CN103477172B - Comprise the dynamic vaccum-pumping equipment of organic aerogel or xerogel - Google Patents

Abstract

The present invention relates to a kind of electrically operated dynamic vaccum-pumping equipment, it includes continuous evacuation region and the working region by the described continuous evacuation region temperature-controllable heat insulation with ambient temperature, and for actively keeping the equipment of vacuum, so that the pressure timing constant in the continuous evacuation region of described equipment is in the pressure limit of regulation, wherein said continuous evacuation region is at least 20 volume % by the cumulative volume occupied by porous and/or cellular heat-barrier material in the apparatus, and described continuous evacuation region comprises at least one organic aerogel and/or organic xerogel.

Description

Comprise the dynamic vaccum-pumping equipment of organic aerogel or xerogel

The present invention relates to a kind of electrically operated dynamic vaccum-pumping equipment, it includes continuous evacuation district Territory and the use region by the described continuous evacuation region temperature-controllable heat insulation with ambient temperature (useful region), and for actively keeping the device of vacuum, so that the taking out continuously of described equipment Pressure in vacuum area is constant in specific pressure limit, described continuous evacuation region be By occupied by porous (porous) and/or cellular (cellular) heat-barrier material in described equipment At least 20 volume % of cumulative volume, and described continuous evacuation region comprises at least one organic gas Gel and/or organic xerogel.

The invention still further relates in electrically operated dynamic vaccum-pumping equipment in continuous evacuation region Organic aerogel or the purposes of organic xerogel, described equipment is in addition to continuous evacuation region, also There is the use region of the temperature-controllable heat insulation with ambient temperature by described continuous evacuation region, And for actively keeping the device of vacuum, so that the pressure in the continuous evacuation region of described equipment Power is constant in specific pressure limit, and described continuous evacuation region is in the apparatus by many At least 30 volume % of the cumulative volume occupied by hole and/or cellular heat-barrier material.

Heat insulation for save the energy be significant.For the energy cost risen steadily, subtract Few CO₂Ordering about and background that heat insulation and cold insulation demand is increased by future day by day of discharge capacity, Heat insulation just becoming more and more important.The demand that day by day increase heat insulation for optimization had both included building Heat insulation, also include the cold insulation in motor-driven, logistics and fixing industry.

Heat insulation device includes a specific use region, and described region is by suitable heat insulation and ring Demarcating in border, uses the temperature in region higher or lower than external temperature.These heat insulation devices include such as Refrigeration machine, fridge, freezer, cold closet, refrigerating box, refrigerator car or boiler.

In the prior art, use space heat insulation with environment by heat-barrier material.

For heat insulation, a large amount of heat-barrier materials are well known, and special due to closed-cell foam Low thermal conductivity makes it play significant role.Closed pore hard polyaminoester (PUR) in these materials The thermal conductivity of foam is minimum.Described hard PUR foam is generally with physical blowing agent (such as alkane Or fluorinated hydrocarbons) foaming, described physical blowing agent has than air lower thermal conductivity and remains itself In the abscess of foam.Main (prevailing) pressure is equivalent to ambient pressure in the foam.

Recently, PUR the vacuum open celled foam prepared or open mesoporous powder bed (such as silicon dioxide gas Gel (Aerosil)) also use with the form of vacuum insulation panel (VIPs).VIPs is follow-up Heat insulation device is used together with conventional thermal barrier material with panel-form in the step that other are other. Such as, VIPs passes through bonding and PUR foam-in-mould now thus is integrated in refrigeration machine, because of This contributes to reducing energy expenditure.The disadvantage of VIPs be manufacture VIPs and be incorporated into be The extra complexity of system.Because VIPs normally constitutes only an overall heat insulation part, need Reach low reduced pressure to obtain the lowest thermal conductivity.In order to make described reduced pressure in system Life-span during remain stable as far as possible, high to the density requirements of sheathing material.Now, generally It is being used herein as metallized aluminum multilamellar paper tinsel or aluminum composite foil.

Another technical scheme is to provide heat insulation overall volume evacuation or local vacuum-pumping, and And described evacuation in principle can dynamically or static realize.With combine VIPs or with traditional heat insulation material Material is by its surrounding phase ratio, and its significant advantage is the cumulative volume constituting heat-barrier material is placed in reduced pressure Under power and therefore required reduced pressure is relatively small compared with conventional VIPs, or available identical Reduced pressure obtains higher effect of heat insulation.This vaccum-pumping equipment itself is usually art technology Known to personnel.

US1898977 describes the refrigeration machine of a kind of vacuum heat-insulation.Described heat-barrier material is flour filler The chamber minimum with consequent size, the most described size is than the mean free path of gas molecule Length is much smaller.In order to avoid the loss in corner thermal conductivity, the metal between outer wall and inwall Layer should be bridged by the material that thermal conductivity is low.Mention kieselguhr (silocel), cork and paper conduct Heat-barrier material.

EP 0 587 546 A1 describes a kind of vacuum-refrigerator being provided with fixed installation vacuum pump. Described vacuum pump is placed on can be by the heat-barrier material evacuation in airtight and air-locked shell.Due to Pumpdown time is longer, it is contemplated that rack is once arranged on user place, just starts pump.In preparation During circulation time that extension fixture is produced by device evacuation, the most described production process meeting Uneconomical.Described pump is the pump that a kind of specific energy expenditure is minimum, and therefore heat insulation owing to improving The energy that performance is saved is considerably beyond the energy needed for operated vacuum pumps.Due to self-energy consumption Too high, therefore conventional vacuum pump is not appropriate for.

Described heat-barrier material is the closed pore PUR foam of Water blown purely.In this case, bubble First foam abscess contains carbon dioxide, and its diffusion rate is higher five times than air.Purpose is to be less than The reduced pressure of 0.1 millibar.

The important technical defect of the method is the pumpdown time needing extremely to grow.This closing by foam Porous causes.Further, it is necessary to reach extremely low pressure fully reduce thermal conductivity.This is with conventional It is correlated with in the high aperture of rigid foam.

EP 0 587 548 A1 describes similar theme, focuses on the closed pore of heat-barrier material herein Character.Describe open celled foam unfavorable, because foot can not be obtained low density herein simultaneously Enough mechanical strengths.

EP 1 335 171 A1 describes a kind of vacuum-refrigerator, and wherein the pumpdown time is by installing The heat-barrier material with network channel shortens.Such as, the suction that rear wall is arranged by spider reticulation Enter passage and carry out evacuation.Mentioned heat-barrier material is open-cell polyurethane and polystyrene.Additionally, Also relate to the problem long with the current material pumpdown time.

WO2005/093349 describes a kind of powder filler vacuum-refrigerator as heat-barrier material. It is pointed out, can either statically or dynamically apply vacuum in principle.Described refrigeration machine without vacuum pump because This function is assumed to be realized by compressor.

WO2004/010042 describes a kind of vacuum-refrigerator including powder bed.A kind of filling mode Be by shell on rear side of opening carry out.It is referred to the different modification sealed subsequently.

WO2010/127947 describes perfect vacuum gating element.Mentioned packing material is perforate PUR, polystyrene or silica flour.

But, equipment described in the prior art has the root hindering it industrially to implement so far Person's character shortcoming.Reason is heat-barrier material used.So far heat-barrier material used at it is In the case of perforate, not there is the suitable pore structure making the pumpdown time the shortest completely.This Even if being because, completely open celled foam hole dimension in hole window (cell window) is little and foam In the case of being largely different from the simple thermosetting plastic foam of ideal form, also can Need the long pumpdown time.Furthermore it is known that the good heat-barrier material of heat-proof quality only with plate or The form (the most in a compressed format) of powder can obtain.Make formed body and device subsequently Required geometry matches, if it would be possible, this is only at very big cost and not convenient and big Could occur under the waste of amount.For powder bed, it is often impossible to be completely filled with the geometry of complexity It is airtight that shape (such as undercutting) maybe can not realize defining completely.

Known perforate heat-barrier material also has the shortcoming forming epidermis in preparation process.This weakens Vaccum, particularly in the case of relatively large continuous evacuation region, because this epidermis The gas filling abscess is prevented to be drawn out of.

Owing to lacking suitable heat-barrier material, the industrial implementation of the most above-mentioned cooling device does not becomes so far Merit.

The vacuum heat-insulation equipment (such as vacuum-refrigerator) of a kind of improvement should have short evacuation Time and the shortest suction time and shorter pump circulation time, and treat continuous evacuation The relatively low demand of the housing in region.

Heat-barrier material should have a following performance simultaneously present in the described continuous evacuation region:

-during generation is heat insulation, material consumption is low in a device

-in the pressure limit of 1 to 10 millibar, thermal conductivity is greatly reduced

-complicated three-dimensional geometrical structure can be set up without post-processing step

-the lowest water vapor absorption ability and low gas sorption capability, it moves for vacuum State keeps particular importance.

It is an object of the invention to explore and a kind of avoid disadvantages mentioned above or taking out of making that its degree reduces true Empty heat insulation device.More specifically, treat that the time setting up required pressure reduction in evacuation volume is (right whole In the pumpdown time being reduced to the pressure specified) should be shorter than prior art.Heat insulation material used Material should have above-mentioned performance.

It has been found, therefore, that the equipment of the present invention and the purposes of the present invention.

Preferred embodiment can be released from claim and description.The knot of preferred embodiment Close without departing from the scope of the present invention.

The equipment of the present invention includes continuous evacuation region, and by described continuous evacuation region with The use region of the temperature-controllable that ambient temperature is heat insulation, and for actively keeping the device of vacuum, So that the pressure in the continuous evacuation region of described equipment is constant in specific pressure limit, institute State continuous evacuation region in the apparatus by occupied by porous and/or cellular heat-barrier material At least 20 volume % of cumulative volume, and to comprise at least one organic in described continuous evacuation region Aeroge and/or organic xerogel.

Term " continuous evacuation region " should be construed to " at least one continuous evacuation in principle Region ".Therefore, the equipment of the present invention may also include several continuous evacuation region defined above, In this case the regional containing aeroge and/or xerogel individually (difference) is taken out continuously Vacuum.Certainly, several this regions can process with a vaccum-pumping equipment.The present invention's it is crucial that Anyway one of above-mentioned zone is always in the apparatus by porous and/or cellular heat insulation material At least 30 volume % of the cumulative volume occupied by material.Optionally two or more are all contained to gas The continuous evacuation region of gel and/or xerogel also can individually meet this standard.

Organic aerogel and organic xerogel are known per se.In the literature, xerogel understands For meaning by the porous material prepared by sol-gal process, by the stagnation temperature less than liquid phase Under degree and critical pressure, (" subcritical neutron ") is dried described liquid phase and removes liquid from gel Phase.On the other hand, when removing liquid phase from gel and being to carry out at supercritical conditions, it is referred to as Aeroge.

In sol-gal process, first prepare colloidal sol based on activity organogel presoma, then Make collosol and gel by cross-linking reaction thus obtain gel.In order to obtain porous material (example from gel Such as xerogel), it is necessary to remove liquid.Hereinafter it is reduced to be dried by this step.

WO-2008/138978 discloses and comprises 30 weight % to 90 weight % at least one is multifunctional Isocyanates and 10 weight % are to the xerogel of at least one multifunctional aromatic amine of 70 weight %, institute The volume weighting average pore size stating xerogel is at most 5 microns.

Continuously evacuation region be in the present invention can the district of space definition in vaccum-pumping equipment continuously Territory, i.e. produces reduced pressure owing to applying vacuum at the one of whole region.

Term " continuous evacuation " mean evacuation after pressure in described region relative to environment pressure The constant reduction of power, the most described region is close with environment for gas diffusion (diffusion of composition of air) Close.Those skilled in the art know the time that pressure reduction the most only can remain limited.After evacuation (i.e. After setting up reduced pressure), need to keep reduced pressure at least 1 hour, especially at least 4 is little Time, the time of more preferably at least 24 hours is to meet " vacuum " and the standard of " airtight ".

The region that uses of temperature-controllable is to reduce relative to the constant temperature of ambient temperature in equipment or rise High region.

It is equal to by the cumulative volume occupied by porous and/or cellular heat-barrier material in the apparatus The most all porous and/or the volume of cellular heat-barrier material and include hole (pore) or Abscess (cell).Porous and/or cellular heat-barrier material are for having wholly or in part by heat-barrier material Surround containing abscess or the material in hole, the most described material includes the first solid phase and gassiness the Two-phase (optionally under reduced pressure or vacuum).Described hole or abscess reduce described heat-barrier material Thermal conductivity.Porous and/or cellular heat-barrier material can have perforate or closed pore.Mixed form is also Possible.This definition includes having hole and/or abscess and be introduced in equipment for heat insulation purpose All material, not only for according to the organic aerogel existing for the present invention and/or xerogel, also spy Wei foam, such as polyurethane foam or foam based on polystyrene.

The continuous evacuation region comprising organic aerogel or xerogel contained according to the present invention Volume is preferably at least 30 volume %, especially at least 40 volume %, more preferably at least 50 volume %, Especially at least 60 volume %, most preferably at least 70 volume %, based in a device by porous and/or Cumulative volume meter occupied by cellular heat-barrier material.

Vacuum is understood to mean that the reduced pressure relative to ambient pressure.Therefore vacuum is relative to ring Border pressure produces reduced pressure.In the context of the present invention, xerogel is understood to mean that by molten Porosity at least 70 volume % prepared by sol-gel and volumetric average pore footpath are at most more than 50 microns Porous materials, wherein liquid phase is by (" secondary facing less than the critical temperature of described liquid phase and critical pressure Boundary's condition ") under be dried and remove from gel.

Correspondingly, aeroge is understood to mean that and is prepared by sol-gal process in the context of the present invention Porosity at least 70 volume % and the porous material at most 50 microns of volumetric average pore footpath, its Middle liquid phase is by higher than the critical temperature of described liquid phase and critical pressure (" supercritical bar Part ") under be dried and remove from gel.

Average pore size measures according to DIN66133 mercury injection method, in the context of the present invention, Average pore size is usually volumetrically weighted average.Pressure sclera remodeling method according to DIN66133 is hole Porosity algoscopy is also carried out with Porosimeter.This includes injecting in porous material sample hydrargyrum.With Macropore is compared, and aperture needs bigger pressure to be full of hydrargyrum, and corresponding pressure/volume diagram can be used Measure pore-size distribution and volume weighting average pore size.

The volume weighting average pore size of porous material preferably at most 20 microns.Porous material Volume weighting average pore size is more preferably up to 10 microns, and even more preferably at most 5 microns also And specifically up to 3 microns.

For lower thermal conductivity, aperture is minimum and porosity height is required.But for For product, volume weighting average pore size has actual lower limit.Generally, the average hole of volume weighting Footpath is at least 50nm, preferably at least 100nm.In many cases, volume weighting is average Aperture is at least 200nm, the most at least 300nm.

The equipment of the present invention is electrically operated.The temperature in the use region of present device is preferred Controlled by positive (active) energy input.The device actively keeping vacuum is preferably The most electrically operated compressor and/or pump.

In first preferred embodiment of the present invention, the equipment of the present invention is refrigeration dress Put, more preferably refrigeration machine, fridge, freezer, electrically operated cold storage container or refrigerator car. Refrigerating plant is such a equipment, uses this equipment by input energy by specific use space Cooling is so that using space colder than ambient temperature (having lower temperature).

In another preferred embodiment of the present invention, the equipment of the present invention is for being used for heating material The equipment of material, particularly boiler.

Dynamically vaccum-pumping equipment is vaccum-pumping equipment as above, wherein by constant vacuum specific Pressure limit in thus actively keep vacuum." actively " is here and hereinafter meant that: by device Repeatable operation keeps vacuum.On the one hand vacuum is kept by the airtight character in described region herein, Keep also by repeatedly reducing pressure.Repeatedly reduce pressure can forever or with a kind of regular the most repeatedly Mode is carried out, preferably by a kind of periodically the most repeatedly in the way of carry out.In contrast, complete evacuation sets Standby for equipment as above, wherein vacuum is from individually applying and by the seal in described region Matter individually maintains.

The said equipment is well known to those skilled in the art itself.According to the organic gas used by the present invention Gel or organic xerogel can advantageously use in all of equipment, and described equipment is true except taking out continuously Outside dummy section, also there is the temperature-controllable heat insulation with ambient temperature by continuous evacuation region Using region, described continuous evacuation region is in a device by the cumulative volume occupied by heat-barrier material At least 20 volume %.For the Technology design of heat insulation device itself without particular limitation.

Particularly preferred equipment is dynamic evacuation refrigerating plant, particularly refrigeration machine.

Suitably dynamically evacuation electric operating refrigeration machine or fridge have one or more airtight every Thermal region, it is shell, wall and/or the door being filled in described refrigeration machine or fridge, and space leads to Cross vacuum lead to be connected with vacuum generating device and described vacuum generating device is described refrigeration machine Or the secure mounting arrangements in fridge.This refrigeration machine or fridge are known in such as US-A 18 In 98 977 and FR-A-26 28 179 and EP-A 0587546.

The Technology design setting up the either statically or dynamically precision of vacuum is uncorrelated with the present invention.On the contrary, when During the continuous evacuation of large volume that will include heat-barrier material, it may be advantageous to use according to used by the present invention Porous material as heat-barrier material.Such as, exist such as the rack described in EP-A 0587546 Can be equipped with vacuum pump in manufacture process, this vacuum pump and the wall of rack and Men Nei's is airtight air-locked Space is connected, and described space is filled with the heat-barrier material of the present invention.When user opens rack, Pump is activated, and then progressively produces extremely low pressure within the long use time, and this means heat insulation effect Fruit stepped up to some months from a week.Or, the compressor used in the device can be used Maintain the reduced pressure in evacuation region, as described in WO2005/093349.

The most preferred organic xerogel and aeroge are as mentioned below.

Organic aerogel or xerogel are preferably based on isocyanates and optionally other are work to isocyanates The component of property.

Organic aerogel or xerogel are more preferably based on isocyanates and to the isocyanates group in activity Point, the component to isocyanates in activity used is at least one multifunctional aromatic amine.Organic gas Gel and/or xerogel are preferably based on polyureas and/or poly-isocyanurate.

" based on polyureas " means in organic xerogel or aeroge at least 50mol%, the most extremely The key of few 70mol%, the especially monomeric unit of at least 90mol% is with urea bond (urea linkage) Exist." based on poly-isocyanurate " means in organic xerogel or aeroge at least 50 The key of mol%, preferably at least 70mol%, the especially monomeric unit of at least 90mol% is with isocyanide Urea acid esters key (isocyanurate linkage) exists." based on polyureas and/or poly-isocyanurate " Mean in organic xerogel or aeroge at least 50mol%, preferably at least 70mol%, especially The key of the monomeric unit of at least 90mol% exists with urea bond and/or isocyanurate-bond.

It is hereinafter referred to as Porous-Organic material according to the organic aerogel used by the present invention or xerogel Material.

Preferably, organic porous material used obtains in the method comprised the following steps:

(a) at least one polyfunctional isocyanate (a1) and at least one multifunctional aromatic amine (a2) in a solvent optionally in the presence of the water as component (a3) and Optionally react in the presence of at least one catalyst (a4)；

B () removes solvent to obtain aeroge or xerogel.

The component (a1) being preferably used in step (a). hereinafter adds to (a4) and ratio To illustrate.

Polyfunctional isocyanate (a1) is hereinafter collectively referred to as component (a1).Correspondingly, multifunctional Aromatic amine (a2) is hereinafter collectively referred to as component (a2).Aobvious to those skilled in the art and Be clear to is that mentioned monomer component exists with reformulations in organic porous material.

In the context of the present invention, the degree of functionality of compound is understood to mean that per molecule active group Number.For monomer component (a1), degree of functionality is the number of per molecule NCO. For the amino of monomer component (a2), degree of functionality means the number of per molecule active amino. The degree of functionality of polyfunctional compound is at least 2.

If by the mixture of compounds different for degree of functionality be used as component (a1) or (a2), then this The weighted average degree of functionality of degree of functionality each compound of each freedom of a little compounds calculates.Multifunctional Compound per molecule includes the above-mentioned functional group of at least two.

Component (a1)

At least one polyfunctional isocyanate is preferably used as component (a1).

In the method for the invention, the consumption of component (a1) is preferably at least 20 weight %, especially At least 30 weight %, more preferably at least 40 weight %, even more desirably at least 55 weight %, special Not at least 68 weight %, are each based on component (a1), (a2) and the gross weight of optional (a3) 100 weight % meters.In the method for the invention, the consumption the most at most 99.8 of component (a1) Weight %, specifically up to 99.3 weight %, more preferably up to 97.5 weight %, it is each based on component (a1), the gross weight 100 weight % meter of (a2) and optional (a3).

Available polyfunctional isocyanate is aromatics, aliphatic series, alicyclic and/or araliphatic isocyanates. These polyfunctional isocyanates are known per se maybe can be prepared by method known per se.Described many officials Can also can use the most as a mixture by isocyanates, component (a1) the most in this case Comprise different polyfunctional isocyanates.Polyfunctional isocyanate as monomeric unit (a1) is every Molecule monomer component has two (hereinafter referred to as diisocyanate) or two or more Carbimide. Ester group.

Specially suitable for diphenyl methane 2,2 '-, 2,4 '-and/or 4,4 '-diisocyanate (MDI), 1,5-naphthalene diisocyanate (NDI), toluene 2,4-and/or 2,6-bis-Carbimide. Ester (TDI), 3,3 '-dimethyl diphenyl diisocyanate, 1,2-diphenylethane diisocyanate And/or PPDI (PPDI), trimethylene diisocyanate, butylidene two isocyanide Acid esters, pentamethylene diisocyanate, hexylidene diisocyanate, heptamethylene diisocyanate and / or inferior octyl diisocyanate, 2-methyl pentylene 1,5-diisocyanate, diethyl butylidene 1,4-diisocyanate, pentylidene 1,5-diisocyanate, butylidene 1,4-diisocyanate, 1-isocyanate group-3,3,5-trimethyl-5-isocyanato methylcyclohexane (isophorone diisocyanate Ester, IPDI), Isosorbide-5-Nitrae-and/or 1,3-double (isocyanatometyl) hexamethylene (HXDI), hexamethylene Alkane 1,4-diisocyanate, 1-hexahydrotoluene 2,4-and/or 2,6-diisocyanate and bicyclo- Hexyl methane 4,4 '-, 2,4 '-and/or 2,2 '-diisocyanate.

Preferably polyfunctional isocyanate (a1) is aromatic isocyanate.Especially when water is used as During component (a3).

The polyfunctional isocyanate of particularly preferred component (a1) is embodiments below:

I) polyfunctional isocyanate based on toluene di-isocyanate(TDI) (TDI), particularly 2,4-TDI Or 2,6-TDI or 2,4-TDI and 2,6-TDI mixture；

Ii) polyfunctional isocyanate based on methyl diphenylene diisocyanate (MDI), especially It is that 2,2 '-MDI or 2,4 '-MDI or 4,4 '-MDI or oligomeric MDI(is the most Phenyl polymethylene isocyanates), or two or three above-mentioned diphenyl methane two is different The mixture of cyanate, or the thick MDI obtained in the preparation process of MDI, Or the MDI of at least one MDI oligomer and at least one above-mentioned low-molecular-weight derives The mixture of thing.

Iii) the aromatic isocyanate of at least one embodiment i) and at least one embodiment are ii) The mixture of aromatic isocyanate.

Particularly preferred polyfunctional isocyanate is oligomeric methylene diphenyl diisocyanate.Oligomeric two Methylenebis phenyl isocyanate (the most oligomeric MDI) be multiple oligomeric condensation product and The thus mixture of the derivant of methyl diphenylene diisocyanate (MDI).Described multifunctional different Cyanate is also preferably made up of the mixture of monomer aromatic diisocyanate and oligomeric MDI.

Oligomeric MDI comprises one or more degrees of functionality more than 2(special 3 or 4 or 5) MDI Multi-ring condensation product.Oligomeric MDI is known and commonly referred to polyphenyl polymethylene isocyanide Acid esters or polymeric MDI.Oligomeric MDI generally mixed by the different MDI based isocyanate of degree of functionality Compound is formed.Generally, oligomeric MDI uses with the form of mixtures with monomer MDI.

(averagely) degree of functionality of the isocyanates comprising oligomeric MDI can be special about 2.2 to about 5 Other 2.4 to 3.5, change in the range of special 2.5 to 3.MDI Quito that this degree of functionality is different The mixture of functional isocyanate is specifically for thick MDI, and it is generally by the MDI system of hydrochloric acid catalysis The standby middle intermediate product prepared as thick MDI produces.

The mixture of polyfunctional isocyanate or multiple polyfunctional isocyanate based on MDI is That know and such as by BASF Polyurethanes GmbH conductSell.

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

The content of the NCO of component (a1) is preferably 5 to 10mmol/g, and special 6 to 9 Mmol/g, particularly preferred 7 to 8.5mmol/g.Those skilled in the art will know that in terms of mmol/g NCO content with g/ when gauge be referred to as equivalent as reciprocal relationship.With mmol/g The content of NCO of meter according to ASTM D-5155-96A by the content meter in terms of weight % Calculate.

In a preferred embodiment, component (a1) is selected from diphenyl methane by least one 4,4 '-diisocyanate, diphenyl-methane 2,4 '-diisocyanate, diphenyl-methane 2,2 '-diisocyanate And polyfunctional isocyanate's composition of oligomeric methylene diphenyl diisocyanate.It is preferable to carry out at this In the case of scheme, component (a1) more preferably comprise oligomeric methylene diphenyl diisocyanate and There is the degree of functionality of at least 2.4.

The viscosity of component (a1) used is for changing in a wide range.The viscosity of component (a1) is excellent Elect 100 to 3000mPa.s, particularly preferred 200 to 2500mPa.s as.

Component (a2)

In a preferred method of the invention, component (a2) is at least one multifunctional aromatic amine.

Component (a2) can be prepared in some cases in situ.In such an implementation, step (a) Reaction carry out in the presence of water (a3).Water reacts with NCO thus produces amino together Time release CO₂.Therefore, polyfunctional amine produces as intermediate product (in situ) in some cases. It is changing into urea bond in the reaction of NCO.

In this preferred embodiment, described reaction is at water (a3) with as component (a2) In the presence of multifunctional aromatic amine, and optionally carry out in the presence of catalyst (a4).

At another also, it is preferred that embodiment in, component (a1) and as component (a2) The reaction of multifunctional aromatic amine is optionally carried out in the presence of catalyst (a4).In this case, There is not water.

Multifunctional aromatic amine itself is well known by persons skilled in the art.Polyfunctional amine is understood to mean that Per molecule has at least two to the isocyanates amine of amino in activity.It is activity to isocyanates Amino be primary amino radical and secondary amino group, the activity generally higher than secondary amino group of primary amino radical.

Multifunctional aromatic amine preferably has bicyclic-aromatic compound (the difunctionality virtue of two primary amino radicals Race's amine), correspondingly there is three rings or the polynuclear aromatic compound of two or more primary amino radical, or above-mentionedization The mixture of compound.The preferred multifunctional aromatic amine of component (a2) is specifically for diamino-diphenyl first The isomer of alkane and derivant.

Described difunctionality bicyclic aromatic amine is particularly preferably those of formula I,

Wherein R¹And R²May be the same or different and be each independently selected from hydrogen and there is 1 to 6 carbon The straight or branched alkyl of atom, and the most all substituent groups Q¹To Q⁵And Q^1’To Q^5’Phase With or different and be each independently selected from hydrogen, primary amino radical and have 1 to 12 carbon atom straight chain or Branched alkyl, wherein alkyl can with other functional groups, premise be compounds of formula I comprise to Few two primary amino radicals, wherein Q¹、Q³And Q⁵In at least one be primary amino radical and Q^1’、Q^3’ And Q^5’In at least one be primary amino radical.

In one embodiment, the alkyl in substituent group Q of formula I selected from methyl, ethyl, N-pro-pyl, isopropyl, normal-butyl, sec-butyl and the tert-butyl group.This compound is hereinafter referred to as Substituted aromatic amine (a2-s).But, accordingly it is also preferred that when substituent group Q is not defined above Amino time all substituent groups Q be hydrogen (so-called unsubstituted multifunctional aromatic amine).

Preferably, the R in formula I¹And R²Identical or different and be each independently selected from hydrogen, primary Amino and the straight or branched alkyl with 1 to 6 carbon atom.Selection of land, R¹And R²Excellent from hydrogen And methyl.It is highly preferred that R¹=R²=H。

Suitable multifunctional aromatic amine (a2) is also specifically for isomer and the derivant of toluenediamine. The isomer of the preferred toluenediamine of component (a2) and derivant specifically for Toluene-2,4-diisocyanate, 4-diamidogen and/ Or Toluene-2,4-diisocyanate, 6-diamidogen and diethyl toluene diamine, particularly 3,5-diethyltoluene-2,4-diamidogen and / or 3,5-diethyltoluene-2,6-diamidogen.

Most preferably, component (a2) comprise at least one selected from 4,4 '-diaminodiphenyl-methane, 2,4 '-diaminodiphenyl-methane, 2,2 '-diaminodiphenyl-methane and oligomeric diamino diphenyl The multifunctional aromatic amine of methane.

Oligomeric diamino diphenyl methane comprises one or more multi-ring methylene bridge of aniline and formaldehyde Connect condensation substance.Oligomeric MDA comprises at least one but usual multiple degree of functionality is more than 2 The MDA oligomer of (special 3 or 4 or 5).Oligomeric MDA be known maybe can by this Known to body prepared by method.Generally, oligomeric MDA is with the form with the mixture of monomer MDA Use.

(averagely) degree of functionality of the polyfunctional amine comprising the component (a2) of oligomeric MDA can be about Change in the range of 2.3 to about 5, special 2.3 to 3.5 and special 2.3 to 3.This degree of functionality Different MDI Quito functional amine's mixture is specifically for thick MDI, and it is generally being urged by hydrochloric acid especially The intermediate product prepared as thick MDI in the aniline changed and the condensation reaction of formaldehyde produces.

It is particularly preferred that at least one multifunctional aromatic amine comprises diaminodiphenyl-methane or diamino The derivant of base diphenyl methane.It is highly preferred that at least one multifunctional aromatic amine comprises oligomeric two Aminodiphenylmethane.Particularly preferably component (a2) comprises oligomeric two as compound (a2) Aminodiphenylmethane and have at least 2.1 total degree of functionality.More particularly, component (a2) Comprise oligomeric diamino diphenyl methane and there is the degree of functionality of at least 2.4.

In the context of the present invention, can be by using substituted multifunctional aromatics in component (a2) Amine controls the activity of primary amino radical.Mentioned and hereinafter referred to as (a2-s) hereinafter described takes The multifunctional aromatic amine in generation can be with above-mentioned (unsubstituted) diaminodiphenyl-methane (in Formulas I All Q be hydrogen, if not NH₂) form of mixtures use, or only use (a2-s).

In the present embodiment, the Q in Formulas I mentioned above²、Q⁴、Q^2’And Q^4’(include relevant Definition) select the most in the following manner: compounds of formula I is connecting relative at least one Have on the α position of the primary amino radical to aromatic ring at least one can with other functional group and containing 1 to The straight or branched alkyl of 12 carbon atoms.

Preferably, Q in the present embodiment²、Q⁴、Q^2’And Q^4’Select in the following manner: take The aromatic amine (a2-s) in generation comprises at least two primary amino radical, and each described primary amino radical has on alpha-position Having can be with other functional group and one or two straight or branched alkane containing 1 to 12 carbon atom Base.If Q²、Q⁴、Q^2’And Q^4’In one or more in the following manner select: it can be to have The straight or branched alkyl of 1 to 12 carbon atom, this alkyl is with other functional groups, preferably amino And/or hydroxyl and/or halogen atom are as these functional groups.

Preferably, amine (a2-s) be selected from 3,3 ', 5,5 '-tetraalkyl-4,4 '-diaminodiphenyl-methane, 3,3 ', 5,5 '-tetraalkyl-2,2 '-diaminodiphenyl-methane and 3,3 ', 5,5 '-tetraalkyl-2,4 '-diaminourea Diphenyl methane, wherein the alkyl on 3,3 ', 5 and 5 ' positions may be the same or different and each independent Ground is selected from the straight or branched alkyl with 1 to 12 carbon atom, and this alkyl can be with other senses Group.Abovementioned alkyl be preferably methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl or The tert-butyl group (the most unsubstituted).

In one embodiment, Duo Gehuo in one or more alkyl of substituent group Q All hydrogen atoms can be replaced by halogen atom (particularly chlorine).Or, one of substituent group Q or In multiple alkyl one, multiple or all hydrogen atom is by NH₂Or OH replaces.However, it is preferred to Alkyl in formula I is made up of carbon and hydrogen.

In an especially preferred embodiment, component (a2-s) comprises 3,3 ', 5,5 '-tetraalkyl -4,4 '-diaminodiphenyl-methane, wherein alkyl may be the same or different and is each independently selected from and has The straight or branched alkyl of 1 to 12 carbon atom, this alkyl is optionally with functional group.Above-mentioned alkane Base is preferably selected from unsubstituted alkyl, particularly methyl, ethyl, n-pro-pyl, isopropyl, positive fourth Base, sec-butyl and the tert-butyl group, more preferably methyl and ethyl.The most particularly preferred 3,3 ', 5,5 '-tetraethyl -4,4 '-diaminodiphenyl-methane and/or 3,3 ', 5,5 '-tetramethyl-4,4 '-diaminodiphenyl-methane.

The above-mentioned polyfunctional amine of component (a2) itself is well known by persons skilled in the art maybe can to pass through Prepared by known method.A kind of known method be aniline or anil with formaldehyde with acid catalyzed instead Should.

As described above, the water as component (a3) can partly replace multifunctional aromatic amine, because The extra multifunctional aromatics of its component (a1) with a certain amount of (precalculating in this case) Isocyanates reaction in-situ is to produce corresponding multifunctional aromatic amine.

As mentioned below, when using water as component (a3), it should preferably observe specific limit Boundary's condition.

As described above, water reacts with NCO thus produces amino, discharges CO simultaneously₂。 Therefore, polyfunctional amine part produces as intermediate product (in situ).Phase after the reaction, many officials Energy amine reacts with NCO thus produces urea bond.Amine causes machinery steady as the generation of intermedium Qualitative height and the generation of the low porous material of thermal conductivity.But, the CO formed₂Must be able to not show Write and destroy gelation process so that the structure of gained porous material is by the shadow with undesirable form Ring.Which results in the preferred upper limit of water content mentioned above (based on component (a1) to (a3) Gross weight meter), wherein this content preferably at most 30 weight %, more preferably up to 25 weight %, Specifically up to 20 weight %.Water content also results in following advantage in described scope: complete in gelation After, it is not necessary to remove any residual water in a complex manner by being dried.

When using water as component (a3), the consumption of water is preferably 0.1 to 30 weight %, especially 0.2 to 25 weight %, more preferably 0.5 to 20 weight %, it is each based on component (a1) to (a4) Gross weight 100 weight % meter.

Within the above range, the preferred amounts of water depends on whether to use catalyst (a4).

In first modification, it includes the use of water, and component (a1) to (a3) is without catalysis React in the presence of agent (a4).In the first embodiment, it has been found that use 5 to 30 Weight %, special 6 to 25 weight %, the water of more preferably 8 to 20 weight % is as component (a3) It is favourable, is each based on the gross weight 100 weight % meter of component (a1) to (a3).

In the case of first embodiment, said components (a1) to (a3) is preferably with following Ratio use, be each based on component (a1) to (a3) gross weight 100 weight % meter: 40 to 94.9 weight %, special 55 to 93.5 weight %, the component (a1) of more preferably 68 to 90 weight %, Many with 0.1 to 30 weight %, special 0.5 to 20 weight %, more preferably 2 to 12 weight % Functional aromatic amine (a2) and 5 to 30 weight %, special 6 to 25 weight %, more preferably 8 Water (a3) to 20 weight %.

Contained by the theory of the cubage amino of active isocyanate base in water content and component (a1) Amount, it is assumed that water reacts completely with the NCO in component (a1) thus forms the ammonia of respective amount Base, is added (total n by this content with the content of gained from component (a2)^Amine).Theoretical remaining NCO base n^NCORelative to theoretical informatics the gained utilization rate of amino that uses hereinafter referred to as Theoretical utilization rate n^NCO/n^Amine, and be the mol ratio of equivalent proportion, i.e. particular functional group.

In above-mentioned first modification, theoretical utilization rate (equivalent proportion) n^NCO/n^AmineCan become in a wide range Change also can be specifically for 0.6 to 5.n^NCO/n^AmineIt is preferably 1 to 1.6, special 1.1 to 1.4.

In second preferred modification, it includes that the use of water, component (a1) exist to (a3) React in the presence of catalyst (a4).In this second embodiment, it has been found that use 0.1 to 15 weight %, special 0.2 to 15 weight %, the water (a3) of more preferably 0.5 to 12 weight % It is favourable, is each based on the gross weight 100 weight % meter of component (a1) to (a3).Upper In the range of stating, creating mechanical performance particularly advantageous gained porous material, this is by particularly advantageous Network structure causes.Network structure is had adverse effect and to porous material by more substantial water Final performance is unfavorable.

In the case of described preferred second modification, said components (a1) to (a3) is preferred Using with following ratio, gross weight 100 weight % being each based on component (a1) to (a3) is counted: 55 to 99.8 weight %, special 65 to 99.3 weight %, more preferably 76 to 97.5 weight % Component (a1), and 0.1 to 30 weight %, special 0.5 to 20 weight %, more preferably 2 to 12 The multifunctional aromatic amine (a2) of weight % and 0.1 to 15 weight %, special 0.2 to 15 weight %, the water (a3) of more preferably 0.5 to 12 weight %.

In above-mentioned second modification, theoretical utilization rate (equivalent proportion) n^NCO/n^AmineIt is preferably 1.01 To 5.It is highly preferred that described equivalent proportion is 1.1 to 3, specifically for 1.1 to 2.This embodiment party In case, n^NCORelative to n^AmineExcess cause when removing solvent porous material (the most dry solidifying Glue) shrinkage factor (shrinkage) reduce, and by leading with the synergism of catalyst (a4) Cause the improvement of the final performance of cancellated improvement and gained porous material.

In second preferred embodiment mentioned above, the reaction of step (a) is at water (a3) In the presence of carry out.In this preferred embodiment, component (a1) mentioned above and (a2) Preferably use with following ratio, be each based on gross weight 100 weight of component (a1) and (a2) % counts: 20 to 80 weight %, special 25 to 75 weight %, more preferably 35 to 68 weight % Component (a1), and 20 to 80 weight %, special 25 to 75 weight %, more preferably 32 to 65 The component (a2) of weight %；Without (a3).

In the above-described embodiment, utilization rate (equivalent proportion) n^NCO/n^AmineIt is preferably 1.01 to 5.Institute State equivalent proportion and be more preferably 1.1 to 3, special 1.1 to 2.The most in this embodiment, n^NCO Relative to n^AmineExcess cause the shrinkage factor of porous material (particularly xerogel) when removing solvent Reduce, and by causing cancellated improvement and institute much with the synergism of catalyst (a4) The improvement of the final performance of Porous materials.

Component (a1) to (a3) is referred to as organogel presoma (A) below.

Catalyst (a4)

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

Available catalyst includes well known by persons skilled in the art in principle and accelerates isocyanates Trimerization reaction (referred to as catalyst for trimerization) and/or reaction (the referred to as gel of isocyanates and amino Catalyst) and/or the reaction (referred to as kicker) of (when using water) isocyanates and water All catalyst.

Corresponding catalyst is known per se, and has different special about above-mentioned three kinds of reactions Property.According to described characteristic, described catalyst is distributed to one or more the above-mentioned types.Ability Field technique personnel also know the reaction in addition to above-mentioned reaction it can also happen that.

Corresponding catalyst is especially characterised by the ratio of its gelation and foaming, such as from Polyurethane [Polyurethanes], the 3rd edition, G.Oertel, Hanser Verlag, Munich is known in page 1993,104 to 110.

When without component (a3) (i.e. without water), trimerization reaction is had by preferred catalyst Significantly activity.It has favorable influence to cancellated homogeneity, causes advantageous particularly Mechanical performance.

When using water as component (a3), preferred catalyst (a4) has the gel of balance Change and foaming ratio, so that the reaction of component (a1) and water is the most excessively accelerated, will not be to netted Structure has a negative impact, and also results in shorter gelation time, so that the demoulding time is favourable Shorten.Preferably catalyst has significant activity to three collecting process simultaneously.This is to netted knot The homogeneity of structure has favorable influence, causes particularly advantageous mechanical performance.

Described catalyst can be monomeric unit (being incorporated to formula catalyst) or non-be incorporated to formula catalyst.

Component (a4) suitably uses with least effective dose (LED).0.01 to 5 weight portion is preferably used, Special 0.1 to 3 weight portion, the component (a4) of the amount of more preferably 0.2 to 2.5 weight portion, base Count in the component (a1), (a2) and (a3) amounting to 100 weight portions.

In component (a4), preferred catalyst is selected from primary amine, secondary amine and tertiary amine, triazine derivatives Thing, organo-metallic compound, metallo-chelate, quaternary ammonium salt, ammonium hydroxide and alkali metal and alkali The hydroxide of earth metal, alkoxide and carboxylate.

Suitably catalyst specifically for highly basic, such as quaternary ammonium base, in alkyl, such as have 1 to 4 The tetraalkylammonium hydroxide of individual carbon atom and hydroxide benzyltrimethylammon.um；Alkali metal hydroxide, Such as potassium hydroxide or sodium hydroxide；And alkali metal alcoholates, such as Feldalat NM, potassium ethoxide and second Sodium alkoxide and potassium isopropoxide.

Suitably catalyst also specifically for alkali metal carboxylate, such as potassium formate, sodium acetate, acetic acid Potassium, 2 ethyl hexanoic acid potassium, Potassium Adipate and sodium benzoate and have 8 to 20(special 10 to 20) individual carbon atom and optionally there is the alkali metal salt of long-chain fatty acid of side OH base.

Suitably catalyst is also specifically for N-hydroxyalkyl quaternary ammonium carboxylate, such as trimethyl hydroxypropyl ammonium Formates.

Organo-metallic compound itself (especially with the form of gel catalyst) is people in the art Member is known, and equally suitable as catalyst (a4).Organo-tin compound (such as 2-ethyl Caproic acid stannum and dibutyl tin laurate) it is preferred component (a4).Further preferably for metal acetyl Acetone solvate, particularly zinc acetylacetonate.

Tertiary amine is well known by persons skilled in the art as gel catalyst and catalyst for trimerization itself. Tertiary amine is particularly preferable as catalyst (a4).Preferably tertiary amine specifically for N, N-dimethyl benzylamine, N, N '-dimethyl piperazine, N, N-dimethyl cyclohexyl amine, N, N ', N "-three (dialkyl aminoalkyl)-s- Hexahydrotriazine (such as N, N ', N "-three (dimethylaminopropyl)-s-hexahydrotriazine), three (diformazans Base amino methyl) phenol, double (2-dimethyl aminoethyl) ether, N, the sub-second of N, N, N, N-pentamethyl two Base triamine, Methylimidazole., DMIZ 1,2 dimethylimidazole, dimethyl benzylamine, 1,6-diazabicyclo [5.4.0] 11 carbon-7-alkene, triethylamine, triethylenediamine (IUPAC:1,4-diazabicyclo [2,2,2] Octane), dimethylaminoethanol amine, dimethylamino propylamine, N, N-dimethylamino ethoxy second Alcohol, N, N, N-trimethylaminoethyl group ethanolamine, triethanolamine, diethanolamine, triisopropanolamine And diisopropanolamine (DIPA).

In component (a4), particularly a preferred catalyst is selected from N, N-dimethyl cyclohexyl amine, double (2- Dimethyl aminoethyl) ether, N, N, N, N, N-five methyl diethylentriamine, Methylimidazole., diformazan Base imidazoles, dimethyl benzylamine, 1,6-diazabicyclo [5.4.0] 11 carbon-7-alkene, three (dimethylaminos Base propyl group) hexahydrotriazine, triethylamine, three (dimethylaminomethyl) phenol, triethylenediamine (diazabicyclo [2,2,2] octane), dimethylaminoethanol amine, dimethylamino propylamine, N, N- Dimethyl amino ethoxy ethanol, N, N, N-trimethylaminoethyl group ethanolamine, triethanolamine, two Ethanolamine, triisopropanolamine, diisopropanolamine (DIPA), metal acetylacetonates, thylhexoic acid ammonium with And the ethyl hexyl hydrochlorate of metal ion.

The use of currently preferred catalyst (a4) causes porous material to have the mechanicalness of improvement Can, specifically result in the compressive strength of improvement.Additionally, the use of catalyst (a4) also reduces solidifying Gel time, i.e. accelerates gelation reaction, has no adverse effect other performances.

Solvent

Carry out in the presence of the solvent for the organic aerogel of the present invention or the preparation of xerogel.

In the context of the present invention, term " solvent " includes that liquid diluent is the most in the narrow sense Solvent and dispersant.This mixture can specifically for true solution, colloid solution or dispersion liquid (such as Emulsion or suspension).The preferred true solution of this mixture.Described solvent is The compound of liquid, preferably organic solvent.

Available solvent includes a kind of organic compound or the mixture of several compound in principle, described Solvent is liquid under the temperature and pressure condition (abbreviation solution condition) of provided mixture.Molten The composition of agent selects in such a way: solvent can dissolve or disperse, and preferably dissolves organic solidifying Glue presoma.In the above-mentioned method for optimizing for preparing organic aerogel or xerogel the most molten Agent, for dissolving the solvent of organic Gel Precursor (A), is completely dissolved organic the most at reaction conditions The solvent of Gel Precursor (A).

First the product of the most described reaction is gel, i.e. passes through solvent swell Viscoelasticity chemical network.Network is typically resulted in for forming the solvent of the good sweller of network There is aperture and little average pore size, and for gained gel, be the solvent of the best sweller Typically result in the macroporous network with big average pore size.

Therefore, the selection of solvent affects target aperture distribution and goal porosity.Solvent generally the most also with Such a mode selects: the overwhelming majority avoid due to the inventive method step (a) period or it Rear formed precipitation product and the precipitation that causes or flocculation.

In the case of selecting suitable solvent, the ratio of precipitation product is typically smaller than 1 weight %, gross weight meter based on mixture.The amount of the precipitated product formed in specific solvent can be passed through Reactant mixture was filtered through before reaching gel point suitable filter to survey with gravimetric method Fixed.

Available solvent includes the solvent for isocyanate-based polymer known in the art.Excellent The solvent of choosing is dissolved constituent (a1), (a2) and the solvent of optional (a3), i.e. in reaction Under the conditions of substantially completely dissolved constituent (a1), composition molten of (a2) and optionally (a3) Agent.Described solvent is preferably inert to component (a1), the most inactive.

Available solvent includes ketone, aldehyde, chain acid alkyl ester, amide (such as Methanamide and N-first Base ketopyrrolidine), sulfoxide (such as dimethyl sulfoxide), aliphatic and alicyclic halogenated hydrocarbons, halo virtue Compounds of group and fluorinated ether.It is also possible to use the mixture of two or more above-claimed cpd.

The solvent that can also be used with is acetal, particularly diethoxymethane, dimethoxymethane and 1,3- Dioxolanes.

Dialkyl ether and cyclic ether also are suitable as solvent.Preferably dialkyl ether is specifically for having 2 To those of 6 carbon atoms, particularly methyl ethyl ether, diethyl ether, methyl-propyl ether, methyl Isopropyl ether, ethyl ether, ethyl isopropyl ether, dipropyl ether, propyl isopropyl ether, two different Propyl ether, methyl butyl ether, methyl-isobutyl ether, methyl tertiary butyl ether(MTBE), ethyl n-butyl ether, second Base isobutyl ether and ethyl tert-butyl oxide.Preferably cyclic ether is specifically for oxolane, dioxane And Pentamethylene oxide..

Preferably solvent is also chain acid alkyl ester, particularly methyl formate, methyl acetate, formic acid Ethyl ester, butyl acetate and ethyl acetate.Preferably halogenated solvent at WO00/24799, the 4th Page the 12nd walks to have been described in page 5 the 4th row.

Aldehyde and/or ketone are preferred solvent.It is suitable as the aldehydes or ketones of solvent specifically for corresponding to formula R²-(CO)-R¹Those, wherein R¹And R²Respectively for hydrogen or there are 1,2,3 or 4 carbon atoms Alkyl.Suitably aldehydes or ketones is specifically for acetaldehyde, propionic aldehyde, hutanal, isobutylaldehyde, 2-ethyl fourth Aldehyde, valeral, isovaleral, 2 methyl pentanal, 2-ethyl hexanal, acrylic aldehyde, methacrolein, bar Bean aldehyde, furfural, acrolein dimer, methacrolein dimer, 1,2,3,6-tetrahydrochysene benzaldehyde, 6- Methyl-3-hexamethylene olefine aldehydr, cyanogen acetaldehyde, glyoxylic acid ethyl ester, benzaldehyde, acetone, metacetone, first Base ethyl ketone, methyl iso-butyl ketone (MIBK), methyl n-butyl ketone, ethyl isopropyl ketone, 2-acetyl group furan Mutter, 2-methoxyl group-4-methylpenta-2-one, Ketohexamethylene and acetophenone.Above-mentioned aldehyde and ketone can also mix Solvate form uses.Particularly preferably there is each substituent group there is the alkyl of up to 3 carbon atoms Ketone and aldehyde as solvent.Extremely particularly preferably general formula R¹(CO)R²Ketone, wherein R¹And R²Each Independently selected from the alkyl with 1 to 3 carbon atom.In the first preferred embodiment, institute Stating ketone is acetone.In another preferred embodiment, two substituent R¹And/or R²In At least one comprises the alkyl with at least 2 carbon atoms, particularly methyl ethyl ketone.Above-mentioned spy Not preferably ketone is used in combination with the inventive method and creates the porous material that average pore size is the least. Purpose without any restrictions, it is believed that owing to the higher affinity of above-mentioned particularly preferred ketone makes institute's shape The pore structure becoming gel has the least hole.

In many cases, especially suitable solvent is by being selected from above-mentioned molten with two or more Agent can the compound of complete miscibility obtain the most each other.

In step (a)., will not shrink in a large number in the dry run of step (b) for acquisition Sufficiently stable gel, in gross weight 100 weight % of component (a1) to (a3) and solvent, The ratio of component (a1) to (a3) generally has to be not less than 5 weight %.Preferably, in component (a1) in gross weight 100 weight % of (a3) and solvent, component (a1) to (a3) Ratio preferably at least 6 weight %, more preferably at least 8 weight %, especially at least 10 weight %.

On the other hand, not in the component (a1) selecting excessive concentrations in the mixture provided To (a3), the porous material with advantageous property otherwise would not be obtained.Generally, at component (a1) To gross weight 100 weight % of (a3) and solvent, the ratio of component (a1) to (a3) is At most 40 weight %.In gross weight 100 weight % of component (a1) to (a3) and solvent, Ratio preferably at most 35 weight % of component (a1) to (a3), more preferably up to 25 weight %, specifically up to 20 weight %.

In gross weight 100 weight % of component (a1) to (a3) and solvent, component (a1) Weight ratio to (a3) preferably amounts to 8 to 25 weight %, special 10 to 20 weight %, more Preferably 12 to 18 weight %.If the amount of raw material is in mentioned scope, can be in dry run Middle acquisition has the porous material of particularly advantageous pore structure, lower thermal conductivity and low-shrinkage.

Reaction in the step (a) of the inventive method preferably provide component (a1), (a2), Carry out after optional (a3) and optional (a4) and solvent.

Preferably, on the one hand provide component (a1) dividually with the solvent of proper ratio respectively, another Aspect provides (a2) and optional (a3) and optional (a4).This being provided separately can be Gelation reaction is optimally controlled before and during mixing.

When using water as component (a3), more preferably it is provided separately component (a3) and component (a1). This avoids water and component (a1) in the case of there is not component (a2) and reacts formation network. Otherwise, water will cause the homogeneity about pore structure and resulting materials with the premixing of component (a1) The unfavorable performance of thermal conductivity.

Carrying out the single mixture that provided before step (a) or multiple mixture also can comprise this Conven-tional adjuvants known to the skilled person is as other compositions.Example is surfactant, one-tenth Core agent, antioxidant, lubricant and demolding aids, dyestuff and pigment, stabilizer (such as water resistant Solution, light, heat or the stabilizer faded), inorganic and/or organic filler, reinforcing agent and insecticide.

Other details of above-mentioned auxiliary agent and additive are found in technical literature such as Plastics Additive Handbook, the 5th edition, H.Zweifel, ed.Hanser Publishers, Munich, 2001, the In 104-127 page.

In order to carry out the reaction in the step (a) of described method for optimizing, it is necessary first to preparation is in step The homogeneous mixture of provided component before the reaction of (a).

The component converted in step (a). can provide in a usual manner.To this end, stirring is preferably used Device or another kind of agitating device obtain well and quickly mix.In order to avoid mixing defect, obtain Time needed for obtaining homogeneous mixture should form the time of at least part of gel than gelation reaction Short.Other mixing condition is frequently not crucial；Such as, can be at 0 to 100 DEG C and 0.1 to 10 (the most at room temperature and pressure) mixing under bar (absolute pressure).Once prepare Homogeneous mixture, preferably just is off agitating device.

This gelation reaction is the addition of polyaddition reaction, more specifically NCO and amino Polyreaction.

It is (the most molten that gel is understood to mean cross-linking system based on the polymer contacted with liquid Dosage form gel (solvogel) or lyogel (lyogel), or use water as liquid: hydrogel (aquagel) Or hydrogel (hydrogel)).This polymer phase forms continuous print three-dimensional network.

In the step (a) of the inventive method, gel is generally formed by standing, the most simply Stand containing needing the container of standing mixt, reaction vessel or reactor (hereinafter referred to as gel Gasifying device).Preferably, do not stir during gelation (gel formation) or mix described mixing Thing, because this can suppress the formation of gel.Have been found that in gelation process covering mixture or It is favourable for sealing gelation device.

Gelation itself is well known by persons skilled in the art and at such as WO-2009/027310, Page 21, the 19th row page-the 23, the 13rd row has been described.

In a preferred method, solvent (being dried) is removed in step (b).In principle, exist Being dried under super critical condition is a kind of selection, preferably with CO₂Or other are applicable to supercritical After solvent described in the solvent exchange of drying purpose.This seasoning itself is people in the art Member is known.Super critical condition shows that temperature and pressure is the most to be removed Liquid phase in a supercritical state.This makes gelinite shrinkage factor fall in removing dissolving agent process Low.From supercritical drying process, the material of gained is referred to as aeroge.

But, in order to simplify this process, preferably by facing less than the liquid in the presence of gel Under the temperature and pressure of boundary's temperature and critical pressure, the liquid in the presence of gel is converted into gaseous state It is dried gained gel.It is referred to as xerogel by the material of sub-critical drying gained.

Gained gel is preferably by less than the critical temperature of solvent and the temperature and pressure of critical pressure Lower is that gaseous state is dried by solvent conversion.Therefore it is dried the most not by using other solvent exchange in advance And remove the solvent in the presence of course of reaction and carry out.

Corresponding method is well known by persons skilled in the art and at WO-2009/027310 equally, Page 26, the 22nd row page-the 28, the 36th row has been described.

Organic aerogel or xerogel used by the present invention can introduce the present invention in many ways and set In standby continuous evacuation region.

Described organic aerogel or organic xerogel can be converted into powder by pulverizing, such as at EP-A Have been described in 11155833.4.Subsequently, powder can be blown into or introduced by aperture take out continuously true Dummy section, such as, have been described in WO2004/010042.

Or, xerogel (such as before being fully cured) under free-flowing can be introduced Evacuation region, such as, introduce the element in the continuous evacuation region of follow-up constitution equipment continuously In.Gel can solidify wherein, the most as described above by solvent removal.

Introduce another preferred modification of the aeroge used by the present invention and xerogel by following methods Step produces: (i) provide as formed body (shaped body) (i.e. preform members (preshaped Part) organic aerogel) or xerogel, the most (ii) with the parts of follow-up present device This formed body is converted.These parts specifically for the modular assembly of present device, especially around The polymer element in the continuous evacuation region in present device.In other words: will include continuously The equipment of the present invention in evacuation region or the modular unit (shell of such as equipment of follow-up equipment And/or the sidewall of equipment or door) set up around preform organic aerogel or xerogel.

Present invention also offers above-mentioned organic aerogel or the xerogel continuous evacuation district at equipment Purposes in territory, described equipment, except described continuous evacuation region, also includes by described company The use region of the temperature-controllable that continuous evacuation region is heat insulation with ambient temperature, described continuous evacuation Region is in the apparatus by the cumulative volume occupied by porous and/or cellular heat-barrier material extremely Few 30 volume %.

Embodiment

Thermal conductivity is measured by double-plate device at 23 DEG C.For this purpose, by central, circular gold Belong to plate to heat in a controlled manner.The same sample of two known thickness is centered around both sides.Sample Outside is connected with thermal control radiator.Heat output closed loop control regulates so that respectively reaching relatively Constant temperature gradient in sample.The electric energy introducing hot plate is symmetrical with heat by said two sample Run off.In order to ensure one dimensional heat transfer, central, circular hot plate surrounds with two concentric retaining rings, by described Retaining ring is maintained at the temperature identical with median plate with one heart.

In order to prepare xerogel, use following compound:

Have the NCO content according to the every 100g31.5g of ASTM D-5155-96A, 2.8 to 2.9 Degree of functionality and according to DIN53018 oligomeric MDI of the viscosity of 550mPa.s at 25 DEG C (M50) (hereinafter referred to " compound M50 ").

3,3 ', 5,5 '-tetraethyl-4,4 '-diaminodiphenyl-methane is (hereinafter referred to as " MDEA ")

Catalyst: triethanolamine

Embodiment 1

By 23.4 acetone solns of weight % compound M50 and the comprising of 2700ml of 2700ml The acetone soln mixing of 1.8 weight %MDEA, 0.9 weight % triethanolamine and 1200g water.? Low viscosity mixtures to clarification.Described mixture is at room temperature stood solidification in 24 hours.Subsequently, Liquid (acetone) is removed by being dried at 20 DEG C for 7 days.Resulting materials has 130g/l's Density.

Pressure-dependent thermal conductivity uses thickness to be 25mm, a length of 320mm and width Sample determination for 450mm.The results are shown in Table 1.

Table 1

Pressure [millibar]	Thermal conductivity [mW/m*K]
		0.01	4.4
0.1	5.3
		1	7.1
10	15
		100	26
1000	34

Embodiment 2(comparative example)

In example 2, a kind of heat insulation rigid foam based on polyurethane and embodiment are prepared 1 compares.

In order to prepare polyurethane foam, use following compound:

Polyhydric alcohol A: the Aethoxy Sklerol formed by sucrose, glycerol and expoxy propane, hydroxyl value 490

Polyhydric alcohol B: the Aethoxy Sklerol formed by propylene glycol and expoxy propane, hydroxyl value 105

Polyhydric alcohol C: the Aethoxy Sklerol formed by propylene glycol and expoxy propane, hydroxyl value 250

Additive 1:B8870(is from the polysiloxane stabilizer of Evonik)

Additive 2:501(is from the open surface activating agent of Evonik)

Catalyst 1:58(is from the tertiary amine of Air Products)

Catalyst 2: the ethylene glycol solution (BASF) of potassium acetate

The NCO content of every 100g31.4 according to ASTM D-5155-96A, degree of functionality About 2.9 and according to DIN53018 oligomeric MDI of viscosity 650mPa.s at 25 DEG C (M70) (hereinafter referred to " compound M70 ").

The raw material specified is made by mixing with isocyanates (compound M70) and react Standby polyol component.Raw materials used amount is found in table 2.Described it is blended in mixing head OK.Reactant mixture is injected in the laboratory mould of the length of side 418 × 700 × 455mm and at mould Tool solidifies.

Table 2

	Embodiment 2C [weight portion]
		Polyhydric alcohol A	44.10
Polyhydric alcohol B	44.10
		Polyhydric alcohol C	9.15
Water	0.55
		Stabilizer	0.90
Catalyst 1	0.50
		Catalyst 2	0.70
Pore-creating agent	1.80
		Pentamethylene.	9.50
Compound M70	194
		Index	244

The sample of size 19 × 19 × 2cm is sawed from thus obtained rigid foam and xerogel Go out and put in airtight film, thin film is being evacuated to after pressure is less than 0.1 millibar by weldering Connect airtight.Measure the pumpdown time (table 3).

Table 3

Relative to the hard PUR foam of the heat-barrier material as refrigeration machine, use based on polyureas Organic xerogel improve thermal conductivity.Meanwhile, the pumpdown time significantly reduces.

Claims (12)

1. an electrically operated dynamic vaccum-pumping equipment, it include continuous evacuation region and by described continuous evacuation region the use region of the temperature-controllable heat insulation with ambient temperature, and for actively keeping the device of vacuum, so that the pressure in the continuous evacuation region of described equipment is constant in specific pressure limit, described continuous evacuation region is at least 20 volume % by the cumulative volume occupied by porous and/or cellular heat-barrier material in the apparatus, and described continuous evacuation region comprises at least one organic aerogel and/or organic xerogel, wherein organic aerogel or xerogel are based on isocyanates with to the isocyanates component in activity, wherein the component to isocyanates in activity used is at least one multifunctional aromatic amine,

The multifunctional aromatic amine of at least one of which has the structure of formula I

Wherein R¹And R²May be the same or different and be each independently selected from hydrogen and there is the straight or branched alkyl of 1 to 6 carbon atom, and the most all substituent groups Q¹To Q⁵And Q^{1 ’}To Q^{5 ’}Identical or different and be each independently selected from hydrogen, primary amino radical and have the straight or branched alkyl of 1 to 12 carbon atom, wherein alkyl can be with other functional groups, and premise is that compounds of formula I comprises at least two primary amino radical, wherein Q¹、Q³And Q⁵In at least one be primary amino radical and Q^{1 ’}、Q^{3 ’}And Q^{5 ’}In at least one be primary amino radical, and

Wherein Q²、Q⁴、Q^{2 ’}And Q^{4 ’}Select in the following manner: compounds of formula I has at least one on the α position of the primary amino radical being connected on aromatic ring relative at least one can be with other functional group and the straight or branched alkyl containing 1 to 12 carbon atom.

2.AsEquipment described in claim 1, wherein said equipment is refrigeration unit.

3.AsEquipment described in claim 1 or 2, wherein said equipment is refrigeration machine.

4.AsEquipment described in claim 1 or 2, wherein the volume weighting average pore size of organic aerogel or xerogel is 50 to 3000nm.

5.AsEquipment described in claim 1 or 2, wherein uses organic xerogel.

6.AsEquipment described in claim 1 or 2, wherein organic aerogel or xerogel based on isocyanates and optionally other to the isocyanates component in activity.

7.AsEquipment described in claim 1 or 2, wherein organic porous material obtains in the method comprised the following steps: (a) at least one polyfunctional isocyanate a1 and at least one multifunctional aromatic amine a2 is optionally reacting as in the presence of the water of component a3 and optionally in the presence of at least one catalyst a4 in a solvent；B () removes described solvent to obtain aeroge or xerogel.

8.AsEquipment described in claim 7, wherein component a1 comprises oligomeric methylene diphenyl diisocyanate and has the degree of functionality of at least 2.4.

9.AsEquipment described in claim 7, wherein component a2 comprises at least one following compound: 4,4 '-diaminodiphenyl-methane, 2,4 '-diaminodiphenyl-methane, 2,2 '-diaminodiphenyl-methane and oligomeric diamino diphenyl methane.

10.AsEquipment described in claim 7, wherein said reaction is carried out in the presence of a catalyst.

11.AsEquipment described in claim 7, wherein said reaction and is optionally carried out in the presence of water a3 in the presence of catalyst a4.

12.AsEquipment described in claim 7, wherein in step (a), the reaction of component a1 and the multifunctional aromatic amine as component a2 is carried out not having in the presence of water a3.