GB2337260A

GB2337260A - Polymer foams containing hydrofluoroethers

Info

Publication number: GB2337260A
Application number: GB9810582A
Authority: GB
Inventors: Mark Stanley Harris; Graham Morgan Edgerley
Original assignee: Kingspan Industrial Insulation Ltd
Current assignee: Kingspan Industrial Insulation Ltd
Priority date: 1998-05-15
Filing date: 1998-05-15
Publication date: 1999-11-17
Also published as: GB9810582D0

Abstract

A polymer foam, e.g. a phenolic foam, includes as a surfactant at least one hydrofluoroether or an azeotrope formulation thereof A portion of the surfactent may be contained in the resin and/or in the foam blowing agent blend. I-methoxy-nonafluorobutane or an azeotrope formulation thereof with trans-1,2-dichloroethylene is preferred.

Description

Y 2337260 1 "A ZR-- and E2Cew' Introducti This invention relates to a Am&

opecially a phenolic ibarn and to a process fbr preparing such fbams from.

Phenolic foams are wuWY 1k hffidmg applications m view of ther th insulation and fire resw Such phenolic foams are prepared by mi=g a phenol fod& with a blowing agent a cell stab and a hardener.

1 EP - A - 0170357 de o fbr preparing a phenolic foam using Freon as a blowing agent, aVmw sulphuric acid as a hardener, and a cell is stabW= d by ethylene oxide or mixtures thereof with proplylene oxide. chlorofluoroc (CFC).

EP-A-W9283 describes dw ma complex blend of materials as an alternative blowing agent to a CM MW as: at 1 one perfluoroalkane (PFA) (esy per orol cane or perftumoheptanc); and at least one component se ftow ogenated chloroduorocarbon (HPC) and a specificall-an or There is a need fbr an en.vbo==tdly timdly.

foam which is easily processed and StaternenlE of Iny-ention According to one aspect the Mir at least one hydrofluer or provides a foam including, as a surfactant, g;- otrope forinulation, E -Kl A ANEL-- 2 Prbly the fo= has a closed cell content of greater than 90% when measured in accordance with B.S. 4370/ASTM D2856.

In a pre embodiment of the inv the fbarn has a k value measured at 90 days or 1 of less than 0.018 W1mT by the xnethod of BS 4370 part 2 at 100C.

In a particularly pref embodunent of the invention the foam is a phenolic foam.

Preferably at least portion of the surfactant is contained in a resin.

Alternatively or additionally at least portion of the sudactant is contained in a foam blowmg agent blend.

In one =bot of dw invention the hydrofiuroether is of the gtmeM fmmula C. FiPC^ wherein:

b = 2a + 1 d = 1 or 2 e = 3 or 5 with the proviso that (i) d = 1 when e = 3 and (h) d = 2 when c = 5 Most prly the hydrofiuroediff hydrofluoer is C4H9OCI-Ii (1- methoxynonafluorobetane).

3 In one embodiment of the invention the hydrofluroecher is in an azeotrope ffirmulation.

In this case, preferably the am formulation is a 50150 formulation of I merhoxy-norobmw wi 1,2, &chbylene.

The azeo Ibrmulation May be ffirmed by a reaction of two or more components, at 1 one comp^ being present m the blown agent blend and at least one component m in the resin.

is The foam may include a fiuoon (WC).

Alternatively or fid 14 the foam includes a hydrogenated chlorofluorocarbon (HCFC).

Tle foam may also include an or cydoe.

Prbly the FICFC is HM Wh (CCIF-CH3).

The invention also provides a agent blend including, as a surfactant, at least one hydroduoroether cif tru Ibrmumtin-n. thereof.

The blend may include the ts as those of the foam.

The Mventlon Anther P" resin including, as a surfactant at le t one hydroduoroether or an or part thereof The invention allo pro a for producing a foam from a resin using a blowing agent blend of the inv W 4 In addition, the invention provides a process for producing a foam according to the imention using a resin and/or a blowing agent blend according to the invention.

Ethers are y strong solvents which can have an adverse cell opening effect on fbam and would die not noy be con as components fbr closed cell fbams. We have however, surprisingly fbund that hydrofluorethers can be ellfectively used as surfactants in fban: & v vvbld2ti In addition to this unexpected use of such ethers, there is the Anther major advantage that these solvents have much less environmental unpact than conventional solvents used in foam minu. Such solvents have a very low global warming potential when compared with conventional solvents used in such foam fbnnul.

is 2 Do The invention is based on the sw fin that the global warming potential of phenolic fbanis can be very significantly reduced by using at least one hydrofluoroether as a blowing agent additive.

The mvention wú be more y understood from the Mowing description thereof given by way of example

ExaMle -1 A phenolic resin was used which was prepared from the ingredients and using the process described in EP-A-0170357 and EP-A-W9283.These specificants are incorporated herein by reference.

Foams we= manu&c in the laboratory using the fbrmulatiom below. Ille chemicals were mixed using a high laboratory st= and dispensed mto a mould having a volume as appioximately 0.03n.?. The mould was subsequently placed in an oven at 70C fbr a urn of 3 hours. After demouldina the fbam was allowed to cool down to m t=perature prior to co- t of thetmal conductivity testin& FoarnA Foam B Phenolic resin 100 100 Blowing agmt HCK 141b 10 10 IE 7100 0.54 0.

Catalyst sulphuric acid (50%) 12 12 is Thermal conductivity t wo Perfomed at ambient and at 700C and the results am shown. m the T&W-w. It is very dear that with= the 11FE additive, the drift in th Mvity is very rapid both at ambient and 7TC whilst with the M 7100 a the thermal conductvlty drifts to a value m the region of 0.0 18 WlmK - OJW-Wlnff, CTlym (WImK at 10OC) Days 4 is 17 42 Foam A Ambient 0.0169,- 0.0184 700C 0.0159 0.0179 0.0193 Foam B Ambient 0.0 184 0.0304 700C 01169 0.0291- 0.0298 A FIFE 7100 is 1-metboxy-nonadhaving the fbrmula C4H9OCK3. It has a boiling point of 600C.

6 Exam 21e 2 Discontinuous block fbam, was manufactured on a commercial scale plant to produce blocks of dimensions of approximately 2440 x 1200 x 100Omm. The foam mix was dispensed through a low pressure rni into a heated mould. The product was put through a three hour cunng cycle prior to demouldL The fbam was manuh according to the fbilowing formon.

amo Phenolic resin (example I): 100pbw Blowing agent HCFC 141b 10.8pbw BYE 71 DE 1.08pbW Catalyst: Sulphuric/ phosphoric acid 11.68pbw is colour: MS black The density of the foam thus fb was 35kg/m3.

M 71 DE is a 50150 blend of WE 7100 with no 1, 2 dichloroethylene of the formula CHCL.CHCL. The material is available from 3M. Ile particular advantage of this material is that is an areo and boils at 40T which gives good proce a r r mistics, especially in producing a laminated product.

We have fbund that foams have excellent thermal conductivity M as fbllows:

Aggd "K" values Condition on manufkc=e 7 days 21 days 42 days 63 days 90 days Ambient 0.0166 0.0146 0.0147 0.0156 0.01660.017 + 700C --- 0.0151 0.0168 0.0171 0.018 0.0182 7 Typical global warming pot fbr perfluoroallanes are as follows:

CF4 C2F6 C3FA CjU C6F14 6500 9200 7000 700' 7400 Thh is in complete contrast m WE 7100 has a global warming potential of 500 and Bn 71DE bedkv warming potential of 2.50. Thus, the use of WE's in phenolic fona has considerable enviromental advantages compared with p cdommounes.

is It is envisaged that the WC wM in the phenolic fbam blowing agent blend of the invention may. be s kir =maple, from one or more of..

HWC 141b HWC 142b HCFC 123 HUC 124 WFC 225ca HWC 225cb CChFiCH3 MCCIF2 CFrMC12 CHCLF2 CH02-WrCF3 CCIFrWrMCIF It is also en that uimb-Wing agent blend may include a suitable hydrogenated fluorocarbon for =ample. from one or more of.

HFC 125 EFC 134 a WC 152 a WC 245fa HIFC 365mft - 01Fz-CHi CF3CH2F CHrWCW3 ECFrCHz-CBF2 CFrCH2-WrCH3 ja 8 The HFC's may be represented by the fbrmula CjhFQ whenenr.

R is an ineW from 1 to 3 P is an integer from 1 to 4 and Q = (2R+2)-P for an open chain HFC and (2R-P) for a cyclic HFC.

It is ftwher en that the phenolic foam blowing agmt blend may include an 21bn, especially n-po, or a cydoe, espe cyclopentane.

The invention is not limited to the embodiments hbefore desmbed which may be varied in.

is 7.

9 Cla A fbam including, as a surhccant at least one hydrofluoroether or an azeotrope fomu.'.--jr WPM.

i- 2. A fb= as dairned in 1 having a stable dosed cell content of greater than 9Wo when meu in &dance with B.S. 4370/ASTM D2856.

3. A fbam as daimed in d" 1 or 2 having a k value measured at 90 days or longer of less than O.0ladivic by the method ofBS 4370 part 2 at 100C. VW_ A foam as claimed in AW preceding claim which is a phenolic fbam.

5. A fbam as cl in to wherein at least portion of the surft is con _retin 6. A foam as cl ta 2t7 lweceding daim wh at least portion of the WM J1 surfactant is con A"n blowing agent blend.

A foam as daimed in of the gmerd:E. v m ill 4i- --.& - when= the hydrofluoroeffier is LOCa wh.

A b =2a+ 1 d= 1 or2 e=3or5 with the pmviso that (I) 4wi when c 3 and CU) when c W il- - 1 A IMEW -- 8. A f as claimed in any preceding claird wherein the hydrofluoroether is Cil9OCH3 (1-methoxy-nonafluorobe=e).

9. A fbam as claimied m any preceding claim wherein the hydrofluotoetba is in an azeotrope formulation.

10. A Ibarn m d in claim 9 wherein the hydrofluoroether h in an azeo fbnnulatLon with U=-1,2oroethylene.

11.A fbam as daimed in 10 wherein the azeotrope fbrmulation is a 50150 ffirmulation of 1-metboxy-nonafluorobm= with trans 1,2, didiloroethylme.

12. A fbam as cl in any of daim 9 to 11 wherein the azeotrope formulation is fbrmed by a reaction of two or more components, at least one component being present in the blowing agent blend and at least one component being pre=t in the resin.

is 13. A foam as dairn in any preceding claim including a hydrogenated fluorocarbon WC).

14. A foam as claimed in any preceding dlaim induding a hydrogenated chlorofluorocarbon (HCFC).

15. A foam as daimed in any prece daim induding an allmne or cydoaUcane.

16. A fbarn as daimed in any of daim 14 to 15 wherein the HWC is HWC 141b (CC laF-CH3).

11 17. A foam subs=ddy as hereinbeffire described with reference to the ex=ples.

18. A fbam blowing inci as a surfactant, at lent one hydrofiuor ofcmoty up e formulation thereof.

19. A blowing M= as claimed. in claim 18, the hydrofluoroether or an aze fmn dxmf being as dairned in any of cla 7 to 11.

20. A blowing agent as claimed in claim 18 or 19 including a hydrogenated == WC).

21. A blowing agent b -m claimed in claim 18, 19 or 20 including a hydrogenated (HCFC).

is 22. A blowing agent 0 d in any of claim 18 to 21 including an albne or cyclo.

23. A blowing agent b in daim, 21 or 22 wherein the HWC is H= 141b (M2F.CMk 24. A blowing agent dally as hemre de= with rekrence to the eles.

25. A fbam resin including, azeotrope ffirmulation, or at leut one hydrofluoroether or an 26. A process for proda a- from a resin using a blowing agent blend as ed in any of cl to 24.

zP 12 27. A process as claimed in claim 26 wherein the resin is as claimed in claim 25.

28. A process fbr producing a foam substantially as hereinbeffire bed with rettrence to the examples.

29. A foam whenever produced by a process as d in any of claims 26 to 28.