Patent US4677003A successfully refreshed from Google Patents.
US4677003A
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US
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Microsuspension process for preparing solvent core sequential polymer dispersion
Assignee: Rohm and Haas Co
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Filing: 1985-04-30
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Granted: 1987-06-30
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Expires: 2005-04-30
Abstract
Abstract The present invention relates to a sequential polymerization process for preparing a water-insoluble dispersion of core/shell particles. In one embodiment the process may be employed to produce a particulate dispersion useful in making water-based coating compositions wherein on drying the particulate dispersion serves as an opacifying agent. In another embodiment the process may be employed to microencapsulate a hydrophobic target material, such as a biocide or herbicide.
Inventors
- 👤 George H. Redlich
- 👤 Ronald W. Novak
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-27 15:39
CPC Classifications
C; C08; C08F; C08F2/00; C08F2/12; C08F2/16; C08F2/22; C08J; C08J3/00; C08J3/12; A; A01; A01N; A01N25/00; A01N25/26; A01N25/28; C08F285/00; C08F291/00; C08F8/00; C08F8/30; C08F8/32; C08F8/44; C08J3/126; C09; C09D; C09D5/00; C09D5/02; C09D5/024; C09D5/028; C09D7/00; C09D7/40; C09D7/45; C09D7/65; C09D7/70; C08J2333/00; C08J2333/04; C08J2333/06; C08J2333/10; C08J2333/12; Y; Y10; Y10S; Y10S525/00; Y10S525/902; Y10S525/911; Y10T; Y10T428/00; Y10T428/29; Y10T428/2982; Y10T428/2984; Y10T428/2985; Y10T428/2987; Y10T428/2989; Y10T428/2991; Y10T428/2998
Claims Analysis
Total Claims: 22
Claim 1
Independent Claim
159 words
A process for preparing an aqueous dispersion of water-insoluble core/shell particles comprising (a) preparing core emulsion by emulsifying in water at high shear a mixture comprising (1) at least one hydrophobic solvent, (2) at least one hydrophilic solvent, (3) initial monomer comprising at least two polymerizable mono-alpha,beta-ethylenically unsaturated compounds wherein said initial monomer includes from about 2 to 4 percent by weight, based on total weight of said initial monomer of alpha,beta-ethylenically unsaturated carboxylic acid monomer, (4) anionic surfactant, (5) water-insoluble emulsion stabilizer, and (6) water-insoluble thermal polymerization initiator, wherein said mixture is a non-solvent for polymer prepared by polymerizing said initial monomer, (b) heating said core emulsion to suspension polymerize said initial monomer, thereby forming core particles, (c) adding at least one base selected from the group consisting of ammonia and the organic amines thereby neutralizing polymerized carboxylic acid and forming core/shell particles, and (d) adding additional monomer whereby said additional monomer is polymerized on said core/shell particles.
Claim 2
Dependent Claim
159 words
A process for preparing an aqueous dispersion of water-insoluble core/shell particles comprising (a) preparing core emulsion by emulsifying in water at high shear a mixture comprising (1) at least one hydrophobic solvent, (2) at least one hydrophilic solvent, (3) initial monomer comprising at least two polymerizable mono-alpha,beta-ethylenically unsaturated compounds wherein said initial monomer includes from about 2 to 4 percent by weight, based on total weight of said initial monomer of alpha,beta-ethylenically unsaturated carboxylic acid monomer, (4) anionic surfactant, (5) water-insoluble emulsion stabilizer, and (6) water-insoluble thermal polymerization initiator, wherein said mixture is a non-solvent for polymer prepared by polymerizing said initial monomer, (b) heating said core emulsion to suspension polymerize said initial monomer, thereby forming core particles, (c) adding at least one base selected from the group consisting of ammonia and the organic amines thereby neutralizing polymerized carboxylic acid and forming core/shell particles, and (d) adding additional monomer whereby said additional monomer is polymerized on said core/shell particles.
Claim 3
Dependent Claim
38 words
The process of claim 1 wherein said initial monomer comprises at least 80% by weight, based on the total weight of said initial monomer, of monomer selected from the group consisting of methyl methacrylate, styrene, and mixtures thereof.
Claim 4
Dependent Claim
63 words
The process of claim 1 wherein the hydrophobic solvent is selected from the group consisting of the acrylic paraffinic hydrocarbons, mixtures of the acyclic paraffinic hydrocarbons and cyclic paraffinic hydrocarbons, and mixtures of acyclic paraffinic hydrocarbons, cyclic paraffinic hydrocarbons and aromatic hydrocarbons wherein said mixtures contain less than about 10% by weight, based on the total weight of the mixture, of aromatic hydrocarbon.
Claim 5
Dependent Claim
30 words
The process of claim 1 wherein the hydrophilic solvent is selected from the group consisting of the isomers of butanol, pentanol, and hexanol, and methyl isobutyl carbinol, and mixtures thereof.
Claim 6
Dependent Claim
21 words
The process of claim 1 wherein the 50% distillation temperature of said hydrophobic solvent is from about 150°C. to 200° C.
Claim 7
Dependent Claim
41 words
The process of claim 1 wherein said initial monomer comprises up to about 10 percent by weight, based on the total weight of said initial monomer, of nonionizable monomer selected from the group consisting of ethyl acrylate, acrylonitrile and mixtures thereof.
Claim 8
Dependent Claim
55 words
The process of claim 1 wherein said water-insoluble emulsion stabilizer is selected from the group consisting of di(C 4 -C 10 )alkyl phthalates, dibutoxyethyl phthalate, n-butyl benzyl phthalate, dimethylcyclohexyl phthalate, dicyclohexylphthalate, diphenyl phthalate, dipropylene glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol di-(2-ethyl butyrate), di(2-ethylhexyl)adipate, di-isooctyl azelate, di-(2-ethyl hexyl)azelate, di-n-butyl sebacate, 1-chlorododecane, hexadecane, and mixtures thereof.
Claim 9
Dependent Claim
14 words
The process of claim 1 wherein said water-insoluble thermal polymerization initiator is lauryl peroxide.
Claim 10
Dependent Claim
16 words
The process of claim 1 wherein said initial monomer comprises at least one multi-alpha,beta-ethylenically unsaturated monomer.
Claim 11
Dependent Claim
23 words
The process of claim 9 wherein said multi-alpha,beta-ethylenically unsaturated monomer comprises no more than about 5 percent by weight of said additional monomer.
Claim 12
Dependent Claim
27 words
The process of claim 1 wherein in said initial monomer comprises at least 80% by weight, based on total weight of said initial monomer, of methyl methacrylate.
Claim 13
Dependent Claim
28 words
The process of claim 1 additionally comprising drying said aqueous dispersion to yield particles which contain single voids and cause opacity in compositions in which they are contained.
Claim 14
Dependent Claim
34 words
A composition comprising an aqueous dispersion of water insoluble core/shell particles prepared by the process of claim 1 wherein the major portion of the core consists of said hydrophobic solvent and said hydrophilic solvent.
Claim 15
Dependent Claim
31 words
The composition of claim 13 wherein said core/shell particles have a average particle size of from about 0.35 to 0.55 microns and a polydipersity index of from about 1.5 to 5.
Claim 16
Dependent Claim
42 words
A process which comprises mixing the aqueous dispersion of water-insoluble core/shell particles of claim 13 with an aqueous dispersion of particulate material selected from the group consisting of pigments, extenders, vinyl addition emulsion polymers, and mixtures thereof, to form a coating composition.
Claim 17
Dependent Claim
55 words
A process according to claim 15 which comprises the additional steps of depositing a film of said coating composition on a solid substrate to be coated and/or impregnated, and subsequently drying the composition, forming single cavities in the core of substantially each of said particles so as to contribute to the opacity of said film.
Claim 18
Dependent Claim
38 words
A composition for coating and/or impregnating a substrate comprising (1) film-forming vinyl addition polymer either dissolved or dispersed in aqueous medium and (2) an aqueous dispersion of water-insoluble core/shell polymer particles prepared by the process of claim 1.
Claim 19
Dependent Claim
141 words
A process for preparing an aqueous dispersion of water-insoluble core/shell particles comprising (a) preparing core emulsion by emulsifying in water at high shear a mixture comprising (1) at least one hydrophobic solvent, (2) at least one hydrophilic solvent, (3) initial monomer comprising at least two polymerizable mono-alpha,beta-ethylenically unsaturated compounds wherein said initial monomer includes from about 2 to 4 percent by weight, based on total weight of said initial monomer, of alpha,beta-ethylenically unsaturated carboxylic acid monomer, (4) anionic surfactant, (5) water-insoluble emulsion stabilizer, and (6) water-insoluble thermal polymerization initiator, wherein said mixture is a non-solvent for polymer prepared by polymerizing said initial monomer, (b) heating said core emulsion to suspension polymerize said initial monomer, thereby forming core particles, and (c) adding at least one base selected from the group consisting of ammonia and the organic amines thereby neutralizing polymerized carboxylic acid.
Claim 20
Dependent Claim
141 words
A process for preparing an aqueous dispersion of water-insoluble core/shell particles comprising (a) preparing core emulsion by emulsifying in water at high shear a mixture comprising (1) at least one hydrophobic solvent, (2) at least one hydrophilic solvent, (3) initial monomer comprising at least two polymerizable mono-alpha,beta-ethylenically unsaturated compounds wherein said initial monomer includes from about 2 to 4 percent by weight, based on total weight of said initial monomer, of alpha,beta-ethylenically unsaturated carboxylic acid monomer, (4) anionic surfactant, (5) water-insoluble emulsion stabilizer, and (6) water-insoluble thermal polymerization initiator, wherein said mixture is a non-solvent for polymer prepared by polymerizing said initial monomer, (b) heating said core emulsion to suspension polymerize said initial monomer, thereby forming core particles, and (c) adding at least one base selected from the group consisting of ammonia and the organic amines thereby neutralizing polymerized carboxylic acid.
Claim 21
Dependent Claim
22 words
The process of claim 18 wherein the hydrophobic solvent is a hydrophobic organic target material and wherein the organic amines are non-nucleophilic.
Claim 22
Dependent Claim
63 words
A composition adapted for coating and/or impregnating comprising an aqueous dispersion of water-insoluble emulsion vinyl addition polymer having an apparent glass transition temperature of about 5°-25° C., water-insoluble core/shell particles of claim 18 at a pigment volume concentration of at least 5%, inorganic pigment and optional extender, wherein the major portion of the core consists of said hydrophobic solvent and said hydrophilic solvent.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1990-06-29 | 1990-12-29 | 1991-06-30 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1994-06-29 | 1994-12-29 | 1995-06-30 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1998-06-29 | 1998-12-29 | 1999-06-30 | $7700.00 | Window Closed / Lapsed |