WO1981000715A1 - Methode de fabrication de mousse de polyurethane a un composant - Google Patents

Methode de fabrication de mousse de polyurethane a un composant Download PDF

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Publication number
WO1981000715A1
WO1981000715A1 PCT/DK1980/000034 DK8000034W WO8100715A1 WO 1981000715 A1 WO1981000715 A1 WO 1981000715A1 DK 8000034 W DK8000034 W DK 8000034W WO 8100715 A1 WO8100715 A1 WO 8100715A1
Authority
WO
WIPO (PCT)
Prior art keywords
activator
pressure
polymer
glycol
container
Prior art date
Application number
PCT/DK1980/000034
Other languages
English (en)
Inventor
B Scholten
Original Assignee
B Scholten
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 B Scholten filed Critical B Scholten
Priority to NL8020343A priority Critical patent/NL190850C/xx
Priority to DE19803049834 priority patent/DE3049834C2/de
Publication of WO1981000715A1 publication Critical patent/WO1981000715A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step

Definitions

  • This method for the manufacture of polyurethane foam is very .advantageous compared to methods for the manu ⁇ facture of two-component polyurethane foam because it does not require a complicated equipment consisting of two containers, a mixing unit with associated spray gun and means for apportioning the components in a definite proportion but may be practised simply by operating a valve on the pressure container holding the pre-polymer.
  • the pressure container may be a so-called aerosol can which is easily operated with one hand seeing that dis ⁇ charge of the foam is started and stopped at will, and the method is therefore especially suited for use in the building industry where the foam is used for insulation, glueing, as a mortar substitute, to secure door frames and window frames, and for the repair of cracks and crevices and to ' fill cavities.
  • a method of the said kind has the drawback that the pre-polymer in the pressure container must have such composition that curing of the discharged foam, which takes place by means of the moisture of the atmosphere, takes a long time.
  • foams hitherto made by this method have the drawback that they exhibit an e -?” pansion pressure after gelation of the foam with the result that it has been necessary to use stayings of e.g. door frames until the polyurethane foam is cured through .
  • the method according to the invention is. different, from the 2-component system in that the added amount of activator is small seeing that it may vary from zero to any desired small amount determined by th.e desired effect.
  • the activator may be for instance an aminoalcohol be- cause such compound has an especially strong influence on the curing time, but according to the invention the activator is preferably a glycol because by means of some glycols it can be obtained that the polyurethane foam becomes pressure-less, i.e. does not show any sub- stantial expansion after gelation so that putting up stayings before discharge of the foam can be dispensed with.
  • Ethylene glycol, propylene glycol- 1,3, butanediol-1,4, and glycerol are especially pre.- ferred.
  • the amount of activator to be used in the method accord ⁇ ing to the invention depends on the desired curing time but is in general much smaller than the amount of pre- polymer, typically 5-10%.
  • the activator can therefore be used in the method accord ⁇ ing to the invention.
  • Monocomponent polyurethane foam on pressure containers is normally supplied as so-called aerosol cans, i.e. pressure containers in which the pre-polymer is present together with the blowing and propelling agent which is a liquid having a steep temperature-pressure curve, e.g. a Freon, and which has a valve which is opened by merely'depressing the discharge tube.
  • aerosol cans i.e. pressure containers in which the pre-polymer is present together with the blowing and propelling agent which is a liquid having a steep temperature-pressure curve, e.g. a Freon, and which has a valve which is opened by merely'depressing the discharge tube.
  • the pressure in the aerosol cans does not exceed 5 atmospheres, and this fact therefore pro- vides possibility of adding the activator, when car ⁇ rying out the method according to the invention, in a particulary simple way which does, not call for any special equipment and does not make it necessary that together with the activator other chemical compounds become introduced which may have an effect on the blow ⁇ ing or the curing.
  • the ac ⁇ tivator is preferably added to the pre-polymer in the pressure container by transfer from another pressure container in which the activator is under a pressure of an inert gas higher than 5 atmospheres.
  • the pres ⁇ sure container with the activator may be e.g. an aero ⁇ sol can with a valve similar to that of the aerosol can with, thepre-polymer so that- ransfer of the activ ⁇ ator can take place merely by pressing the discharge tubes of the two aerosol containers, against each other.
  • the invention further comprises a packing of activator for use in the method according to the in ⁇ vention which packing is characterized in that it is a pressure container in which an activator consisting of an organic hydroxy compound with a molecular weight low-
  • the pressure container is preferably filled to less than 50% with activator, and most suitable to less than 33%.
  • activator can be transferred to the pressure container with the pre-polymer under almost constant pressure and without any substantial increase of the pressure in the pressure container with the pre-polymer.
  • Addition of the activator can also take place in other ways, e.g. the activator can be in an only partially filled small container without pressure and part of the pre-polymer be transferred from the pressure container to this small container. The heat of reaction will then increase the pressure in the small container so much that the contents of the small container then ' --may be transferred to the larger container in which, mixing of the total amounts of pre—polymer and activator then takes place immediately before the discharge of the foam.
  • the main purpose of obtaining a pressure-less foam a pre-polymer of polyol and polyisocyanate is used having such, excess of isocyanate that the equivalent ratio of isocyanate to hydroxyl is between 3:1 and 6:1 and an activator is added consisting of a glycol in an amount of 5-10% by weight of the pre-polymer.
  • the pressure container with the pre-polymer of polyol and polyisocyanate may contain the traditional addi ⁇ tives used for polyurethane foam such as plasticizers, surface active agents and dyestuffs which have no in-
  • the invention is illustrated by the following examples in which there is used as pre-polymer various reaction products of a polyol component and a diphenylmethane diisocyanate .
  • the equivalent ratio of the two com- ponents is varied in some examples to illustrate the range within which a pressure- less foam can be obtained when using different activators .
  • the freedom from pres ⁇ sure is ascertained by measuring the expansion in % of a point around a door frame which is not stayed.
  • a monocomponent polyurethane foam on pressure container has the following composition
  • the mixture is in a pressure container in a standard packing of 1 litre at a pressure of 5 atmospheres at room temperature .
  • the equivalent ratio of isocyanate to hydroxyl is 4.04 : 1.
  • After discharge the foam is touch dry in 20-30 minutes and cures in 5-24 hours , depending on the humidity of the air , in layers 5-10 cm thick .
  • the foam is not pres ⁇ sure-less but shows an expansion of 24 % measured as in- dicated above.
  • the discharged foam is touch dry in 10-15 minutes and cures in 45 minutes and does not show any expansion during or after curing. After addition of the activa ⁇ tor it is possible still after about 12 minutes to dis ⁇ charge foam of the same quality.
  • a commercial 2-component polyurethane foam is: discharged i and measured under the same conditions as in examples 1 and 2 and shows an expansion of 18%.
  • 454 g. of a monocomponent polyurethane foam of the same composition as in example 1 is placed in a standard 530 ml pressure container.
  • 30 g. of propanediol-1,3 is placed in a pressure container with a capacity of 100 ml,and the container is pressurized with nitrogen to a pressure of 12 atmospheres.
  • the contents of the small container is transferred to the large container by con ⁇ necting the discharge tubes of the containers and press them against each other so that the valves are opened whereby the activator (propanediol-1,3) is forced into the large container by the nitrogen pressure.
  • Example 4 is repeated but the 30 g. of propanediol-1,3 are replaced by 36 g. of butanediol-1,4 and instead of nitrogen compressed air is used.
  • the discharged foam is touch, dry in 8 minutes and cures in 50 minutes and shows no expansion.
  • a monocomponent polyurethane foam on pressure container has- the following composition :
  • the mixture is in a pressure container in a standard packing of 1 litre at a pressure of 5 atmospheres at room temperature.
  • An activator consisting of 43.5 g. of diethylene glycol is in a small pressure container having a capacity of 200 ml under a carbon dioxide pressure of 10 atmos ⁇ pheres at room temperature .
  • the activator is transferred in the way described in example 4 to the pressure container with, the monocom ⁇ ponent polyurethane foam whereby the pressure in the larger container rises to 7 atmospheres. After brief shaking the foam is discharged. It is touch dry in 12 minutes and cures in 1 hour.
  • Example 6 is repeated but using as activator 42 g. of pentanediol-1 , 5 .
  • the formed foam is touch, dry after 7 minutes and cured through after 40 minutes. It shows an expansion of 3% .
  • a monocomponent polyurethane foam mixture is prepared by mixing the following components :
  • the mixture is put on standard pressure containers with a capacity of 300 ml with 250 g . in each, and is acti ⁇ vated by introducing in the can immediately before use the following activators : 33 g . of triethylene glycol (example 8 ) , 42 g. of tetraethylene glycol (example 9 ) , and 13 .5 g. of glycerol (example 10) .
  • the formed foams have the properties shown in table 1. Table 1
  • a pressure container with monocomponent polyurethane foam mixture as in examples 8-10 is connected pressure- proof with, a small pressure container of 50 ml con- taining 14 g. of ethylene glycol which, is not under pressure, in such, manner that the small container is be ⁇ low and the large one on top.
  • a small pressure container of 50 ml con- taining 14 g. of ethylene glycol which, is not under pressure, in such, manner that the small container is be ⁇ low and the large one on top.
  • Examples: 8-10 are repeated but using as activator 14 g. of a mixture of equal parts- of glycerol and ethylene glycol. The. formed foam cures in 1 hour without expan ⁇ sion.
  • OMPI Example 12 is repeated but using as activator 15 g. of a mixture in the ratio 1:2 of trimethylolpropane ' and ethylene glycol. The formed foam cures in 50 minutes without expansion.
  • pre-polymers are prepared with, varying ex ⁇ cess of diphenylmethane diisocyanate* as shown in table 2, and these pre-polymers are poured into standard pres- sure cans with, a capacity of 300 ml together with a constant amount of propellant which, is a mixture of Freon 11 and Freon 12.
  • a pressure can with a capacity of 60 ml The amounts of activator used and the properties of the foams are shown in table 3.
  • the same monocomponent polyurethane foam as in example 1 is used but before use an activator is added consisting of 9 g. of diethanolamine and 18 g. of ethylene glycol.
  • the discharged foam is touch dry in 5 minutes and cures in 20 minutes.
  • Example 21 is repeated but the activator is replaced by 10 g. of triethanolamine and 20 g. of propanediol-1,3. The discharged foam is touch dry in 4 minutes and cures in 15 minutes. 13
  • Example 2 is repeated but the dimethylolaminoethanol is omitted from the monocomponent polyurethane foam mixture and is instead added together with the 25 g. of ethylene glycol. Similar results as in example 2 are obtained.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Mousse de polyurethane a un composant preparee en ajoutant a un recipient sous pression contenant le pre-polymere de polyol et un excedent de polyisocyanate avec un agent gonflant et propulseur, juste avant l'emploi, un activateur qui est un compose organique hydroxy avec un poids moleculaire inferieur a 200 et au moins deux groupes primaires hydroxyles ou un melange de ces composes hydroxy qui est liquide a 20 C. L'activateur peut etre ajoute a partir d'un recipient sous pression dans lequel il se trouve a une pression de gaz plus elevee que celle regnant a l'interieur du recipient contenant le pre-polymere. Un emballage d'activateur consiste en un recipient sous pression a l'interieur duquel se trouve l'activateur sous une pression d'un gaz inerte d'au moins 5 atmospheres.
PCT/DK1980/000034 1979-09-14 1980-06-04 Methode de fabrication de mousse de polyurethane a un composant WO1981000715A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
NL8020343A NL190850C (nl) 1979-09-14 1980-06-04 Werkwijze voor het vervaardigen van een polyurethanschuim.
DE19803049834 DE3049834C2 (de) 1979-09-14 1980-06-04 Verfahren zur Herstellung von Einkomponenten-Polyurethanschaum

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DK385779A DK155674C (da) 1979-09-14 1979-09-14 Fremgangsmaade til fremstilling af et monokomponent polyurethanskum
DK3857/79 1979-09-14

Publications (1)

Publication Number Publication Date
WO1981000715A1 true WO1981000715A1 (fr) 1981-03-19

Family

ID=8127525

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DK1980/000034 WO1981000715A1 (fr) 1979-09-14 1980-06-04 Methode de fabrication de mousse de polyurethane a un composant

Country Status (7)

Country Link
EP (1) EP0035534A1 (fr)
BE (1) BE885205A (fr)
CH (1) CH648047A5 (fr)
DE (1) DE3049834C2 (fr)
DK (1) DK155674C (fr)
NL (1) NL190850C (fr)
WO (1) WO1981000715A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007140104A1 (fr) * 2006-05-23 2007-12-06 3M Innovative Properties Company Composition de résine à base de polyuréthane

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030212217A1 (en) * 2002-05-08 2003-11-13 Suresh Sawant Fluorinated activator

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1542280A (fr) * 1967-05-17 1968-10-11 Kerr Chemicals Procédé de fabrication d'une mousse de polyuréthane

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE516512A (fr) * 1951-12-24
GB1086609A (en) * 1965-07-12 1967-10-11 Kerr Chemicals Inc Improvements in or relating to foamed polyurethane resins
FR1484593A (fr) * 1965-07-12 1967-06-09 Kerr Chemicals Procédé et appareil pour fabriquer une résine mousse de polyuréthae
GB1175717A (en) * 1967-09-04 1969-12-23 Kerr Chemicals Inc Improvements in or relating to the Preparation of Polyurethane Foams
BE756238A (fr) * 1969-09-16 1971-03-16 Ici Ltd Compositions a expanser
AU2644771A (en) * 1970-03-18 1972-09-14 Dunlop Australia Limited Cellular polyurethanes
GB1400157A (en) * 1971-12-21 1975-07-16 Ici Ltd Production of foams
NL7703113A (en) * 1977-02-28 1978-08-30 Foam Schaumtechnik Self curing polyurethane foam compsns. - in which all components required for hardening are mixed before application from a pressure storage vessel
DK522777A (da) * 1977-11-25 1979-11-02 B H N V Scholten Komponent polyurethanskum system der kan goeres hurtigtoerrende ved hjaelp af en separat trykbeholder indeholdende et kamikale og som ved hjaelp af et overtryk kan bringes ned i l komponent polyurethanskum systemet

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1542280A (fr) * 1967-05-17 1968-10-11 Kerr Chemicals Procédé de fabrication d'une mousse de polyuréthane

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
J.H. Saunders, K.C. Frisch, "Polyurethanes, Chemistry and Technology, Part II, Technology", published 1964, by Interscience Publishers (New York), see pages 201-204. *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007140104A1 (fr) * 2006-05-23 2007-12-06 3M Innovative Properties Company Composition de résine à base de polyuréthane

Also Published As

Publication number Publication date
DK155674B (da) 1989-05-01
DK155674C (da) 1989-09-04
DE3049834C2 (de) 1987-05-21
EP0035534A1 (fr) 1981-09-16
NL190850C (nl) 1994-09-16
DK385779A (da) 1981-03-15
BE885205A (fr) 1981-03-12
CH648047A5 (de) 1985-02-28
DE3049834T1 (fr) 1982-02-25
NL190850B (nl) 1994-04-18
NL8020343A (nl) 1981-08-03

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