CN109761949A - One kind 2,2- dimethyl -4- methylol -1,3-dioxolane industrial production process - Google Patents
One kind 2,2- dimethyl -4- methylol -1,3-dioxolane industrial production process Download PDFInfo
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- CN109761949A CN109761949A CN201910026118.4A CN201910026118A CN109761949A CN 109761949 A CN109761949 A CN 109761949A CN 201910026118 A CN201910026118 A CN 201910026118A CN 109761949 A CN109761949 A CN 109761949A
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- carboxylic acid
- methylol
- dimethyl
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- 238000009776 industrial production Methods 0.000 title claims abstract description 23
- RNVYQYLELCKWAN-UHFFFAOYSA-N solketal Chemical compound CC1(C)OCC(CO)O1 RNVYQYLELCKWAN-UHFFFAOYSA-N 0.000 title claims description 34
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 115
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 85
- 235000011187 glycerol Nutrition 0.000 claims abstract description 81
- 239000003054 catalyst Substances 0.000 claims abstract description 60
- -1 glycerine ester Chemical class 0.000 claims abstract description 49
- 239000013067 intermediate product Substances 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 230000002378 acidificating effect Effects 0.000 claims abstract description 28
- 239000012670 alkaline solution Substances 0.000 claims abstract description 19
- 238000010719 annulation reaction Methods 0.000 claims abstract description 19
- 239000000047 product Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 230000018044 dehydration Effects 0.000 claims abstract description 11
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 11
- 230000007062 hydrolysis Effects 0.000 claims abstract description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 11
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 10
- 230000032050 esterification Effects 0.000 claims abstract description 10
- 238000005886 esterification reaction Methods 0.000 claims abstract description 10
- 150000001735 carboxylic acids Chemical class 0.000 claims description 60
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 230000002209 hydrophobic effect Effects 0.000 claims description 27
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical group CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 11
- 239000012024 dehydrating agents Substances 0.000 claims description 11
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- ZZTMMVAAULUFCS-UHFFFAOYSA-L disodium;methanedisulfonate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)CS([O-])(=O)=O ZZTMMVAAULUFCS-UHFFFAOYSA-L 0.000 claims description 7
- 150000001768 cations Chemical class 0.000 claims description 6
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 5
- 229910015900 BF3 Inorganic materials 0.000 claims description 5
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 4
- 125000003944 tolyl group Chemical group 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- 230000001681 protective effect Effects 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000000243 solution Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- GJHLWNOWQBUDJX-UHFFFAOYSA-N benzoic acid;propane-1,2,3-triol Chemical compound OCC(O)CO.OC(=O)C1=CC=CC=C1 GJHLWNOWQBUDJX-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 150000004668 long chain fatty acids Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003809 water extraction Methods 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- 241000222519 Agaricus bisporus Species 0.000 description 1
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JEQLMQDIGPQFJR-UHFFFAOYSA-N methanesulfonic acid;sulfuric acid Chemical group CS(O)(=O)=O.OS(O)(=O)=O JEQLMQDIGPQFJR-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- NIXKBAZVOQAHGC-UHFFFAOYSA-N phenylmethanesulfonic acid Chemical compound OS(=O)(=O)CC1=CC=CC=C1 NIXKBAZVOQAHGC-UHFFFAOYSA-N 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses one kind 2,2- dimethyl -4- methylol -1, the industrial production process of 3- dioxolanes, the following steps are included: (1), esterification prepare carboxylic acid list glycerine ester: using glycerine and carboxylic acid as raw material, under conditions of acidic catalyst, the dehydration 0.5-4h at 90-150 DEG C obtains carboxylic acid list glycerine ester；(2), ketal annulation: under the conditions of acidic catalyst, control annulation 0.5-3h at 20-50 DEG C obtains cyclic intermediate product for carboxylic acid list glycerine ester and acetone；(3), hydrolysis: the resulting intermediate product of step (2) is added in alkaline solution, 0.5-1h is reacted at 20-50 DEG C, obtains product.2,2- dimethyl -4- methylol -1,3-dioxolane industrial production process of the invention has the characteristics that technique is environmentally protective, work reaction selectivity is high, feed stock conversion is high.
Description
Technical field
The present invention relates to 2,2- dimethyl -4- methylol -1,3-dioxolane technical fields, specially one kind 2,2- diformazan
Base -4- methylol -1,3-dioxolane industrial production process.
Background technique
2,2- dimethyl -4- methylols -1,3-dioxolane is a kind of from renewable resource, has low volatility
Product.Compared with alcohol ethers solvent, toxicity is lower, to human health and more environment-friendly.Alcohol ethers solvent can be replaced,
For being used as solvent, cosolvent or coalescing agent etc. in the fields such as coating, ink, leather processing；For daily use chemicals and champignon industry
As carrier and solubilizer；For industry cleaning link and electronic chemical product industry.
Current 2,2- dimethyl -4- methylol -1,3-dioxolane industry is divided into two kinds: direct method and indirect method.Directly
Connection is that in acid condition, acetone and the direct ketal reaction of glycerine obtain product；Indirect method is the synthesis side except direct method
Method.Direct method uses strong acid that ketal reaction occurs and generates product and water as catalyst, glycerine and acetone.Currently, whether
The separation of laboratory synthetic reaction or industrialization process, byproduct water is the bottleneck of production, due to product 2,2- dimethyl-
4- methylol -1,3-dioxolane is miscible with water, and unreacted acetone is also mutually dissolved with glycerine with water and product, simultaneously
Glycerine is apt to deteriorate at high temperature.The key of reaction process is the water of generation to be removed system in time, but due to anti-
Various components in system are answered all to be mutually dissolved, separation is difficult, this also makes the practical conversion per pass of reaction very low.It has been reported that at present
Removal acetone method that the water generated is reacted with glycerine there was only dehydrated in situ and azeotropic dehydration, but two methods respectively have it is scarce
Point, such as dehydrated in situ, generally using dehydrating agent such as anhydrous sodium sulfate etc., dehydrating effect is not significant, and will bring to post-processing tired
Difficulty, unit consumption can also improve；And the method for azeotropic dehydration, one side acetone and water do not have azeotropic point, not having band water acts on, another party
Face, the low boiling point (56 oC) of raw material acetone, common water entrainer is all unavailable, and effect is all bad.
Summary of the invention
The object of the present invention is to provide one kind 2,2- dimethyl -4- methylol -1,3-dioxolane industrial production process,
Have the characteristics that technique is environmentally protective, work reaction selectivity is high, feed stock conversion is high.
The present invention can be achieved through the following technical solutions:
The invention discloses one kind 2,2- dimethyl -4- methylol -1,3-dioxolane industrial production process, including following step
It is rapid:
(1), esterification prepares hydrophobic intermediate product carboxylic acid list glycerine ester: using glycerine and carboxylic acid as raw material, in acidity
Under conditions of catalyst, the dehydration 0.5-4h at 90-150 DEG C obtains hydrophobic intermediate product carboxylic acid list glycerine ester；
(2), ketal annulation: carboxylic acid list glycerine ester and acetone control at 20-50 DEG C under the conditions of acidic catalyst
Annulation 0.5-3h obtains hydrophobic cyclic intermediate product；
(3), hydrolysis: by step (2) resulting intermediate productIt is added in alkaline solution, at 20-50 DEG C
0.5-1h is reacted, product 2,2- dimethyl -4- methylol -1,3-dioxolane are obtained.
Its specific reaction process are as follows:
Wherein R is C (n) H (2n+ 1), and n 1-16 or R are C6H5。
Further, in step (1), the molar ratio of glycerine and carboxylic acid is 1:1, and the additional amount of catalyst is glycerine
0.05%-10%.
Further, in step (2), carboxylic acid list glycerine ester and acetone molar ratio are 1:1-10, catalyst charge
For the 0.05%-10% of carboxylic acid list glycerine ester.
Further, step (1) acidic catalyst be methane sulfonic acid, p-methyl benzenesulfonic acid, sodium methanedisulfonate, sulfuric acid, sun from
The mixture of one or more of subtree rouge；
Further, step (2) acidic catalyst be methane sulfonic acid, p-methyl benzenesulfonic acid, sodium methanedisulfonate, boron trifluoride ether,
One or both of resin cation alchlor, sodium bisulfate.
Further, step (3) described alkaline solution is in 18-32wt%NaOH, resin anion (R.A.), 18-32wt%KOH
One or more.
Further, dehydrating agent is additionally added in the step (1), the dehydrating agent is toluene and/or hexamethylene.
As another technical solution of the present invention, stating preparation method may be selected the glycerin monostearate generation of commercialization
For the resulting carboxylic acid list glycerine ester of step (1), the reaction condition of step (2) is kept, is omitted step (1).
Present invention one kind 2,2- dimethyl -4- methylol -1,3-dioxolane industrial production process has with following
Beneficial effect:
The first, technique is environmentally protective, and by preparing hydrophobic intermediate product, whole preparation process is without using desiccant, no
Solid waste can be generated due to desiccant, the long chain fatty acids of addition are reusable, and long chain fatty acids and glycerine can
It is all by physical layering mode for biomass source raw material, in reaction step 1 and 2 by water and separation of oil, energy saving；
The second, reaction selectivity is high, and the esterification basically formed on glycerine 1 reacted by the first step keeps second step ketal anti-
Seasonable reaction selectivity is high, and two adjacent hydroxyls of glycerine are reacted into five-membered ring.
Third, feed stock conversion are high, due to hydrophobic segment previously-introduced in the reaction raw materials by ketal, make ketal reaction mistake
The water energy generated in journey is separated with system automatically, so as to greatly improve the conversion per pass of ketal reaction, ketal of the present invention
React conversion per pass up to 90% or more, conversion ratio with higher.
Specific embodiment
In order that those skilled in the art will better understand the technical solution of the present invention, below with reference to embodiment and to this
Invention product is described in further detail.
The invention discloses one kind 2,2- dimethyl -4- methylol -1,3-dioxolane industrial production process, including with
Lower step:
(1), esterification prepares hydrophobic intermediate product carboxylic acid list glycerine ester: using glycerine and carboxylic acid as raw material, in acidity
Under conditions of catalyst, the dehydration 0.5-4h at 90-150 DEG C obtains hydrophobic intermediate product carboxylic acid list glycerine ester；
(2), ketal annulation: carboxylic acid list glycerine ester and acetone control at 20-50 DEG C under the conditions of acidic catalyst
Annulation 0.5-3h obtains hydrophobic cyclic intermediate product；
(3), hydrolysis: by step (2) resulting intermediate productIt is added in alkaline solution, at 20-50 DEG C
0.5-1h is reacted, product 2,2- dimethyl -4- methylol -1,3-dioxolane are obtained.
Further, in step (1), the molar ratio of glycerine and carboxylic acid is 1:1, and the additional amount of catalyst is glycerine
0.05%-10%.
Further, in step (2), carboxylic acid list glycerine ester and acetone molar ratio are 1:1-10, catalyst charge
For the 0.05%-10% of carboxylic acid list glycerine ester.
Further, step (1) acidic catalyst be methane sulfonic acid, p-methyl benzenesulfonic acid, sodium methanedisulfonate, sulfuric acid, sun from
The mixture of one or more of subtree rouge；
Further, step (2) acidic catalyst be methane sulfonic acid, p-methyl benzenesulfonic acid, sodium methanedisulfonate, boron trifluoride ether,
One or both of resin cation alchlor, sodium bisulfate.
Further, step (3) described alkaline solution is in 18-32wt%NaOH, resin anion (R.A.), 18-32wt%KOH
One or more.
Further, dehydrating agent is additionally added in the step (1), the dehydrating agent is toluene and/or hexamethylene.
As another technical solution of the present invention, stating preparation method may be selected the glycerin monostearate generation of commercialization
For the resulting carboxylic acid list glycerine ester of step (1), the reaction condition of step (2) is kept, is omitted step (1).
Embodiment 1
The invention discloses one kind 2,2- dimethyl -4- methylol -1,3-dioxolane industrial production process, including following step
It is rapid:
(1), esterification prepares hydrophobic intermediate product carboxylic acid list glycerine ester: using glycerine and carboxylic acid as raw material, in acidity
Under conditions of catalyst, the dehydration 2.25h at 150 DEG C obtains hydrophobic intermediate product carboxylic acid list glycerine ester；Glycerine
Molar ratio with carboxylic acid is 1:1, and the additional amount of catalyst is the 0.05% of glycerine.Acidic catalyst is methane sulfonic acid, to toluene
Sulfonic acid.
(2), ketal annulation: carboxylic acid list glycerine ester and acetone control at 50 DEG C under the conditions of acidic catalyst
Annulation 1.75h obtains hydrophobic cyclic intermediate product；Carboxylic acid list glycerine ester is with acetone molar ratio
1:1, catalyst charge are the 0.05% of carboxylic acid list glycerine ester.Acidic catalyst is sulfuric acid methane sulfonic acid.
(3), hydrolysis: by step (2) resulting intermediate productIt is added in alkaline solution, at 50 DEG C
0.75h is reacted, product 2,2- dimethyl -4- methylol -1,3-dioxolane are obtained.The alkaline solution is 18wt%NaOH.
Embodiment 2
The invention discloses one kind 2,2- dimethyl -4- methylol -1,3-dioxolane industrial production process, including following step
It is rapid:
(1), esterification prepares hydrophobic intermediate product carboxylic acid list glycerine ester: using glycerine and carboxylic acid as raw material, in acidity
Under conditions of catalyst, the dehydration 0.5h at 120 DEG C obtains hydrophobic intermediate product carboxylic acid list glycerine ester；Glycerine
Molar ratio with carboxylic acid is 1:1, and the additional amount of catalyst is the 10% of glycerine.Acidic catalyst is sulfuric acid.
(2), ketal annulation: carboxylic acid list glycerine ester and acetone control at 35 DEG C under the conditions of acidic catalyst
Annulation 0.5h obtains hydrophobic cyclic intermediate product；Carboxylic acid list glycerine ester and acetone molar ratio are 1:
10, catalyst charge is the 5% of carboxylic acid list glycerine ester；Acidic catalyst is boron trifluoride ether.
(3), hydrolysis: by step (2) resulting intermediate productIt is added in alkaline solution, at 35 DEG C
0.5h is reacted, product 2,2- dimethyl -4- methylol -1,3-dioxolane are obtained.The alkaline solution is resin anion (R.A.).
Embodiment 3
The invention discloses one kind 2,2- dimethyl -4- methylol -1,3-dioxolane industrial production process, including following step
It is rapid:
(1), esterification prepares hydrophobic intermediate product carboxylic acid list glycerine ester: using glycerine and carboxylic acid as raw material, in acidity
Under conditions of catalyst, the dehydration 4h at 90 DEG C obtains hydrophobic intermediate product carboxylic acid list glycerine ester；Glycerine and carboxylic
The molar ratio of acid is 1:1, and the additional amount of catalyst is the 5% of glycerine.Acidic catalyst is to benzene methanesulfonic acid.
(2), ketal annulation: carboxylic acid list glycerine ester and acetone control at 20 DEG C under the conditions of acidic catalyst
Annulation 3h obtains hydrophobic cyclic intermediate product；Carboxylic acid list glycerine ester and acetone molar ratio are 1:5,
Catalyst charge is the 2% of carboxylic acid list glycerine ester.Acidic catalyst is resin cation.
(3), hydrolysis: by step (2) resulting intermediate productIt is added in alkaline solution, at 20 DEG C
1h is reacted, product 2,2- dimethyl -4- methylol -1,3-dioxolane are obtained.The alkaline solution is 25wt%NaOH, 32wt%
One or more of KOH.
Embodiment 4
The invention discloses one kind 2,2- dimethyl -4- methylol -1,3-dioxolane industrial production process, including following step
It is rapid:
(1), esterification prepares hydrophobic intermediate product carboxylic acid list glycerine ester: using glycerine and carboxylic acid as raw material, in acidity
Under conditions of catalyst, the dehydration 3h at 100 DEG C obtains hydrophobic intermediate product carboxylic acid list glycerine ester；Glycerine with
The molar ratio of carboxylic acid is 1:1, and the additional amount of catalyst is the 6% of glycerine.Acidic catalyst is resin cation.
(2), ketal annulation: carboxylic acid list glycerine ester and acetone control at 40 DEG C under the conditions of acidic catalyst
Annulation 1h obtains hydrophobic cyclic intermediate product；Carboxylic acid list glycerine ester and acetone molar ratio are 1:7,
Catalyst charge is the 3% of carboxylic acid list glycerine ester.Acidic catalyst is methane sulfonic acid, p-methyl benzenesulfonic acid, sodium methanedisulfonate.
(3), hydrolysis: by step (2) resulting intermediate productIt is added in alkaline solution, at 40 DEG C
0.8h is reacted, product 2,2- dimethyl -4- methylol -1,3-dioxolane are obtained.The alkaline solution is 23wt%NaOH, yin
Ion exchange resin.
In the present embodiment, dehydrating agent is additionally added in the step (1), the dehydrating agent is toluene and hexamethylene.
Embodiment 5
The invention discloses one kind 2,2- dimethyl -4- methylol -1,3-dioxolane industrial production process, including following step
It is rapid:
(1), esterification prepares hydrophobic intermediate product carboxylic acid list glycerine ester: using glycerine and carboxylic acid as raw material, in acidity
Under conditions of catalyst, the dehydration 3h at 100 DEG C obtains hydrophobic intermediate product carboxylic acid list glycerine ester；Glycerine with
The molar ratio of carboxylic acid is 1:1, and the additional amount of catalyst is the 6% of glycerine.Acidic catalyst is sulfuric acid.
(2), ketal annulation: carboxylic acid list glycerine ester and acetone control at 40 DEG C under the conditions of acidic catalyst
Annulation 1h obtains hydrophobic cyclic intermediate product；Carboxylic acid list glycerine ester and acetone molar ratio are 1:7,
Catalyst charge is the 3% of carboxylic acid list glycerine ester.Acidic catalyst is boron trifluoride ether.
(3), hydrolysis: by step (2) resulting intermediate productIt is added in alkaline solution, at 40 DEG C
0.8h is reacted, product 2,2- dimethyl -4- methylol -1,3-dioxolane are obtained.The alkaline solution is 23wt%NaOH, yin
Ion exchange resin.
In the present embodiment, dehydrating agent is additionally added in the step (1), the dehydrating agent is hexamethylene.
Embodiment 6
The invention discloses one kind 2,2- dimethyl -4- methylol -1,3-dioxolane industrial production process, including following step
It is rapid:
(1), ketal annulation: the glycerin monostearate and acetone of commercialization control under the conditions of acidic catalyst 30
Annulation 1h at DEG C obtains hydrophobic cyclic intermediate product；Carboxylic acid list glycerine ester is with acetone molar ratio
1:3, catalyst charge are the 4% of carboxylic acid list glycerine ester.Acidic catalyst is methane sulfonic acid.
(2), hydrolysis: by step (1) resulting intermediate productIt is added in alkaline solution, at 30 DEG C
0.6h is reacted, product 2,2- dimethyl -4- methylol -1,3-dioxolane are obtained.The alkaline solution be 28wt%NaOH,
34wt%KOH。
Application Example 1
15.4 kg of glycerin monostearate and 10 kg of acetone, 0.06 kg of catalyst p-methyl benzenesulfonic acid are added into reaction kettle,
40o60min is reacted under C to be terminated, and with water extraction and recovery catalyst, air-distillation recycles excessive propanone, obtains solketal list
16.8 kg of stearate, yield 98%, purity: 98.5%.
Above-mentioned 16.8 kg of intermediate product is added in reaction kettle, is obtained its hydrolysis of ester group by the high steam of 4MPa
To oil be mutually evaporated under reduced pressure and recycle bottom by-product stearic acid, tower top temperature is 120oC, vacuum degree are 90 kpa, and purity can be obtained
For 98.5% 2,2- dimethyl -4- methylol -1,3-dioxolane.
Application Example 2
10 kg of glycerine and 13.26 kg of benzoic acid is added into reaction kettle, 0.05 kg of catalyst methane sulfonic acid is added and with water
Agent toluene 2kg, 150 min are reacted at 120 oC to be terminated, and is recycled catalyst extraction with water, removes raw material through vacuum distillation
Afterwards, intermediary glycerine mono benzoate, yield 97.5%, purity 99% are obtained.
8.5 kg of glycerine mono benzoate and 10 kg of acetone, catalyst methane sulfonic acid 0.025 are added into reaction kettle
Kg, reacting 60min at 35oC terminates, and with water extraction and recovery catalyst, excessive propanone is recycled in air-distillation, and it is sweet to obtain acetone contracting
Oily 9.8 kg of benzoic ether, yield 96%, purity: 98.5%.
Above-mentioned 9.8 kg of intermediate product is added in reaction kettle, 5 kg of NaOH solution of 32wt% is added, 60 oC of heat preservation are stirred
Reaction 30min is mixed, it is 7 that sulphur acid for adjusting pH, which is added, and after split-phase, oil is mutually evaporated under reduced pressure, and bottom benzoic acid recycles, and tower top (steams
Evaporating tower top temperature is 120 oC, and vacuum degree is 90 kpa) 2,2- dimethyl -4- methylol -1,3- bis- that purity is 98.5% can be obtained
Butyl oxide link.
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the present invention in any form；It is all
The those of ordinary skill of the industry can be shown in by specification and described above and swimmingly implement the present invention；But it is all familiar
Professional and technical personnel without departing from the scope of the present invention, makes using disclosed above technology contents
A little variation, modification and evolution equivalent variations, be equivalent embodiment of the invention；Meanwhile all realities according to the present invention
The variation, modification and evolution etc. of matter technology any equivalent variations to the above embodiments, still fall within technology of the invention
Within the protection scope of scheme.
Claims (8)
1. one kind 2,2- dimethyl -4- methylol -1,3-dioxolane industrial production process, it is characterised in that including following step
It is rapid:
(1), esterification prepares hydrophobic intermediate product carboxylic acid list glycerine ester: using glycerine and carboxylic acid as raw material, in acidity
Under conditions of catalyst, the dehydration 0.5-4h at 90-150 DEG C obtains hydrophobic intermediate product carboxylic acid list glycerine ester；
(2), ketal annulation: carboxylic acid list glycerine ester and acetone under the conditions of acidic catalyst, control at 20-50 DEG C at
Ring reacts 0.5-3h, obtains hydrophobic cyclic intermediate product
(3), hydrolysis: by step (2) resulting intermediate productIt is added in alkaline solution, it is anti-at 20-50 DEG C
0.5-1h is answered, product 2,2- dimethyl -4- methylol -1,3-dioxolane are obtained.
2. the industrial production process of 2,2- dimethyl -4- methylol -1,3-dioxolane according to claim 1, special
Sign is: in step (1), the molar ratio of glycerine and carboxylic acid is 1:1, and the additional amount of catalyst is the 0.05%- of glycerine
10%.
3. the industrial production process of 2,2- dimethyl -4- methylol -1,3-dioxolane according to claim 2, special
Sign is: in step (2), carboxylic acid list glycerine ester and acetone molar ratio are 1:1-10, and catalyst charge is carboxylic acid list third
The 0.05%-10% of three alcohol esters.
4. the industrial production process of 2,2- dimethyl -4- methylol -1,3-dioxolane according to claim 3, special
Sign is: step (1) acidic catalyst is methane sulfonic acid, in p-methyl benzenesulfonic acid, sodium methanedisulfonate, sulfuric acid, resin cation
One or more kinds of mixtures.
5. the industrial production process of 2,2- dimethyl -4- methylol -1,3-dioxolane according to claim 2, special
Sign is: step (2) acidic catalyst is methane sulfonic acid, p-methyl benzenesulfonic acid, sodium methanedisulfonate, boron trifluoride ether, cation
One or both of resin alchlor, sodium bisulfate.
6. the industrial production process of 2,2- dimethyl -4- methylol -1,3-dioxolane according to claim 3 or 4,
Be characterized in that:, step (3) described alkaline solution in 18-32wt%NaOH, resin anion (R.A.), 18-32wt%KOH one
Kind is two or more.
7. the industrial production process of 2,2- dimethyl -4- methylol -1,3-dioxolane according to claim 5, special
Sign is: dehydrating agent is additionally added in the step (1), the dehydrating agent is toluene and/or hexamethylene.
8. the industrial production process of 2,2- dimethyl -4- methylol -1,3-dioxolane according to claim 1, special
Sign is: selecting the glycerin monostearate of commercialization to replace step (1) resulting carboxylic acid list glycerine ester, keeps step (2)
Reaction condition, omit step (1).
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| CN104829584A (en) * | 2015-05-19 | 2015-08-12 | 江苏福瑞生物医药有限公司 | Synthesis method of (R)-glyceraldehyde acetonide compound |
| CN108373410A (en) * | 2018-04-11 | 2018-08-07 | 深圳市前海博扬研究院有限公司 | A kind of preparation method of dimethyl hydrine acetate |
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2019
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| CN104829584A (en) * | 2015-05-19 | 2015-08-12 | 江苏福瑞生物医药有限公司 | Synthesis method of (R)-glyceraldehyde acetonide compound |
| CN108373410A (en) * | 2018-04-11 | 2018-08-07 | 深圳市前海博扬研究院有限公司 | A kind of preparation method of dimethyl hydrine acetate |
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