JPH0545523B2 - - Google Patents

Description

[Detailed description of the invention]

Industrial Application Fields The present invention is useful as an additive for improving the physical properties of various synthetic resins, as a crosslinking, curing agent, and vulcanization accelerator in the production of synthetic resins and rubber, as well as in conductive materials, paints, and printing materials. This invention relates to a new type of zeolite composite containing inorganic and organic amines that is widely used as a quality improver for inks, pharmaceuticals, detergents, and other products, and a method for producing the same. Conventional technology Conventionally, zeolite composites include metal-substituted zeolites in which cations in zeolite are replaced with zinc ions or alkaline earth metal ions (Japanese Patent Application Laid-open No. 14542/1983), and zeolites containing amines or amine derivatives. It has been proposed (Japanese Unexamined Patent Publication No. 86436/1983) that contains a substance by infiltrating it. The metal-substituted zeolite is used as a stabilizer for halogen-containing resins, and the zeolite containing amines or amine derivatives is used to protect the surface of metal products from corrosion in the atmosphere. That is, the zeolite composites proposed above do not have diverse functions, as can be understood from the fact that they are used for limited purposes. Problems to be Solved by the Invention The purpose of the present invention is to provide a new type of zeolite composite having various functions, which can be used in a wide range of applications as described above. Zeolites have traditionally been used as molecular sieves and catalysts due to their physical properties derived from their structure and surface activity, and are also used as adsorbents due to their relatively high ion exchange properties and selectivity. Artificial zeolites have been synthesized for the purpose of improving the original specific properties of the above zeolites and are mainly used for each of the above applications.On the other hand, natural zeolites, which are abundantly produced in Japan, have a heterogeneous structure. However, it is not used effectively because it contains impurities. An object of the present invention is to enable not only synthetic zeolites but also natural zeolites in the above-mentioned situation to be effectively utilized as a composite having the various functions described above. The present invention will be explained in detail below. Structure of the Invention The characteristics of the inorganic and organic amine-containing zeolite composite according to the present invention are that amines or their derivatives are added to natural or synthetic zeolite, and Zn, Ba, Pb, Mg, Ca, Al, Sr, Sn,
Sb, Ti, Cd, Fe, Cu, Mn, Co, Ni, Pd, Pt,
It supports at least one component selected from the group consisting of Nh ₄ , B and PO ₄ . Incidentally, the above-mentioned composite of the present invention has a structure in which amines are added to the surface of the zeolite, and at least one of the above-mentioned components is supported in the form of a compound on the outer surface of the zeolite. Therefore, it can be said that the structure is essentially different from the conventional zeolite composite described above. Means for Solving the Problems In the present invention, the zeolites are A type, X type, Y type.
Synthetic and P-type zeolites as well as natural zeolites can be used, and by adding amines to each of these zeolites according to the following procedure, and then supporting at least one of the metal compounds and inorganic compounds, the objective can be achieved. A zeolite composite containing the following inorganic substances and organic amines (hereinafter referred to as the present zeolite composite) can be obtained. Production of the present zeolite composite: Each of the above zeolites with an average particle size of 0.5 to 2μ and a particle size distribution of about 0.1 to 10μ is dispersed in water or an inducing solvent, and then mixed with a homomixer, for example, with a particle size of 1000 to 13.
0.005 to 20 parts by weight, preferably 0.005 to 20 parts by weight, per 100 parts by weight of zeolite, is added to a slurry of approximately 1% to 90% by stirring at 000 rpm and one or more amines or amine derivatives. Add 0.1 to 5 parts by weight and react at a temperature of room temperature to 150° C. with stirring for about 10 minutes to 10 hours to obtain an amine adduct of zeolite. The amines used here include primary amines, secondary amines, tertiary amines, and quaternary ammonium salts, and primary amines include octylamine, laurylamine, stearylamine, and benzylamine. Examples include amines and their hydrochlorides, and secondary amines include dimethylamine,
Examples include diethylamine, and examples of tertiary amines include triethylamine and tributylamine. Furthermore, examples of the amine derivatives used here include hexaethylenetetraamine, cyclohexylamine carbonate, and the like. Incidentally, the organic solvent for dispersing the zeolite is preferably an inert one, such as hydrocarbon-based n-heptane, n-hexane, carbon tetrachloride, petroleum hydrocarbon-based byproducts, and even dioctyl phthalate and diethylhexyl. Plasticizers for synthetic resins such as adipate, polyethylene glycolate, and tricresyl phosphate may also be used. Next, the amine adduct of the zeolite obtained as described above is mixed with each of the above-mentioned water-soluble salts of metals or ammonium, or metal oxides, or phosphates and borates in water or an alkaline or acidic medium. One or more types and room temperature to 150℃
The reaction is carried out under stirring at a temperature of 30 minutes to 48 hours. Water-soluble salts of metals used here include chlorides,
Borate, acetate, or hydroxide forms may be exemplified, and as the phosphate, ortho, acidic, sesquiphosphate, etc. may be used. The reaction between the amine adduct of the zeolite and each of the metal, ammonium, B or PO ₄ compounds is carried out by an ion exchange reaction with the cations in the zeolite and a coprecipitation phenomenon. It is thought that the body can be obtained. The amounts of these metals, ammonium, B, and PO ₄ added to the zeolite are determined by the following formula () x (H ⁺ ₂・M ⁺ ₂・M ²⁺ )・O・Al ₂ O ₃・ySiO ₂・zH ₂
O () (in the formula, H is hydrogen, _M2 is an alkali metal, M is an alkaline earth metal, x is 0.5 to 1.5, y is 1.5
~5.0, z represents 0 to 12) In order to replace part or all of the hydrogen, alkali metal, and alkaline earth metal represented by H ⁺ , M ⁺ ₂ , and M ²⁺ in the zeolite, the above-mentioned 0.2 to 2.5 for x in equation
The molar substitution equivalent is used. Note that when two or more of the above metals, ammonium, B, and PO ₄ compounds are used in the reaction, the reaction is preferably carried out in multiple stages under similar conditions. In addition, when considering the reaction mode mentioned above, it is explained as follows. When the zeolite of the above formula () is reacted with the above-mentioned organic amine, ammonium salt or their derivatives, [x(H ⁺ ₂・M ⁺ ₂・M ²⁺ )・O・Al ₂ O ₃・ySiO ₂・
^zH _{2 O ] A}

【formula】 【formula】

A compound represented by the formula (R, R', R'' and R represent an alkyl group or an aralkyl group, and X represents a halogen) is produced, and then the compound is reacted with the metal ion or inorganic ion listed above. and,
Due to the ion exchange reaction, the formula [xM′nO・Al ₂ O ₃・ySiO ₂・zH ₂ O]・A (where M′ is Zn, Ba, Pb, Mg, Ca, Al,
Sr, Sn, Sb, Ti, Cd, Fe, Cu, Mn, Co, Ni,
The present zeolite complex is obtained, represented by a metal or ammonium salt selected from the group consisting of Pd, Pt, H ₃ PO ₄ , H ₃ BO ₃ etc., where n represents an integer. In addition, when the above compounds obtained by adding the above amines and amine derivatives are reacted with water-soluble salts or oxides of the above metals to coprecipitate, the formula [x(H ⁺ ₂・M ⁺ ₂・M ²⁺ )・O・Al ₂ O ₃・ySiO ₂・
A]・M′(OH) ₂ or [x(H ⁺ ₂・M ⁺ ₂・M ²⁺ )・O・Al ₂ O ₃・ySiO ₂・
A]・M′O(OH) (H, M ₂ , M, x, y, A and M″ in the formula have the same meanings as above) is obtained. As described above. The obtained zeolite composite is dehydrated by filtration or centrifugation, and then dried or calcined at a temperature of 40°C to 800°C to be used as a solid content.The above composite can also be mixed with water or water depending on the purpose. It may be used as a suspension using an organic solvent as a medium, and may also be used with the addition of cationic, anionic, or nonionic surfactants, soda carbonate, Glauber's salt, etc. It is also possible to add and use various organic and inorganic additives.The present invention and its effects will be specifically explained with reference to Examples below.Example 1 This example is based on the present invention. This is an example of the production of a zeolite composite. Naturally produced clinoptilolite type zeolite with an average particle size of 2μ (particle size distribution 0.5 to 10μ, Corta counter method) is dispersed in water to make a 50% slurry liquid. 1.26 g of laurylamine hydrochloride was added to 178 g, and the mixture was stirred at room temperature to 70°C for 30 minutes using a Momo mixer (13000 rpm). A 2% caustic soda solution was added to the resulting mixed slurry (amine adduct). Add phenolphthalein solution until colored,
Next, 6.80 g of anhydrous zinc chloride dissolved in 500 ml of water was gradually added, stirred at 3000 rpm for 6 hours, and then centrifuged to obtain the zeolite composite as a solid. The obtained solid content (yield: 96 g) was dried at 100 °C for 24 hours using a constant temperature dryer (referred to as sample A), and that dried at 250 °C until it reached a constant weight (referred to as sample B). Thermal analysis (TG
As a result, there was almost no difference between the residual water of crystallization between the two. Also,
In this complex, Zn was found to be 5.2% when analyzed by atomic absorption spectrometry.
%, and the IR method (1410cm ^-1 , -CH
−, deformation−, 2850cm ^-1 , 2920cm ^-1 , −CH ₂
-, stretching criteria) laurylamine 1
% was detected. In addition, for each complex (referred to as samples D and E, respectively) produced by the same procedure as above except that the amount of laurylamine hydrochloride was increased to 2.52 g and 3.78 g in the above production example, 1410 cm ^-1 and 2850 when detected by IR method, respectively
A proportional increase in absorption at cm ^-1 and 2920 cm ^-1 was observed. Furthermore, Znn was measured by atomic absorption spectrometry of a composite (referred to as sample C) produced by the same procedure as above except that the amount of zinc chloride anhydride was doubled (13.60 g) in the above example. The content was 12.8%. According to the results of X-ray diffraction of this complex,
It was confirmed that the skeleton of the zeolite clinoptilolite remained intact. Example 2 A-type sodium zeolite (Mizusawa Chemical) 100g
was dispersed in 1500 ml of water, 3.6 g of laurylamine hydrochloride was added, and then a 2% NaOH solution was added until it was colored with phenolphthalein, and the mixture was stirred at room temperature to 90°C at 12000 rpm using a homomixer. did. Next, this is further added with zinc nitrate hexahydrate.
A solution of 150g of 1 dissolved in water was added, and the reaction was allowed to proceed for 3 hours at room temperature to 90°C with stirring (3000 to 6000r.pm), and the resulting reaction product was then centrifuged (2000rpm) to reduce the solid content. Separate, collect and incubate at 100℃ for 24 hours.
The mixture was dried to a constant weight over time to obtain 109 g of this composite. The Zn content of this composite was determined to be 19.5% (dry matter) by atomic absorption spectroscopy, and the laurylamine content was determined to be 1410 cm ^-1 , 2820 cm -1 , 1950 cm ^-1 by infrared absorption spectroscopy.
It was about 2% lower than cm ^-1 . Example 3 Type A zeolite 100 similar to that used in Example 2
g was dispersed in 2000 ml of water, 2.4 g of laurylamine hydrochloride was added thereto, and the 2% NaOH solution was adjusted to pH 9.
The mixture was added until the temperature reached 100.degree. C., and the mixture was reacted at room temperature to 70.degree. C. for 1 hour. Next, 24 g of zinc nitrate hydrate was added to this reaction product.
Add a solution of 30 g of calcium chloride hydrate dissolved in 2000 ml of water, and stir at room temperature to 90°C (3000 to
6000r.pm) for about 6 hours to form this complex 119
I got g. The Zn content of the obtained composite was 5.92% (atomic absorption spectrometry), the Ca content was 3.86%, and 1% laurylamine was detected (infrared absorption spectroscopy). Example 4 100g of A zeolite was dispersed in water from step 2, 2g of diethylamine was added thereto, and the mixture was heated at room temperature for 30 minutes.
A 2% caustic soda solution was added to the dispersion obtained by stirring at 60°C (8000 rpm) to adjust the pH to 9.0.
Next, a mixed aqueous solution of zinc nitrate and barium chloride [Zn(NO ₃ ) ₂・6H ₂ O 32 g + BaCl ₂・2H ₂ O 50 g/
] and stirred at room temperature (3000r.pm).
Allowed time to react. The resulting reaction product was filtered to separate and collect the solid content, washed with water, and vacuum dried at 60°C for 24 hours to form the composite.
Obtained 135g. This composite was found to contain 15.4% Zn and
It was confirmed that it contained 12.1% Ba, and about 1.9% diethylamine based on the infrared absorption spectrum at 1450 cm ^-1 . Example 5 This example shows the production of a zeolite composite supporting various metals and inorganic components. In Example 1, instead of zinc chloride, lead nitrate,
A composite was produced in the same manner as described in Example 1, except that magnesium chloride, aluminum chloride, strontium nitrate, stannous chloride, antimony trichloride, cadmium acetate, orthoboric acid, orthophosphoric acid, and ammonium chloride were used, respectively. did.
As a result of absorbance analysis of each of the obtained complexes, it was confirmed that each of the metals as well as NH ₄ , B, and PO ₄ were contained. Also, 1250cm ^-1
A specific wavelength of laurylamine was detected by infrared absorption spectrum at ~1450 cm ^-1 . Furthermore, each metal is PbO, MgO, CdO, BaO,
It was also found that when oxides such as ZnO were used, a composite was obtained in which an amine was added to the zeolite and each of the metals and inorganic compounds listed above were supported. Example 6 This example shows test results for each of the composites obtained in Example 1, samples A, B, C, D, and E, when each was used for rubber vulcanization. Test method A rubber composition was prepared using the following formulation. SBR (styrene-butadiene rubber) 1500
...100 (parts by weight) Stearic acid (NOF Corporation) ...1 Vulcanization accelerator (DM) ...1.5 〃 〃 (TT) ...0.2 Sulfur ...2.0 This composite sample ...50 Diethylene glycol ...2 In the above formulation, DM represents dibenzothiozyl disulfide, and TT represents tetramethylthiuram disulfide. As a comparative example, silicic anhydride was used instead of this composite.
Using 50 parts by weight, zinc oxide (Mitsui Kinzoku 3
No.) 5 parts by weight was used as a sample. Each sample consisting of the above formulation was made into a sheet at 100℃ using a 6-inch mixing roll, and then
The sheets were pressed at 150° C. and 50 kg/cm ² for 30 minutes to form a sheet with a thickness of 1 mm, and the tensile strength, elongation and hardness of each sheet were measured by conventional methods. The results are shown in Table 1.

[Table] As shown in Table 1, each sample according to the present invention exhibits excellent crosslinking effects as a processing aid in rubber processing and excellent effects as a vulcanization aid. Effects of the Invention As shown in the above examples, the zeolite composite containing inorganic substances and organic amines according to the present invention reacts with various natural and synthetic zeolites with organic amines, quaternary ammonium salts, or derivatives thereof. and then various metals and B or
It can be easily produced by reacting with PO ₄ compounds. The composite thus obtained can be used as a compounding agent in the processing of rubber or plastic, and exhibits good lubricity to prevent roll separation, as well as good crosslinking promotion effects due to amines and promoter effects due to metals. In addition, oxidation resistance, aging resistance,
It has the effect of improving weather resistance and further improving physical properties such as tensile strength, hardness, and elongation.

Claims (1)

[Claims] 1. An amine compound, a quaternary ammonium salt, or a derivative thereof is added to a natural zeolite or a synthetic zeolite, and Zn, Ba, Pb, Mg,
Ca, Al, Sr, Sn, Sb, Ti, Cd, Fe, Cu, Mn,
A zeolite composite containing inorganic substances and organic amines and supporting at least one component selected from the group consisting of Co, Ni, Pd, Pt, NH ₄ , B and PO ₄ . 2 Natural zeolite or synthetic zeolite, in water or an organic solvent, one or two selected from the group consisting of primary amines, secondary amines, tertiary amines, quaternary ammonium salts, and derivatives thereof. Zn, Ba, Pb, Mg, Ca, Al,
Sr, Sn, Sb, Ti, Cd, Fe, Cu, Mn, Co, Ni,
Production of a zeolite composite containing inorganic substances and organic amines characterized by reacting and supporting at least one compound selected from the group consisting of Pd, Pt, NH ₄ , B and PO ₄ Method. 3. The production method according to claim 2, wherein the reaction of adding amines or their derivatives to zeolite is carried out at a temperature of room temperature to 150°C with stirring for 10 minutes to 10 hours. 4. The manufacturing method according to claim 2, wherein the reaction of supporting the metal or inorganic component compound on the amine adduct is carried out in one to several stages at a temperature of room temperature to 150°C for 20 minutes to 48 hours. . 5. The manufacturing method according to claim 2, wherein the metal component compound is in the form of a chloride, salt, hydroxide, or oxide. 6. The manufacturing method according to claim 2, wherein the inorganic component compound is in the form of a borate or a phosphate.