CH616429A5 - Process for the preparation of new organotitanate chelates and their use - Google Patents

Abstract

The new chelates correspond to the formula: <IMAGE> in which the R symbols represent hydrogen or C1-C6 alkyls, B represents an alkene (R)2C &ldurule& or the carbonyl group, A represents nonhydrolysable monovalent organic groups and n = 1 or 2. They are prepared by reaction of a tetra(lower alkyl)titanate with a compound <IMAGE> and 2 moles of a compound A-H. They can be used for facilitating the incorporation of particulate or fibrous inorganic materials in polymers, by mixing them, at temperatures below their decomposition temperature, with the said materials.

Description

The present invention relates to a process for the preparation of new chelates of organic titanates which are particularly useful for treating fine inorganic materials. The treated fillers, in turn, are useful for expanding or extending the polymers.

Inorganic materials have long been used as fillers, pigments, reinforcing fillers and chemical reagents in polymers. They are essentially hydrophilic, that is, they are easily wetted by water and can absorb water. However, their compatibility

and two moles of one or more compounds of formula A-H.

Preferably, the R's are hydrogen, but they can also be methyl, ethyl, or other short-chain alkyl groups. The Rs do not necessarily have to be identical in a particular molecule or in each methylene unit.

The non-hydrolyzable monovalent group (A) can be an acyl, an aryloxy, a thioaryloxy, a sulfonyl, a sulfinyl, a pyrophosphate diester and a phosphate diester. The aryloxy group may be a substituted or unsubstituted phenoxy or naphthyloxy group containing up to 60 carbon atoms. It can be substituted by an alkyl, alkenyl, aryl,

aralkyl, alkaryl, halogen, amino, epoxy, ether, thioether, ester, cyano, carbonyl or aromatic nitro. Preferably, there are no more than three substituents per aromatic ring. The thioaryloxy groups are substantially the same as the above aryloxy groups, except that the phenolic oxygen is replaced by sulfur. Among the aryloxy and thioaryloxy groups, phenoxy or naphthoxy are preferred. The term non-hydrolyzable indicates a group which will not split in a neutral aqueous solution at a temperature below 100 ° C. Hydrolysis can be determined by analysis of the acids or alcohols released.

Acyl, sulfonyl, sulfinyl, diester pyrophosphate and diester phosphate as binding agents, respectively, are represented by the following formulas:

OCOR ', -OSO2R ", -OSOR",

(R "0) 2P (0) 0P (0H) (0> - and (R" 0) P (0) 0-

where R "can be identical to R 'as defined below.

When A is a sulfonyl or sulfinyl group, it is preferable that R "is phenyl, substituted phenyl or an aralkyl group having from 5 to 24 carbon atoms in the alkyl chain. When A is a phosphate group, it is preferable that the group R "has from 6 to 24 carbon atoms, and when A is a pyrophosphate group, it is preferable that the group R" is an alkyl having up to 12 carbon atoms.

In the acyl binding agent (OCOR '), R' can be hydrogen or a monovalent organic group having from 1 to about 100 carbon atoms; in particular, an alkyl, alkenyl, aryl, aralkyl or alkaryl group. The aryl groups can be substituted or unsubstituted phenyl or naphthyl groups, preferably containing up to 60 carbon atoms. In addition, the group R 'can be substituted by halo, amino, epoxy, ether, thioether, ester, cyano, carboxyl and / or aromatic nitro substituents. H can generally have up to six substituents per group R '. The group R 'can contain intermediate heteroatoms such as sulfur or nitrogen in the main or pendant substituents. R 'is preferably a long chain group having 18 carbon atoms. It is better that all R 'are identical.

Examples of specific R binders are: methyl, propyl, cyclopropyl, cyclohexyl, tetra-ethyloctadecyl, 2,4-dichlorobenzyl, l- (3-bromo-4-nitro-7-acetylnaphthyl) -ethyl , 2-cyano-furyl, 3-thiomethyl-2-ethoxy-1-propyl and methallyl.

Examples of suitable binders A include ll-thiopropyl-12-phenyloctadecyl-sulfonyl, 2-nitro-phenylsulfinyl, di (2-omega-chororooctyl) -phenyl phosphate, diisonicotinyl pyrophosphato, 2-nitro-3-iodo -4-fluorothiophenoxy, 2-methalylyphenoxy, phenylsulfinyl, 4-amino-2-bromo-7-naphthylsulfonyl, diphenyl pyrophosphato, diethylhexyl pyrophosphato, di-sec-hexyl-phenyl phosphate, dilauryl phosphate, methylsulfonyl, laurylsul-fonyl and 3-methoxynaphthalene sulfinyl. Examples of aryloxy groups include 2,4-dinitro-6-octyl-7- (2-bromo-3-ethoxyphenyl) -l-naphthoyl and 3-cyano-4-methoxy-6-benzoyl-phenoxy.

There are many examples of groups R '. They include straight chain, branched chain and cyclic alkyl groups such as hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, nonadecyl, eicosyle, docosyle, tetracosyl, cyclohexyle, cycloheptyle, and cyclooctyle. Alkenyl groups include hexenyl, octenyl and dodecenyl.

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Halo-substituted groups include bromohexyl, chlorooctadecyl, iodotetradecyl, and chlorooctahexenyl. One or more halogen atoms can be present, for example in difluorhexyl or tetrabromo-octyl. Ester-substituted aryl and alkyl groups include 4-carboxyethylcapryle and 3-carboxymethylto-luyle. Amino-substituted groups include aminoca-proyl, aminostearyl, aminohexyl, aminolauryl and diaminooctyl.

In addition to the above aliphatic groups, groups containing heteroatoms, such as oxygen, sulfur or nitrogen, can also be used in the chain. Examples of these radicals are ethers of the alkoxyalkyl type, comprising methoxyhexyl and ethoxydecyl. The alkyl-thioalkyl groups include methylthiododecyl groups. Primary, secondary and tertiary amines can also serve as terminal parts of the hydrophobic group. They include diisopropylamino, methylaminohexyl and aminodecyl radicals.

Aryl groups include phenyl and naphthyl and substituted derivatives. Substituted alkyl derivatives include toluyl, xylyl, pseudo-cumyl, mesityl, isodurenyl, durenyl, pen-tamethylphenyl, ethylphenyl, n-propyl-phenyl, cumyl, 1,3, 5-triethylphenyl, styryl, allyl-phenyl, diphenylmethyl, triphenylmethyl, tetraphenylmethyl, 1,3,5-triphenylphenyl. Nitro- and halo-substituted can be represented by chloromitrophenyl, chlorodinitrophenyl, dinitro-toluyl, and trinitroxylyl.

Amino-substituted components include methylaminotoluyl, trimethylaminophenyl, diethylamino-phenyl, aminomethylphenyl, diaminophenyl, ethoxyaminophenyl, chloroaminophenyl, bromo-aminophenyl and phenylaminophenyl. Halo-substituted aryl groups include fluoro-, chloro-, bromo-, iodophenyl, chlorotoluyl, bromo-toluyl, methoxybromophenyl, dimethylaminobromophenyl, trichlorophenyl, bromochlorophenyl and bromoiodophenyl.

Groups derived from aromatic carboxylic acids are also useful. They include methylcarboxylphenyl, dimethylaminocarboxyltoluyle, lauryl-carboxyltoluyle, nitrocarboxyltoluyle, andamino-carboxylphenyl. Groups derived from substituted alkyl esters and benzoic acid amides can also be used. They include amino-carboxylphenyl and methoxycarboxylphenyl.

Titanates in which R 'is an epoxy group include tali oil epoxides (a mixture of alkyl groups having 6 to 22 carbon atoms) containing on average one epoxy group per molecule and glycidol ethers of lauryl or stearyl alcohol.

Substituted naphthyl groups include nitro-naphthyl, chloronaphthyl, aminonaphthyl and carboxynaphthyl.

Examples of compounds which can be prepared according to the present invention include the following:

0CH2C (0) 0Tï (0S0C6H4NH2) 2;

0CH2C (0) 0Ti (0SO2-C6H4Ci2;

H25) (OSO2C6H4NH2);

0CH2C (0) 0Ti [0P (0) (0CsHi7) 2] 2;

OCH2C (0) OTi (OC6H4C (CH3) 2C6Hs) 2;

0CH2C (0) 0Ti [0P (0) (0Ci2H25) 2] 2;

OCH2C (O) OTï (OCOC70Hi4i) 2;

0CH2C (0) 0Ti (0CeH4NH2) 2;

0CH2C (0) 0Ti [0C0 (CH2) 6- (0S02) CH3] 2;

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0CH2C (0) 0Ti (0C0C6H4Cl) [0P (0) (0H) 0P (0) (0CH3) 2];

0CH2C (0) 0Ti [0C6H2 (N02) 3] 2;

0CH2C (0) OTi (2-SCi oH7> 2;

0CH2C (0) 0Ti (0S02C6Hs) 2;

OC2H4C (O) OTi (OCOC70Hi4i) 2;

0C2H4C (0) 0Ti [0C0CH2N (C2H4 (0C2H4) i20CH2C6H4N02] 2;

0C2H4C (0) 0Ti (0C0C72Hi4i) 2 (0C0CH = CH2);

0C2H4C (0) 0Ti [0C0C (C22H43) 3] (0C0CH0C2Hs);

OC2H4C (O) OTÌ [OCOC6H4CH2OCH2C6H3 (C36H73) 2] (OCOC70Hl4l);

OC2H4C (O) OTi [OCOC (CH2Ci0H9) (C22H43) 2] [OCOCH (SC6Hn) 2];

0C2H4C (0) 0Ti [0C0C (CH3) = CH2) 2;

0C2H4C (0) 0Ti (0C0CH2NH2) 2;

0C2H4C (0) 0Ti (0C0CH20CH3) (0C0CHClCH3);

0C2H4C (0) 0Ti (0C0CCl3) 2;

0C2H4C (0) 0Ti (0C0CHBrCH2Cl) (0C0CâH5);

0C2H4C (0) 0Ti (0C0CH2CN [0C0CH2N (CH3) 2];

0C2H4C (0) 0Ti [0C0 (CH2) i4CH3) 2] [0C0C (CH3) = CH2];

0C2H4C (0) 0TÌ [0C0 - ^ - C02 (CH2) nCH3],

where no longer \ _ì

taller than 8 and smaller than 15

0CH2C (0) 0Ti [0P (0) (0C6H4C8Hi7) 2] 2;

0C2H4C (0) 0TÌ [0C0 (CH2) MCH (CH3) 2] 2;

0C2H4C (0) 0Ti [0C0 (CH2) i6CH3] 2;

0C2H4C (0) 0Ti [0C0- ^ ~ ^) - NH2] 2;

0C2H4C (0) 0Ti [0C0 (CH2) sNH2] 2; 0C2H4C (0) 0Ti [0C0CH2CH2NH2] 2;

O

/ \

0C2H4C (0) 0Ti [0C0 (CH2) PCH-CH (CH2) qCH3] 2,

where the sum of p + q is greater than 6 and less than 18.

0CH2CH20Tï [0P (0) (0C8Hi7) 2] 2;

0CH2CH (CH3) 0Ti [0P (0) (0Ci2H25) 2] 2;

0CH2C (C2Hs) 20Ti [0P (0) (0C6H4C8Hi7) 2] 2;

0C (CH3) 2C (0) 0Ti [0C6H2 (N02) 3] 2;

0C2H4C (0) 0Ti [0P (0) (0H) 0P (0) (0C8Hi7) 2] 2;

0C2H4C (0) 0Ti (0CeH4CH3) 2;

0C2H4C (0) 0Ti [0P (0) (0C6Hs) 2] 2;

OC2H4C (O) OTi (OSOCi0H7) 2;

0C2H4C (0) 0Ti (0S02C6H4Br) 2;

0C2H4C (0) 0Ti [OP (0) (C6H4NH2] 2; and

0C2H4C (0) 0Ti (0C6H4NH2) (0S02C6H5).

In an advantageous embodiment of the process, the esters having the formula (OR) 2Ti (A) 2 are reacted with an equimolar amount of 2-hydroxypropionic acid or of hydroxyacetic acid or their substituted carbon derivatives, or alternatively the chelate can first be formed and then the esterification step is carried out. In the case of oxo derivatives (B = R2C), the titanate ester can be reacted with a 1,2- or 1,3-glycol such as ethylene glycol or 1,3-butanediol.

The compounds (OR) 2 Ti (A) 2 can easily be prepared as indicated in the US patents. no. 3,660,134, 3,697,494 and 3,697,495 of the Freeport Sulfur Company.

The inorganic materials can be particulate or fibrous, and have various shapes or sizes, as long as the surfaces react with the hydrolyzable group of the organotitane compound. Examples of inorganic reinforcing materials include metals, clay, carbon black, calcium carbonate, barium sulfate, silica, mica, glass and asbestos. Reactive inorganic materials include metal oxides of zinc, magnesium, lead, and calcium and aluminum, iron filings and iron shavings, and sulfur. Examples of inorganic pigments include titanium dioxide, iron oxides, zinc chromate, overseas blue. From a practical point of view, the particle size of inorganic materials should not exceed 1 mm, and have preferably 0.1 a to 500 | x.

It is imperative that the alkoxy titanium salt is well mixed with the inorganic material to allow the surface of the latter to react sufficiently. The optimum amount of the alkoxy titanium salt to be used depends on the effect to be obtained, the available surface area and the water bound in the inorganic material.

The reaction is facilitated by mixing under suitable conditions. The best results depend on the properties of the alkoxy titanium salt, i.e. whether it is a liquid or a solid, and its decomposition and flash points. We can consider, among other things, the size of the particles, their shape, density, chemical composition. In addition, the treated inorganic material must be completely mixed with the polymer. The appropriate conditions for mixing depend on the type of polymer, whether it is thermoplastic or thermoset, sand, its chemical structure, and the like, as those skilled in the art will readily understand.

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When the inorganic material is pretreated with the organic titanate, it can be mixed in any practical type of intensive mixer, such as a Henschel or Hobart mixer or a Waring mixer. You can even use a mixture by hand. The best times and temperatures are determined to obtain a sensitive reaction between the inorganic material and the organic titanate. Mixing is accomplished under conditions in which the organic titanate is in the liquid phase, at temperatures below the decomposition temperature. While it is desirable for the bulk of the hydrolyzable groups to react in this step, this is not essential if the materials are then mixed with a polymer, since the end of the reaction can take place in this last mixing step.

Processing of the polymer, i.e., the high shear mixing, is generally accomplished at a temperature well above the second order transition temperature of the polymer, desirably at a temperature at which the polymer has a low melt viscosity. For example, a low density polyethylene is better treated at a temperature of the order of 170 to 230 ° C; high density polyethylene at a temperature of 200 to 245 ° C; polystyrene at a temperature of 230 to 260 ° C; and polypropylene at a temperature of 230 to 290 ° C. The mixing temperatures of other polymers are known to those skilled in the art, and can be determined by reference to the existing literature. A wide variety of mixing equipment can be used, for example two-cylinder mills, Banbury mixers, concentric double screws, double screws rotating against the current or in the same direction, and mixers of the ZSK type. Werner and Pfaulder, and Busse mixers.

When the organic titanate and the inorganic materials are dry mixed, complete mixing and / or a complete reaction is not easily obtained, and the reaction can be completed when the treated filler is mixed with the polymer. In this last step, the organic titanate can also react with the polymer if one or more of the groups R ′ reacts with the polymer.

The treated filler can be incorporated into any conventional polymer, whether it is thermoplastic or thermosetting, whether it be rubber or plastic. This is disclosed in detail in the above-mentioned Freeport Sulfur Co. patents. The amount of the filler depends on the particular polymer, the filler and the properties required of the finished product. In general, 10 to 500 parts of the filler can be used per 100 parts of the polymer, and preferably 20 to 250 parts. The optimal amount can easily be determined by those skilled in the art.

While the compounds which can be prepared according to the present invention can be used with each of the above-mentioned fillers, it is particularly surprising that they remain extremely active, even in the presence of large amounts of free water. For this reason, they can be used with wet treated silica, hard or soft clays, talc, aluminum silicate, hydrated alumina and fiberglass. Even if we do not fully understand why chelates retain their activity, they are clearly superior to other titanates, such as those described in the above-mentioned patents of Freeport Sulfur Co., in the presence of moisture.

The example which follows describes a typical mode of preparation according to the present invention.

Example A

Preparation of 2,2-dimethyl-3-oxy-3-phenyl-caproyl acetyl dodecylbenzenesulfonyl titanate

Is introduced into a 1 liter reactor with stirring, equipped with external heating and cooling means, and having possibilities of reflux, distillation and vacuum, a mole of tetraisopropyl titanate. The unit is refluxed at atmospheric pressure. Then, over about half an hour, one mole of dodecylbenzenesulfonic acid is added, then one mole of glacial acetic acid and one mole of 2,2-dimethyl-3-oxy-3-phenyl-caproic acid, in sequence, each time over a half hour period. During the addition of each reagent, a limited release of heat is observed. Once the additions are complete, the reaction mixture is refluxed for one hour at atmospheric pressure. It is then cooled to a temperature below 50 ° C, and the by-product isopropanol is removed by vacuum distillation at a deposition temperature of the order of 150 ° C to 10 mm Hg. The volatilized isopropanol is recovered by trapping it in a receiver cooled by liquid nitrogen. The recovery of isopropanol is of the order of 3.7 moles, that is to say 90% of theory. A small amount of isopropyl acetate is also recovered. As a residue, a white product which is more than 90% pasty compared with the theory is obtained. The purification is carried out by recrystallization in ligroin to form a white crystal (melting point 87-89 ° C).

Example B

Preparation of di (dioctyl-phosphato) ethylene titanate

A mole of tetraisopropyl titanate is introduced into a 1 liter reactor with stirring, equipped with external heating and cooling means, with reflux, distillation and vacuum possibilities. The unit is refluxed at atmospheric pressure. Next, one mole of ethylene glycol is added, followed by two moles of diocetyl hydrogen phosphate over a period of half an hour. A limited release of heat is observed during the addition of each reagent. After completing the additions, the reaction mixture is refluxed for one hour at atmospheric pressure. It is then cooled to a temperature below 50 ° C., and the by-product isopropanol is removed by vacuum distillation at a deposition temperature of the order of 150 ° C., at 10 mm Hg. The volatilized isopropanol and recovered by trapping it in a receiver cooled with liquid nitrogen. The recovery of isopropanol is of the order of 3.7 moles, that is to say 90% of theory. We obtain a white pasty product with more than 90% of theory, as a residue. The purification is carried out by crystallization in ligroine to form a white crystal (melting point 41-43 ° C).

Example C

Following the general procedure described above, additional compounds were prepared in the context of the present invention. The table below describes the particular compound, referring to the complexing binding agent and to the monovalent binders (A and A7), and indicates a physical description, the melting point and the viscosity of the product:

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Physical properties of selected titanium chelates General formula CTi, A, A 'where C is a bivalent complexing binding agent A and A' are monovalent binding agents.

Binding agent complexing Binding agent

A A '

1

Ethylenedioxy

Isostearate

Isostearate

2

Ethylenedioxy

Isostearate

Methacrylate

3

Ethylenedioxy

Methacrylate

Methacrylate

4

Ethylenedioxy

Acrylate

Acrylate

5

Ethylenedioxy

Dioctyl phosphate

Dioctyl phosphate

6

Ethylenedioxy

4-aminobenzenesulfonate

Dodecylbenzene-

sulfonate

7

Ethylenedioxy

Anthranilate

Anthranilate

8

Oxyacetate

Isostearate

Acrylate

9

Oxyacetate

Cumyl phenolate

Cumyl phenolate

10

Oxyacetate

2-formyl phenolate

Phenolate

2-formyl

11

Oxyacetate

Isostearate

Isostearate

12

Oxyacetate

4-aminobenzoate

Isostearate

Table (continued)

Aspect

Point of

Viscosity cps

physical fusion ° C

at 100 ° C

1

Red liquid

3-10

180

2

Solid beige

35-39

105

3

Solid beige

90-93

91

4

Solid beige

Decomposition

-

123-126

5

Amber liquid less than 0

286

6

Gray powder

Decomposition

about 200

7

Black powder

93-98

1250

8

Yellow wax

65-75

130

9

Red powder

83-86

330

10

Black liquid

(wax) 12—16

610

11

White wax

32-39

410

12

Red powder

69-72

320

To demonstrate the use of the compounds, the following examples will be described.

Example I

This example shows the importance of the chelated structure for controlling the viscosity of wet silica in organic dispersions. A dispersion was carried out by mixing 20 parts of wet silica obtained from 0.8 u in a solution of 0.2 part of titanate in 80 parts of heavy mineral oil (flash point of the order of 105 ° C ), in a Waring blender.

Titanate Viscosity of the mixture at 25.5 ° C

No

75,400

Isopropyltriisostearoyl titanate

21800

tri (dioctylphosphato)

23,500

tri isopropyl titanate (dodecylbenzenesulfonyl)

isopropyl titanate

19,800

2-oxyacetyl diisostearoyltitanate

11600

di (dioctylphosphato)

2-oxyacetyl titanate

8,000

di (dodecylbenzenesulfonyl)

2-oxyacetyl titanate

9,400

The first three titanates indicated in the table, while they show a significant reduction in viscosity compared to the control, are nevertheless significantly lower than the three oxyacetyl compounds at the end of the table. It is believed that this effect is achieved because the compounds obtained according to the present invention retain their activity in the presence of moisture present in the silica.

Example II

The effect of selected titanates, on the tensile strength of polypropylene loaded with talc and clay washed with water of 3 u, in systems employing 50% by weight of filler and 0.5% by weight of titanate is shown in the following table:

Titanate

Tensile strength

kg / cm2

Talc clay

No

239,295

Diisostearoyl titanate

2-oxyacetyl

257,309

di (dioctyl-phosphato) titanate

2-oxyacetyl

288,351

65

This example shows the increase in tensile strength in propylene loaded with talc and loaded with clay, with two of the compounds prepared according to the present invention.

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Example III

The effect of selected titanates on the impact resistance by drop of a weight of Nylon 6 loaded with 50% by weight of 3 \ i clay washed with water (Allied 8201) is shown. The charge is pretreated with 2% by weight of titanate before incorporation into the polymer matrix.

Titanate

Resistance to

Shock by

the flexion drops from a

kg / cm2Xl03

weight kgm

No

1.07

0.034

2-oxyacetyl4-aminobenzenesulfonyl

dodecylbenzene sulfonyl titanate

1.52

0.32

di (4-aminobenzoyl) titanate

2-oxyacetyl

1.84

0.18

2-oxyacetyl distearoyl titanate

1.14

0.59

In each case, the treated material has improved flexural strength, and a marked improvement in its impact strength.

Example IV

This example shows the effect of selected titanates on the properties of a polyurethane filled with silica treated by a wet process of 0.8 | x. The formula contains 20% by weight of filler, pretreated with 2.0% by weight of titanate before incorporation.

Titanate

Resistance to

Elongate

traction lies

kg / cm2

%

No

218

330

di (2-hydroxyacetyl) titanate

2-oxyacetyl

278

270

di (dioctyl-phosphato) titanate

2-oxyacetyl

246

390

dimethacryl titanate

2-oxyacetyl

242

300

2-oxyacetyl 4-aminobenzoyl

isostearoyl titanate

274

300

All of the treated compounds show improved tensile strength compared to the control. The phosphate derivative also shows increased elongation. The non-hydrolyzable group A structure has been shown to be important in determining improvements in properties.

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The chemical structure of the above compounds was mainly determined by considering the reagents involved and the by-products formed. In selected cases, elementary analysis, infrared ray analysis and free hydroxyl group analysis were performed. These analyzes verified the postulated chemical structures.

Example V

This example shows the effect of titanate chelates on an uncharged epoxy. Two epoxy hardener mixtures were prepared, containing 80 parts of Epon 828 (trademark) and 20 parts of an aliphatic amine hardener, the Celanese 874 hardener (trademark). To one of these freshly prepared samples, 2 parts of 2-oxyacetyl di (dodecylbenzenesulfonyl) titanate were added. The two mixtures were stirred for 2 minutes and their viscosity was measured on a Brookfield viscometer. The results obtained are shown in the table below.

Organo-titanium compound

Brookfield viscosity

X103cps

No

3.9

di (dodecylbenzenesulfonyl)

2-oxyacetyl titanate

9.4

The above data shows that the latter composition has a considerably higher viscosity than the other sample.

Example VI

This example shows the use of glycol di (dioctyl-phosphato) titanate to improve the coloring effect of pigments in a water-based acrylic paint. The paint used was a white SRW30X from Rowe Products Inc .; and the pigment was a dispersion of a paste (Daniel Products Co. Tint-Ayd No. WD-2228, aqueous dye, Phthalo Blue) containing 32% pigments and 39% solids in total. The glycol di (dioctyl-phosphato) titanate was first mixed with the pigment to form mixtures containing 0.3%, 0.6%, 0.9%, 1.2% and 1.5% of titanate as based on the weight of the dough in dispersion. 0.2 parts of each treated dispersion was added to 100 parts of paint. Observation shows, in comparison with the control, even at the 0.3% level, that there is an increase in dispersion and flow. While an increase in coloration occurred in each case, the improvement in blue coloration was optimal with the sample at 0.9%.

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B

Claims (3)

616429 2. Method according to claim 1, characterized in that A represents an acyloxy, aryloxy, arylthio, aryl- or aral-kyl-sulfonyloxy, aryl- or aralkyl-sulfinyloxy group or a group of formula (R10) 2P (0) 0P (0H) 0- or (R20) 2P (0) 0-, in which R1 and R2 represent hydrogen or a monovalent organic group, R1 preferably being an alkyl group having up to 12 carbon atoms and R2 being preferably a hydrocarbon group having 6 to 24 carbon atoms and the acyl, aryl, aralkyl, alkyl and hydrocarbon groups being unsubstituted or substituted. 3. Use of the new organic titanate chelates according to claim 1 for imparting to particulate or fibrous inorganic materials properties which facilitate their incorporation into polymers, characterized in that said chelates are intimately mixed, at temperatures below their decomposition temperature, to said inorganic materials, so as to allow the surface of the latter to react with the chelates. 45 with polymers is limited. As a result, little use is made of the potential enhancement, color or opacity, or chemical reactivity of organic matter. It has been proposed to use surfactants to facilitate the incorporation of these inorganic materials into polymers. However, known materials have presented numerous drawbacks, such as poor stability in the presence of free water, and a limited ability to completely disperse large quantities of fillers in the polymer. The prior art in this field is illustrated by US patents no. 3,660,134, 3,337,391, 2 CLAIMS 1. Process for the preparation of new chelates of organic titanates of formula: Ti (A) 2 10 in which the Rs are identical or different and represent hydrogen or alkyl groups having from 1 to 6 carbon atoms, n has the value 1 or 2, B represents an "alkylene group (R) aC R having the above meaning, or a carbonyl group and the A are the same or different and represent the non-hydrolysable monovalent organic groups, characterized in that one molar of a tetra titanate (lower alkyl), one mole of a compound of formula OH HO-B- and two moles of one or more compounds of formula A-H. 3 032 570, 3 617 333, 3 846 359, 3 697 474, 2 898 356, 2 809 162, 2 913 469 and 3 856 839 and by the publications listed in Chemical Abstracts 51, 12 961 h (1957), 53, 2094f (1959), 74, 42,016 t (1971) and 75, 129,861 j (1971). To overcome the above shortcomings, the applicant has discovered a new class of organic titanate compounds which allow the formation of a reinforced polymer having a low melt viscosity, improved physical properties, and better pigmentation characteristics than that which was presented according to the prior art. These compounds can be represented by the formula: TÏ (A) 2 in which the Rs are identical or different and represent hydrogen or alkyl groups having from 1 to 6 carbon atoms, n has the value 1 or 2, B represents an alkylene group (R) 2C R having the above meaning, or a carbonyl group and the A are the same or different and represent the non-hydrolysable monovalent organic groups. According to the invention, said compounds are prepared by a process characterized in that they are reacted with each other, in any order, ■ ■ one mole of a tetra titanate (lower alkyl), one mole of a compound of formula so HO-B- K / \ -OH V 7.