JP2022528619A - Polyurethane / polyisocyanurate foam block in the insulation body of the tank, and its preparation process - Google Patents

Abstract

The present invention is a fibrous polyurethane / polyisocyanurate foam block in which the fiber density is 1% by weight to 9.99% by weight of the fiber (10) along the thickness from the lower surface of the block to the upper surface thereof. It relates to a fibrous polyurethane / polyisocyanurate foam block that increases from a low density range of the fiber (10) to a high density range of 10% by weight to 35% by weight of the fiber (10).

Description

The subject of the present invention is a block made of fiber reinforced polyurethane (PUR) and / or polyisocyanurate (PIR) foam attached to a heat insulating body. The block must be as economically viable as possible, while it needs to exhibit very specific mechanical and thermal properties for a particular application. The block made of the foam is a tank incorporated in the membrane structure (also referred to as an integrated tank) or an ultra-low temperature fluid called an ultra-low temperature fluid, specifically, for example, liquefied natural gas (LNG) or liquefied petroleum gas. Used in Type A, B or C self-contained / semi-self-contained tanks capable of accommodating (LPG).

The present invention also relates to a process for preparing a block of these foams from at least one polyisocyanate and at least one polyol.

Finally, the invention was housed in a closed insulation tank using such foam, a vessel provided with at least one such tank, a loading and unloading process for such vessel, and such vessel. Regarding liquid product transfer systems.

Polyurethane PUR foam is a cell-like heat insulating material consisting of fine cells that store gas that may have low thermal conductivity. PUR foams are used in numerous applications, for example in the automotive industry as flexible PUR foams or in thermal insulation as rigid PUR foams. The formation of polyurethane-type foams is well known to those of skill in the art. Its formation involves a multi-component reaction of a polyol (a compound with at least two hydroxyl groups), a polyisocyanate (a compound with at least two isocyanate-NCO functional groups) and a swelling agent, also called a "foaming agent". Will be. This condensation reaction is particularly catalyzed by compounds with basic and / or nucleophilic properties, such as tertiary amines and metal-carboxylate coordination complexes such as tin and bismuth salts. Polyols commonly used in the production of PUR foams are polyether polyols or polyester polyols. As described above, a large number of compounds are required for the formation of PUR foam.

Polyisocyanurate (PIR) and polyurethane / polyisocyanurate (PUR-PIR) foams are also used in the building industry (construction / renovation) and not only provide better fire resistance than PUR, but are also larger. It offers the advantage of providing compressive strength. The process of forming these foams is similar to the process of forming PUR foams. This is because the acquisition of PUR, PIR and PUR-PIR foams depends on the isocyanate / polyol ratio.

PUR, PIR and PUR-PIR foams are well known to those of skill in the art, but the addition of fibers entails special technical problems such as the need for good impregnation of the fibers and is therefore at least topical. There are currently no foams containing relatively large amounts of fiber.

In fact, in the unique technical field of using such a foam for the heat insulating body of the tank, the body is exposed to the internal space of the tank at a very low temperature of about -160 ° C, for example in the case of LNG. Be exposed. On the other hand, the exterior space of the tank, that is, the hull of a ship, which is conventionally considered to be around 20 ° C, may be exposed to a much higher environmental temperature, which is at least the same as or much higher than the temperature of the ambient air and the sea. many.

Therefore, the PUR, PIR and PUR-PIR foam blocks used in the insulation body of such tanks have a very large temperature gradient in their thickness when loading very cold fluids called cryogenic fluids. As a result, a non-uniform shrinkage phenomenon of the foam block occurs. This non-uniform shrinkage of the foam block causes a bimetal effect in which the non-uniform shrinkage of the block in the thickness direction causes the block to sag along its longitudinal axis (both ends tend to be significantly lifted). Traditionally, since the foam block is mechanically or adhesively secured, this sagging significantly reduces the available mechanical properties of the PUR, PIR and PUR-PIR foam blocks, and even more. The thermal properties of the insulation body (incorporating the foam block according to the invention) are locally reduced.

The bimetal effect and the phenomenon of foam block sagging are said to be increasing, sometimes very much, in the thickness of the foam block forming the insulating body for such tanks containing cryogenic liquids. Due to the fact, it has doubled in recent years. Specifically, such tanks consist of a double insulating layer traditionally referred to as the "primary" and "secondary" layers, which are located farthest from the cryogenic liquid. If this is the case, the thickness E of the secondary heat insulating layer is greatly increased in recent structures such as the Mark type. Therefore, the thickness E of the secondary insulation layer varies from 170 mm (millimeters) in the Mark III structure to 300 mm in the Mark III Flex structure and 380 mm in the Mark III Flex + structure.

If the thickness of the secondary insulation layer is significantly larger than the thickness of the primary insulation layer, the bimetal effect and sagging of the secondary insulation layer will have a very detrimental structural effect on the insulation body of the sealed insulation tank.

Structures such as those described in Documents FR 2882 756, WO 2017/2026667, JP 2005225945 are known, but none adequately solve the particular technical problems described above.

At this time, there are no fiber-reinforced or non-fiber-reinforced polyurethane and polyisocyanurate foam blocks that can effectively address this issue. In other words, PURs, PIRs and PUR-PIRs that have thermomechanical stability between their initial state (in a homogeneous thermal environment) and their use state, i.e. when used in a tank containing cryogenic liquids. There is no foam block.

To overcome the problems of distortion and shape instability between these two states of the foam block, specially shaped blocks, specifically blocks with built-in notches or reduced dimensions, are currently being manufactured. .. The purpose is to limit the thermal deformation of each (small) volume element or (small) foam block to an acceptable range. Manufacturing such a small foam block requires a lot of work for cutting, positioning, and joining to each other, which is quite costly. In addition, the presence of many telescopic joints significantly reduces the thermal performance of the tank.

Against this background, the Applicant has succeeded in developing a process for producing polyurethane (PUR) and / or polyisocyanurate (PIR) foams containing a large amount of fibers. This allows the foam to have excellent mechanical and thermal properties, especially when the block is in use, i.e., in a thermal environment where the two surfaces, top and bottom, differ significantly. The mechanical properties as well as their shape / structure can be maintained throughout the foam block.

Accordingly, the present invention is intended to overcome current shortcomings by providing a particularly effective solution for industrially obtaining (very) large fiber reinforced PUR / PIR foams in some cases. ing. Its mechanical / thermal properties are its initial state (in a stationary state and the foam block is in a substantially homogeneous thermal environment) and its use / in which the foam block is in a very homogeneous thermal environment. Optimal for use / use conditions where the difference between the top surface and the bottom surface thereof examined along the thickness E of the block is at least 80 ° C. and even at least 100 ° C. At least substantially similar.

As a result of conducting various studies and analyzes, the Applicant can solve the technical problems associated with the extremely large changes in the thermal environment of the PUR / PIR foam block in use (PUR). ) And / or a polyisocyanurate (PIR) foam block, and its preparation for the purpose of manufacturing / designing it.

Advantageously, according to the preferred embodiment, it is also possible to reduce the production cost of such a fiber reinforced foam very significantly. This is due to the very significant reduction in material loss from the foam block, which was conventionally unavoidable in the prior art when cutting the foam block.

Therefore, the present invention is a fiber-reinforced polyurethane / polyisocyanurate foam block of a heat insulating body of a closed heat insulating tank, and the density of the fiber-reinforced foam block is 30 to 300 kg / m ³ , and the fiber-reinforced polyurethane /. Polyisocyanurate foam blocks exhibit an average fiber density _Tf of 1% to 60% by weight, preferably 2% to 30% of the fibers, and at least 10 centimeters, preferably 10 to 500 centimeters. The fiber-reinforced polyurethane / polyisocyanurate foam block exhibits a width L and a thickness E from the lower surface to the upper surface of the block, which is at least 10 cm, preferably 10 to 100 cm. Contains a fiber reinforced polyurethane / polyisocyanurate foam block composed of cells that advantageously store gas with low thermal conductivity.

The fiber-reinforced polyurethane / polyisocyanurate foam block is composed of a cell having an advantageously low thermal conductivity up to at least 95% by weight of the block, a polyurethane / polyisocyanurate foam, and a fiber. ..

Foam blocks according to the invention are selected from polyurethane (PUR) and / or polyisocyanurate (PIR) foams, preferably fibers such as glass fiber having a single property, and gas trapped in cells. Consists of (mainly) the smallest part of fillers and other functional aids. That is, for the latter, the foam block according to the present invention has a maximum of 5% by weight, more preferably a maximum of 2% by weight or 1% by weight (the fiber-reinforced polyurethane / polyisocyanurate foam block is the block. Consists of a cell that stores gas to at least 98% by weight or 99% by weight, a polyurethane / polyisocyanurate foam, and fibers). This is because the foam block according to the present invention can be obtained by the following work. That is,
-Preferably a single task of preparing the foam in a double band laminator (DBL) (selectively mixing the reactive components of the filler / auxiliary with the fibers),
-The above-mentioned work of a block that has freely expanded on the upper surface, which is conventionally complemented by the cutting work of the upper surface.

The foam is 10% by weight of the fiber from a low density range of 1% by weight to 9.99% by weight of the fiber along the thickness E from the lower surface to the upper surface of the block. It is characterized by increasing in a high density range of% to 35% by weight.

The present invention is particularly applicable, but not limited to, where the foam block is installed in a secondary layer conventionally designated as "secondary". In the present application, the foam block preferably exhibits a thickness of at least 25 centimeters (cm), more preferably at least 30-35 cm.

The expressions "low range" and "high range" are understood to mean two homogeneous portions of a fiber reinforced foam block. The foam is along the thickness E (or its height if the block is located in the insulating body) and along the median plane of the block through the center of the block. Be disconnected.

The terms "upper, upper, upper" and "lower, lower, lower" are understood to mean the meaning and direction given to the foam blocks placed in place in the insulating body of the tank. Thus, when the insulation body is placed in the tank, the top or top surface of the foam block is located near or beside the container in the tank. In contrast, the lower or lower surface of the foam block faces or is located to the outside of the tank, i.e., the tank is incorporated or mounted on a vessel for transport and / or storage of cryogenic liquids. If so, it faces the hull of the ship in particular.

Therefore, in the manufacture or preparation of foam blocks, the concepts or terms "upper, upper, upper" and "lower, lower, lower" are not yet installed, as the foam blocks have not yet been installed in the insulating body of the tank. It is understood that it has no meaning. In other words, the foam block according to the invention is completely prepared to be obtained at the exit of its preparation / production line in a state opposite to the final mounting / assembly state of the tank to the insulating body. It is possible.

The expression "cell storing gas" is derived from the gas infused with the polyurethane / polyisocyanurate foam during the nuclear formation step of the reaction mixture, or directly or indirectly to a chemical or physical foaming agent. It is understood to mean the fact that it presents a closed cell containing a gas of origin, preferably of low thermal conductivity.

The term "fiber", or the expression "fiber reinforced plastic", is understood to mean the fact that fibers can be provided in two separate forms:

-The form of at least one cloth of fibers, in which the fibers are perfectly aligned along at least one direction, in other words, the fibers are in a state of exhibiting at least one suitable fiber direction. The expression "cloth made of fibers" refers to a clear technical definition known to those of skill in the art by itself.

-Or the form of at least one mat consisting of fibers in which the fibers are not clearly oriented, in other words, the fibers are oriented essentially isotropically along the seed plane of the layer of the mat. Similarly, the expression "mat of fibers" refers to a clear technical definition known to those of skill in the art by itself.

According to one embodiment, the expression "a gas having (favorably) low thermal conductivity" is understood to mean a gas generated from a foaming agent. When the foaming agent is said to be "chemical", it depends on the chemical reaction of the foaming agent. When the chemical foaming agent consists of water, it is conventionally carbon dioxide (CO ₂ ). Physical foaming agents include, for example, molecular nitrogen (N ₂ ), molecular oxygen (O ₂ ), carbon dioxide, hydrocarbons, chlorofluorocarbons, hydrochlorocarbons, hydrofluorocarbons, and mixtures thereof, as well as the corresponding alkyl ethers. Is. Physical foaming agents such as molecular nitrogen N ₂ , molecular oxygen O ₂ , or CO ₂ are gaseous. These gases are dispersed or dissolved in the liquid mass of the copolymer under high pressure, for example using a static mixer. By depressurizing the system, the nucleation and growth of bubbles produces a cellular structure.

The expression "average fiber density T _f " takes into account the fiber density expressed as the weight of the fibers relative to the total weight of the fiber reinforced foam block, taking into account the variable local proportions of these fibers (within the block). It is understood as meaning without.

Therefore, the fiber reinforced foam block is used not only in tanks built into the support structure, but also in self-contained / semi-self-contained tanks of type A, B or C according to (IMO) IGC rules, ie LNG and LPG. Also suitable as an external insulation associated with self-contained tanks that store and / or transport very cold liquids such as.

Finally, the thermal properties of the fiber reinforced foam block are at least comparable to those of the prior art non-fiber reinforced foam blocks. More precisely, the foam block was measured at a thickness of E at 20 ° C. at 30 mW / m. Less than K (milliwatt per meter per Kelvin), that is, 0.03 W / m. K, preferably 25 mW / m. Thermal conductivity of less than K, and the top surface of the block is -160 ° C., when the foam block is ready for use and the tank containing the foam block contains LNG, 20 mW. / M. It exhibits a thermal conductivity of less than K.

Other advantageous features of the invention are briefly presented below.

Preferably, the density of the fiber-reinforced foam block is 50 to 250 kg / m ³ , and preferably 90 to 210 kg / m ³ . For foam blocks used in self-supporting type (types B, C) or semi-self-supporting type (type A) tanks, the density range of the fiber reinforced foam block is preferably in the range of 30 to 90 kg / m ³ . Note that in the case of membranes, a more preferred density range is 90-210 kg / m ³ .

Advantageously, the increase in fiber density relative to the total weight of the fiber reinforced polyurethane / polyisocyanurate foam is 0.05% by weight to 1.5% by weight, preferably 1.5% by weight, per centimeter. It corresponds to an increase gradient of 0.2% by weight to 1.2% by weight in% by weight of the fiber per centimeter. These density values should be understood as meaning mean values over the entire block.

Advantageously, at least 60%, preferably at least 80% of the cells that store the gas having a low thermal conductivity advantageously are on the axis of the thickness E of the fiber reinforced polyurethane / polyisocyanurate foam block. It exhibits a stretched or stretched shape along parallel axes.

Preferably, the fiber is made of glass fiber or hemp fiber, preferably made of glass fiber.

Preferably, the fiber is a long continuous fiber.

The expression "fibers are long and continuous" (or "long and continuous fibers") means that the fibers, or, if appropriate, aggregates of aggregates of fibers (fibers that are bonded or fixed to each other), or alone. As implying the fact that at least 90% of the fibers by the total weight of the fibers, whether agglomerates forming the equivalent of a single fiber, exhibit a length of at least 5 centimeters (cm). Understood.

Preferably, the average fiber density T _f is 2% to 25%, preferably 4% to 15%.

Preferably, the foam block according to the invention is provided in the form of a parallelepiped or cube.

This foam block, which exhibits the shape of a parallelepiped or cube, may exhibit one or more local protrusions such as consecutive anchors, even though it can be described as the shape of a parallelepiped or cube, or vice versa. It is clearly understood that the can be hollow or hollow.

According to a preferred embodiment of the present invention, the fiber density in the low range is 2% by weight to 6% by weight of the fiber, and the fiber density in the high range is 12% by weight to 25% by weight of the fiber. Is.

Advantageously, the lower surface and / or the upper surface of the block, preferably the upper surface, engages the engaging means (not shown in the accompanying drawings) of the insulating body to secure the foam block to the body. It exhibits a possible anchor, preferably the anchor is made of a material different from the foam or fiber.

These anchors are advantageously metal elements that exhibit, for example, an L-shaped mounting lug for engaging with the element or component of the insulating body that encloses or houses the fiber reinforced foam block (these anchors are). , Plastics / polymers, or composites of one or more polymers combined with ceramic and / or metallic materials). This part of the insulation body, in the case of a membrane tank, may consist of, for example, a stainless steel or a metal membrane for sealing a manganese-based container, or a type A, B or C self-supporting type. Alternatively, in the case of a semi-self-supporting tank, it may consist of a vapor barrier (which has the technical function of ensuring a seal to the ambient environment outside the tank). In one possibility provided by the present invention, this element or part of the insulation body (in the membrane tank) is an anchor for mechanically maintaining or retaining the fiber reinforced foam block to other insulation body elements. It presents a notch or analog intended to allow engagement with a portion. Of course, these anchors may also have the function of fixing the foam block to the hull in the case of membrane tanks and the function of fixing to the self-supporting structure in the case of type A, B or C self-supporting tanks. It is understood that these anchors are located on the underside of the foam block.

In the context of the present invention, these anchors are at least partially inserted into the fiber reinforced material constituting the lower or upper layer of the fiber reinforced laminate. The anchors are placed on the surface, but the anchors do not protrude from the surface after the foam block is prepared / completed.

Advantageously, in the context of the present invention, these anchors are present only on the top surface of the fiber reinforced foam block, as the anchors are tightly attached to the fiber reinforced foam block due to the high fiber density.

Advantageously, the fiber-reinforced foam block according to the present invention is an organic phosphorus flame retardant in a proportion of 0.1% by weight to 5% by weight, preferably triethyl phosphate (TEP), tris (2-chloroisopropyl). 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 system. Flame retardants, preferably containing red phosphorus, expansive graphite, aluminum oxide hydrate, antimony trioxide, arsenide oxide, ammonium polyphosphate, calcium sulfate or cyanuric acid derivatives, or mixtures thereof.

Further, the present invention
-At least one having at least one closed metal membrane composed of a plurality of metal plates or metal plates capable of providing corrugation and a heat insulating body having at least one heat insulating barrier adjacent to the membrane. A tank built into a support structure with a closed insulation tank, or
-A, B or C type tanks, as defined by the IGC Code, with at least one insulation body.
Concerning a closed insulation tank consisting of.

The tank according to the present invention is characterized in that the heat insulating body comprises a plurality of fiber reinforced polyurethane / polyisocyanurate foam blocks briefly described above.

The expression "IGC code" is understood to mean "international rules on ship structures and equipment for the loading and transport of liquefied gas" that are well known to those of skill in the art, such as the Type B and C tanks mentioned above. To.

In particular, in the IGC Code, the use of the expression "membrane tank" instead of "integrated tank" refers to the same category of tanks specifically equipped for tankers that transport and / or store at least partially liquefied gas. It should be noted that it can be done. The "membrane tank" is incorporated into the support structure, although the type A, B or C tanks are referred to as self-supporting or semi-self-supporting (particularly type A).

The tank comprises a number of fiber reinforced polyurethane / polyisocyanurate foam blocks obtained directly from the preparation process described above.

Finally, the present invention is a vessel for transporting a low temperature liquid product comprising at least one hull and one hermetically sealed tank as briefly described above, wherein the tank is A as defined by the IGC Code. , B or C type tanks, the tank also relates to a vessel placed on or mounted on the hull.

Advantageously, if the tank consists of a tank (membrane tank) built into the support structure, such a vessel comprises at least one sealed insulation tank as described above. The tank comprises two consecutive closed barriers. One is a primary barrier that contacts the product contained in the tank and the other is a secondary barrier that is located between the primary barrier and the support structure and is preferably formed from a portion of the ship's wall. be. These two closed barriers are alternated with the two adiabatic barriers, or a single adiabatic barrier is placed between the primary barrier and the support structure.

Such tanks have traditionally been according to the International Maritime Organization (IMO) code, eg, Type NO 96®, NO 96L03®, NO 96L03 + or NO 96, or Mark III®. It is designated as a Type NO tank containing Mark III® Flex or Flex +, preferably an integrated tank which is a Type NO tank.

Preferably, the tank, referred to as membrane type or type A, B or C, contains liquefied natural gas (LNG) or liquefied gas (LG).

The present invention is also a transfer system for low temperature liquid products, the above-mentioned ship and a heat insulating pipe arranged so as to connect the tank installed on the hull of the ship to a floating or land storage unit. The present invention relates to a transfer system including a pump for driving a flow of a low temperature liquid product from the floating or land storage unit to the ship or from the ship to the floating or land storage unit through the heat insulating pipe.

The present invention also relates to the above-mentioned ship loading and unloading process in which a low temperature liquid product is transported from the floating or land storage unit to the ship or from the ship to the floating or land storage unit via a heat insulating tube. ..

Further, the present invention is a process of a fiber-reinforced polyurethane / polyisocyanurate foam block of a heat insulating body of a closed heat insulating tank, which is simply defined above.
a) A step of mixing the chemical components required to obtain a polyurethane / polyisocyanurate foam, wherein the components are a reactant for obtaining polyurethane / polyisocyanurate and selectively at least one reaction catalyst. And a step comprising selectively at least one emulsifier and at least one foaming agent.
b) In the step of impregnating a plurality of fiber reinforcing materials by the flow of the mixture of the chemical components due to gravity, the fiber reinforcing materials are arranged in the stacked layers and exhibit a variable density, and the upper reinforcing layer is formed. A step of having a fiber density at least equal to the fiber density of the lower reinforcing layer, wherein the fiber reinforcing material extends essentially along a direction perpendicular to the direction of the flow due to gravity.
c) A step of forming and expanding the fiber-reinforced polyurethane / polyisocyanurate foam.
The expansion of the fiber reinforced polyurethane / polyisocyanurate foam is free, i.e., a process that is not constrained by the volume of the closed section, or
The expansion of the fiber reinforced polyurethane / polyisocyanurate foam is physically constrained by the walls of the double band laminator, preferably the distance between the laterally arranged walls is equal to L and horizontally. A double band laminator that forms a tunnel with a rectangular cross section in which the distance between the arranged walls is equal to E and surrounds the fiber reinforced foam that expands to obtain the fiber reinforced polyurethane / polyisocyanurate foam block. The process of being physically constrained by the wall,
The present invention relates to a process for preparing a fiber-reinforced polyurethane / polyisocyanurate foam block.

The expression "cream time" is measured from the mixing of chemical components (a), and the chemical components initiate a polymerization reaction, resulting in the expansion and cross-linking steps (c) (= fibers) of the mixture of components. It is understood to mean the time required to initiate the formation of the reinforced PUR / PIR foam). This cream time is well known to those skilled in the art. In other words, the cream time is the elapsed time from mixing the chemical components at room temperature until the mixture turns white due to the action of nucleation of bubbles (cells storing gas) and expansion of foam. Cream time is measured visually or using an ultrasonic sensor that detects changes in thickness that reflect foam formation.

The expression "the fiber reinforcements extend essentially along the direction perpendicular to the direction of the flow of the mixture of chemical components due to gravity" means that these fiber reinforcements have the above components in the impregnation step (b). It is understood to mean the fact (a) that it is provided in the form of a layer of small thickness extending along a plane perpendicular to the flow direction of the mixture of. Therefore, as shown in FIG. 1, a plurality of fiber reinforcing materials exhibiting a width L, in which the fiber reinforcing materials arranged in the stacked layers are pulled in the longitudinal direction I, are pulled by the gravity of the mixture of chemical components. A mixture of chemical components deposits on the fiber reinforcement from the distributor that allows / allows flow. In other words, the mixture of chemical components is selectively pressured to flow out of the distributor and at least under the influence of its own weight to fall into the laminated fiber layers, whereby these fiber reinforcements are released from the upper layer. It is impregnated to the lower layer.

Of course, if the foam block according to the invention is prepared by expansion called free, the block is subsequently cut at least on the open surface, conventionally the upper surface, which allows for said free expansion, and finally the invention. And obtain a shape that is conventionally a parallelepiped.

In the compositions according to the invention, the use of chemical foaming agents can be combined with the use of physical foaming agents. In this case, the physical foaming agent is preferably mixed with the foamable (co) polymer composition in a liquid or supercritical state and then converted to a gas phase during the expansion step of the PUR / PIR foam.

Chemical and physical foaming agents are well known to those of skill in the art, who will select all in appropriate amounts, depending on the PUR / PIR foam to be obtained.

The term polyol is understood to mean any carbon-based structure with at least two OH groups.

Since PUR, PIR and PUR-PIR foams are obtained according to the isocyanate / polyol ratio, PUR, PIR or PUR-PIR foams are obtained according to this ratio. The ratio of the polyol component to the isocyanate component is
When it is -1: 1 to 1: 1.3, a polyurethane PUR foam is obtained, and
When the ratio is -1: 1.3 to 1: 1.8, a polyurethane-polyisocyanurate PUR-PIR foam is obtained, and a polyurethane-polyisocyanurate PUR-PIR foam is obtained.
When it is -1: 1.8 to 1: 2.8, a polyisocyanurate PIR foam is obtained.

Polyisocyanates suitable for the formation of PUR, PIR and PUR-PIR foams are known to those of skill in the art, such as aromatic, aliphatic, cycloaliphatic and arylaliphatic polyisocyanates and mixtures thereof, advantageously. Contains aromatic polyisocyanates.

Examples of suitable polyisocyanates within the scope of the present invention are the 4,4'-, 2,4'-and 2,2'-isomers of diphenylmethane diisocyanate (MDI), obtained from the polymerization of these isomers. Includes compounds, aromatic isocyanates such as toluene 2,4- and 2,6-diisocyanates (TDI), m- and p-phenylenediisocyanates, and naphthalene 1,5-diisocyanates. Adipose, cycloaliphatic or arylaliphatic isocyanates such as 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 4,1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI). , 4,4'-Dicyclohexylmethane diisocyanate (H12MDI), 1,4-cyclohexane diisocyanate (CHDI), bis (isophorone methyl) cyclohexane (H6XDI, DDI), tetramethylxylylene diisocyanate (TMXDI) and other isocyanates are used. be able to. It is also possible to use any mixture of these diisocyanates. Advantageously, the polyisocyanate is the 4,4'-, 2,4'-and 2,2'-isomers of diphenylmethane diisocyanate (MDI).

Generally, during the formation of PUR, PIR or PUR-PIR foams, a mixture of polyols, polyisocyanates and foaming agents may contain tertiary amines such as N, N-dimethylcyclohexylamine and N, N-dimethylbenzylamine. Alternatively, it is known to add a reaction catalyst selected from organic metal compounds such as bismuth, potassium and tin.

According to a preferred embodiment of the present invention, advantageously, the positioning of the tunnel wall of the double band laminator (DBL) is fiber reinforced polyurethane / polyisocyanurate due to restrictions on the expansion of the fiber reinforced polyurethane / polyisocyanurate foam. The volume of the foam is 85% to 99% of the expansion volume of the same fiber reinforced polyurethane / polyisocyanurate foam in the case of free expansion without the limitation of the wall of such a double band laminator at the outlet of the double band laminator. %, preferably 90% to 99%. In this case, a foam in which the egg-shaped cells are preferably oriented along the axis E is obtained. As a result, in addition to the above-mentioned characteristics in the plane perpendicular to the above-mentioned axis E, the advantageous property of crush resistance along the axis E (measured based on the ISO 844 standard) is obtained. Tests and experiments have been conducted by Applicants to determine the broad and suitable scope described above, but are not presented here for clarity and brevity.

By setting the constraint on the expansion of the fiber-reinforced PUR / PIR foam in the DBL as a specific parameter as described above, at least 60% of the cells storing the gas having low thermal conductivity, usually more than 80%, and further. Provides a fiber reinforced PUR / PIR foam block in which more than 90% of the cells extend longitudinally along an axis parallel to the axis of the foam block thickness E, while the properties and chemical composition of the fiber reinforced material. In addition to the specific choices related to the viscosity of the mixture, a contribution to the perfect homogeneity of the fiber reinforced foam block is obtained. Due to these two properties, the cell orientation and the fiber content T _f in the block being homogeneous at the considered level of block thickness, excellent mechanical properties (compressive strength) along thickness E, And it is possible to obtain a fiber reinforced foam block exhibiting excellent mechanical properties (tensile strength and low thermal shrinkage coefficient) in a plane perpendicular to the thickness direction.

The stretched or stretched shape can be defined by the stretched shape. That is, the stretched or stretched shape has one dimension, length, which is larger than the other dimensions (width and thickness).

According to another embodiment provided by the present invention, the fiber reinforced polyurethane / polyisocyanurate foam is free to expand, i.e., not constrained by the volume of the closed section.

In this example, unlike the embodiment of the preparation according to the present invention using DBL, the preparation of the fiber reinforced polyurethane / polyisocyanurate foam is different from the mold defining a finite volume, and the expansion of the fiber reinforced foam is at least. It is said to be "free expansion" as long as the swelling of the fiber reinforced foam is free on this side or this surface, as it is not constrained on one side or one surface of the expansion. Traditionally, free expansion is performed by omitting the "upper" cover and the sidewalls prevent the foam from overflowing over the sides. The foam naturally bulges upward beyond the upper edge of the sidewall.

Advantageously, following the step of free expansion of the fiber reinforced polyurethane / polyisocyanurate foam, the fiber reinforced foam is cut so as to obtain the fiber reinforced polyurethane / polyisocyanurate foam block described above.

According to one possibility provided by the present invention not shown in the accompanying drawings, immediately after the step of impregnating the fiber reinforcing material, the mixture of the component and at least the foaming agent impregnating the fiber is made from the above-mentioned mixture and the fiber. A pressure application system intended to apply pressure to the top surface of the aggregate (eg, may be a type of roller system called a "nip roll") is applied. While this pressure system allows smoothing of the top surface of the aggregate, the pressure exerted on the aggregate contributes to facilitating the impregnation of the fibers in the above-mentioned mixture. This pressure system can consist of single or double rollers. Their relative positions above the liquid assembly and, optionally below the foam support, are adjusted to force the liquid assembly to spread perfectly uniformly and uniformly. Thus, in this way, an equivalent amount of liquid aggregate is obtained at any position in the section defined by the distance between the two rollers or the upper roller and the conveyor band. In other words, the main purpose of this pressure system is to complement the liquid distributor by helping to make the liquid aggregate uniform in thickness / width prior to its expansion of the main part.

Preferably, the dynamic viscosity η of the component mixture is 30 mPa. s ~ 3000mPa. s, preferably 50 mPa. s-1500 mPa. s.

Advantageously, at least 60% of the cells that store the gas, which advantageously has low thermal conductivity, extend along an axis parallel to the axis of thickness E of the fiber reinforced polyurethane / polyisocyanurate foam block. It exhibits a stretched or stretched shape.

More advantageously, at least 80%, preferably at least 90% of the cells that store gas with low thermal conductivity are on the axis of thickness E of the fiber reinforced polyurethane / polyisocyanurate foam block. It exhibits a stretched or stretched shape along parallel axes.

Advantageously, the properties relating to the extended shape of the cell storing the gas with low thermal conductivity, and their content / proportion in the block according to the invention, are more specifically referred to as the implementation of the preparation process using DBL. It is clearly understood that it is intended for the situation, but is not limited to this scenario at all. This is such a preference for cells that store gas with an advantageous low thermal conductivity in the case of free expansion, more clearly in the absence of an upper wall / cover that limits the expansion of the fiber reinforced foam. This is because the orientation can be obtained.

Preferably, the fiber (fiber reinforcing material) is arranged over the entire width L, and the fiber impregnation step b) with a mixture of a component and a foaming agent for obtaining a fiber-reinforced polyurethane / polyisocyanurate foam is controlled. Simultaneously carried out over the entire width L via the formula liquid distributor.

The term "simultaneously" refers to the impregnation of different fiber reinforcements by allowing the liquid mixture (with the reactant and at least the foaming agent) to reach the fibers along this section at the same time over a section of width L. Is understood to mean the fact that, along the thickness (or height) of the foam block, sections of the same width start or are performed at the same time or at the same rate.

Advantageously, the foaming agent consists of a physical and / or a chemical foaming agent, preferably a combination of the two types.

Preferably, the physical foaming agent is an alkane having at least 4 carbon atoms and a cycloalkane, a dialkyl ether, an ester, a ketone, an acetal, a fluoroalkane having 1 to 8 carbon atoms, a fluoroolefin, and an alkyl chain. It is selected from tetraalkylsilanes having 1 to 3 carbon atoms, in particular tetramethylsilanes, or mixtures thereof.

Examples of compounds in this premise may be propane, n-butane, isobutane, cyclobutane, n-pentane, isopentane, cyclopentane, cyclohexane, dimethyl ether, methyl ethyl ether, methyl butyl ether, methyl formate, acetone, fluoroalkanes. .. As the fluoroalkane, one that does not destroy the ozone layer is selected, and examples thereof include trifluoropropane, 1,1,1,2-tetrafluoroethane, difluoroethane, and heptafluoropropane. Examples of fluoroolefins include 1-chloro-3,3,3-trifluoropropene and 1,1,1,4,4,4-hexafluorobutene (eg, HFO FEA1100 sold by DuPont). be.

According to a preferred embodiment of the invention, the physical effervescent agent selected is 1,1,1,3,3-pentafluoropropane or HFC-245fa (sold by Honeywell), 1,1,1,1. 3,3-Pentafluorobutane or 365mfc (eg Solkane® 365mfc sold by Solvay), 2,3,3,3-tetrafluoroprop-1-ene, 1,1,1,2, 3,3,3-Heptafluoropropane (internationally also called HFC-227ea, sold by DuPont, for example), 1,1,1,4,4,4-hexafluorobutene (eg, sold by DuPont). HFO FEA1100), trans-1-chloro-3,3,3-trifluoropropene (Solstice LBA-Honeywell), or mixtures thereof.

Advantageously, the chemical foaming agent consists of water.

Advantageously, in step a) of mixing the chemical components, the nucleation gas is introduced into at least one polyol compound, preferably under a pressure of 20-250 bar, using a static / dynamic mixer. The nucleation gas accounts for 0-50% by volume of the polyol, preferably 0.05-20% by volume of the polyol.

Preferably, in the step a) of mixing the chemical components, the temperature of each reaction product for obtaining the polyurethane / polyisocyanurate is 10 ° C. to 40 ° C., preferably 15 ° C. to 30 ° C.

Preferably, according to a preferred embodiment of the invention, the final mixing of the flow of polyol, isocyanate, and / or foaming agent is at low pressure (<20 bar) using a dynamic or static mixer. Alternatively, it is carried out with a high pressure (> 50 bar) mixing head.

According to one possibility provided by the present invention, in step a), an organic phosphorus-based flame retardant, preferably triethyl phosphate (TEP), tris (2-chloroisopropyl) phosphate (TCPP), may be added to the mixture. Tris (1,3-dichloroisopropyl) (TDCP), Tris (2-chloroethyl) phosphate or Tris (2,3-dibromopropyl) phosphate, or mixtures thereof, or inorganic flame retardants, especially red phosphorus. , Inorganic flame retardants such as expansive graphite, aluminum oxide hydrate, antimony trioxide, arsenide oxide, ammonium polyphosphate, calcium sulfate, cyanuric acid derivatives, or mixtures thereof.

Further, as the flame retardant, diethylethanephosphonate (DEEP), triethylphosphonate (TEP), dimethylpropylphosphonate (DMPP), and diphenylcrecilphosphonate (DPC) can also be used.

The flame retardant, when present in the compositions according to the invention, is found in an amount of 0.01% to 25% by weight of the PUR / PIR foam.

The following description is made without limitation of the present invention for the purpose of illustration only, with reference to the accompanying drawings.

FIG. 1 is a schematic view showing various steps in the process of preparing a fiber-reinforced PUR / PIR foam block according to the present invention. FIG. 2 is a schematic diagram of an embodiment of a controlled liquid distributor according to the present invention. FIG. 3 shows two sets of heat insulating panels fixed to each other forming a primary heat insulating space and a secondary heat insulating space for a tank, from a plurality of fiber-reinforced polyurethane / polyisocyanurate foam blocks according to the present invention. It is a schematic diagram of the formed heat insulating panel. FIG. 4 is a partial view of a foam block according to the present invention, in which a plurality of anchors are arranged so as to allow the foam block to be fixed or fixed during its preparation. FIG. 5 is a diagram showing an embodiment of an anchor that can be inserted into a foam block according to the present invention along a schematic cross section (in a partially cut-out view). FIG. 6 is a schematic view in which a tank of an LNG tanker and a part of a loading / unloading terminal for this tank are cut out, and two sets of heat insulating panels of the type shown in FIG. 3 are installed in the tank. figure.

Preferably, the preparation of the fiber-reinforced PUR / PIR according to the present invention is carried out in the presence of a catalyst capable of promoting the isocyanate / polyol reaction. Such compounds are described, for example, in a prior art document entitled "Kunstoffhandbuch, Volume 7, Polyurethane", 3rd Edition, 1993, Chapter 3.4.1, published by Carl Hanser Verlag. .. These compounds are composed of amine-based catalysts and catalysts based on organic compounds.

Preferably, the preparation of the fiber reinforced PUR / PIR foam block according to the present invention is in the presence of one or more stabilizers intended to promote the formation of regular cell structures during foam formation. Will be implemented. These compounds are well known to those of skill in the art and include, for example, silicones such as siloxane-oxyalkylene copolymers and foam stabilizers composed of other organic polysiloxanes.

Those skilled in the art will know the amount of stabilizer from 0.5% by weight to 4% by weight of the PUR / PIR foam, depending on the expected reactants.

According to one possibility provided by the present invention, in step a) of the preparation process, the mixture of chemical components is a plasticizer of a carboxylic acid having a monovalent alcohol, such as a polybasic ester, preferably dibasic. It may contain esters or may consist of polymeric plasticizers such as adipic acid, sebacic acid and / or phthalic acid polyesters. Those skilled in the art are known to conventionally assume an amount of 0.05% to 7.5% by weight of the plasticizer of the polyurethane / polyisocyanurate foam, depending on the reactant used. ..

Organic and / or inorganic fillers, especially fortifying fillers, can be a mixture of chemical components such as siliceous minerals, metal oxides (eg, kaolin, titanium or iron oxides) and / or metal salts. is assumed. When such a filler is present in the mixture, its amount is conventionally 0.5% to 15% by weight of the PUR / PIR foam.

The present invention is intended to add technical teaching to the formation of PUR / PIR foams, both in terms of the properties of the essential chemical components and in terms of any functional agent and its respective amounts. Please note that there is no such thing. Those skilled in the art know how to obtain different types of fiber reinforced PUR / PIR foams, and the preparations of the present invention are the properties of the fiber reinforced materials, specifically the fiber densities in different fiber reinforced materials. The specific selection of the foam and the same degree of specific selection of the foam for impregnation of the reinforcing material will be described as a starting point.

Therefore, what the present invention is primarily aimed at herein is not the novel chemical preparation of fiber reinforced PUR / PIR foams, but rather the novel with a special fiber gradient along the thickness or height of the block. Fiber reinforced PUR / PIR foam block. This fiber reinforced foam block has no slack (or minimal slack) and no deformation in the shape / structure of its entire parallelepiped.

Therefore, as shown in FIG. 1, the plurality of fiber reinforcing materials 10 are unwound and parallel to each other on the conveyor band 11 intended to carry these reinforcing materials 10 and the components forming the PUR / PIR foam. It is placed according to the proper arrangement. This is because the impregnation of the fiber reinforcing material 10 is carried out by gravity in the context of the present invention. That is, the mixture 12 of the chemical composition, the foaming agent, and any other functional agent used to obtain the PUR / PIR foam is transferred from the liquid distributor located above the fiber reinforced material 10 to the fiber 10. It is discharged directly.

Therefore, the above-mentioned mixture 12 is applied to all the layers of the fiber reinforcing material 10, and whether these are a plurality of mats or a plurality of cloths for the reinforcing material, the expansion start of the PUR / PIR foam is caused by the fiber reinforcing material. It is necessary to impregnate over the cream time _tc in a very homogeneous manner so that after all 10 is completely impregnated in the mixture 12 or at the earliest at that moment. By doing so, the complete specific distribution of the fibers 10 in the volume of the PUR / PIR foam block is achieved by adhering to the properties of the fiber reinforcement and PUR / PIR foam defined in accordance with the present invention. By achieving the expansion of the PUR / PIR foam while maintaining it, the desired fiber density gradient can be obtained.

The subject matter of the present invention is achieved by arranging the fiber reinforced materials in parallel with each other, that is, in overlapping layers. Each of these reinforcing materials makes it possible to obtain a fiber density (weight of fiber relative to the weight of fiber-reinforced foam considering a predetermined volume), which is larger or smaller than that of others. Therefore, the upper fiber reinforcing material makes it possible to obtain a fiber density higher than the fiber density of the lower layer. More specifically, when all the fiber reinforcing materials are taken into consideration, the upper fiber reinforcing material exhibits a density at least equal to that of the lower fiber reinforcing material. Also, when considering all fiber reinforcements, the upper fiber reinforcement (at the top of the stacked layers) is more than the density of the lower fiber reinforcement (at the bottom of the layers). It exhibits a fiber density that is at least twice as high, and more preferably at least three times higher.

In the context of the definition of the invention that local fiber density is exhibited within the fiber reinforced foam block, the fiber density in the upper half of the block is 10% to 35% by weight of the fiber, preferably 10. 01% to 25% by weight, and in the lower half of the PUR / PIR foam block, defined as 1% to 9.99% by weight of the fiber, preferably 6% to 9.9% by weight of the fiber. It will also be.

According to another aspect of the invention, the positive gradient of fiber density (in terms of the weight of the foam block) in the block is from its lower surface towards its upper surface at (+)% by weight of fiber per centimeter. ) 0.1% by weight to (+) 2% by weight, preferably 0.05% by weight to 1.5% by weight per centimeter, more preferably per centimeter of fiber It will be established in the range of 0.2% by weight to 1.2% by weight in weight%. Of course, this is the average gradient calculated for the height or thickness of the fiber reinforced foam block.

In the context of the present invention, cream times of the components of the mixture 12 for forming PUR / PIR foams are known to those of skill in the art and are selected as follows. The conveyor band 11 transports the aggregate formed from the mixture 12 of the components, the foaming agent and the fibers 10 to, for example, a double band laminator not shown in the accompanying drawings immediately after the expansion of the foam begins, in other words. , PUR / PIR foam expansion is then selected to end with a double band laminator.

In such an embodiment with a double band laminator (DBL), a pressure system using one or two rollers is used before the double band laminator, i.e. with the fiber impregnation region of the mixture and the double band laminator. Are selectively placed between. When using a DBL, the expansion of the foam volume is 30% to 60% of the expansion volume of the same foam when the expansion is free, i.e., without any restrictions. It is carried out by the laminator when it reaches%. By doing so, the double band laminator, in other words, when the expansion of the PUR / PIR foam, in its second expansion phase, almost reaches or relatively near its maximum expansion. The expansion can be suppressed when the foam is in close proximity to all the walls forming the tunnel of rectangular or square cross section of the double band laminator. According to another method presenting a particular choice of preparation according to the invention, the gel point of the mixture of components, i.e., the moment at least 60% of the polymerization of the mixture of components is reached, in other words 70 of the maximum volume expansion of the mixture. The moment of reaching% -80% inevitably occurs within the double band laminator, optionally in the latter half of the length of the double band laminator (ie, closer to the exit than the inlet of the laminator).

Regarding the function of simultaneously discharging the mixture 12 of the chemical component and the foaming agent over the entire width L of the fiber reinforcing material 10, it is provided by the controlled distributor 15 shown in FIG. Such a distributor 15 comprises a supply channel 16 for an aggregate formed from a mixture 12 of a chemical component from a container forming a reactant mixer (not shown in the accompanying drawings) and at least a foaming agent. In the vessel forming the reactant mixer, on the one hand all the chemical components and the foaming agent are mixed, and on the other hand nucleation and further heating of such a mixture is carried out. The liquid aggregate formed from the mixture 12 of the chemical component and the foaming agent then, under pressure, has two identical distribution plates 18 extending along the width L, each of which is substantially equal in length to L / 2. The mixture 12 is distributed to the ends of two laterally extending channels 17 in a distribution plate 18 provided with a plurality of nozzles 19 for allowing the mixture 12 to flow over the fiber reinforcement 10. These flow nozzles 19 consist of an orifice with a calibration cross section exhibiting a predetermined length. Therefore, the length of these nozzles 19 is predetermined so that the liquid flows out at the same flow rate among all the nozzles 19. The purpose of this is to ensure that the impregnation of the fiber reinforced plastic 10 occurs at the same time, i.e. at the same time, across the sections of width L of the fiber reinforced plastic 10 and that the surface densities of the liquids deposited at right angles at each nozzle are equal. Is. By doing so, when considering the section of the width L of the fiber 10, the fibers are impregnated at the same time, so that the impregnation of the layer of the fiber 10 with the mixture 12 is carried out in the same manner at all points of the section. Will be done. This is the outlet of the double band laminator, where the local density of the fibers corresponds exactly to the density of the fibers in each layer of the fiber reinforced plastic at the moment of gravity flow of the mixture 12. Contributes to obtaining the block of.

The controlled liquid distributor 15 shown in FIG. 2 is an exemplary embodiment in which two identical distribution plates 18 are used, as long as the function of simultaneously distributing the liquid onto the width section of the fiber 10 is available. Other designs can be envisioned. Of course, the main technical feature utilized in this example is that it can be lengthened or shortened depending on the route or course of the liquid mixture 12 from the supply duct 16 of the distributor 15 to the assumed flow nozzle 19. There is a difference in the length of the flow nozzle 19.

One of the important points for achieving good impregnation of the fiber reinforcement 10 just before the cream time T _c of the PUR / PIR foam is related to the specific properties of the various fiber reinforcements (chemical composition and foaming). A selection of viscosities of a particular liquid (consisting of a mixture 12 with an agent) that can vary depending on the fiber density. The selected viscosity range and the permeation properties of the fiber reinforced material penetrate well into the first layer of the fiber 10 and the last layer (the lower layer of the fiber 10, i.e. the lowest layer in the fiber reinforced laminated body). ) Must be able to reach subsequent layers. Thereby, the impregnation time ti of the fiber 10 is realized within the time given by the chemical _{composition which substantially corresponds to the cream time t c but} is often shorter than this. The viscosity of the component mixture 12 is such that the impregnation of all fibers 10 over the section of width L by the mixture 12 of the chemical component and the foaming agent is just before the cream time, in other words, the start of expansion of the PUR / PIR foam. It is selected, for example, by heating, adding a plasticizer, and / or some nucleation, as obtained before or shortly thereafter.

Since fiber reinforced foam blocks are intended for use in very specific environments, certain mechanical and thermal properties must be guaranteed. The fiber-reinforced foam block obtained by the preparation according to the present invention conventionally forms a part of the heat insulating body 30. That is, in the example used in FIG. 3, the upper or primary panel 31 and / or the lower or secondary panel 32 of the heat insulating body 30 of the tank 71 intended to receive an ultra-low temperature liquid such as LNG or LPG is formed. do. Such a tank 71 may be, for example, a ground tank, a floating barge or the like (eg, FSRU "Floating Storage Regasification Unit" or FLNG "Floating Liquid Natural Gas"), or an LNG transporting this energy liquid between two ports. It can be installed on ships such as tankers.

The foam block according to the present invention shown in FIG. 4 includes a plurality of anchors 40 dispersedly arranged on various surfaces of the upper surface 41 and the side surfaces 42 and 43 thereof. These anchors 40 are arranged flush with the surfaces of the surfaces 41, 42, 43 of the foam block and do not exhibit their thickness (or not large thickness) covering the foam. / Or do not protect the foam from the outside.

FIG. 5 shows such an anchor 40 in a partially cut-out view. The anchor 40 exhibits a plate 44 extending along a plane. The plate 44 comprises a plurality of orifices 45. Two orifices 45 allow the foam block to be secured to the insulating body of the tank when engaged with mechanical anchoring means, in other words, elements of the insulating body (not shown in the accompanying drawings). It consists of one of the elements. Further, the plate 44 includes a plurality of identical fixed studs 46, as well as a central fixed stud 47 having a dimension larger than that of the fixed stud 46. The function of these studs 46, 47 is to secure the anchor 40 to the fiber reinforced foam block according to the present invention as well as possible. The fixed stud 46 is ideally arranged in the circumferential direction so as to form a circle on the outer circumference or the vicinity of the peripheral edge of the anchor 40.

The anchor 40 shown in FIG. 5 is advantageously mounted on the conveyor band 11, then the studs 46, 47 are directed upwards, and the plate 44 rests on the band 11.

However, as on the block shown in FIG. 4, it can be assumed that these anchors 40 are arranged on the upper surface 41 of the block and further on the side surfaces 42 and 43. In the latter case, it can be advantageously envisioned that the studs 46, 47 are at least slightly embedded in adjacent / continuous fiber mats prior to their impregnation with the polymer foam.

Of course, one of the orifices 45 of the anchor 40 can be used as is to form the female portion of the anchor, but anchors that require the use of a plurality of orifices 45 can also be envisioned. Further, although these orifices 45 consist of anchor solutions, the invention is by no means limited to this embodiment, and one or more anchors 40 with different shapes and different mechanical properties can be envisioned.

Referring to FIG. 6, a partially cut-out view of the LNG tanker shows a closed insulation tank 71, which is mounted on the double hull 72 of a ship and has an overall prismatic shape. The walls of the tank 71 are a primary closed barrier intended to come into contact with the LNG contained in the tank, a secondary closed barrier placed between the primary closed barrier and the ship's double hull 72, and the primary. It comprises two insulating barriers, respectively, located between the closed barrier and the secondary closed barrier and between the secondary closed barrier and the double hull 72.

A loading and unloading pipe 73 located on the upper deck of a ship can be connected to the cargo terminal or landing terminal by a suitable connector so as to transfer LNG cargo from or to the tank 71 in a known manner. ..

FIG. 6 shows an example of a cargo terminal equipped with a loading / unloading station 75, an underwater pipeline 76, and land equipment 77. The loading / unloading station 75 is a fixed offshore facility including a movable arm 74 and a tower 78 that supports the movable arm 74. The movable arm 74 supports a bundle of adiabatic flexible hoses 79 that can be connected to the loading and unloading pipe 73. The swivel movable arm 74 is compatible with LNG tankers of all sizes. A connecting pipeline (not shown) extends inside the tower 78. The loading / unloading station 75 allows the LNG tanker 70 to load and unload from the land equipment 77 and to unload the land equipment 77. The facility comprises a liquefied gas storage tank 80 and a connecting pipeline 81 connected to the loading and unloading station 75 via a submersible pipeline 76. The underwater pipeline 76 allows the liquefied gas to be transferred between the loading and unloading station 75 and the onshore equipment 77 over a long distance, for example over 5 km. This allows the LNG tanker 70 to be maintained at a distance from the coast during loading and unloading operations.

Pumps mounted on the vessel 70 and / or on land equipment 77 and / or pumps on the loading and unloading station 75 are used to generate the pressure required to transfer the liquefied gas. ..

As mentioned above, the subject matter of the invention, i.e., the use or utilization of fiber reinforced polyurethane / polyisocyanurate foam blocks, is not intended to be limited to integrated tanks in support structures and is valid at the time of filing of this patent. IGC Code Type B and C tanks, as well as future versions of this Code, will be provided unless significant changes apply to Type B and C tanks. Furthermore, it is understood that, under the assumption of IGC code changes, other types of tanks may be potential applications for fiber reinforced PUR / PIR foam blocks according to the present invention.

The following introduces some of the experiments and tests performed by the Applicant to evaluate the subject matter and scope of the invention, but other tests / experiments have also been performed and will be provided later as needed / required. It is also expected to be done.

In order to demonstrate the present invention, a polyurethane foam composition incorporating mat-like fibers is used. These fibers are always provided as long continuous fibers. More precisely, the length of these fibers is exactly the same in the composition according to the invention and the composition according to the prior art. Applicants have specifically tested the subject matter of the invention, which has fibers allegedly short (relative to the long, continuous fibers defined above), or the subject matter of the invention provided in the form of a cloth. The results obtained are comparable or substantially similar to those obtained using a mat consisting of long, continuous fibers, as shown below.

Therefore, to ensure only the combination of the fiber density of the fiber reinforced material with the selection of PUR foams that exhibit a very special cream time, or those suitable for identifying the fiber reinforced materials, PIR foams. Other parameters of the block preparation should not be changed or different between the preparation according to the invention and the preparation according to the prior art. As non-exclusive examples, if appropriate, nucleation, the amount of foaming agent, the reaction temperature, the nature and amount of the mixture of chemical components, the ejection process, the injection site of the mixture of chemical components and DBL or free expansion are possible. It can be mentioned the fact that the distance to the device is exactly the same in the case according to the invention and in the case according to the prior art.

Of course, in this example, the present invention will be described using PUR foam for clarity and completeness, but equivalent or substantially similar results can be obtained with PIR foam and PUR / PIR mixture. ing.

Similarly, the free expansion technique is used in the preparation of the fiber reinforced foams shown below, but from the viewpoint of the fiber reinforced foam according to the present invention and the fiber reinforced foam according to the prior art, the applicant is equivalent or It shows that substantially similar results were obtained using DBL.

Furthermore, it is understood that all compositions tested in succession will be examined under the same density conditions. It is understood that this density parameter is involved in the evaluation of performance quality in compressive strength.

The characteristics of the fiber reinforced material and the PUR foam for the composition of the prior art are as follows.

The characteristics of the fiber reinforced material and the PUR foam for the composition of the prior art are as follows.

The cream thyme of the PUR foam used above is the same in all cases where the foam used is considered, so it should be logically the same for the composition according to the prior art and the composition according to the invention. Please note.

After performing the test, some results are simplified below to illustrate the applicant's findings when the fiber reinforcement is provided in the form of at least one mat made of glass fiber.

It should be noted that the first composition in Table 3 (having 8 layers of U809 or U801 for a block having a thickness of 180 mm) consists of the composition according to document FR 2882 756. The results for such compositions according to the document are significantly inferior to the results obtained for the compositions according to the invention (final compositions in Table 3).

As can be seen from the results shown in the above table, the fiber-reinforced foam according to the present invention is very much based on the results of the fiber-reinforced foam according to the prior art with respect to the three criteria considered in the comparison of the obtained fiber-reinforced foams. Remarkably good results are obtained.

Furthermore, it should be noted that the fiber reinforced PUR / PIR foams according to the invention do not exhibit a significant decrease in properties with respect to (very low) thermal conductivity. Therefore, as an example, the following thermal conductivity values can be obtained for the fiber-reinforced foam according to the present invention, which exhibits a fiber density gradient of 1% by weight per cm (from the lower surface to the upper surface of the fiber-reinforced foam block).

Although the present invention has been described in the context of some specific embodiments, the invention is by no means limited to these, and technical equivalents of the described means, and combinations thereof, are within the scope of the invention. In some cases, it is quite clear that they are all included.

The use of the verb "prepare" or "contains" and its conjugations does not preclude the existence of other elements or steps other than those described in the claims.

In the claims, the reference numerals in parentheses should not be construed as limiting the scope of the claims.

Claims (15)

It is a fiber-reinforced polyurethane / polyisocyanurate foam block of the heat insulating body (30) of the sealed heat insulating tank, and the density of the fiber-reinforced foam block is 30 to 300 kg / m ³ , and the fiber-reinforced polyurethane / polyisocyanurate is used. The foam block exhibits an average fiber density _Tf of 1% to 60% by weight, preferably 2% to 30% of the fiber (10) and is at least 10 centimeters, preferably 10 to 500 centimeters. The fiber-reinforced polyurethane / polyisocyanurate foam block exhibits a width L and a thickness E from the lower surface to the upper surface of the block, which is at least 10 cm, preferably 10 to 100 cm. Is a fiber reinforced polyurethane / polyisocyanurate foam block composed of cells that advantageously store gas with low thermal conductivity.
The fiber density is from a low density range of 1% by weight to 9.99% by weight of the fiber (10) along the thickness E from the lower surface of the block to the upper surface (41) of the fiber (10). ) Increases to a high density range of 10% by weight to 35% by weight,
Fiber reinforced polyurethane / polyisocyanurate foam block. The density of the fiber-reinforced foam block is 50 to 250 kg / m ³ , preferably 90 to 210 kg / m ³ .
The fiber-reinforced polyurethane / polyisocyanurate foam block according to claim 1. The increase in fiber density relative to the total weight of the fiber reinforced polyurethane / polyisocyanurate foam is 0.05% to 1.5% by weight, preferably 1 cm in weight% of the fiber per centimeter. It corresponds to an increase gradient of 0.2% by weight to 1.2% by weight in the weight% of the fiber.
The fiber-reinforced polyurethane / polyisocyanurate foam block according to claim 1 or 2. Advantageously at least 60%, preferably at least 80% of the cells that store gas with low thermal conductivity are on an axis parallel to the axis of thickness E of the fiber reinforced polyurethane / polyisocyanurate foam block. Exhibits a stretched or stretched shape,
The fiber-reinforced polyurethane / polyisocyanurate foam block according to any one of claims 1 to 3. The fiber is made of glass fiber or hemp fiber, preferably glass fiber.
The fiber-reinforced polyurethane / polyisocyanurate foam block according to any one of claims 1 to 4. The fibers are long, continuous fibers.
The fiber-reinforced polyurethane / polyisocyanurate foam block according to any one of claims 1 to 5. The average fiber density T _f is 2% to 25%, preferably 4% to 15%.
The fiber-reinforced polyurethane / polyisocyanurate foam block according to any one of claims 1 to 6. The fiber density in the low range is 2% by weight to 6% by weight of the fiber (10), and the fiber density in the high range is 12% by weight to 25% by weight of the fiber (10).
The fiber-reinforced polyurethane / polyisocyanurate foam block according to any one of claims 1 to 7. The lower surface and / or the upper surface (41) of the block, preferably the upper surface (41), is engaged with the engaging means of the heat insulating body (30) so as to fix the foam block to the main body (30). It exhibits a compatible anchor (40), preferably the anchor (40) is composed of a material different from the foam or the fiber.
The fiber-reinforced polyurethane / polyisocyanurate foam block according to any one of claims 1 to 8. Organic phosphorus flame retardants, preferably triethyl phosphate (TEP), tris (2-chloroisopropyl) phosphate (TCPP), tris (1,3-dichloroisopropyl) in a proportion of 0.1% to 5% by weight. Phosphate (TDCP), tris (2-chloroethyl) phosphate or tris (2,3-dibromopropyl) phosphate, or mixtures thereof, or inorganic flame retardants-based flame retardants, preferably red phosphorus, expansive graphite, oxidation. Contains aluminum hydrate, antimony trioxide, arsenide oxide, ammonium polyphosphate, calcium sulfate or cyanuric acid derivatives, or mixtures thereof,
The fiber-reinforced polyurethane / polyisocyanurate foam block according to any one of claims 1 to 9. -At least one having at least one closed metal film composed of a plurality of metal plates or metal plates capable of having a corrugated portion and a heat insulating body (30) having at least one heat insulating barrier adjacent to the film. A tank built into a support structure with a closed insulation tank, or
-Type A, B or C tanks, as defined by the IGC Code, with at least one insulating body (30).
It is a closed insulation tank consisting of
The heat insulating body (30) comprises a plurality of fiber-reinforced polyurethane / polyisocyanurate foam blocks according to any one of claims 1 to 10.
Sealed insulation tank. A ship (70) for transporting a low temperature liquid product comprising at least one hull (72) and one hermetically sealed tank (71) according to claim 11, wherein the tank is the definition of the IGC code. In the case of a type A, B or C tank according to the above, the tank is a ship (70) arranged on the hull or mounted on the ship (70). A transfer system for cold liquid products, wherein the ship (70) according to claim 12 and the tank installed on the hull of the ship are arranged so as to be connected to a floating or land storage unit (77). Insulation pipes (73, 76, 79, 81) and the flow of cold liquid products are driven from the floating or land storage unit to the vessel or from the vessel to the floating or land storage unit through the insulation pipe. With a pump for, and equipped with a transfer system. The cryogenic liquid product is transported from the floating or land storage unit (77) to the vessel or from the vessel to the floating or land storage unit (77) via a heat insulating tube (73, 76, 79, 81). , The loading and unloading process of the vessel (70) according to claim 12. The process for preparing a fiber-reinforced polyurethane / polyisocyanurate foam block for a heat insulating body of a closed heat insulating tank according to any one of claims 1 to 10.
a) A step (12) of mixing the chemical components required to obtain a polyurethane / polyisocyanurate foam, wherein the components are selectively at least one with a reactant for obtaining the polyurethane / polyisocyanurate. A step comprising one reaction catalyst, optionally at least one emulsifier, and at least one foaming agent.
b) In the step of impregnating a plurality of fiber reinforcing materials (10) by the flow of the mixture (12) of the chemical components due to gravity, the fiber reinforcing materials are arranged in the stacked layers and have a variable density. The upper reinforcing layer has a fiber density at least equal to that of the lower reinforcing layer, and the fiber reinforcing material (10) is essentially along the direction perpendicular to the direction of the flow due to gravity. The process of extension and
c) A step of forming and expanding the fiber-reinforced polyurethane / polyisocyanurate foam.
The expansion of the fiber reinforced polyurethane / polyisocyanurate foam is free, i.e., a process that is not constrained by the volume of the closed section, or
The expansion of the fiber reinforced polyurethane / polyisocyanurate foam is physically constrained by the walls of the double band laminator, preferably the distance between the laterally arranged walls is equal to L and horizontally. A double band laminator that forms a tunnel with a rectangular cross section in which the distance between the arranged walls is equal to E and surrounds the fiber reinforced foam that expands to obtain the fiber reinforced polyurethane / polyisocyanurate foam block. The process that is physically constrained by the wall of
The process of preparing a fiber reinforced polyurethane / polyisocyanurate foam block.

Images