WO1991012287A1 - 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 Download PDF

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Publication number
WO1991012287A1
WO1991012287A1 PCT/US1991/000845 US9100845W WO9112287A1 WO 1991012287 A1 WO1991012287 A1 WO 1991012287A1 US 9100845 W US9100845 W US 9100845W WO 9112287 A1 WO9112287 A1 WO 9112287A1
Authority
WO
WIPO (PCT)
Prior art keywords
blowing agent
foam
process according
expansion
mixing zone
Prior art date
Application number
PCT/US1991/000845
Other languages
English (en)
Inventor
Earl N. Doyle
Original Assignee
Doyle Earl N
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 Doyle Earl N filed Critical Doyle Earl N
Publication of WO1991012287A1 publication Critical patent/WO1991012287A1/fr

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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.
PCT/US1991/000845 1990-02-13 1991-02-12 Procede de production de mousses n=c=o et leur pre- et post-expansions regulees WO1991012287A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US47924690A 1990-02-13 1990-02-13
US479,246 1990-02-13

Publications (1)

Publication Number Publication Date
WO1991012287A1 true WO1991012287A1 (fr) 1991-08-22

Family

ID=23903220

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1991/000845 WO1991012287A1 (fr) 1990-02-13 1991-02-12 Procede de production de mousses n=c=o et leur pre- et post-expansions regulees

Country Status (3)

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

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996014354A2 (fr) * 1994-11-02 1996-05-17 Solvay Fluor Und Derivate Gmbh Agents d'expansion contenant du dioxyde de carbone liquide
EP0722975A1 (fr) * 1994-11-28 1996-07-24 Bayer Ag Procédé de dissolution de dioxyde de carbone dans un polymère liquide
US5620710A (en) * 1993-07-14 1997-04-15 Foaming Technologies Cardio Bv Froth system for continuous manufacture of polyurethane foam slab-stocks
US5665287A (en) * 1993-07-14 1997-09-09 Foaming Technologies Cardio Bv Froth process for continous manufacture of polyurethane foam slab-stocks
US5831004A (en) * 1994-10-27 1998-11-03 Affymax Technologies N.V. Inhibitors of metalloproteases, pharmaceutical compositions comprising same and methods of their use
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
USRE37012E1 (en) * 1993-07-14 2001-01-09 Foaming Technologies, Cardio BV Froth system for continuous manufacture of polyurethane foam slab-stocks
DE19502708C2 (de) * 1995-01-28 2003-10-23 Solvay Fluor & Derivate Verfahren zur Herstellung von Ein- oder Mehrkomponenten-Polyurethanschaumstoffen

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4337318A (en) * 1980-09-30 1982-06-29 Doyle Earl N Process for the total pre-expansion of polyurethane foam
US4853417A (en) * 1987-06-19 1989-08-01 Sumitomo Bayer Urethane Co., Ltd Process for manufacturing rigid polyurethane foam
US4931487A (en) * 1988-03-04 1990-06-05 Dow Chemical Company Chain extenders for polyurethanes

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB904003A (en) * 1958-02-06 1962-08-22 Dunlop Rubber Co Method and apparatus for the production of cellular synthetic rubber
GB2116574A (en) * 1982-03-19 1983-09-28 Ici Plc Method of manufacturing polyurethane foams
GB8329628D0 (en) * 1983-11-05 1983-12-07 Rubber & Plastic Res Ass Polyurethanes
DE3916873C2 (de) * 1988-05-27 2003-01-09 Elastogran Gmbh Verfahren zur Herstellung von zellhaltigen Kunststoffen nach dem Polyisocyanat-polyadditionsverfahren und eine Katalysatorkombination hierfür
US4906672A (en) * 1988-07-29 1990-03-06 Pmc, Inc. Blowing agents for polyurethane foam

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4337318A (en) * 1980-09-30 1982-06-29 Doyle Earl N Process for the total pre-expansion of polyurethane foam
US4853417A (en) * 1987-06-19 1989-08-01 Sumitomo Bayer Urethane Co., Ltd Process for manufacturing rigid polyurethane foam
US4931487A (en) * 1988-03-04 1990-06-05 Dow Chemical Company Chain extenders for polyurethanes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0517858A4 *

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE37115E1 (en) * 1993-07-14 2001-03-27 Foaming Technologies Cardio Bv Froth system for continuous manufacture of polyurethane foam slab-stocks
USRE37012E1 (en) * 1993-07-14 2001-01-09 Foaming Technologies, Cardio BV Froth system for continuous manufacture of polyurethane foam slab-stocks
USRE37075E1 (en) * 1993-07-14 2001-02-27 Carlo Fiorentini Froth system for continuous manufacture of polyurethane foam slab-stocks
US5620710A (en) * 1993-07-14 1997-04-15 Foaming Technologies Cardio Bv Froth system for continuous manufacture of polyurethane foam slab-stocks
US5629027A (en) * 1993-07-14 1997-05-13 Foaming Technologies Cardio Bv Froth system for continuous manufacture of polyurethane foam slab-stocks
US5639483A (en) * 1993-07-14 1997-06-17 Foaming Technologies Cardio Bv Froth system for continuous manufacture of polyurethane foam slab-stocks
US5665287A (en) * 1993-07-14 1997-09-09 Foaming Technologies Cardio Bv Froth process for continous manufacture of polyurethane foam slab-stocks
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
US5929278A (en) * 1994-10-27 1999-07-27 Affymax Technologies N.V. Inhibitors of 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
US6307101B1 (en) 1994-10-27 2001-10-23 David A. Campbell Inhibitors of metalloproteases, pharmaceutical compositions comprising same and methods of their use
WO1996014354A3 (fr) * 1994-11-02 1997-02-13 Solvay Fluor & Derivate Agents d'expansion contenant du dioxyde de carbone liquide
WO1996014354A2 (fr) * 1994-11-02 1996-05-17 Solvay Fluor Und Derivate Gmbh Agents d'expansion contenant du dioxyde de carbone liquide
US6303667B1 (en) 1994-11-02 2001-10-16 Solvay Fluor Und Derivate Foaming agents containing liquid carbon dioxide
EP0722975A1 (fr) * 1994-11-28 1996-07-24 Bayer Ag Procédé de dissolution de dioxyde de carbone dans un polymère liquide
DE19502708C2 (de) * 1995-01-28 2003-10-23 Solvay Fluor & Derivate Verfahren zur Herstellung von Ein- oder Mehrkomponenten-Polyurethanschaumstoffen

Also Published As

Publication number Publication date
EP0517858A4 (en) 1993-07-28
CA2075975A1 (fr) 1991-08-14
EP0517858A1 (fr) 1992-12-16

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