KR790001173B1 - Organic titanate salt composition - Google Patents

Abstract

Organo titanate coupling agents, which were dispersed in an organic polymerizable medium to give the reinforced polymer which has low melting viscosity, improved physical property, and better colour, was composed of the following three types. (I) (RO)z Ti(A)×(B)y;(II) (RO)Ti (OCOR') p (D)q; (III) (RO)Ti(OCORb)3. In above formulas R = e.g. monovalent alkyl, alkenyl, alkynyl; A = thioalkyloxy, sulfonyl, sulfinyl, diester phosphate; B = OCOR' or aryloxy; X+Y+Z+ = 4; p+q = 3, X, Y, q = 1, 2, 3 : and Y, P = 0, 1, 2.

Description

Compositions of Organic Titanium Salts

Inorganic materials have long been used in polymers as excipients, pigments, reinforcements and chemical reactants. In general, these inorganic materials are hydrophilic, that is, they can be easily wetted or absorbed by water, but there are limitations to their compatibility with organic polymers. Because of this limited compatibility, the overall location of the color, reinforcement, or chemical reactivity of the inorganic material is not recognized.

To overcome this difficulty, wetting agents have been used to minimize interfacial tension. But wetting agents also have serious drawbacks. In particular, a relatively large amount is required to properly wet finely divided inorganic substances.

When used in large quantities, the wetting agents significantly deviate from the nature of the finished composition. Coupling agents have been developed to overcome this difficulty. These are two mainstreams. The first is the more commonly used silanes with trialkoxyorgano groups. Their activity is based on the chemical interaction between the alkoxy group of the silane and the excipient and the chemical reactivity of the organic matrix with the polymer matrix. This gives a direct chemical association between the polymer and the excipient. These are typically highly flammable, unwieldy, and not readily available in many polymer systems. Where the polymer does not contain a functional group or the excipient does not contain an acidic proton, it is often ineffective because the silanes cannot interact with each other. For example, silanes are ineffective in excipients such as thermoplastic hydrocarbons and carbon blacks and mostly in calcium carbonate and sulfur.

The second group of coupling agents is free-titanate, which can be prepared by reacting tetraalkyl titanates with aliphatic or aromatic carboxylic acids. Of particular interest are the di- or trialkoxy alsyl titanates or some alkoxy triacyl titanates. However, these titanates have serious drawbacks. That is, they tend to decompose at temperatures commonly used to make many polymers; There is a tendency to decolorize some inorganic materials used with the polymer system; And it is incompatible with many polymer systems.

The present invention relates to three novel alkoxy titanium salts and their use. The first group is represented by the following general formula.

(RO) _Z Ti (A) _X (B) _y

In the common sense,

R is an alkynyl or aralkyl group having monovalent alkyl, alkenyl, C ₁ -C ₃₀ carbon atoms or a substituted derivative thereof. The R group is saturated or unsaturated, straight or branched, and may have 1-6 substituents including halogen, amino, epoxy, cyano, ether, thiether, carbonyl, aromatic nitro or acetal. In the specified molecule, all of R's may be the same or different so long as they belong to the above group. The R groups preferably have C ₁ to C ₆ alkyl and all are the same.

The monovalent group (A) may be thio aryloxy, sulfonyl, sulfinyl, diester pyrophosphate and diester phosphate. A thiaryloxy group is a thiophenoxy or thionaphthyloxy group containing up to about 60 carbon atoms, optionally substituted. It may be substituted by alkyl, alkenyl, aryl, aralkyl, alkaryl, halo, amino, epoxy, ether thiomers, esters, cyano, carbonyl or aromatic nitro groups. It is preferable that a substituent is three or less with respect to one aromatic ring. It is preferable that aryl is a thioaryloxy group which is phenyl or naphthyl.

Sulfonyl, sulfinyl, diesterpyro phosphate and diester phosphate ligands are represented by the following general formulas, respectively.

-OSO ₂ R ", -OSOR", (R "O) ₂ P (O) OP (OH) (O) and (R" O) P (O) O-

In the above formula, R "is the same as R 'defined below.

A is sulfonyl or sulfinyl group where in R "is preferably an aralkyl with phenyl, C ₅ ~ C ₂₄ to substituted phenyl, or an alkyl chain (chain). In the A phosphate group where R" is C ₆ ~ C ₂₄ may be of, in the a is payito phosphate group where, R "is preferably alkyl having up to C _12.

Monovalent group (B) may be acyl (OCOR ') or aryloxy (OAr) and R' may be a monovalent organic group having hydrogen or C ₁ -about C ₁₀₀ ; Especially alkyl, alkenyl, aryl, aralkyl or alkaryl groups. The aryl group is preferably a substituted or unsubstituted phenyl or naphthyl group containing up to C ₆₀ . R 'groups may also be substituted with halo, amino, epoxy, ether, thiether, ester, cyano, carboxyl and / or aromatic nitro substituents. In general, up to about C ₆ substituents may be present per R ′ group. The R 'group may contain an intermediate hetero atom such as sulfur or nitrogen in the main or further substituent.

R 'preferably has a long chain group having C ₁₈ . Most preferably R's are all the same. The sum of X, Y and Z in formula (I) must be 4; X and Z are 1,2 or 3; And Y is 0, 1, or 2. Most preferred are these compounds with Z = 1.

The second group of compounds belonging to the scope of the present invention is represented by the following general formula.

(II) (RO) Ti (OCOR ') _P (D) _q

In the above formula, R and R 'are as described above; p + q must be 3; p is 0,1 or 2; q is 1,2 or 3;

D is OCOR _a or OAr; R _a of the (OCOR _a ) group may be the same as defined above for R ′ provided that it is a long chain group containing at least C ₅₀ ; And OAR is as defined above. These organo-titanate compounds having one or more of these elongate carbon chains are particularly effective for coupling agents used in connection with low specific gravity polyethylene. These increase the rate of product as well as the density.

Among these compounds, the third group is represented by the following compounds.

(III) (RO) Ti (OCOR _b ) ₃

Again, R is as described above. The R _b group of (OCOR _b ) can be the same as the R 'defined above, but the total number of carbon atoms in only three R _b groups is 14 or less. It is preferred that all R _b groups are vinyl, methylvinyl or amino methyl.

A wide variety of ligands, subject to the limitations described so far, can be used to practice the present invention. The most suitable depends on the excipient-polymer system and much less on the preservation and / or additive system used.

Examples of special R ligands are as follows; Methyl, furophyll, cycloproprophyll, cyclohexyl, tetraethyl octadecyl, 2,4-diclobenzyl, 1- (3-bromo-4-nitro-7-acetylnaphthyl) -ethyl, 2-cyano -Furyl, 3-thiomethyl-2-ethoxy-1-furophyll and methylyl.

Examples of A ligands useful in the practice of the present invention are 11-thiofurophil-12-phenyloctadecyl-sulfonyl, 2-nitrophenylsulfinyl, di-2-omega-chlorooctyl-phenylphosphate, diisonicoti Nyl pyrophosphato, 2-nitro-3-iodo-4-fluorothiophenoxy, 2-metalylphenoxy, phenyl-sulfinyl, 4-amino-2-buromo-7-naphthylsulfonyl, Diphenyl pyrophosphate, diethylhexylpyrophosphato, di-sec-hexylphenylphosphato, dilaurylphosphato, methylsulfonyl, laurylsulfonyl and 3-methoxynaphthalene sulfinyl. Examples of B ligands include 3-cyano-4-methoxy-6-benzoylphenoxy and 2,4-dinitro-6-octyl-7 (2-bromo-3-ethoxyphenyl) -1-naphtolyl There is this.

Examples of R 'groups are myriad. These are straight chains such as hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, nonadecyl, eicosyl, docosyl, tetracosyl, cyclohexyl, cycloheptyl, and cyclooctyl, Chains with side chains and cyclic alkyl groups. Alkenyl groups include hexenyl, octenyl and dodecenyl.

Halo-substituted groups include bromohexyl, chlorooctadecyl, iodotedecyl, and chlorooctahexenyl. One or more halogen atoms may be present, for example as in difluorohexyl or tetrabromooctyl. Ester-substituted aryl and alkyl groups include 4-carboxyethylcapryl and 3-carboxymethyl toluyl. Amino-substituted groups include aminocaproyl, aminostearyl, aminohexyl, aminolauryl and diamino octyl.

For the above aliphatic groups, groups containing hetero-atoms such as oxygen, sulfur or nitrogen in the chain can be used. Examples of such groups are alkoxyalkyl type ethers including methoxy hexyl and ethoxy decyl. The alkyl thialkyl group is a methyl thiododecyl group. Primary, secondary and tertiary amines can act as the terminal portion of the hydrophobic group. These include diisofurophylamino, methylaminohexyl, and aminodecyl.

Aryl groups include derivatives substituted with phenyl and naphthyl groups. Substituted alkyl derivatives include toluyl, xylyl, pseudocumyl, mesityl, isdurenyl, durrenyl, pentamethylphenyl, ethylphenyl, n-furophylphenyl, cumyl, 1,3,5-tri Ethylphenyl, styryl, allyl-phenyl, diphenylmethyl, triphenylmethyl, tetraphenylmethyl, 1,3,5-triphenylphenyl. Nitro- and halo-substituted examples are chloro nitrophenyl, chloro dinitrophenyl, dinitrotoluol, and trinitroxylyl.

Amine-substituted components include methylamino toluyl, trimethylaminophenyl, diethylaminophenyl, aminomethylphenyl, diaminophenyl, ethoxyaminophenyl, chloroaminophenyl, bromoaminophenyl and phenylaminophenyl. Halo-substituted aryl groups include fluoro-, chloro-, bromo-, iodophenyl, chloro toluyl, bromotoluyl, methoxy-bromophenyl, dimethylaminobromophenyl, trichlorophenyl, bromochloro Phenyl, and bromoyodophenyl.

Groups derived from aromatic carboxylic acids are also useful. These include methyl carboxyphenyl, dimethylamino carboxy toluyl, lauryl carboxy toluyl, nitro carboxy toluyl, and amino carboxy toluyl. Groups derived from substituted alkyl esters and amides of benzoic acid can also be used. These include aminocarboxylphenyl and methoxycarboxylphenyl.

Titanates of R 'epoxide groups contain tall oil epoxides (mixtures of alkyl groups of C ₆ to C ₂₂ ) containing, on average, one epoxy group per molecule and containing glycidol ethers of lauryl or stearyl alcohol. have.

Substituted naphthyl groups include nitro naphthyl, chloro naphthyl, aminonaphthyl and carboxyl naphthyl groups.

As already noted, in the second group of compounds, R _a is the same as R 'except that it is a long chain group having up to C ₅₀ -C ₁₀₀ . Preferred examples of such groups include C ₇₀ H ₁₃₁ , OC ₆ H ₄ COC ₅₅ H ₁₁₁ , CH ₂ CH ₂ (OC ₂ H ₄ ) ₃₀ OCH ₃ , CH [N (C ₁₈ H ₃₇ ) ₃ ] ₂ , C [S (CH ₂ ) ₈ (CH = CH) ₃ C ₇ H ₁₅ ] ₃ , and (CH ₂ ) CH (OCHCHCH ₃ ) ₁₅ CHBrCHCI (CH ₂ ) ₃ CH ₃ .

R _b in the third group of this compound has up to C ₁₄ in total. For example, each R _b is isopurophenyl, vinyl-2-aminoethyl, 1-aminofurophyll, hydroxymethyl, 2,2-dichloroethyl, trimethoxymethyl, cyanomethyl and acetylmethyl. .

Examples of compounds of the present invention are as follows. (iC ₃ H ₇ O) Ti (OSOC ₆ H ₃ NH ₂ ) ₃ ; (iC ₃ H ₇ O) Ti (OSO ₂ -C ₆ H ₄ C ₁₂ H ₂₅ ) ₂ (OSO ₂ C ₆ H ₄ NH ₂ ); (iC ₃ H ₇ O) Ti [OP (O) (OC ₈ H ₁₇ ) ₂ ] ₃ ; (iC ₃ H ₇ O) Ti (OC ₆ H ₄ C (CH ₄ ) ₂ C ₆ H ₅ ) ₃ ; (iC ₃ H ₇ O) Ti [OP (O) (OC ₁₂ H ₂₅ )] ₃ ; (CnC ₁₂ H ₂₅ O) Ti (OSO ₂ C ₅ H ₅ ) ₂ ; (C ₆ H ₅ CH _{2 O} ) Ti (OC _n OH ₁₄₁ ) ₃ ; (iC ₃ H ₇ O) Ti (OCOC ₇₀ H ₁₄₁ ) ₃ ; (C ₆ H ₁₁ O) Ti (OC ₆ H ₄ NH ₂ ) ₃ ; (nC ₄ H ₉ ) ₂ Ti [OPO (OC ₆ H ₄ C ₈ H ₁₇ ) ₂ ] ₂ ; [C ₆ H ₅ O (CH ₂ ) ₃ ] Ti [OCO (CH ₂ ) ₆ (OSO ₂ ) CH ₃ ] ₂ ; [CH ₃ O (CH ₂ ) ₂ O] ₂ Ti (OCOC ₆ H ₄ Cl) [OP (O) (OH) OP (O) (OCH ₃ ) ₂ ]; (CH ₃ O) Ti (2-SC ₁₀ H ₇ ); (iC ₃ H ₇ O) Ti ₄ [OCOCH ₂ N (C ₂ H _4- (OC ₂ H ₄ ) ₁₂ OCH ₂ C ₆ HONO ₂ ] ₃ ; (CH ₃ O) Ti (OCOC ₇₂ H ₁₄₁ ) ₂ (OCOCH = CH ₂ ); (Cl (CH ₂ ) ₄ O) Ti [OCOC (C ₂₂ H ₄₃ ) ₃ ] ₂ (OCOCHOC ₂ H ₅ ); (nC ₁₆ H ₃₁ O) Ti [OCOC ₆ H ₄ CH ₂ OCH ₂ C ₆ H ₃ (C ₃₆ H ₇₃ ) ₂ ] ₂ (OCOC ₇ 0H ₁₃₁ ); and [CH ₃ O (CH ₂ CH ₂ O) ₁₂ ] Ti [OCOC (CH ₂ C ₁₀ H ₉ ) (C ₂₂ H ₄₃ ) ₂ ] ₂ {OCOCH (SC ₆ H ₁₁ ) ₂ ].

Examples of the third group of organic-titanates of the present invention are as follows. (IC ₃ H ₇ O) Ti [OCOC (CH ₃ ) = CH ₂ ) ₃ ; (iC ₃ H ₇ O) Ti (OCOCH ₂ NH ₂ ) ₃ ; (C ₆ H ₁₁ O) Ti (OCOCH ₂ OCH ₃ ) ₂ (COCOCHClCH ₃ ); (CH ₃ O) Ti (OCOCCl ₃ ) ₃ ; (C ₂ H ₅ O) Ti (OCOCHBrCH ₂ Cl) (OCOC ₆ H ₅ ) (OC.OCH ₃ NH ₂ ); and (iC ₃ H ₇ O) Ti (OCOC ₂ H ₅ ) (OCOCH ₂ CN) [OCOCH ₂ N (CH ₃ ) ₂ ]

Another composition according to the present invention consists in reacting the above-mentioned group of alkoxytitanium salts with an inorganic substance, in particular when X is three. The amount of titanate reacted is at least 0.01 parts, preferably 0.1-5 parts, most preferably 0.2 and 2 parts yarn per 100 parts of inorganic solids. The optimal amount required is a function of the inorganic solids, selected alkoxytitanium salts and the degree of grinding of the inorganic solids, ie the effective surface area. The reaction of titanate occurs at the surface of the inorganic excipient. The RO group comes off and an organic hydrophobic surface layer forms on the inorganic solid phase. Unmodified inorganic solids are difficult to disperse in organic media because of their hydrophilic surface. The organic-titanium compound can be introduced into the organic medium (low molecular weight liquid or high molecular weight polymerizable solid) together with the inorganic acid. Alternatively, the organic-titanate can be reacted with an inorganic solid in the first absence of organic medium and then mixed with the latter.

According to the present invention, dispersing an inorganic substance in an organic polymerizable medium comprises: (1) an individual fluidity or higher load of the dispersion in an organic medium; (2) a higher degree of reinforcement using excipients, thereby improving physical properties in the molded polymer; (3) more fully use of chemical reactivity, thereby reducing the amount of inorganic reactive solids required; (4) more effective use of pigments and bleaches; (5) higher inorganic-to-organic ratios in dispersion; And it is achieved by improving the shortening of the mixing time for dispersion.

In addition, according to the present invention, the reaction with a single RO group can be carried out appropriately or in an organic medium to form a solid dispersion, such as a liquid, solid or paste, which can be used to mix the final polymer system. This dispersion is very stable. That is, there is little tendency to harden and become non-dispersed upon deposition, separation or storage.

Furthermore, the present invention eliminates solvents, reduces the cost of the equipment for the process, and reduces the time and energy required to disperse the inorganic solids in the organic solids of liquids or polymers. It is simplified to achieve inorganic dispersion.

The present invention results in the formation of reinforced polymers with unfamiliar belt vascocity, improved physical properties, and better pigmentation than previously present materials.

The practice of the present invention consists of natural or synthetic polymers containing granular or fibrous inorganic materials that produce reinforcements, colorings and chemical reactions with polymers to produce products having excellent physical properties, better processing properties and efficient use of pigments. Prepare the product.

An advantage obtained by the specific practice of the present invention is that it is possible to select what is necessary for the practice of using volatile and flammable solvents and for drying the excipients or recovering the solvents. In addition, the generation of multi-molecular layers is minimized. In addition, the dispersion of the present invention is non-oxidative.

The inorganic material is granular or fibrous and can vary in shape and size as long as the surface can react with the hydrolyzable groups of the organic titanium compound. Examples of inorganic reinforcing agents are metals, clays, carbon black, calcium carbonate, barium sulfate, silica, mica, glass and asbestos. Reactive inorganic materials include zinc, magnesium, lead and calcium and aluminum, iron wire and turning and sulfur. Examples of inorganic pigments include titanium dioxide, iron oxide, zinc chromate, ultramarine blue. As a practical matter, the particle size of the inorganic material should not be larger than 1mm, and 0.1-500μ is preferred.

It is necessary to mix the alkoxy titanium salt with the inorganic material in order to sufficiently react the latter surface. The optimum amount of alkoxy titanium salt used depends on the resulting effect, such as the water used in the inorganic material and the surface area of use of the inorganic material.

The reaction is promoted by mixing at appropriate conditions. The optimal result depends on the nature of the material, whether it is a liquid or a solid, called the alkoxy titanium salt and its decomposition and flash point. Particle size, particle size, specific gravity, chemical composition, and relationship to others must be considered. In addition, the treated inorganic material must be thoroughly mixed with the polymer medium. Appropriate mixing conditions depend on the type of polymer and its chemical structure, whether the polymer is thermoplastic or thermoset, as is readily apparent in the four seasons.

The inorganic material is mixed with the organic titanate in a powerful mixer in a convenient form such as a Henschel or Hobart mixer or a waring mixer when preheated. You can also mix by hand. The optimum time and temperature determine the actual reaction between the inorganic material and the organic titanate to occur. The mixing is carried out at a temperature lower than the decomposition temperature when the organic titanate is in the liquid phase. While most hydrolyzable groups are preferred to react at this stage, this is not necessary for the material to be later mixed with the polymer because the reaction is actually complete in this latter stage.

Polymer processing, ie high shear mixing, is generally carried out above the secondary transition temperature of the polymer, with the temperature at which the polymer has a low melt viscosity. Low density polyethylene, for example, in the temperature range 170 ° -230 ° C., high density polyethylene 200 ° -245 ° C .; Polystyrene is 230 ° -260 ° C; Polypropylene is best processed at 230 ° -290 ° C. Mixing temperatures of other polymers are well known in the four seasons and are determined by reference to the literature. Various mixing equipments are used, for example a two-mill grinder, a Banburg mixer, a two-stage concentric screw, a biaxial screw that rotates in the opposite direction or in the same direction, and a Zsk type mixer of Werner, pfaulder and Busser.

Complete mixing and / or reactions are not readily accomplished when the organic titans and inorganic materials are dry-mixed and the reaction is substantially complete when the treated excipient is mixed with the polymer. In this latter step the organic titanate may also react with the polymeric material if one or more R 'groups are reactive with the polymer.

Treated excipients may be incorporated into conventional polymers and the polymers may be thermoplastic, thermoset, rubber or plastic.

The amount of excipient depends on the individual polymer, the excipient and the required properties of the resulting product. Widely used 10-500 parts excipient per 100 parts polymer and 20-250 parts are preferred. The optimum amount is easily determined by what is known on the watch.

In order to explain the present invention in detail, the following examples are presented. Some of these examples indicate the number of ligands per molecule for the mixed water. In that case the structural formula represents a mixture of compounds and the mixed number is the average number of such ligands in the mixture.

Examples A-C describe the preparation of compounds in the range of formula (I) above.

Example A Preparation of Isooctyl Dri (cumyl Phenoxy) Titanium

1 mole of isooctanol, 3 moles of cumylphenol mixed isomers and greter xylene mixed isomers are added to a pyrex-lined metal container equipped with a stirrer, internal heating and cooling system, steam condenser and effluent trap. After stirring the reactor and flowing nitrogen, 4.2 moles of soamide are added by adjusting the speed while cooling to keep the reaction mass not exceeding about 100 ° C. Ammonia is emitted as a byproduct. Sodamide treatment forms a heavy slurry that is refluxed for 10 minutes to remove dissolved ammonia. One mole of TiCl ₄ is then added over 3 hours while cooling the reactor contents to about 90 ° C. and maintaining this temperature. After adding TiCl ₄ , the resulting mixture was refluxed for 2 hours, cooled to about 100 ° C. and filtered. The filter cake is washed with about 500 ml of xylene and poured out. The wash is combined with the mother liquor and left to stand. When the volatiles are removed, 800 g of sediment having a boiling point of 150 ° C. or higher at 10 mmHg is produced (this is more than 95% of the theoretical yield). Elemental analysis of a dark red paste or a gloss solid, a gold product, is consistent with the formula (iC ₈ H ₁₇ O ₎ Ti [OC ₆ H ₅ C (CH ₃ ) ₂ C ₆ H ₅ ] ₃ .

Example B Preparation of (CH ₃ O) _0.6 Ti [OP (O) (OH) OP (O ((OC ₈ H ₁₇ ) ₂ ) _3.4

The reactor as described in Example A is charged with 1 mole of tetramethyl titanate. Then, with stirring, 3.4 moles of dioctyl pyrophosphoric acid are added over about 1 hour. Cooling is continued externally during addition to maintain the reaction mass at a temperature in the range of 20 ° -55 ° C. The resulting reaction mixture is distilled to a bottom temperature of 150 ° C. to remove substantially all methanol as a byproduct. Elemental analysis of residual yellowish oil

(CH ₃ O) _0.6 Ti [OP (O) (OH) OP (O) (OC ₈ H ₁₇ ) ₂ ] _3.4 . The yield is more than 95% of theory.

Example C Preparation of (O.ClC ₆ H ₄ CH ₂ O) _1.2 Ti (OSO ₂ C ₆ H ₄ NH ₂ ) _2.8

In a reactor as described in Example A, one mole of tetraisopropytitanate solution dissolved in 2 liters of 2,6-dimethylnaphthalene is heated at 200 ° C. While maintaining this temperature for 2.5 hours, 1.25 moles of ortho-chlorobenzyl alcohol and 2.8 moles of amino benzene sulfonic acid mixed isomer are added sequentially. The volatile byproducts (mainly methanol) are distilled off continuously. After cooling the resulting gray solid is filtered, washed with hexane with a cycle and dried in a vacuum oven to yield 565 kg of a gray solid product. (82% yield) This product has elemental analysis and sorrow consistent with the above formula.

The following two examples show the preparation of compounds falling within the above formula (II).

Example D Preparation of (iC ₃ H ₇ O) _0.8 Ti (OCOC ₆₉ H ₁₃₉ ) _3.2

One mole of tetraisopropyl titanate is added to a container as described in Example A. Synthetic saturated fatty acid (C ₆₉ H ₁₃₉ COOH) having an average molecular weight of 1002 is added at a controlled rate to maintain the reaction temperature below 180 ° C. until 3.2 moles are added. The resulting product is a pale brownish brown solid with a melting point of 69-72 ° C and decomposition at about 205 ° C. Elemental analysis is consistent with the above formula and results in 80% of (iC ₃ H ₇ O) Ti (OCOC ₆₉ H ₁₃₉ ) ₃ and 20% of Ti (OCOC ₆₉ H ₁₃₉ ) ₄ . The yield is almost quantitative.

Example E Preparation of (iC ₃ H ₇ O) Ti [OCOC (CH ₃ ) = CH ₂ ] [OCOC ₆ H ₁₂ N (C ₁₈ H ₃₇ ) ₃ ]

One mole of tetraisopropyl titanate is added to a vessel as described in Example A and stirring is started. While controlling the rate, 2 moles of liquefied 6-tristearyl amino caprylic acid are added over 1 hour and 1.4 moles of methacrylic acid are added for about 1.7 hours. The reaction temperature is maintained at about 115 ° C. Removal of the alcohol, dispersion, gives a dark product with a melting point of 121-126 ° C. Elemental analysis of this product is consistent with the above formula.

In order to explain the invention in more detail the following examples are given for the preparation of compounds which fall within the range of formula (III) above.

Example F Preparation of (iC ₃ H ₇ O) _0.7 Ti (OCOC (CH ₃ ) = CH ₂ ) _3.3

One mole of tetraisopropyl titanate is added to a vessel as described in Example A and stirring is started. To maintain the exothermic reaction below about 180 ° C., liquid methacrylic acid is added with controlled speed until 3.50 moles of acid are added. Isopropanol is removed from the reaction product by distillation at 50 mmHg to 150 ° C. to remove volatiles.

The organic titanate thus obtained has an average of 3.3 moles of methacrylate per molecule. The product structure is measured by identifying the free isopropanol and residual methacrylic acid in the reaction. About 0.2 mole of methacrylic acid and isopropyl methacrylate are detected. The physical properties of the product are as follows.

Specific gravity 0.92 at 24 ℃

Flash Point (COC), ° C 120

Pour point, ℃ 130

Decomposition temperature, ℃ 200 or more

Appearance Tan solid

The following examples illustrate the use of the alkoxy titanium salts of the present invention as coupling agents in inorganic excipient polymer systems. All parts are given in weight unless otherwise indicated.

Example 1

100 parts of chloro sulfo combusted polyethylene (trademark of Hypalon 40, EI du Pont de Nemours & Co., Inc.), 4 parts of magnesium oxide semal, 2 parts of low molecular weight polyethylene, 84 parts of calcium carbonate, aromatic oil ( kenplast RD, trademark of Kentrich Petrochemicals, Inc.) 30 parts, 3 parts pentaerythritol 200 and accelerator 2 part (Tetrone A) EI du Pont de Nemours & Co., Inc. trademark). Four formulations were tested.

The first one which was no longer contained except the above was used as a control standard. Formulations A, B and C were added with 1% of the following compounds of the invention relative to excipients.

(iC ₃ H ₇ O) _0.9 Ti (OSO ₂ C ₆ H ₄ C ₁₂ H ₂₅ ) _3.1 ; (iC ₃ H ₇ O) _0.6 Ti (OPO (iC ₈ H ₁₇ O) ₂ ] _3.4 ; and (iC ₃ H ₇ O) _1.1 Ti (OSO ₂ C ₆ H ₄ C ₁₂ H ₂₅ ) _1.7 (OSO ₂ C ₆ H ₄ NH ₂ ) _1.2

All formulations were stored at 152 ° C. for 30 minutes. Table A shows the properties of the four compounds that were originally tested and after oven treatment at 121 ° C. for 7 days.

TABLE A

The data clearly shows that the formulations of the invention have a lower modulus than the control.

In addition, the tear coefficient was markedly weighed for Formulation C.

Example 2

This example shows that (iC ₃ H ₇ O) _0.9 Ti (OSO ₂ C ₆ H ₅ C ₁₂ H ₂₅ ) _3.1 is used to improve the properties of polyvinyl chloride plastisols. 100 parts of PVC resin (Geon 121, a trademark of BF Goodrich Chemical Co.), 100 parts of dioctylphthalate, 3 parts of barium-cadnium stabilizer, and 10 parts of calcium carbonate were prepared as control. A second formulation was prepared using 10 parts of calcium carbonate containing 1% (based on calcium carbonate) of the above organic titanate compound in place of calcium carbonate unmodified. Table B shows the viscosity at the time periods described at 24 ° C. and the original properties of the molded samples obtained after two weeks of plastisol treatment at 24 ° C. The mold was performed at 171 ° C.

TABLE B

In the case of formulation D a low initial viscosity will be described. This is advantageous for suspensions of polyvinyl chromide (PVC) powder resins, where low viscosity reduces energy demand when mixing. In the preceding description, the reduced modulus and hardness of the product of formulation D is therefore important because it is necessary to use a significant amount of plasticizer to reach these properties. Moreover, it is impossible to reduce the hardness and modulus of elasticity while keeping the elongation constant.

Example 3

This example illustrates the use of a compound of the invention that mitigates the properties of soft polyvinyl chromide blends filled with calcium carbonate. Standard formulations were made to include the ratio of PVC resin 100, stabilizer 1 (DS207, NL Industries), dioctylphthalate 67, and a finely powdered calcium carbonate 50 having a normal molecular weight. In addition, five different formulations resulted in the same composition as the standard formulation. Each blend was relaxed by hot mixing at about 88 ° C. for 3 minutes in a suspension blender at a weight ratio of 0.5% based on calcium carbonate among the following compounds.

Formulation Number Organic Titanic Acid Ester Compound

E (iC ₃ H ₇ O) Ti (OSO ₂ C ₆ H ₄ C ₁₂ H ₂₅ ) ₃

F (iC ₃ H ₇ O) Ti [OCOCH (CH ₃ ) ₂ CH ₂ ) ₁₄ ] ₂

G (iC ₃ H ₇ O) _0.8 Ti (OCOC ₇₀ H ₁₄₁ ) _3.2

H (iC ₃ H ₇ O) _1.3 Ti (OCOC ₆ H ₄ NH ₂ ) _2.7

J (iC ₃ H ₇ O) _0.5 Ti [OP (O) (OC ₃ H ₁₇ ) ₂ ] _3.5

The following table shows the formulations detailing the nature of the standard formulation and the notification of the invention.

TABLE C

The above data clearly shows the advantages of the invention formulation. The blends E.F and J show reduced elastic modulus and increased elongation without decreasing tension. Formulation H shows increased elongation without loss of modulus or hardness.

This has a particularly beneficial effect.

Example 4

Four formulations were used to mitigate the properties of the styrene-vedadiene copolymer rubber filled with carbon black to demonstrate the utility of the invention. The first standard formulation is styrene-butadiene copolymer 100, HAF type carbon black 50, zinc oxide 4, sulfur 2, accelerator 1 (trade name of Monsanto, Santoker NS), stearic acid 1, aromatic free The ratio of the additive 10 and antioxidant 2 (neozone A, the brand name of EI DuPont Denemos company) was included. The second standard formulation is the same as the first standard formulation except that the carbon black (to the titanate bond) is retreated with 1% Ca (OCl) ₂ at 38 ° C. for 1 minute to improve sensitivity.

Compounds L and M are (iC ₃ H ₇ O) _0.8 Ti (OSO ₂ C ₆ H ₄ NH ₂ ) _3.2 and (iC ₃ H ₇ O) _1.0 Ti (OC ₆ H ₄ C (CH ₃ ) ₂ C ₆ H ₅ ) ₂ It was the same except including the part.

Table D shows the physical properties of the four formulations after 30 minutes storage at 166 ° C.

TABLE D

The advantages of the invention are indicated by the above data.

The formulation L described shows an increase in both elongation and tension. On the other hand, the formulation M shows a permanent state which is significantly reduced at increased elastic modulus and bursting moment.

The retention of skeletal safety upon rupture is a particularly useful property for such applications as a shock absorber.

Example 5

Herein is shown the compound of the invention which protects the polyethylene filled with minerals from attack by water-soluble acids. Two 1 "x 3" x 1/8 "inch test specimens of 50% by weight magnesium silicate-filled high density polyethylene (one sodium silicate used in the test sample for 1.5 minutes (CH ₃ O) _1.2 Ti in a powerful mixer) (OSO ₂ C ₆ H ₄ C ₁₂ H ₂₅ ) _2.8 1% by weight, in addition to pre-treatment at about 38 ° C, in the same form.

The resulting samples were added to each drop of 8% aqueous hydrochloric acid, covered with a Petri dish (thin glass plate without lid for bacterial culture), and held at 38 ° C. in an oven for 24 hours to evaluate the acid etching resistance. Significant investigations of older test specimens indicate that the untreated specimens had significantly more discolored surface than the treated specimens. Similar observations were made by replacing magnesium silicate with a portion like anhydrous calcium sulfate.

Example 6

This article describes the use of commercially available trialcooxyvinylsilane binders CH ₂ = CH Si (CCH ₂ CH ₂ CCH ₃ ) and compounds of the present invention in the addition of clay-filled peroxides. The comparison of mitigation is shown. The compound of the invention used is (iC ₃ H ₇ O) _0.7 Ti [OCOC (CH ₃ ) = CH ₂ ] _3.5 . Four formulations were made. Each of them has an EPDM (trade name Vistalon 2504 from Axon) 100, an antioxidant (trade name Azerite Resin D from RT Bandelbilt), a zinc oxide of 5, and an aliphatic additive of 20 (free) Oil company brand name, sunpal 2,280), and the ratio of the paste 5 which has a weight ratio of 5: 1 to red viscous oil, and the diker mill peroxide 6.

In addition to the above fact, component 1 included the ratio of hard clay 90 pretreated with 1% of the silanes mentioned above plus 2 modulus per silane. Component 2 comprises a ratio of 90 per weight of hard clay commercially available by silane pretreatment and a ratio of 2 per weight of the inventive compound. And component 3 includes the addition of two parts of titanate ratio to the hard clay pretreated at a ratio of 1% of the weight of the titanate leaf mentioned above. Component 4 was identical to component 3, except that only 10 weight ratios of additive oil jars 10 were used, which are inexpensive in aliphatic.

The aforementioned ingredients were stored at 171 ° C. for 20 minutes.

The following chart shows the results obtained.

TABLE E

The foregoing diagrams show the advantages of the present invention over the use of silane binders. Component numbers 2, 3, and 4 show that the elongation at break was increased and that components 2 and 3 became hardness during the elongation test. Component 4 also showed increased elastic modulus and tensile strength compared to silane component. Of particular note is the increased elongation of 38% at the time of destruction, despite the removal of 50% of the added oil plasticizers, which do not cost much aliphatic.

Example 7

This example shows that (iC ₃ H ₇ O) Ti (OCOC ₆₉ H ₁₃₉ ) ₂ [OCOC (CH ₃ ) = CH ₂ ] was used as a tensile strength modifier for low density polyethylene.

Formulation N was made by combining the following components with two rubber roll mills at room temperature.

100 g of polyethylene resin (Beaculite DYNH, trade name of Union Carbide), 300 g of titanium dioxide and 3 g of dicumyl oxide compound P was 0.6 g of (iC ₃ H ₇ O) _0.8 Ti at 60 ° C. before adding TiO ₂ to the mill. (OCOC ₆₉ H ₁₃₉ ) ₂ [OCOC (CH ₃ ) = CH ₂ ) _{1.2 The} same except that the pretreatment and heating were carried out for 5 minutes in a warping suspension mill. Samples of the formulations were then pressure cast for 20 minutes at a temperature of 177 ° C. for tensile strength testing.

The superiority of the formulation of the present invention was remarkable.

Formulation N had a tensile strength of 1,400 psi while nearly twice that of formulation P, or 2,700 psi.

Example 8

Examples are compounds of the present invention (R) (CH ₃ O) Ti (OCOCH = CH ₂ ) ₃ , (S) (iC ₃ H ₇ O) Ti [OCOC (CH ₃ ) = CH ₂ ] ₃ , (T) (iC ₃ H ₇ O) ₂ Ti (OSO ₂ CH ₂ CH ₂ COCH = CH ₂ ) ₂ and (U) (BrCH ₂ CH ₂ O) Ti [(OP (O) (OCH ₂ CH = CH ₂ )] ₃ Points to its use as a softener in polyester resins.

The formulation was made with cobalt-activated polyester resin (GR643, W.R. Grace trade name) ratio 100 of methyl ethyl ketone peroxide, 60 high area calcium carbonate and 0.3 alkoxytitanium salt as illustrated in the table below. The sample was cast with a dimension of 1/2 × 5 × 1/8 inch and finished for 30 minutes at a sealed temperature. Molded samples were tested and the results are shown in Table F below.

TABLE F

The data clearly show that the solubility is improved by the use of the present organotitanic acid ester. The selection of specific organo titanic acid ester compounds should take into account the moisture content of the mineral filler. Pyrophosphate binders are particularly preferred if there is no water or if there is weakly bound water (eg water washed clay, hydrolyzed silica, alumina gel magnesium silicate, talc, fiberglass and aluminum silicate). This is shown in the following example.

Example 9

A mixture of 30 kaolin (unbaked clay) and 70 mineral oils by weight ratio was made. To this mixture, three organotitanic acid ester compounds of the present invention were added at a weight ratio of 0.6. Brofield viscosities of the four dispersions were compared in the table examples below.

TABLE G

The chart clearly shows that each cargo of the present invention is reducing the viscosity of the viscosity-mineral oil dispersion. Moreover, it is noteworthy that the isopropyl tri (dioctylpyro phosphadodo) titanic acid ester gives a viscosity reduction outside of the erosion. This significantly reduces the energy required for mixing.

Example 10

Viscosity reduction of isopropyl tree (dioxylpirophosphate) non-acid esters is also effective when used with kaolin (unbaked water-washed clay) dispersed in chlorinated paraffins. To demonstrate this, a mixture of kaolin with a weight ratio of 30 and paraffin with a molecular weight of about 580 with chlorination of 70 was prepared. Brockfield viscosity was measured in the absence of organotitanic acid ester and at the addition of 0.3 by weight. The test results indicated that the Brockfield viscosity in cps was reduced from 90,000 to 18,000 at 25 ° C with the addition of titanate salts.

Example 11

This example shows a decrease in the viscosity of isopropyl tri (dioctylpyrophosphate) in talc powder under heavy mineral oil. The standard formulation contained talc with a weight ratio of 60% and heavy mineral oil (flash point of about 105 ° C) of 40%. In the compound treated with titanic acid ester, the aforementioned compound of inorganic ratio 1.8 was mixed in a powder state at 85 ° C. in a warring grinder with talc (3% by weight based on talc). The standard formulation (having 26,500 bloc field viscosity at 25 ° C. compared to the formulation of the invention having only 11,000 viscosities. Talc is another example of a filler with high water content.

Example 12

The effect of the organotitanic acid ester of the present invention on the impact strength of polyvinyl chloride (PVC) is shown in this example. The relative Gardner impact strength of the component comprising 100% rigid PVC was compared to the packed component containing 40% of finely ground calcium carbonate (particle size of 1 to 2 microns). Samples of packed components were also mixed with varying amounts of alkoxy titanic acid ester salts, as is particularly known in Table H below. All of the tests in the table below show filled components excluding the original product, which is 100% rigid PVC.

TABLE H

The chart shows that the impact strength of the surely filled PVC improves in all or all cases of the addition of titanic acid esters. Most notable is the improvement resulting from the addition of pyrophosphate compounds. Gardner impact strength exceeds the impact strength of 100% PVC.

Claims (1)

A composition consisting of an organo-titanium salt, characterized by having one of the following general formulas: (I) (RO) ₂ Ti (A) _X (B) _Y (II) (RO) Ti (OCOR ') _p (D) _q (III) (RO) Ti (OCOR _b ) ₃ R is a monovalent alkyl, alkenyl, alkynyl or C ₁ -C ₃₀ aralkyl group or a substituted derivative thereof; A is thiaryloxy, sulfonyl, sulfinyl, diester pyrophosphate, diester phosphate, or substituted derivatives thereof; B is OCOR 'or OAr; OAr is aryloxy; R is hydrogen or a monovalent organic group of C ₁ to C ₁₀₀ ; X + Y × Z becomes 4; p + q is 3; X, Z and q are 1,2 or 3; And Y and P are 0,1 or 2; D is OCOR _a or OAr; R _a is the same as R ', provided that each group contains at least C ₅₀ , and R _b is identical to R', provided that the total number of carbons in the three R _B groups of one molecule is 14 or less.