JPS63118328A - High-molecular weight poly-beta-alanine polymer and production thereof - Google Patents

Abstract

PURPOSE:To obtain the titled polymer having low metal content, high content of primary amide group and excellent physical properties and useful as a polymer additive, molding material, etc., by polymerizing acrylamide using an extremely small amount of an alkaline earth metal alcoholate as a catalyst. CONSTITUTION:Acrylamide which is preferably dehydrated in advance is polymerized in the presence of <=1/500mol (based on 1mol of the acrylamide) of an alkaline earth metal alcoholate (e.g. calcium methylate) to obtain the objective polymer containing 1.4-10mmol of primary amide group per 1g of the polymer and having a reduced viscosity (etasp/c) of usually 2-15dl/g. The reaction can be smoothly performed optionally in a solvent such as xylene at 80-140 deg.C in the absence of oxygen. The obtained polymer is usually a mixture of a formic acid-soluble component and an insoluble component at a weight ratio of 20:80-100:0.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a high molecular weight poly-β-alanine polymer and a method for producing the same. More specifically, the present invention provides high-quality polymers useful for applications such as polymer additives, molding materials such as films and sheets, paints, adhesives, coatings, printing inks, paper processing agents, soil conditioners, and fiber treatment agents. The present invention relates to a poly-β-alanine polymer having a high degree of polymerization and a method for producing the same.

Prior Art A method for producing poly-β-alanine by hydrogen transfer polymerization of acrylamide was first reported in 1957.
Since then [Journal of American Chemistry/L/
Society (J, Am, Chem, Soc, )
J Vol. 79, p. 3760 (1957)], numerous reports have been made.

This hydrogen transfer polymerization of acrylamide is carried out in a solvent such as toluene, xylene, chlorobenzene, or pyridine using an alkali metal alcoholide in an amount of ~1710 mmol per mole of acrylamide as a catalyst, and N-phenyl as a radical polymerization inhibitor. - It is carried out by heating to a temperature of 80 to 140° C. in the presence of β-naphthylamine or the like.

However, the polymer obtained by such a method contains not only a hydrogen transfer polymer but also a vinyl polymer of acrylamide [Kobunshi Kagaku, Vol. 20, No. 364]
Page (1963)]. Therefore, in the normal hydrogen transfer polymerization of acrylamide, a polymer is produced that is at the bottom of the tank, and the ratio of the hydrogen transfer polymerization portion to the vinyl polymerization portion of this copolymer depends on the type of catalyst used and the responsibility. 1. It depends on the reaction conditions, etc.

For example, when the amount of catalyst relative to acrylamide decreases, the proportion of hydrogen transfer type tends to decrease and the proportion of vinyl polymerization type tends to increase. ′! In addition, the catalyst amount is 1 acrylamide.
It is also well known that when the amount is less than 1/1 0q mole, the polymerization reaction becomes difficult to proceed and the yield of the polymer decreases. For example, using sodium butoxide as a catalyst, the amount of catalyst is '/20 per mole of acrylamide.
It has been reported that when reacting with 0 mol, the polymer yield is 0 to 5% [Priten Chemical Society Japan, Vol. 33, p. 906 (1960)].

In addition, a method has been proposed in which poly-β-alanine is produced by polymerizing acrylamide using approximately 1/3 o mol of calcium ethylate per 1 mol of acrylamide as a polymerization catalyst in M solvent. (Tokuko Show 38-2
6791), the polymer obtained by this method has a reduced viscosity of 1.0 or less and is a low polymer.

Friend, the present inventors have previously discovered and proposed a method for producing poly-β-alanine by hydrogen transfer polymerization of acrylamide using a calcium alcolade having 3 or more carbon atoms as a catalyst. fcc% 1986-2137
Publication No. 22). However, although this method yields poly-β-alanine with a high degree of polymerization, the amount of calcium alcoholade used as a catalyst is limited per mole of acrylamide.

Since the amount is 0.02 mol or more, a large amount of alkaline earth metal (calcium) remains in the obtained polymer, and the amount of primary amide groups in the polymer is also small. It was not a satisfying method.

In this way, in the conventional method, when producing a poly-β-alanine polymer, as mentioned above, a catalyst is used in an extremely large amount of about 1/1° to 1/100 mol per 1 mol of acrylamide. Because alkali metals and alkaline earth metals derived from the catalyst remain in the resulting product and these metals are bound or coordinated to the polymer, normal cleaning operations are not necessary. However, it is difficult to completely remove the metal using special methods such as ion exchange treatment.

Problems to be Solved by the Invention An object of the present invention is to provide a high molecular weight poly-β-alanine polymer having a high content of primary amide groups and a low metal content.

As a result of extensive research to develop a high molecular weight poly-β-alanine polymer with a large number of primary amide groups, the present inventors discovered that it could be used as a catalyst. By using alkaline earth metal alcolade, highly refining the raw material acrylamide and solvent, and devising the polymerization operation, the polymerization reaction proceeds smoothly even though the amount of soil used for the catalyst is significantly less than in conventional methods. They also found that the produced polymer had excellent physical properties, and based on this knowledge, they completed the present invention.

A monoalanine polymer is provided.

According to the present invention, this poly-β-alanine polymer can be produced by polymerizing acrylamide using an alkaline earth metal alcoholade catalyst in an amount of not more than 115 oomol per mol of acrylamide.

The present invention will be explained in detail below.

The poly-β-alanine polymer of the present invention has, as main structural units, a structural unit represented by formula % (1) and a structural unit represented by formula % (1). 0NH2, and the content of the structural unit represented by the formula (II), that is, the content of the primary amide group, is 1.4 to 10 mmol per polymer if. It is a polymer in the range of Moreover, the poly-β-
Alanine polymers have a wide range of molecular weights, from those soluble in formic acid to those insoluble in formic acid, and their reduced viscosity (η sp/c) is 2 di/ or more. As described above, the polymer of the present invention is significantly different from conventional poly-β-alanine in that it has a high content of primary amide groups and a high reduced viscosity of 2 or more.

In the present invention, an alkaline earth metal alcoholade is used as a catalyst. Examples of the alkaline earth metal alcoholade include calcium methylate, calcium ethylate, calcium-n-propylade, and strontium ethylate.

Examples include barium ethylate and magnesium methylate. These catalysts are acrylamide 1
It is necessary to use 175 oo mol or less based on the mole.

Generally, as the amount of catalyst relative to acrylamide decreases, 1
Hydrogen transfer polymers in the polymer decrease, and as a result, the content of primary amide groups increases.

On the other hand, when the amount of catalyst relative to acrylamide increases, the structural unit (I) fcH20H formed by hydrogen transfer polymerization
The content ratio of 2cONH+ increases, and the content ratio of the structural unit (II) -E-OH2CH+ having a primary amide group (!0NH2) decreases. In order to obtain a poly-β-alanine polymer in the range of .4 to 10 mmol, the amount of catalyst is less than ``/soo mol, preferably ``/so, ooo to 1/500 mol per mol of acrylamide. , more preferably in the range of '/3o, oo to 1/500 mole.Also, if the amount of catalyst exceeds '1500 mole, the resulting polymer may be used as a heat stabilizer for polyacetal resin, for example. On the other hand, if this amount is less than '/so, ooo moles, the polymerization reaction will be difficult to proceed, the yield will decrease, and the resulting poly-β-alanine polymer The content of primary amide groups in the polymer becomes too large, and when the polymer is used as a heat stabilizer for polyacetal resin, the heat stabilizing effect is not sufficiently exhibited.

The polymerization reaction in the present invention may be carried out in the absence of a solvent or in the presence of a solvent. As the solvent, for example, xylene, toluene, 0-dichlorobenzene, etc. can be used.

In the polymerization reaction, it is preferable to reduce the amount of water in the reaction system as much as possible, and therefore it is advantageous to remove the water in the solvent and raw material acrylamide in advance. Water in the solvent can be removed by using a dehydrating agent, for example, or
It can be removed by azeotropic distillation. On the other hand, moisture in acrylamide can be reduced by, for example, adding dehumidified air to the acrylamide maintained at a temperature in the range of 40 to 60°C for 10 to 24 hours.
The acrylamide can be removed by waiting for about 5 to 10 hours at a temperature in the range of 40 to 60° C. under a vacuum of 40 to 100 Torr.

Furthermore, since this polymerization reaction is preferably carried out in the absence of oxygen, it is usually carried out using acrylamide from which oxygen has been removed and a solvent under an inert gas atmosphere such as nitrogen or argon. In order to remove acrylamide and oxygen in the solvent, for example, a method of reducing the pressure and then purging with nitrogen or purging with nitrogen gas is used.

Furthermore, if impurities exist in the polymerization system, the desired poly-
Since a β-alanine polymer cannot be obtained, it is preferable to remove impurities from the system as much as possible, and the catalyst used should be stored under a nitrogen gas atmosphere to prevent deterioration due to moisture and oxygen. This is desirable. In the present invention, it is preferable not to use radical polymerization inhibitors such as teramine, which are used in the conventional production of poly-β-alanine polymers. This is because the polymerization inhibitor poisons the catalyst in the same way as the impurities mentioned above, inhibiting the production of the desired polymer.

In the present invention, the reaction temperature is usually selected within the range of 70 to 150°C, preferably 80 to 140°C.

If the reaction temperature is less than 70°C, the reaction rate is too slow to be practical.

The polymerization reaction is carried out, for example, by thoroughly dispersing a predetermined amount of catalyst in a dehydrated and purified solvent, adding dehydrated and purified acrylamide, and heating the mixture in an inert gas atmosphere. As the polymerization method, a batch solution polymerization method, a batch bulk polymerization method, a continuous solution polymerization method, a continuous bulk polymerization method, etc. can be used.

The poly-β-alanine polymer thus obtained is
Generally, it is a mixture of polymers with different degrees of polymerization. That is, depending on the polymerization conditions, the polymerization product may be a formic acid-soluble poly-β-alanine polymer (hereinafter referred to as poly-β-alanine polymer (shu), or this and a formic acid-insoluble poly-β-alanine polymer). It is obtained as a mixture with an alanine polymer [hereinafter referred to as poly-β-alanine polymer (B)]. Generally, when the polymerization temperature is low, only poly-β-alanine polymer (4) is produced. However, when the polymerization temperature is above a certain temperature, poly-β-alanine polymer (B) is produced together with poly-β-alanine polymer (A).

The temperature at which the poly-β-alanine polymer (B) starts to form depends on the soil used for the alkaline earth metal alcoholado catalyst, but generally the polymerization temperature is 95 to 140°C.
Poly-β-alanine polymer (A) begins to be produced, and as the temperature increases, the proportion of polymer (B) increases.

For example, in solution polymerization.

When the reaction temperature is 90°C, poly-β-alanine polymer (B)
is hardly produced, but it is produced at a rate of about 1% at 1 g at 0°C. On the other hand, in bulk polymerization.

For example, an alkaline earth metal catalyst is used for 1 mole of acrylamide at a temperature of t''100.
Poly-β-alanine polymer (B) is polymerized stepwise at 1.5 hours at ℃, 1.5 hours at 110℃, 1.5 hours at 1g0℃, and 1.5 hours at 140℃. 3-5%
generate.

When only the poly-β-alania polymer (A) is produced, this may be separated from the reaction system. On the other hand, when poly-β-alanine polymers (A) and ω) are produced, poly-β-alanine polymers (A) and 03) t-
Can be separated using differences in solubility.

Furthermore, by heat-treating the polymerization product at a temperature of 140 to 180 DEG C., the poly-β-alanine polymer (A) can be converted to (2). For example, heat treatment time is 0
．． In the case of 5 to 3 hours, the poly-β-alanine polymer) is converted to about 40 to 50% (B). Therefore, the polymerization product is heat-treated in this way to convert the poly-β-alanine polymer (A) therein to (B), and then the poly-β-alanine polymer 0) is separated. Good too.

Methods for separating the polymerization reaction product from the reaction-completed solution are 1. For example, in the case of solution polymerization, after removing the solvent by means such as filtration, the acrylamide in the product is washed with an appropriate solvent such as acetone or methanol. It is possible to use a method of removing the

Furthermore, in order to separate the poly-β-alanine polymer (-4) and (B), for example, a mixture of these is added to a solvent that dissolves only the poly-β-alamonopolymer (A), and the mixture is filtered. Poly-β-alanine polymer (B) by means such as
is isolated, while poly-β-alanine polymer (A) is
Pour the filtrate into a solvent such as methanol or acetone,
After the polymer (A) was precipitated.

It can be recovered by means such as filtration.

Examples of the solvent that dissolves only the poly-β-alanine polymer (A) include water and formic acid.

The poly-β-alanine polymers (A) and CB) are
In both cases, the above-mentioned structural unit (1) is used as the main structural unit.
and (It), and the content of the primary amide group is in the range of 1.4 to 10 mmol per 1 g of one polymer. Mayu, the reduced viscosity of the poly-β-alanine polymer (A) is 2 under the measurement conditions of a monovalent electrolytic acid solution and a temperature of 35°C.
It is in the range of ~1'5dl19. Furthermore, poly-β-alanine polymer (A) in the polymer obtained in the present invention
The weight ratio of and 03) is usually 20:80 to 100.
: In the range of 0.

The chemical structure of the poly-β-alanine polymer of the present invention is 1, for example, infrared absorption spectrum, NMR spectrum and differential scanning P! This can be confirmed by measuring the amount. Figures 1 and 8
Figure g3 shows one example of the formic acid-soluble poly-β-alanine polymer (A) of the present invention and one example of the formic acid-insoluble poly-β-alanine polymer (A) of the present invention.
The infrared absorption spectrum of one example of alanine polymer (in alanine polymer) is shown. 3290c1n.

1535crn″″1.1108crn″″, 9
7Zcrr&-' secondary amide group +C0NH+ characteristic absorption (#)% 33550-1.3190c1n-
', 16581M-', and 1617m-1 have characteristic absorptions of primary amide groups (+coNa2). From these results, the poly-β-alanine polymer of the present invention contains:
Secondary amide group +C0NH÷ and primary amide group +
It can be seen that CONH2) is present.

Further, Table 1 shows the DSC analysis results of the poly-β-alanine polymer of the present invention and the DSO analysis results of general poly-β-alanine and polyacrylamide for comparison.

From the results shown in Table 1, it can be seen that the poly-β-alanine polymer of the present invention is not a mere mixture of poly-β-alanine and polyacrylamide; 0NH-) and ÷C
It can be seen that it is a copolymer with H2CH+ as a constituent unit and is 0NH2.

FIG. 2 shows the NMR spectrum of the formic acid-soluble poly-β-alanine polymer. From this NMR spectrum and the above IR spectrum, it is clear that the poly-β-alanine polymer of the present invention has (-CH2CH2CONH-) and -[
Random 0NH with -CH2-CH+ as a constituent unit
2 It has been confirmed that it is a copolymer.0 The poly-β-alanine polymer of the present invention has a primary amide group equivalent to the polymer 1f! + Contains in the range of 1.4 to 10 mmol, but 1.4 to 9.0 mmol,
Particularly preferred is a content in the range of 5.0 to 9.0 mmol.

The poly-β-alanine polymer of the present invention has a composition ratio of 5 (1-
[-CH2CH2CONH+ and structural unit (It) (-
For example, poly-β-alanine consisting only of the structural unit (1) or 0NH2 and poly-β-alanine consisting only of the structural unit (II) have cH2cH+.
The poly-β-alanine polymer of the present invention has different thermal properties and exhibits excellent effects in various uses, compared to a mixture of the poly-β-alanine polymer and I) in the same ratio as the poly-β-alanine polymer of the present invention.

As described above, the poly-β-alania 1 complex of the present invention contains the structural unit (n) having a primary amide group and the structural unit (1) having a secondary amide group.

Since the structural unit (I) has one hydrogen bond for every three carbon atoms, the hydrogen bonding force is strong and the intermolecular bonding force is large. Furthermore, since it contains the structural unit (II) having a primary amide group, it is hydrophilic and has a strong hydrogen bonding force.

Furthermore, as mentioned above, the poly-β-alanine polymer of the present invention is soluble in formic acid and has a reduced viscosity (ηsp/c) of 2 to 15 dll? The formic acid-soluble poly-β-alanine polymer (
Since A) is also soluble in water, it can be used as an aqueous solution for various purposes. This poly-β-alanine polymer (A) has a reduced viscosity of 2 dll? If it is less than 15d7, the mechanical strength and adhesive strength will decrease, and it will be difficult to form it into a film or sheet. When the amount exceeds /l, the solubility in water decreases significantly. This reduced viscosity can be measured by the method described below.

Furthermore, although the formic acid-insoluble poly-β-alanine polymer (B) of the present invention cannot be used as an aqueous solution, it is extremely useful, for example, as a heat stabilizer for polyacetal resin. This poly-β-alanine polymer (B) has a higher molecular weight than the poly-β-alanine polymer (A) and two molecules of primary amide groups react to form an imide group and form a molecule. It is estimated that it contains a cross-linked structure between the two.

Since the poly-β-alanine polymers (4) and (B) of the present invention have the above-mentioned properties, they can be used in molding materials such as films and sheets in addition to being used as polymer additives. It is useful in applications such as paints, adhesives, coatings, printing inks, paper processing agents, soil conditioners, and fiber treatment agents. In particular, the poly-β-alanine polymer of the present invention is excellent as a heat stabilizer for polyacetal resins.

The poly-β-alanine polymers (B) and (B) of the present invention are.

37' produced using formaldehyde (can be used as a scavenger for formaldehyde generated in trace amounts from phenol resins, urea resins, melamine resins, etc.). The powder of the polymer (A) Yano) may be added in a tri-blend at a ratio of 0.1 to 10% by weight, or the poly-β-alanine polymer (A)'t-aqueous solution may be added to remove water. May be evaporated.

The poly-β-alanine polymerization-n<A) of the present invention is useful as an adhesive for paper, aluminum foil, and the like. In this case poly
The β-alanine polymer (A) may be dissolved in water, and this aqueous solution may be coated on paper, aluminum foil, or the like.

Next, the poly-β-alanine polymer (A) of the present invention has excellent performance as a soil conditioner. That is, in general, a suitable balance of air permeability, water retention, and drainage is required for a tomato i structure suitable for growing crops. Sand has good air permeability and drainage, but poor water retention, while clay has good water retention, but poor air permeability and drainage. A well-balanced soil with a good balance of aeration, water retention, and drainage, with a well-developed aggregate structure is desirable. Polymeric polysaccharides and phenol compounds are known as soil agglomeration agents, but these have the disadvantage that they require a long time from a soil ecological standpoint to develop their agglomeration effects. There is. In order to overcome these drawbacks, nonionic polymers such as polyvinyl alcohol, anionic polymers such as polyacrylic acid, and cationic polymers such as polyethyleneimine have been investigated. The agglomerating agent has a weak agglomerating effect,
It also has disadvantages such as poor sustainability of effects.

On the other hand, the poly-β-alanine polymer of the present invention has extremely strong adsorption with soil and has an excellent long-lasting effect. Therefore, the polymer can be used as a ±ill agent. By doing so, it is possible to improve the soil to make it suitable for growing crops. Another use for soil conditioners is sports fields and baseball fields.

By applying the polymer of the present invention to the soil of a golf course, the drainage properties of the soil during rainfall can be significantly improved, and the inconvenience of water puddles can be avoided.

For such uses, generally a 1 to 10% aqueous solution of poly-β-alanine polymer (A) is added per 10 knee cars.
Preferably, it is applied at a rate of about 401 parts.

Effects of the Invention The poly-β-alanine polymer of the present invention has a reduced viscosity of 2.0.
As described above, since the degree of polymerization is high, molded products with excellent mechanical properties, such as films and sheets, can be produced. In addition, the amount of catalyst used is extremely small compared to conventional methods.

The amount of metal contained in the obtained polymer is about 0.1 to 0.02% by weight, whereas in the conventional method it is about 0.5% by weight or more.
The content is very small, about t%, so this
For example, when used as a heat stabilizer for polyacetal resin, it exhibits remarkable effects.

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.

The physical properties of the polymers and compositions in Examples and Comparative Examples were measured and evaluated by the method shown below.

(1) Reduced viscosity (ηsp/c) Polymer 52 is placed in formic acid Zoo- and stirred at room temperature for 2 hours to dissolve. The formic acid solution is then filtered under reduced pressure. 500 methanol is added to this formic acid solution to precipitate a formic acid solution, and after filtering off this precipitate, it is dried under reduced pressure at 80° C. for 10 hours in a vacuum dryer.

After dissolving the sample thus obtained in 99% pure formic acid or more, 200 mesh Tyler-I! A solution with a sample concentration of 197 di is prepared throughout. The reduced viscosity of this solution at a temperature of 35° C. is measured using an Ostwald viscometer.

The reduced viscosity ηsp/c (d7!/f) is calculated using the following formula.

ηsp/c C, dl/f/)= (”/1o-1
)/Nikode, t is the number of seconds the sample solution falls (seconds), t.

is the number of seconds the formic acid falls.

(2) Determination of primary amide groups 0.71 g of the sample polymer and 50% of a 40% by weight aqueous potassium hydroxide solution were added to a flask equipped with a stirrer, and heated at 105 to 110°C for 20 minutes while stirring. Hydrolyzes the class amide group to ammonia. Next, after cooling the contents of the flask to below 50°C, 100 td of methanol was added to distill ammonia together with methanol, and the distillate was added to a sulfuric acid aqueous solution (Vo
ml).

Using this absorption liquid as an indicator, methyl red was used, and 0.1
Neutralize and titrate with a specified hydroxide solution. Let this titration amount be V-. The primary amide group is calculated using the following formula.

Primary amide group (mmot/ri) = 0.1408
(v.

-V) (3) Thermal stability test (weight loss rate) The thermal stability of the polymer is 15% at 250°C in a nitrogen stream.
Evaluate by weight loss rate when heated for minutes. Approximately 50 cm of sample polymer was analyzed using a thermogravimetric analyzer [Daini Seikosha, SSc-5
600H, TG/DTA] Measured in a nitrogen stream.

(4) Retention color In a 1-ounce injection molding machine, the temperature of the cylinder was heated to 230°C, and the color was molded after residence for 20 minutes.The color rank of the molded test piece is expressed by the following symbol.

(5) Contact test A polymer solution is applied onto a glass plate, and the solvent is evaporated and removed to create a polymer film.

The adhesion of the polymer film to the glass plate is evaluated by the following method. That is, use a cutter knife to make a cut in the shape of a 1 mi + x 1 mm goblets on the film until it reaches the glass plate. Next, attach a piece of cellophane tape with a width of 15 mm to the film, then peel off the tape rapidly with one hand.

At this time, the adhesive strength is evaluated by the number of gongs in the film that is peeled off together with the tape.

Example 1 1.6 t of xylene was put into a 2 t reactor equipped with a stirrer, and 0.1 t of calcium propylene was added as a catalyst.
78 F ('/1oo for 1 mole of acrylamide
After the mixture was well dispersed in the solvent, acrylamide 800P was added, and the mixture was reacted at 90° C. for 4 hours while stirring in a nitrogen stream.

After the reaction was completed, the xylene solvent was removed, and the solid material was ground, washed with acetone, and dried. The yield was 7699 (yield 96.1%). When the product was analyzed by infrared absorption spectrum, it was 3290. 1638.1535.1108
．． 9720F+” has a secondary amide group (-CONH-
), with characteristic absorptions of 3355 and 3190.

1658, 1617 ern''''1 has a primary amide group (-
Confirmed that the characteristic absorption of CONH2) exists in NFC
c Fig. 1).

Note that the measurement conditions for the infrared absorption spectrum are as follows.

Apparatus JIR-100FT-IR measurement method: KBr method Furthermore, 13C of the dried product! -NMR was measured (Figure 2). The assignment of each peak is shown below.

36-38 ppm -E-NHCH2CH2C
O+ and fcH20H+ methylene carbon oNa2 42ppm -1-CH2CH+ tertiary carbon 0N
H2 176-180 ppm f-HNCH2CH2G
Carbonyl carbon 0NH2 of O+ and (-cH2cH+) The measurement conditions for 15C-NMR are as follows: Observation frequency: 67.94 MHz Observation width = 20000 Hz Pulse width = 5.8 μs Repetition time: 5. OSKC Integration number: 1000 measurement mode: As a result of structural analysis using Toss method infrared absorption spectrum and NMR spectrum, it was confirmed that the product was a random copolymer consisting of the structural unit (1) C!0NH2.

In addition, the content of primary amide groups is 5% per 1g of polymer.
．． 5 mmot, and the reduced viscosity is 2.3 dl/? A friend of mine. The product decomposed at about 330° C. and the calcium content in the polymer was 53 ppm.

An aqueous solution was prepared by dissolving this polymer in hot water, which was cast onto a Teflon plate and dried in an air open at 1g0°C to form a film with a thickness of about 1 mm.

Thus, the polymer has film-forming properties.

Examples 2 to 5 Using the reaction apparatus used in Example 1, the conditions of acrylamide 1, the amount of solvent, and the type of solvent were the same as in Example 1, the type of catalyst, the molar ratio of catalyst and acrylamide, and the reaction temperature. ,
The reaction time was changed as shown in Table 2.

Table 2 shows the reduced viscosity, primary amide group content, and yield of the obtained polymer. This polymer has engineering R and NM
As a result of structural analysis using R spectrum, structural unit (1)-
E-CH2(!H2C0NH+ and structural unit (11)-
! -0H2CH+ is a random copolymer consisting of C! It was confirmed that 0NH2.

Implementation u6 In Example 1, after heating at 90°C for 4 hours, 1 g
Except for reacting by heating at 0°C for 4 hours.

The reaction was carried out under the same conditions as in Example 1. The resulting polymer had a reduced viscosity of 13.8, and a small amount of the polymer was insoluble in formic acid. In addition, the content of primary amide groups is 6.06 m
mot/? Met.

Example 7 Inner diameter 1.0cn1, outer diameter 1.3cm, length 30℃M
Stainless steel M inner tube, inner diameter 3. Oc! n, outer diameter 3.5
Using a double-tube polymerization machine consisting of a stainless steel outer tube with a length of 30 ay+, silicone oil was circulated as a heat medium in the space between the circular tube and the outer tube, and polymerization was carried out in a first-order manner.

That is, 202 parts of acrylamide monomer and 0.00442 parts of calcium dipropoxide (1/
1 o, ooo moles) are mixed uniformly and charged into the inner tube,
After reducing the pressure in the inner tube system to around 60 torr using a vacuum pump, the atmosphere is replaced with nitrogen gas. 90 in the space between the circular tube and the outer tube
Circulate the silicone oil at ℃ to completely melt the 7-year-old. Next, the temperature of the circulating heating medium silicone oil was raised to 100°C for 1.5 hours, then to 110°C for 1.5 hours, and 1g0
℃ for 1.5 hours, 130°C for 1.5 hours, and finally 170°C for 3 hours, and then cooled.

Next, the rod-shaped polymer in the stainless steel inner tube was taken out, crushed, washed with acetone, and then placed under a vacuum of about 5 Torr for 7
It was dried at 0°C for 24 hours. The conversion rate of monomer to color polymer was calculated using the formula and was 98%.

In addition, as a result of analysis, the content of primary amide groups in one polymer *t
(t is 6.41 mmot/f, and the formic acid solution is 6.41 mmot/f.
0%, and the amount of undissolved matter was 40%. The reduced viscosity of the formic acid soluble portion was 6.1.

Example 8 Powdered terminally acetylated polyoxymethylene resin (Standard load according to ASTM-D-1g38-57T 2.
Melt index at 16Kp and temperature 190℃ is 15
．． 4f/10min) 100 parts by weight, oxidation inhibitor [2゜2
0.25 parts by weight of each of the poly-β-alanine polymers containing primary amide groups prepared in Examples 1 to 7. 5 parts by weight were mixed in a Henschel mixer and extruded at 200°C in an extruder.

Pelletized. This pellet was dried with hot air at 80° C. for 14 hours. The thermal stability and residence layer color of the dried pellets were measured. The results are shown in Table 3.

Comparative Example: Hexamethylene adipamide instead of poly-β-alanine polymer containing primary amide groups.

A pellet was made in the same manner as in Example 8, except that a ternary copolymer polyamide of hexamethylene sepacoamide and caprolactam was used, and the same evaluation was performed. The results f are shown in Table 3.

Comparative Example 2 Polyhexamethylene adipamide (nylon 66) was dispersed in a copolymer of ethylene and methyl acrylate to a poly-β-alanine polymer containing primary amide groups.
A fuvelette was made in the same manner as in Example 8, except that the mixture was made of polyamide and 0.5 heavy equipment was used, and the same evaluation was performed.

The results are shown in Table 3.

Table 3 Implementation f2su9 100 parts by weight of powdered terminally acetylated polyoxymethylene resin, antioxidant (2,2'-methylene bis(
4-methyl-6-t-butylphenol)]0.25
0.2 parts by weight of the primary amide group-containing poly-β-aranilac synthesized in Shigekabu, Jishikabe 1 and Example 2 or 0.2 parts by weight of titanium oxide were mixed in a Henschel mixer, and the mixture was mixed with an extruder. It was extruded and pelletized at 200'C.

The pellets were dried with hot air at 80°C for 14 hours, and Example 8
The weight loss rate was measured using the same method. As a result, f, the fourth
Shown in the table.

Comparative Example 3 Example 9 was carried out in the same manner as in Example 9, except that the ternary copolyamide used in Comparative Example 1 was used instead of the poly-β-alanine polymer containing a primary amide group. The results are shown in Table 4.

Comparative Example 4 The same procedure as in Example 9 was carried out except that the polyamide used in Comparative Example 2 was used instead of the poly-β-alanine polymer containing a primary amide group. The results are shown in Table 4.

Table 4 Example 10 The polymer of Example 1 was dissolved in hot water, coated on a glass plate, and dried to form a thin film. Peelability was examined using cellophane tape in a cross-cut test to check adhesion, and as a result, there was no peeling, indicating that this polymer has excellent adhesive properties.

Example 11 To clay soil 102 was added 20 (1'i) of water containing 1,000 ppm f of the poly-β-alanine polymer of Example 1, stirred well, and then filtered through a glass filter.

The filtration speed at this time is 0.09 m'/yr? It was hr.

As a comparative example, water 2002 was added to the same clay soil 102, stirred well, and then filtered through a glass filter. The filtration rate at this time is 0.03 rrl/w? It was hr. That is, the filtration rate was tripled due to the soil aggregation effect of poly-β-alanine.

Example 1g 10 parts by weight of formic acid was added to 1 part by weight of the polymer obtained in Example 7, stirred, and then filtered to ensure that it was insoluble in formic acid. Separate I, and dry the formic acid insoluble material under vacuum at 100°C. The infrared absorption spectrum of this product is shown in FIG.

From this spectrum, formic acid insoluble matter has primary amide groups +
C0NH2) and a secondary amide group +C0NH-')-. Furthermore, when looking at the entire primary amide group, it was 6.06 m mo17Q. From these analysis results, the formic acid insoluble matter is -E-CH2CH2C
ONH-3-7! : It was confirmed that the polymer has 0NH2 as a constituent unit of fcu2ca+.

The formic acid insoluble matter was blended with polyacetal resin under the same conditions as in Example 8, and the thermal stability and retained layer color of this composition were measured. As a result, the weight loss rate was 0.22 inch, and the coloring rank was A. there were. From these results, it is clear that formic acid insolubles are very effective as stabilizers for polyacetal resins.

[Brief explanation of the drawing]

FIG. 1 and FIG. 3 show an example of a formic acid-soluble poly-β-alanine polymer of the present invention and a formic acid-insoluble poly-β-alanine polymer, respectively.
FIG. 2 is an infrared absorption spectrum diagram of one example of an alanine polymer, and FIG. 2 is a carbon-13 nuclear magnetic resonance spectrum diagram of the formic acid-soluble poly-β-alanine polymer. Patent applicant: Asahi Kasei Industries Co., Ltd. Agent: Meiwa Agata, ← 2

Claims (1)

[Scope of Claims] 1. A high molecular weight poly-β-alanine polymer having 1.4 to 10 mmol of primary amide groups per 1 g of polymer. 2. The poly-β-alanine polymer according to claim 1, which is soluble in formic acid and has a reduced viscosity (ηsp/c) in the range of 2 to 15 dl/g. 3. The poly-β-alanine polymer according to claim 1, which is insoluble in formic acid. 4 Acrylamide at 1/500 per mole thereof
1.4 per gram of polymer, characterized in that it is polymerized using a submolar alkaline earth metal alcolade catalyst.
A method for producing a high molecular weight poly-β-alanine polymer having ~10 mmol of primary amide groups.