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    • 专利摘要:
    The present invention relates to a preparation of a fibrous polyurethane/polyisocyanurate foam block in which the expansion of the foam is constrained by the walls of a double belt laminator forming a tunnel, the positioning of the tunnel walls of the double belt laminator being defined such that the stress on the expansion of the fiberized polyurethane/polyisocyanurate foam leads to a volume of fiberized polyurethane/polyisocyanurate foam, at the outlet of the double-belt laminator, representing between 92% and 99% of the volume of expansion of this same fibered polyurethane/polyisocyanurate foam in the case of free expansion, without the constraint of the walls of such a double band laminator. Figure to be published: figure 1
    公开号:FR3088571A1
    申请号:FR1871590
    申请日:2018-11-19
    公开日:2020-05-22
    发明作者:Laetitia Dewolf；Guillaume De Combarieu
    申请人:Gaztransport et Technigaz SARL；
    IPC主号:
    专利说明:

    Description
    Title of the invention: METHOD AND SYSTEM FOR PREPARING A BLOCK OF POLYURETHANE / POLYISOCYANURATE FOAM FROM A THERMAL INSULATION MASSIF OF A TANK
    Technical Field [0001] The invention relates to a process for the preparation of blocks of polyurethane (PUR) and / or polyisocyanurate (PIR) foams fiberized (containing fibers) from at least one polyisocyanate and at least a polyol, said foam blocks being used within an integrated tank used to accommodate extremely cold, so-called cryogenic fluids, such as Liquefied Natural Gas (LNG) or Liquefied Petroleum Gas (LPG).
    The present invention also relates to a system for implementing the preparation process as well as the PUR and / or PIR blocks which must have, taking into account their specific applications, very specific mechanical and thermal characteristics, while being as economical as possible to produce.
    The present invention finally relates more particularly to sealed and thermally insulating tanks using such foams directly obtained by this preparation process as well as ships equipped with such tanks.
    Technological background [0004] PUR polyurethane foam is a cellular insulator, composed of fine cells which store a gas which may be of low thermal conductivity. PUR foam is used in many applications such as the automotive industry as flexible PUR foam or in thermal insulation as rigid PUR foam. The formation of polyurethane type foams is well known to those skilled in the art. Its formation involves a multi-component reaction between a polyol (compound carrying at least two hydroxy groups), a polyisocyanate (compound carrying at least two isocyanate functions —NCO) and a blowing agent, also designated by the expression "blowing agent". This condensation reaction is in particular catalyzed by compounds with basic and / or nucleophilic characteristics such as tertiary amines or metal-carboxylate coordination complexes such as tin or bismuth salts. The polyols commonly used in the production of PUR foams are polyether polyols or polyester polyols. Thus, a large number of compounds are necessary for the formation of PUR foam.
    Polyisocyanurate (PIR) and polyurethane / polyisocyanurate (PUR-PIR) foams are also used in building (construction / renovation) and have the advantage of providing better fire-fighting properties as well as higher compressive strength than PUR. The process for forming these foams is similar to the process for forming PUR foams. In fact, obtaining PUR, PIR and PUR-PIR foams depends on the isocyanate / polyol ratio.
    Obtaining PUR, PIR and PUR-PIR foams is well known to those skilled in the art, however the addition of fibers involves particular technical problems, in particular if one wishes to obtain a PUR, PIR foam. or fibered PUR-PIR in which the fibers are homogeneously dispersed in the volume of foam.
    Thus, a preparation process is known in which the components necessary for obtaining the PUR, PIR or PUR / PIR foam permeate the fibers, generally present in the form of woven or nonwoven reinforcements, then the mixing of the components swells, possibly initiated by heating and / or the use of catalysts, under the action of the polymerization / crosslinking of the reagents and of the swelling agent. This preparation is called "free expansion" insofar as the expansion of the fiber foam is not constrained on at least one side or on at least one expansion face so that the swelling is free on this side or this face, unlike a mold defining a finished volume. In this preparation, the fiber foam has cells of random shape, that is to say of spherical or oval shape extending in the direction (s) of expansion left free, and the uniform distribution of the fibers in the foam n is not controlled. Thus, such a foam has variable mechanical and thermal properties in its different sections, which is not acceptable when it is desired to obtain a homogeneous block of foam, conventionally having optimum mechanical qualities in a predetermined direction of the block of fiber foam. .
    This is why it has been proposed, in the construction sector, to strongly constrain the expansion of a foam with a double strip laminator in which the expansion of the foam is very strongly constrained by the walls forming a tunnel, in particular the horizontal walls, of such a laminator so that the foam is compressed to have good mechanical properties oriented in the length or width direction of the laminator tunnel.
    However, this type of preparation is not suitable for adding fibers to the foam because the foams using this principle are intended to swell very quickly to reach the walls of the laminator, to obtain adhesion of the foam on the flexible or rigid facings placed between the foam and the tunnel walls. Consequently, the impregnation of the fibers for obtaining a homogeneous fiber foam is very difficult to obtain in this type of preparation. In addition, the strong expansion constraint at the level of the horizontal walls (the upper and lower ones) means that the cells, enclosing a gas with low thermal conductivity, essentially have a flattened or elongated lengthwise shape. and / or the width of the foam block, hence very poor mechanical performance (resistance to compression) in the thickness of the foam block. Mention may be made of document US 20040053035 which discloses such a preparation.
    Furthermore, due to the heterogeneity of the fiber foam obtained, it is often necessary to cut a new block within the block of foam directly obtained at the outlet of the laminator, this resulting in significant material losses and therefore increased production costs. The same is true in the case of free expansion where the loss of material is in the range of 15% to 20%.
    At present, there is no economic preparation process for a block of polyurethane foam and / or fiber polyisocyanurate making it possible to obtain a block having very good mechanical properties in the thickness (or the height), due in particular to a perfect homogeneity of the fibers in the block and an adapted orientation (desired along an axis parallel to the thickness of the foam block) of the cells storing a gas with low thermal conductivity.
    Summary [0012] It is in this context that the applicant has succeeded in developing a process for the production of polyurethane and / or polyisocyanurate foams containing fibers in significant quantity, enabling both the production of a fiber foam having excellent mechanical properties in thickness, while retaining or even improving its thermal insulation performance and very significantly reducing the production cost due to perfect homogeneity of the fiber foam (loss of block material foam is minimal, even negligible).
    The present invention thus intends to remedy the shortcomings of the state of the art by proposing a particularly effective solution, very economical while being simple to implement, to obtain industrially a fiberized PUR / PIR foam whose mechanical properties in thickness are optimal.
    It has been discovered by the applicant, after various studies and analyzes, a preparation of a block of polyurethane foam (PUR) and / or polyisocyanurate (PIR) fiberized capable of solving the economic and technical problems of current preparations, with regard to the specific objectives linked to the final application of such a block of foam.
    Thus, the present invention relates to a method for preparing a block of polyurethane / polyisocyanurate fiber bundle of a thermal insulation mass of a sealed and thermally insulating tank, the block of polyurethane foam / polyisocyanurate fiber being composed of cells storing a gas, advantageously of low thermal conductivity, and being in the form of a parallelepiped of thickness E and width L, the preparation process comprising the following steps:
    a) a step of mixing chemical components necessary for obtaining a polyurethane / polyisocyanurate foam, said components comprising reagents for obtaining polyurethane / polyisocyanurate, optionally at least one reaction catalyst, optionally at least one emulsifier , and at least one blowing agent,
    b) a fiber impregnation step with the above mixture of chemical components, the fibers representing between 1% and 60% by mass,
    c) a step of forming and expanding the polyurethane / polyisocyanurate fiber bundle, said expansion of the polyurethane foam / polyisocyanurate fiber being physically constrained by the walls of a double strip laminator forming a tunnel, of rectangular section with a distance between the walls arranged laterally equal to L and a distance between the walls arranged horizontally equal to E, thus enclosing the expanding fiber foam so as to obtain the aforesaid block of polyurethane foam / fiber polyisocyanurate.
    the method according to the invention being characterized in that the positioning of the walls of the tunnel of the double-strip laminator is defined so that the constraint to the expansion of the polyurethane foam / fibered polyisocyanurate leads to a volume of polyurethane foam / fiber-reinforced polyisocyanurate, at the outlet of the double-strip laminator, representing between 92% and 99% of the expansion volume of this same polyurethane foam / fiber-reinforced polyisocyanurate in the case of free expansion, without the constraint of the walls of such a double strip laminator.
    The expression “this same foam” is understood to mean the fact that, in order to compare the expansion volumes, we consider exactly the same quantities of materials (chemical components necessary for obtaining a polyurethane / polyisocyanurate foam and at least of the blowing agent) in the case of the method according to the invention, with the double strip laminator, and in the case of volume comparison, namely the case of free expansion (without constraint of the walls of the laminator to double strip, typically the upper wall of such a laminator).
    Thanks to the specific configuration of the expansion constraint of the fiberized PUR / PIR foam, one obtains on the one hand a block of fiberized PUR / PIR foam in which at least 60%, generally more than 80% or even more than 90%, cells storing a gas with low thermal conductivity extend longitudinally along an axis parallel to the axis of the thickness E of the foam block and on the other hand contributes to perfect homogeneity of the fiber block , in other words the fibers are distributed homogeneously in the foam block. These two main characteristics make it possible to obtain a block of fiber foam having excellent mechanical properties along thickness E, as demonstrated by tests conducted by the applicant.
    Also, thanks to the method according to the invention, there are very substantial savings, the block of fiber foam being homogeneous and intrinsically having the excellent mechanical properties sought along the axis E, there is no need to achieve subsequent cutting of this block in order to remove end portions in which the fibers would not be present and / or the cells not oriented longitudinally along the axis E. Thus, the amount of material loss in the preparation process according to the invention is established between 0 and 10%, more generally less than 5%.
    Finally, the thermal properties of the fiber foam block are at least equal to those of the fiber foam blocks of the prior art, more precisely the foam block has, in the thickness E, a lower thermal conductivity at 40mW / mK (milliwatt per meter per Kelvin), ie 0.04 W / mK, preferably less than 35 mW / mK, even more preferably less than 30 mW / mK, measured at 20 ° C.
    Thus, the block of fiber foam obtained according to the invention is characterized by its controlled and uniform structure and its mechanical properties, in particular fatigue resistance and resistance to crushing in the thickness direction (measured according to ISO 844), compatible with use in integrated tanks for the storage and / or transport of very cold liquids such as LNG or LPG.
    The expression "a gas (advantageously) with low thermal conductivity" is understood to mean the gas originating from the swelling agent, or by chemical reaction thereof when this agent is said to be "chemical", conventionally carbon (CO 2 ) when the chemical blowing agent consists of water, or by a physical blowing agent such as, for example, nitrogen (N 2 ), dioxygen (O 2 ), carbon dioxide, hydrocarbons, chloroflurocarbons, hydrochlorocarbons, hydrofluorocarbons, hydrochlorofluorocarbons, and mixtures thereof. Physical blowing agents such as molecular nitrogen N 2 or CO 2 are found in the form of gases. These gases are dispersed in the liquid mass of copolymer, for example under high pressure using a static mixer. By depressurizing the system, nucleation and the growth of bubbles generate a cellular structure.
    The use, in the composition according to the invention, of a chemical swelling agent, can be coupled to that of a physical blowing agent. In this case, the physical blowing agent is preferably mixed in liquid or supercritical form with the foamable (co) polymer composition and then converted to the gas phase during the step of expanding the PUR / PIR foam.
    The chemical and physical blowing agents are well known to those skilled in the art who choose each other, in the appropriate quantities, depending on the PUR / PIR foam that he wishes to obtain.
    By polyols is meant any carbon structure carrying at least two OH groups.
    Obtaining PUR, PIR and PUR-PIR foams depending on the isocyanate / polyol ratio, a PUR, PIR or PUR-PIR foam will be obtained according to this ratio. When the ratio between a polyol component and an isocyanate component is:
    - between 1: 1 and 1: 1.3 we will obtain a PUR polyurethane foam,
    - between 1: 1.3 and 1: 1.8 we will obtain a PUR-PIR polyurethane foam,
    - between 1: 1.8 and 1: 2.5 we will obtain a PIR polyurethane foam.
    Polyisocyanates suitable for the formation of PUR, PIR and PUR-PIR foam are known to those skilled in the art and include, for example, aromatic, aliphatic, cycloaliphatic, arylaliphatic polyisocyanates and mixtures thereof, advantageously aromatic polyisocyanates.
    Examples of suitable polyisocyanates in the context of the present invention include aromatic isocyanates such as the 4,4'-, 2,4'- and 2,2'- isomers of diphenylmethane diisocyanate (MDI), any compound derived from the polymerization of these isomers, toluene 2,4- and 2,6-docyanates (TDI), m- and p-phenylene diisocyanate, naphthalene-1,5-docyanates; aliphatic, cycloaliphatic, arylaliphatic isocyanates such as 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (H12MDI), 1,4-cyclohexane diisocyanate (CHDI) , bis (isocyanatomethyl) cyclo-hexane (H6XDI, DDI) and tetramethyxylylene diisocyanate (TMXDI). It is also possible to use any mixtures of these isocyanates. Advantageously, the polyisocyanates are the 4,4'-, 2,4'- and 2,2'- isomers of diphenylmethane diisocyanate (MDI).
    In general, it is known to add during the formation of PUR, PIR or PUR-PIR foams, to the mixture comprising the polyol, the polyisocyanate and the swelling agent, a reaction catalyst which may, for example be chosen from tertiary amines, such as N, N-dimethylcyclohexylam or N, N-dimethylbenzylamine or from organometallic compounds based on bismuth, potassium or tin.
    Other advantageous features of the invention are briefly presented below:
    advantageously, the aforementioned volume of the polyurethane / polyisocyanurate fiberized foam represents between 95% and 99% of the volume of expansion of this same fiberized foam in the case of free expansion, without the constraint of the walls of a laminator to double band;
    - Advantageously, during the step of impregnating fiber masts, the above mixture of components has a viscosity between 30 mPa.s and 1500 mPa.s, preferably between 50 mPa.s and 700 mPa.s;
    This choice of viscosity allows a good and complete impregnation of all the fibers in the time of cream given by the chemical components and at least the swelling agent for the start of the expansion of PUR / PIR foam.
    - According to a possibility offered by the invention, not shown in the appended figures, just after the step of impregnating the fiber masts, a mixture of components and at least one swelling agent impregnating the fibers is applied. pressure application system (which may for example be a roller system, of the type designated “nip roll” in English) intended to apply pressure to the upper face of the assembly consisting of the above mixture and the fibers. This pressure system makes it possible on the one hand to plan the upper face of this assembly and, by the pressure exerted on the assembly, contributes to promoting the impregnation of the fibers in the above mixture. This pressure system can consist of a single or a double roller, the relative positions of which, above the liquid assembly, and possibly below the foam support, are adjusted in such a way that the liquid assembly is forced to spread out perfectly evenly. Thus, in doing so, we obtain, at any point in the section defined by the spacing between the two rollers or of the upper roller and of the conveyor belt, an equivalent quantity of the liquid assembly. In other words, the main purpose of this pressure system is to complete the liquid dispensing device in that it helps to standardize, in thickness / width, the liquid assembly before most of its expansion.
    - According to one embodiment, at the end of the preparation according to the invention, the block of fiber foam has at least 80% of the above cells storing a gas, advantageously with low thermal conductivity, having an elongated or stretched shape according to an axis parallel to the axis of the thickness E of the block of polyurethane foam / fibered polyisocyanurate;
    - Preferably, the block of fiber foam has at least 90%, preferably at least 95%, of the aforesaid cells storing a gas, advantageously with low thermal conductivity have an elongated or stretched shape along an axis parallel to the axis of l thickness E of the block of polyurethane foam / fiber polyisocyanurate;
    - According to an embodiment of the invention, the fibers consist of glass fiber or carbon fibers, preferably glass fibers;
    - Preferably, the fibers are in the form of a plurality of layers of woven or nonwoven reinforcements, preferably of nonwoven / isotropic reinforcements, extending along an orientation plane perpendicular to the thickness E;
    - According to another embodiment, the fibers are arranged over the entire width L and step b) of impregnating the fibers with the mixture of components, in order to obtain a polyurethane / polyisocyanurate foam, and a swelling agent operates, via a controlled liquid distributor, simultaneously over the entire width L;
    The term "simultaneously" means the fact that the liquid mixture (reagents and at least the blowing agent) reaches the fibers, over a section of width L, at the same time all along this section so that the impregnation of the various fiber reinforcements begins or takes place, depending on the thickness (or the height) of the block of foam and for the same section of width, at the same instant or at the same speed.
    - Advantageously, the swelling agent consists of a physical and / or chemical blowing agent, preferably a combination of the two types.
    - Preferably, the physical blowing agent is chosen from alkanes and cycloalkanes having at least 4 carbon atoms, dialkyl ethers, esters, ketones, acetals, fluoroalkanes, fluoro-olefins having between 1 and 8 carbon atoms and tetraalkylsilanes having between 1 and 3 carbon atoms in the alkyl chain, in particular tetramethylsilane, or a mixture of these.
    In this hypothesis, by way of example of compounds, it may be propane, nbutane, isobutane, cyclobutane, n-pentane, isopentane, cyclopentane, cyclohexane, dimethyl ether, methyl ethyl ether, methyl butyl ether, methyl formate, acetone and fluoroalkanes; the fluoroalkanes being chosen are those which do not degrade the ozone layer, for example trifluoropropane, 1,1,1,2-tetrafluoroethane, difluoroethane and heptafluoropropane. Examples of fluoroolefins include 1-chloro-3,3,3-trifluoropropene, 1,1,1,4,4,4-hexafluorobutene (for example HFO FEA1100 sold by the company Dupont).
    According to a preferred embodiment of the invention, the physical blowing agent chosen is 1,1,1,3,3-pentafluoropropane, or HFC-245fa, (marketed by the company Honeywell, the 1,1,1,3,3-pentafluorobutane, or 365mfc, (for example the solkane® 365mfc sold by the company Solvay), 2,3,3,3-tetrafluoroprop-l-ene, 1,1,1 , 2,3,3,3-heptafluoropropane (also designated internationally as HFC-227ea, for example sold by the company Dupont), 1,1,1,4,4,4-hexafluorobutene (for example HFO FEA1100 sold by the company Dupont), trans-chloro-3,3,3-trifluoropropene (solstice LBA - company Honeywell) or a mixture of these.
    advantageously, the chemical blowing agent consists of water, advantageously, the reactants comprise:
    • an isocyanate component comprising one or more isocyanate compounds, said isocyanate compounds having a viscosity of between 100 and 3000 mPa.s at room temperature, and • a polyol component comprising one or more polyol compounds, said polyol compounds having a viscosity of between 200 and 3000 mPa.s at room temperature;
    Preferably, according to a preferred embodiment of the invention, the final mixing of the streams of polyols, isocyanate and / or swelling agent takes place in a mixing head at low pressure (<20 bar) or high pressure ( > 50 bars) using a dynamic or static mixer.
    preferably, during step a) of mixing the chemical components, the temperature of each of the reactants for obtaining polyurethane / polyisocyanurate is between 10 ° C and 40 ° C, preferably between 15 ° C and 30 ° C;
    - according to a possibility offered by the invention, additionally to the mixture, in step a), an organophosphorus flame retardant, advantageously triethylphosphate (TEP), tris (2-chloroiso-propyl) phosphate (TCPP) , tris (1,3-dichloroisopropyl) phosphate (TDCP), tris (2-chloroethyl) phosphate or tris (2,3-dibromopropyl) phosphate, or a mixture thereof, or an inorganic flame retardant, advantageously red phosphorus, expandable graphite, an aluminum oxide hydrate, an antimony trioxide, an arsenic oxide, an ammonium polyphosphate, a calcium sulphate or cyanuric acid derivatives, a mixture of these.
    It may also be envisaged that the flame retardant uses diethyl ethane phosphonate (DEEP), triethyl phosphate (TEP), propyl dimethyl proponate (DMPP) or cresyl diphenyl phosphate (DPC).
    This flame retardant, when present in the composition according to the invention, is in an amount between 0.01% and 25% by weight of the PUR / PIR foam.
    preferably, the fibers represent between 2% and 30% by mass of the above mixture of components.
    The invention also relates to a system for preparing a block of polyurethane / polyisocyanurate fiber bundled with a thermal insulation mass of a sealed and thermally insulating tank, for the implementation of the method previously described, comprising:
    a reaction device receiving chemical components necessary for obtaining a polyurethane / polyisocyanurate foam, said chemical components comprising reagents for obtaining polyurethane / polyisocyanurate, optionally at least one reaction catalyst, optionally at least one emulsifier , and at least one blowing agent,
    a distributor of the above components on fibers, preferably in the form of a plurality of fiber masts, for the impregnation of the latter by these components, preferably via a controlled liquid distributor allowing the fibers to be impregnated simultaneously on their entire width L,
    - a conveyor belt for receiving and transporting the above components and the fiber masts from the impregnation of these fibers by said components until the formation of the block of polyurethane / polyisocyanurate foam, the block of polyurethane / polyisocyanurate fiber bundle formed in the form of a parallelepiped of thickness E and width L,
    - a double strip laminator forming a tunnel, of rectangular section with a distance between the walls arranged laterally equal to L and a distance between the walls arranged horizontally equal to E, thus enclosing the expanding fiber foam so as to obtain the block of foam fiber-reinforced polyurethane / polyisocyanurate.
    the system according to the invention being characterized in that the positioning of the walls of the tunnel of the double-strip laminator is defined so that the constraint to the expansion of the polyurethane foam / fibered polyisocyanurate leads to a volume of polyurethane foam / fibered polyisocyanurate, at the outlet of the double strip laminator, representing between 92% and 99%, preferably between 95% and 99%, of the expansion volume of this same polyurethane foam / fibered polyisocyanurate in the case of free expansion , without the constraint of the walls of a double strip laminator.
    It should be noted that all the characteristics presented above in connection with the process for the preparation of a block of polyurethane foam / fiber polyisocyanurate according to the invention are applicable, where appropriate, to the system for preparing a block of polyurethane / polyisocyanurate fiber, succinctly defined above.
    The invention also relates to a block of polyurethane / polyisocyanurate fiber bundle of a thermal insulation mass of a sealed and thermally insulating tank, directly obtained by the aforementioned preparation process, namely the block of polyurethane foam / fiber polyisocyanurate containing between 1% and 60% by mass of fibers, preferably between 2% and 30%, distributed homogeneously in said block, having a width L of at least ten centimeters, advantageously between 10 and 500 centimeters , and a thickness E of at least ten centimeters, advantageously between 10 and 100 centimeters, the block of fiber-reinforced polyurethane / polyisocyanurate foam being composed of cells storing a gas, advantageously with low thermal conductivity. This block of foam characterized in that its volume represents between 92% and 99%, preferably between 95% and 99%, of the volume of expansion of this same polyurethane foam / polyisocyanate fiber in the case of free expansion , without the constraint of the walls of a double-strip laminator forming a tunnel of rectangular section, and in that at least 60%, preferably at least 80% and more preferably at least 90%, of the above cells storing a gases, advantageously with low thermal conductivity, have an elongated or stretched shape along an axis parallel to the axis of the thickness E of the block of polyurethane foam / fibered polyisocyanurate.
    The expression “homogeneously distributed” is understood to mean the fact that the fibers are present substantially (+/- 3%, or even +/- 2%) in the same percentage by mass in all the areas of the block. foam according to the invention.
    Such a block of foam intrinsically has differentiating characteristics compared to those prepared according to the prior preparation techniques. It can be noted that the characteristics relating to the nature or the quantity of the various elements presented above in connection with the process for preparing the block of fiber foam can define, if necessary, more precisely the block of PUR / PIR foam. fiber bundle according to the invention.
    Advantageously, the density of said foam block is between 50 and 300 kg / m3, preferably between 70 and 170 kg / m 3 .
    The invention also relates to a sealed and thermally insulating tank integrated in a support structure, comprising a sealed and thermally insulating tank comprising at least one waterproof metal membrane composed of a plurality of metal strakes or metal plates which may include corrugations and a thermally insulating block comprising at least one thermally insulating barrier adjacent to said membrane, The tank according to the invention is characterized in that the thermally insulating block comprises the block of polyurethane / fibered polyisocyanurate foam described succinctly above.
    This tank comprises a plurality of blocks of fiber polyurethane / polyisocyanurate fiber obtained directly by the aforementioned preparation process.
    Finally, the invention also relates to a ship for the transport of a cold liquid product, the ship comprising a double hull and a sealed and thermally insulating tank as briefly described above, arranged in the double hull .
    Advantageously, such a vessel comprises at least one sealed and insulating tank as described above, said tank comprising two successive sealing barriers, one primary in contact with a product contained in the tank and the other secondary disposed between the primary barrier and a supporting structure, preferably constituted by at least a portion of the walls of the ship, these two sealing barriers being alternated with two thermally insulating barriers or a single thermally insulating barrier disposed between the primary barrier and the load-bearing structure.
    Such tanks are conventionally designated as integrated tanks according to the code of the International Maritime Organization (IMO), such as for example tanks of type NO 96® or MARK III®.
    Preferably, the tank contains a Liquefied Natural Gas (LNG) or a Liquefied Gas (GL).
    Brief description of the figures. The description which follows is given solely by way of illustration and without limitation, with reference to the appended figures, in which:
    [Fig.l] is a schematic view illustrating the different stages of the preparation process according to the invention;
    [Fig.2] is a schematic representation of an embodiment of a controlled liquid dispenser according to the invention;
    [Fig.3] is a photo taken with an electronic scanning microscope illustrating the cells of the block of polyurethane foam / fiber polyisocyanurate according to the invention;
    [Fig.4] is a schematic view of two sets of thermal insulation panels, fixed one on the other, respectively forming a primary space and a secondary insulation space for a tank, these panels being constituted by a plurality of blocks of polyurethane foam / polyisocyanurate fiber according to the invention;
    [Fig.5] is a cutaway schematic representation of an LNG tank, in which are installed the two sets of thermal insulation panels of the type of those shown in Figure 4, and a terminal loading / unloading of this tank.
    Description of the embodiments Preferably, the preparation of the fiber PUR / PIR according to the invention is carried out in the presence of catalysts making it possible to promote the isocyanate-polyol reaction. Such compounds are described for example in the document of the state of the art entitled "Kunststoffhandbuch, volume 7, Polyurethane", Imprimerie Cari Hanser, 3rd edition 1993, chapter 3.4.1. These compounds include amine catalysts and organic compound catalysts.
    Preferably, the preparation of the fiber PUR / PIR according to the invention is carried out in the presence of one or more stabilizers intended to promote the formation of regular cellular structures during the formation of the foam. These compounds are well known to those skilled in the art and, by way of example, mention may be made of foam stabilizers comprising silicones such as the siloxane-oxyalkylene copolymers and the other organopolysiloxanes.
    Those skilled in the art know the amounts of stabilizers, between 0.5% and 4% by weight of the PUR / PIR foam, to be used depending on the reagents envisaged.
    According to one possibility offered by the invention, during step a), the mixture of chemical components can include plasticizers, for example polybasic esters, preferably dibasic, carboxylic acids with monohydric alcohols, or consist of polymeric plasticizers such as polyesters of adipic, sebacic and / or phthalic acids. A person skilled in the art, depending on the reagents used, knows what quantity of plasticizers is envisaged, conventionally from 0.05% to 7.5% by weight of the polyurethane / polyisocyanurate foam.
    Organic and / or inorganic fillers, in particular reinforcing fillers, can also be envisaged in the mixture of chemical components such as siliceous minerals, metal oxides (for example kaolin, titanium or iron oxides) and / or metal salts. The quantity of these fillers, if they are present in the mixture, is conventionally between 0.5% and 15% by weight of the PUR / PIR foam.
    It should be noted that the present invention does not intend here to add technical teaching to the formation of a PUR / PIR foam, both in terms of the nature of the essential chemical components and optional functional agents and their respective quantities. Those skilled in the art know how to obtain different types of fiberized PUR / PIR foam and the present preparation relates, from a specific stress treatment of the expanding foam in a double strip laminator, to particular choices for improving either the preparation process, for example by suitable selections of temperatures, ranges of viscosities of the components, a specific distribution of these components or a speed of advance of the conveyor belt, or the general qualities of the product finished, for example by the choice of chemical components having particular reactive functions, of swelling agents or of particular fibers, or even by the choice of particular functional agents. Thus, the present invention, as set out here, is not primarily aimed at a new chemical preparation of fiberized PUR / PIR foam but rather a new preparation of a block of fiberized PUR / PIR foam using a double strip laminator .
    Thus, as can be seen in Figure 1, a plurality of fiber reinforcements 10 are unwound and brought in parallel alignment therebetween on or above a conveyor belt 11 intended to conduct these reinforcements 10 and the components forming the PUR / PIR foam. Indeed, the impregnation of the fiber reinforcements 10 is done here by gravity, that is to say that the mixture 12 of components is poured from a liquid distributor located above the fiber reinforcements 10 chemicals, blowing agent (s) and any other functional agents used for obtaining PUR / PIR foam, directly on the fibers 10.
    Thus, the above mixture 12 must permeate all of the fiber reinforcements 10, very evenly, during the cream time so that the start of the expansion of the PUR / PIR foam takes place after or at the earliest just when the fiber reinforcements 10 are well all impregnated with the mixture 12. In so doing, the expansion of the PUR / PIR foam is carried out while preserving perfect homogeneity of the fibers 10 in the volume of the block of PUR / PIR foam.
    The cream time of the components of the mixture 12 to form the PUR / PIR foam is known to those skilled in the art and chosen in such a way that the conveyor belt 11 brings the assembly formed of the mixture 12 of components, the blowing agent and fibers 10 to the double strip laminator, not shown in the appended figures, while the expansion of the foam has just started, in other words the expansion of the PUR / PIR foam ends in the laminator double strip, the pressure system, using one or two rollers, being possibly placed before the double strip laminator (ie between the area of impregnation of the mixture on the fibers and the double strip laminator). More specifically, the expansion of the volume of the foam is carried out in the double strip laminator when the expansion volume of this foam reaches between 30% and 60% of the expansion volume of this same foam when the expansion is left free, ie without any constraint on the upper surface of the mixture 12 and of the fibers 10. In doing so, the double strip laminator constrains the expansion of the PUR / PIR foam in its second expansion phase, when it is close or relatively close to its maximum expansion, that is to say when its expansion brings the foam close to all of the walls, forming a tunnel of rectangular or square section, of the double strip laminator. According to a different way of presenting the specific choices of the preparation according to the invention, the freezing point of the mixture of components, that is to say the time when at least 60% of the polymerization of the mixture of components is reached, in other words 70% to 80% of the maximum volume expansion of the mixture, takes place imperatively in the double strip laminator, possibly in the second half of the length of the double strip laminator (i.e. closer to the outlet of the laminator than to the entry of the latter).
    An important aspect of the preparation according to the invention lies in the good impregnation of the fibers 10 which must be reached before, or just before, the creaming time of the mixture 12 of components intended to obtain the PUR / PIR foam. To do this, mainly two characteristics are required: firstly a choice of specific viscosity range for the mixture 12 of components so as to ensure good penetration of the mixture 12 into, or through, all of the reinforcing layers of fibers 10, and at most during the creaming time of said mixture 12 of components, and on the other hand preferably by a simultaneous distribution, over the entire width L of fiber reinforcements 10, of this mixture 12 of components so that the fibers 10 are impregnated concomitantly over the entire section of width L.
    Regarding this function of simultaneous distribution of the mixture 12 of chemical components and blowing agent over the entire width L of the fiber reinforcements 10, it is here provided by a controlled liquid distributor 15, visible in FIG. 2. A such a dispenser 15 comprises a supply channel 16 of the assembly formed of the mixture 12 of chemical components and at least of the blowing agent from the reservoir forming a reagent mixer, not shown in the appended figures, in which on the one hand all the chemical components and the swelling agent are mixed and, on the other hand, the nucleation or even the heating of such a mixture is carried out. This liquid assembly formed of the mixture 12 of chemical components and of the swelling agent is then distributed, under pressure, in two channels 17 extending transversely to result respectively in two identical distribution plates 18, extending along the width L ( each having a length substantially equal to L / 2), comprising a plurality of nozzles 19 for the flow of said mixture 12 over the fiber reinforcements 10. These flow nozzles 19 consist of orifices of calibrated section having a determined length. The length of these flow nozzles 19 is thus determined so that the liquid leaves with an equal flow rate between all the nozzles 19 so that the impregnation of the fiber reinforcements 10 takes place at the same time, or simultaneously, on the width section L of the fiber reinforcements 10, and that the surface mass of liquid deposited at the level of each nozzle is equal. In doing so, if we consider a section of width L of the fibers 10, the latter are impregnated concurrently so that the impregnation of the layers of fibers 10 by the mixture 12 is carried out, at all points in this section, in an identical manner , which contributes to obtaining a perfectly homogeneous block of fiber foam at the outlet of the double strip laminator.
    The controlled liquid dispenser 15 shown in this figure 2 is an exemplary embodiment in which two identical distribution plates 18 are used but one can envisage a different design, insofar as the function of simultaneous liquid distribution on the width section of the fibers 10 is reached. Of course, the main technical characteristic used here resides in the different lengths of the flow nozzles 19, more or less long depending on the path, or path, of the liquid mixture 12 from the supply conduit 16 of the distributor 15 to the flow nozzle 19 considered.
    Another aspect of importance for achieving a good impregnation of the fiber reinforcements 10 lies in the choice of a specific viscosity of the liquid (consisting of the mixture 12 of chemical components and of the swelling agent). The viscosity range chosen must allow good penetration of the liquid into the first layers of fibers 10, in order to reach the following ones up to the last layer (the lower layer of fibers 10, that is to say the one located lowest in the stack of fiber reinforcements ), so that the impregnation of the fibers 10 is carried out in the period of time given by the chemical components corresponding substantially to the cream time. In other words, the viscosity is chosen, for example by heating, addition of plasticizers and / or by more or less significant nucleation, so that the impregnation of all the fibers 10 by the mixture 12, on a section of width L, is obtained before or just before the creaming time, that is to say before or just before the start of the expansion of the PUR / PIR foam.
    These two parameters, the choice of a suitable viscosity and the simultaneous distribution of the mixture 12 over a section of width L provided here by a controlled liquid distributor 15, are the main parameters for preserving, during the expansion of PUR / PIR foam good homogeneity of the fibers, before the entry of PUR / PIR foam into the double strip laminator. However, the stress exerted by the walls of the double strip laminator is necessary for the good final distribution of the fibers 10 in the foam, thereby contributing very significantly to the perfect homogeneity of the fiber foam.
    FIG. 3 illustrates a sample of PUR / PIR foam obtained according to the invention. Note in this figure the alignment of the length 1 of the cells 20 enclosing a gas with low thermal conductivity in the direction of, or parallel to, the thickness E of the block of PUR / PIR foam. Thus, as is apparent in this figure, a very large majority of these cells 20 has an oval shape, that is to say having a longitudinal extension 1, this extension taking place parallel to or in the axis of the thickness E of the block of fiberized foam at the outlet of the double strip laminator. In addition to the homogeneity of the fibers 10 in the block, this massive orientation of the cells 20 of the foam plays a crucial role in obtaining the excellent mechanical properties which are briefly presented below.
    The preparation for obtaining a fibered PUR / PIR foam according to the invention is characterized by a stress ratio of the expansion of this fibered foam vis-à-vis this same expanded foam without constraint, in other words, the volume of the constrained fiber foam according to the invention is between 92% and 99%, preferably between 95% and 99%, of the volume of this same foam without constraint (free expansion). However, in order to obtain such a block of foam continuously on an industrial scale, the spacing of the facing faces forming the tunnel of the double strip laminator is parameterized, as a function of a flow rate of mixture of chemical components and blowing agent, more precisely the lower and upper faces of the tunnel / laminator in such a way that the foam expansion constraint is established in the aforementioned broad field of the invention, or even in the aforementioned preferred field. The fact remains that, within the framework of a continuous production of such a foam, the flow rate of components and at least of blowing agent is liable to vary and it is necessary to be able to adapt the stress of the double strip laminator to this variation. of debt. It is thus proposed here to install at least one pressure sensor, preferably a plurality of such pressure sensors along the laminator, these sensors being able to measure the pressure exerted by the foam between the lower and upper face of the laminator. Thus, by setting a pressure range corresponding to obtaining a foam expansion constraint according to the wide range or the preferred range of the invention, it is automatically adapted, as a function of the pressure measured with this (s ) sensor (s), the flow of chemical components and blowing agent so as to obtain, in a continuous process, a block of fiber foam according to the invention. The solution proposed here consists in varying the flow of chemical components and / or swelling agent as a function of the pressure measured, but one could also consider varying the pressure, that is to say the spacing between the faces. upper and lower tunnel / laminator, depending on the flow of chemical components and blowing agent measured / calculated. In both cases, the objective is to obtain a fiber foam in the desired stress range, for the manufacture of a block meeting specific expectations, in particular in compressive strength.
    Indeed, the block of fiber foam is intended to be used in a very particular environment, and must therefore guarantee specific mechanical and thermal properties. The block of fiber foam obtained by the preparation according to the present invention thus forms part of a thermal insulation block 30, either in the example used in FIG. 4, in an upper or primary panel 31 and / or a lower panel or secondary 32 of such an insulation block 30 of a tank 71 intended to receive an extremely cold liquid, such as LNG or LPG. Such a tank 71 can equip for example a tank on the ground, a floating barge or the like (such as an ESRU “Eloating Storage Regasification Unit” or an ELNG “Eloating Liquefied Natural Gas”) or even a ship, such as an LNG carrier , transporting this energetic liquid between two ports.
    Referring to Figure 5, a cutaway view of an LNG carrier 70 shows a sealed and insulating tank 71 of generally prismatic shape mounted in the double hull 72 of the ship. The wall of the tank 71 comprises a primary waterproof barrier intended to be in contact with the LNG contained in the tank, a secondary waterproof barrier arranged between the primary waterproof barrier and the double hull 72 of the ship, and two insulating barriers arranged respectively between the primary waterproof barrier and the secondary waterproof barrier and between the secondary waterproof barrier and the double shell 72.
    In a manner known per se, loading / unloading lines 73 arranged on the upper deck of the ship can be connected, by means of appropriate connectors, to a maritime or port terminal for transferring a cargo of LNG from or to the tank. 71.
    FIG. 5 represents an example of a maritime terminal comprising a loading and unloading station 75, an underwater pipe 76 and an onshore installation 77. The loading and unloading station 75 is a fixed offshore installation comprising a movable arm 74 and a tower 78 which supports the movable arm 74. The movable arm 74 carries a bundle of insulated flexible pipes 79 which can be connected to the loading / unloading pipes 73. The movable arm 74 can be adjusted to suit any size LNG carriers. A connection pipe, not shown, extends inside the tower 78. The loading and unloading station 75 allows the loading and unloading of the LNG carrier 70 from or to the onshore installation 77. This comprises liquefied gas storage tanks 80 and connection pipes 81 connected by the submarine pipe 76 to the loading or unloading station 75. The submarine pipe 76 allows the transfer of liquefied gas between the loading or unloading station 75 and the shore installation 77 over a long distance, for example 5 km, which makes it possible to keep the LNG carrier 70 at a great distance from the coast during the loading and unloading operations.
    To generate the pressure necessary for the transfer of the liquefied gas, on-board pumps are implemented in the ship 70 and / or pumps fitted to the shore installation 77 and / or pumps fitted to the loading and unloading station 75.
    In the following, a part of the experiments and tests carried out by the applicant to enable it to appreciate the object of the invention and its scope are presented, it being considered that other tests / experiments have been carried out and will be may be supplied later, if necessary / required.
    The three foam compositions presented below do not include fiber reinforcements, but the Applicant has demonstrated that the results presented below with these foam compositions show similar behavior when the same reinforcement is added. fiber, in equivalent quantity for each composition sample. These three compositions, the first of PUR, the seconds (2a and 2b) of PIR and the third of a PUR / PIR mixture are subjected to different levels of expanding stress, from high stress to unconstrained expansion.
    Composition No. 1 consists of a PUR foam composition and is composed as follows:
    [Tables 1]
    Type of product Rate (% of massPURE) Description Commercial reference of the product Polypi 1 (based on glycerol and sorbitol) 60-75% 385-415 mg KOH / g mixture of polyols based on glyecrol and sorbitol of the Daltolac® type R200, R251, R4Û4, R470, R500. Polyol 2 (aromatic polyester diol) 25-40% 230-250 mg KOH / g aromatic polyester polyol type Stcpanpol® PS-1752, PS2352, PS-3152 isocyanate 95-105% 30-31.5% NCO MDI polymeric isocyanate type Supraseo S5005 Water (chemical blowing agent) 0.05-1.5% | physical blowing agent 3-12% 365mfc / 227ea or î245fa suri autantsilicone 0.5-1.5% PEO / PPO grafted silicone Tegostab® B8404 orB8465 tin haze reaction catalyst 0.05-0.08% DBTL Dabco * T12N
    Composition No. 2a consists of a PIR foam composition and is composed as follows:
    [Tables2]
    Type of product Rate (% ofPIR mass) Description Comm ereï al referenceof the product polyol mixture + water + surfactant + flame retardants + catalyst 100 234 mg KOH / g Voracor® CN815 isocyanate 200-230 30-31.5% NCO Voranate® M220 or M229 type MDI polymeric isocyanate Water (chemical blowing agent) 2-4 physical blowing agent 3-12 245fasilicone surfactant 1-3 grafted siliconePEO / PPO DowDC 193 catalysts 0.5-3. DMBA / DMCHA Voracor * CN626
    Composition No. 2b consists of another PIR foam composition and is composed as follows:
    [Tables3]
    Type of product Rate (% ofPIR mass) Description Reference comrn ercialof the product Polyol 1 64 190-230 mgKOH / g aromatic polyester polyol Polyol 2295-335 mgKOII / g aromatic polyester polyol Flame retardant 10-20triethylphosphate isocyanate 220 30-31.5% NCO MDI polymeric isocyanate of Voranate * type M220 or M229 Water (chemical blowing agent) 0.5-1.5 50% water inpolyol Voracor® CM265 physical blowing agent 2-5 245fasilicone surfactant 1-5 grafted siliconePEO / PPO Dow DC 193 catalysts 1-3 DMBA / DMCI1A Voracor * CN626
    Composition No. 3 consists of a PUR / PIR foam composition (PUR and PIR mixture) and is composed as follows:
    [Tables4]
    Type of product Rate (% ofPUR / PÎR mass) Description Commercial reference of the product Polyol 100 330-390 mgKOH / g blend of aromatic polyester polyols and polyether polyols isocyanate 110-155 30-31.5% NCO Voranate * 'MDI polymeric isocyanate M220 or M229 Water (chemical blowing agent) 0.4-1.5 50% water diluted in a polyol Voracor * CM265 physical blowing agent 4-12 245fasilicone surfactant 1-3 grafted siliconePEO / PPO Dow DC 193 catalysts 2-4 DMBA0.5-2Voracor * CM420 0.5-1 Ammonium carboxylate
    Again, below, only part of the experimental results are presented in order to facilitate reading. However, the applicant is able to present, on the date of filing of this application, the complete results which enabled it to define the invention, from its most general definition to its most specific definitions.
    The PUR / PIR foam produced by free expansion has good mechanical qualities in the thickness E but the losses, to obtain a block of homogeneous fiber foam of parallelepiped shape, are at least 15% or even more than 20 -25%, which is not industrially acceptable. Thus, the value in compression for a free expansion of the composition considered (n ° l, n ° 2a, n ° 2b or n ° 3) is taken as value at 100, respectively in the case PUR, PIR then PUR / PIR, and the measurements for each of the compositions are reported with respect to this calibration at 100, it being understood that the percentage obtained depends on the one hand on the result of the ISO 844 standardized test concerning the “elastic limit” and on the “ compressive strength ”of the test sample.
    Following the completion of the tests, certain results are presented, in a simplified manner, below to illustrate the discoveries of the applicant.
    [Tables5]
    Composition with free compression / expansion ratio % orientation of cells according to thickness E Compressive strength result, produced on test pieces according to ISO 844/100% base (free expansion) Compositions 1 and 3 compressed to 67-68% (ratio final volume compared to the volume "free expansion") less than 50% 44% to 69% Compositions 1 & 3 86% compressed less than 60% 55% Compositions 1 & 3 90% compressed greater than 60% 50% to 68% Compositions 1 & 3 91% compressed greater than 60% 55% to 70% Compositions 1 & 395% compressed 90% 91% Compositions 1 & 397% compressed greater than 90% 105% Compositions 1 & 399% compressed greater than 90% 103% Compositions 1 & 3 free expansion (density: about 130 kg.m 3 ) greater than 90% 100% or 1.25 MPa Compositions 2 (2a and 2b above) compressed to 85% less than 60% 58% Compositions 2 91% compressed greater than 60% 69% Compositions 2 compressed to 92% greater than 60% 92% Compositions 2 compressed at 96% greater than 90% 98%
    Compositions 2 compressed to 97% greater than 90% 104% Compositions 2 compressed to 99% greater than 90% 102% Compositions 2 free expansion (density: about 130 kg.m 3 ) greater than 90% 100% or 1.25 MPa
    As can be seen with the results presented in the table above, only the stress domain according to the invention (noted in bold) makes it possible to obtain or maintain good mechanical properties in thickness E, while by offering economic production since material losses are less than 5%, or even less than 2%.
    Furthermore, it should be noted that the fiber-reinforced PUR / PIR foams according to the invention show no significant deterioration in their property relating to the (very low) thermal conductivity. Thus, by way of example, when the expansion constraint is between 92% and 99% relative to the free expansion (volume ratio) for the three above-mentioned compositions no. 1, no. 2 (a and b) and n ° 3, the following values of thermal conductivity are obtained:
    [Tablesô]
    thermal conductivity (mW / m.K) at-170 ° C at -20 ° C at + 20 ° C 13-16 15-18 23-27
    Although the invention has been described in conjunction with several particular embodiments, it is obvious that it is in no way limited thereto and that it includes all the technical equivalents of the means described as well as their combinations if these are within the scope of the invention.
    The use of the verb "to include", "to understand" or "to include" and of its conjugated forms does not exclude the presence of other elements or other stages than those stated in a claim.
    In the claims, any reference sign in parentheses cannot be interpreted as a limitation of the claim.
    权利要求:
    Claims (1)
    [1" id="c-fr-0001]
    [Claim 1] [Claim 2]
    Claims
    Process for the preparation of a block of polyurethane / polyisocyanurate fiber bundle of a thermal insulation block (30) of a sealed and thermally insulating tank, the block of polyurethane foam / polyisocyanurate fiber bundle being composed of cells (20) storing a gas, advantageously of low thermal conductivity, and being in the form of a parallelepiped of thickness E and width L, the preparation process comprising the following steps:
    a) a mixing step (12) of chemical components necessary for obtaining a polyurethane / polyisocyanurate foam, said components comprising reagents for obtaining polyurethane / polyisocyanurate, optionally at least one reaction catalyst, optionally at at least one emulsifier, and at least one swelling agent,
    b) a fiber impregnation step (10) with the above mixture (12) of chemical components, the fibers (10) representing between 1% and 60% by mass,
    c) a step of forming and expanding the polyurethane / polyisocyanurate fiber bundle, said expansion of the polyurethane foam / polyisocyanurate fiber being physically constrained by the walls of a double strip laminator forming a tunnel, of rectangular section with a distance between the walls arranged laterally equal to L and a distance between the walls arranged horizontally equal to E, thus enclosing the expanding fiber foam so as to obtain the above-mentioned block of polyurethane foam / fiber polyisocyanurate, characterized in that the positioning of the walls of the tunnel of the double strip laminator is defined such that the expansion constraint of the polyurethane foam / polyisocyanurate fiber leads to a volume of polyurethane foam / polyisocyanurate fiber, at the output of the double strip laminator, representing between 92 % and 99% of the expansion volume of this same polyurethane / polyisocyanurate fiber fibered in the case of an expa free space, without the constraint of the walls of such a double strip laminator.
    Method according to claim 1, in which the above-mentioned volume of the polyurethane / polyisocyanurate fiber bundle represents between 95% and 99% of the expansion volume of this same fiber foam in the case of free expansion, without the constraint of the walls from a laminator to
    double band. [Claim 3] Method according to claim 1 or 2, in which, during the step of impregnating fiber masts (10), the above mixture (12) of components has a viscosity of between 30 mPa.s and 1500 mPa.s, preferably between 50 mPa.s and 700 mPa.s. [Claim 4] Method according to any one of the preceding claims, in which at least 60% of the above-mentioned cells (20) storing a gas, advantageously of low thermal conductivity, have an elongated or stretched shape along an axis parallel to the thickness axis E of the polyurethane / polyisocyanurate fiber block. [Claim 5] Method according to any one of the preceding claims, in which at least 80%, preferably at least 90%, of the said cells (20) storing a gas, advantageously with low thermal conductivity, have an elongated or stretched shape along a parallel axis to the axis of the thickness E of the block of polyurethane foam / fibered polyisocyanurate. [Claim 6] Method according to any one of the preceding claims, in which the fibers (10) consist of glass fiber or carbon fibers, preferably glass fibers. [Claim 7] The method of claim 6, wherein the fibers (10) are in the form of a plurality of layers of woven or nonwoven reinforcements, preferably nonwoven / isotropic reinforcements, extending in an orientation plane perpendicular to thickness E. [Claim 8] Method according to any one of the preceding claims, in which the fibers (10) are arranged over the entire width L and step b) of impregnating the fibers (10) with the mixture (12) of components, in order to obtain a polyurethane foam / fiber polyisocyanurate, and a blowing agent operates, via a controlled liquid distributor (15), simultaneously over the entire width L. [Claim 9] A method according to any one of the preceding claims, in which the blowing agent consists of a physical and / or chemical blowing agent, preferably a combination of the two types. [Claim 10] Process according to Claim 9, in which the physical blowing agent is chosen from alkanes and cycloalkanes having at least 4 carbon atoms, dialkyl ethers, esters, ketones, acetals, fluoroalkanes, fluoro- olefins having between 1 and 8 carbon atoms and tetraalkylsilanes having between 1 and 3 carbon atoms in the alkyl chain, in particular tetramethylsilane, or a mixture
    of these. [Claim 11] The method of claim 9, wherein the chemical blowing agent consists of water. [Claim 12] Method according to any one of the preceding claims, in which the reactants comprise:an isocyanate component comprising one or more isocyanate compounds, said isocyanate compounds having a viscosity of between 100 and 3000 mPa.s at room temperature, and- a polyol component comprising one or more polyol compounds, said polyol compounds having a viscosity of between 200 and 3000 mPa.s at room temperature. [Claim 13] Process according to Claim 12, in which, during step a) of mixing (12) of chemical components, nucleation gas is incorporated into at least one polyol compound, preferably using a static mixer / dynamic under a pressure between 20 and 250 bars, the nucleating gas representing between 0 and 50% by volume of polyol, preferably between 0.05 and 20% by volume of the volume of polyol. [Claim 14] Process according to any one of the preceding claims, in which, during step a) of mixing (12) the chemical components, the temperature of each of the reactants for obtaining polyurethane / polyisocyanurate is between 10 ° C and 40 ° C, preferably between 15 ° C and 30 ° C. [Claim 15] Method according to any one of the preceding claims, in which is added to the mixture (12), in step a), an organophosphorus flame retardant, advantageously triethylphosphate (TEP), tris (2-chloroiso-propyl ) phosphate (TCPP), tris (1,3-dichloroisopropyl) phosphate (TDCP), tris (2-chloroethyl) phosphate or tris (2,3-dibromopropyl) phosphate, or a mixture thereof, or a inorganic flame retardant, preferably red phosphorus, expandable graphite, aluminum oxide hydrate, antimony trioxide, arsenic oxide, ammonium polyphosphate, calcium sulfate or derivatives thereof cyanuric acid, a mixture of these. [Claim 16] Method according to any one of the preceding claims, in which the fibers (10) representing between 2% and 30% by mass of the above mixture (12) of components. [Claim 17] System for preparing a block of polyurethane / polyisocyanurate fiber with a thermal insulation mass (30) of a tank
    waterproof and thermally insulating, for implementing the method according to any one of the preceding claims, comprising:
    a reaction device receiving chemical components necessary for obtaining a polyurethane / polyisocyanurate foam, said chemical components comprising reagents for obtaining polyurethane / polyisocyanurate, optionally at least one reaction catalyst, optionally at least one emulsifier , and at least one blowing agent,
    - a distributor of the above components on fibers (10), preferably in the form of a plurality of fiber masts (10), for the impregnation of the latter by these components, preferably via a controlled liquid distributor (15 ) permitting the fibers (10) to be impregnated simultaneously over their entire width L,
    - a conveyor belt for receiving and transporting the above components and the fiber masts (10) from the impregnation of these fibers (10) by said components until the formation of the block of polyurethane foam / fibered polyisocyanurate, the block polyurethane foam / fiber polyisocyanurate formed in the form of a parallelepiped of a thickness E and a width L,
    - a double strip laminator forming a tunnel, of rectangular section with a distance between the walls arranged laterally equal to L and a distance between the walls arranged horizontally equal to E, thus enclosing the expanding fiber foam so as to obtain the block of foam of polyurethane / fibered polyisocyanurate, characterized in that the positioning of the walls of the tunnel of the double-strip laminator is defined so that the expansion constraint of the polyurethane / fibered polyisocyanurate foam leads to a volume of polyurethane / polyisocyanurate foam fiber-reinforced, at the outlet of the double-strip laminator, representing between 92% and 99%, preferably between 95% and 99%, of the volume of expansion of this same polyurethane foam / polyisocyanurate fiber in the case of free expansion, without the stress of the walls of a double strip laminator.
    [Claim 18] Block of polyurethane / polyisocyanurate fiber with a thermal insulation block (30) of a sealed and thermally insulating tank, directly obtained by the process according to any one of Claims 1 to 16, the block fiber polyurethane / polyisocyanurate foam containing between 1% and 60% by mass of fibers (10), [Claim 19] [Claim 20] [Claim 21] preferably between 2% and 30%, distributed homogeneously in said block , having a width L of at least ten centimeters, advantageously between 10 and 500 centimeters, and a thickness E of at least ten centimeters, advantageously between 10 and 100 centimeters, the block of polyurethane foam / fibered polyisocyanurate being composed cells (20) storing a gas, advantageously with low thermal conductivity, characterized in that its volume represents between 92% and 99%, preferably between 95% and 99%, of the expansion volume of this same poly foam urethane / fiber polyisocyanate in the case of free expansion, without the constraint of the walls of a double strip laminator forming a tunnel of rectangular section, and in that at least 60%, preferably at least 90% and so still preferred at least 90%, of the above cells (20) storing a gas, advantageously with low thermal conductivity, have an elongated or stretched shape along an axis parallel to the axis of the thickness E of the block of polyurethane / polyisocyanurate foam fiber.
    Block of fiber polyurethane / polyisocyanurate foam according to the preceding claim, in which the density of said block is between 50 and 300 kg / m 3 , preferably between 70 and 170 kg / m 3 .
    Watertight and thermally insulating tank integrated in a supporting structure, comprising a watertight and thermally insulating tank comprising at least one watertight metallic membrane composed of a plurality of metal strakes (1,2) or metal plates which may include corrugations and a thermally insulating block (30) comprising at least one thermally insulating barrier (5) adjacent to said membrane, characterized in that the thermally insulating block comprises the block of polyurethane foam / fibered polyisocyanurate according to claim 18 or 19.
    Ship (70) for transporting a cold liquid product, the ship comprising a double hull (72) and a sealed and thermally insulating tank (71) according to claim 20 disposed in the double hull.
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    同族专利:
    公开号 | 公开日
    CN111655442A|2020-09-11|
    WO2020104749A3|2020-08-06|
    KR20210091044A|2021-07-21|
    FR3088571B1|2021-12-17|
    RU2020109961A|2021-09-13|
    WO2020104749A2|2020-05-28|
    EP3883737A2|2021-09-29|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3738895A|1967-03-22|1973-06-12|Saint Gobain|Apparatus for making laminated structural panels of cellular foamed resin|
    US3867494A|1973-03-06|1975-02-18|Owens Corning Fiberglass Corp|Method and apparatus for producing fiber reinforced organic foam|
    FR2565522A1|1984-06-06|1985-12-13|Toyo Tire & Rubber Co|Process for manufacturing an article made from fibre-reinforced foam|
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    GB8918218D0|1989-08-09|1989-09-20|Boc Group Plc|Thermal insulation|FR3091705A1|2019-01-16|2020-07-17|Gaztransport Et Technigaz|PROCESS FOR THE PREPARATION OF A BLOCK OF POLYURETHANE / POLYISOCYANURATE FOAM FROM A THERMAL INSULATION MASSIF OF A TANK|
    FR3094451A1|2019-03-26|2020-10-02|Gaztransport Et Technigaz|Polyurethane / polyisocyanurate foam block of a thermal insulation block of a tank and its preparation process|
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    法律状态:
    2019-11-29| PLFP| Fee payment|Year of fee payment: 2 |
    2020-05-22| PLSC| Publication of the preliminary search report|Effective date: 20200522 |
    2020-11-30| PLFP| Fee payment|Year of fee payment: 3 |
    2021-11-30| PLFP| Fee payment|Year of fee payment: 4 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1871590A|FR3088571B1|2018-11-19|2018-11-19|PROCESS AND SYSTEM FOR PREPARING A BLOCK OF POLYURETHANE / POLYISOCYANURATE FOAM FROM A THERMAL INSULATION MASS OF A TANK|FR1871590A| FR3088571B1|2018-11-19|2018-11-19|PROCESS AND SYSTEM FOR PREPARING A BLOCK OF POLYURETHANE / POLYISOCYANURATE FOAM FROM A THERMAL INSULATION MASS OF A TANK|
    KR1020207010024A| KR20210091044A|2018-11-19|2019-11-19|Method and system for making blocks of polyurethane/polyisocyanurate foam of insulating slabs of tanks|
    RU2020109961A| RU2020109961A|2018-11-19|2019-11-19|METHOD AND SYSTEM FOR MANUFACTURING POLYURETHANE / POLYISOCYANURATE FOAM BLOCK FOR HEAT INSULATING TANK PLATE|
    PCT/FR2019/052748| WO2020104749A2|2018-11-19|2019-11-19|Process and system for preparing a block of polyurethane/polyisocyanurate foam of a heat-insulating slab of a tank|
    EP19829288.0A| EP3883737A2|2018-11-19|2019-11-19|Process and system for preparing a block of fiberized polyurethane/polyisocyanurate foam of a heat-insulating slab of a tank|
    CN201980005121.6A| CN111655442A|2018-11-19|2019-11-19|Method and system for making polyurethane/polyisocyanurate foam blocks for insulated panels for tanks|
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