Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Cellular products or processes of preparing a cellular...
Reexamination Certificate
2002-02-06
2003-09-23
Cooney, John M. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Cellular products or processes of preparing a cellular...
C252S182240, C252S182270, C521S155000, C521S174000, C524S762000, C524S765000, C524S773000
Reexamination Certificate
active
06624209
ABSTRACT:
TECHNICAL FIELD
The present invention relates to polymer polyol compositions for producing polyurethane resins, methods for producing the polymer polyol compositions, and a method for producing polyurethane resins or foams thereof using the obtained polymer polyols.
BACKGROUND ART
Polymer compositions or mixtures obtained by polymerizing an ethylenically unsaturated compound in a polyol are generally referred to as polymer polyols, and are used widely as the materials of polyurethane resins such as polyurethane foams or polyurethane elastomers.
It is known that the content of polymer particles in a polymer polyol may be increased to produce a polymer polyol that provides a high quality polyurethane with a greater hardness and a higher elastic modulus. Known methods to obtain such a polymer polyol include a method of polymerizing a vinyl monomer in the presence of a modified polyol, a portion of which has been allowed to react with a coupling agent (a silicon-containing compound, tetrakisalkoxy orthoformate, trialkoxyalkane, dialkoxyalkane, or the like) to increase its molecular weight (e.g. WO 85/04891), a method of polymerizing a vinyl monomer in the presence of a macromer containing an urethane bond (e.g. JP 61(1986)-115919 A), etc.
However, the polymer polyol compositions obtained by the above methods have deficiencies such as poor dispersion stability or deteriorated miscibility with an isocyanate when forming a polyurethane resin, and there were difficulties in handling. Thus, it has been difficult to obtain a polymer polyol composition having good dispersion stability even when the content of polymer particles is high.
The inventors of the present invention have made earnest investigations to solve the above problems, and found that a polymer polyol composition that provides a high quality polyurethane and has a low viscosity can be obtained by having a content of oligomers of not more than a specified amount, thus reaching the present invention. Furthermore, it was also found that the same polymer polyol composition can be obtained by mechanically dispersing or crushing a polymer polyol obtained by polymerizing a monomer in the presence of a specific dispersant, thus reaching the present invention.
Furthermore, the inventors found that the use of a specific compound having an ethylenically-unsaturated group at a terminal (hereinafter referred to as terminal ethylenically-unsaturated group containing compound) and/or a specific reactive dispersant allows the same polymer polyol composition to be obtained, thus providing the present invention.
It is an object of the present invention to provide polymer polyols having a low viscosity and very good dispersion stability even when the concentration of the polymer particles is high, and to provide methods for producing the polymer polyols. Also, it is another object of the present invention to provide a method for producing polyurethane resins using these polymer polyol compositions or foams thereof, wherein the polyurethane resins or foams thereof have good operation efficiency and have high 25% ILD (hardness) and small compression set.
SUMMARY OF THE INVENTION
The present invention is as follows.
[First Invention]
A polymer polyol composition (I) comprising a dispersion medium composed of a polyol (A), or (A) and a diluent (C), and polymer particles (B) dispersed in the dispersion medium, wherein the polymer particles (B) are formed by polymerizing an ethylenically unsaturated compound (b) in a polyol, or in a polyol and the diluent (C); the content of (B) in (I) is from 35 to 75 mass %, based on the mass of (I); and the amount of soluble polymers (P) dissolved in (A) is not more than 5 mass %, based on the mass of (A).
[Second Invention]
A polymer polyol composition (I) comprising a dispersion medium composed of a polyol (A), or (A) and a diluent (C), and polymer particles (B) dispersed in the dispersion medium, wherein the polymer particles (B) are formed by polymerizing an ethylenically unsaturated compound (b) in a polyol, or in a polyol and (C); the content of (B) in (I) is from 35 to 75 mass %, based on the mass of (I); and the viscosity V (mPa·s) of (I) measured by a Brookfield viscosimeter at 25° C. is in the range of an inequality
V
≦(
Va−Va×C/
10){circumflex over ( )}[
e{circumflex over ( )}x],
(1)
where x=0.0010354×Bp{circumflex over ( )}1.5,
Va is a viscosity (mPa·s) of (A) measured by a Brookfield viscosimeter at 25° C.,
C is a content of (C) in (I) (mass %),
Bp is a content of (B) in (I) (mass %),
symbol {circumflex over ( )} indicates a power, and
symbol “e” is the base of the natural logarithm.
[Third Invention]
A polymer polyol composition (II) comprising a polyol (A), and polymer particles (B) dispersed in a dispersion medium composed of a polyol (A), or (A) and a diluent (C), wherein the polymer particles (B) are formed by polymerizing an ethylenically unsaturated compound (b) in a polyol; (b) contains at least 5 mass % of an ethylenically unsaturated compound (b1) having a number-average molecular weight of at least 500; and (b) is polymerized in the presence of a dispersant (D), and in the presence or absence of a diluent (C).
[Fourth Invention]
A polymer polyol composition (III) comprising a polyol (A), and polymer particles (B) dispersed in a dispersion medium composed of a polyol (A), or (A) and a diluent (C), wherein the polymer particles (B) are formed by polymerizing an ethylenically unsaturated compound (b) in a dispersion medium comprising (A) in the presence of a dispersant (D′) to form polymer particles, and mechanically dispersing or crushing the polymer particles, and wherein the difference between the solubility parameter SPd of (D′) and the solubility parameter SPa of (A) is not more than 0.8.
[Fifth Invention]
A method for producing a polymer polyol composition, which method comprises polymerizing an ethylenically unsaturated compound (b) in a polyol (A) in the presence or absence of at least one selected from a dispersant (D) and a diluent (C), wherein the polymer polyol composition (I) or (II) of any of the first, second and third inventions is obtained using (b) containing at least 5 mass % of an ethylenically unsaturated compound (b1) having a number-average molecular weight of at least 500.
[Sixth Invention]
A method for producing the polymer polyol composition (I) of the first or second invention comprising a polyol (A) and polymer particles (B) dispersed in (A), which method comprises separating the polymer particles (B) from a polymer polyol composition obtained by polymerizing an ethylenically unsaturated compound (b) in a polyol; and mechanically dispersing the polymer particles (B) in (A) not containing more than 5 mass % of soluble polymers, based on the mass of (A).
[Seventh Invention]
A method for producing the polymer polyol composition (III) of the fourth invention, which method comprises polymerizing an ethylenically unsaturated compound (b) in a dispersion medium comprising a polyol (A) in the presence of a dispersant (D′) to form polymer particles in a polymer polyol; and mechanically dispersing or crushing the polymer particles, wherein the difference between the solubility parameter SPd of (D′) and the solubility parameter SPa of (A) is not more than 0.8.
[Eighth Invention]
A polymer polyol composition comprising a dispersion medium composed of a polyol (A), or (A) and a diluent (C), and polymer particles (B) dispersed in the dispersion medium, wherein the polymer particles (B) are formed by polymerizing an ethylenically unsaturated compound (b) in the dispersion medium in the presence or absence of a dispersant (D), wherein at least 5 mass % of (b) comprises a terminal ethylenically-unsaturated group containing compound (b3) having a number-average molecular weight of 160 to 490 and a solubility parameter SPb of 9.5 to 13.
[Ninth Invention]
A polymer polyol composition comprising a dispersion medium compos
Furuta Takeshi
Ikeda Kiyoshi
Kawamoto Tetsuji
Kawazoe Tomio
Kitatani Futoshi
Cooney John M.
Merchant & Gould P.C.
Sanyo Chemical Industries Ltd.
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