US20010005740A1 - Process for the production of vinylaromatic polymers, optionally containing an ethylenically unsaturated nitrile - Google Patents
Process for the production of vinylaromatic polymers, optionally containing an ethylenically unsaturated nitrile Download PDFInfo
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- US20010005740A1 US20010005740A1 US09/725,567 US72556700A US2001005740A1 US 20010005740 A1 US20010005740 A1 US 20010005740A1 US 72556700 A US72556700 A US 72556700A US 2001005740 A1 US2001005740 A1 US 2001005740A1
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- reactor
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- tubular reactor
- vinylaromatic
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- 229920000642 polymer Polymers 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 title claims description 16
- 150000002825 nitriles Chemical class 0.000 title claims description 6
- 239000000178 monomer Substances 0.000 claims abstract description 25
- 238000004064 recycling Methods 0.000 claims abstract description 15
- 239000011541 reaction mixture Substances 0.000 claims abstract description 14
- 238000010924 continuous production Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 22
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 8
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000006116 polymerization reaction Methods 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- -1 for instance Chemical compound 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229920000638 styrene acrylonitrile Polymers 0.000 description 5
- YSPDISPRPJFBCV-UHFFFAOYSA-N 1-phenyl-1,2,3,4-tetrahydronaphthalene Chemical compound C12=CC=CC=C2CCCC1C1=CC=CC=C1 YSPDISPRPJFBCV-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- AUHKVLIZXLBQSR-UHFFFAOYSA-N 1,2-dichloro-3-(1,2,2-trichloroethenyl)benzene Chemical compound ClC(Cl)=C(Cl)C1=CC=CC(Cl)=C1Cl AUHKVLIZXLBQSR-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- JUIBLDFFVYKUAC-UHFFFAOYSA-N [5-(2-ethylhexanoylperoxy)-2,5-dimethylhexan-2-yl] 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C(CC)CCCC JUIBLDFFVYKUAC-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000005840 aryl radicals Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- BLNWTAHYTCHDJH-UHFFFAOYSA-O hydroxy(oxo)azanium Chemical compound O[NH+]=O BLNWTAHYTCHDJH-UHFFFAOYSA-O 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1812—Tubular reactors
- B01J19/1837—Loop-type reactors
-
- 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
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
-
- 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/08—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of nitriles
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00027—Process aspects
- B01J2219/00033—Continuous processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00076—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements inside the reactor
- B01J2219/00081—Tubes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00164—Controlling or regulating processes controlling the flow
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Silicon Polymers (AREA)
Abstract
Mass-continuous process for the production of vinylaromatic polymers which comprises feeding a reaction mixture containing at least one vinylaromatic monomer to at least one tubular reactor of the PFR type and operating with a recycling ratio, referring to the recycling flow-rate/feeding flow-rate, of less than 4.
Description
- The present invention relates to a process for the production of vinylaromatic polymers, optionally containing an ethylenically unsaturated nitrile.
- More specifically, the present invention relates to a process for the production of copolymers based on α-methylstyrene and acrylonitrile (α-SAN) with a mass-continuous process.
- In mass-continuous processes for the production of vinylaromatic polymers, such as polystyrene (PS), SAN (styrene-acrylonitrile copolymers), α-SAN, two types of reactors are used: PFR (Plug Flow Reactor) or CFSTR (Continuous Flow Stirred Tank Reactor).
- PFR refers to one or more substantially cylindrical reaction containers in series, wherein the mixture of monomers enters the first reaction container with a conversion which is practically zero (<5-10%), it converts along the reactor and, if present, in the subsequent ones, and is then discharged at the desired conversion, generally 60-80%. Processes which use this type of technology are described, for example, in U.S. Pat. Nos. 2,769,804, 2,989,517 and 4,328,186 or in European patent 752,268.
- CFSTR are reactors with homogeneous mixing in which the reaction mixture composition is the same in any point of the reactor and the conversion at the outlet is equal to that inside. Processes which use this type of technology are described, for example, in U.S. Pat. Nos. 2,769,804 and 3,954,722 or in German patents 2,809,180 and 3,626,319.
- The use of PFR or CFSTR reactors in the polymerization of vinylaromatic polymers has both advantages and drawbacks. For example, the advantages of the PFR reactor can be summarized in process stability, also under gel effect conditions, the possibility of defining an optimum thermal profile, by varying the temperature along the reactor, and the possibility of using up the initiator inside the reactor, thus avoiding degradation problems of the polymer in the subsequent stripping phase of the monomers and residual solvents at a high temperature.
- The disadvantages of PFR reactors, on the other hand, essentially consist in the wide molecular weight distribution of the vinylaromatic polymer produced, the high formation of oligomers of the phenyl tetraline type, owing to the unfavorable reaction selectivity and composition heterogeneity for non-“azeotropic” SAN and α-SAN copolymers.
- The disadvantages of the PFR reactor can be overcome with the use of CFSTR reactors which allow the production of vinylaromatic polymers with a narrow molecular weight distribution, a low formation of oligomers of the phenyl tetraline type for conversions of the monomers higher than 50% and composition homogeneity for SAN and α-SAN copolymers.
- Unfortunately, CFSTR reactors also have various disadvantages which can be overcome with the use of PFR reactors. The two reactors are therefore entirely complementary to each other. Combining a CFSTR reactor and a PFR reactor in a polymerization process of vinylaromatic polymers, has proved to be not very convenient as the sum of the advantages is negatively compensated by the sum of the disadvantages.
- In this situation, to find a process for the production of vinylaromatic polymers which allows the advantages of both types of reactor to be exploited without also being subjected to the disadvantages, would prove to be of enormous industrial interest. The Applicant has succeeded in finding this process.
- The object of the present invention therefore relates to a mass-continuous process for the production of vinylaromatic polymers, which comprises feeding a reaction mixture containing at least one vinylaromatic monomer to at least one tubular reactor of the PFR type and operating with a recycling ratio, referring to recycling flow-rate/feeding flow-rate, of less than 4.
- It has been found, in fact, that the running of a PFR with a low recycling ratio also allows the advantages of CFSTR reactors to be exploited. It is therefore possible with the process of the present invention:
- i. to obtain vinylaromatic polymers having good composition homogeneity and a narrow molecular weight distribution;
- ii. to obtain complete consumption of the initiator leaving the reactor;
- iii. to handle the polymerization with extremely reduced instability and with easily control under gel effect conditions;
- iv. to reduce the formation of oligomers of the phenyl tetraline type for conversions of over 50% of the outgoing monomers;
- v. to optimize the reaction thermal profile.
- According to the process of the present invention, it is possible to obtain the desired results with a single PFR reactor having at least two thermostat-regulation zones or with several PFR in series having a recycling ratio of less than 4 from the last to the first PFR.
- Any vinylaromatic monomer can be used in the process object of the present invention. The traditional vinylaromatic monomer is styrene but other styrene monomers can be used, having one or more hydrogen atoms substituted with C1-C4 alkyl or aryl radicals, a halogen or nitro radical such as, for instance, methylstyrene, α-methylstyrene, mono-, di-, tri-, tetra-, penta-chloro styrene and the corresponding α-methylstyrenes, styrenes alkylated in the nucleus and the corresponding α-methylstyrenes such as ortho- and para-methylstyrene, ortho- and para-ethylstyrene, ortho- and para-methyl-α-methylstyrene, etc., either alone or mixed with each other and/or with styrene.
- The vinylaromatic monomer can be mixed with an ethylenically unsaturated nitrile such as acrylonitrile or methacrylonitrile, for example in quantities ranging from 5 to 60% by weight with respect to the total weight of monomers, or, as an alternative, to the ethylenically unsaturated nitrile or, in addition to this, mixed with other ethylenically unsaturated monomers in such quantities that the vinylaromatic monomer is present in a concentration of over 40% by weight.
- Examples of ethylenically unsaturated monomers are alkyl or cycloalkyl esters of acrylic or methacrylic acid in which the alkyl or cycloalkyl group respectively contain from 1 to 4 carbon atoms and from 4 to 10 carbon atoms such as methylacrylate, methylmethacrylate, ethylacrylate, ethylmethacrylate, butylmethacrylate, cyclohexylmethacrylate, etc. Other ethylenically unsaturated monomers are ethylene, propylene, maleic anhydride, etc.
- An inert solvent, which acts as diluent, is added to the mixture to be polymerized, in a quantity of not more than 20% and preferably from 5 to 15% by weight with respect to the mixture to be polymerized. Examples of suitable inert solvents are aromatic hydrocarbons, as etilbenzene ketones, esters and nitriles which are liquid at the polymerization temperature. In addition to ethylbenzene mentioned above, toluene, xylenes or their mixtures can be used as aromatic hydrocarbons. Examples of ketones are 2-butanone, methylethylketone, cyclohexanone, etc. Other examples of solvents which are particularly suitable for the present process are ethyl acetate and acetonitrile.
- The polymerization initiators are the conventional ones which are generally used in the polymerization of styrene. As an example, organic peroxides such as dibenzoyl peroxide, ter-butyl peroctoate, ter-butyl perbenzoate, di-ter-butyl peroxide, 1,1′-di-terbutyl peroxycyclohexane, 1,1′-di-terbutyl peroxy-3,3,5-trimethylcyclohexane, or azo-derivatives such as 2,2′-azobis(isobutyronitrile), 2,2′-azomethylbutyronitrile), etc., can be mentioned.
- These catalysts are added in a quantity of less than 1% by weight with respect to the monomers, generally from 0.005 to 0.5%.
- Finally, the reaction mixture can contain conventional additives which are used in the polymerization of vinylaromatic monomers such as, for example, antioxidants, stabilizers, lubricants, release agents, etc. Among these additives chain transfer agents are particularly important as it is by means of these that the molecular weight of the polymer is regulated. Examples of chain transfer agents are mercaptans containing from 4 to 18 carbon atoms such as, for example, n-butyl mercaptan, n-octyl mercaptan, ter-dodecyl mercaptan, n-dodecyl mercaptan, or terpinolene or the dimer of α-methylstyrene, etc. The transfer agents are added in a quantity ranging from 0.01 to 1.5% by weight calculated with respect to the vinylaromatic monomer.
- According to the process object of the present invention, particularly interesting results are obtained by feeding a reaction mixture containing α-methylstyrene and acrylonitrile to at least one tubular reactor of the PFR type and using a recycling ratio equal to about 3.
- The PFR reactor has a vertical tubular structure whose length is a multiple of the diameter and inside which the reaction mass is only lightly stirred. The length/diameter ratio is generally higher than 2 and preferably ranges from 3 to 10. Inside the reactor, the reaction temperature is maintained with an increasing profile as far as the outlet of the tubular structure.
- In the case of α-SAN, the polymerization reaction is preferably carried out at temperatures lower than 120° C., with residence times of less than 5 hours, to avoid a high formation of oligomers of the phenyl tetraline type which reduce the thermo-resistance properties of the end polymer. In order to respect this temperature limit and residence time, to avoid having residual initiator at the outlet of the tubular reactor, it is advisable to use polymerization initiators with halving times of less than 1 hour at 100° C. and less than 6 minutes at 120° C.
- A synthesis in a tubular reactor with a recycling ratio ranging from 2 to 3, within the solid range between inlet and outlet of the tubular reactor of 40-60%, with a temperature profile increasing from 85-100° C. at the inlet and 105-120° C. at the outlet, can be considered optimum.
- At the outlet of the tubular reactor, the reaction mixture is then subjected to conventional treatment for the recovery of the polymer produced. This treatment essentially consists in heating the mixture to a temperature of over 190° C. and removing the solvent and non-reacted monomers in an evaporator under vacuum.
- An illustrative but non-limiting example is provided hereunder for a better understanding of the present invention and for its embodiment.
- A reaction apparatus is used, consisting of:
- a container with two inlets and one outlet, equipped with an anchor stirrer, in which the mixing is carried out at a temperature of 60-70° C. between the mixture of monomers, initiator and solvent and the recycled reaction mixture coming from the tubular reactor;
- a gear pump situated at the outlet of the mixer which sends the reaction mixture to the polymerization reactor;
- a 120 liter tubular reactor with one inlet and two outlets, equipped with thermostat-regulating tubes with internal oil circulation, arranged in rows perpendicular to the axis of the reactor, and a stirrer with blades free to rotate in the space between the rows of tubes. This reactor is divided into three thermostat-regulation zones at different temperatures;
- a gear pump which sends the reaction mixture coming from the outlet of the tubular reactor to the stripping system under vacuum;
- a tube which connects an outlet of the tubular reactor with an inlet of the mixer.
- Reaction Conditions
- Composition of the feeding mixture to the mixer: solvent (cyclohexanone) 10% w/w, acrylonitrile 27% w/w, α-methylstyrene 63% w/w, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane 0.35% w/w.
- Reaction thermal profile in the tubular reactor: 1st zone (inlet) 96° C., 2nd zone (intermediate) 103° C., 3rd zone (outlet) 107° C.
- Overall residence time in the reactor (considering the mixing time zero as the conversion in the mixer is negligible) 4.3 hours.
- Recycling ratio (flow-rate of mixture leaving the tubular reactor/flow-rate of mixture of monomers and solvent in the feeding to the mixer) equal to about 3.
- Polymer content: inlet of tubular reactor 38.6% solids (due to recycling), outlet of tubular reactor 51% solids;
- Analysis of the reaction mixture at the outlet of the tubular reactor:
- oligomers 0.444% w/w, residual initiator 0.23% w/w with respect to the feeding, polymer content 51% w/w, acrylonitrile content in the polymer 30.5% w/w, molecular weight of the polymer Mw=98500 dalton.
- The same apparatus, composition of the feeding mixture and residence time as example 1, were maintained.
- Reaction thermal profile in the tubular reactor: 1st zone (inlet) 97° C., 2nd zone (intermediate) 107° C., 3rd zone (outlet) 107° C.
- Recycling ratio (flow-rate of mixture leaving the tubular reactor/flow-rate of mixture of monomers and solvent in the feeding to the mixer) 6.0.
- Polymer content: inlet of tubular reactor 42% solids, outlet of tubular reactor 49% solids;
- Analysis of the reaction mixture at the outlet of the tubular reactor:
- oligomers 0.685% w/w, residual initiator 1.9% w/w with respect to the feeding, polymer content 49% w/w, acrylonitrile content in the polymer 30.5% w/w, molecular weight of the polymer Mw=89100 dalton.
- A mixture having the same composition of feeding mixtures, with the same residence time as example 1, with a reaction temperature of 107° C., was fed in continuous, to a 2 liter mixing reactor, equipped with an anchor stirrer having two turbines and an oil-circulation thermostat-regulation jacket.
- Analysis of the reaction mixture at the outlet of the mixing reactor (CFSTR):
- oligomers 0.604% w/w, residual initiator 2.6% w/w with respect to the feeding, polymer content 47% w/w, acrylonitrile content in the polymer 30.5% w/w, molecular weight of the polymer Mw=83200 dalton.
Claims (4)
1. A mass-continuous process for the production of vinylaromatic polymers, which comprises feeding a reaction mixture containing at least one vinylaromatic monomer to at least one tubular reactor of the PFR type and operating with a recycling ratio, referring to the recycling flow-rate/feeding flow-rate, of less than 4.
2. The process according to , wherein several PFR reactors are adopted in series, having a recycling ratio of less than 4 from the last to the first PFR.
claim 1
3. The process according to or , wherein the vinylaromatic monomer is used in a mixture with an ethylenically unsaturated nitrile in quantities ranging from 5 to 60% by weight with respect to the total weight of the monomers.
claim 1
2
4. The process according to any of the previous claims, wherein the reaction mixture contains α-methylstyrene and acrylonitrile and the tubular reactor operates with a recycling ratio equal to about 3.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ITMI99A2535 | 1999-12-03 | ||
IT1999MI002535A IT1314260B1 (en) | 1999-12-03 | 1999-12-03 | PROCEDURE FOR THE PRODUCTION OF VINYLAROMATIC POLYMERS EVENTUALLY CONTAINING AN ETHYLENICALLY UNSATURATED NITRILE. |
ITMI99A002535 | 1999-12-03 |
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US20010005740A1 true US20010005740A1 (en) | 2001-06-28 |
US6348549B2 US6348549B2 (en) | 2002-02-19 |
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US09/725,567 Expired - Lifetime US6348549B2 (en) | 1999-12-03 | 2000-11-30 | Process for the production of vinylaromatic polymers, optionally containing an ethylenically unsaturated nitrile |
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US (1) | US6348549B2 (en) |
EP (1) | EP1106631B1 (en) |
JP (1) | JP5058407B2 (en) |
AR (1) | AR026686A1 (en) |
BR (1) | BR0005682B1 (en) |
CA (1) | CA2326907C (en) |
CZ (1) | CZ300316B6 (en) |
ES (1) | ES2433009T3 (en) |
HR (1) | HRP20000828B1 (en) |
HU (1) | HU222655B1 (en) |
IT (1) | IT1314260B1 (en) |
NO (1) | NO337551B1 (en) |
PL (1) | PL204237B1 (en) |
RU (1) | RU2209214C2 (en) |
TR (1) | TR200003585A3 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102050928B (en) * | 2009-10-30 | 2012-07-18 | 中国石油天然气股份有限公司 | Method for synthesizing continuous body of inflaming retarding ABS (Acrylonitrile Butadiene Styrene) |
CN113583186A (en) * | 2021-09-09 | 2021-11-02 | 科元控股集团有限公司 | Production method of continuous bulk ABS resin |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5996117B2 (en) * | 2012-09-26 | 2016-09-21 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | Method for producing polymer |
WO2016045020A1 (en) * | 2014-09-24 | 2016-03-31 | 中国纺织科学研究院 | Exchange reaction system, modified polyester production system comprising same, modified polyester production method and modified polyester fibre product |
TR201900627A2 (en) * | 2019-01-15 | 2020-08-21 | Aksa Akrilik Kimya Sanayii Anonim Sirketi | A REACTOR SYSTEM TO PRODUCE A MODACRYLIC POLYMER AND RELATED POLYMER PRODUCTION METHOD |
IT202100017519A1 (en) * | 2021-07-02 | 2023-01-02 | Versalis Spa | PROCEDURE FOR THE PREPARATION OF VINYL AROMATIC POLYMERS. |
Family Cites Families (14)
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NL7700412A (en) * | 1977-01-15 | 1978-07-18 | Synres Internationaal Nv | CONTINUOUS PREPARATION OF POLYMERS IN THE MASS. |
DE2724360B2 (en) * | 1977-05-28 | 1981-03-12 | Bayer Ag, 5090 Leverkusen | Process for the production of thermoplastic molding compositions based on vinyl polymers |
EP0254304B1 (en) * | 1986-07-25 | 1994-09-21 | Dainippon Ink And Chemicals, Inc. | Process for producing high impact styrene resin by continuous bulk polymerization |
JPH0725857B2 (en) * | 1986-07-31 | 1995-03-22 | 大日本インキ化学工業株式会社 | Continuous bulk polymerization of impact-resistant styrenic resin |
JPH07116262B2 (en) * | 1987-01-20 | 1995-12-13 | 三井東圧化学株式会社 | Method for producing α-methylstyrene copolymer |
JP2560342B2 (en) * | 1987-09-11 | 1996-12-04 | 大日本インキ化学工業株式会社 | Continuous bulk polymerization of styrene resin |
DE68925874T2 (en) * | 1988-12-12 | 1996-08-29 | Dainippon Ink & Chemicals | Continuous bulk polymerization process for the production of styrene polymers |
IT1230085B (en) * | 1989-05-24 | 1991-10-05 | Montedipe Spa | PROCESS FOR THE MASS AND CONTINUOUS PRODUCTION OF (CO) AROMATIC SHOCKPROOF VINYL POLYMERS. |
US5256732A (en) * | 1990-08-13 | 1993-10-26 | Dainippon Ink And Chemicals, Inc. | Method for the continuous bulk polymerization for impact resistant styrene resin |
JP2636970B2 (en) * | 1991-02-27 | 1997-08-06 | 出光石油化学株式会社 | Method for producing styrenic polymer |
DE19618678A1 (en) * | 1996-05-09 | 1997-11-13 | Basf Ag | Process for the production of polystyrene by continuous anionic polymerization |
IT1284599B1 (en) * | 1996-09-27 | 1998-05-21 | Enichem Spa | PROCEDURE FOR THE PREPARATION OF RUBBER REINFORCED VINYLAROMATIC POLYMERS |
ITMI981156A1 (en) | 1998-05-26 | 1999-11-26 | Enichem Spa | POLYMERIC COMPOSITIONS |
WO1999062976A1 (en) * | 1998-06-04 | 1999-12-09 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for the preparation of rubber-reinforced styrene resin |
-
1999
- 1999-12-03 IT IT1999MI002535A patent/IT1314260B1/en active
-
2000
- 2000-11-21 CA CA2326907A patent/CA2326907C/en not_active Expired - Lifetime
- 2000-11-28 ES ES00204226T patent/ES2433009T3/en not_active Expired - Lifetime
- 2000-11-28 EP EP00204226.5A patent/EP1106631B1/en not_active Expired - Lifetime
- 2000-11-28 PL PL344149A patent/PL204237B1/en unknown
- 2000-11-30 JP JP2000364891A patent/JP5058407B2/en not_active Expired - Lifetime
- 2000-11-30 RU RU2000129874/04A patent/RU2209214C2/en active
- 2000-11-30 HR HRP20000828AA patent/HRP20000828B1/en not_active IP Right Cessation
- 2000-11-30 CZ CZ20004452A patent/CZ300316B6/en not_active IP Right Cessation
- 2000-11-30 US US09/725,567 patent/US6348549B2/en not_active Expired - Lifetime
- 2000-12-01 HU HU0004781A patent/HU222655B1/en active IP Right Grant
- 2000-12-01 TR TR2000/03585A patent/TR200003585A3/en unknown
- 2000-12-01 AR ARP000106350A patent/AR026686A1/en active IP Right Grant
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102050928B (en) * | 2009-10-30 | 2012-07-18 | 中国石油天然气股份有限公司 | Method for synthesizing continuous body of inflaming retarding ABS (Acrylonitrile Butadiene Styrene) |
CN113583186A (en) * | 2021-09-09 | 2021-11-02 | 科元控股集团有限公司 | Production method of continuous bulk ABS resin |
Also Published As
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HRP20000828B1 (en) | 2014-03-14 |
RU2209214C2 (en) | 2003-07-27 |
JP2001192403A (en) | 2001-07-17 |
NO20006132D0 (en) | 2000-12-01 |
HRP20000828A2 (en) | 2001-06-30 |
JP5058407B2 (en) | 2012-10-24 |
EP1106631B1 (en) | 2013-08-21 |
HUP0004781A3 (en) | 2002-03-28 |
ITMI992535A1 (en) | 2001-06-03 |
IT1314260B1 (en) | 2002-12-06 |
US6348549B2 (en) | 2002-02-19 |
HUP0004781A2 (en) | 2001-07-30 |
HU222655B1 (en) | 2003-09-29 |
CZ20004452A3 (en) | 2001-07-11 |
BR0005682B1 (en) | 2010-12-28 |
NO337551B1 (en) | 2016-05-09 |
PL344149A1 (en) | 2001-06-04 |
BR0005682A (en) | 2001-07-31 |
TR200003585A2 (en) | 2001-09-21 |
EP1106631A1 (en) | 2001-06-13 |
TR200003585A3 (en) | 2001-09-21 |
ITMI992535A0 (en) | 1999-12-03 |
PL204237B1 (en) | 2009-12-31 |
NO20006132L (en) | 2001-06-05 |
CA2326907A1 (en) | 2001-06-03 |
HU0004781D0 (en) | 2001-02-28 |
CZ300316B6 (en) | 2009-04-15 |
AR026686A1 (en) | 2003-02-19 |
ES2433009T3 (en) | 2013-12-05 |
CA2326907C (en) | 2010-04-27 |
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