JPS6218408A - Production of allylthiourea homopolymer of copolymer - Google Patents

Abstract

PURPOSE:To produce the titled (co)polymer useful as a pickling inhibitor or the like, by (co)polymerizing allylthiourea alone or together with a monoallylamine inorganic acid salt in the presence of a specified radical initiator and ZnCl2. CONSTITUTION:0.2-10mol% radical initiator, having an azo group and amidine groups in the molecule, of formula I or II (wherein R and R' are each alkyl, X is an inorganic acid such as HCl, HBr, H2SO4 or HNO3) and 50-150mol% ZnCl2 are added to allylthiourea or a monomer mixture comprising this monomer and a monoallylamine inorganic acid salt, and the obtained mixture is (co)polymerized in a polar solvent such as water or dimethylformamide to obtain an allylthiourea (co)polymer of formula III or IV (wherein n>=10 and 0<j<1).

Description

DETAILED DESCRIPTION OF THE INVENTION TECHNICAL FIELD The present invention relates to a process for producing allylthiourea homopolymers or copolymers. The allylthiourea polymer obtained by the present invention is preferably used as an acidic inhibitor and a carrier for affinity chromatography, although it is not limited thereto.

Prior art and its problems As described in Japanese Patent Application Laid-Open No. 58-201811,
One of the inventors of the present invention (Mr. Harada) synthesized it economically for the first time] Since polyallylamine is a cationic polymer having only primary amino groups, it can be used as a conductive finishing agent for paper, a flocculant, and a dye. In addition to being used as a fixing agent and a bactericidal agent, it can also be used as a starting material for various functional polymers by utilizing the highly reactive primary amino group.

However, the concentration of primary amino groups in the molecule of polyallylamine is too high, which may cause problems depending on the application.

For example, when applying a specific ligand to the primary amino groups of polyallylamine and applying it to affinity chromatography, it is difficult to react the specific ligand to all the primary amino groups, and unreacted primary amino groups There is a possibility that many amino groups remain. If the enzyme is selectively adsorbed and separated under such conditions, there is a possibility that the control of I)H may be impaired or the enzyme may be inactivated by the remaining primary amino groups.

In order to eliminate such adverse effects caused by the high 11-degree primary amino acid in the molecule, it is generally recommended to introduce a neutral group into the polymer side chain of polyallylamine obtained by polymerizing monoallylamine. However, this method requires a large number of steps because the polymer side chain is reacted after polymerization, and is therefore undesirable from an economic point of view.

Therefore, if monoallylamine-free ima can be copolymerized with a neutral monomer, it will be possible to copolymerize it with a neutral monomer in one step
The development of a method for producing such a copolymer has been desired since it is thought that the adverse effects caused by the high concentration of the 17th mino group in the polyallylamine can be eliminated.

Furthermore, it is generally believed that uncharged allyl compounds do not polymerize, so if a homopolymer thereof can be obtained, new and useful applications can be expected.

Means for Solving the Problems As a result of various studies in order to solve the above-mentioned problems, the present inventors found that allylthiourea or allylthiourea and monoallylamine inorganic acid salts were combined into molecules in a harvesting solvent. Homopolymerization or copolymerization is possible in the presence of a radical initiator having an azo group and an amidine group and zinc chloride, and the polymer obtained by this Sino-German polymerization or copolymerization does not have the above-mentioned drawbacks of polyallylamine. First, we discovered that it can be preferably used, for example, as a carrier for affinity chromatography and as a pickling inhibitor that removes only scale and prevents elution of steel materials, and completed the present invention.

Therefore, the gist of the present invention is to homopolymerize allylthio-urea or allylthiourea and monoallylamine fluorine salt in a polar solvent in the presence of a radical initiator having an azo group and an amidine group in the molecule and zinc chloride. or a method for producing an allylthiourea homopolymer or copolymer, which comprises copolymerization.

The present invention will be explained in more detail below.

The radical initiator used in the present invention has an azo group and an amidine group in its molecule, and typical examples thereof include those having the general formula below, but are not limited thereto. Of course.

R t12N 1 1 NH2R'
R' (I) R (I) The amount of this radical initiator added is generally 0.2 to 10 mol%, preferably 0.5 to 2 mol%, particularly preferably 1 mol%, based on the monomer. .

In the present invention, it is essential to use zinc chloride as a polymerization accelerator together with the above-mentioned radical initiator. For example, if 25 mol% or more of zinc chloride is added to the monomer, a polymer can be obtained in good yield. Generally, the yield of the polymer increases as the amount of zinc chloride added increases, but if an extremely large amount of zinc chloride is added, a large amount of solvent is required to dissolve the zinc chloride, and the monomer concentration decreases. Undesirable.

Therefore, in order to carry out the polymerization efficiently, it is particularly desirable to add zinc chloride in an amount of 50 to 150 mole % based on the monomer.

Moreover, the polymerization reaction is carried out in a polar solvent. Examples of solvents include water, DMFlDMSO, and the like.

According to one aspect of the present invention, an allylthiourea homopolymer having the general formula H H2 [n≧10] is prepared by homopolymerizing allylthiourea in a polar solvent in the presence of the aforementioned radical initiator and zinc chloride. is obtained in good yield.

According to another aspect of the present invention, by copolymerizing allylthiourea and monoallylamine inorganic acid salt in a polar solvent in the presence of the above-mentioned radical initiator and zinc chloride,
An allylthiourea copolymer having the general formula (%) can be obtained in good yield.

(Example) Examples will be described below in comparison with comparative examples, but the present invention is not limited to these examples.

Example 1 Monoallylamine hydrochloride (MAA-1-(Cj) and allylthiourea (ATU) were mixed in a predetermined ratio, zinc chloride was added in an amount of 50,100 i5Q mole% based on the total amount of chloride, and water was added. A 70% aqueous solution was prepared.

To these solutions, the following initiator H30H3 82NIINTO12H3CH3 [V-50: Wako Tsumugi Co., Ltd., trade name] was added in an amount of 1 m01e% based on the total monomers, and polymerization was carried out at 60°C for 50 hours. .

After polymerization, the polymerization system was poured into acetone and left for one day. After thoroughly washing the precipitate with methanol, it was filtered and dried to obtain a white powder.

The yield, solubility and viscosity of the obtained substance are shown in Table 1.

In addition, since there is a possibility that zinc chloride is contained in these substances, the content of zinc chloride is determined by atomic absorption spectrometry.
The yield based on total monomer was determined by subtracting the zinc chloride content.

From Table 1, it can be seen that the yield increases as the amount of zinc chloride added increases. Furthermore, as the molar ratio of allylthiourea charged increases, the solubility of the obtained substance in water decreases.

The infrared absorption spectrum of the substance obtained with Nα11 shown in Table 1 is shown in FIG. According to this figure, absorption thought to be caused by the formation of a chelate between the primary amino group and zinc chloride is observed at 1675ca-1, and absorption due to the thiourea group is detected at 1625.1565crR-1.

The 1H-NMR spectrum of this Nα11 substance is shown in FIG. From this figure, 7, 69.7.0 due to thiourea group
An absorption of 9 ppm was observed in addition to the spectrum of polyallylamine hydrochloride.

In addition, Table 1 shows JN02-6, Nα9.10.12.1
3. Infrared absorption spectra of substances 16 to 20 and 1
) 1-NMR spectrum also gave similar results to those obtained in 1q described above.

Due to the above, items 2 to 6, N119 to 13, which are not shown in Table 1,
It is believed that the substances k16-20 are zinc chloride complexes of polymers having the chemical structure of formula (rV) shown below. By treating this with a mineral acid such as hydrochloric acid, the zinc chloride forming the complex could be removed.

NH2.HCJ N1-1 C=S H2 (IV) [n≧10, O<j<l] Further, the infrared absorption spectrum of the substance obtained in Step 14 shown in Table 1 is shown in FIG. According to this figure, absorption due to thiourea group is detected at 1625.1565aR-'. From the 18-NMR spectrum of this IIQ14 substance, absorption at 7, 69.7, o9 ppm due to thiourea group was observed.

Further, the infrared absorption spectrum and 'H-NMR spectrum of the substance obtained with Nα7.21 gave similar results.

Based on these facts, it is considered that the substance obtained with NQ 7.14.21 shown in Table 1 is a polymer having a chemical structure represented by the following formula (II[) or a zinc chloride complex thereof. By treating this with a mineral acid such as hydrochloric acid, it was possible to remove the zinc chloride forming the zinc chloride complex.

H C=S H2 (I [[> [n≧101 Water was added to prepare a 70% aqueous solution.

The initiator used in Example 1 was added to these solutions in an amount of 1 nole% based on the total monomers, and the mixture was heated at 60° C. at 50 hrs.
After polymerization, the same treatment as in Example 1 was carried out to obtain a white powder. Table 2 shows the yield, solubility and viscosity of the substance obtained here.

Systems containing allylthiourea (No. 23 to 23 in Table 2)
The yield of 28) is 11% or less, which is considerably lower than that of Example 1.

Example 2 A 70% aqueous solution of monoallylamine hydrochloride (MAA/TRIC), allylthiourea (ATU), and a 70% aqueous zinc chloride solution were mixed at a predetermined ratio.

The initiator used in Example 1 was added to 1 mo+ of all monomers.
e% was added and polymerized by standing at 60° C. for 50 hours.

When the post-polymerization treatment was carried out in the same manner as in Example 1, a white powder was obtained.

The yield, solubility and viscosity of the obtained substance are shown in Table 3.

The infrared absorption spectra and 1111-1-N spectra of all the substances (Nα29-34) obtained here are shown in Example 1.
The results were similar to those obtained with the material obtained with N011.

Alternatively, these substances can be omitted to be zinc chloride mirrors of the polymer having the chemical structure of formula (IV) as shown in Example 1. By treating this with a mineral acid such as hydrochloric acid, the lead chloride forming the complex could be removed.

Example 3 Heptanoallylamine hydrochloride (MAA-HCj) and allyl diourea (ATU) were mixed in a predetermined ratio, zinc chloride was added at 100 mole% based on the total monomers, water was added, and 7
A 0% aqueous solution was prepared.

To these solutions, the following initiator H3CH3 was added at 1 mole% based on the total monomers, and the mixture was heated at 60°C.
The polymerization was allowed to stand for 50 hours.

When the post-polymerization treatment was carried out in the same manner as in Example 1, a white powder was obtained.

The yield, solubility and viscosity of the obtained substance are shown in Table 4.

The infrared absorption spectra and '1(-NMR spectra of substances N036 to 40 shown in Table 4 are those of Example 1ONQ11.
Infrared absorption spectrum and 'H-N M
The results were similar to those of the R spectrum.

Therefore, the substances N036-40 have the formula (
It is thought to be a polymeric zinc chloride complex with the chemical structure IV). By treating this with a mineral acid such as hydrochloric acid, the zinc chloride forming the complex could be removed.

In addition, the substance obtained with N041 in Table 4 is Nα in Example 1.
Infrared absorption spectrum similar to that of the substance obtained in 14 and '
The H-NMR spectrum is shown.

From this, it is considered that the substance of Nα41 is a polymer having the chemical v4 structure of formula (II[) shown in Example 1 or a zinc chloride complex thereof. By treating this with a mineral acid such as hydrochloric acid, the zinc chloride forming the zinc chloride complex could be removed.

Effects of the Invention According to the present invention, an allylthiourea homopolymer or a copolymer of allylthiourea with monoallylamine nonsilicate, which eliminates the drawbacks of polyallylamine, can be obtained in high yield through a one-step m-polymerization operation. The obtained polymer is preferably used as a carrier for affinity chromatography or as a pickling inhibitor.

[Brief explanation of drawings]

Figures 1 and 2 show an infrared absorption spectrum and an IH-NMR spectrum of the thiourea copolymer obtained according to the present invention, and Figure 3 shows a thiourea single combination obtained according to the present invention. The infrared absorption spectra 1 to 1 are shown.

Claims (1)

[Claims] It is characterized by homopolymerizing or copolymerizing allylthiourea or allylthiourea and a monoallylamine inorganic acid salt in water or a solvent in the presence of a radical initiator having an azo group and an amidine group in the molecule and zinc chloride. A method for producing an allylthiourea homopolymer or copolymer.