EP0517858A1 - Procede de production de mousses n=c=o et leur pre- et post-expansions regulees - Google Patents

Procede de production de mousses n=c=o et leur pre- et post-expansions regulees

Info

Publication number
EP0517858A1
EP0517858A1 EP91907521A EP91907521A EP0517858A1 EP 0517858 A1 EP0517858 A1 EP 0517858A1 EP 91907521 A EP91907521 A EP 91907521A EP 91907521 A EP91907521 A EP 91907521A EP 0517858 A1 EP0517858 A1 EP 0517858A1
Authority
EP
European Patent Office
Prior art keywords
blowing agent
foam
process according
expansion
mixing zone
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Withdrawn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
EP91907521A
Other languages
German (de)
English (en)
Other versions
EP0517858A4 (en
Inventor
Earl N. Doyle
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.)
DOYLE Earl N
Original Assignee
Individual
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
Application filed by Individual filed Critical Individual
Publication of EP0517858A1 publication Critical patent/EP0517858A1/fr
Publication of EP0517858A4 publication Critical patent/EP0517858A4/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/149—Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/127—Mixtures of organic and inorganic blowing agents
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes

Definitions

  • Polyurethanes and other associated polymers based on diisocyanate chemistry are foamed for use in thermal insulation, floatation, and rigidizing applications.
  • these foam products can be employed in refrigeration systems, building materials, storage tanks, truck and railway tankers and cars which form the bulk of the thermal insulation industry.
  • these foams can be used in a flotation environment which encompasses, the filling of cavities in boats, barges, drilling platforms, etc., with low- density foams to prevent sinking of the vessel when accidents occur.
  • These foams have also been used to rigidize aircraft, helicopter blades, automobiles, and the like.
  • the reactants which are reacted with diisocyanates vary greatly depending on the desired end product.
  • the most widely used reactants are those compounds which terminate with an -OH group, -NH group or a -SH group.
  • the other reactant employed in the reaction is selected from diamines, water, dimethylol urea, and even dimethylol elamine, with the diamine being more preferred.
  • the "modified" phenolics are so called, since the reaction is not an acid cure, as in production of pure phenolics.
  • the isocyanates employed in such reactions range in functionality from about 2.0 to about 2.9.
  • the polymers can be prepared using prepolymers which have a functionality well above 3.0.
  • blowing agents In order to foam these polymers into low- density materials, blowing agents are used. In the past, the chlorofluorocarbons were the preferred blowing agents. However, due to the world-wide limitations on, and upcoming elimination of these products, alternative blowing agents must be found.
  • U.S. Patent 4,337,318 to Doyle is an example illustrating alternate blowing agents which have been used to replace the chlorofluorocarbons.
  • liquid carbon dioxide is used to achieve complete and immediate foaming of the polyurethane as it emerges from a mixing zone. This technique is known as "pre-expansion" of the foam. The process occurs in the absence of "post-expansion", i.e., the expansion of the foam which occurs over time after the foam leaves the mixing zone.
  • any desired percentage of pre-expansion and post-expansion may be obtained, where liquid C0 2 is preferably employed as the principal blowing agent, with the further use of co-blowing agents and other techniques such as altering the pressure to the mixing zone that allow for the controlled pre- and post-expansion of the foamed polymer.
  • the process of the present invention comprises:
  • the equipment employed in preforming the above process is essentially the same as the standard equipment employed with conventional processes.
  • either positive-displacement piston-type pumps, or variable-speed gear or vane type pumps may be employed.
  • the only requirement is that the equipment must be capable of producing pressures to the mixing zone on the order of about 300 to about 5000 psi.
  • each pump pumping a separate component to the mixing zone.
  • two or more of the components may be pre- blended and then pumped to the mixing zone a ⁇ a separate stream.
  • formulation ⁇ may be altered, modified, and changed almost instantaneously.
  • the blowing agent(s) may be introduced at any point prior to the mixing zone, e.g., into one or more of the reactant streams, or it may be introduced directly into the mixing zone.
  • the preferred principal blowing agent is liquid carbon dioxide / because of low cost, high gas production, and good stability associated with its use.
  • any liquid gas having a boiling point below approximately -100"F may be used, such as nitrogen, helium, argon, tetrafluoromethane, fluoroform, hexafluoroethane, chlorotrifluoromethane, or mixtures thereof.
  • One technique for controlling the amount of pre- and post-expansion of the foam involves the use of co- blowing agents.
  • Other co-blowing agents include higher- boiling solvents, such as methylene chloride, ethyl chloride, chloroform, methyl chloroform, and hydrochlorofluorocarbons, such as Freon 21, 22, 113, 114 and the like.
  • non-halogenated hydrocarbons such as hexane, heptane, butene-1, butane, and the like may be used.
  • the co-blowing agents may be introduced as a separate stream(s) to the mixing zone, or may be pre- blended into one or more of the other components prior to the mixing zone.
  • the co-blowing agent would compri ⁇ e a minor amount of the total blowing agent, in an amount ⁇ ufficient to provide the desirable amount of post-expansion.
  • water employed as the co-blowing agent
  • about 1 lb. of water provides the same amount of foaming as about 7 lbs. of the liquid carbon dioxide.
  • approximately 3 lbs. of Freon 22 would provide the same amount of foaming as about 2 lbs. of the liquid carbon dioxide.
  • controlled amounts of post expansion of the foam can be obtained by lowering the pressure at which the ingredients are subjected to at the mixing zone.
  • the use of pressures at the mixing zone of about 300-500 psi provides for considerable amounts of post- expansion.
  • the higher the pressure at the mixing zone the lesser the amount of post-expan ⁇ ion i ⁇ derived from the liquid carbon dioxide.
  • the degree of po ⁇ t-expansion is related to the percentage of C0 2 in the mixture. In particular, the higher the percentage of carbon dioxide in the total mix, the lesser the amount of post- expansion that may be obtained.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Procédé de production de mousses polymères à base de la technologie N=C=O, destinées à l'isolation thermique, la flottation, la rigidification et analogue, consistant à utiliser des agents gonflants gazeux liquides, tels que du CO2 liquide dans la production de la mousse. De plus, l'invention concerne la régulation de la quantité de pré-expansion et de post-expansion de la mousse. Cette régulation peut être effectuée à la fois par l'emploi d'un co-agent gonflant ainsi que par la régulation de la pression au niveau de la zone de mélange.
EP19910907521 1990-02-13 1991-02-12 Process for producing n=c=o foams and the controlled pre- and post-expansion thereof Withdrawn EP0517858A4 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US47924690A 1990-02-13 1990-02-13
US479246 1990-02-13

Publications (2)

Publication Number Publication Date
EP0517858A1 true EP0517858A1 (fr) 1992-12-16
EP0517858A4 EP0517858A4 (en) 1993-07-28

Family

ID=23903220

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19910907521 Withdrawn EP0517858A4 (en) 1990-02-13 1991-02-12 Process for producing n=c=o foams and the controlled pre- and post-expansion thereof

Country Status (3)

Country Link
EP (1) EP0517858A4 (fr)
CA (1) CA2075975A1 (fr)
WO (1) WO1991012287A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5665287A (en) * 1993-07-14 1997-09-09 Foaming Technologies Cardio Bv Froth process for continous manufacture of polyurethane foam slab-stocks
TW261577B (fr) * 1993-07-14 1995-11-01 Krypton Internat Sa
IT1270979B (it) * 1993-09-30 1997-05-26 Afros Spa Procedimento e apparecchiatura per la produzione in continuo di schiume poliuretaniche in blocchi
US5840698A (en) * 1994-10-27 1998-11-24 Affymax Technologies N.V. Inhibitors of collagenase-1 and stormelysin-I metalloproteases, pharmaceutical compositions comprising same and methods of their use
US5831004A (en) 1994-10-27 1998-11-03 Affymax Technologies N.V. Inhibitors of metalloproteases, pharmaceutical compositions comprising same and methods of their use
DE19502708C2 (de) * 1995-01-28 2003-10-23 Solvay Fluor & Derivate Verfahren zur Herstellung von Ein- oder Mehrkomponenten-Polyurethanschaumstoffen
DE59501858D1 (de) 1994-11-02 1998-05-14 Solvay Fluor & Derivate Flüssiges kohlendioxid enthaltende treibmittel
DE4442256C1 (de) * 1994-11-28 1996-07-25 Hennecke Gmbh Maschf Verfahren zum Lösen von Kohlendioxid in einem flüssigen Polymer

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3184419A (en) * 1958-02-06 1965-05-18 Dunlop Rubber Co Method for the production of polyurethane foamed material
US4337318A (en) * 1980-09-30 1982-06-29 Doyle Earl N Process for the total pre-expansion of polyurethane foam
EP0089796A1 (fr) * 1982-03-19 1983-09-28 Imperial Chemical Industries Plc Procédé de fabrication de mousses de polyuréthane
EP0145250A1 (fr) * 1983-11-05 1985-06-19 Flexible Foam Research Limited Polyuréthanes
DE3916873A1 (de) * 1988-05-27 1989-12-14 Elastogran Polyurethane Gmbh Verfahren zur herstellung von zellhaltigen kunststoffen nach dem polyisocyanat-polyadditionsverfahren und eine katalysatorkombination hierfuer
EP0353061A2 (fr) * 1988-07-29 1990-01-31 Pmc, Inc. Agents gonflants pour mousses de polyuréthane

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0689102B2 (ja) * 1987-06-19 1994-11-09 住友バイエルウレタン株式会社 硬質ポリウレタンフォ−ムの製造方法
US4931487A (en) * 1988-03-04 1990-06-05 Dow Chemical Company Chain extenders for polyurethanes

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3184419A (en) * 1958-02-06 1965-05-18 Dunlop Rubber Co Method for the production of polyurethane foamed material
US4337318A (en) * 1980-09-30 1982-06-29 Doyle Earl N Process for the total pre-expansion of polyurethane foam
EP0089796A1 (fr) * 1982-03-19 1983-09-28 Imperial Chemical Industries Plc Procédé de fabrication de mousses de polyuréthane
EP0145250A1 (fr) * 1983-11-05 1985-06-19 Flexible Foam Research Limited Polyuréthanes
DE3916873A1 (de) * 1988-05-27 1989-12-14 Elastogran Polyurethane Gmbh Verfahren zur herstellung von zellhaltigen kunststoffen nach dem polyisocyanat-polyadditionsverfahren und eine katalysatorkombination hierfuer
EP0353061A2 (fr) * 1988-07-29 1990-01-31 Pmc, Inc. Agents gonflants pour mousses de polyuréthane

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO9112287A1 *

Also Published As

Publication number Publication date
WO1991012287A1 (fr) 1991-08-22
CA2075975A1 (fr) 1991-08-14
EP0517858A4 (en) 1993-07-28

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