CN109488160A - The method for preparing molded part - Google Patents

Abstract

The invention relates to a composite element comprising a profile and an insulating core surrounded at least to some extent by the profile, wherein the insulating core consists of an organic porous material having a thermal conductivity in the range from 13 to 30 mW, determined according to DIN 12667 /m*K, and a compressive strength greater than 0.20 N/mm ² as determined according to DIN 53421, relates to a method for producing such composite elements and the use of such composite elements for producing windows, doors, refrigerators and/or freezing units and freezers or the use of facade building components.

Description

The method for preparing molded part

The application be the applying date be on November 4th, 2013, application No. is 201380057656.0, entitled " preparation The divisional application of the Chinese patent application of the method for molded part ".

The present invention relates to the composite components for the insulation core for including profile and at least being surrounded to a certain extent by profile, wherein Insulation core is made of organic porous material, and the organic porous material is from 13 according to the thermal conductivity range that DIN 12667 is measured It is greater than 0.20N/mm to 30mW/m*K and according to the compression strength that DIN 53421 is measured², it is related to preparing such composite component Method and such composite component are used to prepare the purposes of window, door, refrigerator and chest freezer or the component as vertical-face building.

The prior art provide it is a variety of for optimizing the measure of the heat transfer properties of composite material, mainly include to hollow cavity or The integration of the hollow cavity of foam filling.Therefore, the technology of preparing of such thermal insulation member is usually complicated, because when using foam When, it has a problem that, i.e., must use difficult technique that foam is inserted into hollow cavity or entirely may be used in thermal insulation member It can be used for foam fill process with the only only a part in space.Compel in terms of due to the growing heat-insulating property to profile Be essential and ask, individual chamber has become smaller and cavity wall becomes thinner, therefore along with finally with mold (tooling) with And extruding technology is relevant difficult and spends.(also become to meet requirement especially relevant in terms of the heat preservation of building construction Must be increasingly stringenter), the processing of heat-insulating material and composite component is by more strict requirements.

For example, 28 44 006 A1 of DE discloses a kind of method for extrusion plastic profile, the plastic material has The core made of foamed plastic, the outer cover that every one side of the core is all made of plastics are surrounded, will wherein use is individually operated Material for outer cover is introduced into extruder die (extuder die), while core material being introduced into the chamber of molding outer cover, wherein The gas in the chamber for being introduced into outer cover is dispersed by extruder die during the foaming of core material.

99/16996 A1 of WO discloses a kind of method of frame section bar for being used to prepare window or door, wherein first by one kind Thermoplastic material prepares external profile, and then the expandable mixtures based on polyurethane are introduced into profile, also, along with mixed The completion for closing object foaming generates between external profile and foam and firmly combines (secure bond).The file also discloses A kind of method, wherein external profile forms first, then, prefabricated instant foaming (ready-foamed) core is inserted into it In.

199 61 306 A1 of DE also discloses a kind of method for preparing profile by extrusion.This profile includes shell and hair The inner core of bubble.In this method, profile shell external first is extruded, and is then filled with expandable material.

DE 1 959 464 also discloses a kind of for persistently squeezing out with the outer cover made of thermoplastic material and having The method of the continuous section bar of foam core, wherein preparing outer cover by extruding by thermoplastic material first, then this outer cover use can The material of foaming is filled.

2 072 743 A2 of EP discloses a kind of method that hollow window frame or hollow doorframe are filled with foam.For this purpose, logical Generation finished product window frame or finished product doorframe can be combined by crossing the plastic material for squeezing out and preparing, then by introducing foamable material bubble Foam filling.

The prior art also discloses the method for being used to prepare such profile with foaming core, wherein the plug-in unit to foam immediately It is recorded by squeezing out in the profile prepared by being inserted into, such as in 02/090703 A2 of DE 202009003392 U1 or WO 's.

10 2,009 037 851 A1 of DE is disclosed for window member, door component and in the profile of facade element Heat-insulated thermal insulation member, it is a kind of for window member, door component and profile for facade element and preparation method thereof.

2 062 717 A1 of EP also discloses that a kind of preparation in coextrusion method has the side of the plastic material of foaming core Method, wherein the expandable material-of expandable material-especially solid-state is coextruded into the chamber of hollow plastic material and wherein Foaming.

However, there is the insulation of bigger insulation effect using other as the demand to insulation aspect becomes more stringent Material is also necessary.For example, for window, without the further space that profile thickness can increase, and must be not Cause to reduce thermal conductivity in the case where any thickness change to improve insulation.

Therefore other heat-insulating materials used other than polyurethane foam in the prior art are organic aerogel and do solidifying Glue has the good performance profile as heat-insulating material.For example, 2012/059388 A1 of WO discloses aeroge and does The purposes of gel and aeroge and xerogel as heat-insulating material and in vacuum heat-insulating plate.Specification also discloses one kind The method for being used to prepare the porous material of aeroge and xerogel form, wherein making at least one polyfunctional isocyanates and packet Include the amine component reaction of at least one multifunctional substituted aromatic amine.

Material disclosed in this document has good heat-insulating property.However, preparation method is prepared for the material of sheet-form Material, therefore method well known in the prior art can not be used so that it is included in the hollow cavity of profile.

Therefore, from the prior art, it is an object of the present invention to provide components, in particular for the structure of window Part can be prepared with good heat-insulating property and by using simple technology.

The present invention passes through including profile and at least to a certain extent by the composite component of the insulation core of profile encirclement come real The existing purpose, wherein the insulation core is made of organic porous material, the organic porous material is measured according to DIN 12667 Thermal conductivity range be from 13 to 30mW/m*K, according to DIN 53421 measure compression strength be greater than 0.20N/mm²。

Composite component of the invention include profile and at least to a certain extent by profile surround insulation core.For this hair Bright purpose, profile herein are solid structure, have the aperture (cutouts) extended along profile or hollow cavity.At this In invention, insulation core is located in these apertures or the hollow cavity of composite component.Therefore, profile at least surrounds exhausted to a certain extent Hot core, and preferably completely surround.Therefore, insulation core extends along profile.

In the present invention, insulation core is made of organic porous material, and the organic porous material is measured according to DIN 12667 Thermal conductivity range be from 13 to 30mW/m*K, according to DIN 53421 measure compression strength be greater than 0.20N/mm²。

Suitable material is essentially known.For example, organic aerogel and xerogel have these properties.

Therefore, a preferred embodiment of the invention provide it is above-mentioned include profile and at least to a certain extent by The composite component for the insulation core that profile surrounds, wherein organic porous material be it is a kind of selected from organic xerogel and organic aerogel and The material of its two or more combination.

Composite component of the invention has unexpected good heat-insulating property.Due to using the organic more of low heat conductivity Porous materials, although the low thickness as defined in the construction technology of heat-insulating material, may be otherwise realization meet it is ever-increasing right The superperformance of heat-insulated aspect urgent need.

Composite component of the invention requires the building element of low u value (heat transfer coefficient) particularly suitable for preparing, and example is Window and door.

In addition, composite component of the invention can be easily with low cost preparation.

It is used to prepare including profile and is at least surrounded to a certain extent by the profile the present invention also provides a kind of It is insulated the continuation method of the composite component of core, wherein the insulation core is made of organic porous material, the organic porous material The thermal conductivity range measured according to DIN 12667 is from 13 to 30mW/m*K, and the compression strength measured according to DIN 53421 is big In 0.20N/mm², wherein the profile is around insulation core construction.

The thermal conductivity range that the organic porous material that the present invention uses is measured according to DIN 12667 is from 13 to 30mW/m* K, especially 13.5 are to 25mW/m*K, and more preferable 14 to 22mW/m*K, particularly preferred 14.5 to 20mW/m*K.

Specifically preferred according to the invention is to use organic aerogel as organic porous material, the thermal conductivity of the organic aerogel Rate range is from 14 to 22mW/m*K particularly preferred 14.5 to 20mW/m*K.

Organic porous material used in the present invention also have according to DIN 53421 measure compression strength be greater than 0.20N/mm², particularly greater than 0.25N/mm², more preferably greater than 0.30N/mm²And particularly preferably more than 0.35N/mm²。

The high compressive strength of the material is a kind of measurement of rigidity and the production and storage for allowing material, and this promotes The processing of composite component during preparation.In addition, the material also has the meaning in structure.

Commonly used in insulation standard rigid foam for example with thermal conductivity range be from 20 to 25mW/m*K, resistance to compression Intensity is only about 0.15N/mm².Although the compression strength of such material can be improved by increasing thickness, can also mention simultaneously Therefore high heat conductance and heat-insulating property will become worse.

For the purpose of the present invention, xerogel is a kind of porous material, and porosity is at least 70 volume % and volume- Average pore size is at most 50 microns, and it has passed through sol-gel process (sol-gel process) preparation, wherein liquid phase Pass through dry removal under the critical-temperature lower than liquid phase and the critical pressure (" undercritical conditions ") lower than liquid phase by gel.

Therefore, for the purpose of the present invention, aeroge is a kind of porous material, porosity be at least 70 volume % and Volume-average pore size is at most 50 microns, and it is prepared by sol-gel process, and wherein liquid phase is by gel in height Pass through dry removal under critical-temperature in the liquid phase and the critical pressure higher than the liquid phase (" super critical condition ").

Average pore size is to be measured according to DIN 66133 by mercury injection method and be in principle body for the object of the invention Product is average.

Preferably, volume-average pore size of porous material is at most 20 microns.It is particularly preferred that the volume-of porous material Average pore size is at most 10 microns, and is very particularly preferably at most 5 microns, and in particular up to 3 microns.

Although the minimum-value aperture with high porosity is desirable, preparation method from the perspective of lower thermal conductivity One actual lower limit is defined to volume-average pore size.The average aperture of volume-is generally at least 50nm, preferably at least 100nm.In many cases, the average aperture of volume-is at least 200nm, especially at least 300nm.

Therefore, a preferred embodiment of the invention provide it is a kind of include profile and at least to a certain extent by The composite component for the insulation core that the profile surrounds, wherein the insulation core is made of organic porous material, the Porous-Organic The thermal conductivity range that material is measured according to DIN 12667 is from 13 to 30mW/m*K, according to the pressure resistance of the measurement of DIN 53421 Degree is greater than 0.20N/mm², and it is a kind of material selected from organic xerogel and organic aerogel and its two or more combinations Material.

It is preferred for the organic xerogel of the purpose of the present invention and aeroge is described as follows.

It is preferred that organic aerogel or xerogel are based on isocyanates and to be optionally based on other and have to isocyanates Reactive component.For example, organic aerogel or xerogel can based on isocyanates and based on OH- function and/or NH- official The compound of energy.

For example, the present invention is preferably based on organic xerogel of polyurethane, polyisocyanurate or polyureas or based on poly- ammonia The organic aerogel of ester, polyisocyanurate or polyureas.

Therefore, a preferred embodiment of the invention provides a kind of including profile and at least to a certain extent by institute The composite component of the insulation core of profile encirclement is stated, as described above, wherein the organic porous material is selected from a kind of following materials Material: organic xerogel based on polyurethane, polyisocyanurate or polyureas；Based on polyurethane, polyisocyanurate or polyureas Organic aerogel；And its two or more combination.

Particularly preferably organic aerogel or xerogel are based on isocyanates and to be based on having isocyanates anti- The component of answering property, wherein using at least one polyfunctional aromatic amine as to isocyanates has reactive component.It is preferred that Be organic xerogel or aeroge is based on polyureas and/or poly-isocyanurate.

" being based on polyureas " means at least 50mol%, preferably at least 70mol% in organic xerogel or aeroge, especially It is the form that the connection of at least monomeric unit of 90mol% takes urethane to connect." be based on polyureas " mean in organic xerogel or At least 50mol%, preferably at least 70mol% in aeroge, the connection of the especially at least monomeric unit of 90mol% take urea to connect The form connect." be based on polyisocyanurate " means in organic xerogel or aeroge at least 50mol%, preferably at least 70mol%, the form that the connection of the especially at least monomeric unit of 90mol% takes isocyanuric acid ester to connect." it is based on polyureas And/or polyisocyanurate " mean at least 50mol%, preferably at least 70mol% in organic xerogel or aeroge, especially It is that the form that urea connects and/or isocyanuric acid ester connects is taken in the connection of at least monomeric unit of 90mol%.

Composite component of the invention also may include the combination of various aeroges and xerogel herein.For mesh of the invention , composite component also may include multiple insulation cores.For the purpose of the present invention, composite component is other than organic porous material It can also include another heat-insulating material, such as polyurethane.

Term organic porous material used in hereafter refers to organic aerogel or xerogel used in the present invention.

Preferably, the organic porous material used obtains in the method comprising following step:

(a) make at least one polyfunctional isocyanates (a1) and at least one polyfunctional aromatic amine (a2) optionally It is reacted in solvent in the presence of water is as component (a3) and optionally in the presence of at least one catalyst (a4)；

(b) solvent is removed to obtain aeroge or xerogel.

It is preferred for the component (a1) of step (a) purpose and is explained as follows to (a4) and quantitative proportion.

The term component (a1) being used below is all polyfunctional isocyanates (a1).Correspondingly, hereinafter The term component (a2) used is all polyfunctional aromatic amines (a2).It is apparent for those of ordinary skills Be that the monomer component mentioned exists in the form of reaction in organic porous material.

For the purpose of the present invention, the degree of functionality of compound means the number of active group in each molecule.In monomer group In the case where dividing (a1), degree of functionality is the number of isocyanates in each molecule.In the feelings of the amino group of monomer component (a2) Under condition, degree of functionality is the number of active amine groups in each molecule.The degree of functionality of polyfunctional compound is at least 2 herein.

If the mixture of the compound with different degrees of functionality is used as component (a1) or (a2), the official of the component Energy degree can be obtained in each case by the number-average of each compound.Polyfunctional compound includes in each molecule At least two aforementioned functional groups.

Component (a1)

It is preferable to use at least one polyfunctional isocyanates as component (a1).

For the purpose of method of the invention, the usage amount of component (a1) is preferably at least 20 weight %, especially at least 30 weight %, particularly preferably at least 40 weight %, very particularly preferably at least 55 weight %, especially at least 68 weight %, Based on component (a1), (a2) if to the total weight of --- related --- (a3) in respective situation, total weight is with 100 weight % Meter.For the purpose of method of the invention, the usage amount of component (a1) is also preferably at most 99.8 weight %, in particular up to 99.3 weight %, particularly preferably at most 97.5 weight % are each based on component (a1), (a2) if to --- related --- (a3) Total weight, total weight is in terms of 100 weight %.

Workable polyfunctional isocyanates is aromatics, aliphatic series, alicyclic and/or araliphatic isocyanates.It is such more The isocyanates of function is known per se or can be prepared by method known per se.Specifically, polyfunctional isocyanic acid Ester also uses as a mixture, and component (a1) further includes various polyfunctional isocyanates in the case.It can use The polyfunctional isocyanates for making monomeric unit (a1) has more than two isocyanates in the molecule of each monomer component Group (wherein term diisocyanate is used for the former below).

Particularly suitable compound is diphenyl methane 2,4 '-, 2,2 '-and/or 4,4 '-diisocyanate (MDI), naphthalene 1,5- diisocyanate (NDI), toluene 2,4- and/or 2,6- diisocyanate (TDI), 3,3 '-dimethyl diphenyl, two isocyanide Acid esters, 1,2- diphenylethane diisocyanate and/or to phenylene vulcabond (PPDI), three, four, five, six, seven and/or Eight methylene diisocyanates, 2- methyl pentamethylene 1,5- diisocyanate, 2- ethylbutylene Isosorbide-5-Nitrae-diisocyanate, five Methylene 1,5- diisocyanate, butylidene Isosorbide-5-Nitrae-diisocyanate, 1- isocyanato- -3,3,5- trimethyl -5- isocyanic acid Root closes hexahydrotoluene (isophorone diisocyanate, IPDI), Isosorbide-5-Nitrae-and/or 1,3- bis- (isocyanatomethyl) hexamethylene (HXDI), hexamethylene Isosorbide-5-Nitrae-diisocyanate, 1- hexahydrotoluene -2,4- and/or -2,6- diisocyanate and dicyclohexyl first Alkane 4,4 '-, 2,4 '-and/or 2,2 '-diisocyanate.

It is preferred that aromatic isocyanate is as polyfunctional isocyanates (a1).This is particularly suitable for water as component (a3) When.

Below it is the particularly preferred embodiment of the polyfunctional isocyanates of component (a1):

I) polyfunctional isocyanates is based on toluene di-isocyanate(TDI) (TDI), especially 2,4-TDI or 2,6-TDI or 2, The mixture of 4- and 2,6-TDI；

Ii) polyfunctional isocyanates is based on methyl diphenylene diisocyanate (MDI), especially 2,2 '-MDI or 2,4 '-MDI or 4,4 '-MDI or oligomeric MDI (it is also referred to as polyphenyl polymethylene isocyanates) or two or three aforementioned two The mixture of methylenebis phenyl isocyanate, or thick MDI (it is generated during preparing MDI) or at least one MDI's is low The mixture of polymers and at least one low molecular weight MDI derivative above-mentioned；

Iii) at least one aromatic isocyanate and embodiment ii of embodiment i)) at least one aromatics isocyanide The mixture of acid esters.

Oligomeric methylene diphenyl diisocyanate is particularly preferable as polyfunctional isocyanates.Oligomeric methylene diphenyl two Isocyanates (hereinafter referred to as oligomeric MDI) includes multiple oligomeric condensates and therefore methyl diphenylene diisocyanate (MDI) Derivative mixture.Polyfunctional isocyanates is also preferably by the mixing of single poly aromatic diisocyanate and oligomeric MDI Object composition.

Oligomeric MDI includes the multicore condensation product that more than one degree of functionality is greater than the MDI of 2 (especially 3 or 4 or 5).It is oligomeric MDI is MDI that is known and being often referred to as polyphenyl polymethylene isocyanates or polymerization.Oligomeric MDI is usually by having not With the isocyanates composition of the MDI class of degree of functionality.Oligomeric MDI with the mixture of monomer MDI usually to use.

(average) degree of functionality of isocyanates including oligomeric MDI can change in the range of from about 2.2 to about 5, especially From 2.4 to 3.5, especially from 2.5 to 3.The mixture of such polyfunctional isocyanates of MDI class with different degrees of functionality has Body is thick MDI, is generated during MDI preparation, usually by hydrochloric acid catalysis, for the form of the intermediate product of thick MDI preparation.

The mixture of polyfunctional isocyanates and a variety of polyfunctional isocyanates based on MDI is known and example It is such as sold by BASF Polyurethanes GmbH, trade name

Preferably, the degree of functionality of component (a1) is at least 2, is especially at least 2.2, and especially preferably at least 2.4.The degree of functionality preferably from 2.2 to 4 and particularly preferably from 2.4 to 3 of component (a1).

The content of the isocyanate groups of component (a1) is preferably from 5 to 10mmol/g, special especially from 6 to 9mmol/g Not preferably from 7 to 8.5mmol/g.Those skilled in the art recognize the content of isocyanate groups (with mmol/g Meter) with referred to as equivalent (with gram/wait meters) characteristic there is reciprocal relation.The content root of isocyanate groups in terms of mmol/g It is obtained according to ASTM D5155-96 A by the content in terms of weight %.

In a preferred embodiment, component (a1) is selected from 4,4 '-diisocyanate of diphenyl methane by least one Ester, 2,4 '-diisocyanate of diphenyl methane, 2,2 '-diisocyanate of diphenyl methane and oligomeric methylene diphenyl two are different The polyfunctional isocyanates of cyanate.For the purpose of the preferred embodiment, component (a1) particularly preferably includes oligomeric Methyl diphenylene diisocyanate and at least 2.4 degree of functionality.

The viscosity of the component (a1) used can change in a wide range.Preferably the viscosity of component (a1) be from 100 to 3000mPa.s, especially from 200 to 2500mPa.s.

Component (a2)

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

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

Component (a2) can be prepared in situ to a certain extent.In the embodiment of this type, for step (a) purpose Reaction carries out in the presence of water (a3).Water is reacted with isocyanate groups generates amino group and releasing along with carbon dioxide It puts.Therefore, polyfunctional amine is prepared in situ as intermediate product to a certain extent.During reaction, they and isocyanide Acid esters group is reacted to form urea connecting key.

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

In another embodiment, it is also preferred that component (a1) and polyfunctional aromatic amine are as component (a2) Reaction optionally carries out in the presence of catalyst (a4).Water (a3) is not present herein.

Polyfunctional aromatic amine sheet is as known to those of ordinary skill in the art.Polyfunctional amine is that each molecule has at least Two have the amine of reactive amino group to isocyanates.Herein to isocyanates have reactive group be primary amine group and Secondary amine group, and the reactivity of primary amine group is generally significantly greater than the reactivity of secondary amine group herein.

Polyfunctional aromatic amine be preferably have there are two primary amine group double-core aromatic compounds (bifunctional aromatic amine), The correspondingly mixture of three cores with more than two primary amine group or multi-nucleus aromatic compound or aforesaid compound.It is especially excellent The polyfunctional aromatic amine of the component (a2) of choosing is the isomers and derivative of diaminodiphenyl-methane.

The double-core aromatic amine for the difunctionality mentioned is particularly preferably those of general formula I compound,

Wherein R¹And R²It may be the same or different and hydrogen and straight chain or branch with 1 to 6 carbon atom can be selected from independently of each other Alkyl group, and wherein all substituent group Q¹To Q⁵And Q^1,To Q^5,It is all identical or different and be selected from independently of each other Hydrogen, primary amine groups and the linear or branched alkyl group group with 1 to 12 carbon atom, wherein alkyl group can have other officials It can roll into a ball, condition is that compounds of formula I includes at least two primary amine groups, wherein Q¹、Q³And Q⁵At least one be primary amine groups Group, and Q^1’、Q^3’And Q^5’At least one be primary amine group.

In one embodiment, methyl, ethyl, positive third are selected from for the alkyl group of the substituent group Q purpose of general formula I Base, isopropyl, normal-butyl, sec-butyl and tert-butyl.Such compound is hereinafter referred to as the aromatic amine (a2-s) replaced.So And, it also may be preferable for be all substituent group Q be all hydrogen, they are not the amino defined above (arts used on that point Language is unsubstituted polyfunctional aromatic amine).

Preferably, for the R of general formula I purpose¹And R²It is identical or different and hydrogen, primary amine group can be selected from independently of each other With the linear or branched alkyl group group with 1 to 6 carbon atom.Preferably, R¹And R²Selected from hydrogen and methyl.It is particularly preferred It is R¹=R²=H.

Other suitable polyfunctional aromatic amines (a2) are specially the isomers and derivative of toluenediamine.It is particularly preferred Isomers and derivative for the toluenediamine of component (a2) purpose are toluene 2,4- diamines and/or toluene 2,6- diamines, with And diethyl toluene diamine, especially 3,5- diethyltoluene -2,4- diamines and/or 3,5- diethyltoluene -2,6- diamines.

Very particularly preferably, component (a2) includes at least one selected from 4,4 '-diaminodiphenyl-methanes, 2,4 '- The polyfunctional aromatics of diaminodiphenyl-methane, 2,2 '-diaminodiphenyl-methanes and oligomeric diamino diphenyl methane Amine.

Oligomeric diamino diphenyl methane includes more than one aniline and multicore methylene-bridge joint condensation product of formaldehyde. Oligomeric MDA includes at least one, but usually oligomer of a variety of degrees of functionality greater than the MDA of 2, especially 3 or 4 or 5.It is oligomeric MDA is known or can be prepared by method known per se.Oligomeric MDA usually makes in the form of with the mixture of monomer MDA With.

(average) degree of functionality of the polyfunctional amine (including oligomeric MDA) of component (a2) can be in the range of from about 2.3 to about 5 Variation, especially from 2.3 to 3.5, and especially from 2.3 to 3.A kind of MDA class polyfunctional amine with different degrees of functionality The specifically thick MDA of this mixture is specifically during aniline and formaldehyde condensation as the intermediate products in thick MDI preparation And prepare, usually by hydrochloric acid catalysis.

It is particularly preferred that at least one polyfunctional aromatic amine includes diaminodiphenyl-methane or diamino-diphenyl The derivative of methane.It is particularly preferred that at least one polyfunctional aromatic amine includes oligomeric diamino diphenyl methane.Especially Preferably, component (a2) includes oligomeric diamino diphenyl methane as compound (a2), and its total degree of functionality is at least 2.1.Specifically, component (a2) includes oligomeric diamino diphenyl methane and its degree of functionality is at least 2.4.

It, can be by using the substituted polyfunctional aromatic amine control for being directed to component (a2) purpose for the purpose of the present invention The reactivity of primary amine group processed.Referring to and being set forth below, hereinafter referred to as (a2-s) substituted polyfunctional aromatic amine It can be used alone or with (wherein Q all in Formulas I is all hydrogen, at this with aforementioned (unsubstituted) diaminodiphenyl-methane They are not NH in meaning₂) mixture form use.

In this embodiment, the Q for above-mentioned Formulas I purpose²、Q⁴、Q^2’And Q^4’(including subsidiary definition) preferably selects To make compounds of formula I that there is at least one tool on the alpha-position relative at least one primary amine group being bound on aromatic ring There is the linear or branched alkyl group of 1 to 12 carbon atom, wherein the alkyl can be with other functional groups.Preferably, herein Q in embodiment²、Q⁴、Q^2’And Q^4’The aromatic amine (a2-s) that may be selected to be makes to replace includes at least two primary amine groups, Alpha-position is respectively provided with one or two linear or branched alkyl group group with 1 to 12 carbon atom, and wherein these alkyl can have There are other functional groups.In this sense, Q²、Q⁴、Q^2’And Q^4’One or more of may be selected to be and make them with 1 to 12 The linear or branched alkyl group of a carbon atom, wherein these alkyl have other functional groups, then preferred amino group and/or hydroxyl Base group and/or halogen atom are as these functional groups.

Preferably, these amines (a2-s) be selected from 3,3 ', 5,5 '-tetraalkyl -4,4 '-diaminodiphenyl-methanes, 3, 3 ', 5,5 '-tetraalkyl -2,2 '-diaminodiphenyl-methanes and 3,3 ', 5,5 '-tetraalkyl -2,4 '-diamino-diphenyl first Alkane, wherein the alkyl in 3,3 ', 5 and 5 ' positions, which may be the same or different and be selected from independently of each other, has the straight of 1 to 12 carbon atom Chain or branched alkyl, wherein these groups can have other functional groups.It is preferred that aforesaid alkyl group: methyl, ethyl, n-propyl, Isopropyl, normal-butyl, sec-butyl or tert-butyl (unsubstituted in each case).

In one embodiment, one in the more than one alkyl of substituent group Q, multiple or all hydrogen atoms can Replaced by halogen atom, is especially replaced by chlorine.Alternatively, one in the more than one alkyl of substituent group Q, it is multiple Or all hydrogen atoms can be by NH₂Or OH replaces.However, it is preferred that the alkyl for general formula I purpose is made of carbon and hydrogen.

In an especially preferred embodiment, component (a2-s) includes 3,3 ', 5,5 '-tetraalkyl -4,4 '-diamino Diphenyl methane, wherein alkyl may be the same or different and independently selected from the linear chain or branched chain alkane with 1 to 12 carbon atom Base, wherein these alkyl can optionally have functional group.Aforesaid alkyl is preferably selected from unsubstituted alkyl, especially methyl, second Base, n-propyl, isopropyl, normal-butyl, sec-butyl or tert-butyl are particularly preferably selected from methyl and ethyl.Very particularly preferably 3, 3 ', 5,5 '-tetraethyl -4,4 '-diaminodiphenyl-methanes and/or 3,3 ', 5,5 '-tetramethyl -4,4 '-diamino-diphenyls Methane.

The polyfunctional amine of component (a2) above-mentioned itself for those of ordinary skill in the art be it is known or It can be prepared by known methods.A kind of known method be aniline or --- respectively, the derivative of aniline --- with formaldehyde in acid Reaction under catalyst.

Such as above-mentioned explanation, water can replace polyfunctional aromatic amine as component (a3) to a certain extent, wherein its with mention The multifunctional aromatic isocyanate reaction in-situ of the additional component (a1) of the amount of preceding calculating is to generate corresponding polyfunctional virtue Race's amine.

Component (a1) to (a3) is used for during term organogel precursor (A) is below.

Catalyst (a4)

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

Can be used in principle those of ordinary skill in the art it is known accelerate isocyanates trimerization reaction (these Know for trimerization catalyst), and/or accelerate isocyanates and amino (these are known as gel catalyst) react and/ Or acceleration isocyanates reacts any of (these are known as kicker) with water --- in the case of using water --- Catalyst.

Corresponding catalyst is known per se, and can be applied in aforementioned three kinds reactions in different ways.Therefore it The one or more of aforementioned type can be assigned to according to performance.In addition, those of ordinary skill in the art recognizes The reaction in addition to above-mentioned reaction can also occur.

Corresponding catalyst can be for example known in poly- especially characterized by the ratio based on their gel and foaming Urethane [Polyurethanes], the 3rd edition, G.Oertel, Hanser Verlag, Munich, 1993, page 104 to page 110.

Without using component (a3) (not using water), preferred catalyst has trimerization reaction method Remarkable activity.This has advantageous effect for the uniformity of reticular structure, to produce particularly advantageous mechanical performance.

In the case where using water as component (a3), preferred catalyst (a4) has the gel of balance and the ratio of foaming Example, so that component (a1) will not excessively be accelerated with reacting for water, has an adverse effect to reticular structure, and at the same time obtaining short Gel time, therefore demoulding time advantageously reduces.Preferred catalyst has significant activity to trimerization reaction simultaneously. This has favorable influence for the uniformity of reticular structure, to generate particularly advantageous engineering properties.

The catalyst can be monomeric unit (combinative catalyst) or can be not combinative.

It is advantageous using the component (a4) of least effective dose (LED).The usage amount of preferred ingredient (a4) is 0.01 to 5 parts by weight, Especially 0.1 to 3 parts by weight, particularly preferred 0.2 to 2.5 parts by weight, based on amount to the components (a1) of 100 parts by weight, (a2) and (a3) it counts.

The catalyst for being preferred for component (a4) purpose is selected from primary amine, secondary amine and tertiary amine, pyrrolotriazine derivatives, organometallic Close object, metallo-chelate, quaternary ammonium salt, hydroxide, alcoholates and the carboxylic acid of ammonium hydroxide and alkali and alkaline earth metal ions Salt.

Suitable catalyst is specially highly basic, such as quaternary ammonium hydroxide, such as has 1 to 4 carbon original in moieties The tetra-alkyl ammonium hydroxide and benzyltrimethylammonium hydroxide of son；Alkali metal hydroxide, such as potassium hydroxide or sodium hydroxide； And alkali alcoholate, such as sodium methoxide, potassium ethoxide and sodium ethoxide and potassium isopropoxide.

Other suitable catalyst are specially the alkali metal salt of carboxylic acid, such as potassium formate, sodium acetate, potassium acetate, 2- ethyl Caproic acid potassium, Potassium Adipate and Sodium Benzoate, and with 8 to 20 (especially 10 to 20) carbon atoms and optionally with the side OH The alkali metal salt of the long chain fatty acids of base.

Other suitable catalyst are specially N- hydroxy alkyl quaternary ammonium carboxylate, such as trihydroxy methyl propylformic acid ammonium.

The example of suitable organic phosphorus compound --- specifically, phospholene (phospholene) oxide --- is 1- methylphospholene oxide, 3- methyl-1-phenyl phospholene oxides, 1- phenyl phospholene oxides, 3- methyl-1-benzyl Phospholene oxides.

Organo-metallic compound is known for those of ordinary skills especially as gel catalyst itself And it also is suitable as catalyst (a4).The organo-tin compound of such as 2 ethyl hexanoic acid tin and dibutyl tin dilaurate etc It is preferred for the purpose of component (a4).Further preferably acetyl acetone salt, especially zinc acetylacetonate.

Quaternary ammonium is to those skilled in the art as gel catalyst and trimerization reaction catalyst itself Know.Quaternary ammonium is particularly preferably by as catalyst (a4).Preferred quaternary ammonium is specially N, N- dimethyl benzyl amine；N, N '-diformazan Base piperazine；N, N- dimethyl cyclohexyl amine；N, N ', N "-three (dialkyl aminoalkyl)-s- hexahydrotriazine, such as N, N ', N "- Three (dimethylaminopropyl)-s- hexahydrotriazines；Three (dimethyl aminomethyl) phenol；Two (2- dimethylaminoethyl) ethers；N, N, N, N, N- Five methyl diethylentriamine；Methylimidazole；Methylimidazole；Aminopropylimidazol；Dimethyl benzyl amine；1,6- diaza two - ten one -7- alkene of ring [5.4.0]；Triethylamine；Triethylenediamine (IUPAC:1,4- diazabicylo [2,2,2] octane)；Diformazan Base aminoethanolamine；Dimethylaminopropylamine；N, N- dimethylaminoethoxyethanol；N, N, N- trimethylaminoethylethanolamine；Three Ethanol amine；Diethanol amine；Triisopropanolamine；And diisopropanolamine (DIPA)；Methyl diethanolamine；Butyl diethanolamine；And hydroxyl second Base aniline.

N, N- dimethyl cyclohexyl amine, bis- (2- dimethylamino second are selected from particularly preferred for the catalyst of component (a4) purpose Base) ether, N, N, N, N, N- five methyl diethylentriamine, methylimidazole, methylimidazole, aminocarbonyl propyl imidazoles, dimethylbenzyl Amine,-ten one -7- alkene of 1,6- diazabicylo [5.4.0], three dimethylamino-propyl Hexahydrotriazines, triethylamine, three (dimethylamino Methyl) phenol, triethylenediamine (diazabicylo [2,2,2] octane), dimethylamino-ethanol amine, dimethylaminopropylamine, N, TMSDMA N dimethylamine base oxethyl ethyl alcohol, N, N, N- trimethylamine groups ehtylethanolamine, triethanolamine, diethanol amine, triisopropanolamine, two Isopropanolamine, methyl diethanolamine, butyl diethanolamine, hydroxyethyl aniline, acetyl acetone salt, thylhexoic acid ammonium and The ethyl hexyl hydrochlorate of metal ion.

The use for being preferred for the catalyst (a4) of the object of the invention is produced with improved mechanical performance --- and it is specific For improved compression strength --- porous material.In addition, the use of catalyst (a4) reduces gel time, such as accelerate Gel reaction, and do not have detrimental effect to other properties.

Solvent

Organic aerogel or xerogel used in the present invention are prepared in the presence of the solvent.

For the purpose of the present invention, term solvent includes liquid diluent, that is, solvent whether in the narrow sense or is dispersed Medium.The mixture is specially true solution, colloidal solution or the dispersion such as lotion or suspension etc.Mixture is preferably True solution.The solvent is the compound for being liquid, preferable organic solvent under the conditions of step (a).

The solvent used includes the mixture of organic compound or multiple compounds in principle, wherein the solvent is providing It is liquid under the temperature condition and pressure condition (referred to as: solution condition) of the mixture.The composition of solvent be selected as make it is described Solvent can dissolve or disperse and (preferably dissolve) organogel precursor.For above-mentioned organic aerogel or the xerogel of being used to prepare The purpose of preferred method, preferred solvent are the solvent for organogel precursor (A), i.e., have been completely dissolved at reaction conditions The solvent of machine gel precursors (A).

Initial reaction product of the reaction in the presence of solvent is gel, i.e., viscous by one kind of solvent swell Elastic chemistry mesh.The mesh of formation is generally produced for the solvent of good sweller (swelling agent) to be had The mesh of pore and small average pore size is generally produced vice versa for the solvent that gained gel is poor sweller and is averaged with big The gross porosity mesh in aperture.

Therefore pore-size distribution needed for the selection of solvent influences and required porosity.The selection of solvent is usually also with such side Formula carries out, since the formation of precipitation reaction product causes during or after greatly to avoid the method for the present invention the step of (a) Precipitating or flocculation.

When selecting suitable solvent, the ratio of precipitation reaction product is usually less than 1 weight %, based on the mixture Total weight.The amount that precipitated product is formed in specific solvent can measure to gravimetric analysis, by the way that the reaction mixture exists Pass through a kind of suitable filter filtering before gel point.

Workable solvent is those solvents known in the state of the art for isocyanates quasi polymer.It is preferred herein Solvent is that those are used for component (a1), (a2) if to the solvent of --- related --- (a3), i.e., at reaction conditions substantially Component (a1), (a2) are completely dissolved if to those of the ingredient of --- related --- (a3) solvent.It may be preferred that described molten Agent be for component (a1) it is inert, i.e., to its without reactivity.

The example of workable solvent is ketone；Aldehyde；Chain acid alkyl ester (alkyl alkanoates)；Amide, such as first Amide and N-Methyl pyrrolidone；Sulfoxide, such as dimethyl sulfoxide；Aliphatic and alicyclic halogenated hydrocarbons；Halogenated aromatic compound；With And fluorine-containing ether.Also the mixture made of two or more above compounds can be used.

It can also be used acetal as solvent, specially diethoxymethane, dimethoxymethane and 1,3-dioxolane.

Dialkyl ether and cyclic ethers also are suitable as solvent.Preferred dialkyl ether is specially that those have 2 to 6 carbon atoms Ether, specially methyl ethyl ether, diethyl ether, methyl-propyl ether, methyl isopropyl ether, ethyl ether, ethyl isopropyl ether, Dipropyl ether, propyl isopropyl ether, Di Iso Propyl Ether, methyl butyl ether, methyl-isobutyl ether, methyl tertiary butyl ether(MTBE), ethyl-are just Butyl ether, ethyl isobutyl ether and ethyl tert-butyl ether (ETBE).Particularly preferred cyclic ethers is tetrahydrofuran, dioxane and tetrahydro pyrrole It mutters.

Other preferred solvents are chain acid alkyl ester, especially methyl formate, methyl acetate, Ethyl formate, butyl acetate And ethyl acetate.Preferred halogenated solvent is recorded in WO 00/24799, the 12nd row of page 4 to the 4th row of page 5.

Aldehyde and/or ketone are preferred solvent.The aldehydes or ketones for being suitable as solvent are specially that those correspond to general formula R²- (CO)-R¹Solvent, wherein R¹And R²For hydrogen or the alkyl with 1,2,3 or 4 carbon atom.Suitable aldehydes or ketones are specially second Aldehyde, propionic aldehyde, n-butanal, isobutylaldehyde, 2- ethyl butyraldehyde, valeral, isopentyl aldehyde (isopentaldehyde), 2 methyl pentanal, 2- second Base hexanal, methacrylaldehyde, methacrolein, crotonaldehyde, furfural, acrolein dimer, methacrolein dimer, 1,2,3,6- tetra- Hydrogen benzaldehyde, 6- methyl -3- hexamethylene olefine aldehydr, cyanaldehyde (cyanacetaldehyde), glyoxylic acid ethyl ester, benzaldehyde, acetone, Metacetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), methyl n-butyl ketone, ethyl isopropyl ketone, 2- acetyl furan, 2- first Oxygroup -4-methyl-2 pentanone, cyclohexanone and acetophenone.The above-mentioned aldehyde and ketone of form of mixtures can also be used.It is particularly preferably each Substituent group, which has, contains the up to ketone of the alkyl of 3 carbon atoms and aldehyde as solvent.Very particularly preferably general formula is R¹(CO)R² Ketone, wherein R¹And R²Independently of each other selected from the alkyl with 1 to 3 carbon atom.In first preferred embodiment In, ketone is acetone.In another preferred embodiment, two substituent Rs¹And/or R²At least one include have at least The alkyl of 2 carbon atoms, especially methyl ethyl ketone.The use of aforementioned particularly preferred ketone combines method of the invention to generate tool There is the porous material of especially small average pore size.There is no the intention of any restrictions, now thinks due to above-mentioned particularly preferred ketone Relatively high compatibility and the pore structure of gel that makes is extremely fine.

In many cases, especially suitable solvent is by using two or more selected from above-mentioned solvent and complete each other What the mixture of miscible compound obtained.

Preferably component (a1), (a2) if to --- it is related --- (a3) and if --- correlation --- (a4), And the solvent provides before the reaction of (a) in an appropriate form the method for the invention the step of.

It may be preferred that on the one hand component (a1) and on the other hand (a2) if to --- related --- (a3) with And --- if correlation --- (a4) is provided separately in the solvent of appropriate components in respective situation.Be provided separately so that Gelling reaction is preferably monitored or controlled before or during mixed processes.

In the case where using water as component (a3), the component (a3) independently of component (a1) is particularly preferably provided.This It avoids to be lauched the case where component (a2) is not present and is reacted with component (a1) and form network.In addition, water and component (a1) Premix results in more unfavorable property in terms of the uniformity of pore structure and the thermal conductivity of resulting materials.

The mixture (s) provided before step (a) is implemented also includes conven-tional adjuvants conduct known in the art Other components.Such as surface reactive material, nucleating agent, oxidation stabilizers, lubricant and demolding aids, dyestuff may be mentioned and filled out Material, the stabilizer for example about hydrolysis, light, heat or colour fading, organic and/or inorganic filler, reinforcing agent and insecticide.

Other details about above-mentioned auxiliary agent and additive can be found in technical literature, for example, Plastics Additives Handbook, the 5th edition, H.Zweifel, ed.Hanser Publishers, Munich, 2001, page 1 and 41-43 pages.

For the reaction in the step of implementing the method (a), it must generate and be provided first before the reaction of step (a) The homogeneous mixture of component.

Reactive component for step (a) purpose can be provided with usual manner.In order to obtain good quick mixing, It is preferred that making blender or other mixing apparatus for this purpose.In order to avoid the defects of mixed process, homogeneous mixture is prepared The period needed should be less than the period that gel reaction causes at least part gel-forming.The usual right and wrong of other mixing conditions Crucial, and for example mixed process can be carried out at 0 to 100 DEG C and under 0.1 to 10bar (absolute pressure), especially in example As carried out under room temperature and atmospheric pressure.After uniform mixture has been made, mixing apparatus is preferably closed immediately.

Gelling reaction includes a sudden reaction, the especially sudden reaction of isocyanate groups and amine or hydroxyl group.

For the purpose of the present invention, the gel is that a kind of cross-linking system contacted based on polymer with liquid (is used Term is lyogel (solvogel or lyogel), or if using water as liquid: hydrogel (aquagel or hydrogel)).Polymer phase herein forms a kind of continuous three-dimensional network.

The purpose of the step of for the method (a), the gel usually passes through standing preparation, i.e., simply by making to wrap Container, reaction kettle or reactor (hereinafter referred to as gel equipment) containing mixture are stood.It may be preferred that in gelatinization (gel Formed) described in mixture no longer undergo further stirring or mixes because this may inhibit the formation of gel.It has demonstrate,proved It is bright covered in gelatinization the mixture or sealing gel equipment be advantageous.

Described gel method itself is known for one skilled in the art and is recorded in such as WO 2009/ 19 rows of page 21 in 027310 are to the row of page 23 13.

For the purpose of the method, solvent is removed in step (b) (drying).In general, can be in supercritical state Process is dried under state, preferably with CO₂Or other solvents for being suitable for supercritical drying purpose replace the laggard of the solvent Row.Such drying means itself is known to those of ordinary skill in the art.The statement of super critical condition means to require removal Liquid phase with the temperature and pressure in the presence of supercriticality.Therefore the contraction of the jel product during solvent removal can be reduced. The material obtained in the supercritical drying process is referred to as aeroge.

However, it is contemplated that the simple application of this method, preferably by critical lower than the liquid including containing in gel Gaseous state is converted to dry gained gel by the liquid contained in gel under the temperature and pressure of temperature and critical pressure.Face from Asia Material obtained in the drying means on boundary is referred to as xerogel.

Preferably, gained gel passes through under the temperature and pressure of critical-temperature and critical pressure lower than the solvent The solvent conversion is dried for gaseous state.It is preferred, therefore, that the drying process exists during reaction by removal The solvent that do not replaced in advance by other solvents carries out.Suitable method is known similarly for those of ordinary skill in the art And the 22nd row of page 26 of WO-2009/027310 is recorded in the 36th row of page 28.

The above method has obtained the organic porous material with superperformance as heat-insulating material.

Preferably, the density range that the organic porous material of insulation core is used as in composite component of the invention is from 70 To 300kg/m³, especially range is from 75 to 250kg/m³, more preferable range is from 85 to 220kg/m³, particularly preferred range is from 90 To 200kg/m³。

Therefore, a preferred embodiment of the invention provide it is a kind of include profile and at least to a certain extent by The profile surround insulation core composite component, as described above, wherein the density range of organic porous material be from 70 to 300kg/m³。

Preferred organic porous material also has heat resistance, allows profile around insulation core continuous structure, i.e., for example exists It is stable in the extrusion process of profile.It is therefore preferable that the heat resistance of organic porous material is greater than 160 DEG C.

Therefore, a preferred embodiment of the invention provide it is a kind of include profile and at least to a certain extent by The composite component for the insulation core that profile surrounds, as described above, wherein the heat resistance of organic porous material is greater than 160 DEG C.

In the present invention it is preferable to use the performance profile that has of organic aerogel and xerogel first make sure it is described compound Element provides good heat-insulating property, secondly, relying on stability, so that composite component is easy preparation.

Therefore, especially it is possible that preparation has the insulation core of required size and shape, then around insulation in the present invention Core constructs the profile.Avoiding problems the complex steps for needing to prepare the heat-insulating material and being inserted into hollow profile.

Insulation core could generally have any need seemed for those of ordinary skills suitable for required application Shape.The cross section of the insulation core can be circular and/or polygon.The shape of the core can also be uniform or non-equal It is even and, for example, it can have aperture, slot, ridge etc., and these shear actions can be carried out parallel or perpendicular to preparation direction.

Insulation core be typically sized to 5 to 250mm, preferably 10 to 150mm, particularly preferred 15 to 100mm, specially 20 to 80mm, and in the case where the core of irregular shape, these sizes describe maximum distance in any direction.

In a preferred embodiment, composite component prepared by the present invention definitely includes one kind by Porous-Organic material Core is insulated made of material.In the present invention, composite component also can have two, three or four and be made of organic porous material Core.When, there are when two, three or four cores, these cores can have identical or different in composite component prepared by the present invention Shape.In the present invention, composite component also can have at least one and be insulated core and at least one made of organic porous material Kind other insulation cores made of other materials (such as polyurethane foam).

Composite component of the invention includes a kind of profile, and wherein the profile is in principle by any possible suitable material group At being especially made of thermoplastic machinability material, or consist of aluminum.

The profile (preferably completely) surrounds the insulation core to a certain extent or completely.In a preferred embodiment party In case, the profile further includes the filler rod being attached on core.

The thickness of profile itself or profile and any filler rod for belonging to profile is generally 1 to 20mm, preferably 2 to 15mm, spy Not preferably 3 to 10mm, and profile herein and filler rod can have identical or different thickness.In a preferred embodiment In, outer cover or filler rod at profile different loci have different thickness；These thickness are identical in the longitudinal direction but in transverse direction It is upper alterable.Such as this depends on the shape of the profile, in turn depends upon subsequent use.

The profile of composite component prepared by the present invention preferably includes at least one thermoplastic material.Suitable thermoplastic material itself For known to those of ordinary skill in the art and for example, selected from those of materials described below: polyolefin, such as acrylic nitrile-butadiene two Alkene-styrene polymer (ABS), poly methyl methacrylate (PMMA), polyethylene (PE), polypropylene (PP), polystyrene (PS) or polyvinyl chloride (PVC)；Condensation polymer, for example, polyamide (PA) such as PA6 or PA6,6, poly-lactic acid ester (polylactate, PLA), polycarbonate (PC), polyester such as polyethylene terephthalate (PET)；Polyether-ether-ketone (PEEK)；Polyadduct, Such as thermoplastic polyurethane, the wooden plastic composite and its mixture.In an especially preferred embodiment, prepared by the present invention The outer cover of the profile include polyvinyl chloride (PVC).Polyvinyl chloride (PVC) and its by the polymerization of vinyl chloride to prepare itself right It is known in those of ordinary skill in the art.

Therefore, a preferred embodiment of the invention provides a kind of composite component, the composite component institute as above It states including profile and at least to a certain extent by the core of profile encirclement, wherein the profile is made of polyvinyl chloride or aluminium.

A particularly preferred embodiment of the present invention provide it is a kind of include profile and at least to a certain extent by The composite component for the insulation core that the profile surrounds, as described above, wherein the profile is made of polyvinyl chloride.

In a preferred embodiment, the profile includes a kind of thermoplastic material of the fusing point lower than 220 DEG C.

For the purpose of the present invention, composite component of the invention can be prepared in various manners, such as continuously prepared or divided Preparation is criticized, the present invention is preferably continuously prepared.

For the purpose of the present invention, in principle many methods can to prepare composite component of the invention, if they Guarantee that insulation core can be accurately introduced into profile.

It is preferably profile herein around insulation core construction.This simplifies the preparation method of composite component of the invention, because For this facilitate the moldings of hollow structure in profile, because insulation core defines the shape of hollow structure.

Therefore, the present invention also provides one kind to be used to prepare one kind including profile and at least to a certain extent by profile packet The continuation method of the composite component of the insulation core enclosed, wherein the insulation core is made of organic porous material, the Porous-Organic Material is from 13 to 30mW/m*K, according to the resistance to compression of the measurement of DIN 53421 according to the range of the thermal conductivity measured of DIN 12667 Intensity is greater than 0.20N/mm², wherein the profile is around insulation core construction.

Therefore, insulation core can be prepared into required shape and store in the present invention, and followed by processing.

Profile herein can be constructed with a variety of different modes, such as by extruder, particularly preferably be squeezed by annular Machine out.

Therefore, a preferred embodiment of the invention, which provides, prepares one kind including profile and at least to a certain degree On the method for the composite component of insulation core surrounded by profile, as described above, wherein the profile is by ring extruder around exhausted Hot core continuous structure.

The present invention one other embodiments also provide one kind and are used to prepare one kind including profile and at least at certain The method of the composite component of the insulation core surrounded in degree by profile, as described above, wherein the profile is around insulation core by multiple Component construction.

For example, in the present invention, profile described herein can be constructed around insulation core by multiple preformed members, but same Can be preforming to component, insertion insulation core, then for example by being closed profile.

If the profile is constructed by multiple preform parts around insulation core, all parts of the profile can be used Different modes are connected to each other, such as by being bonded or by welding or by push-in-mating connection (push-fit Connections) (" cutting ").

Therefore, the profile can be constructed from thermoplasticity machinable material, such as polyvinyl chloride.

Therefore, yet other embodiments provide that prepare a kind of include profile and at least to a certain extent The method of the composite component of the insulation core surrounded by profile, as described above, wherein the profile is made of polyvinyl chloride.

In the present invention, composite component is prepared preferably by ring extruder.This method includes that will be insulated core introducing herein Into the extruder for the extrusion die for being incidentally used to prepare annular profile, to being packed into insulation core by least one thermoplastic material system At profile in and therefore obtain composite component.

Insulation core is introduced into the extruder of a punch die with reproducible profile shapes herein.Then it is intended to be formed outer The thermoplastic material of cover is applied on the core in extruder in the form melted.The embodiment party of this extruder used in the present invention Case is to be recorded in known to those of ordinary skill and for example WO 2009/098068 in the art.

Method of the invention preferably the molten thermoplastic material of profile at a temperature of carry out, such as from 100 to 220 DEG C, Particularly preferably from 130 to 190 DEG C.

At preferably such as from 25 to 180 DEG C of solidification temperature of the thermoplastic material in the downstream of extruder, preferably from 50 to 150 ℃。

Extrusion of thermoplastic material itself is known for those skilled in the art and is recorded in for example " Einf ü hrung in die Kunststoffverarbeitung " [explanation (the Introduction to of plastic processing Plastics processing)], the 5th edition, in September, 2006；87-180 pages；Walter Michaeli；Hanser Fachbuchverlag。

If reinforcer is introduced in profile in the present invention, when being introduced into extruder, this reinforcer can have Its last shape, for example, it is band-like.In this second embodiment, which squeezes with the outer cover of profile simultaneously in an extruder Out.For this purpose, the material of the reinforcer is introduced preferably by extruder with molten condition.

In a preferred embodiment, this is reinforced for the size and maximizing that the size of reinforcer depends on profile The stability of material.Design reinforcer in this way is in order to reduce or at least not increase Heat transmission in profile, such as in window frame or door In frame.

In the present invention, profile can also discontinuously be constructed around insulation core, such as be constructed by multiple preform parts；It should The all parts of profile can differently be connected to each other, such as by being bonded or connecting by welding or by push-in-cooperation Connect (" cutting ").

For the purpose of the present invention, in an alternative, complete profile can also be prepared first, it then will be exhausted Hot core is inserted into preforming hollow cavity.In this embodiment, profile does not surround insulation core construction.

In such substitution method, any conventional method to be introduced to core is insulated in profile, such as can be used use pumping Insertion or pressure insertion are inhaled, it is preferable to use pressure is inserted into.

Therefore an alternate embodiment of the invention also provides a kind of prepare including profile and at least to a certain degree On by profile surround insulation core composite component method, wherein insulation core be made of organic porous material, the Porous-Organic The thermal conductivity range that material is measured according to DIN 12667 is to resist from 13 to 30mW/m*K, and according to what DIN 53421 was measured Compressive Strength is greater than 0.20N/mm²；It will be wherein insulated in core insertion profile using pressure.

Composite component of the invention has low thermal conductivity for identical insulation thickness, thus this makes them suitable for using In building element, such as window or door.

Therefore building envelope individual building component (wall, window) can meet U value limit (U value=heat transfer coefficient, Unit W/m²* K), wherein these components provide good thermal insulation.

Therefore, the purposes the present invention also provides organic porous material as heat-insulating material in profile is described organic more The thermal conductivity range that Porous materials are measured according to DIN 12667 be from 13 to 30mW/m*K, and according to DIN 53421 measure Compression strength is greater than 0.20N/mm²。

Therefore, a preferred embodiment of the invention provides organic porous material as heat-insulating material in profile Purposes, as described above, wherein the profile be used to prepare window, door, refrigerator and chest freezer or the structure as vertical-face building Part

Another embodiment of the present invention also provides composite component of the invention or obtains by means of the present invention Composite component is used to prepare the purposes of window, door, refrigerator and chest freezer or the component as vertical-face building.

Composite component of the invention is suitable for the construction of various building elements, such as window.

Therefore, specifically, another embodiment of the invention also provides a kind of a kind of window including composite component, The composite component include profile and at least to a certain extent by profile surround insulation core, wherein insulation core by Porous-Organic Material composition, the thermal conductivity range which measure according to DIN 12667 is from 13 to 30mW/m*K, and root Compression strength according to DIN53421 measurement is greater than 0.20N/mm²。

The example that embodiment of the present invention is listed below, but do not limit the present invention.Specifically, the present invention also wraps Include the embodiment that combination is obtained and be consequently formed from following subordinate items.

1. it is a kind of including profile and at least to a certain extent by the composite component of the insulation core of profile encirclement, wherein being insulated Core is made of organic porous material, the thermal conductivity range that the organic porous material is measured according to DIN 12667 be from 13 to 30mW/m*K, and 0.20N/mm is greater than according to the compression strength that DIN 53421 is measured²。

2. according to composite component described in embodiment 1, wherein organic porous material is selected from organic xerogel and organic One of aeroge and its two or more combinations.

3. the composite component according to embodiment 1 or 2, wherein organic porous material is one selected from materials described below Kind: organic xerogel based on polyurethane, poly-isocyanurate or polyureas；Based on polyurethane, poly-isocyanurate or polyureas Organic aerogel；And its two or more combination.

4. according to the described in any item composite components of embodiment 1 to 3, wherein the density range of organic porous material be from 70 to 300kg/m³。

5. wherein the heat resistance of organic porous material is greater than according to the described in any item composite components of embodiment 1 to 4 160℃。

6. wherein profile is made of polyvinyl chloride or aluminium according to the described in any item composite components of embodiment 1 to 5.

7. a kind of continuation method for preparing composite component, the composite component include profile and at least to a certain extent by The insulation core that profile surrounds, wherein insulation core is made of organic porous material, which measures according to DIN 12667 Thermal conductivity range be from 13 to 30mW/m*K, and according to DIN 53421 measure compression strength be greater than 0.20N/mm², Described in profile around insulation core construction.

8. according to method described in embodiment 7, wherein the profile surrounds insulation core continuously by ring extruder Construction.

9. according to method described in embodiment 7, wherein the profile is constructed by multiple components around insulation core.

10. according to the described in any item methods of embodiment 7 to 9, wherein the profile is made of polyvinyl chloride.

11. purposes of the organic porous material as heat-insulating material in profile, the organic porous material is according to DIN The thermal conductivity range of 12667 measurements is to be greater than from 13 to 30mW/m*K, and according to the compression strength that DIN 53421 is measured 0.20N/mm²。

12. according to the purposes of embodiment 11, wherein the profile be used to prepare window, door, refrigerator and chest freezer, Or the component as vertical-face building.

13. according to the described in any item composite components of embodiment 1 to 6 or by any according to embodiment 7 to 10 The composite component that method described in obtains is used to prepare window, door, refrigerator and chest freezer or the component as vertical-face building Purposes.

14. it is a kind of including profile and at least to a certain extent by the composite component of the insulation core of profile encirclement, wherein absolutely Hot core is made of organic porous material, the thermal conductivity range which measures according to DIN12667 be from 13 to 30mW/m*K, and 0.20N/mm is greater than according to the compression strength that DIN 53421 is measured², and the organic porous material is one Kind is selected from the material of organic xerogel, organic aerogel and its two or more combinations.

15. it is a kind of including profile and at least to a certain extent by the composite component of the insulation core of profile encirclement, wherein absolutely Hot core is made of organic porous material, the thermal conductivity range which measures according to DIN 12667 be from 13 to 30mW/m*K, and 0.20N/mm is greater than according to the compression strength that DIN 53421 is measured², and the organic porous material is choosing From one kind of materials described below: organic xerogel based on polyurethane, poly-isocyanurate or polyureas；Based on polyurethane, poly- isocyanide The organic aerogel of urea acid esters or polyureas；And its two or more combination.

16. it is a kind of including profile and at least to a certain extent by the composite component of the insulation core of profile encirclement, wherein absolutely Hot core is made of organic porous material, the thermal conductivity range which measures according to DIN 12667 be from 13 to 30mW/m*K, and 0.20N/mm is greater than according to the compression strength that DIN 53421 is measured², and the organic porous material is choosing From one kind of materials described below: organic xerogel based on polyurethane, poly-isocyanurate or polyureas；Based on polyurethane, poly- isocyanide The organic aerogel of urea acid esters or polyureas；And its two or more combination.Wherein the density range of the organic porous material is 70 To 300kg/m³。

17. it is a kind of including profile and at least to a certain extent by the composite component of the insulation core of profile encirclement, wherein absolutely Hot core is made of organic porous material, the thermal conductivity range which measures according to DIN12667 be from 13 to 30mW/m*K, and 0.20N/mm is greater than according to the compression strength that DIN 53421 is measured², and the organic porous material is choosing From one kind of materials described below: organic xerogel based on polyurethane, poly-isocyanurate or polyureas；Based on polyurethane, poly- isocyanide The organic aerogel of urea acid esters or polyureas；And its two or more combinations, wherein the heat resistance of the organic porous material is greater than 160 ℃。

18. wherein the profile is made of polyvinyl chloride or aluminium according to composite component described in embodiment 17.

19. it is a kind of including profile and at least to a certain extent by the composite component of the insulation core of profile encirclement, wherein absolutely Hot core is made of organic porous material, the thermal conductivity range which measures according to DIN12667 be from 13 to 30mW/m*K, and 0.20N/mm is greater than according to the compression strength that DIN 53421 is measured², and the organic porous material is choosing From one kind of materials described below: organic xerogel based on polyurethane, poly-isocyanurate or polyureas；Based on polyurethane, poly- isocyanide The organic aerogel of urea acid esters or polyureas；And its two or more combinations, and wherein the profile is made of polyvinyl chloride or aluminium.

20. a kind of continuation method for preparing composite component, the composite component includes profile and at least to a certain extent The insulation core surrounded by profile, wherein insulation core is made of organic porous material, which surveys according to DIN 12667 Fixed thermal conductivity range is to be greater than 0.20N/mm from 13 to 30mW/m*K, and according to the compression strength that DIN 53421 is measured², Wherein the profile is continuously constructed by ring extruder around insulation core.

21. a kind of continuation method for preparing composite component, the composite component includes profile and at least to a certain extent The insulation core surrounded by profile, wherein insulation core is made of organic porous material, which surveys according to DIN 12667 Fixed thermal conductivity range is to be greater than 0.20N/mm from 13 to 30mW/m*K, and according to the compression strength that DIN 53421 is measured², Wherein the insulation core is inserted into profile under stress.

22. a kind of window including composite component, the composite component includes profile and at least to a certain extent by type The insulation core that material surrounds, wherein insulation core is made of organic porous material, which measures according to DIN 12667 Thermal conductivity range is to be greater than 0.20N/mm from 13 to 30mW/m*K, and according to the compression strength that DIN 53421 is measured²。

23. 4 to 19 described in any item composite components or by any according to embodiment 20 to 22 according to claim 1 The composite component that method described in obtains is used to prepare window, door, refrigerator and chest freezer or the component as vertical-face building Purposes.

Following embodiments help to illustrate the present invention, but to subject of the present invention absolutely without the work of any restrictions With.

Embodiment

Prepare embodiment: aeroge

1. raw material

Gel is prepared using following compounds:

Component a1: oligomeric MDl (M200), the MDI is according to the NCO content of ASTMD5155-96 A 30.9g/100g, degree of functionality are 3 or so, are 2100mPa.s (hereinafter " chemical combination according to viscosity of the DIN 53018 at 25 DEG C Object M200 ").

Component a2:3,3 ', 5,5 '-tetraethyl -4,4 '-diaminodiphenyl-methanes (hereinafter " MDEA ")

Catalyst: butyl diethanolamine, methyl diethanolamine

2. preparing embodiment 1

At 20 DEG C, in glass beaker, 80g compound M200 is dissolved in the 2- butanone of 220g under stiring.? It is in two glass beakers, 8g compound MDEA and 8g butyl glycol amine and 1g is water-soluble in the 2- butanone of 220g.By step (a) two kinds of solution mixing obtained in.This results in the clarified mixtures of low viscosity.It is small that the mixture is stood 24 at room temperature When to harden.Then gel is taken out and in autoclave from glass beaker by using supercritical CO₂It carries out Solvent extraction and dry.

By gel monolith from the autoclave that 25 liters are taken out and be transferred in glass beaker.The acetone of > 99% is filled Enter in autoclave so that gel monolith is completely covered in acetone, then seals autoclave.The method can be prevented solidifying Glue monolithic and supercritical CO₂Contact before gel monolith as organic solvent volatilization and caused by shrink.By gel monolith in CO₂ It is 24 hours dry under steam.Pressure (in drying system) is 115 to 120bar；Temperature is 40 DEG C.Finally, in 40 DEG C of temperature Under in about 45 minutes in a controlled manner by the pressure reduction in system to atmospheric pressure.Autoclave is opened, and is taken out dry The gel monolith of dry mistake.

Obtained porous material has the density of 150g/L.

It is surveyed according to DIN EN 12667 by using the protective heat plate equipment purchased from Hesto (Lambda Control A50) Determine thermal conductivity λ.Thermal conductivity at 10 DEG C is 20.0mW/m*K.

It is 0.87N/mm according to the tensile strength that DIN 53292 is measured²。

It is 15.3N/mm according to the elasticity modulus that DIN 53292 is measured²。

3. preparing embodiment 2

At 20 DEG C, in glass beaker, 80g compound M200 is dissolved in the 2- butanone of 220g under stiring.? It is in two glass beakers, 8g compound MDEA and 8g butyl glycol amine and 2g is water-soluble in the 2- butanone of 220g.By step (a) two kinds of solution mixing obtained in.This results in the clarified mixtures of low viscosity.It is small that the mixture is stood 24 at room temperature When to harden.Then gel is taken out and in autoclave from glass beaker by using supercritical CO₂It carries out Solvent extraction and dry.

By gel monolith from the autoclave that 25 liters are taken out and be transferred in glass beaker.The acetone of > 99% is filled Enter in autoclave so that gel monolith is completely covered in acetone, then seals autoclave.The method can be prevented solidifying Glue monolithic and supercritical CO₂Contact before gel monolith as organic solvent volatilization and caused by shrink.By gel monolith in CO₂ It is 24 hours dry under steam.Pressure (in drying system) is 115 to 120bar；Temperature is 40 DEG C.Finally, in 40 DEG C of temperature Under in about 45 minutes in a controlled manner by the pressure reduction in system to atmospheric pressure.Autoclave is opened, and is taken out dry The gel monolith of dry mistake.

Obtained porous material has the density of 153g/L.

It is surveyed according to DIN EN 12667 by using the protective heat plate equipment purchased from Hesto (Lambda Control A50) Determine thermal conductivity λ.Thermal conductivity at 10 DEG C is 21.0mW/m*K.

It is 0.64N/mm when compressing 5.3% according to the compression strength that DIN 53421 is measured²。

Elasticity modulus is 31N/mm²。

4. preparing embodiment 3

At 20 DEG C, in glass beaker, 80g compound M200 is dissolved in the ethyl acetate of 250g under stiring.? In second glass beaker, 8g compound MDEA and 8g methyl diethanolamine is dissolved in the ethyl acetate of 250g.By step (a) Obtained in the mixing of two kinds of solution.This results in the clarified mixtures of low viscosity.The mixture is stood 24 hours at room temperature To harden.Then gel is taken out and in autoclave from glass beaker by using supercritical CO₂It carries out molten Agent is extracted and is dried.

By gel monolith from the autoclave that 25 liters are taken out and be transferred in glass beaker.The acetone of > 99% is filled Enter in autoclave so that gel monolith is completely covered in acetone, then seals autoclave.The method can be prevented solidifying Glue monolithic and supercritical CO₂Contact before gel monolith as organic solvent volatilization and caused by shrink.By gel monolith in CO₂ It is 24 hours dry under steam.Pressure (in drying system) is 115 to 120bar；Temperature is 40 DEG C.Finally, in 40 DEG C of temperature Under in about 45 minutes in a controlled manner by the pressure reduction in system to atmospheric pressure.Autoclave is opened, and is taken out dry The gel monolith of dry mistake.

Obtained porous material has the density of 110g/L.

It is surveyed according to DIN EN 12667 by using the protective heat plate equipment purchased from Hesto (Lambda Control A50) Determine thermal conductivity λ.Thermal conductivity at 10 DEG C is 20.0mW/m*K.

Compression strength is 0.52N/mm when compressing 10%²。

Claims (5)

1. A continuous process for the production of a composite element comprising a profile and an insulating core surrounded at least to some extent by the profile, wherein the insulating core consists of an organic porous material determined according to DIN 12667 Thermal conductivity ranging from 13 to 30 mW/m*K and compressive strength greater than 0.20 N/mm ² determined according to DIN 53421, wherein the profile is constructed around an insulating core, Wherein the organic porous material is one selected from organic xerogels and organic aerogels and a combination of two or more thereof, wherein the profile is continuously constructed around the insulating core by means of a ring extruder, The organic porous material is one selected from the following materials: polyisocyanurate-based organic xerogel; polyisocyanurate-based organic aerogel; and a combination of two or more thereof. 2. The method of claim 1, wherein the profile is composed of polyvinyl chloride. 3. The method of claim 1 or 2, wherein the organic porous material has a density ranging from 70 to 300 kg/ ^m3 . 4. The method of any one of claims 1 to 3, wherein the heat resistance of the organic porous material is greater than 160°C. 5. Use of the composite element obtained by the method according to any one of claims 1 to 4 for the production of windows, doors, refrigerators and freezers or as elements of facade construction.