CN102153452A - Synthesis method of trimethylolpropane allyl ether - Google Patents
Synthesis method of trimethylolpropane allyl ether Download PDFInfo
- Publication number
- CN102153452A CN102153452A CN2011100410712A CN201110041071A CN102153452A CN 102153452 A CN102153452 A CN 102153452A CN 2011100410712 A CN2011100410712 A CN 2011100410712A CN 201110041071 A CN201110041071 A CN 201110041071A CN 102153452 A CN102153452 A CN 102153452A
- Authority
- CN
- China
- Prior art keywords
- allyl ether
- ether
- reaction
- propane
- trimethylolpropane
- 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.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a synthesis method of trimethylolpropane allyl ether, which comprises the following steps: adding trimethylolpropane, chloropropene and polyether (crown ether) phase transfer catalyst into a reaction kettle according to a ratio of (13-19):(20-30):(0.1-1); heating to 60-150 DEG C; stirring while dropwisely adding 30-60% (mass concentration) alkaline liquor; reacting under reflux for 3-10 hours, wherein the mixture is continuously dewatered in the reflux process; after the mixture is qualified, cooling and washing with water; collecting the water layer, and pumping the oil layer into a rectifying kettle to carry out rectification under vacuum; and collecting the light components rectified out, and adding into the reaction kettle of the next round to achieve repeated utilization. By using the invention, the yield is up to 80-85%; and the phase transfer catalyst can not cause the adverse effect on the subsequent unsaturated resin reaction. In the invention, the reaction material chloropropene is excessive, so the finished product contains chloropropene and hydrolysis byproducts thereof (allyl alcohol and allyl ether) which can not be treated easily when the reaction terminates; and thus, the chloropropene hydrolysis byproducts are used as raw materials for reproduction to be substituted for part of chloropropene, thereby lowering the production cost and solving the environment protection problem in the post treatment process.
Description
[technical field]
The present invention relates to a kind of synthetic method of allyl ether series compound, relate in particular to the synthetic of trihydroxy methyl-propane-allyl ether.
[background technology]
Allyl ether series compound can be used for various coating and organic synthesis work in-process, and use as the raw material of mineral dye dispersion agent, because of having two keys and ehter bond on its molecular structure, utilize the oxidized obstacle that overcomes oxygen inhibition in two key free radical reactions of ehter bond of self, can obviously strengthen the speed of free radical reaction, because, this compounds has from the dryness energy, when participating in making synthetic resins with monomeric form, can give coating that this resin makes to do quick-drying performance certainly, reach the purpose that improves dried coating film speed, thereby can improve art breading efficient and save a large amount of energy, for example be applied in the unsaturated polyester coating, can make and to keep away the just top-grade furniture coating of energy drying at room temperature of oxygen, in addition, can also be applied in waterborne polyester coating and in the amino coating of dryness.The utilization of its characteristic can also be embodied in and be used for ion exchange resin, UV resin, Synolac etc., strengthens the air-drying property and the hardness of resin.
At present, have three pieces of publications about the method for making of trihydroxy methyl-propane-allyl ether is domestic.The manufacture method of CN93103239.3 trimethylolpropane allyl ether, the an alkali metal salt that is to use deleterious organic amine and halogen is as united catalyst, this method is used the catalyzer that has amine, in the product of making, have and contain the residual of amine catalyst, will produce detrimentally affect if need be applied to unsaturated polyester to its reaction when synthetic in the later stage, cause the viscosity growth too fast post-synthesis phase at unsaturated polyester, wayward reaction end.The preparation method of CN99124993.3 trihydroxy methyl-propane-allyl ether, the method that is proposed add a large amount of allyl etherss as reaction medium in reactant, the shortcoming of this method is that the actual recovery of product is very low, all below 40%.Chinese patent 03113544.7 propose a kind of with tetra-n-butyl ammonium bromide as the Preparation of catalysts method, equally can be in finished product residual and make it be used in unsaturated polyester when synthetic, it is too fast that later stage viscosity increases, wayward reaction end.
For above-mentioned reasons, the application of homemade trihydroxy methyl-propane-allyl ether in unsaturated polyester is synthetic has been subjected to serious restriction, and the synthetic producer of unsaturated polyester still adopts the like product of import in a large number, increases raw materials cost.
In addition, in the reaction that has, can adopt a kind of as the raw material of reaction of propenyl chloride, hydrolysis reaction can take place in propenyl chloride, produce vinyl carbinol and allyl ether, this hydrolysis reaction is reversible reaction, in reaction before, consider the influence of propylene chlorohydrin and allyl ether to product quality, generally the light constituent that contains vinyl carbinol and allyl ether can be collected removal separately, light constituent is inflammable and explosive, and huge poison, very strong tear-gas effect is arranged,, can produce a large amount of waste water again if adopt cracking process to handle if handle the very big production safety problem that to produce accidentally, same enterprise and the environment given causes heavy burden and pressure, how dealing carefully with by product, or even how to reclaim and rationally utilize light constituent, all is the problem of the required consideration of this type reaction.
[summary of the invention]
The present invention provides a kind of synthetic method of using the phase-transfer catalyst of ethers for addressing the above problem, not only have and utilize the application of trihydroxy methyl-propane-allyl ether in unsaturated polyester, and improved product yield greatly, recycle and reuse by product simultaneously, reduce the synthetic method of environmental pollution.
The technical scheme that the present invention addresses the above problem is: the synthetic method of trihydroxy methyl-propane-allyl ether involved in the present invention may further comprise the steps: TriMethylolPropane(TMP), propenyl chloride, polyethers (crown ether) class phase-transfer catalyst are reacted Fu by the mass ratio input of 13 ~ 19:20 ~ 30:0.1 ~ 1; Be warming up to 60 ~ 150 ℃, the agitation and dropping mass concentration is 30% ~ 60% alkali lye; Back flow reaction 3 ~ 10 hours, reflux course constantly dewaters, the cooling washing of qualified back; Collect water layer, oil reservoir is squeezed into rectifying Fu rectification under vacuum, collects the light component that rectifying is come out, and drops in the next round reactor to reuse.
Described polyethers (crown ether) class phase-transfer catalyst is polyethers and cyclic crown ether class: as chain polyoxyethylene glycol, chain polyoxyethylene glycol dialkyl ether, 18 hats, 6,15 hats 5, cyclodextrin, the preferred chain polyoxyethylene glycol of the present invention.
The consumption of described phase-transfer catalyst is the 2-6% of TriMethylolPropane(TMP) quality.
The alkali lye of described dropping is sodium hydroxide or potassium hydroxide solution, and massfraction concentration is 50%.
Described dewatering type is the band water that refluxes, and the band aqua that adopts in the band water that refluxes is the propenyl chloride of one of reactant.
The invention has the beneficial effects as follows: the product yield that method involved in the present invention produces reaches 80-85%, adopt phase transition class catalyzer can not cause detrimentally affect to follow-up unsaturated polyester reaction, and such catalyzer is relatively inexpensive, less demanding to processing condition, excessive among the present invention because of the reaction mass propenyl chloride, reaction is when reaching terminal point, is mixed with boiling points such as the hydrolysising by-product vinyl carbinol of propenyl chloride, propenyl chloride and allyl ether in the finished product less than 90 ℃ light constituent.The characteristics that light constituent has is inflammable and explosive, toxicity is big, be difficult for handling, and the present invention with it as the raw material of producing again, replace a part of propenyl chloride, greatly reduce production cost, solve the environmental issue of last handling process, become one step of key in the trihydroxy methyl-propane-allyl ether production in enormous quantities technology.
[embodiment]
In order to make purpose of the present invention, technical scheme and advantage clearer,, the present invention is further elaborated below in conjunction with drawings and Examples.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
The synthetic method of trihydroxy methyl-propane-allyl ether involved in the present invention may further comprise the steps: TriMethylolPropane(TMP), propenyl chloride, polyethers (crown ether) class phase-transfer catalyst are dropped into reaction Fu by 13 ~ 19:20 ~ 30:0.1 ~ 1; Be warming up to 60 ~ 150 ℃, the agitation and dropping mass concentration is 30% ~ 60% alkali lye; Back flow reaction 3 ~ 10 hours, reflux course constantly dewaters, the cooling washing of qualified back; Collect water layer, oil reservoir is squeezed into rectifying Fu rectification under vacuum, collects the light component that rectifying is come out, and drops in the next round reactor to reuse.
Described polyethers (crown ether) class phase-transfer catalyst is polyethers and cyclic crown ether class: as chain polyoxyethylene glycol, chain polyoxyethylene glycol dialkyl ether, 18 hats, 6,15 hats 5, cyclodextrin etc., the preferred chain polyoxyethylene glycol of the present invention.
Because main consideration is applied to trihydroxy methyl-propane-allyl ether in the unsaturated polyester, so can not use amine or ammonium class catalyzer, so select the phase-transfer catalyst of polyethers or crown ether-like, concrete as: chain polyoxyethylene glycol, chain polyoxyethylene glycol dialkyl ether, 18 hats, 6,15 hats 5, cyclodextrin, preferred in the present invention chain polyoxyethylene glycol, as Macrogol 200 (PEG200), poly(oxyethylene glycol) 400, cetomacrogol 1000 etc.Further, preferred poly(oxyethylene glycol) 400.Catalyst consumption is the 0.5-8% of TriMethylolPropane(TMP) quality, is preferably the 1-7% of TriMethylolPropane(TMP) quality, is preferably the 2-6% of TriMethylolPropane(TMP) quality.
The alkali lye of described dropping is sodium hydroxide or potassium hydroxide solution, and massfraction concentration is 50%.
In the present invention, the reaction needed of TriMethylolPropane(TMP) and propenyl chloride is carried out under strong alkaline condition, what adopt is the technology of dripping alkali liquid, because of more in the reaction system as the water yield, propenyl chloride can hydrolysis generate the by product allyl ether, yield is reduced greatly, also can influence simultaneously the quality of product, so the water in the alkali lye and generate water and all will in time take reaction system out of by refluxing.The selection of alkali lye is based on potassium hydroxide, and concentration is advisable with 50%, and consumption is 2 times of molar mass of TriMethylolPropane(TMP).The propenyl chloride of one of band aqua selective reaction material.
TriMethylolPropane(TMP), propenyl chloride, the following 13 ~ 19:20 of polyethers (crown ether) class phase-transfer catalyst ratio ~ 30:0.1 ~ 1 among the present invention, preferred proportion 15:25:0.8.
Be 60-150 ℃ with TriMethylolPropane(TMP), propenyl chloride, temperature when polyethers (crown ether) class phase-transfer catalyst is put into reaction kettle for reaction, preferred 90-110 ℃.
Reaction times of the present invention is according to qualified being as the criterion of detection reaction product content, stratographic analysis when the content of trimethylolpropane allyl ether in the reaction product be qualified terminal point during for 79-85%, when reaching this index common time spent 3-10 hour, during process stabilizing about 6-8 hour.
Because of reaction of the present invention is an inhomogeneous reaction, this class reacts that common speed of reaction is slow, and yield is low, and when not having phase-transfer catalyst, two-phase is isolated mutually, and several reactants can't contact, and react very slow; The existence of phase-transfer catalyst, can with the ionic bond of aqueous phase, and utilize self affinity to organic solvent, in organic phase, impel reaction to take place the reactant transfer of aqueous phase.Polyethers (crown ether) class phase-transfer catalyst has the advantage of himself: do not use expensive special solvent, and do not require waterless operation, simplified technology; Because the existence of polyethers (crown ether) class phase-transfer catalyst makes the negative ion of participating in reaction have high reaction activity and high; Such catalyzer has versatility, is widely used; Atom economy.
Excessive because of the reaction mass propenyl chloride among the present invention, reaction is when reaching terminal point, is mixed with boiling points such as the hydrolysising by-product vinyl carbinol of propenyl chloride, propenyl chloride and allyl ether in the finished product less than 90 ℃ mixture, is called light constituent.The characteristics that light constituent has is inflammable and explosive, toxicity is big, processing to light constituent in domestic patent does not before all propose clear and definite scheme, the present invention with it as the raw material of producing again, replace a part of propenyl chloride, greatly reduce production cost, solve the environmental issue of last handling process, become one step of key in the trihydroxy methyl-propane-allyl ether production in enormous quantities technology.
Embodiment 1:
In the 1000ml four-hole bottle that has stirring, thermometer, reflux exchanger, add TriMethylolPropane(TMP) 200g, propenyl chloride 330g, PEG400 10.6g is warmed up to 110 ℃, and agitation and dropping concentration is 50% potassium hydroxide solution, dripped off in 8 hours, constantly dehydration, water layer is collected in the cooling washing of qualified back, oil reservoir is squeezed into rectifying Fu rectification under vacuum and is got product 265g, yield about 83%.The light component of rectifying is collected, experiment recycling next time.Through stratographic analysis, TriMethylolPropane(TMP) one allyl ethers content is 13.6% in the product, and trimethylolpropane allyl ether content is 82.3%, and trimethylolpropane tris allyl ethers content is 3.8%.
Embodiment 2:
In the 1000ml four-hole bottle that has stirring, thermometer, reflux exchanger, add TriMethylolPropane(TMP) 200g, propenyl chloride 330g, PEG400 10.6g is warmed up to 110 ℃, and agitation and dropping concentration is 50% potassium hydroxide solution, dripped off in 6 hours, constantly dehydration, water layer is collected in the cooling washing of qualified back, oil reservoir is squeezed into rectifying Fu rectification under vacuum and is got product 260g, yield about 81.4%.The light component of rectifying is collected, experiment recycling next time.Through stratographic analysis, TriMethylolPropane(TMP) one allyl ethers content is 14.3% in the product, and trimethylolpropane allyl ether content is 80.3%, and trimethylolpropane tris allyl ethers content is 4.2%.
Embodiment 3:
In the 1000ml four-hole bottle that has stirring, thermometer, reflux exchanger, add TriMethylolPropane(TMP) 200g, propenyl chloride 330g, PEG400 10.6g is warmed up to 110 ℃, and agitation and dropping concentration is 40% potassium hydroxide solution, dripped off in 8 hours, constantly dehydration, water layer is collected in the cooling washing of qualified back, oil reservoir is squeezed into rectifying Fu rectification under vacuum and is got product 262g, yield about 82%.The light component of rectifying is collected, experiment recycling next time.Through stratographic analysis, TriMethylolPropane(TMP) one allyl ethers content is 14.9% in the product, and trimethylolpropane allyl ether content is 80.0%, and trimethylolpropane tris allyl ethers content is 4.3%.
Embodiment 4:
In the 1000ml four-hole bottle that has stirring, thermometer, reflux exchanger, add TriMethylolPropane(TMP) 200g, propenyl chloride 330g, PEG400 12g is warmed up to 110 ℃, and agitation and dropping concentration is 50% potassium hydroxide solution, dripped off in 8 hours, constantly dehydration, water layer is collected in the cooling washing of qualified back, oil reservoir is squeezed into rectifying Fu rectification under vacuum and is got product 260g, yield about 81.5%.The light component of rectifying is collected, experiment recycling next time.Through stratographic analysis, TriMethylolPropane(TMP) one allyl ethers content is 13.2% in the product, and trimethylolpropane allyl ether content is 85.0%, and trimethylolpropane tris allyl ethers content is 1.6%.
Embodiment 5:
In the 1000ml four-hole bottle that has stirring, thermometer, reflux exchanger, add TriMethylolPropane(TMP) 200g, propenyl chloride 330g, 18 hats, 6 15g are warmed up to 110 ℃, and agitation and dropping concentration is 50% potassium hydroxide solution, dripped off in 8 hours, constantly dehydration, water layer is collected in the cooling washing of qualified back, oil reservoir is squeezed into rectifying Fu rectification under vacuum and is got product 264.8g, yield about 82.9%.The light component of rectifying is collected, experiment recycling next time.Through stratographic analysis, TriMethylolPropane(TMP) one allyl ethers content is 14.5% in the product, and trimethylolpropane allyl ether content is 80.1%, and trimethylolpropane tris allyl ethers content is 4.7%.
Embodiment 6:
In the 1000ml four-hole bottle that has stirring, thermometer, reflux exchanger, add TriMethylolPropane(TMP) 200g, propenyl chloride 330g, 15 hats, 5 13g are warmed up to 110 ℃, and agitation and dropping concentration is 50% potassium hydroxide solution, dripped off in 15 hours, constantly dehydration, water layer is collected in the cooling washing of qualified back, oil reservoir is squeezed into rectifying Fu rectification under vacuum and is got product 264.5g, yield about 82.8%.The light component of rectifying is collected, experiment recycling next time.Through stratographic analysis, TriMethylolPropane(TMP) one allyl ethers content is 14.3% in the product, and trimethylolpropane allyl ether content is 80.1%, and trimethylolpropane tris allyl ethers content is 4.9%.
Claims (7)
1. the synthetic method of a trihydroxy methyl-propane-allyl ether may further comprise the steps: TriMethylolPropane(TMP), propenyl chloride, polyethers (crown ether) class phase-transfer catalyst are dropped into reaction Fu by 13 ~ 19:20 ~ 30:0.1 ~ 1; Be warming up to 60 ~ 150 ℃, the agitation and dropping mass concentration is 30% ~ 60% alkali lye; Back flow reaction 3 ~ 10 hours, reflux course constantly dewaters, the cooling washing of qualified back; Collect water layer, oil reservoir is squeezed into rectifying Fu rectification under vacuum, collects the light component that rectifying is come out, and drops in the next round reactor to reuse.
2. according to the synthetic method of the described trihydroxy methyl-propane-allyl ether of claim 1, it is characterized in that described polyethers (crown ether) class phase-transfer catalyst is polyethers and cyclic crown ether class.
3. according to the synthetic method of the described trihydroxy methyl-propane-allyl ether of claim 1, it is characterized in that described polyethers (crown ether) class phase-transfer catalyst is: chain polyoxyethylene glycol, chain polyoxyethylene glycol dialkyl ether, 18 hats, 6,15 hats 5, cyclodextrin.
4. according to the synthetic method of arbitrary described trihydroxy methyl-propane-allyl ether in the claim 1,2,3, it is characterized in that the consumption of described polyethers (crown ether) class phase-transfer catalyst is the 2-6% of TriMethylolPropane(TMP) quality.
5. according to the synthetic method of the described trihydroxy methyl-propane-allyl ether of claim 1, it is characterized in that the alkali lye of described dropping is sodium hydroxide or potassium hydroxide solution, massfraction concentration is 50%.
6. according to the synthetic method of the described trihydroxy methyl-propane-allyl ether of claim 1, it is characterized in that described dewatering type is the band water that refluxes, the band aqua that adopts in the band water that refluxes is the propenyl chloride of one of reactant.
7. according to the synthetic method of the described trihydroxy methyl-propane-allyl ether of claim 1, it is characterized in that the light component that described rectifying is partly deviate from comprises excessive propenyl chloride and hydrolysate vinyl carbinol and allyl ether, can replace a part of propenyl chloride, as the raw material of producing again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100410712A CN102153452A (en) | 2011-02-21 | 2011-02-21 | Synthesis method of trimethylolpropane allyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100410712A CN102153452A (en) | 2011-02-21 | 2011-02-21 | Synthesis method of trimethylolpropane allyl ether |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102153452A true CN102153452A (en) | 2011-08-17 |
Family
ID=44435177
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100410712A Pending CN102153452A (en) | 2011-02-21 | 2011-02-21 | Synthesis method of trimethylolpropane allyl ether |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102153452A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659532A (en) * | 2012-04-18 | 2012-09-12 | 广东石油化工学院 | Method for synthesis of trimethylolpropane diallyl ether |
| CN110156573A (en) * | 2019-07-01 | 2019-08-23 | 南通百川新材料有限公司 | A kind of synthesis technology of trimethylolpropane allyl ether |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1167103A (en) * | 1996-06-04 | 1997-12-10 | 中国石化齐鲁石油化工公司 | Method for preparation of polylol allyl ether |
| CN1301687A (en) * | 1999-12-24 | 2001-07-04 | 中国科学院感光化学研究所 | Method for preparing trihydroxy methyl-propane-allyl ether |
| CN1431184A (en) * | 2003-01-08 | 2003-07-23 | 深圳市飞扬实业有限公司 | Method for preparing trimethylolpropane allyl ether |
-
2011
- 2011-02-21 CN CN2011100410712A patent/CN102153452A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1167103A (en) * | 1996-06-04 | 1997-12-10 | 中国石化齐鲁石油化工公司 | Method for preparation of polylol allyl ether |
| CN1301687A (en) * | 1999-12-24 | 2001-07-04 | 中国科学院感光化学研究所 | Method for preparing trihydroxy methyl-propane-allyl ether |
| CN1431184A (en) * | 2003-01-08 | 2003-07-23 | 深圳市飞扬实业有限公司 | Method for preparing trimethylolpropane allyl ether |
Non-Patent Citations (1)
| Title |
|---|
| 邓礼波等: "TMP选择烯丙醚化及PE气干型改性", 《华南师范大学学报（自然科学版）》, no. 3, 31 December 1995 (1995-12-31), pages 50 - 57 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659532A (en) * | 2012-04-18 | 2012-09-12 | 广东石油化工学院 | Method for synthesis of trimethylolpropane diallyl ether |
| CN102659532B (en) * | 2012-04-18 | 2014-08-27 | 广东石油化工学院 | Method for synthesis of trimethylolpropane diallyl ether |
| CN110156573A (en) * | 2019-07-01 | 2019-08-23 | 南通百川新材料有限公司 | A kind of synthesis technology of trimethylolpropane allyl ether |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101168493B (en) | Preparation method for fluorochlorobenzene | |
| CN110105321A (en) | A kind of method of eutectic ionic liquid catalysis carbon dioxide synthesizing annular carbonate | |
| CN106397368A (en) | Fatty alcohol-polyoxyethylene ether glycidyl ether and preparation method thereof | |
| CN102153452A (en) | Synthesis method of trimethylolpropane allyl ether | |
| CN112206808B (en) | Catalyst for synthesizing isobutyl isobutyrate and preparation method and application thereof | |
| CN102659088B (en) | Water-phase synthesis method of sodium azide | |
| CN104844455A (en) | Method used for catalyzed synthesis of tert-butyl acrylate | |
| JP6461016B2 (en) | Method for producing triazine carbamate | |
| CN103965023B (en) | A kind of preparation method of fluoro-alkyl vinyl ethers | |
| CN100532360C (en) | Method for treating 4 chloro pyridine in solvent | |
| CN103772153B (en) | The synthetic method of the chloro-3-cresols of 4-and system thereof | |
| CN104341456A (en) | (R, R)-1,2-diphenylethylenediamine nickel azide complex and preparation method thereof | |
| CN102659532B (en) | Method for synthesis of trimethylolpropane diallyl ether | |
| CN111841587A (en) | Solid base catalyst and preparation method thereof | |
| CN109851509B (en) | Preparation method of 4, 4' -diaminodiphenylmethane | |
| CN106883129B (en) | Method for preparing m-chloroaniline by using meta-oil | |
| CN105220552A (en) | Utilize the cellulosic method of imidazoles asymmetric Gemini ionic liquid extract | |
| CN110156573A (en) | A kind of synthesis technology of trimethylolpropane allyl ether | |
| CN110172024A (en) | A method of anhydrous ethylenediamine is produced from diamine base silane by-product ethylenediamine-hydrochloride | |
| CN114749213B (en) | Modified polymer resin composite material, preparation method and application thereof, and preparation method of cyclic carbonate | |
| CN111097517B (en) | Catalyst for preparing alkylene carbonate, preparation and application | |
| CN110172041B (en) | Novel method for synthesizing hexazinone | |
| CN102942479A (en) | Method for preparing propylene glycol methyl ether acetate through two-step coupling reaction | |
| CN108569955B (en) | Method for preparing glycerol monomethyl ether by using glycerol and methyl iodide | |
| CN106146264A (en) | The synthetic method of allyl glyceroether |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20110817 |