JP3345826B2 - Graft polymer and its precursor - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a graft polymer having, as a branch polymer, a polymer containing a polyoxyethylene main chain having an acetal and / or aldehyde group at its free end. Further, the present invention relates to a heterotelechelic polymer which is also a precursor of the graft polymer and a method for producing a heterotelechelic polymer having an aldehyde group at one terminal.

[0002]

2. Description of the Related Art A graft polymer is a branched polymer composed of a trunk polymer and a branch polymer, and is known to have various functions according to the properties of both polymers.
For example, by adjusting the proportion of the branch polymer, it is possible to control or complex the function due to the higher-order structure such as forming a domain having a unique orientation, and the function due to the properties of both the branch polymer and the trunk polymer. It becomes possible.

Certain types of graft polymers that have already been proposed focus on emulsifying action, for forming emulsions, and for improving the adhesiveness of interfaces, for bonding composite materials, and for improving hydrophilicity. Focusing on the imparting effect of
It has been applied as a medical polymer or such an application is being studied.

The present inventors have previously found that polyoxyethylene having an aldehyde group at one terminal and a different functional group at the other terminal can be efficiently produced, and have already disclosed the same (see, for example, Japanese Patent Application No. Hei 10-284,197). 6-117262). On the other hand, aldehyde group-containing polymers for modifying proteins and the like by utilizing the reactivity of aldehyde groups and for providing new functional materials are also known. The use of these functional materials is one of the fields to which the polymers disclosed in the above-mentioned Japanese Patent Application No. Hei 6-117262 are used.

[0005] If a graft polymer having a polymer containing an aldehyde group at one end as a branch polymer can be provided, it is possible to provide a new functional polymer having a function exhibited by the graft polymer itself. There will be. However, an aldehyde-polyoxyethylene macromonomer having an aldehyde group at one end and a polymerizable functional group at the other end (hereinafter, referred to as APM) has not been published in the prior art literature, or at least does not include such an aldehyde group. A
An efficient method for producing PM is not known.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a block polymer carrying a branch polymer derived from APM and to provide a precursor useful for a method for efficiently producing them.

[0007]

SUMMARY OF THE INVENTION To provide APM, we provide APM via hydrolysis deacetalization of aldehyde groups from acetal protected APM.
When the production of PM was intended, it was confirmed that side reactions that could not sufficiently achieve the purpose were accompanied. For example, in the case of a methacrylic ester group as a polymerizable functional group, the elimination of the acetal is accompanied by the elimination of the ester group, and in the case of the vinylbenzyl group, the polymerization reaction occurs simultaneously with the elimination of the acetal. confirmed. Further, when the content of the deprotected aldehyde group increases, a side reaction of APM itself due to aldol condensation or the like may occur during the deprotection.

[0008] Surprisingly, however, the acetal-protected APM can be treated in an acetic acid solvent containing a catalytic amount of water without the above-mentioned side reaction and the side reaction of the produced APM itself. It has been found that up to 100% of the protecting group can be eliminated. Thus, it has become possible for the first time to provide a macromonomer having an arbitrarily changed content of the acetal protecting group.

Therefore, according to the present invention, a repeating unit represented by the following formulas (A) and (B) is represented by A: B:
A graft polymer is provided in a relative proportion of 100-1: 99-0.

Formula (A)

[0011]

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Equation (B)

[0013]

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In the above formula, R ¹ and R ² are independently C
_1-6 alkoxy, phenyloxy or phenyl-C
Represents _1-3 alkyloxy, or R ¹ and R
² together form ethylenedioxy (—O—CH (R ′) — CH ₂ —O optionally substituted with C _1-6 alkyl;
—: Wherein R ′ is a hydrogen atom or C _1-6 alkyl), or R ¹ and R ² together represent oxy (＝ O), and R ³ is a hydrogen atom or C _{1 -6} alkyl, L represents carbonyl, C _1-3 alkylene or C _1-3 alkylphenylene, and n is 2 to 10,000.
P is an integer from 1 to 5, Y represents a hydrogen atom or C _1-6 alkyl, and Z is phenyl, C
_1-6 alkyloxycarbonyl, carboxy or formula C
ON (R ″) ₂ (where R ″ is a hydrogen atom or C _1-6 alkyl).

Further, according to the present invention, the compound represented by the following formula (I), which can be conveniently used as a precursor of the above graft polymer and can itself be used for modifying proteins, etc.
There is also provided a heterotelechelic polymer represented by

Formula (I)

[0017]

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In the above formula, R ¹ and R ² are independently C
_1-6 alkoxy, phenyloxy or phenyl-C
Represents _1-3 alkyloxy, or R ¹ and R
² together form ethylenedioxy (—O—CH (R ′) — CH ₂ —O optionally substituted with C _1-6 alkyl;
-: Where R 'represents a hydrogen atom or a C _{1 -6} alkyl) or R ¹ and R ^2, represents an oxy (= O) together, R ³ is a hydrogen atom or a C _{1 -6} alkyl, L represents carbonyl, C _1-3 alkylene or C _1-3 alkylphenylene, and n is 2 to 10,000.
And p is an integer from 1 to 5.

Furthermore, according to the present invention, the following formula (I)
-A)

[0020]

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Wherein R ³ represents a hydrogen atom or C _1-6 alkyl, and L represents carbonyl, C _1-3 alkylene or C _1-6 alkyl.
Represents a _1-3 alkylphenylene, n is an integer of 2 to 10,000, and p is an integer of 1 to 5], which is a method for producing a heterotelechelic polymer represented by the formula (I- b)

[0022]

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Wherein R ^1-b and R ^2-b are independently C
_1-6 alkoxy, phenyloxy or phenyl-C
Represents _1-3 alkyloxy, or R ¹ and R
² together form ethylenedioxy (—O—CH (R ′) — CH ₂ —O optionally substituted with C _1-6 alkyl;
-: Wherein R 'is a hydrogen atom or C _1-6 alkyl), and R ³ , L, n and p are as defined above], A method comprising deacetalization by treatment in acetic acid is also provided.

According to this method, the compound of the formula (Ib) can be converted into the compound of the formula (Ia) substantially without any side reaction.

[0025]

DETAILED DESCRIPTION OF THE INVENTION Among the repeating units represented by formulas (A) and (B) according to the present invention, (A) may be in a state where one or more kinds are mixed. For example, R
A branch polymer in which ¹ and R ² together represent an oxy group (＝ O) and a branch polymer in which R ¹ and R ² represent other than an oxy group (an aldehyde group is protected) are simultaneously bonded to the backbone polymer. Or the aldehyde group may be completely unprotected or, conversely, the aldehyde group may be completely protected as an acetal group. Also, the B unit derived from the comonomer relative to the macromonomer that derives the A unit may be derived from two or more comonomers (that is, Y and / or Z are two or more groups). However, those derived from one kind of comonomer are preferable in production.

Considering that the polymerization reaction of the above macromonomer (and possibly the above comonomer) is usually by radical polymerization, or by grafting a branched polymer (or graft chain) having an aldehyde group at a free end at a predetermined ratio. For inclusion in the polymer, one end of the macromonomer is preferably an aldehyde group that is not acetal protected (ie, APM). Therefore, a preferred graft polymer is a case where R ¹ and R ² of the A unit together represent an oxy group (＝ O). This is not bound by theory, especially from the former point of view, but if one end of the macromonomer is an acetal, its methine group

[0027]

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This is because there is a high possibility that side reactions will occur during radical polymerization.

A unit and B contained in the graft polymer
The unit ratio can be arbitrarily selected depending on the purpose of use of the graft polymer, but for the purpose of the present invention, the A unit is
It is necessary to account for at least 1% of the total number of A units and B units. Such a graft polymer having a low content of the A unit may be advantageously used for immobilizing a macromolecule having a biological activity, for example, an enzyme or an antibody. Also,
Articles applied to living organisms, for example, when used for surface coating of artificial organs and the like, because it is considered that it is advantageous to immobilize a large amount of anticoagulant proteins such as heparin via free terminal aldehyde groups. A graft polymer in which A units derived from APM account for tens of percent or more will be preferred.

In the present invention, the alkyl part of the alkyl and the alkoxy and the alkyl means a linear or branched alkyl group. Thus, the C _1-6 alkyl and alkyl portions of the alkoxy include methyl, ethyl, propyl, iso-propyl, butyl, sec.-
Butyl, tert.-butyl, pentyl, iso-pentyl, hexyl, 2-methylpentyl, 3-methylpentyl and the like. Of these, the alkyl portion of the alkoxy represented by R ¹ and R ² is particularly preferably C _1-3 alkyl.

Therefore, particularly preferred alkoxy as R ¹ and R ² includes methoxy, ethoxy, propoxy and isopropoxy. Also,
R ¹ and R ² are preferably phenyl or phenyl-C _1-3 alkyl, especially benzyl or phenethyl. These groups may be the same or different, but are preferably the same group. R ¹ and R ² are taken together to form ethylenedioxy (—OCH) which may be substituted by C _1-6 alkyl.
(R ′) — CH ₂ O—: wherein R ′ is C _1-6 alkyl), but is preferably ethylenedioxy, propylenedioxy, 1,2-butylenedioxy .

By treating these groups by a method according to another embodiment of the present invention described below, R ¹ and R ² are combined to form oxy (＝ O), that is, an aldehyde group at one end of the molecule. It is convenient to form the APM of the present invention having

R ³ represents a hydrogen atom or C _1-6 alkyl, preferably a hydrogen atom and a methyl group. Also,
L is carbonyl (= C = O), C _1-3 alkylene or C _1-3 alkylphenylene

[0034]

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But preferably carbonyl, methylene and benzylene

[0036]

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Is as follows.

N can be at least one integer from 2 to 10,000. Accordingly, the term "polymer" of the present invention for a branched polymer or a heterotelechelic polymer is used in a concept encompassing an oligomer.

As will be described later, when a heterotelechelic polymer (or macromonomer) is produced by so-called living polymerization, the polyoxyethylene segment becomes
By adjusting the amount of ethylene oxide to be used with respect to the polymerization initiator, a segment having a monomodal molecular weight can be obtained. Therefore, n is 2 to 10,000
Within this range, the number can be extremely narrow, preferably an integer of 10 to 200.

P is an integer of 1 to 5. Preferably, integers of 2 and 3 can be mentioned.

Y and Z defining the unit B represented by the formula (B) are specified by the comonomer used.
Y is a hydrogen atom or C _1-6 alkyl, preferably a hydrogen atom or a methyl group. On the other hand, Z is a group represented by phenyl, C _1-6 alkyloxycarbonyl, carbonyl or the formula CON (R ″) ₂ (where R ″ is a hydrogen atom or C _1-6 alkyl), Preferred are phenyl, methyloxycarbonyl, aminocarbonyl and dimethylaminocarbonyl. Accordingly, the B unit is preferably derived from styrene, methacrylate, acrylate, methacrylamide or acrylamide.

The bonding mode between the A unit and the B unit may be such that the methylene group (or side) and the methylene group (or side) face each other. The group is attached to the other substituted carbon atom.

The following Table I shows an example of the graft polymer of the present invention comprising the above groups or parts.

[0044]

[Table 1]

The above graft polymer can be obtained by polymerizing a heterotelechelic polymer (or macromonomer) represented by the following formula (I) provided as another embodiment of the present invention or by combining the macromonomer with the following formula (II) ) Can be obtained by copolymerization with the comonomer represented by

Formula (I)

[0047]

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In the above formula, R ¹ , R ² , R ³ , L, n and p
Is as defined above.

Formula (II)

[0050]

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In the above formula, Y and Z are as defined above.

The above polymerization or copolymerization is carried out by subjecting the monomers of the formula (I) and optionally of the formula (II) in excessive proportions according to the proportion of A units and optionally B units in the obtained graft polymer. Into an inert solvent,
It can be carried out by a radical polymerization reaction known per se, for example in toluene, in the presence of an initiator, for example an azo compound or a peroxide, or under the action of heat, light or radiation.

On the other hand, the macromonomer of the formula (I) [formulas (Ia) and (Ib)] can be produced according to the following reaction scheme.

Reaction scheme

[0055]

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[0056] In the above formulas, R ^1-b and R ^2-b, among the R ¹ and R ² defined, except when representing a group R ¹ and R ² together, R ¹ And R ² , R ³ , L, n and p are as defined above, X is, for example, a hydroxyl group, a halogen (eg, chlorine or bromine), and M is an alkali metal (eg, ,
Sodium, potassium or cesium).

Production of (ii) from (i): The alkali metal acetal protected alkoxide (A) is reacted with ethylene oxide to obtain a compound (B) having a polyethylene oxide segment added. The compound (A) may be an alkali metal such as sodium or potassium, an organic metal such as sodium naphthalene, potassium naphthalene, cumyl potassium, cumyl cesium or the like, or a compound such as sodium hydroxide or potassium hydroxide using an acetal protected acetal as a metalating agent. It can be obtained by treating with metal hydrogen or the like.

The above-mentioned reaction from (i) to (ii) is carried out in a solvent-free state or, preferably, in an anhydrous aprotic solvent at a wide range of temperatures, for example, -50 ° C to 300 ° C, preferably 10 ° C. ６０60 ° C., conveniently at room temperature (20-30
C). The reaction may be performed under elevated or reduced pressure. The solvent used is not limited, but, for example, benzene, toluene, xylene,
Examples include tetrahydrofuran, dioxane, acetonitrile and the like. Although the reaction vessel is not particularly limited, for example, a round bottom flask, an auto-reave, a pressure-resistant sealed tube, or the like is used. It is preferable that the inside of the reaction vessel can be shielded from the outside air, and it is more preferable that the inside of the reaction vessel can be filled with an inert gas. The concentration of the reaction solution is 0.
It is desirable that the content be 1 to 95% by weight, more preferably 1 to 80% by weight, and most preferably 3 to 10% by weight.

Production of (Ib) from (ii): Formula (i)
without removing the compound of i) from the reaction solution,
-C (R ³⁾ = the compound was added to the reaction CH _2, to stop the above polymerization reaction, groups ^{-L-C (R 3) =} CH
₂ is introduced at the ω end.

The polymer of the formula (Ib) thus produced can be purified, for example, by converting it into an aqueous solution obtained by adding water to a reaction solution, followed by extraction with chloroform, methylene chloride or the like.

Production of (Ia) from (Ib) (desorption of acetal): This step comprises adding an aqueous solution of (Ib) to trifluoroacetic acid, hydrochloric acid, sulfuric acid, nitric acid, formic acid, hydrogen fluoride The reaction can be carried out by adding an acid such as an acid to hydrolyze the acetal. However, under these conditions, the conversion of the acetal to aldehyde by elimination may not always be good, and when the conversion is further increased, a side reaction product is generated, which can be considered to be caused by the aldol condensation of the aldehyde. It should be noted that

More preferably, this step can be efficiently performed by the following method which is another embodiment of the present invention. For example, after dissolving the polymer of formula (I-b) in a mixture of glacial acetic acid and a catalytic amount of water (several percent to 15% by volume / volume),
C) for several hours. This reaction may be carried out under heating if necessary, but is preferably carried out at room temperature in order to eliminate any side reaction. On the contrary, the reaction time can be shortened by increasing the reaction temperature.
In time, almost 100% of the acetal can be converted to the aldehyde without side reactions. The recovery of the product from the reaction mixture can be performed according to the recovery of the above formula (Ib).

Specific examples of the thus obtained heterotelechelic polymer of the formula (I) of the present invention include those shown in Table II below.

[0064]

[Table 2]

The graft polymer provided by the present invention described above has at least one aldehyde group at its free end (e.g., it is possible to hydrolyze all or a part of the compound whose free end is an acetal group to convert it to an aldehyde group, The copolymerization may be carried out by adjusting the proportion of monomers having an acetal group at one end and those having an aldehyde group at one end). Therefore, for example, by coating these polymers on the surface of various articles (for example, medical supplies), the compatibility of living tissue or blood can be increased. Further, if heparin or the like is bound using an aldehyde group at a free terminal, blood compatibility may be further improved.

Further, since these graft polymers are formed into micelles by dispersing in water, they can be expected to be used as dispersion hardeners for paints and the like.

[0067]

Now, the present invention will be described in further detail with reference to specific examples.

Example 1 : Preparation of diethoxypropyl-polyoxyethylene vinylbenzyl

[0069]

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In a reaction vessel, 20 ml of THF and 3,3-
1 mmol of diethoxypropanol and 1 mmol of potassium naphthalene (K-Naph) were added, and the mixture was stirred for 10 minutes under an argon atmosphere to produce a potassium compound of 3,3-diethoxypropanol (potassium 3,3-diethoxypropanoxide). .

To this solution was added 70 mmol of ethylene oxide.
Was added, and the mixture was stirred at room temperature and one atmosphere. The reaction was performed for 50 hours. The reaction solution was further added with 0.3 mmol of K-Naph.
Was added, and the mixture was further stirred for 10 minutes. Then, 10 mmol of p-chloromethylstyrene was added, and the mixture was stirred at room temperature for 3 hours.

Next, extraction with chloroform, washing with saturated saline, dehydration with anhydrous sodium sulfate, and reprecipitation with diethyl ether were performed. The polymer obtained after drying under reduced pressure had a molecular weight by gel filtration chromatography (GPC), and was subjected to a structural analysis using ¹ H and ¹³ C-NMR. ¹ H-NMR and ¹³ C-NMR spectrumgrams are shown in FIGS. 1 (1) and (2).

Example 2 Conversion of Acetal to Aldehyde

[0074]

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Under room temperature at room temperature, 0.1 mmol of diethoxypropyl-polyoxyethylenevinylbenzyl was added.
Was dissolved in 10 ml of THF solvent. Then, 1N-H
5 ml of Cl was added and the mixture was stirred for 1 hour to deprotect the terminal.
Thereafter, extraction with chloroform, washing with saturated saline, dehydration with anhydrous sodium sulfate, and reprecipitation with diethyl ether were performed. After drying under reduced pressure, the resulting polymer was subjected to structural analysis using ¹ H, ¹³ C-NMR. As a result, the resulting polymer was converted into an aldehyde group by hydrolyzing an acetal at one end as represented by the above formula. Was confirmed. ¹ H and ¹³ C-NMR
Are shown in FIGS. 2 (1) and (2), respectively.

Example 3 : 3,3-diethoxy-initiator
Production of heterobifunctional polyoxyethylene (PEO) using 1-propanol, allyl bromide as terminator

[0077]

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In an argon atmosphere at room temperature, the solvent T
3,3-diethoxy-1 as an initiator in 15 ml of HF
-1 mmol of propanol, 1 mmol of K-Naph
The mixture was stirred for 10 minutes and metallized. Thereafter, 70 mmol of ethylene oxide (EO) was added, and the mixture was stirred for 50 hours to carry out polymerization. Before the termination reaction, 2.0 mmol of K-Naph was added again, and the mixture was stirred for 30 minutes. Then, 10 mmol of allyl bromide was added as a terminator, and the mixture was stirred at room temperature for 4 hours to perform a termination reaction. Thereafter, chloroform extraction, washing with saturated saline, dehydration with anhydrous sodium sulfate, and reprecipitation with diethyl ether were performed to obtain the title polymer. After drying under reduced pressure, molecular weight analysis was performed by GPC and structural analysis was performed using ¹ H, ¹³ C-NMR.

The molecular weight of the obtained polymer is about 2,500
The ¹ H-NMR and ¹³ C-NMR spectrumgrams are shown in (1) and (2) of FIG. 3, respectively.

Example 4 Conversion of Acetal to Aldehyde

[0081]

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To the reaction solution after termination reaction prepared according to Example 3, 5 ml of 1N HCl was added and stirred for 1 hour.
Next, chloroform extraction, washing with saturated saline, dehydration with anhydrous sodium sulfate, and reprecipitation with diethyl ether were performed. After drying under reduced pressure, molecular weight analysis and ¹ H, ¹³ C-NMR by GPC
Was used for structural analysis.

The molecular weight of the obtained terminal aldehyde polymer was not substantially changed. ^{The 1} H-NMR and ¹³ C-NMR spectrumgrams are shown in (1) and (2) of FIG. 4, respectively.

Examples 5 to 8 :

[0085]

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Under an argon atmosphere at room temperature in a receiver, 3,3-diethoxy-1-propanol was added to the solvent THF. Next, potassium naphthalene was added and metallized for 10 minutes. Then, add ethylene oxide and add 50
Polymerization was carried out for hours. After completion of the polymerization, methacrylic anhydride was added as a terminator, and a termination reaction was performed for 24 hours.

The respective charged amounts, purification and recovery methods were carried out as shown in Table III-1 below. Benzene was used for lyophilization.

[0088]

[Table 3]

After recovery, molecular weight analysis was performed by GPC. In addition, structural analysis by ¹ H-NMR and ¹³ C-NMR was also performed.

From the structural analysis, it was confirmed that an ester having a methacryloyl group bonded to another terminal hydroxyl group at the acetanol terminal was obtained. The yield and other results are shown in Table I below.
Illustrated in II-2.

[0091]

[Table 4]

FIG. 5 shows the results of GPC of the polymer of Example 8.

Example 9 Conversion of Acetal to Aldehyde The polymer obtained in Example 8 was dissolved in 50 ml of 1N HCl and stirred at room temperature for 6 hours. The polymer was obtained by extraction with chloroform, precipitation in ether, and then drying under reduced pressure. As a result of ¹ H NMR analysis of the obtained polymer, 9.7 was obtained.
A new aldehyde proton signal appeared around ppm and it was confirmed that the conversion of acetal to aldehyde was progressing, but the conversion was about 85%.

Example 10 Conversion of Acetal to Aldehyde The polymer obtained in Example 5 (0.5 g) was converted to 0.1 N H
This was treated in the same manner as in Example 9 except that it was dissolved in Cl (20 ml) and the reaction was carried out for 4 hours. The conversion of acetal to aldehyde by the method of this example was about 61%.

Example 11 Conversion of Acetal to Aldehyde The polymer (0.5 g) obtained in Example 7 was converted to 0.1 N H
This was treated in the same manner as in Example 9 except that it was dissolved in Cl (20 ml) and the reaction was carried out for 3 hours. The conversion of acetal to aldehyde by the method of this example was about 70%.

Example 12 : The polymer (0.5 g) obtained in Example 8 was dissolved in 20 ml of glacial acetic acid, 2 ml of water was added, and the mixture was stirred at room temperature for 1 hour. The polymer was recovered and analyzed by ¹ H NMR and ¹³ C NMR in the same manner as in Example 9. As a result, the conversion from acetal to aldehyde was about 89%.

Example 13 Example 12 was repeated except that the reaction time was changed to 5 hours. The conversion of acetal to aldehyde was confirmed to be 100%. GP
The result of C analysis also showed no change from the precursor acetal polymer, confirming that no by-product was generated.

Example 14 : 3.65 g of the polymer obtained in Example 13, 4 g of methyl methacrylate (MMA) and 0.015 g of azobisisobutyronitrile were added to 35 parts of toluene.
After dissolving in a ml, degassing in an ampoule and then sealing the tube, polymerization was carried out at 50 ° C. for 45 hours. After the polymerization, the polymer was subjected to GPC analysis, dispersed in water, and centrifuged to precipitate the polymer. After the obtained polymer was dried under reduced pressure, it was analyzed by ¹ H NMR. Yield 85
%, And the obtained polymer has 5,
It was confirmed that the MMA unit was 260.

¹ H NMR (δ, ppm): 0.8 (derived from R ³ (= CH ₃ ) of unit A) 2.2 (derived from —CH ₂ — in the backbone polymer of units A and B) 2 .8 (-C adjacent to the free terminal aldehyde group of unit A)
H ₂ - the origin) 3.5~4.0 (-O-CH ₂ units A - and of the unit B -
From COOCH ₃₎ 4.2 (-COOCH ₂ units A - derived from -CHO of the origin) 9.8 (Unit A) Example 15: As in Example 14, the polymer obtained in Example 13 4.51 g, 2.0 g of MMA and 0.015 g of azobisisobutyronitrile were dissolved in toluene (35 ml) and reacted at 60 ° C. for 24 hours. The yield of the obtained polymer was 70%, and the molecular weight of the polymer was 3.3 × 10 ⁴ . ^{From the} result of ¹ H NMR analysis, it was confirmed that the polymer had 5 polyoxyethylene chains and 100 MMA units.

[0100]

According to the present invention, there is provided a graft polymer having a polyoxyethylene segment as a branch polymer and having an aldehyde group (or a protected aldehyde group) at a free terminal, and an efficient method for producing the graft polymer. And a heterotelechelic polymer that can also be used as a precursor in its manufacture.

[Brief description of the drawings]

FIG. 1 shows the ¹ H—N of the polymer obtained according to Example 1.
It is an MR and ¹³ C-NMR spectrumgram ((1) and (2), respectively).

FIG. 2 is a ¹ H-NMR and ¹³ C-NMR spectrumgram ((1) and (2), respectively) of a polymer (an aldehyde group at one terminal) obtained in Example 2.

FIG. 3 shows the ¹ H—N of the polymer obtained according to Example 3.
MR and ¹³ C-NMR spectrograms ((1) and (2), respectively).

FIG. 4 is a ¹ H-NMR and ¹³ C-NMR spectrumgram ((1) and (2), respectively) of a polymer (an aldehyde group at one terminal) obtained in Example 4.

FIG. 5 shows the result of GPC of the polymer obtained in Example 8.

Continuation of the front page (72) Inventor Takahiko Kutsuna 2535 Heights Kimura, Yamazaki 2535, Noda City, Chiba Prefecture (72) Ryutaro Ogawa 335-4 Otaniguchi, Matsudo City, Chiba Prefecture Sampares Shin-Matsudo 1-302 (56) References 7-316285 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 290/00-290/14 C08F 299/00-299/08 C08G 65/00-65/48

Claims (6)

(57) [Claims] 1. A graft polymer comprising repeating units represented by the following formulas (A) and (B), wherein A to B are correlated in a ratio of 100 to 1:99 to 0. Formula (A) Formula (B) Wherein R ¹ and R ² independently represent C _1-6 alkoxy, phenyloxy or phenyl-C _1-3 alkyloxy, or R ¹ and R ² together represent C _1-6 optionally substituted by alkyl ethylenedioxy (-O-CH (R ') - CH 2 -O-: wherein R'
Represents a hydrogen atom or C _1-6 alkyl), or R ¹ and R ² together represent oxy (（O), R ³ represents a hydrogen atom or C _1-6 alkyl, L represents carbonyl, C _1-3 alkylene or C _1-3 alkylphenylene; n is an integer of 2 to 10,000;
Is an integer from 1 to 5, Y represents a hydrogen atom or C _1-6 alkyl, and Z is phenyl, C _1-6 alkyloxycarbonyl, carboxy or the formula CON (R ″) ₂ where R ″ Is a hydrogen atom or C _1-6 alkyl)
Represents a group. 2. The graft polymer according to claim 1, wherein R ¹ and R ² together represent oxy (＝ O). 3. R ¹ and R ² are taken together to form oxy (=
O), R ³ represents a hydrogen atom or methyl, and L represents carbonyl, methylene or benzylene The graft polymer according to claim 1, which represents: 4. A: B is correlated with 99-1: 1-99.
Of is in the ratio, Y represents a hydrogen atom or methyl, and Z is C _1-6 alkyloxycarbonyl, phenyl, an amino carbonyl or dimethylaminocarbonyl, graft polymer according to any of claims 1 to 3. 5. A heterotelechelic polymer represented by the following formula (I). Formula (I) Wherein R ¹ and R ² independently represent C _1-6 alkoxy, phenyloxy or phenyl-C _1-3 alkyloxy, or R ¹ and R ² together represent C _1-6 optionally substituted by alkyl ethylenedioxy (-O-CH (R ') - CH 2 -O-: wherein R'
Represents a hydrogen atom or C _1-6 alkyl), or R ¹ and R ² together represent oxy (（O), R ³ represents a hydrogen atom or C _1-6 alkyl, L represents carbonyl, C _1-3 alkylene or C _1-3 alkylphenylene, n is an integer from 2 to 10,000, and p is an integer from 1 to 5. 6. R ¹ and R ² are taken together to form oxy (=
O) and L is carbonyl or benzylene The heterotelechelic polymer according to claim 5, wherein