Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/44—Polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/40—Post-polymerisation treatment

Definitions

• This invention relates to a process for increasing the molecular weight of poly(alkylene carbonate) polyols.
• Poly(alkylene carbonate) polyols are use- ful in preparing polyurethanes, and as surfactants.
• Polyether polyols and polyester polyols are well-known polymers which can be further polym ⁇ erized with organic polyisocyanates to prepare poly ⁇ urethanes.
• Polyether polyols are prepared by the reaction of hydroxy-containing hydrocarbons, such as an aromatic or aliphatic diol, and use "epoxides" for instance, ethylene oxide and propylene oxide.
• Polyester polyols are prepared by the reaction of poly acids, such as adipic or terephthalic acid, or esters of polyacids, such as dimethyl adipate or dimethyl terephthalate with dihydroxy-containing hydrocarbons, such as aromatic and aliphatic diols.
• Some poly(alkylene carbonate) polyol properties resemble polyester polyol properties while other proper ⁇ ties resemble polyether polyols.
• Polycarbonates produced by these methods may have a functionality of less than two due to inadequate or incomplete ester- ification or transesterification which often prevents the products from forming high molecular weight polymers in subsequent reactions.
• Poly(alkylene carbonate) polyols can be prepared by the method illustrated by Malkemus, US 3,133,113. It is disclosed that an alkylene carbonate such as ethylene carbonate can be reacted with a glycol such as diethylene glycol in a mole ratio in the range of 1.2:1 to 2.5:1 at reduced pressure while removing ethylene glycol formed by the reaction until the reaction is complete.
• the catalyst employed is a mixed zinc borate-alkaline earth metal oxide catalyst.
• Stevens, in US 3,248,414; 3,248,415 and 3,248,416, discloses the preparation of poly(alkylene carbonate) polyols from (1) carbon dioxide and 1,2-epoxides; (2) cyclic carbonates such as ethylene carbonate; or (3) from cyclic carbonates and a 1,2-epoxide.
• a minor amount of a polyol is employed as an initiator.
• the reaction is usually conducted under pressure in the presence of a metal carbonate, metal hydroxide, trisodium phosphate or a tertiary amine.
• Poly(alkylene carbonate) polyols have also been prepared by polymerization of ethylene carbonates under pressure using basic catalysts and a minor amount of glycol as initiator, Buysch et al., US 4,105,641. These products are low in carbonate and high in ether groups concentration due to decomposition of the ethyl ⁇ ene carbonate.
• Stevens' patents discussed herein- before the patentees exposed a poly(alkylene carbonate) polyol derived from ethylene carbonate and mon ⁇ ethylene glycol to temperatures of 160°C at 2 mm Hg (0.27 kPa) pressure to remove unreacted ethylene carbonate.
• Hostetler, US 3,379,693 removed unreacted ethylene carbonate from products similar to poly(alkylene carbonate) polyols by heating them to about 130°C under 1-5 mm Hg (0.13-0.67 kPa) pressure; Maximovich, US 3,896,090 reacted ethylene carbonate with diethylene glycol and treated the reaction product under reduced pressure to remove the unreacted ethylene carbonate and diethylene glycol.
• Several workers have prepared poly(alkyl- ene carbonate) polyols and related materials by con ⁇ trolling an equilibrium between the reaction mate ⁇ rials of a diol and alkylene carbonate and the products of a poly(alkylene carbonate) polyol and monoethylene glycol. The reaction is controlled by the removal of monoethylene glycol.
• the chemistry based on the above equilibrium was improved by Buysch et al., US 4,105,641 by carry- ing out the reactions in a solvent (e.g., cumene) capable of removing monoethylene glycol as an azeo- trope with the solvent.
• a solvent e.g., cumene
• the molecular weights of pol (alkylene carbonate) polyols from alkylene car- bonates have been controlled by either the stoichi- ometry of the reactants, that is, higher alkylene carbonate.to initiator ratios for higher molecular weights, or the removal of monoethylene glycol from the reaction mixture wherein an ethylene carbonate to initiator equivalent ratio of about 1 is used.
• Catalysts are used in most cases, as reaction rates are very slow in the absence of a catalyst.
• high alkylene carbonate to initiator ratios are used to make higher molecular weight pol (alkylene carbonate) polyols
• reaction rates drop severely as higher conversions are approached; long reac ⁇ tion times are required and the products are con ⁇ taminated by unreacted alkylene carbonate. If temperatures are increased to increase the rate, the product decomposition occurs with C0 2 loss.
• the invention is a process for increas ⁇ ing the molecular weight of a poly(alkylene carbon ⁇ ate) polyol which comprises exposing the poly(alkyl ⁇ ene carbonate) polyol to elevated temperatures at which dialkylene glycol, trialkylene glycol, or initiator segments, wherein the initiator has about the same or greater volatility as the dial- kylene glycol or trialkylene glycol segment, are abstracted from the poly(alkylene carbonate) polyol, at a pressure wherein the dialkylene glycol, trial ⁇ kylene glycol or initiator is volatile, and removing the volatile dialkylene glycol, trialkylene glycol or initiator segments from the mass of the poly(al ⁇ kylene carbonate) polyol, under conditions such that the molecular weight of the poly(alkylene car ⁇ bonate) polyol is increased.
• This process allows the preparation of higher molecular weight poly(alkylene carbonate) polyols at faster rates and higher purity than previously prepared in the art. Furthermore, the process allows a great deal of flexibility in the preparation of such polyols with varying degrees of molecular weight.
• the poly(alkylene carbonate) polyols prepared by this process generally have an increased weight percent of carbon dioxide moieties in the backbone of the polymer, and have a lower poly-dispersity index.
• the starting materials in the process of this invention are poly(alkylene carbonate) polyols.
• Such compounds include randomized polymers containing C0 2 moieties and di- and polyalkylene- oxy units.
• the poly(alkylene carbonate) polyols can further contain the residue of an initiator as well as unreacted starting material's and other relatively volatile reaction products.
• Alkylene- oxy moieties refer herein to a series of repeat- ing units which contain an alkylene group bound to an oxygen, wherein the carbons of the alkylene group can be further substituted with a hydrocar- byl moiety.
• Alkyleneoxy moieties can be repre ⁇ sented by the following formula
• R 2 is as herei•nafter defi•ned, and s is an integer of 2 or greater; more preferably between about 2 and 10; even more preferably 2 or 4; and most preferably 2.
• a dialkylene glycol refers herein to 2 alkylene moieties connected by an oxy ⁇ gen and terminated by a hydroxyl group, wherein the alkylene moieties can be substituted with a hydrocarbyl moiety.
• Preferred dialkylene glycol moieties correspond to the formula
• dialkylene glycols include dipropyl- ene glycol, diethylene glycol, 1,2-dibutylene gly ⁇ col, 2,3-dibutylene glycol, and the like.
• Preferred poly(alkylene carbonate) poly ⁇ ols are random polymers of
• R 1 is 3 X)_
• R is separately in each occurrence hydro ⁇ gen, halogen, a nitro group, a cyano group, a l-20 n y drocart> Yl group or a C , 2Q hydrocarbyl group substituted with one or more of the fol ⁇ lowing: a halo, cyano, nitro, thioalkyl, tert- -amino, alkoxy, aryloxy, aralkoxy, carbonyldi- oxyalkyl, carbonyldioxyaryl, carbonyldioxyar- alkyl, alkoxycarbonyl, aryloxycarbonyl, aralk- oxycarbonyl, alkylcarbonyl, arylcarbonyl, aralkylcarbonyl, alkylsulfinyl, arylsulfinyl, aralkylsulfinyl, alkylsulfonyl, arylsulfonyl, or
• R 3 i.s separately in each occurrence an n valent hydrocarbon radical or hydrocarbon radical which can contain one or more hetero- atoms of 0, N or S;
• X is S , 0 , NH,
• n is separately in each occurrence an integer of from 1 to 25; x is 1; y is separately in each occurrence 1 to 40; and z is separately in each occurrence 1 to 100.
• poly(alkylene carbonate) polyols generally corresponds to-the formula
• R 2, R3, X, n and m are as previously defined; p is separately in each occurrence 0 or 1; and q is separately in each occurrence an integer of 1 or greater.
• R 2 i.s preferably hydrogen, C 1 _ 2Q alkyl, , 2Q halo- alkyl, C-,_ 2Q alkenyl or phenyl; R is more prefer ⁇ ably hydrogen, C__ 3 alkyl, C 2 _ 3 alkenyl, or phe ⁇ nyl; R is even more preferably hydrogen, methyl 2 or ethyl; R is even more preferably hydrogen or methyl, and most preferably hydrogen.
• R 3 is pref ⁇ erably an aliphatic or cycloaliphatic hydrocarbon or an aliphatic or cycloaliphatic hydrocarbon con- taining one or more oxygen, nitrogen or sulfur moi- eties; R 3 i.s more preferably a n valent alkane or cycloalkane, or a n valent alkane or cycloalkane containing one or more oxygen, nitrogen or sulfur
• R is even more preferably a n valent c ⁇ _ ⁇ o a lkane or a n valent C_ _ Q alkane substi ⁇ tuted with one or more oxygen moieties.
• X is preferably S, 0 or NH; X is most preferably 0.
• m is 1 to 10, more preferably 1 to 5.
• n is an integer of 1-10, inclusive; more preferably 1-5, inclusive; and most prefer ⁇ ably 1 or 2.
• q is an integer of from 1 to 1000, inclusive; and most preferably an integer of from 1 to 500, inclusive.
• y is 5 to 20, and z is 20 to 50.
• the products of this process are poly-
• the molecular weights of the poly(alkyl ⁇ ene carbonate) polyols prepared by this process can be any molecular weight desired which is above the starting molecular weight. Preferable molecular weights are between 500 and 10,000, with most pre ⁇ ferred molecular weights being between 1,000 and 8,000.
• the products prepared have a poly-dispersity index (M / ), either only slightly higher or in some cases even lower than the starting pol (alkyl ⁇ ene carbonate) polyols. Poly-dispersity indexes are known to increase with increasing molecular weight in step growth polymerization.
• the prod-., ucts prepared contain a higher weight percent of C0 2 in the backbone than the starting materials. Unreacted starting materials and low molecular weight reaction products produced during the preparation of the starting poly(alkylene car ⁇ bonate) polyols are removed.
• the process of this invention preferably involves exposing a poly(alkylene carbonate) polyol to elevated temperatures under reduced pressure con ⁇ ditions so as to cause the splitting off of a dial ⁇ kylene glycol moiety, a trialkylene glycol moiety and/or a moiety which, is as volatile or more vola- tile than the dialkylene glycol or trialkylene gly ⁇ col moiety and removing such volatile components from the reaction mass.
• the dialkylene glycol and/or initiator will volatilize.
• the trialkyl ⁇ ene glycol units can be removed by this process. In general, the lightest fraction which splits from the starting material will be taken off.
• the poly(alkylene carbon ⁇ ate) polyol is a monofunctional species, that is; where the initiator has only one active hydrogen site, under certain circumstances the initiator fragment may be more volatile than the dialkylene glycol fragment and therefore will split off and be removed more readily than the dialkylene glycol portion.
• the initiator is a linear C, spontaneous alco ⁇ hol, the C 1 _ 8 alcohol fragment will be removed before any dialkylene glycol fragments will be removed.
• linear C 1Q or C.. alcohol is used as the initiator
• the linear C, Q or C,., alco ⁇ hol is about as volatile as the dialkylene glycol and therefore should come off at the same time.
• a linear C 12 or greater alcohol is the initiator
• the dialkylene glycol is more volatile and will split off.
• Branched alcohol initiators have somewhat different volatilities and will be split out based on its relative volatility as com- pared to the dialkylene or trialkylene glycol fragment.
• the volatile component can be removed by any method known in the art. Such methods include fractional distillation, fractionation, passing an inert gas over the reaction mass so as to remove the volatile species, and any other method for removing the volatile species condensed by a water-chilled condenser as is known in the art, for example, a falling film still such as a wiped film evaporator is particularly useful.
• a preferred method of con ⁇ densing the distillate is by the use of a water- -chilled condenser.
• the volatile species condensed by the water- -chilled condenser can be recycled to be used as ini ⁇ tiators for the preparation of poly(alkylene carbon- ate) polyols useful as starting materials in this process.
• the process of this invention takes place at any temperature at which the splitting off of the volatile segments occurs.
• the lower temperature limit is that temperature at which the splitting of the volatile component occurs, and the upper limit is that temperature at which the poly(alkylene carbonate) polyol undergoes decom ⁇ position.
• Preferred temperatures are between 150°C and 300°C. More preferred temperatures are between 175°C and 260°C, with between 200°C and 250°C being most preferred.
• Pressures used in this process are those pressures at which the dialkylene glycol or species as volatile or more volatile than dialkyl ⁇ ene glycol will volatilize at the temperatures used.
• Preferable pressures are atmospheric and subatmos- pheric, with subatmospheric pressures being more preferable. More preferable pressures are less than 300 mm Hg (40.0 kPa), even more preferably less than 100 mm Hg (13.3 kPa), even more preferably less than 50 mm Hg (6.67 kPa), and most preferably between 10 and 30 mm Hg (1.33 and 4.00 kPa).
• reaction time for the process of this invention is variable depending on various factors, including temperature, pressure, and the molecular weight of the desired product. At lower pressures, and at higher temperatures, the time to achieve the desired molecular weight is lower.
• the process can be run for a time sufficient to give the desired molecular weight. Reaction times are rela ⁇ tively rapid, only a few hours are required in most cases.
• the process of this invention is gener ⁇ ally performed by exposing the poly(alkylene car ⁇ bonate) polyol in neat form to the processing con ⁇ ditions.
• the process can be performed in a solvent, although performing the process in neat form is preferred.
• Solvents useful include inert organic solvents with a boiling point above that of the dialkylene glycol, or the most volatile species.
• Pol (alkylene carbonate) polyol start ⁇ ing materials useful in this invention are pre- pared by any method known in the art, such as, the condensation of an alkylene carbonate; carbon dioxide and an alkylene oxide; or mixtures of an alkylene carbonate, an alkylene oxide and/or CO-,; with an organic compound containing one or more active hydrogen atoms (initiator) in the presence of an alkaline catalyst or metal salt of an alka ⁇ line compound.
• R 2, R3, X, n, p and q are as hereinbefore defined.
• the pol (alkylene carbon ⁇ ate) polyols can be prepared by reacting a dialkyl carbonate or diaryl with an initiator with two or more hydroxyl moieties. See, for example, US 4,476,293 and US 4,191,705.
• Alkylene carbonates useful in the reac ⁇ tion are those which will react with the reactive hydrogen-containing functional groups. Desirable alkylene carbonates are those corresponding to the mula
• R 2 i.s as previously defined.
• Dialkyl carbonates useful in this inven ⁇ tion include those corresponding to the formula
• R 2 is as previously defined.
• R 2 i.s preferably hydrogen, or a monova- lent C-,_ 20 alkane, C__ 20 haloalkane, C., 2Q alkene or benzene radical.
• R is more preferably hydro ⁇ gen, or a monovalent C.__ alkane, C _ 3 alkene or benzene radical.
• R is most preferably hydrogen, or a monovalent methane or ethane.
• desirable alkylene carbon ⁇ ates include ethylene carbonate, propylene carbon ⁇ ate, butylene carbonate, vinylene carbonate and phenylene carbonate. More preferred alkylene car- bonates include ethylene and propylene carbonate.
• Examples of preferred dialkyl carbonates include dimethyl carbonate, diethyl carbonate and dipropyl carbonate.
• a preferred diaryl carbonate is diphe- nyl carbonate.
• Epoxides useful for preparing starting materials for this invention are those which will react with C0 2 or the functional group on an organic compound wherein the functional group contains an active hydrogen so as to add an ether and carbon- ate unit to the organic compound.
• Desirable epoxides- include those corre ⁇ sponding to the formula
• R 2 i.s as defined above.
• epoxides are the alkyl ⁇ ene oxides, for instance ethylene oxide, propylene oxide, butylene oxide; epihalohydrins, such as epi- bromohydrin and epichlorohydrin; styrene oxide, vinylene oxide, cyclohexene oxide; cyclopentene oxide, cycloheptene oxide, 2,3-epoxy propylphenyl ether and tert-butyl glycidyl ether.
• pre ⁇ ferred epoxides are ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epibro- mohydrin, styrene oxide and vinylene oxide.
• the organic compound containing active hydrogen atoms is a hydrocarbon or hydrocarbon which is substituted with one or more heteroatoms of oxygen, nitrogen or sulfur contain ⁇ ing between 1 and 25 functional groups containing a reactive hydrogen.
• the desirable initi ⁇ ators are those which correspond to the formula
• a functional group containing a reactive hydrogen means herein any moiety which contains a hydrogen- atom which will readily react with an alkylene carbonate, a dialkyl carbonate, diaryl carbonate or an alkylene oxide in the presence of carbon dioxide. More specifically, reactive hydrogen means herein a hydrogen linked directly to an oxy ⁇ gen, nitrogen or sulfur atom, such as is found in a hydroxy, non-tertiary amine, amide, mercapto or carboxyl group.
• the organic compounds containing active hydrogen atoms of this invention contain one or more of the following functional groups, hydroxyls, amines, mercaptans, carboxyls, sulfones, amides, imides, or carbonates.
• the initiators may contain other groups in their backbone structure, such as, for example, sul- fones, sulfoxides, sulfides, amines, amides, ethers, esters, carbonates and the like.
• initiators are polyols such as aliphatic polyether and polyester polyols, cycloaliphatic polyols, aromatic polyols and poly ⁇ ols which further contain oxy or ether groups; polyamines; polymercaptans; polyamides; polycar- boxylic acids; water, alkylolamines and organic compounds which contain two or more of the above- -described functional groups containing reactive hydrogens.
• the preferred classes are the poly ⁇ ols, polyamines and polymercaptans.
• active hydrogen-containing compounds include those described in the U.S. patents incorporated by ref ⁇ erence hereinbefore. Two or more initiators can be used in combination to obtain a poly(alkylene carbonate) polyol.
• Catalysts used in the preparation of poly- ether polyols include alkali metal hydroxides, alka ⁇ line earth metal hydroxides, alkali metal carbonates, alkaline earth metal carbonates, ammonium hydroxide and ammonium carbonate.
• Preferable catalysts for the reaction of an active hydrogen-containing organic compound with an alkylene carbonate, dialkyl carbonate, diaryl carbonate, alkylene oxide and carbon monoxide, or alkylene carbonate in admixture with an alkylene oxide and/or carbon dioxide include ester exchange catalysts.
• preferable catalysts are such metals as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, zinc, aluminum, titanium, cobalt, germanium, tin, lead, antimony, arsenic and cerium as well as the alkoxides thereof.
• Examples of other preferable catalysts are alkali metal carbonates, alkaline earth metal carbonates, ammonium carbonates, alkali metal borates, alkaline earth metal borates, ammo ⁇ nium borates, hydrocarbyloxy titanates, zinc borate, lead borate, zinc oxide, lead silicate, lead arsen- ate, litharge, lead carbonate, antimony trioxide, germanium dioxide, cerium trioxide and aluminum isopropoxide.
• Examples of other preferable cata ⁇ lysts include salts of organic acids of magnesium, calcium, cerium, barium, zinc and titanium, alkali metal stannates, alkaline metal stannates and ammo ⁇ nium stannates.
• borate catalysts include sodium meta-borate, sodium meta-borate tetrahydrate, sodium meta-borate dihydrate, sodium pentaborate pentahydrate, sodium tetraborate decahydrate, .sodium tetraborate pentahydrate, diammonium tetraborate tetrahydrate, ammonium hydrogen tetraborate tetra ⁇ hydrate, lithium ortho-dihydroborate, lithium meta- -borate, lithium tetraborate, lithium pentaborate pentahydrate, potassium meta-borate, potassium tetraborate tetrahydrate, potassium tetraborate pentahydrate, potassium pentaborate tetrahydrate, magnesium meta-borate trihydrate, magnesium dibor- ate, magnesium ortho-borate, calcium meta-borate, calcium tetraborate and strontium tetraborate tetra ⁇ hydrate.
• stannate catalysts include sodium stannate trihydrate, potassium stannate tri
• More preferred catalysts are the alkali metal carbonates, alkaline earth metal carbonates, ammonium carbonates, alkali metal stannates, alka ⁇ line earth metal stannates, alkali metal borates, alkaline earth metal borates and ammonium borates. Even more preferred catalysts are alkali metal car ⁇ bonates, alkali metal borates and alkali metal stan ⁇ nates. Most preferred catalysts are potassium car ⁇ bonate, sodium meta-borate and sodium stannate.
• the choice of catalyst affects the per ⁇ centage of carbon dioxide units in the poly(alkyl- ene carbonate) polyol.
• the poly(alkyl ⁇ ene carbonate) polyol contains between 5 and 35 weight percent of the carbon dioxide.
• the use of most of the catalysts described hereinbefore results in a poly(alkylene carbonate) polyol in which about 10 percent of the units are carbon dioxide units, whereas the use of sodium meta-bor ⁇ ate results in about 25 percent carbon dioxide units, and the use of sodium stannate results in from 30 to 50 percent carbon dioxide units.
• percent means the percentage of the carbon dioxide units based on the total of the car ⁇ bon dioxide units and the alkyleneoxy units.
• a suitable amount of the catalyst is any amount which is catalytic under the reaction condi- tions.
• Preferable catalyst concentrations are between 0.01 and 5 percent by weight based upon the reactants, more preferably between 0.01 to 1.0 percent by weight, and most preferably between 0.05 to 0.1 percent by weight.
• a method of removing alkaline catalysts from polyether polyols and poly(alkylene carbonate) polyols comprises
• the molecular weights and distribution are determined by size 'exclusion chromatography on
• a 5:1 mole ratio of ethylene carbonate (EC)-: diethylene glycol (DEG) is heated with stirring under a nitrogen atmosphere for 7 hours at 150°C using 1.0 weight percent Na-,Sn0 3 3H_,0 as catalyst to give a 98 percent ethylene carbonate conversion; with prod ⁇ uct containing 23.1 weight percent carbon dioxide.
• Part B The product (20 weight percent in ace ⁇ tone) is stirred with Florisil (1 g/10-g product) for 3 hours to remove catalyst, followed by filtra ⁇ tion to remove catalyst and_ concentration to remove acetone. A sample (91.3 g) is placed in a two- -necked boiling flask and several boiling stones are added. The flask is equipped with a thermom ⁇ eter and heating mantel and attached to a distill ⁇ ing apparatus connected to a vacuum source, and subjected to fractionation.
• the maximum pot temperature is 185°C.
• a 10:1 mole ratio of ethylene carbonate (EC) :monoethylene glycol (MEG) is heated with stirring under a nitrogen atmosphere for 24 hours at 135°C using 1.0 weight percent Na 2 Sn0 3 3H 2 0 as catalyst to give a 100 percent ethylene carbonate conversion to a poly- (alkylene carbonate) polyol with 25.8 percent weight percent carbon dioxide.
• the polyol (20 weight percent in acetone) is stirred with Florisil (1 g/10-g polyol) for 2 hours to remove catalyst, followed by filtration and concen ⁇ tration.
• a sample (89.8 g) is subjected to fraction- ation at a maximum pot temperature of 194°C and' a pressure of 0.5 to 1.0 mm Hg (0.07 to 0.13 kPa).
• Distillate (21.2 weight percent) is recovered (3 percent monoethylene glycol, 86 percent diethylene glycol and 6 percent triethylene glycol).
• the residue is a light amber viscous liquid, with 32.1 weight percent carbon dioxide.
• Table I The results are compiled in Table I.
• Part A A 15:1 mole ratio of ethylene carbonate
• Example 1 The catalyst is removed as in Example 1.
• a sample (73.0 g) is subjected to fractionation with a maximum pot temperature of 210°C and a pressure of 0.5 to 0.8 mm Hg (0.07 to 0.11 kPa) to give a 20.7 weight percent distillate of 25 percent ethylene carbonate, 73 percent diethylene glycol and 1 percent monoethylene glycol.
• the residue is a light amber viscous liquid with 30.8 weight percent carbon dioxide.
• Table I The results are compiled in Table I.
• a 50:1 mole ratio of ethylene carbonate (EC) :monoethylene glycol (MEG) is heated with stirring under a nitrogen atmosphere for 88 hours at 135°C using 0.2 weight percent Na 2 SnO_ 3E_ 2 0 as catalyst to give 96.6 percent ethylene carbonate conversion to a poly- (alkylene carbonate) polyol with 27.6 weight percent carbon dioxide.
• Example 5 The catalyst is removed as in Example 1. A sample (184.4 g) is subjected to fractionation with a maximum pot temperature of 210°C and a pressure of 1.3 mm Hg (0.17 kPa) to give an 8.0 weight per- cent distillate of 71.5 percent ethylene carbonate and 25.3 percent diethylene glycol. The residue ' is a light amber viscous liquid with 29.3 weight percent carbon dioxide. The results are compiled in Table I. Example 5
• a 100:1 mole ratio of ethylene carbonate (EC) :monoethylene glycol (MEG) is heated with stirring under a nitrogen atmosphere for 121 hours at 135°C using 0.1 weight percent Na 2 Sn0 3 3H 2 0 as catalyst to give 92.5 percent ethylene carbonate conversion to a poly(alkylene carbonate) polyol with 26.9 weight per ⁇ cent carbon dioxide.
• Example 1 The catalyst is removed as in Example 1.
• a sample (72.7 g ) is subjected to fractionation with a maximum pot temperature of 227°C and a pressure of 1.5 mm Hg (0.20 kPa) to give a 9.4 weight percent distil- lation of 46.3 percent ethylene carbonate, 36.9 percent diethylene glycol and 6.9 percent triethylene glycol.
• the residue is a light amber viscous liquid with 30.0 weight percent carbon dioxide.
• Table I The results are compiled in Table I.
• a 1:2 mole ratio of diethyl carbonate (DEC):- diethylene glycol (DEG) is heated with stirring under a nitrogen atmosphere using 1.0 weight percent Na 2 SnO_ 3H 2 0 as catalyst.
• the pot temperature is allowed to increase from 122°C to 187°C during which time ethanol and some diethyl carbonate are removed from the reactor by distillation.
• the residue is a pol (alkylene car ⁇ bonate) polyol which is a liquid with 27.7 weight percent carbon dioxide.
• Example 2 The catalyst is removed as in Example 2. A sample (97.2 g) is subjected to fractionation at a maximum pot temperature of 215°C and a pressure of 0.3 to 2.0 mm Hg (0.04 to 0.27 kPa) to give a 9.5 weight percent distillate. The residue is a light amber viscous liquid with 33.4 percent carbon dioxide. The results are compiled in Table I.
• PDI stands for poly-dispersity index
• Example 1 shows that advancement of a 5:1 product can increase the molecular weight beyond that of a 50:1 product while reducing the poly-dispersity index (PDI). This is accomplished in only a fraction of the time required to make a 50:1 product.
• Example 2 shows that advancement of a 10:1 product can increase the molecular weight beyond that of a 100:1 product while reducing the poly-dispersity index. This is accomplished in only a fraction of the time required to make a 100:1 product, while remov ⁇ ing volatile impurities.
• Example 3 shows that advancement of a 15:1 product can increase the molecular weight by more than three-fold while maintaining a low poly-dispersity index.
• Example 4 shows that advancement of a 50:1 product can increase the molecular weight to about that of" a - 100:1 product but at greatly reduced poly-dispers ⁇ ity index and with removal of volatile impurities.
• Example 5 shows that the advancement of a 100:1 product can produce a high molecular weight, high purity product with a Tg of -13.9°C.
• Example 6 shows that advancement of a 2:1 DEG:DEC product can increase the molecular weight to about that of a 100:1 product but at a greatly reduced poly- -dispersity index and at much higher reaction rates.
• Part A A 10:1 mole ratio of ethylene carbonate and diethylene glycol is heated with stirring under a nitrogen atmosphere for 3 hours at 175°C using 0.5 weight percent Na 2 Sn0 3 3H 2 0 as catalyst to give 97.5 percent ethylene carbonate conversion to a poly(alkylene carbonate) polyol with 23.7 weight percent carbon dioxide.
• the catalyst is removed as in Example 1.
• a sample (1069.6 g) is subjected to fractional distillation for 2.5 hours with a max- imum pot temperature of 237°C and a pressure of
• the dis ⁇ tillate collected at -78°C accounts for 4.9 weight percent (51.9 g) of the sample charged and has the following assay: 60.23 percent acetone, 24.97 percent dioxane and 8.8 percent water (94.0 per- cent total).
• the residue is a light amber viscous liquid with 29.5 weight percent carbon dioxide, accounts for 77.4 weight percent (828.2 ' g) of the sample charged and has the properties shown in Table II.
• Example 7 shows scale-up data on a pre ⁇ ferred method using a 10:1 product. Reaction rates are rapid; complete distillate analysis is given.
• a 10:1 mole ratio of ethylene carbonate to diethylene glycol is heated with stirring under a nitrogen atmosphere for 24 hours at 135°C using 0.5 weight percent Na 2 Sn0 3 3H 2 0 as catalyst to give 91.6 percent ethylene carbonate conversion to a pol (alkylene carbonate) polyol with 21.3 weight percent carbon dioxide.
• the catalyst is removed as in Example 1.
• Part B A sample (525.8 g) is subjected to fractional distillation for 2.5 hours with a max ⁇ imum pot temperature of 235°C and a pressure of 10 mm Hg (1.3 kPa). Additional samples are sub ⁇ jected to fractional distillation to higher pot temperatures and a pressure of 10 mm Hg (1.3 kPa) The results are given in Table III. TABLE III
• Example 8 shows the effects of final pot temperature on molecular weight build and C0 2 content. High C0 2 content is retained in the prod ⁇ uct even at 275°C.
• a diethylene glycol initiated adduct is made from ethylene oxide and carbon dioxide at 175°C using sodium stannate trihydrate as catalyst.
• the catalyst is removed by the process described in Example 1. The residue is a poly(alkylene car ⁇ bonate) polyol with 17.8 weight percent carbon dioxide.
• Part B A sample (516.5 g) is subjected to fractional distillation for 2.5 hours with a max ⁇ imum pot temperature of 235°C and a pressure of 10 mm Hg (1.3 kPa). Distillate is collected in a water- -chilled condenser ( ⁇ 15°C) and a dry ice-isopro- panol trap (—78°C).
• the distillate collected at 15°C accounts for 31.2 weight percent (161.3 g) of the sample charged and has the following assay: 0.44 percent monoethylene glycol, 0.90 percent dioxane, 6.66 percent ethylene carbonate, 73.7 percent diethylene glycol, 15.19 percent triethyl- ene glycol, 1.29 percent tetraethylene glycol and 0.02 percent water (98.2 percent total).
• the dis ⁇ tillate collected at -78°C accounts for 0.7 weight percent (3.4 g) of the sample charged and has the following assay: 2.36 percent acetone, 85.73 per ⁇ cent dioxane and 2.6 percent water (90.7 percent total).
• the residue is an amber viscous liquid with 20.9 weight percent carbon dioxide, accounts for 67.1 weight percent (346.6 g) of the sample charged and has the properties shown in Table IV.
• Example- 9 shows- scale-up data on a- pre- - ferred method using a product made from ethylene oxide and carbon dioxide. Reaction rates are rapid to give a high molecular weight product with a rela ⁇ tively low poly-dispersity index (compare to 50:1 product) .
• Part A A 10:1 mole ratio of ethylene carbonate to polypropylene glycol having a molecular weight of 425 is heated with stirring under a nitrogen atmos ⁇ phere for 6 hours at 175°C using 0.5 weight percent sodium stannate trihydrate as catalyst to give 98 percent ethylene carbonate conversion to a poly-
• a sample (81.8 g) is subjected to frac ⁇ tional distillation with a maximum pot temperature of 235°C and a pressure of 10 mm Hg (1.3 kPa). Dis- tillate is collected in a water-chilled condenser
• the distillate collected at 15°C accounts for 9.8 weight percent (8.0 g) of the sample charged and has the following assay: 1.02 percent monoethylene glycol, 5.40 percent ethylene carbonate, 76.9 percent dieth ⁇ ylene giycol and 8.13 percent triethylene glycol.
• the distillate collected at -78°C accounts for 2.5 weight percent (2.1 g) of the sample charged and has the following assay: 69.1 percent acetone and 24.7 percent dioxane.
• the residue is a light straw viscous liquid with 12.7 weight percent carbon dioxide, accounts for 86.8 weight percent (71.0 g) of the sample charged and has the properties shown in Table V.
• Example 10 shows that a polypropylene glycol of 425 molecular weight can be used as ini ⁇ tiator.
• a 10:1 product is rapidly advanced to a high molecular weight product with relatively low poly-dispersity index.
• Example 11 shows that a polypropylene glycol of 425 molecular weight can be used as ini ⁇ tiator.
• a 10:1 product is rapidly advanced to a high molecular weight product with relatively low poly-dispersity index.
• Example 11
• a 10:1 mole ratio of ethylene carbonate to 1,4-butanediol is heated with stirring under a nitrogen atmosphere for 7 hours at 150°C using 0.5 weight percent sodium stannate trihydrate as cata ⁇ lyst to give 93 percent ethylene carbonate conver- sion to a poly(alkylene carbonate) polyol with 19.3 weight percent carbon dioxide.
• the catalyst is removed as in Example 1.
• a sample (92.5 g) is subjected to frac ⁇ tional distillation with a maximum pot temperature of 190°C and a pressure of 10 mm Hg (1.3 kPa). Dis- tillate is collected in a water-chilled " condenser ( ⁇ 15°C) and a dry ice-isopropanol trap (—78°C). The distillate collected at 15°C accounts for 25.3 weight percent (23.4 g) of the sample charged and has the following assay: 0.66 percent monoethylene glycol, 17.1 percent 1,4-butanediol, 76.9 percent diethylene glycol and 0.51 percent triethylene glycol.
• the distillate collected at -78°C accounts for 11.1 weight percent (10.3 g) of the sample charged and has the following assay: 22.0 per- cent acetone and 23.8 percent dioxane.
• the resi ⁇ due is a light straw viscous liquid with 25.2 weight percent carbon dioxide, accounts for 52.4 weight percent (23.4 g) of the sample charged and has the properties shown in Table VI . TABLE VI
• Example 11 shows that 1,4-butanediol can be used as initiator.
• a 10:1 product is rapidly advanced to a much higher molecular weight product.
• Some of the 1,4-butanediol is present in the distillate.
• a 10:1 mole ratio of ethylene carbonate to dipropylene glycol is heated with stirring under a nitrogen atmosphere for 4 hours at 175°C using 0.5 weight percent sodium stannate trihydrate as catalyst to give 100 percent ethylene carbonate conversion to a poly(alkylene carbonate) polyol with 14.7 weight percent carbon dioxide.
• the catalyst is removed as in Example 1.
• a sample (89.5 g) is subjected to frac ⁇ tional distillation with a maximum pot temperature of 235°C and a pressure of 10 mm Hg (1.3 kPa). Dis ⁇ tillate is collected in a water-chilled condenser and a dry ice-isopropanol trap. The distillate collected by the water-chilled condenser accounts for 20.2 weight percent (18.1 g) of the sample charged and has the following assay: 0.91 percent dioxane, 39.4 percent diethylene glycol, 55.8 percent dipro- pylene glycol and 0.30 percent triethylene glycol.
• the distillate collected in the dry ice-isopropa- nol trap accounts for 4.0 weight percent (3.6 g) of the sample charged and has the following assay: 24.2 percent acetone and 61.3 percent dioxane.
• the residue is a straw colored viscous liquid with 20.5 weight percent carbon dioxide, accounts for 71.5 weight percent (64.0 g) of the sample charged and has the properties shown in Table VII.
• Example 12 shows that dipropylene gly- col can be used as initiator. A 10:1 product is rapidly advanced to a molecular weight greater than a 50:1 product. Some of the dipropylene glycol is present in the distillate.
• the catalyst was removed as in Example 1.
• a sample (93.2 g) is subjected to fractional distillation with a maximum pot temperature of 235°C and a pressure of 10 mm Hg (1.3 kPa).
• Distillate is collected in a water-chilled condenser and a dry ice- • isopropanol trap.
• the distillate collected by the water-chilled condenser accounts for 10.8 weight percent (10.1 g) of the sample charged and has the following assay: 0.47 percent dioxane, 12.05 percent ethylene carbonate, 76.8 percent diethylene glycol and 2.85 weight percent triethylene glycol.
• the distillate collected in the dry ice-isopropanol trap accounts for 3.4 weight percent (3.2 g) of the sample charged and has the following assay: 85.0 percent acetone and 10.3 percent dioxane.
• the residue is a straw colored vis ⁇ cous liquid with 19.0 percent carbon dioxide, -accounts for 84.8 weight percent (79.0 g) of the sample charged and has the properties shown in Table VIII.
• Example 13 shows that a polyester polyol can be used as initiator. A 10:1 product is rapidly advanced to a much higher molecular weight product.
• the catalyst is removed as in Example 1.
• Part B A sample (91.3 g) is subjected to fractional distillation with a maximum pot temperature of 235°C and a pressure of 10 mm Hg (1.3 kPa). Distillate is collected in a water-chilled condenser and a dry ice- isopropanol trap. The distillate collected by the water-chilled condenser accounts for 13.6 weight per ⁇ cent (12.4 g) of the sample charged and has the fol ⁇ lowing assay: 0.85 percent dioxane, 7.27 percent ethylene carbonate, 51.2 percent diethylene glycol and 1.42 percent triethylene glycol.
• the distillate col- lected in the dry ice-isopropanol trap accounts for 5.8 weight percent (5.3 g) of the sample charged and has the following assay: 89.1 percent acetone and 9.3 percent dioxane.
• the residue is a straw colored viscous liquid with 22.1 percent carbon dioxide, accounts for 80.0 weight percent (73.0 g) of the sample charged and has the properties shown in Table IX.
• Example 14 shows that a different type of polyester, polyol .can.be used- as- ⁇ nit tor. —
• 10:1 product is rapidly advanced to a molecular weight much greater than a 100:1 product while maintaining a relatively low poly-dispersity index.
• a sample (87.1 g) is subjected to frac ⁇ tional distillation with a maximum pot temperature of 200°C and a pressure of 10 mm Hg (1.3 kPa).
• Dis- tillate is collected in a water-chilled condenser and a dry ice-isopropanol trap.
• the distillate collected by the water-chilled condenser accounts for 36.1 weight percent (31.4 g) of the sample charged and has the following assay: 3.68 percent dioxane, 2.03 percent ethylene carbonate, 66.3 percent diethylene glycol, 7.73 percent N-methyldietha- nolamine and 4.?1 percent triethylene glycol.
• the distillate collected in the dry ice-isopropanol trap accounts for 12.6 weight percent (11.0 g) of the sample charged and has the following assay: 30.7 percent acetone and 38.3 percent dioxane.
• the residue is a dark viscous liquid, accounts for 44.3 weight percent (38.6 g) of the .sample charged and has the properties shown in Table X.
• Example 15 shows that a material con ⁇ taining a tertiary nitrogen in its backbone can function as initiator. A 10:1 product is rapidly advanced to a higher molecular weight product.
• Example 16
• a 5:1 mole ratio of ethylene carbonate to thiodiethanol is heated with stirring under a nitrogen atmosphere for 6 hours at 150°C using 1.0 weight percent sodium stannate trihydrate as cata ⁇ lyst to give 92 percent ethylene carbonate conver ⁇ sion to a poly(alkylene carbonate) polyol.
• the catalyst is removed as in Example 1.
• a sample (93.4 g) is subjected to fractional distillation at a pressure of 10 mm Hg (1.3 kPa). Samples for molecular weight determination are removed at various pot temperatures up to 222°C. Distillate is collected in a water-chilled con ⁇ denser and a dry ice-isopropanol trap. The dis ⁇ tillate collected by the water-chilled condenser accounts for 44.4 weight percent (41.5 g) of the sample charged and has the following assay: 0.91 percent dioxane, 13.5 percent ethylene carbonate, 63.4 percent diethylene glycol, 11.3 percent thio ⁇ diethanol and 2.13 percent triethylene glycol.
• Example 16 shows that a material con ⁇ taining sulfur in its backbone can function as initiator.
• the molecular weight of a 5:1 product can be increased nearly five-fold by the process of this invention.
• a sample (97.6 g) is subjected to frac ⁇ tional distillation with a maximum pot temperature of 225°C and a pressure of 10 mm Hg (1.3 kPa).
• Dis- tillate is collected in a water-chilled condenser and a dry ice-isopropanol trap.
• the distillate collected by the water-chilled condenser accounts for 17.5 weight percent (17.1 g) of the sample charged and has the following assay: 0.79 percent monoethyl- ene glycol, 11.9 percent ethylene carbonate, 81.0 percent diethylene glycol and 1.22 percent trieth ⁇ ylene glycol.
• the distillate collected in the dry ice-isopropanol trap accounts for 2.3 weight percent (2.2 g) of the sample charged and has the following assay: 74.3 percent acetone and 16.8 percent dioxane.
• the residue is an amber viscous liquid with 12.9 ' percent carbon dioxide;- accounts ⁇ for 79.7 weight percent (77.8 . g) of the sample charged and has the properties shown in Table XII.
• Example 17 shows that an amino-func- tional material can be used as initiator.
• a 10:1 product is rapidly advanced to a much higher molec ⁇ ular weight product.
• Example 18
• a 50:1 mole ratio of ethylene carbonate to diethylene glycol is heated with stirring under a nitrogen atmosphere for 45 hours at 160°C using 1.0 weight percent sodium metaborate as catalyst to give 100 percent ethylene carbonate conversion to a poly(alkylene carbonate) polyol with 17.8 weight percent carbon dioxide.
• the catalyst is removed as in Example 1.
• a sample (105.7 g) is subjected to frac ⁇ tional distillation with a maximum pot temperature of 235°C and a pressure of 10 mm Hg (1.3 kPa).
• Dis- tillate is collected in a water-chilled condenser and a dry ice-isopropanol trap.
• the distillate collected by the water-chilled condenser accounts for 9.6 weight percent (10.1 g) of the sample charged and has the following assay: 1.19 percent dioxane, 60.9 percent diethylene glycol, 24.8 percent tri ⁇ ethylene glycol and 1.05 percent tetraethylene glycol.
• Example 18 shows that poly(alkylene carbonate) polyols made using sodium metaborate as catalyst can be advanced to much higher molec ⁇ ular weight products by the process of this inven ⁇ tion.
• a 10:1 mole ratio of ethylene carbonate to diethylene glycol is heated with stirring under a nitrogen atmosphere for 3 hours at 150°C using 1.0 weight percent potassium carbonate as catalyst to give 95 percent ethylene carbonate conversion to a poly(alkylene carbonate) polyol with 11.6 weight percent carbon dioxide.
• the catalyst is removed as in Example 1.
• a sample (102.2 g) is subjected to frac ⁇ tional distillation with a maximum pot temperature of 210°C and a pressure of 10 mm Hg (1.3 kPa).
• Distill ⁇ ate is collected in a water-chilled condenser and a dry ice-isopropanol trap.
• the distillate collected by the water-chilled condenser accounts for 20.3 weight percent (20.8 g) of the sample charged and has the following assay: 0.53 percent dioxane, 12.03 percent ethylene carbonate, 19.8 percent diethylene glycol, 35.3 percent triethylene gly ⁇ col and 7.54 percent tetraethylene glycol.
• the distillate collected in the dry ice-isopropanol trap accounts for 4.6 weight percent (4.7 g) of the sample charged and has the following assay: 58.8 percent acetone and 29.5 percent dioxane.
• the residue is an amber viscous liquid with 11.6 percent carbon dioxide, accounts for 69.8 weight percent (71.3 g) of the sample charged and has the properties ' shown in Table XIV.
• Example 19 shows that poly(alkylene carbonate) polyols made using potassium carbon ⁇ ate as catalyst can be advanced to higher molecu ⁇ lar weight products by the process of this inven- tion.
• Example 20 shows that poly(alkylene carbonate) polyols made using potassium carbon ⁇ ate as catalyst can be advanced to higher molecu ⁇ lar weight products by the process of this inven- tion.
• a 5:1 mole ratio of propylene carbon ⁇ ate to diethylene glycol is heated with stirring under a nitrogen atmosphere for 12 hours at 175°C using 1.0 weight percent sodium stannate trihydrate as catalyst to give poly(alkylene carbonate) polyol.
• the catalyst is removed as in Example 1.
• Part B A sample (91.3 g) is subjected to frac ⁇ tional distillation with a maximum pot temperature of 235°C and a pressure of 10 mm Hg (1.3 kPa). Dis ⁇ tillate is collected in a water-chilled condenser and a dry ice-isopropanol trap. The distillate collected by the water-chilled condenser accounts for 62.3 weight percent (56.9 g) of the sample charged and has the following assay: 0.93 percent propylene glycol, 25.6 percent propylene carbonate, 37.2 percent dipropylene glycol and 7.57 percent tri- propylene glycol.
• the distillate collected in the dry ice-isopropanol trap accounts for 3.6 weight percent (3.3 g) of the sample charged and has the following assay: 44.5 percent acetone and 15.9 percent dioxane.
• the residue is an amber viscous liquid, accounts for 32.1 weight percent (29.3 g) of the sample charged and has the properties shown in Table XV. TABLE XV
• Example 20 shows that propylene carbon ⁇ ate can be used to make poly(alkylene carbonate) polyols and that these polyols can be advanced to much higher molecular weights by the process of this invention.
• Part A Preparation of Poly(alkylene carbonate)
• Polyols A-F The desired mole ratio of ethylene car- bonate and alcohol is heated with stirring under a nitrogen atmosphere in the presence of sodium stannate trihydrate (1.0 weight percent) as cata ⁇ lyst to a high ethylene carbonate conversion. Af ⁇ ter reaction is complete, the catalyst is removed by stirring the product (20 weight percent in ace ⁇ tone) with Florisil (1 g/10 g product) for three hours, followed by filtration and solvent removal.
• Poly(alkylene carbonate) Polyol A A portion of Poly(alkylene carbonate) Polyol A is placed in a two-necked, 100-ml boiling flask and several boiling stones are added. The flask is equipped with a thermometer and heating mantle and attached to a distilling apparatus connected to a vacuum source. The polyol is subjected to fractionation to give a residue of 49.1 g of a light amber viscous liquid with a 31.0 weight percent carbon dioxide (96 percent carbon dioxide retention) .
• Example 27 shows that a poly(alkylene carbonate) polyol made using n-hexanol as initia ⁇ tor can be rapidly advanced to a molecular weight greater than a 50:1 product- while maintaining- a lower poly-dispersity index.
• Product analysis by proton nuclear magnetic resonance indicates no detect ⁇ able n-C 8 -C 17 moieties.
• Example 22 A portion of the Pol (alkylene carbonate) Polyol B is fractionated using the same equipment as in Example 21.
• the maximum pot temperature is 191°C at 0.7 mm Hg (0.09 kPa) pressure.
• the distil ⁇ late (17.5 g) contains 93 percent octanol, 2 per ⁇ cent dioxane and 4 percent diethylene glycol.
• the residue (63.4 g) is a light amber viscous liquid with 31.7 weight percent carbon dioxide.
• Example 22 shows that a pol (alkylene carbonate) polyol made using n-octanol as initi ⁇ ator can be rapidly advanced to a molecular weight of about that of a 50:1 product while maintaining a lower poly-dispersity index.
• Polyol C is fractionated using the same equipment as in Example 21.
• the maximum pot temperature is 193°C at 0.7 mm Hg (0.09 kPa) pressure.
• the distillate (12.8 g) con ⁇ tains 86 percent decanol, 12 percent diethylene glycol, 0.5 percent ethylene carbonate and 0.5 percent mono- ethylene glycol.
• the residue (59.8 g) is a light amber viscous liquid with 26.6 weight percent carbon dioxide (90 percent carbon dioxide retention).
• Example 23 shows that a poly(alkylene carbonate) polyol made using n-decanol as initi- ator can be rapidly advanced to a molecular weight greater than a 50:1 product while maintaining a lower poly-dispersity index ⁇ . Nearly half of the initiator remains in the product.
• Example 24 A portion of Pol (alkylene carbonate)
• Polyol D is fractionated using the same equipment as in Example 21.
• the maximum pot temperature is 170°C at l.l mm Hg (0.15 kPa) pressure.
• the distil ⁇ late (11.5 g) contains 65 percent diethylene glycol, 31 percent dodecanol, and 0.5 percent monoethylene glycol.
• the residue (51.9 g) is a light amber vis ⁇ cous liquid with 20.4 weight percent carbon dioxide (100 percent carbon dioxide retention).
• Poly(alkylene carbonate) Polyol ⁇ E is fractionated using-the same- equipment-- - as in Example 21.
• the maximum pot temperature is 194°C at 0.8 mm Hg (0.11 kPa) pressure.
• the distil- late (10.6 g) contains 35 percent ethylene carbon ⁇ ate, 21 percent dodecanol, 41 percent diethylene glycol and 0.5 percent monoethylene glycol.
• the residue (81.3 g) is a light amber viscous liquid with 28.0 weight percent carbon dioxide (94 percent carbon dioxide retention) .
• Examples 24 and 25 show that when a poly(alkylene carbonate) polyol made using n-do- decanol is used as initiator, product advancement to higher molecular weights can occur by the pro ⁇ cess of this invention but the majority of the initiator remains in the product.
• the sample is fractionated using the same equipment as in Example 27 above except that a 50-ml flask was used.
• the maximum pot tempera- ture is 198°C.
• the distillate (3.4 g) contains 95 percent butanol and 3 percent dioxane.
• the residue (33.2 g) is a light amber viscous oil with 28.8 weight percent carbon dioxide (100 percent carbon dioxide retention) .
• the sample (33.7 g) is fractionated using the same equipment as in (A) .
• the maximum pot tem ⁇ perature is 210°C.
• the distillate (3.1 g) contains 93 percent butanol and 5 percent dioxane.
• the resi ⁇ due (30.3 g) is a light amber viscous oil with 26.5 weight percent carbon dioxide (95 percent carbon dioxide retention).
• the sample (36.7 g) is fractionated using the same equipment as in (A).
• the maximum pot tem ⁇ perature is 253°C.
• the distillate (7.6 g) contains 50 percent butanol and 50 percent dioxane.
• the resi- due (23.7 g) is a light amber viscous oil with 26.8 weight percent carbon dioxide (69 percent carbon dioxide retention).
• Example 26 shows the effect of pressure on the molecular weight advancement of pol (alkyl ⁇ ene carbonate) polyols made using n-butanol as ini ⁇ tiator. As the pressure is lower, the C0 2 content and molecular weight increase while the n-butanol content in the product decreases.
• Part A An n-octanol initiated adduct is made from ethylene oxide and carbon dioxide at 150°C using sodium stannate trihydrate as catalyst.
• the catalyst is removed by the procedure described in Examples 21-26.
• the residue is a pol (alkylene car- bonate) polyol with 12.1 weight percent carbon diox ⁇ ide.
• Poly(alkylene carbonate) polyol is fractionated using the same equipment as Example 21.
• the maximum pot temperature is 190°C at 0.3 mm Hg (0.04 kPa) pressure.
• the distillate (17.8 g) contains 79 percent octanol, 1 percent monoethylene glycol and 1 percent diethylene glycol.
• the residue (13.9 g) is a light amber viscous liquid with 25.7 weight percent carbon dioxide.
• the alkanol moieties (97.2 percent) are removed by fractionation.
• Example 27 shows that a poly(alkylene carbonate) polyol made from ethylene oxide and carbon dioxide using n-octanol as initiator can be advanced to a high molecular weight product using the process of this invention.

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