JPS625948B2 - - Google Patents

Description

[Detailed description of the invention]

The invention generally relates to the use of particulate crystalline materials for functional applications to improve or enhance the physical and aesthetic properties of simple polymer compositions, polymer alloys, and polymer and ceramic compositions or alloys. and/or amorphous fillers/extenders and pigments. The present invention generally relates to any inorganic particulate extender/filler/pigment material whose surface or fracture surface is terminated with ions, which represent a typical solid consisting of a three-dimensional continuous atomic lattice. As long as it is interrupted at the end faces and fracture surfaces, it is unsaturated and has a free valence. Regarding this, please refer to the following. (1) Eyler's "The Colloidal Chemistry of Silica and Silicates" (Cornell University Press, New York, 1955, p. 258), (2) Angewante Chemie International Edition, Volume 5, No. 6, 1966 June, page 533. In commercial and industrial applications of simple compositions and alloy compositions of polymer compositions and ceramic compositions, the compositions used may be any (or both or all) of fillers, pigments, and fibrous substances. It is very often desirable to include Inert reinforcing and non-reinforcing fillers, extenders and pigments are
For polymer compositions/polymer alloy compositions,
tensile strength, impact strength, tear resistance, and dielectric constant,
Despite its obvious contribution in physical, chemical and electrical properties such as dielectric breakdown strength,
To make it cheaper and easier to process. Many polymeric compositions that are virtually unusable on their own are combined with suitable particulate and/or fibrous fillers/
By using appropriate amounts of filler pigments it can be transformed into a highly useful and artistic product. The effect of the extender/filler particulate or fibrous pigment materials depends on their nature, the combination of polymers or ceramic compositions, and the actual amount of particulate or fibrous extender/filler pigment present in the combined mixture. (depending on filler addition concentration and/or pigment volume concentration). The presence of unsaturated surface ions on surfaces exposing free unsaturated valences, fractured surfaces or amorphous surfaces can modify the surface functionality of particulate, fibrous or amorphous extenders/fillers/pigments. to increase the reactivity and thus increase the reactivity of the polymer or
Ceramic matrix and two-dimensional and three-dimensional bonding, i.e. polymer/granules, polymer/
Many attempts have been made to create dual and triple surfactants of either or all particulates/fibers. Early studies encouraged the proposition that such modifications might be accomplished using silane coupling agents.
The above documents are referred to. R.L. Kass et al., “Interaction of Alkoxy Silane Coupling Agents with Silica Surf Aces,” Polym, Eng.Sci.197111(1), 11.
18; ML Hare et al.'s “Reactions of
"Chlorosilanes with Silica Surfaces" J.Phys.Chem.1969, 73(7), 2372-8;
Agent as Integral Blend
Inresin-Filler Systems” Modern
Plastics July 1963, 125-138. Reference may also be made to U.S. Pat. No. 3,660,134 (Morris); U.S. Pat. No. 3,948,676 (Laufer); U.S. Pat. , the present invention stands out as a useful, novel and distinct advance thereto. The widespread commercial use of particulate, fibrous, and amorphous filler/extender pigments modified with silanes, isopropyl titanate congeners, and glass resins is relatively costly and poorly understood. This has been delayed due to the current lack of effective general-purpose manufacturing techniques or the variable effectiveness of those techniques. The main object of the present invention is therefore to provide a method for modifying the surface functionality of hydrophilic, particulate, crystalline and/or amorphous mineral materials, which was not available in the prior art. The object of the present invention is to provide a very simple, economical and highly efficient method, whereby these materials can be used in polymeric compositions,
It is readily available and eminently suitable for use as a reinforcing filler/extending pigment in polymer alloy compositions and polymer/ceramic alloy compositions. For this purpose, bifunctional or unilateral coupling agents such as silane coupling agents, isopropyl titanate coupling agents and/or their homologs, and glass resin thermoset silicone coupling agents (siloxane chains with selected OH groups) are used. 0.01 to ambi- or monofunctional treatment agents
5.0% by weight, approximately 21.1℃ ~ 176.7℃ (70〓 ~ 350
Spraying or pouring onto essentially dry hydrophilic particulate crystalline or amorphous filler/extender pigments, stirred alone or in combination in an intensive mixing device at a temperature of achieved by
And the drawbacks of the conventional method are avoided. Particulate crystalline and/or amorphous inorganic materials, and silane coupling agents, either bifunctional or monofunctional, and/or isopropyl, either of the bifunctional or monofunctional type. titanate coupling agent and/or selected
A glass resin thermosetting siloxane coupling agent in a supporting solution of either double- or single-functionality, which is a purified siloxane chain with OH groups, from about 21.1°C to about 176.7°C (70〓 to 350°C) 〓) Leave in contact at the same temperature for at least 1 minute. Particularly advantageous results are obtained when: (a) the particulate crystalline and/or amorphous inorganic material is ionic and/or
Inorganic substances terminated with unsaturated surfaces as reactive hydroxyl functionalities (on this point see: (1) Eyler, The Colloidal Chemistry of Silica and Silicates, Cornell University Press, New York, 1955) Page 258; and (2)
Angewante Hemy International Edition,
5, No. 6, June 1966, p. 533); and (b) a silane coupling agent that is either bifunctional or unifunctional; and/or a silane coupling agent that is bifunctional or Isopropyl titanate coupling agents of either the monofunctional type are substances with only a single hydrolyzable group (monofunctionality), or with one hydrolyzable group and each of the general formula: It is a substance that has both reactive n-Si-X ₃ , R-Si-X ₃ and one functional group having non-reactive 〓-Ti-X, and this non-reactive n can be thermally and hydrolyzed. R is a group such as a single or multiple methyl group bonded to silicon in _a thermally and hydrolytically stable manner, and It is a hydrolyzable group with an alkoxy structure, and active or non-reactive R ⁿ ₃ is a triisostearate group.

and its homologs, bonded to titanium in a thermally and hydrolytically stable manner, where X is a single hydrolyzable group, and a glass resin thermosetting silicone coupling agent. is a purified bifunctional or monofunctional organosilsesquioxane oligomer such that it is a siloxane chain with OH groups selected from more complex silanes. According to the method of the present invention, the particulate crystalline and/or amorphous inorganic material is a solid known as a filler/extender pigment, including both high and low aspect ratios. The term high or low aspect ratio is also known as l/d ratio, i.e. grainy, crystalline and/or
It is the length of the amorphous solid filler/extender pigment divided by the diameter. The bifunctional or monofunctional silane coupling agent used in the process of the invention is advantageously an organosilicon compound having the general formula R--SiX;
In the formula, R is a group bonded to silicon so as to be thermally and hydrolytically stable, and R is aliphatic, cycloaliphatic, amino, polyamino, mercapto, methacrylo, glycidoxy, epoxy, vinyl, aminopropyl, mercaptopropyl, methacrylopropyl, methacrylo-oxypropyl, glycidoxypropyl, epoxypropyl, chloroalkyl, and epoxycyclohexyl, and X is selected from chlorine, bromine, iodine, alkoxy, and acetoxy. It is a hydrolyzable group. The bifunctional or monofunctional isopropyl titanate coupling agent used in the process of the invention is advantageously an organotitanium compound having the general formula R ₃ -TiX, where R is thermally and hydrolytically R is a group selected from the group consisting of isostearoyl, lauryl myristyl, isopropyl, dimethacrylic, triacroyl, dodecylbenzenesulfonyl, diacryl, diisooctyl-phosphate, and X is It is a hydrolyzable group with a monoalkoxy structure. The bifunctional or monofunctional glass resin thermosetting silicone coupling agent used in the process of the invention is advantageously an organosilsesquioxane oligomer containing ladder-shaped siloxane chains. Bifunctional or unifunctional silane coupling agents, and/or bifunctional or unifunctional isopropyl titanate coupling agents,
According to the invention, the interaction of a glass resin thermosetting silicone coupling agent in a supporting solution of the bifunctional or monofunctional type, and/or purified siloxane chains with selected OH groups , by spraying or pouring liquid silanes, titanate analogs or glass resins onto particulate crystalline and/or amorphous inorganic materials while stirring them in a high-intensity stirring device. achieved. Solutions and/or diluents such as n-heptane are not present in the method of the invention;
In other words, this method is not a "slurry mixing" method but a "dry mixing" method. Moreover, the present method involves methods in which particulate, crystalline and/or amorphous inorganic materials are simply rolled over while liquid silane, titanate congeners or glass resin reagents are poured onto them. are distinguished. In the present invention, granular, crystalline and/or amorphous inorganic materials are subjected to intensive agitation by means of "high-intensity" mixing equipment, many of which are used for large-scale mixing operations. Commercially available. The "high-intensity" mixing detailed by the method of the present invention is illustrated by the employment of an apparatus consisting of a single mixing chamber, mixing impellers, and a disk 1 to 2 feet in diameter. However, these vanes or disks are attached to a single shaft passing through the chamber and have a diameter of 200-18,000.
Driven at 100 times per minute. Very advantageously, the frictional heat generated in the particulate, crystalline and/or amorphous inorganic material by such intensive agitation is absorbed by the liquid silane, titanate congener or glass resin and the particulate. It is used to carry out reactions between crystalline and/or amorphous inorganic substances. In other words, the circumferential speed of the stirring blade or disk is a function of the shaft rotation speed per minute and the diameter of the blade or disk, while the circumferential speed and stirring time depend on the speed of the granules and crystals being stirred. The temperature of the granular, crystalline and/or amorphous mineral material being stirred is directly related to the 21.1℃~Approx. 176.7℃ (Approx. 70〓~Approx.
Consideration has been given to achieving a temperature of 350〓),
Thereafter, liquid silane, titanate congeners, or glass resin reagents are sprayed or poured onto them. Of course, additional heating from an external source may be applied if desired for any reason, but the temperature of the stirred solids should be between about 70°C and about 350°C (70°C to about 350°C) before adding the treating agent. Care must be taken to ensure that 〓). The treatment agent selected from the group consisting of liquid silane coupling agents, titanate congeners and glass resin thermosetting silicone coupling agents is a granular, crystalline and/or amorphous inorganic solid that is vigorously agitated. on top of the treatment agent in an amount sufficient to provide from about 0.01 to about 5.0% by weight, based on their weight, of the treatment agent. Below this amount no particulate, crystalline and/or amorphous modified mineral material is produced, and above this amount no additional improvement is provided. The silane coupling agent, titanate congener, or glass resin thermosetting silicone coupling agent and the particulate, crystalline and/or amorphous inorganic material are then combined, preferably under vigorous stirring, at a temperature of about 21.1°C. about
at a temperature of 176.7°C (approximately 70°C to 350°C) for at least about 1 minute, preferably at least about 5 minutes,
The reaction between the liquid silane, titanate congener, or glass resin and the particulate, crystalline and/or amorphous inorganic material is maintained in intimate contact so that the reaction is essentially complete. Once the reaction is complete, the particulate, crystalline and/or amorphous modified inorganic material is cooled and removed from the mixing chamber for use in enhancing the properties of the polymer composition. In the practice of this invention, a silane coupling agent, either bilaterally functional or unilaterally functional; and/or an isopropyl titanate coupling agent, either bilaterally or unilaterally functional;
and/or when using a glass resin thermoset silicone coupling agent, either bifunctional or monofunctional, which is a purified siloxane chain with selected OH groups in a supporting solvent, at least about It has been found to be particularly advantageous to use a reaction temperature of about 300° C. for at least about 1 minute. Undesirable agglomeration of particles of granular, crystalline and/or amorphous mineral substances, which can generally occur when these liquid silanes, titanate complexes or glass resins are used, is thereby avoided. , and a finely divided homogeneous product is produced which is highly effective and completely acceptable as a reinforcing filler in polymeric ceramic compositions. For example, this technique can be used when one or more of the following commercially available silanes are utilized: gamma-glycidoxypropyltrimethoxysilane, aminotrimethoxysilane, and polyaminotrimethoxysilane. Especially applicable. Thermoplastic, thermosetting, and elastic polymer compositions (such as polyvinyl chloride, room temperature curing epoxy resins, and diallyl phthalate resins)
The physical, chemical, and electrical properties (e.g., flexural strength, moisture and chemical resistance, and dielectric constant) of Significant enhancement was achieved by the addition of about 5 to 75% by weight of particulate crystalline and amorphous mineral material, modified using standard methods. These results demonstrate that (a) unmodified, particulate, crystalline and/or amorphous inorganic materials; (b) silane coupling agents, titanate congeners, according to "slurry kneading" methods well known in the art; , or a silane coupling agent, either bifunctional or monofunctional, modified with a glass resin coupling agent, and/or an isopropyl titanate coupling agent, either bifunctional or monofunctional, and ( or) a glass resin thermoset silicone coupling agent in a carrier solution, either double- or single-functional, which is a purified siloxane chain with selected OH groups; and (c) a "dry method" known in the art. This is particularly striking when compared with the results obtained using particulate, crystalline and/or amorphous mineral materials modified with silane according to the "rolling" method. Example 1 Product Processed 454 kg of titanium dioxide, either rutile by the sulfuric acid process or the chlorine process, with an average particle size of approximately 0.06 to 0.25 microns.
(1000 pounds). Treatment Agents Used Methyltrimethoxysilane coupling agent, experimental CH ₃ Si (OCH ₃ ) ₃ mixer Myers Engineering 550 Series Dual Range Dispenser with mixing tank and other convenient and necessary accessories. A quantity of titanium dioxide weighing 454 kg (1000 lb) is placed in a mixing tank. After adding this titanium dioxide, the temperature is approximately 22.2℃ (72〓). Place the lid on the tank. Switch on a single speed high speed shaft fitted with a mixing disc. Next, set the maximum speed to 10 on the variable speed slow shaft with vanes and turn on the switch. After the temperature of the titanium dioxide agglomerate in the tank reached approximately 60℃ (140℃), the single-speed high-speed axis was stopped, while the slow-speed axis was set to 10. Let it operate. Then about 4.54
Kg (10 lbs) of methyltrimethoxysilane,
Through a 1/2 inch tube under a portable storage tank with legs and through an opening in the tank lid, a bed of titanium dioxide being stirred by a slow shaft operating at a setting of 10. fed by gravity inside.
Approximately 4.54 Kg (10 lbs) of methyltrimethoxysilane was dumped from the storage tank onto and into the agitated mass of titanium dioxide, then the aperture in the tank lid was closed and the single-speed high-speed axis Turn on the switch immediately. When the stirred mass of titanium dioxide reaches a temperature of approximately 148.9°C (300°C) as measured by a probe thermometer, the hydrophobization process is considered complete and the shaft is turned off. The treated material is then removed from the tank by a screw conveyor and lifted by a bucket elevator to a storage area from where it is packaged into multi-walled bags or other suitable containers by an air fluidized packaging machine. The treated titanium dioxide in this example is used as a non-water wicking masking pigment dispersed in solvent-based coating systems or electrostatic dry coating powder formulations well known in the art.
One immediate advantage of this type of surface-treated titanium dioxide is its significantly improved non-cohesive dry dispersion performance in electrostatic dry coating powder systems of various polymers. Another direct advantage of this hydrophobized titanium dioxide in solvent-based, hydrocarbon-based systems is that it does not wick moisture into the composition due to its hydrophobicity. Example 2 Product Treated Approximately 454 Kg (1000 lbs) of aluminum trihydrate with an average particle size of 0.38 to 8.5 microns and a surface area of 1 to 15 m ² /g. Treatment agent used Gamma mercapto-propyltrimethoxysilane coupling agent - experimental HSCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ Mixer Myers Engineering 550 dual with mixing tank and other convenient and necessary accessories range dispenser. An amount of aluminum trihydrate weighing approximately 454 Kg (1000 lbs) is placed in a mixing vessel. After adding aluminum trihydrate, the temperature is approximately 21.1℃ (70℃).
〓). Place the lid on the tank. Switch on the single speed high speed shaft with mixing disc.
Next, set the maximum speed to 10 on the variable speed slow shaft with vanes and turn on the switch. Switch on both shafts and after the temperature of the aluminum trihydrate lump reaches 60℃ (140℃), the single speed high speed shaft is stopped, while the slow speed shaft is set to 10 and activated. I'll keep it. Next, place approximately 4.54 Kg (10 lb) of gamma mercapto-propyltrimethoxysilane in a approximately 1/2 cm (1/2
(inch) tube through an opening in the tank lid and directly by gravity into a bed of aluminum trihydrate that is stirred by a slow shaft operating at a setting of 10. do. Approximately 4.54 kg (10 lb) of gamma mercapto-propyltrimethoxysilane was poured from a storage tank onto and into the agitated aluminum trihydrate, and the opening in the tank lid was closed.
Then immediately switch on the single speed high speed axis. The process is considered complete and the shaft is turned off when the stirred mass of aluminum trihydrate reaches a temperature of about 148.9°C (300°) as measured by a probe thermometer. The treated material is then removed from the tank by a screw conveyor, lifted by a bucket elevator into a storage area, and from there transported by a Ramu air-fluo packer to a multi-walled bag or other suitable container. packaged inside. The aluminum trihydrate treated in this example is used as a processing aid and particulate reinforcement for foamed plastic pipes and other types of elastic foams of various densities. The surface-treated aluminum trihydrate is also useful in non-foamed, higher density elastomers based on various polymers in which mercapto functionality is chemically bonded at the interface between the matrix and the granules. It will perform similarly. Example 3 Product processed 99% is below 10 microns and 25%
Cryptocrystalline quarts (diatomaceous earth) with a diameter of 1 micron or less
Approximately 681Kg (1500 lbs) Processing Agents Used Gamma Amino-Propyl-Triethoxy-Silane Coupling Agent - Empirical H ₂ NCH ₂ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ Mixer Mixing Tank and Other Conveniences Myers Engineering 550 Series Dual Range Dispenser with the necessary accessories. A quantity of latent crystalline quartz (diatomaceous earth) weighing approximately 681 kg (1500 lbs) is placed in a mixing tank. After adding the latent crystalline quartz, the temperature is approximately 21.1℃ (70〓). Place the lid on the tank. Then switch on the single speed high speed axis with the disc. Next, set the maximum speed of the variable speed shaft with vanes to 10 and turn it on. 51/2 minutes after turning on both axes, the temperature of the latent crystalline quartz (diatomaceous earth plate) is 60℃ (140℃) as measured with a probe thermometer. Immediately activate the single speed fast axis and meanwhile lower the slow axis to the 1 setting. Next, about 6.81Kg
(15 lbs.) of liquid gamma amino coupling agent approximately 1.27 cm (1/2 cm) below a portable, footed reservoir.
2 inch) tube through an opening in the vessel lid and directly by gravity onto and into the latent crystalline quartz being stirred by both the fast and slow shafts. After emptying approximately 6.81 kg (15 lbs.) of gamma amino coupling agent from the reservoir onto and into the agitated mass of latent crystalline quartz (diatomaceous earth), the opening in the tank lid was closed; Immediately increase the slow axis to setting 10. After 381/2 minutes after starting operation of both the single-speed fast axis and the variable slow-speed axis, the probe thermometer read approximately 148.9°C.
(300〓) reached. This process is considered complete and the axis is stopped.
This treated material is then removed from the tank by a screw conveyor, lifted by a bucket elevator into a storage area, and packed into multi-walled bags or other suitable packaging by an air fluidized packaging machine. Pack into containers. The treated latent crystalline quartz (diatomaceous earth) in this example is used as a reinforcing extender/filler in molded or extruded nylon, where it is subjected to physical stress such as bending, tensile and thermal strain. Properties are improved compared to unfilled nylon. This latent quartz (diatomaceous earth)-filled nylon also shows that unfilled nylon exhibits poorer physical properties after both filled and unfilled nylons are exposed to long-term moisture saturation conditions. However, it maintains good physical properties.

Claims (1)

[Claims] 1 (a) Silane coupling agent, general formula R ₃ -TiX
A titanate coupling agent having the formula (wherein R
is a group bonded to the titanium in a thermally and hydrolytically stable manner and X is a hydrolyzable group), and a glass resin thermosetting silicone coupling agent in a carrier solution. on an essentially dry hydrophilic inorganic solid selected from the group consisting of particulate crystalline inorganic solids and particulate amorphous inorganic solids, excluding microcrystalline novaculilite. based on the weight of the inorganic solid.
Spraying or pouring in an amount of 0.01 to 5% by weight, and establishing contact between the treatment agent and the inorganic solid, using one mixing chamber and multiple units contained therein driven at 200 to 18,000 times/min. While stirring the inorganic solid in a powerful mixing device consisting of mixing blades,
(b) treating the treating agent and the inorganic solid at a temperature of about 21.1°C to about 176.7°C (about 70°C to about 350°C);
at least about 1 at a temperature of ℃ (about 70〓 to about 350〓)
1. A method for making an improved modifier for both polymeric and ceramic compositions, the method comprising: leaving in place for a minute. 2. The method according to claim 1, wherein frictional heat generated in the inorganic solid by an intensive mixing device is used to cause a reaction between the processing agent and the inorganic solid. 3 (a) The silane coupling agent is a bifunctional or monofunctional organosilicon compound having the formula R-SiX ₃ , where R is a group bonded to silicon in a thermally and hydrolytically stable manner. and R is aliphatic, cycloaliphatic, aromatic, amino, polyamino, mercapto, methacrylo, glycidoxy, epoxy, vinyl, aminopropyl, mercaptopropyl, methacrylopropyl, methacrylooxypropyl, glycidoxypropyl , epoxypropyl, chloroalkyl, and epoxycyclohexyl, X is _a hydrolyzable group selected from chlorine, bromine, iodine, alkoxy and acetoxy, ―TiX
is a bifunctional or monofunctional organic titanium compound having R is a group bonded to titanium so as to be thermally and hydrolytically stable, and R is isostearoyl, lauryl-myristyl, isopropyl, dimethacrylic, selected from the group consisting of triacryloyl, phosphite, dodecylbenzenesulfonyl, diacryl, diisooctylphosphate, 4-aminobenzenesulfonyl, and dioctylpyrophosphate, where X is a hydrolyzable group having a monoalkoxy structure, and (c ) the glass resin thermosetting silicone coupling agent is an organosilsesquioxane oligomer with a bifunctional or monofunctional structure containing ladder-shaped siloxane chains, and (d) the hydrophilic inorganic solid is a three-dimensional periodic atomic structure. 2. The method of claim 1, wherein the representative structure includes at least a portion where the array of patterns is interrupted at the solid surface. 4. The method of claim 3, wherein the surface of the hydrophilic inorganic solid contains reactive hydroxyl functionality.