Patentamt

J E u r o p European
a i s c h e sPatent Office Publication number: 0 1 9 2 3 2 5

B1
Office europeen des brevets

EUROPEAN PATENT SPECIFICATION

Date of publication of patent specification: 18.10.89 int ci.4: C 08 G 6 3 / 6 6 , C 08 G 1 8 / 4 2 ,

C 0 8 G 18/40, C 0 8 G 1 8 / 1 4
Application number: 86300244.0
Date of filing: 15.01.86

Polyester polyols, their manufacture and use in polyurethane production.

Priority: 18.02.85 GB 8504096 Proprietor: IMPERIAL CHEMICAL INDUSTRIES

PLC
Imperial Chemical House Millbank
Date of publication of application: London SW1P3JF(GB)
27.08.86 Bulletin 86/35
Inventor: Bentley, James Martyn
Publication of the grant of the patent: Grensstraat 90
18.10.89 Bulletin 89/42 B-1970 Wezembeek-Oppem (BE)
Inventor: Brown, James Peter
Stijn Streuvelslaan 9
Designated Contracting States: B-1960Sterrebeek(BE)
AT BE CH DE FR GB IT LI LU NL SE Inventor: Carroll, William Graham
R Schuitenlaan 15
B-1981 Vossem (BE)
References cited:
EP-A-0153 031
FR-A-2508917 Representative: Colens, Alain M.G.M. et al
Imperial Chemical Industries PLC Legal
Department: Patents P.O. Box 6 Bessemer Road
Welwyn Garden City Hertfordshire AL7 1HD (GB)

in
CM
CO
CM
O)

Note: Within nine months from the publication of the mention of the grant of the European patent, any person may
give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall
Q. be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been
LU paid. (Art. 99(1 ) European patent convention).
Courier Press, Leamington Spa, England.
 EP 0 192 325 B1

Description

The invention relates to polyester polyols of a defined type, to their manufacture by esterification or
transesterification of polyether polyols also of a defined type, with certain polybasic acid species and their
5 conversion to polyurethanes by reaction with polyisocyanates.
The starting polyether polyols to be used in the invention are described in EP—A— 153 031. This Patent
Application discloses polyether polyols having an average hydroxyl value in the range 400 —650 KOH/g
which is an alkoxylated derivative of a polyhydric alcohol itself being a single compound or a mixture of
compounds according to the general formula (I) below:
10

" \ /°"CH2\ /CH2°H

15 Ri1 > O-CH-'

o-ch/ ch^or2
CH-OR

wherein
R1 is — H, —CH3, or —OCH3
20 R2 is —H, —CH20H, or —CH2C(CH20H)3
Where a poiyhydric alcohol is present, other than one of the type defined above, it is preferably
incorporated into the composition such that after alkoxylation the alkoxylated derivative forms at least 5%
by weight of the polyether poiyol composition and the polyhydric alcohol has the general formula (II) or is a
mixture of compounds of that formula,
25
r\ .ch-oh
Nc/ 2 (ID
4^ \ 5
R* NCH,-R3
30 *

wherein R3 and R4, which may be the same or different, are selected from —H, —CH2OH and —CH2OCH3
provided that only one of R3 or R4 may be —CH20CH3, R5 is —OH, —OCH2OH or —OCH2C(CH2OH)3.
Thus a preferred polyether poiyol comprises 10 to 95% of oxyalkylated polyhydric alcohols according
35 to formula I and 5 to 50% of oxyalkylated polyhydric alcohols according to formula (II).
The alkoxylation agent could be propylene oxide, ethylene oxide or butylene oxide or mixtures thereof.
It has now been found unexpectedly that some polyester derivatives of the above polyols provide new
polyois of improved processability suitable for the manufacture of rigid polyurethane foams of fine cell-
structure.
40 Economy has also become a critical factor in rigid foam business and accordingly, another main
advantage resulting from the present invention is that the poiyol are manufactured from two readily
available starting components. The latter are indeed waste by-products from the manufacture of
pentaerythritol on one side and adipic acid or terephthalic acid or derivatives thereof on the other side.
The polybasic acid species used in the preparation of the polyester polyols of the invention include:
45 a) aliphatic dibasic acids or esters of the type ROOC (CH2)n COOR wherein n = 2 to 8 and R is H, methyl
or ethyl or mixtures thereof, preferably mixtures of adipic, glutaric and succinic acids or derivatives thereof,
b) aromatic dibasic acids of the general formula

COOR
so /\ /

ROOC'

wherein R is H, methyl or ethyl and the carboxyl groups are in the ortho, meta or para positions relative to
60 each other or mixtures thereof, preferably dimethyl terephthalate or distillation residues therefrom,
residues from polyethylene terephthalate (PET) manufacture or product from the recycle of PET waste,
c) other aromatic polybasic acids such as benzenetricarboxylic acids or polycarboxy substituted
diphenyls and polyphenyls and the corresponding methyl esters.
Tetrabutyl-o-titanate was used for this invention and is a known catalyst for esterification/
65 transesterification reactions; other catalysts could include stannous octoate or p-tolune sulphonic acid.
 EP 0 192 325 B1

The polyester polyol of the present invention, with an average hydroxyi value in the range 250 to 400
mgKOH/g, may be used in admixture with known polyether polyols, polyester polyols or polyesteramide
polyols. , ,
The present invention includes also the manufacture of polyurethane products, for example
described above, and also includes
5 polyurethane foams, in known manner, from the polyester polyols
polyurethanes product so prepared.
Polyurethanes products are made by reacting a di- or polyisocyanate with the described polyester
be varied
polyol. The nature of the polyurethane product, for example the polyurethane foam may
of factors such as the functionality of the reactants and the presence of active
depending on a variety
10 ingredients.
The organic di- or polyisocyanates may be any of the isocyanates known to be useful for the formation
of polyurethane products such as polyurethane foams. Of particular interest are aromatic di- or
(MDI)
polyisocyanates, for example tolylene diisocyanate and especially diphenylmethane dnsocyanate
which are commercially available in a variety of forms. Suitable diphenylmethane di-isocyanates include
15 a) diphenylmethane 4,4' diisocyanate and mixtures thereof with other isomers of diphenylmethane
diisocyanate; . ,
b) methylene bridged polyphenylpolyisocyanates prepared by phosgenation of mixtures ot
and known as
appropriate polyamines obtained by the condensation of aniline and formaldehyde
'polymeric' MDI, the composition of wich may subsequently be varied by distillation, crystallisation or
20 other separation techniques to give products with a weight average functionality in the range 2 to at least
3.3"'
MDI
c) polymers and oligomers obtained by reacting diphenylmethane diisocyanates or polymeric
with a monomeric glycol or polyhydric alcohol (or mixtures thereof) or with a hydroxyl-ended polyester or
poiyether and known as 'MDI prepolymers'; and
25 d) modified diphenylmethane diisocyanates or 'polymeric MDI' in which a proportion of the isocyanate
biuret or allophanate groups,
groups are converted into other groups such as carbodiimide, uretoneimine,
or in which a proportion of the isocyanate groups are reacted with an isocyanate-reactive compound.
The preparation of the foamed polyurethane materials may be carried out by the general methods fully
described elsewhere. Thus the foam forming components may be mixed continuously or discontinuously
30 in the presence of the gas generating agent to give a foam.
The foam forming gas may be generated by a variety of methods. For example the gas may be carbon
dioxide generated by the reaction of a proporiton of the organic isocyanate with water incorporated in the
reaction mixture. Gas may also be generated by incorporating in the reaction mixture an inert liquid of low
of water
boiling point which vaporises during the exothermic polyurethane foaming reaction. Mixtures
with inert low boiling point liquids may be used if desired. Examples of such liquids are halogenated
35
hydrocarbons such as methylene chloride, halomethanes and haloethanes. Mixtures of these low boiling
also be
point liquids one with another and/or with other substituted or unsubstituted hydrocarbons may
used. Such liquids are usually employed in amounts of from 5% to 50% by weight of the polyester polyol.
Water is usually employed in amounts of from 1% to 10% by weight of the polyester when used as a
40 gas generating a g e n t . . .
basic
Catalysts for the polyurethane forming reaction may also be included, especially tertiary-amines,
and metal compounds. Foam stabilisers such as siloxane alkoxy-ether copolymers may be
compounds
present, together with additives such as pigments, flame retardants, fillers, chain extenders, crosslinking
with the other additives.
agents, plasticisers and anti-oxidants, each being used alone or in combination
45 Examples of the polyester polyols prepared according to the present invention are given below but
could also include use of adipic acid, dimethyl terephthalate and the starting polyether polyols could also
be prepared solely using ethylene oxide or mixture of ethylene-oxide/propylene oxide both by sequential
or concurrrent addition.
The invention is thus illustrated by the following examples.
50
Example 1
5555 parts by weight of a propoxylated polyether polyol A prepared from residues of pentaerythritol
manufacture as defined for the examples 1—3 of EP—A—153 031 and propylene oxide to a hydroxyi value
of 604 mg KOH/g, the residual catalyst being removed by ion exchange before dehydration, were charged
55 to a 7.7 I stainless steel reactor with 1777 parts by weight of mixed dimethyl ester of adipic, glutaric and
succinic acids (in the ratio A:G:S of 20:60:20). 0.29 parts by weight of tetrabutyl-o-titanate were also added.
A nitrogen sparge was established through the reactor contents at a rate of 62 l/h with agitation. The reactor
was fitted with a reflux/fractionation column packed with 5 mm ceramic Raschig rings. Vapour from the top
of the column passed through an air/water condenser system to a suitable calibrated receiver. The reactor
60 contents were heated to 200 —210 deg C at which temperature, methanol commenced distilling from the
column top. 650 parts total distillate were recovered over 6 h during which time the reactor contents had
reached 230 deg C; the column head temperature remained constant at 60—65 deg C. When the column
tops temperature fell to <30 deg C, the column was removed from the reactor and sparging continued via a
side arm on the reactor top at a reactor temperature of 230 deg C for 30 min and any distillate traces
65 collected via a water condenser. The product (C) was then cooled to <100 deg C by applying cooling water
 EP 0192 325 B1

to the reactor coil and discharged from the reactor. The product had the analysis: hydroxyl value 325 mg
KOH/g, acid value 0.17 mg KOH/g, viscosity at 100 deg C of 145 mrrrVs and a methoxyl content of 0.52% as
methanol.

5 Example 2
6329 parts by weight of a polyether poiyol (B) prepared from pentaerythritol residues and propylene
oxide (see EP—A— 153 031 to a hydroxyl value of 545 mg KOH/g, the residual catalyst being removed by
ion exchange before dehydration, were charged to a 7.7 I stainless steel reactor with 1805 parts by weight
of mixed dimethyl esters as in Example 1 and 0.320 parts by weight of tetra butyl-o-titanate. The
io experimental procedure followed that as in Example 1. 700 parts total distillate was collected over 6 h. The
final product (D), after 2 hours on side arm distillation, had the following analysis: hydroxyl value 290 mg
KOH/g, acid value 0.15 mg KOH/g, viscosity at 100 deg C of 69 mm2/s and methoxy content of 0.37% as
methanol.

15 Examples 3—7 (see Table)

The prepared polyester polyols from Examples 1 and 2 above (C, D) were co-blended with (a) their
based polyether polyols (A and B) respectively or (b) polyether poiyol (E), a high functional sucrose amine
product of hydroxyl value 575 mg KOH/g or (c) a combination of (a) or (b) as detailed in the Table.
The average hydroxyl value of the poiyol blend is mentioned.
20 The polyurethane rigid foams, made from the polyester poiyol blends with their parent polyether
poiyol or sucrose-amine polyether or mixtures thereof, are also described in Examples 3 to 7 in the Table.

25

30

35

40

45

50

55

60

65
 EP 0 192 325 B1
TABLE

EXAMPLE 3 4 5 6 7

Polyether
Polyol A Ex.1 18.98 13.61

Polyether
Polyol B Ex.2 14-12
10
Polyester C
Ex.1 18.98 18.99 13.61

IS Polyester D
Ex.2 19.27 14.12

Polyether
polyol E 18.99 9.07 19.27 9.41
20
OH value 465 450 490 430 460

DUMP 3.00 3.00 3.00 3.00 3.00

Silicone B8406 0.50 0.50 0.50 0.50 0.50
25 0.90 0.60 1.50 1.25
Catalyst SFC 0.55
OBTDL 0.005 0.010 0.0075 0.015 0.010
Arcton II 13.00 13.00 13.00 13.00 13.00

30 Suprasec DNR 45.04 44.61 46.60 43,45 44.59

Index 105 105 105 105 105

Cream Time sec 17 13 16 12 14

35 String Time 37 32 36 31 34
Tack Free Time 46 42 46 40 44
End of rise 80 65 75 60 75

Core d e n s i t y
40 34 32 34 34
kg/m3 32
10% compres-
sive s t r e n g t h
KPa 296 279 265 220 223
45 78 82 69 81 88

Dimensional
s t a b i l i t y {% change in length and width, 1 day)
- 15 deg C -2 -0.3 -0.1 0.0 -4
50 + 100 deg C +2 +3 +4 +4 +5

Chemical compositions are expressed in parts by w e i g h t .

55

listed below; names marked by

Proprietary materials or abbreviations used in the foremulations are
asterisk are trademarks.
60

65
 EP 0 192 325 B1

Name Composition Company

Catalyst SFC N.N-dimethyicyciohexyiamine ICI

Surfactant B8406 siloxane copolymerised with Goldschmidt

10 polyether Laboratories

Arcton* 11 trichloromonofluoromethane ICI

is
Suprasec* DNR polymeric MDI . ICI

20 DHHP dimethyl methyiphosphonate Stauffer /Tenneco

OBTDL dibutyltin dilaurate

25
Claims

1. A polyester polyol having an average hydroxyl value in the range 250 to 400 mgKOH/g which
30 comprises the reaction product of
i) a polyhydric alkoxylated derivative which is itself a reaction product of a polyhydric alcohol of the
general formula

EL O-CH, ,CH,OH

R1 X)-CH2/ CH2OR2

40 wherein
R1 is —H, —CH3 or —OCH3 and
R2 is —H, CH2OH or CH2C(CH2OH)3
with one or several alkylene oxides, and
ii) a polycarboxyiic acid selected from the group consisting of dicarboxylic acids or ester of the formula
45 ROOC (CH2)n COOR or of the formula

.COOR

50

55 R00C'

wherein n is 2 to 8 and R is hydrogen, methyl or ethyl, and/or benzenetricarboxylic acid or polycarboxy

substituted diphenyl or polyphenyls and the corresponding methyl esters.
2. A polyester polyol composition comprising a polyester polyol according to claim 1 which also
60 contains at least 5% by weight of a reaction product of an alkoxylated polyhydric derivative of the formula
(II) or/and the polyhydric derivative of formula (II)

65
 EP 0 192 325 B1

r3\ /CH20H
4/C\ (II)
5
5 i

and
wherein R3 and R4 are the same or different and are selected from the group consisting of —H, CH2OH
of R3 R4 be CH2OCH3, and R5 is OH, -CH2OH or -OCH2(CH2OH)3
CH2OCH3 provided that only one or may
with a polycarboxylic acid as defined in claim 1. _
10 3 A polyester polyol composition which is derived from an alkoxylated mixture of compounds having
said composition
hydrogen-containing groups capable of alkoxylation, at least 10 percent by weight of
being a polyester polyol in accordance with claim 1.
4 A polyester polyol composition according to claim 3 in which there is also present at least 5 percent
alcohol or mixture
by weight of a polyester polyol derived from an alkoxylated derivative of a polyhydric
15 thereof of general formula ( I I ) . .
5. A polyester polyol composition according to any one of the claims 1 to 4 in which the alkoxylated
derivatives are propoxylated derivatives.
6. A polyester polyol composition according to any one of the claims 1 to 5 derived from a polyether
which has an average hydroxyi value in the range 490 to 575 mg KOH/g.
20 7. A polyester polyol composition according to any one of the claims 1 to 6 in which the weight average
functionality is in the range 2.3 to 5 . 0 . .
8. A polyester polyol composition comprising a polyester polyol according to any of the claims 1 to / in
which there is also present from 5 to 95 percent by weight of a hydroxy-terminated polyether, polyester or
polyester amide.
25 9. A polyol blend comprising one or more polyols according to any one of the claims 1 to 8.
10. A process for making a polyurethane product by reaction of a polyol according to any one of the
claims 1 to 9 with a polyisocynate.
11. A process for making a rigid polyurethane foam in which a polyol according to any one of the
in the
claims 1 to 9 is reacted with a polyisocyanate of weight average functionality in the range 2.7 to 3.3
30 presence of a blowing agent.
12. A process according to the claims 10 and 11 in which the polyisocyanate comprises methylene
bridged polyphenylpolyisocyanates.
13. A polyurethane product made according to the process of claim 11 or 12.

35 Patentanspriiche

1. Polyesterpolyol mit einer durchschnittlichen Hydroxylzahl in dem Bereich von 250 bis 400 mg KOH/g
dadurch gekennzeichnet, dafi es das Reaktionsprodukt
i) eines mehrwertigen alkoxylierten Derivats, welches selbst ein Reaktionsprodukt eines mehrwertigen
40 Alkohols der allgemeinen Formel

H\ /°"CH2\ /CH2°H

45 k1 X)-CH2/ CH2OR2
worin
R1 —H, —CH3 oder —OCH3 und
R2 —H, —CH2OH oder —CH2C(CH20H)3 bedeuten,
so mit einem oder mehreren Alylenoxiden, und
ii) einer Polycarbonsaure ausgewahlt aus der Gruppe bestehend aus Dicarbonsauren oder Estern der
Formel ROOC(CH2)nCOOR oder der Formel

COOR
55 y\ /

ROOC'

worin n = 2 bis 8 und R Wasserstoff, Methyl oder Ethyl bedeuten, und/oder Benzoltricarbonsaure oder
65 polycarboxysubstiuiertem Diphenyl oder Polyphenylen und den korrespondierenden Methylestem ist.
 EP 0192 325 B1

2. Polyesterpolyolzusammensetzung miteinem Polyesterpolyl nach Anspruch 1,dadurch gekennzeich-

net, daft es auch mindestens 5 Gew.-% eines Reaktionsprodukts eines alkoxylierten mehrwertigen Derivats
der Formel (II) oder/und das mehrwertige Derivat der Formel (II)
5 3
NC/ (ID
^ NCH2-R5
10
worin R3 und R4 gleich oder verschieden sind und aus der Gruppe bestehend aus —H, —CH2OH und
—CH2OCH3 sind, mit der Voraussetzung, daft nur einer der Reste R3 oder R4 CH2OCH3 sein kann, und R5
—OH, —CH2OH oder OCH2(CH2OH)3 ist, mit einer Polycarbonsaure nach Anspruch 1 enthalt.
3. Polyesterpolyolzusammensetzung, welche aus einer alkoxylierten Mischung von Verbindungen,
is welche zur Alkoxylierung fahige, wasserstoff-enthaltende Gruppen enthalt, abgeleitet ist, wobei
mindestens 10 Gew.-% der Zusammensetzung ein Polyesterpolyol nach Anspruch 1 ist.
4. Polyesterpolyolzusammensetzung nach Anspruch 3, dadurch gekennzeichnet, daft auch mindestens
5 Gew.-% eines Polyesterpolyols vorliegt, welches sich aus einem alkoxylierten Derivat eines
mehrwertigen Alkohols oder einer Mischung davon der allgemeinen Formel (II) ableitet.
20 5. Polyesterpolyolzusammensetzung nach einem der Anspruche 1 bis 4, dadurch gekennzeichnet, daft
die alkoxylierten Derivate propoxylierte Derivate sind.
6. Polyesterpolyolzusammensetzung nach einem der Anspruche 1 bis 5, dadurch gekennzeichnet, daft
sie aus einem Polyether mit einer durchschnittlichen Hydroxylzahl im Bereich von 490 bis 575 mg KOH/g
abgeleitet ist.'
25 7. Polyesterpoiyolzusammensetzung nach einem der Anspruche 1 bis 6, dadurch gekennzeichnet, daft
die Massemittelfunktionalitat im Bereich von 2,3 bis 5,0 ist.
8. Eine, ein Polyesterpolyol nach einem der Anspruche 1 bis 7 enthaltende Polyesterzusammen-
setzung, dadurch gekennzeichnet, daft in ihr von 5 bis 95 Gew.-% eines Polyethers, eines Polyesters oder
eines Polyesteramids mit endstandiger Hydroxylgruppe vorliegt.
30 9. Eine, ein oder mehrere Polyole nach einem der Anspruche 1 bis 8 enthaltende Polyolmischung.
10. Verfahren zum Herstellen eines Polyurethanprodukts durch Umsetzung eines Polyols nach einem
der Anspruche 1 bis 9 mit einem Polyisocyanat.
11. Verfahren zum Herstellen eines Polyurethanhartzchaumes, dadurch gekennzeichnet, daft ein Polyol
nach einem der Anspruche 1 bis 9 mit einem Polyisocyanat einer Massemittelfunktionalitat in dem Bereich
35 von 2,7 bis 3,3 in Gegenwart eines Treibmittels umgesetzt wird.
12. Verfahren nach den Anspriichen 10 und 11, dadurch gekennzeichnet, daft das Polyisocyanat
Polyphenylpoiyisocyanate mit Methylenbriicken aufweist.
13. Ein durch ein Verfahren nach Anspruch 11 oder 12 hergestelltes Polyurethanprodukt.

40 Revendications

1. Polyesterpolyol ayant un indice d'hydroxyle moyen de I'intervalle de 250 a 400 mg KOH/g, qui
comprend le produit de reaction
i) d'un derive alcoxyle polyhydroxyle qui est luimeme un produit de reaction d'un alcool polyhydroxyle
45 de la formule generate

H\ /°"CH2\ /CH2°H
C C
so r1 \>-ch2/ \:h2or2

Oil
R1 est —H, —CH3 ou —OCH3, et
ss R2 est —H, CH2OH ou CH2C(CH2OH)3
avec un ou plusieurs oxydes d'alcoylene, et
ii) d'un acide polycarboxylique choisi dans la classe formee par les acides ou esters dicarboxyliques de
formule
ROOC(CH2)nCOOR
60 ou de formule

ROOC fl- ~i COOR

65 \ ^

8
 EP 0 192 325 B1

ou
n represente 2 a 8, et les diphenyles
R rejresente hydrogene, methyle ou ethyle, et/ou les acides benzenetricarboxyliques ou
ou polyphenyles polycarboxy-substitues et les esters methyliques correspondants. " . . .
la revendication 1, qui
2 Composition de polyesterpolyol comprenant un polyesterpolyol suivant
alcoxyle de
contient aussi au moins 5% en poids d'un produit de reaction d'un derive poiyhydroxyle
formule (II) et/ou du derive poiyhydroxyle de formule (II)

io R \
N C 7/ C H 2 (ID
y NCH2-R5

classe formee par —H, —CH2OH

75 ou R3 et R4, qui peuvent etre identiques ou differents, sont choisis dans la
et— CH2OCH3, avec la restriction qu'un seul d'entre R3 et R4 peut etre— CH2OCH3, et R5 est— OH,— OCH2OH
0CH2C(CH20H)3 avec un acide polycarboxylique tel que defini dans la revendication 1.
ou — des
3 Composition de polyesterpolyol qui est issue d'un melange alcoxyle de composes comprenant
de I'hydrogene capables d'alcoxylation, au moins 10% en poids de la composition
radicaux contenant
20 etant un polyesterpolyol suivant la revendication 1. 5 /o en
4 Composition de polyesterpolyol suivant la revendication 3, dans laquelle il y a aussi au moms
issu d'un derive alcoxyle d'un alcool poiyhydroxyle ou melange de celui-ci de
poids d'un polyesterpolyol
formule generate ( I I ) . . , 4 dans .laquelle
. . . les
5. Composition de polyesterpolyol suivant I'une quelconque des revendications 1 a
25 ■derives alcoyles sont des derives propoxyles.
6. Polyesterpolyol suivant I'une quelconque des revendications 1 a 5, issu d un polyether qui a un
indice d'hydroxyle moyen de I'intervaile de 490 a 575 mg KOH/g. _
7. Polyesterpolyol suivant I'une quelconque des revendications 1 a 6, dans lequel la fonctionnalite
moyenne en poids se situe dans I'intervaile de 2,3 a 5,0. des
30 8 Composition de polyester comprenant un polyesterpolyol suivant I'une quelconque
revendications 1 a 7, dans laquelle il y a aussi 5 a 95% en poids d'un pbiyether, polyester ou
polyesteramide a radicaux hydroxyle terminaux.
des
9. Melange de polyols comprenant un ou plusieurs polyols suivant I une quelconque
revendications 1 a 8 . . . ,
35 10. Procede de fabrication d'un produit de polyurethanne par reaction d un polyol suivant I une
quelconque des revendications 1 a 9 avec un polyisocyanate. I
11 Procede de fabrication d'une mousse de polyurethanne rigide, dans lequel un polyol suivant une
revendications 1 9 est mis a reagir avec un polyisocyanate d'une fonctionnalite moyenne
quelconque des a
en poids de I'intervaile de 2,7 a 3,3 en presence d'un agent porophore. des
40 12. Procede suivant les revendications 10 et 11, dans lequel le polyisocyanate comprend
polyphenylpolyisocyanates a pont methylenique.
13. Produit de polyurethanne fabrique par le procede suivant la revendication 11 ou 12.

45

50

55

60

65