CN118388317B - Method for preparing propylene glycol from propylene oxide - Google Patents
Method for preparing propylene glycol from propylene oxide Download PDFInfo
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- CN118388317B CN118388317B CN202410844187.7A CN202410844187A CN118388317B CN 118388317 B CN118388317 B CN 118388317B CN 202410844187 A CN202410844187 A CN 202410844187A CN 118388317 B CN118388317 B CN 118388317B
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 title claims abstract description 70
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 17
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims abstract description 74
- GOOHAUXETOMSMM-VKHMYHEASA-N S-propylene oxide Chemical compound C[C@H]1CO1 GOOHAUXETOMSMM-VKHMYHEASA-N 0.000 claims abstract description 74
- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
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- VZHHNBNSMNNUAD-UHFFFAOYSA-N cobalt 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound [Co].OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VZHHNBNSMNNUAD-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 37
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- 239000000706 filtrate Substances 0.000 claims description 35
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- 238000003756 stirring Methods 0.000 claims description 19
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- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 claims description 3
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 3
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 claims description 2
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- 239000005457 ice water Substances 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 10
- GOOHAUXETOMSMM-GSVOUGTGSA-N R-propylene oxide Chemical compound C[C@@H]1CO1 GOOHAUXETOMSMM-GSVOUGTGSA-N 0.000 description 8
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- 239000012535 impurity Substances 0.000 description 8
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- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
- NOESYZHRGYRDHS-UHFFFAOYSA-N insulin Chemical compound N1C(=O)C(NC(=O)C(CCC(N)=O)NC(=O)C(CCC(O)=O)NC(=O)C(C(C)C)NC(=O)C(NC(=O)CN)C(C)CC)CSSCC(C(NC(CO)C(=O)NC(CC(C)C)C(=O)NC(CC=2C=CC(O)=CC=2)C(=O)NC(CCC(N)=O)C(=O)NC(CC(C)C)C(=O)NC(CCC(O)=O)C(=O)NC(CC(N)=O)C(=O)NC(CC=2C=CC(O)=CC=2)C(=O)NC(CSSCC(NC(=O)C(C(C)C)NC(=O)C(CC(C)C)NC(=O)C(CC=2C=CC(O)=CC=2)NC(=O)C(CC(C)C)NC(=O)C(C)NC(=O)C(CCC(O)=O)NC(=O)C(C(C)C)NC(=O)C(CC(C)C)NC(=O)C(CC=2NC=NC=2)NC(=O)C(CO)NC(=O)CNC2=O)C(=O)NCC(=O)NC(CCC(O)=O)C(=O)NC(CCCNC(N)=N)C(=O)NCC(=O)NC(CC=3C=CC=CC=3)C(=O)NC(CC=3C=CC=CC=3)C(=O)NC(CC=3C=CC(O)=CC=3)C(=O)NC(C(C)O)C(=O)N3C(CCC3)C(=O)NC(CCCCN)C(=O)NC(C)C(O)=O)C(=O)NC(CC(N)=O)C(O)=O)=O)NC(=O)C(C(C)CC)NC(=O)C(CO)NC(=O)C(C(C)O)NC(=O)C1CSSCC2NC(=O)C(CC(C)C)NC(=O)C(NC(=O)C(CCC(N)=O)NC(=O)C(CC(N)=O)NC(=O)C(NC(=O)C(N)CC=1C=CC=CC=1)C(C)C)CC1=CN=CN1 NOESYZHRGYRDHS-UHFFFAOYSA-N 0.000 description 2
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- NCEGJIHRQBRVJQ-UHFFFAOYSA-N 2-amino-3-[3-[2-(phosphonomethyl)phenyl]phenyl]propanoic acid Chemical compound OC(=O)C(N)CC1=CC=CC(C=2C(=CC=CC=2)CP(O)(O)=O)=C1 NCEGJIHRQBRVJQ-UHFFFAOYSA-N 0.000 description 1
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- 102000004877 Insulin Human genes 0.000 description 1
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- 229940123518 Sodium/glucose cotransporter 2 inhibitor Drugs 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- GOADIQFWSVMMRJ-UPGAGZFNSA-N dapagliflozin propanediol monohydrate Chemical compound O.C[C@H](O)CO.C1=CC(OCC)=CC=C1CC1=CC([C@H]2[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)O)=CC=C1Cl GOADIQFWSVMMRJ-UPGAGZFNSA-N 0.000 description 1
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- 229960004556 tenofovir Drugs 0.000 description 1
- VCMJCVGFSROFHV-WZGZYPNHSA-N tenofovir disoproxil fumarate Chemical compound OC(=O)\C=C\C(O)=O.N1=CN=C2N(C[C@@H](C)OCP(=O)(OCOC(=O)OC(C)C)OCOC(=O)OC(C)C)C=NC2=C1N VCMJCVGFSROFHV-WZGZYPNHSA-N 0.000 description 1
- 208000001072 type 2 diabetes mellitus Diseases 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of chemical synthesis, and discloses a method for preparing propylene glycol by using propylene oxide, which adopts a supported S-catalyst Co (Salen)/SBA-15-C8 or Co (Salen)/SBA-16-Bz to carry out resolution reaction on propylene oxide to obtain R-propylene glycol and S-propylene oxide, and then uses solid super acid SO 4 2‑/ZrO2/SBA-15 or perfluorinated sulfonic acid resin to carry out ring opening on the S-propylene oxide to obtain the S-propylene glycol. The invention can fully convert propylene oxide into R-propylene glycol and S-propylene glycol, so that the raw materials are utilized to the maximum extent, and the production efficiency and the benefit of manufacturers are ensured.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and relates to a method for preparing propylene glycol by using propylene oxide.
Background
Propylene glycol is divided into R-propylene glycol and S-propylene glycol due to chiral reasons, wherein the R-propylene glycol and the S-propylene glycol are relatively important medical intermediates, and especially the R-propylene glycol can be used for synthesizing R-propylene carbonate (RPC), and the RPC is an important raw material for synthesizing an anti-AIDS antiviral drug tenofovir (PMBA); s-propylene glycol can be used for synthesizing dapagliflozin (S) -propylene glycol hydrate, which is one of new generation compounds called sodium-glucose cotransporter-2 (SGLT-2) inhibitors, can provide an effect of reducing blood hyperglycemia independent of insulin, is used as a single drug therapy, can be used for improving blood glucose control of adult patients with type II diabetes, and achieves the effect of treating diabetes.
However, the existing production of R-propylene glycol and S-propylene glycol is a single production mode, and the production of R-propylene glycol or S-propylene glycol is produced, because the products are chiral, the production of a single product inevitably causes the problems of low product yield, more obtained other chiral products and difficult treatment, thus seriously affecting the production efficiency and the benefit of manufacturers; and simultaneously producing R-propylene glycol and S-propylene glycol, which are sold as medical intermediates, can save the consumption of raw materials and greatly improve the output value of the product.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: the method for preparing the propylene glycol by using the propylene oxide can fully convert the propylene oxide into the R-propylene glycol and the S-propylene glycol, so that the raw materials are maximally utilized, and the production efficiency and the benefit of manufacturers are ensured.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a method for preparing propylene glycol by using propylene oxide, comprising the following steps:
a. Adding propylene oxide, a supported S-catalyst and p-nitrobenzoic acid into a reaction device at the temperature of 0-20 ℃, dripping water into the mixed solution, after finishing dripping for 2-8 hours, detecting a reaction end point after the reaction is carried out for 2-16 hours under the condition that the specific optical rotation of the S-propylene oxide is-10.0 DEG to-13.7 DEG, and stopping the reaction to obtain the mixed solution of the R-propylene glycol and the S-propylene oxide; wherein the weight ratio of the propylene oxide to the water to the p-nitrobenzoic acid to the supported S-catalyst is 1 (0.1-0.2) (0.001-0.01) (0.01-1.0); the supported S-catalyst is Co (Salen)/SBA-15-C8 or supported catalyst Co (Salen)/SBA-16-Bz;
b. C, carrying out sectional distillation on the feed liquid obtained in the step a to obtain R-propylene glycol and S-propylene oxide; the front-stage distillation adopts normal pressure distillation, water bath distillation is adopted, the water bath temperature is set to 45 ℃, and the water bath temperature is adjusted to 75 ℃ at most according to the propylene oxide distillation speed, so as to obtain S-propylene oxide; filtering the residual feed liquid while the residual feed liquid is hot, and obtaining filtrate, namely a crude product of the R-propylene glycol; the crude product of the R-propylene glycol is distilled under reduced pressure, the vacuum degree is 15mm Hg, and the temperature is 120 ℃ to obtain the R-propylene glycol;
c. Adding water and solid superacid into a reaction device, dropwise adding the S-epoxypropane obtained in the step b into the feed liquid, keeping the dropwise adding temperature at 0-25 ℃, and carrying out heat preservation reaction for 1-6 h to obtain the feed liquid containing the S-propylene glycol; wherein, the weight ratio of S-propylene oxide, water and solid super acid is 1: (1.0-1.5) 0.005-0.05); the solid super acid is SO 4 2-/ZrO2/SBA-15 or perfluorinated sulfonic acid resin;
d. Filtering the material liquid obtained in the step c, and washing the obtained filter cake, namely solid super acid, with methanol for recycling; the obtained filtrate is the crude product of the S-propylene glycol, the crude product of the S-propylene glycol is distilled under reduced pressure, the vacuum degree is 15mm Hg, and the temperature is 120 ℃, thus obtaining the S-propylene glycol.
Preferably, in the step a, the water dripping reaction temperature is 10 ℃, the dripping time is 4 hours, the heat preservation reaction time is 10 hours, and the reaction is stopped when the specific rotation of S-epoxypropane is-12 ℃; the weight ratio of propylene oxide to water, p-nitrobenzoic acid and supported S-catalyst was 1:0.15:0.005:0.5.
Preferably, the supported S-catalyst in the step a is Co (Salen)/SBA-15-C8; the preparation method of Co (Salen)/SBA-15-C8 comprises the following steps: after 1.0g of SBA-15 was stirred and evacuated at 25℃for 6 hours, it was added to methylene chloride (6 ml) containing 0.12g of Co (Salen) (II), and the mixture was heated and refluxed for 24 hours under the protection of argon gas under stirring, and the methylene chloride was distilled off; the obtained solid is added into a solution containing 0.9ml of toluene, 1.25ml of anhydrous trimethoxysilane and 5mmol of octyl trimethoxysilane, and the mixture is heated and refluxed for 24 hours under the protection of argon, and filtered to obtain the solid, and the solid is washed by toluene, dichloromethane and tetrahydrofuran in sequence; namely, the supported catalyst Co (Salen)/SBA-15-C8 is prepared.
Preferably, the filter cake obtained by filtering in the step b, namely the supported S-catalyst, can be recycled after being washed by methanol.
Preferably, in the step c, the dropwise adding temperature is kept at 12.5 ℃, the dropwise adding is completed, and the heat preservation reaction is carried out for 4 hours; the weight ratio of the S-propylene oxide to the water to the solid super acid is 1:0.28:0.016.
Preferably, the solid super acid in the step c is SO 4 2-/ZrO2/SBA-15. The reaction mechanism of solid superacid SO 4 2-/ZrO2/SBA-15 ring-opened epoxypropane is as follows: the solid super acid releases H ＋ in aqueous solution, propylene oxide firstly reacts with H ＋ to generate protonized propylene oxide, water serving as a nucleophile attacks the protonized propylene oxide, and the ring of the propylene oxide is cracked to generate a corresponding product of 1, 2-propylene glycol.
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. the invention adopts a supported S-catalyst to carry out resolution reaction on propylene oxide to obtain R-propylene glycol and S-propylene oxide, and then carries out ring opening on the S-propylene oxide to obtain S-propylene glycol, thus completely utilizing the propylene oxide serving as a raw material and completely converting the propylene oxide into R-propylene glycol and S-propylene glycol;
2. the supported S-catalyst adopted by the invention can be recycled for more than ten times, the catalyst loss is small, and the solid superacid is used for ring opening, so that the recycling can be realized; particularly, the supported S-catalyst Co (Salen)/SBA-15-C8 has stable performance and strong repeatability, can be recycled for a plurality of times, and ensures the production stability; the solid superacid is subjected to ring opening by adopting SO 4 2-/ZrO2/SBA-15, the ring opening efficiency is high, and the yield of the obtained target product is high; the solid super acid is used, so that the recycling can be realized, the purity of the obtained product is high, the yield is high, and the process is safe and environment-friendly.
In a word, the preparation method of the invention fully utilizes the raw material propylene oxide, and the obtained product has high purity, high yield and safe and environment-friendly process; the used supported S-catalyst and solid super acid can be recycled for a plurality of times, and the loss is small; ensuring the production efficiency and the benefits of enterprises.
Drawings
FIG. 1 is a gas chromatogram of the inventive control 1 product;
FIG. 2 is a gas chromatogram of the product of example 2 of the present invention;
FIG. 3 is a gas chromatogram of the inventive control 2 product;
FIG. 4 is a gas chromatogram of the product of example 9 of the present invention.
Detailed Description
Example 1 preparation of supported catalyst Co (Salen)/SBA-15-C8:
1000g of SBA-15 was stirred at 25℃for 6 hours, then added to methylene chloride (6L) containing 120g of Co (II) (Salen), and the mixture was heated under reflux under argon for 24 hours under stirring, and methylene chloride was distilled off to obtain a solid.
The obtained solid was added to a solution containing 0.9L of toluene, 1.25L of anhydrous trimethoxysilane and 5mol of octyltrimethoxysilane, refluxed under the protection of argon for 24 hours, and the obtained solid was filtered and washed with toluene, dichloromethane and tetrahydrofuran in this order; namely, the Co (Salen)/SBA-15-C8 catalyst is prepared.
Comparative example 1 catalytic synthesis of R-propanediol with Co (Salen)
1350G of propylene oxide, 7.0g of p-nitrobenzoic acid and 15.4g of Co (Salen) catalyst are weighed, stirring is started, and the temperature is reduced to 10 ℃ by an ice water bath. 200g of water is added dropwise, after 4 hours, sampling is performed, central control is performed to detect whether the reaction is finished, and the specific rotation of S-epoxypropane is-12.0 ℃ at the end point of the reaction. The reaction was incubated at 10℃for 18h and completed.
And after the central control detection is qualified, distilling the feed liquid to remove the S-epoxypropane, distilling the feed liquid in a water bath for a distillation reaction, setting the water bath temperature to be 45 ℃, properly adjusting the water bath temperature to be 75 ℃ at most according to the distilling speed of the S-epoxypropane, determining that no S-epoxypropane flows out, stopping distilling, and collecting 600 gS-epoxypropane.
After distillation, the mixture was immediately filtered while hot (within half an hour), the filtrate was crude R-propanediol, the filter cake was Co (Salen) catalyst, and the filter cake was washed with methanol until the filtrate was colorless, and dried at 70℃to give 13.5g in 87.7% yield. In the crude product of the R-propylene glycol, the content of the R-propylene glycol is 94.0 percent, the content of the S-propylene oxide is 0.52 percent, and the content of the high-boiling-point impurity is 2.1 percent. Transferring the R-propylene glycol crude product into a rectifying device, starting heating and stirring, vacuumizing to 15mm Hg, and rectifying at room temperature. And in the rectification process, collecting the R-propylene glycol when the temperature reaches 120 ℃. 835.0g of R-propylene glycol were collected, the content of R-propylene glycol was 97.4%, the moisture content was 0.3% and the specific rotation was-16.8 °. The yield of R-propanediol was 94.4% based on R-propylene oxide.
EXAMPLE 2 catalytic Synthesis of R-propanediol with Supported catalyst Co (Salen)/SBA-15-C8
1350G of propylene oxide, 7.0g of p-nitrobenzoic acid and 675g of Co (Salen)/SBA-15-C8 are weighed, stirring is started, and the ice water bath is cooled to 10 ℃. 200g of water was added dropwise thereto, and the reaction was continued at 10℃after 4 hours. Sampling, central control and detection are carried out to determine whether the reaction is completed, and the specific rotation of the S-epoxypropane is-12.0 ℃ at the end point of the reaction. The reaction was completed for 10 hours.
And after the central control detection is qualified, distilling the feed liquid to remove the S-epoxypropane, distilling the feed liquid in a water bath for a distillation reaction, setting the water bath temperature to be 45 ℃, properly adjusting the water bath temperature to be 75 ℃ at most according to the distilling speed of the S-epoxypropane, determining that no S-epoxypropane flows out, stopping distilling, and collecting 610 gS-epoxypropane.
After distillation, immediately filtering while hot (within half an hour), washing the filter cake Co (Salen)/SBA-15-C8 with methanol until the filtrate is colorless, and drying at 70 ℃ to obtain 673.6g with the yield of 99.8%; the filtrate is the crude product of the R-propylene glycol. In the crude product of the R-propylene glycol, the content of the R-propylene glycol is 97.0 percent, the content of the S-propylene oxide is 0.49 percent, and the content of the high-boiling-point impurity is 2.0 percent. Transferring the R-propylene glycol crude product into a rectifying device, starting heating and stirring, vacuumizing to 15mm Hg, and rectifying at room temperature. During the rectification, the collection of R-propanediol was started when the temperature reached 120 ℃. 866.8g of R-propylene glycol were collected together, the R-propylene glycol content was 99.62%, the moisture content was 0.28%, and the specific rotation was-16.9 °. The yield of R-propanediol was 98% based on R-propylene oxide.
EXAMPLE 3 catalytic Synthesis of R-propanediol with Supported catalyst Co (Salen)/SBA-15-C8 (ten times applied)
1350G of propylene oxide, 7.0g of p-nitrobenzoic acid and 675g of Co (Salen)/SBA-15-C8 (ten times applied) are weighed, stirring is started, and the ice water bath is cooled to 10 ℃. 200g of water is added dropwise, the reaction is carried out after 4 hours, the temperature is kept at 10 ℃, the sample is taken out, the control and detection are carried out to determine whether the reaction is finished, the specific rotation of S-epoxypropane is-12.0 ℃ at the end point of the reaction, and the reaction is finished after 20 hours.
And after the central control detection is qualified, distilling the feed liquid to remove the S-epoxypropane, distilling the feed liquid in a water bath for a distillation reaction, setting the water bath temperature to be 45 ℃, properly adjusting the water bath temperature to be 75 ℃ at most according to the distilling speed of the S-epoxypropane, determining that no S-epoxypropane flows out, stopping distilling, and collecting 597g of S-epoxypropane.
After distillation, immediately filtering while the mixture is hot (within half an hour), wherein the filtrate is a crude product of R-propylene glycol, the filter cake is Co (Salen)/SBA-15-C8, washing the filter cake with methanol until the filtrate is colorless, and drying the filtrate at 70 ℃ to obtain 673.1g with the yield of 99.7%. In the crude product of the R-propylene glycol, the content of the R-propylene glycol is 94.0 percent, the content of the S-propylene oxide is 0.5 percent, and the content of the high-boiling-point impurity is 2.1 percent. Transferring the R-propylene glycol crude product into a rectifying device, starting heating and stirring, vacuumizing to 15mm Hg, and rectifying at room temperature. And in the rectification process, collecting the R-propylene glycol when the temperature reaches 120 ℃. 835.8g of R-propylene glycol were collected, the content of R-propylene glycol was 99%, the moisture content was 0.31% and the specific rotation was-16.85 °. The yield of R-propanediol was 94.5% based on R-propylene oxide.
EXAMPLE 4 catalytic Synthesis of R-propanediol with different amounts of Supported catalyst Co (Salen)/SBA-15-C8
1350G of propylene oxide, 7.0g of p-nitrobenzoic acid and 13.5g of Co (Salen)/SBA-15-C8 are weighed, stirring is started, and the ice water bath is cooled to 10 ℃. 200g of water was added dropwise thereto, and the reaction was continued at 10℃after 4 hours. Sampling, central control and detection are carried out to determine whether the reaction is completed, and the specific rotation of the S-epoxypropane is-12.0 ℃ at the end point of the reaction. The reaction was completed for 109 h.
And after the central control detection is qualified, distilling the feed liquid to remove the S-epoxypropane, distilling the feed liquid in a water bath for a distillation reaction, setting the water bath temperature to be 45 ℃, properly adjusting the water bath temperature to be 75 ℃ at most according to the distilling speed of the S-epoxypropane, determining that no S-epoxypropane flows out, stopping distilling, and collecting 586 gS-epoxypropane.
After distillation, the mixture is immediately filtered (within half an hour) while the mixture is hot, the filtrate is crude R-propylene glycol, the filter cake is Co (Salen)/SBA-15-C8, the filter cake is washed by methanol until the filtrate is colorless, and the filtrate is dried at 70 ℃ to obtain 13.4g with the yield of 99.26%. In the crude product of the R-propylene glycol, the content of the R-propylene glycol is 97.0 percent, the content of the S-propylene oxide is 0.5 percent, and the content of the high-boiling-point impurity is 2.3 percent. Transferring the R-propylene glycol crude product into a rectifying device, starting heating and stirring, vacuumizing to 15mm Hg, and rectifying at room temperature. And in the rectification process, collecting the R-propylene glycol when the temperature reaches 120 ℃. 853.5g of R-propylene glycol were collected, the content of R-propylene glycol was 98.5%, the moisture content was 0.3% and the specific rotation was-16.8 °. The yield of R-propanediol was 96.5% based on R-propylene oxide.
EXAMPLE 5 catalytic Synthesis of R-propanediol with different amounts of Supported catalyst Co (Salen)/SBA-15-C8
1350G of propylene oxide, 7.0g of p-nitrobenzoic acid and 1350g of Co (Salen)/SBA-15-C8 are weighed, stirring is started, and the ice water bath is cooled to 10 ℃. 200g of water was added dropwise thereto, and the reaction was continued at 10℃after 4 hours. Sampling, central control and detection are carried out to determine whether the reaction is completed, and the specific rotation of the S-epoxypropane is-12.0 ℃ at the end point of the reaction. The reaction was completed for 4.5 h.
And after the central control detection is qualified, distilling the feed liquid to remove the S-epoxypropane, distilling the feed liquid in a water bath for a distillation reaction, setting the water bath temperature to be 45 ℃, properly adjusting the water bath temperature to be 75 ℃ at most according to the distilling speed of the S-epoxypropane, determining that no S-epoxypropane flows out, stopping distilling, and collecting 613 gS-epoxypropane.
After distillation, immediately filtering while the mixture is hot (within half an hour), wherein the filtrate is a crude product of R-propylene glycol, the filter cake is Co (Salen)/SBA-15-C8, washing the filter cake with methanol until the filtrate is colorless, and drying the filtrate at 70 ℃ to obtain 1347.3g with the yield of 99.8%. In the crude product of the R-propylene glycol, the content of the R-propylene glycol is 98.3 percent, the content of the S-propylene oxide is 0.48 percent, and the content of the high-boiling-point impurity is 1.8 percent. Transferring the R-propylene glycol crude product into a rectifying device, starting heating and stirring, vacuumizing to 15mm Hg, and rectifying at room temperature. And in the rectification process, collecting the R-propylene glycol when the temperature reaches 120 ℃. 867.7g of R-propylene glycol were collected, the content of R-propylene glycol was 99.64%, the moisture content was 0.34% and the specific rotation was-16.98 °. The yield of R-propanediol was 98.1% based on R-propylene oxide.
EXAMPLE 6 catalytic Synthesis of R-propanediol with Supported catalyst Co (Salen)/SBA-16-Bz
1350G of propylene oxide, 7.0g of p-nitrobenzoic acid and 675g of Co (Salen)/SBA-16-Bz are weighed, stirring is started, and the ice water bath is cooled to 10 ℃. 200g of water was added dropwise thereto, and the reaction was continued at 10℃after 4 hours. Sampling, central control and detection are carried out to determine whether the reaction is completed, and the specific rotation of the S-epoxypropane is-12.0 ℃ at the end point of the reaction. The reaction was completed for 12 hours.
And after the central control detection is qualified, distilling the feed liquid to remove the S-epoxypropane, distilling the feed liquid in a water bath for a distillation reaction, setting the water bath temperature to be 45 ℃, properly adjusting the water bath temperature to be 75 ℃ at most according to the distilling speed of the S-epoxypropane, determining that no S-epoxypropane flows out, stopping distilling, and collecting 608 gS-epoxypropane.
After distillation, the mixture was immediately filtered while hot (within half an hour), and the filter cake was Co (Salen)/SBA-16-Bz, washed with methanol until the filtrate was colorless, and dried at 70℃to give 673.0g in 99.7% yield. The filtrate is crude R-propylene glycol, the filter cake is Co (Salen)/SBA-16-Bz, and the filter cake is washed by methanol until the filtrate is colorless for subsequent use. In the crude product of the R-propylene glycol, the content of the R-propylene glycol is 97.7 percent, the content of the S-propylene oxide is 0.5 percent, and the content of the high-boiling-point impurity is 2 percent. Transferring the R-propylene glycol crude product into a rectifying device, starting heating and stirring, vacuumizing to 15mm Hg, and rectifying at room temperature. During the rectification, the collection of R-propanediol was started when the temperature reached 120 ℃. 860.6g of R-propylene glycol were collected, the content of R-propylene glycol was 98.2%, the moisture content was 0.26% and the specific rotation was-16.9 °. The yield of R-propanediol was 97.3% based on R-propylene oxide.
EXAMPLE 7 catalytic Synthesis of R-propanediol with Supported catalyst Co (Salen)/SBA-16-Bz (ten times applied)
1350G of propylene oxide, 7.0g of p-nitrobenzoic acid and 675g of Co (Salen)/SBA-16-Bz (ten times applied) were weighed, stirring was started, and the ice water bath was cooled to 10 ℃. 200g of water was added dropwise thereto, and the reaction was continued at 10℃after 4 hours. Sampling, central control and detection are carried out to determine whether the reaction is completed, and the specific rotation of the S-epoxypropane is-12.0 ℃ at the end point of the reaction. The reaction was completed for 24.5 h.
And after the central control detection is qualified, distilling the feed liquid to remove the S-epoxypropane, distilling the feed liquid in a water bath for a distillation reaction, setting the water bath temperature to be 45 ℃, properly adjusting the water bath temperature to be 75 ℃ at most according to the distilling speed of the S-epoxypropane, determining that no S-epoxypropane flows out, stopping distilling, and collecting 591 gS-epoxypropane.
After distillation, the mixture was immediately filtered while hot (within half an hour), and the filter cake was Co (Salen)/SBA-16-Bz, washed with methanol until the filtrate was colorless, and dried at 70℃to give 671.2g in 99.4% yield. The filtrate is the crude product of the R-propylene glycol. In the crude product of the R-propylene glycol, the content of the R-propylene glycol is 96.3 percent, the content of the S-propylene oxide is 0.6 percent, and the content of the high-boiling-point impurity is 2 percent. Transferring the R-propylene glycol crude product into a rectifying device, starting heating and stirring, vacuumizing to 15mm Hg, and rectifying at room temperature. During the rectification, the collection of R-propanediol was started when the temperature reached 120 ℃. 835.0g of R-propylene glycol were collected, the content of R-propylene glycol was 98.1%, the moisture content was 0.26% and the specific rotation was-16.9 °. The yield of R-propanediol was 94.4% based on R-propylene oxide.
EXAMPLE 8 catalytic Synthesis of R-propanediol with different amounts of Supported catalyst Co (Salen)/SBA-16-Bz
1350G of propylene oxide, 7.0g of p-nitrobenzoic acid and 1350g of Co (Salen)/SBA-16-Bz are weighed, stirring is started, and the ice water bath is cooled to 10 ℃. 200g of water was added dropwise thereto, and the reaction was continued at 10℃after 4 hours. Sampling, central control and detection are carried out to determine whether the reaction is completed, and the specific rotation of the S-epoxypropane is-12.0 ℃ at the end point of the reaction. The reaction was completed for 5.5 h.
And after the central control detection is qualified, distilling the feed liquid to remove the S-epoxypropane, distilling the feed liquid in a water bath for a distillation reaction, setting the water bath temperature to be 45 ℃, properly adjusting the water bath temperature to be 75 ℃ at most according to the distilling speed of the S-epoxypropane, determining that no S-epoxypropane flows out, stopping distilling, and collecting 615g of S-epoxypropane.
After distillation, immediately filtering while the mixture is hot (within half an hour), wherein the filtrate is a crude product of R-propylene glycol, the filter cake is Co (Salen)/SBA-15-C8, washing the filter cake with methanol until the filtrate is colorless, and drying the filtrate at 70 ℃ to obtain 1346g with the yield of 99.7%. In the crude product of the R-propylene glycol, the content of the R-propylene glycol is 98 percent, the content of the S-propylene oxide is 0.49 percent, and the content of the high-boiling-point impurity is 1.9 percent. Transferring the R-propylene glycol crude product into a rectifying device, starting heating and stirring, vacuumizing to 15mm Hg, and rectifying at room temperature. And in the rectification process, collecting the R-propylene glycol when the temperature reaches 120 ℃. 863.3g of R-propanediol was collected, the R-propanediol content was 99.4%, the moisture content was 0.33% and the specific rotation was-16.96 °. The yield of R-propanediol was 97.6% based on R-propylene oxide.
Comparative example 2 Ring opening reaction of S-propylene oxide with hydrochloric acid
140G of water and 8.0g of hydrochloric acid (analytically pure) are added into a reaction bottle, the temperature of the ice-water bath is reduced to 12.5 ℃, 500g of S-propylene oxide is started to be added dropwise, the temperature of the dropwise is kept at 12.5 ℃ for 2 hours, and the dropwise addition is completed, and the reaction is kept for 4 hours. Crude S-propylene glycol feed liquid is obtained, the feed liquid is distilled under reduced pressure, the vacuum degree is 15mm Hg, a front fraction (water) is discharged at 43 ℃, when the temperature is raised to 120 ℃, the collection of a rear fraction S-propylene glycol fine product is started, 577.9g of S-propylene glycol is collected together, the yield is 88.2%, the purity is 95.65%, and the water content is 0.42%.
EXAMPLE 9 Ring opening reaction of S-epoxypropane with solid superacid SO 4 2-/ZrO2/SBA-15
140G of water and 8g of solid super acid SO 4 2-/ZrO2/SBA-15 (purchased from Baihua mall) are added into a reaction bottle, the temperature is reduced to 12.5 ℃ by an ice water bath, 500g of S-propylene oxide is started to be added dropwise, the dropwise temperature is kept at 12.5 ℃, the dropwise addition is completed within 2 hours, and the reaction is carried out for 4 hours under heat preservation. Filtering, wherein the filtrate is crude S-propylene glycol, the filter cake is solid super acid (the filter cake is washed by 100g of methanol for subsequent application), the filtrate is distilled under reduced pressure, the vacuum degree is 15mm Hg, the front fraction (water) is discharged at 43 ℃, when the temperature is raised to 120 ℃, the collection of the fine S-propylene glycol product is started, and 642.1g of S-propylene glycol product is collected, so that the yield is 98%, the purity is 99.86%, and the water content is 0.37%.
EXAMPLE 10 Ring opening reaction of S-epoxypropane with different amounts of solid superacid SO 4 2-/ZrO2/SBA-15
140G of water and 2.5g of solid super acid SO 4 2-/ZrO2/SBA-15 (purchased from Baihua mall) are added into a reaction bottle, the temperature is reduced to 12.5 ℃ by an ice water bath, 500g of S-propylene oxide is started to be added dropwise, the dropwise heating temperature is kept to be 12.5 ℃, the dropwise addition is completed for 2 hours, and the reaction is carried out for 12 hours under heat preservation. Filtering, wherein the filtrate is crude S-propylene glycol, the filter cake is solid super acid (the filter cake is washed by 100g of methanol for subsequent application), the filtrate is distilled under reduced pressure, the vacuum degree is 15mm Hg, the front fraction (water) is discharged at 43 ℃, when the temperature is raised to 120 ℃, the collection of the rear fraction S-propylene glycol refined product is started, 591g of S-propylene glycol is collected together, the yield is 90.2%, the purity is 99.3%, and the water content is 0.35%.
EXAMPLE 11 Ring opening reaction of S-epoxypropane with different amounts of solid superacid SO 4 2-/ZrO2/SBA-15
140G of water and 25.0g of solid super acid SO 4 2-/ZrO2/SBA-15 (purchased from Baihua mall) are added into a reaction bottle, the temperature is reduced to 12.5 ℃ by an ice water bath, 500g of S-propylene oxide is started to be added dropwise, the dropwise heating temperature is kept to be 12.5 ℃, the dropwise addition is completed within 2 hours, and the reaction is carried out for 4 hours under heat preservation. Filtering, wherein the filtrate is crude S-propylene glycol, the filter cake is solid super acid (the filter cake is washed by 100g of methanol for subsequent application), the filtrate is distilled under reduced pressure, the vacuum degree is 15mm Hg, the front fraction (water) is discharged at 43 ℃, when the temperature is raised to 120 ℃, the collection of the rear fraction S-propylene glycol refined product is started, and 642.8g of S-propylene glycol is collected together, so that the yield is 98.1%, the purity is 99.4%, and the moisture is 0.31%.
EXAMPLE 12 Ring opening reaction of S-epoxypropane with solid super acid perfluorosulfonic acid resin
140G of water and 8g of solid super acid perfluorinated sulfonic acid resin are added into a reaction bottle, the temperature is reduced to 12.5 ℃ by an ice water bath, 500g of S-propylene oxide is dripped, the dripping temperature is kept at 12.5 ℃, the dripping is completed within 2 hours, and the reaction is carried out for 4 hours. Filtering, wherein the filtrate is crude S-propylene glycol, the filter cake is solid super acid (the filter cake is washed by 100g of methanol for subsequent application), the filtrate is distilled under reduced pressure, the vacuum degree is 15mm Hg, the front fraction (water) is discharged at 43 ℃, when the temperature is raised to 120 ℃, the collection of the rear fraction S-propylene glycol refined product is started, and 641.4g of S-propylene glycol is collected together, so that the yield is 97.9%, the purity is 99.3%, and the water content is 0.38%.
EXAMPLE 13 Ring opening reaction of S-epoxypropane with different amounts of solid super acid perfluorosulfonic acid resin
140G of water and 25g of solid super acid perfluorinated sulfonic acid resin are added into a reaction bottle, the temperature is reduced to 12.5 ℃ by an ice water bath, 500g of S-propylene oxide is dripped, the dripping temperature is kept at 12.5 ℃, the dripping is completed within 2 hours, and the reaction is carried out for 4 hours. Filtering, wherein the filtrate is crude S-propylene glycol, the filter cake is solid super acid (the filter cake is washed by 100g of methanol for subsequent application), the filtrate is distilled under reduced pressure, the vacuum degree is 15mm Hg, the front fraction (water) is discharged at 43 ℃, when the temperature is raised to 120 ℃, the collection of the rear fraction S-propylene glycol refined product is started, and 642.3g of S-propylene glycol is collected together, so that the yield is 98%, the purity is 99.4%, and the moisture is 0.32%.
The data for the preparation of R-propanediol in examples 2-8 and comparative example 1 are shown in Table 1, and the data for the preparation of S-propanediol in examples 9-13 and comparative example 2 are shown in Table 2.
As can be seen from Table 1, the R-propylene glycol prepared in examples 2 to 8 and comparative example 1 of the present invention, which was prepared by using Co (Salen)/SBA-15-C8 and Co (Salen)/SBA-16-Bz as the supported catalyst, had a higher yield and content than that of Co (Salen) which was not supported on the basis of realizing the recycling of the catalyst, and the obtained R-propylene glycol had a higher content and yield even after ten applications; example 5 the amount of supported catalyst added was doubled over that of example 2, and the content and yield were not significantly increased as compared with example 2, so that example 2 was the optimal reaction condition.
As can be seen from Table 2, in examples 9 to 13 and comparative example 2 of the present invention, the yield and content of S-propanediol prepared from solid superacid were higher than those prepared from hydrochloric acid; wherein example 9 is the optimal process conditions.
The two tables can show that the method for preparing the R-propylene glycol and the S-propylene glycol has the advantages that the supported S-catalyst can be recycled for more than ten times, the catalyst loss is small, and the production stability is ensured; the solid superacid is adopted for ring opening, the ring opening efficiency is high, the yield of the obtained target product is high, the purity of the obtained product is high, and the process is safe and environment-friendly.
It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
Claims (3)
1. A method for preparing propylene glycol by using propylene oxide, which is characterized by comprising the following steps:
a. Adding propylene oxide, a supported S-catalyst and p-nitrobenzoic acid into a reaction device at the temperature of 0-20 ℃, dripping water into the mixed solution, after finishing dripping for 2-8 hours, detecting a reaction end point after the reaction is carried out for 2-16 hours under the condition that the specific optical rotation of the S-propylene oxide is-10.0 DEG to-13.7 DEG, and stopping the reaction to obtain the mixed solution of the R-propylene glycol and the S-propylene oxide; wherein the weight ratio of the propylene oxide to the water to the p-nitrobenzoic acid to the supported S-catalyst is 1 (0.1-0.2) (0.001-0.01) (0.01-1.0); the supported S-catalyst is a supported catalyst Co (Salen)/SBA-15-C8; the preparation method of the supported catalyst Co (Salen)/SBA-15-C8 comprises the following steps: after 1.0g of SBA-15 was stirred and evacuated at 25℃for 6 hours, it was added to 6ml of methylene chloride containing 0.12g of Co (II) (Salen), and the mixture was heated and refluxed for 24 hours under the protection of argon gas under stirring, and the methylene chloride was distilled off; the obtained solid is added into a solution containing 0.9ml of toluene, 1.25ml of anhydrous trimethoxysilane and 5mmol of octyl trimethoxysilane, and the mixture is heated and refluxed for 24 hours under the protection of argon, and filtered to obtain the solid, and the solid is washed by toluene, dichloromethane and tetrahydrofuran in sequence; namely, the supported catalyst Co (Salen)/SBA-15-C8 is prepared;
b. C, carrying out sectional distillation on the feed liquid obtained in the step a to obtain R-propylene glycol and S-propylene oxide; the front-stage distillation adopts normal pressure distillation, water bath distillation is adopted, the water bath temperature is set to 45 ℃, and the water bath temperature is adjusted to 75 ℃ at most according to the propylene oxide distillation speed, so as to obtain S-propylene oxide; filtering the residual feed liquid while the residual feed liquid is hot, and obtaining filtrate, namely a crude product of the R-propylene glycol; the crude product of the R-propylene glycol is distilled under reduced pressure, the vacuum degree is 15mm Hg, and the temperature is 120 ℃ to obtain the R-propylene glycol;
c. Adding water and solid superacid into a reaction device, dropwise adding the S-epoxypropane obtained in the step b into the feed liquid, keeping the dropwise adding temperature at 0-25 ℃, and carrying out heat preservation reaction for 1-6 h to obtain the feed liquid containing the S-propylene glycol; wherein, the weight ratio of S-propylene oxide, water and solid super acid is 1: (1.0-1.5) 0.005-0.05); the solid super acid is SO 4 2-/ZrO2/SBA-15;
d. Filtering the material liquid obtained in the step c, and washing the obtained filter cake, namely solid super acid, with methanol for recycling; the obtained filtrate is the crude product of the S-propylene glycol, the crude product of the S-propylene glycol is distilled under reduced pressure, the vacuum degree is 15mm Hg, and the temperature is 120 ℃, thus obtaining the S-propylene glycol.
2. The method for producing propylene glycol using propylene oxide as defined in claim 1, wherein: the water drop reaction temperature in the step a is 10 ℃, the water drop time is 4 hours, the heat preservation reaction time is 10 hours, and the reaction is stopped when the specific rotation of S-epoxypropane is-12 ℃; the weight ratio of propylene oxide to water, p-nitrobenzoic acid and supported S-catalyst was 1:0.15:0.005:0.5.
3. The method for producing propylene glycol using propylene oxide as defined in claim 1, wherein: c, maintaining the dropwise adding temperature at 12.5 ℃, finishing dropwise adding, and carrying out heat preservation reaction for 4 hours; the weight ratio of the S-propylene oxide to the water to the solid super acid is 1:0.28:0.016.
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