CA2002460A1 - Polymeric polyblend composition - Google Patents
Polymeric polyblend compositionInfo
- Publication number
- CA2002460A1 CA2002460A1 CA002002460A CA2002460A CA2002460A1 CA 2002460 A1 CA2002460 A1 CA 2002460A1 CA 002002460 A CA002002460 A CA 002002460A CA 2002460 A CA2002460 A CA 2002460A CA 2002460 A1 CA2002460 A1 CA 2002460A1
- Authority
- CA
- Canada
- Prior art keywords
- weight percent
- weight
- mixture
- comonomer
- polyblend
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/08—Homopolymers or copolymers of vinylidene chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
ABSTRACT
A method of forming a polymeric polyblend the steps of the method comprising blending a vinylidene chloride interpolymer and a graft copolymer. The graft copolymer is formed from a polymerizable mixture com-prising a comonomer mixture and a preformed polymer which is capable of imbibing the comonomer mixture. The preformed polymer is allowed to contact the comonomer mixture for a length of time and at a temperature such that a selected amount of the comonomer mixture is imbibed therein, and then the polymerizable mixture is polymerized.
A method of forming a polymeric polyblend the steps of the method comprising blending a vinylidene chloride interpolymer and a graft copolymer. The graft copolymer is formed from a polymerizable mixture com-prising a comonomer mixture and a preformed polymer which is capable of imbibing the comonomer mixture. The preformed polymer is allowed to contact the comonomer mixture for a length of time and at a temperature such that a selected amount of the comonomer mixture is imbibed therein, and then the polymerizable mixture is polymerized.
Description
POLYMERIC POLYBLEND COMPOSITION
...
. `~ ' '.
The present invention relates generally to a polyblend of at least two polymers. More particularly, the present invention relates to a processable polyblend ;
of a vinylidene chloride interpolymer and a graft copolymer.
Vinylidene chloride polymers are well-known for their excellent barrier to mass transport of atmos-pheric gases and moisture vapor, as well as good solventresistance. These interpolymers have limited areas of application, however, because of poor melt processing characteristics. In particular, vinylidene chloride interpolymers in a melt plasticized state have poor heat stability and low melt strength. These same ` interpolymers, when fabricated, tend to be brittle and to have low impact strength.
Similarly, olefin polymers are well-known Por their excellent physical properties. Specifically, olefin polymers are easy to mold, inexpensive and have excellent impact toughness. Olefin polymers provide a relatively low degree of barrier to mass transport of 36,368-F
:' 2~
atmospheric gases and water vapor when compared to vinylidene chloride interpolymers.
. . ~
In the past, the problems associated with the poor melt processing characteristics and impact strength of vinylidene chloride interpolymers has been partly ~ ;
avoided by blending said vinylidene chloride ;~
interpolymers with other polymeric resins (e.g., poly~
olefins). The other polymeric resins possess better ~;
melt processing characteristics and impact strength than the vinylidene chloride interpolymers.
:,. ;:, Unfortunately, a blend of the two resins is -;~
friable due to the lack of adhesion between the respec~
tive interfaces. The process of forming physical blends of vinylidene chloride interpolymers with other polymeric resins has proven unsatisfactory in that such `~
blends generally require the presence of a compatibil- ~ -izing agent. While such polyblends represent one 20 possible solution to the poor melt processing char- ~-acteristics and impact strength of vinylidene chloride interpolymers, it is desirable to avoid the problems associated with the use of vinylidene chloride inter- `~
polymers without necessitating the use of compatibil-izing polymers.
It is desirable to produce a polymeric poly-blend possessing the desirable properties of both a vinylidene chloride interpolymer and an olefin polymer, without having to employ a compatibilizer. It is to this goal that the present invention is directed.
The present invention is a polymeric polyblend comprising~
36,368-F -2-(A) a vinylidene chloride interpolymer formed ~`
from an ir~terpolymer mixture which comprises a - vinylidene chloride monomer in an amount of from 60 to 99 weight percent and at least one ethylenically unsaturated comonomer copolymerizable with the ~
vinylidene chloride monomer in an amount of from 40 ~ -to 1 weight percent, said weight percents being based on the total weight of interpolymer monomer mixture; and ~B) from 3 to 60 weight percent, based on the weight of the polyblend, of a graft copolymer formed from a polymerizable mixture comprising: (1) from 95 to 15 weight percent of a comonomer mixture, and (2) from 5 to 85 weight percent of a preformed polymer which is capable of imbibing the comonomer mixture and of having the comonomer mixture graft thereto, said weight percents being based upon the ~ ;
total polymerizable mixture weight;
whereby upon polymerization, the graft copolymer has at least 5 weight percent of the comonomer mixture grafted thereto.
The present invention concerns a polymeric -~
polyblend. Applicant has discovered that the problems associated with vinylidene chloride interpolymers can be ,~
overcome by blending said vinylidene chloride interpolymers with a graft copolymer formed by polymerizing a monomer mixture comprising a vinylidene chloride monomer and another ethylenically unsaturated comonomer in the presence of a preformed polymer. The polymeric polyblend has better melt processing char~
36,368-F -3-,;,.",: ., . . `,,, .~ ,, . ' ' ' '. ' . , ';'. ' ;' '`;' acteristics and better impact strength than vinylidene chloride interpolymers alone.
, ~ .
For the purposes of this invention, it is understood that the term "vinylidene chloride inter-polymer" encompasses both homopolymers, copolymers9 ~ -~
terpolymers, etc. of vinylidene chloride. The vinylidene chloride monomer may be copolymerized with at least one monoethylenically unsaturated monomer.
'~
In preparing the monomer mixture, such mixture ~
contains essentially all of the monomer to be polymer- -~ -ized. Vinylidene chloride monomer is present in an amount of at least about 60 weight percent, based on 15 total weight of the monomer mixture. The preferred -~
ranges, as is known to the skilled artisan, are dependent upon the presence and type of ethylenically unsaturated comonomer copolymerized therewith.
Generally, the ethylenically unsaturated comonomer will ` -~
be present in an amount of between about 40 weight percent and 1 weight percent, based on total weight of `
the monomer mixture.
` :, `'.~`~
The amount of ethylenically unsaturated comonomer is maintained below an amount effective to ~
destroy the semicrystalline character of the interpoly- `
mer. By "semicrystalline charaoter" it is meant that the interpolymer has between 5 percent and 95 percent crystallinity. Crystallinity values depend upon the measuring technique, and as used herein crystallinity is defined by the commonly used density method. See, for example, the discussion by R. A. Wessling, in Chapter 6 , of Polyvinylidene Chloride, Vol. 5, Gordon and Breach `~ ' 36,368-F _4~
,,-,......
: ., :. '::
,.' ~::~,.. .
: -5-Science Publishers, New York, 1977, the teachings of which are incorporated herein by reference.
Suitable ethylenically unsaturated comonomers copolymerizable with the vinylidene chloride monomer include vinyl chloride, alkyl acrylates, alkyl meth-acrylates, acrylic acid, methacrylic acid, itaconic acid, acrylonitrile and methacrylonitrile. The alkyl acrylates and alkyl methacrylates are generally selected to have from 1 to 8 carbon atoms per alkyl group.
Preferably, alkyl acrylates and alkyl methacrylates are selected to have from 1 to 4 carbon atoms per alkyl group. The alkyl acrylates and alkyl methacrylates are most preferably selected from the group consisting of vinyl chloride, methyl acrylate, ethyl acrylate and methylmethacrylate.
When the ethylenically unsaturated comonomer employed is vinyl chloride, the vinyl chloride is pref- ;
20 erably present in an amount of from 30 to 5 percent by -weight Qf interpolymer and the amount of vinylidene chloride is from 70 to 95 percent by weight of ~ ~`
interpolymer. ~ ;
`~
When the ethylenically unsaturated comonomer `
employed is an alkyl acrylate, the alkyl acrylate is preferably present in an amount of from 15 to 2 percent by weight of interpolymer and the amount of vinylidene 30 chloride is from 85 to 98 percent by weight of ~ -interpolymer.
~:
Methods of forming the vinylidene chloride interpolymers suitable for use in the present invention are well-known in the prior art. The vinylidene chlo-36,368-F -5-~:
ride interpolymer is generally formed through an emul-sion or suspension polymerization process. Exemplary of such processes are U.S. Patents 2,558.728; 3.007,903;
...
. `~ ' '.
The present invention relates generally to a polyblend of at least two polymers. More particularly, the present invention relates to a processable polyblend ;
of a vinylidene chloride interpolymer and a graft copolymer.
Vinylidene chloride polymers are well-known for their excellent barrier to mass transport of atmos-pheric gases and moisture vapor, as well as good solventresistance. These interpolymers have limited areas of application, however, because of poor melt processing characteristics. In particular, vinylidene chloride interpolymers in a melt plasticized state have poor heat stability and low melt strength. These same ` interpolymers, when fabricated, tend to be brittle and to have low impact strength.
Similarly, olefin polymers are well-known Por their excellent physical properties. Specifically, olefin polymers are easy to mold, inexpensive and have excellent impact toughness. Olefin polymers provide a relatively low degree of barrier to mass transport of 36,368-F
:' 2~
atmospheric gases and water vapor when compared to vinylidene chloride interpolymers.
. . ~
In the past, the problems associated with the poor melt processing characteristics and impact strength of vinylidene chloride interpolymers has been partly ~ ;
avoided by blending said vinylidene chloride ;~
interpolymers with other polymeric resins (e.g., poly~
olefins). The other polymeric resins possess better ~;
melt processing characteristics and impact strength than the vinylidene chloride interpolymers.
:,. ;:, Unfortunately, a blend of the two resins is -;~
friable due to the lack of adhesion between the respec~
tive interfaces. The process of forming physical blends of vinylidene chloride interpolymers with other polymeric resins has proven unsatisfactory in that such `~
blends generally require the presence of a compatibil- ~ -izing agent. While such polyblends represent one 20 possible solution to the poor melt processing char- ~-acteristics and impact strength of vinylidene chloride interpolymers, it is desirable to avoid the problems associated with the use of vinylidene chloride inter- `~
polymers without necessitating the use of compatibil-izing polymers.
It is desirable to produce a polymeric poly-blend possessing the desirable properties of both a vinylidene chloride interpolymer and an olefin polymer, without having to employ a compatibilizer. It is to this goal that the present invention is directed.
The present invention is a polymeric polyblend comprising~
36,368-F -2-(A) a vinylidene chloride interpolymer formed ~`
from an ir~terpolymer mixture which comprises a - vinylidene chloride monomer in an amount of from 60 to 99 weight percent and at least one ethylenically unsaturated comonomer copolymerizable with the ~
vinylidene chloride monomer in an amount of from 40 ~ -to 1 weight percent, said weight percents being based on the total weight of interpolymer monomer mixture; and ~B) from 3 to 60 weight percent, based on the weight of the polyblend, of a graft copolymer formed from a polymerizable mixture comprising: (1) from 95 to 15 weight percent of a comonomer mixture, and (2) from 5 to 85 weight percent of a preformed polymer which is capable of imbibing the comonomer mixture and of having the comonomer mixture graft thereto, said weight percents being based upon the ~ ;
total polymerizable mixture weight;
whereby upon polymerization, the graft copolymer has at least 5 weight percent of the comonomer mixture grafted thereto.
The present invention concerns a polymeric -~
polyblend. Applicant has discovered that the problems associated with vinylidene chloride interpolymers can be ,~
overcome by blending said vinylidene chloride interpolymers with a graft copolymer formed by polymerizing a monomer mixture comprising a vinylidene chloride monomer and another ethylenically unsaturated comonomer in the presence of a preformed polymer. The polymeric polyblend has better melt processing char~
36,368-F -3-,;,.",: ., . . `,,, .~ ,, . ' ' ' '. ' . , ';'. ' ;' '`;' acteristics and better impact strength than vinylidene chloride interpolymers alone.
, ~ .
For the purposes of this invention, it is understood that the term "vinylidene chloride inter-polymer" encompasses both homopolymers, copolymers9 ~ -~
terpolymers, etc. of vinylidene chloride. The vinylidene chloride monomer may be copolymerized with at least one monoethylenically unsaturated monomer.
'~
In preparing the monomer mixture, such mixture ~
contains essentially all of the monomer to be polymer- -~ -ized. Vinylidene chloride monomer is present in an amount of at least about 60 weight percent, based on 15 total weight of the monomer mixture. The preferred -~
ranges, as is known to the skilled artisan, are dependent upon the presence and type of ethylenically unsaturated comonomer copolymerized therewith.
Generally, the ethylenically unsaturated comonomer will ` -~
be present in an amount of between about 40 weight percent and 1 weight percent, based on total weight of `
the monomer mixture.
` :, `'.~`~
The amount of ethylenically unsaturated comonomer is maintained below an amount effective to ~
destroy the semicrystalline character of the interpoly- `
mer. By "semicrystalline charaoter" it is meant that the interpolymer has between 5 percent and 95 percent crystallinity. Crystallinity values depend upon the measuring technique, and as used herein crystallinity is defined by the commonly used density method. See, for example, the discussion by R. A. Wessling, in Chapter 6 , of Polyvinylidene Chloride, Vol. 5, Gordon and Breach `~ ' 36,368-F _4~
,,-,......
: ., :. '::
,.' ~::~,.. .
: -5-Science Publishers, New York, 1977, the teachings of which are incorporated herein by reference.
Suitable ethylenically unsaturated comonomers copolymerizable with the vinylidene chloride monomer include vinyl chloride, alkyl acrylates, alkyl meth-acrylates, acrylic acid, methacrylic acid, itaconic acid, acrylonitrile and methacrylonitrile. The alkyl acrylates and alkyl methacrylates are generally selected to have from 1 to 8 carbon atoms per alkyl group.
Preferably, alkyl acrylates and alkyl methacrylates are selected to have from 1 to 4 carbon atoms per alkyl group. The alkyl acrylates and alkyl methacrylates are most preferably selected from the group consisting of vinyl chloride, methyl acrylate, ethyl acrylate and methylmethacrylate.
When the ethylenically unsaturated comonomer employed is vinyl chloride, the vinyl chloride is pref- ;
20 erably present in an amount of from 30 to 5 percent by -weight Qf interpolymer and the amount of vinylidene chloride is from 70 to 95 percent by weight of ~ ~`
interpolymer. ~ ;
`~
When the ethylenically unsaturated comonomer `
employed is an alkyl acrylate, the alkyl acrylate is preferably present in an amount of from 15 to 2 percent by weight of interpolymer and the amount of vinylidene 30 chloride is from 85 to 98 percent by weight of ~ -interpolymer.
~:
Methods of forming the vinylidene chloride interpolymers suitable for use in the present invention are well-known in the prior art. The vinylidene chlo-36,368-F -5-~:
ride interpolymer is generally formed through an emul-sion or suspension polymerization process. Exemplary of such processes are U.S. Patents 2,558.728; 3.007,903;
3,642,743; and 3,879,359; and the methods described by R. A. Wessling, in Pol~vinylidene Chloride, Gordon and ~-Breach Science Publishers, New York, 1977, Chapter 3; -all of which are incorporated herein by reference. ;
Typically, the monomeric materials are emulsified or suspended in an aqueous phase. The aqueous phase 10 contains a polymerization initiator and a surface active ;-agent capable of emulsifying or suspending the monomeric materials in the aqueous phase. The polymerization of the monomeric materials is usually carried out with heating and agitation.
After polymerization is complete, the resulting ~-suspension or emulsion of vinylidene chloride inter~
polymer has a majority of an aqueous phase. Thereafter, the slurry is cooled down, fed to a dewatering process to remove the water and dried.
To improve the impact resistance of the vinyl-idene chloride interpolymer, it is blended with a graft -copolymer. The vinylidene chloride interpolymer is present in the polymeric polyblend in an amount ranging~;3~ ;
from a minimum weight percent of about 40, preferably about 60, and most preferably about 70; and a maximum weight percent of about 97, preferably about 92, and ` --30 most preferably about 86, based on total weight of the -~
polymeric polyblend.
The graft copolymer is present in the polymeric polyblend in an amount ranging from a minimum weight - ;~
percent of about 3, preferably about 8, and most ~ :.-:
" ~,. ....
36,368-F -6- ~
''~
preferably about 14; and a maximum weight percent of -about 60, preferably about 40, and most preferably about 30, based on total weight of the polymeric polyblend.
The graft copolymer is prepared from a polym- --erizable mixture comprising two components. The first component is a monomer mixture, the second component is a preformed polymer.
,:
The monomer mixture is present in an amount of from 15 to 95 weight percent of the polymerizable mixture and the preformed polymer is present in an amount of from 85 to 5 weight percent, said weight percents being based upon the total weight of the polymerizable mixture. Preferably, the monomer mixture is present in an amount of from 30 to 90 weight percent of the polymerizable mixture and the preformed polymer is present in an amount of from 70 to 10 weight percent, said weight percents being based upon the total weight of the polymerizable mixture. Most preferably, the monomer mixture is present in an amount of from 60 to 75 weight percent of the polymerizable mixture and the preformed polymer is present in an amount of from about 40 to 25 weight percent, said weight percents based upon the total weight of the polymerizable mixture.
;
In preparing the monomer mixture, such mixture -`
comprises essentially all of the monomer to be polymer- ~ -ilzed. The monomer mixture comprises vinylidene chloride in an amount of from 60 to 99 weight percent, preferably from 65 to 96 weight percent, and most preferably from 70 to 94 weight percent, based on the total monomer mixture weight; and an ethylenically unsaturated comonomer or monomers copolymerizable with the 36,368-F _7_ :
vinylidene chloride monomer in an amount of from 40 to l `
weight percent, preferably from 35 to 4 weight percent, `
- and most preferably from 30 to 6 weight percent. based ~- `
on the total monomer mixture weight.
Suitable ethylenically unsaturated comonomers ~ ;
copolymerizable with the vinylidene chloride monomer ` ~;
include vinyl chloride, alkyl acrylates, alkyl meth~
acrylates, acrylic acid, methacrylic acid, itaconic `"
acid, acrylonitrile and methacrylonitrile. Desirable ethylenically unsaturated monomers copolymerizable with the vinylidene chloride monomer are selected from the `;
group consisting of vinyl chloride, alkyl acrylate, and alkyl methacrylates, the alkyl acrylates and alkyl meth-~`
acrylates having from 1 to 8 carbon atoms per alkyl group. Preferably, the ethylenically unsaturated monomer copolymerizable with the vinylidene chloride ~
monomer is selected from the group consisting of vinyl ~-chloride, methyl acrylate, ethyl acrylate and 20 methylmethacrylate. ;
,, ;~. .,.;
The preformed polymer is selected to be swellable in the monomer mixture and to be capable of `
25 having a sufficient amount of the monomers graft theretoi;
such that, upon polymerization, the preformed graft ;
copolymer provides improved impact strength to the polymeric polyblend. By "swellable" is meant that the -preformed polymer is capable of imbibing the monomer mixture without dissolving therein. By "improved impact strength" is meant that the polymeric polyblend having the graft polymer has a higher impact strength than a polymeric polyblend having the same components in an `~
ungrafted state.
' ` ;~ .' ;,.~. ' 36,368-F -8- -~
~ ' .
The preformed polymer is suitably an olefin polymer. The term "olefin polymer" includes -- homopolymers and copolymers of a-monoolefins and sub-stituted a-monoolefins, particularly a-monoolefins or substituted a-monoolefins having from 4 to 12 carbon atoms. Exemplary a-monoolefins homopolymers include polyethylene (e.g., ultra-low density polyethylene, low denQity polyethylene, linear low density polyethylene, ;
medium density polyethylene, high density polyethylene);
10 polypropylene; poly(butene-1), poly(isobutylene); poly(1 --pentene); poly(1-hexene); and poly(1-octene).
Substituted a-monoolefins include ethyl acrylate, n-butyl acrylate, and i-butyl acrylate, and halogenated a-monoolefin polymers such as vinyl chloride, chlori-nated polyethylene and chlorinated polypropylene. In such halo~enated a-monoolefin polymers, the halogen -~
bonded to the a-monoolefin polymer backbone supplies all ~ -or part of the halogenated organic moiety. Generally, such substituted a-monoolefin polymers contain from 1 to 40 weight percent of chlorine, preferably 5 to 25 weight percent chlorine.
; It is also understood that "olefin polymer"
includes a-monoolefin/a-monoolefin copolymers such as ethylene~propylene copoIymers and ethylene~butene-1 -copolymers; a-monoolefin/substituted a-monoolefin copolymers. ~
The a-monoolefins and substituted a-monoolefins ;-may also be copolymerized with a variety of suitable comonomers such as carbon monoxide and carboxylic acids - -having from 3 to 8 carbon atoms (e.g., ethylene vinyl acetate and ethylene acrylic acid); alkyl or haloalkyl ester of carboxylic acid wherein alkyl or haloalkyl has ` ,`'.~"~'' 36,368-F -9~
- 1o -from l to 12 carbon atoms; a-alkenyl having 2 to 12 car-bon atoms; acyl having l to 12 carbon atoms: carboxylate having from l to 12 carbon atoms; alkoxyl having from l -~
to 12 carbon atoms, and aryloxy having from 6 to 12 carbon atoms. When employing an a-mono-olefin/substituted a-monoolefin copolymer, the substi-tuted a-monoolefins preferably constitute up to about 50 weight percent of the ~opolymer, with the remainder `
being a-monoolefin.
The term "polyolefin" includes polyesters and ~ ;~
copolyesters. Exemplary polyesters and copolyesters ; ;
include polyethylene terepthalate and copolymers ~
thereof. Polyethylene terepthalate includes (a) ;~ ;
15 polymers wherein at least about 97 percent of the ;~
polymer contains repeating ethylene terepthalate units with any remainder being minor amounts of ester-forming components, and (b) copolymers of ethylene terepthalate D .,'',"' ;.
Exemplary polyesters and copolyesters also `~
include Eastman PCCE copolyesters, which are commercially available from Eastman Chemical Products, Inc. PCCE copolyesters are characterized by melting range of 195C to 215C. Specific PCCE copolyesters include PCCE 9965 (1.28 inherent viscosity), PCCE 9964 ~ ~
(1.05 inherent viscosity), and PCCE 9967 (1.16 inherent ;
viscosity).
~ Conventional polymerization techniques, well--known to those skilled in the art, may be u~ed in pro~
ducing the polyesters and copolyesters used in this ~`~
invention.
36,368-F -10_ `. .
'',:;
Preferred olefin polymers include polyethyiene;
chlorinated polyethylene, ethylene/vinyl acetate copol-ymers; ethylene~ethyl acrylate copo]ymers;
ethylene/acrylic acid copolymers; ethylene/propylene copolymers; ethylene/carbon monoxide copolymers; and polyesters and copolyesters. Polyethylene is the most preferred.
It is understood that the preformed polymers may contain polyblends of the above-described olefin polymers. The polyblends may also contain at least one olefin polymer and a nonolefin polymer, provided that at least 5 percent of the monomer mixture is gra~ted to the preformed polymer and the nonolefin polymer is compatible with the olefin polymer.
.
Methods of forming the preformed polymer are well-known to those skilled in the art. A general description of methods suitable for the preparation of the preformed polymers are set forth in the Kirk-Othmer Encvclopedia of Chemical Technolo~v, 3rd edition (1980).
. .
The polymerizable mixture is suitably prepared -~
by phy ically mixing the preformed polymer with the monomer mixture. Generally, the monomer will be imbibed in the preformed polymer in an amount such that at least 5 weight percent, preferably 15 weight percent, most preferably 30 weight percent, of the monomer mixture is grafted to the preformed polymer after polymerization.
The amount of monomer mixture imbibed by the preformed polymer is dependent on the temperature o~ the polymerizable mixture, the size and shape of the ~ ~
preformed polymer, the length of time for which the ~ -;
,'",,''' ~.' .'' 36,368-F _~
,:~
12- !
preformed polymer is allowed to contact the monomer mixture, and. of course. the composition of the monomer - mixture and the preformed polymer. In a preferred ' -embodiment, the time and temperature employed in the reaction are selected so that essentially all of the ;
monomer mixture is imbibed by the preformed polymer.
This is preferred because it allows for the formation of a more intimate blend of the preformed polymer and the polymer formed from the monomer mixture.
Generally, the preformed polymer will be ~
allowed to contact the monomer mixture for a period of ;
time of from Z0 to 2000 minutes, preferably from 240 to 1400 minutes. The preformed polymer will contact the monomer mixture at a temperature of from 50C to 100C, ~
and preferably from 60C to 100C. ~-The monomer mixture will be generally uniformly imbibed within the preformed polymer, providing a rela~
tively homogeneous polymer blend. Consequently, the graft sites between the preformed polymer and the poly-mer formed from the monomer mixture are generally uni-formly di~tributed throughout the graft copolymer. It is preferred that essentially all of the monomer mixture be imbibed by the preformed polymer, because it provides a higher saturation of the preformed polymer with the ~ `
monomer mixture and the concomitant formation of a more intimate blend of the preformed polymer and the polymer 30 formed from the monomer mixture. Typically, the graft ~
polymerization process involves polymerizing the ; ~; ;
monomers in the polymerizable mixture to chemically combine or graft at least a portion of the polymerized monomer mixture on the preformed polymer.
.. . ..
. ' '~ ' 36,368-F -12- ~;
:.... ~:
,s~ =. . ,"~
- :
~ :
The polymerizable mixture is then polymerized such that at least a portion o~ the polymerized monomer -- mixture chemically combines or grafts on the preformed polymer. The polymerizable mixture is suitably polymerized through an emulsion or suspension polymerization process. Emulsion and suspension polym-erization processes are well-known. Generally, the polymerizable mixture is emulsified or suspended in an aqueous medium through the use of emulsifying or sus-pending agentq. An initiator is then added to the solution and polymerization of the monomers allowed to proceed until achieving its desired degree of conYer-sion.
, . . .
The polymeric polyblend may contain additional additives well-known to those skilled in the art.
Exemplary of additives which may be incorporated in the formulation are plasticizers; heat stabilizers; pro-cessing aids; lubricants; light stabilizers such as hindered phenol derivatives; pigments such as titanium dioxide; and the like. Each of these additives is known and several types of each are commercially available.
Blending of the components of the polymeric polyblend can be accomplished by using conventional melt ~-processing techniques for thermally sensitive polymers.
Exemplary melt processing equipment includes heated two--roll compounding mills, Brabender mixers, Banbury ~;~
mixers, single screw extruders, twin screw extruders, and the like, which are constructed for use with thermally sensitive polymers. See, for example, the discussion by R. A. Wessling, in Chapter 11 of Polyvinylidene Chloride, Vol. 5, Gordon and Breach Science Publishers, New York, 1977, the teachings of -''-`'"~"''', .`',"
,~
36,368-F -13-. .: . ~ ~ . . .
: :. "::,: :~
' ' ' '~,"~' "-. ~
!
-14- ~
" . -which are incorporated herein by reference. Desirable ;~
results are obtained when an extruder, either single screw or twin screw, is used.
In using conventional processing equipment for thermally sensitive polymers, three conditions should be ~ -met. Two conditions, which are interrelated, are processing time and processing temperature. In melt ~
processing polymers, it is generally recognized that as --processing temperatures increase, processing times must decrease in order to avoid undesirable results such as polymer degradation. -~
.
Melt processing must be accomplished at a ; `~
15 temperature below that at which decomposition of the ~ -vinylidene chloride interpolymer becomes significant.
A third condition is that sufficient mixing must be generated during melt processing to provide a visually homogeneous blend with a reasonable mixing time. Vinylidene chloride interpolymers may be melt processed at temperatures of up to about 200C provided processing time is less than about one minute. Temper-ature~ greater than about 200C may be employed providedthe processing time is sufficiently short and provided the vinylidene chloride polymer is not in contact with iron or other metallic element~ known to catalyze the degradation of vinylidene chloride interpolymers. For 30 example, vinylidene chloride polymers are melt process- ;
able at temperatures as high as about 230C at process-ing times of less than about ten seconds when the vinylidene chloride polymer forms an inner layer in a coextruded structure. -~'~' '"':
;
36,368-F _14_ , .
~" ': ~' One factor in determining satisfactory mixing times is the melt index of the components of the com-patibilized blend. If component melt indexes are nearly equal, a relatively short mixing time yields satisfactory results.
A second factor in determining satisfactory mixing times is mixing shear rate. All other parameters being equal, a relatively low shear rate is needed when ~
10 the components have a relatively low viscosity or a high ;
melt index. Conversely, a relatively high shear rate is needed when the components have a relatively high viscosity or a low melt index.
A third factor in determining satisfactory -`~
mixing times is temperature. As noted hereinbefore, an ; -upper limit on temperature is the temperature at which decomposition of the vinylidene chloride interpolymer becomes significant. A lower limit on temperature is ~
dictated by the polymer blend component which has the; ~;
greatest melting point. If the temperature does not - ~;
exceed the melting point of that polymer blend compo-nent, a visually homogeneous melt will be difficult, if 25 not impossible, to obtain. ~--. ' .. j.
A fourth factor in determining satisfactory ~`~`v mixing times is mixing efficiency of the melt processing equipment. Certain melt processing equipment mixes more~`-30 efficiently than other melt processing equipment. -~
Selection of melt processing equipment which will pro~
duce a visually homogeneous melt within a reasonable processing time is, however, not difficult and can be -accomplished without undue experimentation. --.' '."' 36,368-F -15- ; ~
. ::, ......
A fifth factor in determining satisfactory mixing times is polymer feed form. The polymeric -- components of the compatible blends are generally available either in finely divided powder form or in pellet form.
Methods of forming the polymeric polyblend into pellets are well-known to those skilled in the art. Any method capable of forming the polymeric polyblends into pellets is suitable for use in the present invention.
For the purposes of this application, the terms ~
"pellet" or "pellets" refer to particles having a min- ~ -imum cross-sectional dimension of at least 1/32 inch, preferably of at least 1/16 inch, and most preferably of at least 1/8 inch, said pellets suitably have a maximum cross-sectional dimension of at least 1/2 inch, beneficially of at least 3/8 inch, and preferably of at least 1/4 inch. An e~emplary Method of forming the polymeric polyblends into pellets includes extruding the mixture through a strand die to form an extruded strand and chopping the extruded strand into pellets.
The polymeric polyblends, in either powder or 25 pellet form, are suitably fabricated into sheets, films, -container and the like. Articles formed from polymeric polyblends according to the present invention possess good barrier to the mass transport of atmospheric gases and water vapor and possess impact strengths.
30 ' `
Further, such polyblends have good solvent resistance. In other words, the polyblends are resistant to absorbing and swelling with solvents, making said polyblends particularly advantageous as 36,368-F -16~
: :
packaging for such products as cooking oils and gasoline.
The following examples are meant to be illus- ~:
trative only and are not intended to limit, in any man-ner, the scope of the invention as set forth in the claims.
Exam~les 0 Polymeric polyblends according to the present -.
invention are prepared with various components set forth ~.
below.
:, .,. ~:: :. .:, Each of the polymeric polyblends used in the . ;
examples is coded and described hereinafter in Table I.
... .
-;
36,368-F -17-. . .~ ..
TABLE I ~-Polymer Components ~
Code Polymer :
PVdC-1 A polymeric composition containing 98% of a vinylidene chloride copolymer, 1% Citroflex A-4, a plasticizer commercially available from Pfizer Chemical Co.; and 1% epoxidized soybean oil, a plasticizer commercially available from Pfizer Chemical Co. The vinylidene chloride interpolymer is formed from a monomer mixture comprising about 80 ~
weight percent vinylidene chloride and ~:
about 20 weight percent vinyl chloride, ~;
based on total monomer mixture weight. The -::::
copolymer has a major melting point of 162C .
and a weight average molecular weight of :
80,000.
20 PVdC-2 A polymeric composition containing 98% of a ::
vinylidene chloride copolymer, 1% Citroflex A-4; and 1% epoxidized soybean oil, a plas-ticizer commercially available from Pfizer ::
Chemical Co. The vinylidene chloride interpolymer i~ formed from a monomer mix- :
ture comprising about 94 weight percent - ~ :
vinylidene chloride and about 6 weight per- -cent methyl acrylate, based on total mono-mer mixture weight. The copolymer has a :
3 major melting point of 165C and a weight average molecular weight of 90,000. ;~
GC-1 A graft copolymer is formed by loading 2850 grams of a low density polyethylene resin, ~ ;:
,: . .~.,.,~, 36,368-F -18~
_19- -commercially available from The Dow Chemi-cal Company under the trade designation PE-~ 641, into a ten-gallon stirred polymeriza~
tion reactor. To the polyethylene in the reactor is added 13,000 grams of demineral-ized water, 0.6 grams of di-tert-butyl-methylphenol; 40 grams of tertiary butyl peroctoate, 6150 grams of vinylidene chlo- ; -ride, 1500 grams of vinyl chloride, 76 grams of epoxidized linseed oil and 17 grams of Methocel~K4M brand cellulose ether ~ ~ -as a suspending agent.
The reactor is sealed, purged with nitrogen and elevated to a temperature of about 25C.
The temperature is gradually raised for about three hours until it reaches about 80C and polymerization is continued for an additional 13 hours. The resultant -polymeric material slurry is vacuum -stripped and recovered. ;~ ~
GC-2 A graft copolymer is formed by repeating ~; `}
the procedures for preparing GC-1 with the ~ -^
exception that 3670 grams of low density polyethylene, 5470 grams of vinylidene chloride and 1360 grams of vinyl chloride are employed instead of the amounts of the same ingredients used in preparing CC-1.
GC-3 A graft copolymer is formed by repeating the procedures used to form GC-1 with the following exceptions: 2850 grams of Kodar PETG 6763, a polyethylene terephthalate (PETG) resin commercially available from --~
:.
36,368-F _19_ ~
.. ~,.,.;~ .
"~","''.''',""'`'' Eastman Chemical Co. , is loaded in place of the polyethylene used in preparing G~
GC-4 A graft copolymer is formed by repeating the procedures used to form GC-1 with the following exceptions: 2850 grams of a PCCE :
9965, a copolyester resin commercially available from the Eastman Kodak Company, is loaded in place of the polyethylene used in preparing GC-1.
GC-5 A graft copolymer is formed by repeating the procedures used to form GC-1 with the following exceptions: 3500 grams of a poly-propylene resin, commercially available from Himont Inc. under the trade designa-tion PP Sb-751, is loaded in place of the polyethylene; 12,000 grams of demineralized ~
water, 0.5 grams of di-tert-butylmethyl :
phenol; 20.0 grams of tertiary butyl per- : ~
octoate, 6580 grams of vinylidene chloride, : .
420 grams of methyl acrylate, 80 grams of epoxidized linseed oil and 20 grams of Methocel~K4M brand cellulose ether as a ~ ~:
suspending agent are e~ployed instead of ~ the amounts of the same ingredients used in : preparing GC-1. ~;~
Polymeric compositions are formed by 30 blending various quantities of the vinylidene chloride ~.
interpolymer and the various graft copolymers from Table The polymeric compositions are formed into a generally homogeneous mixture by dry blending the -36,368-F . -20- `~
'` ' ~ ' '' ` '~'~ ~ ' components. The components are loaded in about 4 lb batches into a Hobart mixer, and mixed for a period of approximately 45 minutes.
The powdery mixtures are extruded through a 1 1/2" single screw extruder having a length to diameter ratio of 12:1. The extruder has the following set temperatures: (a) Zone 1 temperature = 170C; (b) Zone 2 temperature = 174C; and (c) a die temperature = 176C. ;~
From the extruder, the blends are passed to a strand die and extruded into a water bath. From the extruder, the blends are passed to a stranding die, and are extruded into a water bath. The strand is then chopped into pellets, and the pellets are compression molded into a sample suitable for ASTM D-256, Method A.
Physical properties of the resultant polymeric polyblends are determined and are set forth in Table II. -., -. ~. .
~ ~
' ,, ~,-, ~, .
~ . .
~ `
' ' ' ~':~ .:'.
`"','`' ;~''~
, '' ~:"'' ,:..
36,368-F -21~
TABLE II
Exam- Polymer Component Impact Oxygen Code~ Amount~ Stren~th~ Permeability~
1 PVDC-1 65 1.18 0.39 2 PVDC-1 42 1.40 0.54 3 PVDC-1 20 1.58 0.92 4 PVDC-1 65 0.98 0.68 PVDC-1 42 1.12 0.72 6 PVDC-1 65 1.25 0.81 GC-3 35 ~;
7 PVDC-1 65 1.46 0.92 -8 PVDC-2 15 1.12 0.94 9 PVDC-2 30 0.96 0.63 Polymer components aq set forth in Table I.
Amounts are in percentages based upon the total weight of the polyblend.
~ Notched Izod Impact Strength in foot pounds per 2~ inch notch according to American Society of Te ting and Materials Te~t Method D-256, method A.
Oxygen Permeability in (cubic centimeters of ~b oxygen) (mil of sample thickness)/100 square ~-inches (day) (atmosphere of pressure). ~ ;;
As can be seen from the data in the above table, polymeric polyblends of the present invention h~ve a combination of good impact strength and good oxygen permeability. ~ ~
' :' ' ''. ' 36,368-F -22- ~
.::
-23~
::- -:
Although the invention has been described in `~-~
detail with reference to specific examples thereof, it :~
will be understood that variations can be made without ~ -departing from the scope of the invention as described above and as claimed below.
: -`,,, , :, 1 0 ''~
,'~.',.`''''~'-''''' ,",., ~ ,; .
: -~ ~.........
i~ ~ `
. ,, . ~ ; ..
~;~ 25 ~` ~
-:: .~; ~;.:, . ,."
i~ ; I , , ,~ ~,, ", ,, " .
30 ~.
,i.: . ,.; , ~, .
" ., ~
, - . .
` ~,-' '~
.,.,, .,~ ,.....
..': ~.
' ':, '.:
36,368-F -23- .
Typically, the monomeric materials are emulsified or suspended in an aqueous phase. The aqueous phase 10 contains a polymerization initiator and a surface active ;-agent capable of emulsifying or suspending the monomeric materials in the aqueous phase. The polymerization of the monomeric materials is usually carried out with heating and agitation.
After polymerization is complete, the resulting ~-suspension or emulsion of vinylidene chloride inter~
polymer has a majority of an aqueous phase. Thereafter, the slurry is cooled down, fed to a dewatering process to remove the water and dried.
To improve the impact resistance of the vinyl-idene chloride interpolymer, it is blended with a graft -copolymer. The vinylidene chloride interpolymer is present in the polymeric polyblend in an amount ranging~;3~ ;
from a minimum weight percent of about 40, preferably about 60, and most preferably about 70; and a maximum weight percent of about 97, preferably about 92, and ` --30 most preferably about 86, based on total weight of the -~
polymeric polyblend.
The graft copolymer is present in the polymeric polyblend in an amount ranging from a minimum weight - ;~
percent of about 3, preferably about 8, and most ~ :.-:
" ~,. ....
36,368-F -6- ~
''~
preferably about 14; and a maximum weight percent of -about 60, preferably about 40, and most preferably about 30, based on total weight of the polymeric polyblend.
The graft copolymer is prepared from a polym- --erizable mixture comprising two components. The first component is a monomer mixture, the second component is a preformed polymer.
,:
The monomer mixture is present in an amount of from 15 to 95 weight percent of the polymerizable mixture and the preformed polymer is present in an amount of from 85 to 5 weight percent, said weight percents being based upon the total weight of the polymerizable mixture. Preferably, the monomer mixture is present in an amount of from 30 to 90 weight percent of the polymerizable mixture and the preformed polymer is present in an amount of from 70 to 10 weight percent, said weight percents being based upon the total weight of the polymerizable mixture. Most preferably, the monomer mixture is present in an amount of from 60 to 75 weight percent of the polymerizable mixture and the preformed polymer is present in an amount of from about 40 to 25 weight percent, said weight percents based upon the total weight of the polymerizable mixture.
;
In preparing the monomer mixture, such mixture -`
comprises essentially all of the monomer to be polymer- ~ -ilzed. The monomer mixture comprises vinylidene chloride in an amount of from 60 to 99 weight percent, preferably from 65 to 96 weight percent, and most preferably from 70 to 94 weight percent, based on the total monomer mixture weight; and an ethylenically unsaturated comonomer or monomers copolymerizable with the 36,368-F _7_ :
vinylidene chloride monomer in an amount of from 40 to l `
weight percent, preferably from 35 to 4 weight percent, `
- and most preferably from 30 to 6 weight percent. based ~- `
on the total monomer mixture weight.
Suitable ethylenically unsaturated comonomers ~ ;
copolymerizable with the vinylidene chloride monomer ` ~;
include vinyl chloride, alkyl acrylates, alkyl meth~
acrylates, acrylic acid, methacrylic acid, itaconic `"
acid, acrylonitrile and methacrylonitrile. Desirable ethylenically unsaturated monomers copolymerizable with the vinylidene chloride monomer are selected from the `;
group consisting of vinyl chloride, alkyl acrylate, and alkyl methacrylates, the alkyl acrylates and alkyl meth-~`
acrylates having from 1 to 8 carbon atoms per alkyl group. Preferably, the ethylenically unsaturated monomer copolymerizable with the vinylidene chloride ~
monomer is selected from the group consisting of vinyl ~-chloride, methyl acrylate, ethyl acrylate and 20 methylmethacrylate. ;
,, ;~. .,.;
The preformed polymer is selected to be swellable in the monomer mixture and to be capable of `
25 having a sufficient amount of the monomers graft theretoi;
such that, upon polymerization, the preformed graft ;
copolymer provides improved impact strength to the polymeric polyblend. By "swellable" is meant that the -preformed polymer is capable of imbibing the monomer mixture without dissolving therein. By "improved impact strength" is meant that the polymeric polyblend having the graft polymer has a higher impact strength than a polymeric polyblend having the same components in an `~
ungrafted state.
' ` ;~ .' ;,.~. ' 36,368-F -8- -~
~ ' .
The preformed polymer is suitably an olefin polymer. The term "olefin polymer" includes -- homopolymers and copolymers of a-monoolefins and sub-stituted a-monoolefins, particularly a-monoolefins or substituted a-monoolefins having from 4 to 12 carbon atoms. Exemplary a-monoolefins homopolymers include polyethylene (e.g., ultra-low density polyethylene, low denQity polyethylene, linear low density polyethylene, ;
medium density polyethylene, high density polyethylene);
10 polypropylene; poly(butene-1), poly(isobutylene); poly(1 --pentene); poly(1-hexene); and poly(1-octene).
Substituted a-monoolefins include ethyl acrylate, n-butyl acrylate, and i-butyl acrylate, and halogenated a-monoolefin polymers such as vinyl chloride, chlori-nated polyethylene and chlorinated polypropylene. In such halo~enated a-monoolefin polymers, the halogen -~
bonded to the a-monoolefin polymer backbone supplies all ~ -or part of the halogenated organic moiety. Generally, such substituted a-monoolefin polymers contain from 1 to 40 weight percent of chlorine, preferably 5 to 25 weight percent chlorine.
; It is also understood that "olefin polymer"
includes a-monoolefin/a-monoolefin copolymers such as ethylene~propylene copoIymers and ethylene~butene-1 -copolymers; a-monoolefin/substituted a-monoolefin copolymers. ~
The a-monoolefins and substituted a-monoolefins ;-may also be copolymerized with a variety of suitable comonomers such as carbon monoxide and carboxylic acids - -having from 3 to 8 carbon atoms (e.g., ethylene vinyl acetate and ethylene acrylic acid); alkyl or haloalkyl ester of carboxylic acid wherein alkyl or haloalkyl has ` ,`'.~"~'' 36,368-F -9~
- 1o -from l to 12 carbon atoms; a-alkenyl having 2 to 12 car-bon atoms; acyl having l to 12 carbon atoms: carboxylate having from l to 12 carbon atoms; alkoxyl having from l -~
to 12 carbon atoms, and aryloxy having from 6 to 12 carbon atoms. When employing an a-mono-olefin/substituted a-monoolefin copolymer, the substi-tuted a-monoolefins preferably constitute up to about 50 weight percent of the ~opolymer, with the remainder `
being a-monoolefin.
The term "polyolefin" includes polyesters and ~ ;~
copolyesters. Exemplary polyesters and copolyesters ; ;
include polyethylene terepthalate and copolymers ~
thereof. Polyethylene terepthalate includes (a) ;~ ;
15 polymers wherein at least about 97 percent of the ;~
polymer contains repeating ethylene terepthalate units with any remainder being minor amounts of ester-forming components, and (b) copolymers of ethylene terepthalate D .,'',"' ;.
Exemplary polyesters and copolyesters also `~
include Eastman PCCE copolyesters, which are commercially available from Eastman Chemical Products, Inc. PCCE copolyesters are characterized by melting range of 195C to 215C. Specific PCCE copolyesters include PCCE 9965 (1.28 inherent viscosity), PCCE 9964 ~ ~
(1.05 inherent viscosity), and PCCE 9967 (1.16 inherent ;
viscosity).
~ Conventional polymerization techniques, well--known to those skilled in the art, may be u~ed in pro~
ducing the polyesters and copolyesters used in this ~`~
invention.
36,368-F -10_ `. .
'',:;
Preferred olefin polymers include polyethyiene;
chlorinated polyethylene, ethylene/vinyl acetate copol-ymers; ethylene~ethyl acrylate copo]ymers;
ethylene/acrylic acid copolymers; ethylene/propylene copolymers; ethylene/carbon monoxide copolymers; and polyesters and copolyesters. Polyethylene is the most preferred.
It is understood that the preformed polymers may contain polyblends of the above-described olefin polymers. The polyblends may also contain at least one olefin polymer and a nonolefin polymer, provided that at least 5 percent of the monomer mixture is gra~ted to the preformed polymer and the nonolefin polymer is compatible with the olefin polymer.
.
Methods of forming the preformed polymer are well-known to those skilled in the art. A general description of methods suitable for the preparation of the preformed polymers are set forth in the Kirk-Othmer Encvclopedia of Chemical Technolo~v, 3rd edition (1980).
. .
The polymerizable mixture is suitably prepared -~
by phy ically mixing the preformed polymer with the monomer mixture. Generally, the monomer will be imbibed in the preformed polymer in an amount such that at least 5 weight percent, preferably 15 weight percent, most preferably 30 weight percent, of the monomer mixture is grafted to the preformed polymer after polymerization.
The amount of monomer mixture imbibed by the preformed polymer is dependent on the temperature o~ the polymerizable mixture, the size and shape of the ~ ~
preformed polymer, the length of time for which the ~ -;
,'",,''' ~.' .'' 36,368-F _~
,:~
12- !
preformed polymer is allowed to contact the monomer mixture, and. of course. the composition of the monomer - mixture and the preformed polymer. In a preferred ' -embodiment, the time and temperature employed in the reaction are selected so that essentially all of the ;
monomer mixture is imbibed by the preformed polymer.
This is preferred because it allows for the formation of a more intimate blend of the preformed polymer and the polymer formed from the monomer mixture.
Generally, the preformed polymer will be ~
allowed to contact the monomer mixture for a period of ;
time of from Z0 to 2000 minutes, preferably from 240 to 1400 minutes. The preformed polymer will contact the monomer mixture at a temperature of from 50C to 100C, ~
and preferably from 60C to 100C. ~-The monomer mixture will be generally uniformly imbibed within the preformed polymer, providing a rela~
tively homogeneous polymer blend. Consequently, the graft sites between the preformed polymer and the poly-mer formed from the monomer mixture are generally uni-formly di~tributed throughout the graft copolymer. It is preferred that essentially all of the monomer mixture be imbibed by the preformed polymer, because it provides a higher saturation of the preformed polymer with the ~ `
monomer mixture and the concomitant formation of a more intimate blend of the preformed polymer and the polymer 30 formed from the monomer mixture. Typically, the graft ~
polymerization process involves polymerizing the ; ~; ;
monomers in the polymerizable mixture to chemically combine or graft at least a portion of the polymerized monomer mixture on the preformed polymer.
.. . ..
. ' '~ ' 36,368-F -12- ~;
:.... ~:
,s~ =. . ,"~
- :
~ :
The polymerizable mixture is then polymerized such that at least a portion o~ the polymerized monomer -- mixture chemically combines or grafts on the preformed polymer. The polymerizable mixture is suitably polymerized through an emulsion or suspension polymerization process. Emulsion and suspension polym-erization processes are well-known. Generally, the polymerizable mixture is emulsified or suspended in an aqueous medium through the use of emulsifying or sus-pending agentq. An initiator is then added to the solution and polymerization of the monomers allowed to proceed until achieving its desired degree of conYer-sion.
, . . .
The polymeric polyblend may contain additional additives well-known to those skilled in the art.
Exemplary of additives which may be incorporated in the formulation are plasticizers; heat stabilizers; pro-cessing aids; lubricants; light stabilizers such as hindered phenol derivatives; pigments such as titanium dioxide; and the like. Each of these additives is known and several types of each are commercially available.
Blending of the components of the polymeric polyblend can be accomplished by using conventional melt ~-processing techniques for thermally sensitive polymers.
Exemplary melt processing equipment includes heated two--roll compounding mills, Brabender mixers, Banbury ~;~
mixers, single screw extruders, twin screw extruders, and the like, which are constructed for use with thermally sensitive polymers. See, for example, the discussion by R. A. Wessling, in Chapter 11 of Polyvinylidene Chloride, Vol. 5, Gordon and Breach Science Publishers, New York, 1977, the teachings of -''-`'"~"''', .`',"
,~
36,368-F -13-. .: . ~ ~ . . .
: :. "::,: :~
' ' ' '~,"~' "-. ~
!
-14- ~
" . -which are incorporated herein by reference. Desirable ;~
results are obtained when an extruder, either single screw or twin screw, is used.
In using conventional processing equipment for thermally sensitive polymers, three conditions should be ~ -met. Two conditions, which are interrelated, are processing time and processing temperature. In melt ~
processing polymers, it is generally recognized that as --processing temperatures increase, processing times must decrease in order to avoid undesirable results such as polymer degradation. -~
.
Melt processing must be accomplished at a ; `~
15 temperature below that at which decomposition of the ~ -vinylidene chloride interpolymer becomes significant.
A third condition is that sufficient mixing must be generated during melt processing to provide a visually homogeneous blend with a reasonable mixing time. Vinylidene chloride interpolymers may be melt processed at temperatures of up to about 200C provided processing time is less than about one minute. Temper-ature~ greater than about 200C may be employed providedthe processing time is sufficiently short and provided the vinylidene chloride polymer is not in contact with iron or other metallic element~ known to catalyze the degradation of vinylidene chloride interpolymers. For 30 example, vinylidene chloride polymers are melt process- ;
able at temperatures as high as about 230C at process-ing times of less than about ten seconds when the vinylidene chloride polymer forms an inner layer in a coextruded structure. -~'~' '"':
;
36,368-F _14_ , .
~" ': ~' One factor in determining satisfactory mixing times is the melt index of the components of the com-patibilized blend. If component melt indexes are nearly equal, a relatively short mixing time yields satisfactory results.
A second factor in determining satisfactory mixing times is mixing shear rate. All other parameters being equal, a relatively low shear rate is needed when ~
10 the components have a relatively low viscosity or a high ;
melt index. Conversely, a relatively high shear rate is needed when the components have a relatively high viscosity or a low melt index.
A third factor in determining satisfactory -`~
mixing times is temperature. As noted hereinbefore, an ; -upper limit on temperature is the temperature at which decomposition of the vinylidene chloride interpolymer becomes significant. A lower limit on temperature is ~
dictated by the polymer blend component which has the; ~;
greatest melting point. If the temperature does not - ~;
exceed the melting point of that polymer blend compo-nent, a visually homogeneous melt will be difficult, if 25 not impossible, to obtain. ~--. ' .. j.
A fourth factor in determining satisfactory ~`~`v mixing times is mixing efficiency of the melt processing equipment. Certain melt processing equipment mixes more~`-30 efficiently than other melt processing equipment. -~
Selection of melt processing equipment which will pro~
duce a visually homogeneous melt within a reasonable processing time is, however, not difficult and can be -accomplished without undue experimentation. --.' '."' 36,368-F -15- ; ~
. ::, ......
A fifth factor in determining satisfactory mixing times is polymer feed form. The polymeric -- components of the compatible blends are generally available either in finely divided powder form or in pellet form.
Methods of forming the polymeric polyblend into pellets are well-known to those skilled in the art. Any method capable of forming the polymeric polyblends into pellets is suitable for use in the present invention.
For the purposes of this application, the terms ~
"pellet" or "pellets" refer to particles having a min- ~ -imum cross-sectional dimension of at least 1/32 inch, preferably of at least 1/16 inch, and most preferably of at least 1/8 inch, said pellets suitably have a maximum cross-sectional dimension of at least 1/2 inch, beneficially of at least 3/8 inch, and preferably of at least 1/4 inch. An e~emplary Method of forming the polymeric polyblends into pellets includes extruding the mixture through a strand die to form an extruded strand and chopping the extruded strand into pellets.
The polymeric polyblends, in either powder or 25 pellet form, are suitably fabricated into sheets, films, -container and the like. Articles formed from polymeric polyblends according to the present invention possess good barrier to the mass transport of atmospheric gases and water vapor and possess impact strengths.
30 ' `
Further, such polyblends have good solvent resistance. In other words, the polyblends are resistant to absorbing and swelling with solvents, making said polyblends particularly advantageous as 36,368-F -16~
: :
packaging for such products as cooking oils and gasoline.
The following examples are meant to be illus- ~:
trative only and are not intended to limit, in any man-ner, the scope of the invention as set forth in the claims.
Exam~les 0 Polymeric polyblends according to the present -.
invention are prepared with various components set forth ~.
below.
:, .,. ~:: :. .:, Each of the polymeric polyblends used in the . ;
examples is coded and described hereinafter in Table I.
... .
-;
36,368-F -17-. . .~ ..
TABLE I ~-Polymer Components ~
Code Polymer :
PVdC-1 A polymeric composition containing 98% of a vinylidene chloride copolymer, 1% Citroflex A-4, a plasticizer commercially available from Pfizer Chemical Co.; and 1% epoxidized soybean oil, a plasticizer commercially available from Pfizer Chemical Co. The vinylidene chloride interpolymer is formed from a monomer mixture comprising about 80 ~
weight percent vinylidene chloride and ~:
about 20 weight percent vinyl chloride, ~;
based on total monomer mixture weight. The -::::
copolymer has a major melting point of 162C .
and a weight average molecular weight of :
80,000.
20 PVdC-2 A polymeric composition containing 98% of a ::
vinylidene chloride copolymer, 1% Citroflex A-4; and 1% epoxidized soybean oil, a plas-ticizer commercially available from Pfizer ::
Chemical Co. The vinylidene chloride interpolymer i~ formed from a monomer mix- :
ture comprising about 94 weight percent - ~ :
vinylidene chloride and about 6 weight per- -cent methyl acrylate, based on total mono-mer mixture weight. The copolymer has a :
3 major melting point of 165C and a weight average molecular weight of 90,000. ;~
GC-1 A graft copolymer is formed by loading 2850 grams of a low density polyethylene resin, ~ ;:
,: . .~.,.,~, 36,368-F -18~
_19- -commercially available from The Dow Chemi-cal Company under the trade designation PE-~ 641, into a ten-gallon stirred polymeriza~
tion reactor. To the polyethylene in the reactor is added 13,000 grams of demineral-ized water, 0.6 grams of di-tert-butyl-methylphenol; 40 grams of tertiary butyl peroctoate, 6150 grams of vinylidene chlo- ; -ride, 1500 grams of vinyl chloride, 76 grams of epoxidized linseed oil and 17 grams of Methocel~K4M brand cellulose ether ~ ~ -as a suspending agent.
The reactor is sealed, purged with nitrogen and elevated to a temperature of about 25C.
The temperature is gradually raised for about three hours until it reaches about 80C and polymerization is continued for an additional 13 hours. The resultant -polymeric material slurry is vacuum -stripped and recovered. ;~ ~
GC-2 A graft copolymer is formed by repeating ~; `}
the procedures for preparing GC-1 with the ~ -^
exception that 3670 grams of low density polyethylene, 5470 grams of vinylidene chloride and 1360 grams of vinyl chloride are employed instead of the amounts of the same ingredients used in preparing CC-1.
GC-3 A graft copolymer is formed by repeating the procedures used to form GC-1 with the following exceptions: 2850 grams of Kodar PETG 6763, a polyethylene terephthalate (PETG) resin commercially available from --~
:.
36,368-F _19_ ~
.. ~,.,.;~ .
"~","''.''',""'`'' Eastman Chemical Co. , is loaded in place of the polyethylene used in preparing G~
GC-4 A graft copolymer is formed by repeating the procedures used to form GC-1 with the following exceptions: 2850 grams of a PCCE :
9965, a copolyester resin commercially available from the Eastman Kodak Company, is loaded in place of the polyethylene used in preparing GC-1.
GC-5 A graft copolymer is formed by repeating the procedures used to form GC-1 with the following exceptions: 3500 grams of a poly-propylene resin, commercially available from Himont Inc. under the trade designa-tion PP Sb-751, is loaded in place of the polyethylene; 12,000 grams of demineralized ~
water, 0.5 grams of di-tert-butylmethyl :
phenol; 20.0 grams of tertiary butyl per- : ~
octoate, 6580 grams of vinylidene chloride, : .
420 grams of methyl acrylate, 80 grams of epoxidized linseed oil and 20 grams of Methocel~K4M brand cellulose ether as a ~ ~:
suspending agent are e~ployed instead of ~ the amounts of the same ingredients used in : preparing GC-1. ~;~
Polymeric compositions are formed by 30 blending various quantities of the vinylidene chloride ~.
interpolymer and the various graft copolymers from Table The polymeric compositions are formed into a generally homogeneous mixture by dry blending the -36,368-F . -20- `~
'` ' ~ ' '' ` '~'~ ~ ' components. The components are loaded in about 4 lb batches into a Hobart mixer, and mixed for a period of approximately 45 minutes.
The powdery mixtures are extruded through a 1 1/2" single screw extruder having a length to diameter ratio of 12:1. The extruder has the following set temperatures: (a) Zone 1 temperature = 170C; (b) Zone 2 temperature = 174C; and (c) a die temperature = 176C. ;~
From the extruder, the blends are passed to a strand die and extruded into a water bath. From the extruder, the blends are passed to a stranding die, and are extruded into a water bath. The strand is then chopped into pellets, and the pellets are compression molded into a sample suitable for ASTM D-256, Method A.
Physical properties of the resultant polymeric polyblends are determined and are set forth in Table II. -., -. ~. .
~ ~
' ,, ~,-, ~, .
~ . .
~ `
' ' ' ~':~ .:'.
`"','`' ;~''~
, '' ~:"'' ,:..
36,368-F -21~
TABLE II
Exam- Polymer Component Impact Oxygen Code~ Amount~ Stren~th~ Permeability~
1 PVDC-1 65 1.18 0.39 2 PVDC-1 42 1.40 0.54 3 PVDC-1 20 1.58 0.92 4 PVDC-1 65 0.98 0.68 PVDC-1 42 1.12 0.72 6 PVDC-1 65 1.25 0.81 GC-3 35 ~;
7 PVDC-1 65 1.46 0.92 -8 PVDC-2 15 1.12 0.94 9 PVDC-2 30 0.96 0.63 Polymer components aq set forth in Table I.
Amounts are in percentages based upon the total weight of the polyblend.
~ Notched Izod Impact Strength in foot pounds per 2~ inch notch according to American Society of Te ting and Materials Te~t Method D-256, method A.
Oxygen Permeability in (cubic centimeters of ~b oxygen) (mil of sample thickness)/100 square ~-inches (day) (atmosphere of pressure). ~ ;;
As can be seen from the data in the above table, polymeric polyblends of the present invention h~ve a combination of good impact strength and good oxygen permeability. ~ ~
' :' ' ''. ' 36,368-F -22- ~
.::
-23~
::- -:
Although the invention has been described in `~-~
detail with reference to specific examples thereof, it :~
will be understood that variations can be made without ~ -departing from the scope of the invention as described above and as claimed below.
: -`,,, , :, 1 0 ''~
,'~.',.`''''~'-''''' ,",., ~ ,; .
: -~ ~.........
i~ ~ `
. ,, . ~ ; ..
~;~ 25 ~` ~
-:: .~; ~;.:, . ,."
i~ ; I , , ,~ ~,, ", ,, " .
30 ~.
,i.: . ,.; , ~, .
" ., ~
, - . .
` ~,-' '~
.,.,, .,~ ,.....
..': ~.
' ':, '.:
36,368-F -23- .
Claims (20)
1. A polymeric polyblend comprising:
(A) a vinylidene chloride interpolymer; and (B) from 3 to 60 weight percent, based on the weight of the polyblend, of a graft copolymer formed from a polymerizable mixture comprising: (1) from 95 to 15 weight percent of a comonomer mixture, and (2) from 5 to 85 weight percent of a preformed polymer which is capable of imbibing the comonomer mixture and of having the comonomer mixture graft thereto, said weight percents being based upon the total polymerizable mixture weight;
whereby upon polymerization, the graft copolymer has at least 5 weight percent of the comonomer mixture grafted thereto.
(A) a vinylidene chloride interpolymer; and (B) from 3 to 60 weight percent, based on the weight of the polyblend, of a graft copolymer formed from a polymerizable mixture comprising: (1) from 95 to 15 weight percent of a comonomer mixture, and (2) from 5 to 85 weight percent of a preformed polymer which is capable of imbibing the comonomer mixture and of having the comonomer mixture graft thereto, said weight percents being based upon the total polymerizable mixture weight;
whereby upon polymerization, the graft copolymer has at least 5 weight percent of the comonomer mixture grafted thereto.
2. The polymeric polyblend of Claim 1, wherein the vinylidene chloride interpolymer is present in an amount of from 94 to 70 weight percent and the graft copolymer is present in an amount of between 6 and 30 weight percent, said weight percents being based on the total weight of the polyblend.
3. The polymeric polyblend of Claim 2, wherein the vinylidene chloride interpolymer is present in an amount of from 86 to 70 weight percent and the graft copolymer is present in an amount of from 14 to 30 weight percent, said weight percents being based on the total weight of the polyblend.
4. The polymeric polyblend of Claim 3, wherein the polymerizable mixture comprises the comonomer mixture in an amount of from 30 to 90 weight percent and the preformed polymer in an amount of from 70 to 10 weight percent, said weight percents being based on the total weight of the comonomer mixture.
5. The polymeric polyblend of Claim 4, wherein the polymerizable mixture comprises the comonomer mixture in an amount of from 60 to 75 weight percent and the preformed polymer in an amount of from 40 to 25 weight percent, said weight percents being based on the total weight of the comonomer mixture.
6. The polymeric polyblend of Claim 1, wherein the comonomer mixture comprises vinylidene chloride monomer in an amount of from 60 to 99 weight percent and at least one ethylenically unsaturated comonomer copolymerizable therewith in an amount of from 40 to 1 weight percent, said weight percents being based on the total weight of the comonomer mixture.
7. The polymeric polyblend of Claim 6, wherein the comonomer mixture comprises vinylidene chloride monomer in an amount of from 65 to 96 weight percent and at least one ethylenically unsaturated comonomer copolymerizable therewith in an amount of from 35 to 4 weight percent, said weight percents being based on the total weight of the comonomer mixture.
8. The polymeric polyblend of Claim 7, wherein the comonomer mixture comprises vinylidene chloride monomer in an amount of from 70 to 94 weight percent and at least one ethylenically unsaturated comonomer copolymerizable therewith in an amount of from 30 to 6 weight percent, said weight percents being based on the total weight of the comonomer mixture.
9. The polymeric polyblend of Claim 1, wherein the preformed polymer comprises an olefin polymer.
10. The polymeric polyblend of Claim 9, wherein the olefin polymer is selected from the group consisting of ultra-low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene; polypropylene; poly(1-butene), poly(1-pentene), poly(4-methyl-1-pentene), poly(1 -hexene) and poly(1-octene); chlorinated polyethylene;
ethylene vinyl acetate; ethylene-propylene copolymers;
polyesters and copolyesters; ethylene carbon monoxide copolymers; or mixtures thereof.
ethylene vinyl acetate; ethylene-propylene copolymers;
polyesters and copolyesters; ethylene carbon monoxide copolymers; or mixtures thereof.
11. The polymeric polyblend of Claim 1, wherein a sufficient amount of the comonomer mixture is imbibed by the preformed polymer such that at least 15 weight percent of the comonomer mixture is grafted to the preformed polymer.
12. The polymeric polyblend of Claim l, wherein a sufficient amount of the comonomer mixture is imbibed by the preformed polymer such that at least 30 weight percent of the comonomer mixture is grafted to the preformed polymer.
13. A polymeric polyblend comprising:
(A) from 70 to 86 weight percent, based on the total weight of the polyblend, of a vinylidene chloride interpolymer; and (B) from 30 to 14 weight percent, based on the total weight of the polyblend, of a graft copolymer formed from a polymerizable mixture comprising:
(l) from 60 to 75 weight percent of a comonomer mixture, based upon the total polymerizable mixture weight, the comonomer mixture comprising vinylidene chloride monomer in an amount of from 60 to 99 weight percent and at least one ethylenically unsaturated comonomer copolymerizable therewith in an amount of from 40 to 1 weight percent, said weight percents being based on the total weight of the comonomer mixture; and (2) from 40 to 25 weight percent of a preformed polymer, based upon the total polymerizable mixture weight, the preformed polymer being an olefin polymer selected from the group consisting of ultra-low density polyethylene, linear low density polyethylene, medium density polyethylene, high density poly-ethylene; polypropylene; poly(1-butene), poly(1 -pentene), poly(4-methyl-1-pentene), poly(1 -hexene) and poly(1-octene); chlorinated poly-ethylene; ethylene vinyl acetate; ethylene--propylene copolymers; polyesters and copolyesters; ethylene carbon monoxide copolymers; or mixtures thereof:
whereby upon polymerization, the graft copolymer has at least 30 weight percent of the comonomer mixture grafted thereto.
(A) from 70 to 86 weight percent, based on the total weight of the polyblend, of a vinylidene chloride interpolymer; and (B) from 30 to 14 weight percent, based on the total weight of the polyblend, of a graft copolymer formed from a polymerizable mixture comprising:
(l) from 60 to 75 weight percent of a comonomer mixture, based upon the total polymerizable mixture weight, the comonomer mixture comprising vinylidene chloride monomer in an amount of from 60 to 99 weight percent and at least one ethylenically unsaturated comonomer copolymerizable therewith in an amount of from 40 to 1 weight percent, said weight percents being based on the total weight of the comonomer mixture; and (2) from 40 to 25 weight percent of a preformed polymer, based upon the total polymerizable mixture weight, the preformed polymer being an olefin polymer selected from the group consisting of ultra-low density polyethylene, linear low density polyethylene, medium density polyethylene, high density poly-ethylene; polypropylene; poly(1-butene), poly(1 -pentene), poly(4-methyl-1-pentene), poly(1 -hexene) and poly(1-octene); chlorinated poly-ethylene; ethylene vinyl acetate; ethylene--propylene copolymers; polyesters and copolyesters; ethylene carbon monoxide copolymers; or mixtures thereof:
whereby upon polymerization, the graft copolymer has at least 30 weight percent of the comonomer mixture grafted thereto.
14. An improved process for preparing an arti-cle, said process comprising:
(1) providing a polymeric polyblend comprising:
(A) a vinylidene chloride interpolymer; and (B) from 3 to 60 weight percent, based on the weight of the polyblend, of a graft copolymer formed from a polymerizable mixture comprising: (i) from 95 to
(1) providing a polymeric polyblend comprising:
(A) a vinylidene chloride interpolymer; and (B) from 3 to 60 weight percent, based on the weight of the polyblend, of a graft copolymer formed from a polymerizable mixture comprising: (i) from 95 to
15 weight percent of a comonomer mixture, and (ii) from 5 to 85 weight percent of a preformed polymer which is capable of imbibing the comonomer mixture and of having the comonomer mixture graft thereto, said weight percents being based upon the total polymerizable mixture weight;
whereby upon polymerization, the graft copolymer has at least 5 weight percent of the comonomer mixture grafted thereto; and (2) fabricating the polymeric polyblend into an article using a method selected from the group consisting of casting, blowing, extrusion, molding, injection molding, blow molding, coextrusion, laminating, or calendering.
15. An article prepared by the process of Claim 14.
whereby upon polymerization, the graft copolymer has at least 5 weight percent of the comonomer mixture grafted thereto; and (2) fabricating the polymeric polyblend into an article using a method selected from the group consisting of casting, blowing, extrusion, molding, injection molding, blow molding, coextrusion, laminating, or calendering.
15. An article prepared by the process of Claim 14.
16. The article of Claim 15, wherein the arti-cle is a multilayered structure having organic polymer skin layers on each side of the compatibilized polymeric polyblend to form a relatively rigid multilayer container.
17. An improved process for preparing an arti-cle, said process comprising:
(1) providing a polymeric polyblend comprising:
(A) from 70 to 86 weight percent, based on the total weight of the polyblend, of a vinylidene chloride interpolymer formed from a polymerizable mixture which comprises a vinylidene chloride monomer in an amount of from 60 to 99 weight percent and at least one ethylenically unsaturated comonomer copolymerizable with the vinylidene chloride monomer in an amount of from 40 to 1 weight percent, said weight percents being based on the total weight of interpolymer monomer mixture; and (B) from 30 to 14 weight percent, based on the total weight of the polyblend, of a graft copolymer formed from a polymerizable mixture comprising:
(i) from 60 to 75 weight percent of a comonomer mixture, based upon the total polymerizable mixture weight, the comonomer mixture comprising a vinylidene chloride monomer in an amount of from 60 to 99 weight percent and at least one ethylenically unsaturated comonomer copolymerizable therewith in an amount of from 40 to 1 weight percent, said weight percents being based on the total weight of the comonomer mixture; and (ii) from 40 to 25 weight percent of a preformed polymer, based upon the total polymerizable mixture weight, the preformed polymer being an olefin polymer selected from the group consisting of ultra-low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene;
polypropylene; poly(1-butene), poly(1-pentene), poly(4 -methyl-1-pentene), poly(1-hexene) and poly(1-octene);
chlorinated polyethylene; ethylene vinyl acetate;
ethylene-propylene copolymers; polyesters and copolyesters; ethylene carbon monoxide copolymers; or mixtures thereof;
whereby upon polymerization, the graft copoly-mer has at least 30 weight percent of the comonomer mix-ture grafted thereto; and (2) fabricating the polymeric polyblend into an article using a method selected from the group consisting of casting, blowing, extrusion, molding, injection molding, blow molding, coextrusion, laminating or calendering.
(1) providing a polymeric polyblend comprising:
(A) from 70 to 86 weight percent, based on the total weight of the polyblend, of a vinylidene chloride interpolymer formed from a polymerizable mixture which comprises a vinylidene chloride monomer in an amount of from 60 to 99 weight percent and at least one ethylenically unsaturated comonomer copolymerizable with the vinylidene chloride monomer in an amount of from 40 to 1 weight percent, said weight percents being based on the total weight of interpolymer monomer mixture; and (B) from 30 to 14 weight percent, based on the total weight of the polyblend, of a graft copolymer formed from a polymerizable mixture comprising:
(i) from 60 to 75 weight percent of a comonomer mixture, based upon the total polymerizable mixture weight, the comonomer mixture comprising a vinylidene chloride monomer in an amount of from 60 to 99 weight percent and at least one ethylenically unsaturated comonomer copolymerizable therewith in an amount of from 40 to 1 weight percent, said weight percents being based on the total weight of the comonomer mixture; and (ii) from 40 to 25 weight percent of a preformed polymer, based upon the total polymerizable mixture weight, the preformed polymer being an olefin polymer selected from the group consisting of ultra-low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene;
polypropylene; poly(1-butene), poly(1-pentene), poly(4 -methyl-1-pentene), poly(1-hexene) and poly(1-octene);
chlorinated polyethylene; ethylene vinyl acetate;
ethylene-propylene copolymers; polyesters and copolyesters; ethylene carbon monoxide copolymers; or mixtures thereof;
whereby upon polymerization, the graft copoly-mer has at least 30 weight percent of the comonomer mix-ture grafted thereto; and (2) fabricating the polymeric polyblend into an article using a method selected from the group consisting of casting, blowing, extrusion, molding, injection molding, blow molding, coextrusion, laminating or calendering.
18. An article prepared by the process of Claim 17.
19. An article formed from a polymeric polyblend, said polymeric polyblend comprising:
(A) a vinylidene chloride interpolymer; and (B) from 3 to 60 weight percent, based on the weight of the polyblend, of a graft copolymer formed from a polymerizable mixture comprising: (1) from 95 to 15 weight percent of a comonomer mixture, and (2) from 5 to 85 weight percent of a preformed polymer which is capable of imbibing the comonomer mixture and of having the comonomer mixture graft thereto, said weight percents being based upon the total polymerizable mixture weight;
whereby upon polymerization, the graft copoly-mer has at least 5 weight percent of the comonomer mixture grafted thereto.
(A) a vinylidene chloride interpolymer; and (B) from 3 to 60 weight percent, based on the weight of the polyblend, of a graft copolymer formed from a polymerizable mixture comprising: (1) from 95 to 15 weight percent of a comonomer mixture, and (2) from 5 to 85 weight percent of a preformed polymer which is capable of imbibing the comonomer mixture and of having the comonomer mixture graft thereto, said weight percents being based upon the total polymerizable mixture weight;
whereby upon polymerization, the graft copoly-mer has at least 5 weight percent of the comonomer mixture grafted thereto.
20. An article formed from a polymeric polyblend, said polymeric polyblend comprising:
(A) from 70 to 86 weight percent, based on the total weight of the polyblend, of a vinylidene chloride interpolymer formed from an polymerizable mixture which comprises a vinylidene chloride monomer in an amount of from 60 to 99 weight percent and at least one ethylenically unsaturated comonomer copolymerizable with the vinylidene chloride monomer in an amount of from 40 to 1 weight percent, said weight percents being based on the total weight of interpolymer monomer mixture; and (B) from 30 to 14 weight percent, based on the total weight of the polyblend, of a graft copolymer formed from a polymerizable mixture comprising:
(1) from 60 to 75 weight percent of a comonomer mixture, based upon the total polymerizable mixture weight, the comonomer mixture comprising a vinylidene chloride monomer in an amount of from 60 to 99 weight percent and at least one ethylenically unsaturated comonomer copolymerizable therewith in an amount of from 40 to 1 weight percent, said weight percents being based on the total weight of the comonomer mixture; and (2) from 40 to 25 weight percent of a preformed polymer, based upon the total polymerizable mixture weight, the preformed polymer being an olefin polymer selected from the group consisting of ultra-low density polyethylene, linear low density polyethylene, medium density polyethylene, high density poly-ethylene; polypropylene; poly(1-butene), poly(1 -pentene), poly(4-methyl-1-pentene), poly(1 -hexene) and poly(1-octene); chlorinated poly-ethylene; ethylene vinyl acetate; ethylene--propylene copolymers; polyesters and copolyesters; ethylene carbon monoxide copolymers; or mixtures thereof;
whereby upon polymerization, the graft copolymer has at least 30 weight percent of the comonomer mixture grafted thereto.
(A) from 70 to 86 weight percent, based on the total weight of the polyblend, of a vinylidene chloride interpolymer formed from an polymerizable mixture which comprises a vinylidene chloride monomer in an amount of from 60 to 99 weight percent and at least one ethylenically unsaturated comonomer copolymerizable with the vinylidene chloride monomer in an amount of from 40 to 1 weight percent, said weight percents being based on the total weight of interpolymer monomer mixture; and (B) from 30 to 14 weight percent, based on the total weight of the polyblend, of a graft copolymer formed from a polymerizable mixture comprising:
(1) from 60 to 75 weight percent of a comonomer mixture, based upon the total polymerizable mixture weight, the comonomer mixture comprising a vinylidene chloride monomer in an amount of from 60 to 99 weight percent and at least one ethylenically unsaturated comonomer copolymerizable therewith in an amount of from 40 to 1 weight percent, said weight percents being based on the total weight of the comonomer mixture; and (2) from 40 to 25 weight percent of a preformed polymer, based upon the total polymerizable mixture weight, the preformed polymer being an olefin polymer selected from the group consisting of ultra-low density polyethylene, linear low density polyethylene, medium density polyethylene, high density poly-ethylene; polypropylene; poly(1-butene), poly(1 -pentene), poly(4-methyl-1-pentene), poly(1 -hexene) and poly(1-octene); chlorinated poly-ethylene; ethylene vinyl acetate; ethylene--propylene copolymers; polyesters and copolyesters; ethylene carbon monoxide copolymers; or mixtures thereof;
whereby upon polymerization, the graft copolymer has at least 30 weight percent of the comonomer mixture grafted thereto.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US26908388A | 1988-11-09 | 1988-11-09 | |
| US269,083 | 1988-11-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2002460A1 true CA2002460A1 (en) | 1990-05-09 |
Family
ID=23025726
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002002460A Abandoned CA2002460A1 (en) | 1988-11-09 | 1989-11-08 | Polymeric polyblend composition |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR900701923A (en) |
| AU (1) | AU4643689A (en) |
| CA (1) | CA2002460A1 (en) |
| WO (1) | WO1990005030A1 (en) |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4048428A (en) * | 1961-12-05 | 1977-09-13 | W. R. Grace & Co. | Method for preparing a film of vinylidene chloride polymer |
| US4029850A (en) * | 1972-12-27 | 1977-06-14 | Sumitomo Bakelite Company, Limited | Adhesive comprising post-chlorinated polyethylene and polyvinyl chloride |
| CA1041892A (en) * | 1974-04-30 | 1978-11-07 | David H. Dawes | Heat lamination of thermoplastic films |
| DE2707727C3 (en) * | 1977-02-23 | 1981-05-07 | Dynamit Nobel Ag, 5210 Troisdorf | Method for connecting a molded part made of a soft polyvinyl chloride with a molded part made of a polyolefin |
| US4370368A (en) * | 1980-05-07 | 1983-01-25 | Toyo Seikan Kaisha, Ltd. | Plastic bottles and process for preparation thereof |
| US4485062A (en) * | 1983-07-05 | 1984-11-27 | E. I. Du Pont De Nemours And Company | Process for extruding polymers |
| US4536545A (en) * | 1983-10-12 | 1985-08-20 | Occidental Chemical Corporation | Graft polymers of polymerizable monomers and olefin polymers |
-
1989
- 1989-11-08 CA CA002002460A patent/CA2002460A1/en not_active Abandoned
- 1989-11-09 KR KR1019900701462A patent/KR900701923A/en not_active Application Discontinuation
- 1989-11-09 WO PCT/US1989/005150 patent/WO1990005030A1/en unknown
- 1989-11-09 AU AU46436/89A patent/AU4643689A/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| KR900701923A (en) | 1990-12-05 |
| WO1990005030A1 (en) | 1990-05-17 |
| AU4643689A (en) | 1990-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0006291B1 (en) | Blends of a polycarbonate resin and interpolymer modifier and articles formed therefrom | |
| JP3315193B2 (en) | Polymer blend | |
| US5338803A (en) | Modified CPE for PVC impact modification | |
| EP0343181A1 (en) | Low gloss weather and impact resistant resins | |
| US5001192A (en) | Polymeric polyblend composition | |
| EP0411822B1 (en) | Polymeric modifier compositions | |
| JPS6121148A (en) | Composition containing thermoplastic fluorine-containing resin | |
| US4853427A (en) | Composition and method to process polymers including ultrahigh molecular weight polyethylene | |
| US3819554A (en) | Readily processable essentially rigid vinyl chloride polymer compositions | |
| US4950718A (en) | Alloys of vinylidene chloride interpolymers and olefin polymers | |
| JPH0452297B2 (en) | ||
| US4168285A (en) | Blend of a vinyl chloride polymer and an impact modifier | |
| CA2002460A1 (en) | Polymeric polyblend composition | |
| US3163683A (en) | Ternary blends of vinyl chloride polymer-butadiene/acrylonitrile copolymer rubber-ethylene polymer and processes for making the same | |
| EP0467958A4 (en) | Polypropylene-polyester graft copolymer and production method thereof | |
| Hardt | ‘Elasticisation’and plasticisation of PVC with ethylene‐vinyl acetate copolymers | |
| US4871801A (en) | Reactive polyvinyl chloride and polymer products made therefrom | |
| US3435098A (en) | Resin composition of a vinyl chloride polymer blended with an ethylene-vinyl chloride copolymer | |
| US5039749A (en) | Thermoplastic acrylic resin composition | |
| EP0279430A2 (en) | The method of manufacturing a grafted resin composition | |
| US3158665A (en) | Binary polyblends of styrene/acrylonitrile copolymer and chlorosulfonated ethylene polymer | |
| KR920000473B1 (en) | Thermoplastic acril resin composition | |
| EP0344657A2 (en) | Porous copolymer resins | |
| US4975487A (en) | Polymeric polyblend composition | |
| US4206290A (en) | Fire retardant resinous compositions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |