JPS6140691B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel α-dimethylamino-ε-caprolactam polymer. Traditionally, ε-caprolactam polymers have excellent strength, abrasion resistance, dyeability, etc., and are useful for fibers,
Widely used in films, injection molded products, etc. Such ε-caprolactam polymers have been converted into ε-caprolactam copolymers or added with various additives in order to provide them with various uses. In the production of ε-caprolactam polymers having substituents, polymerization is often difficult due to the reactivity of the substituents. For example, in the polymerization of α-amino-ε-caprolactam, under the normal polymerization conditions of ε-caprolactam, the amino group at the α position reacts and gelation occurs, so the polymerization of α-amino-ε-caprolactam is still difficult to obtain. It hasn't been done yet. The present inventors have arrived at the present invention as a result of intensive studies on ε-caprolactam polymers that have excellent performance, and an object of the present invention is to provide a novel ε-caprolactam polymer that has excellent performance. It is provided by. That is, in the present invention, the main chain substantially has the following formula: It consists of a repeating unit and has a relative viscosity of 1.5.
This is a polymer of α-dimethylamino-ε-caprolactam as described above. In the present invention, relative viscosity refers to the relative viscosity measured at 25° C. of a solution in which the polymer of the present invention is dissolved at a concentration of 1 g/100 ml in 98% sulfuric acid as a solvent. The polymer of the present invention preferably has a relative viscosity of 1.5 or more, more preferably 2 to 5. The polymer of the present invention can be produced, for example, by producing α-dimethylamino-ε-caprolactam and polymerizing it as follows. That is, α-dimethylamino-ε-caprolactam is produced, for example, by adding nitrosyl chloride to cyclohexene to obtain bis(1-nitroso-2-chlorocyclohexane), which is then reacted with excess ammonia to form α-aminocyclohexanone oxime. α-Amino-ε-caprolactam can be synthesized by subjecting its hydrochloride to Beckman rearrangement with sulfuric acid, followed by dimethylation with methyl bromide. The polymer of the present invention is α-dimethylamino-ε-
It can be obtained by anionic polymerization of caprolactam. Examples of anionic polymerization catalysts include alkali metals such as sodium metal, potassium metal, and lithium metal, triethylaluminum, diethylzinc,
Organometallic compounds such as ethyl bromide and magnesium are used. In addition, as an anionic polymerization cocatalyst,
N-acetyl-ε-caprolactam, N-phenylphthalimide, N,N'-bis(phenylcarbamyl)-N,N'dimethylurea, N,N-diacetylmethylamine, etc. are used. In the polymerization reaction, the polymerization catalyst and cocatalyst are α-dimethylamino-
Add a predetermined amount of each to ε-caprolactam and dissolve, and polymerize at a temperature of 130 to 250℃ in an inert gas flow.
This is done by heating for several minutes or more.
Thus, the -α-dimethylamino-ε-caprolactam polymer of the present invention can be easily obtained. The polymer of the present invention includes methanol, ethanol,
It is easily soluble in alcohols such as n-propanol, and solvents such as chloroform, trichloroethane, and carbon tetrachloride, and swells in benzene. It is a substance that is insoluble in cyclohexane. Regarding water, it is easily soluble in cold water, but poorly soluble in hot water of 50 to 60°C or higher. Furthermore, the aqueous solution of the polymer of the present invention exhibits basicity and is neutralized with 0.0064 equivalents of acid per 1 g of the polymer.
Polymer salts neutralized with inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as formic acid, acetic acid, benzoic acid, adipic acid, sebacic acid, and terephthalic acid, or polyacrylic acid are more easily exposed to cold and hot water. It becomes molten. When dissolved in a solvent, the solution becomes almost transparent and viscous. When the solution is made into a thin film and the solvent is evaporated, a film-like molded product is obtained. Further, the polymer of the present invention is hygroscopic, and when it absorbs moisture, the surface of the polymer becomes sticky. The novel polymer of the present invention is a substance useful as an adhesive, a sizing agent, a coating agent, a paper strength agent, a resin for printing plates, and the like. Next, examples of the present invention will be shown. Example 1 15.6 g of α-dimethylamino-ε-caprolactam dried to a moisture content of 0.02% or less is melted at 100°C in a nitrogen gas stream. Add metallic sodium to this
0.023g and N-acetyl-ε-caprolactam
Add and dissolve 0.155g. Polymerization temperature 180℃,
Polymerization was carried out at polymerization times of 0.5 hours, 1 hour, and 6 hours to obtain transparent pale yellow polymers (A), (B), and (C) of α-dimethylamino-ε-caprolactam, respectively. The relative viscosities of these polymers (A), (B), and (C) were 2.95, 3.06, and 3.18, respectively. The analytical values of Polymer B were as follows. Elemental analysis (C ₈ H ₁₆ N ₂ O) Theoretical value as _o C: 61.50%, H: 10.32% N: 17.93% Actual value C: 60.9%, H 10.83% N: 17.80% Softening point 108-119℃ 30 Moisture absorption rate at ℃, 70%RH 20.2% Infrared absorption spectrum (IR) main peak: 3300,
2950, 1660, 1560, 1460, 1260, 1040CM ^-1 Nuclear magnetic resonance spectrum (NMR) main peak: 1.5, 2,
2, 2.7, 3.2, 7.0, 7.2ppm Softening point and elemental analysis of polymers (A) and (C),
The IR and NMR measurement results were similar to those for polymer (B). Example 2 10 g of the α-dimethylamino-ε-caprolactam polymer (B) obtained in Example 1 was mixed with the solvent shown in Table 1.
The solution was dissolved in 100 ml and the state of dissolution was observed with the naked eye. The results are shown in Table 1.

【table】

[Table] Example 3 α-dimethylamino-ε- obtained in Example 1
0.755 g of caprolactam polymer (B) was weighed out, and 30 ml of distilled water was added to dissolve it, followed by neutralization titration with 1N hydrochloric acid solution. The pH at the neutralization equivalent point was 3.7, and the titration amount of hydrochloric acid was 0.0064 equivalent per 1 g of polymer.

Claims (1)

[Claims] 1. The main chain substantially has the following formula: A polymer of α-dimethylamino-ε-caprolactam consisting of the repeating unit shown by and having a relative viscosity of 1.5 or more.