JP3879180B2 - Odor removal method for aliphatic polyamine - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to odor removing method aliphatic polyamine down. More particularly, adhesives, coatings, casting materials, epoxy resin composition used in such composite material matrix, in particular two-part epoxy resin composition, odor removal of aliphatic polyamine emissions used as a curing agent for epoxy resin Regarding the method.
[0002]
[Prior art]
A two-part epoxy resin composition consisting of an epoxy resin and a curing agent, which is mixed immediately before use, can be cured at room temperature, can be used without solvent, has no gas generation during curing, and various physical properties after curing Are widely used in applications such as adhesives, paints, primers, sealing agents, casting materials, and matrix resins for fiber reinforced composite materials.
[0003]
As the main component of the curing agent of the two-pack type epoxy resin composition, aliphatic polyamines having excellent room temperature curing properties are widely used.
[0004]
However, aliphatic polyamines often have a strong ammonia-like odor and are often problematic, especially when working indoors.
[0005]
In particular, for construction such as indoor refurbishment and repair of a building that has already been completed and used, the conventional two-pack type epoxy resin composition is used as an adhesive, paint, primer, sealing agent, fiber reinforced composite matrix resin, etc. Considering the effects of odors on residents, it is necessary to take measures such as performing construction work at night or on holidays or moving out of residents during construction work, which causes the construction period to be extended. .
[0006]
[Problems to be solved by the invention]
An object of the present invention is to extremely reduce the odor of a liquid comprising an aliphatic polyamine, and in particular, to extremely reduce the odor of a liquid comprising an aliphatic polyamine used as a curing agent in a two-pack type epoxy resin composition. That is.
[0007]
[Means for Solving the Problems]
Odor removal method aliphatic polyamine emissions of the present invention, in order to solve the above problems, has the following configuration. That is, after removing the volatile odor component dissolved in the liquid from the aliphatic polyamine, the liquid is sealed in an airtight container in a substantially oxygen-free state, sealed with gas, kept at 20 ° C. and in an equilibrium state. gaseous ammonia concentration in a state of reaching to and obtaining said liquid is 100ppm or less, odor removal method aliphatic polyamine down.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The present inventors have found the following regarding the odor of aliphatic polyamines.
[0010]
(A) The cause of the odor which becomes a problem is not aliphatic polyamine itself but highly volatile impurities such as ammonia, and the odor is almost eliminated when these are removed.
[0011]
(B) Once the volatile odor component is removed, if it is stored in the presence of oxygen, the volatile odor component is gradually generated and has a bad odor. There should be no foul odors.
[0012]
Based on this knowledge, the present inventors have reached the present invention as a result of intensive studies.
[0013]
In the present invention, the liquid may be composed of an aliphatic polyamine. Even if the liquid material is a single aliphatic polyamine, the composition is composed of a plurality of aliphatic polyamines or one or more aliphatic polyamines as a main component. It may be a composition containing other components.
[0014]
In the case of a single aliphatic polyamine, a treatment for removing volatile odor components such as ammonia may be performed. Oxygen is also usually removed by the process of removing volatile odor components.
[0015]
In the present invention, when the liquid composed of the aliphatic polyamine is a mixture of a plurality of raw materials, a method of removing the volatile odor components for each raw material and then mixing them in an atmosphere substantially free of oxygen Alternatively, it is possible to use a method of first mixing raw materials and then performing a treatment for removing volatile odor components.
[0016]
An example of a treatment method for removing volatile odor components from a liquid composed of an aliphatic polyamine is a vacuum degassing treatment. This is a method in which a liquid to be treated is decompressed for a certain period of time in a sealed container and returned to normal pressure using a gas substantially free of oxygen. The temperature at which the decompression treatment is performed may be room temperature or may be appropriately heated. Moreover, it is not necessary to stir.
[0017]
In the case of performing a vacuum degassing treatment, a gas substantially free of oxygen can be passed into a liquid composed of an aliphatic polyamine. This method is effective for improving the efficiency of removing volatile odor components. In particular, when a large amount of liquid is processed, there are advantages that the time can be shortened and that the vacuum degree does not need to be increased so much in the decompression process.
[0018]
Another treatment method for removing a volatile odor component from a liquid composed of an aliphatic polyamine is an aeration treatment with a gas substantially free of oxygen. This is a method in which a gas substantially free of oxygen is passed through a liquid to be treated at normal pressure for a certain period of time. The temperature at which the aeration treatment is performed may be room temperature or may be appropriately heated. Moreover, it is not necessary to stir.
[0019]
There is a distillation method as a treatment method for removing a volatile odor component suitable mainly when applied to a single aliphatic polyamine or a raw material in a mixture. For this, either a method of distilling under atmospheric pressure and an atmosphere substantially free of oxygen, or a method of distilling under reduced pressure and returning to normal pressure using a gas substantially free of oxygen is used. .
[0020]
The liquid of the aliphatic polyamine prepared by the method described above is sealed in an airtight container in a substantially oxygen-free state, whereby the odor of the aliphatic polyamine can be removed.
[0021]
As a method of sealing in an airtight container in a substantially oxygen-free state, first, a method of injecting a liquid made of an aliphatic polyamine into a gastight container together with a gas substantially free of oxygen and sealing it is used.
[0022]
Secondly, a method is used in which the entire inner volume of the hermetic container is filled with a liquid composed of an aliphatic polyamine so that the space in which the gas exists is substantially eliminated.
[0023]
In the present invention, any airtight container may be used as long as it has good airtightness and hardly permeates oxygen. Examples include metal, glass, plastic bottles, cans, tanks, and ampoules. In particular, it is preferable to use a metal or plastic squeeze-type tube or bag, an extrusion-type container composed of a piston and a cylinder, etc., since any amount can be used without substantially contacting the contents with air.
[0024]
In the above steps, nitrogen or argon is preferably used as the gas or atmosphere substantially free of oxygen.
[0025]
In the present invention, the aliphatic polyamine means a compound having a plurality of amino groups in the molecule in which carbon atoms directly bonded are sp ³ hybridized. Even an amine having an aromatic ring in the molecule can be regarded as an aliphatic amine having an aromatic substituent as long as the above conditions are satisfied, and corresponds to the aliphatic polyamine in the present invention.
[0026]
Specific examples of the aliphatic polyamine used in the present onset Ming include those shown below.
[0027]
Ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-diaminobutane, hexamethylenediamine, 2,5-dimethyl-2,5-hexanediamine, 2,2,4-trimethylhexamethylenediamine , Diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 4-aminomethyloctamethylenediamine, 3,3′-iminobis (propylamine), 3,3′-methyliminobis (propylamine), bis ( 3-aminopropyl) ether, 1,2-bis (3-aminopropyloxy) ethane, mensendiamine, isophoronediamine, bisaminomethylnorbornane, bis (4-aminocyclohexyl) methane, bis (4-amino-3- Methylcyclohexyl) Tan, 1,3-diaminocyclohexane, 3,9-bis (3-aminopropyl) -2,4,8,10-spiro [5,5] can be exemplified undecane. Examples of the aliphatic polyamine having an aromatic substituent include m-xylylenediamine and tetrachloro-p-xylylenediamine.
[0028]
Also obtained from the reaction of polymerized fatty acids (polyhydric fatty acid mixtures based on dimers of unsaturated fatty acids such as linoleic acid) with polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine. So-called polyamidoamines that can be used can also be suitably used.
[0029]
Also suitable are compounds in which aminoalkyl groups are introduced at both ends of polyethers such as polyethylene glycol and polypropylene glycol, and compounds in which aminoalkyl groups are introduced at both ends of silicone compounds such as polydimethylsiloxane and polymethylphenylsiloxane. be able to.
[0030]
In the present invention, an amine other than an aliphatic polyamine, such as an imidazole, and a curing agent other than an amine, such as a polymercaptan, may be dissolved or dispersed in the liquid comprising an aliphatic polyamine.
[0031]
In the present invention, a phenol compound may be dissolved or dispersed in the liquid comprising the aliphatic polyamine as an aliphatic polyamine curing accelerator. As the phenol compound, diisopropylphenol, nonylphenol and the like are preferably used.
[0032]
Furthermore, in the present invention, the liquid composed of the aliphatic polyamine contains, as other components, plasticizers, dyes, organic pigments, organic pigments such as carbon black and silica, inorganic particles, polymer compounds, antioxidants, ultraviolet absorption. An agent, a coupling agent, a surfactant and the like may be dissolved or dispersed.
[0033]
As a means for evaluating the low odor of a liquid comprising an aliphatic polyamine in the present invention, ammonia contributes the most as an odor component, so the concentration of ammonia in a gas in equilibrium with a liquid comprising an aliphatic polyamine is measured. It is effective to do. The ammonia concentration in the gas indicates the upper limit of odor when working with a liquid composed of an aliphatic polyamine, and is a numerical value proportional to the ammonia concentration in the liquid according to Henry's law.
[0034]
The standard measurement is carried out by sealing a liquid composed of an aliphatic polyamine together with a gas, keeping the temperature at 20 ° C., and quantifying the ammonia concentration in the gas in an equilibrium state. The gas used at this time is not particularly limited as long as it does not react with a liquid composed of an aliphatic polyamine in a short time, such as carbon dioxide. Non-reactive gases include nitrogen and argon. Oxygen in the air reacts with the amine, but usually this is a very slow reaction, so air can be used, and it is preferable because the measurement is simple.
[0035]
In order to reach the equilibrium of the ammonia concentration in the gas, 10 g to 2 kg of the liquid composed of aliphatic polyamine is sealed in a sealed container having a volume 1.2 to 5 times the volume of the liquid composed of aliphatic polyamine together with the gas. It is preferable to carry out by leaving it to stand for 4 hours or more below.
[0036]
For the determination of the ammonia concentration in the gas, a method using gas chromatography or an ammonia detector tube is preferable. In particular, a method using an ammonia detector tube is more preferable because it does not require a large-scale apparatus and can be easily applied at a manufacturing site. As the ammonia detector tube, for example, one commercially available from Gastec Corporation can be used.
[0037]
When measuring the ammonia concentration, open a small opening in the container so that the ammonia concentration in the container does not change as much as possible, and quickly insert the needle of the syringe for gas chromatography and the tip of the detection tube into the container to collect the gas. To do. In order to open a small opening, for example, a method of opening a plug in a pre-opened opening and opening the plug immediately before measurement or a method using a septum is used.
[0038]
If the ammonia concentration in the gas in equilibrium with the liquid comprising the aliphatic polyamine is 100 ppm or less, the irritation is not a problem even if there is a slight ammonia odor, which is preferable. Furthermore, if it is 10 ppm, since an ammonia odor is hardly felt, it is more preferable.
[0039]
In the present invention, when a liquid composed of an aliphatic polyamine is used as a curing agent for an epoxy resin, the hermetic container in which the low-bromated aliphatic polyamine is sealed in the present invention is opened immediately before use, such as before construction. The contents are mixed with an epoxy resin to form an epoxy resin composition. In the present invention, since the liquid composed of the aliphatic polyamine of the contents sealed in the hermetic container is removed from the volatile odor component and is sealed in the hermetic container in a substantially oxygen-free state, it can be used for a long time. Even when stored, there is no generation of odor due to oxidation of the aliphatic polyamine, and there is almost no odor when opened.
[0040]
An epoxy resin is an epoxy compound having a plurality of epoxy groups in the molecule.
[0041]
Examples of the epoxy compound used include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, novolac type epoxy resin, epoxy resin having a fluorene skeleton, and phenol compound. Epoxy resin made from a copolymer of dicyclopentadiene, diglycidyl resorcinol, glycidyl ether type epoxy resin composition such as tetrakis (glycidyloxyphenyl) ethane, tris (glycidyloxyphenyl) methane, tetraglycidyldiaminodiphenylmethane, Glycidylamine type epoxy resins such as triglycidylaminophenol, triglycidylaminocresol, tetraglycidylxylenediamine, vinyl Alicyclic epoxy resins, and mixtures thereof, such as cyclohexene diepoxide and the like.
[0042]
The epoxy resin composition may further contain a compound having one epoxy group in the molecule as a reactive diluent. Examples of the compound having one epoxy group in the molecule include phenyl glycidyl ether, butyl glycidyl ether, allyl glycidyl ether, styrene oxide, and octylene oxide.
[0043]
Furthermore, the epoxy resin composition can contain a component that reacts with an amine other than the epoxy compound. Examples of components that react with amines include isocyanates such as hexamethylene diisocyanate and tolylene diisocyanate. Still another example is an α, β-unsaturated carbonyl compound that undergoes a Michael addition reaction with an amine.
[0044]
The epoxy resin composition has other components such as plasticizers, dyes, organic pigments, carbon black, silica and other organic and inorganic particles, polymer compounds, antioxidants, UV absorbers, coupling agents, and surface activity. An agent or the like can be blended.
[0045]
The epoxy resin composition can be used as an adhesive, a paint, a primer, a sealing agent, a casting material, a matrix resin of a fiber reinforced composite material, and the like.
[0046]
One method of using an epoxy resin composition as a matrix resin for a fiber reinforced composite material is to laminate a reinforcing fiber processed into a sheet shape while impregnating the epoxy resin composition and cure at room temperature or higher. A hand layup method is used. Here, as the reinforcing fiber, carbon fiber, glass fiber, aramid fiber, or the like is used, and as a form in the case of processing into a sheet shape, a woven fabric, a mat, a unidirectional sheet, or the like can be given.
[0047]
The hand lay-up method is used for manufacturing members such as bathtubs, tanks, hulls, and automobile parts, and for repairing and reinforcing fiber-reinforced composite materials and concrete structures.
[0048]
Examples of the method of using the epoxy resin composition as a matrix resin for a fiber-reinforced composite material include a filament winding method and a resin transfer molding method.
[0049]
In the present invention, since the liquid composed of the aliphatic polyamine of the contents sealed in the hermetic container is removed from the volatile odor component and is sealed in the hermetic container in a substantially oxygen-free state, it can be used for a long time. Even when stored, there is little odor generation due to oxidation of the aliphatic polyamine, and there is almost no odor even when opened. Therefore, when working in buildings indoors, especially when refurbishing and repairing buildings that are already in use, epoxy resins are used for adhesives, paints, primers, sealants, matrixes for fiber reinforced composite materials for repair and reinforcement, etc. When used as a curing agent in the composition, the occupant is less likely to be uncomfortable and is preferably used.
[0050]
【Example】
The present invention will be specifically described with reference to examples. In the following examples, the measurement of the ammonia concentration in a gas in equilibrium with a liquid composed of an aliphatic polyamine (hereinafter, only described as “ammonia concentration” in the examples) is performed by measuring the liquid composed of an aliphatic polyamine and the air. This was done by leaving the sealed container in a 20 ° C. environment for 4 hours, opening a small opening, inserting the tip of the ammonia detector tube into the interior, sucking the gas, and reading the discoloration of the detector tube. . As the ammonia detector tube, ammonia No. 3L manufactured by Gastec was used unless otherwise specified.
[0051]
Example 1
50 g of commercially available bisaminomethylnorbornane (manufactured by Mitsui Toatsu) was placed in a flask having a volume of about 200 cm ³ equipped with a three-way cock. The sample felt a strong ammonia odor. When the ammonia concentration at this time was measured using an ammonia detector tube (ammonia No. 3HM, manufactured by Gastec), it was 1400 ppm.
[0052]
Subsequently, this sample was degassed by reducing the pressure to about 200 Pa for 10 minutes using a vacuum pump. In the sample after the treatment, the initial ammonia odor disappeared. Further, the ammonia concentration was measured and found to be 2 ppm.
[0053]
(Example 2)
50 g of bisaminomethylnorbornane (manufactured by Mitsui Toatsu) was placed in a flask having a volume of about 200 cm ³ , and nitrogen gas was passed through the glass tube with the tip in the liquid at a flow rate of 100 cm ³ / min for 1 hour. In the sample after the treatment, the initial ammonia odor disappeared. The ammonia concentration was measured and found to be 8 ppm.
[0054]
(Example 3)
The bisaminomethylnorbornane degassed in the same manner as in Example 1 was returned to normal pressure using nitrogen gas, and the airtight container was sealed. This was left in an oven at 50 ° C. for 20 hours for an aging acceleration test. After cooling to 20 ° C., it was opened and examined for the presence or absence of odor, and no ammonia odor was felt. The ammonia concentration was measured and found to be 4 ppm.
[0055]
Example 4
The bisaminomethylnorbornane degassed in the same manner as in Example 1 was returned to normal pressure using nitrogen gas, and a 10 cm ³ sample was measured in a glass syringe under a nitrogen stream, and the piston was pushed upward and the piston was pushed inside. After removing the bubbles, the tip of the syringe was sealed with a rubber cap. This was left in an oven at 50 ° C. for 20 hours. After cooling to 20 ° C., the cap was removed, the sample was taken out in a separate container and examined for the presence of odor, and no ammonia odor was felt. The container was covered and left at 20 ° C. for 4 hours. The ammonia concentration was measured and found to be 2 ppm.
[0056]
(Comparative Example 1)
The degassed bisaminomethylnorbornane as in Example 1 was returned to normal pressure using air, and the container was sealed. When this was left in an oven at 50 ° C. for 20 hours, cooled to 20 ° C., opened and examined for the presence of odor, a strong ammonia odor was felt. Further, when the ammonia concentration was measured using an ammonia detector tube (ammonia No. 3HM, manufactured by Gastec), it was 2000 ppm.
[0057]
(Example 5)
25 g of bisaminomethylnorbornane (manufactured by Mitsui Toatsu), 25 g of isophoronediamine (manufactured by Wako Pure Chemical Industries), and 2 g of Aerosil 380 (manufactured by Nippon Aerosil) are placed in a flask having a volume of about 200 cm ³ and stirred for 20 minutes with a magnetic stirrer. Was degassed by reducing the pressure to about 200 Pa for 10 minutes. In the sample after the treatment, the ammonia odor before the deaeration treatment disappeared. The ammonia concentration was measured and found to be 4 ppm.
[0058]
(Example 6)
A composition obtained by mixing bisaminomethylnorbornane, isophoronediamine, and Aerosil 380, which had been degassed in the same manner as in Example 5, was returned to normal pressure using nitrogen gas, and the container was sealed. This was left in an oven at 50 ° C. for 20 hours. After cooling to 20 ° C., it was opened and examined for the presence or absence of odor, and no ammonia odor was felt. The ammonia concentration was measured and found to be 5 ppm.
[0059]
(Example 7)
1 kg of bisaminomethylnorbornane (manufactured by Mitsui Toatsu) was placed in a cylindrical separable flask equipped with a gas introduction tube and a stirring blade. Nitrogen was gradually introduced into the bisaminomethylnorbornane from the gas introduction tube, and the pressure was reduced to about 4000 Pa with an aspirator while stirring for 2 hours. The ammonia odor was not felt in the liquid after the treatment. The ammonia concentration was measured and found to be 5 ppm.
[0060]
【The invention's effect】
According to the present invention, particularly suitable for use in large two-pack type epoxy resin be used indoors, it is possible to provide a very small aliphatic polyamine down odor.

Claims (5)

After removing the volatile odor component dissolved in the liquid from the aliphatic polyamine, the liquid is sealed in a hermetic container in a substantially oxygen-free state, sealed with gas and kept at 20 ° C. to reach an equilibrium state. the gaseous ammonia concentration in state is characterized in that to obtain the liquid is 100ppm or less, aliphatic polyamine down method of odor removal. 2. The aliphatic group according to claim 1, wherein the means for removing the volatile odor component is to degas the liquid composed of the aliphatic polyamine under reduced pressure and then to return to normal pressure using a gas substantially free of oxygen. polyamine down method of odor removal. It said means for removing volatile odor components, the liquid consisting of aliphatic polyamines, aliphatic polyamine down method of odor removal of oxygen according to claim 1, wherein is to vent the gas substantially free. The means for enclosing the liquid in an airtight container in a substantially oxygen-free state is to enclose the liquid in an airtight container together with a gas not containing oxygen. odor removal method aliphatic polyamine down. The aliphatic polyamid according to any one of claims 1 to 3, wherein the means for enclosing the liquid in an airtight container in a substantially oxygen-free state is filling the liquid in the entire inner volume of the airtight container. Odor removal method.