Looking for breakthrough ideas for innovation challenges? Try Patsnap Eureka!

Conversion of multihydroxylated-aliphatic hydrocarbon or ester thereof to chlorohydrin

A polyhydroxylation and aliphatic hydrocarbon technology, applied in the direction of organic chemistry, etc., can solve the problems of economical production of inconsistent by-products, hindered reaction rate, low conversion rate, etc., and achieve the effects of improved conversion rate, large conversion rate, and simplified method.

Inactive Publication Date: 2010-02-24
兰科知识产权有限责任公司
View PDF7 Cites 0 Cited by
  • 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
[0019] 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

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • Conversion of multihydroxylated-aliphatic hydrocarbon or ester thereof to chlorohydrin
  • Conversion of multihydroxylated-aliphatic hydrocarbon or ester thereof to chlorohydrin
  • Conversion of multihydroxylated-aliphatic hydrocarbon or ester thereof to chlorohydrin

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0114] Example 1 - Preparation of chlorohydrins from glycerol

[0115] 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

[0116] Example 2 - Preparation of Chlorohydrins from Glycerol / Glyceride Mixtures

[0117] 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

[0118] Example 3 - Preparation of chlorohydrins from crude glycerin

[0119] 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.

[0120] 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.

[0121] After filtration to remove white solids, sodium a...

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

No PUM Login to View More

Abstract

The invention relates to a conversion of multihydroxylated-aliphatic hydrocarbon or ester thereof to chlorohydrin, particularly to a composition containing dichlorohydrin and preparation method thereof. The composition contains about 0.1 mol% to 1 mol% of glycerol and ester thereof, about 4 mol% to 10 mol% of chlorohydrins and ester thereof, about 80 mol% of 1,3-dichlorohydrin and ester thereof, about 1 mol% to 4 mol% of 2,3-dichlorohydrin and ester thereof, and less than 0.3 mol% of chloridized glycerin ether and ester thereof, wherein the ratio of 1,3-dichlorohydrin to 2,3-dichlorohydrin ismore than 8:1. The method comprises the step of contacting multihydroxylated-aliphatic hydrocarbon, ester of multihydroxylated-aliphatic hydrocarbon or the mixture thereof with catalyzer and chlorinehydride source, pressure of which is higher than, equal to or lower than atmospheric pressure.

Description

[0001] This application is a divisional application of a Chinese patent application with the application number 200580022101.8, the application date being July 18, 2005, and the invention title being 'Conversion of polyhydroxylated aliphatic hydrocarbons or their esters to chlorohydrins'. technical field [0002] 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. Background technique [0003] 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. [0004] A known method of making epichlorohydrin involves the hypochlorinati...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
Patent Type & Authority Applications(China)
IPC IPC(8): C07D301/26C07D303/08
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 兰科知识产权有限责任公司
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Patsnap Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Patsnap Eureka Blog
Learn More
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic, Popular Technical Reports.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap|About US| Contact US: help@patsnap.com