CN1305510A - Extrudable vinylidene chloride polymer compositions - Google Patents
Extrudable vinylidene chloride polymer compositions Download PDFInfo
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- CN1305510A CN1305510A CN99807319A CN99807319A CN1305510A CN 1305510 A CN1305510 A CN 1305510A CN 99807319 A CN99807319 A CN 99807319A CN 99807319 A CN99807319 A CN 99807319A CN 1305510 A CN1305510 A CN 1305510A
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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
- C08L27/08—Homopolymers or copolymers of vinylidene chloride
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
- B29K2027/08—PVDC, i.e. polyvinylidene chloride
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of 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
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
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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
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
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Abstract
偏二氯乙烯聚合物组合物,其含有(1)偏二氯乙烯聚合物,其中大量组分是偏二氯乙烯单体,剩余组分是一种或多种可与偏二氯乙烯单体共聚的单烯类不饱和单体,(2)甘油酯和(3)硅氧烷聚合物或聚烯烃,和任选(4)环氧化加工助剂。可将该偏二氯乙烯组合物制成具有单层和多层结构的软质或硬质容器,以用于保存食物、饮料、药物和其它易坏品。Vinylidene chloride polymer composition, which contains (1) vinylidene chloride polymer, wherein a large number of components are vinylidene chloride monomers, and the remaining components are one or more monomers compatible with vinylidene chloride A copolymerized monoethylenically unsaturated monomer, (2) a glyceride and (3) a silicone polymer or polyolefin, and optionally (4) an epoxidized processing aid. The vinylidene chloride composition can be made into soft or hard containers with a single-layer or multi-layer structure for preserving food, drink, medicine and other perishable goods.
Description
The present invention relates to have vinylidene chloride polymer (PVDC) composition of the extrudability of raising.
Be the generation of control PVDC degraded product during melt-processed, before making end article with processing aid such as lubricant (for example in lubricating type with outside lubricating type), alkene wax class and oils and vinylidene chloride polymer blend.But find that after extruding for a long time, it is bonding over-drastic to occur between the metallic surface of vinylidene chloride polymer and extruder screw and mouthful mould under the processing conditions of expectation.This bonding residence time that increases vinylidene chloride polymer, this has promoted degraded, causes assembling on mouth mould surface or a generation mouthful mould mashed prod, and cause producing the carbon gathering on the metallic surface of screw rod and mouthful mould.
Expectation provides vinylidene chloride polymer composition, and it can be extruded with powder or pellet form, and does not have the unacceptable degraded that causes owing to the over-bonded between the metallic surface of PVDC melt and screw rod and mouthful mould.
First aspect, the present invention is vinylidene chloride polymer (PVDC) composition, it contains (1) vinylidene chloride polymer, (2) glyceryl ester and (3) siloxane polymer, and wherein the content of glyceryl ester and siloxane polymer is enough to improve the extrudability of vinylidene chloride polymer.
Second aspect, the present invention is vinylidene chloride polymer (PVDC) composition, it contains (1) vinylidene chloride polymer, (2) glyceryl ester and (3) siloxane polymer and (4) epoxidation processing aid, wherein the content of glyceryl ester, siloxane polymer and epoxidation processing aid is enough to improve the extrudability of vinylidene chloride polymer.
The third aspect, the present invention is vinylidene chloride polymer (PVDC) composition, it contains (1) vinylidene chloride polymer, (2) glyceryl ester and (3) polyolefine, wherein glyceryl ester and polyolefinic content are enough to improve the extrudability of vinylidene chloride polymer.
The inventor has found in PVDC to add glyceryl ester and siloxane polymer or polyolefine and optional epoxidation processing aid can be by reducing the extrudability that improve PVDC to the bondability of the metallic surface of screw rod and mouthful mould.Think that PVDC composition of the present invention has the extrudability of raising.Described in this article term " extrudability of raising " is if mean under the processing conditions that makes polymer composition be in expectation in forcing machine, this polymer composition is more insensitive to heat, so this extrudate has the degradation material of less aggregation form on mouth mould surface, on extruder screw and mouthful mould surface, produce less mashed prod and carbon aggregation, decolouring reduces or produces less hydrogenchloride and the mechanical energy that is used to extrude, promptly the energy that is consumed when extruded polymer owing to the viscosity of rubbing effect and polymer composition is lower than the PVDC composition that does not contain siloxanes/carrier polymer enriched material.
It is well known in the art can be used for vinylidene chloride polymer of the present invention.See also for example United States Patent (USP) 3,642,743 and 3,879,359.The most frequently used PVDC resin is called Saran
TMResin is prepared by Dow Chemical.Term used herein " vinylidene chloride polymer " or " PVDC " comprise the homopolymer of vinylidene chloride, also comprise its multipolymer and terpolymer, wherein main ingredient is a vinylidene chloride, remaining ingredient be one or more can with the monoene class unsaturated monomer of vinylidene copolymerization.The monoene class unsaturated monomer that can be used to prepare vinylidene chloride polymer in the present invention comprises vinylchlorid, alkyl-acrylates, alkyl methacrylate, vinylformic acid, methacrylic acid, methylene-succinic acid, vinyl cyanide and methacrylonitrile.Preferred ethylenically unsaturated monomers comprises vinylchlorid, vinyl cyanide, methacrylonitrile, alkyl-acrylates and alkyl methacrylate.Preferred ethylenically unsaturated monomers comprises that vinylchlorid, vinyl cyanide, methacrylonitrile and each alkyl contain the alkyl-acrylates and the alkyl methacrylate of 1-8 carbon atom.Most preferred ethylenically unsaturated monomers is vinylchlorid, methyl acrylate, ethyl propenoate and methyl methacrylate.
Preferred vinylidene chloride polymer is formed by monomer mixture, this monomer mixture contain general in 60-99 weight % scope vinylidene and the monoene class unsaturated comonomer of 40-1 weight %, wherein said weight % is in the gross weight of vinylidene chloride interpolymer.More preferably, the amount of monoene class unsaturated monomer is in the 40-4 weight % of the gross weight of vinylidene chloride polymer and 40-6 weight % most preferably.
The glyceride type that can be used to prepare vinylidene chloride polymer composition in the present invention is the glyceryl ester that contains 14-22 carbon atom, for example Zerol, glycerine monopalmitate, glyceryl monooleate, glycerine list linoleate, glycerine list linolenate (monolinolenate) and corresponding diester class and three ester classes.Preferred glyceryl ester is Zerol.
The consumption that can be used for glyceryl ester of the present invention depends on the processing conditions that composition and vinylidene chloride polymer composition experienced of vinylidene chloride polymer composition, but usually, this amount is the 0.05-10 weight % in the weight of vinylidene chloride polymer composition, preferably 0.2-5 weight % and most preferably 2 weight %.
The siloxane polymer that can be used to prepare the vinylidene chloride composition in the present invention comprises full-bodied organic silicone oil.What wide region will be represented in term used herein " full-bodied organic silicone oil " has a high-molecular weight silicone materials.The molecular-weight average that these full-bodied organic silicone oils that are characterized by silicon rubber usually contain 20-100% is 50,000 or above siloxane polymer, and the viscosity of 90,000 centipoises is provided more than room temperature.Preferred polysiloxane-based is polydimethylsiloxane, polydimethyl diphenyl siloxane and poly-methyl alkyl aryl siloxanes.Known these liquid are difficult to processing, and owing to its high viscosity is difficult to it is added in traditional blending equipment with the solid thermoplastic polymkeric substance.See also for example United States Patent (USP) 4,446,090.
Use full-bodied organic silicone oil with the form of enriched material in the present invention.Can adopt traditional melt processing by full-bodied siloxane polymer and carrier polymer (for example HDPE) are prepared the siloxane polymer enriched material with the form blend of melt.Spendable traditional melt-processed equipment comprises two roller compounding roller refining machines, Bradley Bender mixing tank, Banbury mixer, single screw extrusion machine and the twin screw extruder through heating.Be desirably in the range estimation that is enough to prepare siloxane polymer and carrier polymer and be the condition of even blend and under the time with siloxane polymer and carrier polymer blend.
The consumption that is used to prepare the siloxane polymer of enriched material in the present invention is the 0.1-99.9 weight % in this enriched material weight, preferred 10-90 weight % and 25-75 weight % most preferably.
The carrier polymer that is used to prepare enriched material in the present invention is to be known in the art to be used to give the carrier polymer of vinylidene chloride polymer with useful performance, for example polyolefins, oxidized polyolefin class, ethylene and acrylate copolymer.The preferred vector polymkeric substance is a polyolefine, is more preferably polyethylene and most preferably is high density polyethylene(HDPE) (HDPE).
The consumption that is used to prepare the carrier polymer of enriched material in the present invention is the 0.1-99.9 weight % in this enriched material weight, preferred 10-90 weight % and 25-75 weight % most preferably.
Most preferred siloxanes/carrier polymer enriched material can obtain with the blend of the 50/50 weight % of full-bodied high molecular polydimethylsiloxane and HDPE from Dow Corning company.
Typically with the siloxanes/carrier polymer enriched material and the vinylidene chloride polymer blend of capacity of the present invention, wherein the consumption of this enriched material is enough to provide siloxanes/carrier polymer enriched material of 0.01-10 weight % in this blend.
The siloxane polymer that can be used for other type of the present invention comprises low viscous organic silicone oil, and for example viscosity is at least the organic silicone oil of about 100 centipoises 25 ℃ the time.
The content of siloxane polymer depends on the processing conditions that composition and vinylidene chloride polymer composition experienced of vinylidene chloride polymer composition in vinylidene chloride polymer composition of the present invention.Usually, the content of the siloxane polymer in vinylidene chloride polymer composition is the 0.005-5.0 weight % in the weight of vinylidene chloride polymer composition, preferably 0.02-0.2 weight % and most preferably 0.1 weight %.
The epoxidation processing aid that can be used for preparing vinylidene chloride polymer composition in the present invention comprises the epoxidized vegetable oil class, for example Toenol 1140, soya-bean oil, Oleum Cocois, Thistle oil, Trisun Oil R 80 and oleum gossypii seminis; With epoxidized fatty acid monoesters class, for example octyl stearate; With epoxidation diester class, for example glyceryl ester of unsaturated fatty acids, for example glycerol dioleate.
The content that can be used for epoxidation stablizer of the present invention depends on the processing conditions that composition and vinylidene chloride polymer composition experienced of vinylidene chloride polymer composition.But usually, this amount is the 0.1-10 weight % in the weight of vinylidene chloride polymer composition, preferably 0.4-4 weight % and most preferably 1 weight %.
Also various conventional additive can be mixed in the vinylidene chloride polymer composition.The type of additive and consumption will depend on several factors.A factor is the desired use of said composition.Second the permission content that factor is an additive in said composition.That is, be subjected to the additive capacity that can add before the disadvantageous effect of unacceptable degree in the physicals of blend.Other factors is obvious to the those of skill in the art in polymer formulation and compounding field.
The example of additive comprises softening agent, thermo-stabilizer, pigment, processing aid, lubricant, filler and antioxidant.Every kind of these additive is known, and the various type products of every kind of additive can obtain from commerce.
The example of lubricant comprises fatty acid, as stearic acid; The ester class is as aliphatic ester, paraffin butter class, glyceride type and aliphatics alcohol ester class; The aliphatics alcohols is as positive stearyl alcohol; Aliphatic amide type, as N, N '-ethylene bis stearamide; The metal-salt of fatty acid is as calcium stearate, Zinic stearas, Magnesium Stearate; With the polyolefin-wax class, as paraffin and oxidic polyethylene.Paraffin and polyethylene wax class and performance thereof and synthetic method such as 24Kirk-Othmer Encyc chemical technology, the 3rd edition, wax class, 473-477 page or leaf (J.Wiley﹠amp; Sons 1980) described.
The available traditional melt processing and the dry blend technology of thermosensitive polymer are mixed additive in the vinylidene chloride polymer composition.Vinylidene chloride polymer composition of the present invention can be carried out melt-processed and be extruded into any suitable end article, for example various films or other goods.As known in the art, these films and goods can come out to prepare by traditional co-extrusion; For example feed block coextrusion, expect road junction mould co-extrusion or the combination of the two more; Injection moulding; Injection moulding altogether; Extrusion molding; Casting; Blowing; Blowing; Calendering; And lamination.
The example of goods comprises the individual layer and the multiwalled film of blowing and curtain coating; Hard and flexible container; The sheet material of hard and foaming; Tubing; Pipe; Rod; Fiber; With various section bars.Lamination is particularly suitable for preparing multi-layer sheet.As known in the art, concrete lamination comprises fusion, promptly by heating and pressurization self-excitation (self-sustaining) veneer bonding is in the same place; Wet adhesive bonding, promptly with tie-layer adhesive with two-layer or multiple-layer laminated, wherein this tackiness agent is hygrometric state coating, removes liquid, and in successive processes incompatible bonding each layer of pressure level by subsequently; Or the heating reactivate, promptly bonding by film and other film that heating will be coated with in advance, and the tackiness agent reactivate that will be coated with in advance, so that it can be bonding after pressurization subsequently is laminated.
Vinylidene chloride polymer composition of the present invention is particularly suitable for making hard and the flexible container with individual layer and multilayered structure, and these containers are used to preserve food, beverage, medicine and other easy bad product.These containers should have excellent mechanical property, and low ventilation property, for example to oxygen, carbonic acid gas, water vapour, unpleasant gas or seasonings, hydro carbons or agrochemicals.
This single layer structure contains vinylidene chloride polymer composition of the present invention.
Multilayered structure contains the blend of (1) one or more layers organic polymer or two or more different organic polymers, identical or different and (2) one or more layers vinylidene chloride polymer composition of the present invention of one deck organic polymer and another layer organic polymer wherein.
Multilayered structure can contain three layers, first skin that comprises the blend of (1) organic polymer or two or more different organic polymers, (2) sandwich layer of vinylidene chloride polymer composition of the present invention, (3) second skin of organic polymer, the organic polymer of this layer and the first outer field organic polymer are identical or different.
Multilayered structure also can contain five layers or seven layers, comprise one or more layers vinylidene chloride polymer composition of the present invention, remaining layer contains the blend of organic polymer or two or more different organic polymers, and wherein one deck organic polymer and another layer organic polymer are identical or different.
Can insert bonding coat between the adjacent layers of multilayered structure, this depends on composition and the method for preparing multilayered structure.
The organic polymer that can be used to prepare multilayered structure in the present invention comprise polyolefins, polyamide-based, based on the polymkeric substance and the chlorinatedpolyolefins class of aromatic monomer.
Term " polyolefine " refers to the polymkeric substance or the multipolymer of ethene, promptly this polymkeric substance derived from ethylene or derived from ethylene and can with one or more monomers of its copolymerization.This polymkeric substance (comprising starting material, its ratio, polymerization temperature, catalyzer and other condition) is well known in the art, and can be purpose of the present invention with reference to relevant document.Can comprise the olefinic monomer, alkene class unsaturated carboxylic acid (simple function and difunctionality) and these the sour derivatives that contain 3-12 carbon atom with other comonomer of vinyl polymerization, as ester class (for example alkyl-acrylates) and anhydrides; Monovinylidene aromatic thing and by the monovinylidene aromatic thing that part replaced except that halogen, as vinylbenzene and vinyl toluene; And carbon monoxide.Can comprise 1-octene, vinylformic acid, methacrylic acid, vinyl-acetic ester and maleic anhydride with the monomeric example of vinyl polymerization.
The polyolefine that can be used to prepare multiple-layer laminated structure in the present invention comprises polypropylene, polyethylene and multipolymer thereof and blend, and ethylene-propylene-diene terpolymer.The LLDPE (LLDPE) that preferred polyolefine is polypropylene, line style high density polyethylene(HDPE) (HDPE), heterogeneous branching is as DOWLEX
TMThe extremely-low density linear polyethylene (ULDPE) of polyvinyl resin (trade(brand)name of Dow Chemical), heterogeneous branching is as ATTANE
TMULDPE (trade(brand)name of Dow Chemical); Homogeneously branched linear ethylene/alpha-olefin copolymer is as TAFMER
TM(trade(brand)name of Mitsui petroleum chemistry company limited) and EXACT
TM(trade(brand)name of Exxon chemical company); Homogeneously branched linear ethylene/alpha-olefinic polymer basically is as AFFINITY
TMThe trade(brand)name ENGAGE of (trade(brand)name of Dow Chemical) and DuPont Dow elastomerics company
Polyolefin elastomer, it can be as United States Patent (USP) 5,272,236 and 5,278, preparation described in 272; With high-pressure free radical polymeric ethene polymers and multipolymer, as new LDPE (film grade) (LDPE), ethylene-acrylic acid (EAA) multipolymer, as PRIMACORTM (trade(brand)name of Dow Chemical), and ethane-acetic acid ethyenyl ester (EVA) multipolymer, as ESCORENE
TMPolymkeric substance (trade(brand)name of Exxon chemical company), and ELVAX
TM(trade(brand)name of E.I.DuPontde Nemours company).Preferred polyolefine is homogeneously branched line style and linear ethylene multipolymer basically, and its density (detecting according to ASTM D-792) is the 0.85-0.99 gram per centimeter
3, weight-average molecular weight is to the ratio (M of number-average molecular weight
w/ M
n) be 1.5-3.0, the melting index that records (detecting according to ASTM D-1238 (190/2.16)) restrains/10 minutes for 0.01-100 and I10/I2 is 6-20 (detecting according to ASTM D-1238 (190/10)).
Usually, the density of high density polyethylene(HDPE) (HDPE) is at least about every cubic centimetre of (g/cc) (ASTM detection method D-1505) of 0.94 gram.Usually use the technology similar to prepare HDPE to preparing LLDPE.These technology such as United States Patent (USP) 2,825,721,2,993,876,3,250,825 and 4,204 are described in 050.The density that is used for preferred HDPE of the present invention is the 0.94-0.99 gram per centimeter
3, measuring its melting index according to ASTM detection method D-1238 is that 0.01-35 restrains per 10 minutes.
Can be used for the polymkeric substance based on aromatic monomer of the present invention and comprise polystyrene, polyvinyltoluene, polyphenylethyl ethene, vinylbenzene/methylstyrene copolymer and vinylbenzene/Benzene Chloride ethylene copolymer.
Can be used for polyamide-based various other nylon of level that comprise of the present invention, as nylon-6, nylon-66 and nylon 12.
The adhesive material that can be used to prepare bonding coat in the present invention comprises ethylene, ethylene/ethyl acrylate multipolymer, ionomer, as United States Patent (USP) 5,443,874 described modified polyolefin classes, as United States Patent (USP) 3,753,769 described acrylic acid terpolymer tackiness agents and as United States Patent (USP) 4,447,494 describedly react Resins, epoxy and acidifying amino-ethyl vinyl polymer to formed tackiness agent.Preferred adhesive material is the polyethylene or the polypropylene of maleic anhydride graft, as ADMER (trade(brand)name of Mitsui petroleum chemistry company) adhesive resin, or ethylene-vinyl acetate copolymer resin, as ELVAX
TM(trade(brand)name of E.I.Du Pont Company).Most preferred adhesive material is ELVAX
TM3175, its melting index is 6, contains 28% vinyl acetate copolymer.The thickness of individual layer of the present invention and multilayered structure can change in wide limited field according to desired use.Usually, the thickness of single layer structure of the present invention is the 0.05-10 mil, preferred 0.2-6 mil, most preferably 0.4-1.8 mil.Usually, the thickness of multilayered structure of the present invention is the 0.05-200 mil, preferred 1-100 mil, and 2-80 mil most preferably, wherein the thickness of PVDC polymer layer is the 0.005-20 mil, preferred 0.2-10 mil, most preferably 0.2-8.0 mil.
Further specify the present invention by following examples.These embodiment only are used for illustration purpose, should not be construed as to limit the scope of the invention.Unless otherwise indicated, all umbers and per-cent are by weight.Embodiment 1-3 and Comparative Examples A and B
Use batching in an embodiment by the following vinylidene chloride copolymer (methyl acrylate of 7.75 weight %, the vinylidene chloride of 92.25 weight %) of traditional high intensity mixer preparation:
Embodiment 1
Vinylidene chloride copolymer 95.27 weight %
Epoxidized soybean oil 1.2 weight %
Zerol 2.0 weight %
Oxidized polyethlene wax 0.18 weight %
Polyethylene wax 0.45 weight %
High density polyethylene(HDPE) 0.90 weight %
Embodiment 2
Vinylidene chloride copolymer 96.475 weight %
Epoxidized soybean oil 1.0 weight %
Zerol 2.0 weight %
Oxidation PE wax 0.1 weight %
Polyethylene wax 0.1 weight %
The siloxanes of high weight-average molecular weight/HDPE enriched material 0.125 weight % Comparative Examples A
Vinylidene chloride copolymer 96.27 weight %
Epoxidized soybean oil 2.2 weight %
Oxidation PE wax 0.18 weight %
PE wax 0.45 weight %
HDPE 0.90 weight % comparative example B
Vinylidene chloride copolymer 96.8 weight %
Epoxidized soybean oil 1.2 weight %
Zerol 2.0 weight % extrusion conditions: experiment in 9 hours, from system's (screw rod, machine barrel and mouthful mould) of cleaning.Speed: 42Ib/ hour, 17 rev/mins, diameter was that 2.5 inches, L/D are 21: 1 forcing machine, individual layer right angle mouth mould.Barrel zone temperature: 150 ℃ (feeding in raw material), 155 ℃ (conversion), 160 ℃ (metering).Die temperature: 173 ℃, nosepiece: 175 ℃, Die-head connecting sleeve: 175 ℃, opening for feed: 38 ℃.
Extrusioning experiment carries out in the equipment of cleaning, and the PVDC batching is respectively extruded 9 hours.When finishing in 9 hours, stop screw rod, a machine barrel and a mouthful mould are fully cooled off.This makes and under the situation of no other degraded polymkeric substance is frozen in mouthful mould.Then the mouth mould is taken apart, when when the mouth mould is removed polymkeric substance, carbon tends to be bonded on the polymkeric substance.By this method can be more different the carbon that produced of PVDC multipolymer batching.After the Comparative Examples A batching was extruded 9 hours, the outside of mouthful mould was by the covering fully of black carbon institute.After the batching of embodiment 1 and 2 was extruded 9 hours, the outside surface of mouthful mould did not all have carbon fully.Stopped the extrusioning experiment of comparative example B batching after 2 hours, this is because the striped of mouthful mould is many, mashed prod many and surface irregularity causes the of poor quality of film.This shows that external lubricant (for example oxidation PE wax, PE wax, HDPE, siloxanes enriched material) must be used in combination with GMS.Machine barrel detects
Under 23 ℃ and 60% relative humidity, detect the machine barrel performance of individual layer blown film (1-2 mil) according to ASTM method D-3985-81.(0.085 centimetre of the machine barrel performance of the film that forms by embodiment 1 batching
3-mil/100 inch
2-normal atmosphere-sky) the machine barrel performance of the film that forms than being prepared burden by Comparative Examples A is (0.11 centimetre
3-mil/100 inch
2-normal atmosphere-sky) better.This improvement in machine barrel is very favourable.Surprisingly machine barrel performance and processing characteristics all obtain to improve, and the improvement of common workability will cause the disadvantageous effect to the machine barrel performance.This is owing to this fact, and the improved stability that promptly contains the GMS batching is (2.0% pair 1.0%) that obtains under the ESO level that reduces.Known liquid stabilisers has disadvantageous effect to the machine barrel performance.Thermostability
Also carrying out two roller roller refinings detects to compare the thermostability of PVDC multipolymer batching.In this detects, 200 grams are placed two on the roller that the corotation of heating changes through the PVDC of blend multipolymer.Then because the heat and the shearing action that produce in the sample cause polymer melt.Relatively remarkable degradation time appears in each sample.Under 180 ℃ roller temperature, detect.After 11 minutes, the Comparative Examples A batching produces little HCL bubble.The batching of embodiment 1 needs to reach in 13.5 minutes the par of generation bubble.This shows that further the batching that contains GMS provides improved thermostability.
Claims (23)
1. vinylidene chloride polymer composition, it contains (1) vinylidene chloride polymer, wherein a large amount of components are vinylidene, remaining ingredient be one or more can with the monoene class unsaturated monomer of vinylidene copolymerization, (2) glyceryl ester and (3) siloxane polymer, with optional epoxidation processing aid, wherein the content of glyceryl ester and siloxane polymer is enough to improve the extrudability of vinylidene chloride polymer.
2. the composition of claim 1, wherein said vinylidene chloride polymer is formed by monomer mixture, this monomer mixture contain the vinylidene of 60-99 weight % and 40-1 weight % can with the monoene class unsaturated comonomer of its copolymerization.
3. the composition of claim 2, wherein said monoene class unsaturated monomer is vinylchlorid, alkyl acrylate, alkyl methacrylate, vinylformic acid, methacrylic acid, methylene-succinic acid, vinyl cyanide or methacrylonitrile.
4. the composition of claim 1, wherein said glyceryl ester is Zerol, glycerine monopalmitate, glyceryl monooleate or its diester or three esters.
5. the composition of claim 1, the content of wherein said glyceryl ester is the 0.05-10 weight % in the weight of said composition.
6. the composition of claim 1, wherein said siloxane polymer is polydimethylsiloxane, polydimethyl diphenyl siloxane or poly-methyl alkyl aryl siloxanes.
7. the composition of claim 1, the content of wherein said siloxane polymer is the 0.001-5 weight % in the weight of said composition.
8. the composition of claim 1, wherein said siloxane polymer is the form that contains the enriched material of carrier polymer.
9. the composition of claim 8, wherein said carrier polymer is polyolefine, oxidized polyolefin, vinyl-vinyl acetate copolymer or acrylate copolymer.
10. the composition of claim 1, wherein said epoxidation processing aid is epoxidized vegetable oil, epoxidized fatty acid monoesters or epoxidation diester.
11. the composition of claim 10, wherein said epoxidation processing aid is Toenol 1140, soya-bean oil, Oleum Cocois, Thistle oil, Trisun Oil R 80, oleum gossypii seminis or octyl stearate.
12. vinylidene chloride polymer composition, it contains (1) vinylidene chloride polymer, wherein a large amount of components are vinylidene, remaining ingredient be one or more can with the monoene class unsaturated monomer of vinylidene copolymerization, (2) glyceryl ester and (3) polyolefine, wherein glyceryl ester and polyolefinic content are enough to improve the extrudability of vinylidene chloride polymer.
13. the composition of claim 12, wherein said polyolefine are high density polyethylene(HDPE), polyethylene wax, oxidized polyethlene wax or its mixture.
14. contain the single layer structure of vinylidene chloride polymer composition, said composition contains (1) vinylidene chloride polymer, wherein a large amount of components are vinylidene, remaining ingredient be one or more can with the monoene class unsaturated monomer of vinylidene copolymerization, (2) glyceryl ester and (3) siloxane polymer, with optional epoxidation processing aid, wherein the content of glyceryl ester and siloxane polymer is enough to improve the extrudability of vinylidene chloride polymer.
15. multilayered structure, it contains the blend of (1) one or more layers organic polymer or two or more different organic polymers, wherein one deck organic polymer and another layer organic polymer are identical or different, (2) one or more layers vinylidene chloride polymer composition, wherein said composition contains (1) vinylidene chloride polymer, wherein a large amount of components are vinylidene, remaining ingredient be one or more can with the monoene class unsaturated monomer of vinylidene copolymerization, (2) glyceryl ester and (3) siloxane polymer, with optional epoxidation processing aid, wherein the content of glyceryl ester and siloxane polymer is enough to improve the extrudability of vinylidene chloride polymer.
16. the multilayered structure of claim 15, it contains first skin of the blend of (1) organic polymer or two or more different organic polymers, (2) sandwich layer of vinylidene chloride polymer composition, (3) second skin of organic polymer, the organic polymer of this layer and the first outer field organic polymer are identical or different.
17. the multilayered structure of claim 15, it contains first skin of (1) vinylidene chloride polymer composition, (2) sandwich layer of the blend of organic polymer or two or more different organic polymers, (3) second skin of organic polymer, the organic polymer of this layer and the organic polymer of sandwich layer are identical or different.
18. the multilayered structure of claim 15 wherein places binder layer between the adjacent layers of multilayered structure.
19. the multilayered structure of claim 15, wherein said organic polymer are polyolefine, polymeric amide or polystyrene.
20. five layers or seven-layer structure, it has (A) one or more layers vinylidene chloride polymer composition, said composition contains (1) vinylidene chloride polymer, wherein a large amount of components are vinylidene, remaining ingredient be one or more can with the monoene class unsaturated monomer of vinylidene copolymerization, (2) glyceryl ester and (3) siloxane polymer, with optional epoxidation processing aid, glyceryl ester wherein, the content of siloxane polymer and epoxidation processing aid is enough to improve the extrudability of vinylidene chloride polymer, (B) rest layers, this layer contains the blend of organic polymer or two or more different organic polymers, and wherein one deck organic polymer and another layer organic polymer are identical or different.
21. five layers or seven-layer structure of claim 20 wherein place binder layer between the adjacent layers of this structure.
22. contain the single or multiple lift structure of vinylidene chloride polymer composition, wherein said composition contains (1) vinylidene chloride polymer, wherein a large amount of components are vinylidene, remaining ingredient be one or more can with the monoene class unsaturated monomer of vinylidene copolymerization, (2) glyceryl ester and (3) polyolefine, wherein glyceryl ester and polyolefinic content are enough to improve the extrudability of vinylidene chloride polymer.
23. soft or rigid container, it has the single layer structure of claim 14, the multilayered structure of claim 15 or the single or multiple lift structure of claim 22.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US8528098P | 1998-05-13 | 1998-05-13 | |
| US60/085,280 | 1998-05-13 |
Publications (1)
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|---|---|
| CN1305510A true CN1305510A (en) | 2001-07-25 |
Family
ID=22190571
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99807319A Pending CN1305510A (en) | 1998-05-13 | 1999-04-28 | Extrudable vinylidene chloride polymer compositions |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP1084189A1 (en) |
| JP (1) | JP2002514672A (en) |
| KR (1) | KR20010043523A (en) |
| CN (1) | CN1305510A (en) |
| AR (1) | AR019292A1 (en) |
| AU (1) | AU750893B2 (en) |
| BR (1) | BR9910684A (en) |
| CA (1) | CA2331495A1 (en) |
| ID (1) | ID28099A (en) |
| NZ (1) | NZ507945A (en) |
| WO (1) | WO1999058603A1 (en) |
| ZA (1) | ZA200006429B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100465224C (en) * | 2003-07-30 | 2009-03-04 | 株式会社吴羽 | 1, 1-dichloroethylene resin film, casing for meat emulsion product, and packaged meat emulsion product |
| CN101228232B (en) * | 2005-07-28 | 2010-12-15 | 株式会社吴羽 | Poly-1, 1-dichloroethylene resin composite, biaxially stretched film, and process for producing the biaxially stretched film |
| CN102131967B (en) * | 2008-08-27 | 2013-08-28 | 陶氏环球技术有限责任公司 | Polyvinylidene chloride compositions and their use in monofilament structures |
| CN106147085A (en) * | 2016-08-24 | 2016-11-23 | 安徽顺彤包装材料有限公司 | A kind of insulation packaging material and preparation method thereof |
| CN107922701A (en) * | 2015-08-31 | 2018-04-17 | 陶氏环球技术有限责任公司 | Vinylidene chloride polymer composition and the product for including it |
| CN107922625A (en) * | 2015-08-31 | 2018-04-17 | 陶氏环球技术有限责任公司 | The method for preparing vinylidene chloride polymer composition |
| CN109206797A (en) * | 2018-08-30 | 2019-01-15 | 奚正华 | It is a kind of based on vinylidene chloride-ethylene-propylene lonitrile copolymer preservative film and preparation method thereof |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030215555A1 (en) * | 2002-05-17 | 2003-11-20 | Kraft Foods Holdings, Inc. | Food containers with improved release characteristics |
| GB0304757D0 (en) * | 2003-03-01 | 2003-04-02 | Rexam Med Packaging Ltd | Polymeric films and packages produced therefrom |
| RU2397183C2 (en) * | 2004-10-12 | 2010-08-20 | Дау Глобал Текнолоджиз Инк. | Alkylacrylate-vinylidene chloride polymer plasticiser |
| JP6339435B2 (en) * | 2014-07-23 | 2018-06-06 | 旭化成株式会社 | Vinylidene chloride resin wrap film |
| JP6567860B2 (en) * | 2015-04-23 | 2019-08-28 | 大同化成株式会社 | Vinylidene chloride resin composition |
| EP3380546A1 (en) * | 2015-11-27 | 2018-10-03 | Solvay SA | Vinylidene chloride polymer composition comprising at least one allyl cinnamate |
| KR102519574B1 (en) * | 2020-09-25 | 2023-04-07 | 에스케이이노베이션 주식회사 | Pvdc-based composite with core-shell structure and method for manufacturing same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6030343B2 (en) * | 1980-01-24 | 1985-07-16 | チッソ株式会社 | Vinyl chloride resin composition |
| JPH01299084A (en) * | 1988-05-27 | 1989-12-01 | Toshiba Corp | Thermal transfer recording material |
| JP3523340B2 (en) * | 1994-08-30 | 2004-04-26 | 呉羽化学工業株式会社 | Vinylidene chloride polymer moldings |
| JPH09151290A (en) * | 1995-09-27 | 1997-06-10 | Kureha Chem Ind Co Ltd | Vinylidene chloride polymer composition and its molded item |
-
1999
- 1999-04-28 WO PCT/US1999/009225 patent/WO1999058603A1/en not_active Ceased
- 1999-04-28 ID IDW20002337A patent/ID28099A/en unknown
- 1999-04-28 CN CN99807319A patent/CN1305510A/en active Pending
- 1999-04-28 BR BR9910684-1A patent/BR9910684A/en not_active IP Right Cessation
- 1999-04-28 CA CA002331495A patent/CA2331495A1/en not_active Abandoned
- 1999-04-28 AU AU37689/99A patent/AU750893B2/en not_active Ceased
- 1999-04-28 NZ NZ507945A patent/NZ507945A/en unknown
- 1999-04-28 KR KR1020007012621A patent/KR20010043523A/en not_active Withdrawn
- 1999-04-28 EP EP99920115A patent/EP1084189A1/en not_active Withdrawn
- 1999-04-28 JP JP2000548401A patent/JP2002514672A/en active Pending
- 1999-05-12 AR ARP990102240A patent/AR019292A1/en not_active Application Discontinuation
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2000
- 2000-11-08 ZA ZA200006429A patent/ZA200006429B/en unknown
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100465224C (en) * | 2003-07-30 | 2009-03-04 | 株式会社吴羽 | 1, 1-dichloroethylene resin film, casing for meat emulsion product, and packaged meat emulsion product |
| CN101228232B (en) * | 2005-07-28 | 2010-12-15 | 株式会社吴羽 | Poly-1, 1-dichloroethylene resin composite, biaxially stretched film, and process for producing the biaxially stretched film |
| CN102131967B (en) * | 2008-08-27 | 2013-08-28 | 陶氏环球技术有限责任公司 | Polyvinylidene chloride compositions and their use in monofilament structures |
| CN107922701A (en) * | 2015-08-31 | 2018-04-17 | 陶氏环球技术有限责任公司 | Vinylidene chloride polymer composition and the product for including it |
| CN107922625A (en) * | 2015-08-31 | 2018-04-17 | 陶氏环球技术有限责任公司 | The method for preparing vinylidene chloride polymer composition |
| CN106147085A (en) * | 2016-08-24 | 2016-11-23 | 安徽顺彤包装材料有限公司 | A kind of insulation packaging material and preparation method thereof |
| CN109206797A (en) * | 2018-08-30 | 2019-01-15 | 奚正华 | It is a kind of based on vinylidene chloride-ethylene-propylene lonitrile copolymer preservative film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20010043523A (en) | 2001-05-25 |
| ID28099A (en) | 2001-05-03 |
| NZ507945A (en) | 2003-02-28 |
| CA2331495A1 (en) | 1999-11-18 |
| ZA200006429B (en) | 2001-11-08 |
| AU750893B2 (en) | 2002-08-01 |
| EP1084189A1 (en) | 2001-03-21 |
| AR019292A1 (en) | 2002-02-13 |
| JP2002514672A (en) | 2002-05-21 |
| AU3768999A (en) | 1999-11-29 |
| WO1999058603A1 (en) | 1999-11-18 |
| BR9910684A (en) | 2001-01-09 |
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