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Conversion of a multihydroxylated-aliphatic hydrocarbon or ester thereof to a chlorohydrin

A technology of polyhydroxylation and aliphatic hydrocarbons, applied in the direction of organic chemistry, the introduction of halogen preparation, etc., can solve the problems of inconsistent by-products in economic production, hindered reaction rate, low conversion rate, etc., and achieve improved conversion rate, large conversion rate, The effect of method simplification

Inactive Publication Date: 2007-06-06
DOW GLOBAL TECH LLC
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Furthermore, these reagents can cause complete chlorination of polyhydroxylated aliphatic hydrocarbons, leading to unwanted RCl by-products, as taught in Viswanathan, et al. Current Science, 1978, 21, 802-803
[0018] In summary, there are at least five major disadvantages for all the above known schemes for the preparation of chlorohydrins from glycerol or any other vicinal-diol, triol or polyhydroxylated aliphatic hydrocarbon: (1) Hydrochlorination of glycerol or any diol The atmospheric pressure process requires a large excess of HCl, usually 7-10 times molar excess
(2) A variant of the above known process is a very slow, batch type reaction which requires 24-48 hours at a temperature in excess of 100°C and no more than 80-90% conversion to the desired chlorohydrins product
(3) Exotic hydrochlorination reagents can drive the reaction by scavenging, but often produce by-products inconsistent with commercial economic production
(5) When the reaction is run at high pressure to control the evaporation of the reactor contents, the low partial pressure of HCl leads to low conversion or hindered reaction rate
All prior art infers that there is an equilibrium limit to this transformation due to the presence of water in the reaction mixture

Method used

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  • Conversion of a multihydroxylated-aliphatic hydrocarbon or ester thereof to a chlorohydrin
  • Conversion of a multihydroxylated-aliphatic hydrocarbon or ester thereof to a chlorohydrin
  • Conversion of a multihydroxylated-aliphatic hydrocarbon or ester thereof to a chlorohydrin

Examples

Experimental program
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Effect test

Embodiment 1

[0109] Example 1 - Preparation of chlorohydrins from glycerol

[0110] to a 100 mL Hastelloy C equipped with a magnetically driven stirrer, internal cooling coil, and thermocouple TM Glycerin (30.0 g, purchased from Sigma-Aldrich Chemical Corporation) and glacial acetic acid (4.5 g, purchased from JT Baker Corporation) were added to the Parr reactor. The reactor was sealed, pressurized to 90 psig with anhydrous hydrogen chloride gas (Airgas Corporation), and heated to 93° C. for 90 minutes and maintained at 90 psig with anhydrous hydrogen chloride gas, after which the reactor was cooled and brought to room temperature (about 25° C. ) to exhaust. The reactor contents (65.9 g) were collected, analyzed by gas chromatography (GC) and found to contain the following products: 1,3-dichloropropan-2-ol and its acetate (92.6 mol% total) and 2,3 - Dichloropropan-1-ol and its acetate (total 1.7 mol%). In addition, many monochlorinated compounds (4.4 mol% in total) and unreacted glycer...

Embodiment 2

[0111] Example 2 - Preparation of Chlorohydrins from Glycerol / Glyceride Mixtures

[0112] To 200mL Hastelloy C TM A 10 mL glass measuring flask containing dry glycerol (Aldrich, pre-dried through molecular sieves, 91 mg, 0.99 mmol) and glycerol triacetate (Aldrich, triacetate of glycerol, 457 mg, 2.10 mmole) was added to the autoclave . The reactor was sealed and pressurized to 40 psig with nitrogen (three pressure cycles) and brought to 110°C with stirring after nitrogen venting. Anhydrous HCl was introduced under a constant pressure of 76 psig and the reaction was allowed to proceed for 3 hours. The reactor was vented to provide a product which was found to comprise 25.90 area % 1,3-dichloropropan-2-ol, 68.34 area % 1,3-dichloro-2-acetoxypropane, 1.57 area % 1,2-dichloro-3-acetoxypropane, 2.86 area % of 2-chloropropane-1,3-diacetoxypropane and no detectable glycerol, triacetin or 1,2 , 3-trichloropropane, as determined analytically by GC flame ionization detection.

Embodiment 3

[0113] Example 3 - Preparation of chlorohydrins from crude glycerin

[0114] To a 100 mL Hastelloy equipped with a magnetically driven stirrer, internal cooling coil, and thermocouple TM Crude glycerin (30.0 g, purchased from Interwest Corporation) and glacial acetic acid (0.6 g, purchased from JT Baker Corporation) were added to the C Parr reactor. The reactor was sealed, pressurized to 120 psig with anhydrous hydrogen chloride gas (Airgas Corporation), and heated to 120° C. for 90 minutes while maintaining the pressure at 120 psig with anhydrous hydrogen chloride gas. After this time, the reactor was cooled and vented at room temperature. The reactor contents (57.2 g) were collected as a moving liquid containing suspended white solids.

[0115] The above procedure was repeated and 58.0 g of reactor contents were collected from the second reaction. The two reaction products (57.2 g and 58.0 g) were then combined.

[0116] After filtration to remove white solids, sodium a...

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Abstract

The present invention relates to a process for converting a multihydroxylated-aliphatic hydrocarbon or ester thereof to a chlorohydrin, by contacting the multihydroxylated-aliphatic hydrocarbon or ester thereof starting material with a source of a superatmospheric partial pressure of hydrogen chloride for a sufficient time and at a sufficient temperature, and wherein such contracting step is carried out without substantial removal of water, to produce the desired chlorohydrin product; wherein the desired product or products can be made in high yield without substantial formation of undesired overchlorinated byproducts. In addition, certain catalysts of the present invention may be used in the present process at superatmospheric, atmospheric and subatmospheric pressure conditions with improved results.

Description

Background of the invention [0001] The present invention relates to a process for the conversion of polyhydroxylated aliphatic hydrocarbons or esters thereof to chlorohydrins. Chlorohydrins can be used to prepare epoxides such as epichlorohydrin. [0002] Epichlorohydrin is a widely used precursor of epoxy resins. Epichlorohydrin is a monomer commonly used for the alkylation of bisphenol A; the resulting diepoxide, either as a free monomer or as an oligomeric diepoxide, can progress to high molecular weight resins such as Used in electrical laminates, can coatings, automotive topcoats and clear coats. [0003] A known method of making epichlorohydrin involves the hypochlorination of allyl chloride to form dichlorohydrins. The dichlorohydrin mixture provides epichlorohydrin from caustic ring closure, which is distilled to high purity (>99.6%). This chlorohydrin process requires two equivalents of chlorine and one equivalent of caustic per mole of epichlorohydrin. [000...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C29/62C07D303/08
Inventor D·J·施雷克W·J·小克吕佩尔R·D·瓦尔言M·E·琼斯R·M·坎贝尔K·卡恩斯B·D·胡克J·R·布里格斯J·G·希普勒
Owner DOW GLOBAL TECH LLC
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