JPS6017347B2 - Insoluble β-aminopropionamide methylated polymonovinyl aromatic compound molded product and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel molded article of an insoluble polymonovinyl aromatic compound having a crosslinked structure with a 3-aminopropionamidomethyl group, and a method for producing the same.

In recent years, the importance of functional polymers has been actively discussed. A typical example of functional polymers that have been used for a long time is ion-exchange resin, but recently it has been used not only for simple exchange of low-molecular ions, but also for more advanced functions, such as adsorption and desorption of medium- and high-molecular substances. , functions such as ion exchange, enzymes, and bacterial cell immobilization are increasingly required. However, conventional ion exchange resins cannot fully meet these requirements. The present inventors have arrived at the present invention as a result of intensive studies to find something that has these advanced functions. The present invention has the following configuration. That is, the present invention provides: '1) per mole of aromatic nucleus in the permanent polymonovinyl aromatic compound, at least 0.01 mole or more is 3-amino/
Inorganic 8-aminopropionamidomethylated polymonovinyl aromatic compound molded product characterized by being substituted with a propionamidomethyl group and '2) Insoluble acrylamide methylated polymonovinyl aromatic compound molded product treated with an amino compound. The present invention relates to a method for producing a molded article of an insoluble P-aminopropionamidomethylated polymonovinyl aromatic compound.

The present invention will be explained in detail below.

The molded product of the present invention is characterized by having an amide group in the middle of the perversion extending from the polymer main chain, and having an amide group at the tip of the side chain.

That is, the amine/group has the ability to act as an active site during ion exchange and adsorption, but if the amide/group is present in the polymer backbone, through a rigid and bulky side chain substituent, or through one or two atoms, If they are bonded together, ion exchange and adsorption of medium to high molecular weight substances cannot be carried out sufficiently due to steric hindrance. In addition, even when an amino group is bonded to the tip of a long and flexible side chain, if that side chain is hydrophobic, it has sufficient ability to ion exchange and adsorb high molecular weight substances while being hydrophilic. unable to demonstrate. On the other hand, in the molded product of the present invention, the amino group is bonded to the aromatic nucleus bonded to the polymer primary mirror via a straight chain consisting of 5 atoms, and the amino group which is the hydrophilic group of the straight mirror is bonded to the aromatic nucleus bonded to the polymer primary mirror. Because of the presence of , it exhibits excellent ability in ion exchange and adsorption of medium and high bases, as well as adsorption of enzymes and bacterial cells. Further, the molded product of the present invention is characterized in that it is technically easy and can be manufactured by a rational method that is highly economical. In the present invention, the insoluble polymonovinyl aromatic compound molded product refers to a molded product made of an insoluble polymonovinyl aromatic compound alone or a substantially inert polymer that has a mechanical strength-maintaining effect (hereinafter abbreviated as reinforcing polymer). This refers to a molded product of a mixture of the following: Specific examples of molded products include particles with a diameter of 500 microns or less, and particles with a thickness of 0.1 to 500 microns or less.
Examples include 500 micron fibers and highly processed products thereof.

The insoluble polymonovinyl aromatic compound referred to in the present invention is
Styrene, Q-methylstyrene, vinyltoluene, pinylxylene, pinylnaphthalene, P-chlorostyrene,
A polymer whose main component is a monovinyl compound having an aromatic nucleus represented by vinyl fluorene, etc., in which the aromatic nucleus in one polymer molecular chain and the aromatic nucleus in another polymer molecular chain mutually form the general formula tCHRtin (in the formula R is hydrogen atom or carbon number 1
~4 alkyl group, n represents an integer of 1 to 12)
A crosslinking group represented by or the general formula CH20)nCH2
- (in the formula, n represents an integer of 1 to 4) means a crosslinked or sulfonyl group-bonded polymer.

The amount of crosslinking group can be adjusted depending on the application, but
Generally, the amount of crosslinking groups is increased for ion exchange of low molecular weight ions, and the amount of crosslinking groups is decreased for adsorption of medium to high molecular weight substances. The 8-aminopropionamidomethyl group referred to in the present invention has the general formula R, R2N-CHR3-CH
R4-CO-NR5-CH2- (in the formula, R,, R2 represents a hydrogen atom, a lower alkyl group, an aryl group, or an aralyl group, R. and R2 may be the same or different, R,, R4, R5 represents a hydrogen atom or a methyl group).

In order to express the function of the molded product of the present invention, the B-aminopropionamide methyl group in the molded product of the present invention contains at least 0.01 mole of aromatic nucleus per mole of the insoluble polymonovinyl aromatic compound, more preferably It is preferable that 0.2 mole or more is substituted.

In general, a large amount of 3-aminopropionamidomethyl group is preferable for applications targeting low-molecular ions, but a certain amount or more is not necessary for adsorption of large substances such as enzymes and bacterial cells. . The method for producing the molded product of the present invention is based on an insoluble acrylamide methylated polymonovinyl aromatic compound molded product (
This is achieved by treating the raw material (hereinafter referred to as molded product) with an amino compound.

There are no particular limitations on the reaction conditions, but usually, the raw material molded product and the amino compound are mixed in the presence or absence of a solvent,
A method of heating at a temperature of 0 to 15 degrees Celsius, more preferably 50 to 100 degrees Celsius, for 0.1 to 2 hours is employed. The amount of acrylamide methyl groups in the molded product can be adjusted by changing the ratio of the raw material molded product and the amino compound used, the reaction temperature, and the reaction time. The raw material molded product is obtained by a method of treating an insoluble polymonovinyl aromatic compound molded product with an acrylamide methylating agent such as N-methylolacrylamide in the presence of an acid catalyst and a swelling agent (Tokuken Showa 52-
51991) can be easily obtained. The amino compounds used in the present invention include ammonia,
In addition to hydroxylamine and hydrazine, it is an organic amino compound having a primary or secondary amino group. Specific examples include methylamine/ethylamine, propylamine, butylamine, dimethylamine, dipropylamine, di(n- phthylamine), morpholine, piperazine, ethylenediamine, hexamethylenediamine, N-methylaniline, N-methylbenzylamine, lysine,
N-methylamine/ethanol, diethylenetriamine,
Examples include bentaethylenehexamine and polyethyleneimine.

Since the reaction between the amino compound and the acrylic group in the molded raw material in the manufacturing method of the molded product of the present invention is a reaction that proceeds quantitatively, the amount of the amino compound used is equivalent to the amount of amino groups required in the molded product. Any above is fine.

In this case, when the amino compound is a secondary monoaminone, the crosslinking density of the molded product does not change, but when the amino compound has one NH2 group or multiple secondary amino groups, the amino compound reacts with multiple acrylic groups,
The crosslinking density of the molded article increases. The increase in crosslink density is suppressed by increasing the amount of amino compound used. Examples of the solvent used in the reaction between the raw material molded product and the amino compound include water, lower alcohols such as methanol, ethyl alcohol, and n-butanol, and ethers such as dioxane and tetrahydrofuran.

Furthermore, when the amino compound is a low boiling point compound, the reaction time can be shortened by carrying out the reaction under pressure. The molded product of the present invention can be used for a wide range of applications, from ion exchange of low-molecular anions to adsorption of medium- and high-molecular weight substances, ion exchange, and immobilization of enzymes and microbial cells, but the most commonly used product will depend on the individual application. It is preferable to select and use a molded product with a specified standard.

For applications requiring high mechanical strength of molded products, molded products containing reinforcing polymers, especially fibers, are preferably used.

The reinforcing polymer is not particularly limited as long as it is physically and chemically inert and can maintain mechanical strength during the manufacturing process of the molded product of the present invention.

Specific examples include polyethylene, polypropylene poly(3-methylbutene-1), poly(4-methylbentene-1)
Examples include crystalline polyQ-olefins such as polyvinyl chloride, poly(halogenated olefins) such as polyvinylidene chloride, polyesters such as polyethylene terephthalate, and polyamides such as polyp-phenylene terephthalamide. . In particular, crystalline polyQ-olefins are most preferred due to their high degree of chemical stability. The arrangement of the reinforcing polymer inside the molded product of the present invention is such that when the molded product is a fiber, the insoluble 8-aminopropionamide methylated polymonovinyl aromatic compound (hereinafter referred to as the "base polymer") and the reinforcing polymer are arranged in a disordered manner. Finely dispersed simple mixed fiber type, core-sheath type composite fiber type in which the reinforcing polymer is the core and the basic polymer is placed on the outside, and the basic polymer is the sea component and the reinforcing polymer is the sea component. There is a type of multicore sea-island type conjugate fiber that has a large number of island components dispersed therein, and each of these types has its own characteristics and can be used effectively.

The single mixed fiber type has the reinforcing polymer protruding outside at a proportion of its mixing ratio, so its adsorption performance is slightly inferior, but it has the advantage of low swelling and shrinkage, while the core-sheath type composite fiber type has the ability to absorb. Although it has the advantage of high performance, it has the disadvantage of large swelling and shrinking, and the core and sheath are likely to peel off as the swelling and shrinkage is repeated. The multicore sea-island type composite fiber type maintains the advantages of both while improving the disadvantages of both, with a large adsorption chamber and high peeling resistance.
Especially excellent. In this case, if 1 to 30% of a chemically stable reinforcing polymer is mixed in the sea component, the swelling and shrinkage will be reduced and the succinic acid resistance will be further improved. Further, the larger the number of islands, the better, but there are technical constraints, and 5 to 30 islands are usually used, and 10 to 20 islands are preferably used. Examples will be described below.

Example 1 Polypropylene (Mitsui Noblen J Pan-G) was used as the island component, 49.5 parts of polystyrene (Styron 666), 1.5 parts of low molecular weight polystyrene (Hima ST-120), 7.5 parts of polypropylene and low molecular weight polypropylene (
Viscol 550P) 1.5 parts of the mixture as the sea component, 255q0 so that the sea-island ratio is sea: island = 60:40.
After melting the composite fiber (16 islands), the multicore Umejima type composite fiber (single weave 3.7 denier, tensile strength 3.4/d, elongation 38%) was drawn by 4 times. I got it.

In a mixed solution of 100 parts of nitrobenzene and 100 parts of 98% sulfuric acid, 5.3 parts of paraformaldehyde was dissolved at 20°C, then the solution was cooled to 0°C, and the temperature was increased from 0 to 5°C.
While maintaining the temperature at ℃, N-methylol acrylamide 16 base was added and dissolved.

100 parts of the multicore sea-island type composite fibers were added to the obtained solution, and the mixture was shaken at 2000 °C for 20 hours to react. The obtained acrylamide methyl synthetic fibers were thoroughly washed with water and methanol, and then vacuum dried at 5,000 °C to obtain a total of 141 parts of acrylamide methyl synthetic fibers. Next, the various amino compounds shown in Table 1 were dissolved in water or methanol to give a concentration of 20%.
and heated under reflux cooling for 8 hours. The 8-aminopropionamidomethylated fibers obtained by washing with water and drying were examined for elemental analysis, water content, anion exchange capacity, and albumin adsorption capacity in the hydrochloride form, and the results shown in Table 1 were obtained. However, the moisture content can be determined by swelling a dry sample (Wo) in water for one day, squeezing it thoroughly, wiping the water on the fiber surface with a filter paper, immediately determining the weight (W), and using the following formula: It is calculated from.

Table 1 Moisture content = bad & W.

The amount of albumin adsorbed is determined by using a sample with a known dry weight (W) at p
The albumin concentration in the aqueous solution before and after adsorption was measured using the copper-Folin reagent method. This is the value calculated using the following formula.

Albumin adsorption amount Ko C Mito San XV [Female/However, in the formula C
, indicates the albumin concentration before adsorption, C2 indicates the albumin concentration after adsorption, and V indicates the amount of aqueous solution used.

For C2, V was adjusted so that the concentration did not fall below 5 o/〆. The exchange capacity is determined by regenerating with a 1N aqueous sodium hydroxide solution, then treating with 1N hydrochloric acid, calculating the number of equivalents of consumed hydrochloric acid from the amount of remaining hydrochloric acid, and calculating that value by calculating the dry weight in grams of the hydrochloride sample. It is the value divided by the number, and this can be considered as the adsorption state for low molecular ions.

The nitrogen content and exchange capacity determined from elemental analysis in the table correspond well.

In the comparative example in the table, the total hydrochloride of aminomethyl synthetic fibers obtained by subjecting the total acrylamide methyl synthetic fibers obtained in this example to 2q Terama far-flow heating in concentrated hydrochloric acid was investigated.

From the table, the fibers of the present invention (dimethylaminopropionamide methyl synthetic fiber review material-1, di-n-propylaminopropionamide methyl synthetic fiber vertical sample 1-2, di-n-butylamino/propionamide methyl synthetic fiber sample-3 and n-butylamino It can be seen that the pyrropionamide methyl synthetic fiber total sample-4) has a larger albumiso adsorption ability than the comparative example, despite having a small exchange capacity and a water content of 4.0 mm.

In particular, dimethylaminopropionamide methylated fiber sample-5 exhibits large albumin adsorption chambers. Example
2 0.005 to 30% of the acrylamide methyl insoluble and soluble polymonovinyl aromatic compound fiber obtained in Example 1
In a 0.005 to 10% dimethylamine aqueous solution containing 1 mole of dimethylamine, treated with 5 pi for 1 to 2 hours,
Each fiber having an exchange capacity shown in Table 2 was obtained.

The amount of albumin adsorbed on the obtained fibers was measured and the results shown in Table 2 were obtained. However, in the table, "Ratio of aromatic nuclei in the base polymer being substituted with 8-aminopropionamide groups" (substitution rate)
is calculated from the exchange capacity using the following formula. 2
93xQ substitution rate=1000-8,. 5×Q×100 where Q is the exchange capacity (meq/night).

Table 2 Example 3 5 anchor parts of polypropylene and 5 anchor parts of polystyrene were simply mixed and melt-spun, and 6 anchor fibers obtained by stretching 4 times were mixed with 90 parts of nitrobenzene, 600 parts of 98% sulfuric acid, and paraformaldehyde. 150 in a solution consisting of 0.09
0 for 30 minutes and then the reaction mixture was given oo
The N-methylolacrylamide 6 base was dissolved while maintaining the temperature at ~15 qo.

After shaking the reaction mixture for 2 q hours, the fibers were washed with water and dried to obtain acrylamide methyl synthetic fiber longitudinal parts. When this was hydrolyzed with hydrochloric acid, it was converted to ami/methyl synthetic fiber total hydrochloride having an exchange capacity of 2.8 heq/night and a water content of 2.1. 30% of the total 11 parts of acrylamide methyl synthetic fiber obtained above
Soak in dimethylamine aqueous solution for 20 minutes, 6000 for 1
A total of 13.8 parts of N,N-dimethylpropionamidomethyl synthetic fibers were obtained by reacting for a calm period.

Claims (1)

[Scope of Claims] 1. An insoluble β-aminopropionamidomethyl, characterized in that at least 0.01 mole per mole of aromatic nucleus in the insoluble polymonovinyl aromatic compound is substituted with a β-aminopropionamidomethyl group. molded polymonovinyl aromatic compound. 2. A method for producing an insoluble β-aminopropionamidomethyl polymonovinyl aromatic compound molded product, which comprises treating an insoluble acrylamide methylated polymonovinyl aromatic compound molded product with an amino compound.