GB2261876A - Compositions for phenol-aldehyde foams based on chlorofluorohydrocarbons - Google Patents
Compositions for phenol-aldehyde foams based on chlorofluorohydrocarbons Download PDFInfo
- Publication number
- GB2261876A GB2261876A GB9224903A GB9224903A GB2261876A GB 2261876 A GB2261876 A GB 2261876A GB 9224903 A GB9224903 A GB 9224903A GB 9224903 A GB9224903 A GB 9224903A GB 2261876 A GB2261876 A GB 2261876A
- Authority
- GB
- United Kingdom
- Prior art keywords
- weight
- parts
- composition
- phenol
- foam
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 50
- 239000006260 foam Substances 0.000 title claims abstract description 29
- 150000005827 chlorofluoro hydrocarbons Chemical class 0.000 title description 5
- 239000003377 acid catalyst Substances 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000007524 organic acids Chemical class 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 11
- 239000004359 castor oil Substances 0.000 claims description 6
- 235000019438 castor oil Nutrition 0.000 claims description 6
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- ZZXDRXVIRVJQBT-UHFFFAOYSA-N 2,3-dimethylbenzenesulfonic acid Chemical compound CC1=CC=CC(S(O)(=O)=O)=C1C ZZXDRXVIRVJQBT-UHFFFAOYSA-N 0.000 claims description 3
- IULJSGIJJZZUMF-UHFFFAOYSA-N 2-hydroxybenzenesulfonic acid Chemical compound OC1=CC=CC=C1S(O)(=O)=O IULJSGIJJZZUMF-UHFFFAOYSA-N 0.000 claims description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 3
- IEORSVTYLWZQJQ-UHFFFAOYSA-N 2-(2-nonylphenoxy)ethanol Chemical compound CCCCCCCCCC1=CC=CC=C1OCCO IEORSVTYLWZQJQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 150000002334 glycols Chemical class 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 229920000847 nonoxynol Polymers 0.000 claims description 2
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- PRPINYUDVPFIRX-UHFFFAOYSA-N 1-naphthaleneacetic acid Chemical compound C1=CC=C2C(CC(=O)O)=CC=CC2=C1 PRPINYUDVPFIRX-UHFFFAOYSA-N 0.000 claims 1
- 239000004721 Polyphenylene oxide Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 125000005314 unsaturated fatty acid group Chemical group 0.000 claims 1
- 239000004604 Blowing Agent Substances 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 238000009413 insulation Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229920001568 phenolic resin Polymers 0.000 description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical group [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N Furaldehyde Natural products O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 2
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- CVLHGLWXLDOELD-UHFFFAOYSA-N 4-(Propan-2-yl)benzenesulfonic acid Chemical compound CC(C)C1=CC=C(S(O)(=O)=O)C=C1 CVLHGLWXLDOELD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- -1 ethylene, propylene Chemical group 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A composition capable of being converted into a foam, comprising a mixture based on a phenol-aldehyde resin, an acid catalyst, dichlorofluoroethane and a surfactant, is characterised in that it essentially consists, per 100 parts by weight of phenol-aldehyde resin, of: - not more than 14 parts by weight of dichlorofluoroethane, - not more than 14 parts by weight of organic acid catalyst, and - not more than 4 parts by weight of surfactant. The dichlorofluoroethane is an environmentally-acceptable blowing agent.
Description
COMPOSITIONS FOR PHENOL-ALDEHYDE FOAMS BASED ON CHLORO- FLUOROHYDROCARBONS The present invention relates to new phenolaldehyde foams whose production and/or use is less damaging to the atmospheric ozone layer than that of foams obtained from chlorofluorocarbons (CFC).
Phenol-aldehyde foams, and more particularly phenol-formaldehyde foams, currently find increased uses in the construction field and in the transportation industry because of their high thermal insulation and fire resistance.
Phenol-formaldehyde foams are known via Patent
Application EP-A-229 877 which are prepared using, as foaming agent, mixtures of trichlorotrifluoroethane and dichlorotrifluoroethane, in an amount of about 5 to 20% by weight of the foamable composition. This document gives as an example, a formulation prepared in the presence of 20% by weight, relative to the phenol-formaldehyde resin, of benzenesulphonic acid as catalyst.
Phenolic foams of low thermal conductivity are also known via Patent Application EP-A-348 199 which are derived from a system comprising a phenolic resin, a blowing agent, a catalyst, a cell stabiliser and a solvent compatible with the resin, and are characterised in that the blowing agent comprises a partially halogenated hydrocarbon chosen from dichlorotrifluoroethane and dichlorofluoroethane. In Example 4 thereof, this document describes a foam formulation comprising 100 parts by weight of phenot-formaldehyde resin, 11.3 parts by weight of monoethylene glycol, 6.2 parts by weight of nylonate ester, 7.5 parts by weight of a mixture of castor oil ethoxylates, 10.9 parts by weight of dichiorofluoroethane and 25 parts by weight of sulphuric acid as catalyst.
This composition is subjected to expansion in a metallic mould for 1 hour.
Finally, Patent Application GB-A-2232 673 describes in its examples formulations comprising, per 100 parts by weight of phenol-formaldehyde resin, 20 to 24 parts by weight of xylenesulphonic acid supplemented with up to 10% by weight of alcohol and/or up to 25% by weight of orthophosphoric acid, and 16 to 208 parts by weight of 1, l-dichloro-1-fluoroethane.
Thus, the concern for protection of the ataos- pheric ozone layer has led, in the field of the production of phenolic foams, to several proposals for replacing completely substituted chlorof luorohydroc arbons as blowing agents. However, these proposals are characterised by highly complex formulations, most often containing azeotropic mixtures of hydrogenated chlorofluorohydrocarbons and presenting technical drawbacks in the course of the foam-producing process.
Thus, the foam formulations of the document
EP-A-348 199 are rendered complex by the presence of a solvent of a very specific nature. They require a long expansion time which adversely affects the productivity and therefore the economy of the production process.
Finally, it is observed that they do not permit complete filling up of the mould, a proportion generally between about 5% and 108 of the volume of the mould remaining unfilled at the end of the expansion time, probably because of insufficient reactivity of the resin towards the other components of the system.
The problem which the present invention intends to resolve consists in proposing a simple, economical and effective means of reducing the harmful effect on the atmospheric ozone layer during the production and use of phenol-aldehyde foams, by developing a formulation capable of completely fflling the mould used for this production and/or capable of expanding in a shorter time compared with those already known up until now, while preserving the good traditional thermal and acoustic insulation properties of phenol-aldehyde foams.
According to the present invention, there is provided a composition capable of being converted into a foam, comprising a mixture based on a phenol-aldehyde resin, an acid catalyst, dichlorofluoroethane and a surfactant, the said composition being characterised in that it essentially consists, per 100 parts by weight of phenol-aldehyde resin, of:: - not more than about 14 parts by weight of dichloro
fluoroethane, - not more than about lr parts by weight of organic
acid catalyst, and - not more than about 4 parts by weight of surfactant,
SurprIsingly, the technical problems mentioned above can be overcome in a simple and effective manner by selecting a specific hydrogenated chlorofluorohydrocarbon (and not an azeotropic mixture of several such halohydrocarbons), an organic catalyst (and not inorganic as in the document EP-A-348 199) and smaller proportions (relative to the resin) of catalyst and foaming agent.
It is also preferred to dispense with the presence of a resin-compatible solvent as recommended in the document
EP-A-348 199.
It is generally preferred, in order to preserve all the advantages of the invention while providing a composition capable of being converted into a foam with industrially acceptable kinetics, that the composition should essentially consist, per 100 parts by weight of phenol-aldehyde resin, of: - about 6 to 12 parts by weight of dichlorofluoro
ethane, - about 4 to 12, more preferably 4 to 10, parts by
weight of organic acid catalyst, and - about I to 3 parts by weight of surfactant.
As organic acid catalyst which may be used in preparing the compositions according to the invention, there may be mentioned benzenesulphonic acid, p-toluenesulphonic acid, xylenesulphonic acid, cumenesulphonic acid, phenolsulphonic acid and mixtures of two or more thereof in all proportions.
As surfactant which may be used in preparing the compositions according to the invention, there may be mentioned unsaturated fatty acid polyalkylene glycol esters, condensates of castor oil and alkylene oxide, castor oil itself or alternatively one of its partially or totally hydrogenated derivatives which are optionally alkoxylated, for example by means of ethylene, propylene or butylene oxides, nonylphenol ethoxylate, polysiloxanepolyether copolymer and some modified silicones.
The compositions according to the invention are preferably free from inorganic acid catalyst such as sulphuric acid or phosphoric acid.
The phenol-aldehyde resin present in the compositions according to the invention is well-known.
It is preferablyobtained by condensation, in a basic medium, of an aldehyde such as furfural or formaldehyde and a phenol in an aldehyde/phenol molar ratio generally of between about 0.8 and 1.5 The present invention also provides a process for producing an object from phenol-aldehyde foam, comprising curing a composition based on a phenol-aldehyde resin in a mould, characterised in that the composition subjected to curing is a composition according to the invention.
The process according to the invention therefore includes a step for heating the composition, preferably at a temperature of from about 30"C to about 60"C, for a period - dependent on the temperature - preferably not exceeding 60 minutes, and more particularly of from about 10 to about 50 minutes. These preferred conditions of duration and temperature allow the composition according to the invention to expand and crosslink while filling the entire mould and providing phenol-aldehyde foam objects with an attractive appearance, possessing a satisfactory thermal insulation coefficient, with reduced contraction and deformation phenomena.
The process according to the invention makes it possible to obtain without difficulty phenol-aldehyde foam objects with very different densities, generally ranging from about 20 to 150 kg/m3.
The present invention further provides the phenol-aldehyde foam objects obtained in conformity with the process described above. As examples of such objects, there may be mentioned slabs and panels of variad forms intended for thermal insulation in the building, civil engineering and transportation industries, as well as blocks for domestic use such as foam blocks for holding flowers.
The Example below is provided by way of illustration of the present invention, with no limitation of its scope being implied.
EXA23PLE
Into a parallelepipedal mould and with a ozone equal to 225 litres, there is injected by means of a
SECMER tricomponent machine a mixture consisting of: - 100 parts by weight of a phenol-fonualdehyde resin
marketed by the company CRAY VALLEY SA under the reference GEDELITE8 12070 CE . and containing, as surfactant, 1.5% by weight of condensate of ethylene
oxide and castor oil marketed by SOCIETE FRANCAISE DORGANOSYNTHESE under the name CEMULSOL, and 1.5E by weight of unsaturated fatty acid polyethylene
glycol ester marketed by the company HARCROS under
the reference ETSYLANE C 40 AH, - 12 parts by weight of dichlorofluoroethane, and - 12 parts by weight of catalyst marketed by the
company CRAY VALLEY SA under the reference C 2961
and consisting of 348 by weight of para-toluene
sulphonic acid, 648 by weight of phenolsulphonic
acid and 28 of water.
The mould is than heated at a temperature of 45"C for 25 minutes. At the end of this time, the expansion of the mixture is complete and the mould is completely filled. The crosslinking of the foam then continues, as the temperature decreases from 45"C back to room temperature, for 36 hours. In order to reduce contraction and deformation phenomena, the mixture is then allowed to stand for a few days before cutting the foam slabs. They have an attractive surface appearance and a satisfactory thermal insulation coefficient, equal to that of slabs obtained using a traditional completely halogenated hydrocarbon foaming agent.
Claims (13)
1. A composition capable of being converted into a foam, comprising a mixture of a phenol-aldehyde resin, an acid catalyst, dichlorotluoroethane and a surfactant, the said composition being characterised in that it essentially Consists, per 100 parts by weight of phenolaldehyde resin, of: - not more than 14 parts by weight of dichlorofluoro- ethane, - not more than 14 parts by weight of organic acid
catalyst, and - not more than 4 parts by weight of surfactant
2. A composition according to Claim 1, characterised in that it assentially consists, per 100 parts by weight of phenol-aldehyde resin, of: - 6 to 12 parts by weight of dichlorofluoroethane, - 4 to 12 parts by weight of organic acid catalyst,
and - 1 to 3 parts by weight of surfactant.
3. A composition according to Claim 2, characterised in that it contains 4 to 10 parts by weight of organic acid catalyst per 100 parts by weight of phenol-aldehyde rasin.
4. A composition according to any one of Claims 1 to 3, characterised in that the organic acid catalyst is selected from benzenesulphons acid, p-toluenesulphonic acid, xylenesulphonic acid, cumenesulphonic acidr phenolsulphonic acid and mixtures of two or more thereof.
5. A composition according to any one of Claims 1 to 4, characterised in that the surfactant is selected from unsaturated fatty acid polyalkylene glycol esters, condensates of castor oil and alkylene oxide, castor oil itself or alternatively one of its partially or totally hydrogenated derivatives which are optionally alkoxylated, nonylphenol ethoxylate, polys iloxane-poly- ether copolymer and modified silicones.
6. A composition according to any one of Claims 1 to 5, characterised in that it is free from inorganic acid catalyst
7. A composition capable of being converted into a foam substantially as hereinbefore described or illustrated in the foregoing Example.
8. A process for producing an object from phenolaldehyde foam, comprising curing a composition based on phenol-aldehyde resin in a mould, characterised in that the composition subjected to curing is a composition according to any one of Claims 1 to 7.
9. A process according to Claim 8, characterised in that the curing of the composition is carried out at a temperature of from 30"C to 60 C.
10. A process according to Claim 8 or 9, characterised in that the curing of the composition is carried out for a period not exceeding 60 minutes.
11. A process according to Claim 8 or 9, characterised in that the curing of the composition is carried out for a period of from 10 to 50 minutes.
12. A process for producing an object from phenolaldehyde foam carried out substantially as hereinbefore described or illustrated in the foregoing Example.
13. Phenol-aldehyde foam objects obtained by a process according to any one of Claims 8 to 12.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9114771A FR2684386B1 (en) | 1991-11-29 | 1991-11-29 | COMPOSITION FOR PHENOL ALDEHYDE FOAM BASED ON DICHLOROFLUOROETHANE. |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB9224903D0 GB9224903D0 (en) | 1993-01-13 |
| GB2261876A true GB2261876A (en) | 1993-06-02 |
| GB2261876B GB2261876B (en) | 1996-01-03 |
Family
ID=9419482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9224903A Expired - Fee Related GB2261876B (en) | 1991-11-29 | 1992-11-27 | Compositions for phenol-aldehyde foams based on chlorofluoro-hydrocarbons |
Country Status (2)
| Country | Link |
|---|---|
| FR (1) | FR2684386B1 (en) |
| GB (1) | GB2261876B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1087056A (en) * | 1963-10-10 | 1967-10-11 | Union Carbide Corp | Improved phenolic foams |
| GB1367908A (en) * | 1971-04-05 | 1974-09-25 | Eltra Corp | Acid resistant phenolic foams |
| GB2207920A (en) * | 1987-05-21 | 1989-02-15 | Stablocel Phenolics Limited | Insulation material |
| GB2207919A (en) * | 1987-05-21 | 1989-02-15 | Stablocel Phenolics Limited | Insulation material |
| EP0348199A1 (en) * | 1988-06-23 | 1989-12-27 | BP Chemicals Limited | A process for producing phenolic foams |
| JPH02123120A (en) * | 1988-10-31 | 1990-05-10 | Matsushita Refrig Co Ltd | Formed heat insulating material |
| GB2226030A (en) * | 1988-12-13 | 1990-06-20 | Ici Plc | Blowing agent |
| GB2232673A (en) * | 1989-04-20 | 1990-12-19 | Albert Edward John Evans | Preparation of a phenolic foam |
| US4986930A (en) * | 1988-10-03 | 1991-01-22 | Allied-Signal Inc. | Polyol-blowing agent compositions with improved storage stability |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4687787A (en) * | 1985-12-20 | 1987-08-18 | Allied Corporation | Foaming system for phenolic foams |
| BE1002739A6 (en) * | 1989-01-03 | 1991-05-21 | Recticel | MAINLY phenolic foam cell formation CLOSED AND METHOD FOR MAKING THIS phenolic foam. |
| GB9001368D0 (en) * | 1990-01-20 | 1990-03-21 | Bp Chem Int Ltd | Blowing agents |
-
1991
- 1991-11-29 FR FR9114771A patent/FR2684386B1/en not_active Expired - Fee Related
-
1992
- 1992-11-27 GB GB9224903A patent/GB2261876B/en not_active Expired - Fee Related
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1087056A (en) * | 1963-10-10 | 1967-10-11 | Union Carbide Corp | Improved phenolic foams |
| GB1367908A (en) * | 1971-04-05 | 1974-09-25 | Eltra Corp | Acid resistant phenolic foams |
| GB2207920A (en) * | 1987-05-21 | 1989-02-15 | Stablocel Phenolics Limited | Insulation material |
| GB2207919A (en) * | 1987-05-21 | 1989-02-15 | Stablocel Phenolics Limited | Insulation material |
| EP0348199A1 (en) * | 1988-06-23 | 1989-12-27 | BP Chemicals Limited | A process for producing phenolic foams |
| US4986930A (en) * | 1988-10-03 | 1991-01-22 | Allied-Signal Inc. | Polyol-blowing agent compositions with improved storage stability |
| JPH02123120A (en) * | 1988-10-31 | 1990-05-10 | Matsushita Refrig Co Ltd | Formed heat insulating material |
| GB2226030A (en) * | 1988-12-13 | 1990-06-20 | Ici Plc | Blowing agent |
| GB2232673A (en) * | 1989-04-20 | 1990-12-19 | Albert Edward John Evans | Preparation of a phenolic foam |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2261876B (en) | 1996-01-03 |
| GB9224903D0 (en) | 1993-01-13 |
| FR2684386B1 (en) | 1995-04-14 |
| FR2684386A1 (en) | 1993-06-04 |
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Effective date: 20001127 |