Two-stage solution polymerization of high molecular weight poly(phosphoesters)
First Claim
1. A process for preparing a phosphoester polymer comprising the recurring monomeric units of formula I:
- ##STR11## wherein;
X is --O-- or --NR"--, where R" is H or alkyl;
L is a divalent organic moiety;
R'"'"' is H, alkyl, alkoxy, aryl, aryloxy, heterocyclic, or heterocycloxy; and
n is between about 25 to 2,000,said process comprising the steps of;
(a) polymerizing in the presence of a solvent p moles of a di-XH compound having formula II;
space="preserve" listing-type="equation">H--X--L--X--H II wherein X and L are as defined above, with q moles, where p≈
q, of a phosphorodihalo compound of formula III;
##STR12## wherein R'"'"' is defined as above and "halo" is Br, Cl or I, to form a polymer of formula I, wherein n is about 12 to 1000, having a first molecular weight Mw1, wherein said solvent is present in an amount greater than about 5 ml of solvent per gram of compound of formula II;
(b) removing at least about 25% of the solvent to form a more concentrated reaction mixture; and
(c) further polymerizing said concentrated reaction mixture for an additional time sufficient to produce a polymer of formula I where n is between about 25 and 2,000, said polymer having a second molecular weight Mw2, which is significantly higher than Mw1.
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Abstract
A process for making a phosphoester polymer comprising the recurring monomeric units of formula I: ##STR1## wherein: X is --O-- or --NR"--, where R" is H or alkyl;
L is a divalent organic moiety;
R'"'"' is H, alkyl, alkoxy, aryl, aryloxy, heterocyclic, or heterocycloxy; and
n is between about 25 to 2,000,
is described. The process comprises the steps of:
(a) polymerizing in the presence of a solvent p moles of a di-XH compound having formula II:
H--X--L--X--H II
wherein X and L are as defined above, with q moles, where p≈q, of a phosphorodihalo compound to form a polymer of formula I, wherein n is about 12 to 1000, having a first molecular weight Mw1, wherein the solvent is present in an amount greater than about 5 ml of solvent per gram of compound of formula II;
(b) removing at least about 25% of the solvent to form a more concentrated reaction mixture; and
(c) further polymerizing the concentrated reaction mixture for an additional time sufficient to produce a polymer of formula I wherein n is between about 25 and 2,000, the polymer having a second molecular weight Mw2, which is significantly higher than Mw1.
44 Citations
38 Claims
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1. A process for preparing a phosphoester polymer comprising the recurring monomeric units of formula I:
- ##STR11## wherein;
X is --O-- or --NR"--, where R" is H or alkyl;L is a divalent organic moiety; R'"'"' is H, alkyl, alkoxy, aryl, aryloxy, heterocyclic, or heterocycloxy; and n is between about 25 to 2,000, said process comprising the steps of; (a) polymerizing in the presence of a solvent p moles of a di-XH compound having formula II;
space="preserve" listing-type="equation">H--X--L--X--H IIwherein X and L are as defined above, with q moles, where p≈
q, of a phosphorodihalo compound of formula III;
##STR12## wherein R'"'"' is defined as above and "halo" is Br, Cl or I, to form a polymer of formula I, wherein n is about 12 to 1000, having a first molecular weight Mw1, wherein said solvent is present in an amount greater than about 5 ml of solvent per gram of compound of formula II;(b) removing at least about 25% of the solvent to form a more concentrated reaction mixture; and (c) further polymerizing said concentrated reaction mixture for an additional time sufficient to produce a polymer of formula I where n is between about 25 and 2,000, said polymer having a second molecular weight Mw2, which is significantly higher than Mw1. - View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19)
- ##STR11## wherein;
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20. A high molecular weight phosphoester polymer comprising the recurring monomeric units of formula I:
- ##STR14## wherein;
X is --O-- or --NR"--, where R" is H or alkyl;L is a divalent organic moiety; R'"'"' is H, alkyl, alkoxy, aryl, aryloxy, heterocyclic, or heterocycloxy; and n is between about 25 to 2,000, wherein said polymer is made by a process comprising the steps of; (a) polymerizing in the presence of a solvent p moles of a di-XH compound having formula II;
space="preserve" listing-type="equation">H--X--L--X--H IIwherein X and L are as defined above, with q moles, where p≈
q, of a phosphorodihalo compound of formula III;
##STR15## wherein R'"'"' is defined as above and "halo" is Br, Cl or I, to form a polymer of formula I, wherein n is about 12 to 1000, having a first molecular weight Mw1, wherein said solvent is present in an amount greater than about 5 ml of solvent per gram of compound of formula II;(b) removing at least about 25% of the solvent to form a more concentrated reaction mixture; and (c) further polymerizing said concentrated reaction mixture for an additional time sufficient to produce a polymer of formula I where n is between about 25 and 2,000, said polymer having a second molecular weight Mw2, which is significantly higher than Mw1. - View Dependent Claims (21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38)
- ##STR14## wherein;
Specification
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- Resources
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Current AssigneeEisai Incorporated (Eisai Medical Research Incorporated), Johns Hopkins University
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Original AssigneeJohns Hopkins University, Guilford Pharmaceuticals Inc. (M G I Pharma Incorporated)
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InventorsZhao, Zhong, Leong, Kam W., Mao, Hai-quan
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Primary Examiner(s)Truong, Duc
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Application NumberUS09/098,620Time in Patent Office559 DaysField of Search528/398, 528/400US Class Current528/398CPC Class CodesC08G 79/04 Phosphorus linked to oxygen...
