EP0000166A1 - Internally coated reaction vessel for use in olefinic polymerization - Google Patents
Internally coated reaction vessel for use in olefinic polymerization Download PDFInfo
- Publication number
- EP0000166A1 EP0000166A1 EP78100189A EP78100189A EP0000166A1 EP 0000166 A1 EP0000166 A1 EP 0000166A1 EP 78100189 A EP78100189 A EP 78100189A EP 78100189 A EP78100189 A EP 78100189A EP 0000166 A1 EP0000166 A1 EP 0000166A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- dye
- reactor
- water
- polymerization
- reaction vessel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 title abstract description 16
- 238000000576 coating method Methods 0.000 claims abstract description 32
- 239000011248 coating agent Substances 0.000 claims abstract description 31
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- -1 vinyl halides Chemical class 0.000 claims abstract description 10
- 239000000975 dye Substances 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 5
- MPVDXIMFBOLMNW-ISLYRVAYSA-N 7-hydroxy-8-[(E)-phenyldiazenyl]naphthalene-1,3-disulfonic acid Chemical group OC1=CC=C2C=C(S(O)(=O)=O)C=C(S(O)(=O)=O)C2=C1\N=N\C1=CC=CC=C1 MPVDXIMFBOLMNW-ISLYRVAYSA-N 0.000 claims description 2
- 229910006069 SO3H Inorganic materials 0.000 claims description 2
- 150000001251 acridines Chemical class 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical group Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 claims description 2
- CTIQLGJVGNGFEW-UHFFFAOYSA-L naphthol yellow S Chemical group [Na+].[Na+].C1=C(S([O-])(=O)=O)C=C2C([O-])=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 CTIQLGJVGNGFEW-UHFFFAOYSA-L 0.000 claims description 2
- 150000004893 oxazines Chemical class 0.000 claims description 2
- MPCYPRXRVWZKGF-UHFFFAOYSA-J tetrasodium 5-amino-3-[[4-[4-[(8-amino-1-hydroxy-3,6-disulfonatonaphthalen-2-yl)diazenyl]phenyl]phenyl]diazenyl]-4-hydroxynaphthalene-2,7-disulfonate Chemical group [Na+].[Na+].[Na+].[Na+].C1=C(S([O-])(=O)=O)C=C2C=C(S([O-])(=O)=O)C(N=NC3=CC=C(C=C3)C3=CC=C(C=C3)N=NC3=C(C=C4C=C(C=C(C4=C3O)N)S([O-])(=O)=O)S([O-])(=O)=O)=C(O)C2=C1N MPCYPRXRVWZKGF-UHFFFAOYSA-J 0.000 claims description 2
- 150000004897 thiazines Chemical class 0.000 claims description 2
- 239000000178 monomer Substances 0.000 abstract description 26
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 6
- 239000008199 coating composition Substances 0.000 abstract description 5
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical group C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000379 polymerizing effect Effects 0.000 abstract description 3
- 229920002554 vinyl polymer Polymers 0.000 abstract description 3
- 239000004615 ingredient Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 23
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 8
- 230000008901 benefit Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- HFVAFDPGUJEFBQ-UHFFFAOYSA-M alizarin red S Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=C(S([O-])(=O)=O)C(O)=C2O HFVAFDPGUJEFBQ-UHFFFAOYSA-M 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- RGCKGOZRHPZPFP-UHFFFAOYSA-N Alizarin Natural products C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 239000000987 azo dye Substances 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-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
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- AEPWOCLBLLCOGZ-UHFFFAOYSA-N 2-cyanoethyl prop-2-enoate Chemical compound C=CC(=O)OCCC#N AEPWOCLBLLCOGZ-UHFFFAOYSA-N 0.000 description 1
- NGPGYVQZGRJHFJ-BUHFOSPRSA-N 4-(4-nitrophenylazo)resorcinol Chemical compound OC1=CC(O)=CC=C1\N=N\C1=CC=C([N+]([O-])=O)C=C1 NGPGYVQZGRJHFJ-BUHFOSPRSA-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
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- DPKHZNPWBDQZCN-UHFFFAOYSA-N acridine orange free base Chemical compound C1=CC(N(C)C)=CC2=NC3=CC(N(C)C)=CC=C3C=C21 DPKHZNPWBDQZCN-UHFFFAOYSA-N 0.000 description 1
- 230000010062 adhesion mechanism Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229940051880 analgesics and antipyretics pyrazolones Drugs 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HWYNRVXFYFQSID-UHFFFAOYSA-M benzo[a]phenoxazin-9-ylidene(dimethyl)azanium;chloride Chemical compound [Cl-].C1=CC=C2C(N=C3C=CC(C=C3O3)=[N+](C)C)=C3C=CC2=C1 HWYNRVXFYFQSID-UHFFFAOYSA-M 0.000 description 1
- DZBUGLKDJFMEHC-UHFFFAOYSA-N benzoquinolinylidene Natural products C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- YVJPMMYYRNHJAU-UHFFFAOYSA-N chembl1206021 Chemical compound C1=C(O)C(C(=O)O)=CC(N=NC=2C=CC(=CC=2)[N+]([O-])=O)=C1 YVJPMMYYRNHJAU-UHFFFAOYSA-N 0.000 description 1
- SXYCCJAPZKHOLS-UHFFFAOYSA-N chembl2008674 Chemical compound [O-][N+](=O)C1=CC=C2C(N=NC3=C4C=CC=CC4=CC=C3O)=C(O)C=C(S(O)(=O)=O)C2=C1 SXYCCJAPZKHOLS-UHFFFAOYSA-N 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000000983 mordant dye Substances 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 239000001005 nitro dye Substances 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002245 particle Substances 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
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- UJMBCXLDXJUMFB-GLCFPVLVSA-K tartrazine Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=NN(C=2C=CC(=CC=2)S([O-])(=O)=O)C(=O)C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 UJMBCXLDXJUMFB-GLCFPVLVSA-K 0.000 description 1
- 229960000943 tartrazine Drugs 0.000 description 1
- 235000012756 tartrazine Nutrition 0.000 description 1
- 239000004149 tartrazine Substances 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 239000000984 vat dye Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 125000001834 xanthenyl group Chemical class C1=CC=CC=2OC3=CC=CC=C3C(C12)* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/002—Scale prevention in a polymerisation reactor or its auxiliary parts
- C08F2/004—Scale prevention in a polymerisation reactor or its auxiliary parts by a prior coating on the reactor walls
Definitions
- a film or coating of a water-soluble dye is applied to the interior surfaces of a polymerization reactor or vessel by merely contacting said surfaces with an aqueous solution of said dye.
- all exposed surfaces in the interior of the reactor, other than the walls, such as the baffles, agitator, and the like, are also treated in like manner.
- the surfaces are sprayed with water or the reactor is filled with water and drained, thereby surprisingly, leaving on said surfaces a tightly .adhering coating or film of the dye, which is not affected by the polymerization.medium in the sense of preventing it from achieving its assigned function, namely, the prevention of polymer buildup on said surfaces.
- dyes suitable in the practice of the present invention are those which contain in their chemical structure one or more of the following radicals: -COONa, -COOH, -SO 3 H, and -SO 3 Na, which radicals may be the same or different on any one dye structure.
- radicals may be the same or different on any one dye structure.
- These groups or radicals are usually attached to an aromatic nucleus. While other groups or radicals are present in most of the dyes, the above-named radicals are necessary for water solubility.
- the classes of dyes with one or more of said radicals are the azo dyes, suchasmonoazo and polyazo dyes; metal-containing azo dyes; mordant dyes; pyrazolones; stilbene dyes; phenols, naphthols; acid anthraquinone dyes; thiazoles; nitro dyes; xanthenes; and solubilized vat dyes, such as indigoids and anthraquinoids.
- the natural ionic dyes are also useful in the practice of the present invention.
- ionic dyes is meant the acridines, azines, oxazines and the thiazines.
- the natural ionic dyes exist as salts in the dry state and all have a heterocyclic ring system in their structure which is positively charged.
- the above-named dyes having one or more of the indicated radicals in their chemical structure there may be named 4-(p-nitrophenylazo)Resorcinol, Direct Blue 2B, Alizarin, Alizarin Yellow R, Alizarin Red S, Orange G, Phenolphthalein, Naphthol Yellow S, Congo Red, Eriochrome Black T. Tartrazine, Alizarin Irisol R, and Indigosol O.
- the ionic dyes there may be named Celestine Blue, Acridine Orange NO, Saframine T, Rhodamine 6G, Meldola's Blue, and Methylene Blue.
- the dye coating solution is made by conventional methods,.using ' heat and agitation where necessary.
- the dye is dissolved in water, preferably demineralized, to an extent such that the solids content of the coating solution does not prevent it being sprayed on the inner surfaces of the reactor through spray nozzles mounted permanently thereon.
- a coating solution having a solids content of water-soluble dye in the range of about 0.1% to about 20.0% by weight is satisfactory.
- the solids content depends upon the molecular weight of the water-soluble dye. That is, the solids content could, in certain instances, be greater than 20.0% or less than 0.1% by weight.
- additives may be employed in the coating solution, if desired, suchasplasticizers, stabilizers, lubricants, or fillers, and the like. Of course, when additives are employed, suitable adjustment in thesolids content of the coating solution is made.
- the preferred concentration of the dye in the coating solution is from 0.1% to 5.0% by weight.
- the temperature of the water when the dye is dissolved therein is not critical. Usually a temperature in the range of about 5°C. to about 100°C. is satisfactory. Agitation during dissolution of the dye is desirable.
- the coating solution is usually applied to the inner reactor surfaces by spraying. However, it is also possible to apply the coating solution by flooding the reactor and then draining, or by brushing or painting on the reactor surfaces, but spraying is the most practical and economical method of application. After spraying the coating solution on the inner surfaces and draining the reactor, the surfaces are sprayed with water and the reactor drained prior to charging the reactor with the polymerization mix.
- the present coating works well on glass or metal surfaces, such as stainless steel, and the like.
- the spraying of the coating solution on the inner surfaces of the reactor with water is believed to have a nonsolvent effect causing the dye to precipitate and adhere to the reactor surfaces. While the exact adhesion mechanism of the coating to the surface is not known for certain, it is believed to involve some type of electrical force or adsorption between the reactor surfaces and the dye. At any rate, the coating composition of the present invention does substantially eliminate polymer buildup on the reactor surfaces and what little polymer buildup, if any, that may occur, is of the "sandy" type which is of such a nature that it is readily removable from the reactor surfaces.
- the polymer buildup to be avoided is what is referred to as "paper buildup" since this type of buildup is very difficult to remove and usually requires hand scraping or a high pressure jet stream of water or other liquid. In either event, the reactor must be opened in order to clean the same which, of course, allows the escape into the atmosphere of unreacted monomer, such as vinyl chloride, which is to be-avbided.
- polymerizations may be run in a coated reactor before having to recoat the surfaces thereof.
- I have found it expeditious, and it is preferred, to coat the internal surfaces of the reactor after each polymerization run therein.
- the spray nozzles permanently mounted at strategic points'on the reactor, it is possible to reach all inner surfaces thereof without opening the reactor.
- the inner surfaces are sprayed with water and the reactor flushed.
- the coating solution is sprayed on the surfaces and the reactor is drained of the excess solution in such a way that the solution can be sent to a recovery system, if desired.
- the reaction to be carried out in the equipment may be commenced immediately, no particular modification of processing techniques being required due to the presence of the coating. Further, utilization of the internally coated reaction vessel of the present invention does not adversely affect the heat stability or other physical and chemical properties of the polymers produced therein.
- the polymerization process is usually conducted at a temperature in the range of about 0°C. to about 100°C. depending upon the particular monomer or monomers being polymerized. However, it is preferred to employ temperatures in the range of about 40°C. to about 70°C., since, at these temperatures polymers having the most beneficial properties are produced.
- the time of the polymerization reaction will normally vary from about 2 to about 15 hours.
- the polymerization process may be carried out at autogenous pressures although superatmospheric pressures of up to 10 atmospheres or more may be employed with some advantage with the more volatile monomers.
- Superatmospheric pressures may also be employed with those monomers having the requisite volatilities at reaction temperatures permitting reflux cooling of the reaction mixture.
- the polymerization process may be carried out utilizing a full reactor technique. That is, the reaction vessel is completely filled with the polymerization medium and kept that way throughout the reaction by constant addition thereto of water or additional make-up liquid containing the monomer or monomers in the same proportion as at start-up. Upon the addition of a certain predetermined about of liquid, the polymerization reaction is terminated, usually by the addition thereto of a short-stopping agent. The necessity for the addition of liquid is due to the shrinkage in volume of the reaction medium produced by the conversion of the monomer or monomers to the polymeric state.
- a rating scale was devised with respect to paper and sandy buildup, as referred to above.
- an uncoated reactor the inner surfaces of which are uncleaned or solvent cleaned, will have both types of buildup and is given a rating of 1.5. Any rating below 1.0 is good or a definite improvement. In other words, 0.0 rating is perfect, and so on.
- the rating on an uncoated reactor after three charges is 1.3. This is used as the control in the Example hereinafter.
- the coating solution after application to the internal surfaces of the reactor, does not have to be dried. Being able to employ water solutions not only has economic advantages, but also eliminates the need for using chemical solutions resulting in ease of handling.
- Coating of the internal surfaces of the polymerization reactor substantially reduces, and in many cases, practically eliminates polymer buildup on said surfaces during the polymerization reaction and thus results in increased production over a unit period of time.
- a little polymer buildup does accumulate on the interior surfaces, it is not of the hard, rough, difficult- to-remove type and is easily removed without employing the difficult tedious scraping methods that are presently necessary in the art.
- the present invention enables one to operate a closed polymerization system, which in the case of vinyl chloride polymerization, it has the advantage of reducing the parts per million of vinyl chloride in the atmosphere of the plant drastically and to a point that meets the new Governmental Regulations. Numerous other advantages of the present invention will be apparent to those skilled in the art.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US80795877A | 1977-06-20 | 1977-06-20 | |
| US807958 | 1977-06-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0000166A1 true EP0000166A1 (en) | 1979-01-10 |
Family
ID=25197523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP78100189A Withdrawn EP0000166A1 (en) | 1977-06-20 | 1978-06-19 | Internally coated reaction vessel for use in olefinic polymerization |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP0000166A1 (enrdf_load_stackoverflow) |
| JP (1) | JPS548690A (enrdf_load_stackoverflow) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0008799A1 (en) * | 1978-09-08 | 1980-03-19 | The B.F. GOODRICH Company | Process for coating reactors using steam application |
| FR2467860A1 (fr) * | 1979-10-22 | 1981-04-30 | Shinetsu Chemical Co | Procede pour la preparation de resines de chlorure de vinyle par polymerisation en suspension |
| EP0029181A1 (de) * | 1979-11-17 | 1981-05-27 | Hoechst Aktiengesellschaft | Verfahren zur Herstellung von Vinylchlorid-Polymerisaten, Mittel zur Beschichtung von Polymerisationsgefässen und dafür verwendbare Derivate von 1,4-(7H)-Benzoxazin |
| EP0096319A1 (en) * | 1982-05-31 | 1983-12-21 | Shin-Etsu Chemical Co., Ltd. | Method for preventing scale deposition in the polymerization of ethylenically unsaturated monomers |
| FR2535325A1 (fr) * | 1982-10-27 | 1984-05-04 | Toyo Soda Mfg Co Ltd | Procede de polymerisation non aqueuse du chlorure de vinyle |
| EP0482593A1 (en) * | 1990-10-23 | 1992-04-29 | Shin-Etsu Chemical Co., Ltd. | Polymer scale preventive agent, polymerization vessel for preventing polymer scale deposition, and process of producing polymer using said vessel |
| US5302639A (en) * | 1990-10-23 | 1994-04-12 | Shin-Etsu Chemical Co., Ltd. | Polymer scale preventive agent |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55155001A (en) * | 1979-05-21 | 1980-12-03 | Shin Etsu Chem Co Ltd | Polymerization of vinyl monomer |
| JPS5978210A (ja) * | 1982-10-27 | 1984-05-07 | Toyo Soda Mfg Co Ltd | 塩化ビニルの非水系重合方法 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2289532A1 (fr) * | 1974-10-31 | 1976-05-28 | Shinetsu Chemical Co | Procede de polymerisation du chlorure de vinyle |
| FR2305449A1 (fr) * | 1975-03-24 | 1976-10-22 | Shinetsu Chemical Co | Procede perfectionne de polymerisation en vrac du chlorure de vinyle |
| FR2318898A1 (fr) * | 1975-07-24 | 1977-02-18 | Shinetsu Chemical Co | Procede de preparation d'une composition de resine de polychlorure de vinyle premelangee |
| US4068059A (en) * | 1977-02-17 | 1978-01-10 | The B. F. Goodrich Company | Internally coated reaction vessel for use in olefinic polymerization |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5224953B2 (enrdf_load_stackoverflow) * | 1974-12-27 | 1977-07-05 | Shinetsu Chemical Co | |
| JPS51112892A (en) * | 1975-03-31 | 1976-10-05 | Shin Etsu Chem Co Ltd | Process for bulk polymerization of vinyl chloride |
-
1978
- 1978-06-16 JP JP7228078A patent/JPS548690A/ja active Granted
- 1978-06-19 EP EP78100189A patent/EP0000166A1/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2289532A1 (fr) * | 1974-10-31 | 1976-05-28 | Shinetsu Chemical Co | Procede de polymerisation du chlorure de vinyle |
| FR2305449A1 (fr) * | 1975-03-24 | 1976-10-22 | Shinetsu Chemical Co | Procede perfectionne de polymerisation en vrac du chlorure de vinyle |
| FR2318898A1 (fr) * | 1975-07-24 | 1977-02-18 | Shinetsu Chemical Co | Procede de preparation d'une composition de resine de polychlorure de vinyle premelangee |
| US4068059A (en) * | 1977-02-17 | 1978-01-10 | The B. F. Goodrich Company | Internally coated reaction vessel for use in olefinic polymerization |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0008799A1 (en) * | 1978-09-08 | 1980-03-19 | The B.F. GOODRICH Company | Process for coating reactors using steam application |
| FR2467860A1 (fr) * | 1979-10-22 | 1981-04-30 | Shinetsu Chemical Co | Procede pour la preparation de resines de chlorure de vinyle par polymerisation en suspension |
| EP0029181A1 (de) * | 1979-11-17 | 1981-05-27 | Hoechst Aktiengesellschaft | Verfahren zur Herstellung von Vinylchlorid-Polymerisaten, Mittel zur Beschichtung von Polymerisationsgefässen und dafür verwendbare Derivate von 1,4-(7H)-Benzoxazin |
| US4374966A (en) * | 1979-11-17 | 1983-02-22 | Hoechst Aktiengesellschaft | Process for the manufacture of vinyl chloride polymers by coating polymerization vessels |
| EP0096319A1 (en) * | 1982-05-31 | 1983-12-21 | Shin-Etsu Chemical Co., Ltd. | Method for preventing scale deposition in the polymerization of ethylenically unsaturated monomers |
| FR2535325A1 (fr) * | 1982-10-27 | 1984-05-04 | Toyo Soda Mfg Co Ltd | Procede de polymerisation non aqueuse du chlorure de vinyle |
| EP0482593A1 (en) * | 1990-10-23 | 1992-04-29 | Shin-Etsu Chemical Co., Ltd. | Polymer scale preventive agent, polymerization vessel for preventing polymer scale deposition, and process of producing polymer using said vessel |
| US5302639A (en) * | 1990-10-23 | 1994-04-12 | Shin-Etsu Chemical Co., Ltd. | Polymer scale preventive agent |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0122281B2 (enrdf_load_stackoverflow) | 1989-04-26 |
| JPS548690A (en) | 1979-01-23 |
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| 18W | Application withdrawn |
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Inventor name: WITENHAFER, DONALD EDWARD |