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US3134830A - Process for the production of shaped parts of plasticized polyethylene - Google Patents

Process for the production of shaped parts of plasticized polyethylene Download PDF

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Publication number
US3134830A
US3134830A US694088A US69408857A US3134830A US 3134830 A US3134830 A US 3134830A US 694088 A US694088 A US 694088A US 69408857 A US69408857 A US 69408857A US 3134830 A US3134830 A US 3134830A
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Prior art keywords
blanks
polyethylene
production
plasticized
compression
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US694088A
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Roelen Otto
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Ruhrchemie AG
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Ruhrchemie AG
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • B29C43/14—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles in several steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B11/00—Making preforms
    • B29B11/06—Making preforms by moulding the material
    • B29B11/12—Compression moulding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/006—Pressing and sintering powders, granules or fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2791/00—Shaping characteristics in general
    • B29C2791/001—Shaping in several steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/25—Solid
    • B29K2105/251—Particles, powder or granules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/25—Solid
    • B29K2105/253—Preform
    • B29K2105/255—Blocks or tablets

Definitions

  • blanks having larger dimensions than those of the finished parts are first produced by mechanical pressure and preferably at room temperature. These blanks are subsequently converted into sintere'd and plasticized polyethylene by the simultaneous use of heat and of mechanical pressure.
  • slabs of 20 x 20 centimeters and 3 cm. thickness may first to be produced by cold-pressing. These slabs may be placed side by side into a die of 1 x 2 meters. If at least one additional compression is now applied while heating, one single sheet of 1 x 2 meters and 3 cm. thickness is obtained. Seams are no longer recognizable in the finished sheet. According to another embodiment of the process of the invention, heating of the individual slab is not effected in the second compression stage but previously as, for example, is an oven under a protective gas atmosphere.
  • the blanks obtained from the first stage consist of prisms having 6 surfaces positioned at right angles .with respect to one another, or of disks of circular or other form with par allel surfaces.
  • the prisms may be arranged side by side in one layer, or the prisms or disks may be placed one upon another. It is advantageous in many cases to place prisms side by side and in layers.
  • the process of the invention is also applicable to the production of shaped parts of plasticized polypropylene.
  • the process of the invention is primarily applicable to high molecular weight polyethylene, i.e., for example, polyethylenes having molecular weights in excess of 100,- 000 and preferably above 500,000.
  • Polyethylene of this type is known as high-density polyethylene and is produced by the polymerization of ethylene at pressures below about 100 kg./ sq. cm. and temperatures up to about 100 C. with the use of catalysts consisting of mixtures of organometallic compounds, especially aluminum alkyl compounds, with compounds of metals of the 4th to 6th subgroups of the periodic table, particularly with titanium compounds as, for example, titanium tetrachloride (see Angewandte Chemie, vol. 67, 541-547 (1955)).
  • Example 1 The polymerization of ethylene was effected in a glass vessel of about 5 liters capacity and equipped with an agitator, into which were filled 2 liters of a C -C hydrocarbon fraction obtained by carbon monoxide hydrogenation. This hydrocarbon fraction had been prepared by hydrogenation, eifected at 250 C., subsequent refining with sulfuric acid, and intensive drying. After flushing of the reaction vessel with ethylene gas and heating to about 50 C., the catalyst solution was added while agitating and passing ethylene through the vessel. The catalyst solution had been prepared by mixing together 100 cc. of the same C C fraction, 1.08 grams of diethyl aluminum monochloride and 0.42 gram of titanium tetrachlo ride, and vigorously shaking the mixture for about 30 minutes. Upon addition to the catalyst solution, the reaction temperature was adjusted to about C. Atmospheric pressure prevailed throughout the reaction as glass equipment cannot be subjected to elevated pressures.
  • the mixture was filtered and the filter residue was treated with times its quantity of 1% aqueous sodium hydroxyide solution in a stirring flask.
  • the mixture was then heated to the boiling point, thereby distilling oil the residue of the hydrocarbon fraction together with the water vapor.
  • the residue from the distillation was finally washed to free it from alkali and was then dried.
  • the polyethylene obtained had a molecular weight of 1,100,000, as determined viscosimetrically.
  • sheets of 100 x 80 cm. were produced by heating the blanks obtained by cold-pressing, in the first compression stage to 160 C. in an oven under a protective gas atmosphere; then the heated slabs were placed side by side into the preheated die of 100 X 80 cm. and compressed in a press which was not heated, or only slightly heated.
  • sheets having the same good properties were obtained.
  • Example 2 Polyethylene as prepared in Example 1, i.e. having a molecular weight of 1,100,000 as determined viscosimetrically, was used in this example, too. 38 kg. of this material, in a die of 50 cm. in width and 80 cm. in length, were cold-pressed at a specific pressure of 130 kg./ sq. cm. This resulted in blanks of 14.2 cm. in thickness.
  • the cold-pressed blanks were compressed into sheets in a heatable press for about 8 hours and at a temperature of 160 C.
  • the sheets, whfie hot, were subsequently placed one upon another and compressed for about minutes under a specific pressure of 18 kg./ sq. cm. with no additional supply of heat.
  • a block of polyethylene was obtained having a weight of 152 kg. and a size of 50 x 80 x 32 The block was completely homogeneous and showed no reduction in strength at the seams.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)

Description

United States Patent "ice 3,134,830 EROCESS FUR THE PRODUCTION OF SHAPED PARTS OF PLASTICIZED PULYETHYLENE Otto Roelen, fiberhausen-Holten, Germany, assignor to Ruhrchernie Alttiengesellschaft, Oberhausen-Holteu,
Germany No Drawing. Filed Nov. 4, 1957, Ser. No. 694,038
Claims priority, application Germany Nov. 5, 1956 3 Claims. (Cl. 2641t2d) It has already been suggested to produce shaped parts of polyethylene by compressing finely divided polyethylene, especially polyethylene powder, having molecular weights above 500,000, e.g. above 1,000,000 in several pressure stages; the compressions in the second pressure stage and, if necessary or desired, in the succeeding pressure stages is carried out with simultaneous heating until the material is plasticized.
Thus, blanks, having larger dimensions than those of the finished parts are first produced by mechanical pressure and preferably at room temperature. These blanks are subsequently converted into sintere'd and plasticized polyethylene by the simultaneous use of heat and of mechanical pressure.
Good results have been obtained by this working method with regard to the quality of the shaped parts produced. Also, the process could be carried out in a simple manner with the devices known in the art. The production of larger shaped parts, however, was limited by the fact that the cold-pressing operation first required very high pressures on the whole surface of the blanks to be finished. The cold-pressing operation requires substantially higher pressures than the succeeding pressure stages effected with the material heated prior to or during the compression.
It has been found that these difliculties can be avoided if the process for the production of shaped parts of plasticized polyethylene mixed, if desired, with other polymers, is carried out in at least two compression stages. In the first of these stages shape-retaining blanks of finely divided material are produced with no increase in temperature which are subsequently plasticized in a second compression stage after having been heated or while being heated; this is done in such a manner that two or more blanks resulting from the first pressure stage are placed together in face-toface position in the second pressure stage, so that they form an integral shaped part or body after having undergone the treatment effected in the second pressure stage.
It has surprisingly been found in this process that the seams between the individual cold-pressed blanks are frequently no longer visible in the space after sintering. Above all, these seams have the same properties with regard to strength as those of the surrounding portions. The important advantage of the process of the invention resides in the fact that it becomes possible to produce substantially larger shaped parts with the same hydraulic press available.
Thus, for example, slabs of 20 x 20 centimeters and 3 cm. thickness may first to be produced by cold-pressing. These slabs may be placed side by side into a die of 1 x 2 meters. If at least one additional compression is now applied while heating, one single sheet of 1 x 2 meters and 3 cm. thickness is obtained. Seams are no longer recognizable in the finished sheet. According to another embodiment of the process of the invention, heating of the individual slab is not effected in the second compression stage but previously as, for example, is an oven under a protective gas atmosphere.
It is also possible by the process of the invention, for example, to stack 5 slabs each of cm. thickness and press them into a block of about 50 cm. thickness. The production of such a block from a single piece would require excessively long heating periods due to the poor 3,134,830 Patented May 26, 1964 heat conductivity of polyethylene so that the production would become uneconomical. Thus, the process of the invention permits the production of blocks of any thickness desired.
In practice, best results are obtained when the pressure applied in the first stage of the process is at least 5 times that of the pressure used in the second stage. According to a specific embodiment of the process, the blanks obtained from the first stage consist of prisms having 6 surfaces positioned at right angles .with respect to one another, or of disks of circular or other form with par allel surfaces. The prisms may be arranged side by side in one layer, or the prisms or disks may be placed one upon another. It is advantageous in many cases to place prisms side by side and in layers.
While in general blanks having the same chemical composition and the same physical properties will be used for the second and, as the case may be, the succeeding compression stages, the process becomes particularly useful by the fact that blanks having different properties can be combined to form an integral shaped part; in that case, it is preferable to operate so that the difierent blanks are arranged in regular order as, for example, in layers.
Thus, it is possible to combine into one piece coldpressed pieces of different qualities, e.g. of dilferent colors, different molecular weights, etc., thereby producing laminates having particular color effects and particular properties with regard to strength.
It is favorable in special cases to incorporate other polymers into the polyethylene. The process of the invention is also applicable to the production of shaped parts of plasticized polypropylene.
The process of the invention is primarily applicable to high molecular weight polyethylene, i.e., for example, polyethylenes having molecular weights in excess of 100,- 000 and preferably above 500,000. Polyethylene of this type is known as high-density polyethylene and is produced by the polymerization of ethylene at pressures below about 100 kg./ sq. cm. and temperatures up to about 100 C. with the use of catalysts consisting of mixtures of organometallic compounds, especially aluminum alkyl compounds, with compounds of metals of the 4th to 6th subgroups of the periodic table, particularly with titanium compounds as, for example, titanium tetrachloride (see Angewandte Chemie, vol. 67, 541-547 (1955)).
The molecular weights stated above have been determined viscosimetrically.
The process according to the invention will now be more fully explained in a number of examples, but it should be understood that these are given by way of illustration and not of limitation and that many changes in the details can be made without departing from the spirit of the invention.
Example 1 The polymerization of ethylene was effected in a glass vessel of about 5 liters capacity and equipped with an agitator, into which were filled 2 liters of a C -C hydrocarbon fraction obtained by carbon monoxide hydrogenation. This hydrocarbon fraction had been prepared by hydrogenation, eifected at 250 C., subsequent refining with sulfuric acid, and intensive drying. After flushing of the reaction vessel with ethylene gas and heating to about 50 C., the catalyst solution was added while agitating and passing ethylene through the vessel. The catalyst solution had been prepared by mixing together 100 cc. of the same C C fraction, 1.08 grams of diethyl aluminum monochloride and 0.42 gram of titanium tetrachlo ride, and vigorously shaking the mixture for about 30 minutes. Upon addition to the catalyst solution, the reaction temperature was adjusted to about C. Atmospheric pressure prevailed throughout the reaction as glass equipment cannot be subjected to elevated pressures.
After 12 hours of reaction, 472 grams of polyethylene had formed.
The mixture was filtered and the filter residue was treated with times its quantity of 1% aqueous sodium hydroxyide solution in a stirring flask. The mixture was then heated to the boiling point, thereby distilling oil the residue of the hydrocarbon fraction together with the water vapor.
The residue from the distillation was finally washed to free it from alkali and was then dried. The polyethylene obtained had a molecular weight of 1,100,000, as determined viscosimetrically.
760 grams of the high molecular weight polyethylene thus prepared and having an average particle size of loop. was placed into a die of 20 cm. in width and 20 cm. in length. The mass was cold-pressed at a specific pressure of 100 kg./sq. cm. and at room temperature whereby blanks of 20 x 20 x 2.8 cm. were obtained.
20 of these blanks, in rows of five, were placed side by side into a die of 100 x 80 cm. The die was placed into a press equiped with heatable pressing plates and subjected to a specific pressure of kg./sq. cm. for 6 hours at a temperature of 150 C. Upon cooling, a sheet of plasticized polyethylene having a weight of about 1.5 kg. was obtained. This sheet was completely homogeneous. After sintering of the sheet, the strength measured at the seams between the original blanks was the same as that of the adjacent portions.
By another embodiment, sheets of 100 x 80 cm. were produced by heating the blanks obtained by cold-pressing, in the first compression stage to 160 C. in an oven under a protective gas atmosphere; then the heated slabs were placed side by side into the preheated die of 100 X 80 cm. and compressed in a press which was not heated, or only slightly heated. Here again, sheets having the same good properties were obtained.
Example 2 Polyethylene as prepared in Example 1, i.e. having a molecular weight of 1,100,000 as determined viscosimetrically, was used in this example, too. 38 kg. of this material, in a die of 50 cm. in width and 80 cm. in length, were cold-pressed at a specific pressure of 130 kg./ sq. cm. This resulted in blanks of 14.2 cm. in thickness.
The cold-pressed blanks were compressed into sheets in a heatable press for about 8 hours and at a temperature of 160 C. The sheets, whfie hot, were subsequently placed one upon another and compressed for about minutes under a specific pressure of 18 kg./ sq. cm. with no additional supply of heat. A block of polyethylene was obtained having a weight of 152 kg. and a size of 50 x 80 x 32 The block was completely homogeneous and showed no reduction in strength at the seams.
It should be understood that the process can be carried outwith equal success when the laminates are subjected in the second compression stage to pressures of 10-25 kg./ sq. cm. at temperatures ranging from 150 to 180 C.
What I claim is:
1. A process for the production of shaped, filled-out solid blocks of plasticized high-density polyethylene in a plurality of compression stages wherein in a first compression stage shape-retaining blanks are produced from finely divided high-density polyethylene which subsequently are plasticized in a second compression stage under application of heat, which comprises compressing said finely divided high-density polyethylene substantially at room-temperature at pressures ranging from 100 to 180 kg./cm. to form said blanks, placing at least tWo of said blanks in a face-to-face position, and compressing the same into an integral and seamless unit by subjecting them to temperatures of 150-180" C. and to pressures of 10 to 25 kg./cm.
2. The process as defined in claim 1, wherein the pressure in said first stage is at least five times that used in said second stage.
3. The process according to claim 1 wherein the blanks obtained in the first stage consist of rectangles having 6 surfaces located at right angles with respect to one another.
4. The process according to claim 1, wherein the blanks obtained in the first stage consist of circular disks with parallel end faces.
5. The process according to claim 1, wherein the shaped blanks of the first compression stage are arranged side by side in one layer, before they are subjected to further compression.
6. The process according to claim 5, wherein the shaped blanks of the first compression stage are arranged in superposed position before they are subjected to further compression.
7. The process according to claim 1, wherein blanks having the same chemical composition and the same physical properties are used.
8. The process according to claim 1, wherein blanks of difierent molecular weight are combined to produce an integral shaped body.
References Cited in the file of this patent UNITED STATES PATENTS 2,428,977 Mares Oct. 14, 1947 2,440,190 Alfthan Apr. 20, 1948 2,597,704 Carlson May 20, 1952 2,736,925 Heisler et al. Mar. 6, 1956 2,800,945 Schilling July 30, 1957 2,824,090 Edwards et al Feb. 18, 1958 FOREIGN PATENTS 610,562 Great Britain Oct. 18, 1948 735,162 Great Britain Aug. 17, 1955 OTHER REFERENCES Polyethylene Grabs the Spotlight, pages -92, 210 ff., pages 89 and 90 cited, appearing in Modern Plastics, September 1955.

Claims (1)

1. A PROCESS FOR THE PRODUCTION OF SHAPED, FILLED-OUT SOLID BLOCKS OF PLASTICIZED HIGH-DENSITY POLYETHYLENE IN A PLURALITY OF COMPRESSION STAGES WHEREIN IN A FIRST COMPRESSION STAGE SHAPE-RETAINING BLANKS ARE PRODUCED FROM FINELY DIVIDIED HIGH-DENSITY POLYETHYLENE WHICH SUBSEQUENTLY ARE PLASTICIZED IN A SECOND COMPRESSION STAGE UNDER APPLICATION OF HEAT, WHICH COMPRISES COMPRESSING SAID FINELY DIVIDED HIGH-DENSITY POLYETHYLENE SUBSTANTIALLY AT ROOM-TEMPERATURE AT PRESSURES RANGING FROM 100 TO 180 KG./CM.2 TO FORM SAID BLANKS, PLACING AT LEAST TWO OF SAID BLANKS IN A FACE-TO-FACE POSITION, AND COMPRESSING THE SAME INTO AN INTEGRAL AND SEAMLESS UNIT BY SUBJECTING THEM TO TEMPERATUES OF 150-180*C. AND TO PRESSURES OF 10 TO 25 KG./CM.2.
US694088A 1956-11-05 1957-11-04 Process for the production of shaped parts of plasticized polyethylene Expired - Lifetime US3134830A (en)

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DER19942A DE1124225B (en) 1956-11-05 1956-11-05 Process for the production of molded bodies from plasticized polyethylene

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BE (1) BE561820A (en)
DE (1) DE1124225B (en)
FR (1) FR1186391A (en)
GB (1) GB853194A (en)
NL (1) NL100964C (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3208900A (en) * 1960-11-25 1965-09-28 Vasco Ind Corp Method of manufacturing decorated molded articles from finely divided thermoplastic materials
US3975481A (en) * 1972-12-01 1976-08-17 Allied Chemical Corporation Method for molding ultra-high molecular weight polyethylene molding powder
US4110391A (en) * 1976-07-31 1978-08-29 Ruhrchemie Aktiengesellschaft Process for the manufacture of molded articles from polyolefins with molecular weights of at least one million
US4164531A (en) * 1975-01-13 1979-08-14 Mitsui Petrochemical Industries, Ltd. Injection molding of ultra high molecular weight polyethylene
EP0179171A3 (en) * 1982-09-29 1987-06-16 The Dow Chemical Company Improved method of forming blanks for the solid-phase forming of thermoplastic articles

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2428977A (en) * 1945-04-17 1947-10-14 Monsanto Chemicals Process for producing decorative articles
US2440190A (en) * 1944-03-01 1948-04-20 Du Pont Preparation of nonporous polytetrafluoroethylene articles
GB610562A (en) * 1946-03-07 1948-10-18 Ashdowns Ltd Improvements in or relating to methods of moulding solid articles in thermosetting moulding compounds
US2597704A (en) * 1949-08-22 1952-05-20 Cosom Ind Inc Process of making hollow bodies from fusible plastic materials
GB735162A (en) * 1952-09-30 1955-08-17 Degussa Process for the production of shaped bodies of polyethylene
US2736925A (en) * 1953-06-08 1956-03-06 Jerome S Heisler Method of forming hollow articles from polyethylene
US2800945A (en) * 1952-02-20 1957-07-30 Paul K Schilling Cup-shaped articles, and method and apparatus for making them
US2824090A (en) * 1955-12-27 1958-02-18 Eastman Kodak Co Polymerization of alpha-olefins with a catalyst mixture of an orthotitanate and an alkyl aluminum halide

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE245148C (en) *
DE1431C (en) * 1877-11-02 r. sarre, Kaiserl. Telegraphen - Direktionsrath /.. D., in Dresden, welcher durch notarielle Cession vom 1. April 1878 seine Rechte an den Königlichen Kommerzienrath G. stobwasser in Berlin übertragen hat Kerosene lamp with regulator
US1716379A (en) * 1924-12-30 1929-06-11 Leysieffer Gustav Method of manufacturing sheets, slabs or molded articles from celluloid or celluloid-like materials

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2440190A (en) * 1944-03-01 1948-04-20 Du Pont Preparation of nonporous polytetrafluoroethylene articles
US2428977A (en) * 1945-04-17 1947-10-14 Monsanto Chemicals Process for producing decorative articles
GB610562A (en) * 1946-03-07 1948-10-18 Ashdowns Ltd Improvements in or relating to methods of moulding solid articles in thermosetting moulding compounds
US2597704A (en) * 1949-08-22 1952-05-20 Cosom Ind Inc Process of making hollow bodies from fusible plastic materials
US2800945A (en) * 1952-02-20 1957-07-30 Paul K Schilling Cup-shaped articles, and method and apparatus for making them
GB735162A (en) * 1952-09-30 1955-08-17 Degussa Process for the production of shaped bodies of polyethylene
US2736925A (en) * 1953-06-08 1956-03-06 Jerome S Heisler Method of forming hollow articles from polyethylene
US2824090A (en) * 1955-12-27 1958-02-18 Eastman Kodak Co Polymerization of alpha-olefins with a catalyst mixture of an orthotitanate and an alkyl aluminum halide

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3208900A (en) * 1960-11-25 1965-09-28 Vasco Ind Corp Method of manufacturing decorated molded articles from finely divided thermoplastic materials
US3975481A (en) * 1972-12-01 1976-08-17 Allied Chemical Corporation Method for molding ultra-high molecular weight polyethylene molding powder
US4164531A (en) * 1975-01-13 1979-08-14 Mitsui Petrochemical Industries, Ltd. Injection molding of ultra high molecular weight polyethylene
US4110391A (en) * 1976-07-31 1978-08-29 Ruhrchemie Aktiengesellschaft Process for the manufacture of molded articles from polyolefins with molecular weights of at least one million
EP0179171A3 (en) * 1982-09-29 1987-06-16 The Dow Chemical Company Improved method of forming blanks for the solid-phase forming of thermoplastic articles

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NL100964C (en)
GB853194A (en) 1960-11-02
DE1124225B (en) 1962-02-22
FR1186391A (en) 1959-08-21

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