Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From carboxylic acid or derivative thereof
Reexamination Certificate
2000-01-24
2003-08-19
Zalukaeva, Tatyana (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From carboxylic acid or derivative thereof
C528S297000, C528S354000, C528S357000, C528S361000, C525S437000, C526S317100
Reexamination Certificate
active
06608170
ABSTRACT:
TECHNICAL FIELD
The invention is directed to a stereospecific poly(lactic acid), to a method of making syndiotactic polymers, for example, syndiotactic poly(lactic acid), and to a catalyst useful in the method.
BACKGROUND OF THE INVENTION
Lactic acid polymers are biodegradable and have potential medical, agricultural and packaging applications.
Atactic poly(lactic acid) has been prepared by polymerization of lactide racemate. It has an amorphous structure.
Isotactic poly(lactic acid) has been prepared by polymerization of (R,R)-lactide or (S,S)-lactide and is crystalline.
Notably absent from the range of available microstructures is syndiotactic poly(lactic acid).
SUMMARY OF THE INVENTION
It is an object of the invention to provide syndiotactic poly (lactic acid).
Therefore, one embodiment of the invention is directed to syndiotactic poly(lactic acid).
Another embodiment of the invention is directed to a method of preparing syndiotactic polymer by selectively opening a cyclic monomer that contains two stereocenters, e.g., of opposite stereochemistry or of the same stereochemistry, and the use of this method to produce syndiotactic poly(lactic acid). For the production of syndiotactic poly(lactic acid), the method involves polymerizing cyclic dimer of lactic acid, e.g., meso-lactide, and comprises subjecting the same oxygen acyl bond in a series of meso-lactide molecules to cleavage to form polymer containing a series of units containing stereocenters, i.e., a sequence of units containing stereocenters, wherein adjacent stereocenters are of the opposite stereochemistry. The cleavages provide lactide ring opening and a series of linear groups for attachment to one another by joining of carbonyl moiety of one to oxygen moiety of the succeeding group. The cleavages are catalyzed by chiral complexes, which function to exhibit kinetic preference for reaction at one oxygen acyl bond site per molecule to the extent of fostering formation and joining of a series of the same units with respect to relative location of enantiomorphoric site and carbonyl and oxygen moieties. The chiral complex can be a chiral metal alkoxide. In one embodiment, the metal of the metal alkoxide is aluminum, and in one embodiment the metal of the metal alkoxide is not yttriumn. A suitable catalyst is prepared by reacting chiral ligand, e.g.,
or the opposite enantiomer and aluminum alkoxide in solvent and then evaporating the solvent and alcohol byproduct.
A novel catalyst is prepared by reacting the chiral ligand (−)-2 with Al(OR)
3
where R is isopropyl, in toluene solvent, and then evaporating the toluene solvent in vacuo.
DETAILED DESCRIPTION
We turn firstly to the syndiotactic poly(lactic acid) herein.
In one embodiment it contains from 20 to 5,000 units and comprises the structure
where n ranges from 20 to 5,000 and contains enantiotopic selectivity greater than 50%, preferably greater than 85%.
In one example herein, the syndiotactic poly(lactic acid) is prepared having the structural formula
where L* is a chiral ligand, M is aluminum and R is H or straight chain or branched alkyl containing 1 to 20 carbon atoms and n ranges from 20 to 5,000; upon work-up L*M is replaced with H.
The syndiotactic poly(lactic acid) prepared in Example I hereafter has a M
n
of 12,030 and a molecular weight distribution of 1.05 and an enantiotopic selectivity of 96%.
We turn now to the method herein for preparing syndiotactic poly(lactic acid). In the method, an a chiral monomer is converted to an a chiral polymer using a chiral catalyst and involves the stereoselective ring-opening polymerization of meso-lactide.
Meso-lactide is a cyclic dimer of lactic acid and has the formula
It contains two enantiotopic O-acyl bonds denoted A and B in the structure below.
It can be synthesized in greater than 99% purity as described in Ger. Offen. DE 3,820,299 (1988) abstracted in Chem. Abstr. 110, 213592w (1989).
The ring-opening polymerization of the meso-lactide can be carried out at a temperature ranging from 0 to 120° C., preferably from 65 to 80° C., using a reaction time ranging from 1 to 80 hours, preferably from 10 to 40 hours in a non-protic solvent, e.g., toluene, using a chiral alkoxide catalyst functional for stereoselective ring-opening of the meso-lactide as an initiator. The molar ratio of catalyst to meso-lactide preferably ranges from 1:20 to 1: 5,000, very preferably from 1:50 to 1:200.
A reaction scheme for the reaction is set forth below where n ranges from 20 to 5,000, L* is a chiral ligand, M is a metal, preferably aluminum, R is H or straight chain or branched alkyl containing 1 to 20 carbon atoms, L*M —OR is a chiral initiator, k
A
is the rate constant for cleavage of bond A and k
B
is the rate constant for cleavage of bond B, and k
A
>>k
B
means that the rate constant for cleavage of bond A is much greater than the rate constant for cleavage of bond B.
The chiral initiator selects between the enantiotopic acyl-oxygen bonds and provides enantiomorphic site control by exhibiting a kinetic preference for reaction at one of the two enantiomorphic sites. L*M is typically replaced by H by reaction with alcohol. For the same reaction scheme except that k
B
>>k
A
, the same syndiotactic polymer is formed.
The catalyst is preferably a chiral metal alkoxide prepared by reacting a chiral ligand with Al(OR)
3
in solvent and then evaporating the solvent. The R in Al(OR)
3
is straight chain or branched alkyl containing 1 to 20 carbon atoms and is, for example, methyl or isopropyl. The chiral ligand is preferably
or the opposite enantiomer. The chiral ligand (−)-2 can be obtained as described in Bernardo, K. B., et al, New J. Chem. 19, 129-131 (1995). The reaction of (−)-2 with Al(OR)
3
where R is isopropyl is readily carried out without significant formation of catalytically-inactive bimetallic byproduct, for example, by reacting in non-protic solvent, e.g., toluene, at 50 to 100° C., for 12 to 60 hours using a 1:1 molar ratio of freshly distilled Al(OR)
3
to (−)-2, and then evaporating the solvent in vacuo. The structure of the chiral metal alkoxide is as yet uncharacterized.
As indicated above, this application claims the benefit of U.S. Provisional Application No. 60/127,003. The entire disclosure of U.S. Provisional Application No. 60/127,003 is incorporated herein by reference.
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Cornell Research Foundation Inc.
Zalukaeva Tatyana
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