JPH03265627A - Production of modified polyether compound - Google Patents

Abstract

PURPOSE:To obtain the title compound useful as the raw material of waterproofing agents, sealants, elastomers, adhesives, etc., by using a process for producing a polyether compound by polymerizing an alkylene oxide through ring opening in the presence of an initiator, wherein a specified initiator and a specified polymerization catalyst are used. CONSTITUTION:A process for producing a polyether compound by polymerizing an alkylene oxide (e.g. propglene oxide) through ring opening in the presence of an initiator, wherein said initiator comprises an active hydrogen-containing hydrocarbon compound and/or a halohydrocarbon compound (e.g. polybutadiene polyol), and the polymerization catalyst comprises a compound metal cyanide complex (e.g. cobalt zinc cyanide/glyme complex).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a modified polyether compound.

[Prior Art] Polyether compounds produced by ring-opening polymerization of alkylene oxide such as propylene oxide or ethylene oxide with a suitable initiator are the so-called polyol components used in the polyurethane industry, surfactants, and their raw materials. It is industrially useful, including the following. Many attempts have been made to improve the performance and functionality of such polyether compounds, but as one of the modified polyether compounds, highly hydrophobic active hydrogen-containing hydrocarbons have been developed. It is conceivable to produce polyether polyols by polymerizing alkylene oxides using the compounds as initiators. Conventionally, alkylene oxybo polymerization has been carried out using an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide as a catalyst, but when a highly hydrophobic initiator is used as a catalyst, The ring-opening addition reaction of alkylene oxide to the active hydrogen-containing group of the initiator becomes extremely disadvantageous, and the alkali metal hydroxide itself acts as an initiator, making it difficult to obtain the desired polyether polyol, which is highly hydrophobic. Polyoxyalkylene glycol that is not bonded to the initiator is produced as a by-product. Therefore, when using a highly hydrophobic active hydrogen-containing polyolefin compound as an initiator, it is necessary to use an alkali metal such as sodium metal or sodium hydride. The active hydrogen-containing groups must be kept as alkali metal salts using alkali metal hydrides. However, in this case, there are disadvantages in that the raw materials are difficult to handle and, particularly, when the initiator is a compound containing an unsaturated group, it is likely to be colored.

[Problems to be Solved by the Invention] The present invention solves the problem of a highly hydrophobic initiator that could not be successfully produced when an alkali metal hydroxide, which is conventionally used as a ring-opening polymerization catalyst for alkylene oxide, was used as a catalyst. The present invention provides a method for practically producing a polyether compound by ring-opening polymerization of an alkylene oxide to a certain active hydrogen-containing hydrocarbon compound.

[Means for Solving the Problems] The present invention provides a method for producing a polyether compound by ring-opening polymerization of alkylene oxide in the presence of an initiator, in which an active hydrogen-containing hydrocarbon compound and/or a halogenated This invention relates to a method using a hydrocarbon compound and a double metal cyanide complex as a polymerization catalyst.

A method using a double metal cyanide complex as a ring-opening polymerization catalyst for alkylene oxide is disclosed in US Pat. No. 3,278,455.
7, No. 3278458, No. 3278459, etc. Specifically, the double metal cyanide complex is a complex containing two or more metals, such as cobalt zinc cyanide-glyme, and having cyanide ions as some or all of the ligands, and alkylene A substance that has the ability to catalyze the ring-opening polymerization reaction of oxides.

In the present invention, alkylene oxide is added to a mixture of an active hydrogen-containing hydrocarbon compound and/or a halogen-containing hydrocarbon compound as an initiator and a double metal cyanide complex under arbitrary reaction temperature conditions to carry out the reaction. Polyether compounds can be produced using At this time, the reaction can be carried out in the presence of a solvent if necessary.

Examples of solvents that can be used include hydrocarbon solvents, halogenated hydrocarbon solvents, and ether solvents. Specific examples of hydrocarbon solvents include hexane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, etc., and examples of halogenated hydrocarbon solvents include methylene chloride, chloroform, carbon tetrachloride, trichloroethane, and tetrachloroethane. .

Examples include chlorobenzene and dichlorobenzene, and examples of ether solvents include diethyl ether, tetrahydrofuran, dioxane, glyme, and dibrame. These may be used alone or in any combination as required.

The initiator used in the present invention is an active hydrogen-containing hydrocarbon compound and/or a halogen-containing hydrocarbon compound, and a monool or polyol having 8 or more carbon atoms is used as the active hydrogen-containing compound. Specifically, higher alcohols and branched higher alcohols such as lauryl alcohol, oleyl alcohol, and synthetic alcohols, liquid polybutadiene containing hydroxyl or carboxyl groups, liquid polychloroprene, liquid polyisoprene, and liquid SBR.
, liquid rubber such as liquid NBR, polyhydroxypolyolefin, hydrogenated liquid rubber, and the like. Examples of alkylene oxides that can be used include ethylene oxide, propylene oxide, butylene oxide, hexene oxide, cyclohexene oxide, styrene oxide, and alkyl or allyl or aryl glycidyl ethers, specifically methyl glycidyl ether, ethyl glycidyl ether, and isobrobyl glycidyl. Examples include ether, butyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, and cresyl glycidyl ether.

[Function] In the present invention, the double metal cyanide complex used as a polymerization catalyst for alkylene oxide easily coordinates with a polar active hydrogen-containing group, so it cannot be used conventionally even if the entire initiator is hydrophobic. Unlike alkali metal hydroxide catalysts, it is believed that the ring-opening addition reaction of alkylene oxide to active hydrogen-containing groups occurs easily. Therefore, even if a highly hydrophobic initiator is used, it is considered that polyether compounds can be produced by ring-opening polymerization of alkylene oxides if a double metal cyanide complex catalyst is used.

[Example] Example 1 A mixture of 500 g of polybutadiene polyol, 100 g of tetrahydrofuran, and 0.15 g of cobalt zinc cyanide/glyme complex was placed in a pressure-resistant container, and propylene oxide was gradually added to the mixture at 100°C under nitrogen atmosphere while stirring. was added to the reaction.

After adding 1100g of propylene oxide,
Heat at 100° C. for an additional hour. After cooling to 60°C, the solvent was distilled off under reduced pressure to obtain a polyether compound. The obtained polyether compound has a water trivalent value of 14.2
Although it was a pale yellow emulsion liquid with a weight of 0'/g, no separation occurred even after it was left at room temperature for 3 months.

Example 2 500g of “Polybutadiene Polyol” and 10g of toluene
0g and cobalt zinc cyanide/glyme complex” 0.2
9 g of the mixture was placed in a pressure-resistant reaction vessel and heated for 1 hour under a nitrogen atmosphere.
Propylene oxide was gradually added and reacted at 00°C with stirring. After adding 1400 g of propylene oxide, the mixture was further heated at 100° C. for 1 hour. 80
After cooling to ℃, the solvent was distilled off under reduced pressure to obtain a polyether compound. The obtained polyether compound was a colorless and transparent l complex with a hydroxyl value of 19.3 "-"'/g, and
No separation occurred even after being left at room temperature for several months.

Example 3 A mixture of 3250 g of polyisoprene polyol and 0.20 g of cobalt zinc cyanide/glyme complex was placed in a pressure-resistant reaction vessel, and propylene oxide was gradually added and reacted with stirring at 100° C. under a nitrogen atmosphere. After adding 1100g of propylene oxide, add 1 more
Heated at loO<0>C for hours. The obtained polyether compound is a colorless liquid with a hydroxyl value of 54-t-KQH of 7 g;
No separation occurred even after being left at room temperature for several months.

Example 4 A mixture of 500 g of "Polychloroprene Polyol", 100 g of tetrahydrofuran, and 0.30 g of cobalt zinc cyanide/glyme complex was placed in a pressure-resistant reaction vessel, and propylene oxide was gradually added and reacted with stirring at 100 °C under a nitrogen atmosphere. .Propylene oxide l00
After adding 0 g, the mixture was further heated at 100° C. for 1 hour. After cooling to 60°C, the solvent was distilled off under reduced pressure to obtain a polyether compound. The obtained polyether compound was a pale yellow wave body with a hydroxyl value of 7.5-g-1toll/, and no separation occurred even after it was left at room temperature for 3 months.

Example 5 1250 g of saturated polyolefin polyol and 5 toluene
0g and cobalt zinc cyanide/glyme complex 0.14g
The mixture of
Propylene oxide was gradually added and reacted at ℃ while stirring. After adding 450 g of propylene oxide, the mixture was further heated to 100° C. for 1 hour. After cooling to 80°C, the solvent was distilled off under reduced pressure to obtain a polyether compound. The obtained polyether compound has a hydroxyl value of 18
．． It was a colorless liquid with a weight of 9'''M ReQ H/g, and no separation occurred even after it was left at room temperature for 3 months.

Example 6 250g of oleyl alcohol and cobalt zinc cyanide/
A mixture of 0.20 g of the glyme complex was placed in a pressure-resistant reaction vessel, and propylene oxide was gradually added and reacted with stirring at 100° C. under a nitrogen atmosphere. After adding 1100g of propylene oxide, add 100g of propylene oxide for another 1 hour.
heated to ℃.

The obtained polyether compound had a hydroxyl value of 39. III
It was a colorless liquid with K −+l OH/g, and no separation occurred even after standing for 3 months.

Comparative Example 1 2 ml of an aqueous solution containing 0.5 g of potassium hydroxide was added to 100 g of "Polybutadiene Polyol", and water was distilled off under reduced pressure while heating to 100°C in a nitrogen atmosphere in a pressure-resistant reaction vessel. 110°C. While stirring, propylene oxide was gradually added and reacted.Propylene oxide 1
After adding 00 g, the mixture was further heated at 110° C. for 1 hour. Unreacted propylene oxide was distilled off under reduced pressure to obtain a crude polyether compound. The obtained polyether compound was opaque and colored brown, and separated after being left at room temperature for one day.

01 Idemitsu Petrochemical Company R-45HT12 Nippon Soda Company G-1000“8 Kuraray Company
TL-1 64 Denki Kagaku Kogyo Co., Ltd. L CRFH-050/6 Idemitsu Petrochemical Co., Ltd. Ebor 96 U.S. Patent No. 3278457, No. 327845
No. 8.

Prepared according to the method described in Publication No. 3278459 [Effect of the invention] The present invention enables ring-opening polymerization of alkylene oxide to a highly hydrophobic initiator, which was difficult when conventionally using an alkali metal hydroxide catalyst. can be done easily.

Claims (3)

[Claims] (1) In a method for producing a polyether compound by ring-opening polymerization of alkylene oxide in the presence of an initiator, an active hydrogen-containing hydrocarbon compound and/or a halogenated hydrocarbon compound is used as an initiator, and as a polymerization catalyst. Method using double metal cyanide complexes. (2) The method according to claim 1, wherein the active hydrogen-containing hydrocarbon compound and the halogenated hydrocarbon compound are monools or polyols having 8 or more carbon atoms. (3) Claim 2 in which the active hydrogen-containing hydrocarbon compound and/or halogenated hydrocarbon compound is an unsaturated group-containing or saturated polyolefin polyol.
The method described in section.