Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From carboxylic acid or derivative thereof
Reexamination Certificate
1999-02-26
2001-06-26
Acquah, Samuel A. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From carboxylic acid or derivative thereof
C528S080000, C528S083000, C528S301000, C528S308000, C528S308600, C525S444000
Reexamination Certificate
active
06252037
ABSTRACT:
The present invention relates to polyether polyol which is preferably used as a material for polyester or moulding, polyurethane elastomer or polyurethane for the manufacture of paint. It also relates to a method for the manufacture of moldable polyester where the above polyether polyol is one of the constituting units.
Polyesters for molding represented by polyethylene terephthalate and polybutylene terephthalate have excellent mechanical properties, heat resistance, etcetera and, therefore, they have been widely used for fibre, sheets, various bottles or films, and the like.
Basically, however, polyester is hydrolyzable and, accordingly, there is a problem that polyester has poor water resistance, alkali resistance and acid resistance whereby there have been many proposals for improving the resistance of polyester to hydrolysis.
As one of the means for improving the resistance of polyester to hydrolysis, there is a proposal where dimer dial is used as a part of polyhydric alcohol (laid-open Japanese patent publication Hei-03/252,419). However, dimer diol has a poor intersolubility with a hydrophilic compound such as ethylene glycol and terephthalic acid and, therefore, its rate of polymerization with such a hydrophilic compound is low. Thus, in the polyester prepared by a polycondensation of the dimer diol with terephthalic acid together with ethylene glycol or the like, an improvement in resistance to hydrolysis is still insufficient.
There are other proposals from the same point of view (laid-open Japanese patent publications Hei-02/263,827 and Hei-06/079,776) where dimer acid is used as a constituting component of polyester but the same problem as in the use of dimer diol occurs as well.
On the other hand, polyethylene terephthalate and polybutylene terephthalate have poor dyeing ability and that is a problem when they are used for fibre. As a means for improving that, there is a proposal where a high-boiling glycol prepared by adding ethylene oxide to alkylene glycol having 4-20 carbon atoms is used as a copolymerizing component (laid-open Japanese patent publication Sho-57/063,325). However, even in the polyester prepared by this method, resistance to hydrolysis is a bit unsatisfactory yet.
The present invention is to offer polyether polyol which shows, although having the same alkylene group as dimer diol as one of the constituting components, an excellent intersolubility with terephthalic acid and with hydrophilic compounds such as ethylene glycol. As a result of using such a polyether polyol as a part of the starting materials, it is now possible to manufacture polyester, polyurethane elastomer and polyurethane paint having an excellent resistance to hydrolysis. The present invention is also to offer a method for the manufacture of said polyester.
The present inventors have conducted an intensive study for solving the above problems and, as a result, have succeeded in accomplishing the present invention.
Thus, the present invention relates to polyether polyol having the following chemical formula (1).
HO—(AO)
m
ZO—(BO)
n
—H (1)
wherein Z is a dimer diol residue; A and B are the same or different alkylene groups having 2-14 carbon atoms; and m and n are the same or different integers of 0 or more where 2≦(m+n)≦40.
The present invention also relates to a method for the manufacture of mouldable polyester which is composed of the above-mentioned polyether polyol, alkylene glycol having 2-14 carbon atoms and aromatic dicarboxylic acid or dialkyl ester thereof wherein the amount of the dimer diol residue mentioned in the above paragraph is at least 1% by weight based on the total amount of all constituting units.
The present invention will be further illustrated as hereunder. Incidentally, the term “dimer diol residue” used in the present invention stands for the residue obtained by removal of two hydroxyl groups from a dimer diol molecule.
The polyether polyol of the present invention is a compound which has the above-mentioned chemical formula (1). Incidentally, polyether polyol where (m+n) in the formula (1) is less than 2 has a poor reactivity in the manufacture of polyester due to a poor intersolubility with terephthalic acid and with hydrophilic compounds such a ethylene glycol while, when (m+n) of the polyether polyol is more than 40, resistances to water and to hydrolysis of the polyester prepared therefrom are poor. Preferred number average molecular weight of the polyether polyol is from 600 to 3,000 in terms of a result calculated from hydroxyl values. When the number average molecular weight of the polyether polyol is less than 600, the reactivity in the manufacture of polyester is poor while, when it is more than 3,000, water resistance of the resulting polyester is poor.
Polyether polyol of the present invention may, for example, be manufactured by a method where alkylene oxide having 2-4 carbon atoms is added to dimer diol.
Dimer diol is a saturated aliphatic diol having 36 carbon atoms prepared by a complete hydrogenation of dimer acid. The dimer acid used as a starting material is obtained by dimerization, with heating, of unsaturated fatty acid having 18 carbon atoms such as oleic acid or linoleic acid. For example, commercially-available products such as Pespol HP-1000 which is sold from Toagosei Co., Ltd. may be used as the dimer diol.
Structurally, dimer diol is a mixture of many geometrical isomers due to a difference in the structure of the alkylene group which is a skeleton. Many branched alkyl groups are attached to the above-mentioned alkylene group in the dimer diol and that might be a reason why polyester and the like where the diner diol is one of the components have excellent resistance to hydrolysis.
Examples of the alkylene oxide having 2-4 carbon atoms are ethylene oxide, propylene oxide, butylene oxide and tetrahydrofuran (hereinafter, abbreviated as THF).
Known methods may be used for adding the above-mentioned alkylene oxide to dimer diol. Thus, when an alkylene oxide having a three-membered ring is used, a dimer diol wherein two hydroxyl groups are converted to alcoholate by sodium hydroxide or potassium hydroxide is heated at 100-140° C., a predetermined amount of alkylene oxide is added thereto with stirring and the alkylene oxide is subjected to an anionic polymerization using the dimer diol alcoholate as an initiating material.
When THF is used as an alkylene oxide, THF is subjected to a cationic ring-opening polymerization at about 0° C. in the presence of boron trifluoride ether salt and then the polymerization is stopped by adding disodium salt of diner diol thereto whereupon the desired polyether polyol is prepared.
Polyether polyol to which alkylene oxide having five or more carbon atoms is added has a high hydrophobicity and is poor in a copolymerizing ability with hydrophilic aromatic dicarboxylic acids.
Reactivity at polyesterification is low when the terminal is a secondary alcohol type in the polyether polyol of the present invention and, therefore, the use of the compound where the terminal is a primary alcohol type is preferred. When propylene oxide or butylene oxide is added to hydroxyl groups of dimer diol, terminals of the resulting polyether polyol become a secondary alcohol type and, in that case, it is preferred that the terminals of the polyether polyol are converted to a primary alcohol type.
Polyether polyol of the present invention can be preferably used as a material for the manufacture of polyester and polyurethane.
Polyurethane is manufactured by the reaction of polyether polyol of the present invention, a short-chain diol such as butanediol and, if necessary, polyester polyol with a polyisocyanate such as diphenylmethane diisocyanate.
In the manufacture of polyurethane by the reaction of a mixture of polyester polyol mainly comprising diner acid or dimer diol and a short-chain diol with polyisocyanate, it is possible to give polyurethane having excellent properties especially when the polyether polyol of the present invention is used as a part of polyhydric alcohol. Thus, po
Kojima Shirou
Mochizuki Katsunobu
Acquah Samuel A.
Heller Ehrman White & McAuliffe LLP
Unichema Chemie B.V.
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