Technical Field
5 The present invention relates to (poly)ol block copolymers with > 70% primary hydroxyl
end groups comprising polycarbonate (A) and polyether carbonate blocks (B) in a
general BA(B)n structure, the process of producing such (poly)ol block copolymers from
a two step process generally carried out in two separate reactions, and products and
compositions incorporating such copolymers or their residues.
1 o Background
It is generally desirable for polyols that are used in polyurethane applications to have
primary hydroxyl end groups, due to the increased reactivity of these primary hydroxyl
groups with isocyanates (compared to less reactive secondary hydroxyls). Polyether
polyols are generally produced by either basic catalysis using sodium or potassium
15 hydroxide or by using so-called double metal cyanide (DMC) catalysts. Advantageously,
hydroxide catalysts are able to react with both ethylene oxide (EO) and propylene oxide
(PO) and can be used to end-cap PO based polyols with EO, resulting in polyols with all
primary hydroxyl end groups. Unfortunately, the hydroxide catalyst process includes a
lengthy purification including neutralisation, filtration and drying. Furthermore, alkaline
20 catalysts promote formation of unsaturated, non-hydroxyl end groups at higher molecular
weights, resulting in reduced functionality of the polyols and poor quality polyurethanes.
DMC catalysts produce polyols with very low amounts of unsaturated end groups even
at higher molecular weights and do not require any purification. However, DMC catalysts
are less reactive with EO than PO and do not effectively end-cap PO polyols with EO to
25 generate polyols with 100% primary hydroxyl end groups. Instead, the EO mostly reacts
into long polyethylene oxide chains leaving the PO polyol with a high molecular weight
component (which results in poor quality polyurethane products) and mostly less reactive
secondary hydroxyl end groups.
In order to produce polyols above -2000 molecular weight with low unsaturation, the
30 desired functionality and a high proportion of primary hydroxyl end groups it has been
necessary to produce a primarily PO based polyol using a DMC catalyst and then endcap
this with EO using hydroxide catalysts entailing a complex purification process. This
is both inefficient and expensive.
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Various methods, such as those disclosed in W02001044347 and W02004111107,
have been suggested to increase the proportion of primary hydroxyl end groups using
DMC catalysts. This generally involves starting with a predominantly PO feed and
increasing the ratio of EO in the feed as the reaction continues. Primary hydroxyl
5 contents of around 40-60% have been demonstrated by this method.
It also known that DMC catalysts can be used with epoxides and carbon dioxide to
produce so called 'polyether carbonate' polyols. Various methods include those
disclosed in W02008058913, W02008013731 and US6762278. Typically, these
processes require high pressures to enable even moderate C02 content within the
1 o polyols. These polyols have primarily been demonstrated with PO and hence have a very
low (<5%) primary hydroxyl content.
US10174151 discloses a method for making a polyether carbonate polyol using a DMC
where a polyol is first made with C02 and PO and then end-capped with increasing ratios
of EO/PO with a DMC in a solvent (cyclic propylene or ethylene carbonate). The
15 maximum primary hydroxyl content demonstrated by this method is 65%.
W02015059068 and US2015/0259475 from Covestro disclose the use of a DMC
catalyst for the production of polyether carbonate polyols from C02 and alkylene oxide
in the presence of a starter compound. Many H-functional starter compounds are listed
including polyether carbonate polyols, polycarbonate polyols and polycarbonates.
20 Polyethercarbonate polyols produced by a DMC alone generally have a structure which
is rich in ether linkages in the centre of the polymer chain and richer in carbonate groups
towards the hydroxyl terminal groups. This is not advantageous as the ether groups are
substantially more stable to heat and basic conditions than the carbonate linkages.
W02010062703 discloses production of block copolymers having a polycarbonate block
25 and a hydrophilic block (e.g. a polyether). Various structures are described generally with
a polyether block having polycarbonate blocks at either end. Some examples include a
polycarbonate block with polyether end blocks. A two pot production is described, using
in some examples a carbonate catalyst in the first reaction to produce an alternating
polycarbonate block, followed by quenching of the reaction, isolation of the polyol from
30 solvents and unreacted monomers and then a second batch reaction with a DMC catalyst
(in the absence of C02) to incorporate the hydrophilic oligomer, such as poly(alkylene
oxide). Some examples use ethylene oxide as the ether block, but no determination is
made of the proportion of primary and secondary hydroxyl end groups. The polymers
have use in enhanced oil recovery.
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It has been advantageously found that by using polycarbonate starters and a DMC
catalyst with epoxides and C02, (poly)ols can be produced with very high primary
hydroxyl content (greater than 70%, even greater than 80% primary hydroxyl end
groups). The use of the carbonate starters (either directly from a first reaction mixture or
5 using purified starters materials) is advantageous in promoting even end-capping with a
DMC catalyst in the presence of C02.
The (poly)ols can be made with varying C02 contents, low degrees of unsaturation, high
primary hydroxyl content and don't require the purification processes used for hydroxide
catalysts. The process is therefore advantageous over metal hydroxide catalysts, DMC
1 o catalysts (alone) and in enabling the use of C02 to make (poly)ols with reduced carbon
footprint.
Advantageously, the low molecular weight polycarbonate (poly)ol starters do not have to
be isolated but can be made in one reactor and transferred directly into the second
without removing any catalyst, unreacted monomer or solvents.
15 Summary of the Invention
According to the first aspect of the invention, there is provided a (poly)ol block copolymer
of general structure B-A-(B)n wherein block A is a polycarbonate or polyester block,
wherein n=t-1 and t =the number of reactive end residues on block A, wherein block B
is a polyethercarbonate block and wherein > 70% of the copolymer chain ends are
20 terminated by primary hydroxyl groups.
Preferably, > 75%, more preferably, >80% of the copolymer chain ends are terminated
by primary hydroxyl groups.
Preferably, the polymer chains are evenly end-capped. By evenly end-capped is meant
that on average more than 75% of the polymer chains are end capped with an EO
25 residue, more typically, more than 85% of the polymer chains are end capped with an
EO residue, most typically, at least 90% of the polymer chains are end capped with an
EO residue.
The A block has typically greater than 70% carbonate linkages and the B block has
typically less than 50% carbonate linkages.
30 The polycarbonate of block A may also be made by any suitable method in addition to
the process as defined in the aspects herein from alkylene oxides and C02. For
example, the polycarbonate diols may be prepared by reaction of phosgene and a
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dihydrocarbyl carbonate such as dimethyl carbonate, diethyl carbonate or diphenyl
carbonate. Examples of polycarbonates are to be found e.g. in EP-A 1359177.
Typically, block A is a polyalkylenecarbonate block, more typically derived from alkylene
oxides and C02, most typically, alkylene oxide and C02 provide at least 90% of the
5 residues in the block, especially, at least 95% of the residues in the block, more
especially, at least 99% of the residues in the block, most especially, about 100% of the
residues in the block are residues of alkylene oxide and C02. Most typically, block A
includes ethylene oxide and/or propylene oxide residues and optionally other alkylene
oxide residues such as butylene oxide, glycidyl ethers, glycidyl esters and glycidyl
1 o carbonates. Typically, at least 50% of the alkylene oxide residues of block A are ethylene
oxide or propylene oxide residues, more typically, at least 70% of the alkylene oxide
residues of block A are ethylene oxide or propylene oxide residues, most typically, at
least 90% of the alkylene oxide residues of block A are ethylene oxide or propylene oxide
residues, especially, ethylene oxide at these levels.
15 Typically, the carbonate of block A is derived from C02 i.e. the carbonates incorporate
C02 residues. Typically, block A has between 70-100% carbonate linkages, more
typically, 80-100%, most typically, 90-100%. The polycarbonate block, A, of the (poly)ol
block copolymer may have at least 76% carbonate linkages, preferably at least 80%
carbonate linkages, more preferably at least 85% carbonate linkages. Block A may have
20 less than 98% carbonate linkages, preferably less than 97% carbonate linkages, more
preferably less than 95% carbonate linkages. Optionally, block A has between 75% and
99% carbonate linkages, preferably between 77% and 95% carbonate linkages, more
preferably between 80% and 90% carbonate linkages.
Surprisingly, block A of the present invention has been found to facilitate the
25 incorporation of more primary hydroxyl terminal ends in the B block. The block A
connected to the respective B block is therefore surprisingly adapted to react with
alkylene oxide so that the (poly)ol block copolymer has > 70% primary hydroxyl ends,
typically, > 75%, more preferably, >80% primary hydroxyl ends
Typically, block B includes ethylene oxide and optionally other alkylene oxide residues.
30 Typically, alkylene oxide residues provide at least 90% of the non-carbonate functional
group residues in the block, especially, at least 95% of the non-carbonate functional
group residues in the block, more especially, at least 99% of the non-carbonate
functional group residues in the block, most especially, about 100% of the noncarbonate
functional group residues in the block are residues of alkylene oxide. Typically,
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ethylene oxide residues form 5-100% of the alkylene oxide residues in block B, more
typically, 10-100%, most typically 10-50% of the alkylene oxide residues. Typically, block
B is a mixture of at least ethylene and propylene oxide residues. Typically, at least 50%
of the alkylene oxide residues of block B are ethylene oxide or propylene oxide residues,
5 more typically, at least 70% of the alkylene oxide residues of block B are ethylene oxide
or propylene oxide residues, most typically, at least 90% of the alkylene oxide residues
of block Bare ethylene oxide or propylene oxide residues, especially, ethylene oxide at
these levels. Generally, to form a primary hydroxyl end, at least the terminal alkylene
oxide residue is an ethylene oxide residue. Typically, at least 70% of the terminal
1 o alkylene oxide residues are ethylene oxide residues, more typically, at least 75%, most
typically, at least 80% of the terminal alkylene oxide residues are ethylene oxide
residues. It is also possible for a small proportion of other alkylene oxides to form a
primary hydroxyl end but such primary hydroxyl arrangements are unusual due to the
preference for ring-opening at the unhindered methylene carbon.
15
Generally, where more than one alkylene oxide is used >50% of the ethylene oxide
residues in block B are incorporated into the copolymer chain nearer to the copolymer
terminal end than the A block terminal end, more typically, > 60% of the ethylene oxide
residues, most typically, at least 70% are so incorporated.
20 Optionally, block B incorporates C02 residues in the carbonate groups. Typically, the
polyethercarbonate blocks, B, of the (poly)ol block copolymer may have less than 40%
carbonate linkages, preferably less than 35% carbonate linkages, more preferably less
than 30% carbonate linkages. Block B may have at least 5% carbonate linkages,
preferably at least 10% carbonate linkages, more preferably at least 15% carbonate
25 linkages. Optionally, block B may have between 1% and 50% carbonate linkages,
preferably between 5% and 45% carbonate linkages, more preferably between 10% and
40% carbonate linkages.
The polyethercarbonate blocks, B, of the (poly)ol block copolymer may have at least 60%
ether linkages, preferably at least 65% ether linkages, more preferably at least 70% ether
30 linkages. The polyethercarbonate blocks, B, of the (poly)ol block copolymer may have
less than 95% ether linkages, preferably less than 90% ether linkages, more preferably
less than 85% ether linkages. Optionally, block B may have between 50% and 99% ether
linkages, preferably between 55% and 95% ether linkages, more preferably between
60% and 90% ether linkages.
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The polycarbonate block, A, of the (poly)ol block copolymer may also comprise ether
linkages. Block A may have less than 24% ether linkages, preferably less than 20% ether
linkages, more preferably less than 15% ether linkages such as less than 10%, for
example less than 5% ether linkages. Block A may have at least 1% ether linkages, such
5 as at least 2% ether linkages or even at least 5% ether linkages. Optionally, block A may
have between 0% and 25% ether linkages, preferably between 1% and 20% ether
linkages, more preferably between 1% and 15% ether linkages.
Optionally, block A of the present invention may be a generally alternating polycarbonate
(poly)ol residue.
10 If the alkylene oxide is asymmetric, then the polycarbonate may have between 0-100%
head to tail linkages, preferably between 40-100% head to tail linkages, more preferably
between 50-100%. The polycarbonate may have a statistical distribution of head to head,
tail to tail and head to tail linkages in the order 1 :2:1, indicating a non-stereoselective
ring opening of the alkylene oxide, or it may preferentially make head to tail linkages in
15 the order of more than 50%, optionally more than 60%, more than 70%, more than 80%,
or more than 90%.
Typically in the (poly)ol block copolymer of the invention ethylene oxide residues form 0-
100% of the alkylene oxide residues in the (poly)ol block copolymer, typically 5-70%,
more typically, 10-60% of the alkylene oxide residues in the (poly)ol block copolymer,
20 most typically, 10-40% of the alkylene oxide residues in the (poly)ol block copolymer
and/or, at least 5%, 10%, 15%, 20%, 25% or 30% of the alkylene oxide residues in the
(poly)ol block copolymer are ethylene oxide residues .
The A block of the present invention with a starter may be defined as -A'-Z'-Z-(Z'-A')nAccordingly,
the polyblock structure of the copolymer may be defined as :
25 B-A'-Z'-Z-(Z'-A'-B)n
wherein n= t-1 and wherein t= the number of terminal OH group residues on the block A;
and wherein each A' is independently a polycarbonate chain having at least 70%
carbonate linkages, and wherein each B is independently a polyethercarbonate chain
having 50-99% ether linkages and at least 1% carbonate linkages and wherein Z'-Z-(Z')n
30 is a starter residue. The (poly)ol has at least 70% primary hydroxyl end groups.
For the avoidance of doubt, when t=1 then n=O and the polyblock structure is:-
8
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8-A'-Z'-Z, the"% of the copolymer chain ends terminated by primary hydroxyl groups"
as claimed refers to the percentage of OH functional chain ends that are so terminated.
The polycarbonate block comprises -A'- which may have the following structure:
0
(I)
wherein the ratio of p:q is at least 7:3; and
10 R61 and R62 depend on the nature of the alkylene oxide used to prepare block A.
The polyethercarbonate block B may have the following structure:
H
0
(II)
wherein the ratio of w:v is greater or equal to 1:1; and
R63 and R64 depend on the nature of the alkylene oxide used to prepare blocks B.
15 Each R61 , R62, R63, or R64 may be independently selected from H, halogen, hydroxyl, or
optionally substituted alkyl (such as methyl, ethyl, propyl, butyl, -CH2CI, -CH2-0R2o, -
CH2-0C(O)R12, or -CH2-0C(O)OR1s), alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl,
heteroaryl, heteroalkyl or heteroalkenyl, preferably selected from H or optionally
substituted alkyl.
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R61 and R62 or R63 and R64 may together form a saturated, partially unsaturated or
unsaturated ring containing carbon and hydrogen atoms, and optionally one or more
heteroatoms.
As set out above, the nature of R61 , R62, R63 and R64 will depend on the alkylene oxide
5 used in the reaction. For example, if the alkylene oxide is cyclohexene oxide (CHO), then
R61 and R62 (or R63 and R64) will together form a six membered alkyl ring (e.g. a cyclohexyl
ring). If the alkylene oxide is ethylene oxide, then R61 and R62 (or R63 and R64) will be H.
If the alkylene oxide is propylene oxide, then R61 (or R63) will be H and R62 (or R64) will
be methyl (or R61 (or R63) will be methyl and R62 (or R64) will be H, depending on how the
1 o alkylene oxide is added into the polymer backbone. If the alkylene oxide is butylene
oxide, then R61 (or R63) will be H and R62 (or R64) will be ethyl (or vice versa). If the
alkylene oxide is styrene oxide, then R61 (or R63) may be hydrogen, and R62 (or R64) may
be phenyl (or vice versa). If the alkylene oxide is a glycidyl ether, then R61 (or R63) will be
an ether group (-CH2-0R2o) and R62 (or R64) will be H (or vice versa). If the alkylene oxide
15 is a glycidyl ester, then R61 (or R63) will be an ester group (-CH2-0C(O)R12) and R62 (or
R64) will be H (or vice versa). If the alkylene oxide is a glycidyl carbonate, then R61 (or
R63) will be a carbonate group (CH2- OC(O)OR1s) and R62 (or R64) will be H (or vice
versa).
It will also be appreciated that if a mixture of alkylene oxides are used, then each
20 occurrence of R61 and/or R62 (or R63 and/or R64) may not be the same, for example if a
mixture of ethylene oxide and propylene oxide are used, R61 (or R63) may be
independently hydrogen or methyl, and R62 (or R64) may be independently hydrogen or
methyl.
Thus, R61 and R62 (or R63 and R64 ) may be independently selected from hydrogen, alkyl
25 or aryl, or R61 and R62 (or R63 and R64 ) may together form a cyclohexyl ring, preferably
R61 and R62 (or R63 and R64 ) may be independently selected from hydrogen, methyl,
ethyl or phenyl, or R61 and R62 (or R63 and R64 ) may together form a cyclohexyl ring.
The identity of Z and Z' will depend on the nature of the starter compound.
30 The starter compound may be of the formula (Ill):
Z can be any group which can have 1 or more, typically, 2 or more -Rz groups attached
to it. Thus, Z may be selected from optionally substituted alkylene, alkenylene,
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alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, cycloalkylene,
cycloalkenylene, hererocycloalkylene, heterocycloalkenylene, arylene, heteroarylene, or
Z may be a combination of any of these groups, for example Z may be an alkylarylene,
heteroalkylarylene, heteroalkylheteroarylene or alkylheteroarylene group. Optionally Z is
5 alkylene, heteroalkylene, arylene, or heteroarylene.
It will be appreciated that a is an integer which is at least 1, typically, at least 2, optionally
a is in the range of between 1 or 2 and 8, optionally a is in the range of between 2 and
6.
Each Rz may be -OH, -NHR', -SH, -C(O)OH, -P(O)(OR')(OH), -PR'(O)(OH)2 or -
10 PR'(O)OH, optionally Rz is selected from -OH, -NHR' or -C(O)OH, optionally each Rz is
-OH, -C(O)OH or a combination thereof (e.g. each W is -OH).
R' may be H, or optionally substituted alkyl, heteroalkyl, aryl, heteroaryl, cycloalkyl or
heterocycloalkyl, optionally R' is H or optionally substituted alkyl.
Z' corresponds to Rz, except that a bond replaces the labile hydrogen atom. Therefore,
15 the identity of each Z' depends on the definition of Rz in the starter compound. Thus, it
will be appreciated that each Z' may be -0-, -NR'-, -S-, -C(O)O-, -P(O)(OR')O-, -
PR'(0)(0-)2 or -PR'(O)O- (wherein R' may be H, or optionally substituted alkyl,
heteroalkyl, aryl, heteroaryl, cycloalkyl or heterocycloalkyl, preferably R' isH or optionally
substituted alkyl), preferably Z' may be -C(O)O-, -NR'- or -0-, more preferably each Z'
20 may be -0-, -C(O)O- or a combination thereof, more preferably each Z' may be -0-.
Preferably, the (poly)ol block copolymer has a molecular weight (Mn) in the range of from
about 300 to 20,000 Da, more preferably in the range of from about 400 to 8000 Da,
most preferably from about 500-6000 Da.
The polycarbonate block, A, of the (poly)ol block copolymer preferably has a molecular
25 weight (Mn) in the range of from about 200 to 4000 Da, more preferably in the range of
from about 200 to 2000 Da, most preferably from about 200 to 1000 Da, especially from
about 400 to 800 Da.
The polyethercarbonate blocks, B, of the (poly)ol block copolymer preferably have a
molecular weight (Mn) in the range offrom about 100 to 20,000 Da, more preferably of
30 from about 200 to 10,000 Da, most preferably from about 200 to 5000 Da.
Alternatively, the polyethercarbonate blocks B and hence also the (poly)ol block
copolymer may have a high molecular weight. The polyethercarbonate blocks B may
have a molecular weight (Mn) of at least about 25,000 Daltons, such as at least about
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40,000 Daltons, e.g. at least about 50,000 Daltons, or at least about 100,000 Daltons.
High molecular weight (poly)ol block copolymers of the present invention may have
molecular weights above about 100,000 Daltons.
The Mn and hence the POl of the polymers may be measured using Gel Permeation
5 Chromatography (GPC). For example, the GPC may be measured using an Agilent 1260
Infinity GPC machine with two Agilent Plgel 1-1-m mixed-D columns in series. The
samples may be measured at room temperature (293K) in THF with a flow rate of
1 mUm in against narrow polystyrene standards (e.g. polystyrene low EasiVials supplied
by Agilent Technologies with a range of Mn from 405 to 49,450 g/mol). Optionally, the
10 samples may be measured against poly(ethylene glycol) standards, such as
polyethylene glycol easivials supplied by Agilent Technologies.
Typically, the mol/mol ratio of block A to block B is in the range 25:1 to 1 :250. Typically
the weight ratio of block A to block B is in the range 50:1 to 1:100.
According to the second aspect of the invention, there is also provided a composition
15 comprising the (poly)ol block copolymer according to the first aspect of the present
invention. The composition may also comprise of one or more additives from those
known in the art. The additives may include, but are not limited to, catalysts, blowing
agents, stabilizers, plasticisers, fillers, flame retardants, defoamers, and antioxidants.
Fillers may be selected from mineral fillers or polymer fillers, for example, styrene-
20 acrylonitrile (SAN) dispersion fillers.
The blowing agents may be selected from chemical blowing agents or physical blowing
agents. Chemical blowing agents typically react with (poly)isocyanates and liberate
volatile compounds such as C02. Physical blowing agents typically vaporize during the
formation of the foam due to their low boiling points. Suitable blowing agents will be
25 known to those skilled in the art, and the amounts of blowing agent added can be a
matter of routine experimentation. One or more physical blowing agents may be used or
one or more chemical blowing agents may be used, in addition one or more physical
blowing agents may be used in conjunction with one or more chemical blowing agents.
Chemical blowing agents include water and formic acid. Both react with a portion of the
30 (poly)isocyanate producing carbon dioxide which can function as the blowing agent.
Alternatively, carbon dioxide may be used directly as a blowing agent, this has the
advantage of avoiding side reactions and lowering urea crosslink formation, if desired
water may be used in conjunction with other blowing agents or on its own.
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Typically, physical blowing agents for use in the current invention may be selected from
acetone, carbon dioxide, optionally substituted hydrocarbons, and chloro/fluorocarbons.
Chloro/fluorocarbons include hydrochlorofluorocarbons, chlorofluorocarbons,
fluorocarbons and chlorocarbons. Fluorocarbon blowing agents are typically selected
5 from the group consisting of: difluoromethane, trifluoromethane, fluoroethane, 1,1-
difluoroethane, 1,1, 1-trifluoroethane, tetrafluoroethanes difluorochloroethane,
dichloromono-fluoromethane, 1, 1-dichloro-1-fluoroethane, 1, 1-difluoro-1 ,2,2-
trichloroethane, chloropentafluoroethane, tetrafluoropropanes, pentafluoropropanes,
hexafluoropropanes, heptafluoropropanes, pentafluorobutanes.
1 o Olefin blowing agents may be incorporated, namely trans-1-chloro-3.3.3-trifluoropropene
(LBA), trans-1 ,3,3,3-tetrafluoro-prop-1-ene (HF0-1234ze), 2,3,3,3-tetrafluoro-propene
(HF0-1234yf), cis-1, 1,1 ,4,4,4-hexafluoro-2-butene (HF0-1336mzz).
Typically, non-halogenated hydrocarbons for use as physical blowing agents may be
selected from butane, isobutane, 2,3-dimethylbutane, n-and i-pentane isomers, hexane
15 isomers, heptane isomers and cycloalkanes including cyclopentane, cyclohexane and
cycloheptane. More typically, non-halogenated hydrocarbons for use as physical blowing
agents may be selected from cyclopentane, iso-pentane and n-pentane.
Typically, where one or more blowing agents are present, they are used in an amount of
from about 0 to about 10 parts, more typically 2-6 parts of the total formulation. Where
20 water is used in conjunction with another blowing agent the ratio of the two blowing
agents can vary widely, e.g. from 1 to 99 parts by weight of water in total blowing agent,
preferably, 25 to 99+ parts by weight water
Preferably, the blowing agent is selected from cyclopentane, iso-pentane, n-pentane.
More preferably the blowing agent is n-pentane.
25 Typical plasticisers may be selected from succinate esters, adipate esters, phthalate
esters, diisooctylphthalate (DIOP), benzoate esters and N,N-bis(2-hydroxyethyl)-2-
aminoethane sulfonic acid (BES).
Typical flame retardants will be known to those skilled in the art, and may be selected
from phosphonamidates, 9,1 0-dihydro-9-oxa-phosphaphenanthrene-1 0-oxide (DOPO),
30 chlorinated phosphate esters, Tris(2-chloroisopropyl)phosphate (TCPP), Triethyl
phosphate (TEP), tris(chloroethyl) phosphate, tris(2,3-dibromopropyl) phosphate, 2,2-
bis(chloromethyl)-1 ,3-propylene bis(di(2-chloroethyl) phosphate), tris(1 ,3-
dichloropropyl) phosphate, tetrakis(2-chloroethyl) ethylene diphosphate, tricresyl
phosphate, cresyl diphenyl phosphate, diammonium phosphate, melamine, melamine
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pyrophosphate, urea phosphate, alumina, boric acid, various halogenated compounds,
antimony oxide, chlorendic acid derivatives, phosphorus containing polyols, bromine
containing polyols, nitrogen containing polyols, and chlorinated paraffins. Flame
retardants may be present in amounts from 0-60 parts of the total mixture.
5 The compositions of the invention can also further comprise a (poly)isocyanate.
Typically, the (poly)isocyanate comprises two or more isocyanate groups per molecule.
Preferably, the (poly)isocyanates are diisocyanates. However, the (poly)isocyanates
may be higher (poly)isocyanates such as triisocyanates, tetraisocyanates, isocyanate
polymers or oligomers, and the like. The (poly)isocyanates may be aliphatic
1 o (poly)isocyanates or derivatives or oligomers of aliphatic (poly)isocyanates or may be
aromatic (poly)isocyanates or derivatives or oligomers of aromatic (poly)isocyanates.
Typically, the (poly)isocyanate component has a functionality of 2 or more. In some
embodiments, the (poly)isocyanate component comprises a mixture of diisocyanates
and higher isocyanates formulated to achieve a particular functionality number for a
15 given application.
In some embodiments, the (poly)isocyanate employed has a functionality greater than 2.
In some embodiments, such (poly)isocyanates have a functionality between 2 to 5, more
typically, 2-4, most typically, 2-3.
Suitable (poly)isocyanates which may be used include aromatic, aliphatic and
20 cycloaliphatic polyisocyanates and combinations thereof. Such polyisocyanates may be
selected from the group consisting of: 1 ,3-Bis(isocyanatomethyl)benzene, 1,3-
Bis(isocyanatomethyl)cyclohexane (H6-XDI), 1 ,4-cyclohexyl diisocyanate, 1,2-
cyclohexyl diisocyanate, 1 ,4-phenylene diisocyanate, 1 ,3-phenylene diisocyanate, 1,4-
tetramethylene diisocyanate, 1 ,6-hexamethylene diisocyanate, 1,6-
25 hexamethylaminediisocyanate (HOI), isophorone diisocyanate (IPDI), 2,4-toluene
diisocyanate (TDI), 2,4,4-trimethylhexamethylene diisocyanate (TMDI), 2,6-toluene
diisocyanate (TDI), 4,4' methylene-bis(cyclohexyl isocyanate) (H12MDI), naphthalene-
1 ,5-diisocyanate, diphenylmethane-2,4'-diisocyanate (MDI), diphenylmethane-4,4'diisocyanate
(M Dl), triphenylmethane-4,4',4"triisocyanate, isocyanatomethyl-1 ,8-octane
30 diisocyanate (TIN), m-tetramethylxylylene diisocyanate (TMXDI), p-tetramethylxylylene
diisocyanate (TMXDI), Tris(p-isocyanatomethyl)thiosulfate, trimethylhexane
diisocyanate, lysine diisocyanate, m-xylylene diisocyanate (XDI), p-xylylene
diisocyanate (XDI), 1 ,3,5-hexamethyl mesitylene triisocyanate, 1-methoxyphenyl-2,4-
diisocyanate, toluene-2,4,6-triisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethyl14
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4,4' -diphenyl diisocyanate, 4,4' -dimethyldiphenyl methane-2,2' ,5,5' -tetraisocyanate and
mixtures of any two or more of these. In addition, the (poly)isocyanates may be selected
from polymeric version of any of these isocyanates, these may have high or low
functionality. Preferred polymeric isocyanates may be selected from MDI, TDI, and
5 polymeric MDI.
According to the third aspect of the invention, there is also provided a polyurethane
produced from the reaction of a polyol block copolymer of the first aspect of the present
invention and a (poly)isocyanate. A polyurethane can also be produced from the reaction
of a composition according to the second aspect of the present invention and a
1 o (poly) isocyanate. The polyurethane may be in the form of a soft foam, a flexible foam,
an integral skin foam, a high resilience foam, a viscoelastic or memory foam, a semirigid
foam, a rigid foam (such as a polyurethane (PUR) foam, a polyisocyanurate (PIR)
foam and/or a spray foam), an elastomer (such as a cast elastomer, a thermoplastic
elastomer (TPU) or a microcellular elastomer), an adhesive (such as a hot melt adhesive,
15 pressure sensitive or a reactive adhesive), a sealant or a coating (such as a waterborne
or solvent dispersion (PUD), a two-component coating, a one component coating, a
solvent free coating). The polyurethane may be formed via a process that involves
extruding, moulding, injection moulding, spraying, foaming, casting and/or curing. The
polyurethane may be formed via a 'one pot' or 'pre-polymer' process.
20 According to the fourth aspect of the present invention, there is also provided a
polyurethane comprising a block copolymer residue according to the first aspect of the
present invention.
The block copolymer residue of the polyurethane of the fourth aspect may include any
one or more features as defined in relation to the first aspect of the invention.
25 According to the fifth aspect of the invention, there is also provided an isocyanate
terminated polyurethane prepolymer comprising the reaction product of the polyol block
copolymer according to the first aspect of the present invention or the composition of the
second aspect of the present invention and an excess of (poly)isocyanate such as at
least >1 mole of isocyanate groups per mole OH groups. The isocyanate terminated
30 prepolymer may be formed into a polyurethane via reaction with one or more chain
extenders (such as water, diols, triols, diamines etc) and/or further polyisocyanates
and/or other additives.
15
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The isocyanate terminated polyurethane prepolymer of the fifth aspect may include any
one or more features as defined in the first aspect of the invention unless such a feature
is mutually exclusive.
Catalysts that may be added to the polyol block copolymer of the first aspect of the
5 present invention and/or compositions of the second aspect of the present invention may
be catalysts for the reaction of (poly)isocyanates and a polyol. These catalysts include
suitable urethane catalysts such as tertiary amine compounds and/or organometallic
compounds.
Optionally, a trimerisation catalyst may be used. An excess of (poly)isocyanate, or more
1 o preferably an excess of polymeric isocyanate relative to polyol may be present so that
polyisocyanurate ring formation is possible when in the presence of a trimerisation
catalyst. Any of these catalysts may be used in conjunction with one or more other
trimerisation catalysts.
According to the sixth aspect of the invention, there is provided a lubricant composition
15 comprising a (poly)ol block copolymer according to the first aspect of the present
invention.
According to the seventh aspect of the invention, there is provided a surfactant
composition comprising a (poly)ol block copolymer according to the first aspect of the
present invention.
20 According to the eighth aspect of the invention, there is also provided a process for
producing a (poly)ol block copolymer comprising the reaction of a DMC catalyst with a
polycarbonate or polyester (poly)ol (co)polymer according to block A of the first aspect,
C02 , ethylene oxide and optionally one or more other alkylene oxides to produce a
(poly)ol block copolymer according to the first aspect or a process for producing a (poly)ol
25 block copolymer comprising a first reaction in a first reactor and a second reaction in a
second reactor; wherein the first reaction is the reaction of a carbonate catalyst with C02
and alkylene oxide, in the presence of a starter and optionally a solvent to produce a
polycarbonate (poly)ol copolymer according to block A of the first aspect and the second
reaction is the reaction of a DMC catalyst with the polycarbonate (poly)ol copolymer of
30 the first reaction, C02 , ethylene oxide and optionally one or more other alkylene oxides
to produce a (poly)ol block copolymer according to the first aspect of the invention.
16
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The process may further comprise a third or further reaction comprising the reaction of
the block copolymer of the first aspect of the invention with a monomer or further
polymerto produce a higher polymer.
The monomer or further polymer may be a (poly) isocyanate and the product of the third
5 or further reaction may be a polyurethane.
According to the ninth aspect of the present invention, there is also provided a process
for producing a (poly)ol block copolymer in a multiple reactor system; the system
comprising a first and second reactor wherein a first reaction takes place in the first
reactor and a second reaction takes place in the second reactor; wherein the first
1 o reaction is the reaction of a carbonate catalyst with C02 and alkylene oxide, in the
presence of a starter and optionally a solvent to produce a polycarbonate (poly)ol
copolymer according to block A of the first aspect and the second reaction is the reaction
of a DMC catalyst with the polycarbonate (poly)ol compound of the first reaction, C02,
ethylene oxide and optionally one or more other alkylene oxides to produce a (poly)ol
15 block copolymer according to the first aspect of the invention.
It is also possible to add the components in separate reactions and reactors.
Advantageously, by this means it is possible to increase activity of the catalysts and this
can lead to a more efficient process, compared with a process in which all of the materials
are provided at the start of one reaction. Large amounts of some of the components
20 present throughout the reaction may reduce efficiency of the catalysts. Reacting this
material in separate reactors can be used to prevent this reduced efficiency of the
catalysts and/or can be used to optimise catalyst activity. The reaction conditions of each
reactor can be tailored to optimise the reactions for each catalyst.
Additionally, not loading the total amount of each component at the start of the reaction
25 and having the catalyst for a first reaction in a separate reactor to the catalyst for the
reaction or second reaction, can provide more even catalysis, and more uniform polymer
products. In addition, polymers having a narrower molecular weight distribution, desired
ratio and distribution along the chain of ether to carbonate linkages, and/or improved
(poly)ol stability are possible.
30 The DMC catalyst can be pre-activated. Such pre-activation may be achieved by mixing
one or both catalysts with alkylene oxide (and optionally other components). Preactivation
of the DMC catalyst is useful as it enables safe control of the reaction
(preventing uncontrolled increase of unreacted monomer content) and removes
unpredictable activation periods.
17
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It will be appreciated that the present invention relates to a reaction in which carbonate
and ether linkages are added to a growing polymer chain. Having separate reactions
allows the first reaction to proceed before a second stage in the reaction. Mixing alkylene
oxide, carbonate catalyst, starter compound and carbon dioxide, may permit growth of a
5 polymer having a high number of carbonate linkages. Thereafter, adding the products
to the DMC catalyst permits the reaction to proceed by adding a higher incidence of ether
linkages to the growing polymer chain. Ether linkages are more thermally stable than
carbonate linkages and less prone to degradation by bases such as the amine catalysts
used in PU formation. Therefore, applications additionally get the benefit of high
1 o carbonate linkages (such as increased strength, chemical resistance, both oil and
hydrolysis resistance etc) that are introduced from the A block whilst retaining the stability
of the (poly)ol through the predominant ether linkages from the B blocks at the ends of
the polymer chains. This benefit is in addition to the high incidence of primary hydroxyl
end groups on the (poly)ol provided by the ethylene oxide.
15 Additional benefits of the invention when carried out in a two-reactor system is to control
the polymerisation reaction, to increase C02 content of the polyethercarbonate (poly)ols
at low pressures (enabling more cost effective processes and plant design) and to make
a product that has high C02 content but good stability and application performance. The
processes herein may allow the product prepared by such processes to be tailored to
20 the necessary requirements.
The (poly)ol block copolymers of the present invention may be prepared from a suitable
alkylene oxide and carbon dioxide in the presence of a starter compound and a
carbonate catalyst for a first reaction; and then ethylene oxide and optionally one or more
other alkylene oxides and carbon dioxide in the presence of a double metal cyanide
25 (OM C) catalyst in a second reaction.
The carbonate catalyst of the present invention may be a catalyst that produces a
polycarbonate (poly)ol with greater than 76% carbonate linkages, preferably greater than
80% carbonate linkages, more preferably greater than 85% carbonate linkages, most
preferably greater than 90% carbonate linkages and such linkage ranges may
30 accordingly be present in block A.
If one of the alkylene oxides used is asymmetric (e.g. propylene oxide), the
polycarbonate (poly)ols may comprise a high proportion of such alkylene oxides in head
to tail linkages, such as greater than 70%, greater than 80% or greater than 90% head
to tail linkages. Alternatively, the polycarbonate (poly)ols with such asymmetric alkylene
18
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oxides may have no stereoselectivity, providing (poly)ols with approximately 50% head
to tail linkages on such residues.
The carbonate catalyst may be heterogeneous or homogeneous.
The carbonate catalyst may be a mono-metallic, bimetallic or multi-metallic
5 homogeneous complex.
10
The carbonate catalyst may comprise phenol or phenolate ligands.
Typically, the carbonate catalyst may be a bimetallic complex comprising phenol or
phenolate ligands. The two metals may be the same or different.
The carbonate catalyst may be a catalyst of formula (IV):
(IV)
wherein:
M is a metal cation represented by M-(L)v;
x is an integer from 1 to 4, preferably x is 1 or 2;
®is a multidentate ligand or plurality of multidentate ligands;
15 Lis a coordinating ligand, for example, L may be a neutral ligand, or an anionic ligand,
preferably one that is capable of ring-opening an alkylene oxide;
v is an integer that independently satisfies the valency of each M, and/or the preferred
coordination geometry of each M or is such that the complex represented by formula (IV)
above has an overall neutral charge. For example, each v may independently be 0, 1, 2
20 or 3, e.g. v may be 1 or 2. When v > 1, each L may be different.

Claims
1. A (poly)ol block copolymer of general structure B-A-(B)n wherein block A is a
polycarbonate block or polyester block, wherein n=t-1 and t = the number of reactive end
residues on block A, wherein block B is a polyethercarbonate block and wherein > 70%
of the copolymer chain ends are terminated by primary 5 hydroxyl groups.
2. A (poly)ol block copolymer according to any preceding claim, wherein the mol/mol
ratio of block A to block B is in the range 25:1 to 1:250.
3. A (poly)ol block copolymer according to any preceding claim, wherein block A is
derived from alkylene oxides and CO2.
10 4. A (poly)ol block copolymer according to any preceding claim, wherein the
alkylene oxides and CO2 provide at least 90% of the residues in the block not including
any starter, especially, at least 95% of the residues in the block, more especially, at least
99% of the residues in the block, most especially, about 100% of the residues in the
block not including any starter are residues of alkylene oxide and CO2.
15 5. A (poly)ol block copolymer according to any preceding claim, wherein block A
has between 70-100% carbonate linkages, more typically, 80-100%, most typically, 90-
100% and/or wherein the polycarbonate block, A, of the (poly)ol block copolymer has at
least 76% carbonate linkages, preferably at least 80% carbonate linkages, more
preferably at least 85% carbonate linkages and/or wherein block A has less than 98%
20 carbonate linkages, preferably less than 97% carbonate linkages, more preferably less
than 95% carbonate linkages and/or optionally, block A has between 75% and 99%
carbonate linkages, preferably between 77% and 95% carbonate linkages, more
preferably between 80% and 90% carbonate linkages.
6. A (poly)ol block copolymer according to any preceding claim, wherein block B is
25 derived from alkylene oxides and CO2.
7. A (poly)ol block copolymer according to any preceding claim, wherein at least 5%
of the alkylene oxide residues of block B are ethylene or propylene oxide residues, more
typically, at least 10% of the alkylene oxide residues of block B are ethylene or propylene
oxide residues, most typically, at least 20% of the alkylene oxide residues of block B are
30 ethylene or propylene oxide residues, optionally, at least 50% of the alkylene oxide
residues of block B are ethylene or propylene oxide residues, most especially, at least
70 or 90% of the alkylene oxide residues of block B are ethylene or propylene oxide
residues.
50
8. A (poly)ol block copolymer according to any preceding claim, wherein at least
70% of the terminal alkylene oxide residues are ethylene oxide residues, more typically,
at least 75%, most typically, at least 80% of the terminal alkylene oxide residues are
ethylene oxide residues.
9. A (poly)ol block copolymer according to any preceding 5 claim, wherein the
polyethercarbonate block(s), B, of the (poly)ol block copolymer have less than 40%
carbonate linkages, preferably less than 35% carbonate linkages, more preferably less
than 30% carbonate linkages and/or block(s) B have at least 5% carbonate linkages,
preferably at least 10% carbonate linkages, more preferably at least 15% carbonate
10 linkages and/or blocks B have between 1% and 50% carbonate linkages, preferably
between 5% and 45% carbonate linkages, more preferably between 10% and 40%
carbonate linkages.
10. A (poly)ol block copolymer according to any preceding claim, wherein the
polyethercarbonate block(s), B, of the (poly)ol block copolymer have at least 60% ether
15 linkages, preferably at least 65% ether linkages, more preferably at least 70% ether
linkages and/or wherein the polyethercarbonate block(s), B, of the (poly)ol block
copolymer have less than 95% ether linkages, preferably less than 90% ether linkages,
more preferably less than 85% ether linkages and/or wherein, block(s) B have between
50% and 99% ether linkages, preferably between 55% and 95% ether linkages, more
20 preferably between 60% and 90% ether linkages.
11. A (poly)ol block copolymer according to any preceding claim, wherein the
polycarbonate block, A, of the (poly)ol block copolymer also comprise ether linkages.
12. A (poly)ol block copolymer according to any preceding claim, wherein the
(poly)block structure of the copolymer is defined as :
25 B-A’-Z’-Z-(Z’-A’-B)n
wherein n= t-1 and wherein t= the number of terminal OH group residues on the block A;
and wherein each A’ is independently a polycarbonate chain having at least 70%
carbonate linkages, and wherein each B is independently a polyethercarbonate chain
having 50-99% ether linkages and at least 1% carbonate linkages and wherein Z’-Z-(Z’)n
30 is a starter residue.
13. A (poly)ol block copolymer according to claim 12, wherein -A’- has the following
structure:
51
wherein the ratio of p:q is at least 7:3;
and block B has the following structure:
wherein the ratio of w:v is greater or equal to 1:1; and
Re1, Re2, Re3 and Re4 depend on the nature of the alkylene oxide used 5 to prepare blocks
A and B.
14. A (poly)ol block copolymer according to any of claims 12-13, wherein the starter
residue depends on the nature of the starter compound, and wherein the starter
compound has the formula (III):
10 Z ( RZ)a (III)
wherein Z can be any group which can have 1 or more, typically, 2 or more –RZ groups
attached to it and may be selected from optionally substituted alkylene, alkenylene,
alkynylene, heteroalkylene, heteroalkenylene, heteroalkynylene, cycloalkylene,
cycloalkenylene, hererocycloalkylene, heterocycloalkenylene, arylene, heteroarylene, or
15 Z may be a combination of any of these groups, for example Z may be an alkylarylene,
heteroalkylarylene, heteroalkylheteroarylene or alkylheteroarylene group;
a is an integer which is at least 1, typically, at least 2, optionally a is in the range of
between 1 or 2 and 8, optionally a is in the range of between 2 and 6;
wherein each RZ may be –OH, -NHR’, –SH, -C(O)OH, -P(O)(OR’)(OH), –PR’(O)(OH)2 or
20 –PR’(O)OH, optionally RZ is selected from –OH, -NHR’ or -C(O)OH, optionally each Rz
is –OH, -C(O)OH or a combination thereof (e.g. each Rz is –OH);
52
wherein R’ may be H, or optionally substituted alkyl, heteroalkyl, aryl, heteroaryl,
cycloalkyl or heterocycloalkyl, optionally R’ is H or optionally substituted alkyl; and
wherein Z’ corresponds to Rz, except that a bond replaces the labile hydrogen atom.
15. A (poly)ol block copolymer according to claim 14 wherein a is an integer which is
5 at least 2
16. A (poly)ol block copolymer according to claim 14, wherein the starter compound
is selected from monofunctional starter substances such as alcohols, phenols, amines,
thiols and carboxylic acid, for example, alcohols such as methanol, ethanol, 1- and 2-
propanol, 1- and 2-butanol, linear or branched C3-C20-monoalcohol such as tert-butanol,
10 3-buten-1-ol, 3-butyn-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-3-butyn-2-ol, propargyl
alcohol, 2-methyl-2-propanol, 1-tert-butoxy-2-propanol, 1-pentanol, 2-pentanol, 3-
pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-
octanol, 2-octanol, 3-octanol, 4-octanol, 1-decanol, 1-dodecanol, phenol, 2-
hydroxybiphenyl, 3-hydroxybiphenyl, 4-hydroxybiphenyl, 2-hydroxypyridine, 3-
15 hydroxypyridine, and 4-hydroxypyridine, mono-ethers or esters of ethylene, propylene,
polyethylene, polypropylene glycols such as ethylene glycol mono-methyl ether and
propylene glycol mono-methyl ether, phenols such as linear or branched C3-C20 alkyl
substituted phenols, for example nonyl-phenols or octyl phenols, monofunctional
carboxylic acids such as formic acid, acetic acid, propionic acid and butyric acid, fatty
20 acids, such as stearic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, benzoic
acid and acrylic acid, and monofunctional thiols such as ethanethiol, propane-1-thiol,
propane-2-thiol, butane-1-thiol, 3-methylbutane-1-thiol, 2-butene-1-thiol, and thiophenol,
or amines such as butylamine, tert-butylamine, pentylamine, hexylamine, aniline,
aziridine, pyrrolidine, piperidine, and morpholine; and/or selected from diols such as 1,2-
25 ethanediol (ethylene glycol), 1-3-propanediol, 1,2-butanediol, 1-3-butanediol, 1,4-
butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-
dodecanediol, 1,4-cyclohexanediol, 1,2-diphenol, 1,3-diphenol, 1,4-diphenol, neopentyl
glycol, catechol, cyclohexenediol, 1,4-cyclohexanedimethanol, dipropylene glycol,
diethylene glycol, tripropylene glycol, triethylene glycol, tetraethylene glycol,
30 polypropylene glycols (PPGs) or polyethylene glycols (PEGs) having an Mn of up to
about 1500g/mol, such as PPG 425, PPG 725, PPG 1000 and the like, triols such as
glycerol, benzenetriol, 1,2,4-butanetriol, 1,2,6-hexanetriol, tris(methylalcohol)propane,
tris(methylalcohol)ethane, tris(methylalcohol)nitropropane, trimethylol propane,
polyethylene oxide triols, polypropylene oxide triols and polyester triols, tetraols such as
53
calix[4]arene, 2,2-bis(methylalcohol)-1,3-propanediol, erythritol, pentaerythritol or
polyalkylene glycols (PEGs or PPGs) having 4–OH groups, polyols, such as sorbitol or
polyalkylene glycols (PEGs or PPGs) having 5 or more –OH groups, or compounds
having mixed functional groups including ethanolamine, diethanolamine,
methyldiethanolamine, and phenyldiethanolamine5 .
17. A (poly)ol block copolymer according to any preceding claim, wherein the (poly)ol
molecular weight (Mn) is in the range 300-20,000 Da and optionally the molecular weight
(Mn) of block A is in the range 200-4000 Da, and wherein optionally the molecular weight
(Mn) of block B is in the range 100-20,000 Da, more typically, the molecular weight (Mn)
10 of block A is 200-2000 Da , more typically 200-1000 Da, most typically 400-800 Da and/or
the molecular weight (Mn) of block B is typically 200-10,000 Da, more typically 200-5000
Da.
18. A (poly)ol block copolymer according to any preceding claim, wherein block A is
a generally alternating polycarbonate (poly)ol residue.
15 19. A composition comprising the (poly)ol block copolymer of any preceding claim,
and one or more additives selected from catalysts, blowing agents, stabilizers,
plasticisers, fillers, flame retardants, and antioxidants.
20. A composition according to claim 19 further comprising a (poly)isocyanate.
21. A polyurethane comprising a block copolymer residue according to any of claims
20 1-18.
22. An isocyanate terminated polyurethane prepolymer comprising a block
copolymer residue according to any of claim 1 to 18.
23. A lubricant composition comprising a (poly)ol block copolymer of any of claims 1
to 18.
25 24. A surfactant composition comprising a (poly)ol block copolymer of any of claims
1 to 18.
25. A process for producing a (poly)ol block copolymer comprising a first reaction in
a first reactor and a second reaction in a second reactor; wherein the first reaction is the
reaction of a carbonate catalyst with CO2 and alkylene oxide, in the presence of a starter
30 and optionally a solvent to produce a polycarbonate (poly)ol copolymer according to
block A of any of claims 1 to 18 and the second reaction is the reaction of a DMC catalyst
with the polycarbonate (poly)ol copolymer of the first reaction, CO2 , ethylene oxide and
54
optionally one or more other alkylene oxides to produce a (poly)ol block copolymer
according to any of claims 1 to 18.
26. A process for producing a (poly)ol block copolymer in a multiple reactor system;
the system comprising a first and second reactor wherein a first reaction takes place in
the first reactor and a second reaction takes place in the second reactor; 5 wherein the
first reaction is the reaction of a carbonate catalyst with CO2 and alkylene oxide, in the
presence of a starter and optionally a solvent to produce a polycarbonate (poly)ol
copolymer according to a starter residue terminated block A of any of claims 1 to 18 and
the second reaction is the reaction of a DMC catalyst with the polycarbonate (poly)ol
10 compound of the first reaction, CO2, ethylene oxide and optionally one or more other
alkylene oxides to produce a (poly)ol block copolymer according to any of claims 1 to 18.
27. A process according to any of claims 25-26, further comprising a reaction
comprising the reaction of the block copolymer of any of claims 1 to 18 with a monomer
or further polymer to produce a higher polymer.
15 28. A process according to claim 27, wherein the monomer or further polymer is a
(poly)isocyanate and the product of the reaction is a polyurethane.
29. A process according to any of claims 25-28, wherein the polycarbonate or
polyester (poly)ol copolymer according to block A of any of claims 1 to 18 is fed into the
reactor or second reactor for the reaction with the DMC catalyst, as a crude reaction
20 mixture, optionally, continuously or semi-continuously, wherein said reactor or second
reactor contains a pre-activated DMC catalyst.
30. A process according to any of claims 25-29, wherein the first reaction is carried
out under CO2 pressure of less than 20 bar, more preferably, less than 10 bar, most
preferably, less than 8 bar.
25 31. A process according to any of claims 29-30, wherein the carbonate catalyst is
present in the crude reaction mixture.
32. A process according to any of claims 29-30, wherein the carbonate catalyst has
been removed from the crude reaction mixture prior to the addition to the reactor or
second reactor.
30 33. A process according to any of claims 25-32 wherein the carbonate catalyst is a
catalyst capable of producing polycarbonate chains with greater than 76% carbonate
linkages.34. A process according to any of claims 25-33, wherein the carbonate catalyst is a
metal catalyst comprising phenol or phenolate ligands.
35. A process according to any of claims 25-34, wherein the polycarbonate or
polyester (poly)ol copolymer according to block A of any of claims 1 to 18 is fed into the
5 reactor or second reactor in a single portion or in a continuous or semi-continuous
manner, optionally wherein the product of the first reaction comprises unreacted alkylene
oxide and/or carbonate catalyst.
36. A polyurethane according to claim 21, wherein the polyurethane is in the form of
a soft foam, a flexible foam, an integral skin foam, a high resilience foam, a viscoelastic
10 or memory foam, a semi-rigid foam, a rigid foam (such as a polyurethane (PUR) foam, a
polyisocyanurate (PIR) foam and/or a spray foam), an elastomer (such as a cast
elastomer, a thermoplastic elastomer (TPU) or a microcellular elastomer), an adhesive
(such as a hot melt adhesive, pressure sensitive or a reactive adhesive), a sealant or a
coating (such as a waterborne or solvent dispersion (PUD), a two-component coating, a
15 one component coating, a solvent free coating).