CN1028431C - Continuous process including recycle stream treatment for prodn. of high impact polystyrene - Google Patents
Continuous process including recycle stream treatment for prodn. of high impact polystyrene Download PDFInfo
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- CN1028431C CN1028431C CN 88108952 CN88108952A CN1028431C CN 1028431 C CN1028431 C CN 1028431C CN 88108952 CN88108952 CN 88108952 CN 88108952 A CN88108952 A CN 88108952A CN 1028431 C CN1028431 C CN 1028431C
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Abstract
A continuous flow process for the production of high impact polystyrene utilizing a recycle stream of volatile materials and utilizing a non-volatile antioxidant; wherein specific types of polymerization inhibiting impurities are removed from a recycle stream prior to feeding or introducing the recycle stream into a styrene polymerization zone. Preferably, the process further comprises the step of monitoring the acidity of the recycle stream and using a free radical initiator which decomposes to form only non-acid by-products.
Description
The present invention relates to produce the method for the polystyrene of high impact strength.Furtherly, the present invention relates to produce Continuous Flow method with the polystyrene that includes the dispersion rubber particle.
Known single ethylidene aromatic compounds enhanced rubber polymer, such as vinylbenzene, Alpha-Methyl benzene second is rare and the ring substituted phenylethylene, be useful to various uses.For example, the rubber that contains the cross-linked rubber discrete particles strengthens styrene polymer, resemble the polyhutadiene that is dispersed in the styrene polymer parent, can be used among a series of different application, comprise inner container of icebox, packing purposes, furniture, housed device and toy.This class rubber strengthens macromolecular material and is commonly referred to as " high impact polystyrene " or " HIPS ".
A currently known methods producing the HIPS polymkeric substance is batch process or suspension method, and polymer reaction is to carry out in single reactor in this method.An advantage of batch process be since whole polymerization process employed be a reactor, thereby the monitoring that HIPS produces is easy.Yet batch process has its defective in essence, and as low yield with increased phase stop time, this makes this method be not suitable for the purpose of lot production.
In order to overcome the defective in lot production of batch process, several continuous flow methods of HIPS have been proposed to produce.These currently known methodss have used a plurality of reactors of arranging serially, and wherein extent of polymerization improves from a reactor to next reactor.Referring to, as the United States Patent (USP) 4,567,232 of the United States Patent (USP) 4,451,612 of the United States Patent (USP) 3,243,481 of the United States Patent (USP) 3,658,946 of Bronstert etc., Ruffing etc., Wang etc. and Echte etc.
These quantity-produced patents have generally provided some devolatilization sections and circulation loop and have sent solvent and unreacted monomer back in the polymerization reaction zone a section.Yet the cycling stream that leaves the devolatilization segmentation has comprised a large amount of impurity, and residue antioxidant and antioxidant degradation production are arranged, and/or free decomposition of initiator by product, and these impurity can have the opposite effect to continuous HIPS working system when being sent back to polymerization reaction zone.In fact when cycling stream was sent back to the initial polymerization reaction section, these impurity can destroy action of free radical initiator and a considerable time is arranged, even can ad infinitum suppress the generation of polyreaction.In addition, this impurity brings unwanted physical properties can for the HIPS polymkeric substance, as fades.
Above-mentioned patent none is recognized the reason or the influence of cycling stream impurity.Similarly, these patents also none any method of the deleterious effect that overcomes the impurity in these cycling streams that need owing to the continuous flow method of producing the HIPS polymkeric substance is provided.
The present invention has overcome the defective of known continuous HIPS working system, furtherly, the invention provides a continuous flow method, in the method, the radical initiator of specific type is used to optimize polyreaction, the antioxidant of specific type is used to prevent unwanted rubber and cinnamic oxidation, and the polyreaction inhibition impurity of specific type is being removed from cycling stream with the cycling stream feeding or before introducing polymerization zone.At one preferably in the specific examples, the present invention further comprises the tart step of monitoring cycling stream.Preferably in the specific examples, used non-volatile antioxidant at another, it is volatile by product that this antioxidant does not decompose when being formed on the inventive method service temperature.In also having an embodiment, the radical initiator of use only resolves into nonacid by product.
Other purposes of the present invention and further advantage can be understood when considering in conjunction with appended accompanying drawing better, and identical number is represented corresponding parts among the figure.
Fig. 1 is the reactor used in the inventive method and the block diagram of equipment.
Fig. 2 is the block diagram of another example of reactor used in the inventive method and equipment.
Fig. 3 has shown the influence of phenylformic acid to the reaction of the styrene polymerization in the presence of radical initiator.
Fig. 4 is the thermo-gravimetric analysis figure of typical oxidation inhibitor.
Referring to Fig. 1 and Fig. 2, the series reaction device used in the enforcement of the continuous HIPS production method of the present invention and the block diagram of equipment have been represented.
With vinylbenzene, polyhutadiene, radical initiator, oxidation inhibitor, and send polymerization reactor 10 to by being identified generally as a feeding tube or several feeding tubes of 15 such as the annexing ingredient of solvent and other additives.Other positions that oxidation inhibitor can be chosen in system add.Here all terms " vinylbenzene " comprise the vinylbenzene of various replacements, as alpha-methyl styrene, such as the ring substituted phenylethylene of p-methylstyrene and right-chlorostyrene, and the vinylbenzene of non-replacement.Typically, mixture in the polymerization reactor in 10 comprises the vinylbenzene of about 75-99% weight part, the polyhutadiene of about 1-15% weight part, the radical initiator of about 0.001-0.2% weight part, the oxidation inhibitor of about 0.05-0.08% weight part, and residue, interpolation component.
Implement all equipment of the present invention and also can comprise addition polymerization device 11, this device is operated under the pre-inversion condition, that is, the external phase here is vinylbenzene-rubber solutions and discontinuous phase is a polystyrene.Before this pre-transform teactor 11 is directly placed polymerization reactor 10, like this, vinylbenzene, polyhutadiene, radical initiator, oxidation inhibitor, and other components be sent to pre-transform teactor 11, and then send the mixture in the pre-transform teactor to polymerization reactor 10.Pre-transform teactor is continuous stirred tank reactor preferably.Oxidation inhibitor is to add after pre-transform teactor preferably, and is for example in feeding tube or flow reactor, as described below.
The discharging of polymerization reactor 10 is sent into another polymerization reactor by pipeline 25, and the latter stage polymerization takes place to transform in this next polymerization reactor.Preferably, this next polymerization reactor is the line style flow reactor, such as the piston-type flow reactor, but also can be tower reactor or other well-known reactors.Fig. 1 has shown single line style flow reactor 20; Fig. 2 has shown two line style flow reactors 21 and 22; And can connect more line style flow reactor successively, and the polyreaction degree increases successively in the reactor that each joins successively, and the temperature and pressure of liquid stream is increasing gradually through the line style flow reactor.Polymerization reactor 20(21,22) discharging is preferably temperature at 155-165 ℃, is lower than 2.31kg/cm
2Carry out under the pressure (40PSI), this material is directly delivered to preheater 30 by pipeline 35 and 45 respectively, delivers to general devolatilization device 40 then, and in the devolatilization device, temperature rises to 235 ℃, and vacuum tightness is about 1333-5333Pa(10-40mmHg).Synthetic HIPS polymkeric substance is shifted out and directly delivers to general pelletizer (not drawing) or allied equipment from devolatilization device 40 by pipeline 55.The HIPS polymkeric substance that so makes has 1.55-3.17m/kg(1.9-3.9 foot/pound) beam type notched Izod impact strength trial value.5.45-10.9m/kg(80-160 that of Gardner inch/pound) falling dart test value, and 150-260kg/cm
2The tensile strength of (2600-4500 pound/per square inch).These HIPS polymkeric substance have excellent color sensation and gloss, and are suitable for many purposes.
Unreacted benzene vinyl monomer and other volatility residual compounds are left devolatilization device 40 as cycling stream, through piping 65.Be preferably condensation in condensing works 66, in jar 67, store and handle, after in cyclic processing device 50, handling again, get back in the system, as shown in Figure 1 at polymerization reactor 10 places by pipeline 75.As shown in Figure 2, except getting back to the system at polymerization reactor 10 places, also selectively get back to system by pipeline 76 or 78 at pre-transform teactor 11 or line style flow reactor 21 places respectively by managing 77.Cyclically utilizing stream contains various impurity.Major impurity in cycling stream is attributable to be present in the product that reacts between material in the cycling stream such as styrene monomer and the antioxidant, from the impurity of rubber, and in the system such as undesirable material of oxygen.Although some cycling stream impurity is harmless, be surprised to find that when cycling stream was introduced into system, some impurity had played retroaction to polymerization process or synthetic HIPS product in the cycling stream.
In continuation method of the present invention, the polymerization of styrene monomer causes by decomposing radical initiator, the free radical of initiated polymerization generally is that radical initiator resolves into one or more one-level free-radical generating, and the one-level free radical reacts initiated polymerization with styrene monomer again.
Typically, radical initiator is to send first polymerization reactor 10 to, and this device is keeping making the condition of radical initiator decomposition, although initiator also can be sent into pre-transform teactor 11 or line style flow reactor 21.Selectively select radical initiator, make it in first polymerization reactor 10, not decompose and decompose under the condition that kept in afterwards the polymerization reactor.Like this, but the styrene polymerization in polymerization reactor 10 reaction thermal initiation just.Perhaps select to make two or more freedom base initiator and usefulness, make a radical initiator in polymerization reactor 10, decompose and another radical initiator at line style flow reactor 20(21,22) in decomposition.
The decomposition that causes styrene monomer polymeric radical initiator has also produced decomposition by-products, and this by product does not participate in polyreaction.In this continuous flow method, the decomposition by-products of this radical initiator is removed from the HIPS polymkeric substance in devolatilization device 40 and is appeared in the cycling stream.
After the influence of component, find acid decomposition by product and this class initiator for reaction of radical initiator, thereby suppressed styrene polymerization in the various cycling streams on having studied cinnamic polymerization.Can be sure of these acid decomposition by products by bringing out radical initiator decomposition and/or the efficient of the radical pair radical initiator that captures spontaneous generation have the opposite effect, and this is opposite with the decomposition that causes radical initiator.Therefore, the acid decomposition by product has reduced and has caused styrene monomer polymeric free radical number effectively, has also reduced the efficient of radical initiator.
Phenylformic acid is an example with this counteractive acid decomposition by product.There is being radical initiator to exist under the situation, the understanding that suppresses styrene polymerization for the phenylformic acid in the cycling stream is tangible especially, because phenylformic acid is the decomposition by-products of uncle-butyl peroxy benzoic ether and dibenzoyl superoxide (radical initiator that the most generally uses in the continuous processing that two class HIPS produce).Phenylformic acid can also produce from the atmospheric oxidation of phenyl aldehyde, and phenyl aldehyde produces from cinnamic oxidation again.Other acidic substance may be present in the polybutadiene rubber.As everyone knows, the phosphite of phenolic antioxidant, sulfur component and replacement is added to rubber with anti-oxidation.
The example of tart radical initiator and their corresponding acid decomposition by products is listed in table 1.These examples show that peroxy free radical initiator is the class initiator useful to this method, but this acidic breakdown products of this class peroxy free radical initiator produced and need not wish effect, and this effect the present invention just will reduce.For understanding, be the aspect of an outstanding initiative of the present invention as this class acidic by-products of producing a root-cause in the HIPS product.
Table 1
Two lauroyl peroxide lauric acid
Two decoyl superoxide are sad
Two caprinoyl superoxide just-capric acid
Two-just-propionyl superoxide propionic acid
Two (3,5, the 5-trimethyl acetyl) superoxide 3,5,5 Trimethylhexanoic acid
Dibenzoyl superoxide phenylformic acid
Two (2,4 dichloro benzene formyl) peroxidase 12, the 4-dichlorobenzoic acid
Two (neighbour-toluyl) superoxide neighbour-tolyl acid
Acetyl cyclohexane sulphonyl superoxide hexanaphthene sulfonic acid
Tert-butyl peroxidation pivalate trimethylacetic acid
Tert-butyl peroxidation-2-ethylhexanoate 2 ethyl hexanoic acid
Tert-butyl peroxidation isobutyrate isopropylformic acid
Tert-butyl peroxide benzoate phenylformic acid
The free radical efficiency of initiation that all above-listed acid decomposition by products are confirmed to be styrene polymerization has disadvantageous effect.
Fig. 3 is to illustrate the benzoic unexpected deleterious effect in the styrene polymerization reaction that has radical initiator tert-butyl peroxide benzoate to exist.Benzoic this restraining effect is that the decomposition by-products of tert-butyl peroxide benzoate and dibenzoyl superoxide causes, and these initiators have been used for polymerizing styrene catalyzed reaction existing considerable time widely.Below table 2 listed the percent polymerization after inhibition time and specified time interval under different tert-butyl peroxide benzoates (TBP) and benzoic ratio, the result is illustrated among Fig. 3 with diagram.
Table 2
At 120 ℃, N
2Down, the styrene polymerization reaction that has TBP and phenylformic acid to exist
TBP: polymer yield (%) the inhibition time of acid each time (branch)
Ratio (branch)
0 10 20 30 40 50 60
1∶0 0 1.0 3.4 4.7 6.7 8.2 9.9 7.5
1∶1 0 0.84 2.4 3.9 4.9 6.6 7.5 7.0
1∶2 0 0.21 2.0 3.8 5.0 6.4 6.8 13.0
1∶4 0 0.42 2.2 4.2 4.4 7.5 8.8 11.0
Clearly illustrate that as table 2 and Fig. 3 the polymerization retardation time is at TBP: the ratio of acid be 1: 1 and 1: 0 o'clock be 1: 2 and 1: 4 o'clock less than ratio significantly.Originally, phenylformic acid helps process of inhibition (referring to the amount that forms polymkeric substance after 10 minutes) significantly.Overcome after inhibition or the retardation, polyreaction is normally carried out.Yet in being with continuous round-robin air-flow, restraining effect may be added continuously in the polymerization reactor because of new circulating current and exist always.
The minimizing of inhibition time has individual mark effect to whole continuous HIPS working system.The result of the minimizing of inhibition time must help improving radical initiator efficient, reduces the residence time in initial polymerization reaction stage and increases productive rate and need not to provide optional equipment.
The method according to this invention; the disadvantageous effect of the acid decomposition by product of radical initiator is avoided by circulating current being guided to the cyclically utilizing treater 50 that is inserted between devolatilization device 40 and the circulating current feeding tube 75, listed radical initiator in this initiator such as tert-butyl peroxide benzoate dibenzoyl superoxide and the table 1.Cyclically utilizing treater 50 comprises at least a sorbent material, and as aluminum oxide or carclazyte, this material can be removed acidic component from circulating current.The example of special sorbent material comprises aluminum oxide, a kind of U.S. atlapulgite, carbon black, silica gel and a kind of high hole high reactivity carclazyte (a kind of aluminum oxide).The size and dimension of cyclically utilizing treater is according to the actual decision of engineering of standard.Be preferably clay tower, remain on 80-120 ℃ and 1.16-1.45kg/cm
2Under the temperature and pressure of (20-25 pound/square inch).
From circulating current, remove all substantially acidic components although the circular treatment device is sure, wish very that also used sorbent material can also remove other impurity from circulating current, comprise known and unknown.What comprise that acid decomposition by product, all impurity have concurrently is extremely disadvantageous combined influence is arranged to the styrene polymerization speed of reaction with to the mean sizes of rubber particles in the synthetics HIPS polymkeric substance, and this influence increases with impurity level.
Another embodiment preferably according to the present invention, the continuous processing of producing HIPS further is included in sends the circulating current of handling back to acidity and purity that polymerisation stream is monitored the circulating current of handling before.Should monitor the acidity of the circulating current of handling and guarantee that the circular treatment device is at the acidic component that reduces effectively in the circulating current.When the circulating current of handling contains when being less than 0.08% acidic component, will consider the acidity of the circulating current that suitably control is handled.Preferably, the air-flow of processing contains and is less than 0.03% acidic component, preferably is less than 0.01%.The circular treatment device should be adjusted in use for some time or regularly or according to the result who monitors circulating current purity again.For example, the carclazyte sorbent material in the clay tower should be changed when the circulating current purity drop.
Can use the acidity of the circulating current that several monitorings handle and/or the method for purity according to the present invention, three preferably monitoring method be: washing pH test, circulation purity test, and total acid value test.
Washing pH test comprises pours the distilled water of equivalent or the recycle sample of deionized water and processing into a separating funnel; Vibrate at least 15 seconds of this separating funnel; Allow each phase layering 5 minutes in the separating funnel, emit the bottom water layer in beaker from separating funnel; Measure the pH value with general pH meter then.If the pH of water is less than 6.5, the circulating current of handling just has unacceptable peracidity composition, and the sorbent material in the circulating current treater just should be changed with the circulating current that guarantees to handle in polymerization system not to the detrimentally affect of styrene polymerization.Preferably, the pH value of water should be 6.8 to 7.0.
The existence of circulation purity test monitoring phenolic compound, this compound and peroxide reactions provide coloring matter, and this material is an effective inhibitors.This test is following to be carried out, and clay treated vinylbenzene is by carclazyte being charged into separating funnel, again vinylbenzene is charged into funnel, allow vinylbenzene and carclazyte place 5 minutes, discharge separating funnel at leisure, filtering vinylbenzene and get to remove the preparation of carclazyte particulate.For the purity test that circulates, prepared a check sample, this blank sample comprises vinylbenzene and four tert-butyl peroxidation-benzoic ethers that 40 milliliters of clay treatment are crossed, and also prepares a sample that contains 40 milliliters of cycling streams of handling and four tert-butyl peroxidation-benzoic ethers.Blank sample and sample were heated 10 minutes at 130-135 ℃ in stove, and naked eyes watch blank sample and sample still not to have yellow to determine to exist.Use the transmissivity of spectrophotometric determination sample again, the assorted wavelength of spectrophotometric is 400nm, transmissivity tailor-made 0% during no sample pipe in the instrument.Blank sample is put into spectrophotometer, and fixed transmissivity at this moment is 100%.Then, sample is put into spectrophotometer, the transmissivity of working sample.The cycling stream of the processing of cleaning is a water white, does not promptly have yellow sign, and transmissivity is greater than 95%.
The best method of the sour composition of the cycling stream that monitoring was handled is the total acid value test.The total acid value test is adapted by ASTM D974-80, may further comprise the steps: prepare titration solvent by 500 milliliters of toluene and 5 ml deionized water are added in 495 milliliters of anhydrous isopropyl alcohol, by the 1.0 right-naphtholbenzines of gram (P-naphtholbenzein) being dissolved in the right-naphtholbenzine indicating liquid of preparation in 100 milliliters the titration solvent.In order to carry out the titration of sample, with the cycling stream that 20 grams were handled, 100 milliliters titration solvent and 10 indicating liquids are as in the suitable vessel of sample solution adding such as flask.With this sample solution do not add stopper vibration until sample fully by dissolution with solvents, then at once in the temperature below 30 ℃ by dripping the 0.01NKOH alcoholic solution and vibrating to disperse KOH to come this sample solution of titration in view of needs.That titration is proceeded to become up to sample solution orange is green or green-and brown.Titrating terminal point kept for 15 seconds constant and definite according to colour-change after splashing into solution.Write down the consumption that reaches the needed 0.01NKOH alcoholic solution of terminal point.Carry out the blank titration of 100 milliliters of titration solvents and 10 indicating liquids, by dripping of the orange generation to green or edge brown colour-change of 0.01NKOH alcoholic solution up to the expression terminal point.Write down the consumption that reaches the needed 0.01NKOH alcoholic solution of blank titration terminal point.Total acid value (T), with KOH(mg)/circulation fluid (g) handled represents, pass through formula: T=((A-B) N * 56.1)/W calculates, A is the milliliter number that is used for the needed KOH solution of sample solution titration in the formula, B is the milliliter number that is used for the needed KOH solution of check sample titration, N is the equivalent concentration of KOH solution, and W is the weight of specimen in use.If total acid value is 0.08 or lower, with regard to think the circulation fluid of handling be cleaning or enough low acid content arranged.Preferably, total acid value should be lower than 0.03, is to be lower than 0.01 better.
Another aspect according to the inventive method, radical initiator, harmful effect as the acid decomposition by product of radical initiator listed in tert-butyl peroxide benzoate, dibenzoyl superoxide and the table 1 can be avoided by carefully selecting radical initiator, and the selection of radical initiator is an importance of the present invention.Suitable radical initiator does not form acidic by-products when being those decomposition.Useful radical initiator is decomposed to form harmless decomposition by-products, this by product not with radical initiator or other polymerization systems in component reaction, such as with the reaction of antioxidant or styrene monomer, suppress the styrene polymerization reaction.Because decomposition by-products is to be recycled to polymerization workshop section in the system, so decomposition by-products just must not reacted with radical initiator, just reactive to the radical initiator right and wrong, and the necessary function that does not have as the chain terminator of styrene polymerization reaction.
The example of useful in the method radical initiator comprises: such as 2,2 '-azo-compound of azo-two-different-butyronitrile and 2,2 ' azo-two (2, the 4-methyl pentane nitrile); Such as the peralcohol of peroxy carbonates, peroxy carbonates has two (just-propyl group) peroxide two carbonic ethers, two (second month in a season-butyl) peroxide, two carbonic ethers, two (2-ethylhexyl) peroxide, two carbonic ethers; Such as dicumyl peroxide, 2,5-dimethyl-2,5-two (tert-butyl peroxy) hexane, tert-butyl dicumyl peroxide ,-two-(tert-butyl peroxy) diisopropyl benzene, two-tert-butyl superoxide, 2,5-dimethyl-2, the dialkyl peroxide of 5-two (tert-butyl peroxidation) hexin-3; Such as 2,5-two hydroperoxies-2,5-dimethylhexane, Cumene Hydroperoxide 80, tert-butyl hydroperoxide, the hydroperoxide of uncle-amyl group hydroperoxide; Such as just-butyl-4, two (tert-butyl peroxy) valerates of 4-, 1,1-two (tert-butyl peroxy)-3,3, the 5-trimethyl-cyclohexane, 1,1-two (tert-butyl peroxy) hexanaphthene, 1,1-two (uncle-amyl peroxy base) hexanaphthene, 2,2-two (tert-butyl peroxy) butane, ethyl-3, the peroxy ketal of 3-two (tert-butyl peroxy) butyric ester.In these radical initiators, the peroxy ketal compound is preferably, ethyl-3 particularly, 3-two (tert-butyl peroxy) butyric ester and 1,1-two (tert-butyl peroxy) hexanaphthene.
Certainly, the also usefulness of special radical initiator or multiple initiator will be decided by the scope of processing parameter of the presently claimed invention, and these processing parameters have polymerization rate, the polymerization degree, temperature of reactor, grafting degree and similar parameters.The amount of used radical initiator is 10 to 2000ppm, is preferably 50 to 600ppm, depends on the total amount of the polymeric system in first polymerization reactor.
Also find the reaction of volatility oxidation inhibitor and oxidation inhibitor decomposition by-products and radical polymerization initiator, thereby suppressed cinnamic polymerization.Can be sure of that these volatility oxidation inhibitor and decomposition by-products have adverse influence by the function of catching the radical pair radical initiator that is produced by the radical initiator decomposition.
Butylated hydroxytoluene (BHT) is an example with volatility oxidation inhibitor of this deleterious effect, the styrene polymerization reaction that BHT in the understanding circulation fluid will be suppressed under the radical initiator existence is a particularly important, because BHT produces the most frequently used oxidation inhibitor among the HIPS in continuous processing.
The method according to this invention is avoided by careful selection oxidation inhibitor such as the deleterious effect of the volatility oxidation inhibitor of BHT.The suitable oxidation inhibitor employed temperature and pressures that are those in producing the HIPS continuous processing comprise that under the temperature of devolatilization device be nonvolatile oxidation inhibitor.Useful oxidation inhibitor and their decomposition by-products are nonvolatile, and therefore can remove from the system of band HIPS product.Non-volatile oxidation inhibitor and by product can not become the part in the circulating fluid, have avoided the unwanted oxidation inhibitor in the polymeric system.Because oxidation inhibitor and by product can not got back in the polymerization reactor with cycling stream, remaining oxidation inhibitor and by product just can not and make it deactivation with the radical initiator reaction, also do not have the function as the chain terminator that makes the styrene polymerization reaction.
Special non-volatile oxidation inhibitor will be by desired processing parameter decision, and processing parameter has polymerization rate, the polymerization degree, temperature of reactor, graft(ing) degree and similar parameters.The amount of used non-volatile antioxidant is 0.05 to 0.15% weight part, depends on the total amount of polymeric system.Oxidation inhibitor must be at 1333-5333Pa(10-40mmHg) under, under 235 ℃ temperature, be nonvolatile at least.
For the person skilled in art, it is evident that the volatility of chemical substance is to measure its distillation under given temperature and pressure or the ability of evaporation.Usually, high polarity, high-molecular weight compounds are in higher temperature volatilization.For example, BHT, molecular weight are 220, and fusing point is 69-70 ℃, and its vapour pressure of 300 ℃ is about 8000Pa(60mmHg), 350 ℃ vapour pressure is about 74,660Pa(560mmHg); And octadecyl-3,5-two-tert-butyl-4-hydroxyl-hydrogenated cinnamate, molecular weight is 531, fusing point is 49-54 ℃, its vapour pressure of 250 ℃ is 533Pa(4mmHg), 300 ℃ evaporation is pressed and is 4000Pa(30mmHg).
Be known that for the person skilled in art, the weight loss of measuring oxidation inhibitor is to determine as the amount that is retained in the oxidation inhibitor in the final product of the function of temperature and pressure as shown in Figure 4, this method is by measuring the sample retention rate when raising with temperature, heating rate is 10 ℃ of per minutes, N under normal atmosphere
NIn.Among Fig. 4, curve 80 is represented BHT, and curve 81 represents 2,2 '-methylene radical-two-(4-methyl-6-tert-butylphenol) is (MBMBP), curve 82 is represented octadecyl-1,5-two-tert-butyl-4-hydroxyl-hydrogenated cinnamate, and curve 83 represents 2,4-pair-(just-the sulfo-octyl group)-6-(4-hydroxyl-3,5-two-uncle-butylbenzene amido)-1,3,5-triazines, curve 84 is represented four-two (methylene radical-3-(3,5-two-uncle-hydroxy phenyl propionic acid)-methane.
In the embodiment of this invention, volatility can be measured according to weight loss in the same manner.Oxidation inhibitor weight loss is less than 1.0%, better less than 0.1%, 9.8 * 10 preferably
4Pa(1 normal atmosphere) N
2In, under 250 ℃, record.Technological temperature and pressure are depended in selection for oxidation inhibitor that give to implement usefulness, and other are such as the factor that could buy on color, solubleness, price and the market etc.This field has many commercially available compounds to can be used as oxidation inhibitor, for example, and referring to " can supply oxidation inhibitor and antiozonidate catalogue " of Goodyear Chemicals, 1982 third editions.This field those skilled in the art just can disclosed basis in front on, need not too many experiment according to volatility parameter discussed above and just can from known oxidation inhibitor, select the oxidation inhibitor of wanting.
The example of useful non-volatile oxidation inhibitor comprises in the inventive method, octadecyl-3,5-two-tert-butyl-4-hydroxyl-hydrogenated cinnamate; 2.4-two (just-the sulfo-octyl group)-6-(4-hydroxyl-3,5-two-uncle-butylbenzene amido)-1,3,5-triazines; And triglycol-two (3-(3 '-tert-butyl-4 '-hydroxyl-5 '-aminomethyl phenyl) propionic ester.
Although the present invention is described with relevant example at this, concerning these those skilled in the art, it is evident that and under the condition that does not break away from spirit of the present invention or appended claim scope, to carry out various changes and improvements.
Claims (33)
1, produce the continuation method of high impact polystyrene, it is characterized in that comprising:
Polymerization comprises the mixture of at least a vinyl aromatic monomers, rubber and non-volatile oxidation inhibitor at least one polymerizer;
Send described mixture in the preheater described mixture of heating, produce warmed-up mixture;
Send described warmed-up mixture to the devolatilization device from the mixture of described heating, to remove volatile constituent, produce high impact polystyrene thus; And
Volatile constituent is sent in described at least one polymerization reactor as cycling stream;
Non-volatile oxidation inhibitor described here shows for 250 ℃ N through selecting
2In, 1 atmospheric weight loss is less than 1.0%.
2, by the described method of claim 1, it is characterized in that described weight loss is less than 0.1%.
3, by the described method of claim 1, it is characterized in that further comprising the following steps:
Described vinyl aromatic monomers of polymerization and rubber are to more than the point of inversion of described mixture in first step polymerization reactor; And
Before sending described mixture to described preheater, described mixture is sent at least one secondary polymerization reaction device with the described mixture of further polymerization.
4,, it is characterized in that described one-level polymerization reactor is individual stirred tank continuously by the described method of claim 3.
5,, it is characterized in that described secondary polymerization reaction device is a line style flow reactor by the described method of claim 4.
6,, it is characterized in that further being included in described preheater before the described mixture of heating the step of described mixture being sent at least one additional line style flow reactor by the described method of claim 5.
7, by the described method of claim 1, it is characterized in that described non-volatile oxidation inhibitor comprises 2 at least one is selected from, 4-pair (just-the sulfo-octyl group)-6-(4-hydroxyl-3,5-two-uncle-butylaniline)-1,3,5-triazine and glycol-two (3-(3 '-tert-butyl-4 '-hydroxyl-5 '-one group of oxidation inhibitor of (aminomethyl phenyl) propionic ester.
8, by the described method of claim 1, it is characterized in that described non-waving property oxidation inhibitor comprises octadecyl-3,5-two-tert-butyl-4-hydroxyl oxidize laurate.
9, produce the continuation method of high impact polystyrene, it is characterized in that:
Send at least one vinyl aromatic monomers, rubber and non-volatile oxidation inhibitor to the one-level continuous stirred tank reactor to form the one-level mixture;
The described one-level mixture of polymerization is to the degree of the point of inversion that is lower than the one-level mixture in described one-level continuous stirred tank reactor;
Send described one-level mixture to the secondary continuous stirred tank reactor;
The described one-level mixture of polymerization is to the degree of the point of inversion that is higher than described one-level mixture in described secondary continuously stirring jar reactor;
Send described one-level mixture to one group and have at least in two line style flow reactors with the described one-level mixture of further polymerization, produce two-stage mixture, the polymerization degree of wherein said one-level mixture progressively increases in described line style flow reactor;
Send described two-stage mixture to preheater and heat described two-stage mixture, produce the mixture of heating;
The mixture of described heating is sent in the devolatilization device to remove volatile constituent from the mixture of described heating, produced high impact polystyrene thus; And
Described volatile constituent is sent at least one described reactor as cycling stream;
Wherein said non-volatile oxidation inhibitor demonstrates at 250 ℃ N through selecting
2In, the weight loss under 1 normal atmosphere is less than 0.1%.
10, produce the continuation method of high impact polystyrene, it is characterized in that,
The mixture of at least a vinyl aromatic monomers of polymerization and rubber in polymerization reactor, described polyreaction is caused by radical initiator, and what this decomposition of initiator formed at least one induced free radical really is non-acid degradation production also;
Send described mixture to preheater to heat described mixture, produce the mixture of heating;
Send the mixture of described heating to the devolatilization device from the mixture of described heating, to remove the volatile constituent of the nonacid decomposition by-products that contains described radical initiator, produce high impact polystyrene thus; And with
Described volatile constituent is sent in the described polymerization reactor as cycling stream;
Wherein in the cycling stream nonacid decomposition by-products be incorporated in the polymerization reactor not can ethene suppressing base aromatic monomer polymerization, and
The secondary biological polymerization of not reacting ethene suppressing base aromatic monomer of wherein nonacid decomposition with radical initiator;
11, by the described method of claim 10, it is characterized in that further comprising the following steps:
The mixture of described vinyl aromatic monomers of polymerization and rubber is to the degree that is higher than more than the described mixture point of inversion in the one-level polymerization reactor;
Before sending described mixture to described preheater, send described mixture at least one secondary polymerization reaction device with the described mixture of further polymerization.
12, by the described method of claim 11, it is characterized in that wherein said one-level polymerization reactor is a continuous stirred tank reactor.
13, by the described method of claim 12, it is characterized in that wherein said secondary polymerization reaction device is the line style flow reactor.
14,, it is characterized in that further being included in the described preheater and before the described compound of heating described mixture is sent at least one additional line style flow reactor by the described method of claim 13.
15, by the described method of claim 10, it is characterized in that described radical initiator is added in the described mixture with 10-2000ppm according to the total amount of described mixture.
16, by the described method of claim 15, it is characterized in that described amount is 50-600ppm according to described mixture total content.
17, by the described method of claim 10, it is characterized in that wherein said radical initiator is an azo-compound.
18, by the described method of claim 17, it is characterized in that described azo-compound contain 2,2 at least one is selected from '-azo-two-isopropyl cyanide and 2,2 '-one group of azo-compound of azo-two-(2, the 4-methyl pentane nitrile).
19, by the described method of claim 10, it is characterized in that described radical initiator is a superoxide.
20, by the described method of claim 19, it is characterized in that described superoxide is that at least one is selected from the one group of superoxide that contains peroxide two carbonic ethers, dialkyl peroxide, hydroperoxide and peroxy ketal.
21,, it is characterized in that described radical initiator is that at least one is selected from and contains ethyl-3,3-two (tert-butyl peroxy) butyric ester and 1, one group of initiator of 1-two (tert-butyl peroxy) hexanaphthene by the described method of claim 10.
22, produce the continuation method of high impact polystyrene, it is characterized in that comprising:
At least a vinyl aromatic monomers, rubber and radical initiator are delivered to the one-level continuous stirred tank reactor to form the one-level mixture;
Described one-level continuous stirred tank reactor is remained on the temperature that described radical initiator decomposes, and described radical initiator is decomposed to form at least one and causes free radical and non-acid decomposition by-products;
The described one-level mixture of polymerization is to the degree of the point of inversion that is lower than the one-level mixture in described one-level continuous stirred tank reactor, and described polyreaction is reacted by described induced free radical and described vinyl aromatic monomers and caused;
Send described one-level mixture to the secondary continuous stirred tank reactor;
In described secondary continuous stirred tank reactor the described one-level mixture of polymerization to the degree of the point of inversion that is higher than the one-level mixture to produce two-stage mixture;
Send described two-stage mixture to one group and have in two line style flow reactors further the described two-stage mixture of polymerization at least and produce three grades of mixtures, the polymerization degree of wherein said two-stage mixture increases in described each line style flow reactor gradually;
Send described three grades of mixtures to preheater, heat described three grades of mixtures and produce the mixture of heating;
Send described heated mixt to the devolatilization device from the mixture of described heating, to remove the volatile constituent of the nonacid decomposition by-products that comprises radical initiator, produce high impact polystyrene thus; And
Send described volatile constituent to described one-level continuous stirred tank reactor as cycling stream;
Wherein the described nonacid decomposition by-products in the cycling stream is introduced the polymerization that described one-level continuous stirred tank reactor does not suppress described vinyl aromatic monomers; And
Wherein said nonacid decomposition by-products and described radical initiator react the monomeric polymerization that does not suppress described vinyl aromatic in described one-level continuous stirred tank reactor.
23, produce the continuation method of high impact polystyrene, it is characterized in that comprising:
The mixture that at least a vinyl aromatic monomers of polymerization and rubber in the presence of the radical initiator are arranged at least one polymerization reactor;
Send described mixture to preheater and heat described mixture, produce the mixture of heating thus;
The mixture of described heating is sent in the mixture of devolatilization device and described heating and removed volatile constituent, produce high impact polystyrene thus;
Send described volatile constituent to the cyclically utilizing treater as cycling stream;
The inhibition impurity of removing initiator in described cyclically utilizing treater from described cycling stream contains the cycling stream of processing of the acidic component by product of the described radical initiator that is less than 0.08% weight part with generation;
Send the cycling stream of described processing to described polymerization reactor.
24, by the described method of claim 23, the cycling stream that it is characterized in that described processing contains and is less than 40% all dirt.
25,, it is characterized in that further comprising the acid content of the cycling stream of monitoring described processing by the described method of claim 24.
26,, it is characterized in that the content of the acid of the cycling stream wherein handled is monitored with acid value test by the described method of claim 25.
27,, it is characterized in that described cycling stream is what to be remained on less than 0.08 acid number by the described method of claim 26.
28,, it is characterized in that described cycling stream is what to be remained on less than 0.03 acid number by the described method of claim 26.
29,, it is characterized in that described cycling stream is what to be remained on less than 0.01 acid number by the described method of claim 26.
30,, it is characterized in that described cycling stream contains and be less than 0.03% described acidic components by product by the described method of claim 23.
31,, it is characterized in that described cycling stream contains and be less than 0.01% described acidic components by product by the described method of claim 23.
32, produce the continuous processing of high impact polystyrene, it is characterized in that comprising:
Send at least a vinyl aromatic monomers, rubber and radical initiator to the one-level continuous stirred tank reactor to form the one-level mixture;
The described one-level mixture of polymerization is to the degree of the point of inversion that is lower than the one-level mixture in described one-level continuous stirred tank reactor;
Send described one-level mixture to the secondary continuous stirred tank reactor;
The described one-level mixture of polymerization produces two-stage mixture to the degree of the point of inversion that is higher than the one-level mixture in described secondary continuous stirred tank reactor;
Send described two-stage mixture at least one line style flow reactor with the described two-stage mixture of further polymerization and produce three grades of mixtures, improve gradually in the polymerization degree of the two-stage mixture described in each described line style flow reactor.
Send described three grades of mixtures to preheater to heat described three grades of mixtures and to produce the mixture of heating;
Send the mixture of described heating to the devolatilization device from the mixture of described heating, to remove volatiles, produce the poly styrene polymer of high impact strength thus;
Send described volatile constituent to the cyclically utilizing treater as cycling stream;
In described cyclically utilizing treater, the inhibition impurity of initiator is removed the cycling stream that contains the processing of the acidic components that are less than 0.08% weight part with generation from described cycling stream, and
The cycling stream of described processing is sent at least one described reactor.
33, by the described method of claim 32, it is characterized in that described at least one line style flow reactor comprises one group at least two line style flow reactors.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/137,743 US4857587A (en) | 1987-12-24 | 1987-12-24 | Continuous process including recycle stream treatment for the production of high impact polystyrene |
| US137,889 | 1987-12-24 | ||
| US138,089 | 1987-12-24 | ||
| US137,743 | 1987-12-24 | ||
| US07/138,089 US4861827A (en) | 1987-12-24 | 1987-12-24 | Continuous process for the production of high impact polystyrene using non-acid forming initiators |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1036211A CN1036211A (en) | 1989-10-11 |
| CN1028431C true CN1028431C (en) | 1995-05-17 |
Family
ID=26835538
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88108952 Expired - Lifetime CN1028431C (en) | 1987-12-24 | 1988-12-24 | Continuous process including recycle stream treatment for prodn. of high impact polystyrene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1028431C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108473739A (en) * | 2015-10-30 | 2018-08-31 | 弗纳技术股份有限公司 | Control the crosslinked alternative in high impact polystyrene |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9096698B2 (en) | 2012-08-09 | 2015-08-04 | Americas Styrenics, LLC | Styrenic resin incorporating recycled polystyrene |
| US8609778B1 (en) | 2012-08-09 | 2013-12-17 | Americas Styrenics, LLC | Styrenic resin incorporating recycled polystyrene |
| CN104558429B (en) * | 2013-10-18 | 2017-11-07 | 中国石油化工股份有限公司 | Polyphenylacetylene combination production method and thus obtained polyphenylacetylene combination |
-
1988
- 1988-12-24 CN CN 88108952 patent/CN1028431C/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108473739A (en) * | 2015-10-30 | 2018-08-31 | 弗纳技术股份有限公司 | Control the crosslinked alternative in high impact polystyrene |
| CN108473739B (en) * | 2015-10-30 | 2022-01-28 | 弗纳技术股份有限公司 | Alternative method of controlling cross-linking in high impact polystyrene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1036211A (en) | 1989-10-11 |
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