US4463137A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Process for the preparation of rubber-modified thermoplastic resins
Assignee: Standard Oil Co
•
Filing: 1982-06-04
•
Granted: 1984-07-31
•
Expires: 2002-06-04
Abstract
Abstract A process for the impact modification of a plastic with a rubber polymer to form a thermoplastic resin in a reactor extruder is provided. The process includes the steps of dissolving a rubber polymer in a solvent selected from the group consisting of ethylenically unsaturated monomers and non-polymerizable organic compounds to form a feed solution, introducing the feed solution into the feed section of a twin screw reactor extruder, introducing a separate feed stream containing a material in sufficient amount to precipitate the rubber polymer, heating the feed solution and feed stream under pressure to a temperature sufficient for polymerization to begin, polymerizing the monomers with the rubber polymer in the reactor extruder to form a thermoplastic resin and extruding the thermoplastic resin through a die. A novel ABS thermoplastic resin is also provided having a uniform distribution of rubber particles dispersed within the plastic phase of the resin, the rubber particles ranging in size of from about 0.01 to 0.25 microns. The thermoplastic portion of resin has an acrylonitrile content of more than about 26 weight percent and can have as much as 60 weight percent.
Inventors
- 👤 Christopher L. Bodolus
- 👤 William J. Miloscia
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-08 18:33
CPC Classifications
C; C08; C08F; C08F279/00; C08F279/02; B; B29; B29C; B29C48/00; B29C48/25; B29C48/36; B29C48/395; B29C48/40; C08F2/00; C08F2/04; C08F2/06; C08F291/00; C08F291/02; Y; Y02; Y02P; Y02P20/00; Y02P20/141; Y02P20/143; Y10; Y10S; Y10S525/00; Y10S525/942
Claims Analysis
Total Claims: 24
Claim 1
Independent Claim
144 words
A process for the preparation of high acrylonitrile resins in a reactor extruder comprising the sequential steps of: dissolving a rubber polymer in a solvent selected from the group consisting of ethylenically unsaturated monomers and non-polymerizable organic compounds to form a feed solution; introducing said feed solution into the feed section of a twin screw reactor extruder; introducing into said feed section a separate liquid feed stream containing a material in sufficient amount to precipitate said rubber polymer, with the proviso that acrylonitrile be provided in at least one step as said ethylenically unsaturated momomer or said material to precipitate said rubber polymer; heating said feed solution and feed stream under pressure to a temperature sufficient for polymerization to begin; polymerizing said monomers around said rubber polymer in said reactor extruder to form a thermoplastic resin; and, extruding said thermoplastic resin through a die.
Claim 2
Dependent Claim
144 words
A process for the preparation of high acrylonitrile resins in a reactor extruder comprising the sequential steps of: dissolving a rubber polymer in a solvent selected from the group consisting of ethylenically unsaturated monomers and non-polymerizable organic compounds to form a feed solution; introducing said feed solution into the feed section of a twin screw reactor extruder; introducing into said feed section a separate liquid feed stream containing a material in sufficient amount to precipitate said rubber polymer, with the proviso that acrylonitrile be provided in at least one step as said ethylenically unsaturated momomer or said material to precipitate said rubber polymer; heating said feed solution and feed stream under pressure to a temperature sufficient for polymerization to begin; polymerizing said monomers around said rubber polymer in said reactor extruder to form a thermoplastic resin; and, extruding said thermoplastic resin through a die.
Claim 3
Dependent Claim
187 words
A process for the preparation of high acrylonitrile resins in a reactor extruder comprising the sequential steps of: dissolving a rubber polymer in a solvent selected from the group consisting of ethylenically unsaturated monomers and non-polymerizable organic compounds to form a feed solution; introducing said feed solution into the feed section of a twin screw reactor extruder; introducing into said feed section a separate liquid feed stream containing a material in sufficient amount to precipitate said rubber polymer and form a dispersion thereof in the feed solution and separate feed stream, with the proviso that acrylonitrile be provided in at least one step as said ethylenically unsaturated monomer or said material to precipitate said rubber polymer; heating said feed solution, feed stream and precipitated rubber under pressure to a temperature sufficient for polymerization to begin; shearing said feed solution and feed stream to maintain said dispersion of precipitated rubber; thereafter reacting said dispersion of precipitated rubber, feed solution and feed stream until at least about 70 weight percent of said feed solution has been converted to a thermoplastic resin; and extruding said thermoplastic resin through a die.
Claim 4
Dependent Claim
187 words
A process for the preparation of high acrylonitrile resins in a reactor extruder comprising the sequential steps of: dissolving a rubber polymer in a solvent selected from the group consisting of ethylenically unsaturated monomers and non-polymerizable organic compounds to form a feed solution; introducing said feed solution into the feed section of a twin screw reactor extruder; introducing into said feed section a separate liquid feed stream containing a material in sufficient amount to precipitate said rubber polymer and form a dispersion thereof in the feed solution and separate feed stream, with the proviso that acrylonitrile be provided in at least one step as said ethylenically unsaturated monomer or said material to precipitate said rubber polymer; heating said feed solution, feed stream and precipitated rubber under pressure to a temperature sufficient for polymerization to begin; shearing said feed solution and feed stream to maintain said dispersion of precipitated rubber; thereafter reacting said dispersion of precipitated rubber, feed solution and feed stream until at least about 70 weight percent of said feed solution has been converted to a thermoplastic resin; and extruding said thermoplastic resin through a die.
Claim 5
Dependent Claim
117 words
The process of claims 1 or 2, wherein the rubber polymer is selected from the group consisting of conjugated diene homopolymers having from four to about 12 carbon atoms, copolymers thereof with monovinyl aromatic monomers having from eight to about 20 carbon atoms, olefinic nitrile monomers having the structure ##STR4## wherein R is hydrogen, a lower alkyl group having from one to four carbon atoms or a halogen, esters of olefinically unsaturated carboxylic acids having the structure ##STR5## wherein R 1 is hydrogen, an alkyl group having from 1 to 30 carbon atoms, or a halogen, and R 2 is an alkyl group having from one to six carbon atoms; atactic polypropylene; epichlorohydrin polyethers; and ethylene-propylene-diene rubber.
Claim 6
Dependent Claim
56 words
The process of claim 3, wherein said ethylenically unsaturated monomer is selected from the group consisting of olefinically unsaturated nitriles having the structure ##STR6## wherein R is hydrogen, a lower alkyl group having from one to four carbon atoms or a halogen; monovinyl aromatic compounds having from eight to about 20 carbon atoms; and mixtures thereof.
Claim 7
Dependent Claim
39 words
The process of claim 4, wherein said feed solution comprises: butadiene rubber as said rubber polymer; acrylonitrile as said olefinically unsaturated nitrile; styrene as said monovinyl aromatic compound; and wherein said material to precipitate said rubber polymer is acrylonitrile.
Claim 8
Dependent Claim
46 words
The process of claims 1 or 2, wherein said step of heating said feed solution and feed stream is conducted in said feed section at a temperature of from about 20° C. to 100° C. and under a pressure of from about 0.69 to 6.9 MPa.
Claim 9
Dependent Claim
32 words
The process of claim 1, wherein said polymerizing step is conducted at a temperature of from 50° C. to 200° C. and under a pressure of from about 0.69 to 6.9 MPa.
Claim 10
Dependent Claim
34 words
The process of claim 2, wherein said shearing and reacting steps are conducted at a temperature of from 50° C. to 200° C. and under a pressure of from about 0.69 to 6.9 MPa.
Claim 11
Dependent Claim
22 words
The process of claim 2, wherein said shearing step imparts a Shear Rate of from about 50 to 300 sec -1 .
Claim 12
Dependent Claim
22 words
The process of claim 2, wherein the time for said shearing and reacting steps ranges from about two to about 20 minutes.
Claim 13
Dependent Claim
20 words
The process of claim 1, wherein the time for said polymerizing step ranges from about two to about 20 minutes.
Claim 14
Dependent Claim
15 words
The process of claims 1 or 2, wherein said reactor extruder has twin, co-rotating screws.
Claim 15
Dependent Claim
124 words
A process for the preparation of rubber modified thermoplastic resins in a reactor extruder comprising the sequential steps of: dissolving a rubber polymer in a solvent selected from the group consisting of ethylenically unsaturated monomers and optionally a non-polymerizable organic compound to form a feed solution; introducing said feed solution into the feed section of a twin screw reactor extruder; introducing into said feed section a separate liquid feed stream containing a material in sufficient amount to precipitate said rubber polymer; heating said feed solution and feed stream under pressure to a temperature sufficient for polymerization to begin; polymerizing said ethylenically unsaturated monomers around said rubber polymer in said reactor extruder to form a thermoplastic resin; and, extruding said thermoplastic resin through a die.
Claim 16
Dependent Claim
124 words
A process for the preparation of rubber modified thermoplastic resins in a reactor extruder comprising the sequential steps of: dissolving a rubber polymer in a solvent selected from the group consisting of ethylenically unsaturated monomers and optionally a non-polymerizable organic compound to form a feed solution; introducing said feed solution into the feed section of a twin screw reactor extruder; introducing into said feed section a separate liquid feed stream containing a material in sufficient amount to precipitate said rubber polymer; heating said feed solution and feed stream under pressure to a temperature sufficient for polymerization to begin; polymerizing said ethylenically unsaturated monomers around said rubber polymer in said reactor extruder to form a thermoplastic resin; and, extruding said thermoplastic resin through a die.
Claim 17
Dependent Claim
22 words
The process of claim 13, wherein the composition of said feed solution comprises from about five to 25 weight percent rubber polymer.
Claim 18
Dependent Claim
115 words
The process of claim 13, wherein the rubber polymer is selected from the group consisting of conjugated diene homopolymers having from four to about 12 carbon atoms, copolymers thereof with monovinyl aromatic monomers having from eight to about 20 carbon atoms, olefinic nitrile monomers having the structure ##STR7## wherein R is hydrogen, a lower alkyl group having from one to four carbon atoms or a halogen, esters of olefinically unsaturated carboxylic acids having the structure ##STR8## wherein R 1 is hydrogen, an alkyl group having from 1 to 30 carbon atoms, or a halogen, and R 2 is an alkyl group having from one to six carbon atoms; atactic polypropylene; epichlorohydrin polyethers; and ethylene-propylene-diene rubber.
Claim 19
Dependent Claim
28 words
The process of claim 15, wherein said ethylenically unsaturated monomer is selected from the group consisting of monovinyl aromatic compounds having from eight to about 20 carbon atoms.
Claim 20
Dependent Claim
34 words
The process of claim 16 wherein said feed solution comprises: butadiene rubber as said rubber polymer and styrene as said monovinyl aromatic compound; and wherein said material to precipitate said rubber polymer is methanol.
Claim 21
Dependent Claim
44 words
The process of claim 13, wherein said step of heating said feed solution and feed stream is conducted in said feed section at a temperature of from about 20° C. to 100° C. and under a pressure of from about 0.69 to 6.9 MPa.
Claim 22
Dependent Claim
32 words
The process of claim 13, wherein said polymerizing step is conducted at a temperature of from 50° C. to 200° C. and under a pressure of from about 0.69 to 6.9 MPa.
Claim 23
Dependent Claim
20 words
The process of claim 13, wherein the time for said polymerizing step ranges from about two to about 20 minutes.
Claim 24
Dependent Claim
13 words
The process of claim 13, wherein said reactor extruder has twin, co-rotating screws.
References Cited (Backward Citations)
US3511895A
Cited
US3780139A
Cited
US3607983A
Cited
US3928495A
Cited
US3931356A
Cited
US4053539A
Cited
US4308354A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1987-07-31 | 1988-01-30 | 1988-07-31 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1991-07-31 | 1992-01-30 | 1992-07-31 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1995-07-31 | 1996-01-30 | 1996-07-31 | $7700.00 | Window Closed / Lapsed |