JPH04202504A - Production of polymer containing functional group at end - Google Patents

Abstract

PURPOSE:To obtain a polymer containing a functional group at the end, readily convertible to another functional group by using a metal element-containing compound and a specific radical source containing a functional group as an initiator and radical-polymerizing a polymerizable monomer in an organic solvent or in a solventless state. CONSTITUTION:A metal element-containing compound and one or more compounds shown by formula I [n is 0-4 integer; R<1> is H or (substituted) 1-4C alkyl; X is functional group such as hydroxy, carboxy, amino, epoxy, aziridinyl, oxazolinyl, azulactone or halogen; Y is group shown by formula II (R<2> is H, 1-4C alkyl, phenyl, etc.), formula III (R<4> is as shown for R<2>) or formula IV (R<5> and R<6> are as shown for R<2>)] are used as an initiator and a polymerizable monomer is radical-polymerized in an organic solvent or in a solventless state to give the objective polymer containing a functional group at the end.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention is useful as a polymer that itself has a reactive group (functional group) at its terminal, and the functional group at the terminal can be reacted by an appropriate method. This invention relates to a method for producing a polymer having a terminal functional group that can be easily converted into another functional group by

(Prior Art) Polymers having one or more functional groups at their terminals can have various good physical properties by utilizing the reactivity of the terminal functional groups and reacting the functional groups in an appropriate manner. It becomes a polymer compound. For example, when used as a raw material for various graft polymers, it is possible to obtain a graft polymer with no unreacted substances that impair physical properties. Also, when used as various additives, the reaction of terminal functional groups It is incorporated into the resin structure to obtain good dispersibility and prevent bleeding.In addition, when it has two or more functional groups at the end, it takes advantage of the reactivity of the end. do,
It is effective as a raw material for linear or mesh resin.

Conventional methods for producing polymers having functional groups at their terminals include the following methods (1) to (2), for example, when vinyl monomers are used as raw material polymerizable monomers.

■ A method of polymerizing using hydrogen peroxide as an initiator to produce a polymer having a hydroxyl group at the end.

(2) A method for producing polymers having various functional groups at their terminals using a mercaptan compound having various functional groups such as 2-mercaptoethanol as a chain transfer agent.

■ A method for producing a polymer having a terminal hydroxyl group by polymerizing methyl methacrylate and/or butyl acrylate in an aqueous nitric acid solution using methanol and a cerium salt as an initiator [Fernanda (F
ernanda) M. B., The Journal
Of the Polymer Science, Part A, Polymer Chemistry (J, Polym, Sci,: P
art A: Polymer Chemistry)
J Vol. 24, pp. 2131-2141 (published in 1986)
reference〕. In this method, first, methanol is used as a radical source having a hydroxyl group (functional group),
This radical source is reacted with a cerium salt, which is a compound containing a metal element, to generate a radical having a hydroxyl group. Then, by radically polymerizing the polymerizable monomer using the generation of this radical as a trigger, and introducing the above-mentioned radical having a hydroxyl group at the end of the product polymer, a polymer having a hydroxyl group at the end can be obtained. I have to.

[Problem to be solved by the invention]

However, the conventional method described above, as explained below,
Each of these has its own drawbacks, and the problem is that it is not easy to industrially synthesize a polymer having a functional group at a terminal easily and inexpensively from many kinds of vinyl monomers.

First, method (2) requires a fairly high temperature to decompose hydrogen peroxide without a catalyst, and various side reactions frequently occur at such high temperatures, so it is necessary to ensure that functional groups are not attached to the terminals. It is difficult to implement. In addition, when a catalyst is used, the decomposition of hydrogen peroxide becomes complicated and many radicals other than OH radicals are generated, so there is still the problem that it is difficult to reliably introduce a functional group to the terminal. .

Next, in the method (2) above, there was a problem that the addition of the mercaptan compound extremely slows down the polymerization and that the odor of the residual mercaptan remains.

Finally, in method (1) above, since a simple alcohol is used as a radical source, its activity is low and the reaction rate with the cerium salt is low. Therefore, the polymerization rate becomes slow. Furthermore, since the polymerization is carried out in an aqueous solvent system, there is a problem that the concentration of the vinyl monomer increases and the types of vinyl monomers that can be used are limited.

As described above, polymers with terminal functional groups can be produced industrially from a wide variety of vinyl monomers, including polar polymerizable monomers such as acrylic esters, methacrylic esters, acrylic acid, and methacrylic acid. At present, the method for producing it has not yet been established.

In view of these circumstances, an object of the present invention is to provide a method for easily, inexpensively, and efficiently obtaining a polymer having a terminal functional group from a wide variety of vinyl monomers.

[Means to solve the problem]

In order to solve the above problems, the inventors have conducted various studies. As a result, we confirmed the following through experiments and completed this invention. That is, when radically polymerizing a polymerizable monomer using a metal element-containing compound and a radical source having a functional group as an initiator, as the radical source, a compound represented by the following general formula (1), which will be described in detail later, is used. By using a compound containing a metal element, the rate of generation of radicals having a functional group generated by the reaction between the radical source and the metal element-containing compound becomes faster. Therefore, the polymerization rate of the polymerizable monomer becomes faster, and the radicals having the above-mentioned functional groups are efficiently introduced into the ends of the product polymer, and as a result, polymers having functional groups at the ends can be easily, inexpensively, and efficiently You can get good results. Moreover, if the monomers are polymerized in an organic solvent or in the absence of a solvent, a wide variety of monomers can be used.

Therefore, the method for producing a polymer having a functional group at the end according to the present invention uses a metal element-containing compound and a radical source having a functional group as an initiator, and radically polymerizes a polymerizable monomer to form a polymer at the end. In the method for producing a polymer having a functional group, at least one selected from among the compounds represented by the following general formula (1) is used as the radical source, and the polymerization of the monomer is carried out in an organic manner. 1. A method for producing a polymer having a functional group at a terminal, the method being carried out in a solvent or in the absence of a solvent.

X-A H-(CHz)n -Y (1) However, in formula (1), n is an integer of O to 4, R' is a hydrogen atom,
Represents an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms having a substituent, and X is a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an aziridinyl group, an oxazolinyl group, an azlactone group, and a halogen. -0-C-R'' (2- 1) -C-
0-R"(2-2)-C-R'
(2-3)-CN (2-
6)-No□ (2-7) -sow R” (2-8)-CF O
(2-9)-OR”
(2-10) represents a substituent. ] The metal element contained in the metal element-containing compound used in this invention is not particularly limited, but for example, C
e, Cu, Mn, V, C01Cr, Zn, Pb, Sn,
Examples include Fe, Ti, and Nb. Only one kind of these may be contained in the metal element-containing compound, or two or more kinds thereof may be contained. Among the above metal elements, there are metal elements that can have two or more oxidation numbers, and for such metal elements, in order to improve the reactivity between the metal element-containing compound and the radical source, Of two or more oxidation numbers, it is preferable that the oxidation number is as large as possible.

For example, CesCu, Mn, V, Zn5Ti.

It is possible for metal elements such as Nb to have two or more oxidation numbers, and among them, tetravalent Ce and divalent Cu
%Tetravalent Mn, trivalent Mn strivalent ■, divalent Z
Preferred are n, tetravalent Ti, trivalent Nb, and the like.

Specific examples of the metal element-containing compound include, but are not particularly limited to, the following compounds. That is, ceric (IV) ammonium nitrate (herein, in the name of a metal element-containing compound, the Roman numeral in parentheses following the metal element name represents the oxidation number of the metal element.

), ceric sulfate (rV) ammonium, cerium nitrate (■), cerium oxide (■), cupric oxide (■),
Iron oxide (■), manganese dioxide (IV), manganese acetate (II), trisacetylacetonatomanganese (III)
), ammonium vanadate (V), zinc oxide (■)
, lead oxide (■), tin oxide (■), cobal naphthenate
-(1[[), iron(III) chloride, cobalt oxide (■
), titanium oxide (■) (anatase type), niobium oxide (
■), chromium oxide (■), etc. Among these, ceric (IV) ammonium nitrate, ceric (IV) ammonium sulfate, cupric oxide (■), manganese dioxide (■), manganese (III) acetate, ) lis acetylacetonatomanganese (ml ) etc. are preferred.

The metal element-containing compounds described above may be used alone or in combination.

As mentioned above, in this invention, monomer polymerization is carried out in an organic solvent or in the absence of a solvent, but when polymerization is carried out in an organic solvent, the metal element-containing compound is dissolved in the organic solvent. It is preferable to use one that does. This is because if it is soluble in an organic solvent, its reactivity with the radical source described later will be improved. However, the present invention is not limited thereto, and it is also possible to use substances that do not dissolve in organic solvents. This is because when polymerization is carried out in an organic solvent, using a metal element-containing compound that does not dissolve in the organic solvent has the advantage that it can be easily separated from the polymer after the polymerization is completed.

The radical source used in this invention has the general formula (
It is necessary that the compound has the structure represented by 1).

This radical source is used in order to introduce a functional group to the end of the polymer, which is the desired product. , azlactone group, and a halogen atom (hereinafter referred to as the "functional group group (δ)") (hereinafter, unless otherwise specified, the "functional group" is It refers to a functional group selected from the functional group group fa).

). Although not particularly limited, among the functional group group (a), those having a hydroxyl group, carboxyl group, or amino group as X are preferable.

In the radical source, in order to stabilize radicals generated by the reaction between the radical source and the metal element-containing compound, Y in the formula (1) is replaced with the formulas (2-1) to (2-2). -12) It is necessary to have a group represented by any one of the above formulas (2-1) to (2-12), although it is not particularly limited. Among these, those having a group represented by the formula (2-1), (2-2), or (2-3) as Y are preferable.

In addition, the radical source has the following functional groups in the molecule:
It may have only one X group. However, the present invention is not limited thereto, and the molecule may have at least one functional group other than the X group, that is, it may have two or more functional groups in its molecule.

For example, as mentioned above, in R' and/or Y in the formula (1), the functional group group (
At least one functional group selected from a) may be included. For example, as mentioned above, R1 may be an alkyl group having 1 to 4 carbon atoms and having a substituent. It may be a functional group.Also, as mentioned above, Y may contain an alkyl group having 1 to 4 carbon atoms having a substituent and/or a phenyl group having a substituent. In that case, the substituent may be a functional group selected from the above functional group group (alO).Of course, Y itself may be a hydroxyl group or a carboxyl group listed in the above functional group group (a). group or an amino group.When R' and/or Y contains a functional group selected from the functional groups (a) as a substituent, the substituent is
It may be the same type as X or a different type. Furthermore, even when Y itself is a hydroxyl group, carboxyl group, or amino group, Y and X may be of the same type or of different types.

The total number of functional groups possessed by the radical source is not particularly limited, but is preferably 3 or less. When the total number of the functional groups is 4 or more, the radical source is introduced at the end of the polymer by a polymerization reaction, and then the resulting polymer is reacted by utilizing the high reactivity of the functional group at the end. This is because the number of functional groups at the end of the polymer is too large and the functional groups are not effectively utilized.

Specific examples of the radical source include, but are not particularly limited to, those having a hydroxyl group as the functional group X include the following compounds. Namely, ethylene glycol monoacetate, propylene glycol monoacetate, 1.2-butanediol monoacetate, 1.3-butanediol monoacetate, 1.4-7"tanediol monoacetate, 1.2" -bentanediol monoacetate, 3-methyl-1,2-butanediol monoacetate, glycerin monoacetate, 1.2.3=butanetriol heptaacetate, 1,2゜3-pentanetriol monoacetate , 2-hydroxypropyl succinate, 2-aminoethyl glycolate, N-2-hydroxyethylacetamide, 3-chloro-2-hydroxypropylsulfonic acid, hydroxyacetone, ethoxyethanol, n-butoxyethanol, phenoxyethanol, 2-hydroxyethoxy-1-chloroethane,
These include 2-hydroxyethoxy-1-bromoethane, phenethyl alcohol, benzyl alcohol, 2,2,2-trifluoroethanol, 2-cyanoethanol, 2-nitroethanol, monoethanolamine, jetanolamine, triethanolamine, and the like. Among these compounds, ethylene glycol monoacetate, hydroxyacetone, ethoxyethanol, n-butoxycetanol and the like are preferred. Furthermore, among these preferred compounds, ethylene glycol monoacetate is particularly preferred. Further, specific examples of the radical source having a functional group other than a hydroxyl group as the functional group X are not particularly limited, and examples include compounds having structures similar to the above-mentioned specific examples of the radical source having a hydroxyl group.

The radical sources described above may be used alone or in combination.

The polymerizable monomer used in this invention is not particularly limited, but examples include acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, cyclohexyl acrylate, and diacrylic acid.
- Ethylhexyl, dodecyl acrylate, stearyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, glycidyl acrylate, 2-N, N-dimethylaminoethyl acrylate and its quaternary salts, monoacrylic acid of polyethylene oxide Acrylic esters such as esters; methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, stearyl methacrylate, 2-methacrylate Methacrylic esters such as hydroxyethyl, hydroxypropyl methacrylate, glycidyl methacrylate, 2-N,N-dimethylaminoethyl methacrylate and its quaternary salts, monomethacrylic ester of polyethylene oxide; maleic acid, maleic anhydride, Monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters and dialkyl esters of fumaric acid; styrene derivatives such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, styrene sulfonic acid; maleimide, methylmaleimide, Maleimide derivatives such as ethylmaleimide, propylmaleimide, butylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; nitrile group-containing polymerizable monomers such as acrylonitrile and methacrylonitrile; acrylamide, methacrylamide, etc. Polymerizable monomers containing amide groups; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, and vinyl benzoate; dienes such as butadiene and isoprene:
Examples include vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol, and the like. These may be used alone or in combination.

The amounts of the metal element-containing compound, radical source, and polymerizable monomer described above are not particularly limited, and can be used within a wide range depending on the properties of the polymer to be obtained. For example, if necessary, the radical source may be used in excess of the metal element-containing compound, or the metal element-containing compound may be used in excess of the radical source.

In the production method of the present invention, in order to increase the variety of usable polymerizable monomers, it is necessary to polymerize the monomers in an organic solvent or in the absence of a solvent.

When monomer polymerization is carried out in an organic solvent, the organic solvent that can be used is not particularly limited, but includes, for example, methanol, ethanol, tetrahydrofuran, 1,4-
Dioxane etc. are preferred.

These organic solvents may be used alone or in combination of two or more. Further, the amount used is not particularly limited.

In the production method of the present invention, a compound serving as an oxidizing agent such as perchloric acid or sodium perchlorate may be added to the reaction system if necessary.

The polymerization temperature is not particularly limited, but is preferably, for example, 20 to 120°C, more preferably 20 to 80°C. If the polymerization temperature is less than 20°C, the reaction rate between the metal element-containing compound and the radical source and the polymerization rate of the polymerizable monomer will be extremely slow, resulting in an extremely low polymerization rate, etc. . In addition, if the polymerization temperature exceeds 120°C, the reaction rate between the metal element-containing compound and the radical source will be extremely slow, and other side reactions will be extremely increased, resulting in the number of functional groups introduced at the end of the polymer. This is because the polymerization temperature exceeds 80°C, the reaction rate between the metal element-containing compound and the radical source and the polymerization rate of the polymerizable monomer slow down, resulting in a decrease in the polymerization rate, etc. It is from.

Regarding the physical properties of the polymer synthesized by the production method of the present invention, the ratio (f) of radicals having functional groups generated from the reaction between the metal element-containing compound and the radical source introduced to each end of the polymer is Small (also 0.
If it is 7, it can exhibit the characteristics as a polymer having a functional group at the end, albeit partially.
preferable. Further, if the ratio (f) is at least 0.9, it is possible to exhibit physical properties equivalent to those of ideal properties, which is very preferable.

[For production]

When the compound represented by (1) above is used as a radical source, a radical having a functional group Polymerization of the polymers produces a polymer having a functional group X at the end. At that time, the above radical also has a Y group, and this Y
Since the radicals are stabilized by the action of the group, the rate of generation of the radicals becomes faster, and as a result, it becomes possible to easily, inexpensively, and efficiently produce a polymer having a functional group at the end.

Furthermore, if the monomers are polymerized in an organic solvent or in the absence of a solvent, a wide variety of monomers can be used.

〔Example〕

Hereinafter, specific examples of the present invention will be described together with comparative examples, but the present invention is not limited to the following examples. Furthermore, in the following Examples and Comparative Examples, "parts" and "%" represent "parts by weight" and "% by weight", respectively.

Example 1 - In a flask equipped with two dropping funnels, a stirrer, a nitrogen inlet, a temperature needle and a reflux condenser, 250 parts of ethanol are added.
229 parts of ethylene glycol monoacetate was charged as a radical source, and the mixture was heated to 53° C. while slowly blowing nitrogen gas. There, ceric nitrate (IV) ammonium 32.
Ethanol solution of ceric nitrate (T'/) ammonium prepared by dissolving 9 parts in 750 parts of ethanol 78
2.9 parts and 12 butyl acrylate as a polymerizable monomer.
8 parts were separately added dropwise from the dropping funnel over 6 hours. During the dropwise addition, the polymerization temperature was maintained at 53±2° C. After the completion of 0 dropwise addition, stirring was continued at the same temperature for an additional 2 hours to complete the polymerization and obtain a solution of polymer [1].

The solution of the polymer [1] at the end of polymerization is colorless and transparent,
The dark reddish-brown color that the ethanolic solution of ceric (IV) ammonium nitrate had before dropping did not remain at all. This is considered to indicate that the ceric (rV) ammonium nitrate added to the polymerization system quickly reacted with the ethylene glycol monoacetate and was completely consumed. Moreover, the polymerization rate calculated from the solid content concentration at this time was 100%.

Subsequently, the remaining ethanol and
Ethylene glycol monoacetate and the like were distilled off. Thereafter, the residue was dissolved in acetone, and the resulting acetone solution was added dropwise to a large excess of water with stirring to perform reprecipitation twice.

The thus obtained precipitate was dried at 45° C. under reduced pressure to purify polymer [1].

The number average molecular weight of the purified polymer [1] was 510 as measured by a vapor pressure molecular weight analyzer (VPO).
It was 0. In addition, the average number of terminal functional groups (number of hydroxyl groups) (T1) is 1.3 (mol/ 1 mol of polymer).

The results and polymerization rates are summarized in Table 1.

Examples 2 to 5 Example 1 except that the types and amounts of the metal element-containing compound, radical source, and polymerizable monomer were changed as shown in Table 1. Polymers [2] to [5] were obtained in the same manner as above.

The number average molecular weight and average number of terminal functional groups (number of hydroxyl groups) (vl) of the obtained polymers [2] to [5] were determined in the same manner as in Example 1, and the results and polymerization rates are summarized in Table 1. Indicated.

Example 6 - In a flask equipped with a stirrer, a nitrogen inlet tube, a thermometer, and a reflux condenser, 500 parts of ethanol, 227 parts of 2-aminoethyl acetate as a radical source, and manganese (IV) dioxide as a metal element-containing compound were added. 96 parts and 100 parts of methyl methacrylate as a polymerizable monomer, heated to 53°C while slowly blowing nitrogen gas, and continued stirring for 6 hours while maintaining the polymerization temperature at 53 ± 2°C. , a solution of polymer [6] was obtained.

The polymerization rate calculated from the solid content concentration at this time was 92%.

Next, the solution of polymer [6] was filtered through a filter paper to remove manganese dioxide (■), and the filtrate was depressurized to 5 wHg and heated to 50 to 60°C to remove residual ethanol and 2-aminoethyl acetate. , methyl methacrylate, etc. were distilled off. Thereafter, the residue was dissolved in acetone, and the resulting acetone solution was added dropwise to a large excess of water with stirring to perform reprecipitation twice. The precipitate thus obtained was dried at 45°C under reduced pressure to form a polymer [6].
was purified.

The number average molecular weight of the purified polymer [6] was determined to be 12,000 by gel permeation chromatography (hereinafter referred to as rGPcJ) using a standard polystyrene calibration curve. radix(
Number of amino groups) (Fn) is the result calculated from the amino group concentration in the polymer determined by potentiometric titration with a p-)luenesulfonic acid acetic acid solution in a dioxane/acetic acid mixed solvent and the above number average molecular weight value. , 1.1. The results and polymerization rates are summarized in Table 1.

Examples 7 to 16 - Example 6 except that the types and amounts of the metal element-containing compound, radical source, and polymerizable monomer were changed as shown in Table 1. Polymers [7] to [16] were obtained in the same manner as above. However, in Example 9, the solvents used during polymerization and reprecipitation were both N and N.
-Change to dimethylformamide.

The number average molecular weight and the average number of terminal functional groups (T1) of the obtained polymers [7] to [16] were measured. The number average molecular weight was measured by GPC using a standard polystyrene calibration curve. In addition, the average number of terminal functional groups (F n) is calculated from the measurement results of the number average molecular weight described above and the concentration of each functional group such as hydroxyl group, amino group, or carboxyl group in the polymer determined as follows. did. The hydroxyl group concentration was determined according to JIS-1557.

The amino group concentration is p- in dioxane/acetic acid mixed solvent.
) Determined by potentiometric titration with a luenesulfonic acid acetic acid solution. Carboxyl group concentration was determined by titration with alcoholic KOH in dioxane solvent. The results and polymerization rates are shown in Table 1.

Example 17 - Polymerization reaction and purification treatment were carried out in the same manner as in Example 1 except that the polymerization temperature was changed to 93±2° C. to obtain polymer [17].

The polymerization rate determined from the solid content concentration of the polymerization solution at the end of polymerization was 45%.

The number average molecular weight of the purified polymer [17] was 28,000 as measured by GPC using a standard polystyrene calibration curve. Further, the average number of terminal functional groups (number of hydroxyl groups) (1) was calculated from OHHI34 determined according to JIS-1557 and the above number average molecular weight, and was 0.7. The results and polymerization rates are summarized in Table 1.

Comparative Example 1 A comparative polymer was obtained by carrying out the polymerization reaction and purification treatment in the same manner as in Example 1, except that 101 parts of ethanol was used instead of 229 parts of ethylene glycol monoacetate. Ta.

The solution of the comparative polymer at the end of polymerization had a reddish-brown color, and the deep reddish-brown color that the ethanolic solution of ceric (IV) ammonium nitrate had before dropping still remained. This indicates that the reaction between the ceric (rV) ammonium nitrate added to the polymerization system and ethanol is slow, and that ceric (IV) ammonium nitrate still remains in the comparative polymer solution even after the polymerization is completed. This is thought to indicate that

Further, the polymerization rate determined from the solid content concentration of the polymerization solution at the end of the polymerization was 28%.

The number average molecular weight of the comparative polymer after purification was 42,000 as measured by GPC using a standard polystyrene calibration curve. Further, the average number of terminal functional groups (number of hydroxyl groups) (Fn) was calculated from OHHI31 determined according to JIS-1557 and the above number average molecular weight, and was 0.8. The results and polymerization rates are summarized in Table 1.

As shown in Table 1, polymers [1] to [16] according to Examples 1 to 16 obtained using a radical source within the scope of the present invention are compared with polymers [1] to [16] obtained using ethanol as a radical source. It was confirmed that compared to the comparative polymer of Example 1, the polymerization rate was higher and the average number of terminal functional groups was higher.

Furthermore, it was confirmed that the polymer [17] according to Example 17 had almost the same average number of terminal functional groups as the comparative polymer according to Comparative Example 1, but had a higher polymerization rate.

Comparative Example 2 In each of Example 1 and Comparative Example 1, changes over time in the residual rate of ceric (IV) ammonium nitrate added to the polymerization system were investigated as follows.

The polymerization solution was sampled every 2 hours until 8 hours after the start of polymerization, and the number of moles of Ce" ions present in each polymerization solution (
A) was measured by redox titration using an aqueous sulfuric acid solution of iron (n) ammonium sulfate (Mohr's salt) using 1,10-phenanthroline as an indicator. The obtained value (A)
From the number of moles (B) of ceric (mV) ammonium nitrate added to the polymerization solution, the residual rate (%) of ceric (IV) ammonium nitrate at each polymerization time.
(C) was calculated according to the following formula (3). The results are shown in Table 2.

C Mi □ From this, it is thought that the reaction between ceric (IV) ammonium nitrate and ethylene glycol monoacetate occurs quickly, and the polymerization initiation rate is also fast.On the other hand, Comparative Example 1 using ethanol as a radical source In the case of ceric (IV) nitrate, the residual rate of ammonium ceric nitrate (IV) was quite high from the initial stage of polymerization, and gradually increased as the polymerization time became longer.
IV) It is thought that the reaction between ammonium and ethanol is quite slow, and the polymerization initiation rate is correspondingly slow.

〔Effect of the invention〕

According to the production method of the present invention, industrially advantageous polymerizable monomers can be selected from a wide range of polymerizable monomers including polar polymerizable monomers such as acrylic acid, acrylic esters, methacrylic acid, and methacrylic esters. By using radical polymerization, a polymer having a functional group at the end can be easily, inexpensively, and efficiently produced.

The polymer having one or more functional groups at the terminal end obtained by the production method of the present invention can exhibit various good physical properties by reacting with an appropriate method by utilizing the reactivity of the terminal functional group. It can be a polymer compound with For example, when used as a raw material for various graft polymers, it is possible to obtain graft polymers free of unreacted substances that impair physical properties. Further, when used as various additives, etc., it is incorporated into the resin structure by reaction of the terminal functional group, and good dispersibility can be obtained and bleeding can be prevented. Furthermore, when it has two or more functional groups at its terminals, it is effective as a raw material for linear or network resins by utilizing the reactivity of its terminals.

The polymers having functional groups at the terminals are also very useful as raw materials for various resins, paints, adhesives, sealants, UV-EB cured resins, etc., taking advantage of the above-mentioned advantages. It is also useful as various resin additives and raw materials thereof.

The polymer having a functional group at the terminal end obtained by the production method of the present invention further has a high reactivity of the terminal functional group, so that the terminal functional group can be converted into another functional group. It can also be used as a precursor for polymers having various terminal functional groups such as (meth)acryloyl groups, incyanate groups, mercapto groups, hydroxyl groups, carboxyl groups, amino groups, epoxy groups, aziridinyl groups, and oxazolinyl groups. Its application range is extremely wide.

For example, among the polymers obtained by the production method of the present invention, a polymer having a carboxyl group or an amino group at the end can be converted into a polymer having a vinyl group at the end. Hydroxyl group, carboxyl group at the end,
A polymer having an amino group, an epoxy group, an aziridinyl group, an oxazolinyl group, or the like can be converted into a polymer having a (meth)acryloyl group at the end. Polymers having a hydroxyl group or an amino group at the end are
It can be converted into a polymer having isocyanate groups at the ends. Polymers having a hydroxyl group, epoxy group, aziridinyl group, or oxazolinyl group at the end are
It can be converted into a polymer having a mercapto group at the end. A polymer having a carboxyl group, an amino group, an epoxy group, an aziridinyl group, an oxazolinyl group, or the like at the end can be converted into a polymer having a hydroxyl group at the end. A polymer having a hydroxyl group, an amino group, an epoxy group, an aziridinyl group, an oxazolinyl group, or the like at the end can be converted into a polymer having a carboxyl group at the end. A polymer having a hydroxyl group, carboxyl group, epoxy group, aziridinyl group, or oxazolinyl group at the end can be converted into a polymer having an amine group at the end. A polymer having a carboxyl group, an amino group, an oxazolinyl group, or the like at the end can be converted into a polymer having an epoxy group at the end. A polymer having a carboxyl group, an amino group, a halogen atom, or the like at the end can be converted into a polymer having an aziridinyl group at the end. Further, a polymer having a carboxyl group or an amino group at the end can be converted into a polymer having an oxazolinyl group at the end.

Agent: Patent Attorney Takehiko Matsumoto

Claims (1)

[Scope of Claims] 1. A method for producing a polymer having a functional group at its terminal by radically polymerizing a polymerizable monomer using a metal element-containing compound and a radical source having a functional group as an initiator, At least one compound selected from the compounds represented by the following general formula (1) is used as the radical source, and the monomer is polymerized in an organic solvent or in the absence of a solvent. A method for producing a polymer having a characteristic terminal functional group. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) However, in formula (1), n is an integer from 0 to 4, and R^1
represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms having a substituent, and X is a hydroxyl group, carboxyl group, amino group, epoxy group, aziridinyl group, oxazolinyl group, azlactone represents a functional group selected from the group consisting of a group and a halogen atom, and Y represents a group represented by any of the following formulas (2-1) to (2-12) ▲ Numerical formula, chemical formula, table etc. ▼ (2-1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2-2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2-3) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ( 2-4) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(2-5) -CN(2-6) -NO_2(2-7) -SO_2R^9(2-8) -CF_2(2-9) - OR^1^0 (2-10) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2-11) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2-12) [Formula (2-1) ~ (2 -12) Medium, R^2 ~ R^1^2
each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms having a substituent, a phenyl group, or a phenyl group having a substituent, and R^1
^3 to R^1^7 each independently represent a hydrogen atom or a substituent. ] 2 The metal element-containing compound is Ce, Cu, Mn, V, C
2. The method for producing a polymer having a terminal functional group according to claim 1, wherein the polymer contains at least one metal element selected from the group consisting of O, Cr, Zn, Pb, Sn, Fe, Ti, and Nb. 3 Ce is tetravalent Ce, Cu is divalent Cu, Mn is tetravalent or trivalent Mn, V is pentavalent V, Zn is divalent Zn, and Ti The method for producing a polymer having a terminal functional group according to claim 2, wherein is tetravalent Ti and is Nb or pentavalent Nb. 4. The radical source does not have a total of four or more functional groups selected from the group consisting of hydroxyl group, carboxyl group, amino group, epoxy group, aziridinyl group, oxazolinyl group, azlactone group, and halogen atom. A method for producing a polymer having a terminal functional group according to any one of claims 1 to 3. 5 The polymerizable monomer is acrylic ester, methacrylic ester, acrylic acid, methacrylic acid, styrene, acrylonitrile, vinyl acetate, fumaric acid, fumaric ester, maleic acid, maleic anhydride, maleic ester, and maleimide. The method for producing a polymer having a terminal functional group according to any one of claims 1 to 4, wherein the polymer is at least one selected from the group consisting of: 6.Claim 1, wherein the temperature during polymerization is 20 to 80°C.
5. A method for producing a polymer having a functional group at an end according to any one of 5 to 5.