CN106800646A - A kind of process for preparing the polycarbonate polyol of hydroxy-end capped rate high in high yield - Google Patents
A kind of process for preparing the polycarbonate polyol of hydroxy-end capped rate high in high yield Download PDFInfo
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- CN106800646A CN106800646A CN201710029203.7A CN201710029203A CN106800646A CN 106800646 A CN106800646 A CN 106800646A CN 201710029203 A CN201710029203 A CN 201710029203A CN 106800646 A CN106800646 A CN 106800646A
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- 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
- C08G64/02—Aliphatic polycarbonates
- C08G64/0208—Aliphatic polycarbonates saturated
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- 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
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- 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
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/305—General preparatory processes using carbonates and alcohols
Abstract
It is main that ester exchange reaction, including atmospheric low-temperature ester exchange stage, temperature rise period, decompression polycondensation phase are carried out by organic carbonate and small molecule diol component the present invention relates to a kind of method for preparing the polycarbonate polyol of hydroxy-end capped rate high in high yield.The inventive method adds organic carbonate using continuity method and addition diol component is blocked in batches, solve in existing polycarbonate polyol building-up process that organic carbonate loss amount is big, conversion ratio is low, side reaction is more, hydroxy-end capped rate is low and the low problem of product yield, synthesized polycarbonate polyol yield ＞ 80%, hydroxy functionality is close to theoretical value.
Description
Technical field
The present invention relates to a kind of preparation method of polycarbonate polyol, more specifically it is related to one kind to prepare in high yield
The method of hydroxy-end capped rate polycarbonate polyol high, belongs to technical field of polymer materials.
Background technology
Polycarbonate polyol refers to the carbonate group containing repetition in molecular backbone, and chain end group is a Type of Collective of hydroxyl
Thing.Because polycarbonate polyol strand has larger compliance, can be by it as the raw material of synthesis of polyurethane soft section
Polyurethane manufactured by raw material has excellent heat resistance, hydrolytic resistance etc., and has application to Synthetic Leather, leather painting
The multiple fields such as layer, binding agent, therefore be increasingly taken seriously as functional high molecule material, the preparation of polycarbonate polyol
Also study hotspot is turned into.
The technique of phosgenation production polycarbonate polyol has not met green due to needing hypertoxic phosgene in production process
The requirement that colour circle is protected.At present, the method predominantly carbon dioxide epoxides copolymerization method of polycarbonate polyol and organic is prepared
Carbonic ester and binary alcohol esters exchange process, Chinese patent CN200710020308.2 disclose a kind of using carbon dioxide and epoxidation
The method that thing regulation copolymerization method prepares polycarbonate polyol, although carbonate group mass contg polycarbonate polyol high can be obtained
Alcohol, but this method can only synthesize the polycarbonate polyol of specific epoxide structure, it is narrower using scope.And ester exchange
Method obtains polycarbonate polyol using organic carbonate and diol reaction, can synthesize many by the species for adjusting dihydroxylic alcohols
Plant the polycarbonate polyol of structure.One kind is disclosed in Chinese patent CN201310208335.8 and CN200910311179.1
Metal oxide gel and hydrotalcite as ester exchange catalyst polycarbonate synthesis polyalcohol method, but it is to synthesis work
Side reaction control, product yield etc. rarely have and are related in skill.There are foreign patent and documents and materials to refer to that ester-interchange method prepares poly- carbonic acid
Ester polyol has that yield is low, and researcher carried out optimization to synthesis technique, such as in Deutsche Bundespatent
DE10343472.0 refers to using the method for addition dimethyl carbonate in batches reducing its loss, but needs to repeat in its technique
The cooling that heats up adds dimethyl carbonate to remove end group, and the molecular weight control to the reaction mechanism mechanism of reaction is very cumbersome, and reaction efficiency is extremely low.This
When external experiment dialkyl carbonate or diaryl carbonate prepare polycarbonate polyol as carbonate source, there is source
Alkyl, aryl in carbonic ester can form alkoxy end-capped polycarbonate polyol, shadow in the problem of polymer ends remaining
Ring its hydroxy-end capped rate.In a word, current polycarbonate polyol synthesis technique has that organic carbonate loss amount is big, side reaction
Many, product yield is low, alkoxy end-capped the problems such as cause actual functionality to be less than theoretical value.
The content of the invention
The deficiency that the present invention exists for existing polycarbonate polyol preparation method, there is provided one kind prepares hydroxyl high in high yield
The process of base ending ratio polycarbonate polyol.Present invention aim to address above-mentioned technical problem, on the one hand improve poly-
The generation of side reaction is reduced while the raw material availability of carbonate polyol, so as to improve its yield；On the other hand it is to reduce
Alkoxy end-capped ratio in polycarbonate polyol product, improves hydroxy-end capped rate, actual hydroxy functionality close to theoretical value,
Reduce adverse effect of the non-hydroxyl end-cap product to its follow-up synthesis of polyurethane material property.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：
A kind of process for preparing the polycarbonate polyol of hydroxy-end capped rate high in high yield, it is characterised in that including
Following steps：
1) the atmospheric low-temperature ester exchange stage：Added by catalyst and containing less than 8 dihydroxylic alcohols of carbon atom under condition of normal pressure
In reactor, stirring is warming up to 90-120 DEG C under inert atmosphere, continuous to adding organic carbonate in reaction system by constant flow rate
Ester component, isothermal reaction；
2) temperature rise period：160-200 DEG C is warming up to, organic carbonate completion of dropping is ensured before rising to maximum temperature, backward
Small molecule dihydroxylic alcohols of the addition containing less than 8 carbon atoms carries out hydroxy-end capped, insulation reaction again in reaction system；
3) depressurize polycondensation phase：Reaction system vacuum is evacuated to -0.08 to -0.09Mpa, polycondensation of depressurizing is obtained final product.
Further, the organic carbonate is the one kind in dimethyl carbonate, diethyl carbonate.
Further, the dihydroxylic alcohols be 1,3-PD, BDO, 1,5-PD, neopentyl glycol, 1,6- oneself two
One kind in alcohol, 1,8- ethohexadiols.
Further, the catalyst is tetraisopropyl titanate or positive four butyl ester of metatitanic acid, and addition is diol component quality
0.01-0.2%.
Further, step 1) described in the ratio between the mole of organic carbonate and dihydroxylic alcohols be (1-1.4)：1.
Further, step 1) in the flow that is persistently added in reactor of organic carbonate to be controlled to every kilogram of inventory every
Hour 50-500g, preferably 100-300 grams, the inventory is the total amount of dihydroxylic alcohols and organic carbonate in reactor.
Further, step 2) described in addition dihydroxylic alcohols amount be step 1) in diol component quality 0.1-5%, it is excellent
Select 1-3%, more preferably 1-2%.
Further, step 1) described in the low temperature ester exchange reaction time be 1-2h, step 2) in reaction time be 1-2h,
Step 3) in decompression polycondensation time be 3-6h.
The principle of the inventive method is as follows：
According to the method that the present invention is provided, continuous addition is controlled by the ester exchange of initial reaction stage low temperature, by preferred flow
Organic carbonate is effectively reduced the loss of organic carbonate, improves ester exchange rate and reduces side reaction odds, while
The secondary dihydroxylic alcohols for adding preferred proportion of ending phase is on the verge of by normal pressure ester exchange to carry out end group, improve hydroxy-end capped
Rate, it is ensured that hydroxy functionality, the polycarbonate polyol actual production of preparation is at least the 80% of theoretical yield, and makrolon is more
, close to theoretical value 2.0, hydroxy-end capped rate is high, there's almost no alkoxy end-capped phenomenon for the hydroxy functionality of first alcohol.
The beneficial effects of the invention are as follows：
1) process of the invention compared with prior art, low boiling organic carbon is avoided by the low temperature ester exchange stage
Acid esters loses in the azeotropic of temperature-rise period, while it is also very big into reaction system persistently to add organic carbonate using preferred flow
Reduce significant loss, not only ensure that ester exchange rate higher also improves the utilization rate of raw material, reduce side reaction
Occur, so as to improve the yield of product, compared with prior art, the 50- of the yield of polycarbonate polyol from theoretical yield
60% improves to more than 80%；
2) dihydroxylic alcohols of the secondary addition preferred proportion of ending phase is on the verge of by normal pressure ester exchange to carry out end group, is carried
Hydroxy-end capped rate high, it is ensured that hydroxy functionality, the hydroxy functionality of the polycarbonate polyol of preparation is close to theoretical value 2.0, hydroxyl
Base ending ratio is high, there's almost no alkoxy end-capped phenomenon, it is possible to increase polycarbonate polyol synthesizes in subsequent polyurethane
Reaction stability in application process, improves the mechanical performance of polyurethane material prepared therefrom；
3) carbon sequestration acid esters persistently add flow-rate ratio simply add in batches more can simple realization process stabilizing, lead to
Excessively stream gauge or peristaltic pump can realize automation mechanized operation or large-scale promotion.
Specific embodiment
Principle of the invention and feature are described below in conjunction with example, example is served only for explaining the present invention, and
It is non-for limiting the scope of the present invention.
Embodiment 1：
A kind of process for preparing polycarbonate polyol, comprises the following steps：
1) to addition 521.93g1,6- hexylene glycols and the fourth of 0.5g catalyst metatitanic acid four in the reactor equipped with rectifier unit
Ester, is passed through after high pure nitrogen emptying to open and stirs and be warming up to 90 DEG C, using peristaltic pump to persistently adding carbonic acid in reaction system
Dimethyl ester amounts to 478.07g, and adding rate is every kilogram of inventory 300g dimethyl carbonate per hour, and addition dimethyl carbonate is total
Used time 4h, wherein temperature control is 90 DEG C, rear isothermal reaction 1h in lasting adding procedure；
2) 180 DEG C and then in 4h are warming up to, period control rectifying tower top temperature is no more than 65 DEG C, after isothermal reaction 1h, to
Add 5.22g1,6- hexylene glycols in reaction system, stirring reaction 1h carries out end group and hydroxy-end capped；
3) when being steamed without cut in question response system, start vacuum plant, -0.09Mpa is evacuated to, after Depressor response 4h
Cooling discharge, prepares polycarbonate polyol.Theoretical yield is 637.46g, and actual receipts amount (accounts for theoretical yield for 579.68g
90.93%), hydroxyl value test result be 56.9mgKOH/g, by nuclear-magnetism and infrared analysis do not occur methyl peak confirm not
Exist alkoxy end-capped, hydroxy functionality f is 1.97, shows that the prepared hydroxy-end capped rate of polycarbonate polyol is high.
Comparative example 1：
Tested using the synthesis technique of present conventional polycarbonate polyol：Add in the reactor equipped with rectifier unit
Enter 478.07g dimethyl carbonates, 521.93g1,6- hexylene glycols and 0.5g catalyst butyl titanates, be passed through high pure nitrogen emptying
Open afterwards and stir and heat up, 180 DEG C are warming up in 5h, period control rectifying tower top temperature is no more than 65 DEG C, after isothermal reaction 1h,
To adding 5.22g1,6- hexylene glycols in reaction system, stirring reaction 1h carries out end group and hydroxy-end capped, in question response system
When being steamed without cut, start vacuum plant, be evacuated to -0.09Mpa, cooling discharge after Depressor response 4h prepares poly- carbonic acid
Ester polyol.Theoretical yield is 637.46g, and actual receipts amount is 337.25g (accounting for the 52.91% of theoretical yield), hydroxyl value test knot
Fruit is 69.1mgKOH/g, and not occurring methyl peak by nuclear-magnetism and infrared analysis confirms in the absence of alkoxy end-capped, hydroxyl official
Energy degree f is 1.94.It is clearly present that molecular weight of product is low compared with the result of embodiment 1, the low problem of yield.
Embodiment 2：
A kind of process for preparing polycarbonate polyol, comprises the following steps：
1) to addition 444.58g1,4- butanediols and the fourth of 0.8g catalyst metatitanic acid four in the reactor equipped with rectifier unit
Ester, is passed through after high pure nitrogen emptying to open and stirs and be warming up to 120 DEG C, using peristaltic pump to persistently adding carbonic acid in reaction system
Dimethyl ester amounts to 555.42g, and adding rate is every kilogram of inventory 190g dimethyl carbonate per hour, and addition dimethyl carbonate is total
Used time 3h, wherein temperature control is 90 DEG C, rear isothermal reaction 1h in lasting adding procedure；
2) 170 DEG C and then in 4h are warming up to, period control rectifying tower top temperature is no more than 65 DEG C, after isothermal reaction 1h, to
Add 6.66g1,4- butanediols in reaction system, stirring reaction 1h carries out end group and hydroxy-end capped；
3) when being steamed without cut in question response system, start vacuum plant, be evacuated to -0.085Mpa, Depressor response 5h
Cooling discharge, prepares polycarbonate polyol afterwards.Theoretical yield is 572.84g, and actual receipts amount is that 505.10g (produce by reasonable opinion
Amount 88.17%), hydroxyl value test result be 59.21mgKOH/g, by nuclear-magnetism and infrared analysis do not occur methyl peak demonstrate,prove
It is real in the absence of alkoxy end-capped, hydroxy functionality f is 1.98, shows that the prepared hydroxy-end capped rate of polycarbonate polyol is high.
Comparative example 2：
To adding 444.58g1,4- butanediols and 0.4g catalyst butyl titanates in the reactor equipped with rectifier unit,
It is passed through to be opened after high pure nitrogen is emptied and stirs and be warming up to 90 DEG C.Using peristaltic pump to persistently adding carbonic acid diformazan in reaction system
Ester amounts to 555.42g, and adding rate is every kilogram of inventory 190g dimethyl carbonate per hour, adds dimethyl carbonate total used time
3h, wherein temperature control is 90 DEG C of constant temperature 1h in lasting adding procedure, then 4h is warming up to 170 DEG C, period control rectifying column
Top temperature is no more than 65 DEG C, after isothermal reaction 1h, when being steamed without cut in question response system, starts vacuum plant, be evacuated to-
0.085Mpa, cooling discharge after Depressor response 5h, prepares polycarbonate polyol.Theoretical yield is 572.84g, actual receipts amount
It is 498.07g (accounting for the 86.95% of theoretical yield) that hydroxyl value test result is 61.37mgKOH/g, by nuclear-magnetism and infrared analysis,
There is the absworption peak of methyl in 1375cm-1 in infrared spectrum, and peak occurs at chemical shift 0.98 in nucleus magnetic hydrogen spectrum, it was demonstrated that
There is methyl in product structure, illustrate to exist in product alkoxy end-capped, it is only 1.86 to be computed hydroxy functionality f, itself and hydroxyl
The deviation of base degree of functionality theoretical value 2.0 is more than 0.10, shows that the prepared hydroxy-end capped rate of polycarbonate polyol is relatively low.
Embodiment 3：
A kind of process for preparing polycarbonate polyol, comprises the following steps：
1) to addition 494.77g1,6- hexylene glycols and the isopropyl of 0.4g catalyst metatitanic acid four in the reactor equipped with rectifier unit
Ester, is passed through after high pure nitrogen emptying to open and stirs and be warming up to 100 DEG C, using peristaltic pump to persistently adding carbonic acid in reaction system
Diethylester amounts to 643.02g, and adding rate is every kilogram of inventory 101g diethyl carbonate per hour, and addition diethyl carbonate is total
Used time 5h, wherein temperature control is 100 DEG C, rear isothermal reaction 1h in lasting adding procedure；
2) 185 DEG C and then in 4h are warming up to, period control rectifying tower top temperature is no more than 78 DEG C, after isothermal reaction 1h, to
Add 0.5g1,6- hexylene glycols in reaction system, stirring reaction 1h carries out end group and hydroxy-end capped；
3) when being steamed without cut in question response system, start vacuum plant, be evacuated to -0.088Mpa, Depressor response 6h
Cooling discharge, prepares polycarbonate polyol afterwards.Theoretical yield is 604.33g, and actual receipts amount (accounts for theoretical yield for 543.5g
89.93%), hydroxyl value test result be 55.74mgKOH/g, by nuclear-magnetism and infrared analysis do not occur methyl peak confirm
In the absence of alkoxy end-capped, hydroxy functionality f is 1.95, shows that the prepared hydroxy-end capped rate of polycarbonate polyol is high.
Embodiment 4：
A kind of process for preparing polycarbonate polyol, comprises the following steps：
1) to addition 682.79g1,8- ethohexadiols and the fourth of 0.35g catalyst metatitanic acid four in the reactor equipped with rectifier unit
Ester, is passed through after high pure nitrogen emptying to open and stirs and be warming up to 95 DEG C, using peristaltic pump to persistently adding carbonic acid in reaction system
Diethylester amounts to 1000.97g, and adding rate is every kilogram of inventory 230g diethyl carbonate per hour, adds diethyl carbonate
Total used time 2.5h, wherein temperature control is 95 DEG C, rear isothermal reaction 1h in lasting adding procedure；
2) 200 DEG C and then in 4h are warming up to, period control rectifying tower top temperature is no more than 78 DEG C, after isothermal reaction 1h, to
Add 10.00g1,4- butanediols in reaction system, stirring reaction 1h carries out end group and hydroxy-end capped；
3) when being steamed without cut in question response system, start vacuum plant, be evacuated to -0.085Mpa, Depressor response 5h
Cooling discharge, prepares polycarbonate polyol afterwards.Theoretical yield is 542.82g, and actual receipts amount is that 453.13g (produce by reasonable opinion
Amount 83.48%), hydroxyl value test result be 58.19mgKOH/g, by nuclear-magnetism and infrared analysis do not occur methyl peak demonstrate,prove
It is real in the absence of alkoxy end-capped, hydroxy functionality f is 1.97, shows that the prepared hydroxy-end capped rate of polycarbonate polyol is high.
Embodiment 5：
A kind of process for preparing polycarbonate polyol, comprises the following steps：
1) it is different to addition 480.53g1,5- pentanediols and 0.05g catalyst metatitanic acid four in the reactor equipped with rectifier unit
Propyl ester, is passed through after high pure nitrogen emptying to open and stirs and be warming up to 90 DEG C, using peristaltic pump to persistently adding carbon in reaction system
Dimethyl phthalate amounts to 519.47g, and adding rate is every kilogram of inventory 50g dimethyl carbonate per hour, adds dimethyl carbonate
Total used time 4.5h, wherein temperature control is 90 DEG C, rear isothermal reaction 1h in lasting adding procedure；
2) 160 DEG C and then in 4h are warming up to, period control rectifying tower top temperature is no more than 65 DEG C, after isothermal reaction 1h, to
Add 24g1,5- pentanediols in reaction system, stirring reaction 1h carries out end group and hydroxy-end capped；
3) when being steamed without cut in question response system, start vacuum plant, be evacuated to -0.085Mpa, Depressor response 3h
Cooling discharge, prepares polycarbonate polyol afterwards.Theoretical yield is 600.58g, and actual receipts amount is that 502.63g (produce by reasonable opinion
Amount 83.69%), hydroxyl value test result be 110.81mgKOH/g, by nuclear-magnetism and infrared analysis do not occur methyl peak demonstrate,prove
It is real in the absence of alkoxy end-capped, hydroxy functionality f is 1.96, shows that the prepared hydroxy-end capped rate of polycarbonate polyol is high.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all it is of the invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.
Claims (10)
1. a kind of process for preparing the polycarbonate polyol of hydroxy-end capped rate high in high yield, it is characterised in that including such as
Lower step：
1) the atmospheric low-temperature ester exchange stage：Under condition of normal pressure reaction is added by catalyst and containing less than 8 dihydroxylic alcohols of carbon atom
In kettle, stirring is warming up to 90-120 DEG C under inert atmosphere, continuous to addition organic carbonate group in reaction system by constant flow rate
Point, isothermal reaction；
2) temperature rise period：160-200 DEG C is warming up to, organic carbonate completion of dropping is ensured before rising to maximum temperature, backward reaction
Small molecule dihydroxylic alcohols of the addition containing less than 8 carbon atoms carries out hydroxy-end capped, insulation reaction again in system；
3) depressurize polycondensation phase：Reaction system vacuum is evacuated to -0.08 to -0.09Mpa, polycondensation of depressurizing is obtained final product.
2. process according to claim 1, it is characterised in that the organic carbonate is dimethyl carbonate, carbonic acid
One kind in diethylester.
3. process according to claim 1, it is characterised in that the dihydroxylic alcohols is 1,3-PD, Isosorbide-5-Nitrae-fourth two
One kind in alcohol, 1,5-PD, neopentyl glycol, 1,6- hexylene glycols, 1,8- ethohexadiols.
4. process according to claim 1, it is characterised in that the catalyst be tetraisopropyl titanate or metatitanic acid just
Four butyl esters, its addition is the 0.01-0.2% of diol component quality.
5. process according to claim 4, it is characterised in that the addition of the catalyst is diol component matter
The 0.05-0.1% of amount.
6. the process according to any one of claim 1-5, it is characterised in that step 1) described in organic carbonate
It is (1-1.4) with the ratio between the mole of dihydroxylic alcohols：1.
7. the process according to any one of claim 1-5, it is characterised in that step 1) in organic carbonate continue
The flow being added in reactor is controlled to every kilogram of inventory 50-500g per hour, and the inventory is binary in reactor
The total amount of alcohol and organic carbonate.
8. process according to claim 7, it is characterised in that step 1) in organic carbonate be persistently added to reaction
Flow in device is controlled to every kilogram of inventory 100-300g per hour.
9. the process according to any one of claim 1-5, it is characterised in that step 2) described in add dihydroxylic alcohols
Amount be step 1) in diol component quality 0.1-5%.
10. the process according to any one of claim 1-5, it is characterised in that step 1) described in low temperature ester hand over
The reaction time is changed for 1-2h, step 2) in time of reaction be 1-2h, step 3) in time of decompression polycondensation be 3-6h.
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Citations (5)
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|---|---|---|---|---|
| US5116929A (en) * | 1988-10-14 | 1992-05-26 | Enichem Synthesis S.P.A. | Copolyester-diol polycarbonates, process for producing them and their use |
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2017
- 2017-01-16 CN CN201710029203.7A patent/CN106800646A/en active Pending
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| US5116929A (en) * | 1988-10-14 | 1992-05-26 | Enichem Synthesis S.P.A. | Copolyester-diol polycarbonates, process for producing them and their use |
| CN1522270A (en) * | 2001-06-27 | 2004-08-18 | Process for producing aliphatic oligocarbonate diols | |
| CN1616396B (en) * | 2003-09-19 | 2010-08-04 | 拜尔材料科学股份公司 | Method for producing aliphatic oligocarbonate polyols |
| CN101029127A (en) * | 2007-04-13 | 2007-09-05 | 中国科学院山西煤炭化学研究所 | Production of fatty oligo-ester carbonate polyhydric alcohol |
| CN104271636A (en) * | 2012-03-28 | 2015-01-07 | 陶氏环球技术有限责任公司 | Yield optimization of polycarbonate polyols |
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Application publication date: 20170606 |