Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From heterocyclic reactant containing as ring atoms oxygen,...
Reexamination Certificate
1998-12-17
2001-03-27
Niland, Patrick D. (Department: 1714)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From heterocyclic reactant containing as ring atoms oxygen,...
C524S507000, C524S589000, C524S590000, C528S044000, C528S065000, C528S085000, C568S620000
Reexamination Certificate
active
06207794
ABSTRACT:
TECHNICAL FIELD
The present invention relates to a polyoxyalkylene polyol and manufacturing method for the same and also derivatives of polyoxyalkylene polyol. Described in more detail, the present invention relates to a polyoxyalkylene polyol and manufacturing method for the same, wherein: an alkylene oxide is addition polymerized to an active hydrogen compound in the presence of a phosphazenium compound catalyst. The present invention also relates to derivatives of this polyoxyalkylene polyol, which are: polymer dispersed polyol, isocyanate terminated prepolymer, polyurethane resin, polyoxyalkylene polyamine, and polyurethane urea resin which uses polyoxyalkylene polyamine as its raw material.
BACKGROUND TECHNOLOGY
Normally, polyoxyalkylene polyol is manufactured on the industrial scale by addition polymerization of alkylene oxide to an active hydrogen compound in the presence of potassium hydroxide (abbreviated as KOH) catalyst. Alkylene oxide is continuously introduced into a reactor which is stocked with KOH catalyst and an active hydrogen compound which is the polymerization initiator. Under conditions of reaction temperature 105~150° C., maximum reaction pressure 490~588 kPa (5~6 kgf/cm
2
), the reaction is continued until the desired molecular weight is achieved. A crude polyoxyalkylene polyol is obtained. Next, the polyoxyalkylene polyol manufacturing is completed through postprocessing refining steps such as: neutralizing the potassium in the crude polyoxyalkylene polyol with an acid such as inorganic acid, or the like, filtering the potassium which is extracted through dehydration, drying, or the like.
In the prior art, many studies have been done to enhance the production of polyoxyalkylene polyol. For example, known methods for increasing the reaction speed of the monomer alkylene oxide include: increasing the alkylene oxide concentration at the time of the reaction, increasing the amount of catalyst, increasing the reaction temperature, or the like.
However, when using KOH catalyst for addition polymerization of propylene oxide which is the most widely used alkylene oxide, it is known that, with the above method, when the molecular weight of polyoxyalkylene polyol is increased, there is a by product of a monool which has an unsaturated group at the ends of the molecule.
Normally, the monool content corresponds to the total unsaturation degree (represented by C═C) of the polyoxyalkylene polyol. Because this monool is low molecular weight compared to the polyoxyalkylene polyol generated in the main reaction, it greatly widens the molecular weight distribution of the polyoxyalkylene polyol and lowers the average functional group number. Therefore, whether it is foam or elastomer, the polyurethane resin, which uses a polyoxyalkylene polyol with a high monool content, experience unfavorable results such as increased hysterisis, reduced hardness, reduced extension, reduced curing, increased permanent compression set, or the like.
Many studies have been done in order to suppress the generation of monool by product and to improve production of polyoxyalkylene polyol. For example, in U.S. Pat. No. 3,829,505 and in U.S. Pat. No. 4,472,560, there is proposed a method, wherein: a double metal cyanide complex (abbreviated as DMC) catalyst is used as a catalyst for the propylene oxide addition polymerization. DMC is described as performing very well as a polymerization catalyst for polypropylene oxide.
However, when using DMC as a catalyst for the addition polymerization of ethylene oxide as the alkylene oxide, DMC is first deactivated by reactions with an oxidant such as gas which contained oxygen, peroxides, sulfuric acid, or the like. Catalyst residue is separated from the polyol. Furthermore, there is a need to addition polymerize ethylene oxide using a catalyst of an alkali metal hydroxide such as KOH or an alkali metal alkoxide or the like (U.S. Pat. No. 5,235,114).
Furthermore in U.S. Pat. No. 5,093,380 (Column 2, lines 58~68), there is disclosed a manufacture method for a flexible polyurethane foam which uses a polyoxyalkylene polyol having a low C═C. This kind of polyoxyalkylene polyol having a low C═C is obtained in the presence of a catalyst other than an alkali catalyst. For example, the catalyst can be diethyl zinc, iron chloride, porphyrin metal, DMC or the like. DMC catalyst is described as a particularly favorable catalyst.
Furthermore, in Japanese Laid-Open Publication No. 4-59825, when manufacturing a polyether using DMC, if the initiator is low molecular weight, problems, such as the reaction of the monoepoxide not occurring or else the reaction speed being extremely slow, are described. In order to solve these problems, it is necessary to use an initiator of a polyoxypropylene glycol which has already addition polymerized a propylene oxide. However, with this method, there is a limitation on the usable polymerization initiator and the manufacturing process becomes complicated.
When polyoxyalkylene polyol is made to be a high molecular weight, there is a tendency for the viscosity of polyoxyalkylene polyol to increase. When DMC is used, this trend is particularly noticeable.
In U.S. Pat. No. 5,300,535, because the viscosity of the high molecular weight polyoxyalkylene polyol which uses DMC as a catalyst is high, the use of acrylate, vinyl ether compounds as viscosity lowering agents is demonstrated (Column 2, line 5~column 4, line 12). As a result of research by the present inventors, when the viscosity of polyol is high, troubles of molding stability and mixing properties occur in the mechanical molding of flexible polyurethane foams. There are also problems of inferior processability and reduced mixing properties with auxiliary agents.
In Japanese Laid Open Publication No. 7-278289, there is disclosed a polyoxyalkylene polyol, wherein: it has a hydroxide value (abbreviated as OHV) of 10~35 mg KOH/g, a maximum monool content of 15 mol %, and a minimum selectivity for Head-to-Tail (abbreviated as T-H) bond of 96%. Furthermore, in this publication, the catalyst for manufacture of polyol is an alkali metal hydroxide which has a purity of 90% by weight or greater and is a composition which contained at least one compound selected from: cesium hydroxide or rubidium hydroxide. The above polyoxyalkylene polyol has a low viscosity even when the monool content is reduced. The resulting flexible polyurethane foam has good mechanical properties. It is a polyoxyalkylene polyol with excellent properties. However, in order to manufacture a polyoxyalkylene polyol with OHV of 15 mgKOH/g and a monool content of 15 mol % or less while using cesium hydroxide as the catalyst, a long reaction time is required. When considering the productivity of the polyol, it is not necessarily a satisfactory catalyst.
For a polymer-dispersed polyol with polyoxyalkylene polyol as the dispersion medium and a polyurethane which uses the polymer-dispersed polyol, their properties are greatly influenced by the structure and composition of the polyoxyalkylene polyol which is the dispersion medium.
In Japanese Laid-Open Patent Publication No.3-14812, a manufacturing method for a polymer dispersed polyol which has polyoxyalkylene polyol as the dispersing medium is demonstrated. The polyoxyalkylene polyol is obtained using diethyl zinc, iron chloride, metal porphyrin, DMC as a catalyst. Furthermore, by reducing the C═C in the polyoxyalkylene polyol, it is stated that the properties of the flexible polyurethane foam which uses the polymer dispersed polyol which has this polyol as a dispersing medium are improved. However, research was conducted by the present inventors on this polymer dispersed polyol which has a polyoxyalkylene polyol as the dispersing medium where the polyoxyalkylene polyol is catalyzed by DMC. The polymer dispersed polyol was found to have a high viscosity, and the flexible polyurethane foam which uses this polymer dispersed polyol was inferior in humid aged compression set.
In Japanese Laid Open Patent Publication Number 7-330843, there is disclosed a polymer
Aoki Masaaki
Hara Yasunori
Izukawa Tsukuru
Matsufuji Mikio
Matsumoto Shinsuke
Burns Doane Swecker & Mathis L.L.P.
Mitsui Chemical, Inc.
Niland Patrick D.
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