CN108456300A - A kind of catalyst and preparation method thereof of controllable polyethylene glycol oxide molecular weight - Google Patents
A kind of catalyst and preparation method thereof of controllable polyethylene glycol oxide molecular weight Download PDFInfo
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- CN108456300A CN108456300A CN201810090505.XA CN201810090505A CN108456300A CN 108456300 A CN108456300 A CN 108456300A CN 201810090505 A CN201810090505 A CN 201810090505A CN 108456300 A CN108456300 A CN 108456300A
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/08—Saturated oxiranes
- C08G65/10—Saturated oxiranes characterised by the catalysts used
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/08—Saturated oxiranes
- C08G65/10—Saturated oxiranes characterised by the catalysts used
- C08G65/12—Saturated oxiranes characterised by the catalysts used containing organo-metallic compounds or metal hydrides
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Abstract
The present invention relates to the catalyst and preparation method thereof of controllable polyethylene glycol oxide molecular weight, 0.5h~4h is reacted under 80 DEG C~10 DEG C of cryogenic conditions generate ammonia calcium complex solution by liquefied ammonia with calcium metal, 0.5h~the 4h that is added after the modifying agent being made of propylene oxide and azo compound that the reaction was continued in a solvent, by deamination, the ripening of heating up, the catalyst is obtained.Compared with prior art, the present invention prepared by catalyst have many advantages, such as high activity, high stability and polymer molecular weight can modulation, in ethylene oxide, (English is write a Chinese character in simplified form：EO in ring-opening polymerization), polyethylene glycol oxide series of products of the molecular weight between 100,000 to 2,000,000 can be prepared.
Description
Technical field
The present invention relates to catalyst, and in particular to a kind of catalytic epoxyethane ring-opening polymerisation generation polyethylene glycol oxide catalyst
Preparation method, a series of middle low molecular weight polyethylene glycol oxide of molecular weight between 100,000 to 2,000,000 can be synthesized.
Background technology
Polyethylene glycol oxide (PEO) be one kind by ethylene oxide through linear polymer made of heterogeneous catalysis ring-opening polymerisation, be
The small water-soluble polymer of a kind of crystallinity, thermoplasticity, chemical toxicity.According to the difference of the degree of polymerization, the molecule of polyethylene glycol oxide
Amount can the variation in 100,000 to 8,000,000.In addition to above-mentioned property, in different molecular weight, PEO also has a series of other superiority
Can, the effects that dispersant, flocculant, thickener, hydraulic pressure drag reducer can be played, in papermaking, medicine, agricultural, daily chemical product, doctor
The various fields extensive application such as medicine, Industrial Engineering.In recent years, low as the application range of polyethylene glycol oxide increasingly expands
The application of molecular weight polyoxyethylene ethylene is further expanded, and market demand gradually increases.
The key technology of polyethylene glycol oxide synthesis is the exploitation of effective catalyst.Polyethylene glycol oxide catalyst common at present
System includes alkyl metal catalyst system, metal alkoxides catalyst system and alkaline earth metal amide catalyst system.No
Polyethylene glycol oxide molecular weight prepared by catalyst with system is also different.United States Patent (USP) (US2006036066) is referred to having
Machine aluminium compound and alkali metal oxide or hydroxide are blended, and obtained catalyst can prepare 20,000~200,000 molecular weight
Polyethylene glycol oxide, but this complex process is related to operation with high pressure, to equipment requirement height.Chinese patent (CN 1306023A) is then
Calcium metal is dissolved in liquefied ammonia, the carriers such as modifying agent and alundum (Al2O3) are added and the catalyst that synthesizes, which has low
The characteristic of warm high activity high yield, prepared polyethylene glycol oxide molecular weight reach 8,000,000, should not prepare low molecular weight PEO productions
Product.Shanghai Chemical Research Inst possess it is multinomial for low molecular weight polyethylene glycol oxide in synthesizing in terms of patent (CN
101392053A, CN 101407579A etc.), the catalyst reported is mainly alkaline-earth metal-ammonia-modifier system, wherein alkali
Earth metal is calcium, strontium etc., epoxyalkane, organic nitrile or organic amine when modifying agent, or catalyst is supported on nano oxygen
In SiClx or mesopore molecular sieve carrier, the catalyst stabilization of synthesis.But the catalyst mentioned in patent CN 101392053A is urged
Change stability is poor, and the polymerization yield of ethylene oxide fluctuates between 60%~98%；It is mentioned in patent (CN 101407579A)
Catalyst to be only capable of preparing molecular weight be the polyethylene glycol oxide between 800,000 to 3,000,000, the polyoxy of more low molecular weight cannot be synthesized
Change ethylene.Chinese patent (103539931 A of CN) reports alkaline earth metals calcium-ammonia-modifying agent catalyst system and catalyzing, modifying agent be by
Propylene oxide and acetonitrile composition, and to suspended liquid catalyst carry out burin-in process, prepare molecular weight between 600,000 to 1,600,000 it
Between PEO, but the catalyst prepared by the patent is unable to PEO of the synthetic molecular weight between 100,000 to 600,000.
Based on ammonia calcium treating system, the present invention is developed by modulation modifying agent type by azo compound and epoxy
The new modified agent prescription of propane composition prepares the catalyst with adjustable polymer molecular weight, and can be by changing
Become type and the dosage of azo compound to adjust the activity of catalyst, synthesizes a series of molecular weight 100,000~2,000,000
Between middle low molecular weight polyethylene glycol oxide.
Invention content
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of controllable polyoxygenateds
The catalyst and preparation method thereof of ethylene molecule amount.
The purpose of the present invention can be achieved through the following technical solutions：A kind of controllable polyethylene glycol oxide molecular weight is urged
The preparation method of agent, which is characterized in that this approach includes the following steps：React raw under cryogenic with calcium metal by liquefied ammonia
Ammonification calcium complex solution, is added after the modifying agent being made of propylene oxide and azo compound that the reaction was continued in a solvent,
By deamination, ripening, the catalyst is obtained.
The volume mass ratio of the liquefied ammonia and calcium metal is：(75~100)：1ml/g；
The mass ratio of the modifying agent oxypropylene and azo compound is (0.1~30)：1；
The mass ratio of the ammonia calcium complex and modifying agent is (0.1~20)：1；
The volume mass ratio of the solvent and modifying agent is (20~100)：1ml/g.
The cryogenic conditions are between -80 DEG C~-10 DEG C, and ammonia calcium complex solution reaction generates ammonia calcium complex solution
Time be 0.5h~4h, be added modifying agent after continue the reaction time be 0.5h~4h.
The azo compound includes：Azobisisoheptonitrile, azodiisobutyronitrile, azobisisovaleronitrile, azo two
Methyl valeronitrile, two cyclohexanenitrile of azo, azo-bis-iso-dimethyl, diisopropyl azodiformate, diethyl azodiformate,
Azo acid dimethyl ester, tert-butyl azodicarboxylate, azobenzene -4,4'- dicarboxylic acid dimethyl esters, azoformic acid dibenzyl
Ester, azodicarbonamide, N, N- diisopropyl azodicarbonamides are one or more in azo dicarbapentaborane dimorpholine.
The reaction dissolvent include n-hexane, hexamethylene, normal heptane, petroleum ether, No. 6 solvent naphthas, No. 120 solvent naphthas,
One or more of No. 180 solvent naphthas mixture.
Required temperature is within the scope of -10 DEG C~30 DEG C when the deamination is handled.
The ripening temperature between 40 DEG C~150 DEG C, the ripening time between 0.5h~4h, wherein old
Change within the scope of preferably 40 DEG C~100 DEG C of temperature.
During the entire process of catalyst synthesis, reaction system is under inert gas shielding always, is strictly in anhydrous nothing
It is carried out in oxygen environment.
Polyethylene glycol oxide of the catalyst prepared by catalytic epoxyethane ring-opening polymerisation is white particle, Neng Gou
The size of regulation and control polyethylene glycol oxide molecular weight, is particularly suitable for the synthesis of low molecular weight PEO, gained polyoxyethylene in wide range
The viscosity average molecular weigh of alkene is between 100,000~2,000,000.
Compared with prior art, modifying agent used in catalyst provided by the invention is azo compound and epoxy third
The mixed solution of alkane can adjust the activity of catalyst by changing type and the dosage of azo compound.The present invention synthesizes
Catalyst have the characteristics that high activity, high stability, every gram of catalyst (in terms of metal) can convert 400g ethylene oxide,
Polymerization yield rate is stablized 96% or more.
Specific implementation mode
It elaborates below to the embodiment of the present invention, the present embodiment is carried out lower based on the technical solution of the present invention
Implement, gives detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1
(1) synthesis of catalyst：
Under the protection of high-purity argon gas, 150ml~200ml liquefied ammonia is collected at -60 DEG C in the four-hole boiling flask of 2000ml.
Under magnetic stirring, 2g Ca are added into flask, and ammonia calcium complex is obtained after reacting 1h；By 2.90g propylene oxide and 1.220g
Two cyclohexanenitrile of azo composition modifying agent is dissolved in 300ml n-hexanes, is then added in above-mentioned ammonia calcium complex, is reacted
1h；Reaction temperature is increased to 0 DEG C and vapors away extra liquefied ammonia by heating；Reaction temperature is finally risen into 60 DEG C of progress ripenings
To get to white what slurried catalyst after 1h.Entire reaction system carries out under high-purity argon gas guard mode.
(2) ethylene oxide polymerization reacts：
Above-mentioned what slurried catalyst is added to churned mechanically, full of argon gas the good 2L reaction kettles of seal
In, 300ml n-hexanes are then added into reaction kettle, add 200g ethylene oxide.Polymerisation is reacted at 20 DEG C~30 DEG C
6h~12h.Prepared polyethylene glycol oxide is white powder particle, and epigranular, synthesized PEO viscosity average molecular weighs are 50
Ten thousand, polymerization yield rate 99.6%.
Embodiment 2
(1) synthesis of catalyst：
The amount of two cyclohexanenitrile of azo is changed to 0.630g, other operating process are same as Example 1.
(2) ethylene oxide polymerization reacts：
Converging operation process is identical as the converging operation process of embodiment 1.The viscous equal molecule of prepared polyethylene glycol oxide
Amount is 250,000, polymerization yield rate 99.8%.
Embodiment 3
(1) synthesis of catalyst：
Modifying agent selects the mixed solution of azodiisobutyronitrile and propylene oxide, takes the amount of azodiisobutyronitrile to be
0.835g, other operating process are same as Example 1.
(2) ethylene oxide polymerization reacts：
Converging operation process is identical as the converging operation process of embodiment 1.The viscous equal molecule of prepared polyethylene glycol oxide
Amount is 440,000, polymerization yield rate 99.9%.
Embodiment 4
(1) synthesis of catalyst：
The ammonia calcium reaction time is 3h, and modifying agent selects the mixed solution of azobis-dimethylvaleronitrile and propylene oxide, takes azo
Methyl pentane nitrile 1.920g, Aging Temperature are 100 DEG C, other operating process are same as Example 1.
(2) ethylene oxide polymerization reacts：
Converging operation process is identical as the converging operation process of embodiment 1.The viscosity average molecular weigh of prepared polyethylene glycol oxide
It is 850,000, polymerization yield rate 100%.
Embodiment 5
(1) synthesis of catalyst：
Aging condition is set as to react 3h at 60 DEG C, other operating process are same as Example 5.
(2) ethylene oxide polymerization reacts：
Converging operation process is identical as the converging operation process of embodiment 1.The viscous equal molecule of prepared polyethylene glycol oxide
Amount is 430,000, and polymerization yield rate is respectively 99.9%.
Embodiment 6
(1) synthesis of catalyst：
Modifying agent selects the mixed solution of azo acid dimethyl ester and propylene oxide, takes the amount of azo acid dimethyl ester
For 1.461g, Aging Temperature is 60 DEG C, digestion time 4h, other operating process are same as Example 1.
(2) ethylene oxide polymerization reacts：
Converging operation process is identical as the converging operation process of embodiment 1.The viscous equal molecule of prepared polyethylene glycol oxide
Amount is 140,000, polymerization yield rate 100%.
Embodiment 7
(1) synthesis of catalyst：
The mixed solution for selecting azo acid dimethyl ester and propylene oxide, takes the amount of azo acid dimethyl ester to be
0.731g, other operating process are same as Example 1.
(2) ethylene oxide polymerization reacts：
Converging operation process is identical as the converging operation process of embodiment 1.The viscous equal molecule of prepared polyethylene glycol oxide
Amount is 190,000, polymerization yield rate 99.1%.
Embodiment 8
(1) synthesis of catalyst：
Modifying agent selects N, the mixed solution of N- diisopropyls azodicarbonamide and propylene oxide to take N, N- diisopropyls
The amount of azodicarbonamide is 0.895g, other operating process are same as Example 1.
(2) ethylene oxide polymerization reacts：
During converging operation, the amount of ethylene oxide be added is 400g, and the amount of n-hexane is 600ml, other polymerizations behaviour
It is identical as 1 converging operation process of embodiment to make process.The viscosity average molecular weigh of prepared polyethylene glycol oxide is 1,130,000, polymerization yield rate
It is 98.9%.
Embodiment 9
(1) synthesis of catalyst：
The operating process of catalyst preparation is identical as 8 catalyst operating process of embodiment.
(2) ethylene oxide polymerization reacts：
During converging operation, the amount of ethylene oxide be added is 600g, and the amount of n-hexane is 900ml, polymerization reaction kettle
Select 10L reaction kettles, other converging operation processes identical as 1 converging operation process of embodiment.Prepared polyethylene glycol oxide glues
Average molecular weight is 1,680,000, polymerization yield rate 100%.
Embodiment 10
(1) synthesis of catalyst：
The operating process of catalyst preparation is identical as 8 catalyst operating process of embodiment.
(2) ethylene oxide polymerization reacts：
During converging operation, the amount of ethylene oxide be added is 800g, and the amount of n-hexane is 1200ml, polymerization reaction kettle
Select 10L reaction kettles, other converging operation processes identical as 1 converging operation process of embodiment.Prepared polyethylene glycol oxide glues
Average molecular weight is 1,920,000, polymerization yield rate 96%.
Embodiment 11
(1) synthesis of catalyst：
It selects azoformic acid dibenzyl ester azo compound to make modifying agent with propylene oxide, takes azoformic acid dibenzyl ester
Amount be 2.307g, take solvent 400ml, Aging Temperature is 40 DEG C, digestion time 3h, other operating process and 1 phase of embodiment
Together.
(2) ethylene oxide polymerization reacts：
Converging operation process is identical as the converging operation process of embodiment 1.The viscous equal molecule of prepared polyethylene glycol oxide
Amount is 200,000, polymerization yield rate 99.6%.
1. each embodiment performance table of table
| Embodiment | Active (g-EO/g-Ca) | Molecular weight/ten thousand | It polymerize yield |
| Embodiment 1 | 100 | 50 | 99.6% |
| Embodiment 2 | 100 | 25 | 99.8% |
| Embodiment 3 | 100 | 44 | 99.9% |
| Embodiment 4 | 100 | 85 | 100% |
| Embodiment 5 | 100 | 43 | 99.9% |
| Embodiment 6 | 100 | 14 | 100% |
| Embodiment 7 | 100 | 19 | 99.1% |
| Embodiment 8 | 200 | 113 | 98.9% |
| Embodiment 9 | 300 | 168 | 100% |
| Embodiment 10 | 400 | 192 | 96.1% |
| Embodiment 11 | 100 | 20 | 99.6% |
By above-described embodiment it is found that catalyst provided by the present invention has high activity, high stable and polymer molecular weight
Can modulation the advantages of, can efficiently prepare polyethylene glycol oxide series of products of the molecular weight between 100,000~2,000,000.
Embodiment 12
A kind of preparation method of the catalyst of controllable polyethylene glycol oxide molecular weight, this approach includes the following steps：In height
Under the protection of pure helium, 4h is reacted under -10 DEG C of cryogenic conditions with calcium metal by liquefied ammonia and generate ammonia calcium complex solution, be added
The reaction was continued in a solvent after the modifying agent be made of propylene oxide and azo compound 0.5h is handled in -10 DEG C of deaminations,
40 DEG C of ripening 4h obtain the catalyst.
Wherein, the volume mass of the liquefied ammonia and calcium metal ratio is：75：1ml/g；The modifying agent oxypropylene
Mass ratio with azo compound is 0.1：1；The volume mass ratio of the ammonia calcium complex and modifying agent is 0.1：1；Institute
The mass ratio of the solvent and modifying agent stated is 20：1.
The azo compound is azobisisoheptonitrile.The solvent is normal heptane.
Embodiment 13
A kind of preparation method of the catalyst of controllable polyethylene glycol oxide molecular weight, this approach includes the following steps：In height
Under the protection of pure helium, 0.5h is reacted under -80 DEG C of cryogenic conditions with calcium metal by liquefied ammonia and generate ammonia calcium complex solution, added
The 4h that enters after the modifying agent being made of propylene oxide and azo compound that the reaction was continued in a solvent, is handled in 30 DEG C of deaminations,
150 DEG C of ripening 0.5h obtain the catalyst.
Wherein, the volume mass of the liquefied ammonia and calcium metal ratio is：100：1ml/g；Epoxy third in the modifying agent
The mass ratio of alkane and azo compound is 30：1；The volume mass ratio of the ammonia calcium complex and modifying agent is 20：1；Institute
The mass ratio of the solvent and modifying agent stated is 100：1.
The azo compound is azo dicarbapentaborane dimorpholine.The solvent includes normal heptane.
Claims (10)
1. a kind of preparation method of the catalyst of controllable polyethylene glycol oxide molecular weight, which is characterized in that this method includes following
Step：It is reacted under cryogenic with calcium metal by liquefied ammonia and generates ammonia calcium complex solution, be added by propylene oxide and azo
The reaction was continued in a solvent after the modifying agent of compound composition, by deamination, ripening, obtains the catalyst.
2. the preparation method of the catalyst of controllable polyethylene glycol oxide molecular weight according to claim 1, which is characterized in that
The volume mass ratio of the liquefied ammonia and calcium metal is：(75~100)：1ml/g；
The mass ratio of the modifying agent oxypropylene and azo compound is (0.1~30)：1；
The mass ratio of the ammonia calcium complex and modifying agent is (0.1~20)：1；
The volume mass ratio of the solvent and modifying agent is (20~100)：1ml/g.
3. the preparation method of the catalyst of controllable polyethylene glycol oxide molecular weight according to claim 1, which is characterized in that
The azo compound includes：Azobisisoheptonitrile, azodiisobutyronitrile, azobisisovaleronitrile, azobis-dimethylvaleronitrile,
Two cyclohexanenitrile of azo, azo-bis-iso-dimethyl, diisopropyl azodiformate, diethyl azodiformate, azo diformazan
Dimethyl phthalate, tert-butyl azodicarboxylate, azobenzene -4,4'- dicarboxylic acid dimethyl esters, azoformic acid dibenzyl ester, azo two
Formamide, N, N- diisopropyl azodicarbonamides are one or more in azo dicarbapentaborane dimorpholine.
4. the preparation method of the catalyst of controllable polyethylene glycol oxide molecular weight according to claim 1, which is characterized in that
The reaction dissolvent, which is that low-carbon is full, closes alkane, be n-hexane, hexamethylene, normal heptane, petroleum ether, No. 6 solvent naphthas, No. 120 it is molten
One or more of agent oil, No. 180 solvent naphthas mixture.
5. the preparation method of the catalyst of controllable polyethylene glycol oxide molecular weight according to claim 1, which is characterized in that
The cryogenic conditions are between -80 DEG C~-10 DEG C, and the time that ammonia calcium complex solution reaction generates ammonia calcium complex solution is
0.5h~4h continues the reaction time as 0.5h~4h after modifying agent is added.
6. the preparation method of the catalyst of controllable polyethylene glycol oxide molecular weight according to claim 1, which is characterized in that
Required reaction temperature is between -10 DEG C~30 DEG C when the described deamination processing, ripening temperature 40 DEG C~150 DEG C it
Between, the ripening time is between 0.5h~4h.
7. the preparation method of the catalyst of controllable polyethylene glycol oxide molecular weight according to claim 6, which is characterized in that
The Aging Temperature is within the scope of 40 DEG C~100 DEG C.
8. the preparation method of the catalyst of controllable polyethylene glycol oxide molecular weight according to claim 1, which is characterized in that
During the entire process of catalyst synthesis, reaction system is under inert gas shielding always, strictly in anhydrous and oxygen-free environment
It carries out.
9. the preparation method of the catalyst of controllable polyethylene glycol oxide molecular weight according to claim 1, which is characterized in that
Polyethylene glycol oxide of the catalyst prepared by catalytic epoxyethane ring-opening polymerisation is white particle, can be in wide range
The molecular weight of interior regulation and control polyethylene glycol oxide, is particularly suitable for the synthesis of low molecular weight PEO, the viscous equal molecule of gained polyethylene glycol oxide
Amount is between 100,000~2,000,000.
10. a kind of catalyst of controllable polyethylene glycol oxide molecular weight, which is characterized in that the catalyst uses claim 1 institute
Method is stated to be made.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109438958A (en) * | 2018-09-19 | 2019-03-08 | 上海化工研究院有限公司 | A kind of preparation method of polyethylene glycol oxide water-solubility membrane |
| CN109796586A (en) * | 2019-01-25 | 2019-05-24 | 上海化工研究院有限公司 | A kind of catalyst preparing polyethylene glycol oxide and its preparation method and application |
| CN113024793A (en) * | 2019-12-25 | 2021-06-25 | 辽宁奥克化学股份有限公司 | Method for synthesizing polyoxyethylene |
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| 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 |
| CN103894137A (en) * | 2014-03-31 | 2014-07-02 | 上海化工研究院 | High-shear reaction kettle and application of kettle to production of suspension polymerization polyethylene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN103894137A (en) * | 2014-03-31 | 2014-07-02 | 上海化工研究院 | High-shear reaction kettle and application of kettle to production of suspension polymerization polyethylene |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109438958A (en) * | 2018-09-19 | 2019-03-08 | 上海化工研究院有限公司 | A kind of preparation method of polyethylene glycol oxide water-solubility membrane |
| CN113845766A (en) * | 2018-09-19 | 2021-12-28 | 上海化工研究院有限公司 | Preparation method of polyoxyethylene water-soluble film |
| CN109796586A (en) * | 2019-01-25 | 2019-05-24 | 上海化工研究院有限公司 | A kind of catalyst preparing polyethylene glycol oxide and its preparation method and application |
| CN109796586B (en) * | 2019-01-25 | 2022-03-18 | 上海化工研究院有限公司 | Catalyst for preparing polyoxyethylene and preparation method and application thereof |
| CN113024793A (en) * | 2019-12-25 | 2021-06-25 | 辽宁奥克化学股份有限公司 | Method for synthesizing polyoxyethylene |
| CN113024793B (en) * | 2019-12-25 | 2022-07-12 | 辽宁奥克化学股份有限公司 | Method for synthesizing polyoxyethylene |
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Application publication date: 20180828 |