A kind of preparation method of 3-methoxy-3-methylbutanol

Abstract

The invention provides a method for preparing 3-methoxy-3-methylbutanol. Under the action of an acidic catalyst, isoprene, water and methanol undergo addition reaction, and 3-methoxy-3-methylbutanol is generated through a one-step reaction in a reactor. The reaction has the characteristics of low raw material cost, mild reaction conditions, high selectivity and high conversion rate.

Description

Technical Field

[0001] The invention relates to a method for synthesizing 3-methoxy-3-methylbutanol, a fine chemical product, and belongs to the technical field of organic chemical synthesis. Background Art

[0002] 3-Methoxy-3-methylbutanol has the advantages of safety, environmental protection, good solubility and compatibility. It can be used as a substitute for alcohol ethers such as ethylene glycol butyl ether (BCS) and dipropylene glycol butyl ether (DPM). It is widely used in many fields such as fragrances, cleaning agents, civilian detergents, emulsions and resin synthesis, printing chemicals, etc.

[0003] The known preparation method of 3-methoxy-3-methylbutanol, the patent document is as follows:

[0004] Patent CN102206142A, under the action of a heterogeneous acidic catalyst, 3-methyl-3-butene-1-ol reacts with methanol to obtain 3-methoxy-3-methylbutanol. The reaction adopts a kettle batch reaction, which has the disadvantages of high reaction temperature, high reaction pressure and long reaction time.

[0005] Patent CN104203890A, under the action of an acidic catalyst, 3-methyl-3-butene-1-ol reacts with methanol to prepare 3-methoxy-3-methylbutanol. During the reaction, the water content of the reaction liquid is controlled to improve the selectivity of 3-methyl-3-butene-1-ol. A dehydration step is added to the reaction process, which increases the complexity of the reaction operation.

[0006] Patent JP8176053, in the presence of a strong acid resin catalyst, 4,4-dimethyl-1,3-dioxane reacts with methanol to prepare 3-methoxy-3-methylbutanol. The selectivity of 3-methoxy-3-methylbutanol is only 40%, there are many side reactions, the economy is poor, and it is not suitable for industrial scale-up.

[0007] From the above analysis of the prior art, it can be seen that the current technology for synthesizing 3-methoxy-3-methylbutanol has the disadvantages of low selectivity, complicated process and high process requirements, and the preparation process of the raw material 3-methyl-3-butene-1-ol is complicated and costly, and the economic benefit of preparing 3-methoxy-3-methylbutanol is poor. Summary of the invention

[0008] The object of the present invention is to provide a method for preparing 3-methoxy-3-methylbutanol from isoprene by a one-step method, wherein the method has the characteristics of low raw material cost, mild reaction conditions, high selectivity and high conversion rate.

[0009] In order to achieve the purpose of the present invention, the following technical scheme is adopted:

[0010] A method for preparing 3-methoxy-3-methylbutanol comprises the following steps: loading a catalyst into a reactor, uniformly mixing raw materials of isoprene, methanol and water according to a proportion, and passing the raw material mixed solution into the reactor for reaction to prepare 3-methoxy-3-methylbutanol.

[0011] In the method of the present invention, the catalyst comprises at least one of an acidic resin, a zeolite molecular sieve and a solid superacid.

[0012] The acidic resin of the present invention includes one or more of a benzene alcohol type strong acid resin, a polysulfonic acid type strong acid resin, and a sulfonic acid type polystyrene resin, specifically including but not limited to D006, DA4340, D005, D001, D002, D-61, DT-012, DT-015, D009, DT-017, DZH, DA330, AMBERLITE TM 200C strong acid cation exchange resin, LANXESS S108, HPR1300H strong acid resin, etc.

[0013] The solid superacid of the present invention comprises SO4 2- / MxOy, specifically including but not limited to SO4 2- / ZrO2、SO4 2- / FeO3、SO4 2- / Al2O3、SO4 2- / TiO2、SO4 2- / Fe3O4、SO4 2- / WO3、SO4 2- / MoO3、SO4 2- / BO3, etc.

[0014] The zeolite molecular sieve described in the present invention includes but is not limited to natural zeolite and synthetic zeolite, specifically including but not limited to H-β type, HY type, ZSM-5 type, HX type, L type, mordenite, montmorillonite, SAPO-3, SAPO-11 and the like.

[0015] In the method of the present invention, the molar ratio of isoprene to methanol and water is 1:(2-20):(2-15), and the preferred molar ratio is 1:(5-15):(4-12).

[0016] In the method of the present invention, the reaction temperature is 30-120°C, the reaction pressure is normal pressure-0.5MPa, preferably the reaction temperature is 40-80°C, the reaction pressure is normal pressure-0.2MPa;

[0017] In the method described in the present invention, the reaction space velocity is 0.2 to 3h -1 , preferably 0.5 to 2 hours -1 ;

[0018] In the method of the present invention, the reaction liquid is purified to obtain high-purity 3-methoxy-3-methylbutanol.

[0019] The technical advantage provided by the present invention is that the raw material isoprene is synthesized by a one-step reaction under the action of an acidic catalyst, wherein olefins are easily subjected to Markovnikov rule electrophilic addition reaction on an acidic catalyst, electrophilic reagents attack the carbon on the double bond, and electrophilic addition reaction is carried out, and some olefins can form a diol intermediate, and an etherification reaction occurs with alcohol under the action of an acidic catalyst, and 3-methoxy-3-methylbutanol is further generated. The synthetic route has a wide range of raw material sources, low cost, and high economic benefits, and adopts a fixed bed one-step reaction method with the advantages of mild reaction conditions, easy operation, and simple process, and the reaction process produces less three wastes and is suitable for the concept of green chemical development. DETAILED DESCRIPTION

[0020] In order to better understand the technical solution of the present invention, the content of the present invention is further described below in conjunction with embodiments, but the content of the present invention is not limited thereto.

[0021] Gas chromatography analysis: Chromatographic instrument: Agilent 7890A, chromatographic column model: DP-5, inner diameter: 320.00 μm, length: 25.0 m, maximum temperature: 325.0°C. Carrier gas: high-purity nitrogen, split ratio: 1:60, detector temperature 280°C, heating program, first 40°C for 4 minutes, then heating to 280°C at 15°C / min for 5 minutes, total running time 25 minutes.

[0022] Example 1

[0023] 100 g of acidic resin D006 was weighed and loaded into a jacketed tubular reactor. Hot oil at 60 °C was introduced into the jacket of the tubular reactor. 500 g of isoprene, 1176.4 g of methanol and 529.4 g of water were mixed evenly and fed from the lower end of the fixed bed. The reaction pressure was normal pressure and the reaction space velocity was 1 h -1 , the product was distilled and separated to obtain pure 3-methoxy-3-methylbutanol. The reaction analysis results are listed in Table 1.

[0024] Example 2

[0025] 120g of catalyst H-ZSM-5 was weighed and loaded into a jacketed tubular reactor. Hot oil at 70°C was introduced into the jacket of the tubular reactor. 450g of isoprene, 2117.6g of methanol and 1191.1g of water were mixed evenly and fed from the lower end of the fixed bed. The reaction pressure was 0.1MPa and the reaction space velocity was 1.8h -1 The product was distilled and separated to obtain pure 3-methoxy-3-methylbutanol. The reaction analysis results are listed in Table 1.

[0026] Example 3

[0027] 100g of catalyst DA4340 was weighed and filled into a jacketed tubular reactor. Hot oil at 40°C was introduced into the jacket of the tubular reactor. 500g of isoprene, 3529.4g of methanol and 1588.2g of water were mixed evenly and fed from the lower end of the fixed bed. The reaction pressure was normal pressure and the reaction space velocity was 0.5h -1 The product was distilled and separated to obtain pure 3-methoxy-3-methylbutanol. The reaction analysis results are listed in Table 1.

[0028] Example 4

[0029] 100g of catalyst DA330 was weighed and loaded into a jacketed tubular reactor. Hot oil at 80°C was introduced into the jacket of the tubular reactor. 500g of isoprene, 4235.2g of methanol and 1985.3g of water were mixed evenly and fed from the lower end of the fixed bed. The reaction pressure was 0.15MPa and the reaction space velocity was 2.5h -1 The product was distilled and separated to obtain pure 3-methoxy-3-methylbutanol. The reaction analysis results are listed in Table 1.

[0030] Example 5

[0031] 150 g of catalyst H-β zeolite molecular sieve (Si / Al=20) was weighed and loaded into a jacketed tubular reactor. Hot oil at 120°C was introduced into the jacket of the tubular reactor. 500 g of isoprene, 3764.7 g of methanol and 1720.6 g of water were mixed evenly and fed from the lower end of the fixed bed. The reaction pressure was 0.5 MPa and the reaction space velocity was 2 h -1 The product was distilled and separated to obtain pure 3-methoxy-3-methylbutanol. The reaction analysis results are listed in Table 1.

[0032] Example 6

[0033] 150g of catalyst SAPO-11 was weighed and loaded into a jacketed tubular reactor. Hot oil at 110°C was introduced into the jacket of the tubular reactor. 650g of isoprene, 2447.1g of methanol and 1720.5g of water were mixed evenly and fed from the lower end of the fixed bed. The reaction pressure was 0.45MPa and the reaction space velocity was 1.5h -1 The product was distilled and separated to obtain pure 3-methoxy-3-methylbutanol. The reaction analysis results are listed in Table 1.

[0034] Example 7

[0035] 130g of catalyst HY molecular sieve was weighed and loaded into a jacketed tubular reactor. Hot oil at 105°C was introduced into the jacket of the tubular reactor. 600g of isoprene, 3388.2g of methanol and 1270.58g of water were mixed evenly and fed from the lower end of the fixed bed. The reaction pressure was 0.35MPa and the reaction space velocity was 1h -1 The product was distilled and separated to obtain pure 3-methoxy-3-methylbutanol. The reaction analysis results are listed in Table 1.

[0036] Example 8

[0037] 160g of catalyst mordenite molecular sieve was weighed and loaded into a jacketed tubular reactor. Hot oil at 115°C was introduced into the jacket of the tubular reactor. 480g of isoprene, 2258.8g of methanol and 1778.8g of water were mixed evenly and fed from the lower end of the fixed bed. The reaction pressure was 0.4MPa and the reaction space velocity was 0.8h -1 The product was distilled and separated to obtain pure 3-methoxy-3-methylbutanol. The reaction analysis results are listed in Table 1.

[0038] Example 9

[0039] Weigh 200g of catalyst SO4 2- / ZrO2 was loaded into a jacketed tubular reactor, hot oil at 90°C was introduced into the jacket of the tubular reactor, 750g of isoprene, 1411.8g of methanol and 992.6g of water were mixed evenly, and the mixture was fed from the lower end of the fixed bed. The reaction pressure was 0.25MPa and the reaction space velocity was 2.2h -1 The product was distilled and separated to obtain pure 3-methoxy-3-methylbutanol. The reaction analysis results are listed in Table 1.

[0040] Example 10

[0041] Weigh 130g of catalyst SO4 2- / Al2O3 was loaded in a jacketed tubular reactor, hot oil at 95°C was introduced into the jacket of the tubular reactor, 500g of isoprene, 4235.2g of methanol and 1985.3g of water were mixed evenly, and the mixture was fed from the lower end of the fixed bed. The reaction pressure was 0.25MPa and the reaction space velocity was 1.6h -1 The product was distilled and separated to obtain pure 3-methoxy-3-methylbutanol. The reaction analysis results are listed in Table 1.

[0042] Embodiment 11

[0043] Weigh 150g of catalyst SO4 2- / Fe3O4 was loaded into a jacketed tubular reactor, and hot oil at 85°C was introduced into the jacket of the tubular reactor. 680g of isoprene, 2880g of methanol and 2160g of water were mixed evenly and fed from the lower end of the fixed bed. The reaction pressure was 0.15MPa and the reaction space velocity was 1.2h -1 The product was distilled and separated to obtain pure 3-methoxy-3-methylbutanol. The reaction analysis results are listed in Table 1.

[0044] Example 12

[0045] Weigh 135g of catalyst SO4 2- / MoO3 was loaded into a jacketed tubular reactor, and hot oil at 100°C was introduced into the jacket of the tubular reactor. 560g of isoprene, 2898.8g of methanol and 1482.3g of water were mixed evenly and fed from the lower end of the fixed bed. The reaction pressure was 0.3MPa and the reaction space velocity was 0.9h -1 The product was distilled and separated to obtain pure 3-methoxy-3-methylbutanol. The reaction analysis results are listed in Table 1.

[0046] Comparative Example 1

[0047] 135g of catalyst DA330 was weighed and loaded into a jacketed tubular reactor. Hot oil at 80°C was introduced into the jacket of the tubular reactor. 510g of 4,4-dimethyl-1,3-dioxane (DMD) and 1406.9g of methanol were mixed evenly and fed from the lower end of the fixed bed. The reaction pressure was normal pressure and the reaction space velocity was 0.9h -1 The product was distilled and separated to obtain pure 3-methoxy-3-methylbutanol. The reaction analysis results are listed in Table 2.

[0048] Comparative Example 2

[0049] 150g of catalyst H-ZSM-5 was weighed and loaded into a jacketed tubular reactor. Hot oil at 70°C was introduced into the jacket of the tubular reactor. 560g of 4,4-dimethyl-1,3-dioxane (DMD) and 772g of methanol were mixed evenly and fed from the lower end of the fixed bed. The reaction pressure was normal pressure and the reaction space velocity was 1.8h -1 The product was distilled and separated to obtain pure 3-methoxy-3-methylbutanol. The reaction analysis results are listed in Table 2.

[0050] Table 1 Example results

[0051]

[0052] Table 2 Comparative Example Results

[0053]

Claims

1. A method for preparing 3-methoxy-3-methylbutanol, comprising the following steps: loading an acidic catalyst into a reactor, uniformly mixing raw materials of isoprene, methanol and water according to a proportion, and passing the raw material mixture into the reactor for reaction to prepare 3-methoxy-3-methylbutanol.

2. The method according to claim 1, characterized in that The catalyst comprises at least one of an acidic resin, a zeolite molecular sieve and a solid superacid.

3. The method according to claim 2, characterized in that The acidic resin includes one or more of a benzol type strong acid resin, a polysulfonic acid type strong acid resin, and a sulfonic acid type polystyrene resin.

4. The method according to claim 2, characterized in that: The acidic resins include D006, DA4340, D005, D001, D002, D-61, DT-012, DT-015, D009, DT-017, DZH, DA330, AMBERLITE TM One or more of 200C strong acid cation exchange resin, LANXESS S108, and HPR1300H strong acid resin.

5. The method according to claim 2, characterized in that: The solid superacid includes SO4 2- / ZrO2、SO4 2- / FeO3、SO4 2- / Al2O3、SO4 2- / TiO2、SO4 2- / Fe3O4、SO4 2- / WO3、SO4 2- / MoO3、SO4 2- / BO3 or more.

6. The method according to claim 2, characterized in that The zeolite molecular sieve includes natural zeolite and / or synthetic zeolite.

7. The method according to claim 2, characterized in that The zeolite molecular sieve includes one or more of H-β type, HY type, ZSM-5 type, HX type, L type, mordenite, montmorillonite, SAPO-3, and SAPO-11.

8. The method according to claim 1, characterized in that The molar ratio of isoprene to methanol and water is 1:(2-20):(2-15).

9. The method according to claim 1, characterized in that: The molar ratio of isoprene to methanol and water is 1:(5-15):(4-12).

10. The method according to claim 1, characterized in that The reaction temperature is 30-120°C, and the reaction pressure is normal pressure-0.5MPa.

11. The method according to claim 1, characterized in that: The reaction temperature is 40-80°C, and the reaction pressure is normal pressure-0.2MPa.

12. The method according to claim 1, characterized in that Reaction space velocity is 0.2~3h -1 .

13. The method according to claim 1, characterized in that Reaction space velocity is 0.5~2h -1 .

Images