Production of random or homogeneous copolymers

Claim 2

A homogeneous melt-extrudable or injection-mouldable copolymer having a reduced viscosity of at least 0.5 but not more than 3 (as measured on a solution of 0.5 g of the copolymer in 100 cm 3 of dimethyl formamide at 25° C.), consisting of 50 to 98 mole % of units of acrylonitrile, 2 to 50 mole % of units of at least one conjugated aromatic olefine which has the formula CH.sub.2 :CR.Ar wherein R is hydrogen or methyl and Ar is an aromatic residue having up to 3 rings or is coumarone or indene, and 0 to 10 mole % of units of other ethylenically unsaturated copolymerizable monomers, the molar ratio of acrylonitrile to conjugated aromatic olefine having about the same value for substantially all the copolymer molecules and the units of conjugated aromatic olefine being randomly distributed in the copolymer molecules, the copolymer being the product of a copolymerization reaction under free-radical polymerization conditions in which the conjugated aromatic olefine is fed to the reaction mixture throughout the polymerization at a rate dependent on the rate of production of heat in the formation of the copolymer.

Claim 3

A copolymer according to claim 1 which contains 80 to 90 mole % of units of acrylonitrile.

Claim 4

An injection-mouldable copolymer according to claim 1 having a reduced viscosity lying between 0.5 and 1.2 (measured on a solution of 0.5 g of the copolymer in 100 cm 3 of dimethylformamide at 25° C.) when the molar ratio of units of acrylonitrile to units of conjugated aromatic olefine is less than 4:1 and lying between 0.5 and 1.8 when the molar ratio is 4:1 or more, having a melt viscosity of at most 5.4 kilopoises when measured at 260° C. at a shear rate of 1000/second, and having an impact strength of at least 2.4 Joules/cm 3 .

Claim 5

A copolymer according to claim 1 in which the predominant units of conjugated aromatic olefine are selected from styrene and α-methylstyrene units.

Claim 6

A copolymer according to claim 1, in which styrene units are the predominant units of conjugated aromatic olefine.

Claim 7

A copolymer according to claim 1 which consists essentially of units of acrylonitrile and units of said conjugated aromatic olefine.

Claim 8

A copolymer according to claim 1 which consists essentially of units of acrylonitrile and units of styrene.

Claim 9

A copolymer according to claim 1 which contains from 1 to 10 mole % of units of other ethylenically unsaturated compounds copolymerized with the acrylonitrile and the conjugated aromatic olefine, the quantity of the units of said other compounds being less than the quantity of units of conjugated aromatic olefine.

Claim 10

A copolymer according to claim 8 in which the units of the other ethylenically unsaturated monomer are selected from units of acenaphthylene, N-vinylcarbazole and its derivatives, maleimide and its N-substituted derivatives, and norbornene and its derivatives.

Claim 11

A copolymer according to claim 9 which contains units of an N-aryl maleimide.

Claim 12

A copolymer as claimed in claim 9 which contains units of N-(o-substituted phenyl) maleimide.

Claim 13

A copolymer as claimed in claim 9 which contains units of 5-cyanonorbornene or methylenenorbornane.

Claim 14

An oriented film having an elongation at break greater than 50% and a 1% secant modulus greater than 350 kgf/mm 2 in the direction of orientation, made from a homogeneous melt-extrudable copolymer having a reduced viscosity of at least 0.5 but not more than 3 (as measured on a solution of 0.5 g of the copolymer in 100 cm 3 of dimethyl formamide at 25° C.), consisting of 50 to 98 mole % of units of acrylonitrile, 2 to 50 mole % of units of at least one conjugated aromatic olefine which has the formula CH.sub.2 : CR.Ar wherein R is hydrogen or methyl and Ar is an aromatic residue having up to 3 rings or is coumarone or indene, and 0 to 10 mole % of units of other ethylenically unsaturated copolymerizable monomers, the molar ratio of acrylonitrile to conjugated aromatic olefine having about the same value for substantially all the copolymer molecules and units of conjugated aromatic olefine being randomly distributed in the copolymer molecules, the copolymer being the product of a copolymerization reaction under free-radical polymerization conditions in which the conjugated aromatic olefine is fed to the reaction mixture throughout the polymerization at the rate at which polymerization proceeds.

Claim 15

An oriented film having an elongation at break greater than 50% and a 1% secant modulus greater than 350 kgf/mm 2 in the direction of orientation, made from a homogeneous melt-extrudable copolymer having a reduced viscosity of at least 0.5 but not more than 3 (as measured on a solution of 0.5 g of the copolymer in 100 cm 3 of dimethyl formamide at 25° C.), consisting of 50 to 98 mole % of units of acrylonitrile, 2 to 50 mole % of units of at least one conjugated aromatic olefine which has the formula CH.sub.2 : CR.Ar wherein R is hydrogen or methyl and Ar is an aromatic residue having up to 3 rings or is coumarone or indene, and 0 to 10 mole % of units of other ethylenically unsaturated copolymerizable monomers, the molar ratio of acrylonitrile to conjugated aromatic olefine having about the same value for substantially all the copolymer molecules and units of conjugated aromatic olefine being randomly distributed in the copolymer molecules, the copolymer being the product of a copolymerization reaction under free-radical polymerization conditions in which the conjugated aromatic olefine is fed to the reaction mixture throughout the polymerization at the rate at which polymerization proceeds.

Claim 16

A film according to claim 13 which is biaxially oriented.

Claim 17

A film according to claim 13 which is uniaxially oriented.

Claim 18

A film according to claim 15 which is thereafter fibrillated.

Claim 19

A film according to claim 16 in the form of twine produced by twisting the film while maintaining it under tension in the direction of orientation.

Claim 20

A film according to claim 13 when used as packaging material for wrapping foodstuffs.

Claim 21

An oriented film made from a homogeneous melt extrudable copolymer consisting of 50 to 90% molar of units of acrylonitrile, 10 to 50% molar of units of styrene and the molar ratio of acrylonitrile to styrene having about the same value for substantially all of the polymer molecules and said styrene units being randomly distributed in the polymer molecules, said copolymer being the product of copolymerizing under free radical polymerization conditions in which styrene is fed to the reaction medium throughout the polymerization at the rate at which polymerization proceeds, said copolymer having a reduced viscosity within the range 0.5 to 3 as measured on a solution of 0.5 g. of the copolymer in 100 cm 3 of dimethylformamide at 25° C., and the film having an elongation at break greater than about 50% and a 1% secant modulus greater than 350 kgf in the direction of orientation.

Claim 22

An oriented film made from a homogeneous melt extrudable copolymer consisting of 50 to 90% molar of units of acrylonitrile, 10 to 50% molar of units of styrene and the molar ratio of acrylonitrile to styrene having about the same value for substantially all of the polymer molecules and said styrene units being randomly distributed in the polymer molecules, said copolymer being the product of copolymerizing under free radical polymerization conditions in which styrene is fed to the reaction medium throughout the polymerization at the rate at which polymerization proceeds, said copolymer having a reduced viscosity within the range 0.5 to 3 as measured on a solution of 0.5 g. of the copolymer in 100 cm 3 of dimethylformamide at 25° C., and the film having an elongation at break greater than about 50% and a 1% secant modulus greater than 350 kgf in the direction of orientation.

Claim 23

An oriented film according to claim 19 in which the copolymer contains 80 to 90% molar of units of acrylonitrile.

Claim 24

An oriented film according to claim 19 in which the copolymer contains 66 to 80% molar of units of acrylonitrile.

Claim 25

An oriented film made from a homogeneous melt extrudable copolymer consisting of 50 to 90% molar of units of acrylonitrile, 10 to 50% molar of units of styrene and from 1 to 10% of units of other ethylenically unsaturated compounds copolymerized with the acrylonitrile and the styrene, the quantity of the units of said other compounds being less than the quantity of styrene units, the molar proportions of acrylonitrile, styrene and said other ethylenically unsaturated compounds having about the same value for substantially all of the polymer molecules and the units being randomly distributed in the polymer molecules, said copolymer being the product of copolymerizing under free radical polymerization conditions in which styrene is fed to the reaction medium during polymerization at the rate at which polymerization proceeds, said copolymer having a reduced viscosity within the range 0.5 to 3 as measured on a solution of 0.5 g of the copolymer in 100 cm 3 of dimethylformamide at 25° C., and the film having an elongation at break greater than about 50% and a 1% secant modulus greater than 350 kgf in the direction of orientation.

Claim 26

An oriented film made from a homogeneous melt extrudable copolymer consisting of 50 to 90% molar of units of acrylonitrile, 10 to 50% molar of units of styrene and from 1 to 10% of units of other ethylenically unsaturated compounds copolymerized with the acrylonitrile and the styrene, the quantity of the units of said other compounds being less than the quantity of styrene units, the molar proportions of acrylonitrile, styrene and said other ethylenically unsaturated compounds having about the same value for substantially all of the polymer molecules and the units being randomly distributed in the polymer molecules, said copolymer being the product of copolymerizing under free radical polymerization conditions in which styrene is fed to the reaction medium during polymerization at the rate at which polymerization proceeds, said copolymer having a reduced viscosity within the range 0.5 to 3 as measured on a solution of 0.5 g of the copolymer in 100 cm 3 of dimethylformamide at 25° C., and the film having an elongation at break greater than about 50% and a 1% secant modulus greater than 350 kgf in the direction of orientation.

Claim 27

An oriented film according to claim 22 in which the copolymer contains 80 to 90% molar of units of acrylonitrile.

Claim 28

An oriented film according to claim 22 in which the copolymer contains 66 to 80% molar of units of acrylonitrile.

Claim 29

A homogeneous melt extrudable copolymer consisting of 50 to 90% molar of units of acrylonitrile and 10 to 50% molar of units of styrene, the molar ratio of acrylonitrile to styrene having about the same value for substantially all of the polymer molecules and said styrene units being randomly distributed in the polymer molecules, said copolymer being the product of copolymerizing under free radical polymerization conditions in which styrene is fed to the reaction medium throughout the polymerization at a rate dependent on the rate of production of heat in the formation of the copolymer, said copolymer having a reduced viscosity within the range 0.5 to 3 as measured on a solution of 0.5 g. of the copolymer in 100 cm 3 of dimethylformamide at 25° C., and said polymer being capable of forming a melt extruded oriented film having an elongation at break greater than about 50% and a 1% secant modulus greater than 350 kgf in the direction of orientation.

Claim 30

A homogeneous melt extrudable copolymer consisting of 50 to 90% molar of units of acrylonitrile and 10 to 50% molar of units of styrene, the molar ratio of acrylonitrile to styrene having about the same value for substantially all of the polymer molecules and said styrene units being randomly distributed in the polymer molecules, said copolymer being the product of copolymerizing under free radical polymerization conditions in which styrene is fed to the reaction medium throughout the polymerization at a rate dependent on the rate of production of heat in the formation of the copolymer, said copolymer having a reduced viscosity within the range 0.5 to 3 as measured on a solution of 0.5 g. of the copolymer in 100 cm 3 of dimethylformamide at 25° C., and said polymer being capable of forming a melt extruded oriented film having an elongation at break greater than about 50% and a 1% secant modulus greater than 350 kgf in the direction of orientation.

Claim 31

A copolymer according to claim 25 in which the copolymer contains 80 to 90% molar of units of acrylonitrile.

Claim 32

A copolymer according to claim 25 in which the copolymer contains 66 to 80% molar of units of acrylonitrile.

Claim 33

A homogeneous melt extrudable copolymer consisting of 50 to 90% molar of units of acrylonitrile, 10 to 50% molar of units of styrene and from 1 to 10% of units of other ethylenically unsaturated compounds copolymerized with the acrylonitrile and the styrene, the quantity of the units of said other compounds being less than the quantity of styrene units, the molar proportions of acrylonitrile, styrene and said other ethylenically unsaturated compounds having about the same value for substantially all of the polymer molecules and the units being randomly distributed in the polymer molecules, said copolymer being the product of copolymerizing under free radical polymerization conditions in which styrene is fed to the reaction medium during polymerization at a rate dependent on the rate of production of heat in the formation of the copolymer, said copolymer having a reduced viscosity within the range 0.5 to 3 as measured on a solution of 0.5 g of the copolymer 100 cm 3 of dimethylformamide at 25° C., and said polymer being capable of forming a melt extruded oriented film having an elongation at break greater than about 50% and a 1% secant modulus greater than 350 kgf in the direction of orientation.

Claim 34

A homogeneous melt extrudable copolymer consisting of 50 to 90% molar of units of acrylonitrile, 10 to 50% molar of units of styrene and from 1 to 10% of units of other ethylenically unsaturated compounds copolymerized with the acrylonitrile and the styrene, the quantity of the units of said other compounds being less than the quantity of styrene units, the molar proportions of acrylonitrile, styrene and said other ethylenically unsaturated compounds having about the same value for substantially all of the polymer molecules and the units being randomly distributed in the polymer molecules, said copolymer being the product of copolymerizing under free radical polymerization conditions in which styrene is fed to the reaction medium during polymerization at a rate dependent on the rate of production of heat in the formation of the copolymer, said copolymer having a reduced viscosity within the range 0.5 to 3 as measured on a solution of 0.5 g of the copolymer 100 cm 3 of dimethylformamide at 25° C., and said polymer being capable of forming a melt extruded oriented film having an elongation at break greater than about 50% and a 1% secant modulus greater than 350 kgf in the direction of orientation.

Claim 35

A copolymer according to claim 28 in which the copolymer contains 80 to 90% molar of units of acrylonitrile.

Claim 36

A copolymer according to claim 28 in which the copolymer contains 66 to 80% molar of units of acrylonitrile.

Claim 37

A homogeneous melt extrudable copolymer consisting of 50 to 90% molar of units of acrylonitrile, 10 to 50% molar of units of styrene and the molar ratio of acrylonitrile to styrene having about the same value for substantially all of the polymer molecules and said styrene units being randomly distributed in the polymer molecules, said copolymer being the product of copolymerizing under free radical polymerization conditions in which styrene is fed to the reaction medium throughout the polymerization at the rate at which polymerization proceeds, said copolymer having a reduced viscosity within the range 0.5 to 3 as measured on a solution of 0.5 g of the copolymer in 100 cm 3 of dimethylformamide at 25° C., and said copolymer being capable of forming, by melt extrusion into a film which is then oriented, an oriented film having an elongation at break greater than about 50% and a 1% secant modulus greater than 350 kgf in the direction of orientation.

Claim 38

A homogeneous melt extrudable copolymer consisting of 50 to 90% molar of units of acrylonitrile, 10 to 50% molar of units of styrene and the molar ratio of acrylonitrile to styrene having about the same value for substantially all of the polymer molecules and said styrene units being randomly distributed in the polymer molecules, said copolymer being the product of copolymerizing under free radical polymerization conditions in which styrene is fed to the reaction medium throughout the polymerization at the rate at which polymerization proceeds, said copolymer having a reduced viscosity within the range 0.5 to 3 as measured on a solution of 0.5 g of the copolymer in 100 cm 3 of dimethylformamide at 25° C., and said copolymer being capable of forming, by melt extrusion into a film which is then oriented, an oriented film having an elongation at break greater than about 50% and a 1% secant modulus greater than 350 kgf in the direction of orientation.

Claim 39

A copolymer according to claim 31 which contains 80 to 90% molar of units of acrylonitrile.

Claim 40

A copolymer according to claim 31 which contains 66 to 80% molar of units of acrylonitrile.

Claim 41

A product as set forth in claim 31 in which there is fed to the reaction medium throughout the polymerization a monomer feed consisting essentially of styrene.

Claim 42

A product as set forth in claim 31 in which there is fed to the reaction medium throughout the polymerization a monomer feed which includes acrylonitrile in addition to styrene.

Claim 43

A homogeneous melt extrudable copolymer consisting of 50 to 90% molar of units of acrylonitrile, 10 to 50% molar of units of styrene and from 1 to 10% of units of other ethylenically unsaturated compounds copolymerized with the acrylonitrile and the styrene, the quantity of the units of said other compounds being less than the quantity of styrene units, the molar proportions of acrylonitrile, styrene and said other ethylenically unsaturated compounds having about the same value for substantially all of the polymer molecules and the units being randomly distributed in the polymer molecules, said copolymer being the product of copolymerizing under free radical polymerization conditions in which styrene is fed to the reaction medium during polymerization at the rate at which polymerization proceeds, said copolymer having a reduced viscosity within the range 0.5 to 3 as measured on a solution of 0.5 g of the copolymer in 100 cm 3 of dimethylformamide at 25° C., and said copolymer being capable of forming, by melt extrusion into a film which is then oriented, an oriented film having an elongation at break greater than about 50% and a 1% secant modulus greater than 350 kgf in the direction of orientation.

Claim 44

A homogeneous melt extrudable copolymer consisting of 50 to 90% molar of units of acrylonitrile, 10 to 50% molar of units of styrene and from 1 to 10% of units of other ethylenically unsaturated compounds copolymerized with the acrylonitrile and the styrene, the quantity of the units of said other compounds being less than the quantity of styrene units, the molar proportions of acrylonitrile, styrene and said other ethylenically unsaturated compounds having about the same value for substantially all of the polymer molecules and the units being randomly distributed in the polymer molecules, said copolymer being the product of copolymerizing under free radical polymerization conditions in which styrene is fed to the reaction medium during polymerization at the rate at which polymerization proceeds, said copolymer having a reduced viscosity within the range 0.5 to 3 as measured on a solution of 0.5 g of the copolymer in 100 cm 3 of dimethylformamide at 25° C., and said copolymer being capable of forming, by melt extrusion into a film which is then oriented, an oriented film having an elongation at break greater than about 50% and a 1% secant modulus greater than 350 kgf in the direction of orientation.

Claim 45

A copolymer according to claim 36 which contains 80 to 90% molar of units of acrylonitrile.

Claim 46

A copolymer according to claim 36 which contains 66 to 80% molar of units of acrylonitrile.

Claim 47

A product as set forth in claim 36 in which there is fed to the reaction medium during the polymerization a monomer feed consisting essentially of styrene.

Claim 48

A product as set forth in claim 36 in which there is fed to the reaction medium during the polymerization a monomer feed which includes acrylonitrile in addition to styrene.

Claim 49

A homogeneous melt extrudable copolymer having a reduced viscosity of at least 0.5 but not more than 3 (as measured on a solution of 0.5 g of the copolymer in 100 cm 3 of dimethylformamide at 25° C.), consisting of 50 to 98 mole % of units of acrylonitrile, 2 to 50 mole % of units of at least one conjugated aromatic olefin which has the formula CH.sub.2 :CR.Ar wherein R is hydrogen or methyl and Ar is an aromatic residue having up to 3 rings or is coumarone or indene, and 0 to 10 mole % of units of other ethylenically unsaturated copolymerizable monomers, the molar ratio of acrylonitrile to conjugated aromatic olefin having about the same value for substantially all the copolymer molecules and units of conjugated aromatic olefin being randomly distributed in the copolymer molecules, the copolymer being the product of a copolymerization reaction under free radical polymerization conditions in which the conjugated aromatic olefin is fed to the reaction mixture throughout the polymerization at the rate at which polymerization proceeds, said copolymer being capable of forming, by melt extrusion into a film which is then oriented, an oriented film having an elongation at break greater than 50% and a 1% secant modulus greater than 350 kgf/mm 2 in the direction of orientation.

Claim 50

A homogeneous melt extrudable copolymer having a reduced viscosity of at least 0.5 but not more than 3 (as measured on a solution of 0.5 g of the copolymer in 100 cm 3 of dimethylformamide at 25° C.), consisting of 50 to 98 mole % of units of acrylonitrile, 2 to 50 mole % of units of at least one conjugated aromatic olefin which has the formula CH.sub.2 :CR.Ar wherein R is hydrogen or methyl and Ar is an aromatic residue having up to 3 rings or is coumarone or indene, and 0 to 10 mole % of units of other ethylenically unsaturated copolymerizable monomers, the molar ratio of acrylonitrile to conjugated aromatic olefin having about the same value for substantially all the copolymer molecules and units of conjugated aromatic olefin being randomly distributed in the copolymer molecules, the copolymer being the product of a copolymerization reaction under free radical polymerization conditions in which the conjugated aromatic olefin is fed to the reaction mixture throughout the polymerization at the rate at which polymerization proceeds, said copolymer being capable of forming, by melt extrusion into a film which is then oriented, an oriented film having an elongation at break greater than 50% and a 1% secant modulus greater than 350 kgf/mm 2 in the direction of orientation.

Claim 51

A product as set forth in claim 41 in which there is fed to the reaction medium throughout the polymerization a monomer feed which consists essentially of styrene.

Claim 52

A product as set forth in claim 41 in which there is fed to the reaction medium throughout the polymerization a monomer feed which includes acrylonitrile in addition to said aromatic olefin.