JP5090826B2 - Granulation method of polyoxyethylene ether of bisphenol A - Google Patents

Description

  The present invention relates to granular polyoxyethylene ether (A) of bisphenol A. More specifically, the present invention relates to a granulation method of polyoxyethylene ether (A) of bisphenol A, which is granular without being pulverized and thus has excellent handleability.

  The melting point of polyoxyethylene ether (A) of bisphenol A varies depending on the number of moles of ethylene oxide added, but solidification is very slow even when the melted product is cooled. For example, even if it has a melting point of 100 ° C. or higher, it is necessary to leave it at room temperature for about 1 to 2 days for solidification. For this reason, under the present circumstances, after the molten material is poured into a container such as a stainless steel vat, it is solidified by leaving it at room temperature for about 1 to 2 days, and then the solidified material is pulverized. In this method, since the solidification process takes time, productivity is poor.

Since the melted polyoxyethylene ether (A) of bisphenol A is very slow in solidification, it is industrially very difficult to solidify as fine particles by using a flaker or by spraying. It is.
The polyoxyethylene ether (A) of bisphenol A produced by cooling solidification and pulverization has a wide particle size distribution, and there are coarse particles and fine powders. When coarse particles are present, the filling line is blocked when the polyoxyethylene ether (A) is taken out from the stirring bowl, so that the handleability is deteriorated. On the other hand, the presence of a fine powder product causes a dust explosion of the fine powder, and the handleability deteriorates.

As a method of solidifying the melt, there is a method of cooling and solidifying after dissolving the melt in an organic solvent that mutually dissolves (for example, Patent Document 1).
By using this method, a substance that takes time to solidify can be easily solidified. However, after solidification, a step of pulverization is required, and productivity is poor.

Further, there is a method in which the melt is brought into contact with a cooling medium that does not dissolve in the melt to cool and solidify the melt (for example, Patent Document 2).
However, since polyoxyethylene ether (A) of bisphenol A is very slow to solidify, it is difficult to produce by this method.
JP 58-24525 A JP 2000-302855 A

  Therefore, a method and a composition for producing bisphenol A polyoxyethylene ether (A) having a narrow particle distribution, no fine powder, and almost spherical shape, which are excellent in productivity and handleability and have few impurities are provided. The purpose is to do.

The inventors of the present invention have reached the present invention as a result of studies to achieve the above object.
That is, in the present invention, in the presence of molten bisphenol A polyoxyethylene ether (A) and water and / or an organic solvent (B), a shearing force is applied to form droplets of the (A). A method for producing granular bisphenol A polyoxyethylene ether (A) characterized by cooling and granulating; and passing through a sieve having a mesh opening of 22.4 mm and on a 0.5 mm sieve Granular bisphenol A polyoxyethylene characterized in that the ratio of the remaining particles to all particles is 60% by weight or more, the circularity is 0.40 to 1.00, and the CPR is 100 or less. Ether (A).

The method for producing polyoxyethylene ether of bisphenol A by the present inventor can perform granulation without using pulverization without using special equipment such as a molten droplet generator described in Patent Document 2. As a result, it is possible to obtain a polyoxyethylene ether of bisphenol A that is more productive than conventional products and has excellent handleability.
In addition, since there is no fine powder product that is inherent to pulverization, there is no worry of causing a dust explosion of fine powder, and since the shape is nearly spherical compared to the pulverized product, it has excellent fluidity and the supply line is blocked. It is easy to handle.
Further, since impurities such as a catalyst contained in the molten bisphenol A polyoxyethylene ether (A) are dissolved in water and / or the organic solvent (B), the polyoxyethylene ether of bisphenol A with less impurities ( A) can be obtained.

  One of the embodiments of the present invention is to apply a shear force in the presence of molten polyoxyethylene ether of bisphenol A (A) and water and / or an organic solvent (B) to form droplets of the (A). Is formed, cooled, and granulated, which is the manufacturing method of (A).

  Although the polyoxyethylene ether (A) of bisphenol A depends on the number of moles of ethylene oxide added, 1.5 to 3.0 mole adducts and 30 mol or more adducts are generally solid at room temperature. A compound. However, it takes about 1 to 2 days to solidify the melt at room temperature.

  Also, when the polyoxyethylene ether (A) of bisphenol A in a molten state is cooled in the presence of water (B1) alone, organic solvent (B2) alone, or a mixture of water and organic solvent (B) However, it takes time to solidify when no shear force is applied.

  By cooling the polyoxyethylene ether (A) of bisphenol A into droplets having a small particle diameter in a state where a shearing force is applied, it is possible to solidify in a short time.

When the polyoxyethylene ether (A) of bisphenol A in a molten state is brought into a state where shearing force is applied in water and / or an organic solvent (B) by a method described later, the water and / or the organic solvent (B) In this state, small droplets of polyoxyethylene ether (A) of bisphenol A in a molten state are dispersed.
When the small droplets in the molten state are cooled while the shear force is applied, the polyoxyethylene ether (A) of bisphenol A solidifies as particles having a size depending on the droplets at the time of dispersion. To do.

  A specific method for forming a droplet of polyoxyethylene ether of bisphenol A in water and / or an organic solvent (B) by applying a shearing force is particularly limited as long as the droplet exists in a dispersed state. Not. For example, the following methods are exemplified.

(I) For example, a method of forming droplets of polyoxyethylene ether (A) of bisphenol A by stirring in a stirring tank equipped with stirring blades having a shape such as a Max blend stirring blade or a spiral stirring blade.
(Ii) A method of forming droplets of bisphenol A polyoxyethylene ether (A) by applying a shearing force using a planetary mixer.
(Iii) A method in which a shearing force is applied using a homogenizer to form droplets of polyoxyethylene ether (A) of bisphenol A.
(Iv) A method of forming droplets of bisphenol A polyoxyethylene ether (A) by applying a shearing force using an inline mixer such as a static mixer.

  A specific method for solidifying the liquid droplets of polyoxyethylene ether (A) of bisphenol A formed in water and / or the organic solvent (B) by applying a shearing force is not particularly limited. For example, the following methods are exemplified.

(I) A method of allowing a cooling medium such as cold water to flow outside the stirring bowl to cool and solidify the droplets of polyoxyethylene ether (A) of bisphenol A inside through the wall surface of the bowl.
(Ii) A droplet of polyoxyethylene ether of bisphenol A (A) is formed in water and / or organic solvent (B ′) by applying a shearing force, and then formed into water and / or organic solvent (B). A method of cooling and solidifying by putting it in.

  Regarding the magnitude of the shear force when forming a droplet by applying a shear force between the polyoxyethylene ether of bisphenol A (A) and water and / or an organic solvent (B), the polyoxyethylene ether of the bisphenol A in a molten state is used. At least a shearing force is required to achieve a dispersed state in which droplets of oxyethylene ether (A) are generated.

Furthermore, since the droplets are almost solidified into particles with the diameter of the droplets, a shearing force is required so that the droplet size becomes the target particle size for granulation. That is, the particle diameter of the granular oxyphenol ether (A) of bisphenol A depends on the size of the droplets of the polyoxyethylene ether (A) of bisphenol A in the molten state. Therefore, in order to obtain a predetermined particle size, it is necessary to adjust the shearing method and the magnitude of the shearing force.
When the shearing force is increased, the size of the molten bisphenol A polyoxyethylene ether (A) droplet is reduced. As a result, the particle diameter of granular bisphenol A polyoxyethylene ether (A) is reduced.

  In the present invention, “system” means mixing of (A) and (B) when melted (A) and (B) are mixed, and then shearing force is applied and cooled and granulated in that state. Represents a system.

The weight ratio of polyoxyethylene ether of bisphenol A in the system in this case to water and / or organic solvent (B) is usually (A) / (B) = 2 / 98-60 / 40, Preferably it is 2 / 98-50 / 50, More preferably, it is 2 / 98-45 / 55. In addition, "water and / or organic solvent" means the total amount when water and an organic solvent are used in combination.
When the weight ratio (A) / (B) of (A) to (B) is in the range of 60/40 to 100/0, the polyoxyethylene ether (A) of bisphenol A is not granular but is preferably in the form of a mass. Absent.
Moreover, since productivity falls in the range of 0/100-2/98, it is unpreferable.

The charging method of polyoxyethylene ether (A) of bisphenol A and water and / or organic solvent (B) is not particularly limited, and (B) may be water alone, organic solvent alone, or a mixture of water and organic solvent. It can be either batch input or split input.
For example, the following methods are exemplified.
(I) After mixing the melted (A) and (B), a shearing force is applied, and in this state, cooling is performed.
A method of granulating.
(Ii) After mixing the melted (A) and (B ′), the shear force is applied
A method of granulating by dripping into another (B).
(Iii) A method in which the melted (A ′) and (B ′) are mixed and then dropped into the mixed system of (A) and (B) in a state where a shearing force is applied to perform granulation.
(Iv) A method of granulating the molten (A) by dropping it into a single system (B) in a state where a shearing force is applied.
(V) A method in which the melted (A ′) is dropped into a mixed system of (A) and (B) in a state where a shearing force is applied to perform granulation.

Among the methods for adding these polyoxyethylene ethers (A) of bisphenol A and water and / or organic solvent (B), from the viewpoint of production cost, the preheating of (B) is less (ii) to (v) ) Is preferred.
Moreover, the method of (i)-(iii) which produces a droplet previously from a stable surface of quality is preferable.

Due to these factors, the methods (ii) and (iii) are preferred.

The weight ratio of water (B1) and / or organic solvent (B2) is not particularly limited, and any of water (B1) alone, a mixture of water (B1) and organic solvent (B2), and organic solvent (B2) alone. Good. However, when the organic solvent (B2) is contained, some VOC (volatile organic compound) remains even when the organic solvent is removed when the granular (A) is isolated. The amount of the organic solvent used should be small, preferably (B1) / (B2) = 50 / 50-100 / 0, more preferably (B1) / (B2) = 75 / 25-100 / 0. Most preferably, water (B1) is used alone.
Further, when the organic solvent (B2) is used, a part of the polyoxyethylene ether (A) of bisphenol A is dissolved in the organic solvent, so that the yield of the granular (A) is lowered. Also from this, it is better that the amount of the organic solvent used is small.

Regarding water (B1), industrial water, tap water, ion-exchanged water, distilled water and the like can be used, but there is no particular limitation, and an acid or a base may be added.
About water (B1), Preferably they are ion-exchange water and distilled water.

  As the organic solvent (B2), the solubility of the polyoxyethylene ether (A) of bisphenol A at 25 ° C. is usually 150 g or less because the polyoxyethylene ether (A) of granular bisphenol A is hardly dissolved. The solvent must be 100 g). Preferably, the solubility is 60 g or less (100 g of solvent), more preferably the solubility is 30 g or less (100 g of solvent).

  Examples of such an organic solvent (B2) include isopropanol, toluene, xylene, methanol, cyclohexane, acetic acid, acetonitrile, ethylene glycol, glycerin, diethylene glycol monobutyl ether, 2,2'-iminodiethanol and the like.

  Of these, xylene, glycerin, and diethylene glycol monobutyl ether are preferred because their boiling points are sufficiently higher than the melting temperature of the polyoxyethylene ether (A) of bisphenol A.

  The organic solvent (B2) may be used alone or in combination of two or more.

In the present invention, the melting point represents the melting peak temperature described in JIS K 7121-1987 “Method for measuring plastic transition temperature”. When there are a plurality of melting peak temperatures, it represents the maximum peak.
In addition, the test piece whose drying loss is 1.0% or less is used for the test piece which calculates | requires melting temperature. This loss on drying represents the loss on drying as described in JIS K 0067-1992 “Method for reducing weight of chemical products and test method for residue”.

The melting point of the polyoxyethylene ether (A) of bisphenol A varies depending on the number of moles of ethylene oxide added, but is 40 to 150 ° C. Preferably it is 50-140 degreeC, More preferably, it is 60-130 degreeC.
A melting point of less than 40 ° C. is not preferable because it does not solidify quickly during cooling.
If the melting point is higher than 150 ° C., solidification occurs immediately after mixing with water and / or the organic solvent (B), and uniform granular bisphenol A polyoxyethylene ether (A) cannot be obtained.

The particle size of granular bisphenol A polyoxyethylene ether (A) is such that the proportion of particles passing through a sieve having an aperture of 22.4 mm and remaining on the sieve having a size of 0.5 mm is 60% by weight or more. It is.
Preferably, the proportion of particles passing through a sieve having an aperture of 8.0 mm and remaining on the sieve having a size of 0.5 mm is 60% by weight or more. More preferably, the proportion of particles passing through a sieve having an aperture of 8.0 mm and remaining on the sieve having a mesh size of 0.5 mm is 80% by weight or more.
Preferably, the ratio of particles passing through a sieve having an aperture of 22.4 mm and remaining on the sieve having a mesh size of 0.5 mm is 70% by weight or more, more preferably 80% by weight or more. is there.

If there are many particles of granular bisphenol A polyoxyethylene ether (A) having a diameter of 22.4 mm or more, problems such as clogging of the filling line at the time of taking out from the stirrer occur, resulting in poor handling. Therefore, it is not preferable.
On the other hand, if there are a large number of particles having a particle size of 0.5 mm or less, the dust rises and causes the health of the worker to be deteriorated or causes a dust explosion, which is not preferable.

  The CPR in the present invention is a CPR value described in JIS K 1557-4 “Plastics—Testing Method for Polyurethane Raw Material Polyol—Part 4: Determination of Basicity”, and is a micro of basic substance in 30 g of polyol. Equivalent value (milli equivalent in 30 g of polyol).

The CPR of the polyoxyethylene ether (A) of granular bisphenol A is 100 or less, preferably 50 or less, more preferably 30 or less.
When CPR exceeds 100, it is not preferable because the composition of the present invention is colored when used as a raw material for unsaturated polyester resin, polyester resin, polyurethane resin and the like.

In the present invention, the degree of circularity of the granular bisphenol A polyoxyethylene ether (A) is usually 0.40 to 1.00, preferably 0.55 to 1.00, more preferably 0.70. ~ 1.00.
When the circularity is less than 0.4, the unevenness increases, and the particles do not roll, so that the handleability is deteriorated.
In the present invention, the degree of circularity of each individual fine particle does not have to be in the above range, and an average value (preferably an average value of 50, more preferably an average value of 100) is within the above range. Good.

Here, the degree of circularity is a value calculated by the following equation, and can be measured and calculated by photographing particles with a microscope and processing the photograph (for example, a microscope VK-8500 manufactured by Keyence Corporation). And image analysis using the accompanying shape analysis software VK-H1A7; a particle size / shape distribution measuring instrument PITA-1 manufactured by Seishin Co., Ltd.).

Circularity = 4πF / L ²
However, F: Projected area of particles L: Projected perimeter of particles Note that the degree of circularity is described in “Chapter 3 Construction of Non-Contact Full-Field Strain Measurement Committee Research Report on Degradation and Hardening Process of Concrete”. Experiments and research using optical full-field measurement in the field (3.6) Aggregate shape evaluation using digital technology ".

  In the present invention, “poly” in the polyoxyethylene ether (A) of bisphenol A represents 0 or more added moles of ethylene oxide.

  The temperature at which the droplets are mixed by mixing the polyoxyethylene ether (A) of bisphenol A with water and / or the organic solvent (B) is not particularly limited.

The temperature at which the polyoxyethylene ether (A) of bisphenol A and water and / or the organic solvent (B) are cooled and solidified by applying a shearing force is below the melting point of the polyoxyethylene ether (A) of bisphenol A. It is necessary to be.
For example, a polyoxyethylene ether (A) of bisphenol A having a hydroxyl value of 346 generally has a shearing force higher than a dispersion state in which droplets of a polyoxyethylene ether (A) of bisphenol A in a molten state are generated. Solidify in 45-65 ° C in a very short time. Therefore, if it cools below this temperature, it can be solidified.

There is no particular limitation on the cooling time by applying a shearing force in the presence of polyoxyethylene ether (A) of bisphenol A and water and / or an organic solvent (B).
When the polyoxyethylene ether (A) of bisphenol A and water and / or the organic solvent (B) are mixed together and then cooled and granulated, the cooling may be performed at a rate of 20 ° C. or more per hour. preferable.

  In a water and / or organic solvent (B) subjected to shearing force, a polyoxyethylene ether (A) of bisphenol A or a polyoxyethylene ether (A) of bisphenol A and water and / or an organic solvent (B) The dropping speed when dropping the mixture is not particularly limited.

  The method for removing water and / or the organic solvent (B) after granulation is not particularly limited, and hot air drying, infrared drying, indirect heating drying (vacuum drying, stirring type dryer, drum dryer), concentration device ( For example, a method using a thickener) and a dehydrator (for example, a centrifugal dehydrator, a belt press dehydrator, a filter press dehydrator, and a capillary dehydrator) can be used.

  The granular polyoxyethylene ether (A) of bisphenol A of the present invention is useful as a modifier for unsaturated polyester resins, polyester resins, polyurethane resins, epoxy resins, acrylic resins, and polycarbonates. Further, the hydroxyl group in the molecule can be modified (for example, epoxy modification with epichlorohydrin, allyl modification with allyl chloride, acrylic modification with (meth) acrylic acid, etc.) and used as a resin raw material.

  The present invention will be specifically described below with reference to production examples and examples, but the present invention is not limited thereto.

Production Example 1
Bisphenol A (228 g, 1 mol) and potassium hydroxide (0.3 g) were placed in a stainless steel autoclave equipped with stirring and temperature control functions, and heated and melted at 160 ° C. in a nitrogen atmosphere. After melting, 96.8 g (2.2 mol) of ethylene oxide was added dropwise at 160 ° C. over 5 hours. Then, it was made to stir at 160 degreeC for 3 hours, and the polyoxyethylene ether (A-0) of the melted bisphenol A was obtained. The hydroxyl value of polyoxyethylene ether (A-0) of bisphenol A was 346. The melting point was 108 ° C.

Example 1
A pressure-resistant reactor having an internal volume of 1100 ml equipped with a thermometer, a stirrer, and a nitrogen inlet was charged with 100 g of polyoxyethylene ether (A-0) of bisphenol A in a molten state at 105 ° C. and 400 g of ion-exchanged water at 80 ° C. This mixture was heated at 95 ° C. for 1 hour to melt.
After melting, the mixture was stirred at 95 ° C. and 1500 rpm for 1 hour. Next, while continuing stirring at 1500 rpm, the system temperature was gradually cooled from 95 ° C. to 25 ° C. over 1 hour, and the droplets were solidified and granulated.
After granulation, water is removed by filtration under reduced pressure using a filter paper, and moisture is completely removed by drying under reduced pressure at 60 ° C. for 3 hours. The granular bisphenol A polyoxyethylene ether (A-1) of the present invention is removed. )

Example 2
The granular bisphenol A polyoxyethylene ether (A-2) of the present invention was obtained in the same manner except that 400 g of ion-exchanged water in Example 1 was replaced with 320 g of ion-exchanged water and 80 g of isopropanol.
In addition, the solubility of isopropanol with respect to 100g of water in 25 degreeC of the polyoxyethylene ether (A) of bisphenol A is 5g.

Example 3
A pressure-resistant reactor having an internal volume of 1100 ml equipped with a thermometer, a stirrer and a nitrogen inlet was charged with 100 g of polyoxyethylene ether (A-0) of bisphenol A in a molten state at 105 ° C. and 100 g of ion-exchanged water. After heating and heating at 95 ° C. for 1 hour, the mixture was stirred at 1500 rpm for 1 hour to form droplets.
A pressure-resistant reactor with an internal volume of 1100 ml equipped with another thermometer, stirrer and nitrogen inlet was charged with 300 g of ion-exchanged water at 25 ° C., and the mixture containing the above droplets was added for 5 minutes while stirring at 1500 rpm. And solidified and granulated. The inside of the system at this time was cooled and kept at a temperature of 40 ° C. or lower.
After granulation, it is filtered under reduced pressure using filter paper, and further dried under reduced pressure at 60 ° C. for 3 hours to completely remove moisture, thereby obtaining granular bisphenol A polyoxyethylene ether (A-3) of the present invention. It was.

Comparative Example 1
100 g of polyoxyethylene ether (A-0) of bisphenol A in a molten state at 105 ° C. was poured into a stainless steel container, and then cooled and solidified with a low-temperature incubator at 5 ° C. It took 2 days to fully solidify. The solidified product was pulverized using a flaker to obtain bisphenol A polyoxyethylene ether (A′-1) of Comparative Example.

  The particle diameter, circularity, and CPR of the produced (A-1) to (A-3) and (A′-1) were measured. The results are shown in Table 1.

<Measurement method of hydroxyl value>
The hydroxyl value was determined according to the method described in JIS K1557-1 “Plastics—Polyurethane raw material polyol test method—Part 1: Determination of hydroxyl value”.

<Measuring method of particle size by sieving>
The particle size was determined by performing a dry sieving test (manual sieving) in accordance with JIS Z 8815-1994 “General Rules for Sieving Test Methods” to obtain a percentage on the sieve.
A 50 g sample was used for the dry screening test. The sieves used were 0.5 mm, 2.8 mm, 8.00 mm, and 22.4 mm.

<Measurement method of circularity>
Image analysis was performed using a microscope VK-8500 manufactured by Keyence Corporation and the accompanying shape analysis software VK-H1A7 manufactured by the company, and the circularity was measured.

<Measurement method of CPR>
CPR was measured according to the method described in JIS K 1557-4 “Plastics—Testing Method for Polyurethane Raw Material Polyol—Part 4: How to Obtain Basicity”.

  As can be seen from Table 1, in the composition of the present invention, Comparative Example 1 produced by pulverization accounts for 70% by weight of less than 0.5 mm, whereas Examples 1 to 3 of the present invention are all. It can be seen that there are almost no fine powder products of less than 0.5 mm and coarse particles of 22.4 mm or more. It can also be seen that the degree of circularity is high and close to spherical. Further, it can be seen that the CPR is low, so that there are few impurities.

  The granular material of the present invention has almost no fine powder that is inherent to pulverization, so there is no worry of causing a dust explosion of the fine powder, and its shape is nearly spherical compared to the pulverized product, so it has excellent fluidity and impurities. Therefore, it is useful as a modifier for polyester, epoxy resin, acrylic resin, and polycarbonate.

Claims (8)

  In the presence of molten polyoxyethylene ether of bisphenol A (A) and water and / or organic solvent (B), a shearing force is applied to form droplets of (A), which are cooled. A process for producing a granular polyoxyethylene ether (A) of bisphenol A, characterized by granulating.   The bisphenol A polyoxyethylene ether (A) according to claim 1, wherein the organic solvent (B) has a solubility of the polyoxyethylene ether (A) of bisphenol A at 25 ° C of 150 g or less (100 g of solvent). Production method.   The weight ratio (A) / (B) of the polyoxyethylene ether (A) of the bisphenol A to water and / or the organic solvent (B) in the system is 2/98 to 60/40. The manufacturing method of polyoxyethylene ether (A) of bisphenol A as described in 2.   Drops of molten bisphenol A polyoxyethylene ether (A) present in water and / or organic solvent (B ′) are put into sheared water and / or organic solvent (B). The method for producing a polyoxyethylene ether (A) of bisphenol A according to claim 1 or 2, which is solidified.   The melting point of the polyoxyethylene ether (A) of the bisphenol A is 40 to 150 ° C. The method for producing the polyoxyethylene ether (A) of bisphenol A according to any one of claims 1 to 4.   The ratio of the particles passing through a sieve having a mesh opening of 22.4 mm and remaining on the sieve having a size of 0.5 mm to the total particles is 60% by weight or more. Production method of polyoxyethylene ether (A).   Circularity is 0.40-1.00, The manufacturing method of the polyoxyethylene ether (A) of the granular bisphenol A in any one of Claims 1-6.   The proportion of particles passing through a sieve having an aperture of 22.4 mm and remaining on the sieve having a size of 0.5 mm is 60% by weight or more, and the circularity is 0.40 to 1.00, Granular polyoxyethylene ether (A) of bisphenol A having a CPR of 100 or less.