ACRYLATE COPOLYMER MICROSPHERES

• US 3,691,140 A
• Filed: 03/09/1970
• Issued: 09/12/1972
• Est. Priority Date: 03/09/1970
• Status: Expired due to Term

• Current Assignee: Spencer Ferguson Silver, 3 M Center
• Original Assignee: Spencer Ferguson Silver, 3 M Center
• Inventors: Spencer Ferguson Silver, 3 M Center
• Primary Examiner(s): Harry Wong, Jr.
• Application Number:
  US05/017,880
• Time in Patent Office: 918 Days
• Field of Search: 260/86.1N,79.3,78.5,80.73,80.8,80.81
• US Class Current: 526/240
• CPC Class Codes: C08F 220/1804 C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
• CPC Class Codes: C08F 220/1805 C5-(meth)acrylate, e.g. pentyl (meth)acrylate
• CPC Class Codes: C08F 220/1806 C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
• CPC Class Codes: C08F 220/1808 C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
• CPC Class Codes: C08F 220/1811 C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
• CPC Class Codes: Y10S 524/903 Aerosol compositions

Abstract

Infusible, solvent-dispersible, solvent-insoluble, inherently tacky, elastomeric copolymer microspheres consist essentially of about 90 percent to about 99.5 percent by weight of at least one alkyl acrylate ester and about 10 to about 0.5 percent by weight of at least one monomer selected from the group consisting of substantially oil-insoluble, water-soluble, ionic monomers and maleic anhydride. The microspheres are prepared by aqueous suspension polymerization utilizing emulsifier in an amount greater than the critical micelle concentration in the absence of externally added protective colloids or the like.

Claims

2. The microspheres of claim 1 wherein the acrylate ester is iso-octyl acrylate and the ionic monomer is trimethylamine methacrylimide.

3. The microspheres of claim 1 wherein the acrylate monomer is iso-octyl acrylate and the ionic monomer is trimethylamine p-vinyl benzimide.

4. The microspheres of claim 1 wherein the acrylate monomer is iso-octyl acrylate and the ionic monomer is 1,1-dimethyl-1-(2,3-dihydroxypropyl)amine methacrylimide.

5. The microspheres of claim 1 wherein the acry-late monomer is iso-octyl acrylate and the ionic monomer is N,N-dimethyl-N-( Beta -methacryloxyethyl)ammonium propionate betaine.

6. The microspheres of claim 1 wherein the acrylate monomer is iso-octyl acrylate and the ionic monomer is ammonium acrylate.

7. The microspheres of claim 1 wherein the acrylate monomer is iso-octyl acrylate and the ionic monomer is 4,4,9-trimethyl-4-azonia-7-oxo-8-oxa-dec-9-ene-1-sulfonate.

8. The microspheres of claim 1 wherein the acrylate monomer is iso-octyl acrylate and the ionic monomer is sodium acrylate.

9. The microspheres of claim 1 wherein the acrylate monomer is iso-octyl acrylate and the other monomer is maleic anhydride.

10. The microspheres of claim 1 wherein the acrylate monomer is 4-methyl-2-pentyl acrylate and the ionic monomer is trimethylamine methacrylimide.

11. The microspheres of claim 1 wherein the acrylate monomer is 2-methylbutyl acrylate and the other monomer is maleic anhydride.

12. The microspheres of claim 1 containing at least two of said alkyl acrylate ester monomers.

13. The microspheres of claim 12 wherein the ionic monomer is trimethylamine methacrylimide and the acrylate monomers are iso-octyl acrylate and 4-methyl-2-pentyl acrylate.

14. The microspheres of claim 12 wherein the ionic monomer is trimethylamine methacrylimide and the acrylate monomers are iso-octyl acrylate and tert-butyl acrylate.

15. The microspheres of claim 12 wherein the ionic monomer is trimethylamine methacrylimide and the acrylate monomers are 4-methyl-2-pentyl acrylate and iso-bornyl acrylate.

16. Infusible, non-polar organic liquid dispersible, non-polar organic liquid insoluble, inherently tacky, elastomeric copolymer microspheres consisting essentially of about 98 to about 99.5 percent by weight of one or more oleophilic, water-emulsifiable alkyl acrylate esters, at least one of said esters being selected from the group consisting of iso-octyl acrylate, 4-methyl-2-pentyl acrylate, 2-methylbutyl acrylate, and sec-butyl acrylate and about 2 percent to about 0.5 percent by weight of one or more monomers selected from the group consisting of trimethylamine methacrylimide, trimethylamine p-vinyl benzimide, ammonium acrylate, sodium acrylate, N,N-dimethyl-N-( Beta -methacryloxyethyl) ammonium propionate betaine, 1,1-dimethyl-1-(2-hydroxypropyl) amine methacrylimide, 4,4,9-trimethyl-4-azonia-7-oxo-8-oxa-9-decene-1-sulphonate, 1,1-dimethyl-1(2,3-dihydroxypropyl) amine methacrylimide, and maleic anhydride, said copolymer having been prepared by aqueous suspension polymerization in the presence of an anion emulsifier at a level above said emulsifier'"'"''"'"'s critical micelle concentration.

17. The microspheres of claim 16 wherein at least one acrylate monomer is iso-octyl acrylate and the ionic monomer is ammonium acrylate.

18. The microspheres of claim 16 wherein at least one acrylate monomer is iso-octyl acrylate and the other monomer is maleic anhydride.

19. A suspension polymerization process of preparing the microspheres of claim 1 comprising the steps of:

charging to a reaction vessel, about 90 to about 99.5 percent by weight of one or more oleophilic, water-emulsifiable alkyl acrylate ester monomers, at least one of said esters being selected from the group consisting of iso-octyl acrylate, 4-methyl-2-pentyl acrylate, 2-methylbutyl acrylate, and sec-butyl acrylate, about 10 to about 0.5 percent by weight of one or more monomers selected from the group consisting of trimethylamine methacrylimide, trimethyl-amine p-vinyl benzimide, ammonium acrylate, sodium acrylate, N,N-dimethyl-N-( Beta -methacryloxyethyl) ammonium propionate betaine, 1,1-dimethyl-1-(2-hydroxypropyl) amine methacrylimide, 4,4,9-trimethyl-4-azonia-7-oxo-8-oxa-9-decene-1-sulphonate, 1,1-dimethyl-1-(2,3-dihydroxypropyl) amine methacrylimide, and maleic anhydride, not greater than 0.6 weight percent of a substantially water-insoluble, oil-soluble polymerization initiator, water, and an anionic emulsifier at a level above its critical micelle concentration, agitating the reactor charge to create an emulsion, and heating said emulsion while maintaining said agitation, whereby elastomeric, non-polar organic liquid dispersible copolymer spheres are formed from said emulsion.