JPS5959703A - Polymerization of vinyl monomer - Google Patents

Abstract

PURPOSE:To polymerize a vinyl monomer quickly, by polymerizing the monomer in the presence of a metal porphyrin compound, a water-soluble polymer and water. CONSTITUTION:A vinyl monomer (e.g., ethyl methacrylate) is added to water in which at least one metal porphyrin compound selected from the group consisting of copper chlorophyllin, iron chlorophyllin, and vitamin B12, and at least one water-soluble polymer selected from the group consisting of ribonucleic acid, poly(alpha-amino acid), poly(alpha-alanine), and oligoamide, and the mixture is heated to room temp. -85 deg.C to polymerize the monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to a method for polymerizing vinyl monomers.

Conventionally, in the thermal polymerization of vinyl monomers, for example, benzoyl peroxide, azobisgutylontolyl, etc. are used as polymerization initiators, which decompose with heat to generate radicals, and the radicals initiate polymerization. There were many. For example, benzoyl peroxide decomposes to generate radicals as shown in the diagram below.

Furthermore, the following publication discloses that the polymerization of ethyl methacrylate (hereinafter abbreviated as -FMMA) starts in the presence of a water-soluble polymer and copper ions. (Publications or journals; BullChem Soc, Jp
n, vo151, page 1456, published in 1978)
OI'; 1 lZj ., a) Shows the coordination structure of monomer molecules present at the interface between water-soluble polymer, copper ion, and water bathed in K water.

Figure 1(b) shows the hydrogen rearrangement of MMA from water of the copper ion that has the above coordination structure, and the resulting formation! Indicates a radical that empties. The above-mentioned publication reports that radicals are generated as described above, and this initiates polymerization.

However, in the above polymerization method, in a system consisting only of copper ions and water-soluble polymers, the hydrogen abstraction force from water is small;
There were problems such as a very slow polymerization rate.

7 In order to solve these problems, the present inventors conducted extensive research, and as a result, they discovered a vinyl monomer that rapidly polymerizes vinyl monomers by the presence of vinyl monomers, metal porphyrin compounds, water-bathable polymers, and water. The purpose is to obtain a method for polymerizing monomers.

Specifically, as shown in Figure 2, a glass ampoule is filled with gold-4 porphyrin and a water-soluble polymer dissolved in water, then vinyl monomer is added, degassed under reduced pressure, and then sealed. Place the tube at room temperature or at a suitable temperature (approximately 85°C).
), a polymerization reaction occurs and a high molecular weight polymer is produced.

Examples of metal porphyrin compounds that can be applied in this invention include copper chlorophyllin, iron chlorophyllin, and vitamin B1.
2 can be given. As water bath polymers, H, ribonucleic acid (R
N A ), poly(α-amino acid), poly(β-alanine), and oligoamide. Examples of vinyl monomers include V, i:, MMA, ethyl methacrylate, propyl methacrylate, and ethyl methacrylate, but the invention is not limited thereto. In the figure, (1) is a ViMMA layer, and (2) is an aqueous layer containing Kanata porphyrin and a water-soluble polymer.

In addition, in FIG. 3(a), copper chlorophyllin, ribonucleic acid,
The coordination structure existing in water and MMA systems is shown in Figure 3(b) K
The mechanism of polymerization is shown. That is, copper chlorophyllin and ribonucleic acid form a complex to form a hydrophobic region, and water is arranged on the copper ion of copper chlorophyllin. Furthermore, the structure is such that MMA is adsorbed on the molecular surface of steel chlorophyllin.

In this state, water ice Ig y); is transferred to M + J A, generating radicals, and this radical is M M A
It initiates the polymerization of

This invention will be described in detail by carrying out the implementation below.
However, the present invention is not limited thereby.

Example: Copper talolopyrin natrichum 100 N and ribonucleic acid 0
．． A solution of 02f in 10y of water is placed in a glass ampoule as shown in Figure 2, then MMA3y is added, the tube is sealed after degassing under reduced pressure F, and heated to 85°C to obtain a polymer. Figure 4 shows the correlation between the heating time [k1r] and the conversion rate [%] of the produced polymer. It can be seen that the conversion rate increases linearly with time.

Example 2 The amount of sodium copper chlorophyllin in Example 1 was changed to O, Cy, and 1 to 1, respectively. Polymers were obtained in the same manner as in Example 1, with a heating time of 2 hours and a temperature of 10 to 100 g.

Figure 5 shows the added copper chlorophyllin sodium concentration [■]
and the conversion range of the produced polymer]. According to the results, it can be seen that the conversion rate increases with the amount of copper chlorophyllin sodium added up to 100 μl of copper chlorophyllin sodium.

Example 3 The amount of sodium copper chlorophyllin in Example 1 was reduced to 1
．． 25~, and the amount of ribonucleic acid was 0. O19,0015
*, 0.02~ or 003~, and the heating time was 2 hours, otherwise the polymer was obtained in the same manner as in Example 1. Figure 6 shows the conversion rate [%] of the added protein polynucleotide [・] and the poly produced.
]. It can be seen that the conversion rate increases according to the amount of ribonucleic acid added.

Example 4 The heating temperature in Example 1 was 70'C, 175C,
A polymer was obtained in the same manner as in Example 1 except that the temperature was 80°C, 185°C, or 90°C, and the heating time was 2 hours. FIG. 7 shows the correlation between the heating temperature ['C] and the conversion weight of the produced boly. According to the results, it can be seen that the conversion rate increases linearly with temperature in the range of 70°C to 90°C.

Example 5 Example II/Kokore I'''Ant ay, 1y, 2 respectively
y, 3p, 5y or 6y, the heating leakage was 2 hours, and the other conditions were Example 1 (!: A polymer was obtained in the same manner.

Figure 8: MMA fracture (2) and yield of produced polymer 1z
It shows the correlation with l. According to the results, it can be seen that the conversion rate varies linearly with the amount of MMA.

Example 6 Steel chlorophyllin sodium 100 ~ and ribonucleic acid ~ 20 ~ were dissolved in 10 y of water and put into a test tube, 3 y of RL MA was added thereon, and the test tube was sealed for degassing.

The mixture was kept in a fork bath at 85° C. for 200 hours, and the seal was opened and poured into a large amount of methanol, yielding about 22 polymers. The molecular weight of this polymer was approximately 300,000, and the polymerization rate in this system was found to be approximately three times faster than that in the copper ion, water, and water-soluble polymer threads of the aforementioned publication.

Example 7-IO A reaction was carried out in the same manner as in Example 6 using a system of a vinyl compound, a metal porphyrin, and a water-soluble polymer, by appropriately combining each component.

The reaction conditions and results of Examples 6 to 10 and Comparative Examples are shown in Table 1.

As explained above, the present invention provides a vinyl monomer,
In the presence of a metalloporphyrin compound, water-soluble bacterial molecules, and water, a vinyl heptamer polymerization method can be carried out in which vinyl heptamers are carried and polymerized.

[Brief explanation of drawings]

Figure 1 (a) is a diagram showing the coordination structure of each component in the conventional polymerization method, Figure 1 (b) is a diagram showing the polymerization mechanism in the conventional polymerization method, and Figure 2 is a diagram showing the mechanism of polymerization in the conventional polymerization method. FIG. 3(a) is a front view of a glass ampoule in which reaction J is carried out, and FIG. 3(b) is a diagram of the coordination structure of each component in this invention. 4 is a correlation diagram showing the relationship between the conversion rate of the polymer produced according to this invention and the heating time, and FIG. FIG. 6 is a correlation diagram showing the correlation between the conversion rate of the polymer produced according to the present invention and the amount of liponucleic acid added, and FIG.
The figure is a correlation diagram showing the correlation between the conversion rate of the produced polymer and the heating time according to the present invention, and FIG. 8 is the correlation diagram showing the correlation between the yield of the polymer of the present invention and the amount of MMA added. In the figure, (1) is M M A )@, and (2) is the water layer. Figure 4 Heat time [hr]
Figure 1O: ``Amount of acid in January [Regulation No. 1° Figure kasentapi ['C] Figure 8 Amount of HMA [Bessen viscous'', written by Masa Ura (spontaneous) 11゛Director General゛1c; of! ], Display of 'Bf'l '4111r;11; Address: Higashiichi, Tokyo (1112-3, Marunouchi, Ta-ku) Name (+1 (lI) -1) Representative: Ryodenki Co., Ltd. Representative Yuhito Taikata, 8th Division, 4 Agent Address: 111-ku, Tokyo, Tokyo Marunouchi nail j″1
, 12 total 3; -5, Detailed explanation of the disclosure in the amended acid specification column 6, Contents of the amendment (υ What does "Azobisphthyrontolyl" say in the 6th line of page 2 of the specification?) (2) On page 7, line 8, [heating INL degree J] should be corrected as “azobisbutyronitrile.”
"Heating time" is corrected. that's all

Claims (4)

[Claims] (1) A method for polymerizing vinyl monomers in which vinyl monomers are polymerized in the presence of a porphyrin compound, a water-soluble polymer, and water. (2) The metal porphyrin compound proboscis is copper chlorophyllin,
A method for polymerizing a vinyl monomer according to claim 1, which is at least one of iron rolophylline and vitamin 1312. (3) Mizuitani polymers can be used for liponucleic acid (RNA), poly(
A method for polymerizing a vinyl monomer according to claim 1 or 2, which is at least one of α-amino it), poly(β-alanine), and oligoamide. (4) The vinyl monomer is at least one of methyl methacrylate, ethyl methacrylate, ethyl methacrylate, and n-glythyl methacrylate. Polymerization method of vinyl monomer.