Polyoxyalkylenepolyols and process for producing ring-opened...

Details Polyoxyalkylenepolyols and process for producing ring-opened... Polyoxyalkylenepolyols and process for producing ring-opened...

2001-03-07

2003-03-11

Gorr, Rachel (Department: 1711)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

From reactant having at least one -n=c=x group as well as...

C568S010000, C568S075000, C568S620000, C568S623000, C528S077000, C528S319000, C528S323000, C528S354000, C528S357000, C528S370000, C528S371000, C528S377000, C528S378000, C528S409000, C528S410000, C528S423000, C528S424000, C564S443000, C564S505000, C252S182270

Reexamination Certificate

active

06531566

ABSTRACT:

TECHNICAL FIELD
The present invention relates to polyoxyalkylene polyols or monools having the proportion of terminal primary hydroxyl groups of not less than 40%; to a method of preparing ring-opening polymerization products by ring-opening addition polymerization of a heterocyclic compound; and to polyol compositions for use as polyol components for polyurethane resins, epoxy resins and like thermosetting resins. More particularly, it relates to polyoxyalkylene polyols having increased reactivity with isocyanato groups or the like without impairing their hydrophobicity; to a method of effecting ring-opening polymerization of cyclic compounds in the presence of a specific catalyst; and to the use of said compounds as polyol components for thermosetting resins.
BACKGROUND ART
Polyols such as polyoxyalkylene polyols obtained by ring-opening reaction of a monoepoxide, such as an alkylene oxide, with an active hydrogen-containing compound are in wide use as starting materials for thermosetting resins such as polyurethanes, as surfactants, as lubricants and in other fields of application.
The method so far widely used for the production of polyethers comprises reacting a monoepoxide in the presence of an alkaline catalyst. Used as the alkaline catalyst are alkali metal compounds such as potassium hydroxide and sodium hydroxide. As an alternative, the method is also known which comprises carrying out the reaction of a monoepoxide using a BF
3
complex, zinc hexacyanocobaltate or a like composite metal cyanide complex as the catalyst.
Polyoxyalkylene polyols obtained by ring-opening reaction of an &agr;,&bgr;-epoxides such as propylene oxide, epichlorohydrin, styrene oxide or laurylene oxide in the presence of such catalyst have very low proportion of terminal primary hydroxyl groups (generally not more than 2% when potassium hydroxide is used, for instance), most of the terminal hydroxyl groups being secondary hydroxyl groups. Therefore, such polyols have insufficient reactivity for use as polyol components for thermosetting resins. For example, they have low reactivity with isocyanate groups in isocyanate-containing compounds (tolylene diisocyanate etc.) and have insufficient reactivity when they are used as polyol components for urethane resins.
For securing sufficient reactivity with isocyanate groups, the terminal hydroxyl groups is required to be primary hydroxyl groups. For this purpose, a method is known which comprises performing ring-opening reaction of alkylene oxides to obtain polyoxyalkylene polyols, and then subjecting ethylene oxide to ring-opening reaction therewith, thus generating terminal primary hydroxyl groups. However, since the polyethylene oxide portions are hydrophilic, such method reduces the hydrophobicity of polyoxyalkylene polyols. When such polyols are used, there arises a problem in that the physical and other characteristics of the resulting urethane resins vary widely depending on humidity.
On the other hand, for ring-opening polymerization of carbonates, thiocarbonates, dithiocarbonates and like cyclic compounds, a method has been used which comprises effecting ring-opening polymerization in the presence of an acid catalyst such as BF
3
.
However, this method of producing ring-opening polymerization products, which comprises effecting ring-opening polymerization of carbonates, thiocarbonates, dithiocarbonates and like cyclic compounds in the presence of such a catalyst, has a problem in that carbon dioxide, carbon oxide sulfide, carbon disulfide or the like is eliminated during ring-opening addition polymerization of such cyclic compounds, leading to low yields of the ring-opening polymerization products derived from the cyclic compounds. In addition, in the step of ring-opening polymerization, such a catalyst must be used in an amount almost equivalent to growing chain terminals, so that a large quantity of the catalyst remains in the polymers produced. In certain fields of application of the ring-opening polymerization products thus obtained, the residual catalyst has significant adverse effects, hence it is necessary to remove the catalyst by treatment following the ring-opening polymerization.
In view of the foregoing, the present invention has its object to provide polyol compositions having sufficient reactivity for use as materials for thermosetting resins without impairing the hydrophobicity of polyoxyalkylene polyols; polyoxyalkylene polyols suited for use in this polyol compositions; a method of producing this polyoxyalkylene polyols; and a method of producing ring-opening polymerization products by subjecting a cyclic compound to ring-opening addition polymerization in the presence of a specific catalyst.
SUMMARY OF INVENTION
The present inventors made intensive investigations in an attempt to solve the above problems and, as a result, found that:
(1) polyoxyalkylene polyols having the proportion of terminal primary hydroxyl groups of not less than 40% have sufficient reactivity as polyol components for thermosetting resins while retaining the hydrophobicity thereof;
(2) such polyoxyalkylene polyols having the proportion of terminal primary hydroxyl groups of not less than 40% can be obtained by adding an epoxy containing compound to an active hydrogen-containing compound in the presence of a catalyst having a specific chemical structure and;
(3) the yield is very high when a cyclic compound is subjected to ring-opening addition polymerization in the presence of a specific catalyst. These findings have now led to completion of the present invention.
Thus, the present invention consists in polyoxyalkylene polyols or monools (I) of the general formula (1) below, characterized in that not less than 40% of the terminally located hydroxyl-containing groups, namely —AO—H groups, are primary hydroxyl-containing groups of the general formula (2) below:
R
1
—[—(ZO)
p
—(AO)
q
—H]
m
(1)
wherein:
in the formula (1), R
1
is a group having a valence of m as derived from a compound selected from the group consisting of water, an alcohol compound, a phenol compound, an amino-containing compound, a carboxyl-containing compound, a thiol-containing compound and a phosphoric acid compound by removal of its active hydrogen atom or atoms; Z is an alkylene group containing 2 to 12 carbon atoms or a cycloalkylene group containing 6 to 12 carbon atoms, each of which may contain at least one halogen atom or aryl group or both as substituents; A is an alkylene group containing 3 to 12 carbon atoms or a cycloalkylene group containing 6 to 12 carbon atoms, each of which may contain at least one halogen atom or aryl group or both as substituents; m is an integer of 1 or 2 to 100; p is an integer of 0 or 1 or more and q is an integer of 1 or more, p+q being equal to 1 to 200; and in the formula (2), R
2
is an alkyl group containing 1 to 10 carbon atoms or an aryl group containing 6 to 10 carbon atoms, each of which may be substituted by a halogen atom or atoms.
The present invention also consists in a method of producing ring-opening polymerization products, which comprises subjecting a heterocyclic compound (d) of the general formula (5) below to ring-opening addition polymerization with an active hydrogen-containing compound (b) of the general formula (3) below in the presence of at least one catalyst (c) selected from the group consisting of compounds having the general formula (4-1) below, compounds of the general formula (4-2) below and compounds of the general formula (4-3) below:
R
1
—[—(ZO)
p
—H]
m
  (3)
X—(—R
3
)
2
  (4-1)
wherein:
in the formula (3), R
1
is a group having a valence of m as derived from a compound selected from the group consisting of water, an alcohol compound, a phenol compound, an amino-containing compound, a carboxyl-containing compound, a thiol-containing compound and a phosphoric acid compound by removal of its active hydrogen atom or atoms; Z is an alkylene group containing 2 to 12 carbon atoms or a cycloalkylene group containing 6 to 12 carbon atoms, each of which may contain at least on

Affiliated with

Also associated with

Rating

Polyoxyalkylenepolyols and process for producing ring-opened... does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Polyoxyalkylenepolyols and process for producing ring-opened..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Polyoxyalkylenepolyols and process for producing ring-opened... will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-3015629