WO2012016952A1

WO2012016952A1 - High-temperature-stable sheet silicates having an increased layer separation

Info

Publication number: WO2012016952A1
Application number: PCT/EP2011/063225
Authority: WO
Inventors: Peter GRÖPPEL; André GRÜBEL; Rolf Mülhaupt; Michael Nedelcu; Meik Wissert
Original assignee: Siemens Aktiengesellschaft
Priority date: 2010-08-02
Filing date: 2011-08-01
Publication date: 2012-02-09
Also published as: DE102010033029A1

Abstract

The invention relates to high-temperature-stable sheet silicates having an increased layer separation. The sheet silicates can be produced by means of the following process steps: provision of a sheet silicate comprising cations (4) which electrostatically bond at least two individual layers of the sheet silicate; replacement of at least part of the cations (4) of the sheet silicate by organic cations (5) of an organophilicizing reagent (9a, 9b), where the organophilicizing reagent comprises at least one imide group (7).

Description

High temperature stable phyllosilicates with increased

layer separation

The present invention relates to the technical field of organophilic phyllosilicates, their preparation and their use in deformable molding compositions and in finished moldings or composite materials, in particular in nanocomposites (nanocomposites).

Organophilic phyllosilicates based on

quaternary ammonium compounds and phyllosilicates and their nanocomposites with thermoplastics were in US-A-4 810 ^λ ^λ 734 by Kawasumi et al. , US-A-4 889 ^λ ^λ 885 of Usuki et al. and US ^Pat. No. 4,994,911 to Okada et al. introduced. Organophilic sheet silicates based on quaternary ammonium compounds and phyllosilicates and their nanocomposites with epoxy resins have been described in WO 96/08526 by Gianellis et al. introduced. The problem of low thermal stability of organophilic phyllosilicates based on phyllosilicates and quaternary ammonium compounds by Hofmann elimination is

known from the literature and much discussed, e.g. in Clays and Clay Minerals, 52 (2), 171-179, 2004. Common ways to increase the thermal stabilities are replacing the

Ammonium compounds by phosphonium compounds. These organophilic sheet silicates and their nanocomposites are described in WO 98/10012 by M.W. Ellsworth explains. Another common method in the literature is the replacement of quaternary ammonium compounds with amidine compounds, e.g. in the technical literature in Chem. Mater., 14,3776-3785, discussed in 2002 and in DE 699 07 162 T2 by Zilg et al. explained. The present invention is based on the object, the thermal stability of organophilic

To increase phyllosilicates.

This object is achieved by in the independent

Claims solved solutions. advantageous Embodiments of the invention are specified in further claims.

According to one aspect of the invention is a

Process for the preparation of an organophilic phyllosilicate presented. In a process step is a

Layered silicate provided which comprises cations which at least two individual layers of the layered silicate

connects electrostatically. In a further process step, at least a part of the cations of the layered silicate is replaced by organic cations of an organophilization reagent. The organophilicating reagent comprises at least one imide group.

According to a further aspect of the invention, an organophilic layered silicate is proposed, which according to the process for the preparation of the organophilic

Layer silicate was produced. According to a further aspect of the invention, an organophilic layered silicate is proposed which comprises at least two individual layers

includes. The individual layers are at least partially electrostatically connected by organic cations. At least part of the organic cations comprises an imide group. According to a further aspect of the invention, a use of such organophilic phyllosilicates in deformable

Molding compounds or in finished moldings or

Composite materials proposed.

According to a further aspect of the invention, a use of a Organophilierungsreagenzes for

Preparation of an organophilic sheet silicate from a sheet silicate disclosed. The organophilicating reagent comprises at least one imide group.

The term organophilic is to be understood as a substance which is dispersible in an organic material. The invention will be described below with reference to

Drawing explained in more detail, for example:

Figures 1A and 1B show formulas of two

Organophilization reagents according to preferred embodiments of the invention;

Figures 2A, 2B, 2C, 2D show a chemical

Reacting anhydrides with amines to produce an organophylating reagent;

FIG. 3 shows results of the thermal

Characterization of organophilic phyllosilicates by thermogravimetry (TGA);

FIG. 4 shows results of

Morphology studies based on imidamine-modified montmorillonite (PGV).

Figures 1A and 1B each show a formula for a chemical compound of imidamine-based

Organophilicating reagents 9a, 9b, which are assigned to

Organophilization of sheet silicates according to preferred

From embodiments of the invention can be used. In the

Figures 1A and 1B are nearly identical, but the compound in Figure 1A has a protonatable nitrogen atom 8, while in the compound of Figure 1B an already protonated nitrogen atom 8 'is present. According to one embodiment of the invention, the organophilicizing reagent comprises at least one, preferably two or more functional imide groups 7a, 7b, 7c, 7d. According to further preferred embodiments, one or more or all of the imide groups of a compound comprise any choice of alkyl radical, alkenyl radical, aryl radical and / or an alkylaryl radical with or without further

functional groups. In the formulas of FIGS. 1A and 1B, R is an alkyl radical and / or an alkenyl radical and / or an aryl radical and / or an alkylaryl radical. R does not always have to be the same in a formula, but can be combined arbitrarily, which is through the

different reference numerals 3a, 3b, 3c, 3d for R

is illustrated. For example, 3c may be an alkyl radical and 3d an aryl radical. In FIG. 1B, X is any cation 4

(also called counterion or original cation) of the original phyllosilicate, which is used for

Organophilization of the layered silicate is replaced by the organophilic cation 5. The cation 4 is therefore not part of the Organophilierungsreagenzes.

The illustrated in Figures 1A and 1B

Substance classes were used to the best of our knowledge for the first time to modify phyllosilicates. With conventional methods are thus novel organophilic

Phyllosilicates with properties that differ from common organophilic phyllosilicates based on

Clearly delineate ammonium compounds and phyllosilicates, accessible.

The outstanding thermal stability and

Layer expansion of the resulting organophilic

Layered silicates are shown below in Table 1 in comparison with conventional quaternary ammonium compounds:

In Table 1, in the first column, the

Organophilic layered silage (OSS) applied, while in the second column, the associated Organophilierungsreagenz (also called Organophilant called). In the third column, the layer expansion d is plotted, which was measured by means of a Wide Angle X-Ray Spectroscopy (WAXS), where d is the distance between two layers of the respective

Phyllosilicates represented in nanometers.

Table 1 shows measured film widening d and thermal stabilities T _d of organophilic sheet sililates

(OSS). On the one hand, the layer expansions d and thermal stabilities T _d of known OSS were measured, namely Montmorillonite (MMT), modified with octadecylamine

Montmorillonite (MMT-ODA) and dimethyloctadecyl ammonium modified montmorillonite (MMT-DMODA). On the other hand, Table 1 also shows measured layer expansions d and thermal stabilities T of OSS in comparison with the above known OSS, namely, dodecenyl-modified montmorillonites (MMT-IA1), phthalate-modified montmorillonites (MMT-IA2 ), methyl-modified montmorillonite (MMT-IA3 / 4) and naphthyl-modified montmorillonite (MMT-IA5).

An illustration of the exact structural formulas of

Organophilization reactions can be found in FIGS. 2A, 2B, 2C, 2D. Due to the high layer widening and special

Thermostability will be available in combination with thermoplastics and thermosets new nanocomposites.

conventional amines.

It can be clearly seen from Table 1 that: all of the montmorillonites modified with imidamine have markedly increased thermal stabilities T _d . In the case of dodecenyl modified montmorillonite results even an increased thermal stability T _d of up to 350 ° C and a

Layer expansion d of 3.8-3.9 nanometers.

First nanocomposites were by

Melt compounding with a polypropylene compound (PP), polyamide-6 (PA6), polyparaphenylene sulfide and compounding with an epoxy resin (ER).

According to preferred embodiments of the invention, the nanocomposites, but also other composites with organophilic phyllosilicates are in exfoliated form

contain. The organophilic phyllosilicates are characterized by particularly high layer widening and outstanding

Temperature stability off. This allows the production of novel nanocomposites from the inventive

organophilic phyllosilicates with thermoplastics or

Epoxy resins.

It was found that organophilic

Phyllosilicates based on imidamine-modified

Phyllosilicates, an outstanding layer expansion of up to 4 nm (WAXS) and very high thermal stabilities of up to 360 ° C (thermogravimetric analysis TGA, nitrogen N ₂ , 10 Kelvin / min) have. The preparation of organophilic phyllosilicates based on imidamines is possible in a conventional manner. Especially with epoxy resins can be the

Imidamin tailor-made of the epoxy hardener diethylenetriamine (DETA) and an anhydride, optionally the anhydride component of the resin / anhydride hardener system. The compatibility between organophilic phyllosilicate and epoxy resin is thus increased. Organophilic phyllosilicates based on

Imidamines offer through the easy accessibility and

simple synthesis of price advantages over the less available, toxic and expensive phosphonium compounds and the most biocidal amidine compounds.

The following is a preferred method

Preparation of an Oranophilierungsreagenzes by means of

Imidamine 1 (imidamine with dodecenyl radical) described: Under N2 atmosphere are 2 equivalents

Dodecynilsuccinic anhydride (DDSA) in a two-necked flask equipped with stirrer and melted at 60 ° C. Over 1 hour, 1 equivalent of diethyl tetraamine (DETA) is added dropwise with stirring. This forms a highly viscous solution. The reaction mixture is heated to 150 ° C with further stirring. The reaction is carried out under these conditions for 1 hour. For another hour, excess starting material and water at 150 ° C and 7 mbar pressure is separated. There were obtained 98% of the target substance as a highly viscous orange liquid.

A selection of successful imidamine syntheses is the

Figures 2A, 2B, 2C, 2D can be seen. For the synthesis, typically an anhydride 51a, 51b, 51c, 51d is treated with an amine 52a, 52b, 52c, 52d under preferred conditions 53a, 53b,

53c, 53d a chemical reaction, from which in each case the desired imide amine 54a, 54b, 54c, 54d emerges. The following are the chemical reactions of Figure 2A-2D

Imidamine:

FIG. 2A imidamine with a dodecenyl radical (54a)

Figure 2B imidamine with a phthalic residue (54b);

FIG. 2C imidamine with a methyl radical (54c);

Figure 2D imidamine with a naphthyl radical (54d).

In the following, the cation exchange will be described. In other words, it describes how original cations of a layered silicate could be exchanged for organic cations of an organophilicizing reagent according to a preferred embodiment of the invention:

The sheet silicates were first swollen in 80 ° C warm deionized water (H 2 O) 2 hours and

then an equivalent amount of imidamine and a

Equivalent amount of concentrated hydrochloric acid (HCl) was added. The reaction mixture was stirred for a further 4 hours at 80 ° C, separated and washed free of chloride with deionized water (H ₂ 0). The resulting solid was heated at 60 ° C for 48 Dried hours and ground with a centrifugal mill to 80 μπι.

Results of the thermal characterization of the organophilic phyllosilicates by means of thermogravimetry (TGA) are shown in FIG. The abscissa represents the temperature in ° C to which the organophilic sheet silicates were exposed, while the ordinate represents the weight percentage (mass wt.%). Measurement curve 11 shows the temperature stability of already known dimethyloctadecylammonium (DMODA) modified montmorillonite (PGV). The measured curves 21, 22, 23, 24, 25 represent the measured values

Temperature resistances of with imidamine 1 (measurement curve 21), imidamine 2 (measurement curve 22), imidamine 3 (measurement curve 23), imidamine 4 (measurement curve 24) or imidamine 5 (measurement curve 25)

modified montmorillonite (PGV).

The significantly increased thermal stability is based on the comparison of imidbasierter curves 21-25 with the

Measurement curve 11 for dimethyloctadecylammonium (DMODA) modified montmorillonite (PGV) clearly visible.

While the temperature resistance of with

Dimethyloctadecylammonium (DMODA) modified

Montmorillonite (PGV) already kinks about 250 ° C, modified with imidamine (IA1-IA5) montmorillonites (PGV) are stable to significantly higher temperatures. FIG. 4 shows results of

Morphology studies based on different imidamine-modified montmorillonites (PGV). Similar to column 3 of Table 1, the peaks of the traces indicate the layer spacing of the individual organophilic ones

Phyllosilicates. LIST OF REFERENCE NUMBERS

3a, 3b, 3c, 3d alkyl radical, alkenyl radical, aryl radical and / or an alkylaryl radical

4 cation, original cation 5 organic cation, modified cation

7a, 7b, 7c, 7d imide group

8, 8 'nitrogen atom

9a, 9b Organophilating reagent

11, 21-25, 31-35 traces 51a, 51b, 51c, 51d anhydride

52a, 52b, 52c, 52d amine

53a, 53b, 53c, 53d Conditions

54a imidamine with a dodecenyl residue

54b imidamine with a phthalic radical 54c imidamine with a methyl radical

54d imidamine with a naphthyl radical

Claims

Claims.

1. Process for the preparation of an organophilic

Phyllosilicates, comprising the process steps:

Providing a layered silicate which comprises cations (4) which comprise at least two individual layers of the

Phyllosilicates combines electrostatically;

Replacing at least part of the cations (4) of the

Phyllosilicates by organic cations (5) of a

Organophilating reagents (9a, 9b), wherein the

Organophilating reagent (9a, 9b) comprises at least one imide group (7a, 7b, 7c, 7d).

2. The method according to claim 1,

characterized in that

the phyllosilicate is a phyllosilicate from the group of

Two-layer and / or three-layer layered silicates is.

3. The method according to any one of the preceding claims, characterized in that

the organophilicating reagent (9a, 9b) comprises an imideamine (54a, 54b, 54c, 54d).

4. The method according to any one of the preceding claims, characterized in that

the imide group is an alkyl radical (3a, 3b, 3c, 3d), alkenyl radical (3a, 3b, 3c, 3d), aryl radical (3a, 3b, 3c, 3d) and / or an alkylaryl radical (3a , 3b, 3c, 3d) with or without others

includes functional groups.

5. The method according to any one of the preceding claims, characterized in that

the imide group (7a, 7b, 7c, 7d) comprises a dodecenyl radical.

6. The method according to any one of the preceding claims, characterized in that the imide group (7a, 7b, 7c, 7d) comprises a phthalic residue.

7. The method according to any one of the preceding claims,

characterized in that

the imide group (7a, 7b, 7c, 7d) comprises a methyl radical.

8. The method according to any one of the preceding claims,

characterized in that

the imide group (7a, 7b, 7c, 7d) comprises a naphthyl radical.

9. Organophilic phyllosilicate, characterized in that it according to a method according to one of the preceding

Claims was made.

10. An organophilic sheet silicate comprising at least two

Individual layers which are at least partially electrostatically connected by organic cations (5);

characterized in that

at least a part of the organic cations (5) one

Imide group (7a, 7b, 7c, 7d).

11. An organophilic layered silicate according to claim 10,

characterized in that

the organophilic phyllosilicate is a phyllosilicate from the

Group of two-layered phyllosilicates and / or three-layer phyllosilicates is.

12. Organophilic layered silicate according to claim 10 or 11, characterized in that

at least part of the organic cations (5) comprise imideamine (54a, 54b, 54c, 54d).

13. Organophilic layered silicate according to any one of claims 10-12, characterized in that

the imide group (7a, 7b, 7c, 7d) is an alkyl radical (3a, 3b, 3c, 3d), alkenyl radical (3a, 3b, 3c, 3d), aryl radical (3a, 3b, 3c, 3d) or alkylaryl moiety (3a, 3b, 3c, 3d) with or without further functional groups.

14. An organophilic layered silicate according to any one of claims 10-13, characterized in that

the imide group (7a, 7b, 7c, 7d) comprises a dodecenyl radical.

15. Organophilic layered silicate according to any one of claims 10-14, characterized in that

the imide group (7a, 7b, 7c, 7d) comprises a phthalic residue.

16. An organophilic layered silicate according to any one of claims 10-15, characterized in that

the imide group (7a, 7b, 7c, 7d) comprises a methyl radical.

17. An organophilic layered silicate according to any one of claims 10-16, characterized in that

the imide group (7a, 7b, 7c, 7d) comprises a naphthyl radical.

18. Use of an organophilic phyllosilicate according to one of the claims 9-17 in deformable molding materials or in

manufactured moldings or composite materials.

19. Use of an organophilicizing reagent (9a, 9b) for the preparation of an organophilic phyllosilicate from a

Phyllosilicate,

dadruch marked that

the organophilicating reagent (9a, 9b) at least one

Imide group (7a, 7b, 7c, 7d).

20. Use according to claim 19,

characterized in that

the phyllosilicate is a phyllosilicate from the group of

Two-layered phyllosilicates and / or three-layer phyllosilicates.

21. Use according to claim 19 or 20, characterized in that

22. Use according to any one of claims 19-21,

characterized in that

the imide group (7a, 7b, 7c, 7d) is an alkyl radical, alkenyl radical, aryl radical or alkylaryl radical with or without further

includes functional groups.

23. Use according to any one of claims 19-22,

characterized in that

the imide group (7a, 7b, 7c, 7d) comprises a dodecenyl radical.

24. Use according to any one of claims 19-23,

characterized in that

the imide group (7a, 7b, 7c, 7d) comprises a phthalic residue.

25. Use according to any one of claims 19-24,

characterized in that

the imide group (7a, 7b, 7c, 7d) comprises a methyl radical.

26. Use according to any one of claims 19-25

characterized in that

the imide group (7a, 7b, 7c, 7d) comprises a naphthyl radical.