US2653919A - Aqueous polyethylene dispersions produced by subjecting molten polymer in water to ahigh rate of shear - Google Patents

Aqueous polyethylene dispersions produced by subjecting molten polymer in water to ahigh rate of shear Download PDF

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US2653919A
US2653919A US183475A US18347550A US2653919A US 2653919 A US2653919 A US 2653919A US 183475 A US183475 A US 183475A US 18347550 A US18347550 A US 18347550A US 2653919 A US2653919 A US 2653919A
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water
shear
polyethylene
normally solid
pressure
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Hunter Edward
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Imperial Chemical Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene

Definitions

  • dispersions of normally solid polyethylene by a process which, comprises passing moltennormally solid polyethylene with water, at a temperature above 115 C. and at sufficient pressure to keep the water in "the liquid'state, through an emulsifying device, and then releasin'g'the pressure.
  • Convenient emulsifying devices are any machines which provide high rates; of shear and keep a substantial pressure on' the materials besure casing.
  • the rate of shear is one of the factors which determines the particle size of the dispersed norm'allysolid polyethylene, but a suitable rate is provided by either of these types of emulsifying device.
  • Colloid mills have two surfaces situated within. about one-hundredth of a centimetre moving at high speed'relative'to each other, and the rate of shear is-determined by the speed and the gap. They canbe adapted so that the mixture is under pressure. Suitable conditions for a 10 centimetre diameter mill, for example, are that the gap shall be between and thousandths of a centimetre.
  • the temperature of operation must be above 115 (3., which is the melting point of normally solid polyethylene, and as normally solid polyethylene does not produce a free-flowing liquid 2 when melted, it is preferably at least 130
  • The'top temperature is limited both by the critical temperature above which water cannot be a liquid and by the'decomposition of normallysolid polyethylene, and preferably does not exceed'2 '50 0;; when emulsifying agents are present it is limited by the temperature at'which'they become inactive, which is generally about 160 C.
  • the minimum pressure needed exceeds the vapour pressure of water at the operating temperature, and is thereforeat least2 atmospheres absolute and generally at least 3-6' atmospheres. For convenience, however, we prefer to use rather high pressures between 20 and atmospheres.
  • the amount of water used is between 1 and 5 parts by weight per part of normally solid polyethylene, preferably between 2 and 5 parts by weight per part of normally solid polyethylene. It. is not commercially attractive to make dispersions which contain as little as 15% of normally solid polyethylene, and technical difiiculties arise in making dispersions containing as much as 35% of solid ethylene polymers.
  • an emulsifying agent inorder to assist in preparing the dispersion and to increase its stability. Agents which are not decomposed at 'the'emulsiflcation temperature are effective, and of these we prefer the fatty acid compounds known broadly as soaps, for example the potassium and sodium salts of stearic, palmitic, and other long chain carboxylic acids, as-
  • the water and normally solidip'ol'yethylene can within about 10 seconds of leaving the emulsifying device, in order to avoid coalescence of the particles. This is done by making the connecting space between the blow-off valve where the pressure is released and the outlet of the emulsifying device as small as possible. The releasing of the pressure can be done into the air so as to allow steam to flash oil and thus cool the emulsion to 100 C., but we prefer to cool further than this by blowing off the dispersion direct into some cooled dispersion at 3060
  • the normally solid polythene particles in the dispersions obtained by this process can readily be made as small as 5-20 microns.
  • the invention is illustrated by the following example.
  • Example A colloid mill with a gap of .01 cm. and a cm. diameter rotor in a steel casing to withstand pressures up to 100 atm. was fitted with a pressure release valve for delivering the dispersion, a pressure tight gland for the drive, and a steam jacket. It was also fitted with two feed pipes, one of which led from a water heater fed by a pump from a stock tank while the other led from a heater for the normally solid poly ethylene fed by a screw extrusion pump. 300 kgm. of water with 6.6 kgm. of triethanolamine were mixed in the stock tank. 100 kgm.
  • normally solid polythene (Alkathene brand of polythene, Grade 70, Alkathene being a registered trade-mark) were mixed with 10 kgm. of stearic acid on steam-heated rubber milling rolls and fed into the hopper of the screw extrusion pump.
  • the aqueous phase was fed into the mill at a rate of 20 kgm./hr. and the pressure release valve adjusted to maintain a pressure of 40 atm. in the mill.
  • the steam was then turned on to the steam jacket of the mill, and the electric heaters for the water and the normally solid polythene switched on. When the water, normally solid polyethylene and mill temperatures had reached 150 C. the mill was started and run at 7500 R. P. M.
  • the average particle size of the dispersed normally solid polyethylene was 10 microns Dispersions made according to the process of this invention are of most value in coating paper in order to waterproof it, and in impregnating fabrics to stiffen them.
  • the normally solid polythene retains its well known toughness, which is such an important factor in its use for coating and impregnating materials.
  • a process for the manufacture of polyethylene dispersions which comprise subjecting a mixture of molten, normally solid polyethylene and one to five parts by weight of water per part of polyethylene at a temperature above 115 C. and at a suflicient pressure to keep the water in the liquid state, to a high rate of shear such that the dispersed particles of said polyethylene have an average particle size of from about 5 to 20 microns, and then releasing the pressure.
  • a process as claimed in claim 1 carried out at a temperature between 130 and 250 C. and at a pressure between 20 and atmospheres.
  • a process as claimed in claim 1 carried out in the presence of a soap as an emulsifying agent, the soap being made in situ by having a higher fatty acid dissolved in the normally solid polyethylene and a base dissolved in the aqueous phase.
  • a process as claimed in claim 1 in which an emulsifying agent is employed and in which the amount of emulsifying agent is between 1 and 10 parts by weight per parts of normally solid polyethylene.
  • a process as claimed in claim 1 carried out in the presence of an emulsifying agent and at a temperature between and C.

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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Colloid Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Description

Patented Sept. 29, 1953 AQUEOUS POLY-ETHYLENE DISPERSIONS- PRODUCED BY .SUBJECTING MOLTEN POLYMER; IN WATER TO A HIGH RATE OF SHEAR Edward Hunter, Northwich, England, assignor to Imperial Chemical Industries Limited, a corporation of 'Grea-tBritain No Drawing.
Application September 6, 1950,
Serial No. 183,475.. In Great Britain September 28, 1949- 10 Claims. 1,
Several. methods have been described. for the manufacture of dispersions of polythene referred to hereinafter as normally solid polyethylene. They include aqueous polymerisation to .give polymers directly as an emulsion; dissolving the material in. a solvent, emulsifying the solution with Water, and removing the solvent; and milling the solid materialwith dispersing. agents or protective colloids, and adding water. These methods rarely give good quality stable dispersions, and are often expensive.
We have found that although normally solid. polyethylene does not produce a free-flowing liquid when melted, and. has a-high viscosity, yet we can emulsify molten polythene with water ina colloid mill or similar device.
According to the presentiinvention, we manufacture dispersions of normally solid polyethylene by a process which, comprises passing moltennormally solid polyethylene with water, at a temperature above 115 C. and at sufficient pressure to keep the water in "the liquid'state, through an emulsifying device, and then releasin'g'the pressure.
Convenient emulsifying devices are any machines which provide high rates; of shear and keep a substantial pressure on' the materials besure casing. The rate of shear is one of the factors which determines the particle size of the dispersed norm'allysolid polyethylene, but a suitable rate is provided by either of these types of emulsifying device. Colloid mills have two surfaces situated within. about one-hundredth of a centimetre moving at high speed'relative'to each other, and the rate of shear is-determined by the speed and the gap. They canbe adapted so that the mixture is under pressure. Suitable conditions for a 10 centimetre diameter mill, for example, are that the gap shall be between and thousandths of a centimetre. and the rotor shall rotate atbe'twe'en 5000 and" 15,000 revolutions per minute. When workin inza homogenizer we pump, hot liquidwat'er under pressure, with molten polythene, through a narrow opening between a valve and its seat; the rate of shear is determined by the rate of flow and the size of gap. Both machines are modified so that the water feed and the polythene feed are hot and above two atmospheres pressure.
The temperature of operation must be above 115 (3., which is the melting point of normally solid polyethylene, and as normally solid polyethylene does not produce a free-flowing liquid 2 when melted, it is preferably at least 130 The'top temperature is limited both by the critical temperature above which water cannot be a liquid and by the'decomposition of normallysolid polyethylene, and preferably does not exceed'2 '50 0;; when emulsifying agents are present it is limited by the temperature at'which'they become inactive, which is generally about 160 C. The minimum pressure needed exceeds the vapour pressure of water at the operating temperature, and is thereforeat least2 atmospheres absolute and generally at least 3-6' atmospheres. For convenience, however, we prefer to use rather high pressures between 20 and atmospheres.
The amount of water used is between 1 and 5 parts by weight per part of normally solid polyethylene, preferably between 2 and 5 parts by weight per part of normally solid polyethylene. It. is not commercially attractive to make dispersions which contain as little as 15% of normally solid polyethylene, and technical difiiculties arise in making dispersions containing as much as 35% of solid ethylene polymers. We also prefer to add an emulsifying agent inorder to assist in preparing the dispersion and to increase its stability. Agents which are not decomposed at 'the'emulsiflcation temperature are effective, and of these we prefer the fatty acid compounds known broadly as soaps, for example the potassium and sodium salts of stearic, palmitic, and other long chain carboxylic acids, as-
well as compounds of these acids with other bases such as triethan'ol'am'ine. "They are most advantageously introduced by incorporatingthe carboxylic acid in the normally solid polyethylene and-dissolving the basic compound in the water; so "that during emulsifl'cation the agent is formed in 'situ. Theamount of agent required is usually between 1 and 20 parts by weight per parts of normally solid polyethyl'ene, the optimum result beingobtained'with between 5 and 15 parts.
The water and normally solidip'ol'yethylenecan within about 10 seconds of leaving the emulsifying device, in order to avoid coalescence of the particles. This is done by making the connecting space between the blow-off valve where the pressure is released and the outlet of the emulsifying device as small as possible. The releasing of the pressure can be done into the air so as to allow steam to flash oil and thus cool the emulsion to 100 C., but we prefer to cool further than this by blowing off the dispersion direct into some cooled dispersion at 3060 The normally solid polythene particles in the dispersions obtained by this process can readily be made as small as 5-20 microns.
The invention is illustrated by the following example.
Example A colloid mill with a gap of .01 cm. and a cm. diameter rotor in a steel casing to withstand pressures up to 100 atm. was fitted with a pressure release valve for delivering the dispersion, a pressure tight gland for the drive, and a steam jacket. It was also fitted with two feed pipes, one of which led from a water heater fed by a pump from a stock tank while the other led from a heater for the normally solid poly ethylene fed by a screw extrusion pump. 300 kgm. of water with 6.6 kgm. of triethanolamine were mixed in the stock tank. 100 kgm. of normally solid polythene (Alkathene brand of polythene, Grade 70, Alkathene being a registered trade-mark) were mixed with 10 kgm. of stearic acid on steam-heated rubber milling rolls and fed into the hopper of the screw extrusion pump. The aqueous phase was fed into the mill at a rate of 20 kgm./hr. and the pressure release valve adjusted to maintain a pressure of 40 atm. in the mill. The steam was then turned on to the steam jacket of the mill, and the electric heaters for the water and the normally solid polythene switched on. When the water, normally solid polyethylene and mill temperatures had reached 150 C. the mill was started and run at 7500 R. P. M. and the screw extrusion pump started so as to feed the normally solid polythene mixture at a rate of 10 kgm./hr. The exit from the pressure release valve was at the bottom of an open l-litre tank fitted with an overflow delivering into a receiver. 2 litres of aqueous phase at 35 C. were circulated through this tank and through a cooler. The dispersion emerged from the release valve, mixed with and gradually displaced the aqueous phase in the cooling system, so that after mins. a dispersion containing 30% normally solid polyethylene was being collected from the overflow. The average particle size of the dispersed normally solid polyethylene was 10 microns Dispersions made according to the process of this invention are of most value in coating paper in order to waterproof it, and in impregnating fabrics to stiffen them. The normally solid polythene retains its well known toughness, which is such an important factor in its use for coating and impregnating materials.
What I claim is:
1. A process for the manufacture of polyethylene dispersions which comprise subjecting a mixture of molten, normally solid polyethylene and one to five parts by weight of water per part of polyethylene at a temperature above 115 C. and at a suflicient pressure to keep the water in the liquid state, to a high rate of shear such that the dispersed particles of said polyethylene have an average particle size of from about 5 to 20 microns, and then releasing the pressure.
2. A process as claimed in claim 1 carried out at a temperature between 130 and 250 C. and at a pressure between 20 and atmospheres.
3. A process as claimed in claim 1 wherein between 2 and 5 parts by weight of water are used per part of normally solid polyethylene.
4. A process as claimed in claim 1 carried out in the presence of an emulsifying agent.
5. A process as claimed in claim 1 carried out in the presence of a soap as an emulsifying agent, the soap being made in situ by having a higher fatty acid dissolved in the normally solid polyethylene and a base dissolved in the aqueous phase.
6. A process as claimed in claim 1 in which an emulsifying agent is employed and in which the amount of emulsifying agent is between 1 and 10 parts by weight per parts of normally solid polyethylene.
'7. A process as claimed in claim 1 carried out in the presence of an emulsifying agent and at a temperature between and C.
8. A process as claimed in claim 1 in which the emulsion is rapidly cooled immediately after the pressure has been released.
9. A process as claimed in claim 1 in which the pressure is released within 10 seconds after J the dispersion has been subjected to a high rate References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,290,794 Alvarado July 21, 1942 2,313,144 Gomm Mar. 9, 1943 2,386,674 Flint et al. Oct. 9, 1945 OTHER REFERENCES Carbide and Carbon Chemicals Corp.: Emulsions, seventh edition, April 15, 1946, pages 8 and 9.

Claims (1)

1. A PROCESS FOR THE MANUFACTURE OF POLYETHYLENE DISPERSIONS WHICH COMPRISE SUBJECTING A MIXTURE OF MOLTEN, NORMALLY SOLID POLYETHYLENE AND ONE TO FIVE PARTS BY WEIGHT OF WATER PER PART OF POLYETHYLENE AT A TEMPERATURE ABOVE 115* C. AND AT A SUFFICIENT PRESSURE TO KEEP THE WATER IN THE LIQUID STATE, TO A HIGH RATE OF SHEAR SUCH THAT THE DISPERSED PARTICLES OF SAID POLYETHYLENE HAVE AN AVERAGE PARTICLE SIZE OF FROM ABOUT 5 TO 20 MICRONS, AND THEN RELEASING THE PRESSURE.
US183475A 1949-09-28 1950-09-06 Aqueous polyethylene dispersions produced by subjecting molten polymer in water to ahigh rate of shear Expired - Lifetime US2653919A (en)

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Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2841506A (en) * 1953-06-15 1958-07-01 Swift & Co Protective composition
US2917412A (en) * 1958-05-12 1959-12-15 Robert M Reinhardt Process for the production of cellulosic textiles with permanent creases and improved soil and abrasion resistance
US2924538A (en) * 1956-04-16 1960-02-09 Allied Chem Dense papers and process for preparing them
US2995533A (en) * 1961-08-08 Coatings for masonry building units
US3055853A (en) * 1957-09-06 1962-09-25 Kerr Mc Gee Oil Ind Inc Synthetic resin-in-water emulsion, process for preparing same, and process for sizing cellulose therewith
US3103459A (en) * 1963-09-10 Paperboard corrugating medium treatment
US3239371A (en) * 1962-05-28 1966-03-08 Gulf Oil Corp Paper products surface sized with polyethylene and method of making the same
US3244652A (en) * 1961-04-21 1966-04-05 Gulf Oil Corp Stable polyethylene latices
US3245831A (en) * 1961-04-21 1966-04-12 Gulf Oil Corp Process of finishing textiles with mechanically stable latex of emulsified particles of emulsion-polymerized nonoxidized polyethylene
US3247141A (en) * 1961-04-21 1966-04-19 Gulf Oil Corp Emulsion polishes comprising polyethylene, wax and resin
US3265649A (en) * 1961-01-09 1966-08-09 Faltings Volkert Process for refining polyolefins by an addition of metal salts of inorganic or organic acids
US3284233A (en) * 1960-05-13 1966-11-08 Johnson & Johnson Bonded nonwoven fabrics and binders for the manufacture thereof
US3296162A (en) * 1961-04-21 1967-01-03 Gulf Oil Corp Stable latices comprising polyethylene particles coated with emulsifying agents
US3412035A (en) * 1963-04-22 1968-11-19 Switzer Brothers Inc Method for producing fine pigment particles in a liquid vehicle
US3412104A (en) * 1963-06-28 1968-11-19 Switzer Brothers Inc Printing ink production
US3412034A (en) * 1963-04-22 1968-11-19 Switzer Brothers Inc Method for producing fine pigment particles in a liquid vehicle
US3427193A (en) * 1964-01-15 1969-02-11 Grace W R & Co Shrink resistant impregnated wool
US3432339A (en) * 1965-03-03 1969-03-11 Nat Distillers Chem Corp Process for coating substrates with polymers
US3796366A (en) * 1971-07-26 1974-03-12 Cosden Oil & Chem Co Anti-static plastic articles
US4123403A (en) * 1977-06-27 1978-10-31 The Dow Chemical Company Continuous process for preparing aqueous polymer microsuspensions
US4148768A (en) * 1977-08-15 1979-04-10 National Distillers And Chemical Corporation Polymer dispersion process
US4148766A (en) * 1977-08-15 1979-04-10 National Distillers And Chemical Corporation Polymer dispersion process
US4150003A (en) * 1977-08-15 1979-04-17 National Distillers And Chemical Corporation Polymer dispersion process
US4151133A (en) * 1977-08-15 1979-04-24 National Distillers And Chemical Corporation Polymer dispersion process
DE3910901A1 (en) * 1989-04-04 1990-10-11 Ppg Ind Deutschland Gmbh METHOD FOR PRODUCING AN AQUEOUS PARTICULAR DISPERSION OF A CHLORINE POLYOLEFIN AND USE THEREOF IN AQUEOUS COATING COMPOSITIONS
EP1873190A1 (en) * 2006-05-30 2008-01-02 Vagotex Windtex S.p.A. Method for the mechano-chemical treatment of materials comprising at least one polymer in the liquid state and products obtainable by said method
US20090194450A1 (en) * 2008-02-01 2009-08-06 Thierry Jean-Luc Dabadie Coating Compositions, Coated Substrates and Hermetic Seals Made Therefrom Having Improved Low Temperature Sealing and Hot Tack Properties

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL100221C (en) * 1956-05-24
BE627665A (en) * 1962-01-27
WO2003027170A1 (en) * 2001-09-15 2003-04-03 Siemens Axiva Gmbh & Co. Kg Method for the production of fine particles from fusible solids

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2290794A (en) * 1938-09-08 1942-07-21 Du Pont Aqueous dispersions of ethylene polymers
US2313144A (en) * 1938-06-07 1943-03-09 Ici Ltd Production of aqueous dispersions of ethylene polymer
US2386674A (en) * 1940-01-02 1945-10-09 Ici Ltd Pulverulent materials and dispersions produced thence

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2313144A (en) * 1938-06-07 1943-03-09 Ici Ltd Production of aqueous dispersions of ethylene polymer
US2290794A (en) * 1938-09-08 1942-07-21 Du Pont Aqueous dispersions of ethylene polymers
US2386674A (en) * 1940-01-02 1945-10-09 Ici Ltd Pulverulent materials and dispersions produced thence

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2995533A (en) * 1961-08-08 Coatings for masonry building units
US3103459A (en) * 1963-09-10 Paperboard corrugating medium treatment
US2841506A (en) * 1953-06-15 1958-07-01 Swift & Co Protective composition
US2924538A (en) * 1956-04-16 1960-02-09 Allied Chem Dense papers and process for preparing them
US3055853A (en) * 1957-09-06 1962-09-25 Kerr Mc Gee Oil Ind Inc Synthetic resin-in-water emulsion, process for preparing same, and process for sizing cellulose therewith
US2917412A (en) * 1958-05-12 1959-12-15 Robert M Reinhardt Process for the production of cellulosic textiles with permanent creases and improved soil and abrasion resistance
US3284233A (en) * 1960-05-13 1966-11-08 Johnson & Johnson Bonded nonwoven fabrics and binders for the manufacture thereof
US3265649A (en) * 1961-01-09 1966-08-09 Faltings Volkert Process for refining polyolefins by an addition of metal salts of inorganic or organic acids
US3247141A (en) * 1961-04-21 1966-04-19 Gulf Oil Corp Emulsion polishes comprising polyethylene, wax and resin
US3245831A (en) * 1961-04-21 1966-04-12 Gulf Oil Corp Process of finishing textiles with mechanically stable latex of emulsified particles of emulsion-polymerized nonoxidized polyethylene
US3244652A (en) * 1961-04-21 1966-04-05 Gulf Oil Corp Stable polyethylene latices
US3296162A (en) * 1961-04-21 1967-01-03 Gulf Oil Corp Stable latices comprising polyethylene particles coated with emulsifying agents
US3239371A (en) * 1962-05-28 1966-03-08 Gulf Oil Corp Paper products surface sized with polyethylene and method of making the same
US3412034A (en) * 1963-04-22 1968-11-19 Switzer Brothers Inc Method for producing fine pigment particles in a liquid vehicle
US3412035A (en) * 1963-04-22 1968-11-19 Switzer Brothers Inc Method for producing fine pigment particles in a liquid vehicle
US3412104A (en) * 1963-06-28 1968-11-19 Switzer Brothers Inc Printing ink production
US3427193A (en) * 1964-01-15 1969-02-11 Grace W R & Co Shrink resistant impregnated wool
US3432339A (en) * 1965-03-03 1969-03-11 Nat Distillers Chem Corp Process for coating substrates with polymers
US3796366A (en) * 1971-07-26 1974-03-12 Cosden Oil & Chem Co Anti-static plastic articles
US4123403A (en) * 1977-06-27 1978-10-31 The Dow Chemical Company Continuous process for preparing aqueous polymer microsuspensions
US4148768A (en) * 1977-08-15 1979-04-10 National Distillers And Chemical Corporation Polymer dispersion process
US4148766A (en) * 1977-08-15 1979-04-10 National Distillers And Chemical Corporation Polymer dispersion process
US4150003A (en) * 1977-08-15 1979-04-17 National Distillers And Chemical Corporation Polymer dispersion process
US4151133A (en) * 1977-08-15 1979-04-24 National Distillers And Chemical Corporation Polymer dispersion process
DE3910901A1 (en) * 1989-04-04 1990-10-11 Ppg Ind Deutschland Gmbh METHOD FOR PRODUCING AN AQUEOUS PARTICULAR DISPERSION OF A CHLORINE POLYOLEFIN AND USE THEREOF IN AQUEOUS COATING COMPOSITIONS
EP1873190A1 (en) * 2006-05-30 2008-01-02 Vagotex Windtex S.p.A. Method for the mechano-chemical treatment of materials comprising at least one polymer in the liquid state and products obtainable by said method
US20080045658A1 (en) * 2006-05-30 2008-02-21 Vagotex Windtex Spa Method for Mechano-Chemically Treating Materials Comprising at least a Polymer in the Liquid State and Products Obtainable with such Method
US20090194450A1 (en) * 2008-02-01 2009-08-06 Thierry Jean-Luc Dabadie Coating Compositions, Coated Substrates and Hermetic Seals Made Therefrom Having Improved Low Temperature Sealing and Hot Tack Properties
US8129032B2 (en) * 2008-02-01 2012-03-06 Exxonmobil Oil Corporation Coating compositions, coated substrates and hermetic seals made therefrom having improved low temperature sealing and hot tack properties
US8202623B2 (en) 2008-02-01 2012-06-19 Exxonmobil Oil Corporation Coating compositions, coated substrates and hermetic seals made therefrom having improved low temperature sealing and hot tack properties

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GB671968A (en) 1952-05-14
FR1024822A (en) 1953-04-07
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