Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From silicon reactant having at least one...
Reexamination Certificate
2001-04-11
2003-01-07
Dawson, Robert (Department: 1712)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From silicon reactant having at least one...
C525S403000, C568S673000, C568S303000, C528S076000, C528S414000, C528S412000, C528S015000, C562S400000, C562S887000
Reexamination Certificate
active
06503995
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a method of producing a crosslinkable silyl group-containing polyoxyalkylene polymer and a method of producing a polyoxyalkylene polymer containing at least one crosslinkable silyl group and at least one hydroxy group.
PRIOR ART
Crosslinkable silyl group-containing polyoxyalkylene polymers are widely used as raw material polymers in sealing materials, adhesives, coating materials and the like for architectural or industrial use. As illustrated in Japanese Kokai Publication Sho-50-156599, Japanese Kokai Publication Sho-52-73998 and Japanese Kokai Publication Hei-03-72527, for instance, such crosslinkable silyl group-containing polyoxyalkylene polymers are produced mainly by introducing an unsaturated group such as an allyl or methallyl group into a polyoxyalkylene polymer utilizing its terminal hydroxyl group and reacting the thus-produced unsaturated group-terminated polyoxyalkylene polymer with a compound having a hydrogen-silicon bond and a crosslinkable silyl group in each molecule in the manner of hydrosilylation. However, in such production processes, byproducts or impurities, such as salts, are formed in the step of unsaturated group introduction and, therefore, a step of purification for the purpose of removing these is required. Thus problems arise, namely the production process becomes lengthy and complicated and a large amount of waste is generated.
As a method of producing a crosslinkable silyl group-containing polyoxyalkylene polymer which may possibly reduce the formation of byproducts and shorten the production process, there may be mentioned, for example, the method disclosed in Japanese Kokai Publication Hei-3-79627 which comprises subjecting a monoepoxide not having an unsaturated group to ring opening polymerization using a double metal cyanide complex catalyst, then reacting the polymerization product with an unsaturated group-containing monoepoxide and reacting the thus-produced, polyoxyalkylene polymer having at least one unsaturated group and at least one alcoholic hydroxyl group with a compound having a hydrogen-silicon bond and a crosslinkable silyl group in each molecule in the manner of hydrosilylation.
According to this production method, such byproducts as salts are not formed in the step of unsaturated group introduction. However, the double metal cyanide complex used as the catalyst becomes mixed in the polyoxyalkylene polymer. This double metal cyanide complex is capable of inhibiting the hydrosilylation reaction and, further, capable of promoting the dehydration condensation reaction between a hydrogen-silicon bond and a hydroxyl group, the condensation reaction between a hydroxyl group and a crosslinkable silyl group or the disproportionation reaction of substituents on a silicon atom. Therefore, problems arise when the hydrosilylation reaction is carried out without removing the double metal cyanide complex from the polyoxyalkylene polymer; for example, the hydrosilylation yield will be low, or the condensation reaction of a hydrogen-silicon bond with a hydroxyl group proceeds, resulting in an increased viscosity, or the condensation reaction of a crosslinkable silyl group with a hydroxyl group progresses, also resulting in an increased viscosity. If such side reactions involving the hydroxyl group proceeds, it becomes difficult to carry out a further reaction utilizing the hydroxyl group. Therefore, for realizing efficient crosslinkable silyl group introduction and retaining the hydroxyl group in the polymer at a high remaining percentage, it is necessary to remove the double metal cyanide complex or purify the polymer prior to hydrosilylation. This produces a problem, namely renders the production process complicated.
Further, a method of producing a polyoxyalkylene polymer having at least one crosslinkable silyl group and at least one hydroxyl group in each molecule is disclosed in Japanese Kokai Publication Hei-05-125176 which comprises reacting a polyoxyalkylene polymer having at least one unsaturated group and at least one alcoholic hydroxyl group in each molecule as produced by using a double metal cyanide complex with a compound having a hydrogen-silicon bond and a crosslinkable silyl group in each molecule in the manner of hydrosilylation. However, when the method disclosed in the above-cited publication is carried out without removing the double metal cyanide complex, the hydrosilylation yield is low and the percentage of the remaining hydroxyl group in the polymer is low. In addition to these problems, the low percentage of the hydroxyl group in polymer causes a problem; when a reaction utilizing the hydroxyl group, for example the coupling reaction, is carried out, the yield is low. If the double metal cyanide complex is eliminated from the polyoxyalkylene polymer, or the polymer is purified, for solving such problems, the production process will become lengthy and complicated and problems of waste water and waste generation, for instance, will arise.
Another method of producing a crosslinkable silyl group-containing polyoxyalkylene polymer is described in Japanese Kokai Publication Hei-05-43679 and Japanese Kokai Publication Hei-06-172648 which comprises mutually coupling two allyl-terminated polyoxyalkylene monool molecules and then subjecting the coupling product to hydrosilylation with an alkoxysilane. However, it is a problem with this method that the coupling reaction catalyst often inhibits the hydrosilylation reaction. There is another problem: when the coupling reaction is carried out using an isocyanato group-containing compound, for instance, the hydrosilylation catalyst is required in large amounts since the urethane bond inhibits the hydrosilylation reaction. This is economically disadvantageous. There are further problems; when the allyl-terminated polyoxyalkylene monool is produced by polymerization using a double metal cyanide complex as a catalyst, the double metal cyanide complex remaining in the polymer inhibits the hydrosilylation reaction, so that a purification step is required or it is necessary to use the hydrosilylation catalyst in large amounts.
In view of the above-mentioned state of the art, it is an object of the present invention to provide a method of producing a polyoxyalkylene polymer having at least one crosslinkable silyl group and at least one hydroxyl group in each molecule expediently in high yields from polyoxyalkylene polymers having at least one unsaturated group and at least one alcoholic hydroxyl group in each molecule substantially without removing impurities, in particular the double metal cyanide complex, from the starting polymers or without purifying the same.
Another object of the invention is to provide a method of producing a crosslinkable silyl group-containing polyoxyalkylene polymer expediently in high yields by preparing polyoxyalkylene polymers having at least one crosslinkable silyl group and at least one hydroxyl group in each molecule from polyoxyalkylene polymers having at least one unsaturated group and at least one alcoholic hydroxyl group in each molecule substantially without removing impurities, in particular the double metal cyanide complex, therefrom or without purifying the same while suppressing side reactions in which the crosslinkable silyl group and/or hydroxyl group is involved and further carrying out the coupling reaction in which the hydroxyl group is involved, while suppressing side reactions such as condensation reactions in which the crosslinkable silyl group and/or hydroxyl group is involved.
SUMMARY OF THE INVENTION
The invention thus provides a method of producing a polyoxyalkylene polymer having at least one crosslinkable silyl group and at least one hydroxyl group in each molecule which comprises
treating a polyoxyalkylene polymer having at least one unsaturated group and at least one alcoholic hydroxyl group in each molecule and an impurity double metal cyanide complex as mixed therein with a metal-coordinating compound,
then adding a compound having a hydrogen-silicon bond and a crosslinkabl
Asai Yousuke
Fujita Masayuki
Harada Hajime
Iwakiri Hiroshi
Kawamura Takeshi
Armstrong Westerman & Hattori, LLP
Dawson Robert
Kaneka Corporation
Peng Kuo-Liang
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