Ionene modified small polymeric beads

• US 4,046,750 A
• Filed: 09/30/1974
• Issued: 09/06/1977
• Est. Priority Date: 09/30/1974
• Status: Expired due to Term

• Current Assignee: California Institute of Technology
• Original Assignee: California Institute of Technology
• Inventors: Rembaum, Alan
• Primary Examiner(s): Kight, III, John
• Application Number:
  US05/510,786
• Time in Patent Office: 1,072 Days
• Field of Search: 260/80.73, 260/80.3 N, 260/86.1 R, 260/86.1 N, 260/86.1 E
• US Class Current: 526/310
• CPC Class Codes: A61K 9/5138 obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyvinyl pyrrolidone, poly(meth)acrylates
• CPC Class Codes: C08F 8/32 by reaction with amines

Abstract

Linear ionene polyquaternary cationic polymeric segments are bonded by means of the Menshutkin reaction (quaternization) to biocompatible, extremely small, porous particles containing halide or tertiary amine sites which are centers for attachment of the segments. The modified beads in the form of emulsions or suspensions offer a large, positively-charged surface area capable of irreversibly binding polyanions such as heparin, DNA, RNA or bile acids to remove them from solution or of reversibly binding monoanions such as penicillin, pesticides, sex attractants and the like for slow release from the suspension.

Claims

1. A composition of matter comprising:

small, synthetic, organic, polymeric spherical particles having a diameter from 100 A. to 100 microns which are the cross-linked, addition polymerization product of a mono-unsaturated, acrylic monomer substituted with ionene reactive chloro, bromo, iodo or tertiary amine sites with 0.1 to 30% by weight of a diene or triene capable of addition polymerization with the unsaturated group of the acrylic monomer and having covalently bonded to at least one of said sites linear, polyquaternary ionene segments having an average charge of at least one intrapolymeric quaternary nitrogen for an average of every twelve chain atoms such that the halogen content of the segments is from 1 meg to 30 meg per gram of particle to form a particle of the structure;

##STR9## where R¹¹ is methyl, R⁹ and R¹⁰ are divalent aliphatic, aromatic or heterocyclic groups containing at least 3 carbon atoms, or R⁹ combined with R¹¹ form a cyclic group, W is chloro, bromo, or iodo and n is an integer.

2. A composition according to claim 1 in which the particle has a diameter form 500A. to 2 microns.

3. A composition according to claim 1 in which the acrylic monomer is present in an amount of from 2-30% by weight of the particle and is selected from compounds of the formula:

##STR10## where R¹ is hydrogen or lower alkyl of 1-8 carbon atoms, R² is alkylene of 1-12 carbon atoms and Z is chloro, bromo, iodo or ##STR11## where R³ and R⁴ are alkyl of 1-3 carbon atoms.

4. A composition according to claim 3 in which the acrylic monomer is selected from dimethylaminoethylmethacrylate and 2-bromoethylmethacrylate.

5. A composition according to claim 3 in which the particle contains up to 97% by weight of at least one compatible comonomer selected from lower alkyl methacrylate, acrylic acid, methacrylic acid, styrene, vinyl toluene, acrylamide, hydroxyalkyl acrylate, or amino alkyl acrylates.

6. A composition according to claim 5 in which the comonomer is selected from compounds of the formula:

##STR12## where R⁵ is hydrogen or lower alkyl of 1-8 carbon atoms, R⁶ is alkylene of 1-12 carbon atoms and Y is OH or ##STR13## where R⁷ is hydrogen and R⁸ is hydrogen, lower alkyl of 1-8 carbon atoms or lower alkoxy of 1-8 carbon atoms

7. A composition according to claim 6 in which the comonomer is selected from hydroxyethylmethacrylate, hydroxypropylmethacrylate and 2-aminoethylmethacrylate.

8. A composition according to claim 1 in which R⁹ and R¹⁰ are alkylene from 3 to 16 carbon atoms and said segments have a molecular weight from 1,500 to 60,000.