EP0000400A1 - Verfahren zum Verhindern der Polymerkrustenabscheidung an den Reaktorwänden - Google Patents

Verfahren zum Verhindern der Polymerkrustenabscheidung an den Reaktorwänden Download PDF

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Publication number
EP0000400A1
EP0000400A1 EP78100399A EP78100399A EP0000400A1 EP 0000400 A1 EP0000400 A1 EP 0000400A1 EP 78100399 A EP78100399 A EP 78100399A EP 78100399 A EP78100399 A EP 78100399A EP 0000400 A1 EP0000400 A1 EP 0000400A1
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EP
European Patent Office
Prior art keywords
reactor
polymerization
reaction
acid
polyaromatic amine
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Withdrawn
Application number
EP78100399A
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English (en)
French (fr)
Inventor
Louis Cohen
James Bernard Haehn
Donald Edward Witenhafer
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Goodrich Corp
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BF Goodrich Corp
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Filing date
Publication date
Application filed by BF Goodrich Corp filed Critical BF Goodrich Corp
Publication of EP0000400A1 publication Critical patent/EP0000400A1/de
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    • 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 coating composition comprising a straight chain polyaromatic amine dissolved in an aqueous acid solution, such as aqueous HC1, for example, polymer buildup on said surfaces of the reactor is essentially eliminated. Due to the nature of the coating composition, it can be applied to the inner surfaces of the reactor without opening the same thus providing a closed polymerization system. In polymerizing the olefinic monomers, the same is done in an aqueous polymerization medium which is kept in constant contact with said coated surfaces throughout the polymerization reaction.
  • a film or coating of a polyaromatic amine is applied to the interior surfaces of a polymerization reactor or vessel by merely contacting said surfaces with an aqueous acid solution of said polyaromatic amine.
  • 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 polymerization medium can be introduced to the reactor and the reaction started without the necessity of drying the surfaces prior to said introduction of the polymerization medium.
  • the exact mechanism by which the polyaromatic amine coating or film functions to prevent buildup of polymeric scale on the interior surfaces of the reaction vessel is not certain but it is believed to be a free radical destroying mechanism or free radical trapping mechanism. This is believed to be so because aromatic diamines are known to destroy free radicals, for example, as in their well-known activity as antioxidants. Thus, with the destruction of the free radicals by the polyaromatic amine coating or film, polymerization on the interior surfaces of the reactor is inhibited.
  • the polyaromatic amines useful in the practice of the present invention are made by the self-condensation reaction of a polyamino benzene. Generally, such reactions are carried out with heat in the presence of an acidic catalyst.
  • the polyaromatic amines thus formed have the following general structure: wherein R is H or NH 2 , n is an integer from 0 to 5 and x and y are 1 or 2.
  • R is H or NH 2
  • n is an integer from 0 to 5
  • x and y are 1 or 2.
  • the polyamino benzenes there may be named the ortho-, meta-, and para- phenylene diamines and triamino benzenes.
  • polyaromatic amines are possible when triamino benzenes are employed.
  • any two or more of the above amines can be reacted together or cocondensed.
  • the molecular weight or degree of condensation of the polyaromatic amine depends upon the time and temperature of heating; and the kind and concentration of the catalyst. When reacting two amines together, they are employed in approximately equal molar proportions. Polyaromatic amines having a molecular weight in the range of about 250 to about 1000 are satisfactory for use in the present invention. Suffice it to say that the particular polyaromatic amine should have a molecular weight such that it is workable and soluble in an aqueous acid solution so that it can be easily applied to the inner surfaces of the reactor. We have found that polyaromatic amines having a molecular weight in the range of about 300 to about 600 are preferred.
  • the softening point of the polyaromatic amine is determined as follows: the polyaromatic amine is melted and cast into a split aluminum mold to make a cube which is 1/2 inch on a side. The mold is cooled, the cube removed therefrom and allowed to cool thoroughly. The cube is then attached to a thermometer bulb by heating the bulb to a temperature in excess of the expected softening point and laying it on the side of the cube, then cooling to 35°C. The thermometer with the cube attached is inserted into a mercury bath which has been preheated to 35°C. The insertion is made so that the top face of side of the cube is one inch below the mercury surface. The mercury bath is then heated at a rate of 4°C. per minute.
  • the softening point is determined as the temperature at which, as the cube moves upward, the cube just breaks the surface of the mercury. It is to be noted that the cube should crawl up on the thermometer and not "pop up.” This is accomplished by carefully controlling the rate of rise in temperature of the mercury bath.
  • an acid catalyst is employed.
  • HC1 the most effective catalyst.
  • other useful catalysts may likewise be employed, such as, for example, methane sulfonic acid, benzene sulfonic acid, sulfanilic acid, phosphoric acid, iodine, benzene disulfonic acid, hydrogen bromide (HBr), hydrogen iodide (HI), aluminum chloride, and the like.
  • concentration of catalyst will vary depending upon the particular one used. It has been found, however, that a catalyst concentration of from about 0.005 mole to about 0.20 mole per mole of the compound or compounds being self-condensed, or cocondensed, is satisfactory. At any rate, the amount of catalyst employed is not critical.
  • the temperature of the reaction will vary depending upon the time of the reaction and the molecular weight desired in the final product. For example, one can heat the reaction ingredients to 315°C. rapidly and then hold at that temperature for various periods of time. Also, the reaction ingredients can be heated to various temperatures above 300°C. and immediately cooled. When this latter procedure is employed, we define the time of reaction as 0 hours. Accordingly, the temperature of the reaction will vary from about 150°C. to about 360°C. and the time of reaction will vary from about 0 hour to about 3 hours. The preferred range of reaction temperature is from 175°C. to 330°C. and the time of reaction from 0 hour to 1 hour. It is understood, of course, that the particular time and temperature selected is dependent upon the catalyst employed and the final molecular weight desired.
  • the polyaromatic amine coating solution is made by conventional methods, using heat and agitation where necessary.
  • the polyaromatic amine is dissolved in the appropriate aqueous acid solution 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 polyaromatic amine 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 polyaromatic amine. 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, such as plasticizers-, stabilizers, lubricants, or fillers, and the like. Of course, when additives are employed, suitable adjustment in the solids content of the coating solution is made.
  • the aqueous acid solutions used in making the coating solutions of the instant invention are those made from inorganic and organic acids.
  • Representatives of the inorganic acids are hydrochloric, sulfuric, phosphoric, and the like.
  • organic acids there may be named acetic acid, formic acid, chloroacetic acid and toluene sulfonic acid, etc.
  • the most important point is that the acid chosen must give the proper pH in aqueous solution. Usually, a pH in the range of about 1 to about 5 is satisfactory. A preferred pH range is from 1.5 to 3.
  • the temperature of the aqueous acid solution when the polyaromatic amine is dissolved therein is not critical. Usually a temperature in the range of about 5°C, to about 100°C. is satisfactory. A preferred pH range is from 1.5 to 3.
  • the temperature of the aqueous acid solution when the polyaromatic amine 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 polyaromatic amine is desirable and in some instances necessary.
  • the concentration of the acid in the aqueous solution may be varied between about 0.01% by weight to about 20.0% by weight. The preferred concentration of acid is from 0,05% to 2.0% by weight.
  • 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, 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 polymerization reaction can be started immediately without further treatment of said surfaces. However, it has been found that best results are obtained when after applying the coating solution to the surfaces of 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 equally well on glass or metal surfaces, such as stainless steel, and the like.
  • 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.
  • polymerizations may be run in a coated reactor before having to recoat the surfaces thereof.
  • the spray nozzles permanently mounted at strategic points on the reactor, it is possible to reach all inner surfaces thereof. After each polymerization is complete and the reactor is drained, the inner surfaces are sprayed with water and the reactor flushed. Then 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 amount of liquid, the polymerization reaction is terminated, usually be 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.
  • the self-condensation product of m-phenylenediamine (m-PDA) was made for use in this Example.
  • the polyaromatic amine was made by charging 109 grams of m-PDA to a flask equipped with a reflux condenser and heating to a temperature of 200°C. After reaching this temperature, 0.5 gram of AlC13 catalyst was added and the temperature was raised to 250°C. Heating at 250°C. was continued for 11 hours and the NH 3 coming off was collected in a water trap. Thereafter the reaction mixture was vacuum distilled in order to remove any unreacted diamine.
  • the resulting polyaromatic amine or condensed m-PDA had a softening point of 64°C.
  • the polyaromatic amine was dissolved in 0.1 N-HC1 i give a 1.5% by weight solution of self-condensed m-PDA.
  • the pH of the resultant coating solution was 2.7.
  • the internal surfaces of a polymerization reactor were coated with this solution and then rinsed with water. The following recipe was then charged to the reactor in usual fashion:
  • the polymerization reaction was carried out in a full reactor, that is, sufficient water was added to fill the reactor, and at a temperature of 57°C. with agitation. The reaction was continued with addition of water as the reaction mixture shrank because of formation of polymer in order to keep the reactor full. The reaction was discontinued upon the additior of 400 grams of water. After removal of the contents of the reactor the internal surfaces were classified or rated with the following results: paper buildup 0.0 and sandy buildup 0.01. This clearly shows the superiority of the use of a coated reactor over an uncoated reactor.
  • the cycle is repeated with each batch without opening the polymerizer. This is accomplished by using spray nozzles mounted in the dome of the reaction vessel or polymerizer, spraying the coating solution on the interior surfaces, draining, and recovering, if desired, spraying with water through the same nozzles, draining and then charging the polymerization mixture. After polymerization, the contents are removed and the interior rinsed with water by means of the spray nozzles. Thereafter the cycle is repeated without opening the reactor. Numerous other advantages of the present invention will be apparent to those skilled in the art.

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  • 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)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
EP78100399A 1977-07-15 1978-07-14 Verfahren zum Verhindern der Polymerkrustenabscheidung an den Reaktorwänden Withdrawn EP0000400A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US05/815,977 US4255470A (en) 1977-07-15 1977-07-15 Process for preventing polymer buildup in a polymerization reactor
US815977 1977-07-15

Publications (1)

Publication Number Publication Date
EP0000400A1 true EP0000400A1 (de) 1979-01-24

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EP78100399A Withdrawn EP0000400A1 (de) 1977-07-15 1978-07-14 Verfahren zum Verhindern der Polymerkrustenabscheidung an den Reaktorwänden

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US (1) US4255470A (de)
EP (1) EP0000400A1 (de)
JP (1) JPS5420089A (de)
IN (1) IN148956B (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2598710A1 (fr) * 1986-05-16 1987-11-20 Europ Vinyls Corp Italia Spa Procede de polymerisation en suspension aqueuse de monomeres vinyliques halogenes
US4713434A (en) * 1982-06-11 1987-12-15 Rohm Gmbh Chemische Fabrik Continuous emulsion polymerization process

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4297320A (en) * 1979-04-30 1981-10-27 The B. F. Goodrich Company Coating polymerization reactors with the reaction products of thiodiphenols and a bleach
US4532311A (en) * 1981-03-26 1985-07-30 Union Carbide Corporation Process for reducing sheeting during polymerization of alpha-olefins
JPH0615567B2 (ja) * 1989-05-02 1994-03-02 信越化学工業株式会社 重合体スケールの付着防止方法
JPH0768289B2 (ja) * 1990-03-08 1995-07-26 台灣塑膠工業股▲ひん▼有限公司 塩化ビニル重合体製造用の重合反応器
JPH03115305A (ja) * 1990-05-25 1991-05-16 Shin Etsu Chem Co Ltd 重合体スケールの付着防止方法および重合体スケール付着防止剤
EP1687248B1 (de) * 2003-11-20 2011-06-01 SOLVAY (Société Anonyme) Verfahren zur herstellung von dichlorpropanol aus glycerin und einem chlorinierungsmittel in anwesenheit von einem katalysator ausgewählt aus adipin- und glutarsaeure
EP1885671A1 (de) * 2005-05-20 2008-02-13 Solvay SA Verfahren zur herstellung eines chlorhydrins ausgehend von einem mehrfach hydroxilierten aliphatischen kohlenwasserstoff
KR20080037618A (ko) 2005-05-20 2008-04-30 솔베이(소시에떼아노님) 폴리히드록실화 지방족 탄화수소 및 염소화제 간의 반응에의한 클로로히드린 제조 방법
EP2043984A1 (de) * 2006-06-14 2009-04-08 Solvay S.A. Rohes produkt auf glyzerinbasis, verfahren zu dessen aufreinigung und dessen verwendung bei der herstellung von dichlorpropanol
US20100032617A1 (en) * 2007-02-20 2010-02-11 Solvay (Societe Anonyme) Process for manufacturing epichlorohydrin
FR2913421B1 (fr) * 2007-03-07 2009-05-15 Solvay Procede de fabrication de dichloropropanol.
FR2913684B1 (fr) * 2007-03-14 2012-09-14 Solvay Procede de fabrication de dichloropropanol
TW200911740A (en) 2007-06-01 2009-03-16 Solvay Process for manufacturing a chlorohydrin
TW200911693A (en) * 2007-06-12 2009-03-16 Solvay Aqueous composition containing a salt, manufacturing process and use
TWI500609B (zh) * 2007-06-12 2015-09-21 Solvay 含有環氧氯丙烷的產品，其製備及其不同應用中的用途
JP2011502032A (ja) * 2007-10-02 2011-01-20 ソルヴェイ（ソシエテ アノニム） 容器の耐腐食性を向上させるためのケイ素を含有する組成物の使用
FR2925045B1 (fr) 2007-12-17 2012-02-24 Solvay Produit a base de glycerol, procede pour son obtention et son utilisation dans la fabrication de dichloropropanol
TWI478875B (zh) * 2008-01-31 2015-04-01 Solvay 使水性組成物中之有機物質降解之方法
CN101980995B (zh) 2008-04-03 2014-06-18 索尔维公司 包含甘油的组合物、获得该组合物的方法以及它们在二氯丙醇生产中的用途
FR2935968B1 (fr) 2008-09-12 2010-09-10 Solvay Procede pour la purification de chlorure d'hydrogene
FR2939434B1 (fr) * 2008-12-08 2012-05-18 Solvay Procede de traitement de glycerol.
JP6049087B2 (ja) 2010-09-30 2016-12-21 ソルヴェイ（ソシエテ アノニム） 天然起源のエピクロロヒドリンの誘導体

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2362165A1 (fr) * 1976-08-16 1978-03-17 Goodrich Co B F Reacteur a revetement interne destine a etre utilise pour des polymerisations olefiniques

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4024330A (en) * 1975-04-08 1977-05-17 The B. F. Goodrich Company Internally coated reaction vessel and process for coating the same

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2362165A1 (fr) * 1976-08-16 1978-03-17 Goodrich Co B F Reacteur a revetement interne destine a etre utilise pour des polymerisations olefiniques

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4713434A (en) * 1982-06-11 1987-12-15 Rohm Gmbh Chemische Fabrik Continuous emulsion polymerization process
FR2598710A1 (fr) * 1986-05-16 1987-11-20 Europ Vinyls Corp Italia Spa Procede de polymerisation en suspension aqueuse de monomeres vinyliques halogenes
GB2190604A (en) * 1986-05-16 1987-11-25 Europ Vinyls Corp Process for the polymerization in aqueous suspension of halogen-containing vinylic monomers
BE1000425A5 (fr) * 1986-05-16 1988-12-06 Europ Vinyls Corp Italia Procede de polymerisation en suspension aqueuse de monomeres vinyliques halogenes.
GB2190604B (en) * 1986-05-16 1990-05-30 Europ Vinyls Corp Process for the polymerization in aqueous suspension of halogen-containing vinylic monomers

Also Published As

Publication number Publication date
IN148956B (de) 1981-07-25
US4255470A (en) 1981-03-10
JPS5420089A (en) 1979-02-15

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