阅读说明：本技术 粒状混合氧化物材料和在其基础上的隔热组合物 (Particulate mixed oxide material and thermal insulation composition based thereon ) 是由 U·努姆里奇 C·默尔斯 B·格哈尔茨-克尔特 B·拉扎尔 M·盖斯勒 于 2019-07-09 设计创作，主要内容包括：疏水化的粒状材料,其包含30-95重量％的基于二氧化硅和至少一种金属M的氧化物的热解混合氧化物,和5-70重量％的至少一种选自由碳化硅、二氧化锆、钛铁矿、钛酸铁、硅酸锆、氧化锰、石墨、炭黑及其混合物组成的组的IR遮光剂,所述金属M选自Al、Ti和Fe,其中金属M氧化物在混合氧化物中的含量为0.1-10重量％。(Hydrophobized particulate material comprising 30 to 95 wt.% of pyrogenic mixed oxides based on silicon dioxide and at least one oxide of a metal M selected from Al, Ti and Fe, and 5 to 70 wt.% of at least one IR screening agent selected from the group consisting of silicon carbide, zirconium dioxide, ilmenite, iron titanate, zirconium silicate, manganese oxide, graphite, carbon black and mixtures thereof, wherein the content of metal M oxide in the mixed oxide is 0.1 to 10 wt.%.)

1. Hydrophobized particulate material, comprising 30 to 95 wt.% of mixed oxides based on silicon dioxide and at least one oxide of a metal M, and 5 to 70 wt.% of at least one IR opacifier selected from the group consisting of silicon carbide, zirconium dioxide, ilmenite, iron titanate, zirconium silicate, manganese oxide, graphite, carbon black and mixtures thereof, the metal M being selected from Al, Ti and Fe, and the content of the oxide of the metal M in the mixed oxides being 0.1 to 10 wt.%.

2. The hydrophobized particulate material of claim 1,

it is characterized in that the preparation method is characterized in that,

the mixed oxide is a fumed silica-alumina mixed oxide.

3. The hydrophobized particulate material of any of claims 1 to 2,

it is characterized in that the preparation method is characterized in that,

the particulate material has a methanol wettability of 10% to 80% methanol in a methanol/water mixture.

4. The hydrophobized particulate material of any of claims 1 to 3,

it is characterized in that the preparation method is characterized in that,

the particulate material has a numerical median particle size d of greater than 10 [ mu ] m₅₀。

5. The hydrophobized particulate material of any of claims 1 to 4,

it is characterized in that the preparation method is characterized in that,

the particulate material is substantially free of particles smaller than 200 μm.

6. The hydrophobized particulate material of any of claims 1 to 5,

it is characterized in that the preparation method is characterized in that,

the hydrophobized particulate material has a particle size of 50 to 400m²BET surface area in g.

7. The hydrophobized particulate material of any of claims 1 to 6,

it is characterized in that the preparation method is characterized in that,

the particulate material has a tamped density of 50-300 g/L.

8. The hydrophobized particulate material of any of claims 1 to 7,

it is characterized in that the preparation method is characterized in that,

the particulate material has a hydroxyl group density of no greater than 0.3 mmolOH/g.

9. A process for preparing a hydrophobised particulate material according to any one of claims 1 to 8, the process comprising the steps of:

a) mixing a mixed oxide based on hydrophilic silica with at least one IR opacifier;

b) densifying the mixture obtained in step a) to produce a hydrophilic particulate material;

c) subjecting the hydrophilic particulate material produced in step b) to a heat treatment at a temperature of 200 ℃, -1200 ℃;

d) hydrophobicizing the hydrophilic particulate material which has been subjected to a heat treatment in step c) with a hydrophobicizing agent.

10. A process for preparing a hydrophobised particulate material according to any one of claims 1 to 8, the process comprising the steps of:

a) mixing a mixed oxide based on hydrophilic silica with at least one IR opacifier;

b) densifying the mixture obtained in step a) to produce a hydrophilic particulate material;

c) treating the hydrophilic particulate material produced in step b) with ammonia;

d) hydrophobizing the hydrophilic particulate material treated with ammonia in step c) with a hydrophobizing agent.

11. A thermal insulation composition comprising the hydrophobized particulate material of any of claims 1-5.

12. The thermal insulating composition of claim 8 comprising at least one organic binder selected from the group consisting of: (meth) acrylates, alkyds, epoxies, gum arabic, casein, vegetable oils, polyurethanes, silicones, hybrid systems comprising silicone-based ingredients and other organic ingredients, waxes, cellulose gums and mixtures thereof.

13. A thermal insulation composition as claimed in any one of claims 8-9 comprising at least one inorganic binder selected from the group consisting of: quicklime, dolomitic lime, gypsum, anhydrite, hydraulic lime, cement, masonry cement, and mixtures thereof.

14. Use of the granular material according to any one of claims 1-5 for thermal and/or acoustic insulation.

Examples

Preparation of silica granular Material A (comparative example)

The preparation of hydrophobized silica particulate material comprising IR opacifiers was carried out according to PCT/EP 2018/051142:

mixing

20 wt% of 1000F silicon carbide (Carsimet) (manufacturer: Keyvest) and 80 wt% of the silicon carbide (Carsimet) were mixed by a Minox PSM 300HN/1MK plowshare mixer200 hydrophilic silica (BET 200 m)²G, manufacturer: EVONIK Resource Effect GmbH).

Densification

Prepared as described above, was densified using a Grenzebach densification roller (Vacupress VP 160/220)The mixture of 200 and silicon carbide is densified. The tamped density of the obtained granular material is adjusted by the applied contact pressure, roll speed and reduced pressure. The vacuum applied is less than 300 mbar absolute. The roll speed was 5rpm and the pressure was 2000N.

Sintering/hardening

In a process fromGmbSubsequent thermal hardening was performed in an XR 310 chamber kiln from H. For this purpose, layers of the bed having a height of at most 5cm are subjected to a temperature program. The heating rate (ramp) is 300K/h until the target temperature is 950 ℃; the heat preservation time is 3 hours; the sample was then allowed to cool (without active cooling) until removed.

Hydrophobization

The final hydrophobization of the thermally hardened particulate material is carried out in the gas phase at elevated temperature. For this purpose, Hexamethyldisilazane (HMDS) as hydrophobizing agent is evaporated and is carried out by the reduced pressure method according to the method of example 1 of WO 2013/013714a 1. The sample was heated in a desiccator to above 100 ℃ and then evacuated. Subsequently, gaseous HMDS was passed into the dryer until the pressure rose to 300 mbar. After the sample was purged with air, it was removed from the desiccator.

Sieving/classifying

To obtain the desired size fraction, the thermally hardened granular material is first fed to a vibrating screen mill (manufacturer: FREWITT) with a mesh size of 3150 μm in order to establish an upper limit for the particles and thus to remove particles above this upper limit. This is followed by the desired classification of the particle size fraction, for example 200-1190 μm or 1190-3150 μm. This was done using a model LS18S shaker from Sweco. The average particle size of the sieve fraction of the particulate material A of 200-1190 μm was d₅₀＝580μm。

Preparation of silica-alumina particulate Material B according to the invention

Silica-alumina particulate material B was prepared similarly to silica particulate material A except thatMOX 170 (fumed silica-alumina mixed oxide containing about 1 wt% alumina, BET 170m²G, manufacturer: EVONIK Resource Effect GmbH) instead of raw material200 c, and the sintering temperature in the sintering/hardening step is lowered to 850 c. 200-1190 μm of granular material BThe average particle size of the sieve fraction is d₅₀＝440μm。

The binder used

Adhesive A: acronal Eco 6270 (manufacturer: BASF); an acrylic functional binder system.

And (3) adhesive B: coatosil DR (manufacturer: Momentive); a siloxane functionalized binder system.

Viscosity measurement

The measurement of the dynamic viscosity of the formulation (mixture of binder and granular material) was carried out using a rotary viscometer Brookfield DV2T Extra. The spindle and rotation speed were chosen according to the viscosity range given in the manual.

General Experimental description for measuring the viscosity of compositions containing particulate materials after various storage times

Preparation of the formulation:

the binder (276g) was filled into a cylindrical glass vessel having a diameter of 9.5cm and stirred with a propeller stirrer at 600 rpm. The granular material (24g, sieve fraction 200. sub.1190 μm) was gradually added to the stirred binder and stirring was continued until a homogeneous mixture had been obtained, i.e. all the granular material was incorporated into the binder-containing mixture.

Measurement:

the dynamic viscosity of all samples was measured immediately after their preparation. The sample was closed with an impermeable lid and additionally sealed with Parafilm M foil. The so-blocked samples were stored at two different temperatures (25 ℃ and 40 ℃) without stirring, opened after a defined storage time for the measurement of the dynamic viscosity as described before, and blocked again for further storage. All samples were measured twice a week over a three week period to observe their thickening behavior.

Examples

Comparative example 1

The granular material A was tested with binder A at 25 ℃ according to the general experimental description (sieve fraction 200-.

Example 1

The granular material B was tested with binder A at 25 ℃ according to the general experimental description (sieve fraction 200-.

Comparative example 2

The granular material A was tested with binder A at 40 ℃ according to the general experimental description (sieve fraction 200-.

Example 2

The granular material B was tested with binder A at 40 ℃ according to the general experimental description (sieve fraction 200-.

Comparative example 3

The granular material A was tested with binder B at 25 ℃ according to the general experimental description (sieve fraction 200-.

Example 3

The granular material B was tested with binder B at 25 ℃ according to the general experimental description (sieve fraction 200-.

Comparative example 4

The granular material A was tested with binder B at 40 ℃ according to the general experimental description (sieve fraction 200-.

Example 4

The granular material B was tested with binder B at 40 ℃ according to the general experimental description (sieve fraction 200. sup. 1190 μm).

Comparative example 5

The granular material A (sieve fraction 200-₅₀Fine powder with an average particle size of 208 μm. The powder was tested with binder a at 25 ℃ according to the general experimental description.

Example 5

The granular material B (sieve fraction 200-₅₀Fine powder with an average particle size of 158 μm. The powder was tested with binder a at 25 ℃ according to the general experimental description.

The results of the viscosity measurements after different storage times are summarized in table 1. These results clearly show that the compositions according to the invention containing a particulate material based on mixed oxides (examples 1 to 5) provide a significantly lower viscosity compared to a similar material based on pure silica (comparative examples 1 to 5).

TABLE 1