JPS62501080A - Method for increasing the molecular weight of poly(alkylene carbonate) polyols - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention aims to increase the molecular weight of poly(alkylene carbonate) polyol. Regarding the method.

Poly(algylene car, 34 nate) polyol is used in the production of polyurethane. Useful as a surfactant.

Polyether polyols and polyester polyols are used to produce polyurethane. A well-known polymer that can be further polymerized with organic polyisocyanates to It is. Polyether polyols are hydroxy-containing hydrocarbons, such as aromatic or aliphatic diols and 1 epoxy V' such as ethylene oxide and propylene oxide. It is produced by reaction with Polyester polyols are polyacids, e.g. Dipic acid or terephthalic acid, or esters of polyacids such as dimethyl adipe or dimethyl terephthalate and dihydroxy-containing hydrocarbons, e.g. aromatic produced by reaction with group and aliphatic diols.

Some poly(alkylene carbonate) polyol properties are similar to polyester polyols. ol properties and other properties are similar to polyether polyols.

Phosgenation process (in which hydrogen chloride is produced or a base, such as pyridine or carbonic esters of alcohols or phenols, preferably preferably with the aid of diphenyl carbonate, and in some cases transesterification catalysts. Polycarbonate is produced from aliphatic dihydroxy compounds by the transesterification method. It is known to create In both cases, phosdan or - It is essential to use a mixture of carbon oxide and chlorine.

The methods involved in the production and handling of It is difficult and expensive due to the high cost of materials due to corrosion. This is an ecological issue accompanying. This is because the air used is contaminated with hydrogen chloride or the runoff water is This is because it is contaminated by IJium (chloride).

Polycarbonate produced by these methods using dihydrocarbyl compounds In subsequent reactions, the product can be used to form high molecular weight polymers. Due to insufficient or incomplete esterification or transesterification that often prevents It will have a functionality of 2 or more.

Poly(alkylene carnate) polyols are exemplified by Mmlkemus (U.S. Pat. No. 3,133,113). a Lukylene cargoes, such as ethylene cargoes, complete their reaction. under reduced pressure while removing the ethylene glycol formed by the reaction until glycol, such as diethylene glycol, in a molar ratio ranging from 1.2:1 to 2.5:1. It is disclosed that it can be reacted with a recall. The catalyst used is mixed Zinc borate-alkaline earth metal oxide catalyst.

U.S. Patent Nos. 3,248,414; 3,248,415 and 3,24 No. 8,416, 5tevsns (1) carbon dioxide and 1,2-epo Oxide: (2) a cyclic carbonate, such as ethylene carbonate; or (Poly(alkylev carb) from 3-cyclic carbonate and 1,2-epoxide Discloses a method for producing polyol (Nate). A small amount of polyol is used as an initiator be done. The reaction typically involves metal carbonates, metal hydroxides, and trisodium phosphates. The process is carried out under pressure in the presence of amines or tertiary amines.

Poly(alkylev carbonate) polyols are also. As a basic catalyst and initiator Ethylene carbs are produced by polymerization of nates under pressure using a small amount of glycol. (Buyach et al., U.S. Patent No. 4,105,641) . These products are produced by the decomposition of ethylene carbonate, resulting in a concentration of carbonate groups. low degree and high concentration of ether groups. The characteristics of St. In this patent, the patentee removes the unreacted ethylene cargo. In order to Poly(alkylene carboxylic acid) derived from monoethylene glycol exposed polyol. Ho5ts+tl*r (US patent no. 3.379.693) is similar to poly(alkylev carbonate) polyol. under a pressure of 1 to 5 mHg (0.13 to 0.67 kPa) Remove unreacted ethylene cargoes by heating them to about 130 °C at nate was removed.

Maximovich (U.S. Patent No. 3,896,090) Cargonate is reacted with diethylene glycol, and the reaction product is Ethylene cargoes and diethylene glycol that did not react when treated under reduced pressure removed.

Some researchers have used diol and alkylev carbonate reactants and poly( alkylev carbonate) with the products of polyol and monoethylene glycol. poly(alkylene carbonate) polyols and and related substances. The reaction is mediated by the removal of monoethylene glycol. It is adjusted accordingly.

Malk@mas (U.S. Patent No. 3,133,113) is a distillate For simultaneous removal of monoethylene glycol, 10 sm in the presence of a certain catalyst Ethylene cargo at 125°C to 130°C under reduced pressure of Hg (1,3 kPa) and diethylene glycol were reacted. After this time, the starting material was removed. this The method is that the ethylene car undergoes nate conversion while the monoethylene glycol is removed. Volatile ethylene condenses as a solid into the system, strictly plugging and reducing It has disadvantages due to the presence of cargoes. This method requires a very large amount of The linker needs Nate.

Springmann et al. (U.S. Pat. No. 3,313,782) We further investigated this method under reduced pressure in the presence of a medium and limited the reaction conditions. ; the reaction temperature is lower than the boiling point of alkylev carbonate, but It should be high enough to distill the monoethylene glycol.

Ll et al. (U.S. Pat. No. 4,131,731) have disclosed During the reaction with the anchorage, a stepwise reduction in pressure is used, where the final step is It was the removal of monoethylene glycol. RT permit holder is Alkylene Cargo that ester should have a boiling point 4.9°C higher than monoethylene glycol. Their reaction conditions were characterized by:

The equilibrium-based chemistry above describes monoethylene glycol as an azeotrope with the solvent. by carrying out the reaction in a solvent (e.g. cumene) that can remove , Buymch et al. (U.S. Pat. No. 4,105,641). It was.

In the above, -9 (alkylene carbonate) from alkylene carbonate /liol molecular weight is based on the stoichiometric amount of reactants (i.e., high alkali for high molecular weight). carbonate:initiator ratio) or monoethylene glycol from the reaction mixture. (where an ethylene chloride:initiator equivalence ratio of approximately 1 is used) It has been adjusted by one of the following.

A catalyst is most likely not used if the reaction rate is much slower in the absence of a catalyst. used. The high alkylene carbonate:initiator ratio is (lukylene carbonate) reaction rate when used to produce polyols decreases sharply as high conversion rates are approached; long reaction times are required and The product is contaminated by unreacted alkylene cargoes. There is. If the temperature is increased to increase its rate, the decomposition of the product is CO □ Occurs with loss. In the present invention, the rate of molecular weight production is accompanied by CO2 loss. Don't go fast. The choice of catalyst is poly(alkylene carbonate) polyol molecules. has an effect on CO2 retention and CO2 retention.

In each method, the selection of the ratio of starting reactants and catalyst depends on the polyester that can be produced. (Alkyrenker♂ne-))zt? provides an upper limit on the molecular weight of lJ-ol Ta. Furthermore, the products of such processes are of relatively low molecular weight and Such a wide molecule! Has a range. i.e. they have a high polydispersity index, and Often contaminated by unreacted starting materials and relatively low molecular weight reaction intermediates. It is. Additionally, the specific reactants and catalyst ratios used are dependent on the backbone of the chain. and has a significant effect on the amount of carbon dioxide component.

What is needed is the catalyst used in stoichiometric amounts and appropriate reaction rates. High molecular weight poly(alkylene carbonate) containing no low molecular weight contaminants. This is a poor method to produce nate)/liol. Furthermore, it is necessary is a polymeric poly(alkylene carnate) with a relatively low polydispersity index. ) A method for producing polyols. What is also needed is a high diacid Enables production of poly(alkylene carbonate) polyols with carbon content It's a method.

The present invention relates to dialkylene glycols, trialkylene glycols or initiator segment (the initiator is a dialkylene glycol or trialkylene glycol segment) (has a volatility about the same as or even higher than that of carbonate) to a high temperature extracted from a polyol, the dialkylene glycol, The poly(alkylene glycol) or the initiator is evaporated at a pressure that - gonate) polyol, and the poly(alkylene carnate) - Under conditions where the molecular weight of the lyol increases, the poly(alkylene carnate) polyamide Volatile dialkylene glycol, trialkylene glycol or poly(alkylene carbonate) polyol comprising removing the initiator. This is the only way to increase the molecular weight of the polymer.

This method produces high-quality products at a faster rate and higher purity than previously produced in the industry. This enables the production of secondary poly(alkylene carnate) polyols.

Furthermore, the method is applicable to the production of such polyols with various molecular weight degrees. It has considerable flexibility. Poly(alkylene carbonate) produced by this method Polyols have a high weight percent carbon dioxide content in the polymer backbone. and generally have a low polydispersity index.

The starting material in the process of the invention is a bosu (alkylene carnate) polyol. It is. Such compounds have a CO2 component and no and polyalkyleneoxyyl Contains a randomized polymer containing knits. That poly(alkylenka) -gonate) polyol is further treated with residues of initiator and unreacted starting material. as well as other relatively volatile reaction products. The alkyleneoxy component binds to oxygen. For a series of repeating units containing combined alkylene groups, where the carbon of the alkylev group The elements can be further substituted with hydrocarpyl moieties. The alkyleneoxy component is , the following formula: %formula%) [wherein R2 is 2 or more as defined below, and - is 2 or greater. Must be an integer; more preferably between about 2 and 10; even more preferably 2 or 4; and most preferably 2. Gia Lukylene glycol is a hydroxyl-terminated 2 with respect to one alkylene component, where the alkylene component is a hydrocarbyl component. It can be permuted in many ways. A preferred dialkylene glycol component has the following formula: %formula%) [wherein R2 is defined below].

・The preferred V% poly(alkylene/car-nate) polyol has the following formula: ・ [In the formula, R1 is R'-(X); R is water*, ha ron, nitro group, cyano group, C1-2o hydrocarbyl group or one or more ) and many of the following groups: halo, cyano, nitro, 'thioalkyl, t@rt-ami No, alkoxy, aryloxy, aralkoxy, cal? Nyldioxyalkyl , Cal is nyldioxyaryl, Cal? Nyldioxyaralkyl, alkoxyca is nil, aryloxycar is nil, aralkoxycar is nyl, alkylcar bunyl, arylcarzanyl, acylkylcarzanyl, alkylsulfinyl, Arylsulfinyl, aralkylsulfinyl, alkylsulfinyl, arylsulfinyl C1-2o hydrogen polysubstituted with lsulfonyl or aralkylsulfonyl groups R is a locarpyl group; R is an n-valent hydrocarbon group or 1 or It is also a hydrocarbon group containing many heteroatoms (0, N or S): m is 1 or more) is also a large integer: n is 1 to 25, each existing separately. is an integer; X is 1: y must be an integer from 1 to 40, each existing separately; and 2 is an arrangement of 1 to 100, each existing separately.] It is a random polymer.

One preferred class of -9 (alkylevcar nate) polyols is commonly to the following formula: [where R, R, X, n and m are the previously defined conventions: q is 0 or 1 that exists separately; and q is 1 or 1 that exists separately. is also a large integer].

In the formula defined above, R2 is preferably hydrogen.

C1-2o alkyl, C1-2o haloalkyl, C1-2゜alkenyl or is phenyl): R2 is more preferably hydrogen, C1-3 alkyl, C2-, R2 is more preferably hydrogen, methyl or phenyl; R2 is even more preferably hydrogen or methyl; and most preferably Preferably hydrogen. R3 is preferably an aliphatic or alicyclic hydrocarbon or Also, aliphatic or cycloaliphatic carbon containing a large amount of oxygen, nitrogen or sulfur components. R3 is more preferably n-valent alkane or cycloalkaline. (or one or more) is also a lot of oxygen.

J is an n-valent alkane or cycloalkane containing nitrogen or sulfur component. ): R3 is even more preferably an n-valent C alkane or 1 or ~10 It is also a C1-1o alkane which is polysubstituted with many oxygen components. X is good Preferably, X is S, 0, or O; most preferably, X is O. Preferably, m is 1-10, preferably 1-5. Preferably, n is 1 to 10 (1 and 1 Must be an integer from 1 to 5 (including 0); preferably from 1 to 5 (including 1 and 5); The most preferred is 1 or 2. Preferably, q is between 1 and 1000 (1 and 1 and most preferably an integer between 1 and 500 (including 1 and 500); ) is an integer. Preferably y is 5 to 20, and 2 is 20 to 50. It is.

The product of this method is similar to the starting poly(alkylene carnate) polyol. It is also a poly(alkylene carbonate) polyol with a high molecular weight. child Molecular weight of poly(alkylene carbonate) polyol produced by the method of can be a desired molecular weight that is higher than the starting molecular weight. preferable The molecular weight should be between 500 and io, ooo, and the most preferred molecular weight is 1,0 It is between 00 and 8,000. The product produced is based on the starting poly(alkylene carbonate). - is slightly higher than the nate) polyol, or in some cases even lower. has a polydispersity index (Mw/Mn). The polydispersity index is the graded growth weight. It is known that the molecular weight increases as the molecular weight increases. manufactured generation The material contains a high weight percent CO□ in the backbone as well as the starting material. Starting material that did not react The starting poly(alkylene car) is a nate. ) removed during polyol production.

The method of the invention preferably comprises a dialkylene glycol component, a trialkylene glycol component, Recall components and/or dialkylene glycols present or as volatiles or cause the separation of components that are more volatile than the triple glycol component. In order to strain the poly(alkylevcar nate) polyol at high temperature under reduced pressure conditions. exposing and removing such volatile components from the reaction mass. general Typically, the nor'alkylene glycol and/or initiator will volatilize. used The precision and CO2O2 content values that are Lukylene glycol can be separated. Poly(alkylene carbonate) If the polyol starting material does not contain dialkylene glycol units, thoria Lukylene glycol units can be removed by this method. In general, The lightest fraction that separates from the starting material will be removed. -Li(alkylene) carbonate) polyols are monofunctional, i.e. the initiator is only one Because they have active hydrogen sites, in these embodiments the initiator flag may be activated under certain circumstances. The sialkylene glycol fragments are also volatile and Therefore, the dialkylene glycol moiety is also more easily separated and removed. There will be. When the initiator is a linear C1-8 alcohol, dialkylene glycol Before the call fragment would be removed, the C1,8 alcohol fragment will be removed. Linear C1° or C1, alcohol used as initiator when the C or C1 alcohol is the same as dialkylene glycol. are volatile and therefore should be separated at the same time. Linear C12 or its If a large alcohol is the initiator, the dialkylene glycol is is more volatile and will separate. Branched alcohol initiators are somewhat sialkylene glycol or trialkylene glycol. may be separated based on their relative volatility compared to call fragments. Dew.

Volatile components may be removed by methods known in the art. like that The method is fractional distillation.

including passing an inert gas over the reaction mass to remove volatile species; As is known in the art, volatile species condensed by a water cooler such as Other methods for removal, such as falling film stills g fllm 5till), for example, a wiped film evaporator (wiped film evaporator) fjlm evaporator) is particularly useful. for condensing distillate A preferred method of is by the use of a water cooler. Most volatile components, and For example, acetone and water (both introduced during catalyst removal) and nooxane (this (a small amount of water may be present during decomposition) under reduced pressure conditions used. and can be condensed using a dry ice condenser. by water cooler The condensed volatile species are recycled and the I (fulkylene carbonate)/Used as an initiator for the production of lyol. obtain.

The process of the invention is carried out at a temperature at which separation of volatile segments occurs. Lower temperature limit is the temperature at which the volatile components separate and separate, and the upper temperature limit is the temperature at which the volatile components This is the temperature at which the polyol (carbonate) decomposes. The preferred temperature is 150℃~ It is between 300°C. The preferred temperature is between 175℃ and 260℃, and A temperature between 200°C and 250°C is most preferred.

The pressures used in this method also include dialkylene glycols or species as volatiles. Dialkylene glycol is also a more volatile species, which evaporates at the temperature used. This is the pressure that will occur. Preferred pressures are atmospheric pressure and reduced pressure, and reduced pressure Gayop is preferable.

The preferred pressure is as low as 300 mHg (40, OkPa), and Even more preferable is 100ms+Hg (13,3kPa), which is also low. More preferably as low as 50 Hg (6,67 kPa) and most preferably is between 10 and 30 mHg (1,33 and 4.00 kPa).

Before carrying out this method, a poly(alkylene carnate) polyol is produced. Therefore, it is preferable to remove the used catalyst. Because such touch The medium is a poly(alkylene carbonate) polymer at the temperatures used in this method. This is because it causes decomposition of the oar.

Trace amounts of such catalysts can be present without significant decomposition. large amount The catalyst is preferably removed before carrying out the promotion process. very low catalyst The combination of short reaction times in the presence of high molecular weight structures with minimal decomposition Depending on e.g. temperature, pressure and molecular weight of the desired product, Ru. At low pressures and high temperatures, the time to achieve the desired molecular weight is short. how to do that can be carried out for a sufficient time to obtain the desired molecular weight. Reaction time is compared In most cases, only a few hours are required.

The method of the present invention generally involves processing poly(alkylene carbonate) in a form appropriate to the processing conditions. ) by exposing the polyol. This method is suitable for Although it is preferred to carry out the method, it may be carried out in a solvent. Useful melt The medium has a boiling point higher than that of the dialkylene glycol or most volatile species. Contains an inert organic solvent.

Poly(alkylene carnate) polyol starting materials useful in the present invention include: Any method known in the art, such as alkaline catalysts or alkaline compounds. alkylene carbonate: carbon dioxide and alkylene oxide in the presence of metal salts of : or alkylevcar is nate, alkylene oxide and/or CO□; Reyoshi is also activated by condensation with an organic compound (initiator) containing many activated water molecules. Manufactured by Examples of Kolera's poly(alkylene carbonate) polyols and this Methods for producing these polyols are described by Maylmovlch, USA. Patent No. 3,896,090: Maxlmoviah, U.S. Patent No. 3,68 No. 9,462; Springmann, U.S. Pat. No. 3,313,782: SL@v@ns e U.S. Patent No. 3.24m'8,416; Stsvenm #U.S. Patent No. 3,248,415; and 5taven, s., USA Included in Patent No. 3,248,414.

Examples of useful I(alkylene carnate) polyol starting materials have the following formula: [In the formula, s　R2a　R’　#　X　s　n　e　P and q are the previously defined It is expressed by

On the other hand, poly(alkylene carbonate) polyols are sialyl carbonate or a diaryl and an initiator having two or more hydroxyl molecules. It can be produced by reacting ξ and K.

For example, U.S. Patent No. 4,476.293 and U.S. Patent No. 4.191, See No. 705.

The alkylene carbonates useful in the reaction have reactive hydrogen-containing functional groups. It is something that will likely react. Preferred alkylene carbonates have the following formula: where R2 is as defined above.

Dialkyl carnates useful in the present invention have the following formula: and preferably a linear equation: where R2 is the previously defined formula.

R is preferably hydrogen or a monovalent C alkane, 1 to 40 C1-20 haloalkane #C1-20 alkene or benzene group. R2 is More preferably hydrogen, or a monovalent C1-3 alkane, C2-, alkene or ben It is a zen group. R2 is most preferably hydrogen, or monovalent methane or ethane .

Examples of preferred alkylene carbs include ethylene carbs and propylene carbs. -ganate, buterenecapo $-), vinylencar z4-) and 7E2 V7fJ -Including & Nate. More preferred alkylene carbonates are ethylene and propylene carbonates. Pirenkar includes Nate. An example of a preferred dialkyl carbonate is dimethyl carbonate, diethyl carbonate and dialkyl carbonate. Like The new diaryl car is nate and the diphenyl car is nate.

Epoxides useful for preparing the starting materials for this invention include CO2 or organic Functional groups on a compound (containing active hydrogen) to add nits.

Preferred epoxides have the following formula: where R2 is the same as defined above.

Among the preferred epoxides are alkylene oxides, such as ethylene oxide, polymer oxides, Lopyrene, tstyrene oxide; epihalohydrin, taboebibromohydrin and Shrimp chlorohydrin; styrene oxide, vinylene oxide, cyclohexene oxide; oxidation Cyclopentene 12 cycloheptene, 2,3-epoxyglobylphenyl ether and human t@rt-butyl glycidyl ether. Among the preferred epoxides Includes ethylene oxide, propylene oxide, butylene oxide, shrimp chlorohydrin, Bibromohydrin, styrene oxide and vinylene oxide.

Organic compounds containing active hydrogen atoms (initiators) are hydrocarbons or 1 containing reactive hydrogen atoms. one or more of oxygen, nitrogen or sulfur, containing between ~250 functional groups It is a hydrocarbon that is tu-substituted by a heteroatom. Among the preferred initiators are: Formula:% formula%) where R', X and n are the same as defined above.

Functional groups containing reactive hydrogen are converted to alkylene carbs in the presence of carbon dioxide.

Noalkyl carbonate, diaryl car? easily with nates or alkylene oxides In the present invention, any component containing a hydrogen atom that will react is meant.

More specifically, a reactive hydrogen is one that is directly bonded to an oxygen, nitrogen or sulfur atom. ・Hydrogen that is Found in mido, marcabuto or carboxyl groups.

The active hydrogen atom-containing organic compound (initiator) of the present invention comprises one or more The following functional groups: hydroxyl, amine, mercaptan, cargoxyl, sulfone, Contains amides, imides or carbonates. Furthermore, the initiators are Other groups on the structure, such as sulfone, sulfoxide, sulfide, amine, amino carbonates, ethers, esters, carbonates, and the like.

Among the preferred initiators are polyols such as aliphatic polyethers and polyethers. Sterpolyol.

Cycloaliphatic polyols, aromatic polyols and oxy- or polymeric mercagutans; polyamide 2 or more, containing water, alkylolamine and reactive hydrogen. There are also organic compounds containing many of the above functional groups. The preferred class is polio polymers, polyamines, and polymerkabutanes. Examples of active hydrogen-containing compounds are The contents of the U.S. patents incorporated herein by reference are hereby incorporated by reference. -2 or more initiators, including poly(alkylene carbonate) Can be used in combination to obtain oars = - The catalysts used in the production of polyether polyols are alkali metal hydroxides, Alkaline earth metal hydroxides, alkali metal carzanates, alkaline earth metals carbonate, ammonium hydroxide and ammonium carbonate.

Active hydrogen-containing organic compounds, alkylene carbonates, and dialkyl carbonates , sialyl carbonate, alkylene oxide and -carbon oxide, or alkylene oxide for reaction with alkylene carbonate mixed with carbon dioxide and/or carbon dioxide. Preferred catalysts include ester-substituted catalysts. Among the preferred catalysts are lithium, Sodium, potassium, lupine.

Cesium, magnesium, calcium, trontium, barium, zinc, aluminum Luminium, titanium.

Cobalt, germanium, M, lead, antimony, arsenic and cerium and their alkyl There is lucoxide. Examples of other preferred catalysts include alkali metal carbonates, alkali metal carbonates, alkali earth metal carbonate, ammonia pentacarbonate, alkali metal carbonate acid salts, alkaline earth metal borates, ammonium borates, hydrocarbyloxythi tanate, zinc borate, lead borate, zinc oxide, lead silicate, lead arsenate, litharge, lead carbonate, Antimony trioxide, r-rumanium dioxide, cerium trioxide and hyaluminum iso There is propoxide. Examples of other preferred catalysts include magnesium, calcium, Salts of organic acids of aluminum, zinc and titanium.

Alkali metal stannate, alkali metal stannate and ammonium stannate.

Examples of borate catalysts are sodium metaborate, sodium metaborate tetrahydrate, Sodium borate pentahydrate, pentafnj acid) IJum pentahydrate, l! ! aJl& Sodium + hydrate, sodium tetraphosphate pentahydrate, zoammonium tetraborate tetrahydrate ammonium hydrogen tetraborate tetrahydrate, lithium ortho-dihydroborate, metaborate Lithium oxide, lithium tetraborate, lithium pentahydrate, potassium metaborate, tetraborate Potassium borate tetrahydrate.

4 fj) I l! & potassium pentahydrate, potassium pentaborate tetrahydrate.

Magnesium Metaborate Trihydrate, Dijijll & Magnesium, Orthoborate Mag nesium, calcium metaborate.

Contains calcium tetraborate and strontium tetraborate tetrahydrate. An example of a stannate catalyst is , sodium stannate trihydrate, potassium stannate trihydrate, potassium stannate hydrate, tin Contains acid noranium trihydrate and magnesium stannate trihydrate.

Preferred catalysts include alkali metal carbonates and alkaline earth metal carbonates. ammonium carbonate, alkali metal stannate, alkaline earth metal catalytic acid. The medium includes alkali metal cardinates, alkali metal borates and alkali metal borates. It is a stannate.

The most preferred catalysts are potassium carbonate, sodium metaborate and sodium stannate. be.

Catalyst selection is carbon dioxide in poly(alkylene carbonate) polyols Does not affect unit percentage. General K, poly(alkylene carbonate) The polyol contains 5-35% by weight carbon dioxide. Most of the previously mentioned The use of catalysts is particularly important in poly(alkylene) where approximately 10% of the units are carbon dioxide units. However, the use of sodium metaborate yields approximately 25 carbon dioxide units, and the use of sodium stannate yields 3 yielding 0 to 504 b carbon dioxide units. In such a relationship, partners Cents are based on the sum of carbon dioxide units and alkyleneoxy units. Means the percentage of carbon oxide units.

A suitable amount of catalyst is any amount that is catalytic under the reaction conditions. preferred touch The medium concentration is from 0.01 to 5% by weight, based on the reactants, more preferably from 0.01 to 1%. ．． 0% by weight, and most preferably 0.05-0.1% by weight.

I-reather polyol and poly(alkylene carbonate) polyol The method for removing the alkaline catalyst is (&) Polyether polyol or poly(alkylene carbonate) in neutral solvent ) dissolve the polyol; (b) dissolve the polyether polyol or pre(alkylene); carbonate) polyol solution and an alkaline catalyst to absorb the alkaline catalyst. a sufficient amount of absorbent to absorb the catalyst, and the absorbent to absorb the alkaline catalyst. contacting at a temperature between about -30°C and 110°C under conditions; and (c) physically separating the absorbent from the polyol solution.

The following examples are for illustrative purposes only and are not intended to limit the scope of the invention or claims. . Unless otherwise limited, all parts and percentages are by weight.

Molecular weight and distribution were determined serially using tetrahydro7 run (TI(F)) as the mobile phase. Wat@rs TJ1traatyrag*’l@1000A and 10,00 Determined by size exclusion chromatography on a zero column and narrow range molecular Calibrate with a poly(ethylene glycol) standard).

5:10 molar ratio of ethylene glycol (EC) and diethylene glycol (DE) C) at 150°C using 1.0 wt s of Na, Sn0.3H,O as a catalyst. 7 hours.

Heat with stirring under a nitrogen atmosphere, and add 98% ethylene chloride. Get nate conversion rate , and the product contains 23.1 wt-carbon dioxide.

No mother - B = The product (20 wt Is in acetone) was dissolved in Florisil (1,9/10-.9 product) for 3 hours to remove the catalyst, then filter to remove the catalyst. , and concentrate to remove acetone. Sample (91,3,l, 2- Place the neck in a boiling flask and add a few boiling stones to dry. That flask is A distillation apparatus equipped with a thermometer and heating mantle and connected to a vacuum source. connected and left to their own devices.

Maximum pot temperature is 185°C. The pressure is 0.5 to 1.0 mWg (0, 07-0.13 kPa). Distillate (24g) is collected (9 2% diethylene glycol and 7% ethylene car? Nate).

The residue is a pale amber viscous liquid with 29.0% carbon dioxide by weight. Ru. The results are shown in Table 1.

Ethylene glycol (EC):monoethylene glycol (EC) with a molarization ratio of 10:1. MEG) using 1.0 wt% Na25nO,3H20 as a catalyst. Heating at 35°C for 24 hours with stirring under nitrogen atmosphere, 25.8% by weight of diacid 100% ethylene to poly(alkylene carnate) polyol with carbon The linker gets the nate conversion rate.

Parable B: The polyol (20% by weight in acetone) was mixed with 7'loridyl (1,9/1O- J polyol) for 2 hours to remove the catalyst, then filter and concentrate. sa sample (89.8 g) at a maximum pot temperature of 194°C and 0.5-1.0 mHg. (0.07 to 0.13 kpm). Distillate (21, (2% by weight) (3% monoethylene glycol, 86% diethylene glycol) It is a pale amber viscous liquid containing 60% triethylene glycol.

The results are shown in Table 1.

15:1 molarization of ethylene glycol (EC) and diethylene glycol (D EC) using 1.0 wt% Na25n033H20 as catalyst, ℃ for 8 hours with stirring under a nitrogen atmosphere, and 21.8 wt. 95.7% ethylene carbonate to poly(alkylene carnate) polyol with -Tene-) Obtain the conversion rate.

Note B: The catalyst is removed as in Example 1. Sample (7a, oIi), 210 Maximum pot temperature in °C and 0.5-0.8 mHg (0,07-0.11 kPa 20.7 wt. of distillate (25 g. of ethylene) 73% diethylene glycol and 1% monoethylene glycol ).

The residue is a pale amber viscous liquid with 30.8% carbon dioxide by weight. Ru. The results are shown in Table 1.

Ethylene car with a 50:10 molar ratio? Ne) (EC): Monoether glycol (MEG) using 0.2wt i% Na2.5nOs 3H20 as the four medium. , heated at 135°C for 88 hours with stirring under nitrogen atmosphere to give 27.6 wt. 96.6% to carbon dioxide (alkylene carbonate) polyol Ethylene car obtains nate conversion rate.

/ Parable B: The catalyst is removed as in Example 1. Sample (184.4g), 210 maximum pit temperature of 8.0 F% distillate (71.5% ethylene carbide). and 25.3 m of diethylene dalicol). The residue is 29.3 It is a thin amber viscous liquid with a weight of -90% carbon dioxide. The results are shown in Table 1. show.

100:1 molar ratio of ethylene carbonate (EC):monoethylene glycol (MEG) using 0.1 wt% Na25n0.3H20 as a catalyst. 121 hours at 135°C 1. Heating with stirring under nitrogen atmosphere, 26.9% by weight 92.5 to 17 (alkylene carnate) polyol with carbon dioxide of % ethylene car obtains nate conversion rate.

ノ4'-)B: The catalyst is removed as in Example 1. Sample (72,7N), t- At a maximum pot temperature of 1227 °C and a pressure of 1.5 m% (0,20 kPm, ) 9.4% by weight distillate (46.3% ethylene carbonate) , 36.9% diethylene glycol and 6.9% triethylene glycol) get. The residue is a pale amber viscosity with 30.0 wt. It is a liquid. The results are shown in Table 1.

l: 2 mol of 2 ethylene carbonate) (DEC) diethylene glycol (DEC) using 1.0 wt% Na25n033■20 as a catalyst. Heat while stirring in an elementary atmosphere. Set the pot temperature to 122°C to 187°C. and while the ethanol and some diethyl alcohol evaporate the nates. It is removed from the reactor by distillation. The residue contains 27.7% carbon dioxide by weight. The liquid poly(alkylene carboxylate) 4-riol has

Nogichito B: The catalyst is removed as in Example 2. Sample (97,2!ri, 215℃ maximum pot temperature and 0.3~2.0 mug (0.04~0.27 kPa )) to obtain a distillate of 9.5 liters. The residue is 33 ．． It is a thin amber viscous liquid with 4% carbon dioxide. The result is MI Shown in the table.

Example 1 shows that the promotion of the 5:1 product is 5:1 while the polydispersity index (PDI) is reduced by 1. This shows that it is possible to increase the molecular weight beyond the promotion of 0:1 products. ,this is, Achieved in only a fraction of the time required to produce a 50:1 product be done. Example 2 shows that the promotion of the 10:,1 product reduces the polydispersity index while This shows that it is possible to increase the molecular weight by more than 100:1 product promotion. child This is necessary to produce a 100:1 product 1 while removing volatile impurities. This can be achieved in only a fraction of the time required. Example 3 shows that the promotion of the 15:1 product is We show that it is possible to increase the molecular weight by more than 3 times while maintaining a low polydispersity index. vinegar.

Example 4 shows that the promotion of a 50:1 product is equivalent to the promotion of a 100:1 product per molecule it- However, it has a very low polydispersity index and is highly volatile. This shows that it is possible to remove sexual impurities.

Example 5 shows that the promotion of the 100:1 product is a high molecular weight product with a Tg of -13.9°C. It shows that high purity products can be produced. Example 6 is 2:1 DEG : Promotion of DEC products can increase the molecular weight as well as promotion of 100:1 products. However, it has a very high polydispersity index and a very fast reaction rate. Show that.

Part A: 10:1 molar ratio of ethylene carbonate:diethylene glycol as catalyst Using 0.5 wt% Na25n0,3H202, nitrogen at 175°C for 3 hours, Poly(alkylene chloride) containing 23.7% by weight of carbon dioxide was heated with stirring under air. 97.5% ethylene carnate conversion rate to polyol obtain. The catalyst is removed as in Example 1.

Part B: The sample (1069,6p) was heated to a maximum pot temperature of 237°C and 10 mHg. Subject to fractional distillation at a pressure of (1,3 kPa) for 2.5 hours. distillate, water Cooler (~15℃) and dry ice-Inglono Mother Shield Dry 7' (~ -78°C). The distillate collected at 15°C is used to fill the sandals. It accounts for 16.7% by weight (179,1Ii) and has the following assay value: 0.30 % monoethylene glycol, 1.51% dioxane, 10.49% ethylene Cargonate, 76.21% diethylene glycol, 10.04% trie tyrene/”li-x-pv, 0.70% tetraethylene glycol and 0.05 J water (99,4% total). Distillate collected at -78°C is charged to the sump. occupies 4.9 weight% (51,9,?) of Le, and has the following test: 60.2 3% acetone, 24.97ts Nodio*san and 8.8% water (94.0-mer total). The residue is a pale amber viscosity with 29.5% carbon dioxide by weight. It is filled with sexual fluid, accounting for 77.4% by weight (828,2,P) of the sandal filled. , and has the characteristics shown in Table ①.

Table ■ Example 7 shows expanded data based on the preferred method using a 10:1 product. reaction Speed is fast; complete distillate analysis is provided.

10:1 molar ratio of ethylene carbonate:diethylene glycol as catalyst 0.5 wt% Na□5n033H20 at 135°C for 24 hours with nitrogen'' #Heat under pressure with stirring under ambient air, and add poly( Alkylene carbonate) 91.6% ethylene carbonate conversion to polyol Get the rate. The catalyst is removed as in Example 1.

/4-), 13: Sangur (525, 8, 9) with a maximum pot temperature of 235 °C and 10 smog Subject to fractional distillation for 2.5 hours at a pressure of (1.3 kPm). More/G fractionated at a higher pot temperature and a pressure of 10 mHg (1,3 kPa). do.

The results are given in Table m.

vision Example 8 shows the effect of final pot temperature on molecular weight structure and CO2 content. high The high CO content is retained in the product even at 275°C.

Adduct gold initiated by diethylene glycol, sodium stannate as catalyst Produced from ethylene oxide and carbon dioxide at 175°C using trihydrate. catalyst is removed by the second son method described in Example 1. The residue was 17.8% by weight. Sump with carbon dioxide (alkylene carnate) polyol/I/ (516,51) maximum pot temperature of t-1235 °C and 10 mI (g (1, Subject to fractional distillation at a pressure of 3-kP+a) for 2.5 hours. Distillate, water cooled (~15°C) and dry ice-isoglopa shieldra, f (~-78°C). Collect more. The distillate collected at 15 °C is charged to the sample l7) 31.2 Heavy f! [occupies (1st, 39) and has the following test: 0.44% mono Ethylene glycol, 0.901 dioxane, 6.66% ethylene car ), 73.7J diethylene glycol, 15.19% triethylene glycol cole, 1.29% tetraethylene glycol and 0.02 t water (98,2 total). The distillate collected at -78°C is 0.7% by weight of the sample to be filled. % (3,4y) and has the following test: 2.36 t acetone, 85 ．． 73% dioxane and 2.6% water (90.7% total). The residue is 20 ．． It is an amber viscous liquid with 9 mi'It% carbon dioxide and is filled with It accounts for 67.1% by weight (346.6iF) of the sample sample and is shown in Table ■. It has the following characteristics.

Table ■ No -17,86214286711,560 Yes 67.1 20.9 4365197341412.098 Example 9 is from ethylene oxide and carbon dioxide Figure 2 shows expanded data based on a preferred method of using the product produced. The reaction rate is Fast, high molecular weight product with low polydispersity index (when compared to 50:1 product) give a product.

Ethylene car with a mol ratio of 10:1? nate: polypropylene glycol (425 gold with 0 molecular weight, 0.531ii% sodium stannate trihydrate as fluxing medium Heat at 175°C for 6 hours with stirring under a nitrogen atmosphere using a 10.8 9 to Isu (alkylene carnate) polyol with wt% carbon dioxide 8 thiethylene carbonate conversion is obtained. The catalyst was removed as in Example 1. be done.

Part B: s/f (81,8 N) at a maximum pot temperature of 235°C and 10 wHg (1 , 3 kPa'). The distillate was stored in a water cooler (~15°C). and collected in a dry ice-isopronol trap (~-78°C). 15 The distillate collected at °C accounts for 9.8% by weight (s,oy) of the sample to be and has the following assay: 1.02% monoethylene dalico, 5,40 of ethylene carbonate, 76.9' of diethylene glycol and 8.13 % triethylene glycol. The distillate collected at -78°C is 2.5% by weight of the pull (2, II) and has the following assay: 69.1% of acetone and 24.7 of dioxane. The residue is 12.7% by weight of dioxide A thin straw-colored viscous liquid containing carbon, Mitsuru JJ [Reta? sample of 86.8 % by weight (71,0,9) and has the properties shown in Table 7.

Table 7 Accelerated residue CO2 molecular weight r-ta No -10,813238171562,1,91 Yes, fl, 6.8 12.7 3021187038912.08 Example 10 is a polyester with a molecular weight of 425. It is shown that propylene glycol can be used as an initiator.

10:1 products rapidly promote to high molecular weight products with relatively low polydispersity index be done.

A 10:10 molar ratio of ethylene carbonate:1,4-butanediol was used as a catalyst. using 0.5% by weight of sodium stannate trihydrate at 150°C for 7 hours. Heating with stirring in an elementary atmosphere, poly( 93 ethylene carbonate conversion rate to polyol (alkylene carbonate) obtain. The catalyst is removed as in Example 1.

Noso B: The sample (92,5F) was heated to a maximum pot temperature of 190℃ and 10■Hg (1, Subject to fractional distillation under a pressure of 3 kPa). The distillate was stored in a water cooler (~15°C) and and dry ice-isopropano-/I/):llF, 7° (~-78°C ) to collect. The distillate collected at 15°C weighs 25.3% of the packed sample. % (23,4,9) and has the following test: 0.66% monoethylene glycol, 17.1% 1,4-butanediol, 76.9% diethylene Glycol and 0.51% triethylene glycol. Steam collected at -78℃ The distillate occupies 11.1 parts (10,3 g) of the packed sample, and Have the following assay: 22. O% acetone and 23.8% dioxane. So The residue is a pale straw-colored viscous liquid with 25.2% carbon dioxide by weight. and accounted for 52.4% by weight (23,41) of the filled sample, and Table It has the characteristics shown in .

Table ■ Accelerated residue CO2 molecular weight data No -19,32583574891,37 Yes 52.4 26.2 1 16181913321.63 Example 11 uses 1,4-butanediol as the initiator. Indicates that it can be used as The 10:1 product rapidly promotes higher molecular weight products. will be advanced. Some of the 1,4-butanediol is present in the distillate.

A 10:1 molar ratio of ethylene carbonate dipropylene glycol was used as a catalyst. and nitrogen at 175°C for 4 hours using 0.5 fl-fl sodium stannate trihydrate. Poly( 100% ethylene carbon & $-t conversion rate to alkylene power-〆nate) polyol get. The catalyst was removed as in Example 1 by adding a sample (89.5 g) to 235 The maximum pot temperature of ℃ and the pressure of 10-Hg (1.3 kPa) Let's sleep. The distillate was stored in a water cooler and a dry ice-isoglo 9-nor trap. collect. The distillate collected by the water cooler is 20.2 % by weight (18,1,9) and has the following assay: 0.91% dioxin Sun, 39.4% diethylene glycol, 55. El diethylene glycol and 0.30% triethylene glycol. Dry Ice - Isoglono 9 Nor The distillate collected in the trap is 4.0% by weight + i% (3%) of the loaded sample. , 6#) and has the following assays: 24.2% acetone and 61.3 % dioxane. The residue is straw colored with 20.5 cm of carbon dioxide. The viscous liquid is 71.5 times filled, and the filling is 64, ON. and the properties shown in Table ① of the residue CO2 molecular weight data. No -14,77944618701,89 Yes 71.5 20.5 3 48519213817 1.99 Example 12 uses dipropylene glycol as the initiator Indicates that it can be used as The 10:1 product is also higher than the 50:1 product. Rapidly promotes molecular weight products. Some of the dipropylene glycol is distilled Exist in things.

lO: 100 molar ratio ethylene cargo: 4-lyester polyol (Form rex■11-225, hydroxyl-functional diethylene glycol adipate, Mw=500, manufactured by witeo) with 0.5 wt f&% as catalyst using sodium stannate trihydrate at 175°C for 3.5 hours under a nitrogen atmosphere. Heat with stirring and add 18.7% by weight carbon dioxide; A conversion rate of 97.3 thiethylene carlinate to polyol was obtained.

The catalyst was removed as in Example 1.

Part B: Sample (93,21) was heated to a maximum pot temperature of 235°C and 10 wHg (1 , 3kPa) to undergo fractional distillation. The distillate is stored in a water cooler and dryer. Collect it in a isoglu 9-nord trap. collected by water cooler The distillate accounts for 10.8% by weight (10,1,9)t of the packed sample; and have the following assay: 0.47% dioxane, 12.05ts ethylene carbon. 76.8% diethylene glycol.

and 2.85% triethylene glycol. Dry ice The nine-distillate collected by Rudra, Zo was 3.4% by weight (3%) of the packed sample. , 21) and have the following assays: 85.0% acetone and 10.3 % dioxane. The residue is straw-colored with 19.0% carbon dioxide by weight. 84.8 weight ttlb (79,0,9) of the sample filled with viscous liquid. and has the properties shown in Table 1.

Table 1 No -18,71573104118411,77 Yes 84.8 19. 0 3485 2098 4513 2.15 Example 13 is polyester polyol indicates that the compound can be used as an initiator. 10:1 products have higher molecular weight products are rapidly promoted.

Example 14 10:1 molar ratio of ethylene carbonate:polyester polyol [poly(cap) rolactone) diol, Mw = 530) as a catalyst with o, 5 tit tin. using sodium chloride trihydrate at 175°C for 4 hours under nitrogen atmosphere with stirring. Poly(alkylene cargo) with 19.2% carbon dioxide by weight ) 97.9 thiethylene cargenate conversion to polyol was obtained. The catalyst is as in Example 1. The removed sample (91.3 g) was heated to a maximum pot temperature of 235°C. and subjected to fractional distillation at a pressure of 10 ■Hg (1.3 kPa). distillate, water Collect in condenser and dry ice-isoglomerol trap. water cooler The nine distillates collected by , 9) and has the following assay: 0.85% dioxane, 7.27 % ethylene carbonate, 51.2% diethylene glycol and 1.42% of triethylene glycol. Collected by dry ice-isoglupanol trap The concentrated distillate accounts for 5.81 fKi (5.3 g) of the packed sangre. , and has the following assays: 89.1% acetone and 9.3% dioxane.

The residue is a straw-colored viscous liquid with 22.1% by weight of carbon dioxide-A. and has the characteristics shown in Table 2.

Table ■ Promoted residue CO□ Molecular weight data (f1%) (heavy layer) peak Mn My PDI No -19,21968117522131,88 Yes 80.0 22.1 6145303370152.31 Example 14 was different It is shown that polyester polyols of the type can be used as initiators. 10 The :1 product has a higher polydispersity index than the Zoo:1 product while maintaining a relatively low polydispersity index. is also rapidly promoted to higher molecular weight products.

! O: 1 molar ratio of ethylene car FK nitride N-methyljetanolamine, 5 hours at 135° C. using 0.5 wt. of sodium stannate trihydrate as a catalyst. Poly(alkylene carbinate) polio is heated under a nitrogen atmosphere with stirring. get the rules. The catalyst is removed as in Example 1.

Part B: Sample (87, s.i.) was heated to a maximum pot temperature of 200°C and 10 wmHg. Subject to fractional distillation at a pressure of (1.3 kPa). Transfer the distillate to a water cooler and Collect in a Lyice-Isoblocknol trap. collected by water cooler The distillate accounted for 36.1% by weight (31,4,P) of the packed sample. , and have the following assays: 3.68 inches of noxa/, 2.03 inches of ethylene. carbonate, 66.3% diethylene glycol, 7.73% N-methyldi Ethanolamine and 4.21% triethylene glycol. Rye ice-i The distillate collected by Sogronoshieldra, 7° is one of the filled sangurs. It accounts for 2.6 TL amount% (11,0,F) and has the following verification fee: 3 (17% It is an acetic viscous liquid with 44.3 characteristics of the filled sample.

Table X No -2643135731,83 Yes 44.3 1450 98922 422.27 Example 15 is a material containing a tertiary nitrogen in its backbone acts as an initiator Show what you can do. 10:1 products rapidly promote to higher molecular weight products be done.

Ethylene carbonate:thiodiethanol/I/l-1 catalyst with a molar ratio of 5:1 using 1.0% by weight of sodium stannate trihydrate at 150°C for 6 hours in a nitrogen atmosphere. Poly(alkylene carbinate) polyol is heated under ambient air with stirring. Obtain 92cs ethylene cargenate conversion. The catalyst was removed as in Example 1. be removed.

Part B: Sanguru (9a, 411) t, minute at a pressure of 1 OsmHg (1,3 kPa) Leave it to me. Samples for molecular weight determination were incubated at various pot temperatures up to 222°C. Remove with degree.

Collect the distillate in a water cooler and dry ice-isoglu-dashieldra, f. Ru. The distillate collected by the water cooler was 44.4% by weight of the loaded sample. C4x, 51) and has the following assay = 0.91% dioxane, 1 3.5% ethylene carbonate, 63.4% diethylene glycol, 11. 3-thiogentanol and 2.13% triethylene glycol. Dry eye The distillate collected by the suisoglono-9 nord trap was added to the packed sample. accounts for 11.0 weight% (lo, 3II) of and has the following test: 5.73 % acetone and 71.8% dioxane. The residue is a dark amber viscosity. 33.2% by weight (31,0,?) of the filled sample. occupy The molecular weight structure as a function of pot temperature is given in Table X.

Table X Product of Noyato A 419 366 583 1.59170 1093 6 86 1324 1.93195 2179 1101 2532 2.302 15 3278 1455 3767 2.59222 1889 1048 2568 2.45 Example 16 uses a material containing sulfur in its main chain as an initiator. Show that you can function. 5:1 product molecules ft-5 to the method of the present invention Therefore, it can be increased nearly five times.

10:1 molar ratio of ethylene carzanate: aminated poly(propylene glycol) call) (JafLamlnaD-400* Mw=430 e Texaseo Jeffer@onCheml Division products) as catalysts. and 0.5% by weight of sodium stannate trihydrate at 135°C for 19 hours. Heating with stirring in an elementary atmosphere, poly( 96 ethylene carcinase to polyol (alkylene carzanate) nate conversion rate obtain. The catalyst is removed as in Example 1.

Enemy B: Samples (, 97, 61) were heated to a maximum pot temperature of 225°C and "0" Hg ( Subject to fractional distillation under a pressure of 1.3 kPa). Distillate” into a water cooler and a Iai-inogurupashidra, collected by f. The water is collected in a water cooler. The distillate occupies 17.5 folds (17,1!i) of the packed sample; and have the following assay: 0.79% monoethylene glycol, 11.9% ethylene glycol. tylene cargoonate, 81.0% diethylene glycol and 1.22% trichloride. Liethylene glycol. Dry ice luisogrono mother shieldra, collected by f. The distillate accounted for 2.3% by weight (2,2,9) of the filled sandal; Near 3.4% acetone and 16.8% dioxane with the following assays.・ The residue must be filled with an amber viscous liquid with 12.9 Ls of carbon dioxide. It accounted for 79.7% by weight (77.8Ii) of the loaded sample and was shown in the second cut. It has the characteristics of

Table M No -11,184370814972,11 Yes 79.7 12.9 3415183748612.651J17 is an amino-functional material initiator It is used as a symbol to indicate prayer. The 10:1 product is rapidly promoted quickly.

50:1 molar ratio of ethylene carginate:diethylene glycol as catalyst Using 1.0ift* sodium metaborate at 160°C for 45 hours in a nitrogen atmosphere. Poly(alkylene chloride) containing 17.8 tons of carbon dioxide was heated under air with stirring. ethylene carbonate) to obtain 100% ethylene carbonate conversion rate to polyol . The catalyst is sandal (105,7!1) removed as in Example 1, 23 Minutes with a maximum pot temperature of 5 °C and a pressure of 10 m, Hg (1,3 kPa) Leave it to me. Pour the distillate into a water cooler and Collect by tap. The distillate collected by the water cooler is then (1,0,1,9)' and has the following assay: 1 ．． 19% dioxane, 60.9% diethylene glycol, 24.8% tri Ethylene glycol and 1.05% tetraethylene glycol. dry ice - The distillate collected by the isoglupanol trap is 4.1 occupies the ffi quantity chi (4, a#) and has the following test: 83.4 chi of acetone and 3.47% of dioxane. The residue is 21.0% carbon dioxide A very pale yellow viscous liquid with ．． It occupies 21 JL (91.2!) and has the characteristics shown in Table 2.

Table xm No -17,8128475414451,91 Yes 86.2 21.0 2900138931842.29 Example 18 uses sodium metaborate as a catalyst The poly(alkylene carbonate) polyol produced using the method of the present invention shows that higher molecular weight products can be promoted by

ethylene cargenate:thiethylene glycol in a molar ratio of 10:1<2) as a catalyst. Using 1.0% by weight of potassium carbonate as Poly(alkylene) containing 11.6% carbon dioxide was heated with stirring at 95 thiethylene carbonate) to polyol to obtain carbonate conversion.

The catalyst is removed as in Example 1.

Part B: The sample (102,2I) was heated to a maximum pot temperature of 210°C and 10 wHg ( Subject to fractional distillation at a pressure of 1.3 kPa). M distillate, water cooler and dry Collect by ice-isozolopashi wrap. Vapor collected by water cooler 'The distillate accounts for 20.3% by weight (20,8,P)'t of the packed sample, and has the following assay: 0.53% dioxane, 12.0:l ethylene carbonate. 19.8% diethylene glycol, 35.3% triethylene glycol Recall and 7.54% of tetraethylene glycol. dry ice - isoglu The distillate collected by Pashira was 4.6% by weight of the packed sample. % (4,7,9) and has the following assays: 58.8% acetone and 29.5% dioxane. The residue has 11.6 wt-carbon dioxide Amber viscous liquid, 69.8% by weight of the filled sample (71,3&) t” and has the properties shown in Table W.

Table xIv Accelerated residue CO2 molecular weight data Taka (weight 11%) CM%) Peak Mn My PDI No -11,6 6784487511,68 yes 69.8 11.6 969 684108 91.59 Example 19 is a poly(alkylene oxide) prepared using potassium carbonate as a catalyst. carbonate) polyols are converted into higher molecular weight products by the method of the present invention. Indicates that it can be promoted.

Propylene carbinate:diethylene glycol in a molar ratio of 5:l was used as the catalyst. using sodium stannate trihydrate at 175 °C for 12 h. Poly(alkylene cargoonate) polyol is heated under a nitrogen atmosphere with stirring. get le. The catalyst is removed as in Example 1.

Part'B: Sun 7″, A/(91,3, SF) with a maximum pot temperature of 235°C and 10cm Subject to fractional distillation at a pressure of HE (1.3 kPa). The distillate is stored in a water cooler and Collect with dry ice-isozolopashi wrap. Collect water in water cooler The distillate accounted for 62.3II% (56.9F) of the packed sample; and has the following assay: 0.93% glupylene glycol, 25.6% glupylene glycol. Birenkar? Nate, 372. dipropylene glycol and 7-57% Tripropylene glycol. 1. Tri-Isopropylene 2. Puyoshi collection The collected distillate accounts for 3.6% by weight (3,3y) of the packed sample; with the following assay = 44.5% acetone and 15.9+% dioxane.

The residue is an amber viscous liquid and accounts for 32.1% by weight of the filled sandal. (29.3 g) and has the properties shown in Table W.

Table xv No 213 316 535 1.69 Yes 32.1 41011958 52942.70 Example 20 Using glubilene carnate (cargonate) polyols, and these polyols shows that molecules can be promoted to higher molecular weights by the method of the present invention. .

f) A: Production of poly(alkylene carbonate) polyols A-F.

The desired molar ratio of ethylene carbonate):flucol was added as a catalyst to sodium stannate. Heating with stirring under nitrogen in the presence of polyhydric trihydrate (1,0-fold dihydrate), Obtain the anchorage conversion rate. After the reaction was completed, Florisil (IJi) was added for 3 hours. ’/l0JF product) by stirring the product (200 wt. in acetone). The catalyst is removed by filtration and the solvent is removed.

Table X■ Bori (alkylene cargoonate) polyol An-hexanol 10 25. 5 150 98.0 Bn-Octano-tv 10 22.0 160 100 ．． 0Cn-decanol 10 22.0 160 99.4Dn-dodecanol 5 21.5 160 100.0゜En-Dodecano y 20 23.5 160 96.5 Fn-butanol 10 25.0 160 99.6 Some Poly(alkylene carzanate) polyol A was heated in a 1001Rt boiling furnace with two necks. Place it in a stove and add a few boiling stones. The flask is a thermometer and a cloak a vacuum source (connected to a distillation apparatus).

The polyol was subjected to fractionation and contained 31.0% carbon dioxide (96% carbon dioxide) by weight. A thin amber viscous liquid residue 49.1F is obtained with a carbon content of 49.1F.

No. 1 table Molecular weight data c.

Peak Mn My Mz PDI (iji%) Before fractionation 1063 507 1077 1668 2.122 26.5 After separation 3539 1935 3436 5193 1.775 31.0 Example 21 uses n-hexane as an initiator. Poly(alkylene carbonate) rf produced using nol! Riolu is Higher molecular weight products than 1.5°:1 products while maintaining low polydispersity index Shows that it can be rapidly promoted. Product analysis by proton NMR detects Point out the impossible n-08-C, component.

A portion of the poly(alkylene carbonate) polyol B was added to the same apparatus t as in Example 21. It was separated using Maximum pot temperature is 0.7wHg (0.09kPa) pressure The temperature is 191°C. Distillate (17,5F) is 93chi octatool, 2chi Contains dioxane and 4 diethylene glycol, 11/□. The residue (a3 ．． 4II) is a thin amber viscous liquid with 31.7 wt. Ru.

Chapter X”, Table 1 Before sorting 7B5 450 889 1407 1.972 23.4 After sorting 35 39 2092 3593 5026 1.718 31.7 Lower dispersion index However, there is some molecular weight promotion.

Example 22 is a poly(alkylene) prepared using n-octatool as an initiator. carginate) polyol in a 50:1 formation while maintaining a low polydispersity index. Tobori (alkylene carbonate) polyamide which can be rapidly promoted depending on the molecular weight of the substance All c6, fractionated using the same equipment as Example 21. Maximum pot temperature is 0.7 The temperature is 193° C. at w+Hg (0.09 kPa) pressure.

The distillate (12.8 g) contains 86% decanol, 12% diethylene glyco 0.5% ethylene carbonate and 0.5% monoethylene glycol Including files. The residue (59.8 g) was mixed with 26.6 Mkes of carbon dioxide (90 g). It is a thin amber viscous liquid with a residual carbon dioxide content of .

Table xX Before sorting 1063 555 1304 4886 2.351 24.6 After sorting 3321 1901 3240 4751 1.704 26.6 Example 23 Poly(alkylene carbonate) produced using n-decanol as an initiator The polyol has a higher content than the 50:1 product while maintaining a low polydispersity index. We show that molecular mass can be rapidly promoted. # Almost half of the initiator remains in the product. Exists.

Example 24 Some poly(Alkylekker nate) 1 and Liol D, same equipment as Example 21 Separate using. Its maximum pot temperature is 1.1 mmHg (0.15 kP a) FE force is i70°C. Its distillate (11.5 g) is 65 g. Ethylene glycol, 31-dodecanol and 0.5-monoethylene glyco Contains rule i. The residue (sl, 9y) is 20.4 times - carbon dioxide (10 It is a pale amber viscous liquid with a residual carbon content of 0.0%.

No. 1 table Before sorting 358 329 546 764 1.657 15.7 After sorting 57 0 742 1417 5768 1.909 20.0 Although there was a molecular weight promotion , but most of the initiator remained in the product.

Some poly(alkylene carbonate) polyols Ei, Example 21. the same equipment as Separate by using. The maximum pot temperature is 0.8 mHg (0.11 kPa) ) pressure is 194°C. The distillate (10,6, iF) contains 35% ethylene carzanate, 21% dodecanol, 41% diethylene glycol and 0. Contains 5% monoethylene glyco-/I/l-. The residue (81.3J) is 2 Pale amber viscosity with 8.0 g of carbon dioxide (94 g of carbon dioxide remaining) It is a sexual fluid.

Table xxtt Before sorting 1B73 685 1995 4950 2.910 25.7 After sorting 2950 1943 3209 4’1B7 1.652 28.0 Chi dispersibility There is some molecular weight promotion while lowering the index. However, most of the time of initiator remains in the product.

Examples 24 and 25 are poly(alkylene carbs made using n-dodecanol). Bonato) 7J? When lyol is used as an initiator, it leads to high molecular weight products. Product accelerating sound, which can be caused by the method of the invention, but hardly The initiator converts some of the poly(alkylene carbonate) polyol F into a product. Separate using a few different pressures.

(A) At a pressure of 40 ■Hg (5.3 kPm): The sample was prepared as in Example 27 above. Separate using the same equipment. However, a 50-ml flask was used. maximum pot temperature is 198°C. The distillate (3,4 J) contains 95 t of butanol and 3 t of Contains dioxane.

The residue (aa, Zll) contains 28.8 parts by weight of carbon dioxide (IOO) of the diacid It is a thin amber viscous oil with a high carbon content (residual carbon content).

(B) At 100 wHg (13,3 kPa) pressure: Sample (33,7, 9) Gold, (fractionated using the same equipment as to). Maximum pot temperature is 210°C.

The distillation of 7 9m (3,1!y) is 93% butanol and 5d oxane containing gold. nothing. The residue is 26.5ivk% carbon dioxide (95% carbon dioxide residual rate) It is a thin amber viscous oil.

(C) At 760 mHg (101,3 kPa) pressure: Sample (36,71 ) Gold, separated using the same equipment vi as in (A). Its maximum pot temperature is 253℃ be.

The distillation 1 (7, 6, 9) contains 50% butanol and 50% nooxane. include. The residue contains 26.8% by weight of carbon dioxide (69% residual carbon dioxide) ) is a thin amber viscous oil.

Before sorting 881 590 92813181.571253℃ 1151 7 15 1153 1638 1.612 po, g/760M (101,3kPa) 210℃OL641 866 1535 2201 1.773198℃ 2 135　1242　2144　3022　1.725 Debt promotion is available at each location. occurs when the fractionation pressure decreases, and increases as the fractionation pressure decreases.

% Co2 Co2 Butanol Tiptanol B Before sorting 25.1 9.38 253℃ 26.8 31.1 3.29 77.3 Door 760m (101,3kPa) C210℃ 26.5 5.0 3.19 69.3 po, )/100 i (13-3kP a) 3 28.8 * 1.00 90.6 at 198℃ Example 26 Poly(alkylene carboxylic acid) prepared using monobutanol as an initiator. Figure 2 shows the effect of pressure on the molecular weight promotion of (gonate) polyols. pressure is low As the CO2 content and molecular weight increase, however, the n ~ Tanol content will be lower.

n-octatool-initiated aguku) f, using sodium stannate trihydrate as a catalyst It is prepared from ethylene oxide and carbon dioxide at 150'C. Catalyst, example The residue is a poly(alkylene cargo) with 12.1% carbon dioxide by weight. ) is a polyol.

A poly(alkylene carbonate) polyol was fractionated using the same equipment as in Example 21. do. Its maximum point.

The temperature is 0.3 wHg (0.04 kPa) and the pressure is 190'C.

The distillate (17,8, P) contains 79 units of octatool, 1 unit of monoethylene Contains glycol and 1% noethylene glycol. The residue (13,91) is a pale amber viscous liquid with 25.7 wt% carbon dioxide. Arca The nol component (97.2 inches) was removed by fractionation.

No. table Before sorting 234 229 2B3 354 1.235 12. ．． 47 after 1 separation 23 1878 4832 8040 2.572 25.7 Kana molecular weight promotion Susumu exists.

Example 27 shows ethylene oxide and carbon dioxide using n-octatool as the initiator. Poly(alkylene carbonate) polyols prepared from This is shown to promote the use of high molecular weight products.

Brief description of the drawing international search report ``・・---・-mu・-・C-ura, lI+PCT/US86101384

Claims (9)

[Claims] 1. Method for increasing the molecular weight of poly(alkylene carbonate) polyols dialkylene glycol, trialkylene glycol or initiator segment (the initiator is a dialkylene glycol or trialkylene glycol segment) poly(alkylene) with about the same or higher volatility than The dialkylene glycol, The poly(alkylene glycol) or the initiator is evaporated at a pressure that (alkylene carbonate) polyol and the poly(alkylene carbonate) polyol. Under conditions that increase the molecular weight of the poly(alkylene carbonate) Volatile dialkylene glycol, trialkylene glycol or a method comprising removing the initiator. 2. 2. The method of claim 1, wherein said pressure is reduced pressure. 3. 3. A method according to claim 2, wherein said temperature is between 150<0>C and 300<0>C. 4. Claims in which the pressure is 300 mmHg (40.0 kPa) or lower The method described in box 3. 5. The poly(alkylene carbonate) polyol has the following formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R1 is R3-(X)n; R2 is each independently present hydrogen or rogene, nitro group, cyano group, C1-20 hydrocarbyl group or one or more Also many of the following groups: halo, cyano, nitro, thioalkyl, tert-amino, Alkoxy, aryloxy, aralkoxy, carbonyldioxyalkyl, carbonyl carbonyldioxyaryl, carbonyldioxyaralkyl, alkoxycarbo Nyl, aryloxycarbonyl, aralkoxycarbonyl, alkylcarbonyl arylcarbonyl, aralkylcarbonyl, alkylsulfinyl, arylcarbonyl, arylcarbonyl, aralkylcarbonyl, alkylsulfinyl lsulfinyl, aralkylsulfinyl, alkylsulfonyl, arylsulfinyl C1-20 hydrocarbyl substituted with sulfonyl or aralkylsulfonyl group is a building group; R3 is an n-valent hydrocarbon group, which is present separately, or one or more of them; is a hydrocarbon group containing more heteroatoms (0, N or S); m is an integer greater than or equal to 1; n is an integer of 1 to 25, each occurring separately; is an integer; x is 1; y is an integer from 1 to 40, each occurring separately; and z is an integer from 1 to 100 that exists separately.] 5. The method according to claim 4, wherein the langum polymer corresponds to . 6. R2 is hydrogen, C1-20 alkyl, C1-20 haloalkyl, C1-2 0 alkenyl or phenyl; R3 is an aliphatic or alicyclic hydrocarbon or Aliphatic or cycloaliphatic containing one or more oxygen, sulfur or nitrogen components is a hydrocarbon of the formula; X is S, O or NH; m is 1 to 10 (including 1 and 10); n is 1 to 10 (including 1 and 10) is an integer; y is from 5 to 20 (including 5 and 20); and 6. The method according to claim 5, wherein z is 20 to 50 (including 20 and 50). 7. R2 is hydrogen, C1-3 alkyl, C2-3 alkenyl or phenyl; the law of nature; R3 is n-valent alkane or cycloalkane or oxygen, sulfur or nitrogen component is an n-valent alkane or cycloalkane containing; n is 1 to 5 (including 1 and 5); and n is 1 to 5 (including 1 and 5); 7. The method of claim 6, wherein the number is an integer. 8. R2 is hydrogen, methyl or ethyl; R3 is an n-valent C1-10 alkane and n is 1 or 2 The method according to claim 7. 9. The poly(alkylene carbonate) polyol has the following formula: ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R2 is hydrogen, halogen, nitro group, cyano group, C1-20 hydrocarpyl group or one or more of the following groups: halo, sia -, nitro, thioalkyl, tert-amino, alkoxy, aryloxy, aralkoxy, carbonyldioxyalkyl, carbonyldioxyaryl, carbonyldioxyaryl Rubonyldioxyaralkyl, alkoxycarbonyl, aryloxycarbonyl , aralkoxycarbonyl, alkylcarbonyl, arylcarbonyl, aralkoxycarponyl alkylcarbonyl, alkylsulfinyl, arylsulfinyl, aralkyl Sulfinyl, alkylsulfonyl, arylsulfonyl or aralkylsulfonyl a C1-20 hydrocarpyl group substituted with a nyl group; R3 is each independently present n-valent hydrocarbon group or one or more groups; is a hydrocarbon group containing a terror atom (0, N or S); X is S, O, NH, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas, tables, etc. There are ▼, or ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼; m is an integer greater than or equal to 1; n is an integer of 1 to 25, each occurring separately; is an integer; p is 0 or 1, each occurring separately; and q is an integer of 1 to 1 or larger, each existing separately. The method according to claim 4.