CN101942084B - 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
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 34
- 229920000909 polytetrahydrofuran Polymers 0.000 title abstract description 29
- 239000002253 acid Substances 0.000 title abstract description 7
- 150000002910 rare earth metals Chemical class 0.000 title abstract description 5
- 150000001875 compounds Chemical class 0.000 title abstract 4
- 238000007036 catalytic synthesis reaction Methods 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 7
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 7
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 4
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 170
- -1 trifluoromethanesulfonic acid rare earth compound Chemical class 0.000 claims description 40
- 238000006555 catalytic reaction Methods 0.000 claims description 37
- 229920001519 homopolymer Polymers 0.000 claims description 35
- 239000000178 monomer Substances 0.000 claims description 16
- 239000004593 Epoxy Substances 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 11
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052775 Thulium Inorganic materials 0.000 claims description 4
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 20
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 125000002947 alkylene group Chemical group 0.000 abstract 1
- 229910052746 lanthanum Inorganic materials 0.000 abstract 1
- 230000001988 toxicity Effects 0.000 abstract 1
- 231100000419 toxicity Toxicity 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 239000000047 product Substances 0.000 description 16
- 238000005406 washing Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000004090 dissolution Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 239000012074 organic phase Substances 0.000 description 11
- 238000001291 vacuum drying Methods 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002761 deinking Substances 0.000 description 1
- WICQXESQFGXSKV-UHFFFAOYSA-N disulfuryl fluoride Chemical compound FS(=O)(=O)OS(F)(=O)=O WICQXESQFGXSKV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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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 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 THF homopolymer, particularly a kind of method with the synthetic THF homopolymer of trifluoromethanesulfonic acid rare earth compound catalysis.
Technical background
THF homopolymer (being called for short " PTHF ") is also referred to as the polyoxybutylene glycol, is the multi-usage midbody 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 as dispersion agent or be used for the deinking etc. of waste paper.
[U.S. Pat 5393866] such as nineteen ninety-five N.Murai reported a kind of fluosulfonic acid homogeneous catalyst catalysis 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 one type can catalysis THF ring-opening polymerization catalyzer, 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] are with (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, when water-content in the system is 3 times of equivalents of catalyzer, loses catalytic effect and Et
3Al is inflammable and explosive substances, uses and transport all very inconvenience in the industry.
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, obtains the PTHF product of one or both ends ester group, needs process acidolysis or hydrolysis just can obtain the THF homopolymer 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] is with the oleum system catalysis tetrahydrofuran by polymerization of anhydrous chlorides of rase earth elements and 50%, and obtaining relative viscosity-average molecular weight is 10,000 to 1.5 ten thousand, and 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 catalystsystem, 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 THF homopolymer of trifluoromethanesulfonic acid rare earth compound catalysis.With the epoxy alkane is promotor, obtains that molecular weight is controlled in a big way, MWD is narrower, colourless, purified two ends are the THF homopolymer of hydroxyl.
A kind of method with the synthetic THF homopolymer 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 THF homopolymer; The mol ratio of described catalyzer and monomer 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 THF, toluene, normal hexane or 1-methyl-4-NSC 158165 hexafluorophosphate.
A kind of method with the synthetic THF homopolymer 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 THF homopolymer; The mol ratio of described catalyzer and monomer 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 THF, toluene, normal hexane or 1-methyl-4-NSC 158165 hexafluorophosphate.
With prior art relatively, the present invention has following advantage: 1) need not 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 property, 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 THF homopolymer 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 THF homopolymer dispersion index that other catalysts obtain is generally more than 2.0.
Embodiment
Embodiment 1:
A kind of method with the synthetic THF homopolymer of trifluoromethanesulfonic acid rare earth compound catalysis adds monomer THF and catalyzer Y (OSO in the exsiccant reactor drum
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 is removed catalyzer with water washing, and organic phase is used 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 THF homopolymer 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 THF homopolymer 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 THF homopolymer 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 THF homopolymer 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 THF homopolymer 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 THF homopolymer 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 THF homopolymer 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 THF homopolymer 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 THF homopolymer of trifluoromethanesulfonic acid rare earth compound catalysis adds monomer THF and catalyzer La (OSO in the exsiccant reactor drum
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 is removed catalyzer with water washing, and organic phase is used 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 THF homopolymer of trifluoromethanesulfonic acid rare earth compound catalysis adds monomer THF and catalyzer Dy (OSO in the exsiccant reactor drum
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 is removed catalyzer with water washing, and organic phase is used 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 THF homopolymer of trifluoromethanesulfonic acid rare earth compound catalysis adds monomer THF and catalyzer Lu (OSO in the exsiccant reactor drum
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 is removed catalyzer with water washing, and organic phase is used 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 THF homopolymer of trifluoromethanesulfonic acid rare earth compound catalysis adds monomer THF and catalyst S c (OSO in the exsiccant reactor drum
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 is removed catalyzer with water washing, and organic phase is used 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 THF homopolymer of trifluoromethanesulfonic acid rare earth compound catalysis adds monomer THF and catalyzer Y (OSO in the exsiccant reactor drum
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 is removed catalyzer with water washing, and organic phase is used 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 THF homopolymer of trifluoromethanesulfonic acid rare earth compound catalysis adds monomer THF and catalyzer Y (OSO in the exsiccant reactor drum
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 is removed catalyzer with water washing, and organic phase is used 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 THF homopolymer of trifluoromethanesulfonic acid rare earth compound catalysis adds monomer THF and catalyzer Y (OSO in the exsiccant reactor drum
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 is removed catalyzer with water washing, and organic phase is used 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 THF homopolymer of trifluoromethanesulfonic acid rare earth compound catalysis adds toluene (with the THF equal-volume), monomer THF and catalyzer Y (OSO in the exsiccant reactor drum
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 is removed catalyzer with water washing, and organic phase is used 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 THF homopolymer 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 drum
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 is removed catalyzer with water washing, and organic phase is used 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 THF homopolymer of trifluoromethanesulfonic acid rare earth compound catalysis adds 1-methyl-4-NSC 158165 hexafluorophosphate (with the THF equal-volume), monomer THF and catalyzer Y (OSO in the exsiccant reactor drum
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 is removed catalyzer with water washing, and organic phase is used 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 THF homopolymer of trifluoromethanesulfonic acid rare earth compound catalysis; It is characterized in that: 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 THF homopolymer; The mol ratio of described catalyzer and monomer 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-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 THF, toluene, normal hexane or 1-methyl-4-NSC 158165 hexafluorophosphate.
2. the method with the synthetic THF homopolymer of trifluoromethanesulfonic acid rare earth compound catalysis according to claim 1; It is characterized in that: the mol ratio of catalyzer and monomer THF is 1: 500 to 1: 4800; The mol ratio of catalyzer and promotor epoxy alkane is 1: 5 to 1: 15; Temperature of reaction is 10 ℃ to 40 ℃, and the reaction times is 0.75 to 72 hour.
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| CN111072954B (en) * | 2019-12-27 | 2021-01-08 | 浙江大学 | Polytetrahydrofuran-polyamino acid block copolymer and synthetic method thereof |
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