CA2353571A1 - Halogen-containing vinyl polymer resins and processes for the preparation thereof - Google Patents
Halogen-containing vinyl polymer resins and processes for the preparation thereof Download PDFInfo
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- CA2353571A1 CA2353571A1 CA002353571A CA2353571A CA2353571A1 CA 2353571 A1 CA2353571 A1 CA 2353571A1 CA 002353571 A CA002353571 A CA 002353571A CA 2353571 A CA2353571 A CA 2353571A CA 2353571 A1 CA2353571 A1 CA 2353571A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
- C08J3/215—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase at least one additive being also premixed with a liquid phase
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/14—Treatment of polymer emulsions
- C08F6/22—Coagulation
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use 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; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- Extrusion Moulding Of Plastics Or The Like (AREA)
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Abstract
Halogen-containing vinyl polymer resins in the form of co-coagulates of particles of halogen-containing vinyl polymer resins and particles which are chosen from the group of processing aids, stabilisers, plasticizers and/or other polymer resins which particles are substantially homogeneously distributed throughout. These co-coagulates are substantially free of polymer dust and fines and are substantially free from lumping and crusting. These co-coagulates are further "ready-to-use", do not require blending or the addition of further components thereto before being extruded, and present good flowability, thermal stability and extrudability.
Description
Halosten-containing vinyl polymer resins and processes for the preparation thereof The present invention relates to halogen-containing vinyl polymer resins, and in particular halogen-containing vinyl polymer resins formed by polymerisation in aqueous emulsion, processes for the preparation of such resins by co-coagulation with other emulsions, the use of such resins for the formation of articles therefrom by extrusion and the extruded articles obtained therefrom.
Traditionally, halogen-containing vinyl polymer resins formed by polymerisation in aqueous emulsion are coagulated producing larger coagulated polymer particles. The liquid portion of the emulsion is then removed from the coagulated polymer leaving a dry coagulated halogen-containing vinyl polymer resin.
The polymer resins formed in this fashion include fines and dust (particles which, generally speaking, are less than about 45 microns in size) of the resin.
To produce a polymer blend for extrusion, these dry halogen-containing vinyl polymer resins are then normally blended with other materials, such as stabilisers, plasticizers, processing aids and other polymers, in a blender (mixer) to form a polymer blend. This polymer blend is then extn~ded forming extruded articles.
Unfortunately, the presence of fines and dust in the polymer resins is at least partially responsible for the formation of "sticky" particles which are the source of several problems which occur when forming (blending) and extruding of the polymer blends.
Due to their tendency to melt more rapidly than larger particles under the heat, frictional and otherwise, to which they are exposed during blending, fines and dust tend to be "sticky", particularly when a high-speed blender is used.
These "sticky" particles tend to adhere not only to one another and to other resin particles, but also to the blades of the blender. The adherence of these "sticky"
polymer fines and dust to one another is problematic in that it leads to the formation of lumps which causes problems in the extrusion feed. The adherence of these "sticky" polymer fines and dust to the blades of the blender is problematic in that it encrusts them which leads to poor blending and results in a lower quality product (polymer blend) being obtained unless important investments are made and processing downtime incurred to clean the encrusted blades.
Furthermore, fines and dust of polymer resins have limited capabilities to absorb liquids (such as epoxidized soybean oil and liquid plasticizers) that are S added to the resin during blending. This results in a poorly stabilised or a poorly plasticized polymer resin. This is particularly problematic when the liquid does not fully penetrate the polymer resin being blended, such as when the resin is that of a barrier polymer, like polyvinylidene chloride (PVDC), which resist such penetration.
The addition of solid additives, such as processing aids or other polymers results in a blend which is heterogeneous by nature and which is subject to segregation during transport and feeding during extrusion, resulting in uneven feeding and inducing variations in the backpressure which is undesirable, particularly where the extrusion of PVDC is involved.
Further, during extrusion, poorly stabilised.fines and dust of polymer resin tend to segregate in the extrusion feed hopper, resulting in uneven feeding and inducing variations in the backpressure in the extruder. Furthermore, such fines and dust tend to require longer residence times in the extruder during which time they are exposed to heat from the extruder which turns them dark or black. The presence of such dark or black particles in the extruded product is highly undesirable, particularly when the final product is a film.
Solutions proposed to avoid the above-mentioned problems have, for the most part, centered on avoiding the formation of "sticky" particles of polymer resin (and not on avoiding the formation of the polymer fines and dust). In _. 25 particular, resort has been made to the incorporation of stabilisers, such as epoxidized soybean oil (ESO), in the polymer resin during emulsion polymerisation. However, such a solution has not been entirely satisfactory in solving the problem in that the addition of ESO (even at concentrations as low as 4 parts per thousand) during polymerisation, even under the form of an emulsion, leads to the formation of sludge in the autoclave. Such sludge detrimentally affects the process and the products later extruded therefrom.
Thus, it can be seen that it would be highly desirable to provide a halogen-containing vinyl polymer resin which is substantially free of dust and fines, and in particular, such a polymer resin which has a thermal stabiliser, such as ESO, incorporated therein.
Traditionally, halogen-containing vinyl polymer resins formed by polymerisation in aqueous emulsion are coagulated producing larger coagulated polymer particles. The liquid portion of the emulsion is then removed from the coagulated polymer leaving a dry coagulated halogen-containing vinyl polymer resin.
The polymer resins formed in this fashion include fines and dust (particles which, generally speaking, are less than about 45 microns in size) of the resin.
To produce a polymer blend for extrusion, these dry halogen-containing vinyl polymer resins are then normally blended with other materials, such as stabilisers, plasticizers, processing aids and other polymers, in a blender (mixer) to form a polymer blend. This polymer blend is then extn~ded forming extruded articles.
Unfortunately, the presence of fines and dust in the polymer resins is at least partially responsible for the formation of "sticky" particles which are the source of several problems which occur when forming (blending) and extruding of the polymer blends.
Due to their tendency to melt more rapidly than larger particles under the heat, frictional and otherwise, to which they are exposed during blending, fines and dust tend to be "sticky", particularly when a high-speed blender is used.
These "sticky" particles tend to adhere not only to one another and to other resin particles, but also to the blades of the blender. The adherence of these "sticky"
polymer fines and dust to one another is problematic in that it leads to the formation of lumps which causes problems in the extrusion feed. The adherence of these "sticky" polymer fines and dust to the blades of the blender is problematic in that it encrusts them which leads to poor blending and results in a lower quality product (polymer blend) being obtained unless important investments are made and processing downtime incurred to clean the encrusted blades.
Furthermore, fines and dust of polymer resins have limited capabilities to absorb liquids (such as epoxidized soybean oil and liquid plasticizers) that are S added to the resin during blending. This results in a poorly stabilised or a poorly plasticized polymer resin. This is particularly problematic when the liquid does not fully penetrate the polymer resin being blended, such as when the resin is that of a barrier polymer, like polyvinylidene chloride (PVDC), which resist such penetration.
The addition of solid additives, such as processing aids or other polymers results in a blend which is heterogeneous by nature and which is subject to segregation during transport and feeding during extrusion, resulting in uneven feeding and inducing variations in the backpressure which is undesirable, particularly where the extrusion of PVDC is involved.
Further, during extrusion, poorly stabilised.fines and dust of polymer resin tend to segregate in the extrusion feed hopper, resulting in uneven feeding and inducing variations in the backpressure in the extruder. Furthermore, such fines and dust tend to require longer residence times in the extruder during which time they are exposed to heat from the extruder which turns them dark or black. The presence of such dark or black particles in the extruded product is highly undesirable, particularly when the final product is a film.
Solutions proposed to avoid the above-mentioned problems have, for the most part, centered on avoiding the formation of "sticky" particles of polymer resin (and not on avoiding the formation of the polymer fines and dust). In _. 25 particular, resort has been made to the incorporation of stabilisers, such as epoxidized soybean oil (ESO), in the polymer resin during emulsion polymerisation. However, such a solution has not been entirely satisfactory in solving the problem in that the addition of ESO (even at concentrations as low as 4 parts per thousand) during polymerisation, even under the form of an emulsion, leads to the formation of sludge in the autoclave. Such sludge detrimentally affects the process and the products later extruded therefrom.
Thus, it can be seen that it would be highly desirable to provide a halogen-containing vinyl polymer resin which is substantially free of dust and fines, and in particular, such a polymer resin which has a thermal stabiliser, such as ESO, incorporated therein.
Accordingly, there remains a need to provide a solution to the above-mentioned problems by providing a halogen-containing vinyl polymer resin, and in particular a vinylidene chloride polymer resin, that is prepared by polymerisation in an aqueous emulsion, which polymer resin is substantially free of polymer fines and dust. There remains a further need to provide such a substantially fine and dust free polymer resin which has a thermal stabiliser, such as ESO, incorporated therein, so that the resin has good thermal stability, flowability and extrudability and is less prone to lumping than conventional polymer resins.
It is a primary object of the present invention to provide halogen-containing vinyl polymer resins which have improved thermal stability, flowability and extrudability and which are less prone to lumping than conventional halogen-containing vinyl polymer resins.
In this regard, it is a further primary object to provide such resins which have those desired additives, such as processing aids, stabilisers (such as thermal stabilisers, plasticizers and/or other polymers, incorporated therein, so that such additives do not need to be added later, so that blending of the resin is avoided and so that a resin which is "ready-to-use" (that is to say, a resin that may be directly employed without the necessity for any further treatment, mixing or other processing) is provided.
It is a further primary object of the present invention to provide such polymer resins in the form of a co-coagulate having a substantially homogeneous distribution of the halogen-containing vinyl polymer resin and of those other substances, such as processing aids, stabilisers (such as thermal stabilisers), plasticizers and/or other polymers which are desired to be included therewith.
It is a still further primary object of the present invention to provide such halogen-containing vinyl polymer resins which are substantially free of polymer dust and fines.
A further primary object of the present invention is to provide processes for the preparation of such halogen-containing vinyl polymer resins and such co-coagulates. In this regard, it is a further primary object of the present invention to provide novel processes for including those desired additives, such as stabilisers, processing aids, plasticizers and other polymers with the polymer resin without the need for, and eliminating the step of, blending.
It is a primary object of the present invention to provide halogen-containing vinyl polymer resins which have improved thermal stability, flowability and extrudability and which are less prone to lumping than conventional halogen-containing vinyl polymer resins.
In this regard, it is a further primary object to provide such resins which have those desired additives, such as processing aids, stabilisers (such as thermal stabilisers, plasticizers and/or other polymers, incorporated therein, so that such additives do not need to be added later, so that blending of the resin is avoided and so that a resin which is "ready-to-use" (that is to say, a resin that may be directly employed without the necessity for any further treatment, mixing or other processing) is provided.
It is a further primary object of the present invention to provide such polymer resins in the form of a co-coagulate having a substantially homogeneous distribution of the halogen-containing vinyl polymer resin and of those other substances, such as processing aids, stabilisers (such as thermal stabilisers), plasticizers and/or other polymers which are desired to be included therewith.
It is a still further primary object of the present invention to provide such halogen-containing vinyl polymer resins which are substantially free of polymer dust and fines.
A further primary object of the present invention is to provide processes for the preparation of such halogen-containing vinyl polymer resins and such co-coagulates. In this regard, it is a further primary object of the present invention to provide novel processes for including those desired additives, such as stabilisers, processing aids, plasticizers and other polymers with the polymer resin without the need for, and eliminating the step of, blending.
It is a still further object of the present invention to provide methods and to use such halogen-containing vinyl polymer resins and such co-coagulates to form extruded articles.
A still further object of the present invention is to provide extruded articles formed from such halogen-containing vinyl polymer resins and such co-coagulates.
In accordance with the teachings of the present invention, disclosed herein are halogen-containing vinyl polymer resins in the form of co-coagulates of particles of halogen-containing vinyl polymer resins and particles which are chosen from the group (comprised) of processing aids, stabilisers (such as thermal stabilisers), plasticizers and/or other polymer resins. These co-coagulates are substantially free of polymer dust and fines and are substantially free from lumping and crusting. Also, by having those additives (that is to say, the processing aids, stabilisers (such as thermal stabilisers), plasticizers and/or I S other polymer resins which are desired to be included therewith) which are desired to be included with the halogen-containing vinyl polymer resin, these co-coagulates have halogen-containing vinyl polymer resins which are "ready-to-use", do not require blending or the addition of further components thereto before being extruded, and present good flowability, thermal stability and extrudability.
As used herein, the term "halogen-containing vinyl polymer" refers to those (homo- and co-) polymers which are formed by the polymerisation of halogen-containing vinyl monomers. Such polymers may be obtained by any known means. However, preferred is the radical polymerisation in aqueous emulsion of halogen-containing vinyl monomers (either by themselves for forming halogen-containing vinyl homopolymers or with other copolymerizable monomers, such as vinylic esters, vinylic ethers, acrylic acids, acrylic esters, acrylic nitriles, acrylic amides, methacrylic acids, methacrylic esters, methacrylic amides, styrene, styrenic derivatives, butadiene, olefins such as ethylene and propylene, itaconic acid and malefic anhydride for forming halogen-containing vinyl copolymers). Examples of such halogen-containing vinyl polymers are polyvinylidene chloride (PVDC), polyvinyl chloride (PVC) and polyvinylidene fluoride (PVDF).
As used herein, the term "halogen-containing vinyl polymer resin" refers to those (homo- and co-) polymer resins which are formed by the polymerisation of halogen-containing vinyl monomers. Such polymer resins may be obtained by any known means. However, preferred is the radical polymerisation in aqueous emulsion of halogen-containing vinyl monomers (either by themselves for forming halogen-containing vinyl homopolymers or with other copolymerizable monomers, such as vinylic esters, vinylic ethers, acrylic acids, acrylic esters, acrylic nitrites, acrylic amides, methacrylic acids, methacrylic esters, methacrylic amides, styrene, styrenic derivatives, butadiene, olefins such as ethylene and propylene, itaconic acid and malefic anhydride for forming halogen-containing vinyl copolymers). Examples of such halogen-containing vinyl polymer resins are polyvinylidene chloride (PVDC), polyvinyl chloride (PVC) and polyvinylidene fluoride (PVDF).
The co-coagulates of the present invention are further characterized in that the particles of halogen-containing vinyl polymer resins and the particles chosen from the group (comprised) of processing aids, stabilisers (such as thermal stabilisers), plasticizers and other polymer resins are substantially homogeneously distributed throughout the diameter of each individual co-coagulate.
Preferably, the particles of the halogen-containing vinyl polymer resins of the co-coagulates of the present invention are formed from by radical polymerisation in aqueous emulsion of at least one halogen-containing vinyl monomer and at least one other monomer.
As used herein, the term "radical polymerisation in an aqueous emulsion"
is used to describe those radical polymerisation reactions which are carried out in an aqueous milieu in the presence of emulsifying agents and radical initiators.
This definition specifically includes "classical" polymerisation in an aqueous emulsion, in which one employs hydrosoluble radical initiators, as well as microsuspension polymerisation (sometimes referred to as homogeneous aqueous dispersions) in which one employs oleosoluble initiators.
Polymerisation in this manner provides an emulsion of monomer droplets by a strong mechanical agitation in the presence of emulsifying agents.
As used herein, the term "aqueous dispersion" (sometimes also referred to as "latex") is used to describe the polymer dispersion in water obtained after radical polymerisation in an aqueous emulsion.
As used herein, the term "vinyl monomer" refers to those monomers possessing a terminal olefin insaturation substituted by at least one other atom.
As used herein, the term "halogen-containing vinyl monomer" refers to those vinyl monomers possessing a terminal olefin insaturation substituted by at least one halogen atom. Examples of such monomers are vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene and hexafluoropropylene. Preferred are vinylidene chloride (VDC) and vinyl chloride (VC).
It is further preferred that the particles of the halogen-containing vinyl polymer resins of the co-coagulates of the present invention are particles of chloride-containing vinyl polymer resins. Examples of such chloride-containing vinyl polymer resins are polyvinyl chloride (PVC) having vinyl chloride monomers, and polyvinylidene chloride (PVDC) having vinylidene chloride monomers.
As used herein, the term "chloride-containing vinyl polymer resin" refers to those (homo- and co-) polymer resins which are formed by the polymerisation of chloride-containing vinyl monomers. Such polymer resins may be obtained by any known means. However, preferred is the radical polymerisation in aqueous emulsion of chloride-containing vinyl monomers (either by themselves for forming chloride-containing vinyl homopolymers or with other copolymerizable monomers, such as vinylic esters, vinylic ethers, acrylic acids, acrylic esters, acrylic nitriles, acrylic amides, methacrylic acids, methacrylic esters, methacrylic amides, styrene, styrenic derivatives, butadiene, olefins such as ethylene and propylene, itaconic acid and malefic anhydride for forming copolymers). Examples of such chloride-containing vinyl polymer resins are polyvinylidene chloride (PVDC} and polyvinyl chloride (PVC).
As used herein, the term "chloride-containing vinyl polymer" refers to _, 25 those (homo- and co-) polymers which are formed by the polymerisation of chloride-containing vinyl monomers. Such polymers may be may be obtained by any known means. However, preferred is the radical polymerisation in aqueous emulsion of chloride-containing vinyl monomers (either by themselves for forming chloride-containing vinyl homopolymers or with other copolymerizable monomers, such as vinylic esters, vinylic ethers, acrylic acids, acrylic esters, acrylic nitriles, acrylic amides, methacrylic acids, methacrylic esters, methacrylic amides, styrene, styrenic derivatives, butadiene, olefins such as ethylene and propylene, itaconic acid and malefic anhydride for forming copolymers).
Examples of such chloride-containing vinyl polymers are polyvinylidene chloride (PVDC) and polyvinyl chloride (PVC).
As noted above, the particles of the halogen-containing vinyl polymer resins of the co-coagulates of the present invention may also be particles of halogen-containing vinyl copolymer resins having halogen-containing vinyl monomers and at least one other monomer.
Preferred in this regard is that the particles of chloride-containing vinyl copolymer resins are particles of copolymers comprised of chloride-containing vinyl monomers and at least one other monomer. Examples of such particles of copolymers are particles comprised of vinyl chloride monomers and at least one other monomer and particles comprised of vinylidene chloride monomers and at least one other monomer.
As used herein, the term "chloride-containing vinyl monomer" refers to those vinyl monomers possessing a terminal olefin insaturation substituted by at least one chloride atom. Examples of such monomers are vinylidene chloride (VDC) and vinyl chloride (VC).
Further preferred in this regard are particles of copolymers comprised of two different halogen-containing vinyl monomers, and in particular vinylidene chloride monomers and vinyl chloride monomers. In this regard, in one embodiment, the halogen-containing vinyl copolymer resin of the present invention includes a vinylidene chloride/vinyl chloride (VDC/VC) resin.
Particularly preferred is the VDC/VC copolymer emulsion resin.
Still further preferred in this regard are particles of copolymers comprised of two different halogen-containing vinyl monomers (in particular vinylidene chloride monomers and vinyl chloride monomers) and at least one other monomer. Of particular preference is that the other monomers be monomers of acrylates and/or methacrylates. Further particularly preferred in this regard is that the other monomers are monomers of glycidylmethacrylate.
As used herein, monomers of (metha)acrylates are those monomers having the following general formula CH2=CR1R2 in which R1 is selected from the group consisting of hydrogen and methyl radical and in which R2 is selected from the group consisting of -CN radical and -CO-OR3 radical in which R3 is selected from the group consisting of hydrogen, alkyl radicals containing from 1 to 18 carbon atoms, alkoxyalkyl radicals having from 1 to 10 carbon atoms and -NR4R5 radicals, in which R4 and RS are selected from the -g-group consisting of hydrogen and an alkyl radical containing from 1 to 10 carbon atoms.
Alternatively, these copolymer resins of the co-coagulates of the present invention are formed by the polymerisation in emulsion of a halogen-containing vinyl monomer and a monomer or monomers which do not contain a halogen. In this regard, in one embodiment, the halogen-containing vinyl copolymer resin of the present invention includes a vinylidene chloride/methyl acrylate (VDC/MA) resin. Further in this regard, in another embodiment, the halogen-containing vinyl copolymer resin of the co-coagulates of the present invention include a vinylidene chloride/methyl acrylate/glycidylemethacrylate (VDC/NiA/GMA) resin.
When such copolymers contain vinylidene chloride, it is preferred that the vinylidene chloride be the majority halogen-containing vinyl monomer.
In this respect, it is preferred that the copolymer resin has at least about 50% (w/w) of vinylidene chloride. Further preferred is that the polymer resin has at least about 60% (w/w) of vinylidene chloride. Still further preferred is that the polymer resin has at least about 70% (w/w) of vinylidene chloride.
Further in this respect, it is preferred that the copolymer resin has no more than about 95% (w/w) of vinylidene chloride. Further preferred is that the polymer resin has no more than about 85% (w/w) of vinylidene chloride. Still further preferred is that the polymer resin has no more about 75% (w/w) of vinylidene chloride.
Most preferred is that the copolymer resin has about 70% (wlw) to about 75% (w/w) of vinylidene chloride, with about 72% (w/w) of vinylidene chloride being especially preferred.
As used herein, the term "majority halogen-containing vinyl monomer"
refers to that halogen-containing vinyl monomer which comprises at least 50%
(w/w) of the halogen-containing vinyl copolymer resin of which it forms a part.
It is contemplated herein that, in the co-coagulates of the present invention, the particles of the halogen-containing vinyl polymer resin will be solids.
Preferably, the particles selected from the group (comprised) of processing aids, stabilisers (such as thermal stabilisers), plasticizers and other polymer resins which may be included in the co-coagulates of the present invention are also provided in aqueous emulsion.
While not being limited thereto, it is contemplated herein that examples of particles of processing aids which may be included in the co-coagulates of the WO 00/32679 PC'f/EP99/09372 _g-present invention include particles of acrylates, methacrylates, stearates, waxes and polyolefins.
While not being limited thereto, it is contemplated herein that examples of particles of stabilisers (such as thermal stabilisers) which may be included to be included in the co-coagulates of the present invention include epoxidized soybean oil (ESO) and HCl scavengers (such as hydrotatcite-like compounds).
If desired, the stabiliser which is incorporated into the halogen-containing vinyl polymer resins of the co-coagulates of the present invention may be any conventional stabiliser (or liquid processing aid) which is capable of coagulating with the vinyl polymer. Particularly preferred in this regard are emulsions of epoxidized soya oil (ESO).
Preferably, the co-coagulates have approximately at least about 0.5%
(w/w) of stabiliser. Also preferred is that the co-coagulates have approximately at least about 2% (w/w) of stabiliser. Further preferred that the co-coagulates have approximately at least about 4% (w/w) of stabiliser.
It is noted that in this manner, when the stabiliser is an emulsion of ESO
and when the liquid medium is an aqueous emulsion, the stabiliser is very homogeneously distributed throughout the individual co-coagulates.
We have found that incorporation of the stabiliser into the resin in this manner (as a coagulation aid) significantly increases the quantity of co-coagulates which are formed that have a diameter of at least about 45 microns.
We have further found that use of the stabiliser in this manner (as a coagulation aid) significantly reduces the stickiness (of the resin and) of the co coagulates obtained.
_, 25 In addition, we believe that the presence of the emulsifier in the ESO
plays a role in internal lubrication during extrusion of the co-coagulates of the present invention.
While not being limited thereto, it is contemplated herein that examples of particles of plasticizers to be included in the co-coagulates of the present invention are selected from the group (comprised) of debutyl sebacate, acetyl tributyl citrate, dioctyl adipate (DOA), latexes of butadiene-styrene and polycaprolactones, such as s-caprolactones.
While not being limited thereto, it is contemplated herein that examples of particles of other polymer resins to be included in the co-coagulates of the present invention are selected from the group (comprised) of homopolymers and copolymers having monomers of vinyl chloride, vinylidene chloride, vinylidene fluoride, ethylene vinyl acetate and ethylene methyl acrylate.
It is contemplated herein that the particles selected from the group (comprised) of processing aids, stabilisers (such as thermal stabilisers), plasticizers and other polymer resins of the present invention may be either liquids and/or solids.
In another aspect of the present invention, disclosed herein is a process for the preparation of the halogen-containing vinyl polymer resin containing co-coagulates of the present invention.
The process for preparing the co-coagulates of the present invention includes the steps of (co)polymerisation, co-coagulation and drying. This process in characterised by co-coagulating the halogen-containing vinyl polymer resin and the stabiliser (and, thereby avoiding the necessity for any blending thereof).
In the step of (co)polymerisation, at least one halogen-containing vinyl monomer is polymerised, whereby an emulsion is formed having particles of the (co)polymer resin therein.
The step of (co)polymerisation of the process of the present invention, involves the (co)polymerisation of at least one halogen-containing vinyl monomer. It is contemplated herein that such (co)polymerisation may be radical (co)polymerisation, particularly where the formation of (co)polymer resins having VC and/or VDC and/or VDF monomers are desired. It is further contemplated that (co)polymerisation may be radical (co)polymerisation in an aqueous medium, and in particular radical (co)polymerisation in an aqueous 4 25 emulsion, once again in particular where the formation of (co)polymer resins having VC and/or VDC monomers are desired.
The invention is particularly adapted to such "classical" (co)polymerisation in an aqueous emulsion which is performed in those conditions well-known to those skilled in the art. It is therefor that the (co)polymerisation be performed with the use of emulsifying agents and hydrosoluble initiators present in quantities well-known to those skilled in the art.
Examples of such emulsifying agents are anionic emulsifying agents and nonionic emulsifying agents. Examples of anionic emulsifying agents are sulfonate waxes, alkyl sulfonates, alkyl sulphates, alkylaryl mono and disulfonates and alkylsulfosuccinates. Examples of nonionic emulsifying agents are derivatives of alkyl- and alkylarylethoxylates.
Examples of hydrosoluble initiators are hydrosoluble peroxides such as persulfates of alkaline metals persulfates of ammonium, hydrogen peroxides, perborates and t-butyl hydroperoxide used only in association with a reducer.
Radical (co)polymerizations in an aqueous emulsion are performed in autoclaves. Monomers, initiators and an emulsifier are all introduced into the autoclave. The temperature within the autoclave is then increased and agitation started. Typical temperatures range from about 30°C to about 90°C.
(Co)polymerisation time ranges from about 5 to about 15 hours. At the end of the (co)polymerisation reaction, the autoclave is degassed and stripping is started to remove individual monomers which may remain. The emulsion is then transferred to the co-coagulator for co-coagulation.
In the step of co-coagulation, the particles of the polymer resin in the emulsion and any other particles in the emulsion are co-coagulated, whereby a co-coagulate having the particles of the polymer resin is formed.
The step of co-coagulation of the process of the present invention involves the addition of a salt to the anionic emulsion to provoke co-coagulation of the polymer and formation of a co-coagulate.
According to the teachings of the present invention, the emulsion of the other compound is added to the aqueous emulsion including the polymer resin during co-coagulation simultaneously with the co-coagulating salt.
In the drying step, the co-coagulates having the particles of the polymer resin are dried, whereby co-coagulates having dry particles of the halogen-containing vinyl polymer resin is formed.
The step of separating the liquid medium from the polymer resin of the process of the present invention involves the elimination of a substantial portion of the liquid from the co-coagulate, whereby the co-coagulate in the form of a powder is provided. Such drying step may include removal of portions of the liquid from the co-coagulates having the polymer resin by, for example, decanting, filtration, etc. to provide a cake. The drying step may further include drying the cake so as to provide the co-coagulates having the polymer resin in the form of a powder.
The process of the present invention is particularly characterised by adding to the emulsion, which has the particles of the halogen-containing vinyl polymer resin therein, at least one other emulsion having particles of a substance selected from the group (comprised) of stabilisers, processing aids, plasticizers and other polymers and co-coagulating these two emulsions (the emulsion having the particles of the polymer resin and the emulsion having the at least one other emulsion having the particles of the substance selected from the group (comprised) of stabilisers, processing aids, plasticizers and other polymers).
In this fashion, a co-coagulate comprised of particles of halogen-containing vinyl polymer resins and particles chosen from the group (comprised) of processing aids, stabilisers (such as thermal stabilisers), plasticizers and/or other polymer resins is formed.
The emulsions of the above-described process, and the contents thereof, will vary according to the various co-coagulates having the halogen-containing vinyl polymer resin which are desired to be produced therefrom.
In still another aspect of the present invention, disclosed herein is the use of the co-coagulates of the present invention which have the particles of halogen-containing polymer resins and the particles chosen from the group (comprised) of processing aids, stabilisers (such as thermal stabilisers), plasticizers and/or other polymer resins for the formation of extruded articles.
The polymer/stabiliser resins of the present invention may be used to foim articles. In this regard, it is contemplated that the polymer/stabiliser resin will be extruded in an extruder for forming extrudable articles, such mono- layer and multilayer barrier films and foils. Further in this regard, it is noted that it is believed that the presence of the emulsifier in the ESO could play a role in internal lubrication during extrusion.
In a still another aspect of the present invention, disclosed herein are extruded articles which are formed from the co-coagulates of the present invention which have the particles of halogen-containing polymer resins and the _. 25 particles chosen from the group (comprised) of processing aids, stabilisers (such as thermal stabilisers), plasticizers and/or other polymer resins.
By co-coagulating the emulsion which contains the halogen-containing vinyl polymer (before blending) with the emulsions) having either the desired processing aids, stabilisers (such as thermal stabilisers), plasticizers and/or other polymer resins in accordance with the present invention, the co-coagulates of the present invention are formed so that each co-coagulate is an intimate mixture of each component (that is to say, the particles of these various components are substantially homogeneously distributed throughout each co-coagulate).
Accordingly, the co-coagulates of the present invention form a very homogenous 3 5 blend.
In this fashion, stabilisers, such as ESO, which are incorporated therein, act as an internal lubricant which is of particular interest where resins are involved that have poor stability, such as is particularly notable in the case of barrier polymers, such as PVDC.
Further, by being co-coagulated according to the process of the present invention, the particles of the base emulsions, which are typically less than 0.5 microns in size, are formed into larger co-coagulates. A substantial portion of these co-coagulates are larger than about 45 microns in size, so that the resins comprised of such co-coagulates are substantially free of polymer dust and fines.
As used herein, the term "emulsion resin" is used to refer to a resin that is obtained from an aqueous emulsion prepared using radical polymerisation in an aqueous emulsion.
The process of the present invention presents, above all, the advantage that the polymerisation itself is not effected (no sludge formation, no problems of residual monomers, etc.) and that the particles of those other components (such as the processing aids, stabilisers -- and particularly ESO --, plasticizers and/or other polymer resins) is always well incorporated and, therefor, well protected.
In this regard, we note that in contrast to suspension polymerisation's (where ESO can be placed directly into the polymerisation reactor during polymerisation), this is not possible where emulsion polymerisation is involved due to the formation of sludge which such an addition provokes, even when an emulsified ESO is used. Thus, the process of the present invention provides a manner where such ESO can be satisfactorily incorporated into the polymer resin.
In addition, we believe that the presence of the emulsifier in the ESO plays a role in internal lubrication during extrusion of the co-coagulates of the present invention.
Other important characteristics of the co-coagulates, notably their thermal stability, the barrier properties thereof and their extrudability, are at least equivalent to or superior to those in comparison to a premix. In this regard, we note that while premixes may tend to be not extrudable due to extensive lumping, the "ready-to-use" co-coagulates of the present invention give rise to very stable extrusion conditions.
The halogen-containing vinyl polymer resins of the co-coagulates of the present invention may be either homopolymers or copolymers. It is contemplated that copolymers of the co-coagulates of the present invention may be formed by either copolymerization or by independent polymerization and subsequent blending.
Preferably, these copolymer resins of the co-coagulates of the present invention are formed by the polymerisation in emulsion of at least two different halogen-containing vinyl monomers.
The above-described properties of the co-coagulates of the present invention, and particularly those properties of increased particles size and reduced stickiness, which are obtained by the process of the present invention permits the co-coagulates having the polymer resin/stabiliser to be used without any blending. Further, the co-coagulates of the present invention are less prone to both crusting the blades of the blender and to lumping (the formation of less and/or smaller lumps). In this fashion, the co-coagulates of the present invention prESent good flowability, thermal stability and extrudability.
Having thus described the invention, the following examples are now presented which are for illustrative purposes only are not meant to limit the scope of the present invention.
Exam le Polymerisation Into a 16 liter autoclave was introduced 6150 cm3 of demineralized water.
Then, under agitation of 160 rpm using an impeller, 390 cm3 of a solution of 110 g/1 tetrapropylbenzene sulfonate, 4590 g of VDC monomer and 1910 g of VC monomer were added and the temperature of the autoclave was set at 4b°C.
At 44°C, 110 cm3of an aqueous solution of 20 g/1 erythorbic acid was added to the solution in the autoclave followed by the successive addition of __ 25 100 cm3 of an aqueous solution of 3.5 g/1 H202.
minutes later, an aqueous solution (3 g/1) of erythorbic acid and an aqueous solution of 0.8 g/l H202 were injected continuously (at respective rates of 100 cm3/hour) for about 450 minutes.
After depressurising the autoclave for about 3 hours, the autoclave was 30 cooled to ambient temperature. Then 2500 cm3of demineralized water was added to dilute the VDC based latex.
Co-coa~uiation according to the invention Into a first 150 litre vat, regulated by a water jacket, 30 litres of demineralized water and 0.7 litres of an aqueous solution of aluminium sulphate (8.6 g/1) was added.
WO 00/32679 PCT/EP99/093'I2 The vat was then put under agitation at 200 rpm and the temperature thereof was adjusted to about 15 °C.
23 litres of the formed VDC latex along with 1 litre of an emulsion of epoxidized Soya bean oil (at 250 g/1) were then evenly and continuously added in parallel to the first vat for about 20 minutes.
The first vat was then heated to 70°C and maintained at that temperature for 90 minutes.
The vat was then cooled to room temperature, producing a slurry having the co-coagulate therein.
Coagulation ~ classical means (for comparison) Into a second 150 litre vat, regulated by a water jacket, 30 litres of demineralized water and 0.7 litres of an aqueous solution of aluminium sulphate (8.6 g11) was added.
The second vat was then put under agitation at 200 rpm and the temperature thereof was adjusted to about 15°C.
23 litres of the formed VDC latex is then even and continuously added in parallel to the second vat for about 20 minutes.
The second vat was then heated to 70°C and maintained at that temperature for 90 minutes.
The second vat was then cooled to room temperature, producing a slurry having a conventional coagulate.
Dr~rlng The slurries from the first and the second vats were then dried by, first, separating the liquid from the solid in an ESCHER WYSS~ system. In this fashion, a "cake" of the co-coagulates of the present invention (from vat 1) and a "cake" having traditional coagulates (from vat 2) are formed.
The cakes were then dried in a Munster~ fluidised bed with an air temperature at entry of about 60°C until the volatile material content thereof was reduced to less than 0.3 % (w/w).
The particle sizes of the co-coagulate particles of the two cakes were then measured and the results thereof given below in Table 1.
Table 1 Particle Size of Co-coa ulates (in microns) Sample > 850-450 450-250 250-150 150-45 <_45 Cake 1 662 246 64 15 8 5 Co-coagulates Cake 2 229 208 190 212 93 28 Coagulates
A still further object of the present invention is to provide extruded articles formed from such halogen-containing vinyl polymer resins and such co-coagulates.
In accordance with the teachings of the present invention, disclosed herein are halogen-containing vinyl polymer resins in the form of co-coagulates of particles of halogen-containing vinyl polymer resins and particles which are chosen from the group (comprised) of processing aids, stabilisers (such as thermal stabilisers), plasticizers and/or other polymer resins. These co-coagulates are substantially free of polymer dust and fines and are substantially free from lumping and crusting. Also, by having those additives (that is to say, the processing aids, stabilisers (such as thermal stabilisers), plasticizers and/or I S other polymer resins which are desired to be included therewith) which are desired to be included with the halogen-containing vinyl polymer resin, these co-coagulates have halogen-containing vinyl polymer resins which are "ready-to-use", do not require blending or the addition of further components thereto before being extruded, and present good flowability, thermal stability and extrudability.
As used herein, the term "halogen-containing vinyl polymer" refers to those (homo- and co-) polymers which are formed by the polymerisation of halogen-containing vinyl monomers. Such polymers may be obtained by any known means. However, preferred is the radical polymerisation in aqueous emulsion of halogen-containing vinyl monomers (either by themselves for forming halogen-containing vinyl homopolymers or with other copolymerizable monomers, such as vinylic esters, vinylic ethers, acrylic acids, acrylic esters, acrylic nitriles, acrylic amides, methacrylic acids, methacrylic esters, methacrylic amides, styrene, styrenic derivatives, butadiene, olefins such as ethylene and propylene, itaconic acid and malefic anhydride for forming halogen-containing vinyl copolymers). Examples of such halogen-containing vinyl polymers are polyvinylidene chloride (PVDC), polyvinyl chloride (PVC) and polyvinylidene fluoride (PVDF).
As used herein, the term "halogen-containing vinyl polymer resin" refers to those (homo- and co-) polymer resins which are formed by the polymerisation of halogen-containing vinyl monomers. Such polymer resins may be obtained by any known means. However, preferred is the radical polymerisation in aqueous emulsion of halogen-containing vinyl monomers (either by themselves for forming halogen-containing vinyl homopolymers or with other copolymerizable monomers, such as vinylic esters, vinylic ethers, acrylic acids, acrylic esters, acrylic nitrites, acrylic amides, methacrylic acids, methacrylic esters, methacrylic amides, styrene, styrenic derivatives, butadiene, olefins such as ethylene and propylene, itaconic acid and malefic anhydride for forming halogen-containing vinyl copolymers). Examples of such halogen-containing vinyl polymer resins are polyvinylidene chloride (PVDC), polyvinyl chloride (PVC) and polyvinylidene fluoride (PVDF).
The co-coagulates of the present invention are further characterized in that the particles of halogen-containing vinyl polymer resins and the particles chosen from the group (comprised) of processing aids, stabilisers (such as thermal stabilisers), plasticizers and other polymer resins are substantially homogeneously distributed throughout the diameter of each individual co-coagulate.
Preferably, the particles of the halogen-containing vinyl polymer resins of the co-coagulates of the present invention are formed from by radical polymerisation in aqueous emulsion of at least one halogen-containing vinyl monomer and at least one other monomer.
As used herein, the term "radical polymerisation in an aqueous emulsion"
is used to describe those radical polymerisation reactions which are carried out in an aqueous milieu in the presence of emulsifying agents and radical initiators.
This definition specifically includes "classical" polymerisation in an aqueous emulsion, in which one employs hydrosoluble radical initiators, as well as microsuspension polymerisation (sometimes referred to as homogeneous aqueous dispersions) in which one employs oleosoluble initiators.
Polymerisation in this manner provides an emulsion of monomer droplets by a strong mechanical agitation in the presence of emulsifying agents.
As used herein, the term "aqueous dispersion" (sometimes also referred to as "latex") is used to describe the polymer dispersion in water obtained after radical polymerisation in an aqueous emulsion.
As used herein, the term "vinyl monomer" refers to those monomers possessing a terminal olefin insaturation substituted by at least one other atom.
As used herein, the term "halogen-containing vinyl monomer" refers to those vinyl monomers possessing a terminal olefin insaturation substituted by at least one halogen atom. Examples of such monomers are vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene and hexafluoropropylene. Preferred are vinylidene chloride (VDC) and vinyl chloride (VC).
It is further preferred that the particles of the halogen-containing vinyl polymer resins of the co-coagulates of the present invention are particles of chloride-containing vinyl polymer resins. Examples of such chloride-containing vinyl polymer resins are polyvinyl chloride (PVC) having vinyl chloride monomers, and polyvinylidene chloride (PVDC) having vinylidene chloride monomers.
As used herein, the term "chloride-containing vinyl polymer resin" refers to those (homo- and co-) polymer resins which are formed by the polymerisation of chloride-containing vinyl monomers. Such polymer resins may be obtained by any known means. However, preferred is the radical polymerisation in aqueous emulsion of chloride-containing vinyl monomers (either by themselves for forming chloride-containing vinyl homopolymers or with other copolymerizable monomers, such as vinylic esters, vinylic ethers, acrylic acids, acrylic esters, acrylic nitriles, acrylic amides, methacrylic acids, methacrylic esters, methacrylic amides, styrene, styrenic derivatives, butadiene, olefins such as ethylene and propylene, itaconic acid and malefic anhydride for forming copolymers). Examples of such chloride-containing vinyl polymer resins are polyvinylidene chloride (PVDC} and polyvinyl chloride (PVC).
As used herein, the term "chloride-containing vinyl polymer" refers to _, 25 those (homo- and co-) polymers which are formed by the polymerisation of chloride-containing vinyl monomers. Such polymers may be may be obtained by any known means. However, preferred is the radical polymerisation in aqueous emulsion of chloride-containing vinyl monomers (either by themselves for forming chloride-containing vinyl homopolymers or with other copolymerizable monomers, such as vinylic esters, vinylic ethers, acrylic acids, acrylic esters, acrylic nitriles, acrylic amides, methacrylic acids, methacrylic esters, methacrylic amides, styrene, styrenic derivatives, butadiene, olefins such as ethylene and propylene, itaconic acid and malefic anhydride for forming copolymers).
Examples of such chloride-containing vinyl polymers are polyvinylidene chloride (PVDC) and polyvinyl chloride (PVC).
As noted above, the particles of the halogen-containing vinyl polymer resins of the co-coagulates of the present invention may also be particles of halogen-containing vinyl copolymer resins having halogen-containing vinyl monomers and at least one other monomer.
Preferred in this regard is that the particles of chloride-containing vinyl copolymer resins are particles of copolymers comprised of chloride-containing vinyl monomers and at least one other monomer. Examples of such particles of copolymers are particles comprised of vinyl chloride monomers and at least one other monomer and particles comprised of vinylidene chloride monomers and at least one other monomer.
As used herein, the term "chloride-containing vinyl monomer" refers to those vinyl monomers possessing a terminal olefin insaturation substituted by at least one chloride atom. Examples of such monomers are vinylidene chloride (VDC) and vinyl chloride (VC).
Further preferred in this regard are particles of copolymers comprised of two different halogen-containing vinyl monomers, and in particular vinylidene chloride monomers and vinyl chloride monomers. In this regard, in one embodiment, the halogen-containing vinyl copolymer resin of the present invention includes a vinylidene chloride/vinyl chloride (VDC/VC) resin.
Particularly preferred is the VDC/VC copolymer emulsion resin.
Still further preferred in this regard are particles of copolymers comprised of two different halogen-containing vinyl monomers (in particular vinylidene chloride monomers and vinyl chloride monomers) and at least one other monomer. Of particular preference is that the other monomers be monomers of acrylates and/or methacrylates. Further particularly preferred in this regard is that the other monomers are monomers of glycidylmethacrylate.
As used herein, monomers of (metha)acrylates are those monomers having the following general formula CH2=CR1R2 in which R1 is selected from the group consisting of hydrogen and methyl radical and in which R2 is selected from the group consisting of -CN radical and -CO-OR3 radical in which R3 is selected from the group consisting of hydrogen, alkyl radicals containing from 1 to 18 carbon atoms, alkoxyalkyl radicals having from 1 to 10 carbon atoms and -NR4R5 radicals, in which R4 and RS are selected from the -g-group consisting of hydrogen and an alkyl radical containing from 1 to 10 carbon atoms.
Alternatively, these copolymer resins of the co-coagulates of the present invention are formed by the polymerisation in emulsion of a halogen-containing vinyl monomer and a monomer or monomers which do not contain a halogen. In this regard, in one embodiment, the halogen-containing vinyl copolymer resin of the present invention includes a vinylidene chloride/methyl acrylate (VDC/MA) resin. Further in this regard, in another embodiment, the halogen-containing vinyl copolymer resin of the co-coagulates of the present invention include a vinylidene chloride/methyl acrylate/glycidylemethacrylate (VDC/NiA/GMA) resin.
When such copolymers contain vinylidene chloride, it is preferred that the vinylidene chloride be the majority halogen-containing vinyl monomer.
In this respect, it is preferred that the copolymer resin has at least about 50% (w/w) of vinylidene chloride. Further preferred is that the polymer resin has at least about 60% (w/w) of vinylidene chloride. Still further preferred is that the polymer resin has at least about 70% (w/w) of vinylidene chloride.
Further in this respect, it is preferred that the copolymer resin has no more than about 95% (w/w) of vinylidene chloride. Further preferred is that the polymer resin has no more than about 85% (w/w) of vinylidene chloride. Still further preferred is that the polymer resin has no more about 75% (w/w) of vinylidene chloride.
Most preferred is that the copolymer resin has about 70% (wlw) to about 75% (w/w) of vinylidene chloride, with about 72% (w/w) of vinylidene chloride being especially preferred.
As used herein, the term "majority halogen-containing vinyl monomer"
refers to that halogen-containing vinyl monomer which comprises at least 50%
(w/w) of the halogen-containing vinyl copolymer resin of which it forms a part.
It is contemplated herein that, in the co-coagulates of the present invention, the particles of the halogen-containing vinyl polymer resin will be solids.
Preferably, the particles selected from the group (comprised) of processing aids, stabilisers (such as thermal stabilisers), plasticizers and other polymer resins which may be included in the co-coagulates of the present invention are also provided in aqueous emulsion.
While not being limited thereto, it is contemplated herein that examples of particles of processing aids which may be included in the co-coagulates of the WO 00/32679 PC'f/EP99/09372 _g-present invention include particles of acrylates, methacrylates, stearates, waxes and polyolefins.
While not being limited thereto, it is contemplated herein that examples of particles of stabilisers (such as thermal stabilisers) which may be included to be included in the co-coagulates of the present invention include epoxidized soybean oil (ESO) and HCl scavengers (such as hydrotatcite-like compounds).
If desired, the stabiliser which is incorporated into the halogen-containing vinyl polymer resins of the co-coagulates of the present invention may be any conventional stabiliser (or liquid processing aid) which is capable of coagulating with the vinyl polymer. Particularly preferred in this regard are emulsions of epoxidized soya oil (ESO).
Preferably, the co-coagulates have approximately at least about 0.5%
(w/w) of stabiliser. Also preferred is that the co-coagulates have approximately at least about 2% (w/w) of stabiliser. Further preferred that the co-coagulates have approximately at least about 4% (w/w) of stabiliser.
It is noted that in this manner, when the stabiliser is an emulsion of ESO
and when the liquid medium is an aqueous emulsion, the stabiliser is very homogeneously distributed throughout the individual co-coagulates.
We have found that incorporation of the stabiliser into the resin in this manner (as a coagulation aid) significantly increases the quantity of co-coagulates which are formed that have a diameter of at least about 45 microns.
We have further found that use of the stabiliser in this manner (as a coagulation aid) significantly reduces the stickiness (of the resin and) of the co coagulates obtained.
_, 25 In addition, we believe that the presence of the emulsifier in the ESO
plays a role in internal lubrication during extrusion of the co-coagulates of the present invention.
While not being limited thereto, it is contemplated herein that examples of particles of plasticizers to be included in the co-coagulates of the present invention are selected from the group (comprised) of debutyl sebacate, acetyl tributyl citrate, dioctyl adipate (DOA), latexes of butadiene-styrene and polycaprolactones, such as s-caprolactones.
While not being limited thereto, it is contemplated herein that examples of particles of other polymer resins to be included in the co-coagulates of the present invention are selected from the group (comprised) of homopolymers and copolymers having monomers of vinyl chloride, vinylidene chloride, vinylidene fluoride, ethylene vinyl acetate and ethylene methyl acrylate.
It is contemplated herein that the particles selected from the group (comprised) of processing aids, stabilisers (such as thermal stabilisers), plasticizers and other polymer resins of the present invention may be either liquids and/or solids.
In another aspect of the present invention, disclosed herein is a process for the preparation of the halogen-containing vinyl polymer resin containing co-coagulates of the present invention.
The process for preparing the co-coagulates of the present invention includes the steps of (co)polymerisation, co-coagulation and drying. This process in characterised by co-coagulating the halogen-containing vinyl polymer resin and the stabiliser (and, thereby avoiding the necessity for any blending thereof).
In the step of (co)polymerisation, at least one halogen-containing vinyl monomer is polymerised, whereby an emulsion is formed having particles of the (co)polymer resin therein.
The step of (co)polymerisation of the process of the present invention, involves the (co)polymerisation of at least one halogen-containing vinyl monomer. It is contemplated herein that such (co)polymerisation may be radical (co)polymerisation, particularly where the formation of (co)polymer resins having VC and/or VDC and/or VDF monomers are desired. It is further contemplated that (co)polymerisation may be radical (co)polymerisation in an aqueous medium, and in particular radical (co)polymerisation in an aqueous 4 25 emulsion, once again in particular where the formation of (co)polymer resins having VC and/or VDC monomers are desired.
The invention is particularly adapted to such "classical" (co)polymerisation in an aqueous emulsion which is performed in those conditions well-known to those skilled in the art. It is therefor that the (co)polymerisation be performed with the use of emulsifying agents and hydrosoluble initiators present in quantities well-known to those skilled in the art.
Examples of such emulsifying agents are anionic emulsifying agents and nonionic emulsifying agents. Examples of anionic emulsifying agents are sulfonate waxes, alkyl sulfonates, alkyl sulphates, alkylaryl mono and disulfonates and alkylsulfosuccinates. Examples of nonionic emulsifying agents are derivatives of alkyl- and alkylarylethoxylates.
Examples of hydrosoluble initiators are hydrosoluble peroxides such as persulfates of alkaline metals persulfates of ammonium, hydrogen peroxides, perborates and t-butyl hydroperoxide used only in association with a reducer.
Radical (co)polymerizations in an aqueous emulsion are performed in autoclaves. Monomers, initiators and an emulsifier are all introduced into the autoclave. The temperature within the autoclave is then increased and agitation started. Typical temperatures range from about 30°C to about 90°C.
(Co)polymerisation time ranges from about 5 to about 15 hours. At the end of the (co)polymerisation reaction, the autoclave is degassed and stripping is started to remove individual monomers which may remain. The emulsion is then transferred to the co-coagulator for co-coagulation.
In the step of co-coagulation, the particles of the polymer resin in the emulsion and any other particles in the emulsion are co-coagulated, whereby a co-coagulate having the particles of the polymer resin is formed.
The step of co-coagulation of the process of the present invention involves the addition of a salt to the anionic emulsion to provoke co-coagulation of the polymer and formation of a co-coagulate.
According to the teachings of the present invention, the emulsion of the other compound is added to the aqueous emulsion including the polymer resin during co-coagulation simultaneously with the co-coagulating salt.
In the drying step, the co-coagulates having the particles of the polymer resin are dried, whereby co-coagulates having dry particles of the halogen-containing vinyl polymer resin is formed.
The step of separating the liquid medium from the polymer resin of the process of the present invention involves the elimination of a substantial portion of the liquid from the co-coagulate, whereby the co-coagulate in the form of a powder is provided. Such drying step may include removal of portions of the liquid from the co-coagulates having the polymer resin by, for example, decanting, filtration, etc. to provide a cake. The drying step may further include drying the cake so as to provide the co-coagulates having the polymer resin in the form of a powder.
The process of the present invention is particularly characterised by adding to the emulsion, which has the particles of the halogen-containing vinyl polymer resin therein, at least one other emulsion having particles of a substance selected from the group (comprised) of stabilisers, processing aids, plasticizers and other polymers and co-coagulating these two emulsions (the emulsion having the particles of the polymer resin and the emulsion having the at least one other emulsion having the particles of the substance selected from the group (comprised) of stabilisers, processing aids, plasticizers and other polymers).
In this fashion, a co-coagulate comprised of particles of halogen-containing vinyl polymer resins and particles chosen from the group (comprised) of processing aids, stabilisers (such as thermal stabilisers), plasticizers and/or other polymer resins is formed.
The emulsions of the above-described process, and the contents thereof, will vary according to the various co-coagulates having the halogen-containing vinyl polymer resin which are desired to be produced therefrom.
In still another aspect of the present invention, disclosed herein is the use of the co-coagulates of the present invention which have the particles of halogen-containing polymer resins and the particles chosen from the group (comprised) of processing aids, stabilisers (such as thermal stabilisers), plasticizers and/or other polymer resins for the formation of extruded articles.
The polymer/stabiliser resins of the present invention may be used to foim articles. In this regard, it is contemplated that the polymer/stabiliser resin will be extruded in an extruder for forming extrudable articles, such mono- layer and multilayer barrier films and foils. Further in this regard, it is noted that it is believed that the presence of the emulsifier in the ESO could play a role in internal lubrication during extrusion.
In a still another aspect of the present invention, disclosed herein are extruded articles which are formed from the co-coagulates of the present invention which have the particles of halogen-containing polymer resins and the _. 25 particles chosen from the group (comprised) of processing aids, stabilisers (such as thermal stabilisers), plasticizers and/or other polymer resins.
By co-coagulating the emulsion which contains the halogen-containing vinyl polymer (before blending) with the emulsions) having either the desired processing aids, stabilisers (such as thermal stabilisers), plasticizers and/or other polymer resins in accordance with the present invention, the co-coagulates of the present invention are formed so that each co-coagulate is an intimate mixture of each component (that is to say, the particles of these various components are substantially homogeneously distributed throughout each co-coagulate).
Accordingly, the co-coagulates of the present invention form a very homogenous 3 5 blend.
In this fashion, stabilisers, such as ESO, which are incorporated therein, act as an internal lubricant which is of particular interest where resins are involved that have poor stability, such as is particularly notable in the case of barrier polymers, such as PVDC.
Further, by being co-coagulated according to the process of the present invention, the particles of the base emulsions, which are typically less than 0.5 microns in size, are formed into larger co-coagulates. A substantial portion of these co-coagulates are larger than about 45 microns in size, so that the resins comprised of such co-coagulates are substantially free of polymer dust and fines.
As used herein, the term "emulsion resin" is used to refer to a resin that is obtained from an aqueous emulsion prepared using radical polymerisation in an aqueous emulsion.
The process of the present invention presents, above all, the advantage that the polymerisation itself is not effected (no sludge formation, no problems of residual monomers, etc.) and that the particles of those other components (such as the processing aids, stabilisers -- and particularly ESO --, plasticizers and/or other polymer resins) is always well incorporated and, therefor, well protected.
In this regard, we note that in contrast to suspension polymerisation's (where ESO can be placed directly into the polymerisation reactor during polymerisation), this is not possible where emulsion polymerisation is involved due to the formation of sludge which such an addition provokes, even when an emulsified ESO is used. Thus, the process of the present invention provides a manner where such ESO can be satisfactorily incorporated into the polymer resin.
In addition, we believe that the presence of the emulsifier in the ESO plays a role in internal lubrication during extrusion of the co-coagulates of the present invention.
Other important characteristics of the co-coagulates, notably their thermal stability, the barrier properties thereof and their extrudability, are at least equivalent to or superior to those in comparison to a premix. In this regard, we note that while premixes may tend to be not extrudable due to extensive lumping, the "ready-to-use" co-coagulates of the present invention give rise to very stable extrusion conditions.
The halogen-containing vinyl polymer resins of the co-coagulates of the present invention may be either homopolymers or copolymers. It is contemplated that copolymers of the co-coagulates of the present invention may be formed by either copolymerization or by independent polymerization and subsequent blending.
Preferably, these copolymer resins of the co-coagulates of the present invention are formed by the polymerisation in emulsion of at least two different halogen-containing vinyl monomers.
The above-described properties of the co-coagulates of the present invention, and particularly those properties of increased particles size and reduced stickiness, which are obtained by the process of the present invention permits the co-coagulates having the polymer resin/stabiliser to be used without any blending. Further, the co-coagulates of the present invention are less prone to both crusting the blades of the blender and to lumping (the formation of less and/or smaller lumps). In this fashion, the co-coagulates of the present invention prESent good flowability, thermal stability and extrudability.
Having thus described the invention, the following examples are now presented which are for illustrative purposes only are not meant to limit the scope of the present invention.
Exam le Polymerisation Into a 16 liter autoclave was introduced 6150 cm3 of demineralized water.
Then, under agitation of 160 rpm using an impeller, 390 cm3 of a solution of 110 g/1 tetrapropylbenzene sulfonate, 4590 g of VDC monomer and 1910 g of VC monomer were added and the temperature of the autoclave was set at 4b°C.
At 44°C, 110 cm3of an aqueous solution of 20 g/1 erythorbic acid was added to the solution in the autoclave followed by the successive addition of __ 25 100 cm3 of an aqueous solution of 3.5 g/1 H202.
minutes later, an aqueous solution (3 g/1) of erythorbic acid and an aqueous solution of 0.8 g/l H202 were injected continuously (at respective rates of 100 cm3/hour) for about 450 minutes.
After depressurising the autoclave for about 3 hours, the autoclave was 30 cooled to ambient temperature. Then 2500 cm3of demineralized water was added to dilute the VDC based latex.
Co-coa~uiation according to the invention Into a first 150 litre vat, regulated by a water jacket, 30 litres of demineralized water and 0.7 litres of an aqueous solution of aluminium sulphate (8.6 g/1) was added.
WO 00/32679 PCT/EP99/093'I2 The vat was then put under agitation at 200 rpm and the temperature thereof was adjusted to about 15 °C.
23 litres of the formed VDC latex along with 1 litre of an emulsion of epoxidized Soya bean oil (at 250 g/1) were then evenly and continuously added in parallel to the first vat for about 20 minutes.
The first vat was then heated to 70°C and maintained at that temperature for 90 minutes.
The vat was then cooled to room temperature, producing a slurry having the co-coagulate therein.
Coagulation ~ classical means (for comparison) Into a second 150 litre vat, regulated by a water jacket, 30 litres of demineralized water and 0.7 litres of an aqueous solution of aluminium sulphate (8.6 g11) was added.
The second vat was then put under agitation at 200 rpm and the temperature thereof was adjusted to about 15°C.
23 litres of the formed VDC latex is then even and continuously added in parallel to the second vat for about 20 minutes.
The second vat was then heated to 70°C and maintained at that temperature for 90 minutes.
The second vat was then cooled to room temperature, producing a slurry having a conventional coagulate.
Dr~rlng The slurries from the first and the second vats were then dried by, first, separating the liquid from the solid in an ESCHER WYSS~ system. In this fashion, a "cake" of the co-coagulates of the present invention (from vat 1) and a "cake" having traditional coagulates (from vat 2) are formed.
The cakes were then dried in a Munster~ fluidised bed with an air temperature at entry of about 60°C until the volatile material content thereof was reduced to less than 0.3 % (w/w).
The particle sizes of the co-coagulate particles of the two cakes were then measured and the results thereof given below in Table 1.
Table 1 Particle Size of Co-coa ulates (in microns) Sample > 850-450 450-250 250-150 150-45 <_45 Cake 1 662 246 64 15 8 5 Co-coagulates Cake 2 229 208 190 212 93 28 Coagulates
Claims (12)
1 - A vinylidene chloride polymer resin characterised in that the resin is fret of dust and fines of the polymer resin and in that the resin is comprised of co-coagulates of particles of vinylidene chloride polymer resins and particles chosen from the group consisting of processing aids, stabilisers (such as thermal stabilisers), plasticizers and/or other polymer resins.
2 - The vinylidene chloride polymer resin according to claim 1, further characterised in that the particles of vinylidene chloride polymer resins and the particles chosen from the group consisting of processing aids, stabilisers (such as thermal stabilisers), plasticizers and other polymer resins of the co-coagulates are homogeneously distributed throughout the diameter of each co-coagulate.
3 - The vinylidene chloride polymer resin according to any of claims 1 to 2, further characterised in that they particles of the vinylidene chloride polymer resins are particles of copolymers of vinylidene chloride monomers and at least one other monomer.
4 - The vinylidene chloride polymer resin according to claim 3, further characterised in that the particles of the vinylidene chloride polymer resins are particles of copolymers of vinylidene chloride monomers and vinyl chloride monomers.
5 - The vinylidene chloride polymer resin according to claim 3, further characterised in that the particles of the vinylidene chloride polymer resins are particles of copolymers of vinylidene chloride monomers and monomers of acrylates or methacrylates.
6 - The vinylidene chloride polymer resin according to claim 5, further characterised in that the particles of the vinylidene chloride polymer resins are particles of copolymers of vinylidene chloride monomer's and glycidylmethacrylate monomers.
7 - The vinylidene chloride polymer resin according to any of claims 1 to 6, further characterised in that the particles of stabilisers are epoxidized soybean oil (ESO).
8 - A process for the preparation of a vinylidene chloride polymer resin free of dust and fines of the polymer resin including the steps of polymerising a vinylidene chloride monomer, whereby an emulsion is formed having the polymer, coagulation of the polymer in the emulsion, whereby a coagulated polymer is formed and drying of the coagulated polymer, whereby a dry vinylidene chloride polymer resin is formed, the process being characterised by adding to the emulsion having the polymer an emulsion including a substance selected from the group of stabilisers, processing aids, plasticizers and other polymers and co-coagulating the emulsion having the polymer and the emulsion having the substance, whereby a co-coagulated polymer resin is formed.
9 - The process according to claim 8, further characterised is that the stabiliser added to the polymer resin and co-coagulated therewith is epoxidized soybean oil (ESO).
10 - The process according to any of claims 8 to 9, further characterised by the copolymerization of a vinylidene chloride monomer and another monomer, whereby an emulsion is formed having a vinylidene chloride-containing copolymer is formed.
11 - Use of the vinylidene chloride-containing polymer resins of any of claims 1 to 7, for the formation of extrudable articles.
12 - Extruded articles characterised by being formed from the vinylidene chloride-containing polymer resins of any of claims 1 to 7.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9826524A GB2344345A (en) | 1998-12-02 | 1998-12-02 | Halogen-containing vinyl polymer resins |
| GB9826524.2 | 1998-12-02 | ||
| PCT/EP1999/009372 WO2000032679A1 (en) | 1998-12-02 | 1999-11-30 | Halogen-containing vinyl polymer resins and processes for the preparation thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2353571A1 true CA2353571A1 (en) | 2000-06-08 |
Family
ID=10843536
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002353571A Abandoned CA2353571A1 (en) | 1998-12-02 | 1999-11-30 | Halogen-containing vinyl polymer resins and processes for the preparation thereof |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP1137692A1 (en) |
| JP (1) | JP2002531616A (en) |
| CN (1) | CN1334840A (en) |
| AU (1) | AU1779100A (en) |
| BR (1) | BR9915884A (en) |
| CA (1) | CA2353571A1 (en) |
| GB (1) | GB2344345A (en) |
| MX (1) | MXPA01005502A (en) |
| WO (1) | WO2000032679A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1202142C (en) | 1998-08-18 | 2005-05-18 | 陶氏环球技术公司 | Extrudable barrier polymer compositions, process for preparing same and monolayer or multilayer structures comprising the compositions |
| EP2215160B1 (en) | 2007-11-22 | 2011-04-20 | SOLVAY (Société Anonyme) | Composition of at least one vinylidene chloride copolymer |
| JP6936435B2 (en) * | 2017-04-27 | 2021-09-15 | 新日本理化株式会社 | Vinyl chloride resin composition with suppressed coloring when used at high temperatures |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE483422A (en) * | 1946-12-13 | |||
| BE580193A (en) * | 1958-07-11 | 1959-12-29 | Du Pont | Process for the preparation of a constituent particle of a sheet from synthetic polymer latex. |
| NL6700053A (en) * | 1967-01-03 | 1968-07-04 | ||
| SE371448B (en) * | 1967-10-05 | 1974-11-18 | Goodrich Co B F | |
| US3948842A (en) * | 1970-06-23 | 1976-04-06 | Stauffer Chemical Company | Fire retardant polymeric additives of vinylidene halides with bis(hydrocarbyl) vinyl phosphonates and C1 -C20 alkylesters of acrylic and methacrylic acids |
| DE3105817A1 (en) * | 1981-02-18 | 1982-09-09 | Chemische Werke Hüls AG, 4370 Marl | METHOD FOR PRODUCING POLYVINYL CHLORIDE AND THE USE THEREOF FOR PRODUCING FILMS ON HIGH-SPEED CALENDARS |
| IT1190352B (en) * | 1985-04-05 | 1988-02-16 | Montefluos Spa | PROCEDURE FOR THE PRODUCTION OF A COMPOSITE MATERIAL BASED ON A POLYMER MATRIX |
| RU2149164C1 (en) * | 1994-02-25 | 2000-05-20 | Дайкин Индастриз, Лтд | Method of preparing molded polytetrafluoroethylene with lubricant, tape squeeze and dehydration apparatus, and method for dehydration of wet solid materials |
| JP3947234B2 (en) * | 1994-03-31 | 2007-07-18 | 日本ゼオン株式会社 | Manufacturing method of vinyl chloride resin for paste processing |
| US6040370A (en) * | 1997-04-17 | 2000-03-21 | General Electric Company | Aqueous fluoropolymer dispersion and method for making fluoropolymer-containing thermoplastic resin composition |
-
1998
- 1998-12-02 GB GB9826524A patent/GB2344345A/en not_active Withdrawn
-
1999
- 1999-11-30 CN CN99815896.8A patent/CN1334840A/en active Pending
- 1999-11-30 CA CA002353571A patent/CA2353571A1/en not_active Abandoned
- 1999-11-30 WO PCT/EP1999/009372 patent/WO2000032679A1/en not_active Application Discontinuation
- 1999-11-30 EP EP99961039A patent/EP1137692A1/en not_active Withdrawn
- 1999-11-30 MX MXPA01005502A patent/MXPA01005502A/en unknown
- 1999-11-30 JP JP2000585317A patent/JP2002531616A/en active Pending
- 1999-11-30 AU AU17791/00A patent/AU1779100A/en not_active Abandoned
- 1999-11-30 BR BR9915884-1A patent/BR9915884A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| WO2000032679A1 (en) | 2000-06-08 |
| CN1334840A (en) | 2002-02-06 |
| JP2002531616A (en) | 2002-09-24 |
| EP1137692A1 (en) | 2001-10-04 |
| GB2344345A (en) | 2000-06-07 |
| GB9826524D0 (en) | 1999-01-27 |
| AU1779100A (en) | 2000-06-19 |
| BR9915884A (en) | 2001-12-11 |
| MXPA01005502A (en) | 2002-04-10 |
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