SE450708B - COMPOSITION CONTAINING FINALLY DISTRIBUTED INORGANIC MATERIAL AND AN ORGANIC TITANATE FOR USE AS FILLING OR PIGMENT IN POLYMER MATERIAL - Google Patents

Description

R "is an alkyl, alkenyl, aryl or alkaryl group or an alkyl, halo, amino or ether substituted derivative thereof, wherein R 'contains up to 100 carbon atoms and R" up to 24 carbon atoms; and n is 1 or 2; wherein the particle surfaces of the inorganic material are reactive with respect to the hydrolyzable group of the organic titanate.

Preferably R represents hydrogen, with R may also represent methyl, ethyl or other short chain alkyl groups. All the groups represented by R need not be the same in a particular molecule or on each methylene unit.

The monovalent, non-hydrolyzable group (A) may be acyl, phenoxy, sulfonyl, sulfinyl, diester pyrosulfate or diester phosphate.

By "non-hydrolyzable" is meant that the group in question is not cleaved in neutral aqueous solution at a temperature below 100 ° C; Hydrolysis can be determined by analysis of liberated acids or alcohols.

The acyl, sulfonyl, sulfinyl, diester pyrophosphate and diester phosphate ligands are represented by the following formulas -OCOR ', -OSOZR ", -OSOR", (R "O) 2 P (0) OP (OH) (O) R "O) P (O) O- where R 'and R" have the meanings given above. When A is a sulfonyl or sulfinyl group, it is preferred that R "is phenyl, substituted phenyl or aralkyl having 5-24 carbon atoms in the alkyl chain. When A is a phosphate group it is preferred that R "contains 6-24 carbon atoms and when A is a pyrophosphate group it is preferred that R" is alkyl_with up to 12 carbon atoms.

In the acyl ligand (OCOR '), R' may represent hydrogen or a monovalent group of the indicated type having between 1 and 100 carbon atoms. Special mention may be made of an alkyl, alkenyl, aryl or alkaryl group. The aryl groups may be substituted or unsubstituted phenyl or naphthyl groups, preferably containing up to 60 carbon atoms. In addition, the group represented by R 'may be substituted with a halogen, amino or ether substituent. In general, there may be up to about 6 substituents on each of the groups represented by R '. The groups represented by R 'may further contain intermediate heteroatoms, such as sulfur or nitrogen atoms in the major part or in the substituents attached thereto. R 'preferably represents a long chain group of 18 carbon atoms. Ideally, all the groups represented by R 'are equal to each other. Examples of ligands represented by R are methyl, propyl, cyclopropyl and cyclohexyl and metallallyl. Examples of ligands represented by A which are useful for the purpose of the invention are 11-thiopropyl-1,2-phenyloctadecylsulfonyl, di (2-omega-chloroctyl) -phenylphosphate, diisonicotinyl-pyrophosphate. fato, phenylsulfinyl, 4-amino-2-bromo-7-naphthylsulfonyl, diphenylpyrophosphato, diethylhyxyl-pyrophosphato, di-sec-hexylphenylphosphato, dilaurylphosphato, methylsulfonyl and laurylsulfonyl.

There are many examples of groups represented by R '. These include straight-chain, branched and cyclic alkyl groups such as hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl-octadecyl, nonadecyl, eicosyl, docosyl, tetracosyl, cyclohexyl, cycloheptyl and cyclooctyl. Examples of alkenyl groups which may be mentioned are hexenyl, octenyl and dodecenyl.

Halogen-substituted groups include bromhexyl, chloro-octadecyl, iodotetradecyl and chloro-octahexenyl. One or more halogen atoms may be present, for example in difluorhexyl or tetrabromooctyl. Ester-substituted aryl and alkyl groups include 4-carboxyethylcapryl and 3-carboxymethyltoluyl. Amino-substituted groups include aminocaproyl, aminostearyl, aminohexyl, aminolauryl and diaminooctyl.

Among the aryl groups may be mentioned phenyl and naphthyl and substituted derivatives thereof. Substituted alkyl derivatives include toluyl, xylyl, pseudocumyl, mesityl, isodurenyl, durenyl, pentamethylphenyl, ethylphenyl, n-propylphenyl, cumyl, 1,3,5-triethylphenyl, styryl, allylphenyl, diphenylmethyl, triphenylmethyl, , 5-triphenylphenyl. Among the amino-substituted components are methylaminotoluyl, trimethylaminophenyl, diethylaminophenyl, aminomethylphenyl, diaminophenyl, ethoxyaminophenyl, chloraminophenyl, bromoaminophenyl and phenylaminophenyl. Halogen-substituted aryl groups include fluorine, chlorine, bromine, iodophenyl, chlorotoluyl, bromotoluyl, methoxybromophenyl, dimethylaminobromophenyl, trichlorophenyl, bromochlorophenyl and bromiodiodophenyl. Groups derived from aromatic carboxylic acids are also useful. These include methylcarboxylphenyl, dimethylaminocarboxyltoluyl, laurylcarboxyltoluyl, nitrocarboxyltoluyl and aminocarboxylphenyl. Groups derived from substituted alkyl esters and amides of benzoic acid may also be used. These include aminocarboxylphenyl and methoxycarboxyphenyl. Among the titanates in which A is a phenoxy group may be mentioned tall oil epoxides (a mixture of alkyl groups having 6-22 carbon atoms) containing on average one epoxy group per molecule and glycidol ethers of lauryl and stearyl alcohol.

Substituted naphthyl groups include chloronaphthyl and aminonaphthyl.

The organotanic chelates of the invention can be prepared by reacting the esters of formula (OR) 2 Ti (A) 2 with an equimolar amount of 2-hydroxypropionic acid or hydroxyacetic acid or their carbon-substituted derivatives. To prepare the oxo derivatives (B = R 2 C), the titanate ester is reacted with a 1,2- or 1,3-glycol, such as ethylene glycol or 1,3-butanediol.

The compounds (OR) 2Ti (A) 2 can be readily prepared as disclosed in U.S. Pat. Nos. 3,660,134, 3,697,494 and 3,697,495.

The inorganic materials may be particulate or fibrous with varying particle shape or size, if only the surfaces are reactive towards the hydrolyzable group in the titanium organic compound. Examples of inorganic reinforcing materials (active fillers) are metals, clay, carbon black, calcium carbonate, barium sulphate, silica, mica, glass and asbestos. Reactive inorganic materials include metal oxides of zinc, magnesium, lead and calcium and aluminum, iron filings and turning chips and sulfur. Examples of inorganic pigments are titanium dioxide, iron oxides, zinc chromate, ultramarine blue. As a practical rule, the particle size of the inorganic materials should not exceed 1 mm and preferably be between 0.1 and 500 μm. It is important that the alkoxytitanium salt be thoroughly mixed with the inorganic material so that the surface of the latter can react sufficiently. The optimal amount of alkoxytitanium salt for use depends on the desired effect, the available surface area and on the amount of water bound in the inorganic material.

The reaction is facilitated by mixing under suitable conditions. Optimal results depend on the properties of the alkoxy titanium salt, namely whether it is a liquid or a solid, as well as on its decomposition and "flash point". the geometry of the particles, the specific gravity and the chemical composition. In addition, the treated inorganic material must be carefully mixed with the polymeric medium. The suitable mixing conditions depend on the type of polymer, i.e. whether the polymer is a thermoplastic or a thermoset, the chemical structure of the polymer, etc., which is obvious to the person skilled in the art in the industrial field in question.

When the inorganic material is pretreated with the organic titanate, it can be mixed in an intensive mixer of any suitable type, for example in a Henschel or Hobart mixer or a Waring kneader. Even mixing by hand can be applied.

Optimal time and temperature are determined to obtain a significant reaction between the inorganic material and the organic titanate.

The mixing is carried out under such conditions that the organic titanate is present in the liquid phase, at temperatures below the decomposition temperature. Although it is desirable that the major amount of the hydrolyzable groups react in this step, this is not necessary when the materials are later mixed with a polymer, since substantial compaction of the reaction can occur during this later mixing.

The polymer processing, for example the mixing with high shear, is generally carried out at a temperature which is well above the second order conversion temperature of the polymer, preferably at a temperature at which the polymer has a low melt viscosity. Examples are that low density polyethylene is best processed at a temperature between 170 and 250 ° C, that high density polyethylene is best processed between 200 and 245 ° C, that polystyrene is best processed between 250 and 260 ° C and that polypropylene best processed between 250 and 290 ° C. Temperatures for mixing other polymers are well known to those skilled in the art and can be read from the literature. A wide variety of mixing devices can be used, for example a twin-roll mill, a Banbury mixer, a mixer with twin concentric screws, a counter- and co-rotating twin screw or a Werner, Pfaulder or Busse mixer of the ZSKet type. When the organic titanate and the inorganic materials are dry blended, complete mixing and / or reaction is not easily achieved and the reaction can be substantially complete when the treated filler is blended with the polymer. In this latter step, the organic titanate may also react with the polymeric material if one or more of the groups represented by R 'is reactive with the polymer.

The treated filler can be blended into any of the conventional polymeric materials, whether thermoplastic or curing, whether rubber or plastic. These are described in U.S. Pat. Nos. 5,144, 5,697,494 and 5,697,495, all of which are incorporated herein by reference. The amount of filler depends on the particular polymeric material used, the filler and the properties that the final product is desired to have. 10-500 of the filler can be used, preferably 20-250 parts per 100 parts of polymer. The optimum amount can be easily determined by the person skilled in the art.

Although the compounds of the present invention may be used in combination with any of the above 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 together with wet-produced silica, soft or hard clays, vanaium, aluminum alumina, hyaratia aluminum aia or fiberglass.

Although it is not yet entirely clear why the chelate compounds retain their activity, it can be seen that they are clearly superior to other titanates, such as those described in the aforementioned U.S. Patents 5,660,154, 5,697,494 and 5,697,4955 in presence of moisture.

The following examples describe typical methods of preparing the compounds of the invention. Example A: Preparation of 2,2-dimethyl-5-g-1-5-phenyl-caprylicacetyl-dodecylbenzenesulfonyl-titanate. In a 1 liter reaction vessel equipped with external heating / cooling and reflux / distillation charge and connected to a vacuum pump, 1.0 mol of tetraisopropyl titanate was charged. The reaction vessel was set to reflux at atmospheric pressure. Then 1.0 mole of dodecylbenzenesulfonic acid was added over the course of about 1/2 hour, then 1.0 mole of glacial acetic acid was added over the course of a 4/2 hour followed by 4.0 hours. mol of 2,2-dimethyl-3-oxy-5-phenylcaproic acid, which was also added over the course of a 4/2 hour. A limited heat evolution was observed upon the addition of each of the reactants. After the addition was complete, the reaction mixture was refluxed for 1 hour at atmospheric pressure. The reaction mixture was then cooled to below 50 ° C and the by-product isopropanol was distilled off in vacuo to a temperature in the bladder (bottoms) of about 150 ° C at 40 mmHg. The isopropanol was recovered in a trap immersed in liquid condensed to liquid. About 5.7 moles, i.e. 90% of the theoretical amount of isopropanol was recovered. A small amount of isopropyl acetate was also recovered. As a product, a residue was obtained in the form of a white paste in more than 90% of the theoretically calculated amount. The purification was accomplished by recrystallization from ligroin to give white crystals, m.p. 87-89 ° C.

Example B: Preparation of di (dioctylphosphato) ethyl titanate. A fl liter reaction vessel equipped with external heating / cooling and fitted for reflux / distillation and connected to a vacuum pump was charged with 4.0 moles of tetraisopropyl titanate. First, reflux was carried out at atmospheric pressure, after which 1.0 mole of ethylene glycol was added over the course of 1/2 hour followed by 2.0 moles of dioctyl hydrogen phosphate, which was likewise added over the course of 1/2 hour. Limited heat generation was observed during the addition of each of the reactants. After the addition was complete, the reaction mixture was refluxed for 4 hours at atmospheric pressure. The reaction mixture was then cooled to a temperature below 50 ° G and the by-product isopropanol was distilled off in vacuo to a temperature in the bladder (bottoms) of about 150 ° G at 10 mmHg. The isopropanol was recovered in a trap immersed in liquid-condensed nitrogen. The recovery of isopropanol was about 5.7 moles, i.e. 90% of the theoretically calculated amount. As a product, a residue was obtained in the form of a white paste in an amount corresponding to 90% of the theoretically calculated. Purification was accomplished by recrystallization from ligroin to give white crystals, m.p. 44-45 ° C.

Example C: In the manner set forth above, additional compounds falling within the scope of the invention were prepared. In the table below, the compounds are defined by the chelating ligand and the monovalent ligands (A and A '). Furthermore, there is a physical description of the product, information about its melting point and about its viscosity. 450 708 xv omm Nmamm .Hwkåøm »Hfmn vmnmwvmom fl vwom fl wßo fl wamnd .uwvoum fi wo En: mmumm Nmb HSN» Pwnmmvmom fl vø fi mwvmomw vwvmom flfi o. Bm. "_. Ewa snake wrlmv G fl mbv Omm fi MXF uHmbm Io fl mm fi hahoulm PMO al ww al hanovfm ßmvmom fi NØ iff wwlmm .. .nwb fifi m» bwn um f O fl mw al hñøo Pm al odmm fi hñso vøvmo al uno conv Qïmw .i A? F u f p fl ow pm fififl m umäwpmom al »muwo f xo ommv æmlmm Hwbadm Pumbm» et al wndnuäm vm fl u al mnndm .uno al unw al HVM Qom .Hmmwm al's microns al if fi dm al wm vm fl ow al dm | 35mm f m f NMO fl mm HWB fi dm vumnw L al Mon. f homvo fi l fl mm al mßo flfifl MLA Ünowø f m f HVM .wxmpmkf mmm o .Hmu al's .oømmmwønß al w »mumom f h f o f u uwmmow f h f O fl ø Ünowwnw al Hum Aw flflflfl mvnm flfl mm | wmvummr ._» My vm al Huu fl m UNO .Qu al w al Hum K mmlom ._ um fi Huu al mßma vw al hmmmu f m f .Unowvmm fi hum etc. mvwpdm Ewan November MMAm wmwnmwmw fi wp p f m f ApoA pmnmßmow al al näwnw al NPM conv ovvm wMmpWP oa nßnmwvmom al vmnwmpmøm al .Unowø al et al Hum oøoov v? wn al nvw fi WMP a. 4 .o .wäm fifl mo .p al ämoxm f ø P. .pMÉQpHmaW mm f m f may WVA flfl ßßm f wm Nah m3 vnmkf fi .Hm fi dmw flfi .møämbdm .Hm on. al oo 4 .noo .o al MWW al ønmsnmbß .ww al AEV al wßßw fl mm dm Hm now Hmm .Lïm fifi so Hwšuom cmø flfl w vdamu fifl mwwn. MUHNP mo fl .Hm fl mu fi w fl mww æv fi m flfl wu fi nmhm 10 45 20 25 \ N 35 40 g 450 vos The following examples show the use of the compounds according to up p- the finding.

Example I: This example shows the importance of the chelate structure for viscosity control of wet silica in organic dispersions. A dispersion was prepared by mixing 20 parts of wet-produced silica with a particle size of 0.8 μm in a solution of 0.2 parts of titanate in 80 parts of heavy mineral oil (flash point about 105 ° C) in a Waring kneader. 'Titanate * Mixture Viscosity _______ ____ ¿ë @ aêâ fi ïïL ____ None _ 75,400 Isopropyl-triisostearoyl-titanate 21,800 Isopropyl-tri-tri-dioctylphosphato) -titanate-_ 25,500 Isopropyl-tri (dodecylbenzenesulfonyl-8-titrone-2-acetone-2-titanium (dioctylphosphato) -titanate 8,000 2-acetyl-di (dodecylbenzenesulfonyl) -titanate 9,400 The first three titanates in the table above are, although effective in reducing viscosity compared to the control sample, nevertheless significantly inferior to the three acetyl compounds for which in the lower part of the table. It is believed that this effect is obtained due to the fact that the compounds of the invention retain their activity in the presence of the moisture present in the silica. Example II: Effect of selected titanate on the tensile strength of polypropylene containing water-washed clay with a particle size of 5 .mu.m and talc as filler in systems with 50% by weight of filler and 0.5% by weight of titanate are shown in the following table: 'Titanate Tensile strength, MPa lars! @ lë_ None 25.44 28.96 2-Acetyl-diisostearoyl-titanate 25.17 50.54 2-Acutyl-di (dioctylphosphato) -titanate 28.27 54.47 It appears from this example that both the one with talc and the one with clay filled polypropylene has a higher tensile strength; if they contain a compound of the present invention.

Example III: The effect of the selected titanates on the impact strength (Dart) of Nylon 6 (Allied-8204) containing as filler 50% by weight of water washed clay with particle size 5 μm is shown in this example.

Filling agent fär 'is dyed with 2% by weight of titanate, before being mixed into the polymer matrix. 10 '15 20 25 50 55 40 10 450. 708 Titanate Flexural Elongation at Break, Impact Resistance (Darts) MPa Nm None '405 0.34 2-Acetyl-4-aminobenzene-149 5.16 sulfonyl-dodecylbenzene sulfonyl-titanate 2-acetyl-di (4-aminobenzoyl) - 481 1.84 titanate 2-acetyl-distearoyl titanate 142 s 5176 In each case, the treated material gave an improved flexural strength and a marked improvement in impact strength.

Example Gel IV: In this example, the effect of the selected titanate of the present invention is shown on the properties of polyurethane filled with 0.8 μm particle size wet silica. The mixture contained 20% by weight of filler, which was pretreated with 2.0% by weight of titanate, before being incorporated into the polymer.

Titanate Tensile strength, Elongation at break, MPa% None - 21.37 550 2-acetyl-di (2-hydroxy-27.23 270 acetyl) titanate 2-acetyl-di (dioctyl-phosphate) - 24.15 590 titanate 2-acetyl- dimethacrylic titanate 25.79 500 2-acetyl-4-aminobenzoyl-26.89 500 isostearoyl titanate All of the treated fillers gave an improved yield strength compared to the control sample. The phosphate derivative also provided improved elongation at break. The structure of the non-hydrolyzable group A has been shown to be important in determining the property improvements.

The chemical structure of the above compounds was determined primarily by considering the reactants and the by-products formed. In selected cases, elemental analysis, IR analysis and analysis of free hydroxyl groups were performed. These analyzes verified the assumed chemical structure.

Example V: This example shows the effect of titanate chelate on an unfilled epoxy polymer. Two epoxy hardener mixtures were prepared containing 80 parts of EPON 828 and 20 parts of an aliphatic amine hardener, namely CEIANESE 874. To one of these newly prepared samples was added 2 parts of 2-acetyl-di (dodecylbenzenesulfonyl) -titanate. Both mixtures were stirred for 2 minutes and their viscosity was determined in a Brookfield viscometer; The results obtained are compiled in the following table. a) 10 ll 45 0 7 Û 8 Titanium organic compound Brookfield viscosity x 405 cP 'Insen 5.9 2-acetyl-di (dodecylbenzenesulfonyl) -white: 9.4 The above data show that the last mixture had a significantly higher viscosity than the second tried. Example VI: This example shows the use of ethylene di (dioctyl phosphato) titanate to improve the coloring effect of pigments in an aqueous acrylic paint. The color used was SRW5OX White (Rowe Products Inc.) and the pigment paste dispersion (Daniel Products Co.).

Tint ~ Ayd # šWD-2228, Aqneous Tinting Color, Phthalo Blue) containing 52% pigment and a total of 59% solids. Ethylene di (dioctylphosphato) titanate was first mixed into the pigment to form mixtures containing 0.5; 0.6; 0.9; 4.2; and 4.5% titanate by weight of the pasta dispersion. To samples of the paint of 100 parts each were added 0.2 parts of any of the treated pasta dispersions. Upon observation, it turned out that already 0.5% gave improved dispersion and flow in comparison with the control sample. Although the staining was increased in all cases, the improvement of the blue stain was optimal by 0.9% of the sample.

Claims (13)

LT! 10 15 20 25 30 35 450 708 12 Patent claims 1. Composition based on finely divided inorganic material for use as a filler or pigment for polymeric materials or for dyeing, opacifying, extending, reinforcing, etc. of polymeric materials, characterized in that it contains an organic titanate with the general formula O (Rzon / d Tiwaz \\\\ * --- 0 --- "',,, / ff) B where A is a group which is not cleaved in neutral aqueous solution at a temperature below 100 ° C and which is an aralkyl or halo-substituted or unsubstituted phenoxy group having up to 60 carbon atoms, -OCOR ', -OSO2R ", -OSOR", (R "o) 21> (o) oP (oH) (o ) - or (R "o) zP (o) o-, wherein the two groups represented by A are mutually equal or different; B is R 2 Cif or a carbonyl group; R is hydrogen or an alkyl group having 1-6 carbon atoms; each of R 'and R "is an alkyl, alkenyl, aryl or alkaryl group or an alkyl-, halo-, amino- or ether-substituted derivative thereof, wherein R' contains up to 100 carbon atoms and R" up to 24 carbon atoms; and n is 1 or 2; wherein the particle surfaces of the inorganic material are reactive with respect to the hydrolyzable group of the organic titanate. 2. A composition according to claim 1, characterized in that A is -OSOZR "or -OSOR" and R "is phenyl, alkyl- or amino-substituted phenyl or aralkyl having 5-24 carbon atoms in the alkyl moiety. 3. A composition according to claim 1, characterized in that A is (R "O) 2 P (O) O- and R" contains 6-24 carbon atoms. 10 15 20 25 30 35 450 708 Composition according to Claim 1, characterized in that A is (R "O) 2 P (O) OP (OH) O- and R" is an alkyl group having up to 12 carbon atoms. 5. A composition according to claim 1, characterized in that R 'is a long chain group having 18 carbon atoms. Composition according to Claim 1, characterized in that A is phenoxy. Composition according to Claim 1, characterized in that the non-hydrolysable groups are -OCOR 'having 1 to 18 carbon atoms. Composition according to Claim 1, characterized in that the organic titanate has the formula o II cH ----- o oïc - R '2 \\ ~ T_f // l en 0 / \ oc R' 2 no wherein R 'contains 18 carbon atoms. Composition according to Claim 1, characterized in that the organic titanate has the formula cH ---- o o-Pw omopotoa fi 2 \ T. / 2 in a ----- oz x 2 0- P (o) (about oPo (oR ") 2 where R" is an alkyl group having up to 12 carbon atoms. Composition according to Claim 1, characterized in that the organic titanate has the formula 10 450 450 708 IQ oc |: --- o \ Ti / o - P (o) (oH) oPo (oR ") 2 (o) (o) (oH) oPo (oR ") 2 where R" is an alkyl group having up to 12 carbon atoms. A composition according to claim 10, in that R "is an octyl group. 12. A composition according to claim 1, characterized in that the organic titanate has the formula o C. ---- '-_ O \ Ti / QPQ ._ (ORIWZ cuz 0 / \ o1> o - (oR ") 2 where R "is an alkyl group having 6-24 carbon atoms. Composition according to Claim 12, in that R "is an octyl group. K ä n n e t e c k n a d åk»