CN1324068C - Prepn process of catalyst for ring opening polymerization of ethylene oxide - Google Patents
Prepn process of catalyst for ring opening polymerization of ethylene oxide Download PDFInfo
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- CN1324068C CN1324068C CNB2004100539742A CN200410053974A CN1324068C CN 1324068 C CN1324068 C CN 1324068C CN B2004100539742 A CNB2004100539742 A CN B2004100539742A CN 200410053974 A CN200410053974 A CN 200410053974A CN 1324068 C CN1324068 C CN 1324068C
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Abstract
The present invention relates to a method for preparing catalyst for ring opening polymerization of epoxy ethane. Calcium metal having larger than 99.5 percent of purity is dissolved in liquid ammonia and the molar ratio of ammonia to the calcium metal is from 10 to 100: 1. Modifying agent which is composed of propylene oxide and acetonitrile, and carriers are added. The molar ratio of the propylene oxide to the calcium metal is from 0.1 to 2: 1, the molar ratio of the acetonitrile to the calcium metal is from 0.1 to 1: 1, and the weight ratio of the carrier to the calcium metal is from 0.1 to 5: 1. The carrier is one of the kind of nanometer silicon dioxide or a nanometer mesoporous molecular sieve. The reaction temperature is from 70 DEG C below zero to 34 DEG C below zero. After the reaction reacts fully, the excess liquid ammonia is vaporized. The remaining product forms slurry by using saturated alkane slurry agent having high boiling point so as to obtain grey slurry catalyst finally. The catalyst prepared by the method of the present invention obviously enhances the activity of the catalyst and the stability of storage. The present invention is used for ring opening polymerization of epoxy ethane.
Description
Technical field
The present invention relates to a kind of epoxyethane ring-expansion polymerization Preparation of catalysts method.
Background technology
Ring-opening polymerization belongs to anionoid polymerization mechanism, and used heterogeneous catalyst has alkaline-earth metal amide system, zinc alkyl(s)-pure system, aluminum alkoxide-water-ketene system, aluminum alkyls-water-methyl ethyl diketone system etc.Wherein alkaline-earth metal amide system receives much concern owing to its special advantages.
In the prior art, U.S. combinating carbide company discloses two pieces of patents that are used for epoxyethane ring-expansion polymerization, and (USP4193892, USP3127358), and catalyzer has obtained molecular weight greater than 6,000,000 polyoxyethylene (PEO) thus.Though two pieces of U.S. Patent Publications the alkaline-earth metal catalyst of epoxyethane ring-expansion polymerization, be characterized in having at normal temperatures high reactivity, but these patents all do not provide concrete catalyst preparation process, and up to the present also do not have the report about lower molecular weight polyoxyethylene method for preparing catalyst.
Summary of the invention
The purpose of this invention is to provide a kind of epoxyethane ring-expansion polymerization Preparation of catalysts method, a kind of lower molecular weight polyoxyethylene Preparation of catalysts method particularly is provided.This catalyzer is used for the ring-opening polymerization of oxyethane by alkaline earth metals calcium, ammonia, properties-correcting agent, carrier and solvent composition.
The present invention realizes like this.This epoxyethane ring-expansion polymerization Preparation of catalysts method is that calcium metal is dissolved in the liquefied ammonia, the purity of calcium metal is greater than 99.5%, the mol ratio of ammonia and calcium metal is 10～100: 1, add properties-correcting agent and carrier then, properties-correcting agent is made up of propylene oxide and acetonitrile, the mol ratio of propylene oxide and calcium metal is 0.1～2: 1, the mol ratio of acetonitrile and calcium metal is 0.1～1: 1, carrier and calcium metal weight ratio be 0.1～5: 1, described carrier is a kind of in nano silicon or the nano mesoporous molecular screen, and it is-70 ℃～-34 ℃ that reaction process keeps temperature.After question response is abundant excessive liquefied ammonia is evaporated, remaining product high boiling point saturated alkane slurry agent slurryization, its boiling point obtains greyish white paste-like catalyzer at last at 100 ℃～200 ℃.
Carrier among the present invention is preferably the gas phase nano grade silicon dioxide.
Carrier nano mesoporous molecular screen among the present invention is to choose any one kind of them among MCM-41, the MCM-48, and its structure is the hexagonal hole road, and homogeneous is arranged, and perhaps structure is that the duct is cubic, aperture 1.6～10nm, specific surface area 500～1200m
2/ g.
The propylene oxide among the present invention and the mol ratio of calcium metal are preferably 0.4～1: 1.
The acetonitrile among the present invention and the mol ratio of calcium metal are preferably 0.2～0.6: 1.
High boiling point saturated alkane slurry agent among the present invention is preferably normal heptane.
High boiling point saturated alkane slurry agent among the present invention is preferably normal hexane.
The present invention is dissolved in alkaline earth metals calcium in the ammonia of dehydration, forms " six ammonia calcium " (Ca (NH
3)
6) compound, add properties-correcting agent and carrier then.The catalyst activity height that obtains thus, the use temperature scope is big, and polymerization yield height, the molecular weight of resulting polyoxyethylene are 5～2,000,000.
The present invention is owing to added and have high-specific surface area (specific surface area is at 500～1200m
2/ g) nanometer grade silica and nano mesoporous molecular screen as carrier, increased the quantity of catalytic active center, improved the distribution of catalytic active center, increased the contact area of catalytic active center and reactant, obviously improved activity of such catalysts and stability in storage at carrier surface.Catalyzer of the present invention is used for the ring-opening polymerization of oxyethane, and polymeric reaction temperature is-10 ℃～60 ℃, and polymerization time is 2～10 hours, and the molecular weight of the polyoxyethylene that obtains is 5～2,000,000.
Embodiment
Further specify the present invention below by specific descriptions, but embodiment not a limitation of the present invention to the embodiment of the invention.
Embodiment 1
(1) Preparation of catalysts
Under agitation with purity greater than 99.5% 8g calcium metal, 400mL dehydration liquefied ammonia adds have been got rid of in the there-necked flask of empty G﹠W in advance, flask places liquid nitrogen-acetone low temperature to bathe.Keep nitrogen atmosphere, add the 12mL propylene oxide then, the 5mL acetonitrile, 1g gas phase nano grade silicon dioxide maintains the temperature at-70 ℃～-35 ℃.Fully after the reaction, at room temperature, with reaction product normal heptane slurryization, obtain canescence slurry catalyst 127.6g at last with excessive liquefied ammonia evaporation.
(2) polymerization of oxyethane
The 10L enamel reaction still that polymerization reaction kettle stirs for band.Adopt the rhythmic reaction mode, catalyzer, 2.4L120# solvent oil and the 800g oxyethane of disposable adding step (1) preparation.At 0 ℃～50 ℃ following polymerization 5h.The gained polyoxyethylene is a white granular, epigranular, and molecular weight is 78.6 ten thousand.
Embodiment 2
(1) Preparation of catalysts
Remove the 12mL propylene oxide, the 5mL acetonitrile changes the 13.5mL propylene oxide into, the 5.4mL acetonitrile, and reaction product is outside the pale of civilization with the normal hexane slurry, and all the other operations are identical with embodiment 1, make 132.0g canescence catalyst slurry liquid.
(2) polymerization of oxyethane
With the catalyzer of above-mentioned preparation, except that the 120# solvent oil and 560g oxyethane that add 1700mL, remaining working method is identical with embodiment 1 step (2), carry out the polymerization of oxyethane, the gained polyoxyethylene is a white granular, epigranular, and molecular weight is 23.2 ten thousand.
Embodiment 3
(1) Preparation of catalysts
Except that 1g gas phase nano grade silicon dioxide is changed into the 2g gas phase nano grade silicon dioxide, all the other operations are identical with embodiment 1, make 134.4g canescence catalyst slurry liquid.
(2) polymerization of oxyethane
With the catalyzer of above-mentioned preparation, adopt the identical method of embodiment 1 step (2) to carry out the polymerization of oxyethane, the gained polyoxyethylene is a white granular, epigranular, molecular weight is 74.2 ten thousand.
Embodiment 4
(1) Preparation of catalysts
Except that 1g gas phase nano grade silicon dioxide being changed into the mesoporous MCM-41 molecular sieve of 1g, all the other operations are identical with embodiment 1, make 129.4g canescence catalyst slurry liquid.
(2) polymerization of oxyethane
With the catalyzer of above-mentioned preparation, adopt the identical method of embodiment 1 step (2) to carry out the polymerization of oxyethane, the gained polyoxyethylene is a white granular, epigranular, molecular weight is 69.8 ten thousand.
Embodiment 5
(1) Preparation of catalysts
Remove the 12mL propylene oxide, the 5mL acetonitrile changes the 12.8mL propylene oxide into, and 4.1mL acetonitrile, 1g gas phase nano grade silicon dioxide change into outside the mesoporous MCM-48 molecular sieve of 1g, and all the other operations are identical with embodiment 1, make 129.5g canescence catalyst slurry liquid.
(2) polymerization of oxyethane
With the catalyzer of above-mentioned preparation, adopt the identical method of embodiment 1 step (2) to carry out the polymerization of oxyethane, the gained polyoxyethylene is a white granular, epigranular, molecular weight is 102.6 ten thousand.
Embodiment 6
(1) Preparation of catalysts
Remove the 12mL propylene oxide, the 5mL acetonitrile changes the 10mL propylene oxide into, and outside the 4mL acetonitrile, all the other operations are identical with embodiment 1, make 124.6g canescence catalyst slurry liquid.
(2) polymerization of oxyethane
With the catalyzer of above-mentioned preparation, adopt the identical method of embodiment 1 step (2) to carry out the polymerization of oxyethane, the gained polyoxyethylene is a white granular, epigranular, molecular weight is 114.3 ten thousand.
Claims (7)
1, a kind of epoxyethane ring-expansion polymerization Preparation of catalysts method, it is characterized in that calcium metal is dissolved in the liquefied ammonia, the purity of calcium metal is greater than 99.5%, the mol ratio of ammonia and calcium metal is 10～100: 1, add properties-correcting agent and carrier then, properties-correcting agent is made up of propylene oxide and acetonitrile, the mol ratio of propylene oxide and calcium metal is 0.1～2: 1, the mol ratio of acetonitrile and calcium metal is 0.1～1: 1, carrier and calcium metal weight ratio be 0.1～5: 1, described carrier is a kind of in nano silicon or the nano mesoporous molecular screen, and the specific surface area of nano silicon is 500～1200m
2/ g, the structure of nano mesoporous molecular screen is the hexagonal hole road, and homogeneous is arranged, and perhaps structure is that the duct is cubic, aperture 1.6～10nm, specific surface area 500～1200m
2/ g, it is-70 ℃～-34 ℃ that reaction process keeps temperature, after question response is abundant excessive liquefied ammonia is evaporated, remaining product high boiling point saturated alkane slurry agent slurryization, its boiling point obtains greyish white paste-like catalyzer at last at 100 ℃～200 ℃.
2, epoxyethane ring-expansion polymerization Preparation of catalysts method according to claim 1 is characterized in that carrier is the gas phase nano grade silicon dioxide.
3, epoxyethane ring-expansion polymerization Preparation of catalysts method according to claim 1 is characterized in that the carrier nano mesoporous molecular screen is to choose any one kind of them among MCM-41, the MCM-48.
4, epoxyethane ring-expansion polymerization Preparation of catalysts method according to claim 1, the mol ratio that it is characterized in that propylene oxide and calcium metal is 0.4～1: 1.
5, epoxyethane ring-expansion polymerization Preparation of catalysts method according to claim 1, the mol ratio that it is characterized in that acetonitrile and calcium metal is 0.2～0.6: 1.
6, epoxyethane ring-expansion polymerization Preparation of catalysts method according to claim 1 is characterized in that the agent of high boiling point saturated alkane slurry is a normal heptane.
7, epoxyethane ring-expansion polymerization Preparation of catalysts method according to claim 1 is characterized in that the agent of high boiling point saturated alkane slurry is a normal hexane.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2004100539742A CN1324068C (en) | 2004-08-24 | 2004-08-24 | Prepn process of catalyst for ring opening polymerization of ethylene oxide |
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|---|---|---|---|
| CNB2004100539742A CN1324068C (en) | 2004-08-24 | 2004-08-24 | Prepn process of catalyst for ring opening polymerization of ethylene oxide |
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| CN1740209A CN1740209A (en) | 2006-03-01 |
| CN1324068C true CN1324068C (en) | 2007-07-04 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101392052B (en) * | 2007-09-18 | 2011-07-27 | 上海化工研究院 | Method for preparing composite catalyst applied to epoxyethane ring-expansion polymerization |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101392053B (en) * | 2007-09-18 | 2011-04-06 | 上海化工研究院 | Method for preparing composite catalyst applied to alkylene oxide ring-expansion polymerization and use |
| CN102002159B (en) * | 2010-11-05 | 2013-05-22 | 中国蓝星（集团）股份有限公司 | Method for preparing polyphenyl ether |
| CN102030896B (en) * | 2010-11-15 | 2012-06-13 | 上海豪胜化工科技有限公司 | Polyalkylene oxide catalyst with medium-low molecular weight and preparation method thereof |
| JP2015508108A (en) | 2012-01-30 | 2015-03-16 | ダウ グローバル テクノロジーズ エルエルシー | Process for preparing an olefin oxide polymerization catalyst |
| EP2809703B1 (en) | 2012-01-30 | 2016-08-03 | Dow Global Technologies LLC | Process for preparing high molecular weight polymers by polymerizing epoxide monomers |
| CN103539931A (en) * | 2013-11-01 | 2014-01-29 | 上海联胜化工有限公司 | Preparation method of catalyst for synthesizing medium and low-molecular weight polyethylene oxide |
| CN105504258B (en) * | 2016-01-28 | 2018-11-27 | 上海化工研究院有限公司 | The loaded catalyst of synthesis low molecular weight polyethylene glycol oxide and its preparation and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4193892A (en) * | 1976-11-11 | 1980-03-18 | Union Carbide Corporation | Process for preparing olefin oxide polymerization catalysts by aging the catalysts |
| US4267309A (en) * | 1978-07-28 | 1981-05-12 | Union Carbide Corporation | Process for preparing olefin oxide polymerization catalysts |
| CN1114644C (en) * | 2000-12-29 | 2003-07-16 | 中国科学院长春应用化学研究所 | Process for synthesizing catalyst of open-loop polymerizing ethylene oxide |
-
2004
- 2004-08-24 CN CNB2004100539742A patent/CN1324068C/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4193892A (en) * | 1976-11-11 | 1980-03-18 | Union Carbide Corporation | Process for preparing olefin oxide polymerization catalysts by aging the catalysts |
| US4267309A (en) * | 1978-07-28 | 1981-05-12 | Union Carbide Corporation | Process for preparing olefin oxide polymerization catalysts |
| CN1114644C (en) * | 2000-12-29 | 2003-07-16 | 中国科学院长春应用化学研究所 | Process for synthesizing catalyst of open-loop polymerizing ethylene oxide |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101392052B (en) * | 2007-09-18 | 2011-07-27 | 上海化工研究院 | Method for preparing composite catalyst applied to epoxyethane ring-expansion polymerization |
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| CN1740209A (en) | 2006-03-01 |
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Assignee: Shanghai Liansheng Chemical Co., Ltd. Assignor: Shanghai Research Institute of Chemical Industry Contract fulfillment period: 2007.8.1 to 2012.7.31 contract change Contract record no.: 2008310000087 Denomination of invention: Prepn process of catalyst for ring opening polymerization of ethylene oxide Granted publication date: 20070704 License type: Exclusive license Record date: 2008.9.25 |
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Free format text: EXCLUSIVE LICENCE; TIME LIMIT OF IMPLEMENTING CONTACT: 2007.8.1 TO 2012.7.31 Name of requester: SHANGHAI LIAN SHENG CHEMICAL CO., LTD. Effective date: 20080925 |
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Owner name: SHANGHAI LIANSHENG CHEMICAL CO., LTD. SHANGHAI HAO Effective date: 20120917 |
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Effective date of registration: 20120917 Address after: 200062 Shanghai Yunling Road No. 345 Patentee after: Shanghai Research Institute of Chemical Industry Patentee after: Shanghai Liansheng Chemical Co., Ltd. Patentee after: Shanghai Haosheng Chemical Technology Co., Ltd. Address before: 200062 Shanghai Yunling Road No. 345 Patentee before: Shanghai Research Institute of Chemical Industry |
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Address after: 200062 Shanghai Yunling Road No. 345 Patentee after: Shanghai Research Institute of Chemical Industry Patentee after: Shanghai Liansheng Chemical Co., Ltd. Patentee after: Shanghai Haosheng Chemical Technology Co., Ltd. Address before: 200062 Shanghai Yunling Road No. 345 Patentee before: Shanghai Research Institute of Chemical Industry Patentee before: Shanghai Liansheng Chemical Co., Ltd. Patentee before: Shanghai Haosheng Chemical Technology Co., Ltd. |