JPS6138206B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a low-viscosity extender, and more specifically, the present invention relates to a method for producing a low-viscosity extender, and more specifically, 180 to 210% of the residual oil by-produced during the synthesis of phenols via hydroperoxide.
This is a method for producing a low viscosity extender for synthetic resins, which comprises polymerizing a by-product oil having a boiling point range of .degree. C. in the presence of activated clay or a Friedel-Crafts catalyst. The filler used here refers to a material used in combination with a synthetic resin to lower the viscosity of a resin compound, improve handling workability, or improve chemical properties such as water resistance, chemical resistance, and even physical resistance. is a general term for those whose bending resistance, impact resistance, tensile strength, elongation tear strength, etc. can be modified as appropriate depending on the use of the main resin. Conventionally, the most well-known fillers are bituminous substances such as coal tar, coal tar pitch, asphalt, and gilsonite, but other materials used for dilution include phthalates such as dioctyl phthalate and dibutyl phthalate. Acid esters, benzoic acid esters such as ethylene glycol dibenzoate and propylene glycol dibenzoate, adipic acid derivatives such as dicapryl adipate, phosphate triesters such as tributyl phosphate, trioctyl phosphate, and tricresyl phosphate, ethylene In addition to polyglycols such as glycol and polypropylene glycol, styrene oxide, allyl glycidyl ether, phenyl glycidyl ether, butyl glycidyl ether, versatate glycidyl ester, and the like are known as reactive diluents especially for epoxy resins. Such extenders are generally blended into the main synthetic resin together with inorganic fillers, pigments, and sometimes solvents, etc., and these compounds are used for various purposes such as paints, flooring materials, sealants, and waterproofing materials. The main objectives of adding fillers are to lower the viscosity and improve workability, lower the price, and improve the physical properties. However, when using such a formulation, if the amount of filler used is increased in order to improve workability, the physical strength and chemical properties of the resulting coating film will be impaired, and furthermore, the weather resistance and durability will be reduced. On the other hand, if the amount of filler used is reduced, the viscosity of the compound will generally increase, depending on the type of resin used, and handling and workability during work will be poor. In that case, the workability is improved by diluting with a large amount of organic solvent. However, in recent years, air pollution due to the emission of organic solvents has become a problem, and there has been a strong demand for formulations such as non-solvent type formulations that do not use any solvent or solventless type formulations that use only a small amount of solvent. However, in order to improve the workability of the formulation without using solvents, the extender used must have as low a viscosity as possible, and even when the cured coating of the formulation is used on exposed surfaces, Volatile components from the paint film must be kept as low as possible. This is because if there are a lot of volatile components, they will evaporate from the exposed surface during long periods of use, causing problems with air pollution, and of course, shrinkage from the surface will cause cracks, etc. This is because the original performance cannot be exhibited, and a practical coating film suitable for each application cannot be obtained. Based on these facts, the present inventors have improved the workability during construction of resin compounds when used as extenders for epoxy resins or urethane resins in synthetic resins, etc., and have improved the resulting cured coating film. The present invention was developed as a result of efforts to produce extenders that provide light resistance, flexibility, impact resistance, and other superior properties. That is, the present invention involves polymerizing a by-product oil having a boiling point range of 180 to 210°C among the residual oils produced during the synthesis of phenols via hydroperoxide in the presence of activated clay or a Friedel-Crafts catalyst. The present invention provides a method for producing a low viscosity extender, which comprises: Here, the residual oil that is produced as a by-product during the synthesis of phenols via hydroperoxide is the synthesis of phenol by the cumene method, the synthesis of cresol by the cymene method, or the synthesis of hydroquinone or resorcinol from diisopropylbenzene. When synthesizing phenols via hydroperoxide, it refers to a high-boiling fraction obtained after separating target phenols from acid decomposition products of hydroperoxide. Such residual oils are usually methylacetophenone,
It contains isopropyl phenol, isopropylbenzyl alcohol, etc. and has a characteristic odor, but in the present invention, the by-product with a boiling point range of 180 to 210 °C is used after removing upper odor components from the residual oil. The polymer has no characteristic odor and can be advantageously used as a filler. As mentioned above, the by-product oil used in the present invention is a residual oil that is produced as a by-product during the synthesis of phenols from which hydroperoxide is extracted.
Although the temperature is 210°C, it is particularly preferable to use a by-product oil with a boiling point range of 180 to 210°C from which the above-mentioned characteristic odor components and low-boiling components have been removed from the residual oil by-produced during resol synthesis by the cymene method. The catalyst applied to the present invention is activated clay or a Friedel-Crafts catalyst, and aluminum chloride, aluminum bromide, boron trifluoride, complexes thereof, and the like are effectively used as the Friedel-Crafts catalyst. The type and amount of catalyst to be used are appropriately selected depending on the desired reaction rate, viscosity of the product, difficulty in removing the catalyst, etc., but the amount of catalyst used is usually 0.3 to 3 parts per 100 parts by weight of by-product oil. be. The polymerization reaction is usually carried out at 10-180°C, and the polymerization temperature has an important effect on the viscosity of the product.
That is, when the polymerization temperature is low, the molecular weight of the product increases and the viscosity tends to increase, and when the polymerization temperature is high, the viscosity of the product tends to decrease. For example, under certain conditions, the polymerization temperature is 140~
At 180°C, the viscosity of the product at 25°C is approx.
0.5 to 4 poise, and at 70 to 75°C it is about 50 to 80 poise, so by choosing the reaction temperature, products with the viscosity required for each application can be freely produced. can. The reaction time is appropriately selected depending on the polymerization temperature, the type and amount of the catalyst, the viscosity of the desired product, etc., but is usually in the range of 1 to 10 hours. After the polymerization reaction is completed, the catalyst is distilled off and the desired polymerization product has a viscosity of 0.5 poise (25℃).
Obtained as a liquid product. When the product thus obtained is used as an extender, if its viscosity is too low, when it is cured, the evaporation of volatile components from the surface increases over a long period of time, causing shrinkage. If the viscosity is too large, the viscosity of the compound will increase and workability will decrease, so the viscosity of the polymerized product should be 0.5 to 200.
It is preferable to set the polymerization reaction conditions so that the polymerization reaction temperature is 1 to 100 poise (25°C), more preferably 1 to 100 poise (25°C). Particularly when producing a non-solvent type or solventless type formulation, it is necessary to set the conditions so that the viscosity of the product is 1 to 40 poise (25°C). The polymerization product obtained according to the present invention can be advantageously used as an extender, especially for epoxy resins or urethane resins, and can be used in resin formulations by adding pigments, fillers, various additives, and, if necessary, solvents. It is used for various purposes such as materials, furniture, paints, flooring materials, sealants, and waterproofing agents. Conventionally, urethane resins basically consist of a urethane prepolymer and its crosslinking agent, such as 3,3'-dichloro-4,4'-diaminodiphenylmethane (hereinafter referred to as DCDAM), and the crosslinking agent is Because it is a solid, it has been used by dissolving it in, for example, dioctyl phthalate, petroleum heavy oil, coal-based heavy oil, etc. However, the polymerization product obtained by the present invention can also be used as a solid.
Since it has the same dissolving power for DCDAM as these diluents, it can be used in exactly the same way as these diluents. Of course, as an embodiment of blending the extender of the present invention with DCDAM, it can be used not only as a solvent for DCDAM as described above, but also as a component. This also applies to other urethane resin crosslinking materials such as 4,4'-diaminodiphenylmethane. The present invention will be explained below using examples. however,
In the middle part of the example, % indicates the weight unit. Example 1 Among the residual oil by-produced during the synthesis of cresol by the cymene method, 100 parts of the by-product oil with a boiling point range of 180 to 204°C (main fraction boiling point 184°C) and 0.5 part of activated clay were charged into a flask, After carrying out the polymerization reaction at 150°C for 2 hours, the catalyst was filtered off. Then 170℃, 40
Vacuum distillation was performed at mmHg to remove unreacted components to obtain a polymerized product having a viscosity of 1 poise (25°C). Example 2 100 parts of the same by-product oil as used in Example 1 and 1 part of boron trifluoride were charged into a flask, and after reacting at 95 to 105°C for 1 hour, the flask was washed with water to remove the catalyst.
Thereafter, vacuum distillation was performed at 170° C. and 40 mmHg to remove unreacted components to obtain a polymerized product with a viscosity of 16 poise (25° C.). Example 3 The same procedure as in Example 1 was carried out except that the reaction temperature was changed to 75 to 80°C, and the viscosity was 60 poise (25°C).
A polymerization product was obtained. Reference Example 1 Table 1 shows the properties of each polymerization product obtained in Examples 1 to 3.

[Table] Reference Example 2 Using the polymerization product obtained in Example 2 as an extender, a urethane flooring material was prepared according to a conventional method. Table 2 shows the physical properties of the urethane flooring material obtained. For comparison, urethane flooring materials were similarly prepared using commercially available diothyl phthalate and polyethylene glycol dibenzoate. Its physical properties are shown in Table 2.

[Table] Reference Example 3 Using the polymerization products obtained in Examples 1 and 2 as an extender, a sealing material was prepared according to the formulation shown in Table 3, and the cured coating film of the sealing material was formed into a sheet, and carbon arc The light resistance was investigated by irradiating it with ultraviolet light using a type ultraviolet irradiation device. The results are shown in Table 4. Similarly, Tables 3 and 4 show formulation examples and light resistance test results using commercially available fillers.

[Table] As mentioned above, the polymerization product obtained by the present invention has excellent properties as a bulking material, and in addition, it has been used as a bulking material that has been commercially available in the past in order to utilize by-product oil, which is industrial waste. It has the excellent feature of being extremely inexpensive compared to other materials.

[Table] In addition, in the present invention, since a low-viscosity extender can be produced, it becomes easy to design a non-solvent type or solvent-less type formulation that can fully comply with the emission regulations of organic solvents. In addition, when the filler obtained according to the present invention was used in place of the tar component in a solvent-free tar epoxy composition, there was no significant difference in corrosion resistance from that containing the tar component. Table 5 shows formulation examples of solvent-free compositions.

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Claims (1)

[Claims] 1 Among the residual oils produced as by-products during the synthesis of phenols via hydroperoxide, 180-210℃
A method for producing a low-viscosity extender, which comprises polymerizing a by-product oil having a boiling point range of 100 to 100% in the presence of activated clay or a Friedel-Crafts catalyst.