阅读说明：本技术 一种基于整体有机气凝胶的模制品 (Molded product based on integral organic aerogel ) 是由 S·莫瓦海德 M·诺比斯 M·弗力可 W·勒尔斯贝格 D·温里克 于 2020-04-09 设计创作，主要内容包括：一种基于整体有机气凝胶的模制品,其密度为60至300kg/m～(3),热导率为12至17.8mW/m＊K,具有大于30体积％的直径小于150nm的孔,且具有大于20体积％的直径小于27nm的孔,基于总的孔体积计,以及通过压缩制备模制品的方法。(A moulding based on monolithic organic aerogels having a density of from 60 to 300kg/m 3 A thermal conductivity of from 12 to 17.8 mW/m.multidot.K, having more than 30% by volume of pores having a diameter of less than 150nm and having more than 20% by volume of pores having a diameter of less than 27nm, based on the total pore volume, and a process for producing moldings by compression.)

1. A moulding based on monolithic organic aerogels having a density of from 60 to 300kg/m³The thermal conductivity is from 12 to 17.8 mW/m.multidot.K, and more than 30% by volume of the pores have a diameter of less than 150nm, and more than 20% by volume of the pores have a diameter of less than 27nm, based on the total pore volume.

2. The molded article of claim 1, having a compressive strength of 600-700 kPa.

3. The molding as claimed in claim 1 or 2, having a flexural strength of 1000-.

4. A molded article according to any of claims 1 to 3, wherein the organic aerogel is a monolithic aerogel based on Polyurethane (PU) and/or Polyurea (PUR) having a Polyisocyanurate (PIR) structure of less than 80%.

5. The molded article of any one of claims 1 to 4, in the form of a sheet having a thickness in the range of 100 μm to 10 mm.

6. A preparation method of the product has a density of 60-300 kg/m³The process for the production of monolithic organic aerogel-based moldings, which comprises mixing a mixture having a density of from 50 to 140kg/m³The organic aerogel-based molding of (1) is compressed by a compression factor of 5 to 70 vol%.

7. The process according to claim 6 for the preparation of a moulding according to any one of claims 1 to 5.

8. The method according to claim 6 or 7, which comprises unidirectionally compressing the organic aerogel-based molding in the form of a sheet in a thickness direction of the sheet.

9. Process according to claims 6 to 8, wherein the compression is carried out in a hydraulic or pneumatic press at a moulding temperature of 10 to 80 ℃ and 0.12 to 10MPa/1000em²Under pressure of (c).

10. A process for preparing a moulding according to any of claims 1 to 5, comprising the following steps

a) Reacting a mixture (A) comprising at least one polyfunctional isocyanate (a1), at least one aromatic amine (a2) and at least one catalyst (a3) in the presence of a solvent (B) to form a gel,

b) drying the gel obtained in step b) under supercritical conditions,

c) optionally cutting the dried gel into sheets having a thickness of 0.1 to 10mm, and

d) compressing the dried gel to a density of 100 to 300kg/m³。

11. A thermal insulation material comprising a sheet-form moulding according to claim 5 as aerogel layer a) and at least one covering layer C) having a thickness of from 10 μm to 1 mm.

12. A method of making the insulating material according to claim 11, comprising the steps of:

a) reacting a mixture (A) comprising at least one polyfunctional isocyanate (a1), at least one aromatic amine (a2) and at least one catalyst (a3) in the presence of a solvent (B) to form a gel,

b) drying the gel obtained in step b) under supercritical conditions to form a monolithic aerogel),

c) optionally cutting the dried gel into sheets having a thickness of 0.1 to 10mm,

d) compressing the monolithic aerogel of step b) to a density of 100 to 300kg/m³To obtain the aerogel layer a),

e) at least one cover layer C) is optionally applied to the layer a) obtained in step C) by means of an adhesive layer B).

13. Use of a moulded article according to any one of claims 1 to 5 or an insulating material according to claim 11 as an insulating material in buildings and constructions, refrigeration equipment, electronic equipment, aerospace and batteries.

Examples

The method comprises the following steps:

according to DIN EN 12667: 2001-05 thermal conductivity was measured at 10 ℃ using a heat flow meter from Hesto (Lambda Control A50). For laminated and non-laminated sheets with a thickness of 1-2mm, a stack of up to 9 sheets (15 cm) can be measured.

Compressive strength according to DIN EN ISO 844: 2014-11 was measured at 6% strain.

Flexural strength to DIN EN 12089: 2013-06 is determined by a three-point bending test. The fixation points are 50mm apart. The maximum bending radius is 90 °. The sample size was approximately 100x20 mm. The one-side laminated samples were pressed on the laminated side.

Friability was determined by rolling friability testing according to ASTM C421-77 using samples of length and width 25x25mm and thicknesses reported in table 4.

Using Nova 4000e pore size analyzer from Quantachrome Instruments according to DIN 66134: 1998-02 pore volume. Approximately 15-20mg of the sample was removed from the original sample and placed in a measuring glass cell. The sample was degassed at 60 ℃ for 15 hours under a vacuum of 50mm Hg to remove any adsorbed components on the sample. The sample was weighed again before surface area and pore size analysis.

Surface area measurement: the specific surface area was determined by Brunauer-Emmet-Teller (BET) method using low temperature nitrogen adsorption analysis (at boiling point of nitrogen, 77K) in the IUPAC recommended range of P/P0 (0.05-0.30). The 1/((w. (P0/P-1))) vs P/P0 plot yields a linear plot with a correlation coefficient (r) above 0.999.

Pore size distribution: the low temperature nitrogen adsorption-desorption curve was determined in the range of P/P0 (0.05-0.99). The pore size distribution was determined using Barret-Joyner-Halenda (BJH method) which uses a pore filling kelvin model for a given pore size. The theoretical maximum pore size measurable by this method is 190 nm.

Pore volume (occupied by pores less than 190 nm): the total mesopore volume is determined from the total volume (vads) of nitrogen adsorbed on the pores (under s.t.p conditions) at P/P0 ═ 0.99 and this value is then multiplied by a conversion factor that provides the value of liquid nitrogen filled in the pores.

The total pore volume of the monolithic organic aerogel sample was calculated as the difference between the specific volume of the sample and the specific volume of the solid polymer (framework volume). The specific volume of the solid polymer may be in accordance with ISO 12154: 2014-04 is measured by pycnometer. In the examples, the isocyanate-based polymer has a specific volume of 0.65cm³/g。

Materials:

m200 oligomeric MDI (Lupranat M200), NCO content of 30.9g/100g according to ASTM D-5155-96A, functionality of around 3, viscosity of 2100 mPas at 25 ℃ according to DIN 53018.

MDEA 3, 3 ', 5, 5 ' -tetraethyl-4, 4 ' -diaminodiphenylmethane

MEK methyl ethyl ketone

Ksorbat solution potassium sorbate dissolved in monoethylene glycol (5%)

TBA citrate tetrabutylammonium citrate (25% by weight in MEG)

Exolit OP560 phosphorus polyol

Scotch tape (CB 1):

transparent PP tape (5 cm wide) about 0.06mm thick with contact adhesive: (e-adhesive tape)

Fabric reinforced tape (CB 2):

polymer tapes (5 cm wide) about 0.3mm thick with fabric reinforcing and contact adhesives: (4651 white)

Paper (CB 3):

office paper 80g/m²With a manually applied layer of solid adhesive(s) ((Original solid glue)

Graphite foil (CFB 4):

graphite foil about 25 μm thick with 10 μm electrically insulating polymer layer and contact adhesive (heat sink foil of ProGraphite)

Aluminum coated paper (CFB 5):

aluminum coated paper about 0.3mm thick with contact adhesive

Mineral wool (CFB 6):

fireproof mineral wool (Innobra MIV 520P) of about 0.6mm thickness with a manually applied layer of solid glue adhesive(s) ((II))Original solid glue)

Example 1

In a polypropylene container, 48g M200 was stirred in 220g MEK at 20 ℃ to produce a clear solution. Similarly, 8g MDEA, 2g Ksorbate solution (5% in MEG), 2g Exolit OP560 and 4g butanol were dissolved in 220g MEK to obtain a second solution. The solutions were combined in a rectangular container (20x20cm x5cm tall) by pouring one solution into the other, forming a homogeneous mixture of low viscosity. The vessel was capped and the mixture gelled for 24 hours at room temperature. The resulting monolithic gel plate was dried by solvent extraction in a 25l autoclave with scCO2 to give a porous material.

Using a hydraulic press (Schmidt Maschinenterchnik) with platens (30X30cm) at 25 ℃ in the range 30-60kN/900cm²The resulting plate was compressed for 2 seconds at a pressing speed of 22.8cm/min (examples 1-1 and 1-2).

A wrench was placed on top of the multi-well plate of example 1-C and compressed. The wrench then imprints its logo on the surface of the plate.

Example 2

In a polypropylene container, 25.6g M200 was stirred in 146.67g of MEK at 20 ℃ to produce a clear solution. Similarly, 5.33g MDEA, 1.33g Ksorbate solution (5% in MEG), 1.33g Exolit OP560 and 2.67g butanol were dissolved in 146.67g MEK to obtain a second solution. The solutions were combined in a rectangular container (16x16cm x3cm high) by pouring one solution into the other, forming a homogeneous mixture of low viscosity. The vessel was capped and the mixture gelled for 24 hours at room temperature. The resulting monolithic gel plates were used in a 25l autoclave with scCO₂And extracting and drying by using a solvent to obtain the porous material.

Using a hydraulic press (Schmidt Maschinenterchnik) with platens (30X30cm) at 25 ℃ in the range 30-60kN/900cm²The resulting plate was compressed for 2 seconds at a pressing speed of 22.8cm/min (examples 2-1, 2-2, 2-3, 2-4).

Example 3-C

In a polypropylene container, 22.4g M200 was stirred in 121.6g MEK at 20 ℃ to produce a clear solution. Similarly, 5.33g MDEA, 1.33g Ksorbate solution (5% in MEG), 1.33g Exolit OP560 and 2.67g butanol were dissolved in 121.6g MEK to obtain a second solution. The solutions were combined in a rectangular container (16x16cm x3cm tall) by pouring one solution into the other, forming a homogeneous mixture of low viscosity. The vessel was capped and the mixture gelled for 24 hours at room temperature. The resulting monolithic gel plate was dried by solvent extraction in a 25l autoclave with scCO2 to give a porous material.

Example 4-C

In a polypropylene container, 22.4g M200 was stirred in 96.8g mek at 20 ℃ to produce a clear solution. Similarly, 5.33g MDEA, 1.33g Ksorbate solution (5% in MEG), 1.33g Exolit OP560 and 2.67g butanol were dissolved in 96.8g MEK to obtain a second solution. The solutions were combined in a rectangular container (16x16cm x3cm tall) by pouring one solution into the other, forming a homogeneous mixture of low viscosity. The vessel was capped and the mixture gelled for 24 hours at room temperature. The resulting monolithic gel plate was dried by solvent extraction in a 25l autoclave with scCO2 to give a porous material.

Example 5-C

In a polypropylene container, 22.4g M200 was stirred in 54.3g MEK at 20 ℃ to produce a clear solution. Similarly, 5.33g MDEA, 1.33g Ksorbate solution (5% in MEG), 1.33g Exolit OP560 and 2.67g butanol were dissolved in 54.3g MEK to obtain a second solution. The solutions were combined in a rectangular container (16x16cm x3cm tall) by pouring one solution into the other, forming a homogeneous mixture of low viscosity. The vessel was capped and the mixture gelled for 24 hours at room temperature. The resulting monolithic gel plate was dried by solvent extraction in a 25l autoclave with scCO2 to give a porous material.

The results are summarized in table 1. Compressed cellular boards exhibit significantly lower thermal conductivity and higher flexural strength at higher densities.

Example 6:

preparation of compressed monolithic aerogel layer a 1:

in a polypropylene container, 48g M200 was stirred in 220g MEK at 20 ℃ to produce a clear solution. Similarly, 6g MDEA, 2g Ksorbate solution, 2g Exolit OP560 and 6g butanol were dissolved in 220g MEK to obtain a second solution. The solutions were combined in a rectangular container (20cm x20cm x5cm tall) by pouring one solution into the other to form a homogeneous mixture of low viscosity. The vessel was capped and the mixture gelled for 24 hours at room temperature. The resulting monolithic gel plate was dried by solvent extraction in a 25l autoclave with scCO2 to give a porous material.

A 15x15x1.5cm plate of porous material was cut into 15x15cm and 1-3mm thick sheets using a band saw.

Preparation of compressed monolithic aerogel layer a 2:

a hydraulic press (Schmidt Maschinenterchnik) with platens (30X30cm) was used at 25 ℃ at 30-60kN/900cm²The porous plate for the entire aerogel layer a1 obtained as described above was compressed for 2 seconds at a pressing speed of 20-25 cm/min. In table 1, the thickness reduction is listed as% compression.

Examples 6-1 to 6-11

Pre-cut adhesive tape (CB1), fabric tape (CB2), paper with a layer of solid glue adhesive (CB3), graphite foil (CFB4), aluminum coated paper (CFB5) or strips of mineral wool with a layer of solid glue adhesive (CFB6) were manually pressed together with the adhesive layer onto the integral aerogel layers a1 and a 2. In the case of CB1 and CB2, one layer of tape was used on each side for samples having a width of 5cm or less. For samples having a width in excess of 5cm, the tape layers were applied in a manner that created an overlap of about 5-10mm between the layers. The laminate structure, thickness and mechanical properties of the insulation material are summarized in table 1.

Examples 6-3 to 6-7, 6-8, 6-10, and 6-11 showed no delamination in the three-point bending test, and no delamination occurred when the outer tape layer was bent. The minimum diameter is the diameter that does not significantly break when bent or crimped. In the case of a sheet with a laminate on one side, the sheet is bent over the side without the cover layer. A sheet is considered to be non-reusable if the material breaks and/or partially delaminates after bending to the minimum rolling diameter.

The results are summarized in table 2.

Example 7

In a polypropylene container, 48g M200 was stirred in 220g MEK at 20 ℃ to produce a clear solution. Similarly, 8g of MDEA, 2g of Ksorbate solution (5% in MEG), 2g of Exolit OP560 and 4g of 1-butanol were dissolved in 220g of MEK to obtain a second solution. The solutions were combined in a rectangular container (20x20cm x5cm high) by pouring one solution into the other, forming a homogeneous mixture of low viscosity. The vessel was capped and the mixture gelled for 24 hours at room temperature. The resulting monolithic gel plates were used in a 25l autoclave with scCO₂Drying by solvent extraction yields a porous material.

A hydraulic press (Schmidt Maschinenterchnik) with platens (30X30cm) was used at 25 ℃ at 30-60kN/900cm²The obtained multi-well plate was compressed for 2 seconds at a pressing speed of 22.8cm/min (examples 7-C to 7.4). The results are summarized in table 3.

Example 8

In a polypropylene vessel, 25.6g M200 was stirred in 220g MEK at 20 ℃ to produce a clear solution. Similarly, 5.44g of MDEA, 0.67g of TBA-Citrat solution (25% in MEG), 1g of Exolit OP560 and 2.67g of 1-butanol were dissolved in 220g of MEK to obtain a second solution. The solutions were combined in a rectangular container (20x20cm x5cm high) by pouring one solution into the other, forming a homogeneous mixture of low viscosity. The vessel was capped and the mixture gelled for 24 hours at room temperature. The resulting monolithic gel plates were used in a 25l autoclave with scCO₂And extracting and drying by using a solvent to obtain the porous material.

Using a hydraulic press (Schmidt Maschinenterchnik) with platens (30X30cm) at 25 ℃ in the range 30-60kN/900cm²The obtained multi-well plate was compressed for 2 seconds at a pressing speed of 22.8cm/min (examples 8-C to 8.4). The results are summarized in table 3.

Examples 9 to 12

Example 9 was repeated using different amounts and concentrations of the raw materials shown in table 5 to obtain monolithic aerogel samples having different densities and thicknesses.

Using a hydraulic press (Schmidt Maschinenterchnik) with platens (30X30cm) at 25 ℃ in the range 30-60kN/900cm²The resulting porous plate was compressed for 2 seconds at a pressing speed of 22.8cm/min to obtain a compressed plate having a thickness of about 8 mm. The results are summarized in table 4.

Examples 11-4 showed a mass loss of 0.3 wt% in the friability test, which is much lower than the 1.7 wt% mass loss of comparative example 10-C.

Examples 13 and 14

All steps were carried out at 20 ℃. Examples 13(1 wt% alginate) and 14(2 wt% alginate) were prepared by adding 28g (13) or 56g (14) of sodium alginate to 2500g of water in a beaker and stirring overnight with a laboratory stirrer. Then, 8.2g (13) or 16.3g (14) of calcium carbonate powder was dispersed in water using a rotor-stator mixer, and the resulting dispersion was immediately added to the alginate solution while stirring. 6.8g (13) or 13.6g (14) D-glucono-delta-lactone (GDL) were dissolved in 66.7g of water by vigorous stirring for 10s, and the resulting solution was added to 750g of alginate/calcium carbonate mixture, and the resulting mixture was stirred for 30 s. The mixture was immediately poured into a 20x20cm polymer mold to a height of 10-15mm and the filled mold was left overnight to gel the mixture. The liquid drained from the gel during gelation was removed every 2-6 hours. The gel plates obtained were aged for 24h in 750g of a previously prepared calcium chloride solution (15g of calcium chloride in 2975g of water). The gel liquid was converted from aqueous solution to ethanol by placing the gel slab in each 750g of an aqueous solution of 20 vol%, 40 vol%, 60 vol%, 80 vol% ethanol for 24h and finally in pure ethanol for 24 h. The gel plates were dried using supercritical carbon dioxide to obtain alginate multiwell plates.

Using a hydraulic press (Schmidt Maschinenterchnik) with platens (30X30cm) at 25 ℃ in the range 30-60kN/900cm²The obtained multi-well plate was compressed for 2 seconds at a pressing speed of 22.8cm/min to obtain a compressed plate having a thickness of about 8 mm. The results are summarized in table 4.