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Claims  |
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What is claimed is:
1. A polyol (D) having a hydroxyl value of from 180 to 700 mgKOH/g which
comprises (i) polyol (a), polyol (b) and polyol (d), or(ii) polyol (a),
polyol (b), polyol (c) and polyol (d):
said polyol (a) having a hydroxyl value of from 140 to 350 mgKOH/g and
being prepared by the addition of from 1.0 to 4.5 moles of an alkylene
oxide to one equivalent of hydroxyl of a phenol resin or a mixture hereof
having a number average molecular weight of from 650 to 1400, an average
functionality of from 3 to 8 and the formula (I):
##STR4##
wherein R.sub.1 is a hydrogen atom, alkyl having from 1 to 9 carbon
atoms, halogen atom selected from chlorine, bromine and fluorine, or
hydroxyl, m is an integer of from 1 to 3, n is an integer of from 1 to 6,
and X and Y are same or different divalent groups selected from the group
consisting of an alkylene having from 1 to 10 carbon atoms, xylylene, oxy,
thio and sulfonyl or bonded group of the above-mentioned groups; said
polyol (b) having a hydroxyl value of 240 to 800 mgKOH/g and being
obtained by adding from 0.5 to 3.0 moles of an alkylene oxide to one
equivalent of active hydrogen in an alkanolamine series compound of a
mixture thereof having the formula (II):
NR.sub.2 R.sub.2 R.sub.3 (II)
wherein R.sub.2 and R.sub.3 are respectively a hydrogen atom, hydroxyethyl
or hydroxyisopropyl, R.sub.2 and R.sub.3 are same or different and
excluding the case wherein both R.sub.2 and R.sub.3 are hydrogen atoms;
said polyol (c) having a hydroxyl value of 130 to 750 mgkoh/g and being
obtained by the addition of from 0.5 to 6.5 moles of an alkylene oxide to
one equivalent of hydroxyl group in an active halogen containing compound
which is an aliphatic polyhydroxy compound having average functionality of
from 2 to 8 or a mixture thereof; and said polyol (d) having a hydroxyl
value of from 150 to 700 mgKOH/g and being obtained by adding from 1.0 to
9.0 moles of an alkylene oxide to one equivalent of active hydrogen in an
amino phenol series compound or a mixture thereof having a number average
molecular weight of from 100 to 200, an average functionality of from 3 to
6, and formula (III):
##STR5##
wherein R.sub.0 is a hydrogen atom, aliphatic hydrocarbon group having
from 1 to 5 carbon atoms, or alicyclic hydrocarbon group, q is an integer
of from 1 to 2, and p is an integer of from 1 to 2.
2. The polyol(D) of claim 1 wherein the phenol resin is a novolak resin
represented by the formula (I) wherein R.sub.1 is a hydrogen atom and both
X and Y are methylene.
3. The polyol(D) of claim 2 wherein the novolak resin has a number average
molecular weight of from 650 to 900, average functionality of from 3 to 8,
and a softening point of from 75.degree. to 120.degree. C.
4. The polyol(D) of claim 1 having a polyol(a)/polyol(b) ratio of from 0.25
to 4.0 by weight, a polyol(a)/polyol(c) ratio of from 0.1 to 4.0 by
weight, and a polyol(a)/polyol(d) ratio of about 1.0.
5. A polyol(E) having a hydroxyl value of from 180 to 700 mgKOH which
comprises (i) polyol(a), polyol(b) and polyol(e), or (ii) polyol(a),
polyol(b), polyol(c) and polyol(e), polyol(a), polyol(b) and polyol(c)
being the same as polyol(a), polyol(b) and polyol(c) according to claim 1,
said polyol(e) having a hydroxyl value of from 150 to 700 mgKOH/g and
being obtained by adding from 1.0 to 9.0 moles of an alkylene oxide to one
equivalent of active hydrogen in a polyphenylpolyxylylenepolyamine series
compound or a mixture thereof having a number average molecular weight of
from 300 to 1500, average functionality of from 4 to 8 and the formula
(IV):
##STR6##
wherein R is a hydrogen atom, aliphatic hydrocarbon group having from 1 to
10 carbon atoms, or an alicyclic hydrocarbon group, Z is xylylene group
and s is an integer of from 0 to 10.
6. Polyol(E) of claim 5, having a polyol(e)/polyol(b) ratio of from 0.25 to
4.0 by weight and polyol(e)/polyol(c) ratio of from 0.1 to 4.0 by weight.
7. A polyurethane resin obtained by the reaction of a polyol with an
organic polyisocyanate, a portion or the whole of said polyol comprising
the polyol(D) of claim 1.
8. A polyurethane resin obtained by the reaction of polyol with an organic
polyisocyanate, a portion or the whole of said polyol comprising the
polyol (E) of claim 5.
9. The polyurethane resin of claim 8 wherein the organic polyisocyanate
comprises an isocyanate terminated prepolymer.
10. The polyurethane resin of claim 8 wherein the equivalent ratio of an
isocyanate group in the organic polyisocyanate to a hydroxyl group in the
polyol is in the range of from 0.8 to 5.0.
11. A rigid polyurethane foam obtained by the reaction of an organic
polyisocyanate with a resin premix comprising a polyol, foaming agent,
catalyst, cell regulator, other additives and optionally an auxiliary
foaming agent, said polyol comprising a portion or the whole of polyol(D)
of claim 1, said foaming agent comprising a single compound or a mixture
thereof selected from the group consisting of a hydrochlorofluorocarbon or
a hydrofluorocarbon.
12. A rigid polyurethane foam obtained by the reaction of an organic
polyisocyanate with a resin premix comprising a polyol, foaming agent,
catalyst, cell regulator, other additives and optionally an auxiliary
foaming agent, said polyol comprising a portion or the whole of polyol (E)
of claim 5, said foaming agent comprising a single compound or a mixture
thereof selected from the group consisting of a hydrochlorofluorocarbon or
a hydrofluorocarbon.
13. The rigid polyurethane foam of claim 12 wherein the
hydrochlorofluorocarbon is 2,2-dichloro-1,1,1-trifluoroethane,
1,1-dichloro-1-fluoroethane or 1-chloro-1,1-difluoromethane, and the
hydrofluorocarbon is 1,1,1,2-tetrafluoroethane or 1,1-difluoroethane.
14. The rigid polyurethane foam of claim 12 wherein the auxiliary foaming
agent is water, a low boiling point compound or mixtures thereof.
15. The rigid polyurethane foam of claim 12 wherein the organic
polyisocyanate comprises an isocyanate terminated prepolymer.
16. The rigid polyurethane foam of claim 12 wherein the equivalent ratio of
an isocyanate group in the organic polyisocyanate to a hydroxyl group in
the polyol is in the range of from 0.8 to 5.0.
17. A preparation process of a rigid polyurethane foam by reacting an
organic polyisocyanate with a resin premix comprising a polyol, foaming
agent, catalyst, cell regulator other additives and optionally an
auxiliary foaming agent, said polyol comprising a portion or the whole of
polyol(D) of claim 1, said foaming agent comprising a single compound or a
mixture thereof selected from the group consisting of a
hydrochlorofluorocarbon or a hydrofluorocarbon.
18. A preparation process of a rigid polyurethane foam by reacting an
organic polyisocyanate with a resin premix comprising a polyol, foaming
agent, catalyst, cell regulator other additives and optionally an
auxiliary foaming agent, said polyol comprising a portion or the whole of
polyol (E) of claim 5, said foaming agent comprising a single compound or
mixture thereof selected from the group consisting of a
hydrochlorofluorocarbon or a hydrofluorocarbon.
19. The preparation process of claim 18 wherein a portion or the whole of
the organic polyisocyanate comprises an isocyanate terminated prepolymer.
20. The preparation process of claim 18 wherein the equivalent ratio of an
isocyanate group in the organic polyisocyanate to a hydroxyl group in the
polyol is in the range of from 0.8 to 5.0.
21. A preparation process of a rigid polyurethane foam composite by
reacting an organic polyisocyanate with a premix comprising a polyol,
foaming agent, catalyst, cell regulator, other additives and optionally an
auxiliary foaming agent to form a rigid polyurethane foam on a face
material or in a cavity surrounded by a plurality of face material, said
polyol comprising a portion or the whole of polyol(D) of claim 1, said
foaming agent comprising a single compound or a mixture thereof select
from the group consisting of a hydrochlorofluorocarbon and a
hydrofluorocarbon.
22. A preparation process of a rigid polyurethane foam composite by
reacting an organic polyisocyanate with a premix comprising a polyol,
foaming agent, catalyst, cell regulator, other additives and optionally an
auxiliary foaming agent to form a rigid polyurethane foam on a face
material or in a cavity surrounded by a plurality of face material, said
polyol comprising a portion or the whole of polyol (E) of claim 9, said
foaming agent comprising a single compound or a mixture thereof select
from the group consisting of a hydrochlorofluorocarbon and a
hydrofluorocarbon.
23. The preparation process of claim 1 wherein the rigid polyurethane foam
is formed by a coating, pouring or spraying process.
24. The preparation process of claim 22 wherein a portion or the whole of
the organic polyisocyanate comprises an isocyanate terminated prepolymer.
25. The preparation process of claim 22 wherein the equivalent ratio of an
isocyanate group in the organic polyisocyanate to a hydroxyl group in the
polyol is in the range of from 0.8 to 5.0.
26. A rigid polyurethane foam obtained by reacting an organic
polyisocyanate with a resin premix comprising a polyol, foaming agent,
catalyst, cell regulator, other additives and optionally an auxiliary
foaming agent, said polyol comprising a portion or the whole of polyol (G)
having a hydroxyl value of from 180 to 700 mgKOH/g and said polyol(G)
comprising (i) polyol (a), polyol (b) and polyol (f), or (ii) polyol (a),
polyol (b), polyol (c) and polyol (f), polyol (a), polyol (b) and polyol
(c) being the same as polyol (a), polyol (b) and polyol (c) according to
claim 2, said polyol (f) having a hydroxyl value of from 150 to 700
mgKOH/g and being obtained by the addition of from 1.0 to 9.0 moles of an
alkylene oxide to one equivalent of active hydrogen in
polymethylenepolyphenylpolyamine and, said foaming agent comprising a
compound or a mixture thereof selected from the group consisting of a
hydrochlorofluorocarbon and a hydrofluorocarbon.
27. The rigid polyurethane foam of claim 26 wherein a portion or the whole
of the organic polyisocyanate comprises an isocyanate terminated
prepolymer.
28. The rigid polyurethane foam of claim 26 wherein the equivalent ratio of
an isocyanate group in the organic polyisocyanate to a hydroxyl group of
the polyol is in the range of from 0.8 to 5.0.
29. A preparation process of rigid polyurethane foam by the reaction of an
organic polyisocyanate with a resin premix comprising polyol, foaming
agent, catalyst, cell regulator, other additives and optionally an
auxiliary foaming agent, said polyol comprising a portion or the whole of
poyol (G) according to claim 26 having a hydroxyl value of from 180 to 700
mgKOH/g and said foaming agent comprising a compound or a mixture thereof
selected from the group consisting of a hydrochlorofluorocarbon and a
hydrofluorocarbon.
30. The preparation process of claim 29 wherein a portion or the whole of
the organic polyisocyanate comprises an isocyanate terminated prepolymer.
31. The preparation process of claim 29 wherein the equivalent ratio of an
isocyanate group in the organic polyisocyanate to a hydroxyl group in the
polyol is in the range of from 0.8 to 5.0.
32. A preparation process of a rigid polyurethane foam composite by the
reaction of an organic polyisocyanate with a resin premix comprising a
polyol, foaming agent, catalyst, cell regulator, at least one other
additive, and optionally, an auxiliary foaming agent to form rigid
polyurethane foam on a face material or in a cavity surrounded by a
plurality of face material, said polyol comprising a portion or the whole
of polyol (G) according to claim 30 having a hydroxyl value of from 180 to
700 mgKOH/g, and said foaming agent comprising a compound or a mixture
thereof selected from the group consisting of a hydrochlorofluorocarbon
and a hydrofluorocarbon.
33. The preparation process of claim 32 wherein a portion or the whole of
the organic polyisocyanate comprises an isocyanate terminated prepolymer.
34. The preparation process of claim 32 wherein the equivalent ratio of an
isocyanate group in the organic polyisocyanate to a hydroxyl group in the
polyol is in the range of from 0.8 to 5.0.
35. The preparation process of claim 32 wherein the rigid polyurethane foam
is formed by coating, pouring or spraying.
36. The polyurethane resin of claim 7 wherein the organic polyisocyanate
comprises an isocyanate terminated prepolymer.
37. The polyurethane resin of claim 7 wherein the equivalent ratio of an
isocyanate group in the organic polyisocyanate to a hydroxyl group in the
polyol is in the range of 0.8 to 5.0.
38. The rigid polyurethane foam of claim 11 wherein the
hydrochlorofluorocarbon is 2,2-dichloro-1,1,1-trifluoroethane,
1,1-dichloro-1-fluoroethane or 1-chloro-1,1-difluoromethane, and the
hydrofluorocarbon is 1,1,1,2-tetrafluoroethane or 1,1-difluoroethane.
39. The rigid polyurethane foam of claim 11 wherein the auxiliary foaming
agent is water, a low boiling point compound or mixture thereof.
40. The rigid polyurethane foam of claim 11 wherein the organic
polyisocyanate comprises an isocyanate terminated prepolymer.
41. The rigid polyurethane foam of claim 11 wherein the equivalent ratio of
an isocyanate group in the organic polyisocyanate to a hydroxyl group in
the polyol is in the range of from 0.8 to 5.0.
42. The preparation process of claim 17 wherein a portion or the whole of
the organic polyisocyanate comprises an isocyanate terminated prepolymer.
43. The preparation process of claim 17 wherein the equivalent ratio of an
isocyanate group in the organic polyisocyanate to a hydroxyl group in the
polyol is in the range of form 0.8 to 5.0.
44. The preparation process of claim 21 wherein the rigid polyurethane foam
is formed by a coating, pouring or spraying process.
45. The preparation process of claim 21 wherein a portion or the whole of
the organic polyisocyanate comprises an isocyanate terminated prepolymer.
46. The preparation process of claim 21 wherein the equivalent ratio of an
isocyanate group in the organic polyisocyanate to a hydroxyl group in the
polyol is in the range of from 0.8 to 5.0. |
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Claims |
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Description |
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BACKGROUND OF THE INVENTION
(a) Field of the Invention
The present invention relates to a polyol, polyurethane resin, rigid
polyurethane foam, preparation process thereof and a composite of said
rigid polyurethane foam.
More particularly, the polyol used in the present invention, which is a
phenyl resin based polyol mixed with an aminophenol based polyol or
polyphenylpolyxylylenepolyamine based polyol or
polymethylenepolyphenylpolyamine based polyol is a raw material for
preparing polyurethane resins resistant to dissolving in
hydrochlorofluorocarbons (hereinafter abbreviated as HCFC) and
hydrofluorocarbons (hereinafter abbreviated as HFC) which are foaming
agents of very low public hazards. The polyol can provide rigid a
polyurethane foam and its composite by using the above foaming agents
The rigid polyurethane foam according to the invention has particularly
excellent properties as they are equivalent to those of conventional
polyurethane foams obtained by the use of chlorofluorocarbons (hereinafter
abbreviated as CFC) as foaming agents. Hence, the rigid polyurethane foam
of the present invention is extremely useful for the insulating materials
or the insulating structural materials of electric refrigerators, freezing
warehouses, insulation panels, ships and vehicles.
(b) Description of the Prior Art
Rigid polyurethane foam has excellent heat insulation properties and low
temperature dimensional stability, and thus, various composites prepared
therefrom are widely used for refrigerators, freezing ware houses,
building wall faces, ceilings, heat insulation and structural materials
for ships and vehicles, and the heat insulating and protective covers of
instruments.
Further, large numbers of composites containing the rigid polyurethane foam
formed on a sheet of face material or in a cavity surrounded by a
plurality of face materials have already been manufactured by a batch
process or a continuous process.
In the present manufacturing process of polyurethane foams, CFC such as
CFC-11 and CFC-12 are generally used as foaming agents. These compounds
have recently been recognized as materials which cause environmental
destruction such as the disruption of the ozone layer or enhancement of
the green house effect. Accordingly, restrictions have recently been
imposed upon the manufacture and use of these compounds.
At the same time, attention has been focused on HCFC such as
2,2-dichloro-1,1,1-(trifluoroethane (HCFC-123),
1,1-dichloro-1-fluoroethane (HCFC-141b) 1-chloro-1,1-difluoroethane
(HCFC-142b), and 1-chloro-1,1-difluoromethane (HCFC-22), and additionally,
HFC such as 1,1,1,2-tetrafluoroethane (HFC-134a) and 1,1-difluoroethane
(HFC-152a), which cause much less environment destruction, as substitutes
for CFC-11 and CFC-12. However, it has been found that HCFC and HFC have a
higher dissolving power an polyurethane resins compared with CFC, and
hence have the disadvantage of severely deteriorating the properties of
resulting polyurethane foams. For example, they reduce closed cell content
and foam strength. Particularly it has been found by the present inventors
that in the manufacture of rigid polyurethane foams, HCFC and HFC dissolve
the cell walls of closed cells in the course of foaming and drastically
lower heat insulation effects which is a characteristic property of rigid
polyurethane foams.
Consequently, there is a great desire for a novel polyurethane resin which
avoids the above problems. The conventional polyoxyalkylene polyol used as
a raw material in the production of polyurethane resin exhibits a
viscosity decrease with an increase in the amount of alkylene oxide added.
As a result, operations in polyurethane foam production can be conducted
with ease. It has been found that an excess addition of alkylene oxide
leads to a dissolution of polyurethane resin into HCFC and HFC, and tends
to make application of these foaming agents substantially impossible. On
the other hand, when the amount of alkylene oxide added is reduced, it has
been discovered that a resistance to dissoling in HCFC and HFC is improved
slightly, but the polyol becomes solid or extremely viscous and solubility
between each raw material decreases. As a result, it is very difficult to
handle, and a satisfactory product cannot be obtained.
Particularly in the production of rigid polyurethane foam, viscosity of the
polyol and solubility between the polyol, foaming agent and organic
polyisocyanate are necessary. Unfortunately, a polyol which has a
viscosity suitable for foaming and provides excellent mixing and
dispersing ability in HCFC and HFC has never been found.
Japanese TOKKAI-SHO 57-151613(1982) and TOKKAI-SHO 57-151614(1982) disclose
methods of blending low molecular weight polyol in order to decrease the
viscosity of mixtures of amine based polyols and aromatic based polyester
polyols (alkylene oxide was not added).
TOKKAI-Sho 51-105394 (1976) discloses a mixed polyol having a hydroxyl
value of 200.about.500 mgKOH/g comprising a novolak based polyol, aromatic
amine based polyol and an aliphatic polyol. TOKKAI-Sho 63-264616 and
TOKKAI-Hei 1-135824 disclose mixed polyols comprising novolak resin based
polyols having hydroxyl values of 50.about.350 mgKOH/g, polyetherpolyols
and/or polyesterpolyols. But they do not disclose the polyols of the
present invention and the rigid polyurethane foam produced from the polyol
and HCFC or HFC.
SUMMARY OF THE INVENTION
The present invention relates to a polyol, polyurethane resin, rigid
polyurethane foam, preparation process therefor and a preparation process
of a rigid polyurethane foam composite.
The polyol used in the present invention comprises a phenol resin based
polyol mixed with an aminophenol based polyol or a
polyphenylpolyxylylenepolyamine based polyol or a
polymethylenepolyphenylpolyamine based polyol.
The above polyurethane resin, foam and composite have a resistance to
dissolution in hydrochlorofluorocarbons and hydrofluorocarbons, and are
foaming agents which exhibit very low public hazard.
The above-mentioned foams have excellent physical properties equivalent to
those of conventional polyurethane foams obtained by using
chlorofluorocarbons, and hence are very useful as a thermal insulation
material or a thermal insulation structure for refrigerators, freezers,
insulation panels, ships or vehicles.
DETAILED DESCRIPTION OF THE INVENTION
The primary object of the present invention is, particularly in the
production of a rigid polyurethane foam, to provide a polyol which gives
equivalent operation efficiency in polyurethane foaming operation and
equivalent resultant foam properties to conventional CFC, even though HCFC
and/or HFC having very low hazards are used.
As a result of an intensive investigation in order to achieve the above
object, the present inventors have completed the present invention.
That is, the aspect of the present invention is illustrated by the
following (1) to (6).
(1) Polyol(D) comprising phenol resin based polyol(A) and aminophenol based
polyol (B) in a ratio (A)/(B) of from 0.25 to 4.0 by weight, said polyol
(D) having a hydroxyl value of from 180 to 700 mgKOH/g.
(2) Poyol(E) comprising phenol resin based polyol(A) and
polyphenylpolyxylylenepolyamine base polyol(C) in a (A)/(C) ratio of from
0.25 to 4.0 by weight, said polyol(E) having a hydroxyl value of from 180
to 700 mgKOH.g.
(3) A polyurethane resin obtained by the reaction of a polyol with an
organic polyisocyanate wherein a portion or the whole of said polyol is
the polyol(D) described in (1) or the polyol(E) described in (2).
(4) A rigid polyurethane foam obtained by the reaction of an organic
polyisocyanate with a resin premix comprising a polyol, foaming agent,
catalyst, cell regulator and other additives, said polyol comprising the
polyol(D) described in (1), the polyol(E) described in (2), or a polyol
(G) comprising a phenol resin based polyol (A) and
polyphenylpolymethylenepolyamine based polyol(F), said foaming agent
comprising a compound or a mixture thereof selected from the group
consisting of a HCFC and HFC, said foaming agent additionally comprising
an auxiliary foaming agent, if desired.
(5) A preparation process of the rigid polyurethane foam described in (4).
(6) A preparation process of a rigid polyurethane foam composite by
reacting an organic polyisocyanate with a resin premix comprising a
polyol, foaming agent, catalyst, cell regulator and other additives to
form a rigid polyurethane foam on a face material or in a cavity
surrounded by a plurality of face materials, said polyol comprising
polyol(D) described in (1), polyol(E) described in (2), or a polyol (G)
comprising phenol resin based polyol (A) and
polyphenylpolymethylenepolyamine base polyol(F), said foaming agent
comprising a compound or a mixture thereof selected from the group
consisting of a HCFC and a HFC, said foaming agent additionally comprising
an auxiliary foaming agent, if desired.
The polyol for use in the present invention is the above polyol(D),
polyol(E) and polyol(G).
Polyol(D) used in the present invention comprises as one component, phenol
resin based polyol (A) and as another component, aminophenol based polyol
(B).
Phenol resin based polyol(A) used in the invention comprises polyol(a) and
polyol(b) or polyol (a) and polyol(c); said polyol(a) having a hydroxyl
value of from 140 to 350 mgKOH/g and being prepared by the addition of
from 1.0 to 4.5 moles of an alkylene oxide to one equivalent of hydroxyl
of a phenol resin or a mixture thereof having a number average molecular
weight (hereinafter abbreviated as (Mn)) of from 650 to 1400, an average
functionality of from 3 to 8 and a structure of the formula (I):
##STR1##
wherein R.sub.1 is a hydrogen atom, alkyl having from 1 to 9 carbon atoms,
halogen atom selected from chlorine, bromine and fluorine, or hydroxyl, m
is an integer of from 1 to 3, n is an integer of from 1 to 6, and X and Y
are same or different divalent group selected from the group consisting of
an alkylene having from 1 to 10 carbon atoms, xylylene, oxy, thio and
sulfonyl or bonded group of the above-mentioned groups; said polyol(b)
having a hydroxyl value of 240 to 800 mgKOH/g and being obtained by adding
from 0.5 to 3.0 moles of an alkylene oxide to one equivalent of active
hydrogen in an alkanolamine series compound or a mixture thereof having
the formula (II):
NR.sub.2 R.sub.2 R.sub.3 (II)
wherein R.sub.2 and R.sub.3 are respectively a hydrogen atom, hydroxyethyl
or hydroxyisopropyl, R.sub.2 and R.sub.3 are same or different and
excluding the case wherein both R.sub.2 and R.sub.3 are hydrogen atoms;
said polyol(c) having a hydroxyl value of 130 to 750 mgKOH/g and being
obtained by the addition of from 0.8 to 6.5 moles of an alkylene oxide to
one equivalent of hydroxyl in an active hydrogen containing compound which
is an aliphatic polyhydroxy compound having functionality of from 2 to 8
or a mixture thereof.
The suitable phenol resin for use in the invention includes, for example,
reaction products of phenols such as phenol, cresol, butylphenol,
nonylphenol, chlorophenol, resorcinol, hydroquinone, catechol, guaiacol,
bisphenol A or bisphenol S with aldehydes such as formaldehyde or
acetaldehyde, .alpha.,.alpha.'-dimethoxyxylene, .alpha.,
.alpha.'-dichloroxylene or sulfur. The reaction is carried out by known
methods.
The preferred phenol resin is a novolak resin which has the formula (I)
wherein R.sub.1 is a hydrogen atom and both X and Y are methylene, and has
(Mn) of 650 to 900, average functionality of 3 to 8, and a softening point
of 75.degree. to 120.degree. C.
The alkylene oxide used for the present invention includes, for example
ethylene oxide, propylene oxide and butylene oxide. The alkylene oxide may
be used singly or in combination.
It was found that when mole numbers of alkylene oxide addition are
increased, solubility resistance to HCFC or HFC is generally decreased.
When (Mn) of the phenol resin is less than 650, any of the polyurethane
resins derived from the reaction with organic polyisocyanate have a
tendency to dissolve in HCFC and HFC.
On the other hand, (Mn) of the phenol resin exceeding 1400 leads to high
viscosity in any mixing ratio, poor dispersibility in HCFC and HFC,
inferior operation efficiency in reaction, with organic polyisocyanate.
The suitable polyol (a) for use in the invention is obtained by the
addition of 1.0 to 4.5 moles of alkylene oxide to 1 equivalent of the
hydroxyl group in the phenol resin. Alkylene oxide of less than 1.0 mole,
that is, a large amount of remaining phenolic hydroxyl group, causes
unfavorable reduction of physical properties in the resulting polyurethane
foam. On the other hand, an alkylene oxide addition exceeding 4.5 mole
eliminates resistance to HCFC or HFC of the resulting polyurethane resin,
although viscosity is reduced and dispersibility in HCFC and HFC becomes
better.
When the phenol resin has an average functionality of less than 3, the
resulting polyurethane resin made from (a) and (b) or (a) and (c)
decreases resistance to HCFC and HFC. On the other hand, an average
functionality exceeding 8 leads to a disadvange of rendering the
polyurethane resin brittle.
The alkanolamine for use in the invention includes, for example,
monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine,
diisopropanolamine and triisopropanolamine.
The suitable polyol (b) used in the invention is obtained by the addition
of 0.5 to 3.0 moles of alkylene oxide to 1 equivalent of active hydrogen
in the alkanolamine.
When the amount of alkylene oxide is less than 0.5 mole per equivalent of
active hydrogen of alkanolamine, crosslinking activity of alkanolamine
remains, and hence, deteriorates physical properties of the resulting
polyurethane foam. An amount of alkylene oxide exceeding 3.0 moles also
decreasses foam properties and the resulting polyurethane foam cannot be
used practically.
The polyols (a) and (b) used in the invention are preferably used in a
mixing ratio (a)/(b) of 0.25 to 4.0 by weight. A mixing ratio exceeding
4.0 causes high viscosity and poor dispersibility and dissolving in HCFC
and HFC, and also leads to unfavorable operation problems in the
preparation of a polyurethane resin. On the other hand, a mixing ratio
less than 0.25 is unsuitable because of inferior properties of resulting
polyurethane foams and a deterioration of resistance to dissolving in HCFC
or HFC.
The suitable aliphatic polyhydroxy compounds used for the present invention
are a single compound or a mixture of two or more compounds selected from
the group consisting of a glycols, polyhydric alcohols and a
polysaccharides having 2 to 8 functionality. Exemplary aliphatic
polyhydroxy compounds include glycols such as ethylene glycol, diethylene
glycol, propylene glycol, dipropylene glycol, butanediol, neopentyl
glycol, cyclohexane dimethanol and cyclohexane tetramethanol; polyhydric
alcohols such as glycerol, trimethylolethane, trimethylolpropane, and
pentaerythritol; and polysaccharides such as methylglucoside, sorbitol,
mannitol, dulcitol and sucrose.
Preferred mole numbers of alkylene oxide addition are from 0.5 to 6.5 moles
per equivalent of the hydroxyl in the aliphatic polyhydroxy compound. An
alkylene oxide addition of less than 0.5 mole makes the resultant
polyurethane foam brittle. On the other hand, an addition exceeding 6.5
moles lowers resistance to HCFC and HFC of the polyurethane resin
obtained.
The polyols (a) and (c) which are intiated with the phenol resin and
aliphatic polyhydroxy compound, respectivley, are preferably mixed in the
ratio (a)/(c) of 0.1 to 4.0 by weight. A mixing ratio less than 0.1
reduces resistance to HCFC or HFC of polyurethane resin prepared by
reacting in the presence of a catalyst. On the other hand, a mixing ratio
exceeding 4.0 leads to a disadvantage of poor operation efficiency due to
too high viscosity in the preparation of polyurethane resin.
Aminophenol based polyol (B) comprises polyol(d) having a hydroxyl value of
from 150 to 700 mgKOH/g and polyol(b) or polyol (d) and polyol(c)
described in the phenol resin base polyol (A), said polyol(d) being
obtained by adding from 1.0 to 9.0 moles of an alkylene oxide to one
equivalent of active hydrogen in an aminophenol series compounds or a
mixture thereof having a (Mn) of from 100 to 200, average functionality of
from 3 to 6, and a structure of the formula (III):
##STR2##
wherein R.sub.0 is a hydrogen atom, aliphatic hydrocarbon group having
from 1 to 5 carbon atoms, or alicyclic hydrocarbon, q is an integer of
from 1 to 2, and p is an integer of from 1 to 2.
Exemplary suitable aminophenol compounds include aminophenol, aminocresol,
aminoethylphenol, aminobutylphenol, aminoresorcinol, aminopyrocatechol,
aminohydroquinone, aminohomocatechol, aminocresorcinol, aminoorcinol,
diaminophenol, diaminocaresol.
Aminophenol based polyol(B) comprises polyol(d) and polyol(b) or polyol (d)
and polyol(c) in a (d)/(b) ratio of from 0.25 to 4.0 by weight and a
(d)/(c) ratio of from 0.1 to 4.0 by weight. The reason for the selection
Of these mixing ratios is the same as (a)/(b) and (a)/(c) in the case of
phenol resin based polyol(A).
Polyol(D) comprises phenol resin based polyol(A) and aminophenol based
polyol(B) in a (A)/(B) retio of from 0.25 to 4.0 by weight and has a
hydroxyl value of from 180 to 700 mgKOH/g.
Even though polyol(A) is used singly, the rigid polyurethane foam obtained
by using HCFC and/or HFC as foaming agents exhibits relatively good
physical properties. When polyol(A) is used in combination with polyol(B),
foam properties such as heat conductivity, compressive strength, and low
temperature dimensional stability can be further improved. A (A)/(B) ratio
deviating from the range of from 0.25 to 4.0 leads to inferior properties
of the foam.
Another polyol (E) of the present invention comprises as one component,
afore-mentioned phenol resin based poplyol (A) and as another component,
polyphenylpolyxylylenepolyamine based polyol (C).
Polyphenylpolyxylylenepolyamine based polyol(C) used in the present
invention comprises a polyol(e) having a hydroxyl value of from 150 to 700
mgKOH/g and polyol(b) or polyol (b) and polyol(c) described above, said
polyol(e) being obtained by adding from 1.0 to 9.0 moles of an alkylene
oxide to one equivalent of active hydrogen in a
polyphenylpolyxylylenepolyamine series compound or a mixture thereof
having the formula (IV):
##STR3##
wherein R is a hydrogen atom, aliphatic hydrocarbon group having 1 to 10
carbon atoms, or an alicyclic hydrocarbon group, Z is a xylylene group and
s is an integer of from 0 to 10.
Above polyphenylpolyxylylenepolyamine series compound for use in the
invention includes, for example, .alpha., .alpha.'-bis (4-aminophenyl)
xylene, polyphenylpolyxylylenepolyamine, mixture thereof derivatives,
isomer and oligomer of these compounds.
When the amount of alkylene oxide is less than 1.0 mol per equivalent of
the amino group, that is, many amino groups remain control of the foaming
reaction becomes difficult and the resulting poloyurethane foam shows an
unfavorable deterioration of physical properties. On the other hand, an
alkylene oxide addition exceeding 9.0 moles leads to inferior physical
properties, although viscosity is reduced and dispersing ability in HCFC
and HFC becomes better.
The alkanolamine which can be used has been described above.
The polyol(b) used in the invention is obtained by the addition of 0.5 to
3.0 moles of alkylene oxide to 1 equivalent of active hydrogen in the
alkanolamine.
When the amount of alkylene oxide is less than 0.5 mole per equivalent of
active hydrogen of alkanolamine, crosslinking activity of alkanolamine
remains and hence deteriorates physical properties of the resulting
polyurethane foam. An amount of alkylene oxide exceeding 3.0 moles also
decreases foam properties even in a polyol mixing ratio (e)/(b) of above
4.0 and the resulting polyurethane foam cannot be used practically.
The polyol (e) and (b) for use in the invention are preferably used in a
mixing ratio (e)/(b) of 0.25 to 4.0 by weight. A mixing ratio exceeding
4.0 causes high viscosity and poor dispersibility in HCFC and HFC and also
leads to unfavorable operation problems in the preparation of a
polyurethane resin. On the other hand, a mixing ratio less than 0.25 is
unsuitable because of inferior properties of the resulting polyurethane
foams.
The aliphatic polyhydroxy compound which can be used has been described
above.
The preferred amount of an alkylene oxide added to the aliphatic
polyhydroxy compound is from 0.5 to 6.5 moles per equivalent of hydroxyl
group in the aliphatic polyhydroxy compound. Addition of less than 0.5
mole makes resulting polyurethane foams brittle. On the other hand, an
amount exceeding 6.5 moles decreases resistance of the resulting
polyurethane resin to dissolution in HCFC and HFC.
Polyphenylpolyxylylenepolyamine initiated polyol(e) and aliphatic
polyhydroxy compound initiated polyol(c) are preferably mixed in a (e)/(c)
ratio of from 0.1 to 4.0 by weight. A ratio less than 0.1 lowers
resistance to dissolving in HCFC and HFC of polyurethane resin prepared in
the presence of a catalyst. On the other hand, a ratio exceeding 4.0
causes too high of a viscosity of the resulting mixture and hence has a
disadvantage of poor operation efficiency in the production of a
polyurethane resin.
Polyol(E) is obtained by mixing polyol(A) and polyol(C) in a (A)/(C) ratio
of from 0.25 to 4.0 by weight and has a hydroxyl value of from 180 to 700
mgKOH/g.
Although polyol(A) is used singly, the foam obtained by using HCFC and/or
HFC as foaming agents exhibits relatively good physical properties. When
polyol(A) is used in combination with polyol(C), much better results can
be obtained on foam properties such as heat conductivity, compressive
strength and dimensional stability. However, a ratio (A)/(C) deviating
from the range of from 0.25 to 4.0 leads to inferior properties of the
polyurethane foam obtained by using HCFC and/or HFC as foaming agents.
Consequently, a preferred (A)/(C) ratio is in the range of from 0.25 to
4.0.
Polyol (G) used for preparing a rigid polyurethane foam and composite
thereof according to the present invention comprises as one component,
afore-mentioned phenol resin based polyol (A) and as another component,
polymethylenepolyphenylpolyamine based polyol (F).
Polyol (F) comprises polyol(f) having hydroxyl value of 150.about.700
mgKOH/g, adding alkylene oxide of 1.0.about.9.0 mol per 1 equivalent of
amino group in a polymethylenepolyphenypolyamine and aforementioned polyol
(b) or polyol (f) and polyol (c).
It is preferable that the mixing ratio in weight of polyol (f) and polyol
(b), i.e. (f)/(b) is 0.25.about.4.0, and that of polyol (f) and polyol
(c), i.e. (f)/(c) is 0.1.about.4.0.
Polyol (G) is a mixture of polyol (A) and polyol (F) in which the mixing
ratio in weight, i.e. (A)/(F) is 0.25.about.4.0, and hydroxyl value of the
mixture is 180.about.700 mgKOH/g.
The relationship among mixing ratio of (f)/(b), (f)/(c) and (A)/(F),
hydroxyl value of mixed polyols, physical properties of polyurethane,
operation efficiency and effect of combination use of polyol (A) and
polyol (F) is the same as that Of polyol (D) and polyol (E).
A suitable polymethylenepolyphenylpolyamine for use in the present
invention includes, for example, polymethylenepolyphenylpolyamine, which
is used commonly as a raw material of
polymethylenepolyphenylpolyisocyanate, 4,4'-diaminodiphenylmethane which
is separated from the polymethylenepolyphenylpolyamine, its isomer or a
mixture of these isomers.
The catalyst which can be used in the present invention for the addition
reaction of alkylene oxide to a single compound or mixture of phenol
resin, alkanolamine series compound, aliphatic polyhydroxy compound,
aminophenol series compound, polyphenylpoly xylylenepolyamine and
polymethylenepolyphenylpolyamine as a starting materials, is an amine
catalyst and an alkali metal hy | | |
