JP6755297B2 - How to manufacture profile elements - Google Patents

Description

The present invention is a composite element comprising a profile and an insulating core at least to some extent surrounded by the profile, wherein the insulating core is 13-30 mW as measured according to DIN12667. A composite element composed of an organic porous material having a thermal conductivity in the range of / m * K and a compressive strength of more than 0.20 N / mm ² measured according to DIN 53421, a method for producing this type of composite element. , And how to use this type of composite element for manufacturing windows, doors, refrigerators, and chest freezer, or for elements for facade construction.

Prior art provides a variety of proposals for optimizing the heat transfer properties of composite profiles, primarily with the integration of hollow chambers or foam-filled hollow chambers. To do. If foam is used, a difficult process must be used to insert the foam into the hollow chamber, or only a small portion of the total available space in the insulation element is the foam filling process. Manufacturing techniques for this type of insulation element are therefore often complex, as there is a problem with either being available for. Due to the increasingly stringent requirements recognized for the insulation properties of the profile, the individual chambers are much smaller and the walls are much smaller, with the resulting difficulties and costs associated with tooling and extrusion technology. It's getting thinner. Insulation materials and processing of composite elements are subject to even more stringent requirements to meet the increasingly stringent requirements for insulation in home construction.

DE2844006A1 is, for example, a method of extruding a plastic profile having a foamed plastic core surrounded on all sides by a plastic jacket, introducing a material for the jacket into an extruder die. A single operation is used to introduce the core material into the cavity of the jacket, which is molded at the same time, and the gas introduced into the cavity of the jacket during the foaming of the core material is the extruder die. Disclose how it is dissipated by.

WO99 / 16996A1 is a method of making frame profiles for windows or doors, in which the outer profile is first produced from a thermoplastic and then a polyurethane-based foamable mixture is introduced into the profile to foam the mixture. With the completion of, a method is disclosed in which a secure bond is created between the outer profile and the foam. The literature also discloses how the outer profile is first molded and then the prefabricated and prefabricated cores are inserted into the same.

DE19961306A1 also discloses a method of producing a profile via extrusion. This profile includes an outer shell and a foamed inner core. In this method, the outer profile shell is first extruded and then filled with an effervescent material.

DE1959464 is also a method of continuously extruding a jacket made of a thermoplastic material and a continuous profile having a foam core, wherein the jacket is first manufactured from the thermoplastic material by extrusion molding and then Discloses how this is filled with a foamable material.

EP2072 743A2 discloses a method of filling a hollow window frame or a hollow door frame with foam. For this reason, the plastic profile produced by extrusion is combined to obtain a finished window frame or finished door frame, which is then filled with foam by the introduction of a foamable material. ..

The prior art also discloses a method of making this type of profile with a foam core, eg, in DE2009003392U1 or WO02 / 090703A2, in which a pre-foamed insert is inserted into a profile made by extrusion. To do.

DE1020009037851A1 discloses insulation elements for insulation in profiles for window elements, door elements, and façade elements, profiles for window elements, door elements, and façade elements, and methods for manufacturing them.

EP2062717A1 is also a method of producing a plastic profile with a foam core in a coextrusion process in which the foamable material is coextruded into the cavity of the hollow plastic profile, especially in the solid state. Disclose the method of foaming.

However, the perceived requirements for insulation are even more stringent, and it is also necessary to use other insulating materials that have greater insulating effects. As an example, in the case of windows, there is no further room to increase the thickness of the profile, and in order to improve insulation, the thermal conductivity must be reduced without any change in thickness.

Therefore, the other insulating material used in the prior art, along with the polyurethane foam, is an organic airgel or xerogel with a good property profile for use as an insulating material. As an example, WO2012 / 059388A1 discloses aerogels and xerogels, and how they are used as insulating materials for aerogels and xerogels and in vacuum insulation panels. The specification is also a method of producing a porous material in the form of an airgel or xerogel, in which at least one polyfunctional isocyanate is reacted with an amine component containing at least one polyfunctional substituted aromatic amine. Disclose the method.

DE2844006A1 WO99 / 16996A1 DE19961306A1 DE1959464 EP2072 743A2 DE202009003392U1 WO02 / 090703A2 DE102009037851A1 EP2062717A1 WO2012 / 059388A1

The materials disclosed in that document have good thermal insulation properties. However, the manufacturing process produces sheet-like materials, and therefore it is not possible to use the processes known from the prior art for incorporation of profile elements in hollow chambers.

Therefore, starting from the prior art, an object of the present invention has been to provide elements, especially for window structures, which have good thermal insulation properties and can be manufactured using simple process techniques. ..

The present invention is a composite element comprising a profile and an insulating core at least to some extent surrounded by the profile, wherein the insulating core is in the range of 13-30 mW / m * K measured according to DIN12667. Achieved by a composite element characterized by being composed of an organic porous material having a thermal conductivity and a compressive strength of greater than 0.20 N / mm ² measured according to DIN 53421.

The composite elements of the present invention include a profile and an insulating core that is at least somewhat enclosed by the profile. For the purposes of the present invention, the profile is a solid structure with cutouts or hollow chambers extending along the profile. In the present invention, the location of the insulating core is within these notches or hollow chambers in the composite element. Thereby, the profile surrounds the insulating core, at least to some extent, preferably completely. Thereby, the adiabatic core extends along the profile.

In the present invention, the adiabatic core is composed of an organic porous material having a thermal conductivity in the range of 13 to 30 mW / m * K measured according to DIN 12667 and a compressive strength of more than 0.20 N / mm ² measured according to DIN 53421. Will be done.

Suitable materials are known in principle. As an example, organic xerogels or organic airgels have these properties.

Therefore, a preferred embodiment of the present invention is, as described above, a profile and a composite element comprising a heat insulating core surrounded by the profile at least to some extent, wherein the organic porous material is an organic xerogel and an organic airgel, and Provided is a composite material element which is one kind selected from the group consisting of two or more kinds of combinations thereof.

The composite elements of the present invention have surprisingly good thermal insulation properties. Due to the low thermal conductivity of the organic porous materials used, despite the low thickness specified by construction technology for insulation materials, they achieve good properties that meet increasingly stringent requirements for insulation. It is possible to do.

The composite elements of the present invention are particularly suitable for producing architectural elements (eg, windows and doors) that require a low U value (heat conduction coefficient).

Further, the composite material element of the present invention can be manufactured in ring units and at low cost.

The present invention is further a continuous method of producing a profile and a composite element comprising an insulating core at least to some extent surrounded by the profile, wherein the insulating core is measured according to DIN 12667 at 13-30 mW / m *. It is composed of an organic porous material having a thermal conductivity in the range of K and a compressive strength of more than 0.20 N / mm ² measured according to DIN 53421, characterized in that the profile is made around the adiabatic core. Provide a way to do it.

The organic porous material used in the present invention is in the range of 13-30 mW / m * K measured according to DIN12667, particularly in the range of 13.5-25 mW / m * K, more preferably 14-22 mW / m. It has a thermal conductivity in the range of * K, particularly preferably in the range of 14.5 to 20 mW / m * K.

As the organic porous material, it is particularly preferable in the present invention to use an organic airgel having a thermal conductivity in the range of 14 to 22 mW / m * K, particularly preferably in the range of 14.5 to 20 mW / m * K. ..

Organic porous material used in the present invention is also greater than the measured 0.20 N / mm ² according to DIN53421, in particular greater than 0.25 N / mm ^2, more preferably greater than 0.30 N / mm ^2, in particular It also preferably has a compressive strength of greater than 0.35 N / mm ² .

The high compressive strength of the material is an indicator of stiffness, allowing the material to be manufactured and stored, which facilitates processing during the manufacture of the composite element. Also, the material can have structural significance.

Standard rigid foams commonly used for insulation have, for example, a thermal conductivity in the range of 20-25 mW / m * K and a compressive strength of only about 0.15 N / mm ² . The compressive strength of that type of material can be increased by increasing the thickness, but there will be a concomitant increase in thermal conductivity and therefore a decrease in thermal insulation properties.

For the purposes of the present invention, the xerogel has a porosity of at least 70% by volume and a volume average pore size of up to 50 micrometer, and the liquid phase is below the critical temperature of the liquid phase and below the critical pressure (subcritical). It is a porous material produced by the sol-gel method, which is removed from the gel by drying under the conditions).

Correspondingly, for the purposes of the present invention, the airgel has a porosity of at least 70% by volume and a volume average pore size of up to 50 micrometer, and the temperature at which the liquid phase exceeds the critical temperature of the liquid phase. Moreover, it is a porous material produced by the sol-gel method, which is removed from the gel by drying at a pressure exceeding the critical pressure (supercritical conditions).

The average pore size is measured by means of mercury intrusion measurement according to DIN66133 and is, in principle, a volume average for the purposes of the present invention.

The volume average pore size of the porous material is preferably 20 micrometers at the maximum. The volume average pore size of the porous material is particularly preferably 10 micrometers at the maximum, 5 micrometers at the maximum, and 3 micrometers at the maximum.

From the standpoint of low thermal conductivity, high porosity and minimum pore size are desirable, but the manufacturing process specifies a substantial lower limit for volume average pore size. The volume average pore diameter is generally at least 50 nm, preferably 100 nm. In many examples, the volume average pore size is at least 200 nm, especially at least 300 nm.

Thereby, a preferred embodiment of the invention is a composite element comprising a profile and an insulating core at least to some extent surrounded by the profile, wherein the insulating core is measured according to DIN 12667 at 13-30 mW / m *. Selected from the group consisting of organic xerogels and organic airgels, and combinations of two or more thereof, having a thermal conductivity in the range of K and a compressive strength of more than 0.20 N / mm ² measured according to DIN 53421. Provided is a composite material element composed of one kind of organic porous material.

Preferred organic xerogels and airgels for the purposes of the present invention are described below.

The organic airgel or xerogel is preferably based on isocyanates and optionally other components that are reactive with isocyanates. By way of example, organic airgels or xerogels can be based on isocyanates, as well as OH-functional and / or NH-functional compounds.

In the present invention, as an example, an organic xerogel based on polyurethane, polyisocyanurate, or polyurea, or an organic airgel based on polyurethane, polyisocyanurate, or polyurea is preferable.

Thereby, a preferred embodiment of the present invention is, as described above, a profile and a composite element comprising an insulating core surrounded by the profile to at least some extent, wherein the organic porous material is polyurethane, polyisocyanurate. Alternatively, there is provided a composite element which is one selected from the group consisting of an organic xerogel based on polyurea, polyurethane, polyisocyanurate, or an organic airgel based on polyurea, and a combination thereof.

The organic airgel or xerogel is based on isocyanate and a component reactive with isocyanate, and it is particularly preferable that at least one polyfunctional aromatic amine is used as the component reactive with isocyanate. The organic xerogel or airgel is preferably based on polyurea and / or polyisocyanurate.

"Based on polyurea" means that at least 50 mol%, preferably at least 70 mol%, particularly at least 90 mol% of the bonds of the monomeric units in an organic xerogel or airgel take the form of urethane bonds. "Based on polyurea" means that at least 50 mol%, preferably at least 70 mol%, particularly at least 90 mol% of the bonds of the monomeric units in an organic xerogel or airgel take the form of urea bonds. By "based on polyisocyanurate" is meant that at least 50 mol%, preferably at least 70 mol%, particularly at least 90 mol% of the bonds of the monomeric units in an organic xerogel or airgel take the form of isocyanurate bonds. "Based on polyurea and / or polyisocyanurate" means that at least 50 mol%, preferably at least 70 mol%, particularly at least 90 mol% of the bond of the monomer unit in the organic xerogel or airgel is urea bond and / or isocyanurate. It means taking the form of a bond.

As used herein, the composite elements of the present invention also include various combinations of airgels and xerogels. For the purposes of the present invention, the composite element may also include multiple insulating cores. For the purposes of the present invention, the composite element can also include another insulating material, such as polyurethane, along with the organic porous material.

The term, organic porous material, is used below to refer to the organic airgel or xerogel used in the present invention.

The organic porous material used is the following steps:
(A) In the solvent, at least one polyfunctional isocyanate (a1) and at least one polyfunctional aromatic amine (a2), optionally in the presence of water as a component (a3), and optionally at least one. Reaction in the presence of the catalyst (a4),
(B) Removal of solvent to obtain airgel or xerogel,
It is preferable to obtain it by a method including.

The components (a1) to (a4) preferably used for the step (a), and their amount ratios, will be described below.

The term, component (a1) is used below for all polyfunctional isocyanates (a1). Correspondingly, the term, component (a2) is used below for all polyfunctional aromatic amines (a2). It will be apparent to those skilled in the art that the mentioned monomeric components are present in reactive form in the organic porous material.

For the purposes of the present invention, the functional value of a compound means the number of reactive groups per molecule. In the case of the monomer component (a1), the functional value is the number of isocyanate groups per molecule. In the case of the amino group of the monomer component (a2), the functional value is the number of reactive amino groups per molecule. As used herein, polyfunctional compounds have at least two functional values.

When a mixture of compounds with different functional values is used as component (a1) or (a2), the functional value of the component is in each case obtained from the number average of the functional values of the individual compounds. The polyfunctional compound contains at least two of the above functional groups per molecule.

Ingredient (a1)
It is preferable to use at least one polyfunctional isocyanate as the component (a1).

For the purposes of the method of the invention, the amount of component (a1) used is, in each case, the total mass (100% by weight) of component (a1), (a2), and applicable (a3). It is preferably at least 20% by mass, particularly at least 30% by mass, particularly preferably at least 40% by mass, extremely particularly preferably at least 55% by mass, and particularly at least 68% by mass. Further, for the purpose of the method of the present invention, the amount of the component (a1) used is the total mass (100% by mass) of the components (a1), (a2), and the applicable case (a3) in each case. There is), preferably a maximum of 99.8% by mass, particularly a maximum of 99.3% by mass, and particularly preferably a maximum of 97.5% by mass.

Polyfunctional isocyanates that can be used are aromatic, aliphatic, alicyclic, and / or aromatic aliphatic isocyanates. This type of polyfunctional isocyanate can be produced by methods known per se or per se. The polyfunctional isocyanate can also be used, especially in the form of a mixture, in which case component (a1) comprises a variety of polyfunctional isocyanates. The polyfunctional isocyanate that can be used as the monomer unit (a1) has two or more isocyanate groups per molecule of the monomer component (hereinafter, the term diisocyanate is used for the former).

Particularly suitable compounds are diphenylmethane 2,2'-, 2,4'- and / or 4,4'-diisocyanate (MDI), naphthylene 1,5-diisocyanate (NDI), trilene 2,4- and / or 2. , 6-Diisocyanate (TDI), 3,3'-dimethylbiphenyldiisocyanate, 1,2-diphenylethanediisocyanate and / or p-phenylene diisocyanate (PPDI), tri-, tetra-, penta-, hexa-, hepta-, And / or octamethylene diisocyanate, 2-methylpentamethylene 1,5-diisocyanate, 2-ethylbutylene 1,4-diisocyanate, pentamethylene 1,5-diisocyanate, butylene 1,4-diisocyanate, 1-isophorone-3,3 , 5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1,4- and / or 1,3-bis (isocyanatomethyl) cyclohexane (HXDI), cyclohexane 1,4-diisocyanate, 1-methyl Cyclohexane 2,4- and / or 2,6-diisocyanate and dicyclohexylmethane 4,4'-, 2,4'-and / or 2,2'-diisocyanate.

Aromatic isocyanate is preferable as the polyfunctional isocyanate (a1). This is especially true when water is used as component (a3).

The following are particularly preferred embodiments of the polyfunctional isocyanate of component (a1).

i) Toluene diisocyanates (TDIs), especially polyfunctional isocyanates based on 2,4-TDI, or 2,6-TDI, or mixtures of 2,4- and 2,6-TDI;
ii) Diphenylmethane diisocyanate (MDI), especially 2,2'-MDI, or 2,4'-MDI, or 4,4'-MDI, or oligomeric MDI (also referred to as polyphenylpolymethylene isocyanate), or above. A poly based on a mixture of two or three diphenylmethane diisocyanates, or a mixture of crude MDI obtained during the production of MDI, or at least one oligomer of MDI, and at least one of the above low molecular weight MDI derivatives. Functional isocyanate;
iii) A mixture of at least one aromatic isocyanate of embodiment i) and at least one aromatic isocyanate of embodiment ii).

Oligomer diphenylmethane diisocyanate is particularly preferable as a polyfunctional isocyanate. Oligomer diphenylmethane diisocyanate (hereinafter referred to as oligomer MDI) is accompanied by a mixture of a plurality of oligomer condensates and the resulting diphenylmethane diisocyanate derivative. The polyfunctional isocyanate can also preferably be composed of a mixture of monomeric aromatic diisocyanates and oligomeric MDIs.

Oligomer MDI comprises a polynuclear condensate of one or more MDIs having a functional value greater than 2, particularly 3 or 4 or 5. Oligomer MDI is known and is often referred to as polyphenylpolymethylene isocyanate, or polymer MDI. Oligomer MDI is usually composed of a mixture of MDI-based isocyanates with different functional values. Oligomer MDI is commonly used in mixtures with monomeric MDI.

The (average) functional value of isocyanates containing oligomeric MDI can vary in the range of about 2.2 to about 5, in particular in the range of 2.4 to 3.5, in particular in the range of 2.5 to 3. A mixture of MDI-based polyfunctional isocyanates with different functional values of this type is a crude MDI produced in the form of an intermediate product of crude MDI production, especially during the production of MDI, usually carried out with a catalyst with hydrochloric acid. ..

Mixtures of MDI-based polyfunctional isocyanates and multiple polyfunctional isocyanates are known and are commercially available, for example, from BASF Polyurehanes GmbH under the Trademark Luplanat®.

The functional value of the component (a1) is preferably at least 2, particularly at least 2.2, particularly preferably at least 2.4. The functional value of the component (a1) is preferably 2.2 to 4, particularly preferably 2.4 to 3.

The content of the isocyanate group in the component (a1) is preferably 5 to 10 mmol / g, particularly 6 to 9 mmol / g, and particularly preferably 7 to 8.5 mmol / g. Those skilled in the art know that the content of isocyanate groups in mmol / g and the properties known as equivalents in g / equivalent are interrelated. The content of isocyanate groups at mmol / g is obtained from the content in% by weight according to ASTM D-5155-96A.

In a preferred embodiment, the component (a1) is at least one polyfunctional isocyanate selected from diphenylmethane 4,4'-diisocyanate, diphenylmethane 2,4'-diisocyanate, diphenylmethane 2,2'-diisocyanate and oligomeric diphenylmethane diisocyanate. Consists of. For the purposes of this preferred embodiment, component (a1) particularly preferably comprises an oligomeric diphenylmethane diisocyanate and has a functional value of at least 2.4.

The viscosity of the component (a1) used can vary widely. The component (a1) is 100 to 3000 mPa. s, especially 200-2500 mPa. It has a viscosity of s.

Ingredient (a2)
The present invention uses at least one polyfunctional OH-functionalized or NH-functionalized compound as the component (a2).

For the purposes of the preferred method of the invention, component (a2) is at least one polyfunctional aromatic amine.

The component (a2) can be produced in-situ to some extent. In this type of embodiment, the reaction for step (a) is carried out in the presence of water (a3). Water reacts with isocyanate groups to release CO ₂ and give amino groups. Therefore, polyfunctional amines are, to some extent, produced as intermediate products (in situ). In the course of the reaction, they are reacted with isocyanate groups to give urea bonds.

In this preferred embodiment, the reaction is carried out in the presence of water (a3) and, optionally, the catalyst (a4) in the presence of a polyfunctional aromatic amine as component (a2).

Similarly preferred, in another embodiment, the reaction of the polyfunctional aromatic amines as component (a1) and component (a2) is optionally carried out in the presence of catalyst (a4). There is no water (a3) here.

Polyfunctional aromatic amines are themselves known to those of skill in the art. Polyfunctional amines are amines that have at least two amino groups that are reactive with isocyanates per molecule. Here, the reactive groups for isocyanates are primary and secondary amino groups, where the reactivity of the primary amino group is generally significantly higher than that of the secondary amino group. ..

The polyfunctional aromatic amine preferably has a binuclear aromatic compound having two primary amino groups (bifunctional aromatic amine), as well as having more than two primary amino groups. A tri- or polynuclear aromatic compound, or a mixture of the above compounds. The polyfunctional aromatic amine of the particularly preferable component (a2) is an isomer and a derivative of diaminodiphenylmethane.

The above bifunctional dikaryon aromatic amines are particularly preferably of the general formula I.

[In the formula, R ¹ and R ² may be the same or different, and are independently selected from linear or branched alkyl groups having hydrogen and 1 to 6 carbon atoms, and all substituents. Q ¹ to Q ⁵ and Q ^{1 '~Q 5'} are the same or different, each independently, hydrogen, primary amino groups, and straight-chain or branched having 1 to 12 carbon atoms It is selected from alkyl groups (where the alkyl group may have additional functional groups) (where the compounds of general formula I contain at least two primary amino groups, Q ¹ , Q ³ and Q. ^{(As long} as at least one of ⁵ is a primary amino group and at least one of Q ^1' , Q ^3'and Q ^5'is a primary amino group). ]

In one embodiment, the alkyl group for the substituent Q of general formula I is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl. This type of compound is hereinafter referred to as a substituted aromatic amine (a2-s). However, if they are not amino groups as defined above, it is equally preferred that all substituents Q are hydrogen (the term used is unsubstituted polyfunctional aromatic amines).

R ¹ and R ² for the general formula I are the same or different and are linear or branched alkyl groups having hydrogen, a primary amino group, and 1 to 6 carbon atoms independently of each other. It is preferable to be selected from. R ¹ and R ² are preferably selected from hydrogen and methyl. Particularly preferably, R ¹ = R ² = H.

Other suitable polyfunctional aromatic amines (a2) are especially isomers and derivatives of toluenediamine. Particularly preferred toluene isomers and derivatives for component (a2) are toluene-2,4-diamine and / or toluene-2,6-diamine and diethyltoluenediamine, especially 3,5-diethyltoluened-2. , 4-Diamine and / or 3,5-diethyltoluene-2,6-diamine.

The component (a2) may contain at least one polyfunctional aromatic amine selected from 4,4'-diaminodiphenylmethane, 2,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane and oligomeric diaminodiphenylmethane. Very particularly preferred.

Oligomer diaminodiphenylmethane contains one or more polynuclear methylene cross-linked condensates of aniline and formaldehyde. Oligomer MDA comprises at least one, usually multiple, oligomers of MDA having more than 2, especially 3 or 4 or 5 functional values. Oligomer MDA is known and can be produced by methods known per se. Oligomer MDA is usually used in the form of a mixture with monomeric MDA.

The (average) functional value of the polyfunctional amine of component (a2), which comprises the oligomeric MDA, is about 2.3 to about 5, especially 2.3 to 3.5, especially 2.3 to 3. Can vary in range. One such mixture of MDA-based polyfunctional amines with various functional values is produced as an intermediate in the condensation of aniline and formaldehyde, which is usually catalyzed by hydrochloric acid, especially in the production of crude MDI. It is a crude MDA.

It is particularly preferable that at least one polyfunctional aromatic amine contains diaminodiphenylmethane or a derivative of diaminodiphenylmethane. It is particularly preferable that at least one polyfunctional aromatic amine contains the oligomer diaminodiphenylmethane. It is particularly preferable that the component (a2) contains the oligomer diaminodiphenylmethane as the component (a2) and the total functional value is at least 2.1. In particular, component (a2) contains the oligomeric diaminodiphenylmethane, which has a functional value of at least 2.4.

For the purposes of the present invention, it is possible to control the reactivity of the primary amine using substituted polyfunctional aromatic amines for component (a2). The above-mentioned and below-described substituted polyfunctional aromatic amines (hereinafter referred to as (a2-s)) may be used alone or as the above-mentioned (unsubstituted) diaminodiphenylmethane (all Qs in the formula I may be). If they are not NH ₂ , they are hydrogen) and can be used in mixtures.

In this embodiment, Q ^2, Q 4 for the above formula I, ^Q 2 ^', and Q ^4', including the provision of attendant, preferably, the compounds of general formula I, bound to an aromatic ring A linear or branched alkyl group having at least 1 to 12 carbon atoms at the α-position for at least one primary amino group (which may have additional functional groups). Is selected to have. In this ^embodiment, Q ^{2, Q} 4, Q ^{2 ',} and Q ^4' is a substituted aromatic amine (a2-s) is, in α-position, one or two, respectively, 1 to 12 carbons It is preferably selected to contain at least two primary amino groups, which are linear or branched alkyl groups with atoms, which may have additional functional groups. ^{Q 2, Q 4, Q 2} ', and Q ^4' is selected to be a linear or branched alkyl group which has 1 to 12 carbon atoms (which has an additional functional group) If so, the functional groups are preferably an amino group and / or a hydroxy group, and / or a halogen atom.

Amine (a2-s) is 3,3', 5,5'-tetraalkyl-4,4'-diaminodiphenylmethane, 3,3', 5,5'-tetraalkyl-2,2'-diaminodiphenylmethane, And 3,3', 5,5'-tetraalkyl-2,4'-diaminodiphenylmethane (where the alkyl groups at the 3,3', 5, and 5'positions are the same or different and independent of each other. It is preferably selected from the group consisting of linear or branched alkyl groups having 1 to 12 carbon atoms, which may have additional functional groups. The above alkyl group is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl (unsubstituted in each case).

In one embodiment, one, more, or all of the hydrogen atoms of one or more alkyl groups of substituent Q may be substituted with halogen atoms, especially chlorine. Alternatively, one, more, or all of the hydrogen atoms of one or more alkyl groups of substituent Q may be substituted with NH ₂ or OH. However, the alkyl group for general formula I is preferably composed of carbon and hydrogen.

In a particularly preferred embodiment, the component (a2-s) is 3,3', 5,5'-tetraalkyl-4,4'-diaminodiphenylmethane, the alkyl groups being the same or different and independent. It includes those selected from linear or branched alkyl groups having 1 to 12 carbon atoms (which may optionally have functional groups). The above alkyl groups are preferably selected from unsubstituted alkyl groups, particularly methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl, and particularly preferably methyl and ethyl. Butyl. 3,3', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane and / or 3,3', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane are highly preferred.

The polyfunctional amine of the above component (a2) is known to those skilled in the art by itself, or can be produced by a known method. One of these known methods is the reaction of aniline or an aniline derivative with formaldehyde together with an acid catalyst.

As described above, as component (a3), water can replace polyfunctional aromatic amines to some extent, but it reacts with a pre-calculated amount of polyfunctional aromatic isocyanate of additional component (a1). This is because the corresponding polyfunctional aromatic amine can be obtained on the spot.

The term organic gel precursor (A) is used below for components (a1)-(a3).

Catalyst (a4)
In a preferred embodiment, the method of the invention is preferably carried out in the presence of at least one catalyst as component (a4).

The catalysts that can be used are, in principle, known to those skilled in the art and accelerate the trimerization of isocyanates (these are known as trimerization catalysts) and / or accelerate the reaction of isocyanates with transamination (these). Are known as gelation catalysts) and / or all catalysts that accelerate the reaction of isocyanates with water (these are known as foaming catalysts) when water is used.

Corresponding catalysts are known in their own right and function differently for the above three reactions. Therefore, they may be assigned one or more of the above types depending on their performance. Those skilled in the art also know that reactions other than the above reactions can occur.

Corresponding catalysts can be characterized, among other things, on the basis of their gelation ratio to foaming, eg, Polyurehane [Polyurehanes] 3rd edition, G.M. Known by Oeterl, Hanser Verlag, Munich, 1993, pp. 104-110.

If component (a3) is not used, i.e. water is not used, the preferred catalyst has significant activity with respect to the quantification process. This has an advantageous effect on the uniformity of the network structure, resulting in particularly advantageous mechanical properties.

When water is used as the component (a3), the preferred catalyst (a4) has a short gelation time at the same time so that the reaction between the component (a1) and water is not over-accelerated with adverse effects on the network structure. It has a gelling ratio to balanced foaming so that it is obtained and thereby shortens the mold release time advantageously. Preferred catalysts also have significant activity with respect to trimerization. This has an advantageous effect on the uniformity of the network structure, and particularly advantageous mechanical properties are obtained.

The catalyst can be a monomer unit (incorporable catalyst) or can not be incorporated.

It is advantageous to use the minimum effective amount of component (a4). Based on 100 parts by mass of the whole of the components (a1), (a2) and (a3), the component (a4) was added to 0.01 to 5 parts by mass, particularly 0.1 to 3 parts by mass, particularly preferably 0. It is preferable to use 2 to 2.5 parts by mass.

Preferred catalysts for component (a4) are primary, secondary and tertiary amines, triazine derivatives, organometallic compounds, metal chelates, quaternary ammonium salts, ammonium hydroxide, and alkali metals, and It is selected from the group consisting of hydroxides, alkoxides, and carboxylates of alkaline earth metals.

Suitable catalysts are particularly strong bases, such as tetraalkylammonium hydroxide having 1 to 4 carbon atoms in the alkyl moiety, and quaternary ammonium hydroxide such as benzyltrimethylammonium hydroxide, such as potassium hydroxide or. Alkali metal hydroxides such as sodium hydroxide, and alkali metal alkoxides such as, for example, sodium methoxide, potassium ethoxide, and sodium ethoxide, and potassium isoproxide.

Other suitable catalysts are alkali metal salts of carboxylic acids, such as potassium formate, sodium acetate, potassium acetate, potassium 2-ethylhexanoate, potassium adipate, and sodium benzoate, 8 to 20, especially 10 to 10. An alkali metal salt of a long-chain fatty acid having 20 carbon atoms and optionally a pendant OH group.

Other suitable catalysts are especially N-hydroxyalkyl quaternary ammonium carboxylates, such as trimethylhydroxypropylammonium formate.

Suitable organophosphorus compounds, especially those of phosphorene, are 1-methylphosphoren oxide, 3-methyl-1-phenylphosphoren oxide, 1-phenylphosphoren oxide, 3-methyl-1-benzylphosphoren oxide. ..

The organometallic compound itself is known to those of skill in the art as a gelation catalyst in particular and is also suitable as a catalyst (a4). Organic tin compounds such as tin 2-ethylhexanoate and dibutyltin dilaurate are preferred due to component (a4). Further, metal acetylacetonate, particularly zinc acetylacetonate is preferable.

Tertiary amines are themselves known to those of skill in the art as gelation catalysts and trimerization catalysts. The tertiary amine is particularly preferable as the catalyst (a4). Preferred tertiary amines are particularly N, N-dimethylbenzylamine, N, N'-dimethylpiperazin, N, N-dimethylcyclohexylamines such as N, N', N "-tris (dimethylaminopropyl) -s. -N, N', N "-tris (dialkylaminoalkyl) -s-hexahydrotriazine, tris (dimethylaminomethyl) phenol, bis (2-dimethylaminoethyl) ether, N, N, N such as hexahydrotriazine , N, N-pentamethyldiethylenetriamine, methylimidazole, dimethylimidazole, aminopropylimidazole, methylbenzylamine, 1,6-diazabicyclo [5.4.0] undec-7-ene, trimethylamine, triethylenediamine (IUPAC: 1, 4-diazabicyclo [2.2.2] octane), dimethylaminoethanolamine, dimethylaminopropylamine, N, N-dimethylaminoethoxyethanol, N, N, N-trimethylaminoethylethanolamine, triethanolamine, diethanolamine, Triisopropanolamine and diisopropanolamine, methyldiethanolamine, butyldiethanolamine, and hydroxyethylaniline.

Preferred catalysts for solving for component (a4) are N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, N, N, N, N, N-pentamethyldiethylenetriamine, methylimidazole, dimethylimidazole. , Aminopropyl imidazole, dimethylbenzylamine, 1,6-diazabicyclo [5.4.0] undec-7-ene, trisdimethylaminopropylhexahydrotriazine, triethylamine, tris (dimethylaminomethyl) phenol, triethylenediamine (diazabicyclo [ 2.2.2] Octane), dimethylaminoethanolamine, dimethylaminopropylamine, N, N-dimethylaminoethoxyethanol, N, N, N-trimethylaminoethylethanolamine, triethanolamine, diethanolamine, triisopropanolamine, It is selected from the group consisting of diisopropanolamine, methyldiethanolamine, butyldiethanolamine, hydroxyethylaniline, metal acetylacetonate, ammonium ethylhexanoate, and ethylhexanoate of metal ions.

The use of the preferred catalyst (a4) for the purposes of the present invention results in a porous material with improved mechanical properties, especially improved compressive strength. Also, the use of the catalyst (a4) reduces the gelation time, i.e., the gelation reaction is accelerated without any adverse effect on other properties.

Solvent
The organic airgel or xerogel used in the present invention is produced in the presence of a solvent.

For the purposes of the present invention, the term, solvent, includes not only liquid diluents, or solvents in the narrow sense, but also dispersion media. The mixture can be in particular an intrinsic solution, a colloidal solution, or a dispersion such as an emulsion or suspension. The mixture is preferably a true solution. The solvent is a compound that is liquid under the conditions of step (a), and is preferably an organic solvent.

In principle, the solvent used may include an organic compound or a mixture of a plurality of compounds, and the solvent is a liquid under the temperature and pressure conditions (simplified solution conditions) to which the mixture is supplied. The composition of the solvent is chosen such that the solvent is capable of dissolving or dispersing, preferably dissolving, the organic gel precursor. For the above preferred methods for producing organic airgels, or organic xerogels, the preferred solvent is the solvent for the organic gel precursor (A), i.e. the organic gel precursor (A) under reaction conditions. It dissolves completely.

The initial reactive organism of the reaction in the presence of a solvent is a gel, a chemical network of viscoelasticity swollen with a solvent. Solvents that are good leavening agents for the formed networks usually result in networks with fine pores and a small average pore size, while the resulting gels are inadequate leavening agents. It usually results in a network of coarse pores with a large average pore size.

Therefore, the choice of solvent affects the desired pore size distribution and desired porosity. Solvent selection is also usually carried out during or after step (a) of the method of the invention so as to substantially avoid precipitation or aggregation by the formation of a precipitation reaction product.

When a suitable solvent is selected, the proportion of precipitation-reactive organisms is typically less than 1% by weight based on the total mass of the mixture. The amount of precipitate product formed in a particular solvent can be measured by gravimetric methods by filtering the reaction mixture through a suitable filter prior to the gel point.

The solvents that can be used are those known from the prior art and are solvents for isocyanate-based polymers. Here, the preferred solvent is a solvent for the components (a1), (a2) and, if applicable, (a3), that is, the components (a1), (a2,) and, if applicable, (a3). It dissolves substantially completely under reaction conditions. The solvent is preferably inert to the component (a1), that is, does not react with it.

Examples of solvents that can be used are ketones, aldehydes, alkyl alkanoates, amides such as formamide and N-methylpyrrolidone, sulfoxides such as dimethyl sulfoxide, aliphatic, and alicyclic halogenated hydrocarbons, halogenated aromatic compounds. And fluorinated ethers. It is also possible to use a mixture consisting of two or more of the above compounds.

Acetals, especially diethoxymethane, dimethoxymethane, and 1,3-dioxolane can also be used as solvents.

Dialkyl ethers and cyclic ethers are also suitable as solvents. Preferred dialkyl ethers are particularly those having 2 to 6 carbon atoms, particularly methyl ethyl ether, diethyl ether, methyl propyl ether, methyl isopropyl ether, propyl ethyl ether, ethyl isopropyl ether, dipropyl ether, propyl isopropyl ether, diisopropyl. Ether, methyl butyl ether, methyl isobutyl ether, methyl t-butyl ether, ethyl n-butyl ether, ethyl isobutyl ether, and ethyl t-butyl ether. Particularly preferred cyclic ethers are tetrahydrofuran, dioxane, and tetrahydropyran.

Other preferred solvents are alkyl alkanoates, especially methyl formate, methyl acetate, ethyl formate, butyl acetate, and ethyl acetate. Preferred halogenated solvents are described on WO 00/24799, page 4, lines 12-5, lines 4.

Aldehydes and / or ketones are preferred solvents. Aldehydes or ketones suitable as solvents are in particular the general formula R ^2- (CO) -R ¹ (in the formula, R ¹ and R ² are hydrogens or alkyls with 1, 2, 3 or 4 carbon atoms. It is equivalent to). Suitable aldehydes or ketones are, in particular, acetaldehyde, propionaldehyde, n-butylaldehyde, isobutylaldehyde, 2-ethylbutylaldehyde, barrel aldehyde, isopentoaldehyde, 2-methylpentaldehyde, 2-ethylhexaaldehyde, achlorine, metachlorine. , Crotonaldehyde, furfural, achlorein dimer, metachlorine dimer, 1,2,3,6-tetrahydrobenzaldehyde, 6-methyl-3-cyclohexenealdehyde, cyanacetaldehyde, ethylglycoxylate, benzaldehyde, acetone, diethyl Ketone, methyl ethyl ketone, methyl isobutyl ketone, methyl-n-butyl ketone, ethyl isopropyl ketone, 2-acetylfuran, 2-methoxy-4-methoxypentane-2-one, cyclohexanone and acetphenone. The above aldehydes and ketones can also be used in the form of mixtures. As the solvent, ketones and aldehydes having an alkyl group having 3 or less carbon atoms per substituent are particularly preferable. Ketones of the general formula R ¹ (CO) R ² (wherein R ¹ and R ² are independently selected from alkyl groups having 1-3 carbon atoms) are highly preferred. In the first preferred embodiment, the ketone is acetone. In another preferred embodiment, at least one of the two substituents R ¹ and / or R ² comprises an alkyl group having at least two carbon atoms, in particular methyl ethyl ketone. The use of the above particularly preferred ketones in combination by the method of the present invention results in a porous material having a particularly small average pore size. Without any limitation, the pore structure of the resulting gel is considered to be particularly fine due to the high affinity of the above particularly preferred ketones.

In many cases, a particularly suitable solvent is obtained by using a mixture of two or more compounds selected from the above solvents and completely miscible with each other.

Ingredients (a1), (a2), and (a3), if applicable, and (a4), if applicable, and the solvent in appropriate form prior to the reaction in step (a) of the method of the invention. Be supplied.

On the one hand, component (a), and on the other hand, (a2) and, if applicable, (a3), and, if applicable, (a4), are each supplied separately in the appropriate portion of the solvent. Is preferable. Separate feeds allow ideal monitoring or control of the gelling reaction before or during the mixing process.

When water is used as the component (a3), it is particularly preferred to supply the component (a3) separately from the component (a1). This avoids the reaction of water with the component (a1), which involves the formation of a network in the absence of the component (a2). Otherwise, premixing with the water component (a1) results in a reduction in favorable properties with respect to the uniformity of the pore structure and thermal conductivity of the resulting material.

The mixture (s) supplied prior to step (a) may also include, as additional components, an auxiliary agent known to those of skill in the art. Such are examples of surfactant substances, nucleating agents, oxidation stabilizers, lubricants and mold release agents, dyes and pigments such as stabilizers against hydrolysis, light, heat, or discoloration, inorganics, and / Alternatively, organic fillers, reinforcing agents, and biocides may be mentioned.

Further details regarding the above-mentioned auxiliaries and additives can be found in technical literature such as Plastics Adaptive Handbook, 5th edition, H. et al. Zweifel, ed. It can be found in Hanser Publicers, Munich, 2001, pages 1, and 41-43.

In order to carry out the reaction in step (a) of the method of the present invention, it is first necessary to produce a homogeneous mixture of components fed prior to the reaction in step (a).

The components reacted for step (a) can be supplied in a conventional manner. It is preferred that a stirrer, or other mixing device, be used for this purpose in order to achieve good and rapid agitation. To avoid defects in the mixing process, the period required to produce a homogeneous mixture should be short in relation to the period during which the gelation reaction results in at least partial gel formation. Other mixing conditions are generally not important, for example, the mixing process is at 0-100 ° C. and 0.01-1.0 MPa (0.1-10 bar) (absolute pressure), especially at room temperature and high. Can be performed at atmospheric pressure. The mixer is preferably switched off when a uniform mixture is produced.

The gelation reaction involves a heavy addition reaction, particularly an isocyanate group and an amino group or hydroxy group heavy addition reaction.

For the purposes of the present invention, the gel is a polymer-based crosslinked system in contact with a liquid (the term used is sorbogel or riogel, or when water is used as a liquid: aquagel or hydrogel). Is. Here, the polymer phase forms a continuous, three-dimensional network.

For the purposes of step (a) of the method of the invention, the gel is usually standing, i.e., simply the container, reaction vessel, or reactor (hereinafter referred to as the gelling device) in which the mixture is present. It is generated by setting. It is preferable that the gel mixture is no longer agitated or mixed during gelation (gel formation), as it can interfere with gel formation. During the gelation process, it has been found to be advantageous to cover the mixture or seal the gelling device.

The gelling process is known to those skilled in the art by itself and is described, for example, in WO2009 / 027310, pp. 21, pp. 19-23, pp. 13.

For the purposes of the method of the invention, the solvent is removed (drying) in step (b). In principle, it is possible to carry out the drying process after replacing the drying process with supercritical conditions, preferably the solvent with CO ₂ or another solvent suitable for the purpose of drying under supercritical conditions. This type of drying process is itself known to those of skill in the art. The supercritical condition indicates the temperature and pressure at which the liquid phase requiring removal is placed in the supercritical state. This can reduce the shrinkage of the gel product during removal of the solvent. The material obtained from the drying process under supercritical conditions is called airgel.

However, from the point of view of the simple processing of the process, the resulting gel is converted from the liquid contained in the gel into a gaseous state at a temperature and pressure below the critical temperature and pressure of the liquid contained in the gel. It is preferable to dry it. The material obtained from the drying process under subcritical conditions is called xerogel.

The resulting gel is preferably dried by converting the solvent into a gaseous state at temperatures and pressures below the critical temperature and pressure of the solvent. Thereby, the drying process is preferably carried out by removing the solvent present during the reaction period without prior replacement with another solvent. Suitable methods are also known to those of skill in the art and are described in WO-2009 / 027310, pages 26, 22-28, 36.

By the above method, an organic porous material having good properties can be obtained for use as a heat insulating material.

Organic porous material used as insulation core in composite elements of the present invention, the range of 70~300kg / ^{m 3,} in particular in the range of 75~250kg / ^{m 3,} more preferably in the range of 85~220kg / ^{m 3,} Particularly preferably, it has a density in the range of 90 to 200 kg / m ³ .

Thereby, a preferred embodiment of the present invention is, as described above, a composite element comprising a profile and an insulating core surrounded by the profile to at least some extent, wherein the organic porous material is 70-300 kg / m. A composite element having a density in the range of ³ is provided.

Also preferred organic porous materials allow a continuous structure of the profile around the adiabatic core, i.e. have heat resistance that is stable during extrusion molding of the profile, for example. Thereby, the preferred organic porous material has a heat resistance of more than 160 ° C.

Thereby, a preferred embodiment of the present invention is, as described above, a profile and a composite element comprising a heat insulating core surrounded by the profile at least to some extent, wherein the organic porous material has a heat resistance of more than 160 ° C. Provided is a composite material element having a property.

The organic aerogels and xerogels preferably used in the present invention first ensure that the composite element provides good thermal insulation and secondly, for stability reasons, the composite element is easy to use. It has a characteristic profile that enables manufacturing.

Thus, in particular, in the present invention, it is possible to manufacture an insulating core with the desired dimensions and shape and then create a profile around the insulating core. This avoids the complex process that requires the manufacture of hollow profiles and then the insertion of insulating material into them.

Insulation cores can generally have any desired shape that will appear to those skilled in the art to be suitable for the desired application. The cross-sectional shape of the adiabatic core can be circular and / or polygonal. Also, the shape of the core can be uniform or non-uniform, for example, it can have cutouts, grooves, ridges, etc., and these profile effects are parallel to the direction of the product or Can be formed vertically.

The dimensions of the insulating core are generally 5 to 200 mm, the microphone is 10 to 150 mm, particularly preferably 15 to 100 mm, especially 20 to 80 mm, and for non-uniformly shaped cores, these dimensions are in all directions. Represents the maximum distance in.

In a preferred embodiment, the invention comprises exactly one type of adiabatic core composed of an organic porous material. In the present invention, the composite element may also include two, three or four cores made of an organic porous material. If two, three or four cores are present in the composite elements manufactured in the present invention, they may have the same or different shapes. In the present invention, the composite element may also have at least one adiabatic core made of an organic porous material and at least one adiabatic core made of another material, for example polyurethane foam. The composite material of the present invention includes a profile, which in principle can be composed of any possible suitable material, in particular a thermoplastically processable material, or aluminum.

Here the profile surrounds the insulating core to some extent or completely, preferably completely. In a preferred embodiment, the profile also comprises a fillet attached to the core.

The thickness of the profile itself, or the profile and any flat edges belonging to the profile, is generally 1 to 20 mm, preferably 2 to 15 mm, particularly preferably 3 to 10 mm, where the profile and flat edges are the same or different. Can have a thickness. In a preferred embodiment, the jacket or flat edges have different thicknesses at different positions in the profile, the thicknesses being the same in the longitudinal direction but varying in the lateral direction. This depends, for example, on the shape of the profile, which also depends on later use.

The profile of the composite element produced in the present invention preferably comprises at least one thermoplastic material. Suitable thermoplastic materials are themselves a process to those skilled in the art, such as acrylonitrile-butadiene-styrene (ABS), polymethylmethacrylate (PMMA), polyethylene (PE), polypropylene (PP), polystyrene, or polyvinyl chloride ( Polyolefins such as PVC), eg PA6 or PA6,6, polycondensates such as polylactic acid (PLA), polycarbonate (PC), eg polyesters such as polyethylene terephthalate (PET), polyether ether ketone (PEEK), thermoplastic polyurethane Such as heavy adducts, wood plastic composites, and mixtures thereof. In one particularly preferred embodiment, the profile jacket produced in the present invention comprises polyvinyl chloride (PVC). Its production via the polymerization of polyvinyl chloride (PVC) and vinyl chloride is itself known to those of skill in the art.

Thereby, a preferred embodiment of the present invention is a composite element comprising a profile and an insulating core at least to some extent surrounded by the profile, as described above, wherein the profile is composed of polyvinyl chloride or aluminum. Provides composite elements.

A particularly preferred embodiment of the present invention is a composite element comprising a profile and an insulating core at least to some extent surrounded by the profile, as described above, wherein the profile is composed of polyvinyl chloride. I will provide a.

In a preferred embodiment, the profile comprises a thermoplastic material having a melting point of less than 220 ° C.

For the purposes of the present invention, the composite elements of the present invention can be produced in a variety of ways, eg, continuously or in batches, with preference given to continuous production.

For the purposes of the present invention, various methods are, in principle, possible to produce the composite elements of the present invention, provided that they reliably introduce the insulating core into the profile with an accurate fit. ..

Here the profile is preferably made around the adiabatic core. This simplifies the manufacturing process for composite elements of the present invention, as the insulating core defines the shape of the hollow structure, facilitating the molding of the hollow structure in the profile.

Accordingly, the present invention is also a continuous method of producing a profile and a composite element comprising an insulating core at least to some extent surrounded by the profile, wherein the insulating core is measured according to DIN12667 at 13-30 mW /. Composed of an organic porous material with thermal conductivity in the m * K range and compressive strength greater than 0.20 N / mm ² measured according to DIN 53421, the profile is made around the adiabatic core (constrruct). ) Is also provided.

Therefore, in the present invention, the insulating core can be manufactured in the desired shape, stored and then further processed.

Here, the profile can be made in various ways, for example by means of an extruder, particularly preferably by means of a ring extruder.

Thereby, a preferred embodiment of the present invention is, as described above, a method of producing a profile and a composite element comprising an insulating core at least to some extent surrounded by the profile, wherein the profile is used in a ring extruder. By means, a method of making continuously around the adiabatic core is provided.

A further embodiment of the invention is also a method of making a profile and a composite element comprising an insulating core at least to some extent surrounded by the profile, as described above, wherein the profile is placed around the insulating core. Also provided is a method of making from multiple parts.

As an example, here in the present invention, a profile can be made from a plurality of preformed portions around an insulating core, but similarly a portion of the preformed insulating core is inserted and then The profile can be sealed by means of an extruder, for example.

If the profile is made from multiple preformed pieces around the insulation core, the individual parts of the profile will be pushed in different ways from each other, for example via gluing or welding or by pushing. Can be connected via -fit connection) (“clipping”).

Therefore, the profile can preferably be made from a thermoplastically processable material, such as polyvinyl chloride.

Thereby, a preferred embodiment of the present invention is, as described above, a method of producing a profile and a composite element comprising an insulating core at least to some extent surrounded by the profile, wherein the profile is made of polyvinyl chloride. Provides a method of composition.

The composite element can preferably be manufactured by means of a ring extruder in the present invention. Here, the method of the present invention completely wraps an insulating core with a profile composed of at least one thermoplastic material, whereby an extruded die fitted with a ring profile for manufacturing to obtain a composite element. Includes the introduction of an insulating core into an extruder with an extrusion die.

Here the insulation core is introduced into an extruder containing a die that duplicates the shape of the profile. The thermoplastic material of interest for forming the jacket is then applied in a melted state on the core in an extruder. Examples of this extruder used in the present invention are well known to those of skill in the art and are described, for example, in WO2009 / 098068.

The method of the present invention is preferably carried out at a temperature at which the thermoplastic material of the profile is melted, for example 100-220 ° C, particularly preferably 130-190 ° C.

The temperature at which the thermoplastic material hardens downstream of the extruder is preferably, for example, 25 to 180 ° C, preferably 50 to 150 ° C.

Extrusion molding of thermoplastic materials is known to those of skill in the art and, for example, "Einfuehrung in die Kunststoffeverarbeitung" (Introduction to Plastic Processing), 5th Edition, September 2006, pp. 87-180, Walter Michaeli; Hanser. It is described in Fachbuchverlag.

If the stiffener is introduced into the profile of the present invention, the stiffener may have its final shape, eg stripped, when introduced into the extruder. In the second embodiment, the stiffener is extruded in the extruder at the same time as the profile jacket. For this reason, the reinforcing material is preferably introduced in a melted state by an extruder.
In a preferred embodiment, the dimensions of the stiffener depend on the dimensions of the profile and can maximize the stability of the reinforced profile. Here, the design of the stiffener is such that heat transport is reduced, or at least not increased, in profiles, for example in window frames, or door frames.

In the present invention, the profiles are made discontinuously around the adiabatic core, eg, from a plurality of preformed portions, and the portions of the individual profiles are welded in different ways, eg via adhesion or welding. Can be connected via a push-in connection (“clipping”).

In another method, for the purposes of the present invention, it is also possible to first produce a complete profile and then introduce the insulating core into a preformed hollow chamber.

In a modification of this method, any conventional method may use, for example, an insertion using suction, or an insertion using pressure, preferably an insertion using pressure, to introduce an insulating core into the profile.

Accordingly, another embodiment of the invention is also a method of producing a profile and a composite element comprising an insulating core at least to some extent surrounded by the profile, wherein the insulating core is measured according to DIN 12667 13- To insert the adiabatic core into the profile, composed of an organic porous material having a thermal conductivity in the range of 30 mW / m * K and a compressive strength of over 0.20 N / mm ² measured according to DIN 53421. Provide a method characterized in that pressure is used in.

The composite elements of the present invention have low thermal conductivity for the same insulation thickness, which makes them suitable for use for architectural elements such as windows or doors.

Therefore, it is possible to meet the U value limit (U value = heat transfer coefficient (W / m ² * K)) for the individual components (walls, windows) of the shell of the building, which are good. Can provide thermal insulation.

Therefore, the present invention also relates to an organic porous material having a thermal conductivity in the range of 13-30 mW / m * K measured according to DIN 12667 and a compressive strength greater than 0.20 N / mm ² measured according to DIN 53421. Provided is a method of use as a heat insulating material in a profile.

Thereby, a preferred embodiment of the present invention is, as described above, a method of using an organic porous material as a heat insulating material in a profile, wherein the profile comprises a window, a door, a refrigerator, and a large box freezer. Provided are methods of use used for manufacturing or for elements for façade structures.

A further embodiment of the invention is also for making windows, doors, refrigerators, and large box-type freezers of the composite elements of the invention, or the composite elements obtained by the methods of the invention, or façade structures. Provides usage for the element for.

The composite elements of the present invention are suitable for various architectural elements such as window structures.

Thus, another embodiment of the invention is, in particular, a window comprising a profile and a composite element comprising an insulating core at least somewhat enclosed by the profile, wherein the insulating core was measured according to DIN1266713. Provided is a window composed of an organic porous material having a thermal conductivity in the range of ~ 30 mW / m * K and a compressive strength of greater than 0.20 N / mm ² measured according to DIN 53421.

Examples of embodiments of the present invention are listed below, but are not intended to limit the present invention. In particular, the invention also includes embodiments that derive from, and thereby form combinations, the dependencies described below.

1. 1. A composite element comprising a profile and an insulating core at least to some extent surrounded by the profile, wherein the insulating core is measured according to a thermal conductivity in the range of 13-30 mW / m * K measured according to DIN12667, and DIN53421. A composite material element composed of an organic porous material having a compressive strength of more than 0.20 N / mm ² .

2. 2. The composite material element according to the first embodiment, wherein the organic porous material is one selected from the group consisting of an organic xerogel, an organic airgel, and a combination of two or more thereof.

3. 3. The organic porous material is selected from the group consisting of polyurethane, polyisocyanurates, or polyurea-based organic xerogels, polyurethanes, polyisocyanurates, or polyurea-based organic airgels, and combinations thereof. The composite material element according to the first or second embodiment.

4. The composite element according to any one of embodiments 1 to ³ , wherein the organic porous material has a density in the range of 70 to 300 kg / m ³ .

5. The composite material element according to any one of Embodiments 1 to 4, wherein the organic porous material has a heat resistance of more than 160 ° C.

6. The composite element according to any of embodiments 1-5, wherein the profile is composed of polyvinyl chloride or aluminum.

7. A continuous method of producing a profile and a composite element containing an insulating core at least to some extent surrounded by the profile, wherein the insulating core has a thermal range of 13-30 mW / m * K measured according to DIN12667. A method comprising the organic porous material having a conductivity and a compressive strength greater than 0.20 N / mm ² measured according to DIN 53421, wherein the profile is made around the adiabatic core.

8. 7. The method of embodiment 7, wherein the profile is continuously made around the insulating core by means of a ring extruder.

9. The method according to embodiment 7, wherein the profile is made from a plurality of parts around the adiabatic core.

10. The method according to any of embodiments 7-9, wherein the profile is composed of polyvinyl chloride.

11. Use of an organic porous material with a thermal conductivity in the range of 13-30 mW / m * K measured according to DIN12667 and a compressive strength greater than 0.20 N / mm ² measured according to DIN53421 as a heat insulating material in the profile. Method.

12. 11. The method of use according to embodiment 11, wherein the profile is used to make windows, doors, refrigerators, and large box freezers, or for elements for façade structures.

13. A window, a door, a refrigerator, and a large box-type freezer of the composite material element according to any one of embodiments 1 to 6 or the composite material element obtained by the method according to any one of claims 7 to 10 are manufactured. For use, or for elements for façade structures.

14. A composite element that includes a profile and an insulating core that is at least to some extent surrounded by the profile, wherein the insulating core has a thermal conductivity in the range of 13-30 mW / m * K measured according to DIN12667, and measured according to DIN53421. It is composed of an organic porous material having a compressive strength of more than 0.20 N / mm ² and selected from the group consisting of an organic xerogel and an organic airgel, and a combination of two or more thereof. A composite element characterized by.

15. A composite element comprising a profile and an insulating core at least to some extent surrounded by the profile, wherein the insulating core is measured according to a thermal conductivity in the range of 13-30 mW / m * K measured according to DIN12667, and DIN53421. Polyurethane, polyisocyanurate, or polyurea-based organic xerogel, polyurethane, polyisocyanurate, or polyurea-based organic airgel, and two or more of them, having a compressive strength of more than 0.20 N / mm ^2. A composite material element characterized by being composed of an organic porous material which is one kind selected from the group consisting of a combination of.

16. A composite element that includes a profile and an insulating core that is at least to some extent surrounded by the profile, wherein the insulating core has a thermal conductivity in the range of 13-30 mW / m * K measured according to DIN12667, and measured according to DIN53421. Polyurethane, polyisocyanurate, or polyurea-based organic xerogel, polyurethane, polyisocyanurate, or polyurea-based organic airgel, and two or more of them, having a compressive strength of more than 0.20 N / mm ^2. A composite material element composed of an organic porous material which is one kind selected from the group consisting of a combination of the above, wherein the organic porous material has a density in the range of 70 to 300 kg / m ³ .

17. A composite element that includes a profile and an insulating core that is at least to some extent surrounded by the profile, wherein the insulating core has a thermal conductivity in the range of 13-30 mW / m * K measured according to DIN12667, and measured according to DIN53421. Polyurethane, polyisocyanurate, or polyurea-based organic xerogel, polyurethane, polyisocyanurate, or polyurea-based organic airgel, and two or more of them, having a compressive strength of more than 0.20 N / mm ^2. A composite material element composed of an organic porous material which is one kind selected from the group consisting of the combination of the above, and characterized in that the organic porous material has a heat resistance of more than 160 ° C.

18. The composite element according to embodiment 17, wherein the profile is composed of polyvinyl chloride or aluminum.

19. A composite element that includes a profile and an insulating core that is at least to some extent surrounded by the profile, wherein the insulating core has a thermal conductivity in the range of 13-30 mW / m * K measured according to DIN12667, and measured according to DIN53421. Polyurethane, polyisocyanurate, or polyurea-based organic xerogel, polyurethane, polyisocyanurate, or polyurea-based organic airgel, and two or more of them, having a compressive strength of more than 0.20 N / mm ^2. A composite material element composed of an organic porous material, which is one selected from the group consisting of a combination of the above, and characterized in that the profile is composed of polyvinyl chloride or aluminum.

20. A continuous method of producing a profile and a composite element containing an insulating core at least somewhat enclosed by the profile, wherein the insulating core has a thermal range of 13-30 mW / m * K measured according to DIN12667. Composed of an organic porous material having a conductivity and a compressive strength greater than 0.20 N / mm ² measured according to DIN 53421, the profile is continuously made around the adiabatic core by means of a ring extruder. A method characterized by doing.

21. A method of manufacturing a profile and a composite element comprising an insulating core at least to some extent surrounded by the profile, wherein the insulating core has a thermal conductivity in the range of 13-30 mW / m * K measured according to DIN12667. And a method comprising the organic porous material having a compressive strength of greater than 0.20 N / mm ² measured according to DIN 53421, wherein the insulating core is inserted into the profile under pressure.

22. A window containing a profile and a composite element containing an insulating core at least to some extent surrounded by the profile, wherein the insulating core has a thermal conductivity in the range of 13-30 mW / m * K measured according to DIN12667, and A window composed of an organic porous material having a compressive strength greater than 0.20 N / mm ² measured according to DIN 53421.

23. Manufacture windows, doors, refrigerators, and large box-type freezers of the composite element according to any of embodiments 14-19, or the composite element obtained by the method according to any of embodiments 20-22. For use, or for elements for façade structures.

The following examples are useful for explaining the present invention, but have no limiting effect on the content of the present invention.

[Manufacturing example: Airgel]
1. 1. Starting material The following compounds were used to make the gel.

Ingredients a1: According to ASTM D5155-96A, an NCO content of 30.9 g per 100 g, a functional value of approximately 3, and according to DIN53018, 2100 mPa. Oligomer MDI (Lupranat® M200) having a viscosity of s (hereinafter, “Compound M200”).
Component a2: 3,3', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane (hereinafter, "MDEA").
Catalyst: Butyl diethanolamine, Methyl diethanolamine

2. 2. Manufacturing example 1
80 g of compound M200 was dissolved in 220 g of 2-butanone in a glass beaker with stirring at 20 ° C. 8 g of compound MDEA, 8 g of butyldiethanolamine, and 1 g of water were dissolved in 220 g of 2-butanone in a second glass beaker. The two solutions from step (a) were mixed. This gave a low viscosity transparent mixture. The mixture was left at room temperature for 24 hours to cure. The gel was then removed from the glass beaker and dried in an autoclave via solvent extraction using supercritical CO ₂ .

The gel monolith was removed from the glass beaker and transferred to a 25 L autoclave. The autoclave was filled with> 99% acetone so that the acetone completely covered the monolith, and then the autoclave was sealed. This method can prevent the monolith from shrinking due to evaporation of the organic solvent before it comes into contact with supercritical CO ₂ . The monolith was dried in a CO ₂ stream for 24 hours. The pressure (in the drying system) was 11.5-12.0 MPa (115-120 bar) and the temperature was 40 ° C. Finally, the pressure in the system was reduced to atmospheric pressure in a controlled manner within a period of about 45 minutes at 40 ° C. The autoclave was opened and the dried monolith was removed.

The resulting porous material had a density of 150 g / L.

The thermal conductivity λ was measured according to DIN EN 12667 using a protective hot plate device (Lambda Control A50) manufactured by Hesto. The thermal conductivity was 20.0 mW / m * K at 10 ° C.

The tensile strength was 0.87 N / mm ² as measured according to DIN 53292.

The elastic modulus was measured according to DIN 53292 and was 15.3 N / mm ² .

3. 3. Manufacturing example 2
80 g of compound M200 was dissolved in 220 g of 2-butanone in a glass beaker with stirring at 20 ° C. 8 g of compound MDEA, 8 g of butyldiethanolamine, and 2 g of water were dissolved in 220 g of 2-butanone in a second glass beaker. The two solutions from step (a) were mixed. This gave a low viscosity transparent mixture. The mixture was left at room temperature for 24 hours to cure. The gel was then removed from the glass beaker and dried in an autoclave via solvent extraction using supercritical CO ₂ .

The gel monolith was removed from the glass beaker and transferred to a 25 L autoclave. The autoclave was filled with> 99% acetone so that the acetone completely covered the monolith, and then the autoclave was sealed. This method can prevent the monolith from shrinking due to evaporation of the organic solvent before it comes into contact with supercritical CO ₂ . The monolith was dried in a CO ₂ stream for 24 hours. The pressure (in the drying system) was 11.5-12.0 MPa (115-120 bar) and the temperature was 40 ° C. Finally, the pressure in the system was reduced to atmospheric pressure in a controlled manner within a period of about 45 minutes at 40 ° C. The autoclave was opened and the dried monolith was removed.

The resulting porous material had a density of 153 g / L.

The thermal conductivity λ was measured according to DIN EN12667 using a protective hot plate device (Lambda Control A50) manufactured by Hesto. The thermal conductivity was 21.0 mW / m * K at 10 ° C.

The compression strength was measured according to DIN 53421 and was 0.64 N / mm ² for 5.3% compression.

The elastic modulus was 31 N / mm ² .

4. Manufacturing example 3
80 g of compound M200 was dissolved in 250 g of ethyl acetate in a glass beaker at 20 ° C. with stirring. 8 g of compound MDEA and 8 g of methyldiethanolamine were dissolved in 250 g of ethyl acetate in a second glass beaker. The two solutions from step (a) were mixed. This gave a low viscosity transparent mixture. The mixture was left at room temperature for 24 hours to cure. The gel was then removed from the glass beaker and dried in an autoclave via solvent extraction using supercritical CO ₂ .

The gel monolith was removed from the glass beaker and transferred to a 25 L autoclave. The autoclave was filled with> 99% acetone so that the acetone completely covered the monolith, and then the autoclave was sealed. This method can prevent the monolith from shrinking due to evaporation of the organic solvent before it comes into contact with supercritical CO ₂ . The monolith was dried in a CO ₂ stream for 24 hours. The pressure (in the drying system) was 11.5-12.0 MPa (115-120 bar) and the temperature was 40 ° C. Finally, the pressure in the system was reduced to atmospheric pressure in a controlled manner within a period of about 45 minutes at 40 ° C. The autoclave was opened and the dried monolith was removed.

The resulting porous material had a density of 110 g / L.

The thermal conductivity λ was measured according to DIN EN12667 using a protective hot plate device (Lambda Control A50) manufactured by Hesto. The thermal conductivity was 20.0 mW / m * K at 10 ° C.

The compression strength was 0.52 N / mm ² with respect to 10% compression.

Claims (4)

A continuous method of manufacturing a profile and a composite element containing an insulating core at least somewhat enclosed by the profile.
The adiabatic core is composed of an organic porous material having a thermal conductivity in the range of 13-25 mW / m * K measured according to DIN 12667 and a compressive strength greater than 0.30 N / mm ² measured according to DIN 53421. The profile was made around the insulation core and
The profile comprises making it continuously around the insulating core at a temperature in the range of 100-220 ° C. by means of a ring extruder, and the profile comprises at least one thermoplastic material. And the organic porous material is one selected from the group consisting of an organic xerogel and an organic airgel, and a combination of two or more thereof, and the organic porous material is an organic xerogel based on polyisocyanurate. organic aerogels based on polyisocyanurate, and 1 Tanedea selected from the group consisting of combinations of two or more thereof is,
A method characterized in that the composite element is used to manufacture windows, doors, refrigerators, and large box freezers, or to manufacture elements for façade structures . The method of claim 1, wherein the profile is composed of polyvinyl chloride. The method according to claim 1 or 2, wherein the organic porous material has a density in the range of 70 to 300 kg / m ³ . The method according to any one of claims 1 to 3, wherein the organic porous material has a heat resistance of more than 160 ° C.