A POLYOL BLOCK COPOLYMER

Abstract

A (poly)ol block copolymer of general structure B-A-(B)n, wherein block A is a polycarbonate block or polyester block, 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 hydroxyl groups, and a process of producing such copolymers and products incorporating such copolymers.

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 hydroxyl groups.

2-97. (canceled)

98. The (poly)ol block copolymer according to claim 1, wherein the mol/mol ratio of block A to block B is in the range 25:1 to 1:250.

99. The (poly)ol block copolymer according to claim 1, wherein block A is derived from alkylene oxides and CO.sub.2.

100. The (poly)ol block copolymer according to claim 1, wherein the alkylene oxides and CO.sub.2 provide at least 90% of the residues in the block not including any starter.

101. The (poly)ol block copolymer according to claim 1, wherein block A has between 70-100% carbonate linkages.

102. The (poly)ol block copolymer according to claim 1, wherein block B is derived from alkylene oxides and CO.sub.2.

103. The (poly)ol block copolymer according to claim 1, wherein at least 5% of the alkylene oxide residues of block B are ethylene or propylene oxide residues.

104. The (poly)ol block copolymer according to claim 1, wherein at least 70% of the terminal alkylene oxide residues are ethylene oxide residues.

105. The (poly)ol block copolymer according to claim 1, wherein the polyethercarbonate block(s), B, of the (poly)ol block copolymer have less than 40% carbonate linkages.

106. The (poly)ol block copolymer according to claim 1, wherein the polyethercarbonate block(s), B, of the (poly)ol block copolymer have at least 60% ether linkages.

107. The (poly)ol block copolymer according to claim 1, wherein the polycarbonate block, A, of the (poly)ol block copolymer also comprise ether linkages.

108. The (poly)ol block copolymer according to claim 1, wherein the (poly)block structure of the copolymer is defined as:
B-A′-Z′—Z—(Z′-A′-B).sub.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′).sub.n is a starter residue.

109. The (poly)ol block copolymer according to claim 108, wherein -A′- has the following structure: ##STR00008## wherein the ratio of p:q is at least 7:3; and block B has the following structure: ##STR00009## wherein the ratio of w:v is greater or equal to 1:1; and R.sup.e1, R.sup.e2, R.sup.e3 and R.sup.e4 depend on the nature of the alkylene oxide used to prepare blocks A and B.

110. The (poly)ol block copolymer according to claim 108, wherein the starter residue depends on the nature of the starter compound, and wherein the starter compound has the formula (III):
Z—(R.sup.Z).sub.a  (III) wherein Z can be any group which can have 1 or more, typically, 2 or more —R.sup.Z groups attached to it and may be selected from optionally substituted alkylene, alkenylene, 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; 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 R.sup.Z may be —OH, —NHR′, —SH, —C(O)OH, —P(O)(OR′)(OH), —PR′(O)(OH).sub.2 or —PR′(O)OH, optionally R.sup.Z is selected from —OH, —NHR′ or —C(O)OH, optionally each R.sup.z is —OH, —C(O)OH or a combination thereof (e.g. each R.sup.z is —OH); 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 R.sup.z, except that a bond replaces the labile hydrogen atom.

111. The (poly)ol block copolymer according to claim 110, wherein a is an integer which is at least 2

112. The (poly)ol block copolymer according to claim 110, 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 C.sub.3-C.sub.20-monoalcohol such as tert-butanol, 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-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 C.sub.3-C.sub.20 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 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-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, polypropylene glycols (PPGs) or polyethylene glycols (PEGs) having an Mn of up to about 1500 g/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 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 phenyldiethanolamine.

113. The (poly)ol block copolymer according to claim 1, 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.

114. The (poly)ol block copolymer according to claim 1, wherein block A is a generally alternating polycarbonate (poly)ol residue.

115. The composition comprising the (poly)ol block copolymer of claim 1, and one or more additives selected from catalysts, blowing agents, stabilizers, plasticisers, fillers, flame retardants, and antioxidants.

116. The composition according to claim 115, further comprising a (poly)isocyanate.

117. A polyurethane comprising a block copolymer residue according to claim 1.

118. An isocyanate terminated polyurethane prepolymer comprising a block copolymer residue according to claim 1.

119. A lubricant composition comprising a (poly)ol block copolymer of claim 1.

120. A surfactant composition comprising a (poly)ol block copolymer of claim 1.

121. 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 CO.sub.2 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 claim 1 and the second reaction is the reaction of a DMC catalyst with the polycarbonate (poly)ol copolymer of the first reaction, CO.sub.2, ethylene oxide and optionally one or more other alkylene oxides to produce a (poly)ol block copolymer according to claim 1.

122. 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 reaction is the reaction of a carbonate catalyst with CO.sub.2 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 claim 1 and the second reaction is the reaction of a DMC catalyst with the polycarbonate (poly)ol compound of the first reaction, CO.sub.2, ethylene oxide and optionally one or more other alkylene oxides to produce a (poly)ol block copolymer according to claim 1.

123. The process according to claim 121, further comprising a reaction comprising the reaction of the block copolymer of claim 1 with a monomer or further polymer to produce a higher polymer.

124. The process according to claim 123, wherein the monomer or further polymer is a (poly)isocyanate and the product of the reaction is a polyurethane.

125. The process according to claim 123, wherein the polycarbonate or polyester (poly)ol copolymer according to block A of claim 1 is fed into the reactor or second reactor for the reaction with the DMC catalyst, as a crude reaction mixture, optionally, continuously or semi-continuously, wherein said reactor or second reactor contains a pre-activated DMC catalyst.

126. The process according to claim 121, wherein the first reaction is carried out under CO.sub.2 pressure of less than 20 bar, more preferably, less than 10 bar, most preferably, less than 8 bar.

127. The process according to claim 125, wherein the carbonate catalyst is present in the crude reaction mixture.

128. The process according to claim 125, wherein the carbonate catalyst has been removed from the crude reaction mixture prior to the addition to the reactor or second reactor.

129. The process according to claim 121, wherein the carbonate catalyst is a catalyst capable of producing polycarbonate chains with greater than 76% carbonate linkages.

130. The process according to claim 121, wherein the carbonate catalyst is a metal catalyst comprising phenol or phenolate ligands.

131. A process according to claim 25, wherein the polycarbonate or polyester (poly)ol copolymer according to block A of claim 1 is fed into the 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.

132. A polyurethane according to claim 20, wherein the polyurethane is in the form of a soft foam, a flexible foam, an integral skin foam, a high resilience foam, a viscoelastic 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 one component coating, a solvent free coating).

Description

EXAMPLES

Experimental

Example 1: Comparative Example of with PO Only in Second Vessel (98% Secondary)

[0261] Hexanediol (2.9 g), catalyst (1) (0.2 g) and EO (30 mL) were added into a 100 mL reactor. The vessel was heated to 75° C. and pressurised to 20 bar with CO.sub.2 and stirred for 16 hours, after which it was cooled and vented. This resulted in a ca. 1100 g/mol polyethylene carbonate polyol. The contents of the reactor were transferred into a Schlenk tube, along with the addition of PO (6 mL) and EtOAc (20 mL).

[0262] In a separate 100 mL reactor, 9.2 mg of DMC catalyst and PPG400 (0.4 ml) were added. Ethyl acetate (15 ml) was injected into the vessel. The vessel was heated to 130° C., 2×0.5 g of PO were added to confirm activity of the DMC catalyst.

[0263] The reactor was cooled to 85° C. at 4.5 bar with CO.sub.2. The first reaction mixture was then added via a HPLC pump. Addition occurred over 1 hour. The reaction was continued for 3 hours before the addition of PO (14 g) over 0.5 hours. A reaction was run for a further 16 hours before the reactor was cooled to below 10° C. and the pressure was released. NMR and GPC were measured immediately.

Example 2: Comparative Example with Polyether Starter

[0264] PPG400 (15 ml) and DMC (9 mg) were added to a 100 mL reactor and heated to 130° C. under vacuum. Four 6 g slugs of PO were added over several hours, each time waiting for the active DMC to be observed. EO was added (3×9 mL) under a pressure of CO.sub.2, with intervals of 2 hours, ensuring DMC remained active before each addition.

Example 3

[0265] Example 3 was carried out as per example 1 except, hexanediol (2.75 g) was used to make polyethylene carbonate-polyol of 1200 g/mol, and PO (10 mL) and EtOAc (15 ml) were added to the Schlenk. Instead of the final PO addition in reactor 2, EO (9 mL) was added to end-cap the polyol.

Example 4

[0266] Example 4 was carried out as per example 1 except, hexanediol (2.75 g) was used to make polyethylene carbonate-polyol of 1200 g/mol, and EtOAc (15 mL) added to the Schlenk. Instead of the final PO addition in reactor 2, EO (9 ml) was added to end-cap the polyol.

TABLE-US-00001 Overall M.sub.n Primary end Primary end Example Conversion % CO.sub.2 wt % EO:PO g/mol PDI groups % (M1).sup.$ groups % (M2)* 1 - 100 20.0 1.00 2050 1.29 0 12 Comp. 2 - 100 0 ~1 1640 1.36 56 67 Comp. 3 - 100 21.3 3.53 1980 1.21 79 78 Invention 4 - 100 18.0 5.50 1740 1.28 81 83 Invention .sup.$Method 1 - Ref: Journal of Cellular Plastics, January/February, 1974, Page 43. T. Groom, J. S. Babiec, Jr. and B. G. Van Leuwen *Method 2 - Hofmann et al., United States Patent, 2019, U.S. Pat. No. 10,174,151 B2

[0267] Two different literature methods were used to determine the primary hydroxyl content of the polyols.

[0268] Comparative example 1 demonstrates the very low percentage of primary end-groups produced when propylene oxide is used as the sole epoxide in the second reaction. Method 1 did not determine any primary hydroxyl groups, whilst method 2 determined 12% primary hydroxyl groups. The DMC catalyst is generally known to produce ˜3% primary end groups when reacted with PO alone, so method 1 appears more reliable.

[0269] Comparative example 2 was conducted with an ethylene oxide end cap but a polyether was used as the starter instead of a polycarbonate. Method 1 determined only 56% primary hydroxyl end groups, whilst method 2 was slightly higher at 67%.

[0270] Examples 3 and 4 (of the invention) used a polycarbonate starter produced by reaction of a carbonate catalyst, starter, CO.sub.2 and ethylene oxide. They differ in that example 3 used a mixture of PO and EO in the second reactor, whilst example 4 used only EO in the second reactor (apart from the 1 g PO used to activate the DMC catalyst). Examples 3 and 4 showed approximately 80% primary hydroxyl end groups, even though PO was used to activate the DMC catalyst. This demonstrates the introduction of a polycarbonate starter substantially increases the primary hydroxyl content under identical conditions.