New plastics additives based on modified silica, their use and processes for their preparation

(42) Date of commencement of the patent: 15. 9.1991 (45) Date of issue: 25. 3. 1992 (56) Documentation:

US-PS2993809 DE-0S1645679 (73)

Patentee:

GREBER GERD DR.

A-2540 BAD VÖSLAU, LOWER AUSTRIA (AT).

CQ

AT 394 371 (54) NEW PLASTIC ADDITIVES BASED ON MODIFIED SILICON DIOXIDE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE (57) Migration-grade and physiologically acceptable plastic additives based on modified silica. By reaction of finely divided silicon dioxide with silicon-containing hydrogen-containing organodichlorosilanes, in particular methyldichlorosilane, H-Si groups were first introduced into the SiO 2 via hydrolysis-stable siloxane bonds₂ Particles introduced.

By addition of the H-Si groups to CC multiple bonds containing compounds containing other reactive groups (eg. CH ₂ = CH-C & H -, H0-, NH ₂ ~ i HOOC, HS, -CONH ₂, -N = C = O, 2-0xacyclopropyl,

-C Η ₄ N ₂⁺ X may include one

Variety of novel silica derivatives, such as pigments, flame retardants, light stabilizers, antioxidants, optical brighteners, heat stabilizers, vinyl monomer grafted fillers, and novel reactive fillers for the curing of isocyanate, epoxide,

Alkyd or unsaturated polyester resins or for the vulcanization of polysiloxanes or polydienes to the corresponding rubbers.

OT <3078313

AT 394 371 B

The invention relates to novel plastic additives based on modified aerosils, which have high temperature resistance, good compatibility and migration fastness, processes for their preparation and their use.

Additives of all kinds play an extremely important role in the processing and packaging of plastics. So are, for example Two very important classes of plastic - namely polyolefins and polyvinyl chloride - can not be thermally processed without decomposition, nor can they be used under normal conditions without the addition of stabilizers. For the technical use of additives in addition to the actual effect, a number of other conditions of crucial importance, such. B. Compatibility with the polymer, resistance to processing and use temperature, migration fastness and physiological safety, which are usually not all equally well met, so that compromises are necessary. Thus, the fundamental disadvantage of all low molecular weight additives is that they are often difficult to incorporate, not really fast, partially volatile and physiologically inert. Polymeric additives - in which the active groups are incorporated either in the main or side chain of macromolecules - are indeed migration-wise, but often incompatible with the substrate due to the polarity of the overall molecule, and not thermally and chemically resistant enough.

Although inorganic additives have high temperature resistance, but usually also have some disadvantages of low molecular weight additives, in particular a poor compatibility with organic plastics. Thus, finely divided silica, as z. B. under the brand name "Aerosil" from the company. Degussa is sold, - very often as a thickener or filler - eg. for silicone rubbers - used. The following always refers to this product. The strong hydrophilicity of the Aerosilteilchen - due to the surface silanol groups - but causes a very poor wettability and compatibility with organic solvents or plastics, which not only prepares for incorporation, but can also lead to migration effects (particle migration) ,

The actual problem solution in the field of plastic additives is therefore still on the development of additives with high migration fastness, good compatibility high temperature resistance and physiological safety.

Object of the present invention was to develop new plastic additives that meet these requirements.

It has now been found that this object can be achieved with the aid of modified aerosils which contain covalently bound additive components.

The invention relates to novel, migration-genuine and physiologically harmless plastic additives based on silica of the formula II

<img file="AT394371B_D0001.tif" />

, (H) wherein Rj is an aliphatic, aliphatic-aromatic or aromatic radical, preferably a methyl radical

The invention further relates to novel, migration-genuine and physiologically harmless plastic additives based on silica of the formula ΙΠ

<img file="AT394371B_D0002.tif" />

, (III) wherein R | has the above meaning, R₂ for -CH₂-CH₂- or -CH (CH / and X is an aliphatic, aliphatic-aromatic, aromatic or heteroaromatic radical, which may optionally contain further reactive groups, in particular polymerizable double bonds, HO-, H₂N, HS, HOOC, H / i CO, CH₂-CH-, or OCN groups, and R₂-X can also mean vinyl.

O

-2AT394 371B

The process for the preparation of the silica-based additives according to the invention is characterized in that

a) under anhydrous conditions finely divided silicas with an organochlorosilane I.

CI

<img file="AT394371B_D0003.tif" />

, (D wherein Rj is an aliphatic, aliphatic-aromatic or aromatic radical, to derivatives with covalently linked via hydrolysis-resistant siloxane bonds Π residues

<img file="AT394371B_D0004.tif" />

(H) wherein Rj has the above meaning, and

b) optionally adding the resulting H-Si-containing silica derivatives Π to C = C multiple bond derivatives to give products ΠΙ

<img file="AT394371B_D0005.tif" />

, (IID wherein Rp Rβ and X have the meanings given above, and

c) optionally subsequently subsequently converted silica derivatives and ΙΠ with copolymerizable monomers or formaldehyde, isocyanate or epoxy resin precursors or reactive additive components.

According to the invention, commercially available Aerosil (grain diameter 10-20 nm, silanol group content eg 1 meq / g) is mixed with organodichlorosilane - preferably dimethylchlorosilane - in an inert solvent, such as e.g. As dioxane, THF, toluene, benzene, xylene optionally in the presence of bases - eg. Dimethylaniline, triethylamine - reacted as an acid scavenger with good stirring at temperatures of - 20 to +100 ° C.

The isolation and purification of the insoluble products of the formula II is carried out in a simple manner by Abfiltirieren, optionally rinsing to remove the salts and drying. The silanol groups react virtually quantitatively with the organodichlorosilane, depending on the molar ratio of silanol groups to organodichlorosilane products result with up to 5 meq H-Si groups / g.

The modified aerosils thus obtained are very interesting because of their reactive H-Si groups

Additives that z. B. can be successfully used as reactive fillers in the vulcanization of addition-crosslinking silicone rubbers. They are covalently bound by reaction with the vinyl group-containing component in the crosslinked system, resulting in improvements in the mechanical properties of such

Silicone rubber leads.

-3AT 394 371 Β

The Aerosil derivatives of the formula II according to the invention can be further converted by reaction with CC multiple-bond derivatives, which may optionally contain other reactive groups in a variety of new products of formula III with a variety of applications in the additive sector. So you get z. B. by reaction with vinylacetic acid, vinyl chloride, vinyl acetate, vinyl isocyanate, Vinylhamstoff, Acrylsäurebzw. Methacrylic acid, their esters and amides, acrylonitrile, maleic or Fumaric acid, its esters and amides, allyl alcohol, amine, isocyanate, urea, mercaptan, glycidyl ether, acetylene, propargyl alcohol, amine, chloride, acetic acid, Aerosil derivatives of formula III with OH, NH₂-, SH-, COOH-, COORj-NCO-, Cl-, CONH₂, Epoxy, CH₂= CH groups in the radical X. By adding aerosils of the formula II to only one multiple bond in compounds containing two or more polymerizable multiple bonds, for. As divinylbenzene, di- or polyfunctional acrylates or methacrylates, dienes, acetylene, vinyl or Isopropenylacetylen obtained products of formula III with polymerizable double bonds in the radical X.

The reactions of the Aerosil derivatives of formula II with C = C double bond derivatives according to the invention either without solvent or in inert solvents, such as. As benzene, toluene, xylene, dioxane, in the presence of catalysts such as Raney nickel, Pt on activated carbon, in particular with H₂PtClg performed at reaction temperatures of 50 to 200 ° C with good stirring.

Again, the isolation and purification of the derivatives is carried out in a simple manner by filtering off, washing and drying the insoluble Aerosil derivatives.

The Aerosil derivatives of the formula erfindungsgemäßen according to the invention are suitable, for example, as reactive fillers for a wide variety of lacquer and resin formulations, eg. B.

- Aerosil derivatives with OH, NH₂- or COOH groups for isocyanate, alkyd or epoxy resins

- Aerosil derivatives with CH₂-CH- groups for epoxy resins o

- Aerosil derivatives with CONH₂- or melamine residues for aminoplasts

- Aerosil derivatives with polymerizable double bonds for unsaturated polyesters

- Aerosil derivatives with SH groups for rubbers based on polydiene or thiokol.

The Aerosil derivatives of the formula III having polymerizable double bonds in the radical X can be radically copolymerized with polymerizable monomers. As such are, for example, S tyrol, α-Methy lstyrol, styrene derivatives IV ch = ch₂

I, (IV) ^XIRX₃ wherein R = Si, -CH, -CH, -Si-, -CH (CH₃) -Si-, -CH = CH-Si-,

III

I

-C - si- and X. = X₂= X, = -ORi, -OCOR ,, -NHRi, -N (R₁)₂-C1 || I 12 3 1

CH₂

X_x = X₂ = CH₃ and X₃ = - [- O-Si (CH₃)₂-]_n-X₁ mean and R | has the above meaning

With hydrophobic monomers such. As styrene, butadiene or styrene derivatives of formula IV is obtained hydrophobized aerosils that can be much easier than Aerosil incorporated into organic resin or coating systems and also migrate less, with hydrophilic monomers such. As acrylamide, Hydroxyethylraethaerylat or N-vinylpyrrolidone result in highly hydrophilic aerosils with good compatibility with aqueous systems.

However, such aerosil derivatives with grafted-on polymer chains can also be prepared by the use of SHG group-containing aerosils of the formula III as regulators in free-radical polymerizations.

-4AT 394 371 B

For copolymerization according to the invention it is also possible to use monomers with functional groups, for example NH₂Groups or their precursors (NO₂- or N = C groups), which are converted after polymerization in amino groups, use. As a result, a concentration effect is achieved and gives Aerosil derivatives with high occupancy of, for example, amino groups, which may be important for further reactions with reactive additive components, since in this way arise Aerosil additives with high active ingredient content.

Aerosil derivatives of the formula ΙΠ with additional reactive groups can be implemented according to the invention by further reactions with suitable additive components to form new additives based on Aerosil, z. B. obtained by diazotization of Aerosil derivatives with aromatic amino groups and subsequent coupling with

- Dye components, such as. For example, resorcinol, p-cresol, α- or ß-naphthol and their derivatives (1-amino-8-naphthol-3,6-disulfonic acid "Η-acid"), 2-hydroxy-3-naphthoesäureanilid and derivatives, ("naphthol AS "derivatives), hydroxyanthraquinones, or other dye-chemically-known coupling components Aerosil based pigments

- Sunscreen components, such. B. 2-hydroxy or 2,4-dihydroxybenzophenone and their derivatives, hydroxyphenylbenzotriazole derivatives Aerosil-based light stabilizers

- Antioxidant components, such as. As phenols with one or two ortho-permanent tert. Butyl groups - 2,6-di-tert-butylphenol, 2,2'-methylenebis (6-tert-butylphenol) 4,4'-thiobis (6-tert-butylphenol), p-phenylenediamine or naphthylamine derivatives - Antioxidants based on Aerosil.

However, such additives can also be prepared by reacting reactive Aerosil derivatives of the formula II or III with suitable reactive additive components, such. By reaction of H-Si- or OH-, NH₂-, SH- or CH₂With -CH- containing aerosils with

O

- Dye components with COOH, COC1 or -SOßHbzw. -SO₂Cl groups from the class of the azo dyes, anthraquinone dyes, triphenylmethane, phthalocyanine dyes or other known dye classes, reactive dyes based on cyanuric chloride or divinylsulfone,

- Flame retardant components with allyl, COOH or COC1 or carboxylic anhydride groups, eg. Tribromophenyl allyl ether, 2,2-bis- (4-allyloxy-3,5-dibromophenyl) -propane, hexachloromethylenophthalic anhydride (HET acid ethers), tetrachlorophthalic anhydride, 4-chloroformylanilino-bis (dimethylamino) phosphoric triamide, bis-allylamino-4 -chlorformylanilino-phosporsäuretriamid

Lichlschutzmittel componentsmitCOOH or COCl groups, for example, p-NJ4-dimethylaminobenzoyl chloride,

4-methoxycinnamic acid chloride, 2-carboxy-2^.-hydroxy-4'-methylbenzophenone, 2-cyano-3-phenylcinnamic acid

Antioxidants components with COOH or COCl groups, e.g. For example, 4-hydroxy-3,5-di-teitbutylbenzoesäure, 1- (4-hydroxy-3,5-di-tert-butyl) amino-3,5-dichlorotriazine, 3- (3,5-di-tert. butyl-4-hydroxyphenyl) propionic acid chloride

- Heat stabilizer components, such as. As organotin carboxylates, sulfur-containing organotin compounds with carboxyl groups, eg. B. dibutyltin bis (thioglycolic acid), Dialkylzinnmaleinate

- Optical brightener components, such as 5,6-benzocoumarin-3-carboxylic acid, 4- (2H-naphtho [l, 2-d] -triazol2-yl) -stilbene-4'-carboxylic acid or vice versa by reaction of COOH, NCO, CH₂Groups containing aerosils with correspondingly reactive additive components, eg. B.

- Dye components with OH, NH₂Groups from all known dye classes

Flame retardant components, such as tetrabromobisphenol-A, dibromopentaerythritol

- Light stabilizer components, such as 2,2,6,6-tetramethyl-4-amino-piperidine, 2,2,6,6-tetramethyl-4hydroxy-piperidine 2-hydroxy or 2,4-Dihydroxibenzophenone

- Heat stabilizer components, such as. B. bis-trialkyltin oxides.

These reactions of the aerosils of formula ΙΠ to other additives are carried out under the usual conditions in organic chemistry for the reaction types in question; so z. B. Reactions of OH or NH₂Group containing Aerosil derivatives with COCl-containing additive components according to Schotten Baumann in the presence of bases as acid scavenger. Since these are always heterogeneous reactions, good mixing by stirring or rolling is required.

A particular advantage of the method according to the invention is the simple isolation and purification of

Products, because all-natural catalysts and by-products can be separated by simple Waschvorgäage.

-5AT 394 371 B

Example 1;

Silylation of Aerosil 200 with dichloromethylsilane

100 g Aerosil 200 (Fa. Degussa) are degassed in a high vacuum at 100 ° C. for 8 hours. This degassed gel is suspended in 2250 ml of absolute dioxane and 17 g of dimethylaniline are added dropwise 7 g of dichloromethylsilane are added dropwise over one hour and the reaction mixture is then stirred for a further 2 hours at room temperature. washed salt-free with methanol and dried under high vacuum at 110 ° for 3 hours. Yield: 82 g of dry Aerosil. Silane H determination for this product was 0.49 meq Si-H / g Aerosil.

An addition of 10% of this saturated aerosol to a commercially available addition-crosslinking silicone rubber mixture (eg vinyl-Si component Silgel 604 A and H-Si component Silgel 604 B from Wacker) and subsequent vulcanization at 70 ° C. results in a silicone rubber with 10-15% higher tear strength and elongation at break than the same mixture with unmodified Aerosil.

Example 2:

Addition of techn. Divinylbenzene to H-Si-Aerosil

In a 1 liter one-necked flask, 50 g of H-Si-Aerosil prepared according to Ex. 1 are mixed with 750 ml of absolute dioxane. With stirring, 150 ml of technical divinylbenzene previously distilled in vacuo over calcium chloride and 7.5 g of hydroquinone are added. The reaction mixture is heated under reflux and after one hour 0.5 ml of a 0.25 molar isopropanol solution of PtClg.ö ^ O added as a catalyst, the reaction mixture is heated under reflux for a further 18 hours then the solvent is distilled off in vacuo and the product a large Büchner funnel twice with benzene and washed three times with methanol. It is first dried at 60 ° C, last solvent residues are removed under high vacuum at 80 ° C.

Yield: 46 g of 4-vinylphenyl-modified Aerosil (DVB-Aerosil)

Assignment: 0.22 meq CC double bonds / g

Example 3:

Addition of pure p-divinylbenzene to H-Si-Aerosil

In a 500 ml one-necked flask, 12 g of H-Si-Aerosil prepared according to Ex 1 are mixed with 200 ml of absolute dioxane. With stirring, 12 g of pure 1,4-di vinylbenzene and 3 g of hydroquinone are added. The reaction mixture is refluxed, and after one hour, added to it is 02 ml of a 0.25 molar isopropanol solution of ^ PtClg.o ^ O as a catalyst. The reaction mixture is heated under reflux for a further 18 hours, then the solvent is distilled off in vacuo and the product is washed twice on a large Buchner funnel with benzene and three times with methanol. It is dried at 60 ° C, last solvent residues are removed at 80 ° C under high vacuum

Yield: 11.5 g of 4-vinylphenyl-modified Aerosil

Occupancy: 0.44 meq CC double bonds / g

Example 4:

Additions of ethylene glycol diacrylate to H-Si-Aerosil

In a 500 ml flask, 20 g of silylated Aerosil, prepared according to Example 1, mixed with 300 ml of absolute dioxane and added with stirring, 30 g of ethylene glycol diacrylate and 3 g of hydroquinone. The reaction mixture is heated to reflux and 0.5 ml of a 025 molar isopropanol solution of ^ PtClg.ö ^ O added as a catalyst. After refluxing for about 20 hours, the solvent is distilled off in vacuo and the product is filtered off, washed twice with benzene and three times with methanol and dried at 70 ° C in a vacuum.

Yield: 18 g of acryloyloxyethyl-modified Aerosil

Occupancy: 0.40 meq CC double bonds / g

Example 5:

Addition of acetylene to H-Si-Aerosil

In a 500 ml flask 10 g sily lated Aerosil prepared according to Example 1, mixed with 200 ml of absolute THF, 0.5 ml of a 025 molar solution of ^ PtCl ^ .ö ^ O added in isopropanol and stirring

Refluxing for 3 hours acetylene introduced. The product is filtered off, washed with benzene and methanol and dried at 60 ° C in a vacuum

-6AT394 371B

Yield: 9.5 g of vinyl-modified Aerosil

Assignment: 0.38 meq CC double bonds / g

Example 6:

Addition of allyl alcohol to H-Si-Aerosil

In a 500 ml flask, 12 g of H-Si-Aerosil, prepared according to Example 1, mixed with 200 ml of absolute dioxane, added 20 ml of allyl alcohol and stirred under reflux for 1S Then 0.5 ml of a 0.25 molar solution of H₂PtClg.H₂O in isopropanol and stirred for a further 16 hours under reflux. The product is filtered off, washed with benzene and methanol and dried in vacuo at 80 ° C.

Yield: 10 g of Aerosil containing OH groups

Occupancy: 2.8%

Example 7:

Addition of N-trimethylsilyl-AUylamine to Silylated Aerosil

In a flamed 250 ml two-necked flask with reflux condenser, drying tube and septum 20 g of H-Si-Aerosil, prepared according to Ex 1, in 100 ml of abs. Dioxane suspended with exclusion of water and injected through the septum 10 g (10-fold excess) N-TMS-allylamine After 0.5 hours of refluxing, 3 ml of 0.1 molar catalyst solutions are injected through the septum and refluxed for a further 24 hours.

To split off the TAS protective group, the solvent is filtered off with suction through a reverse frit and the Aerosil is boiled with 100 ml of methanol for 1 hour. The methanol is filtered off with suction through a glass frit and the product is washed twice with acetone. After drying in a drying oven, the last solvent residues are removed under high vacuum at 90 ° C./0.005 mbar. An ignition loss at 800 ° C was found to be 2.2% (theoretical 2.33%)

The determination of the amino group content in the gel is carried out by a titration with perchloric acid in glacial acetic acid.

Yield: 18 g, 0.37 mill. NH₂/ g (90% relative to the H-Si occupancy)

Example 8:

Addition of Allylurea to H-Si-Aerosil

In a 500 ml one-necked flask 25 g of H-Si-Aerosil, prepared according to Ex. 1, with 200 ml of absolute dioxane and 10 g of allyl urea. The reaction mixture is stirred with a magnetic stirrer and heated to reflux with the exclusion of water. After 1 hour, 0.5 ml of a 0.25 molar isopropanol solution of platinum chloroauric acid are added as a catalyst. The reaction mixture is allowed to reflux for a further 24 hours. The still hot solvent is filtered off with suction in a warmed glass sintered frit and washed twice with methanol and twice with acetone. It was first dried at 50 ° C in a drying oven and then removed last solvent residues on the high vacuum pump. The loss on ignition at 800 ° C is 4.02% (theoretically 4.1%).

This product can be incorporated as a reactive filler in commercial urea or melamine resin molding compounds. Hardened specimens of such, with CONH₂Aerosil-filled molding compounds have better elastic properties than non-modified Aerosil-filled resins.

Example 9:

Addition of AHylglycidylether to H-Si-Aerosil

The procedure of Example 6 is repeated, with the difference that 12 g of H-Si-Aerosil are reacted with 20 ml of allyl glycidyl ether.

Yield: 12.5 g of epoxy group-containing Aerosil

Occupancy: 33%

Bgigpigl IQ;

Addition of AUylisocyanate to H-Si-Aerosil

The procedure of Example 6 is repeated, with the difference that 5 g of H-Si-Aerosil are reacted with 7 g of allyl isocyanate.

Yield: 4.5 g of isocyanate-modified Aerosil

Occupancy: 2.3%

-AT 394 371 Β

Example 11:

Addition of acrylic acid to H-Si-Aerosil

The procedure of Example 6 is repeated, with the difference that 20 g of H-Si-Aerosil and 15 ml of acrylic acid are used.

Yield: 18 g of carboxyl groups modified Aerosil

Occupancy: 1.9%

Example 12:

Copolymerization of styrene with DVB Aerosil

In a 250 ml three-necked flask equipped with Anschützaufsatz, 2 dropping funnels, a reflux condenser and an inlet tube, 4 g of DVB Aerosil, prepared according to Ex 2, suspended in 50 ml of absolute benzene. One dropping funnel is charged with 20 ml of pure styrene, the second with a solution of 1.5 g of AiBN in 50 ml of absolute benzene. Then the whole apparatus is purged with dry nitrogen and the reaction mixture heated to 60 °. Both initiator solution and styrene are added in 8 portions by the hour. The total reaction time was 24 hours at 60 °. After the reaction, the solvent is distilled off and the residue is extracted in the Soxhlet for 48 hours with benzene. The Aerosil is then dried at 110 ° for 3 hours under high vacuum.

The yield is 3.9 g and the loss on ignition showed a polymer coverage of 16%.

Example 13:

Copolymerization of acrylonitrile on DVB Aerosil

For the polymerization, dried and freshly distilled acrylonitrile was used.

In a 250 ml three-necked flask equipped with Anschützaufsatz, 2 dropping funnels, a reflux condenser and an inlet tube, 6 g DVB Aerosil, prepared according to Ex. 2, suspended in 70 ml of absolute dimethylformamide. One dropping funnel is filled with 30 ml of acrylonitrile, the second with a solution of 1.5 g of AiBN in 50 ml of DMF. Then the whole apparatus is purged with dry nitrogen and the reaction mixture heated to 60 °. Both initiator solution and acrylonitrile are added in 8 portions by the hour.

The reaction mixture is centrifuged after cooling and the settled product portion is slurried several times in DMF and again centrifuged off. Finally, the pure product was dried under high vacuum at 110 ° for 3 hours.

3.5 g,

Polymer coverage: 11.2% (best by loss on ignition)

Example 14:

Copolymerization of acrylic acid ethyl ester on DVB Aerosil

The acrylic ester used was previously dried with calcium chloride and distilled.

In a 250 ml three-necked flask equipped with Anschützaufsatz, two dropping funnels, a reflux condenser and an inlet tube, 6 g of DVB Aerosil, prepared according to Ex. 3, suspended in 70 ml of absolute benzene. One dropping funnel is filled with 30 ml of pure ethyl acrylate, the second with a solution of 1.5 g of AiBN in 50 ml of absolute benzene. Then the whole apparatus is purged with dry nitrogen and the reaction mixture is heated to 60 °. Both initiator solution and acrylic ester are dissolved in 8 Portions added by the hour The total reaction time, during which the viscosity of the reaction mixture increased considerably, was 24 hours at 60 °. After the reaction, the solvent was distilled off, extracted with benzene in a Soxhletextraktor and dried under high vacuum for 3 hours The yield was 5.8 g, the loss on ignition showed a polymer occupancy of 20%.

Example 15:

Copolymerization of DVB-Aerosil with 3-nitrostyrene and reduction of the nitro groups g DVB-Aerosil, prepared according to Example 2, are initially charged in 100 ml of absolute benzene and heated to 60 ° C. under nitrogen. Then solutions of 10 g of nitrostyrene and 2 g of AiBN in 40 ml of benzene per hour are added in eight portions. The total reaction time was 24 hours. Thereafter, the gel was extracted with benzene in Soxhlet for 48 hours and dried

Loss on ignition: 11.4%

Yield: 9.5 g of NO₂Groups-preserving Aerosil copolymer content based on monomer use 13%.

-8AT394 371B

To reduce the nitro groups on the polymer-modified Aerosil to amino groups, 3 g of NO₂- Aerosil dispersed in 50 ml of pyridine and added to a saturated solution of 3 g of sodium dithionite in water. The reaction mixture is stirred at room temperature for 90 minutes and then evaporated in vacuo. The gel is washed with water and methanol and dried

NH₂Group occupancy (determined by diazotization) 0.45 meq / g

Yield: 2.5 g

Example 16:

Copolymerization of DVB Aerosil with 4-aminostyrene

7.2 g of DVB Aerosil (prepared according to Ex. 2) are initially charged in 70 ml of absolute toluene and heated to 60 ° C. under nitrogen. Then, solutions of Ί2 g of 4-aminostyrene and 1.5 g of AiBN in respectively 40 ml of toluene were introduced into eight portions added every hour. The total reaction time was 24 hours. Thereafter, the gel is extracted for 48 hours in Soxhlet with benzene and methanol and dried

Ignition loss: 5.5%

Yield: 7 g of polymer-modified Aerosil No. 9

Copolymer fraction based on monomer use 5.8%

Amino group occupancy (best, by diazotization): 0.20 meq / g

Example 17:

Copolymerization of DVB-Aerosil with benzylidene-4-methacryloyloxanine g DVB-Aerosil (prepared according to Ex. 2) are prepared in 100 ml of absolute benzene and heated to 60 ° C. under nitrogen. Then solutions of 10 g of monomer and 2 g of AiBN in 40 ml of benzene per hour are added in eight portions. The total reaction time at 60 ° C was 24 hours. Thereafter, the gel is extracted with benzene for 48 hours and dried.

Loss on ignition: 26%

Yield: 9.8 g of polymer-modified Aerosil

Copolymer content based on monomer use 35%

To release the amino groups, 5 g of gel are stirred for 30 minutes in 100 ml of 5N HCl, washed with water and methanol and dried

NH₂Group occupancy (determined by diazotization) 0.75 meq / g

Yield: 4 g of polymer modified Aerosil

Example 18:

Copolymerization of DVB-Aerosil with 4-aminophenylmethacrylamide g Aerosil 3 (prepared according to Ex. 3) are introduced into 100 ml of absolute methanol and heated to 60 ° C. under nitrogen. Then suspensions of 20 g of monomer and 4 g of AiBN in 50 ml of methanol in eight portions are added hourly. The total reaction time at 60 ° C was 24 hours. Thereafter, the gel was extracted with methanol for 48 hours and dried

Loss on ignition: 52%, NH₂Group occupancy: 2.8 meq / g

Yield: 20 g of polymer-modified Aerosil

CopolymeranteÜ based on monomer use 54%

Example 19:

Production of pigments based on Aerosil

a) by coupling of diazotized aerosils with dye components

General procedure for the diazotization of aromat. Amino groups on aerosils and coupling of

Diazonium salts g Aerosil with aromatic NH₂Groups (prepared according to Ex. 15-18) are suspended in 100 ml of 0, 1 N HCl and at 0-5 ° C as long as 0, in NaNO₂Added solutions until a KJ starch paper for minutes past the last

Addition indicated a small excess of nitrite. Thereafter, the reaction mixture 250 mg of the respective

-9AT 394 371 B

Coupling component was added and added dropwise at 5-10 ° C as long as 0, ln NaOH until a pH of 8 is reached After 15 minutes, the reaction mixture is acidified with HCl, the gel is filtered off, extracted with water and acetone and dried.

The amino-containing Aerosil prepared according to Example 18 gives the following products:

Coupling component Hue of the pigment Yield Loss on ignition (g) (%)

Naphthol reddish brown 2.8 66

Resorcin orange 2.5 58 p-cresol greenish-yellow 3.0 53

b) by reaction of NH₂Groups containing aerosils with COCl-containing dye components

General procedure:

g of the respective COOH-containing dye components are heated in 120 ml of thionyl chloride for 2 hours under reflux. Then, the excess thionyl chloride is distilled off completely in vacuo and the residue taken up in 200 ml of absolute benzene. After addition of 10 ml of absolute pyridine and 1.5 g of the respective NH₂Groups modified Aerosils, the reaction mixture is heated under reflux for 2 hours. Thereafter, the pigment is filtered off, extracted with benzene and methanol until the extractor effluent is colorless, and dried.

<td>NH₂-Aerosil Ex. No. 2</td><td>dye</td><td>hue</td><td>yield G</td><td>loss on ignition %</td>

<td>17</td><td>4 - [(2,5-dichloro- phenyl) azo] -3- hydroxy-2-naphthalene carboxylic acid</td><td>yellow</td><td>22</td><td>38</td>

<td>18</td><td>5-methoxy-3 [(l- [4- nitrophenyljamino carbonyl) -2-oxopropyl azojbenzolsäure</td><td>maroon</td><td>2.3</td><td>65</td>

Example 20:

Preparation of aerosol-based light stabilizers

a) by coupling of diazotized aerosils with light stabilizer components

The procedure of Example 19a is repeated, with the difference that coupling-capable light stabilizers are used as coupling components, e.g. B.

<td>NH₂-Aerosil</td><td>Lichtschutzmittel- component</td><td>yield G</td><td>loss on ignition %</td>

<td>17</td><td>2,2'-dihydroxy-4' methoxy-benzophenone</td><td>2.0</td><td>35</td>

<td>18</td><td>2- (2-hydroxy) -2H-</td><td>2.2</td><td>63</td>

4-methoxy-benzotriazol

-10AT 394 371B

b) by reaction of NH₂Group containing aerosils with COOH or COCl groups containing sunscreen components.

The procedure of Example 19b is repeated, except that light stabilizer components containing COOH groups are used, e.g. B.

<td>NH₂-Aerosil</td><td>Lichtschutzmittel- component</td><td>yield G</td><td>loss on ignition %</td>

<td>18</td><td>2-hydroxy-4-methyl-2'- carboxybenzophenone</td><td>2.2</td><td>69</td>

<td>18</td><td>2-cyano-3-phenylcinnamate</td><td>2.1</td><td>59</td>

c) by reaction of COOH-containing aerosils with OH or NH₂Group containing light stabilizer components

General share rule:

g COOH-containing Aerosil (prepared, for example, according to Example 11) are suspended in a mixture of 30 ml of abs. Benzene and 30 ml of thionyl chloride are refluxed for 2 hours with stirring. The Aerosil is filtered off, washed with abs. Benzene washed and 20 ml abs. Pyridine suspended. Then the OH or NH₂Group-containing component was added and stirred for 3 hours under reflux. The modified Aerosil is filtered off, extracted several times with benzene and methanol and dried in vacuo

<td>COOH Aerosil</td><td>Lichtschutzmittel-</td><td>yield</td><td>loss on ignition</td>

<td>Ex.</td><td>component</td><td>G</td><td>%</td>

<td>11</td><td>2,2,6,6-tetramethyl-4- aminopiperidine</td><td>2.1</td><td>8th</td>

<td>11</td><td>2 ^ '- dihydroxy-4'-methyl</td><td>2.0</td><td>6</td>

benzophenone

Example 21:

Preparation of Aerosil Based Antioxidants

a) by coupling diazotized aerosils with antioxidant components.

The procedure of Example 19a is repeated, except that coupling antioxidant components are employed, e.g. B.

<td>NH₂-Aerosil</td><td>Antioxidantien- component</td><td>yield G</td><td>loss on ignition %</td>

<td>18</td><td>2,6-di-tert-butylphenol</td><td>2.1</td><td>61</td>

<td>18</td><td>4-Anilinoanilin</td><td>2.1</td><td>63</td>

b) by reaction of NH₂Groups containing aerosils containing COOH or COCl groups

Antioxidants components

The procedure of Example 19b is repeated, with the difference that containing COOH groups

Antioxidants components are used.

-11AT 394 371 B

<td>NH₂-Aerosil</td><td>Antioxidantien- component</td><td>yield G</td><td>loss on ignition %</td>

<td>17</td><td>3- (3,5-di-tert-butyl-4-hydro- xy-phenyl) propionic acid</td><td>2.0</td><td>33</td>

<td>18</td><td>1- (4-hydroxy-3,5-di-tert-butylamino) -3,5-dichlorotriazine</td><td>22</td><td>68</td>

<td colspan="2">Example 22: Preparation of Aerosil based flame retardants</td><td></td><td></td>

a) by addition of CC double bonds containing flame retardant components to H-Si-Aerosil 2 g H-Si-Aerosil, prepared according to Ex. 1, calf in 30 ml abs. Toluene with 1 g of flame retardant component and

0.1 ml H₂PtClg-6-H₂Refluxed for 5 hours Then the solvent is distilled off and the product is washed with toluene and methanol and dried in vacuo.

<td>H-Si Aerosil</td><td>Flame retardant component</td><td>yield</td><td>loss on ignition</td>

<td>Ex.</td><td></td><td>G</td><td>%</td>

<td>1</td><td>pentabromophenyl</td><td>2.4</td><td>15</td>

<td>1</td><td>2,2-bis (4-allyloxy-3,5-di- -bromophenyl) propane</td><td>2.3</td><td>13</td>

b) by reaction of NH₂Group containing aerosils with COOH or COCl-containing flame retardant components

The procedure of Example 19b is repeated, with the difference that COOH-containing flame retardant components are used, for. B.

<td>NHn-Aerosil Ex.</td><td>Flame retardant component</td><td>yield G</td><td>loss on ignition %</td>

<td>17</td><td>4-carboxyanilino-bis- (di- methyl-amino) phosphoric acid triamide</td><td>22</td><td>39</td>

<td>17</td><td>4-carboxyanilino-bis-allyl amino triamide</td><td>2.3</td><td>42</td>

<td>17</td><td>Hexachlorendomethylentetra- hydrophthalic</td><td>2.5</td><td>48</td>

-12AT 394 371Β