US3903200A
Expired / Lapsed
US
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Continuous mass polymerization process for ABS polymeric polyblends
Assignee: Monsanto Co
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Filing: 1974-03-07
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Granted: 1975-09-02
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Expires: 1994-03-07
Abstract
Abstract This invention relates to a process for the continuous mass polymerization of a monomer formulation comprising at least principally of a monoalkenylaromatic monomer and an ethylenically unsaturated nitrile monomer having dispersed therein a first grafted diene rubber to form a first partially polymerized mixture; dispersing a second grafted rubber in said first mixture forming a second partially polymerized mixture and polymerizing said second mixture to form a third partially polymerized mixture followed by devolatilization said third mixture to form a polyblend of the polymer of said monomer and said dispersed grafted diene rubber having a bimodal particle size distribution.
Inventors
- 👤 David L Cincera
- 👤 William O Dalton
- 👤 Michael B Jastrzebski
- 👤 Charles E Wyman
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 10:11
CPC Classifications
C; C08; C08F; C08F279/00; C08F279/02; Y; Y10; Y10S; Y10S260/00; Y10S260/28
Claims Analysis
Total Claims: 30
Claim 1
Independent Claim
383 words
IN A CONTINUOUS MASS POLYMERIZATION PROCESS FOR PREPARING A POLYMERIC POLYBLEND, THE STEPS COMPRISING: A. CONTINUOUSLY MASS POLYMERIZING MONOMERS CONTAINING 0.1 TO 15% BY WEIGHT OF A SOLUBLE DIENE RUBBER SO AS TO CONVERT 10 TO 40% OF SAID MONOMERS TO A POLYMER, GRAFT AT LEAST A PORTION OF SAID POLYMER ON SAID DIENE RUBBER AND DISPERSE SAID RUBBER AS A FIRST GRAFTED DIENE RUBBERMONOMER PHASE IN A MONOMER-POLYMER PHASE, TO PROVIDE A FIRST PARTIALLY POLYMERIZED MIXTURE, SAID MONOMERS COMPRISING AT LEAST PRINCIPALLY A MONOALKENLAROMATIC MONOMER AND AN ETHYLENICALLY UNSATURATED NITRILE MONOMER, SAD FIRST GRAFTED DIENE RUBBER-MONOMER PHASE BEING DISPERSED BY SHEARING AGITATION OF SAID FIRST PARTIALLY POLYMERIZATION MIXTURE, AS RUBBER-MONOMER PARTICLES HAVING AN AVERAGE PARTICLE SIZE OF 0.7 TO 10 MICRONS AND HAVING PRESENT OCCLUDED AND GRAFTED POLYMER, B. CONTINUOUSLY WITHDRAWING SAID FIRST PARTIALLY POLYMERIZED MIXTURE FROM STEP (A), C. CONTINUOUSLY DISPERSING A SECOND GRAFTED DIENE RUBBER INTO SAID FIRST PARTIALLY POLYMERIZED MIXTURE, SAID SECOND GRAFTED RUBBER COMPRISING CROSSLINKED RUBBER PARTICLES HAVING A SWELLING INDEX OF AT LEAST 2, AN AVERAGE PARTICLE SIZE OF 0.01 TO 0.5 MICRONS AND BEING GRAFTED WITH ABOUT 0.1 TO 2.5 PARTS OF SAID MONOMERS PER 1 PART OF RUBBER FORMING A SECOND PARTIALLY POLYMERIZED MIXTURE CONTAINING 1 TO 30 WEIGHT PERCENT OF SAID FIRST AND SECOND GRAFTED DIENE RUBBERS WHEREIN THE SECOND GRAFTED RUBBER COMPRISES FROM ABOUT 50 TO 97% OF THE TOTAL WEIGHT OF SAID FIRST AND SECOND GRAFTED DIENE RUBBERS, D. CONTINUOUSLY MASS POLYMERIZING SAID SECOND PARTIALLY POLYMERIZED MIXTURE UNDER SHEARING AGITATION UNTIL THE POLYMERIZATION OF SAID MONOMER FORMULATION HAS REACHED A CONVERSION OF ABOUT 25 TO 80% TO PROVIDE A THRID PARTIALLY POLYMERIZED MIXTURE, E. CONTINUOUSLY DEVOLATILIZING SAID THRID PARTIALLY POLYMERIZED MIXTURE TO PROVIDE A POLYMERIC POLYBLEND COMPRISING ABOUT 2 TO 40% BY WEIGHT OF SAID FIRST AND SECOND GRAFTED DIENE RUBBERS WHEREIN SAID SECOND GRAFTED DIENE RUBBER COMPRISES ABOUT 50 TO 97% OF THE TOTAL WEIGHT OF SAID FIRST AND SECOND GRAFTED DIENE RUBBERS, THE REMAINDER UP TO 100%, BEING POLYMER OF SAID MONOMERS, SAID FIRST GRAFTED DIENE RUBBERS BEING DISPERSED AS RUBBER PARTICLES HAVING AN AVERAGE PARTICLE SIZE OF 0.7 TO 10 MICRONS, A SWELLING INDEX OF AT LEAST 5 AND HAVING PRESENT OCCLUDED AND GRAFTED POLYMER IN AN AMOUNT OF ABOUT 1 TO 5 PARTS PER EACH PART OF RUBBER.
Claim 2
Dependent Claim
383 words
IN A CONTINUOUS MASS POLYMERIZATION PROCESS FOR PREPARING A POLYMERIC POLYBLEND, THE STEPS COMPRISING: A. CONTINUOUSLY MASS POLYMERIZING MONOMERS CONTAINING 0.1 TO 15% BY WEIGHT OF A SOLUBLE DIENE RUBBER SO AS TO CONVERT 10 TO 40% OF SAID MONOMERS TO A POLYMER, GRAFT AT LEAST A PORTION OF SAID POLYMER ON SAID DIENE RUBBER AND DISPERSE SAID RUBBER AS A FIRST GRAFTED DIENE RUBBERMONOMER PHASE IN A MONOMER-POLYMER PHASE, TO PROVIDE A FIRST PARTIALLY POLYMERIZED MIXTURE, SAID MONOMERS COMPRISING AT LEAST PRINCIPALLY A MONOALKENLAROMATIC MONOMER AND AN ETHYLENICALLY UNSATURATED NITRILE MONOMER, SAD FIRST GRAFTED DIENE RUBBER-MONOMER PHASE BEING DISPERSED BY SHEARING AGITATION OF SAID FIRST PARTIALLY POLYMERIZATION MIXTURE, AS RUBBER-MONOMER PARTICLES HAVING AN AVERAGE PARTICLE SIZE OF 0.7 TO 10 MICRONS AND HAVING PRESENT OCCLUDED AND GRAFTED POLYMER, B. CONTINUOUSLY WITHDRAWING SAID FIRST PARTIALLY POLYMERIZED MIXTURE FROM STEP (A), C. CONTINUOUSLY DISPERSING A SECOND GRAFTED DIENE RUBBER INTO SAID FIRST PARTIALLY POLYMERIZED MIXTURE, SAID SECOND GRAFTED RUBBER COMPRISING CROSSLINKED RUBBER PARTICLES HAVING A SWELLING INDEX OF AT LEAST 2, AN AVERAGE PARTICLE SIZE OF 0.01 TO 0.5 MICRONS AND BEING GRAFTED WITH ABOUT 0.1 TO 2.5 PARTS OF SAID MONOMERS PER 1 PART OF RUBBER FORMING A SECOND PARTIALLY POLYMERIZED MIXTURE CONTAINING 1 TO 30 WEIGHT PERCENT OF SAID FIRST AND SECOND GRAFTED DIENE RUBBERS WHEREIN THE SECOND GRAFTED RUBBER COMPRISES FROM ABOUT 50 TO 97% OF THE TOTAL WEIGHT OF SAID FIRST AND SECOND GRAFTED DIENE RUBBERS, D. CONTINUOUSLY MASS POLYMERIZING SAID SECOND PARTIALLY POLYMERIZED MIXTURE UNDER SHEARING AGITATION UNTIL THE POLYMERIZATION OF SAID MONOMER FORMULATION HAS REACHED A CONVERSION OF ABOUT 25 TO 80% TO PROVIDE A THRID PARTIALLY POLYMERIZED MIXTURE, E. CONTINUOUSLY DEVOLATILIZING SAID THRID PARTIALLY POLYMERIZED MIXTURE TO PROVIDE A POLYMERIC POLYBLEND COMPRISING ABOUT 2 TO 40% BY WEIGHT OF SAID FIRST AND SECOND GRAFTED DIENE RUBBERS WHEREIN SAID SECOND GRAFTED DIENE RUBBER COMPRISES ABOUT 50 TO 97% OF THE TOTAL WEIGHT OF SAID FIRST AND SECOND GRAFTED DIENE RUBBERS, THE REMAINDER UP TO 100%, BEING POLYMER OF SAID MONOMERS, SAID FIRST GRAFTED DIENE RUBBERS BEING DISPERSED AS RUBBER PARTICLES HAVING AN AVERAGE PARTICLE SIZE OF 0.7 TO 10 MICRONS, A SWELLING INDEX OF AT LEAST 5 AND HAVING PRESENT OCCLUDED AND GRAFTED POLYMER IN AN AMOUNT OF ABOUT 1 TO 5 PARTS PER EACH PART OF RUBBER.
Claim 3
Dependent Claim
22 words
A process of claim 1, wherein said monoalkenylaromatic monomer is styrene, said ethylenically unsaturated monomer is acrylonitrile and said diene rubber polybutadiene.
Claim 4
Dependent Claim
12 words
A process of claim 1, wherein said monoalkenyl aromatic monomer is styrene.
Claim 5
Dependent Claim
13 words
A process of claim 1, wherein said ethylenically unsaturated nitrile monomer is acrylonitrile.
Claim 6
Dependent Claim
25 words
A process of claim 1, wherein the said monoalkenylaromatic monomer and said ethylenically unsaturated nitrile monomer comprise at least 75% by weight of said monomers.
Claim 7
Dependent Claim
28 words
A process of claim 1, wherein said diene rubber of the first and second grafted is butadiene, butadiene-styrene, butadiene-acrylonitrile, butadiene-styrene-acrylonitrile, chloroprene, chloroprene-butadiene, chloroprene-styrene, chloroprene-acrylonitrile, chloroprene-styrene-acrylonitrile and mixtures thereof.
Claim 8
Dependent Claim
29 words
A process of claim 1, wherein the diene rubber of said first and second grafted rubber contains at least 50% by weight of a conjugated 1,3 butadiene monomer moiety.
Claim 9
Dependent Claim
37 words
A process of claim 1, wherein said soluble diene rubber of said first grafted rubber is polybutadiene having a cis isomer content of about 30 to 98% and a Tg range of from about -50*C. to -105*C.
Claim 10
Dependent Claim
24 words
A process of claim 1, wherein said first and second grafted rubbers of step (E) have a swelling index of about 2 to 50.
Claim 11
Dependent Claim
21 words
A process of claim 1, wherein the polymer formed has an average molecular weight of from about 40,000 to 150,000 Staudinger.
Claim 12
Dependent Claim
26 words
A process of claim 1, wherein the polymerization of step (A) is conducted at temperatures of about 100* to 150*C. under superatmosphere pressure with shearing agitation.
Claim 13
Dependent Claim
35 words
A process of claim 1, wherein the polymerization of step (A) and (D) are carried out with said monomer formulation having present about 0.001 to 3.0 percent by weight of a free radical generating catalyst.
Claim 14
Dependent Claim
38 words
A process of claim 1, wherein said free radical generating catalyst is selected from the group consisting of di-tert-butyl peroxide, tert-butyl peracetate, benzoyl peroxide, lauroyl peroxide, tert-butyl perbenzoate, dicumyl peroxide, tert-butyl peroxide and isopropyl carbonate or mixtures thereof.
Claim 15
Dependent Claim
14 words
A process of claim 13, wherein said free radical generating catalyst is tert-butyl peracetate.
Claim 16
Dependent Claim
14 words
A process of claim 13, wherein said free radical generating catalyst is di-tert-butyl peroxide.
Claim 17
Dependent Claim
21 words
A process of claim 1, wherein the continuous mass polymerization of step (D) is conducted at temperatures of 130* to 180*C.
Claim 18
Dependent Claim
27 words
A process of claim 1, wherein the polymerization of step (D) is controlled thermally by evaporating and removal of said monomers under isobaric conditions and shearing agitation.
Claim 19
Dependent Claim
32 words
A process of claim 17, wherein the evaporated and removed monomers are liquified and returned to the polymerizing partially polymerized second mixture at a rate such that steady state polymerization is maintained.
Claim 20
Dependent Claim
46 words
A process of claim 17, wherein the polymerization of step (D) is conducted progressively under substantially linear flow through 2-15 polymerization stages, said stages operating under substantially constant gravimetric fillage of from about 15 to 90% of their volume of said polymerizing second partially polymerized mixture.
Claim 21
Dependent Claim
31 words
A process of claim 19, wherein the evaporated and removed monomers are liquified and returned to at least one polymerization stage at a rate such that steady state polymerization is maintained.
Claim 22
Dependent Claim
20 words
A process of claim 20, wherein the evaporated and removed monomers are liquified and returned to the first polymerization stage.
Claim 23
Dependent Claim
25 words
A process of claim 1, wherein said devolatilizing of step (E) is carried out at temperatures of about 200* to 250*C. under a subatmospheric pressure.
Claim 24
Dependent Claim
23 words
A process of claim 22, wherein said first grafted rubber is crosslinked in step (E) to a swelling Index of at least 5.
Claim 25
Dependent Claim
130 words
A process of claim 1, wherein the second grafted diene rubber dispersed in step (C) is contained in a mixture comprising on an 100% weight percent basis, from about 30-60 weight percent of said second grafted diene rubber; about 0.1 to 20 weight percent of said polymer; about 20 to 70 weight percent of said monomer and a saturated solvent and from about 0 to 40 weight percent of water, said second grafted diene rubber having a swelling index of at least 2, said first and said second grafted rubbers being present in said second partially polymerized mixture in an amount of from about 1 to 30 weight percent wherein said second grafted rubber comprises about 50 to 97% of the total weight of said first and second grafted rubbers.
Claim 26
Dependent Claim
40 words
A process of claim 1, wherein the second grafted rubber dispersed in step (C) is contained in a mixture of said monomers; said monoalkenylaromatic monomer and said ethylenically unsaturated nitrile monomer comprising at least 75% by weight of said monomers.
Claim 27
Dependent Claim
21 words
A process of claim 25, wherein said ethylenically unsaturated nitrile monomer constitutes at least about 50% by weight of said monomers.
Claim 28
Dependent Claim
29 words
A process of claim 25, wherein the second grafted rubber is contained in said monomers in an amount of from about 1 to 40 weight percent of said monomers.
Claim 29
Dependent Claim
58 words
A process of claim 1, wherein step (B) includes withdrawing said first partially polymerized mixture from step (A) and adding said monomers in an amount sufficient to adjust the weight percent of the first graft rubber to a predetermined weight percent less than that contained in the first partially polymerized mixture forming a diluted first partially polymerized mixture.
Claim 30
Dependent Claim
23 words
A process of claim 28, wherein said monomers are added in about the same proportions as contained in the first partially polymerized mixture.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1978-09-01 | 1979-03-03 | 1979-09-02 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1982-09-01 | 1983-03-03 | 1983-09-02 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1986-09-01 | 1987-03-03 | 1987-09-02 | $7700.00 | Window Closed / Lapsed |