US3312610A - Electrolytic process for producing phosphine - Google Patents

Electrolytic process for producing phosphine Download PDF

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Publication number
US3312610A
US3312610A US262496A US26249663A US3312610A US 3312610 A US3312610 A US 3312610A US 262496 A US262496 A US 262496A US 26249663 A US26249663 A US 26249663A US 3312610 A US3312610 A US 3312610A
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US
United States
Prior art keywords
cathode
phosphorus
gas
phosphine
cell
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.)
Expired - Lifetime
Application number
US262496A
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English (en)
Inventor
George T Miller
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Occidental Chemical Corp
Original Assignee
Hooker Chemical Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to GB26293/59A priority Critical patent/GB889639A/en
Priority to US45567A priority patent/US3109787A/en
Priority claimed from US45669A external-priority patent/US3109795A/en
Priority to FR834368A priority patent/FR1270717A/fr
Priority to DEA35249A priority patent/DE1112722B/de
Application filed by Hooker Chemical Corp filed Critical Hooker Chemical Corp
Priority claimed from US262497A external-priority patent/US3251756A/en
Priority to US262498A priority patent/US3337433A/en
Priority to US262496A priority patent/US3312610A/en
Priority to FR965831A priority patent/FR85417E/fr
Priority to FR965830A priority patent/FR85416E/fr
Priority to FR965832A priority patent/FR85418E/fr
Priority to DEH51937A priority patent/DE1210424B/de
Priority to DE1964H0051939 priority patent/DE1210426C2/de
Priority to GB9213/64A priority patent/GB1042392A/en
Priority to GB9214/64A priority patent/GB1042393A/en
Priority to GB9212/64A priority patent/GB1042391A/en
Priority to DEH51938A priority patent/DE1210425B/de
Priority to BE694670D priority patent/BE694670A/xx
Priority to BE694669D priority patent/BE694669A/xx
Priority to BE694671D priority patent/BE694671A/xx
Publication of US3312610A publication Critical patent/US3312610A/en
Application granted granted Critical
Assigned to OCCIDENTAL CHEMICAL CORPORATION reassignment OCCIDENTAL CHEMICAL CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE APRIL 1, 1982. Assignors: HOOKER CHEMICALS & PLASTICS CORP.
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms

Definitions

  • This invention relates to a process for the preparation of phosphine. More particularly, it relates to electrolytic processes for the preparation of phosphine, including suitable apparatus for elfecting such processes.
  • molten phosphorus reacts with hydrogen gas or ions being produced at one of the electrodes in the cell to yield phosphine, one of the desired products.
  • Other end products are also obtainable, depending on the electrolyte utilized in the cell.
  • the phosphorus is not consumed completely and becomes viscous after a period of time. When this occurs, it is the phosphorus that is replenished or replaced because the viscous phosphorus reduces the efiiciency of the cell and decreases the yield of phosphine.
  • the proc ess and apparatus of the present invention provides for an efficient utilization of phosphorus and greatly increases the yield of phosphine therefrom.
  • phosphine may be prepared by contacting an anode and a cathode with an electrolyte, a portion of said cathode being in contact with phosphorus, maintaining a layer of phosphorus on a surface of said cathode, maintaining an electric current between said anode and said cathode through said electrolyte, and purging said phosphorus with a reducing gas, so that the phosphorus is maintained in a non-viscous form and phosphine is recovered in the region of the cathode.
  • there must be a source of hydrogen for phosphine production and this may be an aqueous electrolyte or one otherwise capable of yielding hydrogen to react with the phosphorus.
  • FIG. 1 is a central vertical sectional view of the apparatus of this invention along 1-1
  • FIG. 2 is a horizontal sectional view along 2-2.
  • cell vessel contains anode compartment 12, anode 14, cathode compartment 16, and cathode 18.
  • a porous or permeable diaphragm separates anode and cathode compartments and separates the Patented Apr. 4, 1967 electrolyte into anolyte 17 and catholyte 19 sections.
  • Phosphorus 24 in a liquid state is present in the cathode compartment 16.
  • Diaphragm 20 is covered or coated on the side thereof facing the liquid phosphorus, where it may otherwise contact the phosphorus, with a coating, cover or sheath 22, against which phosphorus does not adhere, so that it does not wet the diaphragm, which action is evidenced by convex meniscus 21.
  • Ports 26 and 28 permit the addition and removal, either continuously or batchwise, of anolyte from anode section 12.
  • Ports 30 and 32 permit the addition and removal, either continuously or batchwise, of catholyte from the cathode section 16.
  • Port 34 permits the addition and removal of phosphorus from a cathode section 16.
  • Sufiicient phosphorus 24 is added to the cathode compartment 16 to contact the lower portion or edge of cathode 18, permitting contact of the phosphorus with a greater surface of the cathode by a wetting action.
  • Anolyte gas discharge port 36 is provided in the top of the anode section 12 to remove anolyte gas from the electrolytic cell.
  • Catholyte gas discharge port 38 is provided on the top of cathode section 16 to remove catholyte gas.
  • Gas-liquid interfaces are indicated at 15.
  • Conduit 60 carries the catholytic discharge gas to gas-liquid separator means 62, which may be a condenser, centrifuge or other suitable apparatus. Here the gas and liquid electrolyte, which may be carried over, are separated. The liquid phase 19 is returned to the electrolyte 19 in the cell by conventional return means or pipe 61.
  • Conduit 64 carries the catholyte gas to condenser 66, where some of the electrolyte which has come over in a gas phase may be condensed and returned to the cell 10.
  • Uncondensed gases principally phosphine are then delivered through conduit 68 to pump 70 or to a storage area or other suitable receiver. Generally, only a minor proportion of the catholyte gas is shunted through conduit 68 to be recycled through conduit 72 via pump 70 through port 73 and into the phosphorus 24 at 74.
  • Electrolyzing current to the electrodes is transmitted by anode electrical cable or connector 46 and cathode electrical cable or connector 48, joining the anode and cathode to the positive and negative poles at plugs 42 and 43, respectively, of a source of direct current 50.
  • a heating or cooling means such as a constant temperature bath, not shown, may be employed to maintain the cell at or near a desired operating temperature.
  • Cell vessel 10 may be constructed of any material capable of resisting corrosion by the electrolyte and other materials employed in the cell. Typical examples of suitable materials of construction for cell vessel 10 include glass, glazed ceramics, tantalum, titanium, hard rubber, polyethylene, rigid materials coated with phenol-formaldehyde resin and the like.
  • the purging gas of this invention may be any suitable reducing type gas.
  • Suitable reducing gases include hydrogen, phosphine, hydrogen sulfide, carbon monoxide, hydrogen cyanide, saturated and unsaturated hydrocarbon gases, such as ethane, methane, butane, butene, acetylene gases, and other natural fuel type gases and mixtures thereof.
  • the gases herein may be delivered from an external or internal source through conduit 72, purge the phosphorus, and leave through port 38. It is highly preferred that a portion of the cathodic gas is recycled to purge the phosphorus.
  • the rate at which this gas is delivered to the phosphorus may vary from between about 0.5 liter and liters per hour per square foot of cathode area.
  • cathode gas which may be recycled may vary between about and 90 percent of the total gas produced at the cathode.
  • the preferredamount of cathode gas which may be recycled is between about 60 and 75 percent of the total cathode gas. However, optimum results are obtained when between about and percent of the cathode gas is recycled.
  • An increased current density results at the cathode the phosphorus utilized in the production of phosphine in the cell may be maintained within the cell for a longer period of time, thus yielding more phosphine per unit of phosphorus placed in the cell, and phosphorus is made to contact the cathode more efficiently due to the formation of phosphorus droplets as films which adhere and climb or wick-up the cathode surface more readily.
  • the viscosity of elemental phosphorus is about 1.55 centipoises measured at about 50 degrees centigrade.
  • the viscosity of the phosphorus in the cell is about 8 or 9 centipoises at 50 degrees centigrade, the cell efficiency is reduced to such a level that the phosphorus should be replenished for efiicient operation.
  • the viscosity is usually maintained between 1.6 and 4.5 centipoises.
  • Very favorable results also are obtainable when the viscosity is maintained at between about 1.55 and 7 centipoises by a reducing gas, all measurements being taken at 50 degrees centigrade on an Ostwalk-Fenshi type viscometer.
  • Diaphragm 20 which separates the anode section 12 from cathode section 16, may be a porous or semipermeable material resistant to the cell contents and capable of maintaining the anode and cathode gases separate, but allowing the electrolyte to pass through. The phosphorus is also held in the catholyte section of the cell.
  • suitable materials for use as a diaphragm include porous Alundum, porous porcelain, resin impregnated wool felt, and various other separators of the types which may be normally employed in the lead storage batteries.
  • Solid materials having a hydrogen overvoltage, as normally measured in the absence of phosphorus, exceeding the hydrogen overvoltage of smooth platinum may be desirably employed as the cathode.
  • Typical cathodic materials include lead, amalgamated lead, cadmium, tin,
  • cathodes aluminum, nickel, alloys of nickel, such as Mu Metal (an alloy containing 77.2 percent nickel, 4.8 percent cop- 7 per, 1.5 percent chromium, and 14.9 percent iron), Monel, copper, silver, bismuth, and alloys thereof.
  • Mu Metal an alloy containing 77.2 percent nickel, 4.8 percent cop- 7 per, 1.5 percent chromium, and 14.9 percent iron
  • Monel copper, silver, bismuth, and alloys thereof.
  • lead-tin, lead-bismuth, and tin-bismuth alloys may be employed.
  • the cathode may be a plate as illustrated in the drawing. Mats of metallic wool and porous metal sheets may also be employed if desired. It is also suitable to utilize a liquid molten mercury cathode in the practice of the present invention.
  • Suitable anode materials include lead, platinum, lead peroxide, graphite and other materials of construction capable of conducting current and resisting corrosion under the conditions of electrolysis employed.
  • a lead plate with grooves is employed as the cathode and a graphite plate is employed as the anode. Under these conditions, it has been found that the wicking effect of the lead cathode is markedly improved.
  • the electrolyte may be a salt or other organic or inorganic electrolyte which is non-reactive with molten phosphorus and which is capable of forming hydrogen gas or ions under the electrolytic conditions employed.
  • suitable compounds in aqueous solution, which may be employed as the catholyte include hydrochloric acid, sodium chloride, lithium chloride, potassium chloride, sodium sulfate, potassium sulfate, monosodiumphosphate, disodiumphosphate, acidic acid, ammonium hydroxide, phosphoric acid, sulfuric acid, and mixtures thereof.
  • the concentration of a compound in the aqueous electrolyte may vary from about 1 to about 95 percent, but is usually between about 5 and about percent, and is preferably between about 10 and about 50 percent.
  • Suitable non-aqueous electrolytes may also be employed in the present invention, e. g., sodium hydride.
  • Suitable concentrations of the metal ions may be between about 0.01 and 5 percent by weight of the electrolyte. However, between about 0.02 percent and 3 percent by weight of electrolyte may also be utilized. Preferably though, between about 0.02 and 15 percent by weight of electrolyte may be utilized.
  • ions of metals such as antimony bismuth, lead, tin, cadmium, mercury, silver, zinc, cobalt, calcium, barium, and mixtures thereof may be employed.
  • the metal ions may be placed in the electrolyte by employing a consumable anode of the desired metal or metals such as a lead anode,
  • metal ions are formed in the catholyte and transferred to the area adjacent to the cathode.
  • Salts or other compounds of the metals such as chlorides, phosphates, acetates, and the like may be dissolved in the electrolyte if desired.
  • finely divided metal in elemental form is dissolved in the electrolyte.
  • the temperature of the catholyte and anolyte should be maintained above the melting point of phosphorus (about forty-four degrees centigrade), and below the boiling point of the electrolyte. Temperatures between about sixty degrees centigrade and one hundred and ten degrees centigrade are generally satisfactory, but optimum yields of phosphine are obtained at temperatures between about seventy degrees centigrade and about one hundred degrees centigrade.
  • the catholyte gas is predominantly phosphine, but contains some hydrogen.
  • the anolyte gas composition depends on the overvoltages of the anions in the anolyte with reference to the anode material, as well as on the electrolyte.
  • the anolyte gas predominates in oxygen if sulfuric acid or phosphoric acid is utilized with a platinum anode, whereas for the same anode, chlorine predominates if hydrochloric acid is used as an anolyte.
  • the cop-reduction of anodic oxidation products may be carried out in the anode compartment of the cell of this invention without departing from the spirit of the invention.
  • the phosphine-containing gas produced at the cathode has a relatively high concentration of phosphine usually more than 60 percent, and it may be as high as percent phosphine by volume or higher.
  • the catholyte gas is substanti-ally free from other phosphorus hydrides.
  • Liquid phosphorus (40 parts) was charged to an electrolytic phosphine cell.
  • the cell contained a lead cathode and a graphite anode.
  • the electrolyte in the cell consisted of 10 percent hydrochloric acid with about 0.04 percent finely divided elemental lead, dissolved therein.
  • the cell was divided into anolyte and catholyte sections by an Alundum diaphragm coated with glass fabric.
  • Example 2 Additional melted phosphorus (60 parts) at 50 degrees centigrade was added to the phosphine producing cell of Example 1. Operating conditions were kept the same except for the use of hydrogen gas to treat or purge the phosphorus. This all was operated for seven consecutive days with intermittent analyses of the catholyte gas. Over this period of time, the liquid phosphorus did not become viscous and analyses of the catohlyte gas showed between 70 and 75 percent phosphine present in the cathode gas.
  • Example 3 Phosphorus was added to the cell and Example 2 was repeated except that about 40 percent of the cathode gas was recycled to purge the phosphorus, and no extra hydrogen was used. After 24 hours, the recycling of the catholyte gas was stopped and the cell continued in operation. The percent of phosphine in the cathode gas, without passing recycled cathode gas into the cell, was then analyzed over a period of about an hour, as indicated in Table I.
  • preparing phosphine electrolytically (a) contacting an anode and a cathode with an electrolyte, a portion of said cathode being in contact with a body of liquid phosphorus;
  • reducing gas is selected from the group consisting of hydrogen, phosphine, hydrogen sulfide, carbon monoxide, hydrogen cyanide, saturated and unsaturated hydrocarbon gases and mixtures thereof.
  • a process for preparing phosphine electrolytically comprising the steps of:

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Glass Compositions (AREA)
US262496A 1959-07-31 1963-03-04 Electrolytic process for producing phosphine Expired - Lifetime US3312610A (en)

Priority Applications (18)

Application Number Priority Date Filing Date Title
GB26293/59A GB889639A (en) 1959-07-31 1959-07-31 Improvements in or relating to the production of phosphine
US45567A US3109787A (en) 1959-07-31 1960-07-27 Production of phosphine
FR834368A FR1270717A (fr) 1959-07-31 1960-07-29 Procédé de production de la phosphine par voie électrolytique
DEA35249A DE1112722B (de) 1959-07-31 1960-08-01 Verfahren zur elektrolytischen Herstellung von Phosphin
US262498A US3337433A (en) 1959-07-31 1963-03-04 Electrolytic process
US262496A US3312610A (en) 1959-07-31 1963-03-04 Electrolytic process for producing phosphine
FR965831A FR85417E (fr) 1959-07-31 1964-03-03 Procédé de production de la phosphine par voie électrolytique
FR965830A FR85416E (fr) 1959-07-31 1964-03-03 Procédé de production de la phosphine par voie électrolytique
FR965832A FR85418E (fr) 1959-07-31 1964-03-03 Procédé de production de la phosphine par voie électrolytique
DEH51938A DE1210425B (de) 1959-07-31 1964-03-04 Verfahren zur elektrolytischen Herstellung von Phosphin
DEH51937A DE1210424B (de) 1959-07-31 1964-03-04 Verfahren zur elektrolytischen Herstellung von Phosphin
DE1964H0051939 DE1210426C2 (de) 1959-07-31 1964-03-04 Verfahren zur elektrolytischen Herstellung von Phosphin
GB9213/64A GB1042392A (en) 1959-07-31 1964-03-04 Electrolytic cell, and process for producing phosphine therewith
GB9214/64A GB1042393A (en) 1959-07-31 1964-03-04 Process and apparatus for producing phosphine
GB9212/64A GB1042391A (en) 1959-07-31 1964-03-04 Electrolytic cell, and process for producing phosphine therewith
BE694671D BE694671A (de) 1959-07-31 1967-02-27
BE694669D BE694669A (de) 1959-07-31 1967-02-27
BE694670D BE694670A (de) 1959-07-31 1967-02-27

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
GB26293/59A GB889639A (en) 1959-07-31 1959-07-31 Improvements in or relating to the production of phosphine
US45669A US3109795A (en) 1960-07-27 1960-07-27 Method of preparing phosphine
US29249663A 1963-03-04 1963-03-04
US262496A US3312610A (en) 1959-07-31 1963-03-04 Electrolytic process for producing phosphine
US262498A US3337433A (en) 1959-07-31 1963-03-04 Electrolytic process
US262497A US3251756A (en) 1963-03-04 1963-03-04 Electrolytic process for making phosphine

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US3312610A true US3312610A (en) 1967-04-04

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US262496A Expired - Lifetime US3312610A (en) 1959-07-31 1963-03-04 Electrolytic process for producing phosphine
US262498A Expired - Lifetime US3337433A (en) 1959-07-31 1963-03-04 Electrolytic process

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Application Number Title Priority Date Filing Date
US262498A Expired - Lifetime US3337433A (en) 1959-07-31 1963-03-04 Electrolytic process

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US (2) US3312610A (de)
BE (3) BE694669A (de)
DE (4) DE1112722B (de)
GB (4) GB889639A (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3404076A (en) * 1965-04-15 1968-10-01 Shell Oil Co Electrolytic preparation of hydrides
DE102007033445A1 (de) * 2007-07-18 2009-01-22 Monopharm Handelsgesellschaft Mbh Diaphragmalyse-Verfahren und Verwendung der nach dem Verfahren erhaltenen Produkte
DE102011055186A1 (de) * 2011-11-09 2013-05-16 Monopharm Beratungs- Und Handelsgesellschaft Mbh Verfahren zur Herstellung eines Katholyts und dessen Verwendung

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1926837A (en) * 1931-07-10 1933-09-12 Martin E Cupery Electrolytic reduction of organic nitro compounds
US2719822A (en) * 1952-01-10 1955-10-04 Universal Oil Prod Co Production of chlorine from hydrogen chloride
US2780593A (en) * 1951-09-01 1957-02-05 New Jersey Zinc Co Production of metallic titanium
US3109788A (en) * 1960-07-27 1963-11-05 Hooker Chemical Corp Electrolytic production of phosphine

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1094315A (en) * 1912-11-16 1914-04-21 Hood Rubber Co Inc PROCESS FOR PRODUCING 1.3-GLYCOLS, (β-GLYCOLS.)
BE491944A (de) * 1948-12-27
US2944956A (en) * 1956-11-16 1960-07-12 Dow Chemical Co Chlorine cell having protected diaphragm
US3017338A (en) * 1958-03-03 1962-01-16 Diamond Alkali Co Electrolytic process and apparatus
US3109795A (en) * 1960-07-27 1963-11-05 Hooker Chemical Corp Method of preparing phosphine

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1926837A (en) * 1931-07-10 1933-09-12 Martin E Cupery Electrolytic reduction of organic nitro compounds
US2780593A (en) * 1951-09-01 1957-02-05 New Jersey Zinc Co Production of metallic titanium
US2719822A (en) * 1952-01-10 1955-10-04 Universal Oil Prod Co Production of chlorine from hydrogen chloride
US3109788A (en) * 1960-07-27 1963-11-05 Hooker Chemical Corp Electrolytic production of phosphine

Also Published As

Publication number Publication date
US3337433A (en) 1967-08-22
BE694669A (de) 1967-07-31
DE1210426C2 (de) 1966-09-22
DE1210426B (de) 1966-02-10
DE1210424B (de) 1966-02-10
GB1042391A (en) 1966-09-14
GB1042393A (en) 1966-09-14
BE694670A (de) 1967-07-31
GB889639A (en) 1962-02-21
DE1112722B (de) 1961-08-17
GB1042392A (en) 1966-09-14
DE1210425B (de) 1966-02-10
BE694671A (de) 1967-07-31

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Free format text: CHANGE OF NAME;ASSIGNOR:HOOKER CHEMICALS & PLASTICS CORP.;REEL/FRAME:004109/0487

Effective date: 19820330