WO2000040643A1 - Procede de production de mousses synthetiques pouvant etre chargees - Google Patents

Procede de production de mousses synthetiques pouvant etre chargees Download PDF

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Publication number
WO2000040643A1
WO2000040643A1 PCT/EP1999/010154 EP9910154W WO0040643A1 WO 2000040643 A1 WO2000040643 A1 WO 2000040643A1 EP 9910154 W EP9910154 W EP 9910154W WO 0040643 A1 WO0040643 A1 WO 0040643A1
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WO
WIPO (PCT)
Prior art keywords
base polymer
extruder
plastic foams
chemical blowing
agents
Prior art date
Application number
PCT/EP1999/010154
Other languages
German (de)
English (en)
Inventor
Bernhard Bartnick
Dieter Krampitz
Original Assignee
Cognis Deutschland Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cognis Deutschland Gmbh filed Critical Cognis Deutschland Gmbh
Publication of WO2000040643A1 publication Critical patent/WO2000040643A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/024—Preparation or use of a blowing agent concentrate, i.e. masterbatch in a foamable composition

Definitions

  • the invention relates to a process for producing loadable plastic foams, wherein a chemical blowing agent is added to at least one thermoplastic base polymer, the mass melts, mixed before and / or after melting, and the mixture is cooled to form a pourable, porous carrier material, with the proviso that one works in an extruder or multi-screw kneader extruder and at least occasionally introduces an inert gas into the melt of the base polymer and chemical blowing agent.
  • the extrusion is carried out in the presence of a wetting agent.
  • Polymers consist of molecular chains with numerous, practically endlessly repeating building blocks, which differ in terms of the physical properties of low molecular weight compounds. For example, polymers have high tensile strengths and elasticity compared to low molecular weight compounds.
  • additives are mixed into polymerized plastic materials. That way you can Base polymers can be adapted to individual needs with regard to the desired properties.
  • a base polymer or a mixture of a plurality of base polymers with one or more additives is heated, melted, mixed and converted into a pourable form, for example into carrier materials loaded with additives in granular form. These are also called additive masterbatches.
  • thermoplastic base polymers mixes them with foaming aids, melts and mixes the mass and, after cooling, gives a pourable porous carrier material which is then loaded with a desired additive.
  • foaming aids Azodicarbonamides and citric acid derivatives are disclosed as suitable foaming aids.
  • an inert gas for example nitrogen, is introduced at least temporarily into the melt of base polymers and foaming aids in order to achieve particularly high porosities.
  • Plastic foams as is common in the art - are understood to mean plastics that can be loaded with additives due to the presence of internal cavities.
  • the loading should be possible in a simple manner in such a way that the plastic foam according to the invention, which is a porous carrier material, is mixed with at least one additive and with this one at below the melting point of the base polymers used to produce the plastic foam, but above that Melting point of the additive lying temperature is mixed; the additive flows into the inner cavities of the plastic foam, d. H. Due to its special structure, the plastic foam absorbs the liquid additives like a sponge.
  • additives are understood to mean plastic additives.
  • the present invention relates to a process for producing loadable plastic foams, a chemical blowing agent, the composition, being added to at least one thermoplastic base polymer melts, mixes before and / or after melting, and the mixture cools to form a pourable, porous carrier material, with the proviso that one works in an extruder or multi-screw kneader-extruder and at least temporarily an inert gas in the melt of the base polymer and initiates chemical blowing agent and wherein the extrusion is carried out in the presence of a wetting agent.
  • the products accessible by the process according to the present invention are pourable, porous carrier materials and are referred to below - as has also been done above - as plastic foams.
  • the plastic foams accessible by the process according to the invention have macro-pores which are interconnected. This can be demonstrated, for example, by scanning electron micrographs of longitudinal or cross sections of the plastic foams.
  • the pores have a diameter of the order of 100 ⁇ m and are ellipsoidal, the ratio of the longest to the shortest inner diameter being 2: 1 to 5: 1.
  • wetting agent is known to the person skilled in the art, in particular to the surfactant expert.
  • Wetting agents are natural or synthetic substances that reduce the surface tension of water or other liquids in solution. Wetting agents are therefore surfactants.
  • the type of wetting agent there are no restrictions per se within the scope of the present invention. In principle, all wetting agents known to those skilled in the art of surfactants can be used.
  • the wetting agent used is an ester of organic carboxylic acids with 8 to 22 carbon atoms and alcohols with 1 to 22 carbon atoms, sorbitan esters, ethoxylated fatty acid esters and water-soluble salts of mono- and / or disulfosuccinates.
  • Alkali salts of di-iso-hexylsulfosuccinate and di-iso-octylsulfosuccinate are particularly preferred.
  • the wetting agents which can be used both individually and as a mixture with one another, are used in an amount of from 0.01 to 5% by weight, based on the base polymers.
  • the integration of the wetting agents in the plastic foam has the effect, in particular, that loading of the plastic foam with plastic additives is easier. This means in particular that the degree of loading of the plastic foams produced according to the invention is generally 5 to 20% higher than the degree of loading of comparable foams, in which, however, the extrusion was carried out in the absence of wetting agents.
  • the chemical blowing agent is used in an amount of 0.01 to 5% by weight and in particular in an amount of 0.1 to 2% by weight, based on the base polymers. Either one or more substances can be used as chemical blowing agents.
  • the chemical blowing agent is preferably selected from the group of the diazo compounds, N-nitroso compounds, sulfohydrazides, urea derivatives, guanidine derivatives, borohydride / water systems, citric acid and its esters, carbonates and hydrogen carbonates. In a preferred embodiment of the present invention, carbonates, hydrogen carbonates, citric acid and their esters or mixtures of these compounds are used as chemical blowing agents.
  • the extruder is operated in a temperature range from 100 to 265 ° C., a pressure range from 50 to 100 bar and a screw speed of 50 to 100 rpm.
  • the optimal extrusion temperatures depend essentially on the type of base polymers used, especially their melt flow indices (MFI). Unless as Base polymer an ethylene-vinyl acetate copolymer is used, a temperature in the range of 100 to 120 ° C in the feed zone of the extruder and a temperature in the range of 160 to 180 ° C is preferably set. If polypropylene is used as the base polymer, a temperature in the range of 130 to 150 ° C.
  • LDPE low density polyethylene
  • a temperature in the range of 120 to 140 ° C. is preferably set in the feed zone of the extruder and a temperature in the range of 180 to 210 ° C. in the nozzle area.
  • an inert gas is introduced at least temporarily into the melt of the base polymer and chemical blowing agent.
  • the inert gas is introduced into the extruder, which contains the melt of the base polymer and chemical blowing agent.
  • the introduction of the inert gas preferably takes place during the entire extrusion process.
  • the gas is introduced, in particular, as a fine spray, the amount of the gas depending in particular on the type of base polymer, the proportion of chemical blowing agent and the temperature and the total amount of the melt.
  • Gas pressures are preferably set to values which are 5 to 30 bar above the extrusion pressure.
  • the amount of gas is preferably set to a value in the range from 50 to 100% by volume, based on the volume of the extruded polymers; “Volume” means the throughput of the polymer per time (volume output in liters per hour).
  • the chemical blowing agents mentioned are compounds which split off gases by chemical reactions and in the polymeric Matrix of the base polymer (s) can create internal cavities.
  • the gases released are, for example, carbon dioxide or nitrogen and do not contain any explosive components.
  • the cleavage is preferably carried out in a relatively small temperature / all, namely the decomposition temperature range of the chemical blowing agent (s) used, and adapted to the processing temperature of the base polymer (s) used.
  • the chemical blowing agents can basically be divided into two groups. Blowing agents with an endothermic decomposition reaction require a constant supply of heat for decomposition and gas elimination. Depending on the type of blowing agent, decomposition starts relatively early at 85 ° C and proceeds slowly and evenly. It is ended as soon as heat is no longer applied and the foamed molded part has cooled below the decomposition temperature of the blowing agent.
  • the gas pressure of endothermic blowing agents is usually in the range from about 8 to 10 bar. Examples of endothermic blowing agents are mixtures of carbonates and hydrogen carbonates. A particularly attractive representative of this type of blowing agent is sodium hydrogen carbonate.
  • Blowing agents with an exothermic decomposition reaction require starting energy in order to quasi-explosively release gas when the decomposition temperature is reached.
  • the gas pressure of exothermic blowing agents is usually around 12 to 15 bar.
  • exothermic blowing agents are sulfohydrazides and semicarbazides. 4,4-Oxybis-benzenesulfohydrazide and toluene-4-sulfonohydrazide may be mentioned as examples in this connection.
  • the plastic foam produced by the process according to the invention ie the porous extrudate, is made with suitable, known per se Devices transferred into granular or pellet-shaped carrier material, for example by strand granulation.
  • base polymers to be used in the course of the method according to the invention which are thermoplastic materials, can in themselves be chosen as desired.
  • suitable base polymers are:
  • Homopolymers of an ⁇ -olefin with two to eight carbon atoms copolymers of two corresponding ⁇ -olefins, preferably copolymers of ethylene, ethylene homopolymers such as HDPE (high density polyethylene), LDPE (low density polyethylene), VLDPE (very low density polyethylene), LLEPE (linear low density polyethylene), MDPE (medium density polyethylene), UHMPE (ultra high molecular polyethylene), VPE (cross-linked polyethylene), HPPE (high pressure polyethylene), isotactic polypropylene, syndiotactic polypropylene, metallocene-catalyzed polypropylene , impact-modified polypropylene, random copolymers based on ethylene and propylene, block copolymers based on ethylene and propylene, homopolymers based on 1-butylene, 1-pentylene, 1-hexylene, 1-octylene, isobutylene, 2-methyl -1
  • Ethylene propylene rubber also modified with diene (EPR), styrene-butadiene-styrene copolymers (SBS), styrene-ethylene-butylene-styrene copolymers (SEBS) and mixtures thereof.
  • EPR diene
  • SBS styrene-butadiene-styrene copolymers
  • SEBS styrene-ethylene-butylene-styrene copolymers
  • the extruded strand is subjected to compression and / or overstretching.
  • Compression and / or overstretching of the extruded strand means the following: As soon as the strand has left the outlet nozzle of the extruder, it is subjected to a mechanical process in which it experiences compressive and / or tensile forces.
  • compressive forces can be exerted on the extruded strand by passing the strand between two rolls, adjusting the distance between the roll surfaces so that it is less than the diameter of the strand.
  • this so-called roller gap is set in such a way that it is 50 to 95% of the diameter of the strand.
  • the application of tensile forces on the strand leads to the strand being stretched or stretched in the longitudinal direction.
  • the hyperextension is set to a value of 10 to 50%.
  • a hyperextension to a desired value can be achieved, for example, by setting the withdrawal speed of the strand accordingly. If both extrusion and overstretching of the extruded strand are carried out, both conceivable embodiments are possible, that is, one can either initially carry out compression and then hyperextension or first hyperextension and then compression.
  • nucleating agent is understood to mean a crystallization accelerator.
  • nucleating agent is also used synonymously for the term “nucleating agent” in the specialist literature. Nucleating agents are particularly important in the processing of plastics because they influence the crystal growth rate of polymers. The number and size of the spherulites formed are determined by adding nucleating agents to the base polymer.
  • nucleated polymers have a more fine-grained structure than non-nucleated ones, which is noticeable in their physicochemical properties; for example, coarse spherolithic plastics with the same crystalline content are more brittle and less transparent or translucent than those with a fine spherulitic structure.
  • the nucleating agent which can consist of one or more compounds, also causes the lamella structure of the plastic foam obtainable by the process according to the invention to be particularly fine and uniform.
  • the nucleating agent is used in an amount of 0.001 to 5.0% by weight, based on the base polymers. The range from 0.1 to 0.8% by weight is particularly preferred.
  • the nucleating agent is preferably incorporated before the extrusion, ie the nucleating agent is suspended in a melt of base polymers and chemical blowing agent and this mixture is then subjected to extrusion.
  • Suitable nucleating agents are, in particular, substances which are wettable or absorbable by the base polymer, are insoluble in the base polymer, have a melting point which is above the melting point of the base polymer and which, moreover, are in the most finely divided form - generally with Particle sizes in the range from about 1 to 10 ⁇ m - in which polymer melt are homogeneously dispersible.
  • inorganic substances such as talc, silica or kaolin are used as nucleating agents.
  • suitable organic compounds which are suitable as nucleating agents are salts of mono- or polycarboxylic acids.
  • the structure of the plastic foams produced according to the invention is characterized to a large extent by elliptical macro-pores which are interconnected, it is understandable that loading of the plastic foams with any additives is possible in a simple manner.
  • the plastic foam produced according to the invention is mixed with at least one additive and mixed with this at a temperature below the melting point of the base polymer used in the production of the plastic foam, but above the melting point of the additive.
  • the additives can be chosen as desired from the additives known per se to those skilled in the art for processing thermoplastic materials.
  • suitable additives are: antistatic agents, antifoggants, antioxidants, UV stabilizers, adhesives, calendering aids, mold release agents, lubricants, release agents, lubricants, plasticizers, fragrances, flame retardants, fillers, crosslinking agents and agents for increasing the thermostability.
  • the additive-loaded plastic foams are also known as additive masterbatches. These additive masterbatches can be used in the processing of bulk plastics. These bulk plastics can be processed in any way per se; extrusion, calendering, injection molding and blow molding processes are particularly mentioned here.
  • the present invention furthermore relates to the use of the plastic foams produced by the process of the present invention for the additization of bulk plastics.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

L'invention concerne un procédé permettant de préparer des mousses synthétiques pouvant être chargées, selon lequel on ajoute un agent porogène chimique à au moins un polymère thermoplastique de base. La matière est fondue, mélangée avant et/ou après la fusion et le mélange obtenu est refroidi de manière à former un matériau support poreux en vrac, sous réserve d'utiliser une extrudeuse ou une malaxeuse-extrudeuse à arbres multiples et d'injecter au moins par moments un gaz inerte dans la matière fondue de polymère de base et d'agent porogène chimique. L'extrusion s'effectue en présence d'un agent mouillant.
PCT/EP1999/010154 1999-01-08 1999-12-21 Procede de production de mousses synthetiques pouvant etre chargees WO2000040643A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1999100490 DE19900490A1 (de) 1999-01-08 1999-01-08 Verfahren zur Herstellung beladbarer Kunststoffschäume
DE19900490.0 1999-01-08

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Publication Number Publication Date
WO2000040643A1 true WO2000040643A1 (fr) 2000-07-13

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007090451A1 (fr) * 2006-02-08 2007-08-16 Henkel Ag & Co. Kgaa Accumulateur de fluides

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994016876A1 (fr) * 1993-01-26 1994-08-04 The Dow Chemical Company Mousse a alveoles agrandies et procede de fabrication de ladite mousse
EP0657489A1 (fr) * 1993-12-08 1995-06-14 "Brugg"-Kabel Ag Matière de support poreuse chargée d'additifs
US5643969A (en) * 1995-08-11 1997-07-01 Nippon Unicar Company Limited Expandable resin composition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994016876A1 (fr) * 1993-01-26 1994-08-04 The Dow Chemical Company Mousse a alveoles agrandies et procede de fabrication de ladite mousse
EP0657489A1 (fr) * 1993-12-08 1995-06-14 "Brugg"-Kabel Ag Matière de support poreuse chargée d'additifs
US5643969A (en) * 1995-08-11 1997-07-01 Nippon Unicar Company Limited Expandable resin composition

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007090451A1 (fr) * 2006-02-08 2007-08-16 Henkel Ag & Co. Kgaa Accumulateur de fluides
US8093197B2 (en) 2006-02-08 2012-01-10 Henkel Ag & Co. Kgaa Fluid reservoir

Also Published As

Publication number Publication date
DE19900490A1 (de) 2000-07-13

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