CN101942084A - Method for catalytic synthesis of polytetrahydrofuran in the presence of trifloromethanesulfonic acid rare earth metallic compounds - Google Patents
Method for catalytic synthesis of polytetrahydrofuran in the presence of trifloromethanesulfonic acid rare earth metallic compounds Download PDFInfo
- Publication number
- CN101942084A CN101942084A CN 201010289754 CN201010289754A CN101942084A CN 101942084 A CN101942084 A CN 101942084A CN 201010289754 CN201010289754 CN 201010289754 CN 201010289754 A CN201010289754 A CN 201010289754A CN 101942084 A CN101942084 A CN 101942084A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- polytetrahydrofuran
- acid rare
- thf
- molecular weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention provides a method for catalytic synthesis of polytetrahydrofuran in the presence of trifloromethanesulfonic acid rare earth metallic compounds. The method comprises the following steps of: in a reaction solvent, catalyzing ring-opening polymerization of polytetrahydrofuran by using trifloromethanesulfonic acid rare earth metallic compounds as a catalyst and alkylene oxide as an accelerating agent to synthesize the colorless and clean polytetrahydrofuran, of which the molecular weight is 3,000 to 130,000, the distribution index is 1.2 to 1.7 and both ends are hydroxyl-terminated, wherein the rare earth metallic compounds comprise Sc, Y and La to Lu. Compared with the prior art, the method has the advantages that: the catalyst used in the invention has little toxicity, no corrosivity and high yield of polymers, and the conversion rate can reach 60 percent after the reaction is performed at room temperature for 2.5 hours.
Description
Technical field
The present invention relates to a kind of method of synthetic polytetrahydrofuran, particularly a kind of method with the synthetic polytetrahydrofuran of trifluoromethanesulfonic acid rare earth compound catalysis.
Technical background
Polytetrahydrofuran (being called for short " PTHF ") is also referred to as the polyoxybutylene glycol, is the multi-usage intermediate in plastics and the synthetic fiber industry product.In the preparation of urethane, polyester and polyurethane elastomer, use especially, become plasticising segment component as soft section.In addition, PTHF also is a kind of valuable auxiliary agent, as dispersion agent or be used for deinking of waste paper etc.
[U.S. Pat 5393866] such as nineteen ninety-five N.Murai reported a kind of fluosulfonic acid homogeneous catalyst catalysis tetrahydrofuran (THF) (being called for short " THF ") polymeric method.This method can the composite number average molecular weight at 1000 to 2000 PTHF, yield need add alkali after reaction finishes and stop unreacted strong acid about 50%, and employed acid can't thoroughly remove totally, it is yellow that polymerisate is.The use of strong acid catalyst has big corrodibility to conversion unit.
[J.Macromol.Sci.-Chem.A 1973 for fluorosulfonic anhydride, 7,1399-1413] also be the catalyzer that a class can catalysis THF ring-opening polymerization, under the bigger epoxy alkane of some ring strain promotes the catalysis tetrahydrofuran by polymerization obtain molecular weight 500 to 5500, the PTHF of dispersion index 2.0 to 2.2.Though the corrodibility of this catalyzer is lower than fluosulfonic acid, itself has severe toxicity acid anhydrides, and operational difficulty is not suitable for large-scale industrial application.
Rare earth catalyst can the catalysis tetrahydrofuran ring opening polymerization.Jin Yingtai etc. [catalysis journal 1993,14,329-332] (CF
3CO
2)
3RE (RE=Sm, Ce, Pr, Nd etc.) and Et
3Al is catalysis THF polymerization under the effect of promotor oxyethane, and polymerization yield rate is not high under the room temperature, is heated to 50 ℃ of productive rates and just can reaches 40%.This system is very responsive to water, loses catalytic effect and Et when water-content in the system is 3 times of equivalents of catalyzer
3Al is inflammable and explosive substances, industrial use and transport all very inconvenient.
Patent report [international monopoly WO 9409055] trifluoromethanesulfonic acid metal (Co, V, Nb, W, Sr, Ti etc. were arranged in 1994, thulium is wherein also arranged) catalyzer, need be that promotor exists ability catalysis THF ring-opening polymerization down all with acyl chlorides, acid or acid anhydrides, polyreaction will neutralize with alkali, obtain the PTHF product of one or both ends ester group, need process acidolysis or hydrolysis just can obtain the polytetrahydrofuran of both-end hydroxyl with practical value, and the molecular weight of product wider distribution that obtains, range of application is restricted.
Report such as an aromatic plant metioned in ancient books in Shen [polymer journal 1997, (3), 347-352] oleum system catalysis tetrahydrofuran by polymerization of anhydrous chlorides of rase earth elements and 50%, obtaining relative viscosity-average molecular weight is 10,000 to 1.5 ten thousand, two ends are the PTHF of hydroxyl.The employed NdCl of every 100g monomer
3Be respectively 0.156g and 0.516g with the consumption of 50% oleum.Although the consumption of oleum is less than other catalyst system, the use of oleum still can influence the color and luster of product to a certain extent, and production unit is caused heavy corrosion.
Summary of the invention
The purpose of this invention is to provide a kind of method with the synthetic polytetrahydrofuran of trifluoromethanesulfonic acid rare earth compound catalysis.With the epoxy alkane is promotor, obtains that molecular weight is controlled in a big way, molecular weight distribution is narrower, colourless, purified two ends are the polytetrahydrofuran of hydroxyl.
A kind of method with the synthetic polytetrahydrofuran of trifluoromethanesulfonic acid rare earth compound catalysis, with the trifluoromethanesulfonic acid rare earth compound is catalyzer, and epoxy alkane is a promotor, in reaction solvent, catalysis tetrahydrofuran ring opening polymerization, synthetic molecular weight are 0.3 ten thousand to 130,000 polytetrahydrofuran; The mol ratio of described catalyzer and monomer tetrahydrofuran (THF) is 1: 100 to 1: 10000, and the mol ratio of catalyzer and promotor epoxy alkane is 1: 1.2 to 1: 20, and temperature of reaction is-25 ℃ to 55 ℃, and the reaction times is 0.75 to 72 hour; Thulium in the described trifluoromethanesulfonic acid rare earth compound is any one among Sc, Y, the La to Lu; The promotor epoxy alkane is a kind of in propylene oxide, oxyethane, cyclohexene oxide or the Styrene oxide 98min.; Reaction solvent is a kind of in tetrahydrofuran (THF), toluene, normal hexane or 1-methyl-4-butyl imidazole hexafluorophosphate.
A kind of method with the synthetic polytetrahydrofuran of trifluoromethanesulfonic acid rare earth compound catalysis, with the trifluoromethanesulfonic acid rare earth compound is catalyzer, and epoxy alkane is a promotor, in reaction solvent, catalysis tetrahydrofuran ring opening polymerization, synthetic molecular weight are 0.3 ten thousand to 130,000 polytetrahydrofuran; The mol ratio of described catalyzer and monomer tetrahydrofuran (THF) is 1: 500 to 1: 4800, and the mol ratio of catalyzer and promotor epoxy alkane is 1: 5 to 1: 15, and temperature of reaction is 10 ℃ to 40 ℃, and the reaction times is 0.75 to 72 hour; Thulium in the described trifluoromethanesulfonic acid rare earth compound is any one among Sc, Y, the La to Lu; The promotor epoxy alkane is a kind of in propylene oxide, oxyethane, cyclohexene oxide or the Styrene oxide 98min.; Reaction solvent is a kind of in tetrahydrofuran (THF), toluene, normal hexane or 1-methyl-4-butyl imidazole hexafluorophosphate.
With prior art relatively, the present invention has following advantage: 1) do not need to add acid or acid anhydrides, nontoxic, the non-corrosiveness of catalyzer, the polymerisate aftertreatment is simple, only need simple washing to remove catalyzer and get final product, not volume exogenously added alkali neutralization, production unit can not produce corrosion, not high to equipment requirements, operation expense is low; 2) Preparation of Catalyst is easy, has satisfactory stability, and is all insensitive to empty G﹠W, do not have the danger of combustion explosion, but prolonged preservation is used; 3) catalyst reaction is active high, and consumption is few, and catalyst levels can be low to moderate ten thousand/; Post-reaction treatment is simple, the catalyst residue amount is few; 4) synthetic polytetrahydrofuran product is colourless pure, and molecular weight is adjustable in 0.3 ten thousand to 130,000 intervals, dispersion index narrower (between 1.2 to 1.7), and the polytetrahydrofuran dispersion index that other catalysts obtain is generally more than 2.0.
Embodiment
Embodiment 1:
A kind of method with the synthetic polytetrahydrofuran of trifluoromethanesulfonic acid rare earth compound catalysis adds monomer THF and catalyzer Y (OSO in the exsiccant reactor
2CF
3)
3, treat to add propylene oxide PO, three's mol ratio THF: PO: Y (OSO after the catalyst dissolution
2CF
3)
3=500: 15: 1, behind 25 ℃ of following reaction 2.5h, add CHCl
3Dissolving washes with water and removes catalyzer, organic phase MgSO
4Drying is poured in the methyl alcohol after concentrating and is precipitated, and obtains colourless pure PTHF product, productive rate 62% 50 ℃ of following vacuum-dryings.Polymericular weight and distribute to adopt Waters-1515 gel permeation chromatograph (THF is a solvent, 40 ℃, flow velocity 1.0mL/min, polystyrene standards) to record molecular weight 4.3 ten thousand, molecular weight distributing index 1.5.
Embodiment 2:
A kind of method with the synthetic polytetrahydrofuran of trifluoromethanesulfonic acid rare earth compound catalysis, THF: PO: Y (OSO
2CF
3)
3=100: 5: 1, temperature of reaction was 25 ℃, and the reaction times is 0.75h.The PTHF productive rate is 60%, molecular weight 2.5 ten thousand, molecular weight distributing index 1.6, and all the other are identical with embodiment 1.
Embodiment 3:
A kind of method with the synthetic polytetrahydrofuran of trifluoromethanesulfonic acid rare earth compound catalysis, THF: PO: Y (OSO
2CF
3)
3=4800: 15: 1, temperature of reaction was 25 ℃, and the reaction times is 48h.The PTHF productive rate is 29%, molecular weight 130,000, molecular weight distributing index 1.5, and all the other are identical with embodiment 1.
Embodiment 4:
A kind of method with the synthetic polytetrahydrofuran of trifluoromethanesulfonic acid rare earth compound catalysis, THF: PO: Y (OSO
2CF
3)
3=10000: 15: 1, temperature of reaction was 25 ℃, and the reaction times is 72h.The PTHF productive rate is 9.2%, molecular weight 4.6 ten thousand, molecular weight distributing index 1.5, and all the other are identical with embodiment 1.
Embodiment 5:
A kind of method with the synthetic polytetrahydrofuran of trifluoromethanesulfonic acid rare earth compound catalysis, THF: PO: Y (OSO
2CF
3)
3=500: 1.2: 1, temperature of reaction was 25 ℃, and the reaction times is 2.5h.The PTHF productive rate is 28%, molecular weight 7.9 ten thousand, molecular weight distributing index 1.5, and all the other are identical with embodiment 1.
Embodiment 6:
A kind of method with the synthetic polytetrahydrofuran of trifluoromethanesulfonic acid rare earth compound catalysis, THF: PO: Y (OSO
2CF
3)
3=500: 20: 1, temperature of reaction was 25 ℃, and the reaction times is 2.5h.The PTHF productive rate is 53%, molecular weight 3.5 ten thousand, molecular weight distributing index 1.5, and all the other are identical with embodiment 1.
Embodiment 7:
A kind of method with the synthetic polytetrahydrofuran of trifluoromethanesulfonic acid rare earth compound catalysis, THF: PO: Y (OSO
2CF
3)
3=1400: 15: 1, temperature of reaction was-25 ℃, and the reaction times is 2.5h.The PTHF productive rate is 0.5%, molecular weight 0.3 ten thousand, molecular weight distributing index 1.2, and all the other are identical with embodiment 1.
Embodiment 8:
A kind of method with the synthetic polytetrahydrofuran of trifluoromethanesulfonic acid rare earth compound catalysis, THF: PO: Y (OSO
2CF
3)
3=1400: 15: 1, temperature of reaction was 10 ℃, and the reaction times is 2.5h.The PTHF productive rate is 10%, molecular weight 2.3 ten thousand, molecular weight distributing index 1.5, and all the other are identical with embodiment 1.
Embodiment 9:
A kind of method with the synthetic polytetrahydrofuran of trifluoromethanesulfonic acid rare earth compound catalysis, THF: PO: Y (OSO
2CF
3)
3=1400: 15: 1, temperature of reaction was 55 ℃, and the reaction times is 2.5h.The PTHF productive rate is 20%, molecular weight 3.1 ten thousand, molecular weight distributing index 1.6, and all the other are identical with embodiment 1.
Embodiment 10:
A kind of method with the synthetic polytetrahydrofuran of trifluoromethanesulfonic acid rare earth compound catalysis adds monomer THF and catalyzer La (OSO in the exsiccant reactor
2CF
3)
3, treat to add propylene oxide PO, three's mol ratio THF: PO: La (OSO after the catalyst dissolution
2CF
3)
3=500: 15: 1, behind 25 ℃ of following reaction 2.5h, add CHCl
3Dissolving washes with water and removes catalyzer, organic phase MgSO
4Drying is poured in the methyl alcohol after concentrating and is precipitated, and obtains colourless pure PTHF product, productive rate 32%, molecular weight 3.2 ten thousand, molecular weight distributing index 1.7 50 ℃ of following vacuum-dryings.
Embodiment 11:
A kind of method with the synthetic polytetrahydrofuran of trifluoromethanesulfonic acid rare earth compound catalysis adds monomer THF and catalyzer Dy (OSO in the exsiccant reactor
2CF
3)
3, treat to add propylene oxide PO, three's mol ratio THF: PO: Dy (OSO after the catalyst dissolution
2CF
3)
3=500: 5: 1, behind 25 ℃ of following reaction 2.5h, add CHCl
3Dissolving washes with water and removes catalyzer, organic phase MgSO
4Drying is poured in the methyl alcohol after concentrating and is precipitated, and obtains colourless pure PTHF product, productive rate 45%, molecular weight 8.0 ten thousand, molecular weight distributing index 1.4 50 ℃ of following vacuum-dryings.
Embodiment 12:
A kind of method with the synthetic polytetrahydrofuran of trifluoromethanesulfonic acid rare earth compound catalysis adds monomer THF and catalyzer Lu (OSO in the exsiccant reactor
2CF
3)
3, treat to add propylene oxide PO, three's mol ratio THF: PO: Lu (OSO after the catalyst dissolution
2CF
3)
3=500: 15: 1, behind 25 ℃ of following reaction 2.5h, add CHCl
3Dissolving washes with water and removes catalyzer, organic phase MgSO
4Drying is poured in the methyl alcohol after concentrating and is precipitated, and obtains colourless pure PTHF product, productive rate 49%, molecular weight 5.0 ten thousand, molecular weight distributing index 1.6 50 ℃ of following vacuum-dryings.
Embodiment 13:
A kind of method with the synthetic polytetrahydrofuran of trifluoromethanesulfonic acid rare earth compound catalysis adds monomer THF and catalyst S c (OSO in the exsiccant reactor
2CF
3)
3, treat to add propylene oxide PO, three's mol ratio THF: PO: Sc (OSO after the catalyst dissolution
2CF
3)
3=500: 15: 1, behind 25 ℃ of following reaction 2.5h, add CHCl
3Dissolving washes with water and removes catalyzer, organic phase MgSO
4Drying is poured in the methyl alcohol after concentrating and is precipitated, and obtains colourless pure PTHF product, productive rate 39%, molecular weight 1.6 ten thousand, molecular weight distributing index 1.6 50 ℃ of following vacuum-dryings.
Embodiment 14:
A kind of method with the synthetic polytetrahydrofuran of trifluoromethanesulfonic acid rare earth compound catalysis adds monomer THF and catalyzer Y (OSO in the exsiccant reactor
2CF
3)
3, treat to add oxyethane EO, three's mol ratio THF: EO: Y (OSO after the catalyst dissolution
2CF
3)
3=500: 9: 1, behind 25 ℃ of following reaction 2.5h, add CHCl
3Dissolving washes with water and removes catalyzer, organic phase MgSO
4Drying is poured in the methyl alcohol after concentrating and is precipitated, and obtains colourless pure PTHF product, productive rate 45%, molecular weight 9.9 ten thousand, molecular weight distributing index 1.4 50 ℃ of following vacuum-dryings.
Embodiment 15:
A kind of method with the synthetic polytetrahydrofuran of trifluoromethanesulfonic acid rare earth compound catalysis adds monomer THF and catalyzer Y (OSO in the exsiccant reactor
2CF
3)
3, treat to add Styrene oxide 98min. SO, three's mol ratio THF: SO: Y (OSO after the catalyst dissolution
2CF
3)
3=500: 15: 1, behind 25 ℃ of following reaction 2.5h, add CHCl
3Dissolving washes with water and removes catalyzer, organic phase MgSO
4Drying is poured in the methyl alcohol after concentrating and is precipitated, and obtains colourless pure PTHF product, productive rate 7.1%, molecular weight 4.0 ten thousand, molecular weight distributing index 1.3 50 ℃ of following vacuum-dryings.
Embodiment 16:
A kind of method with the synthetic polytetrahydrofuran of trifluoromethanesulfonic acid rare earth compound catalysis adds monomer THF and catalyzer Y (OSO in the exsiccant reactor
2CF
3)
3, treat to add cyclohexene oxide CHO, three's mol ratio THF: CHO: Y (OSO after the catalyst dissolution
2CF
3)
3=500: 10: 1, behind 25 ℃ of following reaction 2.5h, add CHCl
3Dissolving washes with water and removes catalyzer, organic phase MgSO
4Drying is poured in the methyl alcohol after concentrating and is precipitated, and obtains colourless pure PTHF product, productive rate 41%, molecular weight 4.3 ten thousand, molecular weight distributing index 1.5 50 ℃ of following vacuum-dryings.
Embodiment 17:
A kind of method with the synthetic polytetrahydrofuran of trifluoromethanesulfonic acid rare earth compound catalysis adds toluene (with the THF equal-volume), monomer THF and catalyzer Y (OSO in the exsiccant reactor
2CF
3)
3, treat to add propylene oxide PO, mol ratio THF: PO: Y (OSO after the catalyst dissolution
2CF
3)
3=500: 15: 1, behind 25 ℃ of following reaction 2.5h, add CHCl
3Dissolving washes with water and removes catalyzer, organic phase MgSO
4Drying is poured in the methyl alcohol after concentrating and is precipitated, and obtains colourless pure PTHF product, productive rate 13%, molecular weight 1.5 ten thousand, molecular weight distributing index 1.4 50 ℃ of following vacuum-dryings.
Embodiment 18:
A kind of method with the synthetic polytetrahydrofuran of trifluoromethanesulfonic acid rare earth compound catalysis adds normal hexane (with the THF equal-volume), monomer THF and catalyzer Y (OSO in the exsiccant reactor
2CF
3)
3, treat to add propylene oxide PO, mol ratio THF: PO: Y (OSO after the catalyst dissolution
2CF
3)
3=500: 15: 1, behind 25 ℃ of following reaction 2.5h, add CHCl
3Dissolving washes with water and removes catalyzer, organic phase MgSO
4Drying is poured in the methyl alcohol after concentrating and is precipitated, and obtains colourless pure PTHF product, productive rate 13%, molecular weight 1.6 ten thousand, molecular weight distributing index 1.4 50 ℃ of following vacuum-dryings.
Embodiment 19:
A kind of method with the synthetic polytetrahydrofuran of trifluoromethanesulfonic acid rare earth compound catalysis adds 1-methyl-4-butyl imidazole hexafluorophosphate (with the THF equal-volume), monomer THF and catalyzer Y (OSO in the exsiccant reactor
2CF
3)
3, treat to add propylene oxide PO, three's mol ratio THF: PO: Y (OSO after the catalyst dissolution
2CF
3)
3=500: 15: 1, behind 25 ℃ of following reaction 2.5h, add CHCl
3Dissolving washes with water and removes catalyzer, organic phase MgSO
4Drying is poured in the methyl alcohol after concentrating and is precipitated, and obtains colourless pure PTHF product, productive rate 36%, molecular weight 4.6 ten thousand, molecular weight distributing index 1.6 50 ℃ of following vacuum-dryings.
Claims (2)
1. method with the synthetic polytetrahydrofuran of trifluoromethanesulfonic acid rare earth compound catalysis, with the trifluoromethanesulfonic acid rare earth compound is catalyzer, epoxy alkane is a promotor, in reaction solvent, catalysis tetrahydrofuran ring opening polymerization, synthetic molecular weight are 0.3 ten thousand to 130,000 polytetrahydrofuran; The mol ratio of described catalyzer and monomer tetrahydrofuran (THF) is 1: 100 to 1: 10000, and the mol ratio of catalyzer and promotor epoxy alkane is 1: 1.2 to 1: 20, and temperature of reaction is-25 ℃ to 55 ℃, and the reaction times is 0.75 to 72 hour; Thulium in the described trifluoromethanesulfonic acid rare earth compound is any one among Sc, Y, the La to Lu; The promotor epoxy alkane is a kind of in propylene oxide, oxyethane, cyclohexene oxide or the Styrene oxide 98min.; Reaction solvent is a kind of in tetrahydrofuran (THF), toluene, normal hexane or 1-methyl-4-butyl imidazole hexafluorophosphate.
2. method with the synthetic polytetrahydrofuran of trifluoromethanesulfonic acid rare earth compound catalysis, with the trifluoromethanesulfonic acid rare earth compound is catalyzer, epoxy alkane is a promotor, in reaction solvent, catalysis tetrahydrofuran ring opening polymerization, synthetic molecular weight are 0.3 ten thousand to 130,000 polytetrahydrofuran; The mol ratio of described catalyzer and monomer tetrahydrofuran (THF) is 1: 500 to 1: 4800, and the mol ratio of catalyzer and promotor epoxy alkane is 1: 5 to 1: 15, and temperature of reaction is 10 ℃ to 40 ℃, and the reaction times is 0.75 to 72 hour; Thulium in the described trifluoromethanesulfonic acid rare earth compound is any one among Sc, Y, the La to Lu; The promotor epoxy alkane is a kind of in propylene oxide, oxyethane, cyclohexene oxide or the Styrene oxide 98min.; Reaction solvent is a kind of in tetrahydrofuran (THF), toluene, normal hexane or 1-methyl-4-butyl imidazole hexafluorophosphate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102897545A CN101942084B (en) | 2010-09-25 | 2010-09-25 | Method for catalytic synthesis of polytetrahydrofuran in the presence of trifloromethanesulfonic acid rare earth metallic compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102897545A CN101942084B (en) | 2010-09-25 | 2010-09-25 | Method for catalytic synthesis of polytetrahydrofuran in the presence of trifloromethanesulfonic acid rare earth metallic compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101942084A true CN101942084A (en) | 2011-01-12 |
| CN101942084B CN101942084B (en) | 2012-01-25 |
Family
ID=43434305
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102897545A Active CN101942084B (en) | 2010-09-25 | 2010-09-25 | Method for catalytic synthesis of polytetrahydrofuran in the presence of trifloromethanesulfonic acid rare earth metallic compounds |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101942084B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106220840A (en) * | 2016-08-18 | 2016-12-14 | 浙江大学 | A kind of synthetic method of hyperbranched poly oxolane |
| CN111072954A (en) * | 2019-12-27 | 2020-04-28 | 浙江大学 | Polytetrahydrofuran-polyamino acid block copolymer and synthetic method thereof |
| CN112876665A (en) * | 2021-02-04 | 2021-06-01 | 浙江大学 | Method for synthesizing polyester or polyether ester containing polyunsaturated side group by using rare earth catalyst and post-modification method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3842019A (en) * | 1969-04-04 | 1974-10-15 | Minnesota Mining & Mfg | Use of sulfonic acid salts in cationic polymerization |
| EP0442635A1 (en) * | 1990-02-12 | 1991-08-21 | Minnesota Mining And Manufacturing Company | Novel initiators for cationic polymerization |
| JP2554413B2 (en) * | 1990-07-05 | 1996-11-13 | ユニオン・カーバイド・ケミカルズ・アンド・プラスティックス・カンパニー・インコーポレイテッド | Reduction of halide contamination in alkoxysilane |
| CN1092682C (en) * | 1994-10-28 | 2002-10-16 | 纳幕尔杜邦公司 | Polymerization of cyclic ethers using selected metal compound catalysts |
| CN1968916A (en) * | 2004-06-18 | 2007-05-23 | 纳幕尔杜邦公司 | Process for preparation of polytrimethylene ether glycols |
| CN101842412A (en) * | 2007-11-01 | 2010-09-22 | 纳幕尔杜邦公司 | The preparation of polytrimethylene ether glycol |
-
2010
- 2010-09-25 CN CN2010102897545A patent/CN101942084B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3842019A (en) * | 1969-04-04 | 1974-10-15 | Minnesota Mining & Mfg | Use of sulfonic acid salts in cationic polymerization |
| EP0442635A1 (en) * | 1990-02-12 | 1991-08-21 | Minnesota Mining And Manufacturing Company | Novel initiators for cationic polymerization |
| JP2554413B2 (en) * | 1990-07-05 | 1996-11-13 | ユニオン・カーバイド・ケミカルズ・アンド・プラスティックス・カンパニー・インコーポレイテッド | Reduction of halide contamination in alkoxysilane |
| CN1092682C (en) * | 1994-10-28 | 2002-10-16 | 纳幕尔杜邦公司 | Polymerization of cyclic ethers using selected metal compound catalysts |
| CN1968916A (en) * | 2004-06-18 | 2007-05-23 | 纳幕尔杜邦公司 | Process for preparation of polytrimethylene ether glycols |
| CN101842412A (en) * | 2007-11-01 | 2010-09-22 | 纳幕尔杜邦公司 | The preparation of polytrimethylene ether glycol |
Non-Patent Citations (2)
| Title |
|---|
| 《催化学报》 19930731 李凤富，金鹰泰，管伟刚，裴奉奎，王佛松 稀土催化四氢呋喃开环聚合 329-332 第14卷, 第4期 2 * |
| 《高等学校化学学报》 20070630 朱蔚璞, 童晓薇, 沈之荃 三氟甲磺酸稀土催化epsilon-己内酯开环聚合 第28卷, 第6期 2 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106220840A (en) * | 2016-08-18 | 2016-12-14 | 浙江大学 | A kind of synthetic method of hyperbranched poly oxolane |
| CN111072954A (en) * | 2019-12-27 | 2020-04-28 | 浙江大学 | Polytetrahydrofuran-polyamino acid block copolymer and synthetic method thereof |
| CN112876665A (en) * | 2021-02-04 | 2021-06-01 | 浙江大学 | Method for synthesizing polyester or polyether ester containing polyunsaturated side group by using rare earth catalyst and post-modification method thereof |
| CN112876665B (en) * | 2021-02-04 | 2022-03-18 | 浙江大学 | Method for synthesizing polyester or polyether ester containing polyunsaturated side group by using rare earth catalyst and post-modification method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101942084B (en) | 2012-01-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1200506B1 (en) | Polymerization of ethylene oxide using metal cyanide catalsyts | |
| CA2177871C (en) | Process for making ethylene oxide-capped polyols from double metal cyanide-catalyzed polyols | |
| CN101108896B (en) | High water content tolerant process for the production of polyethers | |
| CN101967226B (en) | Method for synthesizing high-activity high molecular weight polyether polyalcohol | |
| EP1173498B1 (en) | Long-chain polyether polyols with a high proportion of primary oh groups | |
| EP3129419B1 (en) | Method for the preparation of polyoxymethylene block copolymers | |
| CN101942084B (en) | Method for catalytic synthesis of polytetrahydrofuran in the presence of trifloromethanesulfonic acid rare earth metallic compounds | |
| CN101851329A (en) | Starter feed stream acidification in dmc-catalyzed process for the production of polyether polyols | |
| KR970010829A (en) | Improved polyether-containing double metal cyanide catalysts | |
| US6642423B2 (en) | Polymerization of ethylene oxide using metal cyanide catalysts | |
| CN108239265A (en) | Organic phosphazenium catalyst and its preparation method and application | |
| Jang et al. | Facile room-temperature preparation of flexible polyurethane foams from carbon dioxide based poly (ether carbonate) polyols with a reduced generation of acetaldehyde | |
| US5659089A (en) | Process for making poly(2-methyl-1,3-propanediol) | |
| CN104910369B (en) | A kind of preparation method of tetrahydrofuran copolyether | |
| JPH10510315A (en) | Polyether glycols and alcohols derived from 3,4-epoxy-1-butene, tetrahydrofuran and initiator | |
| US5262562A (en) | Polyether glycol production by polymerization of tetrahydrofuran | |
| CA2391924A1 (en) | Method for producing polyether polyols | |
| EP1448663B1 (en) | Process for the alkoxylation of organic compounds | |
| CN101274966A (en) | Acyclic lithium alkylide evocating agent with hydroxylic protected by silane, preparation thereof and application thereof | |
| KR102661311B1 (en) | Continuous process for producing polyether polyols | |
| CN114891200A (en) | Ionic liquid catalyst and method for catalytically synthesizing tetrahydrofuran ethylene oxide copolyether by using same | |
| Taquet et al. | A possible route to the controlled synthesis of polymethyloxirane oligomers using bimetallic μ‐oxoalkoxides | |
| CN116082627A (en) | Epoxy group end-capped fatty alcohol polyether and end-capping method of fatty alcohol polyether | |
| CN101602851A (en) | A kind of method and specific equipment for preparing polytetramethylene ether diol | |
| Shen et al. | Highly active rare earth catalysts for the solution polymerization of ε-caprolactone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |