DK166485B - SYNTACTIC HEATING MATERIAL HEATING MATERIAL, APPARATUS AND PROCEDURE FOR ITS MANUFACTURING AND INSULATING COMPONENTS INCLUDING SUCH MATERIAL - Google Patents
SYNTACTIC HEATING MATERIAL HEATING MATERIAL, APPARATUS AND PROCEDURE FOR ITS MANUFACTURING AND INSULATING COMPONENTS INCLUDING SUCH MATERIAL Download PDFInfo
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- DK166485B DK166485B DK182787A DK182787A DK166485B DK 166485 B DK166485 B DK 166485B DK 182787 A DK182787 A DK 182787A DK 182787 A DK182787 A DK 182787A DK 166485 B DK166485 B DK 166485B
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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
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/58—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising fillers only, e.g. particles, powder, beads, flakes, spheres
- B29C70/66—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising fillers only, e.g. particles, powder, beads, flakes, spheres the filler comprising hollow constituents, e.g. syntactic foam
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L59/00—Thermal insulation in general
- F16L59/06—Arrangements using an air layer or vacuum
- F16L59/07—Arrangements using an air layer or vacuum the air layer being enclosed by one or more layers of insulation
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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
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0058—Liquid or visquous
- B29K2105/0064—Latex, emulsion or dispersion
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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
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/16—Fillers
- B29K2105/165—Hollow fillers, e.g. microballoons or expanded particles
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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
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/24—Condition, form or state of moulded material or of the material to be shaped crosslinked or vulcanised
-
- 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
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
- Resistance Heating (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Thermal Insulation (AREA)
- Press Drives And Press Lines (AREA)
- Insulating Bodies (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
- Moulding By Coating Moulds (AREA)
- Manufacture Of Motors, Generators (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Cookers (AREA)
Abstract
Description
iin
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Den foreliggende opfindelse angår et varmeisoleringsmateriale af syntaktisk type, en fremgangsmåde og et apparat til dets fremstilling samt isoleringsmidler omfattende et sådant materiale.The present invention relates to a syntactic type thermal insulation material, to a method and apparatus for its preparation, and to insulating agents comprising such material.
Det er kendt at udnyttelsen af off-shore oliefelter kræver trans-5 port af den udvundne olie eller gas via undersøiske rørsystemer eller ledninger, som bør varmeisoleres. De materialer, der benyttes hertil, . bør ikke blot have gode varmeisoleringsegenskaber; men de bør desuden kunne modstå de høje hydrostatiske tryk, som forekommer på bunden af havet og bevare deres egenskaber ved anvendelsestemperaturerne, som kan 10 være af størrelsesordenen 120°C.It is known that the utilization of off-shore oil fields requires transport of the recovered oil or gas via subsea piping systems or conduits which should be heat insulated. The materials used for this purpose. should not only have good thermal insulation properties; but they should also be able to withstand the high hydrostatic pressures that occur at the bottom of the sea and maintain their properties at the application temperatures, which can be of the order of 120 ° C.
Til dette formål er der allerede foreslået udformninger omfattende en kappe af et materiale af polyurethan- eller PVC-skumtype med lille varmeledningskoefficient. Da disse materialer for det førstes vedkommende ikke i sig selv har tilstrækkelige mekaniske egenskaber, navnlig med 15 hensyn til de hydrostatiske trykpåvirkninger, og for det andets vedkommende med hensyn til de hydrostatiske trykpåvirkninger og temperaturen, må man forbinde disse skummaterialer med andre midler beregnet til at give den samlede konstruktion de krævede egenskaber.For this purpose, designs have already been proposed comprising a sheath of a polyurethane or PVC foam type material with a low heat conduction coefficient. Since, on the one hand, these materials do not in themselves have sufficient mechanical properties, in particular with regard to the hydrostatic pressure effects and, secondly, with regard to the hydrostatic pressure effects and the temperature, these foam materials must be connected with other means intended to: give the overall design the required properties.
Man kan så forestille sig at anvende andre kendte materialer med 20 lav varmeledningskoefficient, f.eks. et kompositmateriale indeholdende hule gi asmi krokugler i en matrix af polyesterharpiks. Eet sådant syntaktisk polyesterskum beskrives f.eks. i GB-A-1.372.845.One can then imagine using other known materials with a low heat conduction coefficient, e.g. a composite material containing hollow gi asthma hook balls in a polyester resin matrix. One such syntactic polyester foam is described e.g. in GB-A-1,372,845.
Hvis et sådant materiale frembyder gode mekaniske egenskaber, navnlig stivhed, alt imedens det er betydeligt lettere end de sædvanlige ma-25 terialer, kan det kun bringes til anvendelse på meget speciel måde inden for området beskyttelse af undersøiske ledninger.If such material presents good mechanical properties, especially stiffness, while considerably lighter than the usual materials, it can only be used in a very special way in the field of submarine protection.
Til anvendelser i forbindelse med udnyttelse af off-shore oliefelter eller generelt til varmeisolering af rørsystemer, der transporterer et fluidum, som udviser en temperaturgradient, som er forhøjet i forhold 30 til omgivelserne som f.eks. nedgravede rørsystemer til fjernvarmeforsyning, bør isoleringsmidlerne imidlertid ikke blot frembyde de ovenfor anførte egenskaber, men bør desuden kunne tåle forholdsvis betydelige deformationer, uden at der forekommer beskadigelser, såsom brud dér, hvor materialet er nødsaget til at følge formen af en overflade med svag 35 krumningsradius.For applications in the utilization of off-shore oil fields or generally for thermal insulation of pipe systems carrying a fluid exhibiting a temperature gradient which is elevated relative to the environment, e.g. however, the insulating agents should not only provide the above-mentioned properties but also be able to withstand relatively significant deformations without damaging such as fractures where the material is forced to follow the shape of a surface with a slight radius of curvature. .
Årsagen hertil er, at uanset hvilken teknik, der anvendes til undersøisk anbringelse af ledningerne - anvendelse af en pram, hvorpå successive og tilstødende sektioner forbindes indbyrdes og derefter ned 2The reason for this is that whatever technique is used for submarine placement of the wires - the use of a barge on which successive and adjacent sections are interconnected and then down 2
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sænkes, eller samling på landjorden efterfulgt af bugsering af den samlede ledning under vandet - opstår der bøjningszoner i ledningen, som kan føre til ødelæggelser af varmeisoleringsmidlerne, når materialet, der anvendes til sådanne midler, ikke er tilstrækkeligt bøjeligt.lowered, or assembled on land, followed by towing of the entire conduit underwater - bending zones in the conduit occur which can lead to destruction of the thermal insulators when the material used for such agents is not sufficiently flexible.
5 Fra DE-A-2 648 595 kendes ligeledes et syntaktisk materiale bestå ende af en matrix af polybutadien omfattende 50-80% 1,2 enheder og med en middel molekyl vægt under 100.000, i hvilket der er indlejret hule gi asmi krokugler i et generelt forhold på 5-50 vægtdele mikrokugler til 100 dele polybutadien. Det opnåede materiale beskrives i det nævnte do-10 kument som egnet til udførelse af genstande beregnet til at modstå høje hydrostatiske tryk uden absorption af vand, for eksempel til fremstilling af overtræk på dykkerdragter eller ubåde. Det er ikke beregnet til at blive brugt som varmeisoleringsmateriale, og den foreliggende opfindelse har netop som formål at tilvejebringe et varmeisoleringsmateriale 15 af syntaktisk type, som på tilfredsstillende måde opfylder de ovenfor omtalte modstridende krav, nemlig at frembyde en lav varmeledningskoefficient og høj modstand mod hydrostatiske tryk, og det op til temperaturer på mindst 115-120°C samtidig med en sådan deformationsevne, at materialet kan formes eller tåle en deformation, som en svag krumningsra-20 dius giver det lokalt, uden at miste sine gode egenskaber.DE-A-2 648 595 also discloses a syntactic material consisting of a matrix of polybutadiene comprising 50-80% 1.2 units and having an average molecular weight below 100,000, in which hollow gi general ratio of 5-50 parts by weight of microspheres to 100 parts of polybutadiene. The material obtained is described in the said document as suitable for carrying out articles intended to withstand high hydrostatic pressures without absorption of water, for example for the manufacture of coveralls on diving suits or submarines. It is not intended to be used as a heat insulating material, and the present invention has for its object to provide a syntactic type thermal insulating material 15 which satisfies satisfactorily with the above-mentioned contradictory requirements, namely to present a low heat conduction coefficient and high resistance to hydrostatic pressure and up to temperatures of at least 115-120 ° C at the same time as such deformation capability that the material can be shaped or withstand a deformation that a weak radius of curvature gives it locally, without losing its good properties.
Det er ligeledes et formål med opfindelsen at tilvejebringe en fremgangsmåde til industriel fremstilling af et sådant materiale omfattende en matrix indeholdende et fyldstof af hule gi asmi krokugler.It is also an object of the invention to provide a process for the industrial manufacture of such a material comprising a matrix containing a filler of hollow gi asthmatic beads.
Det er yderligere et.formål med opfindelsen at tilvejebringe et 25 varmeisoleringsmiddel, der gør brug af et sådant syntaktisk materiale, og som specielt er tilpasset efter dets anvendelse på rørsystemer til udnyttelse af off-shore olie- og/eller gasfelter eller til nedgravede rørledninger til fjernvarmesystemer som eksempel.It is a further object of the invention to provide a heat insulating agent which makes use of such a syntactic material and which is specially adapted to its use on piping systems for utilizing offshore oil and / or gas fields or for buried pipelines for district heating systems as an example.
Disse formål opfyldes ifølge opfindelsen af et varmeisoleringsmate-30 riale af syntaktisk type med en densitet mellem ca. 0,5 og 0,65 og en varmeledningskoefficient λ mellem ca. 90 og 130 mWnf^K"*, hvilket materiale kan modstå en temperatur på ca. 120°C, idet det er praktisk taget fri for flydning ved denne temperatur under et hydrostatisk tryk på ca.These objects are fulfilled according to the invention by a syntactic-type thermal insulation material having a density between approx. 0.5 and 0.65 and a heat conduction coefficient λ between approx. 90 and 130 mWnf ^ K ", which can withstand a temperature of about 120 ° C, being practically free of flow at this temperature under a hydrostatic pressure of approx.
40 Bar og desuden er tilstrækkelig fleksibelt til at kunne undergå en 35 forlængelse på 7-10% uden brud og uden tab af sine egenskaber, hvilket materiale er opnået ved i en matrix at inkorporere et fyldstof af hule gi asmi krokugler i en mængde på 40-80 volumen-% i forhold til matrixen, hvilken er valgt blandt elastomerer af typen naturkautsjuk, polychloro-40 Bar and additionally is sufficiently flexible to undergo a 7-10% elongation without breakage and without loss of its properties, which material is obtained by incorporating in a matrix a filler of hollow gi asthma hook balls in an amount of 40 -80% by volume relative to the matrix selected from elastomers of the natural rubber type, polychloro-
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3 pren, styren-butadien-copolymerer (SBR), butadien-acrylonitrilcopolyme-rer (NBR), polynorbornen, ethylen-propylen-dien-monomerer (EPDM), butyl-kautsjukker og dermed analoge, idet bindingen af de hule gi asmi krokugler til matrixen er opnået ved hjælp af et koblingsmiddel bestående af et 5 isocyanat eller en organofunktionel silan, som forefindes i en mængde mellem 1 og 10 vægt% i forhold til elastomermatrixen.3 prene, styrene-butadiene copolymers (SBR), butadiene-acrylonitrile copolymers (NBR), polynorbornene, ethylene-propylene-diene monomers (EPDM), butyl rubber sugars, and thus analogs, the binding of the hollow gamma asthmic beads to the matrix is obtained by a coupling agent consisting of an isocyanate or an organofunctional silane which is present in an amount between 1 and 10% by weight relative to the elastomer matrix.
Fremgangsmåden ifølge opfindelsen til fremstilling af et syntaktisk materiale som det ovenfor definerede er ejendommelig ved, at man inkorporerer fyldstoffet af hule gi asmi krokugler i matrixen, blander fyld-10 stoffet og matrixen uden anvendelse af større forskydningskræfter, indtil der opnås et homogent produkt, og underkaster produktet en tværbindingsbehandling.The process of the invention for producing a syntactic material as defined above is characterized by incorporating the filler of hollow gi asmic hook beads into the matrix, mixing the filler and matrix without using greater shear forces until a homogeneous product is obtained, and the product undergoes a crosslinking treatment.
I en udførelsesform er tværbindingsbehandlingen e'n vulkanisering.In one embodiment, the crosslinking treatment is a vulcanization.
I en udførelsesform er matrixen i form af en latex.In one embodiment, the matrix is in the form of a latex.
15 De hule gi asmi krokugler behandles så ved hjælp af et koblingsmid del, såsom en organofunktionel silan, før de inkorporeres i latexen.The hollow gi asthma hook beads are then processed by a coupling agent moiety, such as an organofunctional silane, before being incorporated into the latex.
I en udførelsesform er matrixen i form af en solution.In one embodiment, the matrix is in the form of a solution.
De hule gi asmi krokugler inkorporeres så i matrixen samtidig med, at der til sidstnævnte sættes et gi as-elastomerkoblingsmiddel, såsom et 20 isocyanat eller en organofunktionel silan.The hollow gi asthma hook beads are then incorporated into the matrix while adding a gi ash elastomer coupling agent such as an isocyanate or organofunctional silane.
Matrixen kan være i flydende form.The matrix may be in liquid form.
Alternativt er den i pulverform.Alternatively, it is in powder form.
Pulveret fås med fordel direkte fra elastomerfremstillingsproces-sen, eller det fås som alternativ ved kryogenformaling af en elastomer 25 alene eller af en blanding af en eller flere elastomerer og ingredienser, såsom fyldstoffer, beskyttelsesmidler og vulkaniseringsmidler.The powder is advantageously obtained directly from the elastomer manufacturing process or alternatively obtained by cryogenic milling of an elastomer alone or by a mixture of one or more elastomers and ingredients such as fillers, protectants and vulcanizing agents.
Opfindelsen angår ligeledes en fremgangsmåde til fremstilling af et materiale af ovennævnte type, der er ejendommelig ved, at det homogene produkt bestående af matrixen og fyldstoffet af hule gi asmi krokugler af-30 lejres i form af et tyndt lag på en bærer, at dette lag om ønsket underkastes en koagulering efterfulgt af en tørring, og at disse operationer gentages indtil opnåelse af en ønsket tykkelse af materialet, som så underkastes tværbindingsbehandling, såsom en vulkanisering.The invention also relates to a process for the preparation of a material of the above-mentioned type, characterized in that the homogeneous product consisting of the matrix and the filler of hollow asymmetric beads is deposited in the form of a thin layer on a support, such that if desired, a coagulation is followed, followed by a drying, and these operations are repeated until a desired thickness of the material is obtained, which is then subjected to cross-linking treatment, such as a vulcanization.
Ifølge et andet træk ved opfindelsen aflejres hvert af lagene med 35 rakel på en passende bærer til en tykkelse mellem 0,5 og 1 mm.According to another feature of the invention, each of the layers is deposited with 35 racks on a suitable carrier to a thickness between 0.5 and 1 mm.
I en fordelagtig udførelsesform udføres fremgangsmåden ifølge opfindelsen kontinuert i flere tilstødende beholdere i horisontalt eller vertikalt arrangement, idet der mellem beholderne er indskudt zoner til 4In an advantageous embodiment, the method according to the invention is carried out continuously in several adjacent containers in horizontal or vertical arrangement, with zones being inserted between the containers for 4
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tørring og til sidst en vulkaniseringszone.drying and eventually a vulcanization zone.
Et varmeisoleringsmateriale ifølge opfindelsen, som navnlig kan anvendes til varmeisolering af transportrørsystemer for et fluidum, der frembyder en temperaturgradient i forhold til det omgivende rum, såsom 5 en ledning til transport af olie eller gas fra et off-shore oliefelt eller et fjernvarmerørsystem, er ejendommeligt ved, at det omfatter en kappe af syntaktisk materiale som ovenfor defineret, hvilken kappe på sine forreste og bageste frontale flader er afgrænset af bølgede overflader af konjugeret form, som tillader sammenføjning af tilstødende 10 kapper.A thermal insulation material according to the invention which can be used particularly for heat insulation of conveyor pipe systems for a fluid which provides a temperature gradient with respect to the surrounding space, such as a pipe for transporting oil or gas from an offshore oil field or a district heating pipe system, is peculiar in that it comprises a sheath of syntactic material as defined above, which sheath on its front and rear frontal faces is bounded by corrugated surfaces of conjugated form which permit joining of adjacent sheaths.
I en fordelagtig udførelsesform, hvor rørsystemet i egentlig forstand er overtrukket med et i og for sig kendt antikorrosionsi ag, anbringes kapperne ved glidning på dette lag og forbindes med dette ved hjælp af klæbemidler med højt modul, navnlig af epoxytype, og de tilstø-15 dende kapper forbindes desuden med hinanden ved hjælp af klæbemidler med lavt modul, navnlig af polyurethan-, polysulfid- og/eller polychloro-prentype.In an advantageous embodiment, in which the pipe system is in the true sense coated with a known anti-corrosion agent, the sheaths are applied by sliding on this layer and connected thereto by means of high modulus adhesives, especially of epoxy type, and the supports. these sheaths are additionally connected to each other by means of low modulus adhesives, in particular of polyurethane, polysulfide and / or polychloro printing type.
En bedre forståelse af opfindelsen vil kunne fås af den følgende beskrivelse, der tjener til eksempel, og under henvisning til tegningen, 20 hvor figur 1 er en meget skematisk afbildning af et apparat til fremstilling af et materiale ifølge opfindelsen, og figur 2 er en partiel skematisk afbildning i snit af et varmeisoleringsmiddel ifølge opfindelsen.A better understanding of the invention can be obtained from the following description which serves, for example, and with reference to the drawing, wherein Figure 1 is a very schematic representation of an apparatus for making a material according to the invention and Figure 2 is a partial schematic sectional view of a heat insulating agent according to the invention.
25 Til opnåelse af et syntaktisk materiale med lav varmeledning af størrelsesordenen 90-130 mWrn^K’*, som kan modstå temperaturer af størrelsesordenen 120°C, praktisk taget er frit for flydning ved denne temperatur under et hydrostatisk tryk af størrelsesordenen 40 bar, og som bl.a. er tilstrækkeligt bøjeligt til at kunne tåle en forlængelse på 7-30 10% uden brud og uden at miste sine egenskaber, indlejres der ifølge opfindelsen et fyldstof af hule gi asmi krokugler i en mængde på 40-80 vol% i en matrix valgt blandt elastomerer af typen naturkautsjuk, polychloro-pren, styren-butadien-copolymerer (SBR), butadien-acrylonitril-copolyme-rer (NBR), polybornen, ethyl en-propylen-dien-monomerer (EPDM), butyl-35 kautsjukker og dermed analoge.To obtain a low heat conductive syntactic material of the order of 90-130 mWrn ^ K '*, which can withstand temperatures of the order of 120 ° C, is practically free of flow at this temperature under a hydrostatic pressure of the order of 40 bar, and which include is sufficiently flexible to withstand an extension of 7-30 10% without breakage and without losing its properties, according to the invention, a filler of hollow gi asmic hook balls is embedded in an amount of 40-80 vol% in a matrix selected from elastomers. of the type natural rubber, polychloroprene, styrene-butadiene copolymers (SBR), butadiene-acrylonitrile copolymers (NBR), polybornene, ethylene-propylene-diene monomers (EPDM), butyl rubber, and the like.
Matrixen gør det muligt for det syntaktiske materiale ifølge opfindelsen at opnå de ønskede bøjelighedsegenskaber, medens anvendelsen af hule gi asmi krokugler gør det muligt i matrixen at indføre gas, som erThe matrix allows the syntactic material of the invention to achieve the desired flexural properties, while the use of hollow gi asmi hook balls enables gas to be introduced into the matrix which is
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5 favorabel med hensyn til opnåelse af en lav varmeledningskoefficient samtidig med, at de foreskrevne egenskaber med hensyn til modstandsdygtighed over for tryk sikres på grund af den sfæriske form af partiklerne i fyldstoffet, hvortil der er knyttet et højt modul og en specifik ibo-5 ende modstandsdygtighed.5 favorable for obtaining a low heat conduction coefficient while ensuring the prescribed pressure resistance properties due to the spherical shape of the particles in the filler to which a high modulus and specific inherent end are attached. resistance.
Tilsætningen af hule gi asmikrokugler med en trykstyrke på under 4000 psi til en matrix af elastomermateriale kan imidlertid ikke udføres ved hjælp af de sædvanlige teknikker til inkorporering af mineralske fyldstoffer eller carbon black i kautsjuk eller lignende. Forsøg udført 10 af ansøgeren på "BANBURY"-blandere eller på åbne blandere med cylindre har alle ført til uacceptable produkter, idet gi asmi krokuglerne er blevet knust af de høje forskydningskræfter, som er nødvendige for at fordele dem godt i kautsjukken.However, the addition of hollow gi asmicrospheres with a compressive strength of less than 4000 psi to a matrix of elastomeric material cannot be accomplished by the usual techniques for incorporating mineral fillers or carbon black into rubber or the like. Attempts made by the applicant on "BANBURY" mixers or on open mixers with cylinders have all led to unacceptable products, as the asmia hook balls have been crushed by the high shear forces needed to distribute them well in the rubber.
Efter at have forladt denne forsøgslinie har ansøgeren overraskende 15 konstateret, at gode resultater kan opnås ved at inkorporere de hule gi asmi krokugler i elastomermatrixen i pulverform eller i flydende form og det ved fremgangsmåder, som ikke udsætter gi asmi krokuglerne for større forskydningskræfter, som er tilbøjelige til at knuse dem.Having left this test line, the applicant has surprisingly found that good results can be obtained by incorporating the hollow gi asmi hook balls into the powder or liquid form elastomer matrix and that by methods which do not expose the asmi hook balls to greater shear forces which are prone to crushing them.
Mere præcist udføres blandingen af de hule gi asmi krokugler og ela-20 stomeren i flydende tilstand ifølge en første udførelsesform ved, at mi-krokuglerne inkorporeres i matrixen, medens denne er i form af en latex.More precisely, the mixture of the hollow gi asthmatic hook beads and the elastomer in liquid state according to a first embodiment is carried out by incorporating the micro beads into the matrix while in the form of a latex.
Sidstnævnte formuleres ved at følge sædvanlige fremgangsmåder.The latter is formulated by following usual procedures.
I betragtning af at det dels ikke er muligt at indføre tørre fyldstoffer i en latex, og dels at adhæsionen af de hule gi asmi krokugler til 25 elastomermatrixen ikke kan opnås direkte, kan de hule gi asmi krokugler ifølge opfindelsen først behandles ved hjælp af et gi as-elastomerkob-lingsmiddel, såsom en organofunktionel s i 1 an, og de således behandlede hule gi asmi krokugler derefter bringes i suspension i vand tilsat et la-texfortykningsmiddel.Since it is partly impossible to introduce dry fillers into a latex, and partly that the adhesion of the hollow gi asmi hook beads to the elastomer matrix cannot be achieved directly, the hollow gi asmi hook balls of the invention can first be treated by a gi as-elastomer coupling agent, such as an organofunctional screen, and the hollow asi treated acmi beads thus treated are then suspended in water with a latex thickener.
30 Efter kort tids henstand, som fremkalder eliminering af luft fra suspensionen, hældes latexen langsomt i suspensionen af hule glasmikro-kugler under omrøring til opnåelse af en homogen blanding, men uden udøvelse af tryk og uden udøvelse af større forskydningskræfter som ovenfor anført.After a short period of time which induces elimination of air from the suspension, the latex is slowly poured into the suspension of hollow glass microspheres with stirring to obtain a homogeneous mixture, but without exerting pressure and without exerting greater shear forces as indicated above.
35 Hvis den valgte koagulationsmetode er en koagulation ved indvirk ning af varme, indføres der derefter et passende middel til varmefølsom koagulation i blandingen.If the coagulation method chosen is a coagulation by the action of heat, then a suitable agent for heat sensitive coagulation is introduced into the mixture.
Uanset om et sådant middel er tilsat den homogene blanding ellerWhether such an agent is added to the homogeneous mixture or
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6 ej, anbringes denne derefter ved hjælp af en rakel som et tyndt lag på en bærer, såsom et metalbånd, hvor man går videre til koagulation af la-texpartiet enten ved indvirkning af et eksternt koagulationsmiddel, som på forhånd er fordelt som pulver over bæreren, eller ved indvirkning af 5 varme eller endnu engang ved dehydratisering eller ved indvirkning af kulde.6, it is then applied by means of a doctor blade as a thin layer to a support, such as a metal band, which proceeds to coagulation of the latex part either by the action of an external coagulant, which is previously distributed as powder over the support. , or by the action of heat or once again by dehydration or by the effect of cold.
Efter koagulering og om ønsket uddrivning af vand fra latexen tørres det aflejrede tynde lag, f.eks. ved hjælp af en ventileret strøm af varm luft eller yderligere ved hjælp af infrarød stråling.After coagulation and, if desired, expelling water from the latex, the deposited thin layer is dried, e.g. by means of a ventilated stream of hot air or further by means of infrared radiation.
10 Tørringen udføres dels på en sådan måde, at den er afsluttet inden for et forholdsvis kort tidsrum og således tillader en fremstilling, som kan gennemføres industrielt på økonomisk måde, og dels på en sådan måde, at der ikke viser sig nogen diskontinuitet ved grænsefladen mellem hule glaskugler og latex, som er tilbøjelig til at føre til en porøsitet' af 15 det færdige produkt.The drying is carried out partly in such a way that it is completed within a relatively short period of time and thus permits an manufacture which can be carried out industrially economically, and partly in such a way that there is no discontinuity at the interface between hollow glass beads and latex which tend to lead to a porosity of the finished product.
Når et første tyndt lag er opnået ved at gå frem på denne måde, føres dette tilbage for dannelse af et nyt lag, og dette lige til der er opnået en måtte, hvis tykkelse er den, som er valgt til isoleringsmaterialet, som så vulkaniseres ved hjælp af sædvanlige fremgangsmåder til 20 vulkanisering af kautsjuk.When a first thin layer is obtained by proceeding in this way, it is returned to form a new layer and this until a mat is obtained, the thickness of which is selected for the insulating material which is then vulcanized by using usual methods of vulcanization of rubber.
I en anden udførelsesform af opfindelsen sker inkorporeringen af de hule gi asmi krokugler i en elastomersolution.In another embodiment of the invention, the incorporation of the hollow gi asmi hook balls occurs in an elastomer solution.
I denne udførelsesform bringes elastomeren, som er af en hvilken som helst type, som er tilbøjelig til at danne en solution, i opløsning 25 i et passende opløsningsmiddel, og de hule gi asmi krokugler, som på forhånd er behandlet som angivet ovenfor, dvs. til hvilke man har knyttet et glas-elastomerkoblingsmiddel, f.eks. et isocyanat eller en organo-funktionel sil an, i tilstand af et tørt pulver i elastomersolutionen under omrøring, men uden tryk, og uden at der skabes større forskydnings-30 kræfter.In this embodiment, the elastomer, which is of any type, which is prone to form a solution, is brought into solution 25 in a suitable solvent, and the hollow gi asthma beads, which are pre-treated as indicated above, i.e. to which a glass elastomer coupling agent, e.g. an isocyanate or organo-functional silane, in the state of a dry powder in the elastomer solution while stirring, but without pressure, and without creating greater shear forces.
Proceduren er derefter som beskrevet ovenfor for latexen, dvs. rakel påføring af et tyndt lag af den homogene blanding på et metal bånd eller lignende, tørring af dette lag under iagttagelse af de ovenfor anførte betingelser, aflejring af et nyt lag af blandingen og tørring af 35 dette nye lag etc., indtil der opnås det nødvendige antal lag til ved overlejring at danne en måtte med den ønskede tykkelse af isoleringsmateriale. Når denne tykkelse er opnået, holdes måtten samlet under tryk, og enheden underkastes derefter en vulkaniseringsbehandling som angivetThe procedure is then as described above for the latex, ie. applying a thin layer of the homogeneous mixture to a metal band or the like, drying that layer under the conditions set out above, depositing a new layer of the mixture and drying this new layer etc. until it is obtained required number of layers to form a mat with the desired thickness of insulating material by overlaying. When this thickness is achieved, the mat is kept under pressure and the unit is then subjected to a vulcanization treatment as indicated.
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7 ovenfor.7 above.
Ifølge endnu en udførelsesform af opfindelsen opnås blandingen af hule gi asmi krokugler og elastomermatrixen ved at inkorporere gi asmi krokuglerne, som på forhånd er behandlet for til sidst at muliggøre ti 1 -5 fredsstillende adhæsion af disse til matrixen, i en elastomer i flydende tilstand.According to yet another embodiment of the invention, the mixture of hollow gi asmic hook beads and the elastomer matrix is obtained by incorporating the gi asmi hook balls which are pre-treated to eventually enable ten-to-5 peaceful adhesion to the matrix in a liquid state elastomer.
En sådan fremgangsmåde kan bringes til anvendelse på de elastomerer, som findes i handelen i denne form, hvad enten det drejer sig om enkelt- eller tokomponentprodukter, dvs. på elastomerer af type som dem, 10 der kendes under betegnelsen flydende nitriler, polybutadiener og andre.Such a method can be applied to the elastomers commercially available in this form, whether single or two-component products, i.e. on elastomers of type such as those known under the term liquid nitriles, polybutadiene and others.
Efter opnåelse af en homogen blanding af de hule gi asmi krokugler og elastomerer i flydende tilstand går man frem som angivet umiddelbart ovenfor i forbindelse med en elastomersolution, imidlertid uden at gøre brug af en tørringsoperation.After obtaining a homogeneous mixture of the hollow gi asthma hook beads and liquid elastomers, proceed as indicated immediately above in connection with an elastomer solution, however, without using a drying operation.
15 I endnu en anden udførelsesform inkorporeres de hule gi asmi krokug ler i elastomeren, medens denne er i pulverform.In yet another embodiment, the hollow gi asthma hook balls are incorporated into the elastomer while in powder form.
I denne udførelsesform, som er velegnet til fremstilling af varmeisoleringsmaterialer, hvori matrixen er en elastomer af nitril-, poly-norbornen- eller SBR-type eller af naturkautsjuktype, udføres inkorpo-20 reringen af de hule gi asmi krokugler i en pulverblander, hvori der først ud over elastomeren i pulverform, indføres de sædvanlige ingredienser til elastomerblandinger, dvs. fyldstoffer, beskyttelsesmidler, eventuelle vulkaniseringsmidler, tværbindingsmidler etc. og derefter lidt efter lidt de hule gi asmi krokugler, som på forhånd er behandlet med et kob-25 lingsmiddel, såsom en organosilan for at sikre tilfredsstillende adhæsion af fyldstoffet og matrixen.In this embodiment, which is suitable for the production of heat insulating materials in which the matrix is a nitrile, poly-norbornene or SBR-type or natural-gum-type elastomer, the incorporation of the hollow gamma asthma hook beads is carried out in a powder mixer wherein first, in addition to the elastomer in powder form, the usual ingredients for elastomer blends are introduced, i.e. fillers, protective agents, any vulcanizing agents, cross-linking agents, etc., and then gradually the hollow gi asmic hook balls which are pre-treated with a coupling agent such as an organosilane to ensure satisfactory adhesion of the filler and matrix.
Når pulverblandingen er tilstrækkeligt homogen, indføres den i fø-detragten på en ekstruder, såsom en strengpresse med snekke, idet pul verets passage gennem ekstruderen bidrager til opnåelse af en god homoge-30 nitet af blandingen, medens man ved et passende valg af ekstrudermundstykket ved udgangen fra dette opnår varmeisoleringsmaterialet i den ønskede form og de ønskede dimensioner.When the powder mixture is sufficiently homogeneous, it is introduced into the feed on an extruder, such as a screw extruder, the powder passing through the extruder contributing to obtaining a good homogeneity of the mixture, while selecting a suitable extruder nozzle at the output thereof achieves the heat insulation material in the desired shape and dimensions.
Vulkaniseringen af elastomeren udføres derefter på sædvanlig måde, med fordel ved en kontinuert proces, såsom en passage gennem en tunnel 35 med varm luft, ved UHF-bestråling etc.The vulcanization of the elastomer is then carried out in the usual manner, with the benefit of a continuous process, such as passage through a hot air tunnel 35, by UHF radiation, etc.
I den umiddelbart ovenfor beskrevne udførelsesform fås elastomer-pulveret med fordel direkte fra elastomerfabrikationsprocessen.In the embodiment described above, the elastomer powder is advantageously obtained directly from the elastomer fabrication process.
Pulveret kan også fås ved kryogenformaling.The powder can also be obtained by cryogenic milling.
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8 I en udførel sesform af denne fremgangsmåde fremstiller man først til opnåelse af et pulver en blanding af elastomer og sædvanlige ingredienser til sådanne blandinger, hvorefter der udføres en kryogenforma-ling efterfulgt af en fremgangsmåde til inkorporering af forbehandlede, 5 hule gi asmi krokugler i blandingen, som derefter indføres i strengpressens fødetragt.In one embodiment of this method, a mixture of elastomer and usual ingredients for such mixtures is first prepared to obtain a powder, after which a cryogenic formulation is followed, followed by a method of incorporating pretreated, 5 hollow gi asthmatic beads into the mixture. which is then inserted into the feed funnel of the string press.
Til udøvelse af fremgangsmåden ved en diskontinuert proces kan der ifølge opfindelsen benyttes et apparat af den type, som er vist meget skematisk i figur 1. Det omfatter monteret i en ramme 10 et endeløst me-10 tal bånd 11 drevet af en motor 12 via en kædetransmission 13, og hvis horisontale operative dele 14 og 15 for størstedelens vedkommende befinder sig i en tunnel 20 forsynet med ramper med infrarød stråling 21 og/eller modstandsvarmeelementer, og til hvilke udgangskanalen 22 for en ventilator 23 er knyttet til udtagning og udtømning af vanddampen eller opløs-15 ningsmiddeldampene, idet reguleringen af luftmængden sker ved hjælp af et spjæld 24. Opstrøms for kanalen 22 i det endeløse bånds 11 fremføringsretning er der endnu en kanal 25, som udmunder i tunnelen 20. I denne er der anbragt elektriske modstande med varmeribber 26 og/eller ramper med infrarød stråling til tværbindingsbehandlingen. En ventilator 20 27 sikrer cirkulation af den varme luft, hvis mængde reguleres ved hjælp af et spjæld 28.For carrying out the method of a discontinuous process, an apparatus of the type shown very schematically in Figure 1. can be used according to the invention. It comprises mounted in a frame 10 an endless number of strips 11 driven by a motor 12 via a chain transmission 13, and the horizontal operative parts 14 and 15 are for the most part in a tunnel 20 provided with ramps with infrared radiation 21 and / or resistance heating elements, to which the output channel 22 of a fan 23 is connected to the extraction and discharge of the water vapor or the solvent vapors, the flow of air being regulated by means of a damper 24. Upstream of the channel 22 in the forward direction of the endless band 11, there is another channel 25 which opens into the tunnel 20. In this, electrical resistors with heat ribs 26 are placed. and / or infrared radiation ramps for the crosslinking treatment. A fan 20 27 ensures circulation of the hot air, the amount of which is regulated by means of a damper 28.
I et sådant apparat og som belyst ovenfor aflejres den homogene blanding af hule gi asmi krokugler og elastomer i form af et tyndt lag på den øvre del 14 af det endeløse bånd uden for tunnelen 20 og i nærheden 25 af begyndelsen af delen 14 som vist ved pilen F. En rakel 29 og en modcylinder 19 gør det muligt at regulere tykkelsen af det aflejrede lag. Derudover er der en cylinder 18, hvis afstand til båndet 11 kan reguleres ved hjælp af midlerne 17, og som er anbragt mellem kanalerne 22 og 25 og gør det muligt at regulere tykkelsen af den ved fremstilling af 30 successive, tynde lag opnåede måtte som ovenfor beskrevet.In such an apparatus and as illustrated above, the homogeneous mixture of hollow gi asthmatic hook beads and elastomers is deposited in the form of a thin layer on the upper portion 14 of the endless band outside the tunnel 20 and in the vicinity 25 of the beginning of the portion 14 as shown by arrow F. A rocker 29 and a counter-cylinder 19 allow the thickness of the deposited layer to be adjusted. In addition, there is a cylinder 18, the distance of which to the band 11 can be controlled by means 17, which is arranged between the channels 22 and 25 and allows the thickness of the mat obtained by producing 30 successive thin layers to be adjusted as above. described.
Ved en kontinuert fremgangsmåde benyttes der et antal beholdere anbragt ved siden af hinanden i horisontalt eller vertikalt arrangement, hvoraf en er beregnet til at indeholde latexen, en anden koagulationsmidlerne etc., og som gennemløbes af et endeløst transportbånd, som suc-35 cessivt gennemløber zoner til tørring, f.eks. ved hjælp af en infrarød stråling, zoner til vulkanisering, igen returnerer til latexbeholderen etc.In a continuous process, a plurality of containers placed side by side in horizontal or vertical arrangement, one of which is intended to contain the latex, another of the coagulants, etc., is used and which is traversed by an endless conveyor belt which successively traverses zones. for drying, e.g. by means of an infrared radiation, zones for vulcanization, returns to the latex container, etc.
Opfindelsen illustreres nærmere i det følgende ved eksempler påThe invention is further illustrated by the following examples
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9 forskellige formuleringer af varmeisoleringsmaterialet ifølge opfindelsen, uden at angivelserne på nogen måde skal have nogen begrænsende karakter.9 different formulations of the thermal insulation material according to the invention, without the indications being of any limiting nature.
5 I - Materialer opnået ud fra en latex Eksempel 15 I - Materials obtained from a latex Example 1
En latex A fremstilles ud fra følgende vægtmængder i forhold til 10 kautsjuken:A latex A is prepared from the following weight amounts in relation to the 10 chewing gum:
Naturkautsjuklatex (NR) 100Natural rubber latex (NR) 100
Soda til stabilisering af latexen 0,3Soda for stabilizing the latex 0.3
Svovl 1,5Sulfur 1.5
Zinkoxid 1,5 15 "Wingstay L" (en antioxidant, der sælges under denne betegnelse af firmaet Goodyear) 1,0Zinc Oxide 1.5 "Wingstay L" (an antioxidant sold under this designation by Goodyear) 1.0
Zn-MBT (zinkmercaptobenzothiazol som vulkaniseringsaccelerator) 1,2 20 Zn-DEDC (zinkdiethyldithiocarbamat som vulkaniseringsaccelerator) 0,05Zn-MBT (zinc mercaptobenzothiazole as vulcanization accelerator) 1.2 Zn-DEDC (zinc diethyldithiocarbamate as vulcanization accelerator) 0.05
Til denne latex sættes 35 vægtdele svarende til 48 vol% hule glasmi krokugler solgt under betegnelsen "B 37/2000" af 25 firmaet 3M.To this latex are added 35 parts by weight, corresponding to 48% by volume of hollow glass beads sold under the designation "B 37/2000" by 25 company 3M.
Disse mikrokugler har en reel middeldensitet af størrelsesordenen 0,37, en trykstyrke af størrelsesordenen 14 MPa og en sådan granulome-tri, at mindst 3 vægt% af gi asmi krokuglerne tilbageholdes på en 100 mesh sigte (149 μηι).These microspheres have a real mean density of the order of 0.37, a compressive strength of the order of 14 MPa, and such a granulometry that at least 3% by weight of the gi asmi crocobiles are retained on a 100 mesh screen (149 μηι).
30 Forud for inkorporeringen i latexen er de hule gi asmi krokugler ble vet fugtet med en vandig opløsning af en aminosilan, såsom den, der sælges af firmaet Dow Corning under betegnelsen "Z 6020" og derefter tørret.30 Prior to incorporation into the latex, the hollow gi asthma hook beads were moistened with an aqueous solution of an aminosilane such as that sold by Dow Corning under the designation "Z 6020" and then dried.
Efter intim blanding af de hule gi asmi krokugler og latexen frem-35 stilles der ved den ovenfor angivne teknik, dvs. aflejring med rakelen på metal båndet i det i figur 1 viste apparat af lag, hvis tykkelse er mellem 0,5 og 1 mm. Koagulationen opnås ved en dehydrat i sering i tørreovn efterfulgt af tørring ved 80°C i 2 timer og 40°C i 12 timer.After intimate mixing of the hollow gi asthmatic hook beads and the latex, the above-mentioned technique, i.e. deposition with the metal band rib in the layer apparatus shown in Figure 1, the thickness of which is between 0.5 and 1 mm. The coagulation is obtained by a dehydrate in a drying oven followed by drying at 80 ° C for 2 hours and 40 ° C for 12 hours.
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Til fremstilling af en plade af varmeisoleringsmateriale med en tykkelse på ca. 10 mm aflejres mellem et dusin og en snes lag, og enheden vulkaniseres ved lav temperatur af størrelsesordenen 115°C i et tidsrum på ca. 20 min.For the manufacture of a plate of heat insulating material having a thickness of approx. 10 mm is deposited between a dozen and a dozen layers and the unit is vulcanized at low temperature on the order of 115 ° C for a period of approx. 20 min.
5 Det opnåede materiale har en densitet d = 0,57 og en varmelednings- koefficient λ = 96 mWm"*K~^.The material obtained has a density d = 0.57 and a heat conduction coefficient λ = 96 mWm "* K ~ ^.
Eksempel 2Example 2
En latex B med følgende sammensætning i vægtdele i forhold til 10 kautsjukken fremstilles:A latex B having the following composition in parts by weight relative to the rubber jaw is prepared:
Polychloroprenlatex (CR) (såsom den, der sælges af firmaet Bayer under betegnelsen "Baypren T") 100 15 Potaske 0,35Polychloroprene latex (CR) (such as the one sold by Bayer under the designation "Baypren T") 100 15 Pot bag 0.35
Svovl 1,0Sulfur 1.0
Zinkoxid 5,0 "Wingstay L" (antioxidant) 1,5Zinc Oxide 5.0 "Wingstay L" (Antioxidant) 1.5
Stabilisator 1,0 20 Emulgator 1,5 ZN-MBT som accelerator 1,0Stabilizer 1.0 Emulsifier 1.5 ZN-MBT as accelerator 1.0
De anvendte hule gi asmi krokugler er af typen "B 28/750" fra firmaet 3M med en reel middel densitet på 0,28, en trykstyrke på 5,2 MPa og en 25 sådan granulometri, at mindst 5 vægt% tilbageholdes på en 80 mesh sigte (177 Mm).The hollow gi asthmatic beads used are of type "B 28/750" from Company 3M with a real mean density of 0.28, a compressive strength of 5.2 MPa and a granulometry such that at least 5% by weight is retained on an 80 mesh screen (177 mm).
For at udføre sammenligningsforsøg inkorporeres hule glasmikrokug-ler behandlet som i eksempel 1 i latex B i forskellige forhold, hvorefter der gås frem som i eksempel 1, dvs. at der fremstilles elementære 30 lag med en tykkelse mellem 0,5 og 1 mm. I dette eksempel opnås koagulationen altid ved kulde, og den efterfølges af en tørring i tørreovn til konstant vægt.To perform comparative experiments, hollow glass microspheres treated as in Example 1 of Latex B are incorporated in various ratios and then proceed as in Example 1, ie. that elemental layers are made having a thickness between 0.5 and 1 mm. In this example, the coagulation is always achieved by cold, followed by a drying oven at constant weight.
Til fremstilling af en plade af isoleringsmateriale med en tykkelse på ca. 10 mm overlejres som en måtte et dusin elementære lag eller mere, 35 og enheden vulkaniseres ved 125°C i ca. 20 min.For making a sheet of insulating material having a thickness of approx. 10 mm is superimposed as one dozen or more elemental layers, 35 and the unit is vulcanized at 125 ° C for approx. 20 min.
De opnåede resultater er sammenstillet i tabel I nedenfor, for eksemplerne 2A, 2B og 2C.The results obtained are summarized in Table I below, for Examples 2A, 2B and 2C.
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Tabel ITable I
Eks. Latex Mængde mi kro- Densitet af op- Varmelednings-kugler nået materiale koefficient 5 "B 28/750" λ i mWnfV1 vægt volumen 2A B 25 60 0,67 119 10 2B B 34 70 0,57 108 2C B 47 80 0,52 88 II - Materialer opnået ud fra en solution 15Ex. Latex Quantity in crown Density of Heat Conduction Balls reached material coefficient 5 "B 28/750" λ in mWnfV1 weight volume 2A B 25 60 0.67 119 10 2B B 34 70 0.57 108 2C B 47 80 0, 52 88 II - Materials obtained from a solution 15
Eksempel 3 Først fremstilles følgende sammensætning i vægtdele i forhold til kautsjukken: 20 Polychloropren af den type, der sælges af firmaet Di sti 1 gi 1 under betegnelsen "Butaclor M C 322" 100Example 3 First, the following composition is prepared in parts by weight relative to the rubber: 20 Polychloroprene of the type sold by the company Di sti 1 g 1 under the designation "Butaclor M C 322" 100
Carbon black 60Carbon black 60
Aromatisk plastificeringsmiddel 16 25 Magnesiumoxid 4Aromatic plasticizer 16 25 Magnesium oxide 4
Zinkoxid 5Zinc oxide 5
Stearinsyre 0,5Stearic acid 0.5
Antioxidant 4Antioxidant 4
Accelerator ETU 0,5 30 Accelerator DTMT 0,5Accelerator ETU 0.5 30 Accelerator DTMT 0.5
Derefter fremstilles en solution af kautsjuk ved sammenblanding med 2,5 vægtdele trichlorethyl en for hver vægtdel af sammensætningen.Then, a solution of rubber is prepared by admixing with 2.5 parts by weight of trichlorethyl one for each part by weight of the composition.
Til den således fremstillede solution sættes 39 vægtdele svarende 35 til 70 vol% gi asmi krokugler af typen "37/2000", der sælges af firmaet 3M, og hvis egenskaber er angivet ovenfor i forbindelse med eksempel 1 samt som koblingsmiddel et isocyanat som det, der sælges af firmaet Bayer under betegnelsen "Desmodur RP".To the solution thus prepared are added 39 parts by weight corresponding to 35 to 70% by volume of asmi "37/2000" hook balls sold by the company 3M and whose properties are listed above in connection with Example 1 and as coupling agent an isocyanate such as that. sold by Bayer under the designation "Desmodur RP".
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De hule gi asmi krokugler indføres i opløsningen under omrøring og ved en teknik analog med den, der er angivet i eksempel 1 og 2, dvs. at der ved aflejring af blandingen på en passende bærer ved hjælp af en rakel fremstilles elementære, tynde lag med en tykkelse af større!sesorde-5 nen 0,5-1 mm.The hollow gi asthma hook beads are introduced into the solution with stirring and by a technique analogous to that set forth in Examples 1 and 2, i.e. that, by depositing the mixture on a suitable support, elemental, thin layers having a thickness of the order of 0.5-1 mm are prepared by means of a blade.
Lagene tørres i en tørreovn ved en temperatur af størrelsesordenen 70°C, til der opnås en konstant vægt, dvs. indtil det procentuelle vægttab, som skyldes eliminering af opløsningsmiddel, ikke længere varierer væsentligt.The layers are dried in a drying oven at a temperature of about 70 ° C until a constant weight is obtained, ie. until the percentage weight loss due to solvent elimination no longer varies significantly.
10 Efter indbyrdes forening af et dusin lag eller flere til opnåelse af en plade med en tykkelse på ca. 10 mm, med fordel ved hjælp af en presse af sædvanlig type, underkastes pladen en vulkaniseringsbehandling, der udføres ved 150°C i et tidsrum på ca. 20 min.10 After mutually joining a dozen layers or more to obtain a sheet having a thickness of approx. 10 mm, advantageously by means of a press of the usual type, the plate is subjected to a vulcanization treatment which is carried out at 150 ° C for a period of approx. 20 min.
Det opnåede varmeisoleringsmateriale har følgende egenskaber: 15The heat insulation material obtained has the following properties: 15
Densitet d = 0,55Density d = 0.55
Varmeledningskoefficient λ = 97 mWm’^K~*Heat conduction coefficient λ = 97 mWm '^ K ~ *
Som alternativ er opløsningsmidlet toluen, der anvendes i en iden-20 tisk mængde, dvs. 2,5 vægtdele toluen for hver vægtdel af sammensætningen.Alternatively, the solvent is toluene used in an identical amount, i.e. 2.5 parts by weight of toluene for each part by weight of the composition.
III - Materialer opnået ud fra en pulverform!g elastomer 25 Eksempel 4III - Materials obtained from a powder form elastomer 25 Example 4
Den anvendte kautsjuk er af ni tril type med følgende sammensætning i vægtdele i forhold til kautsjukken:The rubber used is nine trill type with the following composition in parts by weight relative to the rubber:
Nitrilkautsjuk af den type, der sælges 30 af firmaet Goodyear under betegnelsen "Chemigium P.83" 100Nitrile rubber of the type sold by Goodyear under the designation "Chemigium P.83" 100
Dioctylphthalat 60Dioctyl phthalate 60
Zinkoxid 5Zinc oxide 5
Stearinsyre 1 35 Svovl 1,25Stearic Acid 1 35 Sulfur 1.25
Accelerator MTMT 0,4Accelerator MTMT 0.4
De hule gi asmi krokugler er sådanne, som sælges af firmaet 3M underThe hollow gi asmi hook balls are those sold by the company 3M below
DK 166485 BDK 166485 B
13 betegnelsen "38/4000", dvs. hule gi asmi krokugler med en reel middeldensitet på 0,38 og en trykstyrke på 28 MPa.13 "38/4000", ie. hollow give asthma hook beads with a real mean density of 0.38 and a compressive strength of 28 MPa.
Disse hule gi asmi krokugler behandles som angivet i eksempel 1, hvorefter de sættes til elastomerpulveret i en mængde på 70 vægtdele 5 svarende til 60 vol%, og den homogene blanding ekstruderes.These hollow gamma asthmatic beads are treated as in Example 1, then they are added to the elastomer powder in an amount of 70 parts by weight equal to 60% by volume and the homogeneous mixture is extruded.
Dét opnåede materiale vulkaniseres ved 150°C i ca. 20 min..The material obtained is vulcanized at 150 ° C for approx. 20 min ..
Dets egenskaber er som følger:Its properties are as follows:
Densitet d = 0,65 -1 -1Density d = 0.65 -1 -1
10 Varmeledningskoefficient λ = 110 mWm K10 Heat conduction coefficient λ = 110 mWm K
Eksempel 5 Først fremstilles en blanding af pulver med følgende sammensætning i vægtdele i forhold til kautsjukken: 15Example 5 First, a mixture of powders having the following composition is made in parts by weight relative to the chewing gum: 15
Kautsjuk solgt af firmaet CDF under betegnelsen i "Norsorex" 100Kautskuk sold by the company CDF under the designation in "Norsorex" 100
ZnO 5ZnO 5
Sterinsyre 1 20 CBS 3Steric Acid 1 20 CBS 3
Svovl 2 "Somil A P" 300Sulfur 2 "Somil A P" 300
Til denne sammensætning sættes så hule gi asmi krokugler 25 af den i eksempel 2 anvendte type, der sælges af firmaet 3M under betegnelsen "B 28/750".To this composition are then added hollow gi asmi hook balls 25 of the type used in Example 2 sold by the company 3M under the designation "B 28/750".
Disse hule gi asmi krokugler, som er forbehandlet ved den i eksempel 1 beskrevne fremgangsmåde, tilsættes i en mængde på 244 vægtdele, dvs.These hollow gi asthma hook balls, which are pretreated by the procedure described in Example 1, are added in an amount of 244 parts by weight, ie.
60 vol%.60 vol%.
30 Den homogene blanding formes derefter ved simpel aflejring med ra kel eller passage gennem et formeorgan.The homogeneous mixture is then formed by simple deposition by slab or passage through a molding member.
Det opnåede materiale vulkaniseres og har følgende egenskaber:The material obtained is vulcanized and has the following properties:
Densitet d = 0,65 35 Varmeledningskoefficient λ = 126 mWm~*K~*Density d = 0.65 Heat conduction coefficient λ = 126 mWm ~ * K ~ *
Det viser sig således, at materialet ifølge opfindelsen frembyder gode varmeisoleringsegenskaber til det tilstræbte formål med en koeffiThus, it is found that the material of the invention presents good thermal insulation properties for the purpose of a coefficient.
DK 166485 BDK 166485 B
14 cient λ af størrelsesordenen 90-130 mWm^K"1 samt gode trykstyrkeegenskaber samtidig med, at det let kan deformeres.14 cient λ of the order of 90-130 mWm ^ K "1 as well as good compressive properties while being easily deformable.
Blandt andet giver den perfekte adhæsion af de hule gi asmi krokugler til matrixen, hvori de er indlejret, materialet ifølge opfindelsen frem-5 ragende væskebarriereegenskaber, idet den navnligt muliggør opnåelse af et materiale, som modsætter sig indtrængning af vand, herunder ved temperaturer af størrelsesordenen 120°C og højere.Among other things, the perfect adhesion of the hollow gi asmic hook beads to the matrix in which they are embedded provides the material of the invention with excellent fluid barrier properties, in particular enabling a material to resist water penetration, including at temperatures of the order of magnitude. 120 ° C and higher.
Materialet ifølge opfindelsen finder således en specielt fordelagtig anvendelse ved beskyttelse af ledninger til transport af varmt flui-10 dum, enten det så drejer sig om .vanddamp i fjernvarmerørsystemer eller gas eller olie i undersøiske rørledninger.Thus, the material of the invention finds a particularly advantageous use in protecting pipelines for transporting hot fluid, whether in the case of water vapor in district heating piping systems or gas or oil in subsea pipelines.
I sidstnævnte tilfælde kan varmeisoleringsmaterialet ifølge opfindelsen specielt udformes som kapper 30, figur 2, hvis ene frontale flade 31 udviser et ringformet fremspring 32, og hvis modsatte frontale flade 15 33 fremviser en ringformet reces 34 af en form, som er konjugeret med fremspringets 32.In the latter case, the thermal insulation material of the invention can be specially formed as sheaths 30, Figure 2, whose one frontal surface 31 exhibits an annular projection 32 and the opposite frontal surface 33 of which exhibits an annular recess 34 of a shape conjugated to the protrusion 32.
Til varmeisolering af en ledning dækkes det egentlige rørsystem 40 først med et i og for sig kendt antikorrosionsi ag 41, hvorpå kapperne eller mufferne 30 skubbes på ved glidning, og med hvilket de om ønsket 20 forenes ved hjælp af adhæsiver af typen med højt modul, såsom epoxy. Den konjugerede, bølgede form af de forreste og bageste frontale flader af kappen eller muffen, hvorpå der anbringes lim eller klæbemiddel af type med lavt modul, såsom polyurethaner, polysulfider og/eller polychloro-prener til sammenføjning af tilstødende kapper eller muffer bidrager til 25 opnåelse af bedre varmeisoleringsegenskaber.For thermal insulation of a conduit, the actual pipe system 40 is first covered with a known anti-corrosion agent 41, upon which the sheaths or sleeves 30 are pushed on by sliding and, if desired, they are joined by means of high module type adhesives. such as epoxy. The conjugated, wavy shape of the front and rear frontal faces of the sheath or sleeve to which glue or adhesive of low modulus type, such as polyurethanes, polysulfides and / or polychloroprene, is applied to join adjacent sheaths or sleeves contributes to the achievement. of better thermal insulation properties.
På i og for sig kendt måde kan kappen af tilstødende og tilgrænsende muffer eller kapper, hvis tykkelse kan være af størrelsesordenen 5-40 mm om nødvendigt overtrækkes med et eller flere andre beskyttelseselementer, f.eks. af metal eller plastmateriale.In a manner known per se, the sheath of adjacent and adjacent sleeves or sheaths, the thickness of which may be of the order of 5-40 mm, may, if necessary, be coated with one or more other protective elements, e.g. of metal or plastic material.
30 Som alternativ og takket være bøjeligheden og deformerbarheden af materialet ifølge opfindelsen kan beskyttelseskappen opnås ved på laget 41 at vikle og klæbe et bånd af syntaktisk materiale som ovenfor defineret.Alternatively, and thanks to the flexibility and deformability of the material of the invention, the protective sheath can be obtained by winding and adhering to a band of syntactic material as defined above.
Claims (15)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8512332 | 1985-08-13 | ||
| FR8512332A FR2586215B1 (en) | 1985-08-13 | 1985-08-13 | THERMAL INSULATION MATERIAL OF THE SYNTACTIC TYPE, MACHINE AND METHOD FOR THE PRODUCTION THEREOF, AND INSULATION MEANS COMPRISING SUCH A MATERIAL |
| FR8600285 | 1986-08-11 | ||
| PCT/FR1986/000285 WO1987001070A1 (en) | 1985-08-13 | 1986-08-11 | Sheet insulating material of the syntactic type, machine and method for the fabrication thereof and insulating means comprising such material |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| DK182787D0 DK182787D0 (en) | 1987-04-09 |
| DK182787A DK182787A (en) | 1987-04-09 |
| DK166485B true DK166485B (en) | 1993-06-01 |
| DK166485C DK166485C (en) | 1993-10-11 |
Family
ID=9322199
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK182787A DK166485C (en) | 1985-08-13 | 1987-04-09 | SYNTACTIC HEATING MATERIAL HEATING MATERIAL, APPARATUS AND PROCEDURE FOR ITS MANUFACTURING AND INSULATING COMPONENTS INCLUDING SUCH MATERIAL |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0233234B1 (en) |
| JP (1) | JPS63500872A (en) |
| AT (1) | ATE65739T1 (en) |
| AU (1) | AU6195886A (en) |
| DE (1) | DE3680660D1 (en) |
| DK (1) | DK166485C (en) |
| FR (2) | FR2586215B1 (en) |
| NO (1) | NO171370C (en) |
| WO (1) | WO1987001070A1 (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3786797T2 (en) * | 1986-04-10 | 1993-11-18 | Gulf Rubber Pty Ltd | PRESSURE-RESISTANT RUBBER COMPOSITION OF LOW DENSITY. |
| US5665795A (en) * | 1993-03-01 | 1997-09-09 | Nippon Zeon Co., Ltd. | Resin compositions and molded articles |
| JP2698528B2 (en) * | 1993-03-26 | 1998-01-19 | 日本碍子株式会社 | Electrical insulator used for non-ceramic insulator housing |
| US5587231A (en) * | 1994-07-29 | 1996-12-24 | Isorcd, Inc. | Syntactic foam core material and method of manufacture |
| FR2732974B1 (en) * | 1995-04-11 | 1997-05-16 | Atochem Elf Sa | STRIP COMPRISING A POLYMERIC MATERIAL LOADED WITH HOLLOW MICROSPHERES (FOAM) |
| EP0890678A1 (en) * | 1997-07-12 | 1999-01-13 | Paul Müller Technische Produkte GmbH | Intermediate layer for vibrational damping |
| NL1007764C2 (en) * | 1997-12-10 | 1999-06-11 | Descol Kunststof Chem Bv | Polyurethane composition for fabricating seamless floors, especially shock-absorbing sports floors |
| DE10046298B4 (en) * | 2000-09-19 | 2008-11-20 | Technum Gmbh | Use of a lightweight material for crash protection |
| DE10129232A1 (en) | 2001-06-19 | 2003-01-02 | Basf Ag | Process for the production of syntactic polyurethane |
| DE10358368A1 (en) | 2003-12-11 | 2005-07-07 | Basf Ag | Syntactic polyurethanes and their use for off-shore insulation |
| DE10358371A1 (en) | 2003-12-11 | 2005-07-28 | Basf Ag | Syntactic polyurethane containing oil, preferably castor oil |
| EP2039496A1 (en) * | 2007-09-20 | 2009-03-25 | ABB Research Ltd. | A method of producing a rubber product |
| US8500127B2 (en) * | 2010-07-27 | 2013-08-06 | Vetco Gray Inc. | Bi-directional metal-to-metal seal |
| FR2973473B1 (en) | 2011-03-29 | 2014-06-13 | Saipem Sa | THERMAL INSULATION AND / OR RIGID FLOATABILITY MATERIAL FOR UNDERWATER DRIVING |
| GB2516047B8 (en) * | 2013-07-09 | 2017-02-08 | Balmoral Comtec Ltd | Material |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR619915A (en) * | 1926-07-21 | 1927-04-12 | interlocking elements for heat and cold insulation | |
| FR1239174A (en) * | 1958-11-03 | 1960-08-19 | Protective coating for pipes and similar tubular elements | |
| GB877254A (en) * | 1959-07-07 | 1961-09-13 | Ici Ltd | Improvements in or relating to preformed thermal insulating lagging |
| NL287627A (en) * | 1962-01-11 | |||
| GB1195568A (en) * | 1966-08-23 | 1970-06-17 | Trw Inc | Foam Resins |
| FR1546182A (en) * | 1966-12-01 | 1968-11-15 | Minnesota Mining & Mfg | Polyurethane resins |
| US3510392A (en) * | 1968-09-16 | 1970-05-05 | Pittsburgh Corning Corp | Glass nodules in cellular polyurethane |
| GB1372845A (en) * | 1971-12-15 | 1974-11-06 | Vickers Ltd | Syntactic foam elements |
| FR2245478A2 (en) * | 1973-09-12 | 1975-04-25 | Lacollonge Cie Lyon Genie Chim | Incorporating part of vulcanising system into rubber sheets - and coating with soln. of remaining system to cause vulcanisation, used e.g. in lining prodn |
| US3856721A (en) * | 1973-10-16 | 1974-12-24 | Firestone Tire & Rubber Co | Syntactic foams and their preparation |
| CA1065530A (en) * | 1975-09-18 | 1979-10-30 | Jack R. Harper | Flame retardant rigid polyurethane syntactic foam |
| FR2346403A1 (en) * | 1975-10-31 | 1977-10-28 | Inst Francais Du Petrole | IMPROVED LIGHTNESS RESINS AND THEIR PREPARATION |
| GB1556612A (en) * | 1976-06-11 | 1979-11-28 | Metzger A C | Sound attenuating compositions |
| FR2361438A1 (en) * | 1976-08-11 | 1978-03-10 | Inst Francais Du Petrole | COMPOSITIONS OF LIGHTENED RESINS AND THEIR PREPARATION |
| GB2021230B (en) * | 1978-04-28 | 1982-05-19 | Nippon Asbestos Co Ltd | Heat insulation systems |
-
1985
- 1985-08-13 FR FR8512332A patent/FR2586215B1/en not_active Expired
- 1985-09-30 FR FR858514435A patent/FR2587934B1/en not_active Expired
-
1986
- 1986-08-11 AT AT86904850T patent/ATE65739T1/en not_active IP Right Cessation
- 1986-08-11 AU AU61958/86A patent/AU6195886A/en not_active Abandoned
- 1986-08-11 WO PCT/FR1986/000285 patent/WO1987001070A1/en active IP Right Grant
- 1986-08-11 JP JP61504414A patent/JPS63500872A/en active Pending
- 1986-08-11 EP EP86904850A patent/EP0233234B1/en not_active Expired - Lifetime
- 1986-08-11 DE DE8686904850T patent/DE3680660D1/en not_active Expired - Fee Related
-
1987
- 1987-04-09 DK DK182787A patent/DK166485C/en active
- 1987-04-10 NO NO87871511A patent/NO171370C/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DK166485C (en) | 1993-10-11 |
| DK182787D0 (en) | 1987-04-09 |
| WO1987001070A1 (en) | 1987-02-26 |
| FR2586215A1 (en) | 1987-02-20 |
| FR2586215B1 (en) | 1988-09-02 |
| DE3680660D1 (en) | 1991-09-05 |
| NO871511D0 (en) | 1987-04-10 |
| JPS63500872A (en) | 1988-03-31 |
| FR2587934B1 (en) | 1989-02-03 |
| DK182787A (en) | 1987-04-09 |
| EP0233234B1 (en) | 1991-07-31 |
| AU6195886A (en) | 1987-03-10 |
| FR2587934A2 (en) | 1987-04-03 |
| NO171370C (en) | 1993-03-03 |
| ATE65739T1 (en) | 1991-08-15 |
| NO171370B (en) | 1992-11-23 |
| EP0233234A1 (en) | 1987-08-26 |
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