Continuous process for the preparation of ABS type polyblends

Claim 2

A CONTINUOUS MASS POLYMERIZATION PROCESS FOR THE PREPARATION OF AN ABS TYPE POLYBLEND, THE STEPS COMPRISING: A. CONTINUOUSLY CHARGING A MONOMER COMPOSITION COMPRISING AT LEAST ONE ALKENYL NITRILE MONOMER OF THE FORMULA:

Claim 3

SAID LIQUID PHASE FILLING SAID REACTION ZONE TO AN EXTENT OF FROM ABOUT 10 TO 95 PERCENT BY VOLUME AND COMPRISING SAID MONOMER COMPOSITION,

Claim 4

SAID LIQUID PHASE FILLING SAID REACTION ZONE TO AN EXTENT OF FROM ABOUT 10 TO 95 PERCENT BY VOLUME AND COMPRISING SAID MONOMER COMPOSITION,

Claim 5

AT LEAST ABOUT 10 PERCENT OF THE HEAT OF REACTION IS REMOVED FROM SAID REACTION ZONE BY SAID VAPOR PHASE REMOVAL,

Claim 6

AT LEAST ABOUT 10 PERCENT OF THE HEAT OF REACTION IS REMOVED FROM SAID REACTION ZONE BY SAID VAPOR PHASE REMOVAL,

Claim 7

AT A RATE SUBSTANTIALLY EQUAL TO THE TOTAL RATE AT WHICH MONOMERS ARE POLYMERIZED IN SAID REACTION ZONE, AND REMOVED FROM SAID REACTION ZONE, AND

Claim 8

AT A RATE SUBSTANTIALLY EQUAL TO THE TOTAL RATE AT WHICH MONOMERS ARE POLYMERIZED IN SAID REACTION ZONE, AND REMOVED FROM SAID REACTION ZONE, AND

Claim 9

IN A RATIO OF TOTAL ALKENYL NITRILE MONOMERS TO TOTAL MONOALKENYL AROMATIC MONOMERS SUCH THAT BOTH A SUBSTANTIALLY CONSTANT SAID MONOMER COMPOSITION IS EFFECTIVELY MAINTAINED IN SAID LIQUID PHASE IN SAID REACTION ZONE AND IN SAID MATRIX COPOLYMER FORMED FROM SAID MONOMER COMPOSITION, J. THE INTERRELATIONSHIP BETWEEN SAID CHARGING, SAID LIQUID PHASE REMOVAL, AND SAID SUBSTANTIALLY CONSTANT TEMPERATURE AND CORRESPONDING SUBSTANTIALLY CONSTANT PRESSURE IN SAID REACTION ZONE BEING SUCH THAT: A. THE WEIGHT PERCENT OF SAID MATRIX COPOLYMER IN SAID LIQUID PHASE IN SAID REACTION ZONE IS MAINTAINED AT A SUBSTANTIALLY PREDETERMINED CONSTANT VALUE, B. THE RATE AT WHICH SAID MATRIX COMPLYMER IS FORMED FROM SAID MONOMER COMPOSITION IN SAID REACTION ZONE RANGES FROM ABOUT 0.05 TO 2.0 POUNDS OF SAID MATRIX COMPLYMER PRODUCED PER POUND OF SAID LIQUID PHASE PER HOUR. K. THE INTERRELATIONSHIP IN SAID REACTION ZONE BETWEEN SAID MIXING ACTION AND SAID VAPOR PHASE REMOVAL BEING SUCH THAT SAID REACTION SYSTEM IS MAINTAINED UNDER SUBSTANTIALLY ISOTHERMAL CONDITIONS, L. THE INTERRELATIONSHIP BETWEEN SAID CHARGING, SAID VAPOR PHASE REMOVAL, AND SAID REACTION ZONE BEING SUCH THAT:

Claim 10

IN A RATIO OF TOTAL ALKENYL NITRILE MONOMERS TO TOTAL MONOALKENYL AROMATIC MONOMERS SUCH THAT BOTH A SUBSTANTIALLY CONSTANT SAID MONOMER COMPOSITION IS EFFECTIVELY MAINTAINED IN SAID LIQUID PHASE IN SAID REACTION ZONE AND IN SAID MATRIX COPOLYMER FORMED FROM SAID MONOMER COMPOSITION, J. THE INTERRELATIONSHIP BETWEEN SAID CHARGING, SAID LIQUID PHASE REMOVAL, AND SAID SUBSTANTIALLY CONSTANT TEMPERATURE AND CORRESPONDING SUBSTANTIALLY CONSTANT PRESSURE IN SAID REACTION ZONE BEING SUCH THAT: A. THE WEIGHT PERCENT OF SAID MATRIX COPOLYMER IN SAID LIQUID PHASE IN SAID REACTION ZONE IS MAINTAINED AT A SUBSTANTIALLY PREDETERMINED CONSTANT VALUE, B. THE RATE AT WHICH SAID MATRIX COMPLYMER IS FORMED FROM SAID MONOMER COMPOSITION IN SAID REACTION ZONE RANGES FROM ABOUT 0.05 TO 2.0 POUNDS OF SAID MATRIX COMPLYMER PRODUCED PER POUND OF SAID LIQUID PHASE PER HOUR. K. THE INTERRELATIONSHIP IN SAID REACTION ZONE BETWEEN SAID MIXING ACTION AND SAID VAPOR PHASE REMOVAL BEING SUCH THAT SAID REACTION SYSTEM IS MAINTAINED UNDER SUBSTANTIALLY ISOTHERMAL CONDITIONS, L. THE INTERRELATIONSHIP BETWEEN SAID CHARGING, SAID VAPOR PHASE REMOVAL, AND SAID REACTION ZONE BEING SUCH THAT:

Claim 11

UP TO ABOUT 90 PERCENT OF THE HEAT OF REACTION IS ABSORBED BY SAID CHARGING, AND

Claim 12

UP TO ABOUT 90 PERCENT OF THE HEAT OF REACTION IS ABSORBED BY SAID CHARGING, AND

Claim 13

SAID VAPOR PHASE FILLING THE BALANCE UP TO 100 PERCENT BY VOLUME OF SAID REACTION ZONE, THE EXACT COMPOSITION OF SAID VAPOR PHASE BEING IN SUBSTANTIAL EQUILIBRIUM WITH THE EXACT COMPOSITION OF SAID LIQUID PHASE, C. CONTINUOUSLY SUBJECTING SAID REACTION SYSTEM IN SAID REACTION ZONE TO MIXING ACTION SUFFICIENT TO MAINTAIN A SUBSTANTIALLY UNIFORM COMPOSITION DISTRIBUTION THROUGHOUT SAID LIQUID PHASE IN SAID REACTION ZONE, D. CONTINUOUSLY MASS POLYMERIZING SAID MONOMERS AT A TEMPERATURE FROM ABOUT 100* TO 180*C. AND A PRESSURE OF FROM ABOUT 5 TO 150 PSIA FORMING A MATRIX COPOLYMER DISSOLVED IN SAID LIQUID PHASE, WHILE SIMULTANEOUSLY AND, E. CONTINUOUSLY DISPERSING UNIFORMLY A FIRST AND SECOND GRAFTED DIENE RUBBER INTO SAID LIQUID PHASE UNDER THE MIXING ACTION OF STEP (C), AND DURING THE POLYMERIZATION OF STEP (D), SAID FIRST GRAFTED DIENE RUBBER BEING DISPERSED AS RUBBER PARTICLES HAVING A WEIGHT AVERAGE PARTICLE SIZE OF ABOUT 0.7 TO 10 MICRONS, A SWELLING INDEX OF AT LEAST ABOUT 5 AND HAVING PRESENT OCCLUDED AND GRAFTED COPOLYMER IN AN AMOUNT OF FROM ABOUT 1 TO 5 PARTS PER PART OF RUBBER, SAID SECOND GRAFTED DIENE RUBBER BEING DISPERSED AS RUBBER PARTICLES HAVING A WEIGHT AVERAGE PARTICLE SIZE OF ABOUT 0.1 TO 0.5 MICRONS, A SWELLING INDEX OF AT LEAST ABOUT 2 AND BEING GRAFTED WITH ABOUT 0.1 TO 2.5 PARTS OF COPOLYMER PER PART OF RUBBER, SAID SECOND GRAFTED RUBBER COMPRISING FROM ABOUT 70 TO 97% OF THE TOTAL WEIGHT OF SAID FIRST AND SECOND GRAFTED DIENE RUBBERS DISPERSED PROVIDING A BIMODAL PARTICLE SIZE DISTRIBUTION OF SAID FIRST AND SECOND GRAFTED RUBBER PARTICLES IN SAID LIQUID PHASE, F. CONTINUOUSLY REMOVING SAID VAPOR PHASE FROM SAID REACTION ZONE AT A RATE SUFFICIENT TO MAINTAIN, IN COMBINATION WITH ANY HEAT OF REACTION BEING ABSORBEF IN SAID REACTION ZONE BY SAID CHARGING OF MONOMERS AND WITH ANY HEAT OF REACTION BEING REMOVED FROM SAID REACTION ZONE THROUGH THE PERIPHERAL BOUNDARIES THEREOF, IN SAID REACTION ZONE A SUBSTANTIALLY CONSTANT TEMPERATURE AND A CORRESPONDING SUBSTANTIALLY CONSTANT PRESSURE WITHIN THE RESPECTIVE TEMPERATURE AND PRESSURE RANGES ABOVE SPECIFIED, G. CONTINUOUSLY REMOVING SAID LIQUID PHASE FROM SAID REACTION ZONE AT A RATE SUFFICIENT TO MAINTAIN THE ABOVE SPECIFIED VOLUME OF SAID LIQUID PHASE, H. CONTINUOUSLY SEPARATING SAID MATRIX COPOLYMER AND SAID FIRST AND SECOND GRAFTED RUBBERS FROM SAID LIQUID PHASE REMOVED IN STEP (G) AS AN ABS POLYBLEND, I. SAID CHARGING ADDITIONALLY BEING CONDUCTED:

Claim 14

SAID VAPOR PHASE FILLING THE BALANCE UP TO 100 PERCENT BY VOLUME OF SAID REACTION ZONE, THE EXACT COMPOSITION OF SAID VAPOR PHASE BEING IN SUBSTANTIAL EQUILIBRIUM WITH THE EXACT COMPOSITION OF SAID LIQUID PHASE, C. CONTINUOUSLY SUBJECTING SAID REACTION SYSTEM IN SAID REACTION ZONE TO MIXING ACTION SUFFICIENT TO MAINTAIN A SUBSTANTIALLY UNIFORM COMPOSITION DISTRIBUTION THROUGHOUT SAID LIQUID PHASE IN SAID REACTION ZONE, D. CONTINUOUSLY MASS POLYMERIZING SAID MONOMERS AT A TEMPERATURE FROM ABOUT 100* TO 180*C. AND A PRESSURE OF FROM ABOUT 5 TO 150 PSIA FORMING A MATRIX COPOLYMER DISSOLVED IN SAID LIQUID PHASE, WHILE SIMULTANEOUSLY AND, E. CONTINUOUSLY DISPERSING UNIFORMLY A FIRST AND SECOND GRAFTED DIENE RUBBER INTO SAID LIQUID PHASE UNDER THE MIXING ACTION OF STEP (C), AND DURING THE POLYMERIZATION OF STEP (D), SAID FIRST GRAFTED DIENE RUBBER BEING DISPERSED AS RUBBER PARTICLES HAVING A WEIGHT AVERAGE PARTICLE SIZE OF ABOUT 0.7 TO 10 MICRONS, A SWELLING INDEX OF AT LEAST ABOUT 5 AND HAVING PRESENT OCCLUDED AND GRAFTED COPOLYMER IN AN AMOUNT OF FROM ABOUT 1 TO 5 PARTS PER PART OF RUBBER, SAID SECOND GRAFTED DIENE RUBBER BEING DISPERSED AS RUBBER PARTICLES HAVING A WEIGHT AVERAGE PARTICLE SIZE OF ABOUT 0.1 TO 0.5 MICRONS, A SWELLING INDEX OF AT LEAST ABOUT 2 AND BEING GRAFTED WITH ABOUT 0.1 TO 2.5 PARTS OF COPOLYMER PER PART OF RUBBER, SAID SECOND GRAFTED RUBBER COMPRISING FROM ABOUT 70 TO 97% OF THE TOTAL WEIGHT OF SAID FIRST AND SECOND GRAFTED DIENE RUBBERS DISPERSED PROVIDING A BIMODAL PARTICLE SIZE DISTRIBUTION OF SAID FIRST AND SECOND GRAFTED RUBBER PARTICLES IN SAID LIQUID PHASE, F. CONTINUOUSLY REMOVING SAID VAPOR PHASE FROM SAID REACTION ZONE AT A RATE SUFFICIENT TO MAINTAIN, IN COMBINATION WITH ANY HEAT OF REACTION BEING ABSORBEF IN SAID REACTION ZONE BY SAID CHARGING OF MONOMERS AND WITH ANY HEAT OF REACTION BEING REMOVED FROM SAID REACTION ZONE THROUGH THE PERIPHERAL BOUNDARIES THEREOF, IN SAID REACTION ZONE A SUBSTANTIALLY CONSTANT TEMPERATURE AND A CORRESPONDING SUBSTANTIALLY CONSTANT PRESSURE WITHIN THE RESPECTIVE TEMPERATURE AND PRESSURE RANGES ABOVE SPECIFIED, G. CONTINUOUSLY REMOVING SAID LIQUID PHASE FROM SAID REACTION ZONE AT A RATE SUFFICIENT TO MAINTAIN THE ABOVE SPECIFIED VOLUME OF SAID LIQUID PHASE, H. CONTINUOUSLY SEPARATING SAID MATRIX COPOLYMER AND SAID FIRST AND SECOND GRAFTED RUBBERS FROM SAID LIQUID PHASE REMOVED IN STEP (G) AS AN ABS POLYBLEND, I. SAID CHARGING ADDITIONALLY BEING CONDUCTED:

Claim 15

from about 15 to 75 percent of the heat of reaction is absorbed by said charging, and

Claim 16

from about 15 to 75 percent of the heat of reaction is absorbed by said charging, and

Claim 17

A process of claim 1, wherein said monoalkenyl aromatic monomer and said alkenyl nitrile monomer comprise at least about 75% by weight of said monomer composition.

Claim 18

in a ratio of total alkenyl nitrile monomers to total monoalkenyl aromatic monomers such that both a substantially constant said monomer composition is effectively maintained in said liquid phase in said reaction zone and in said matrix copolymer formed from said monomer composition, J. the interrelationship between said charging, said liquid phasE removal, and said substantially constant temperature and corresponding substantially constant pressure in said reaction zone being such that: a. the weight percentage of said matrix copolymer in said liquid phase in said reaction zone is maintained at a substantially predetermined constant value, b. the rate at which said matrix copolymer is formed from said monomer composition in said reaction zone ranges from about 0.05 to 2.0 pounds of said matrix copolymer produced per pound of said liquid phase per hour. K. the interrelationship in said reaction zone between said mixing action and said vapor phase removal being such that said reaction system is maintained under substantially isothermal conditions, L. the interrelationship between said charging, said vapor phase removal, and said reaction zone being such that:

Claim 19

in a ratio of total alkenyl nitrile monomers to total monoalkenyl aromatic monomers such that both a substantially constant said monomer composition is effectively maintained in said liquid phase in said reaction zone and in said matrix copolymer formed from said monomer composition, J. the interrelationship between said charging, said liquid phasE removal, and said substantially constant temperature and corresponding substantially constant pressure in said reaction zone being such that: a. the weight percentage of said matrix copolymer in said liquid phase in said reaction zone is maintained at a substantially predetermined constant value, b. the rate at which said matrix copolymer is formed from said monomer composition in said reaction zone ranges from about 0.05 to 2.0 pounds of said matrix copolymer produced per pound of said liquid phase per hour. K. the interrelationship in said reaction zone between said mixing action and said vapor phase removal being such that said reaction system is maintained under substantially isothermal conditions, L. the interrelationship between said charging, said vapor phase removal, and said reaction zone being such that:

Claim 20

up to about 90 percent of the heat of reaction is absorbed by said charging, and

Claim 21

up to about 90 percent of the heat of reaction is absorbed by said charging, and

Claim 22

said vapor phase filling the balance up to 100 percent by volume of said reaction zone, the exact composition of said vapor phase being in substantial equilibrium with the exact composition of said liquid phase, C. continuously subjecting said reaction system in said reaction zone to mixing action sufficient to maintain a substantially uniform composition distribution throughout said liquid phase in said reaction zone, D. continuously mass polymerizing said monomers at a temperature from about 100* to 180*C. and a pressure of from about 5 to 150 psia forming a matrix copolymer dissolved in said liquid phase, while simultaneously and, E. continuously dispersing uniformly a first and second grafted diene rubber into said liquid phase under the mixing action of step (C), and during the polymerization of step (D), said first grafted diene rubber being dispersed as rubber particles having a weight average particle size of about 0.7 to 10 microns, a swelling index of at least about 5 and having present occluded and grafted copolymer in an amount of from about 1 to 5 parts per part of rubber, said second grafted diene rubber being dispersed as rubber particles having a weight average particle size of about 0.1 to 0.5 microns, a swelling index of at least about 2 and being grafted with about 0.1 to 2.5 parts of copolymer per part of rubber, said second grafted rubber comprising from about 70 to 97% of the total weight of said first and second grafted diene rubbers dispersed providing a bimodal particle size distribution of said first and second grafted rubber particles in said liquid phase, F. continuously removing said vapor phase from said reaction zone at a rate sufficient to maintain, in combination with any heat of reaction being absorbed in said reaction zone by said charging of monomers and with any heat of reaction being removed from said reaction zone through the peripheral boundaries thereof, in said reaction zone a substantially constant temperature and a corresponding substantially constant pressure within the respective temperature and pressure ranges above specified, G. continuously removing said liquid phase from said reaction zone at a rate sufficient to maintain the above specified volume of said liquid phase, H. continuously separating said matrix copolymer and said first and second grafted rubbers from said liquid phase removed in step (G) as an ABS polyblend, I. said charging additionally being conducted:

Claim 23

said vapor phase filling the balance up to 100 percent by volume of said reaction zone, the exact composition of said vapor phase being in substantial equilibrium with the exact composition of said liquid phase, C. continuously subjecting said reaction system in said reaction zone to mixing action sufficient to maintain a substantially uniform composition distribution throughout said liquid phase in said reaction zone, D. continuously mass polymerizing said monomers at a temperature from about 100* to 180*C. and a pressure of from about 5 to 150 psia forming a matrix copolymer dissolved in said liquid phase, while simultaneously and, E. continuously dispersing uniformly a first and second grafted diene rubber into said liquid phase under the mixing action of step (C), and during the polymerization of step (D), said first grafted diene rubber being dispersed as rubber particles having a weight average particle size of about 0.7 to 10 microns, a swelling index of at least about 5 and having present occluded and grafted copolymer in an amount of from about 1 to 5 parts per part of rubber, said second grafted diene rubber being dispersed as rubber particles having a weight average particle size of about 0.1 to 0.5 microns, a swelling index of at least about 2 and being grafted with about 0.1 to 2.5 parts of copolymer per part of rubber, said second grafted rubber comprising from about 70 to 97% of the total weight of said first and second grafted diene rubbers dispersed providing a bimodal particle size distribution of said first and second grafted rubber particles in said liquid phase, F. continuously removing said vapor phase from said reaction zone at a rate sufficient to maintain, in combination with any heat of reaction being absorbed in said reaction zone by said charging of monomers and with any heat of reaction being removed from said reaction zone through the peripheral boundaries thereof, in said reaction zone a substantially constant temperature and a corresponding substantially constant pressure within the respective temperature and pressure ranges above specified, G. continuously removing said liquid phase from said reaction zone at a rate sufficient to maintain the above specified volume of said liquid phase, H. continuously separating said matrix copolymer and said first and second grafted rubbers from said liquid phase removed in step (G) as an ABS polyblend, I. said charging additionally being conducted:

Claim 24

rolling action in a generally peripherally located and generally horizontally extending region in said zone, said region extending circumferentially about the entire internal periphery of said zone, said region being continuously moving in a direction which is generally normal to the horizontal, said rolling action being produced by a similarly so moving band of pressure located adjacent to, but following behind, said region, said band of pressure exerting a force on said liquid phase in said regioN at least sufficient to cause movement of a portion of said liquid phase in said region along a roughly cross-sectionally circular path normally away from the adjacent internal periphery of said zone adjacent to said band of pressure towards the interior of said zone a distance which is generally less than the maximum distance across said zone at a given peripheral position and then back towards said internal periphery forwardly of said band of pressure before moving towards said band of pressure, there being a shear rate between said internal periphery and said zone of pressure of at least about 5 sec. 1,

Claim 25

rolling action in a generally peripherally located and generally horizontally extending region in said zone, said region extending circumferentially about the entire internal periphery of said zone, said region being continuously moving in a direction which is generally normal to the horizontal, said rolling action being produced by a similarly so moving band of pressure located adjacent to, but following behind, said region, said band of pressure exerting a force on said liquid phase in said regioN at least sufficient to cause movement of a portion of said liquid phase in said region along a roughly cross-sectionally circular path normally away from the adjacent internal periphery of said zone adjacent to said band of pressure towards the interior of said zone a distance which is generally less than the maximum distance across said zone at a given peripheral position and then back towards said internal periphery forwardly of said band of pressure before moving towards said band of pressure, there being a shear rate between said internal periphery and said zone of pressure of at least about 5 sec. 1,

Claim 26

horizontal displacement in said zone in a longitudinal circulatory manner at a cycle rate such that the actual volume of said liquid phase moved from one end region of said treating zone to the opposite end region thereof and back within one minute is equivalent to from about one-tenth to 30 times the total volume of said liquid phase in said zone, such equivalent volume and the horizontal circulation rate for such liquid phase so moved, respectively, being approximately proportional to said cyclical vertical displacement cycle rate in any given instance, while continuously maintaining substantially the total volume of said liquid phase in said zone under laminar flow conditions.

Claim 27

horizontal displacement in said zone in a longitudinal circulatory manner at a cycle rate such that the actual volume of said liquid phase moved from one end region of said treating zone to the opposite end region thereof and back within one minute is equivalent to from about one-tenth to 30 times the total volume of said liquid phase in said zone, such equivalent volume and the horizontal circulation rate for such liquid phase so moved, respectively, being approximately proportional to said cyclical vertical displacement cycle rate in any given instance, while continuously maintaining substantially the total volume of said liquid phase in said zone under laminar flow conditions.

Claim 28

A process of claim 1, wherein said monomer composition comprises from about 1 to 99% by weight of an alkenyl nitrile monomer and from about 1 to 99% by weight of a monoalkenyl aromatic monomer.

Claim 29

from about minus 10 to 10 percent of the heat of reaction is removed through the peripheral boundaries of said reaction zone through heat transfer.

Claim 30

from about minus 10 to 10 percent of the heat of reaction is removed through the peripheral boundaries of said reaction zone through heat transfer.

Claim 31

UP TO ABOUT 50 PERCENT OF HEAT OF REACTION IS REMOVED THROUGH THE PERIPHERAL BOUNDARIES OF SAID REACTION ZONE THROUGH HEAT TRANSFER.

Claim 32

UP TO ABOUT 50 PERCENT OF HEAT OF REACTION IS REMOVED THROUGH THE PERIPHERAL BOUNDARIES OF SAID REACTION ZONE THROUGH HEAT TRANSFER.

Claim 33

up to about 50 percent of the heat of reaction is removed through the peripheral boundaries of said reaction zone through heat transfer.

Claim 34

up to about 50 percent of the heat of reaction is removed through the peripheral boundaries of said reaction zone through heat transfer.

Claim 35

A process of claim 1, wherein said monoalkenyl aromatic monomer is styrene.

Claim 36

A process of claim 1, wherein said alkenyl aromatic monomer is acrylonitrile.

Claim 37

A process of claim 1, wherein said monoalkenyl aromatic monomer is styrene, and said alkenyl nitrile monomer is acrylonitrile.

Claim 38

A process of claim 1, wherein said monoalkenyl aromatic monomer is alpha-methylstyrene.

Claim 39

A process of claim 1, wherein said alkenyl nitrile monomer is methacrylonitrile.

Claim 40

The process of claim 1, wherein said vapor phase so removed is condensed and returned to said reaction zone as a portion of monomers so charged thereto.

Claim 41

The process of claim 1, wherein the weight percentage of said matrix copolymer formed in said liquid phase is at least about 35.

Claim 42

The process of claim 1, wherein the weight percentage of said matrix copolymer in said liquid phase ranges from about 35 to 80.

Claim 43

The process of claim 1, wherein the rate of conversion of monomers to matrix copolymer ranges from about 0.1 to 1.0 pounds of matrix copolymer produced per pound of said liquid phase per hour.

Claim 44

The process of claim 1, wherein the viscosity of said liquid phase ranges from about 50,000 to 250,000 centipoises at said constant temperature and at 10 sec. 1 shear rate.

Claim 45

The process of claim 1, wherein additionally from about 0.01 to 2 weight percent of a chain transfer agent, based on total monomer composition charged, is continuously charged to said reaction zone.

Claim 46

The process of claim 14, wherein said chain transfer agent is terpinolene.

Claim 47

The process of claim 1, wherein additionally from about 0.01 to 15 weight percent based on total monomer composition charged of a solvent liquid is charged to said reaction zone at a rate sufficient to keep the quantity of said solvent liquid in said reaction zone at a substantially constant value.

Claim 48

The process of claim 16, wherein said solvent liquid is ethyl benzene and the copolymer product contains less than about 50 weight percent alkenyl nitrile compound.

Claim 49

The process of claim 16, wherein said solvent lqiuid is methyl ethyl ketone and the matrix copolymer product contains less than about 50 weight percent monoalkenyl aromatic compound.

Claim 50

The process of claim 1, wherein the Relationship between said charging, said vapor phase removal and said reaction zone being such that:

Claim 51

The process of claim 19, wherein the relationship between said charging and said vapor phase removal is such that about one-third of the heat of reaction is removed by said vapor phase removal and about the remaining two-thirds of said heat of reaction is removed by said charging.

Claim 52

The process of claim 1, wherein additionally from about 0.005 to 1 weight percent of a polymerization initiator, baased on total monomer composition charged, is continuously charged to said reaction zone.

Claim 53

The process of claim 21, wherein said initiator is detertiary butyl peroxide.

Claim 54

The process of claim 1, wherein the ABS polyblend produced comprises a matrix copolymer of styrene and acrylonitrile monomers and a first and second grafted diene rubber grafted with styrene and acrylonitrile.

Claim 55

The process of claim 23, wherein said matrix copolymer comprises from about 5 to 85 weight percent acrylonitrile and from about 15 to 95 weight percent styrene.

Claim 56

The process of claim 1, wherein the ABS polyblend produced comprises a matrix copolymer of styrene and methacrylonitrile monomers and first and second grafted diene rubber grafted with styrene and methacrylonitrile.

Claim 57

The process of claim 25, wherein said matrix copolymer comprises on a 100 weight percent basis from about 60 to 95 weight percent methacrylonitrile, and, correspondingly, from about 5 to 40 weight percent styrene.

Claim 58

The process of claim 1, wherein the matrix copolymer produced comprises a copolymer of from about 5 to 40 weight percent styrene, from about 40 to 70 weight percent acrylonitrile, and from about 5 to 30 weight percent methacrylonitrile on a 100 total weight percent basis.

Claim 59

The process of claim 1, wherein the ABS polyblend produced is separated from said liquid phase using at least one stage of wiped film devolatilization in step (H).

Claim 60

The process of claim 1, wherein said mixing action is produced by subjecting said liquid phase in said reaction zone simultaneously to a combination of:

Claim 61

A process of claim 1, wherein said first grafted diene rubber is dispersed in said liquid phase as crosslinked 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 copolymer in an amount of about 1 to 5 parts per each part of rubber, said second grafted diene rubber being dispersed as crosslinked rubber particles having an average particle size of 0.01 to 0.5 microns, a swelling index of at least 2 and being grafted with about 0.1 to 2.5 parts of said copolymer per 1 part of rubber, said first and second grafted rubbers being dispersed in said liquid phase in an amount of from about 1 to 40 weight percent based on said liquid phase wherein said second grafted rubber comprises about 50 to 97% of the total weight of said first and second grafted rubbers.

Claim 62

A process of claim 1, wherein said diene rubber of said first and second grafted diene rubber is butadiene, butadiene-styrene, butadiene-acrylonitrile, butadiene-styrene-acrylonitrile, chloroprene, chloroprene-butadiene, chloroprene-styrene, chloroprene-acrylonitrile, chloroprene-styrene-acrylonitrile and mixtures thereof.

Claim 63

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 64

A process of claim 1, wherein said 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 65

A process of claim 1, wherein the first grafted diene rubber dispersed in step (E) is contained in a dispersion comprising said monomer composition having dispersed therein from about 0.1 to 15% by weight of said first grafted rubber.

Claim 66

A process of claim 1, wherein the second grafted diene rubber dispersed in step (E) is contained in a dispersion comprising said monomer composition having dispersed therein from about 1 to 40% by weight of said second grafted rubber.

Claim 67

A process of claim 1, wherein the first grafted rubber has occluded and grafted copolymers of substantially the same monomer composition as the matrix copolymer of the ABS polyblend and the second grafted rubber has grafted copolymer of substantially the same monomer composition as the matrix copolymer of the ABS polyblend.

Claim 68

A process of claim 1, wherein the second grafted diene rubber dispersed in step (E) is contained in a monomersolvent 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 a copolymer of said monomers, about 20 to 70 weight percent of said monomers and a saturated solvent and from about 0 to 40 weight percent of water.

Claim 69

A process of claim 1, wherein separation step (H) produces an ABS polyblend comprising about 2 to 80% by weight of said first and second grafted diene rubber wherein said second grafted diene rubber comprises about 70 to 97% of the total weight of said first and second grafted diene rubbers, the remainder up to 100% by weight comprising matrix copolymers of said monomers, said first and second grafted diene rubbers being dispersed in said ABS polyblend as rubber particles having a bimodal particle size distribution wherein said first grafted diene rubber particles being crosslinked, having an average particle size of about 0.7 to 10 microns, a swelling index of at least about 5 and having present occluded and grafted copolymer in an amount of about 1 to 5 parts per each part of rubber, said second diene rubber particles being crosslinked, having an average particle size of about 0.1 to 0.5 microns, a swelling index of at least 2 and being grafted with about 0.1 to 2.5 parts of copolymer per each part of rubber.