AU621551B2 - Creation of Inventions and Patents with Artificial Intelligence

AU621551B2 – A method, a compound, and a blowing agent for making plastic foam
– Google Patents

AU621551B2 – A method, a compound, and a blowing agent for making plastic foam
– Google Patents
A method, a compound, and a blowing agent for making plastic foam

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Publication number
AU621551B2

AU621551B2
AU21225/88A
AU2122588A
AU621551B2
AU 621551 B2
AU621551 B2
AU 621551B2
AU 21225/88 A
AU21225/88 A
AU 21225/88A
AU 2122588 A
AU2122588 A
AU 2122588A
AU 621551 B2
AU621551 B2
AU 621551B2
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AU
Australia
Prior art keywords
blowing agent
component
compound
document
mixture
Prior art date
1987-07-16
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AU21225/88A
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AU2122588A
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Inventor
Hans Jorgen Ostergaard
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1987-07-16
Filing date
1988-07-14
Publication date
1992-03-19

1987-07-16
Priority claimed from DK370187A
external-priority
patent/DK370187D0/en

1987-12-23
Priority claimed from DK682887A
external-priority
patent/DK682887D0/en

1988-07-14
Application filed by Individual
filed
Critical
Individual

1988-07-14
Priority claimed from PCT/DK1988/000120
external-priority
patent/WO1989000594A1/en

1989-02-13
Publication of AU2122588A
publication
Critical
patent/AU2122588A/en

1992-03-19
Application granted
granted
Critical

1992-03-19
Publication of AU621551B2
publication
Critical
patent/AU621551B2/en

2008-07-14
Anticipated expiration
legal-status
Critical

Status
Ceased
legal-status
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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

C08J9/143—Halogen containing compounds

C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only

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

Description

1.
W-AI-21225/88 I e SPCT ORLD INTELLECTUAL PROPERTY ORGANIZATION INTERNATIONAL APPLICATION 6
B
2 iNEDiLNIAR PATiNT COOPERATION TREATY (PCT) (51) International Patent Classification 4 (11) International Publication Number: WO 89/ 00594 C08J 9/14, C08G 18/14 Al (43) International Publication Date: 26 January 1989 (26.01,89) (21) International Application Number: PCT/DK88/00120 (81) Designated States: AT, AT (European patent), AU, BB, E (European patent), ,BG, BJ (OAPI patent), BR, (22) International Filing Date: 14 July 1988 (14.07.88) CF (OAPI patent), CG (OAPI patent), CH, CH (European patent), CM (OAPI patent), DE, DE (European patent), DK, FI, FR (European patent), GA (31) Priority Application Numbers: 3701/87 (OAPI patent), GB, GB (European patent), HU, IT 6828/87 (European patent), JP, KP, KR, LK, LU, LU (European patent), MC, MG, ML (OAPI patent), MR (OA- (32) Priority Dates: 16 July 1987 (16.07,87) PI patent), MW, NL, NL (European patent), NO, 23 December 1987 (23.12,87) RO, SD, SE, SE (European patent), SN (OAPI pitent), SU, TD (OAPI patent), TG (OAPI patent), US, (33) Priority Country: DK Published (71)(72) Applicant and Inventor: OSTERGAARD, Hans, With international search report.
Jargen [DK/DK]; Egevej IA, Logten, DK-8541 Sk6dstrup (DK).
(74) Agent: SKOTT-JENSEN, Lemmingvej 225, DK- APR 19 8361 Hasselager (DK).
AUSTRALIAN
1 3FEB1989 PATENT
OFFICE
(54) Title: A METHOD, A COMPOUND, AND A BLOWING AGENT FOR MAKING PLASTIC FOAM (57) Abstract It is well known that the use of the blowing agent monofluortrichlormethane, also called Freon 11 or R-l 1, for the production of polyurethae foam is highly disadvantage -us in that R-11 has a decomposing effect on the ozone layer around our planet. In spite of a vast scientific research it has not so Car been possible to provide a practically usable substitute for R-11, but such a substitute of a simple nature is provided by the invention. According to the invention use is made of a mixture of rpecific substances, which are generally undangerous in use and also otherwise advantageous, but the boiling points of wh'”h are so remote from the usual working temperature that each one of the substances will be totally unusable for the purpose, The two primary substances are l.l.l.trichloroethane and R-22 with boiling points 75-76°C and 41 0 C, respectively; when these substances are mixed and are mixed into the compound to be foamed the process conditions will widely correspond to the use of R-ll, though further advantages are achievable.
WO 89/00594 PCT/DK88/00120 A method, a compound, and a blowing agent for making plastic foam.
The present invention relates to-a method, a compound and i blowing agent for the production of foamed plastics, primarily of polyurethane.
The widespread production of PU fram products is based on the use of a mixture of a polyol system and a blowing agent embodied by a liquid having a relatively low boiling temperature, this mixture being brought to react with isocyanate to produce a polymerization of the polyol, whereby heat is generated sufficiently to cause the blowing agent to boil and to thereby produce vapour conditioning the formation of blisters or lt lls in the material.
A blowing agent well suited for this pvrpose is monofluortrichloromethane, also called Freon 11, CFC-11 or R-11, the boiling point of which is approximately 24 0 C, i.e. just suitable for a foam production under normal room temperature conditions. A large proportion of the relevant products is used for heat insulation purposes, and to this end it is also important that R-11 has a high molecular weight, as the vapour filling of the cells will hereby contribute to a high insulation capacity.
Thus, through many years the production of PU foam products has been based on the use of the relatively cheap and easily accessible R-11, but as now known it has been found that there are heavy environmental problems connected therewith, as the R-11 seems responsible for a certain destruction of the protective ozone layer surrounding our planet.
WO 89/00594 PCT/DK88/00120 2 On this background huge scientific efforts have been made for finding a practically applicable substitute for R-11, but so far without usable results. There are plenty of proposals from the world of the laboratories, where several presumed useful ingredients have been suggested, but practically all having the important drawback that neither now nor in any near future these ingredients will be accessible in any commercially realistic manner.
The methodic research for an R-11-substiture has, naturally, been concentrated primarily about the group of liquids related to R-11, i.e. the halogenated carbon hydrogens, of whichi several show the desired high molecular weight. Some of these liquids could be well usable as a bloing agent, even without badly influelpcing the said ozone layer, but unfortunately with certain unacceptable drawbacks. As an example, methylenechloride having a boiling point of some 47oC could perhaps be usable, but may be non-healthy.
When such beforehand unusable liquids are sorted out from the said relevant group of liquids only very few liquids will be left, and the remaining liquids, unfortunately,suffer from the drawback that their boiling points are either far too high or far too low to be relevant or the required boiling at a temperature reasonably close to normal room temperatures. Thus, the boiling point of R-22 is some -400C.
It should be mentioned that just R-22 nevertheless has been suggested as a blowing agent long before the recent scientific research bas(d on the said ozone problems. Thus, already in US-A-3.391.993 it is emphasized that R-22 is advantageous to R-12 in that it is more easily soluble in the polyol and a good solubility is decisive for the vapour generation conditioning a low density of the foam product.
It is evident, however, that R-11 is or has been irvantageous suggste as blwin aget lng efor th reent cie- Uficresarc bas.d n te sid ooneprolems Ths^ l- 3 to R-12, partly because it is still better soluble aWtd partly because it can be handled at room temperature at ambient pressure, It has also been suggested to use as a blowing agent various mixtures of the different relevant liquids, e.g. R-11 and R-12 or R-11 and R-22, but Lhis has not led to industrially usable results for mixtures without R-11. In most cases, where R-11 is not used, it is prescribed to use foaming machines, where an initial foaming takes place under the influence of one mixture component already in a delivery nozzle, while the other component is added reparately immediately next to the nozzle, viz. such that until the mixing of the comonents it has been possible to handle the components separately by suitable respective temperature and pressure conditions. In practice, however, it is of course highly preferential to make use of a compound already including all the required blowing agent and being usable at ambient temperature 15 and pressure merely by being led together with the isocyanate. This is what has been possible with the uie of R-11.
An R-ll-free blowing agent for such a use at a commercial scale has not beeni provided by the scientific research so far, but such an agent is provided by the present invention.
According to a first embodiment of the present invention there is provided a method of foaming up a plastics compound for producing a plastics foam, whereby a liquid mixture of a basic compound is boiled with a blowing agent having a first component comprising at least one of 1.1.1. trlchloroethane, trlchloroethylene and perchloroethylene, and a 25 second component having a boiling point which is lower than that of the 6 first component but greatly di~fezetCr~ m ambient temperature and which is miscible with the first component, to cause the basic compound to expand to form a plastics foam.
According to a second embodiment of the present invention there is provided a composition including a blowing agent for conversion into a plastics foam product by boiling a basic compound with a blowing agent, characterized in that the blowing agent has a first component comprising at least one of I.I.I1 trichloroethane, trichloroethylene and perchloroethylene, and a second component having a boiling point which is lower than that of the first component but greatlyy\ dcffberEtea- ambient temperature and which is miscible with the first component, to cause the basic compound to expand to form a plastics foam.
L~ TM /GSA/1716R i’
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According to a third embodiment of the present invention there is provided a substance mixturefo=*use as a substitute for nzonedecomposing halogenated hydrocarbons, primarily but not exclusively for use as a blowing agent, characterized in that it is composed of a first component comprising at least one of I1.1. trichloroethane, trichloroethylene and perchloroethylone, and a second component having a boiling point which is lower than that of the first component but greatly mtai f f e.m4n- ambient temperature and which is miscible with the first component, wherein the substance when boiled with a basic compound will cause the basic compound to expand to form a plastics foam.
According to the invention it has been found that an excellent blowing agent can be obtained as a mixture of two liquids selected directly from the relevant group of substances, but each one being absolutely unusable by having a biling temperature widely different from S: 15 the ambient temperature. t(nYBf the e substance is 11.1, trichloro- “ethane, the boiling point of which is as high as 75-76’C, while the other 1 substance is difluoromonochloromethane, i.e. the said R-22, the boiling point of which is as low as approximately -41 0 C. 1.1,1. trichloroethane is a cheap, soluble, well usuable substance, which has a high molecular weight; the relatively very high boiling point thereof can be lowered by admixing it with the low boiling R-22, which is also a well usable substance of a relatively high solubility. Despite the widely different boiling points of the two substances it has been found that they are extremely well suited to form a mixture having a boiling point or a 25 boiling point range very close to that of R-11, such that the simple mixture according to the invention will be usuable almost directly as a substitute for R-11. It is extra advantageous that the boiling point may be adjusted according to the circumstances by adding more or less R-22 to the 1.1.1. trichloroethane, preferably in the proportion range of 5-30 parts to 100 parts, respectively.
Preferably the blowing agent comprises difluoromoochloromethane and 1.1.1. trichloroethane in a weight ratio of 1:3 or less.
In this connection it is important that the mixture is extremely well soluble in the usual polyol systems. By the said coiiposition v 4 rlation the mixture itself will have a boiling point range of some hiea when present as effectively dissolved in the polyol system I/GSA/1716R 4A the starting boiling point of the system will be some 25-40*C, which is ideal and widely corresponding to the use of R-ll.
R-22 itself is not as soluble as R-ll, but with the presence of 1.1I1. trichloroethane the solubility becomes perfect, and it is fully possible to obtain foam densities as low as with the use of R-ll.
Generally it is a surprising fact that the two substances with their different characters and their mutual boiling point difference of more than 100 0 C act, in the mixture, widely just like R-ll.
S
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tMP. GSA/1716R WO 89/00594 PCT/DK88/60120 This also applies to a cElrtain degree with respect to the catalyst; used for ensuring a uniform and reasonably rapid foaming and setting of the foam. For some applications an acceptable foam production is achievable solely by substituting R-11 for the blowing agent according to the invention, while otherwise maintaining a conventi.onal dispensary and normal process conditions. Many different dispensaries are in use, scene even involving secrecies, but it has been f6dind that usable foam products may be manut~ctured as here disclosed, based on various common dispensaries referring to R-11.
However, the mere substitution of R-11 for the blowing agent of this invention will not normally result in a foam product of the same high quality as with the use of R-11. The broad boiling range of the agent changes the process conditions, and it may well be observed that the vapour generation towards the end of the foaming process is diminished to such a degree that the material is widely polymerized and stabilized before the foam is fully 4developed, whereby the density of the foam product may be undesirably high. It has been found, however, that this drawback can be avoided quite simply, viz. by supplementing the starting catalyst by a further catalyst specialized to be operative at an increased temperature in the compound being foamed.
It is remarkable that this desired effect is in :act achievable with the use of already well known catalysts developed for accelerating the final setting of the foam product. Such catalysts, based on tertiary amines and known e.g. as DABCO 33 LV and/or DABCO WT (Air Products, USA), also show the inherent effect of promotiig the vaporization of any remaining amount of blowing agcnt; while WO 89/00594 PCT/DK88/00120 6 in R-11-based systems such a remaining amount will typically be very small the corresponding amount in connection with the invention will be much larger due to the widened boiling point interval of the blowing agent, but nevertheless it has been found that the said known catalyst even used at a relatively low p-rcentage as explained in more detail below is able to promote the vaporization even of the said higher amount of ‘remaining blowing agent’ at the higher temperature level. Although the discussed catalysts have been developed pirticularly for use in R-11-based systems they seem to be directly applicable with the invention without any noticeable drawbacks, and they make it possible to obtain foam products without R-11 and with quite low densities, e.g. down to 3 15-20 kg/cm3, It is already known that a limited use of water in the basic compound is advantageous, particularly in the initial phase of the foaming process, where the water reacts with the isocyanate so as to develop free CO 2 which contributes to the foaming process. It is also known, as mentioned, to make use of a starting catalyst, particularly PM-DETA, which promotes the vapour generation particularly in the initial phase. Another such catalyst is triethylamine, which, however, has a highly unpleasant smell. What is worth noting here is that both the water and the sa.d- Si starting catalysts aria ully applicable with their respective advantages also in systems according to the present invention. M-DETA pentamethyl diethylen triamine.
With the traditional use of R-11 is connected a considerable cooling of the compound by the evaporation of the R-11, and for ensuring the required rapid supply of energy for increasing the temperature of the foam in production it is WO 89/00594 ‘NO 8900594PCT/DK88/00120 7 or has been necessary to make use of a relatively large amount of catalyst, Generally, in connection with the invention it is possible to use a reduced amount of catalyst, because the vaporization of the blowing agent takes place in a less abrupt manner and over a broader temperature interval, this involving a reduced instant energy demand ,and therewith reduced catalyst costs.
In’ donnection with foam production it is well knk’ wn to use special stabilizing agents, so-called surf actants, for stabilizing the cell walls. For use in R-11-systems such surfactants have been developed to a desired high degree of solubility, such that the first developed surfactants, which are now rather cheap, are used in steadily decreasing amounts due to their solubility being relatively poor. With the inventiton, however, just these ‘poor’ and cheap surfactants are to be preferred, because the blowing agent mixture is a very efficient solvent; the surfactants tend to be inoperative if they are too effectively dissolved, so for that reason the ‘better’ and more expensive surfactants, generally, will not be too advantageous.
It is well known that in R-11 compounds an undesired formation of foam imay take place at temperatures even slightly above normal working temperature, due to the R-11 boiling at some 24 0 C. it will be appreciated that this problem is eliminated or considerably reduced by the present invention because of the associated higher boiling point intierval.
In practice this will mean that based on the invention it Is possible to prepare the basic compounds including polyol(s), catalysts, stabilizers and blowing agent for shipping in ordinary cont~iners evan to warm, places, without the containers having to be particularly pressure re~istent.
WO 89/00594 PCT/DK88/00120 8 The 1.1.1. trichloroethane has a molecular weight which is only slightly lower than that of R-11, i.e. the ne :.y produced foam will be heat insulating almost as effectively as with the use of R-11. It is very important, however, that R-11 with its relatively low boiling point is not filling the cells in any particularly stable or durable manner, while the blowing agent of this invention will fill the cells much more durably, without relatively soon being gradually replaced by air. This leads to the very important result that the general long time insulation effect of the material will be even better compared with the use of R-11.
While the use of the blowing agent according to the invention has thus been found to involve several highly valuable advantages it is worth noting that some inhe7ent disadvantages, which might exist, have not been observed.
The blowing agent may be prepared and sold as a mixture, but the more relevant sales product will be the entire compound including polyol blowing agent and other components, readyf for use with isocyanate added ther&to in fully conventional manner.
The blowing agent mixture can be prepared in a very simple manner by introducing R-22 from a pressure vessel holding the R-22 in its liquid phase intct a pressure container holding the 1.1.1. trichloroethane. The resulting mixture may then under ambient pressure be added to the liquid compound% consisting of a mixture of polyol, catalysts, surfactant and possible further ingredients, preferably by stirring, whereafter the entire mixture may be filled in ordinary drums to be shipped.
At the place of use the mixture may be handled and used WO 89/00594 PCT/DK88/00120 9 almost exactly or conventionally as had it been an R-11based compound, i.e. in admixture with isocyanate, and it should be emphasized that the foaming may proceed as an ordinary free foaming without any differentiated handling of the components of the blowing agent mixture. A single special precaution may be desirable when the foam is produced in a moulding cavity, viz. to keep the walls of the moulding cavity heated a little more than with the use of R-11 systems; ithas been normal practice to heat the walls to some 400C in order to avoid a surface compaction of the foam, which would occur as a result of the blowing agent being cooled next to the surface, and since the boiling temperature in the present connection is normally increased it may be preferable to heat the cavity walls e.g. up to 5G-60C.
In the following the invention is illustrated by some examples: Example 1: It is desired to produce a heat insulating foam, e.g. for filling out in situ a connector mantle pipe over a joint in a district heating pipelinet and it is desired to use a fully conventional polyol and catalyst system to be handled fully conventionally, all with the one exception that a blowing agent according to the invention is used, in lieu of R-11. The basic compound is as follows: ICI Daltolac P 160 basic polyol (OH value 540) 0.373 kg ARCO Arcol 3541 basic polyol (OH value 490) 0.373 kg Shell Caradol 36-3 basic polyol (oH value 36) 0.046 kg Glycerine 0.025 kg Water 0.008 kg BASF Triethylamine (amine catalyst) 0.011 kg 11
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WO 89/00594 PCTiDK88/00120 BP Polyurax SR 242 (surfactant) Blowing agent 10 parts 1.1.1. trichloroethane parts R-22 0.014 kg 0.150 kg 1.000 kg To this compound was added 1 kg ICI Suprasec DNR MDI isocyanate, and the following data were observed: Cream time (starting time) Gel time (fiber time) Rise time Tack-free time Free rise density Core temperatire Max. core temperature reached after 45 secs 200 sees 250 sees 250 secs 48 kg/m 3 131° C 840 sees ExamDle 2: A refrigerator unit is to be provided with an insulation of a widely homogeneous foam with low density. A basic compound of the following formulation is used: ARCO Arcol 3544, Medium molecular weight polyoxypropylene pyoyol i kg ARCO Arcol 3770, Aromatic amine polyoxypropylene ether polyol 0.074 kg Goldschmidt Tegostab B 1048 (surfactant) 0.015 kg Water 0.007 kg BASF PM-DETA (amine catalyst) 0.003 kg *Air Products DABCO 33 LV (tertiary amine catalyst) 0.012 kg Blowing agent “20” as in example 1 0.314 kg 1.000 kg To this compound was added Shell Caradate 30 MDI isocyanate in weight proportion 1:1, and following data were observed: WO 89/00594 PCT/DK88/00120 Cream time (starting time) Gel time (fiber time) Rise time Tack-free time Free rise density Core temperature Max. core temperature reached after 21 secs 75 sees 90 sees 90 secs 22.4 kg/m 3 119° C 570 secs Exapile 3: The-preparation according to Example 2 was repeated with the sole difference that the composition of the blowing agent “20” (see Zxample 1) was changed to 85:10:5 p.b.w.
of 1.1.1. trichloroethane, R-22 and butane, respectively.
All other data were the same, or found to be practically 3 unchanged; the density, however, vas reduced to 21 kg/m Example 4: A semi flexible PUR foam for furniture arm rests was based on the following compound: Shell Caradol 36-3 basic polyol (OH value 36) BASF Butanediol 1.4 TCPP (fire retarder) DMEA (amine catalyst) DBTL (.tin catalyst) Blowing agent 85:10:5 as in Example 3 0.680 kg 0.136 kg 0.068 kg 0.014 kg 0.001 kg 0.1-02 kg 1.000 kg To this compound was added ICI Suprasec VM 10 pure MDI isocyanate in weight proportion 1:0.4, and following data were observed: Cream time (starting time) Gel time (fiber time) Rise time Tack-free time Free riso density Core temperature Max. core temperature reached after 15 secs 20 secs 20 secs 25 secs 357 kg/mr 3 110° C 420 secs -4 PCT/D K88/OO hO WO 89/00594 Example For the continuous production of a spray foam to be sprayad onto building surfaces such as roof undersides as a stabilizing and insulating la~ye thereon the following basic compound was used: Shall Caradol 585 amine initiated polyol (0H 585) ICI Daltolac P 1 60 base polyol (OH, 540) ARCOArcol 3541 polyether polyol (OH 490) Triethanolainine 85% (amine catalyrst) Tall oil Texaco DMEA (amine catalyst) BASF PM-DETA (amine catalyst)* DBTL Organic tin catalyst Trichloropropyle phosphate (fi.re retar~der) Goldschmidt Tegostab B 1048 (surfactant) Water (if desired) Blowingq agent “120” as in Example 1 0.323 kg 0.143 kq 0.143 kg 0.034 kg 0.041 kg 0.039 kg 0.008 kg 0.001 kg 0.103 kg 0.124 kg 0.002 kg 0.147 k,- The compoundi was mixed with Bayer Desmody=. 44V20 MDI-isocyanate in the weight ratio 1:11 and the following data were observed: Czzeaiig time, (starting time) Gel time (fiber time) F~ise time Tack-free time Free rise density Core temperature Max. core temperatu7;e reached after 7-8 secs: 15 secs 30 secs 20 secs 42.4 kg/cm 3 165 0 C 300 secoi Example 6: A light polyethor furniture foam (slab stock) is produced based on the following compound:
I
M
ii__ wo $9/00594 PCT/DK88/00120 Shell Caradol 36-3 basic polyol DBTL (organic tin catalyst) Goldschmidt Tegostab BF 2370 (surfactant) BASF PM-DETA (amine catalyst) Water Blowing agent “20” as in Example 1 0.832 kg 0.003 kg 0.008 kg 0.002 kg 0.030 kg 0.125 kg To this compound was added Bayer toluene diisocyanate (TD3-80/20) in weight proportion 1:0.383, and the following data were observed: Cream time (starting time) Rise time Free rise density 5 sees 80 sees 20.2 kg/cm Example 7: For the production of a f’re retarded polyisocyanurate filling foam (PIUR) the following basic system is used: ARCO Arcol 3541, Polyoxypropylene polyether polyol (OH 475) 0.689 kg Air Products Dabco TMR-2 (trimerisation catalyst) 0.024 kg Goldschmidt Tegostab B 1048 (surfactant) 0.010 kg Water 0.002 kg Blowing agent “20” as in Example 1 0.275 kg 1.000 kg To this compound was added Bayer Desmodur 44V20 MDI isocyanate in weight ratio 1:1, and following data were observed: Cream time (starting time) Gel time (fiber time) Rise time Tack-free time Free rise density Core temperature Max. core temperature reached after 30 sees 65 sees 77 secs 75 secs 39.2 kg/cm 3 1535 C 390 secs tageous to R-12 in that it is more easily soluble in the polyol r-nd a good solubility is decisive for the vapour generation conditioning a low density of the foam product.
It is evident, however, that R-11 is or has been -ivantageous i WO 89/00594 PCT/DK88/00120 14 Example 8: For comparison two similar basic compounds of a standard polyol and a blowing agent in the form of R-11 and (see Example respectively, were prepared. In both cases the same formulation was used, viz.
Polyoxprropylene polyether polyole (OH 475) 0.714 kg Blowing agent 0.286 kg In both cases a compound boiling point of 33 C was found.
An important difference was found in that the mixture with R-11 shows a vapour pressure of 0.17 bars at 250 C, while the mixture with blowing agent “20” according to the invention did not reveal any measurable overpressure.
Generally, confer Example 3, the blowing agent according to the invention may be modified by the addition of a minor amount of butane, which has a good blowing capacity, i.e.
develops a relatively high vapour volume. In principle the R-22 component could be replaced by butane, but a certain content of R-22 is desirable in practie for obtaining a sufficient solub0kity of the blowing agent. Usable equivalents to butane will be propane and pentane, i.e. saturated hydrocarbons having three to five carbon atoms. A preferred percentage thereof will be about five, hardly exceeding ten.
In most of the examples is used a blowing agent “20” referring to 20 parts of R22 in 100 parts of 1.i.1. trichloroethane. This proportion has been found suitable for use in Denmark, but in warmer climates the boiling point of the basic compound should preferably be somewhat higher, i.e.
the proportion of R-22 should be smaller, e.g. only 10-15 parts, while under arctic conditions it should be higher Normally the R-22 proportion will range between 10 and parts per 100 parts of 1.1.1. trichloroethane, but in WO 89/00594 PCT/DK88/00120 extreme cases the R-22 proportion can qo down to 5 parts and up to some 30 parts, all parts being parts by weight.
By an incorporation of butane or the like the total amount of low boiling blowing agent may be somewhat smaller than with the use of R-22 alone; the above mentioned proportion of 85:10:5 will thus correspond to some 100:17:6 by weight for 1.1.1. trichloroethane and R-22/butane, respectively.
It is to be mentioned that there are two substances, viz.
trichloroethylene and perchloroethylene, which are widely equivalent ‘.to 1.1.1. trichloroathane and moreover are of a commercially available type. There is a reason to believe that one or both of these substances may at least partly substitute the 1.1.1. trichloroethane in the present connection. However, the invention is devoted bt the practical commercial exploitation of the R-11-free blowing agent, and it will comprise the use of these other substances only to the extent these are found applicable in commercial practice.
Thr blowing agent according to the invention will be well suited for the foaming up of systems or compounds other than just PUR-systems, e.g. for the foaming up of PVC, epoxy; unsaturated polyesters, phenoles, polystyrene, etc., where the foaming process is much simpler and where it is often actual to aim at a higher insulation effect and of course at the use of cheap and generally non-dangerous substances.
It has been measured that -the presence of free vapour of 1.1.1. trichloroethane immediately above the foamed up mixture is very low, less ;than half the international TLV (threshold limit value),, k WO 89/00594 PCT/DK38/00120 16 As well know, also in other fields of the art there are problems with respect to various “Freon” types contributing to attack the ozone layer of the stratosphere, and it will be appreciated that the mixture or blowing agent according to the invention may well be able to substitute the doubtful Freon substances in several connections. Such uses will be within the scope of the invention to the extent they are commercially realistic, e.g. as refrigerants or blowing agents for other purposes. Thus, theinvention will comprise the discussed mixture as far as it is usable, directly or as a basic mixed substance for further modifi.cation for particular purposes.
Some experts are of the opinion that also R-22 belongs to the said ‘doubtful’ CFC-substances; even if this is true it will be appreciated that the R-22 constitutes the minor fraction of the two main ingredients in the present sixture, so it will still be an important result that at least a drastic reduction of the use of ‘doubtful substances’ will be obtainable, until something still better might be found.
It should be mentiod that the foregoing examples refer to laboratory tests under free rise conditions and at a room and ingredient temperature of 21 C. By associated practical experiments in production it was found that the trends of changes between laboratory results and’practical results were almost exactly the same as with the use of R-11, and so were the effects of changed production conditions, i.e.
to the skilled person there will be no need to describe this in more detail.

Claims (18)

1. A method of foaming up a plastics compound for producing a plastics foam, whereby a liquid mixture of a basic compound is boiled with a blowing agent having a first component comprising at least one of 1.1.1. trichloroethane, trichloroethylene and perchloroethylene, and a second component having a boiling point which is lower than that of the first component but greatly dkBgfe nt f-omAnambient temperature and which is miscible with the first component, to cause the basic compound to expand to form a plastics foam.

2. A method according to claim 1, wherein said plastics compound is polyurethane.

3. A method according to claim 1 or 2, in which the second component is difluoromonochloromethane.

4. A method according to any one of claims 1 to 3, in which the 15 blowing agent comprises difluoromonochloromethane and 1.1.1. trichloroethane in a weight ratio of 1:3 or less.

5. A method according to any one of claims 1 to 3, in which the blowing agent further comprises propane, butane or pentane, preferably substituting a part of the second component. 20

6. A method according to claim 5, in which the blowing agent substantially constitutes a mixture of 1.1.1. trlchloroethane, difluorochloromethane and one of propane, butane and pentane In a weight ratio of the magnitude 85:10:5, respectively.

7. A method according to any one of claims 1 to 6, whereby a 25 catalyst is used for promoting the vapour production of the blowing agent, characterized by the use of at least two different catalysts, which are selectively active over respective temperature ranges at the beginning and the end of the boiling point interval of the compound as conditioned by the said blowing agent mixture.

8. A composition Including a blowing agent for conversion Into a plastics foam product by boiling a basic compound with a blowing agent, characterized in that the blowing agent has a first component comprising at least one of 1.1.1. trichloroethane, trchloroethylene and perchloroethylene, and a second component having a boiling point which Is lower than that of the first component but greatlyjd Efe frpom-ambient 1716R 18 temperature and which is miscible with the first component, to cause the basic compound to expand to form a plastics foam.

9. A composition according to claim 8, in which the second component is difluoromonochloromethane.

10. A composition according to claim 8 or 9, in which the blowing agent further comprises propane, butane or pentane.

11. A composition according to any one of claims 8 to 10 and further comprising at least two different catalysts, which are selectively active over respective temperature ranges adjacent the beginning and the end of the,boiling point interval of the compound as conditioned by the said blowing agent mixture,

12. A composition according to claim 11 and further comprising a tardily soluble surfactant. 5

*13, A substance mixtureA e=w=se as a substitute for ozone- 15 decomposing halogenated hydrocarbons, primarily but not exclusively for use as a blowing agent, characterized in that it is composed of a first component comprising at least one of 1.1.1. trichloroethane, trichloroethylene and perchloroethylene, and a second component having a boiling point which is lower than that of the first component but greatly 20 f-tfFrLe–e amblent temperature and which is miscible with the first component, wherein the substance when boiled with a basic compound will cause the basic compound to expand to form a plastics foam.

14, A substance mixture according to claim 13, in which the second component is difluoromonochloromethane. o 25

15. A substance mixture according to claim 13 or~1, In which the substance mixture further compri’ses propane, butane or pentane.

16. A method of foaming up a plastics compound for producing a plastics foam substantially as herein described with reference to any one of the Examples. 4 30

17. A composition including a blowing agent for conversion into a plastics foam product by boiling a basic compound with a blowing agent substantially as herein described with reference to any one of the Examples. I TMS/GSA/17t6R k~ 19

18. A substance mixture for use as a substitute for ozone- decomposing halogenated hydrocarbons substantially as herein described with reference to any one of tIh. Examples. DATED this TWELFTH day of SEPTEMBER 1991 Hans Jorgen Ostergaard Patent At~torneys for the Applicant SPRLJSON FERGUSON 99 9 9 9 9 9. 9 99 9. 9 1 .9 9 9 99 9 *9 99 9 9 999999 9 9′ 9999 9*99 9 9 9999 9 9 9 9 9 .99.9. 9 9 71 6R I INTERNATIONAL SEARCH REPORT Internatlovial Application No PCT/DK88/00120 1.CLASBIFCAION 01SUajXCTr MATTERt (it several classification symbols apply, Indicate aig)I According to International Patent Classification (IPC) or to both National Classification and IPC J4 C 08 J 9/14, C 08 G 18/14 It. FIELDS UEIIIARCHED Minimum Documentation Searched CIkslficationSse Clasaification Symbols IPO 4 IC 08 J 9/00, 9/14; C 08 G 18/14 US Cl 521:131, 159 Documentation 3serch~.d other than Minimum Documenitation to the Extent that such Documents are Included In the Fieldi’ Searched I SE, NO, DK, FI classes as above 1l1. DOCUMENTS CONSIDERED TO 81 FRELEVANT’ Category” Citation of Document, 11 with indication, where appropriate, of the relevant passagesi Is Relev~ant to Claim No, t A DE, C2, 2 930 881 (OHASHI ET AL) I 1-10 i14 May 1980 See col, 1-8, especially col. 6, lines 35-44 A DE, Al, 2 918 552 (EITLE. W. ET AL) 1-10 November 19791 See claims 1–‘I A US, A, 4 251 639 (JARRE ET AL) 1-10 17 February 1981 See col. 1-5, especi~ally col, 4, lines 67-68-co,, 5, lines 1-11 Special caof”0lee of cited docum~ntji 1 later document publishied after the International filing data document ‘defining the general state of the art which Is not Or priority date and riot in conflict with the application but considereJ to be of particular roeevance cited to, understand the principle or theory underlying the invention earlier document hut published on or after the International 119″ document of particular rslovarsceI, the claimed invention filing dalt cannot be considered novel ;t cannot be conaidered to document W h may throw doubts on priority claim(si or Involve an Inventive step which Is cited to establish the publication date of another document of particular relov~incal the claimed Invention citation or other special reason (as specified) cannot be considered to Involve ;n inventive step when the document referring to an oral diviclosit.e, use, exhibition or documnent is combined with one or More other auch dociJ- other means ments, ilch combination being obvious to a person skilled document published prior to ttoi international Ailing date but In the art. later than the priority date clefmed document member of the “eai patent family IVo CIPTIFICATION Date of the Actual Completion of the interatImonal Search Date of Mailing of this Iriternotiont sarch Report
1988-10-26- 1988 -10- 2 8 Internationl *4archine Authority ISgafeo uhrzdOt~ Swedish Paitent Of’rie D~J~v Form PCTIISA /2i0 (second sheet (jeeww7ir i”)

AU21225/88A
1987-07-16
1988-07-14
A method, a compound, and a blowing agent for making plastic foam

Ceased

AU621551B2
(en)

Applications Claiming Priority (5)

Application Number
Priority Date
Filing Date
Title

DK3701/87

1987-07-16

DK370187A

DK370187D0
(en)

1987-07-16
1987-07-16

PROCEDURE FOR FOAMING PLASTIC MATERIALS AND FUEL FOR USE THEREOF

DK682887A

DK682887D0
(en)

1987-12-23
1987-12-23

PROCEDURE FOR FOAMING PLASTIC MATERIALS AND FUEL FOR USE THEREOF

DK6828/87

1987-12-23

PCT/DK1988/000120

WO1989000594A1
(en)

1987-07-16
1988-07-14
A method, a compound, and a blowing agent for making plastic foam

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AU2122588A

AU2122588A
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1989-02-13

AU621551B2
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AU621551B2
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1992-03-19

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Ceased

AU621551B2
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1987-07-16
1988-07-14
A method, a compound, and a blowing agent for making plastic foam

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Cited By (1)

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Assignee
Title

AU633101B2
(en)

1989-06-12
1993-01-21
Dow Chemical Company, The
A process for preparing flexible polyurethane foam using 1,1,1-trichloroethane as a blowing agent

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Bridgestone Tire Co Ltd

Method of producing flameproof polyisocyanurate foams

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Basf Aktiengesellschaft

Manufacture of flexible foams

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(en)

1988-02-22
1989-08-24

E.I. Du Pont De Nemours And Company

Closed-cell polyurethane foam compositions

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1988-07-14
AU
AU21225/88A
patent/AU621551B2/en
not_active
Ceased

1990

1990-01-15
NO
NO90900200A
patent/NO900200L/en
unknown

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US4251639A
(en)

1978-04-11
1981-02-17
Basf Aktiengesellschaft
Manufacture of flexible foams

GB2033912A
(en)

1978-11-10
1980-05-29
Bridgestone Tire Co Ltd
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AU3014889A
(en)

1988-02-22
1989-08-24
E.I. Du Pont De Nemours And Company
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AU633101B2
(en)

1989-06-12
1993-01-21
Dow Chemical Company, The
A process for preparing flexible polyurethane foam using 1,1,1-trichloroethane as a blowing agent

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NO900200L
(en)

1990-01-15

NO900200D0
(en)

1990-01-15

AU2122588A
(en)

1989-02-13

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