WO2007053051A1 - Procede de traitement d'un materiau polymere thermoplastique au moyen d'une matrice revetue - Google Patents

Procede de traitement d'un materiau polymere thermoplastique au moyen d'une matrice revetue Download PDF

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Publication number
WO2007053051A1
WO2007053051A1 PCT/RU2005/000541 RU2005000541W WO2007053051A1 WO 2007053051 A1 WO2007053051 A1 WO 2007053051A1 RU 2005000541 W RU2005000541 W RU 2005000541W WO 2007053051 A1 WO2007053051 A1 WO 2007053051A1
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Prior art keywords
acids
salts
curing agent
processing
die
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PCT/RU2005/000541
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English (en)
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Oleg Leonidovich Kulikov
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Oleg Leonidovich Kulikov
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Priority to PCT/RU2005/000541 priority Critical patent/WO2007053051A1/fr
Publication of WO2007053051A1 publication Critical patent/WO2007053051A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
    • B29C33/60—Releasing, lubricating or separating agents
    • B29C33/62—Releasing, lubricating or separating agents based on polymers or oligomers
    • B29C33/64—Silicone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/27—Cleaning; Purging; Avoiding contamination
    • B29C48/272—Cleaning; Purging; Avoiding contamination of dies
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M155/00—Lubricating compositions characterised by the additive being a macromolecular compound containing atoms of elements not provided for in groups C10M143/00 - C10M153/00
    • C10M155/02—Monomer containing silicon
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M155/00—Lubricating compositions characterised by the additive being a macromolecular compound containing atoms of elements not provided for in groups C10M143/00 - C10M153/00
    • C10M155/04—Monomer containing boron
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/123—Reaction products obtained by phosphorus or phosphorus-containing compounds, e.g. P x S x with organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/503—Extruder machines or parts thereof characterised by the material or by their manufacturing process
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/02—Unspecified siloxanes; Silicones
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/05—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/36—Release agents or mold release agents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/08—Solids

Definitions

  • the present invention relates generally to processing of thermoplastic polymeric material by extrusion, blow molding and injection molding More
  • the present invention provides a method of improving the melt processing of polyolefin resins
  • the present invention relates partly to lubricating compositions comprising anti-wear and extreme pressure additives
  • compositions containing a variety of ingredients in relatively small, but critical amounts
  • ingredients may be generally categorized into two classes, namely Product Additives and Processing Additives
  • Illustrative of the Product Additives are the reinforcing and non-reinforcing
  • the Processing Additives facilitate processing Foremost among these additives are lubricants, sometimes referred to as release agents, which prevent sticking of the thermoplastic polymer to fabrication surfaces such as extruder screws, extrusion dies, rolls, injection molds, and the like As an
  • thermoplastic polymeric material based on polymers with narrow molecular weight distribution
  • ultra high molecular weight siloxane gum Based on ultra high molecular weight siloxane gum (viscosity is about 15-20 Pas), these materials form dispersion within the polymer melt, controlling the mobility of the siloxane and virtually eliminating screw slip [http //www dowcoming com 121], The use of ultra high molecular weight siloxane gum shows improvement in melt flow at relatively high concentration of the additives what makes the method prohibitively expansive.
  • the Processing Additive is a polymeric material being thermodynamically not compatible with the thermoplastic polymeric material and having molecular weight from 500 to 100,000 and at least two monofunctional radicals on its molecule selected from hydroxy, alkoxy, epoxy, carboxy and amino radicals, while the Processing Adjuvant is based on material with a molecule having at least two monofunctional radicals wherein at least one functional radical provides preferential absorption over the Processing Additive for the fabrication surface and wherein at least one other functional radical is capable of bonding with the Processing Additive, wherein the Processing Additive and the Processing Adjuvant are present in the ratio from 50 1 to 1 20, preferably 5 1 to 1 5 and most preferably 2 1 to 1 :2.
  • the examples of the Processing Additive are polyether polyols, silicone- polyether block copolymers, polyamines, polycarboxylic acids, polycarboxylic anhydrides and epoxy resins
  • Examples of the Processing Adjuvant are organodenvatives of carboxylates, phosphates, thiophosphates, phosphonates, sulfates, phosphonic acids, carboxylic acids, sulfites, phosphorous acids, phosphoric acids, sulfuric acids, sulfonates, phosphates, thiophosphites and ammonia
  • thermoplastic polymeric material which preferably consist of a combination of a silicone-glycol copolymer having carbinol- terminated grafts ( ⁇ e , having --COH end radical on the side chains) and a Phosphorous based Processing Adjuvant were disclosed by Leung et al in [P S Leung,
  • Processing Additives in combination with Processing Adjuvant is known also from [D E Priester, et al Processing aid system for polyolefins U S Patent No 5,707,569 January 13, 1998, U S Class 264/39 /9/] where the Processing Additive is a fluoropolymer and the Processing Adjuvant is selected from polyvinylacetate, ethylene/vinyl acetate copolymer, ethylene/acrylic acid copolymer, ethylene/methacrylic acid copolymer, ethylene/vinyl alcohol copolymer, polyvinyl alcohol or ionomer
  • the Processing Additive is a fluoropolymer
  • the Processing Adjuvant is selected from polyvinylacetate, ethylene/vinyl acetate copolymer, ethylene/acrylic acid copolymer, ethylene/methacrylic acid copolymer, ethylene/vinyl alcohol copolymer, polyvinyl alcohol or ionomer
  • TPUEs are characterized by strong hydrogen bonds between diisocyanates as well as physical bonding of the molecules due to phase separation of soft and hard segments of TPUEs
  • thermoplastic elastomers are thermodynamically compatible with many polymers having polar radicals
  • Processing Additives in extrusion at elevated temperatures (above 23O°C) as well as for extrusion and injection molding of various elastomeric compositions, Polyurethanes, Polyamides, Polycarbonates, and Polysulphones
  • the method to get a rubbery but yet plastic product by treatment of liquid polymeric dimethyl siloxane with boric oxide was first described in [R R McGregor and E L. Warrick, Treating Silicone Polymer with boric oxide, US Patent No 2,431 ,878, Dec 2, 1947 /17/]
  • Bouncing putty based on organosiloxane-boron compound was described in [J G E Wright, Process for making a puttylike elastic- plastic siloxane derivative composition containing zinc hydroxide, US Patent No 2,541 ,851 , Feb 13, 1951 /18/]
  • the process for making puttylike elastic-plastic siloxane derivative composition comprises heating a mixture comprising liquid polymeric dimethylsiloxane and from 5 to 25 per cent, by weight, based on the weight of the polymeric dimethylsiloxane, of a compound of boron selected from the group consisting of Pyroboric acid, boric anhydride, boric acid, borax, and hydrolyzed esters of boric
  • Silly Putty demonstrates the richness and complexity of behavior that simple materials (often referred as the simplest material with visco-elasticity) can produce If rolled into a ball and dropped, the material bounces like rubber However, upon longer inspection the material is seen to sag under its own weight although the putty does not flow indefinitely on a flat surface It flows only above some threshold shear so it behaves like a plastic of Bingham In addition, if a shock or impulsive load is applied to the putty, it will shatter [http //www campoly com/notes/sillyputty pdf /20/] Silly Putty is known as a Dilatant Compound but in the range of load frequencies from 0 1 to 40 Hz it is closer to viscoelastic fluids or "Maxwell liquids" in their classical definition, see [W L Wilkinson, Non-Newtonian fluids, Pergamon Press, NY, 1960 /21/].
  • Viscosity of Silly Putty also depends on time of shearing and fluid undergoes a decrease in viscosity with time of kneading that is showing tixotropic behavior
  • a viscoelastic material is one which possesses both elastic and viscous properties and its rheological behavior is much more complex in comparison to the dilatant material
  • Viscoelastic materials could show either shear-thinning (drop of viscosity with an increase in shear rate) or shear-thickening ( ⁇ e.
  • PVA Slime Another well known viscoelastic substance having properties similar to the bouncing putty is a PVA Slime which could be made in reaction of Polyvinyl Alcohol (PVA) molecules with borax (sodium tetraborate)
  • Boundary or Extreme-pressure (E, P.) lubricants While under normal conditions termed “hydrodynamic", a film of lubricant is maintained between the relatively moving surfaces governed by lubricant parameters, and principally viscosity. However, when load is increased, clearance between the surfaces is reduced, or when speeds of moving surfaces are such that the film of oil cannot be maintained, the condition of "boundary lubrication" is reached, governed largely by the parameters of the contacting surfaces At still more severe conditions, significant destructive contact manifests itself in various forms such as wear and metal fatigue as measured by ridging and pitting It is the role of extreme-pressure (E. P.) additives to prevent this from happening For the most part, E.
  • P agents have been oil soluble or easily dispersed as a stable dispersion in the oil, and largely have been organic compounds chemically reacted to contain sulfur, halogen (principally chlorine), Phosphorous, carboxyl, or carboxylate salt radicals, which react with the metal surface under boundary lubrication conditions.
  • Stable dispersions of boric acids and hydrated metal borates have also been found to be effective as E P. agents.
  • the hydrated alkali metal borates used in the prior art as E P. agents have an empirical formula: XM 2 O • B 2 O 3 • yhbO wherein M is an alkali metal, preferably sodium or potassium, and x is a positive number from about 0 2 to 3.
  • M is an alkali metal, preferably sodium or potassium
  • x is a positive number from about 0 2 to 3.
  • the alkali metal borate is at least partly neutralized with an acidic anion of phosphoric or sulfuric acid.
  • the quantity of the acid anion is used to bring the pH of an aqueous solution of the neutralized borate into the range from 6 to 8.
  • the processing improvements such as an inhibition of surface defects in the extrusion and/or molding of filled thermoplastics, a reduction in the pressure-to-fill during injection molding will be made apparent from the description and examples which follow
  • Another object of the present invention is to increase of output rates and/or reduce the power consumption, operating pressure and fabrication temperature of the process without adversely affecting the physical properties of the fabricated product
  • One other object of the present invention is to improve water tolerance of the anti-wear and E P additives for lubricating liquids
  • the viscoelastic substance based on compounds containing boron and oxygen can be used as a novel class of versatile Processing Additives. It was further unexpectedly discovered that performances of said Processing Additives can be improved by the use in composition of said viscoelastic substances of following chemicals- compounds containing alkali metals, compounds containing phosphorous and oxygen and compounds containing aluminum and oxygen.
  • the novel Processing Additives are broadly useful and superior to the conventional Processing Additives of the prior art for a variety of thermoplastic resin systems. It was also unexpectedly discovered that the viscoelastic substance based on siloxanes could be used a novel class of boundary lubricants or anti-wear and extreme pressure agents in lubricating oils and being superior to the prior art in water tolerance.
  • a method of processing of molten thermoplastic polymeric material in fabrication equipment comprises that a layer of a viscoelastic substance cured by a compound containing boron and oxygen coats at least a portion of the rigid wall which is in a contact with said thermoplast.
  • the curing agent is selected from the group of chemical compounds consisting of boron oxide, boric acids, solvable in water salts of boric acids, esters of boric acids, amines of boric acids and mixtures thereof.
  • the additive polymeric substance is selected from the group of polymers bearing in their molecules at least two monofunctional radicals selected from the group consisting of hydrogen, halogen, hydroxyl, alkoxyl, carboxyl, oxime, epoxide, amine, or isocyanate.
  • the additive polymeric substance is selected from the group consisting of functionalized siloxanes, functionalized hydrocarbons, functionalized copolymers of hydrocarbons and siloxanes, functionalized fluo ⁇ nated polymers and mixtures thereof.
  • reaction between the curing agent and the additive polymeric substance is effected in the presence of a catalyst.
  • the catalyst is selected from the group of chemical compounds consisting of phosphoric acids, polyphosphohc acids, phosphorus pentoxide, salts of alkali metals and phosphoric acids, salts of alkali metals and polyphospho ⁇ c acids, salts of aluminum hydroxide and phosphoric acids, salts of ferric hydroxide and phosphoric acids, aluminum hydroxide and mixtures thereof and provided that an amount of said catalyst is selected from the condition that the ratio of the number of phosphorus atoms to the number of boron atoms is in the range from 0 01 to 1.
  • the viscoelastic substance contains inorganic fillers in an amount from 1 to 50 weight %
  • the inorganic fillers are selected from the group of mineral powders with particles having plate-like structure consisting of mica, talc, natural and synthetic clay, hexagonal BN, and mixtures thereof
  • the method comprises blending the thermoplast with the viscoelastic substance in an amount selected from the range from 0 001 to 10 parts, per hundred parts of the thermoplast, wherein said viscoelastic substance deposits at the rigid wall of fabrication equipment which is in a contact with said thermoplast.
  • the method comprises simultaneous or separate in time blending the thermoplast with the curing agent based on the compound containing boron and oxygen and the additive polymeric substance reactive toward said curing agent, and provided that an amount of said components is selected from the range from 0 001 to 10 parts, per hundred parts of the thermoplast, wherein said components deposit and react at the rigid wall of fabrication equipment which is in a contact with said thermoplast.
  • the composition of the viscoelastic substance is selected from the condition that elasticity of the viscoelastic substance is above to that of the thermoplastic polymeric material and said elasticity is measured at maximum temperature of processing and at frequency 10 Hz.
  • the method comprises extrusion of the thermoplastic polymeric material through a die wherein a layer of the viscoelastic substance having at least 40 nm thickness coats at least a portion of the die land area adjacent to the die exit and having length at least 10% from the die gap width
  • a composition of a thermoplastic polymeric material comprises a main thermoplastic polymer and a processing additive in an amount selected from the range from 0 001 to 10 parts, per hundred parts of said thermoplast, wherein said thermoplast is a polyolefin resin and said processing additive is a viscoelastic product of the reaction of silanols with a curing agent based on a compound containing boron and oxygen
  • the curing agent for the processing additive is selected from the group of chemical compounds consisting of boron oxide, boric acids, salts of boric acids and hydroxides of alkali metals, esters of boric acids, amines of boric acids and mixtures thereof and provided the condition that the ratio of the total number of alkali metal atoms to the total number of boron atoms is in the range from 0 1 to 1
  • the curing agent for the processing additive additionally comprises a catalyst and said catalyst is selected from the group consisting of phosphoric acids, polyphosphoric acids, phosphorus pentoxide, salts of alkali metals and phosphoric acids, salts of alkali metals and polyphosphoric acids, salts of aluminum hydroxide and phosphoric acids, salts of ferric hydroxide and phosphoric acids, aluminum hydroxide and mixtures thereof and provided that the ratio of the total number of phosphorus atoms to the total number of boron atoms is in
  • a lubricating composition comprises an oil or grease of lubricating viscosity based on non-polar hydrocarbons and dispersed therein a minor amount of an anti-wear or extreme pressure agent wherein said agent is a product of the reaction of silanols with a curing agent based on a boron-oxygen containing compound
  • the curing agent for the anti-wear agent is selected from the group of chemical compounds consisting of boron oxide, boric acids, salts of boric acids and hydroxides of alkali metals, esters of boric acids, amines of boric acids and mixtures thereof and provided a condition that the ratio of the total number of alkali metal atoms to the total number of boron atoms is in the range from O 1 to 1
  • the curing agent for the anti-wear agent additionally comprises a catalyst and said catalyst is selected from the group consisting of phosphoric acids, polyphospho ⁇ c acids, phosphorus pentoxide, salts of alkali metals and phosphoric acids, salts of alkali metals and polyphospho ⁇ c acids and mixtures thereof and provided that an amount of said catalyst is selected from the condition that the ratio of the total number of phosphorus atoms to the total number of boron atoms is in the range from 0 01 to 1
  • thermoplastic polymeric material refers to the substance based on organic polymers which can be plastically deformed at temperatures below a decomposition point
  • the thermoplastic polymeric material generally useful in the present invention include the cross-linkable or vulcanizable elastomers, as long as they can be fabricated by standard thermoplastic melt processing techniques such as extrusion, milling, calendering, injection molding and/or melt spinning into fibers
  • One important polymer group is the addition polymers including the polyolefins, fluorocarbon polymers, vinyls, styrenics, acrylics and methacrylics, diene elastomers, thermoplastic elastomers and polyacetals
  • Another major group comprises the condensation polymers including the polyesters, polyamids, polycarbonates, polysulfones and polyurethanes
  • Still another polymer group is the thermoplastic cellulosic ethers and esters
  • olefin polymers Most preferable are the olefin polymers, copolymers, terpolymers and the blends thereof
  • interpolymers of olefin monomers such as ethylene, propylene, butene-1 , isobutylene, pentene-1 , hexene-1 , 4-methyl pentene-1 , octene- 1 , nonene-1 and decene-1
  • interpolymers with dienes such as ethylidene norbornene, cyclopentadiene and hexadiene
  • interpolymers with polar monomers such as vinyl acetate, vinyl alcohol, acrylic acid and methacrylic acid, their esters and salts, acrylamide and methacrylamide and N-alkyl versions thereof, carbon monoxide and the like
  • polar monomers such as vinyl acetate, vinyl alcohol, acrylic acid and methacrylic acid, their esters and salts, acrylamide and methacrylamide and N-alky
  • the above polymers and interpolymers are available in various types and grades and may be formulated with other ingredients into powders, pellets, flakes, granules, liquid resins or solutions They are well known in the art and further description thereof is considered unnecessary. These polymers are transformed into plastic articles by a variety of processes The present invention finds particular utility in extrusion and molding operations, and most preferably in film extrusion and injection molding.
  • a material is elastic if it changes shape due to an applied load, but that when the load is removed, recovers its original shape
  • a viscoelastic material is that one which possesses both elastic and viscous properties
  • a viscoelastic fluid is a viscoelastic material capable to flow under applied load
  • a gum is a sticky substance showing viscosity compatible with that of the thermoplastic polymeric material at processing temperature.
  • a tangent of losses tan ( alpha.) G2/G1 that is the ratio of imaginary part of the Young's modulus G2 to its real part G1 is a measure of elasticity in solid mechanics
  • the material is elastic if G2/G1 ⁇ 1 and it is viscous if G2/G1 > 1.
  • Visco-elasticity of polymeric melts indicates that the material acts as a viscous liquid over a long time period, but acts as an elastic solid over a short time period.
  • viscoelastic materials can demonstrate shear-thining that is drop in viscosity as shear rate increases or shear-thickening (dilatant behavior) that is increase in viscosity as shear rate increases
  • Processing Additives are essentially not compatible thermodynamically with the thermoplastic polymeric material. Processing Additives are evaluated on pressure reduction and elimination of melt fracture.
  • Antiblock agent the material that roughen the surface of plastic films to reduce their tendency to stick together These materials may include synthetic silica, diatomaceous earth, and talc
  • Curing agent In accordance to [http. //www spec ⁇ alchem4polymers com/resources/glossary
  • cure corresponds to a change in the properties of a polymeric system by a chemical reaction, which, for example, may be condensation, polymerization, vulcanization or addition, usually accompanied by the action of either heat or a catalyst or both, and with or without pressure
  • a curing agent is a catalytic or reactive agent that brings the change when added to a resin.
  • boron oxide has been found as an effective agent or a reagent, which turns low viscosity dimethylsilicone fluid to gummy-like products resembling natural rubber in their elasticity.
  • compounds containing boron and oxygen we consider following compounds containing boron and oxygen as curing agents' boron oxide, boric acids, solvable in water salts of boric acids, esters of boric acids, boron amides and mixtures thereof
  • Boric acids refer to 3 compounds orthoboric acid (also called boracic acid, H 3 BO 3 or B 2 O 3 3H 2 O), metaboric acid (HBO 2 or B 2 O 3 H 2 O), and tetraboric acid (also called pyroboric, H 4 B 4 O 7 or 2(B 2 O 3 ) H 2 O)
  • Orthoboric acid has a boiling point at 30O°C It dehydrates to form metaboric acid and tetraboric acid above 17O°C and 300°C respectively.
  • Orthoboric acid is poorly soluble in cold water (4 - 5 g/100 ml at 2O°C) but dissolves readily in hot water, in alcohols and glycerol. Borate salts
  • boric acid salts are alkaline metal salts, alkaline earth metal salts or ammonium salts of boric acid. More specific examples are sodium borates such as sodium metaborate, sodium diborate, sodium tetraborate, sodium pentaborate, sodium hexaborate, and sodium octaborate, potassium borates such as potassium metaborate, potassium tetraborate, potassium pentaborate, potassium hexaborate, and potassium octaborate, calcium borates such as calcium metaborate, calcium diborate, tricalcium tetraborate, pentacalcium tetraborate, and calcium hexaborate, magnesium borates such as magnesium metaborate, magnesium diborate, trimagnesium tetraborate, pentamagnesium tetraborate, and magnesium hexaborate, and ammonium borates such as ammonium metaborate, ammonium tetraborate, ammonium pentaborate, and am
  • Orthoboric acid B(OH) 3 and boron oxide B 2 O 3 on heating at 100 - 17O°C readily reacts with alcohols and phenols
  • Alcohols can be polyhydric, e g. glycols and polyols.
  • the boric acid esters include mono-, d ⁇ - and t ⁇ -substituted organic esters of boric acid with alcohols and phenols Lower alcohols, e g , methanol, ethanol, propanol, butanol, octanol, diols (glycols), and polyols, i.e , those having less than about 10 Carbon atoms, are especially useful for preparing the boric acid esters for the purpose of this invention Specific examples are monomethylborate, dimethylborate, trimethylborate, monoethylborate, diethylborate, triethylborate, monopropylborate, dipropylborate, tripropylborate, monobutyl
  • a catalyst is a substance that accelerates the rate of a chemical reaction without itself being transformed or consumed by the reaction
  • the viscoelastic substance can be prepared in presence of a catalyst which is selected from the group including phosphoric acids, polyphospho ⁇ c acids, phosphorus pentoxide, salts of alkali metals and phosphoric acids, salts of alkali metals and polyphosphoric acids, aluminum hydroxide, salts of phosphoric acid and aluminum hydroxide, salts of phosphoric acid and ferric hydroxide, hydrolysable salts of aluminum hydroxide or ferric hydroxide, selected from AICI 3 , AI 2 (SO 4 ) 3 , AI(H 2 PO 4 ), FeCI 3 Fine grounded or liquid catalyst can be mixed with the additive polymeric substance simultaneously or separate in time with the curing agent If it is used the catalyst comprises from 0 001 to 10 per cent by weight of the additive polymeric substance Most preferably an amount of said catalyst is selected from the condition that the ratio of the number of phosphorus atoms to the number of
  • phosphoric acids and derivatives used are orthophosphoric acid, methaphospho ⁇ c acid, phosphorus acid, polyphosphoric acids such as tripolyphosphoric acid, the polymetaphospho ⁇ c acids, and the like, and compounds derived from the esterification thereof
  • Phosphates are any salt, ester or anion of phosphoric acids
  • Specific examples of the phosphoric acids salts are alkaline metal salts, alkaline earth metal salts or ammonium salts of phosphoric acids Functionalized hydrocarbon fluid or gum
  • Functional radical is, in organic chemistry, a group of atoms within a molecule that is responsible for certain properties of the molecule and reactions in which it takes part
  • Organic compounds are frequently classified according to the functional radical or radicals they contain
  • methanol, ethanol, and isopropanol are all classified as alcohols since each contains a functional hydroxyl radical.
  • Functional radicals are attached to carbon backbone and give molecules different properties
  • the functionalized hydrocarbon fluid or gum is selected showing viscosity measured at maximum temperature of processing and at 0 1 Hz shear rate below to that of thermoplastic polymeric material and having on their molecules at least two monofunctional radicals independently selected from the group consisting of hydrogen, halogen, hydroxyl, alkoxyl, carboxyl, oxime, epoxide, amine, isocyanate . It has been found that a broad range of functionalized hydrocarbon fluids and gums may be utilized in accordance with this invention.
  • Suitable functionalized hydrocarbon fluids may come from the following classes of compounds glycols, macro glycols and polyols of aromatic, aliphatic, and combinations thereof, aromatic diamines and polyamines, alkanolamines and hydroxy acylamines, linear and branched polyol esters, polyol ethers, and caprolactone polyols, e g diols, triols, etc
  • the functionalized hydrocarbon based fluid or gum preferably contains at least two hydroxyl radicals in the molecule.
  • the hydroxyl radicals may be located at the ends of the molecule, they may be distributed along the chain or they may be located both at the ends as well as along the chain Preferably, the hydroxyls reside at the molecular chain ends When the hydroxyls are located only along the chain, the terminal radicals may be any non-reactive moiety.
  • Reaction products of boric acids or esters with functionalized hydrocarbon liquids are unstable to hydrolysis.
  • Siloxanes have extreme hydrophobicity in comparison to the functionalized hydrocarbon fluids Therefore the use of the functionalized siloxane fluid or gum in composition of the Processing Additives is preferable Functionalized silicone (siloxane) fluid or gum
  • Siloxanes are a class of both organic and inorganic chemical compounds which consist entirely of silicon, oxygen, and the group selected from hydrogen, alkyl, haloalkyl, aryl, haloaryl, aralkyl, polyether, imino, epoxy or vinyl. Siloxanes are also known as "silicones" or "silicone elastomers”. Siloxane based fluid or gum is a polymeric material with molecular weight ranging from 20 to 2,000,000 [http //www fluorochemsilanes co uk /41/] It can be linear or branched, low viscosity (from about 1 mPas to 100,000) or high viscosity (from 100,000 to 2,000,000 mPas).
  • the functionalized siloxane based fluid or gum preferably contains at least two hydroxyl radicals in the molecule.
  • the most common alkyl radicals include methyl, phenyl, and vinyl radicals and most preferably a methyl radical.
  • a suitable siloxane based fluid or gum may be a linear or branched organo-modified silicone polymer or copolymer
  • the functionalized siloxane based fluid or gum is selected showing viscosity below to that of thermoplastic polymeric material at maximum temperature of processing and at 0 1 Hz shear rate and having on their molecules at least two hydroxyl radicals.
  • the hydroxyl radicals may be located at the ends of the molecule, they may be distributed along the chain or they may be located both at the ends as well as along the chain
  • the hydroxyls reside at the molecular chain ends in the form of diorganohydroxysiloxy radicals, such as dimethylhydroxysiloxy, diphenylhydroxysiloxy, and methylphenylhydroxysiloxy, inter alia Chemical structure of these functional siloxane fluids is close to HO-R 2 S ⁇ O-(R 2 SiO)n-R 2 Si-OH, where R is an alkyl radical
  • polydimethylsiloxanes have received the most attentions due to their unique properties, such as extremely low glass transition temperature (-123°C), very low surface energies (20-21 dynes/cm), hydrophobicity, good thermal and oxidative stability, high gas permeability, excellent atomic oxygen resistance, biocompatibility, low dielectric constant, and low solubility parameter and relatively low cost.
  • the glass transition temperature of the siloxane will increase, as well as the thermal and the oxidative stability, and organic solubility characteristics
  • the service temperature is up to 29O°C
  • the terminal radicals of the diorgano-modified silicones may be any non- reactive moiety, typically a triorganosiloxy species such as trimethylsiloxy.
  • siloxane based fluid or gum Mixtures of two or more such polymers or copolymers may be employed as the siloxane based fluid or gum It is also preferred, although not critical, that during the processing of the thermoplastic polymeric material the siloxane based fluid or gum has a viscosity lower than that of the molten thermoplastic polymer. Most preferably the viscosity of the additive is at least ten times lower than that of the molten thermoplastic polymer during processing.
  • a condensation reaction (also known as a dehydration reaction) is a chemical reaction in which two molecules or moieties react with each other with the concurrent loss of by-product, e g. water or alcohol.
  • condensation reaction catalysts can be base catalysts including metal hydroxides such as potassium hydroxide and sodium hydroxide, metal salts such as silanolates, carboxylates, and carbonates, ammonia, amines, and titanates such as tetrabutyl titanates, and combinations thereof, see [U S. Pat No 4,639,489 to Aizawa et al., Jan 27, 1987 /42/]
  • Silicone resins As used herein, the term "resin” describes a silicone composition wherein the molecular structure is arranged in a predominantly three-dimensional network. Silicone resins are commercially available with molecular weight ranging from 2000 to 300,000 and having from 0 2 to 5% of silanol content
  • Fillers are relatively inert materials that are added to some plastics in amounts ranging from about 1 to 60 per cent to improve hardness, abrasion resistance, impact strength, solvent resistance and to modify electrical characteristics Some are added to plastic materials primarily to lower cost
  • the most common fillers are fumed silica or hydrated silica, carbon black, calcium carbonate, calcium sulphate, talc, diatomaceous earth, silica, alumina, bentonite, clay, ferric oxide, zinc hydroxide, wood flour, metallic powders and combinations thereof
  • BN powers having high content of B 2 O 3 can be used both as a curing agent and filler
  • clays are aluminosilicates, which have a sheet-like (layered) structure, and consist of silica SiO 4 tetrahedra bonded to alumina AlO ⁇ octahedra in a variety of ways A 2 1 ratio of the tetrahedra to the octahedra results in smectite clays, the most common of which is montmorillonite Other metals such as magnesium may replace the aluminium in the crystal structure Depending on the precise chemical composition of the clay, the sheets bear a charge on the surface and edges, this charge being balanced by counter-ions, which reside in part in the inter-layer spacing of the clay The thickness of the layers (platelets) is of the order of 1 nm and aspect ratios are high, typically 100-1500 The clay platelets are truly nanoparticulate The platelets are not totally rigid, but have a degree of flexibility The negatively charged surface of the clay can adsorb polar liquids (e g water) as well as various ions present
  • the general process of forming the viscoelastic substance of the invention comprises blending of the functionalised hydrocarbons, siloxanes, block copolymers of hydrocarbons and siloxanes, fluo ⁇ nated functionalised hydrocarbons and/or mixtures thereof with the curing agent and heating of the blend to temperature from about 7O°C to about 25O°C, preferably within the range from about 100°C to about 15O°C until an increase in viscosity is effected
  • the viscoelastic substance made from functionalized hydrocarbons is unstable to hydrolysis Siloxanes are hydrophobic and the viscoelastic substance made from functionalized siloxanes is more stable for storage in wet atmosphere Therefore the use of functionalized siloxanes is advantageous when the viscoeiastic substance is supposed to contact moisture during long storage.
  • silanols that are functionalized siloxanes terminated with hydroxyl radicals are relatively cheap chemical products. Therefore the use of silanols is preferable.
  • silanols react with boric acid resulting to monoesters H-O-(R 2 SI-O) N -H + B(OH) 3 -> (H-O) 2 -B-O-(R 2 SI-O) N -B-(O-H) 2
  • the catalysts can be strong Br ⁇ nsted acids like sulfuric acid, phosphoric and polyphospho ⁇ c acid, Lewis acids (e g. AICI 3 , FeCI 3 ), or combinations thereof Viscosity of the composition grows due to hydrogen bonding between the esters A noticeable change in viscosity happens if the number of boron atoms in a curing agent is above the number of hydroxyl radicals in silanols.
  • the filler having plate-like structure is preferably provided as a powder
  • powder means a mass of particles having a normal particle size less than about 0.1 mm, typically on the order of 0.1-100 microns, preferably less than 25 microns for the coarsest particles.
  • the milling mixture includes milling media and a milling liquid
  • the milling liquid comprises between about 70 and 95 wt % of the milling mixture
  • the milling liquid may be water, methanol, ethanol, propanol, or butanol
  • the liquid is any one in which B 2 O 3 is soluble, e g ethanol
  • the liquid is any one in which both E ⁇ C ⁇ and an alkali base are soluble, e g water.
  • compositions containing boron and oxygen between the molten thermoplastic polymer and the fabrication surface provide a number of advantages in polymer melt processing
  • Said viscoelastic material is immiscible with thermoplastic polymeric material, it deposits at the fabrication surface and work as a processing aid
  • Functionalized hydrocarbons are normally present in industrial grades of thermoplastic polymeric material, e g.
  • additives of special functionalized hydrocarbons and/or siloxanes to produce the viscoelastic substance in situ at the walls of the fabrication surface or to use additives of the viscoelastic substance produced in reaction of the functionalized hydrocarbons and/or siloxanes with the curing agent
  • a masterbatch (or concentrate), which preferably contains from about 1 to 10, more preferably from 2.5 to 5, weight percent of the viscoelastic material, or a curing agent and additive polymeric material in proportion that reaction between the components results in the viscoelastic material
  • the master batch may be granulated or pelletized, dry-blended with the matrix resin and this blend then extruded The use of this masterbatch technique results in a more uniform dispersion in the matrix resin.
  • the resin used in the preparation of the masterbatch may be the same as, or different from, the main polyolefin resin Preferably, the two are of the same general type (e.g. polyethylene in the masterbatch and as the main component of the thermoplast).
  • the viscoelastic substance or the reacting components can be supplied as a solution, emulsion or dispersion in a volatile fluid having boiling temperature below temperature of melting of the thermoplastic polymers, e g methanol, water
  • a volatile fluid having boiling temperature below temperature of melting of the thermoplastic polymers e g methanol, water
  • the use of functionalized fluids having boiling temperature above maximum temperature of processing is advantageous to prevent foaming of the product by not totally reacted components It is possible to obtain a relatively uniform dispersion of the additives in the matrix by injecting of the low viscous liquid carrier with the additives along the feeding zone of a screw section of an extruder while polyolefin pellets are fed in through the hopper thereof
  • the use of low viscous liquid as a liquid carrier will improve uniformity of the dispersion of the processing aid
  • the vapors of the liquid carrier will leave the extruder between solid granules of the thermoplastic polymer
  • the reacting components can be selected having temperature of boiling below temperature of melting of the thermoplastic polymer Examples are trimethyl borate (trimethyl ester of boric acid - (CH 3 O) 3 B - temperature of boiling is about 68 - 69°C) and low molecular weight Siloxanes terminated with hydroxyl radicals
  • the use of volatile reactants simplifies dispersion of the viscoelastic fluid as the reaction goes partly in a gaseous phase and the reaction products deposit at the surface of fabrication equipment and polymer granules in the feeding zone of a screw extruder
  • the use of the volatile reactants may result in nano-composites, i e dispersion of nanometer size scale elastic particles in the polymer matrix and provide an additional benefit in improvement of toughness of brittle polymers
  • the use of the volatile reactants may result in a stable dispersion of nanometer size scale elastic particles in the lubricating liquid and provide an additional benefit in improvement of anti-wear properties of the additives
  • Figure 1 presents plots of the viscosity and the elasticity parameter (G1/G2) vs load frequency for LL1201
  • Figure 2 presents characteristic curves, i e plots of the pressure vs extrusion rate for tubular dies 12 and 32 mm as well as for a sharp diaphragm (orifice) at 165°C
  • Figure 3 presents characteristic curves for extrusion through the tubular die 6 32 mm coated by polyester AS2060 and by the polyester (91 5%) cured by boric acid (8 5%)
  • Figure 4 presents characteristic curves for extrusion through the die coated by BDO ( ⁇ e 1 ,4-Butaned ⁇ ol, 60%) or Glycerol (60%) cured by boric acid (40%)
  • Figure 5 presents plots of the viscosity and the elasticity parameter (G1/G2) vs load frequency for DOW 3-0133 (99%) cured by boric acid (1 %)
  • Figure 6 presents plots of the viscosity and the elasticity parameter (
  • Baycoll AS2060 from Bayer is a slightly branched polyester polyol, equivalent hydroxyl content 1 73-1 91 %, viscosity 1000 mPa-s at 75°C Baycoll AD5027 from Bayer is a linear polyester diol, equivalent hydroxyl content 0 87%, viscosity 2800 mPa-s at 75°C ELASTOSIL RT K from Wacker Chemie is a pourable, condensation-curing two- component silicone rubber that vulcanizes at room temperature in presence of a tin catalyst (4% curing agent T40) It is recommended for mould making and as a flexible mould release agent Its viscosity at 23°C - 12 000 Pa-s. The raw silicone rubber was used here without the catalyst
  • MQ RESIN POWDER from Wacker Chemie is the co-hydrolysis product of tetraalkoxysilane (Q resin) and trimethylethoxysilane (M resin)
  • Q resin tetraalkoxysilane
  • M resin trimethylethoxysilane
  • the chemical structure of MQ Resin Powder is a three dimensional network of polysilicic acid units terminated with trimethylsilyl radicals
  • a few ethoxy and hydroxy functional radicals are also present ⁇ SILRES® 601 from Wacker Chemie is a Solid Silicone Resin for Powder
  • Coatings OH radical content is about 5%
  • SilGel® 612 from Wacker Chemie is a pourable, addition-curing, two-component silicone rubber that cures at room temperature to a very soft, gel-like vulcanizate.
  • AK 100,000 from Wacker Chemie is a high molecular weight polydimethyl siloxane, viscosity 100,000 mPa-s
  • G1/G2 ratio instead of the inversed value tan ( alpha ) is more convenient to present data of viscosity and elasticity at one plot
  • Many molten polymers manifest viscous (G1/G2 ⁇ 1 , i e. fluid-like) behavior at low frequencies and elastic (G1/G2 > 1 , solid-like) behavior at high frequencies
  • G1/G2 > 1 solid-like behavior at high frequencies
  • Complex viscosity and the ratio G1/G2 versus frequency are presented in Figure 1 for temperature 165°C Molten LLDPE shows shear thinning and its viscosity drops as frequency of load is increasing at fixed level of stress.
  • a ram extruder from Loomis with a barrel of 60 200 mm (D ⁇ ameter*Length) and a hydraulically driven piston was used to extrude molten PE from a die
  • the piston velocity was controlled from a computer Values of the pressure and of the piston position were digitized during extrusion and transmitted to the computer for records
  • the die and extrudate were illuminated by a stroboscope and appearances were video recorded by a camcorder at 25 frames/sec
  • the stroboscope was synchronized with the camcorder and the video records were triggered simultaneously with the data records to get precise correspondence between them
  • the characteristic curve of pressure versus velocity is presented in Figure 2 for steel dies having diameter 6 mm by a solid line for the length 32 mm, by a dashed line for length 12 mm and by a dotted line for a sharp diaphragm (orifice)
  • the diaphragm was made from a steel disk (2 mm thickness) and having conical entrance with full angle 90°
  • the onsets of sharkskin are marked at the curves by crosses in circles (7 4, 6 3, 4.7 mm/s)
  • Boric acid as a curing agent was blended with Glycerol or with 1 ,4-Butaned ⁇ ol and heated to temperature about 14O°C When an intensive foaming of the reacting materials at about 14O°C was finished the product was heated to about 19O°C for an hour
  • Hydrocarbon functionalized fluids having filler cured by boric acid
  • a solution of t ⁇ - ⁇ sopropyl borate was prepared by stirring together 5 p b w. of boric acid and 95 p.b w. of isopropanol until dissolved
  • the solution was added dropwise to DOW 4-2737 or DOW 3-0133, the blend was vigorously stirred, heated above 14O°C and cured at temperature 17O°C for about 24 hours
  • Mechanical characteristics of the products were measured at 165°C Plots of viscosity and the ratio G1/G2 versus frequency are presented in Figure 5 for DOW 3-0133 with 1 % of boric acid and in Figure 6 for DOW 4-2737 with 12% of boric acid
  • the measurements were made at temperature 165°C. Both compositions show shear- thinning behavior (viscosity drops as frequency of load at fixed stress is increasing) at frequencies above 1 Hz Plots of complex viscosity measured at 0 1 Hz and
  • the viscoelastic substance produced from a blend of boric acid with DOW 4- 2737 in the ratio 2 3 was used to coat the die inside
  • the characteristic curve is presented in Figure 9 by a dashed line
  • the onset of sharkskin is marked at the curve by a cross (105 mm/s)
  • We observed low lubrication at velocity below 6 mm/s There was lubrication in the range of velocities from 6 to 145 mm/s with maximum change in pressure 20% in comparison to the reference curve for a clean die
  • At velocity about 5 5 mm/s some wavy dullness was present at the extrudate surface but it is disappeared at velocities above 7 mm/s
  • Sharkskin defects appeared in narrow strips at velocity above 81 mm/s
  • Stick-slip transitions were observed in range of velocities from 190 to 235 mm/s and super-flow in the range from 235 to 415 mm/s
  • the extrudate was deformed by wavy distortions at velocity above
  • Siloxane fluid DOW 4-2737 (68%) was blended with powder of borax (8%), aluminum hydroxide (17%) and glycerol (7%). The blend was cured by heating to 14O°C during 3 hours and 12 hours at temperature 95°C The die was coated inside by this viscoelastic substance and extrusion was done as it is described above Characteristic curve is presented in Figure 11 by a dashed line The onset of sharkskin was detected at about 108 mm/s
  • a solution of tri-methyl borate was prepared by stirring together 10 p b w. of boric acid and 90 p b w of methanol until dissolved.
  • a solution of sodium hydroxide was prepared by stirring together 4.7 p.b w of sodium hydroxide and 95.3 p b.w of methanol until dissolved.
  • the solution of the t ⁇ -methyl borate was added dropwise to DOW Q1-3563, the blend was vigorously stirred to produce emulsion and then the solution of the sodium hydroxide was added dropwise
  • the blend was stirred, heated to about 14O°C, till an increase in viscosity is effected and then cured at temperature 95°C This viscoelastic substance was used to coat the die inside and extrusion was done as it is described above.
  • EXAMPLE 9 Siloxanes cured by borax and phosphoric acid
  • a solution of phosphoric acid was prepared by stirring together 5 p.b w of an ortho-phosphoric acid and 95 p b w of methanol until dissolved
  • the reaction between functionalized siloxanes and borates in presence of alkali-metal ions accelerates when the alkali-metal ions are partly neutralized by an acid, preferably by a phosphoric acid Siloxane fluid Q1-3563 (2 g) was blended with the solution of phosphoric acid and heated under stirring to about 15O°C
  • the blend was foaming and its viscosity was increasing Borax in powder (0 22 g) was added then, the blend was mixed and heated again After the reaction was finished the product was arranged for 12 hours in a drying shelf at 95°C.
  • Amount of phosphoric acid was varied. Plots of viscosity measured at 0 1 Hz and of elasticity (G1/G2) measured at 10 2 Hz vs. the ratio of the number of phosphorus atoms to the number of boron atoms are presented in Figure 12
  • the reaction rate is too slow when the ratio of the number of phosphoric atoms to the number of boron atoms is below 0.01.
  • the product has low elasticity when the ratio of the number of alkali-metal atoms to the number of boron atoms borax is above 1 EXAMPLE 10
  • Siloxanes cured by a blend of boric and phosphoric acids Siloxanes cured by a blend of boric and phosphoric acids
  • Siloxane fluid Q1-3563 (2 g) was blended with the solution of phosphoric acid and heated under stirring to about 150°C. The blend was foaming and its viscosity was increasing When blended with the phosphoric acid and heated to about 140°C the low molecular weight siloxane fluid turns into a viscous liquid but hydrogen bonding is weak and both the acid and siloxanes evaporate when heated above 155°C. A solution of tri-methyl borate was added (0 1 1 g of Boric acid) the blend was mixed and heated again. After viscosity increased the product was cured in a drying chamber at 95°C for 12 hours.
  • Amounts of phosphoric acid in the products were varied Plots of viscosity measured at 0 1 Hz and of elasticity (G1/G2) measured at 10 2 Hz vs the ratio of the number of phosphorus atoms to the number of boron atoms are presented in Figure 13. There is no noticeable impact of the catalyst when the ratio of the number of phosphoric atoms to the number of boron atoms is below 0 01 The product has too low viscosity when the ratio of the number of phosphorus atoms to the number of boron atoms is above 1
  • EXAMPLE 12 Siloxanes cured by a blend of borax and sodium orthophosphate Powder of sodium orthophosphate hydrate (Na 3 PO 4 * 12H 2 O) was added slowly to the Dow Q 1-3563 (2 g) under stirring at about 140°C till solved Then borax in powder (0.22 g) was added under stirring at about 140°C Amounts of sodium orthophosphate in the products were varied The blends were cured at temperature 95°C Properties of the products are presented in Table 3 The products show too low plasticity when the ratio of the number of sodium atoms to the number of boron atoms is above 1 The products show too low viscosity when the ratio of the number of phosphorus atoms to the number of boron atoms is above 1. EXAMPLE 13 Blends od siloxanes with resins or rubbers cured by boric acid
  • the viscoelastic substance produced from blends of silicone resin SilRez with boric acid was used to coat the die inside.
  • the characteristic curve is presented in Figure 14 by a dashed line
  • the onset of sharkskin is marked at the curve by a cross (25 mm/s)
  • the viscoelastic substance produced from blends of siloxane fluid DOW 4-2737 (49%), silicone MQ Resin (50%) with boric acid (1 %) was used to coat the die inside
  • the characteristic curve is presented in Figure 14 by a dotted line.
  • the onset of sharkskin is marked at the curve by a cross (25 mm/s)
  • the viscoelastic substance produced from blends of siloxane fluid DOW 4-2737 (86%), silicone rubber SiIGeI 612 (13%) with boric acid (1%) was used to coat the die inside.
  • the characteristic curve is presented in Figure 14 by a dash-dotted line
  • the onset of sharkskin is marked at the curve by a cross (153 mm/s) and presented for comparison in Table 1 (No 14) in the column marked "w agent” that is "with a curing agent”
  • the use of elastic composition results in better lubrication and further delay of the melt fracture onset
  • the onsets of sharkskin are marked at the curves by crosses in circles
  • Borax was used in some experiments instead of the solution of the tri-methyl borate Powder of borax and inorganic fillers was added slowly to the blend of the DOW 4-2737 (80%) and DOW 3-0133 (20%). Then the product was heated to about 14O°C and cured at temperature 95°C. Following inorganic fillers were used aluminum hydrate, kaolin, bentonite, mica, BN, silica, fumed silica Only products made with aluminum hydrate are stable to hydration resinous solids at room temperature while others turn to viscous liquids after a week of storage in open air
  • the viscoelastic substance based on compositions containing Borax (9 3%) and DOW 4-2737 (56.3%), phosphoric acid (2.6%), BDO (2 8%), and Graphite (29%) was prepared as it is described above With the use of the die coated by the viscoelastic substance no lubrication was observed in velocity range from 1 to 8 mm/s.
  • the characteristic curve is presented in Figure 15 by a dashed line.
  • the onset of sharkskin is marked at the curve by a cross (63 mm/s) Macroscopic slip was detected above 233 mm/s
  • the viscoelastic substance based on compositions containing boric acid (2 9%), DOW 3-0133 (18.0%), DOW 4-2737 (70 3%), and mica (8.8%) was prepared as it is described above
  • the characteristic curve is presented in Figure 14 by a dashed line
  • the onset of sharkskin is marked at the curve by a cross (198 mm/s)
  • the viscoelastic substance based on compositions containing boric acid (3 2%), DOW 4-2737 (75.7%), silicone rubber SiIGeI 612 (7.5%), and mica (13.6%) was prepared as it is described above With the use of the die coated by the elastic viscoelastic substance much better lubrication was observed in the range from 1 to 8 mm/s in comparison to the use of the composition having no rubber additives
  • the characteristic curve is presented in Figure 14 by a dotted line
  • the onset of sharkskin is marked at the curve by a cross (124 mm/s)
  • Boric acid was used as a curing agent and blended with LLDPE in a following way It was dissolved in isopropanole to 5% concentration 8 4 g of the solution having about 0 42 g of boric acid was poured into a plastic bag with 1 kg of LLDPE granules. The content of the bag was thoroughly mixed and the solution was dried off by a jet of compressed air Content of the plastic bag was loaded into an extruder barrel, heated and molten there Induction time to suppress sharkskin was measured at V about 50 mm/s with the use of the die 3 35 22 mm from quartz glass. The die was heated by open flame to about 600°C just before an extrusion trial to burn out any organic contamination. Extrusion was done at velocity about 50 mm/s for 20 mm. Then an extrusion trial was done with a velocity ramp from 4 to 50 mm/s Melt fracture defects appeared at velocity above 40 mm/s.
  • boric acid was used to coat the die surface
  • the die 6 32 mm from steel was used First the extrusion the die was exposed to open flame and heated to 600 °C to burn out any organic contamination Then powder of boric acid was supplied inside the die so that under heating boric acid was molten and inner surface of the die was coated by a glassy layer of boron oxide.
  • ELASTOSIL RT K from Wacker Chermie was added to a plastic bag with 1 kg of LLDPE granules. The content of the bag was thoroughly mixed by a jet of compressed air Then it was loaded into an extruder barrel and molten there.
  • EXAMPLE 17 The use of a blend of siloxane fluid and boric acid as Processing Additive 0.75 g of ELASTOSIL RT K from Wacker Chemie was added to a plastic bag with 0 5 kg of LLDPE granules. The content of the bag was thoroughly mixed by a jet of compressed air 4 g of a 5% solution of t ⁇ -isopropyl borate (0 2 g of boric acid) was poured into another plastic bag with 0 5 kg of LLDPE granules The content of this bag was thoroughly mixed and the solution was dried off by a jet of compressed air. Content of both plastic bags was mixed together and loaded into an extruder barrel, heated and molten there
  • the present invention has an obvious and clear distinction from the prototype.
  • sinanols are added into a polyolefin resin together with a catalyst such as phosphoric acid and a curing agent such as borax That is the phosphoric acid is a catalyst for the reaction of borax with silanols while in the prototype it is a Processing Adjuvant and no curing agent is used
  • a catalyst such as phosphoric acid
  • a curing agent such as borax

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Abstract

L'invention concerne un procédé de traitement d'un matériau polymère thermoplastique (thermoplaste) dans un équipement de fabrication, tel qu'une matrice d'extrusion, consistant à revêtir la paroi de la matrice au moyen d'une couche d'une substance viscoélastique, telle qu'un silanol ou un polyol durci au moyen d'un borate. Un thermoplaste peut comprendre un additif de traitement, tel qu'un silanol ou un polyol conjointement avec un agent de durcissement, tel qu'un borate ou pouvant comprendre un silanol ou un polyol durci par un borate. Un lubrifiant peut comprendre un additif anti-usure, tel qu'un silanol durci au moyen d'un borate. Une réaction entre le silanol et le polyol avec l'agent de durcissement peut être exécutée en présence d'un catalyseur, tel qu'un phosphate. On peut citer parmi des paramètres améliorés dans le traitement du polymère : une pression d'extrusion réduite et une fracture de fusion réduite ou éliminée. Les additifs anti-usure présentent une tolérance à l'eau améliorée.
PCT/RU2005/000541 2005-11-03 2005-11-03 Procede de traitement d'un materiau polymere thermoplastique au moyen d'une matrice revetue WO2007053051A1 (fr)

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WO2011082294A1 (fr) 2009-12-30 2011-07-07 Dow Global Technologies Llc Procédé d'extrusion d'un polymère
WO2016176034A1 (fr) 2015-04-30 2016-11-03 Dow Global Technologies Llc Pdms à terminaison hydroxyle en tant qu'additif de contrôle de durcissement pour la réticulation par silane de polyoléfines
US20190185672A1 (en) * 2016-08-04 2019-06-20 The Provost, Fellows, Foundation Scholars, & The Othe Members of Board, of The College of The Holy Viscoelastic conductive nanomaterial-polymer nanocomposites and sensing devices comprising the composite material
US20210009768A1 (en) * 2018-04-05 2021-01-14 Ddp Specialty Electronic Materials Us 9, Llc Thermoplastic composition

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GB1421776A (en) * 1972-12-05 1976-01-21 Mineralimpex Magyar Olaj Es Ba Procedure for the manufacutre of silicone pastes
GB1570780A (en) * 1975-12-29 1980-07-09 Sws Silicones Corp Metal-coating organopolysiloxane compositions
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011082294A1 (fr) 2009-12-30 2011-07-07 Dow Global Technologies Llc Procédé d'extrusion d'un polymère
WO2016176034A1 (fr) 2015-04-30 2016-11-03 Dow Global Technologies Llc Pdms à terminaison hydroxyle en tant qu'additif de contrôle de durcissement pour la réticulation par silane de polyoléfines
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