CN1083414C - One-step synthesizing process of 2,5-dimethyl-2,5-hexanediol - Google Patents
One-step synthesizing process of 2,5-dimethyl-2,5-hexanediol Download PDFInfo
- Publication number
- CN1083414C CN1083414C CN99115101A CN99115101A CN1083414C CN 1083414 C CN1083414 C CN 1083414C CN 99115101 A CN99115101 A CN 99115101A CN 99115101 A CN99115101 A CN 99115101A CN 1083414 C CN1083414 C CN 1083414C
- Authority
- CN
- China
- Prior art keywords
- dimethyl
- hydrogenation
- hexin
- glycol
- hexylene glycol
- 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.)
- Expired - Fee Related
Links
Abstract
The present invention provides a one-step synthesizing method of 2, 5-dimethyl-2, 5-hexanediol, which comprises the following steps: one-step synthesizing 2, 5-dimethyl-3-ethyne-2, 5-diol from ethyne and acetone under ordinary pressure in an o-xylene solution with isobutylanol potassium as a catalyst; after being hydrolyzed, neutralized, concentrated, crystallized and centrifugally separated, the 2, 5-dimethyl-3-ethyne-2, 5-diol is hydrogenated to produce 2, 5-dimethyl-2, 5-hexanediol in a high or medium pressure reactor under the pressure of 0-5.5MPa and with Reney nickel as a catalyst. The present invention has the advantages of short process, high product quality, low production cost and no waste liquid discharge, and is favorable to environmental protection and the health of operators.
Description
What the present invention relates to is a kind ofly to be used for industrial or to produce higher effective and lower toxic pesticide pyrethroid insectide, a rubber crosslinker 2,5-is two-and the main raw material-2 of hexane, 5-dimethyl-2,5-hexylene glycol-step synthesis method.
Adopt both at home and abroad at present and produce 2,5-dimethyl-3-hexin-2,5-glycol (being called for short diformazan, basic hexin glycol), hydrogenation makes 2,5-dimethyl-2,5-hexylene glycol (being called for short the dimethyl hexylene glycol), its main method is as follows:
1, normal pressure ethynylation method: produce dimethyl hexin glycol in two steps: earlier acetylene, acetone are being carried out ethynylation with excessive powder potassium hydroxide as catalyzer under the normal pressure in solvent (benzene), generate dimethyl hexin two potassium alcoholates, generate dimethyl hexin glycol in hydrolysis under the acidic conditions (acidifying after the first hydrolysis that has) again.Shortening gets the dimethyl hexylene glycol.Product per ton consumes 2 tons in potassium hydroxide, 1.7 tons of benzene, the cost height, and powdered potassium hydroxide dust and benzene are bigger to production environment harm.
2, pressurization ethynylation method: produce dimethyl hexin glycol in two steps; Earlier acetylene, acetone are depressed ethynylation in solvent (benzene, liquefied ammonia etc.) adding, generate 2-methyl-3-butyne-2-alcohol (tube claims methylbutynol), with acetone condensation reaction in the solvent that contains excessive powder potassium hydroxide (benzene), generate dimethyl hexin glycol again.Shortening gets the dimethyl hexylene glycol.Long flow path, by product is many, and raw material consumption and cost are higher.
3, there is research to replace powder potassium hydroxide to make catalyzer both at home and abroad with different (just) butanols potassio, acetylene, acetone are reacted in xylene solvent make the hexin glycol.It is raw material with methylbutynol and acetone directly that research is also arranged, and dimethyl hexin glycol is produced in condensation reaction in propyl carbinol or isobutyl potassium alcoholate-dimethylbenzene suspension, the recyclable repeated use of potassium hydroxide.But there is azeotrope each other in organic solvent composition complexity, is difficult to go out purer dimethylbenzene and propyl carbinol or isopropylcarbinol by fractionation by distillation and reuses, and cost is higher, and environmental pollution is big, realizes products production.
4, shortening adopts reactor batch operation and two kinds of methods of shell-and-tube reactor fixed bed continuous hydrogenation.Domestic employing reactor intermittent type hydrogenation, hydrogenation pressure 0～3.0MPa.Long reaction time, catalyst levels is higher, and the complete difficulty of hydrogenation is big.
In view of above reason, the objective of the invention is in order to provide a kind of flow process short, the quality product height, production cost is low, and no discharging of waste liquid helps the 2.5-dimethyl-2 of environment protection and operator ' s health, 5-hexylene glycol one-step synthesis.
Synthesis method of the present invention comprises that acetylene, acetone makes one-step synthesis 2 in the o-Xylol solution of catalyzer in the isobutyl potassium alcoholate under normal pressure, 5-dimethyl-3-hexin-2, the 5-glycol, through hydrolysis, neutralization, concentrate, after crystallization and centrifugation come out, in (height) press in the reactor with drawing Buddhist nun's nickel to make catalyzer, hydrogenation makes 2,5-dimethyl-2, the 5-hexylene glycol, isopropylcarbinol, o-Xylol that potassium hydroxide aqueous solution that hydrolysis generates and distillation are told are recycled and reused for produces isobutyl potassium alcoholate xylene solution.
Above-mentioned contain the isobutyl potassium alcoholate to make the temperature of the o-Xylol solution of catalyzer be 30～40 ℃, mol ratio by acetone and acetylene is 1.8～2.2: 1, successively acetylene, acetone are fed o-Xylol solution, at normal pressure and 30-40 ℃ of following powerful stirring reaction, Synthetic 2,5-dimethyl-3-hexin-2, the 5-glycol.
Above-mentioned 2,5-dimethyl-3-hexin-2 is after the 5-glycol hydrolysis layering, upper oil phase is with hydrochloric acid pH=5～6 that neutralize, underpressure distillation, segmentation steam isopropylcarbinol and o-Xylol, and concentrated solution is sent into the crystallizer tank crystallisation by cooling, isolate 2,5-dimethyl-3-hexin-2,5-two alcohol crystals are with 2,5-dimethyl-3-hexin-2,5-two alcohol crystals are sent into the hydrogenation still after being dissolved in ethanol, and what add 0.5-1.0% draws Buddhist nun's nickel catalyzator, hydrogenation under 30～160 ℃ and 0～5.5MPa pressure, generate 2,5-dimethyl-2,5-hexylene glycol solution, precipitation is sent into concentration kettle after removing and drawing Buddhist nun's nickel catalyzator, distilling out ethanol under 78～88 ℃ reuses, with 2,5-dimethyl-2,5-hexylene glycol solution crystallization, separate, get 2 in dry, 5-dimethyl-2, the 5-hexylene glycol.
Above-mentioned 2, the hydrogenation that 5-dimethyl-3-hexin-2,5-glycol are sent in the hydrogenation reaction kettle is a three phases, fs control pressure 0-2MPa, 30～150 ℃ of temperature of reaction, the hydrogenation time is 2～3 hours, subordinate phase control pressure 2.0～4.6MPa, 150～160 ℃ of temperature of reaction, the hydrogenation time is 1～2 hour, phase III control pressure 4.6～5.5MPa, 160～180 ℃ of temperature of reaction, the hydrogenation time is 5～7 hours.
The present invention is a raw material with acetylene, acetone, the o-Xylol solution of potassium alcoholate catalyzer is made medium, in the reactor that special stirring reaction function is arranged, one-step synthesis 2,5-dimethyl-3-hexin-2,5-glycol, (height) presses hydrogenation production higher-grade 2 in again in reactor, 5-dimethyl-2, the 5-hexylene glycol, its ultimate principle is:
Compare with domestic and international production method, the present invention has following advantage:
1, flow process is short, side reaction is few, in (height) press hydrogenation reaction fully, existing other production method quality product height, purity reaches 〉=99.7%, occupies the leading level in the world.
2, isopropylcarbinol and o-Xylol do not have azeotrope, and easily separated must purelyr the repeated use reduced cost.
3, the recyclable potassium hydroxide consumption of producing isobutyl potassium alcoholate, product per ton that is recycled and reused for of the potassium hydroxide aqueous solution after the hydrolysis is than the few 1.5-1.6 ton of normal pressure ethynylation method.
4, the existing additive method of production cost reduces 15-20%.
5, no discharging of waste liquid.Solvent for use is little 1.5 times than the toxicity of benzene, adds that boiling point is higher, helps protecting environment and operator ' s health.
Introduce embodiments of the invention below:
The embodiment of the invention is as follows:
1, medium manufacturing: in the potassium alcoholate reactor, add concentration and be 12.2 moles KOH aqueous solution 170L, isopropylcarbinol 1300L, start to stir after being warmed up to 95 ℃ and carry out dehydration reaction.Reclaim isopropylcarbinol more than needed after the still temperature rise to 135 ℃, add 660 liters of o-Xylol solvents and make the medium that contain isobutyl potassium alcoholate catalyzer.Its reaction formula is as follows:
More than reaction is a reversible, constantly water sepn is discharged in reaction process, keeps reaction to carry out to the right.
2, dimethyl hexin glycol is synthetic: being cooled to below 35 ℃ in medium input dimethyl hexin glycol reactor, is that (throughput ratio was 6.1 * 10 in 2: 1 by the mol ratio of acetone and acetylene
-3: 1, show " 6.1 " on the controlling board) ratio add acetylene and acetone successively, keep 30～40 ℃ of still temperature, under the forceful action of specific function agitator, carry out condensation reaction, one-step synthesis dimethyl hexin glycol.
3, hydrolysis neutralization
After condensation reaction stops, material is sent into hydrolytic decomposition pot to add acetylene consumption kilogram and counts 9-10 water doubly and be hydrolyzed, after the static layering lower floor's alkali lye recovery is recycled and reused for manufacturing isobutyl potassium alcoholate, upper strata fluid is sent into neutralizing well and is added acid layering to the pH=5-6, upper strata dimethyl hexin glycol solution is sent to distillation, and lower floor's KCl liquid is sent into the storage pond and is produced the KCl product.
4, concentrate distillation
Dimethyl hexin glycol solution is sent into heating heat in the distiller, temperature begins underpressure distillation after reaching 89 ℃, and cut is sent into rectifying tower Separation and Recovery isopropylcarbinol and o-Xylol.Concentrate and control 90-94 ℃ of tower top temperature in the still-process.When concentrated solution reaches the hexin dosage by 12 times (when Tc is 25 ℃) to 16 times (when Tc is 5 ℃) of kilogram, stop distillation, send into crystallizer tank.
5, Crystallization Separation
After dimethyl hexin glycol concentrated solution is sent into crystallizer tank, with putting into whizzer after 17-18 ℃ of water cooling 3-4 hour to 25 ℃ (or be cooled to 5 ℃ with icy salt solution), be dimethyl hexin two alcohol crystals in the machine, the centrifugal mother liquor reclaims and repeats to distill.
6, hydrogenation
To add in the dissolution kettle through air-dry 320-330 kilogram dimethyl hexin glycol, and, send into magnetictransmission and stir in the hydrogenation reaction kettle, and add the 1.6-3.3 kilogram simultaneously and draw Buddhist nun's nickel catalyzator with the dissolving of 450-470L hexanol.Hydrogenation carries out in three stages; Fs control pressure 0-2.0MPa, temperature of reaction 30-150 ℃, the time is 2～3 hours; Subordinate phase control pressure 2.0～4.6MPa, temperature of reaction 150-160 ℃, the time is 1～2 hour; Phase III control pressure 4.6-5.5MPa, temperature of reaction 160-180 ℃, the time is 5～7 hours.The about 8-10 of all processes hour, send into quantizer after finishing reaction (sampling and measuring hydrogenation is complete).
7, concentrate distillation
The dimethyl hexylene glycol liquid that precipitation is removed the nickel catalyzator powder is sent in the heating distiller and is heated, temperature reaches 79 ℃ and begins to distillate ethanol, reclaims and reuses, and later controlled temperature is no more than 88 ℃, after distillating ethanol 310-330L, stop distillation, concentrated solution is sent into crystallizer tank.
8, Crystallization Separation
After dimethyl hexylene glycol concentrated solution is sent into crystallizer tank, with icy salt solution cooling 3-4 hour, putting into whizzer after reducing the temperature to 5 ℃ and separate, be dimethyl hexylene glycol crystal in the machine, concentrates from the mother liquor that goes out and repeats to distill.
9, drying
Adopt boulton process, be that dry machine temperature reaches 50 ℃ after, the dimethyl hexylene glycol is placed in the drying machine, be decompressed to-0.04 to-0.06MPa, keeps 50 ℃, 2-4 hour, must product dimethyl hexylene glycol.
The inventive method provides the basic raw material assurance for development China pyrethrin agricultural chemicals, a rubber crosslinker and other related productss, provides essential condition for increasing China's product new variety and improving the throughput that has relevant device now.
Claims (4)
1,2,5-dimethyl-2,5-hexylene glycol one-step synthesis is characterized in that synthesis method comprises that acetylene, acetone makes one-step synthesis 2 in the o-Xylol solution of catalyzer in the isobutyl potassium alcoholate under normal pressure, 5-dimethyl-3-hexin-2, the 5-glycol, through hydrolysis, neutralization, concentrate, after crystallization and centrifugation come out, in the mesohigh reactor, make catalyzer with drawing Buddhist nun's nickel, 0-5.5MPa hydrogenation makes 2 under the pressure, 5-dimethyl-2,5-hexylene glycol.
2, according to claim 12,5-dimethyl-2,5-hexylene glycol one-step synthesis, it is characterized in that containing the isobutyl potassium alcoholate, to make the temperature of the o-Xylol solution of catalyzer be 30～40 ℃, is 1.8～2.2: 1 by the mol ratio of acetone and acetylene, successively acetylene, acetone fed o-Xylol solution, at normal pressure and 30-40 ℃ of following powerful stirring reaction, Synthetic 2,5-dimethyl-3-hexin-2,5-glycol.
3, according to claim 1 and 22,5-dimethyl-2,5-hexylene glycol one-step synthesis is characterized in that Synthetic 2,5-dimethyl-3-hexin-2, after the 5-glycol hydrolysis layering, upper oil phase is with hydrochloric acid pH=5～6 that neutralize, underpressure distillation, steam isopropylcarbinol and o-Xylol, concentrated solution is sent into the crystallizer tank crystallisation by cooling, isolates 2,5-dimethyl-3-hexin-2,5-two alcohol crystals, with 2,5-dimethyl-3-hexin-2,5-two alcohol crystals are sent into the hydrogenation still after being dissolved in ethanol, what add 0.5-1.0% draws Buddhist nun's nickel catalyzator, hydrogenation under 30～160 ℃ and 0～5.5MPa pressure generates 2,5-dimethyl-2,5-hexylene glycol solution, precipitation is sent into concentration kettle after removing and drawing Buddhist nun's nickel catalyzator, distills out ethanol and reuse under 78～88 ℃, with 2,5-dimethyl-2,5-hexylene glycol solution crystallization, separate, dry 2,5-dimethyl-2,5-hexylene glycol product.
4, according to claim 1 and 22,5-dimethyl-2,5-hexylene glycol one-step synthesis, it is characterized in that 2,5-dimethyl-3-hexin-2, the hydrogenation that the 5-glycol is sent in the hydrogenation reaction kettle is a three phases, fs control pressure 0-2MPa, 30～150 ℃ of temperature of reaction, the hydrogenation time is 2～3 hours, subordinate phase control pressure 2.0～4.6MPa, 150～160 ℃ of temperature of reaction, the hydrogenation time is 1～2 hour, phase III control pressure 4.6～5.5MPa, 160～180 ℃ of temperature of reaction, the hydrogenation time is 5～7 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99115101A CN1083414C (en) | 1999-08-25 | 1999-08-25 | One-step synthesizing process of 2,5-dimethyl-2,5-hexanediol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99115101A CN1083414C (en) | 1999-08-25 | 1999-08-25 | One-step synthesizing process of 2,5-dimethyl-2,5-hexanediol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1247181A CN1247181A (en) | 2000-03-15 |
| CN1083414C true CN1083414C (en) | 2002-04-24 |
Family
ID=5278117
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99115101A Expired - Fee Related CN1083414C (en) | 1999-08-25 | 1999-08-25 | One-step synthesizing process of 2,5-dimethyl-2,5-hexanediol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1083414C (en) |
Families Citing this family (44)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101234950B (en) * | 2008-02-02 | 2010-12-29 | 泸州富邦化工有限公司 | Technique for producing 2,5-dimethyl-2,5-hexandiol by extraction and decompression distillation method |
| CN102633602A (en) * | 2012-04-26 | 2012-08-15 | 江苏泰特尔化工有限公司 | Method for preparing 3-hexine-2,5-glycol under ordinary pressure |
| IN2014DN10741A (en) * | 2012-07-11 | 2015-09-04 | Lonza Ag | |
| CN103910606B (en) * | 2013-07-09 | 2016-05-25 | 泸州宏达有机化工厂 | Ethynylation condensation method is produced 2,5-dimethyl-2, the method for 5-hexylene glycol |
| CN109574806B (en) * | 2017-09-29 | 2021-10-29 | 中国科学院大连化学物理研究所 | Method for preparing hexanediol by catalytic hydrogenation of hexynediol |
| CN108929196A (en) * | 2018-08-22 | 2018-12-04 | 西南化工研究设计院有限公司 | A kind of aftertreatment technology and system producing 2,5- dimethyl -3- hexin -2,5- glycol |
| KR102434452B1 (en) | 2018-11-28 | 2022-08-19 | 주식회사 엘지화학 | Prepration method of cross-linking compound |
| CN109735928B (en) * | 2018-12-27 | 2020-10-16 | 江苏恒力化纤股份有限公司 | Teslin cloth and preparation method thereof |
| CN109735957B (en) * | 2018-12-27 | 2020-11-06 | 江苏恒力化纤股份有限公司 | Polyester composite fully drawn yarn and preparation method thereof |
| CN109750372B (en) * | 2018-12-27 | 2020-05-22 | 江苏恒力化纤股份有限公司 | Wool-like polyester filament and preparation method thereof |
| CN109750370B (en) * | 2018-12-27 | 2020-11-06 | 江苏恒力化纤股份有限公司 | Full-dull network elastic yarn and preparation method thereof |
| CN109750367B (en) * | 2018-12-27 | 2020-10-16 | 江苏恒力化纤股份有限公司 | Polyester industrial yarn for automobile air bag and preparation method thereof |
| CN109735925B (en) * | 2018-12-27 | 2020-11-06 | 江苏恒力化纤股份有限公司 | Polyester FDY (fully drawn yarn) easy to dye and degrade and preparation method thereof |
| CN109680353B (en) * | 2018-12-27 | 2020-07-03 | 江苏恒力化纤股份有限公司 | Cationic dyeable polyester fiber and preparation method thereof |
| CN109735919B (en) * | 2018-12-27 | 2020-10-16 | 江苏恒力化纤股份有限公司 | Heptanediol modified polyester fiber with tertiary butyl side group and preparation method thereof |
| CN109735940B (en) * | 2018-12-27 | 2020-08-14 | 江苏恒力化纤股份有限公司 | Preparation method of deep-float linen-like polyester fiber |
| CN109722737B (en) * | 2018-12-27 | 2020-08-14 | 江苏恒力化纤股份有限公司 | Modified polyester fiber containing solid base catalyst and preparation method thereof |
| CN109735927B (en) * | 2018-12-27 | 2020-10-16 | 江苏恒力化纤股份有限公司 | Full-dull polyester low stretch yarn and preparation method thereof |
| CN109722740B (en) * | 2018-12-27 | 2020-10-16 | 江苏恒力化纤股份有限公司 | Degradable polyester fiber and preparation method thereof |
| CN109735947B (en) * | 2018-12-27 | 2020-10-16 | 江苏恒力化纤股份有限公司 | Water-repellent canvas and preparation method thereof |
| CN109666983B (en) * | 2018-12-27 | 2020-07-07 | 江苏恒力化纤股份有限公司 | Method for improving dye uptake of polyester FDY (fully drawn yarn) fibers |
| CN109518297B (en) * | 2018-12-27 | 2020-10-13 | 江苏恒力化纤股份有限公司 | Hollow polyester filament yarn and preparation method thereof |
| CN109735943B (en) * | 2018-12-27 | 2020-10-16 | 江苏恒力化纤股份有限公司 | Easy-to-dye polyester POY fiber and preparation method thereof |
| CN109735934B (en) * | 2018-12-27 | 2020-10-16 | 江苏恒力化纤股份有限公司 | Full-dull terylene pre-oriented yarn and preparation method thereof |
| CN109735945B (en) * | 2018-12-27 | 2020-10-16 | 江苏恒力化纤股份有限公司 | Polyester industrial yarn for camouflage and covering and preparation method thereof |
| CN109735939B (en) * | 2018-12-27 | 2020-10-16 | 江苏恒力化纤股份有限公司 | Melt direct spinning on-line addition colored polyester fiber and preparation method thereof |
| CN109735931B (en) * | 2018-12-27 | 2020-10-16 | 江苏恒力化纤股份有限公司 | Preparation method of polyester industrial yarn for traction belt |
| CN109763194B (en) * | 2018-12-27 | 2020-10-16 | 江苏恒力化纤股份有限公司 | Preparation method of polyester industrial yarn for tire cord |
| CN109722728B (en) * | 2018-12-27 | 2020-07-03 | 江苏恒力化纤股份有限公司 | PBT-containing double-component elastic yarn and preparation method thereof |
| CN109735930B (en) * | 2018-12-27 | 2020-10-16 | 江苏恒力化纤股份有限公司 | Full-dull polyester drawn yarn and preparation method thereof |
| CN109750371B (en) * | 2018-12-27 | 2020-10-16 | 江苏恒力化纤股份有限公司 | Super-bright polyester filament yarn for cross-stitch embroidery and preparation method thereof |
| CN109750379B (en) * | 2018-12-27 | 2020-10-16 | 江苏恒力化纤股份有限公司 | Ultra-bright polyester low stretch yarn and preparation method thereof |
| CN109750375B (en) * | 2018-12-27 | 2020-10-16 | 江苏恒力化纤股份有限公司 | Lightweight thermal fiber and preparation method thereof |
| CN109735933B (en) * | 2018-12-27 | 2020-10-13 | 江苏恒力化纤股份有限公司 | Polyester industrial yarn for safety belt and preparation method thereof |
| CN109722733B (en) * | 2018-12-27 | 2020-10-13 | 江苏恒力化纤股份有限公司 | Polyester industrial yarn for military bags and preparation method thereof |
| CN109735935B (en) * | 2018-12-27 | 2020-08-14 | 江苏恒力化纤股份有限公司 | Preparation method of marine polyester cable rope |
| CN109750380B (en) * | 2018-12-27 | 2020-10-16 | 江苏恒力化纤股份有限公司 | Preparation method of polyester lamp box advertisement cloth |
| CN109706542B (en) * | 2018-12-27 | 2020-07-07 | 江苏恒力化纤股份有限公司 | Flame-retardant polyester fiber and preparation method thereof |
| CN109666989B (en) * | 2018-12-27 | 2020-10-13 | 江苏恒力化纤股份有限公司 | Superfine denier polyester low stretch yarn and preparation method thereof |
| CN109735942B (en) * | 2018-12-27 | 2020-07-07 | 江苏恒力化纤股份有限公司 | High-modulus low-shrinkage activated polyester industrial yarn and preparation method thereof |
| CN109750376B (en) * | 2018-12-27 | 2021-01-01 | 江苏恒力化纤股份有限公司 | Terylene heat-resistant canvas and preparation method thereof |
| CN110511127B (en) * | 2019-09-16 | 2022-08-05 | 万华化学集团股份有限公司 | Method for preparing alpha-hydroxy ketone by using ethynylation reaction by-product |
| CN115594566B (en) * | 2022-09-22 | 2023-12-29 | 山东阳谷华泰化工股份有限公司 | Synthesis method of 2, 5-dimethyl-2, 5-hexanediol |
| CN115894172A (en) * | 2022-10-14 | 2023-04-04 | 青岛科技大学 | Continuous production system and method of 2, 5-dimethyl-2, 5-hexanediol |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3449445A (en) * | 1967-03-17 | 1969-06-10 | Gaf Corp | Process of preparing 1,4-butanediol |
| GB1329815A (en) * | 1970-02-25 | 1973-09-12 | Basf Ag | Production of tertiary acetylenic glycols by reaction of acetylene with ketones |
| US4960959A (en) * | 1987-04-04 | 1990-10-02 | Huels Aktiengesellschaft | Process for the manufacture of alkynediols by reaction of ketones with acetylene |
-
1999
- 1999-08-25 CN CN99115101A patent/CN1083414C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3449445A (en) * | 1967-03-17 | 1969-06-10 | Gaf Corp | Process of preparing 1,4-butanediol |
| GB1329815A (en) * | 1970-02-25 | 1973-09-12 | Basf Ag | Production of tertiary acetylenic glycols by reaction of acetylene with ketones |
| US4960959A (en) * | 1987-04-04 | 1990-10-02 | Huels Aktiengesellschaft | Process for the manufacture of alkynediols by reaction of ketones with acetylene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1247181A (en) | 2000-03-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1083414C (en) | One-step synthesizing process of 2,5-dimethyl-2,5-hexanediol | |
| US6031128A (en) | Process for manufacturing terephthalic acid | |
| KR100983349B1 (en) | Chemical process for recycling polyethylene terephthalate (pet) wastes | |
| CA2229207C (en) | Recovery of caprolactam from nylon-6 scrap | |
| CN104066705A (en) | Process to prepare levulinic acid | |
| CN102015611A (en) | A process for preparation of formate salt | |
| CN100455612C (en) | Method for removing aluminum trichloride and purifying products in C5 petroleum resin production process | |
| CN102241606A (en) | Clean production method of N-cyanoethylaniline | |
| JP2006232701A (en) | Method for recovering ester monomer from polyester fiber waste | |
| CN101698639B (en) | Method for recycling sodium formate products from coarse sodium formate of byproduct of polyhydric alcohol | |
| KR102126236B1 (en) | Method for producing dioctylterephthalate and antifreeze simultaneously by using polyethyleneterephthalate | |
| CN103787894B (en) | The method of tolylene diamine is reclaimed in the residue waste material formed from tolylene diisocyanate preparation process | |
| EP1138663B1 (en) | Method for recovery of terephthalic acid from a material containing poly(ethylene terephthalates) | |
| CN110372496A (en) | A kind of method of electrodialysis purification neopentyl glycol sodium formate mixed liquor | |
| CN109160880B (en) | Preparation method of ethyl benzoate | |
| CN100506832C (en) | Method for preparing acephate | |
| CN1304359C (en) | Process for synthesizing propylene glycol monomethyl ether acetate (PMA) | |
| KR100224466B1 (en) | Process for producing terephthalic acid(1) | |
| CN1039225C (en) | Synthesizing process for levocarvol | |
| JP2003267904A (en) | Method for producing ditrimethylolpropane | |
| CN115109008A (en) | Method for prolonging reuse of toluene solvent in preparation of 2-chloro-5-chloromethyl thiazole | |
| CN109456184B (en) | Synthetic preparation method of wintergreen oil | |
| CN110885288B (en) | Synthesis method of isooctyl p-methoxycinnamate | |
| CN102268294A (en) | Recovery method of butanone-toluene solvent in dewaxing process of lubricating oil | |
| KR100228737B1 (en) | Method for producing dialkylmalinate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |