymeric monomer intermixture, comprising:
30-100%(weight) one or more monomers are selected from C
8-12Vi-ny l aromatic monomers, C
2-8Olefinically unsaturated nitriles or mixture;
0-60%(weight) C
4-8Conjugated diene;
0-10%(weight) one or more monomers are selected from and contain C
3-9Ethylenic unsaturated acid, C
3-9Alkene family unsaturated aldehyde, described C
3-9The amide derivatives of ethylenic unsaturated acid, and C
3-9The C of ethylenic unsaturated acid
1-8Alkyl or alkanol derivatives.
Best vi-ny l aromatic monomers comprises vinylbenzene, alpha-methyl styrene, P-vinyl toluene, chloro-styrene, bromstyrol, and Vinylstyrene.Best nitrile is a vinyl cyanide.Preferably these monomeric initial amounts are that 30 of total monomer composition arrives 100%(weight).
Best dienes is isoprene and divinyl.These monomeric amounts can be up to about 60%(weight of total monomer mixture amount).
Initial monomeric mixture can select to contain up to 10%(weight) the monomer.The monomer comprises ethylenic unsaturated acid, alkene unsaturated aldehyde, olefinic unsaturated amides.Cannot be substituted or can be by C
1-4Alkyl or chain triacontanol base and C
3-9The C of ethylenic unsaturated acid
1-8Alkyl or chain triacontanol ester replace.Suitable monomer comprises vinylformic acid, methacrylic acid, fumaric acid, methylene-succinic acid, propenal, Methylacrylaldehyde, phenylacrolein, acrylamide, Methacrylamide, N hydroxymethyl acrylamide, N-methylol-Methacrylamide, methacrylic ester, methyl methacrylic acid ester, the ethyl propylene acid esters, ethyl methacrylic acid ester, EDIA, ethylene glycol methacrylic acid ester, ethylhexyl acrylate and ethylhexyl methacrylic acid ester.
Method of the present invention is specially adapted to following monomer component, vinylbenzene, alpha-methyl styrene, P-vinyl toluene, divinyl or isoprene and one or more above-mentioned monomer.
Method of the present invention will be carried out under certain temperature and pressure condition, in case the obvious degradation of emulsion or unstable effect.At 100 ℃, the vapour pressure of water is the 760mm mercury column.From 50 to 100 ℃ of the suitable temperature and pressure scopes of method of the present invention, pressure is from 92 to 760mm mercury column.
Best temperature/pressure condition is from about 50 ℃, and the 92mm mercury column arrives about 80 ℃, the 355mm mercury column.The most best temperature/pressure condition is from about 50 ℃, and the 92mm mercury column arrives about 70 ℃, the 283mm mercury column.The thermal history that adds in the method is very important, makes emulsion that significantly unstable effect and degraded not take place.Those skilled in the art can do an emulsion little sample testing at an easy rate, are exposed under the specific temperature and pressure, surpass the given time, look at whether to have tangible degraded or unstable effect.
According to the present invention, per 100 parts of heavy polymkeric substance add the free radical generating agent of 0.01 part of weight at least in emulsion.Free radical generating agent comprises pharmaceutical chemicals or decomposes under treatment temp and generate the mixture of radical, as hydrogen peroxide, and organic azo or contain nearly two azo-compounds of 12 carbon atoms.Should carefully choose superoxide or azo or two azo raw materials, will decompose under the working conditions in control.
Suitable free radical generating agent comprises redox system, contains oxygenant such as hydrogen peroxide or organo-peroxide or contains the nearly hydroperoxide of 12 carbon atoms, mixes with reductive agent.Appropriate reductant comprises reducing sugar and acid derivative thereof, reduction-sulfurization thing such as basic metal dithionite, or transistion metal compound.
Suitable superoxide and hydroperoxide comprise hydrogen peroxide, peroxidation benzene and t-butyl hydroperoxide.
Appropriate reductant comprises iron or cobalt complex, or reducing sugar or their derivative, as mannitol or gluconate.Reductive agent can be a sulphur, and as alkali or alkaline-earth sulfate or dithionite, best reductive agent is a sodium sulfite.
The useful especially free radical generating agent that is used for styrene butadiene type emulsion is t-butyl-hydroperoxide and sodium sulfite.Preferably about 0.08 part of the amount of total free radical generating agent in the polymkeric substance of per 100 parts of weights, contains the superoxide and the metal dithionite of about equivalent in the emulsion.
In the emulsion, the polymer solids of per 100 parts of weights adds the radical initiator system of about 0.01 part of weight at least.It is economical only placing restrictions on excessive free-radical generator.The useful free radical generating agent above limiting the quantity of is about 0.20 part of weight, the emulsion polymer of per 100 parts of weights.The consumption of free radical generating agent from about 0.01 to about 0.15 part of weight, the emulsion polymer of per 100 parts of weights.The weight range of suitable free-radical generator from about 0.04 to about 0.08 part of weight, the solid polymer of per 100 parts of weights.
Method of the present invention is not used in monomeric initial polymerization reaction, and present method is applied to steam stripped tower, devolatilization subsequently usually.
Method of the present invention also can be applicable to emulsion, and about 80% monomer is transformed into after the polymkeric substance in reactor, carries out devolatilization.
Example
Following example is used for illustrating the present invention, does not limit the present invention.
Example is gone into 4 liter styrene butadiene samples of latex in device, and devolatilization, handles according to different aspect of the present invention or prior art.Sample is put into the 12 liter flasks that are immersed in thermostatic bath.Flask and vacuum pump link, the vapour pressure of control sample.By this way, sample is never seethed with excitement, boiling, backflow and vapo(u)r blasting.
The free radical generating agent that contains t-butyl hydroperoxide and sodium sulfite is joined in the system.In an example, free-radical generator adds with " small-particle " form, about 0.05 part per 100 parts monomers of add-on.Refluxing and under the vapo(u)r blasting condition, testing.Per hour increase the about add-on of free radical generating agent and be 0.5 part, under boiling, backflow and vapo(u)r blasting condition, carry out.Samples of latex is carried out periodic test to residual styrene.Then, with the percentage composition (logarithmic scale) of residual styrene to the time (hour) (linear graduation) mapping.Data provide in Fig. 1.Also made theoretical vapor distillation figure among the figure.
These figure show, method of the present invention, its efficient approximately are two times without the common steam desorb of free-radical generator. This improvement has reduced energy consumption and has significantly reduced the needed time of emulsion stripping. Also increased output.
Claims (10)
1, the treatment process of one or more monomeric emulsion, the monomer of at least 80% (weight) polymerization, present method comprises makes described emulsion reach certain temperature and pressure condition, make the vapour pressure of the vapour pressure of water in the room temperature environment less than water in the emulsion, not significantly degraded or unstable effect, in the emulsion of per hour handling, per 100 parts heavy polymkeric substance is introduced the free radical generating agent at least about 0.01 part of weight, up to residual monomer content be not more than emulsion weight 0.05% till.
2, according to the method for claim 1, described temperature is to be to 760mmHg from 50 from about 92mmHg to about 100 ℃ and pressure.
3, according to the method for claim 2: the amount of the free radical generating agent of adding from about 0.01 to the polymkeric substance of about 0.10 part of (weight) per 100 parts of weight per hour.
4, according to the method for claim 3, free radical generating agent is hydrogen peroxide or azo or two azo-compounds that contain 12 carbon atoms of as many as.
5, according to the method for claim 3, described free radical generating agent is a redox system, wherein, oxygenant is selected with containing the organic hydroperoxide that reaches 12 carbon atoms from organo-peroxide, with reductive agent be from containing reducing sugar, the acid derivative of reducing sugar, the reduction-sulfurization thing is selected in the group of transistion metal compound.
6, according to the method for claim 5, wherein, redox system is from organo-peroxide or contains and select the organic hydroperoxide of 12 carbon atoms of as many as and reductive agent is a sulfide.
7, according to the method for claim 6, wherein, oxygenant is C
1-4Alkyl peroxide or hydroperoxide and reductive agent are sodium sulfites.
8, according to the method for claim 2, described heating and pressure condition are to remain in the reflux exchanger.
9, according to the method for claim 2, described heating and pressure condition are to remain in the steam stripped device.
10, according to the method for claim 2, from following groups, select one or more monomers:
C
8-12Vi-ny l aromatic monomers cannot be substituted or can be by C
1-4Alkyl or chain triacontanol base or chlorine or bromine atom replace;
C
4-8Conjugation worker's alkene;
C
3-9Ethylenically unsaturated carboxylic acids;
C
3-9Alkene unsaturated aldehyde;
C
3-9The amide derivatives of ethylenic unsaturated acid in the presence of nitrogen-atoms, cannot be substituted or can be by C
1-4Alkyl, alkanol or chain triacontanol base replace;
C
1-8Alkyl or C
3-9The chain triacontanol ester of ethylenically unsaturated carboxylic acids, alkyl or alkanol can be side chain or straight chain;
C
2-8Alkenyl or C
1-9Saturated carboxylic acid chain triacontanol ester, alkenyl or chain triacontanol base can be side chain or straight chain;
C
2-8Olefinically unsaturated nitriles; With
Vinyl or vinylidene chlorine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85101585A CN85101585B (en) | 1985-04-01 | 1985-04-01 | Method for one or more monomer(s) containing emulsion treatment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85101585A CN85101585B (en) | 1985-04-01 | 1985-04-01 | Method for one or more monomer(s) containing emulsion treatment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85101585A true CN85101585A (en) | 1985-12-20 |
| CN85101585B CN85101585B (en) | 1987-03-25 |
Family
ID=4791919
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85101585A Expired CN85101585B (en) | 1985-04-01 | 1985-04-01 | Method for one or more monomer(s) containing emulsion treatment |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN85101585B (en) |
-
1985
- 1985-04-01 CN CN85101585A patent/CN85101585B/en not_active Expired
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| Publication number | Publication date |
|---|---|
| CN85101585B (en) | 1987-03-25 |
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