CN104030887A - Method for preparing 2-methyl-1-acetenyl-2-amylene-1-ol - Google Patents
Method for preparing 2-methyl-1-acetenyl-2-amylene-1-ol Download PDFInfo
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- CN104030887A CN104030887A CN201410269580.4A CN201410269580A CN104030887A CN 104030887 A CN104030887 A CN 104030887A CN 201410269580 A CN201410269580 A CN 201410269580A CN 104030887 A CN104030887 A CN 104030887A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
- C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
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Abstract
The invention provides a method for preparing 2-methyl-1-acetenyl-2-amylene-1-ol. The method comprises the following steps: firstly, stirring propionaldehyde in a mixture liquid of inorganic base and carbonate salt to perform condensation reaction at normal temperature, collecting an oil phase, and performing reduced pressure distillation to prepare a 2-methyl-2-amylene aldehyde intermediate product; secondly, adding sodium amide and methylbenzene at minus 34 DEG C to minus 45 DEG C of liquid ammonia, introducing an acetylene gas to react sufficiently, subsequently flowing into 2-methyl-2-amylene aldehyde for reaction, after the reaction is completed, volatilizing liquid ammonia, adding hydrochloric acid for hydrolysis, and performing reduced pressure distillation and rectification on an organic layer, thereby preparing 2-methyl-1-acetenyl-2-amylene-1-ol. 2-methyl-1-acetenyl-2-amylene-1-ol prepared by using the method has the advantages of simplicity and convenience to operate, low in energy consumption, high in purity, high in yield, low in production cost, beneficial for industrial on-scale production, and the like.
Description
Technical field
The invention belongs to fine chemical technology field, relate in particular to the preparation method of a kind of 2-methyl isophthalic acid-ethynyl-2-amylene-1-ol.
Background technology
2-methyl isophthalic acid-ethynyl-2-amylene-1-ol belongs to a kind of in " alkynol ", be synthetic alkynes valerate (having another name called Prallethrin, code name S-2852) and alkynes penta permethrin (code name S-2876) etc. efficiently, one of the main intermediate of the novel pyrethroid insecticides of low toxicity.Main production process is that propionic aldehyde plays self condensation reaction generation 2-methyl-2-pentenal serving under base catalysis, then in liquefied ammonia, reacts generation 2-methyl isophthalic acid-ethynyl-2-amylene-1-ol with sodium carbide.Reaction formula is as follows:
The first step:
+ H
2O
Second step:
NaNH
2+ HC ≡ CH →
liquefied ammonianaC ≡ CH
About the preparation of 2-methyl isophthalic acid-ethynyl-2-amylene-1-ol both at home and abroad almost nobody apply for patent of invention.Domestic since the eighties in last century, only have the report of fragmentary synthetic alkynol aspect.
Being coated with monarch rinses etc. and to mention organolithium or Grignard reagent method in 1990 < < agricultural chemicals > the 5th phases of >, by HC ~ CM (M=Li, MgBr) in tetrahydrofuran (THF), react and make 2-methyl isophthalic acid-ethynyl-2-amylene-1-ol with 2-methyl-2-pentenal serving, but its cost is very high, react more complicated, productive rate is lower.
Synthetic > > mono-literary composition of the < < " alkynol " that the people such as Wang Tiantao delivered on the 3rd > > of phase < < chemical industry in Jiangsu Province in 1991, has mentioned the method for synthetic alkynol in two steps.The first step first generates 2-methyl-2-pentenal serving by propionic aldehyde in self condensation reaction under 80-85 ℃ of catalysis of 2% sodium hydroxide solution, collect oil reservoir washing 2 times again normal pressure 137-140 ℃ of distillation obtain 2-methyl-2-pentenal serving product, yield 83%, purity 98%.Second step is to exist under the condition of liquefied ammonia at-35 ~-50 ℃, drops into sodium amide, passes into acetylene, is added dropwise to 2-methyl-2-pentenal serving.Drip and finish, under equality of temperature, continue reaction 4h, then add equimolar ammonium chloride reaction 1h, vapor away liquefied ammonia.Liquefied ammonia is evaporated completely, respectively adds half water and methylbenzene extraction of liquefied ammonia volume, and washing organic layer, to neutral, with anhydrous sodium sulfate drying, underpressure distillation, is collected the cut of 112～115 ℃/10kpa, obtains finished product, productive rate 86%, purity >98%.The first step reaction concentration of sodium hydroxide solution of this article is higher, and temperature of reaction, up to 80-85 ℃, adopts air distillation, and temperature reaches 137-140 ℃, and productive rate is lower, causes production cost and energy consumption higher.Second step reaction exists liquefied ammonia usage quantity very large, and the reaction times is longer, has under liquefied ammonia condition the solid ammonium chloride difficulty that feeds intake, and liquefied ammonia, toluene do not reuse etc. and to cause cost still higher, operate more difficult, the not high deficiency of productive rate.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of 2-methyl isophthalic acid-ethynyl-2-preparation method of amylene-1-ol, and the method is simple to operate, and liquefied ammonia, toluene equal solvent can be realized recycling, and product yield is higher, and purity is higher, and cost is lower.
The technical scheme solving the problems of the technologies described above is: the preparation method of a kind of 2-methyl isophthalic acid-ethynyl-2-amylene-1-ol, comprises the following steps:
(1), the first step reaction:
(1), by the weight ratio of water and propionic aldehyde, be that 1-3:1 calculates the water yield, water is added in reactor, then adds respectively a kind of mineral alkali and a kind of carbonate salt to be configured to respectively containing alkali 0.1-0.8% with containing the mixed-alkali solution of carbonate salt 1-4% by the water yield;
(2), the chuck recirculated water of opening reactor is incubated, and opens the stirring of reactor, in the ratio of (1), measure after propionic aldehyde stream and add propionic aldehyde and enter reactor;
(3), add after propionic aldehyde, make its naturally cooling, continue reaction 1-2h, process sampling is analyzed, when product 2-methyl-2-pentenal serving content >=95%, during raw material propionic aldehyde content≤1%, termination reaction;
(4), stop stirring, stratification 10-30 minute, releases the alkali lye water layer of bottom, after the washing of upper oil phase product, is retained in reactor;
(5), utilize distillation tower on reactor to carry out underpressure distillation, between vacuum tightness-0.090 ~-0.095Mpa, 70 ~ 95 ℃ of tower reactor temperature, directly all extraction is arrived in olefine aldehydr Receiving bin, can collect purity >=98%, the 2-methyl-2-pentenal serving intermediate product that meets next step reaction use is stand-by;
(2), second step reaction:
(1), by toluene: sodium amide weight ratio is that 3-6:1 calculates toluene consumption, and toluene is put in alkynol reactor, opens the stirring of reactor, drops into required sodium amide by the charging opening on reactor;
(2), open freezing water for cooling, temperature of reaction kettle is dropped to-34 ~-45 ℃, by liquefied ammonia: sodium amide weight ratio is to drop in reactor after 3-6:1 calculates liquefied ammonia consumption;
(3), pass into excessive acetylene, to guarantee that sodium amide all generates sodium carbide;
(4), by 2-methyl-2-pentenal serving: sodium amide weight ratio is that 1.8-2.5:1 calculates 2-methyl-2-pentenal serving consumption, 2-methyl-2-pentenal serving is at the uniform velocity added in alkynol reactor, after adding 2-methyl-2-pentenal serving, continue reaction 30-60 minute, stop stirring standing 10-40 minute layering;
(5) or lower floor's product put into alkynol hydrolysis kettle, the liquefied ammonia on upper strata is stayed in alkynol reactor and is reused; Or all prods is put into hydrolysis kettle;
(6), start alkynol hydrolysis kettle and stir, the liquefied ammonia that comes is carried in the volatilization that heats up secretly, ammonia is absorbed and is made ammoniacal liquor by ammonia absorption groove, until the temperature in hydrolysis kettle is progressively raised to 15 ℃, stops stirring when above;
(7), be evaporated completely after liquefied ammonia, more suitably lower the temperature, temperature in the kettle is dropped to-20 ℃ ~ 10 ℃;
(8), by hydrochloric acid scale tank, configure the hydrochloric acid of 10-20% concentration, after temperature has fallen in hydrolysis kettle, stream adds hydrochloric acid and enters hydrolysis kettle hydrolysis, controls temperature in the kettle not higher than 40 ℃; When pH value is during to acidity, stop acid adding, standing 10-30 minute layering;
(9), the water layer of lower floor is released, upper strata organic layer makes its pH value to neutrality through washing, and organic layer sucks in alkynol still kettle;
(10), control vacuum tightness-0.090 ~-0.096Mpa, tower reactor temperature 30-60 ℃, extraction toluene, in toluene Receiving bin, can be collected most of purity >=85%, meets the toluene of recycling;
(11), the further rectifying again of residue still bed material, first at tower reactor 70-90 ℃, under vacuum tightness-0.095 ~-0.099Mpa, the low-boiling-point substances such as remaining a small amount of toluene are steamed; Again in tower reactor 100-120 ℃, tower top 70-90 ℃, under vacuum tightness-0.097 ~-0.10Mpa, rectifying goes out 2-methyl isophthalic acid-ethynyl-2-amylene-1-ol product that purity is greater than 98%.
Step the (one) .(1) alkali described in is sodium hydroxide or potassium hydroxide, and described carbonate salt is sodium carbonate or salt of wormwood.
Use the inventive method, the productive rate of 2-methyl isophthalic acid-ethynyl-2-amylene-1-ol can reach more than 90%.Compare with existing synthetic 2-methyl isophthalic acid-ethynyl-2-amylene-1-ol method, the invention has the advantages that:
(1), the method for preparing 2-methyl-2-pentenal serving intermediates is easier, temperature requirement is not high, energy consumption is lower.The catalyzer that preparation 2-methyl-2-pentenal serving intermediates are used is conventional alkali and carbonate salt mixed-alkali solution, and because of lower containing alkaline concentration, reaction process is gentle steady, and two kinds of alkali and salt can be by different proportional arrangement; Reaction only needs to carry out under normal temperature, does not need special regulating and controlling temperature; Use underpressure distillation, both significantly fallen distillation temperature, improved again separating effect, Energy Intensity Reduction is remarkable; In reaction process, do not use solvent, reduced the step that reclaims solvent, directly standing separation in reactor, not only simplifies the operation but also further reduced energy consumption.
(2), the usage quantity of liquefied ammonia significantly reduces, and accomplish that liquefied ammonia repeatedly utilizes and the volatilization of part liquefied ammonia after absorb and make ammoniacal liquor, and then significantly reduced production cost.
(3), toluene can repeatedly utilize, the toluene distilling can return and reacts and do not affect productive rate, has also significantly reduced production cost.
(4), with salt acid substitution ammonium chloride, simplified the operation that feeds intake, reduced hydrolysis time, play the effect of raising labour efficiency.
(5), product yield is higher, can reach more than 90%, purity is higher, all more than 98%, and then makes production cost lower, is beneficial to large-scale industrialization and produces.
Accompanying drawing explanation
Fig. 1: the production equipment of the first step reaction of the present invention.
Fig. 2: the production equipment of second step reaction of the present invention.
In figure: 1-olefine aldehydr reactor, 2-propionic aldehyde charging opening, 3-water charging opening, 4-olefine aldehydr distillation tower, 5-olefine aldehydr Receiving bin, 6-buck receiving tank, 7-alkynol reactor, 8-hydrochloric acid scale tank, 9-ammonia absorption groove, 10-alkynol hydrolysis kettle, 11-alkynol still kettle, 12-toluene Receiving bin, 13-alkynol rectifying still, 14-low-boiling-point substance Receiving bin, 15-product Receiving bin.
Embodiment
Embodiment 1: the preparation method of a kind of 2-methyl isophthalic acid-ethynyl-2-amylene-1-ol, comprises the following steps:
(1), the first step reaction
(1), by the weight ratio of water and propionic aldehyde, be that 2.5:1 calculates the water yield, Living Water is added in olefine aldehydr reactor, then adds respectively NaOH and K by the water yield
2cO
3be configured to the 0.1%NaOH aqueous solution and 2.5% K
2cO
3aqueous solution liquid.
(2) the chuck recirculated water (water is normal temperature) of, opening reactor is incubated, aldol reaction is thermopositive reaction, the recirculated water that passes into normal temperature at reacting kettle jacketing is to prevent that reactor temperature is overheated, production process does not need to measure especially temperature, as long as the recirculated water that passes into normal temperature at reacting kettle jacketing just can meet technical requirements.Open the stirring of reactor, by the ratio of (1), measure after propionic aldehyde stream and add propionic aldehyde and enter reactor, observe and record temperature, pressure, for production provides reference.
(3), add after propionic aldehyde, make its naturally cooling, continue reaction 1-2h, process sampling is analyzed, when product 2-methyl-2-pentenal serving content >=95%, during raw material propionic aldehyde content≤1%, termination reaction.Stop stirring, stratification 20 minutes, is released the alkali lye water layer of bottom to enter buck receiving tank by visor at the bottom of observing response still still, and upper oil phase product is washed neutrality and is retained in reactor.
(4), utilize olefine aldehydr distillation tower on reactor to carry out underpressure distillation, between vacuum tightness-0.090 ~-0.095Mpa, 70 ~ 95 ℃ of tower reactor temperature, directly all extraction is arrived in olefine aldehydr Receiving bin, can collect purity >=98%, meet the 2-methyl-2-pentenal serving intermediate product that next step reaction is used.
(2), second step reaction:
(1), by toluene: sodium amide weight ratio is that 6:1 calculates toluene consumption, and toluene is put in alkynol reactor.The stirring of opening reactor, drops into required sodium amide by the charging opening on reactor.
(2), open freezing water for cooling, temperature of reaction kettle is dropped to-34 ~-45 ℃.By liquefied ammonia: sodium amide weight ratio is to drop in reactor after 4.5:1 calculates liquefied ammonia consumption.
(3), open acetylene gas main valve, observe and record temperature, pressure, acetylene flow of reactor etc., pass into excessive acetylene, to guarantee that sodium amide all generates sodium carbide.
(4), by 2-methyl-2-pentenal serving: sodium amide weight ratio is that 2.4:1 calculates 2-methyl-2-pentenal serving consumption, and 2-methyl-2-pentenal serving is at the uniform velocity added in alkynol reactor.After adding 2-methyl-2-pentenal serving, continue reaction 50 minutes, layering in standing 30 minutes.
(5), open alkynol reactor still bottom valve, lower floor's product is put into alkynol hydrolysis kettle.
(6), the liquefied ammonia on upper strata can be stayed in alkynol reactor and reuse.
(7), start alkynol hydrolysis kettle and stir, the liquefied ammonia that comes is carried in the volatilization that heats up secretly, ammonia is absorbed and is made ammoniacal liquor by ammonia absorption groove, until the temperature in hydrolysis kettle is raised to 15 ℃, stops stirring when above.
(8), be evaporated completely after liquefied ammonia, more suitably lower the temperature, temperature in the kettle is dropped to 5 ℃ of left and right.
(9), by hydrochloric acid scale tank, configure the hydrochloric acid of 12% concentration, after temperature has fallen in hydrolysis kettle, stream adds hydrochloric acid and enters hydrolysis kettle hydrolysis, controls acid adding flow velocity and makes temperature in the kettle not higher than 40 ℃.When pH value reaches acidity, stop acid adding, layering in standing 20 minutes.
(10), by hydrolysis kettle still bottom valve, the water layer of lower floor is released, upper strata organic layer makes its pH value to neutral through washing, and organic layer sucks in alkynol still kettle.
(11), control vacuum tightness-0.090 ~-0.096Mpa, tower reactor temperature 30-60 ℃, extraction toluene, in toluene Receiving bin, can be collected most of purity >=85%, meets the toluene of recycling.
(12), residue still bed material enters the further rectifying again of alkynol rectifying still, first at tower reactor 70-90 ℃, under vacuum tightness-0.095 ~-0.099Mpa, the low-boiling-point substances such as remaining a small amount of toluene are steamed.Again in tower reactor 100-120 ℃, tower top 70-90 ℃, under vacuum tightness-0.097 ~-0.10Mpa, rectifying goes out 2-methyl isophthalic acid-ethynyl-2-amylene-1-ol product that purity is greater than 98%.
A kind of conversion as the present embodiment, (2), second step reaction: in (5) step, also all prods in alkynol reactor can be put into alkynol hydrolysis kettle together, liquefied ammonia all evaporates into ammonia in hydrolysis kettle, is absorbed and is made ammoniacal liquor afterwards by ammonia absorption groove.
Alkali of the present invention can be sodium hydroxide, potassium hydroxide, and carbonate salt can be the solid Industrial Salts such as sodium carbonate, salt of wormwood, and solid sodium hydroxide wherein can replace in proportion with 32% sodium hydroxide liquid caustic soda.
Claims (2)
1. a preparation method for 2-methyl isophthalic acid-ethynyl-2-amylene-1-ol, is characterized in that: comprise the following steps:
(1), the first step reaction:
(1), by the weight ratio of water and propionic aldehyde, be that 1-3:1 calculates the water yield, water is added in reactor, then adds respectively a kind of mineral alkali and a kind of carbonate salt to be configured to respectively containing alkali 0.1-0.8% with containing the mixed-alkali solution of carbonate salt 1-4% by the water yield;
(2), the chuck recirculated water of opening reactor is incubated, and opens the stirring of reactor, in the ratio of (1), measure after propionic aldehyde stream and add propionic aldehyde and enter reactor;
(3), add after propionic aldehyde, make its naturally cooling, continue reaction 1-2h, process sampling is analyzed, when product 2-methyl-2-pentenal serving content >=95%, during raw material propionic aldehyde content≤1%, termination reaction;
(4), stop stirring, stratification 10-30 minute, releases the alkali lye water layer of bottom, after the washing of upper oil phase product, is retained in reactor;
(5), utilize distillation tower on reactor to carry out underpressure distillation, between vacuum tightness-0.090 ~-0.095Mpa, 70 ~ 95 ℃ of tower reactor temperature, directly all extraction is arrived in olefine aldehydr Receiving bin, can collect purity >=98%, the 2-methyl-2-pentenal serving intermediate product that meets next step reaction use is stand-by;
(2), second step reaction:
(1), by toluene: sodium amide weight ratio is that 3-6:1 calculates toluene consumption, and toluene is put in alkynol reactor, opens the stirring of reactor, drops into required sodium amide by the charging opening on reactor;
(2), open freezing water for cooling, temperature of reaction kettle is dropped to-34 ~-45 ℃, by liquefied ammonia: sodium amide weight ratio is to drop in reactor after 3-6:1 calculates liquefied ammonia consumption;
(3), pass into excessive acetylene, to guarantee that sodium amide all generates sodium carbide;
(4), by 2-methyl-2-pentenal serving: sodium amide weight ratio is that 1.8-2.5:1 calculates 2-methyl-2-pentenal serving consumption, 2-methyl-2-pentenal serving is at the uniform velocity added in alkynol reactor, after adding 2-methyl-2-pentenal serving, continue reaction 30-60 minute, stop stirring standing 10-40 minute layering;
(5) or lower floor's product put into alkynol hydrolysis kettle, the liquefied ammonia on upper strata is stayed in alkynol reactor and is reused; Or all prods is put into hydrolysis kettle;
(6), start alkynol hydrolysis kettle and stir, the liquefied ammonia that comes is carried in the volatilization that heats up secretly, ammonia is absorbed and is made ammoniacal liquor by ammonia absorption groove, until the temperature in hydrolysis kettle is progressively raised to 15 ℃, stops stirring when above;
(7), be evaporated completely after liquefied ammonia, more suitably lower the temperature, temperature in the kettle is dropped to-20 ℃ ~ 10 ℃;
(8), by hydrochloric acid scale tank, configure the hydrochloric acid of 10-20% concentration, after temperature has fallen in hydrolysis kettle, stream adds hydrochloric acid and enters hydrolysis kettle hydrolysis, controls temperature in the kettle not higher than 40 ℃; When pH value is during to acidity, stop acid adding, standing 10-30 minute layering;
(9), the water layer of lower floor is released, upper strata organic layer makes its pH value to neutrality through washing, and organic layer sucks in alkynol still kettle;
(10), control vacuum tightness-0.090 ~-0.096Mpa, tower reactor temperature 30-60 ℃, extraction toluene, in toluene Receiving bin, can be collected most of purity >=85%, meets the toluene of recycling;
(11), the further rectifying again of residue still bed material, first at tower reactor 70-90 ℃, under vacuum tightness-0.095 ~-0.099Mpa, the low-boiling-point substances such as remaining a small amount of toluene are steamed; Again in tower reactor 100-120 ℃, tower top 70-90 ℃, under vacuum tightness-0.097 ~-0.10Mpa, rectifying goes out 2-methyl isophthalic acid-ethynyl-2-amylene-1-ol product that purity is greater than 98%.
2. the new process of production of a kind of 2-methyl-2-pentenal serving according to claim 1, is characterized in that: the mineral alkali step the () .(1) is sodium hydroxide or potassium hydroxide, and described carbonate salt is sodium carbonate or salt of wormwood.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108059585A (en) * | 2016-11-07 | 2018-05-22 | 江苏扬农化工股份有限公司 | The preparation method of 2- methyl-1s-acetenyl -2- amylene-1-ols |
| CN112898335A (en) * | 2021-01-22 | 2021-06-04 | 山东万盛新材料有限公司 | Preparation method of low-odor phosphate ester TCPP |
-
2014
- 2014-06-17 CN CN201410269580.4A patent/CN104030887B/en active Active
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108059585A (en) * | 2016-11-07 | 2018-05-22 | 江苏扬农化工股份有限公司 | The preparation method of 2- methyl-1s-acetenyl -2- amylene-1-ols |
| CN108059585B (en) * | 2016-11-07 | 2020-06-09 | 江苏扬农化工股份有限公司 | Preparation method of 2-methyl-1-ethynyl-2-penten-1-ol |
| CN112898335A (en) * | 2021-01-22 | 2021-06-04 | 山东万盛新材料有限公司 | Preparation method of low-odor phosphate ester TCPP |
| CN112898335B (en) * | 2021-01-22 | 2022-09-20 | 山东万盛新材料有限公司 | Preparation method of low-odor phosphate ester TCPP |
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