Organo-titanate catalysts for preparing pure macrocyclic...

Details Organo-titanate catalysts for preparing pure macrocyclic... Organo-titanate catalysts for preparing pure macrocyclic...

2001-10-09

2004-09-07

Boykin, Terressa (Department: 1711)

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

Synthetic resins

Treating polymer containing material or treating a solid...

C528S271000, C528S272000, C528S279000, C528S481000

Reexamination Certificate

active

06787632

ABSTRACT:

TECHNICAL FIELD
This invention generally relates to catalysts. More particularly, the invention relates to organo-titanate catalysts useful for preparing macrocyclic oligoesters.
BACKGROUND INFORMATION
Linear polyesters such as poly(alkylene terephthalate) are generally known and commercially available where the alkylene typically has 2 to 8 carbon atoms. Linear polyesters have many valuable characteristics including strength, toughness, high gloss, and solvent resistance. Linear polyesters are conventionally prepared by the reaction of a diol with a dicarboxylic acid or its functional derivative, typically a diacid halide or ester. Linear polyesters may be fabricated into articles of manufacture by a number of techniques including extrusion, compression molding, and injection molding.
Recently, macrocyclic oligoesters were developed which are precursors to linear polyesters. Macrocyclic oligoesters exhibit low melt viscosity, which can be advantageous in some applications. Furthermore, certain macrocyclic oligoesters melt and polymerize at temperatures well below the melting point of the resulting polymer. Upon melting and in the presence of an appropriate catalyst, polymerization and crystallization can occur virtually isothermally.
One method for synthesis of the macrocyclic oligoesters includes the step of contacting a diol of the formula HO—A—OH with a diacid chloride of the formula:
where A is an alkylene, or a cycloalkylene or a mono- or polyoxyalkylene group; and B is a divalent aromatic or alicyclic group. The reaction typically is conducted in the presence of at least one amine that has substantially no steric hindrance around the basic nitrogen atom. An illustrative example of such amines is 1,4-diazabicyclo[2.2.2]octane (DABCO). The reaction usually is conducted under substantially anhydrous conditions in a substantially water immiscible organic solvent such as methylene chloride. The temperature of the reaction typically is between about −25° C. and about 25° C. See, e.g., U.S. Pat. No. 5,039,783 to Brunelle et al.
Macrocyclic oligoesters may also be prepared via the condensation of a diacid chloride with at least one bis(hydroxyalkyl) ester such as bis(4-hydroxybutyl) terephthalate in the presence of a highly unhindered amine or a mixture thereof with at least one other tertiary amine such as triethylamine, in a substantially inert organic solvent such as methylene chloride, chlorobenzene, or a mixture thereof. See, e.g., U.S. Pat. No. 5,231,161 to Brunelle et al.
Another method for preparing macrocyclic oligoesters is to depolymerize linear polyester polymers in the presence of an organotin or titanate compound. In this method, linear polyesters are converted to macrocyclic oligoesters by heating a mixture of a linear polyester, an organic solvent, and a trans-esterification catalyst such as a tin or titanium compound. The solvents used, such as o-xylene and o-dichlorobenzene, usually are substantially free of oxygen and water. See, e.g., U.S. Pat. Nos. 5,407,984 to Brunelle et al. and 5,668,186 to Brunelle et al.
To be useful for the preparation of macrocyclic oligoesters, the organo-titanate catalyst should be soluble in the solvent of the depolymerization reaction, should be in a physical state that allows it to be readily added to the reaction, and should be an active catalyst capable of establishing the desired equilibrium in a reasonable time. Catalysts prepared from tetraisopropyl titanate and two equivalents of butanediol, for example, tend to polymerize and gel from solution. To circumvent this gelation, diethylene glycol was used to substitute part of the butanediol. One technique for preparation of organo-titanate catalysts uses butanediol together with diethylene glycol. See, U.S. Pat. No. 5,710,086 to Brunelle et al. Catalysts prepared according to this method contain moieties of diethylene glycol, which are later incorporated into the macrocyclic oligoesters prepared using the catalysts. The incorporation of diethylene glycol moieties causes deleterious effects on the mechanical properties (e.g., modulus) and thermal properties (e.g., melting point and heat distortion temperature) of the polyester prepared from the macrocyclic oligoesters.
Unfortunately, it is desirable for certain applications such as automotive paint oven or rapid molding and cycle time to employ pure macrocyclic oligoesters, i.e., macrocyclic oligoesters substantially free from macrocyclic co-oligoesters. To conduct molding at high speed, the material (e.g., polybutylene terephthalate polymerized from macrocyclic oligoesters) that is molded needs to crystallize rapidly. High purity is thus required. Also, in making a part by automotive paint oven, the part is less likely to deflect if the material (e.g., polybutylene terephthalate polymerized from macrocyclic oligoesters) has a high heat distortion temperature. In addition, higher crystallinity generally leads to higher modulus and better creep resistance. Furthermore, employing pure macrocyclic oligoesters (e.g., macrocyclic butylene oligoesters) simplifies the manufacturing and product-recovering process as there is no contamination with other diols (e.g., diols derived from diethylene glycol). Methods that lead to pure macrocyclic oligoesters are thus desired.
SUMMARY OF THE INVENTION
It has been discovered that organo-titanate catalysts of the invention are useful for preparing macrocyclic oligoesters that are substantially free from macrocyclic co-oligoesters. Further, the organo-titanate catalysts of the invention may be used to prepare macrocyclic co-oligoesters.
In one aspect, the invention is directed to a mixture of reaction products of
x
(Ti—(OR
1
)
4
)+
y
(HO—R
2
—OH)+
z
((HO)—C(R
3
)(R
4
)—W—C(R
5
)(R
6
)—(OH)).
The mixture is substantially free from di-functional diols other than HO—R
2
—OH. Each R
1
is independently a C
1
-C
10
alkyl group. R
2
is a C
2
-C
6
alkylene group. Each of R
3
, R
4
, R
5
, and R
6
is independently a hydrogen atom or a C
1
-C
4
alkyl group except that at least one on R
3
and R
4
is a C
1
-C
4
alkyl group and at least one of R
5
and R
6
is a C
1
-C
4
alkyl group. W is an oxygen atom, a sulfur atom, a nitrogen-containing group, a phosphorus-containing group, or a C
1
-C
4
alkylene group. Each of x and y is greater than 0. In addition, y is larger than z.
In another aspect, the invention is directed to a mixture of reaction products of
n
(Ti—(OR
1
)
4
)+(2
n−m
)(HO—R
2
—OH)+
m
((HO)—C(R
3
)(R
4
)—W—C(R
5
)(R
6
)—(OH)).
The mixture is substantially free from di-functional diols. Each R
1
is independently a C
1
-C
10
alkyl group. R
2
is a C
2
-C
6
alkylene group. Each of R
3
, R
4
, R
5
, and R
6
is independently a hydrogen atom or a C
1
-C
4
alkyl group except that at least one of R
3
and R
4
is a C
1
-C
4
alkyl group and at least one of R
5
and R
6
is a C
1
-C
4
alkyl group. W is an oxygen atom, a sulfur atom, a nitrogen-containing group, a phosphorus-containing group, or a C
1
-C
4
alkylene group. Each of m and n is greater than 0.
In yet another aspect, the invention is directed to a mixture of reaction products of
n
(Ti—(OR
1
)
4
)+
m
(HO—R
2
—OH).
Each R
1
is independently a C
1
-C
10
alkyl group. R
2
is a C
2
-C
6
alkylene group. Each of m and n is greater than 0. The ratio of m to n is greater than 2.
In yet another aspect, the invention is directed to a method for depolymerizing a polyester. The method includes providing one or more of above-described mixtures of reaction products; contacting, in the presence of heat, a mixture including: a polyester, an organic solvent which is substantially free of oxygen and water, and one of the above-described mixtures, to produce macrocyclic oligoesters substantially free from macrocyclic co-oligoesters.
The foregoing and other objects, aspects, features, and advantages of the invention will become more apparent from the following description and claims.
DESCRIPTION
According to the present invention, organo-titanate catalysts are prepared that are useful for catalyzi

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