JPS5915337B2 - Method for producing inorganic dispersions in polymeric media - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Inorganic materials have long been used as fillers, pigments, reinforcing agents and chemical reactants in polymers.

They are hydrophilic in nature, ie they wet easily with water or absorb water. However, they are limited in their compatibility with polymers. Therefore, the reinforcing potential of inorganic materials,
Has inferior utility due to color or opacity, or chemical reactivity. For example, zinc oxide is a commonly used ingredient in rubber formulations.

When ground zinc oxide is added to a rubber formulation as a dry powder, it is difficult to completely disperse it into the rubber. On the other hand, predispersion of zinc oxide, a plasticizer for rubber, in an organic medium provides a hard paste that is dust-free, easy to weigh, and aids in dispersion into the rubber 15. Similarly, other ground inorganic solids such as magnesium oxide, calcium oxide, other metal oxides, and fillers such as clay, calcium carbonate, colloidal silica and carbon black may be added to the rubber or plastic compound prior to addition to the organic compound. Predispersed in plasticizers or polymers. Organotitanium compounds are well known.

For example, as described in U.S. Pat.
Various products are prepared by 5 reactions. Organotitanates having di- or tri-alkyl hydrolyzable groups and thus only one or two non-hydrolyzable organic groups are used on the surface of inorganic materials, as for example in U.S. Pat. No. 3,660,134. It is used to treat 30 to make it hydrophilic. Such di- or tri-alkyl hydrolyzable titanates form multilayers or wrap around inorganic particles, reducing the usefulness of the organic titanate;
Similarly, the bond 35 between the inorganic particle surface and the organic continuous phase is weakened. This reaction is accomplished by adding the organic titanate to a dispersion of the inorganic material in an inert solvent such as naphtha, trichloroethylene, toluene or hexane.

Once the reaction is complete, the solvent is removed and the treated, dried inorganic material is subsequently introduced into an organic polymer system. For example, in US Pat. No. 3,697,475, such treated inorganic fillers are added to thermoplastic polymer films. The novel organic titanate used in the present invention has the formula T1(0R)4-n(0C0R')n (where 0R
is a hydrolyzable group, R is a non-hydrolyzable group, and n is on average more than 3 and up to 3.5, preferably from 3.1 to 3.
．． 25).

The above compounds are preferred for treating inorganic solids for the reasons given below. The composition materials dispersed in the polymers of the present invention have the general formula above, where n is greater than 3 up to 3.5, preferably greater than 3, and most preferably from 3.1 to 3.25. It is a reaction product of an organic titanate with an inorganic solid and an inorganic solid.

The required amount of organic titanate is at least 0.1 parts, preferably from 0.5 to 10 parts per 100 parts of inorganic solids. This reaction occurs on the surface of the inorganic solid, thereby removing hydrolyzable groups and forming bonds, thus forming an organic, hydrophobic surface layer on the inorganic solid. This inorganic solid is difficult to disperse in organic media prior to surface modification due to its hydrophilic surface. However, when this organotitanium compound is introduced into an organic medium (low molecular weight liquid or high molecular weight polymer solid), the surface of this inorganic solid becomes wet;
Agglomerates are easily broken into individual particles and dispersions with improved properties are formed. On the other hand, the organic titanate may first be reacted with an inorganic solid in the absence of an organic medium and then mixed with an organic medium. The method of the invention converts the surface of an inorganic substance from a hydrophilic to a hydrophobic state by reaction, preferably in an organic medium.

This preferred method eliminates the intermediate steps of dispersing the inorganic material in a solvent, reacting, filtering and drying the inorganic solid before dispersing it in the polymer in the prior art.
In accordance with the present invention, dispersion of inorganic substances in organic polymeric media can be achieved by (1) low viscosity or high loading of the dispersion in organic media;
2) a high degree of reinforcement through the use of fillers, thereby obtaining improved physical properties of the filled polymer; (3) more complete utilization of chemical reactivity, thereby reducing the amount of inorganic reactive solids required; 4) more efficient use of pigments and opacifiers, (
5) improved inorganic to organic ratios in the dispersion; and (6) shorter mixing times to obtain dispersion, etc.

Also according to the invention, the reaction of the organotitanate with a single hydrolyzable group is carried out neat or in an organic medium,
Liquid, solid, or pasty solid dispersions may be formed that can be used in the formulation of the final polymeric system.

Such dispersions are very stable, ie, they do not tend to settle, separate, or solidify into a non-dispersed state during storage. Additionally, the present invention improves the composition of inorganic dispersions by eliminating solvents, reducing the cost of processing equipment, and reducing the time and energy required to disperse inorganic solid materials into liquid or polymeric organic solids. To simplify the production of The object of the present invention is achieved by the production of a new liquid ester which simplifies the in situ production.

The present invention forms reinforced polymers with lower melt viscosities, improved physical properties, and better pigment properties than found with prior art materials.

Practicing the present invention reinforces, colors, or chemically reacts with polymers to produce products with superior physical properties, better processing properties, and more effective pigment utilization. A product consisting of a natural or synthetic polymer containing particulate or fibrous inorganic material is provided.

That is, the reaction products obtained by the process of the present invention are useful as fillers for reinforcing the physical properties of polymers and for improving the dispersibility and compatibility of materials in organic media.

Advantages obtained by practicing this aspect of the invention include the elimination of the use of volatile and flammable solvents as required by the prior art.

There is thus no need to dry the filler or recover the solvent. Furthermore, since there is only one hydrolyzable group in the organic titanate reactant, there is no possibility of forming a multilayer. Similarly, practice of the present invention provides non-oxidizing dispersions. The preparation of representative organotitanium compounds is described in U.S. Pat.
It is described in No. 193.

Although many compounds of this basic starting material Tl(0R)4 are used in the preparation of polyesters, tetraisopropyl titanate is preferred from the point of view of reactivity and economy. Referring to the above formula, R forming part of the hydrolyzable group may be a straight chain, branched or cyclic alkyl group having from 1 to 5 carbon atoms per molecule. This group includes methyl, ethyl, n- and isopropyl, n-, secondary- and t-butyl, pentyl and cyclopentyl. "Hydrolyzable" means 1 in an aqueous solution having a pH of about 7.
It means a group that cleaves at a temperature lower than 00°C. Hydrolysis is measured by analyzing the acids and alcohols liberated. Conversely, "non-hydrolyzable" refers to a group that does not hydrolyze under the above conditions. Non-hydrolyzable group (
For 0C0R, these are preferably between 6 and 2
It is formed from organic acids having 4 carbon atoms, such as stearic acid, isostearic acid, oleic acid, linoleic acid, palmitic acid, lauric acid and tall oil acid.

Isostearic acid is particularly advantageous because it forms triesters that are liquid at room temperature and are easily soluble in organic media. Additionally, at least one R-blast must have a long chain as defined below to provide the necessary viscosity reduction to the reaction product of organic titanate and inorganic material.
As an example, the two w groups may be isopropyl and the long chain R may be lauryl. Most desirable are materials that can be easily liquefied or dissolved at normal mixing temperatures. Equivalent polytitanates may be used as well. ' The R group is preferably an alkyl group having up to 24 carbon atoms, an alkenyl group having up to 18 carbon atoms, or an alkenyl group having up to 18 carbon atoms.
It is an aralkyl group having up to 4 carbon atoms.

If the R5 group is a long chain group, it must have at least 6 carbon atoms. Furthermore, the above groups may be substituted with halo, nitro, amino, carboxyl, epoxy or hydroxyl ether or ester groups. Generally from 1 to 6 such substitutions occur. Furthermore, the w group may contain intermediate heteroatoms such as oxygen, sulfur or nitrogen in the chain. It is not necessary that all R groups in the organotitanate compound be the same.

These may be mixtures of two or more groups, the preparation of which will be readily understood by those skilled in the art. For example, the Ti(0R)4 starting material is reacted with two or more organic acids. The choice of R' group for the organotitanate will vary depending on the particular application.

The optimum group depends on the filler and the monomeric or polymeric organic material and the desired properties of the filler material. One of ordinary skill in the art will be able to determine, with limited experimentation, the appropriate organic titanate for a particular application from the teachings herein.
There are multiple examples of w groups. 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. Alkenyl groups include hexenyl, octenyl and dodecenyl. Groups derived from saturated and unsaturated fatty acids are likewise useful.

In these cases, the 0C0R' group may be caproyl, caprylyl, powerfuryl, lauryl, myristyl, palmityl, stearyl, aratidyl, behenyl, lignoceryl, dodecylenyl, palmitoleyl, oleyl, ricinoleyl, linoleyl, linolenyl, and gadoleyl.
Halo monosubstituents include bromohexyl, chlorooctadecyl, iodotetradecyl and chlorooctahexenyl. One or more halogen atoms may be present, for example in difluorohexyl or tetrabromooctyl. Ethyl-substituted aryl and alkyl groups include 4-carboxyethylcapryl and 3-carboxymethyltolyl. Amino monosubstituents include aminocaproyl, aminostearyl, aminohexyl, aminolauryl and diaminooctyl. In addition to the aliphatic radicals mentioned above, radicals containing heteroatoms such as oxygen, sulfur or nitrogen in the chain can likewise be used. Examples of these groups are ethers of the alkoxyalkyl type, including methoxyhexyl and ethoxydecyl. Alkylthioalkyl groups include methylthiododecyl groups. Primary, secondary and tertiary amines likewise act as terminal ends for hydrophobic groups. These include diisopropylamino, methylaminohexyl, and aminodecyl. Aryl groups include phenyl and naphthyl groups and substituted derivatives. Substituted alkyl derivatives include tolyl, xylyl, psudocumyl, tanthyl, isodeyurenyl, duelenyl, pentamesalphenyl, ethyl phenyl, n-propylphenyl, cumyl, 1,3,5-triethylphenyl, styryl, allyl phenyl, diphenylmethyl, triphenyl. Includes methyl, tetraphenylmethyl, 1,3,5-triphenylphenyl. Nitro mono- and halo substitutions include thalolonitrophenyl, chlorodinitrophenyl, dinitrotoluol,
and trinitroxylyl. Amine monosubstituted components include methylaminotolyl, trimethylaminophenyl, diethylaminophenyl, aminomethylphenyl,
Includes diaminophenyl, ethoxyaminophenyl, chloroaminophenyl, promoaminophenyl and phenylaminophenyl.

Halo-substituted aryl groups include mono-fluoro, mono-chloro, mono-bromo, iodophenyl, chlorotolyl, bromotolyl, methoxypromophenyl, dimethoxyaminopromophenyl, trichlorophenyl, bromochlorophenyl,
and promoiodophenyl. Groups derived from aromatic carboxylic acids are also useful.

These include methylcarboxylphenyl, dimethylaminocarboxyltoluyl, laurylcarboxyltolyl, nitrocarboxylphenyl, and aminocarboxylphenyl. Groups derived from substituted alkyl esters and amides of benzoic acid are likewise used. These include aminocarboxyphenyl and methoxycarboxyphenyl. Titanates in which w is an epoxy group include tall oil epoxides (mixtures of 6 to 22 carbon alkyl groups) containing an average of 1 epoxy group per molecule and glycidol ethers of lauryl or stearyl alcohol.

Substituted naphthyl groups include nitronaphthyl, chloronaphthyl,
Contains aminonaphthyl and carboxynaphthyl groups.

Particular compounds prepared and operative in the practice of this invention include (where n is greater than 8 and less than 15);
(However, the sum of p+q is more than 6 and less than 18.

)including. The inorganic material may be granular or fibrous and of any shape or size, the surface of which is reactive with the hydrolyzable groups of the organotitanium compound through hydroxyl groups or absorbed water, or both. .

Examples of inorganic reinforcing materials include metals, clays, carbon black, calcium carbonate, barium sulfate, silica mica, glass and asbestos. Examples of reactive inorganic materials include lead, magnesium, lead, and metal compounds of calcium and aluminum, iron shavings and sawdust, and sulfur. Examples of inorganic pigments include titanium dioxide, iron oxide, zinc chromate, and ultramarine blue.
As a practical matter, the particle size of the inorganic material should not be larger than 1 mm, preferably between 1 micron and 500 microns. It is essential that the organic titanate be properly mixed with the surface of the inorganic material in order to react sufficiently with the surface thereof.

The optimum amount of titanate used will vary depending on the effect achieved, the available surface area of the inorganic material and the water bound therein. The reaction is facilitated by mixing under appropriate conditions.

The optimum result depends on the nature of the titanate, ie whether it is liquid or solid, and its decomposition and flash points. Particular consideration must be given to particle size, particle shape, specific gravity and chemical composition. Furthermore, the treated inorganic material must be thoroughly mixed with the polymeric medium. Suitable mixing conditions will depend on the type of polymer, whether it is thermoplastic or thermoset, its chemical structure, etc., as will be readily understood by those skilled in the art. When this inorganic material is pretreated with organic titanates,
Mixing may be carried out in any conventional type of forced mixer, such as a Penn shell or Hobart mixer or a Waring blender. Hand mixing may be used. Optimal times and temperatures are determined to obtain substantial reaction between the inorganic material and the organic titanate. Under conditions where the organic titanate is in the liquid phase,
Mixing takes place at a temperature below the decomposition temperature. Although it is desirable that most of the hydrolyzable groups are reacted at this stage,
This is not essential when the material is later mixed with the polymer since substantial completion of the reaction occurs in a later mixing step. Polymer processing, such as high shear mixing, is generally carried out at temperatures well above the polymer's dicatetic rearrangement temperature, preferably at temperatures at which the polymer has a low melt viscosity.

For example, low density polyethylene performs best at temperatures between 35' and 450'F C1, high density polyethylene at 40' and 475'F, polystyrene at 45' and 500'F, and polypropylene at 4500 and 550'F. Processed. The temperature at which other polymers are mixed is well known to those skilled in the art and can be determined by reference to published literature. Various mixing devices are used, such as double roll mills, Banbury mixers, double concentric screws, counter- or co-rotating pair screws, and Werna and Faudler and Booth mixers of the ZSK type.
When organic titanates and inorganic materials are dry blended, complete mixing and/or reaction is not easily achieved;
The reaction is then substantially complete when the treated filler is mixed with the polymer.

At this later stage, the organotitanate will react with the polymeric material as well when one or more of the R groups is reactive with the polymer. To further explain the invention:
An example of this is shown below.

Example A: Preparation of Organic Titanate Esters One mole of tetraisopropylzatanate is placed in a vessel equipped with a stirrer, internal heating and cooling equipment, a vapor condenser, a distillation trap, and a liquid-solid feed inlet.

Begin stirring the tetraisopropyl titanate at room temperature. Liquid isostearic acid is metered into the container at a constant rate, but the exothermic reaction is allowed to continue for about 35 minutes until 3.19 moles of acid have been added.
“Keep it below F. Isopropanol from the reaction product 1500C50m77! Remove foreign volatiles by distillation with Hg. The organic titanate thus obtained is
It has an average of 3.19 moles of isostearate per molecule. This material is referred to hereinafter as [isostearate 3.19 ester]. This ester structure is determined by detecting isopropanol and residual isostearic acid liberated from the reaction. A typical experiment shows that approximately 3.1 to 3.3 moles of isopropanol are recovered. Unreacted isostearic acid is virtually undetectable. The physical properties of this ester are as follows. Specific gravity, 74 quality F0.944 Flash point (COC), 'F3l5 Viscosity, L, 74\CPSl2O Pour point, lower Lower than -5, decomposition point, 'F
Over 4OO, Cardner Color 15 Maximum Appearance Red Oily Liquid Instead of adding 3.19 moles of isostearic acid, 1.
Repeat the above experiment except adding 0, 2.0 and 3.0 moles.

This corresponds to 1, 2 and 3 moles of isostearate groups/
A mixture of isopropyl isostearate titanates having an average value of molecules is produced. Example B This example shows the effect of mixing isostearate 3.19 ester with various fillers dispersed in naphthenic oil.

Fillers used include calcium carbonate, calcined resin, high surface area silica, carbon black, and chemically oxidized carbon black. The effect of varying percentages of titanate ester on the final product viscosity is also shown in the data below. The above data clearly demonstrate that materials reacted in situ with titanate esters produce dispersions with substantially reduced Bruckfield viscosities.

A significant reduction in viscosity is especially shown with calcium carbonate, calcined resin, and carbon black. This reduced viscosity makes the mixing of these fillers with organic type materials much easier and provides improved dispersions with lower energy requirements for mixing. Example C This example, using the method of Example B, shows the effect of other organotitanate compounds on the viscosity of calcium carbonate in a naphthenic mineral oil dispersion.

The composition tested contains 50 parts by weight of oil, 5 parts of precipitated calcium carbonate and 0.5% (based on CacO3) of titanate ester. The results are shown below. The table above shows the acute effect on the viscosity of the titanate esters of the present invention. In the last two examples, the non-monohydrolyzable groups are short chain groups and are outside the scope of the invention. In such a case,
The viscosity of the CacO3-filled oil remains virtually unchanged. The effect of isopropyl titanate isostearate on the dispersion and the chemical reactivity of zinc oxide is shown in the examples below.

Example D Effect of Isostearate Ester on Dispersion of Zinc Oxide in Organic Media Permeability (ASTM Test Falls Dl23l)
, 74° F. The greater the isostearate ester penetration, the more fluid the mixture is.

After aging, this isostearate 3.19 ester provides the most desirable penetration properties. It can be seen from the data that desirably 3 or slightly more moles of isostearate in the titanate ester provides the most stable flowable mixtures. 10 when making a rubber compound with a zinc oxide dispersion treated as described in Example D.
A dispersion made with this isostearate 3.19 ester was compared with the same zinc oxide in untreated powder form in a natural rubber formulation, except that % less zinc oxide was used.

The formulation and test results are shown in Example 1 below. Example 1 Effects of treated zinc oxide dispersions in natural rubber formulations Physical properties Stress at 300% elongation, PS(S'). Tensile strength PS (
Ox? Elongation (odor, hardness, shore A ([-]), speed of press-cure and depression rheometer 1, 290'Fl6O seconds, preheating, 60 minutes motor, 100 range; 3, arc, in Example 1. The table below shows the significant improvement in physical properties of natural rubber formulations achieved using isostearate 3.19 ester treated zinc oxide surfaces even when 10% less zinc oxide is used.

The tensile strength increases by 30%, the elongation increases by 10%, and the stress at 300% elongation increases by 10%. It is also important that the hardness does not change.
Mu[me] plasticity is more than twice as high at 250'F;
Rheometer data at 90'F shows that treated zinc oxide gives stronger cure. Example 2 below demonstrates the improvement in properties obtained when using the zinc oxide dispersion made with the isostearate 3.19 ester of Reference Example 1 in an oil-carbon black extended SBR (styrene-butadiene rubber) formulation. shows. Example 2 Influence of treated zinc oxide dispersion in styrene-butadiene rubber formulation Physical properties Stress at 300% elongation PSI (S), tensile strength PSI ('
T! ), % elongation (E), hardness Shore A ((4) Cure speed and subside rheometer, 280A F 160 seconds preheating, 60 minutes motor 50 range, 10 arc, rheometer 1, 3
40'Fl 6O seconds preheat, 12 minutes motor, 50 range, 1° arc This data for Example 2 is 10%
Shows equivalent or improved physical properties when using less zinc oxide.

In actual processing, isostearate 3.
The 19 ester treated zinc oxide dispersion is added to the rubber compound at about 1/4 to 1/5 of that required for untreated zinc oxide powder. Furthermore, this treated zinc oxide powder is non-dusty. The above data also shows that formulations containing this treated zinc oxide dispersion exhibit a high degree of reactivity as well as a stronger final cure as evidenced by an increase in torque compared to untreated zinc oxide. Indicates that it has. Example 3 below
, 4 and 5 demonstrate the effectiveness of isostearate 3.19 ester in reducing the viscosity of dispersions of various inorganic solids in hydrocarbon oils.

A dispersion of zinc oxide in a hydrocarbon oil can be prepared using isostearate 3.
When reacted with 19 ester, it gives a significantly reduced viscosity. Example 3 In situ (1 ns) with isostearate 3.19 ester
The viscosity reduction of the zinc oxide dispersion in hydrocarbon oil due to the i.t.u. reaction was 83%.

The viscosity of titanium oxide dispersions is similarly reduced by isostearate 3.19 ester, as shown in Example 4 below.

Example 4 In situ (Ins) with isostearate 3.19 ester
The viscosity reduction of the titanium dioxide dispersion in hydrocarbon oil by the itu) reaction was 99%.

The viscosity of carbon black dispersions in hydrocarbon oils is similarly reduced by the same esters, as shown in Example 5 below. Example 5 In situ (I) reaction with this isostearate 3.19 ester
The viscosity reduction of the carbon black dispersion in hydrocarbon oil due to the in situ reaction was 56%.

The viscosity of a dispersion of calcium carbonate in a liquid epoxy resin is as shown in Example 6 below.
9 decreases when ester is added. Example 6 In situ treatment of this isostearate with 3.19 ester
tu) The viscosity reduction of the calcium carbonate dispersion in the liquid epoxy resin due to the reaction was 80%.

The viscosity of a dispersion of colloidal silica in liquid polysulfide rubber is reduced by the addition of isostearate 3.19 ester, as shown in Example 7 below.

Example 7 The permeability of a paste dispersion of calcium carbonate in liquid (thiocol) polysulfide rubber is
．． It increased when 19 esters were added.

On the other hand, when the amount of calcium carbonate in the dispersion was increased by 50%, the permeability remained the same with the addition of increased isostearate 3.19 ester.

These effects are shown in Example 8 below. Example 8 Dispersions of Examples 4-9 were initially prepared without isostearate 3.19 ester by premixing the pigment or filler with an organic liquid medium using a pony mixer.

This preblend was then milled on a three roll mill to form the final dispersion. Viscosity or permeability measurements were also made for control comparisons. The effectiveness of the titanate ester was then evaluated by a second test in which the titanate ester was added to an organic liquid medium and a dispersion was made as described above.

Viscosity measurements carried out on new batches show a very significant viscosity reduction and show that the isostearate esters of the invention are suitable for use with a wide variety of inorganic substances and in different liquids. It is shown to be effective in organic media. This viscosity reduction means that inorganic materials treated by the methods presented herein (1) can be used at higher loadings and (2) are more completely dispersed in the organic medium and into the final product. , and (3) show that it is possible to create viscosity levels that provide improved manufacturing processes such as lower energy requirements for mixing or pumping such dispersions. These examples show that the inorganic material does not need to be pretreated and this surface modification can be done in situ (I) by the use of isostearate titanate esters.
nsitu).

Similarly, the esters are effective in reducing the viscosity of a wide variety of inorganic materials in a wide variety of organic media. Example 9 below demonstrates the effectiveness of isostearate 3.19 ester in obtaining short mixing times and low viscosities of magnesium oxide dispersions in hydrocarbon oils.

In actual mixing, it is necessary to additionally add magnesium oxide to the hydrocarbon oil in order to obtain the maximum loading of inorganic to organic matter in the shortest possible time. The table below displays this method and the results obtained. Example
9 The resulting dispersion requires 31% less mixing time;
Made 30% softer.

Example 10 The effect of reacting isostearate 3.19 ester in low density polyethylene (LDPEI specific gravity 0.918) with calcium carbonate (precipitated small particle size grade) is shown in the table below.

This table shows that 70 parts of calcium carbonate is 28 parts of LDPE
Compare the melt viscosity vs. time to create a dispersion of calcium carbonate in low density polyethylene having a melt index of 7. In these experiments, 2.85% isostearate 3.19 ester (based on calcium carbonate) was added before the start of mixing in the Brabender high force mixer.

Mixing was carried out at a maximum temperature of 200° F. and 82 RPM using a 5 Kg weight on the ram, and melt viscosity was observed by measuring the torque (g-m) applied to the mixer. The isostearate ester was omitted and the other two dispersion aids, aluminum tristearate and polyglycerol 400 monooleate, were added at the same concentration, namely 2.
Similar experiments were performed using 85% (based on CacO3).

The results are also shown in the table below. When no additives were used, the torque after 30 seconds of mixing was 20009 m2 and after 190 seconds it was 1750 m2.

When using isostearate 3.19 ester, the torque dropped to 12509 square meters in 30 seconds and 750 in 190 seconds, indicating a significant decrease in melt viscosity in a very short time.

When using aluminum tristearate, the torque is 19009 square meters after 30 seconds and 19
It drops to 1250 after 0 seconds, which is much higher than the titanate ester.

The polyglycerol 400 monooleate additive produced a torque of 2,1509 m2 after 30 seconds of mixing and a torque of 1,000 m2 after 190 seconds of mixing. 7
0% CacO3 dispersion 1:9 with additional LDPE polymer
Additional tests in which films were made by mixing at a ratio of 3.19 and then by profile film extrusion similarly demonstrated the effectiveness of isostearate 3.19 ester as a dispersant.

The resulting film was then visually examined to determine the number of residual agglomerated particles per square foot.

When no dispersion aid additive was used, 312 aggregates/
The square feet were warm. When using the titanate ester, the number of agglomerates was reduced to 16/square foot. Example 11 This example is the same as used in Example 10.

Titanium dioxide was used as the inorganic dispersed phase in the same LPDE as used in Example 10. 2.6
A dispersion was made with 75 parts TiO2 using 7% dispersion additive (based on TiO2) and 23 parts LDPE.

The table below shows that without the dispersion aid additive, the torque on the Brabender mixer after 30 seconds was 2,2509 square meters and dropped to 1,100 after 180 seconds.

When the isostearate 3.19 ester was added, the torque dropped to 1,2509 square meters after 30 seconds and was 750 after 180 seconds. When the TlO2 dispersion was reduced to a concentration of 7.5% and a proof film was made, the number of aggregates/square foot without additives was 6.
00, and for isocyanate esters the aggregate count was reduced to 150/ft2.

There was also a very significant increase in opacity and white color. The table also shows that polyglycerol 400 monooleate is inferior in the case of TiO2 dispersions, while aluminum stearate is superior to titanate ester as a dispersant.

Example 12 The method in this example is the same as Examples 10 and 11.

The inorganic dispersed phase is yellow iron oxide and contains 50 parts of 4% dispersion additive (based on iron oxide) and 48 parts of LDPE.
was used. The table below shows the results. When no dispersion additive was used, the torque on the Brabender was 2,5009 m2 after 30 seconds and 1,500 m2 after 180 seconds.
It was 000.

When adding isostearate 3.19 ester, 30
The torque after seconds was also 2,5009 square meters, but after 180 seconds the torque dropped to 750. When this yellow oxide dispersion was reduced to 5% concentration and converted to a profile film, the aggregate count was 685/square foot without dispersing additive.

When the isostearate 3.19 ester was added, the aggregate count decreased to 113/square foot. The above table is
Similarly, titanate esters were shown to be superior to aluminum stearate or polyglycerol 400 monooleate in lowering melt viscosity. Example 13 To study the effect of impact strength, tensile strength and melt index properties of injection molding grade high density polyethylene (HDPE) with mineral fillers at 30-60% loading, isostearate 3.19 titanate ester was used.

A laboratory Banbury machine was used to master patch this organic titanate with HDPE at a concentration of 5%.

The resulting blend was placed in a copperant grinder for 14
It was ground using a mesh screen and then dry blended with the filler in a pen shell mixer to give the desired filler to organic titanate ratio. This dry blend was desired using a 3 minute cycle time, 60 psi ram pressure, and a drop temperature of 200'F. It was further mixed with HDPE to provide filler.

The final formulation was ground and tested at 0.105×0.
The tiles were injection molded with dimensions of 500 x 2.375 inches. The molding was done at 400'F, 1000 psi injection pressure, ram forward, 10 seconds, and mold closure time of 15 seconds. The results obtained are shown in the table below.

The table above shows that isostearate 3.19 ester works most effectively with calcium carbonate and barium sulfate.

This 30% filler/HDPE system with organic titanate has better impact strength than the equivalent filled system without the titanate ester. 40% filler containing calcium carbonate, calcium metasilicate, and barium sulfate/
In the case of HDPE systems, impact strength was equal to or better than high density polyethylene. Additionally, the hardness or tensile modulus of this calcium carbonate-filled HDPE is significantly reduced by 3% organotitanate. Surprisingly, this decreases as the filling increases. Even though the modulus is greatly reduced, the tensile strength remains relatively constant up to 60% filling. Finally, the melt index of this barium sulfate- or calcium carbonate-loaded HDPE remains reasonably constant.

At 60% filling, it has the same flow properties as 100% HDPE without filler.

Example 14 This example describes the application of the present invention to filled low density polyethylene.

Unfilled polyethylene sweetened with 40% calcium carbonate was tested for volume resistance (V.R.), tensile strength, modulus, elongation and tear strength, and 1% as a coupling agent.
, 2% and 3% of the uninvented isostearate 3.19 ester were dry blended and then filled with calcium carbonate.

The results are shown in the table below. It is noted that treatment with organic titanates improves elongation and tear strength compared to untreated filled materials.

However, it should be noted that these properties are not restored to the level of unfilled polyethylene. Example 15 This example shows the effect of isostearate 3.19 ester dry blended with calcium carbonate on the impact strength of filled polypropylene.

In these experiments, unfilled polypropylene, 40% by weight
A 40 wt. Heat aged and non-aged impact strength are compared for polypropylene filled with calcium carbonate. 15
Heat aging at 0° C. is an accelerated test for long-term aging effects at ambient temperature.

This dry blend is made using a high force pen shell mixer at 3600 rpm at ambient temperature. for at least 30 seconds. The table below shows the impact strength of unaged and heat aged samples.

The above data demonstrate that the addition of the isostearate 3.19 ester of the present invention substantially maintains the impact strength of the filled polypropylene despite heat aging, while the isostearate 3.19 ester addition substantially maintains the impact strength of the filled polypropylene despite heat aging.
It is clearly shown that without the 19 ester, the filled polypropylene loses its impact strength (becomes brittle) to a significant extent.

This data also shows that the impact strength of filled polypropylene is greatly improved by the use of 3% isostearate 3.19 ester. Example 16 This example evaluates the effect of isostearate 3.19 ester on calcium carbonate filled polypropylene.

Two methods are used to determine the effect of the mixing method on the physical properties of the final product. In the first method, calcium carbonate and an organic titanate compound are mixed in a pen shell mixer for 30 minutes.
Dry blend for 1 minute at 600 rpm. This mixing initially occurs at room temperature, but the mixture increases in temperature during the mixing operation. Test samples are then prepared by dry blending with polypropylene followed by single screw injection molding at 450'F. In the second method, the materials from the Hensiel Millennium are blended in a high shear double concentric mixer at 4500P. The sample is then injection molded at this same temperature. The table below shows the results obtained. The above table clearly shows that the treated calcium carbonate containing polypropylene has substantially improved properties compared to the untreated material.

When 0.6% organic titanate is used, impact strength is significantly improved.

The use of double concentric screws, also used in Method 2, provides further improved properties. This more high shear mixing is hypothesized to provide a more complete reaction between the organic titanate and the inorganic material. Example 17 This example shows the application of the invention to polystyrene.

The table below shows polystyrene, calcium carbonate and 50/5
Figure 3 shows a comparison of specific gravity and melt index of polystyrene mixed with 0.0 and 50/50 mixed polystyrene with calcium carbonate pretreated with 0.5 parts of isostearate 3.19 ester. The titanate ester and calcium carbonate were first dry blended under atmospheric conditions in a high shear dry blender. Add this filler to 2 roll mixer 1 middle 3
The mixture was mixed with polystyrene at a temperature of 0.07 T until complete mixing. The sheets were ground and the specific gravity and melt index were measured. The table above shows that treated filled polystyrene is more easily molded.

Unprocessed filled polystyrene has a melt index that indicates that it cannot be easily molded with conventional equipment. Example 18 This example demonstrates the use of isobutyltri(6-aminocaproyl) for the improvement of the properties of 50% clay-filled nylon 66.
Indicates the use of titanates.

50% by weight nylon 66, 49.8% by weight clay, and 0.2% by weight by blending the clay, titanate ester, and nylon 66 in a pair of screw extruders at 600 nm for 1 minute. titanate ester (
(as defined below).

After mixing is complete, samples are injection molded and physical properties are measured. These titanate esters, mainly isobutyltri(6-aminocaproyl) titanate, have the formula [(
C2H5XOH3)CHO]4-.

Tl[0C0(CH2)5NH2]. (However, n is 2.
8, 3, 4 and 3.7). The table below is
The properties of these 50% clay filled nylons are shown.

Chang↓VP口1 The above table shows that the flexural strength and tensile strength of 50% clay filled nylon are optimal when n=3.4.

This data shows that isobutyl tri(6-aminocaproyl) titanate ester, which also contains 3.4 moles of aminocaproyl groups, is effective in improving the strength of clay-filled nylon 66. The present invention is a method as described in the claims, but also includes the following embodiments.

(1) A method as claimed in the claims in which the organic titanate is reacted with the surface of the inorganic material prior to mixing with the polymeric medium.

(2) A method as claimed in the claims, in which the organic titanate is reacted in situ during mixing of the three components with the inorganic substance and the polymeric material.

Claims (1)

[Claims] 1 An inorganic substance has the formula Ti(OR)_4_-_n(OOO
R')_n (wherein R is an alkyl group having 1 to 5 carbon atoms, OOOR' is a group derived from an organic acid having 6 to 24 carbon atoms, and n is an average of 3 3.5) in a polymeric medium, thereby forming a dispersion of the reaction product of the inorganic material and the organic titanate in the polymeric medium. A method for producing a dispersion of a finely divided inorganic substance in a polymer, comprising: