WO2007043082A2 - Plasticised pvc and chlorinated polyethylene cpe-based compound, method for obtaining said compound, and multi-layer material comprising said compound coupled with a different type of polymer - Google Patents
Plasticised pvc and chlorinated polyethylene cpe-based compound, method for obtaining said compound, and multi-layer material comprising said compound coupled with a different type of polymer Download PDFInfo
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- WO2007043082A2 WO2007043082A2 PCT/IT2006/000708 IT2006000708W WO2007043082A2 WO 2007043082 A2 WO2007043082 A2 WO 2007043082A2 IT 2006000708 W IT2006000708 W IT 2006000708W WO 2007043082 A2 WO2007043082 A2 WO 2007043082A2
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 45
- 239000004709 Chlorinated polyethylene Substances 0.000 title claims abstract description 35
- 229920000642 polymer Polymers 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 title claims description 18
- 238000000034 method Methods 0.000 title claims description 10
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 52
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 17
- 229920000098 polyolefin Polymers 0.000 claims description 15
- 239000004014 plasticizer Substances 0.000 claims description 7
- 235000013305 food Nutrition 0.000 claims description 6
- 238000009472 formulation Methods 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims description 3
- BKUSIKGSPSFQAC-RRKCRQDMSA-N 2'-deoxyinosine-5'-diphosphate Chemical compound O1[C@H](CO[P@@](O)(=O)OP(O)(O)=O)[C@@H](O)C[C@@H]1N1C(NC=NC2=O)=C2N=C1 BKUSIKGSPSFQAC-RRKCRQDMSA-N 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- 102100035474 DNA polymerase kappa Human genes 0.000 claims description 2
- 101710108091 DNA polymerase kappa Proteins 0.000 claims description 2
- 235000010469 Glycine max Nutrition 0.000 claims description 2
- 244000068988 Glycine max Species 0.000 claims description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- -1 polyethylene Polymers 0.000 description 14
- 239000004698 Polyethylene Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 239000004743 Polypropylene Substances 0.000 description 8
- 229920000573 polyethylene Polymers 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 6
- 230000008878 coupling Effects 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
- 238000005859 coupling reaction Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920002943 EPDM rubber Polymers 0.000 description 3
- 229920006124 polyolefin elastomer Polymers 0.000 description 3
- 230000008092 positive effect Effects 0.000 description 3
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 3
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- BJRMDQLATQGMCQ-UHFFFAOYSA-N C=C.C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 Chemical compound C=C.C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 BJRMDQLATQGMCQ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 238000009954 braiding Methods 0.000 description 1
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- CKQVRZJOMJRTOY-UHFFFAOYSA-N octadecanoic acid;propane-1,2,3-triol Chemical compound OCC(O)CO.CCCCCCCCCCCCCCCCCC(O)=O CKQVRZJOMJRTOY-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 229920005630 polypropylene random copolymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a non-planar shape
- B32B1/08—Tubular products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2323/00—Polyalkenes
- B32B2323/04—Polyethylene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2327/00—Polyvinylhalogenides
- B32B2327/06—PVC, i.e. polyvinylchloride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2597/00—Tubular articles, e.g. hoses, pipes
Definitions
- Plasticised PVC and chlorinated polyethylene CPE-based compound method for obtaining said compound, and multilayer material comprising said compound coupled with a different type of polymer
- the present invention relates to a plasticised polyvinyl chloride PVC and chlorinated polyethylene CPE- based compound.
- the present invention relates to a compound suitable for the production of products obtained for example by coextrusion or overextrusion or overmoulding, consisting of a layer of material made of said compound and a layer of a different type of polymer, in particular a polyolefin or a thermoplastic rubber.
- the material disclosed is applied in particular for the production of synthetic resin products, for example pipes, footwear components, etc.
- Plasticised polyvinyl chloride PVC is an amorphous and polar polymer with the plasticiser molecules inserted between the polymer chains.
- the plasticiser makes it "rubbery - elastic" and as a result of these features it is a material widely used in diverse fields of application such as flexible pipes for transporting liquids which may even be aggressive, food substances and gases, seals, footwear or footwear components, films for food and non-food packaging, etc.
- plasticised PVC is the fact that it can be painted and glued.
- Polyolefins (polypropylene homopolymer, copolymer or random copolymer; high density, low density, linear, ultrahigh density polyethylene, etc.) are apolar polymers used, among other things, for applications similar to those of plasticised PVC.
- Thermoplastic rubbers (SBS styrene butadiene styrene, SEBS styrene ethylene butadiene styrene, PP/EPDM polypropylene with ethylene propylene diene monomers , etc . ) , which exploit irreversible and reversible cross-links, cover applications in which elasticity is the fundamental requirement.
- plasticised PVC for direct contact with drinking water or where a chemical or thermal resistance that cannot be guaranteed by plasticised PVC is required, or for aesthetic reasons or to house inserts in technical components, etc.
- use can be made of polyolefins or thermoplastic rubbers which cannot normally be painted or moulded or glued or sealed with plasticised PVC, preventing the production of products consisting of polymers of very different types, usually due to their polarity or apolarity.
- chlorinated polyethylene CPE is a material used in the formulations of rigid PVC as a shockproof additive and to improve the behaviour of the compound relative to cold.
- chlorinated polyethylene CPE is also used as a universal coupling agent in polyolefins or as a homogenising agent for scrap and waste from various types of plastic material.
- Document US-A-4910245 describes a vulcanisation method used to mix a CPE and a PE by vulcanising them.
- Document US-A-5087669 describes how to give shockproof properties to a mixture of rigid PVC with CPE without raising the melting point, mixing it with oxidised PE.
- Patent US-A-5274013 describes insulating jackets for electric cables made of moisture-resistant CPE.
- patent US-A-5286795 describes a method for obtaining a partly vulcanised chlorosulfonated CPE or PE.
- the present invention aims to supply a material able to overcome the disadvantages typical of the prior art, and in particular a compound consisting of plasticised polyvinyl chloride PVC suitably modified with CPE of a suitable grade, on its own or with the addition of thermoplastic rubbers, thermoplastic polyurethane, polyethylene, ethylene vinyl acetate, for the production of multi-layer products in which the various layers consist of different types of polymers, for example : multi-layer pipes suitable for transporting food substances, gases, aggressive liquids, with barrier effect, etc.
- claims outline particularly advantageous embodiments of the material disclosed. Moreover, claim 8 describes a method for obtaining such a compound. Finally, claims 9 to 11 describe a multi-layer product in which at least one layer is made of a compound in accordance with the present invention.
- the compound disclosed substantially consists of a mixture of polyvinyl chloride PVC resin comprising suitable additives to make it plasticised and workable, and chlorinated polyethylene CEE.
- the plasticised PVC and chlorinated polyethylene CPE-based material is a certain quantity of the material (polyolefin or thermoplastic rubber) on which the plasticised and CPE compound will subsequently be made to adhere.
- the coupling is optimum in terms of its closeness and stability.
- the close and .stable coupling between the two layers, made of PVC and PE can only be guaranteed by using a layer made in accordance with the present invention, using the plasticised PVC and CPE-based compound, if necessary adding a certain quantity of polyethylene.
- the resulting product is a flexible, elastic pipe which is waterproof and can be moulded, thus grouping together the set of positive properties of the polymers of which the pipe consists.
- the plasticised PVC and chlorinated polyethylene CPE-based material can be stably coupled with polypropylene or with a thermoplastic rubber, obtaining a multi-layer product with the same positive properties as the respective starting materials, the multi-layer product being characterised by a stably and practically inseparable coupling between the various layers, unlike the prior art solutions .
- the table below shows a basic formulation for obtaining a plasticised PVC and CPE-based material, designed to be stably coupled with a polyolefin or a thermoplastic rubber in a multi-layer product.
- the PVC resin to be used may have different coefficient K values (for example from 50 to 100) depending on the applications.
- coefficient K well known to experts in the field, consists of a number indicating the length of the polymer chain, that is to say, the molecular weight. The greater the length of the molecule, the greater the molecular weight and the viscosity and the higher the K value will be.
- Selection of a PVC resin in suspension to be inserted in a formulation must be made firstly considering its "K value" which must be suited to the properties to be given to the final compound. Therefore, for example to obtain a compound with excellent mechanical properties it is a good idea to use a resin with a high K (80 - 100), bearing in mind that the mixture obtained will be difficult to work due to the high level of viscosity.
- a lower coefficient K (60 - 65) allows a compound which is easily transformable but has inferior mechanical properties to be obtained.
- the plasticiser may be a phthalic ester such as the common DOP, DINP, DIDP or a polymeric plasticiser, a citrate, an adipate, a benzoate, a cycloparaffin ester, etc. or a mixture of them, based on the final properties to be obtained, in particular the resistance to extraction of the plasticiser, suitability for contact with foodstuffs, behaviour at low temperatures, etc.
- a phthalic ester such as the common DOP, DINP, DIDP or a polymeric plasticiser, a citrate, an adipate, a benzoate, a cycloparaffin ester, etc. or a mixture of them, based on the final properties to be obtained, in particular the resistance to extraction of the plasticiser, suitability for contact with foodstuffs, behaviour at low temperatures, etc.
- the stabiliser may be of various types, a calcium zinc stabiliser currently being preferred due to its low environmental impact;
- the lubricant is stearic acid, or stearine, and has the function of lubricating the compound during the various passages for transformation from powder to pellet and, subsequently, from pellet to product. Lubrication is required to prevent the melted polymer from adhering to the metal walls of the machine which works it. In this way there is no unwanted separation which would cause the compound to melt . . before time and so it prevents a shorting of thermal stability times; finally, the CPE may be of various types depending on the final application (extrusion or moulding) and the performance to be obtained.
- a turbo-mixer and an extruder are used to produce the compound in accordance with the present invention.
- the components of the mixture are loaded in the correct proportions in the turbo-mixer which mixes them together, heating them until they reach the compound temperature of around 110 - 12O 0 C.
- the dry-blend obtained in this way is unloaded into a slow mixer -designed to cool the mixture to around 70 0 C.
- any additives required which cannot be inserted and heated to 12O 0 C in the turbo-mixer are added, for example thermoplastic rubber or expanding agents.
- pelletising step preferably using an extruder with twin screws, counter-rotating or co- rotating with suitable cutting force for a compound containing PVC.
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
A plasticised polyvinyl chloride PVC-based compound, suitable for use in the production of multi-layer products obtained for example by coextrusion or overextrusion or overmoulding, consisting of at least one layer made of said compound and one layer made of a different type of polymer, includes a predetermined quantity of chlorinated polyethylene CPE.
Description
Plasticised PVC and chlorinated polyethylene CPE-based compound, method for obtaining said compound, and multilayer material comprising said compound coupled with a different type of polymer
**********
TECHNICAL FIELD
The present invention relates to a plasticised polyvinyl chloride PVC and chlorinated polyethylene CPE- based compound.
More specifically, the present invention relates to a compound suitable for the production of products obtained for example by coextrusion or overextrusion or overmoulding, consisting of a layer of material made of said compound and a layer of a different type of polymer, in particular a polyolefin or a thermoplastic rubber.
The material disclosed is applied in particular for the production of synthetic resin products, for example pipes, footwear components, etc.
BACKGROUND ART
Plasticised polyvinyl chloride PVC is an amorphous and polar polymer with the plasticiser molecules inserted between the polymer chains. The plasticiser makes it "rubbery - elastic" and as a result of these features it is a material widely used in diverse fields of application such as flexible pipes for transporting liquids which may even be aggressive, food substances and gases, seals, footwear or footwear components, films for food and non-food packaging, etc.
Amongst the most appreciated features of plasticised
PVC are the fact that it can be painted and glued.
Polyolefins (polypropylene homopolymer, copolymer or random copolymer; high density, low density, linear, ultrahigh density polyethylene, etc.) are apolar polymers used, among other things, for applications similar to those of plasticised PVC.
Thermoplastic rubbers,. (SBS styrene butadiene styrene, SEBS styrene ethylene butadiene styrene, PP/EPDM polypropylene with ethylene propylene diene monomers , etc . ) , which exploit irreversible and reversible cross-links, cover applications in which elasticity is the fundamental requirement.
In some applications the use of polymers specifically targeted to obtain particular technical effects is preferable.
For example, for direct contact with drinking water or where a chemical or thermal resistance that cannot be guaranteed by plasticised PVC is required, or for aesthetic reasons or to house inserts in technical components, etc. For these applications use can be made of polyolefins or thermoplastic rubbers which cannot normally be painted or moulded or glued or sealed with plasticised PVC, preventing the production of products consisting of polymers of very different types, usually due to their polarity or apolarity. In the case of flexible pipes, whether they are produced using the pipe coaxial extrusion technique, with polyester yarn braiding, or obtained with the spiral coextrusion technique with rigid PVC or with a metal spiral, it is not currently possible to stably couple a layer of polyethylene or polypropylene or thermoplastic rubber with a layer of plasticised PVC.
The need for a pipe consisting of two or more layers of different types depends on the type of liquid or fluid which must pass inside it, the desired barrier effect features, the possibility of moulding or gluing required or the flexibility the pipe must have.
For example, it is not currently possible to produce a pipe with the inner layer made of polyethylene or polypropylene for the passage of drinking water or petrol and to cover it with an outer layer of plasticised PVC. Similarly, it is not currently possible to produce polyolefin or thermoplastic rubber inserts for footwear made of plasticised PVC which are closely stuck to the structure of the footwear.
Therefore, in general when attempts are made to use coextrusion, overextrusion or overmoulding to couple a plasticised PVC with a polyolefin (polypropylene, polyethylene) or with a thermoplastic rubber (SBS, SEBS, PP/EPDM), no adhesion is obtained due to the incompatibility of the different polymers. In addition, chlorinated polyethylene CPE is a material used in the formulations of rigid PVC as a shockproof additive and to improve the behaviour of the compound relative to cold.
Moreover, chlorinated polyethylene CPE is also used as a universal coupling agent in polyolefins or as a homogenising agent for scrap and waste from various types of plastic material.
Document US-A-4910245 describes a vulcanisation method used to mix a CPE and a PE by vulcanising them. Document US-A-5087669 describes how to give shockproof properties to a mixture of rigid PVC with CPE without
raising the melting point, mixing it with oxidised PE.
Patent US-A-5274013 describes insulating jackets for electric cables made of moisture-resistant CPE.
Finally, patent US-A-5286795 describes a method for obtaining a partly vulcanised chlorosulfonated CPE or PE.
DISCLOSURE, OF THE INVENTION
The present invention aims to supply a material able to overcome the disadvantages typical of the prior art, and in particular a compound consisting of plasticised polyvinyl chloride PVC suitably modified with CPE of a suitable grade, on its own or with the addition of thermoplastic rubbers, thermoplastic polyurethane, polyethylene, ethylene vinyl acetate, for the production of multi-layer products in which the various layers consist of different types of polymers, for example : multi-layer pipes suitable for transporting food substances, gases, aggressive liquids, with barrier effect, etc. made using axial coextrusion or with continuous spiral technology; footwear components such as soles with polyolefin inserts encased in PVC; accessories for valves; coextruded seals; various types of electric cables such as coaxial and multi-wire .
This aim is achieved by a compound which has the features described in the main claim.
The dependent claims outline particularly advantageous embodiments of the material disclosed. Moreover, claim 8 describes a method for obtaining such a compound.
Finally, claims 9 to 11 describe a multi-layer product in which at least one layer is made of a compound in accordance with the present invention.
The compound disclosed substantially consists of a mixture of polyvinyl chloride PVC resin comprising suitable additives to make it plasticised and workable, and chlorinated polyethylene CEE.
Surprisingly, experiments carried out by the Applicant demonstrated that such material can easily be coextruded, or overextruded, or overmoulded with polyolefins or with thermoplastic rubbers which could not previously be stably coupled with simple plasticised PVC.
In a particularly advantageous embodiment of the invention, also added to the plasticised PVC and chlorinated polyethylene CPE-based material is a certain quantity of the material (polyolefin or thermoplastic rubber) on which the plasticised and CPE compound will subsequently be made to adhere. In this case the coupling is optimum in terms of its closeness and stability. By way of example, in the case of production of a multi-layer pipe reinforced with polyester yarn, where the inner layer is polyethylene and the outer layer is PVC, the close and .stable coupling between the two layers, made of PVC and PE, can only be guaranteed by using a layer made in accordance with the present invention, using the plasticised PVC and CPE-based compound, if necessary adding a certain quantity of polyethylene. The resulting product is a flexible, elastic pipe which is waterproof and can be moulded, thus grouping together the set of positive properties of the polymers of which the pipe consists.
Similarly, the plasticised PVC and chlorinated
polyethylene CPE-based material can be stably coupled with polypropylene or with a thermoplastic rubber, obtaining a multi-layer product with the same positive properties as the respective starting materials, the multi-layer product being characterised by a stably and practically inseparable coupling between the various layers, unlike the prior art solutions .
DESCRIPTION OF SOME EMBODIMENTS OF THE INVENTION Several different embodiments of the plasticised PVC and chlorinated polyethylene CPE-based material in accordance with the present invention are described below.
The table below shows a basic formulation for obtaining a plasticised PVC and CPE-based material, designed to be stably coupled with a polyolefin or a thermoplastic rubber in a multi-layer product.
The PVC resin to be used may have different coefficient K values (for example from 50 to 100) depending on the applications. In this context it should be remembered that said coefficient K, well known to experts in the field,
consists of a number indicating the length of the polymer chain, that is to say, the molecular weight. The greater the length of the molecule, the greater the molecular weight and the viscosity and the higher the K value will be. Selection of a PVC resin in suspension to be inserted in a formulation must be made firstly considering its "K value" which must be suited to the properties to be given to the final compound. Therefore, for example to obtain a compound with excellent mechanical properties it is a good idea to use a resin with a high K (80 - 100), bearing in mind that the mixture obtained will be difficult to work due to the high level of viscosity.
In contrast, a lower coefficient K (60 - 65) allows a compound which is easily transformable but has inferior mechanical properties to be obtained.
With reference to other aspects of the previous table: the plasticiser may be a phthalic ester such as the common DOP, DINP, DIDP or a polymeric plasticiser, a citrate, an adipate, a benzoate, a cycloparaffin ester, etc. or a mixture of them, based on the final properties to be obtained, in particular the resistance to extraction of the plasticiser, suitability for contact with foodstuffs, behaviour at low temperatures, etc. ; • the epoxidised soya-bean oil has a coupling agent function, since it has a positive synergic effect with the calcium zinc stabiliser packet; the stabiliser may be of various types, a calcium zinc stabiliser currently being preferred due to its low environmental impact; the lubricant is stearic acid, or stearine, and has the
function of lubricating the compound during the various passages for transformation from powder to pellet and, subsequently, from pellet to product. Lubrication is required to prevent the melted polymer from adhering to the metal walls of the machine which works it. In this way there is no unwanted separation which would cause the compound to melt ..before time and so it prevents a shorting of thermal stability times; finally, the CPE may be of various types depending on the final application (extrusion or moulding) and the performance to be obtained.
The tables below show several specific formulations which demonstrated the possibility of obtaining a multilayer material with stable and close coupling between a plasticised PVC and, respectively, polyethylene, polypropylene, thermoplastic rubber.
Example 1
Example 3
* * * * *
Description of methods for obtaining a plasticised PVC and CPE-based compound in accordance with the invention
According to a particularly advantageous embodiment, a turbo-mixer and an extruder are used to produce the compound in accordance with the present invention.
The components of the mixture are loaded in the correct proportions in the turbo-mixer which mixes them together, heating them until they reach the compound temperature of around 110 - 12O0C.
The dry-blend obtained in this way is unloaded into a slow mixer -designed to cool the mixture to around 700C.
At this point any additives required which cannot be
inserted and heated to 12O0C in the turbo-mixer are added, for example thermoplastic rubber or expanding agents.
This is followed by the pelletising step, preferably using an extruder with twin screws, counter-rotating or co- rotating with suitable cutting force for a compound containing PVC.
The approximate thermal profile, pressures and speeds are shown in the following tables:
Table A
88 mm extruder. L/D 20
125mm extruder. L/D 26
Use of such methods allows the obtainment of an end product consisting of a compound basically consisting of plasticised PVC and CPE, suitable for close and stable coupling with a different type of polymer such as a polyolefin or a thermoplastic rubber.
Thanks to the use, in accordance with the invention, of chlorinated polyethylene together with the basic formulation of the PVC, a compound is obtained which is designed to be
overmoulded, extruded or overextruded with a polyolefin or with a thermoplastic rubber, to form a multi-layer material in which the basic components (PVC and polyolefin, or PVC and thermoplastic rubber), in spite of their different polarity, adhere to one another closely and stably, unlike the prior art solutions in which the layers of PVC separate extremely easily from the,, coupled layers of polyolefin or thermoplastic rubber.
This makes possible a whole series of new applications, advantageously using the positive properties of both PVC and polyolefins or thermoplastic rubbers. For example, it is possible to obtain multi-layer pipes suitable for transporting food substances, gases, aggressive liquids, with barrier effect, etc., footwear components such as soles with polyolefin inserts encased in PVC, accessories for valves, coextruded seals, various types of electric cables such as coaxial and multi-wire.
Claims
1 . A plasticised polyvinyl chloride PVC-based compound, suitable for use in the production of multi-layer products obtained for example by coextrusion or overextrusion or overmoulding, consisting of at least one layer made of said compound and one layer made of a different type of polymer , characterised in that the compound includes a predetermined quantity of chlorinated polyethylene CPE .
2 . The compound according to claim 1 , characterised in that the plasticiser consists of a phthalic ester such as DOP , DINP , DIDP or a polymeric plasticiser, a citrate , an adipate , a benzoate , a cycloparaf fin ester, etc . or a mixture of them.
3 . The compound according to either of the foregoing claims , characterised in that it comprises a stabiliser, for example calcium zinc-based.
4. The compound according to any of the foregoing claims , characterised in that it also comprises a predetermined quantity of epoxidised soya-bean oil .
5. The compound according to any of the foregoing claims, characterised in that it also comprises a predetermined quantity of lubricating agent.
6. The compound according to any of the foregoing claims, characterised in that in one formulation it consists of the components shown in the following table:
7. The compound according to any of the foregoing claims, characterised in that a predetermined quantity of the polymer with which the compound must subsequently be coupled to form a multi-layer product is added to it.
8. A method for obtaining a compound according to any of the foregoing claims, wherein a turbo-mixer and an extruder are used, characterised in that the components of the mixture are loaded in the appropriate proportions in the turbo-mixer which mixes them together, heating them to a compound temperature of around 110 - 12O0C, and also characterised in that the dry-blend obtained in this way is unloaded into a slow mixer to cool the mixture to around 7O0C, and also characterised in that any additives required which cannot be inserted and heated to 1200C in the turbo- mixer are then added, for example thermoplastic rubber or expanding agents, and in that the resulting material is then subjected to pelletising, preferably using an extruder with twin screws counter-rotating or co- rotating with suitable cutting force for a compound containing PVC.
9. A multi-layer product obtained by coextrusion or overextrusion or overmoulding polymers of different types and with different polarities, wherein at least one layer consists of polyvinyl chloride PVC, characterised in that the polyvinyl chloride PVC is plasticised, in that it comprises a predetermined quantity of chlorinated polyethylene CPE, and in that it is made of a compound according to any of the foregoing claims.
10. The product according to claim 9, characterised in that the layer coupled with the layer made of the plasticised PVC and chlorinated polyethylene CPE compound is coupled with a layer consisting of a polyolefin or a thermoplastic rubber or an expanding agent.
11. The product according to claim 9 or 10, characterised in that it consists of: - a multi-layer pipe suitable for transporting food substances, gases, aggressive liquids, with barrier effect, etc. made using axial coextrusion or with continuous spiral technology; or a footwear component such as a sole with polyolefin insert encased in PVC; or an accessory for valves; or a coextruded seal; or an electric cable, such as a coaxial or multi-wire cable.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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IT000127A ITVR20050127A1 (en) | 2005-10-12 | 2005-10-12 | PLASTICIZED PVC COMPOUND AND CHLORINATED CPE POLYETHYLENE, METHOD FOR OBTAINING SUCH COMPOUND, AS WELL AS THE MULTILAYERED MATERIAL INCLUDING SUCH COMPOUNDS PAIRED WITH A DIFFERENT NATURE POLYMER. |
ITVR2005A000127 | 2005-10-12 |
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CN103627095A (en) * | 2013-11-05 | 2014-03-12 | 沈阳化工大学 | Chlorinated polyethylene/polyvinyl chloride (PVC) blend elastic material and preparation method thereof |
WO2018004724A1 (en) * | 2016-06-28 | 2018-01-04 | Troendle John B | Glueless dustless composite flooring material system |
US10343381B2 (en) | 2016-06-28 | 2019-07-09 | John B. Troendle | Method of producing a glueless dustless composite flooring material system |
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US10889040B2 (en) | 2016-06-28 | 2021-01-12 | John B. Troendle | Method of producing a glueless dustless composite flooring material system |
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WO2002094610A2 (en) * | 2001-05-22 | 2002-11-28 | Atofina | Composite skin for instrument panel and other parts of vehicle passenger compartment, method for making same and composition used for preparing same and method for producing it |
DE20312108U1 (en) * | 2003-08-06 | 2003-11-06 | Rehau Ag & Co | Reinforced flexible PVC water pipe, e.g. for washing machines, has an inner tube with a water-contacting layer containing PVC, rubber, chlorinated polyethylene, acrylate or methyl methacrylate copolymer and additives |
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CN103627095A (en) * | 2013-11-05 | 2014-03-12 | 沈阳化工大学 | Chlorinated polyethylene/polyvinyl chloride (PVC) blend elastic material and preparation method thereof |
WO2018004724A1 (en) * | 2016-06-28 | 2018-01-04 | Troendle John B | Glueless dustless composite flooring material system |
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US10343381B2 (en) | 2016-06-28 | 2019-07-09 | John B. Troendle | Method of producing a glueless dustless composite flooring material system |
US10662656B2 (en) | 2016-06-28 | 2020-05-26 | John B. Troendle | Glueless dustless composite flooring material system |
US10889040B2 (en) | 2016-06-28 | 2021-01-12 | John B. Troendle | Method of producing a glueless dustless composite flooring material system |
US11248380B2 (en) | 2016-06-28 | 2022-02-15 | Sunrise Spc Technology, Llc | Glueless dustless composite flooring material system |
CN112876783A (en) * | 2021-01-18 | 2021-06-01 | 江西正博实业有限公司 | High-strength plastic sole material and preparation method thereof |
US11951716B2 (en) * | 2021-04-01 | 2024-04-09 | Johns Manville | Hybrid roofing membrane and methods of making same |
Also Published As
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ITVR20050127A1 (en) | 2007-04-13 |
WO2007043082A3 (en) | 2007-06-21 |
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