JP2009280728A - Method for producing epoxy group-containing polymer and its derivative - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for industrially producing an epoxy group-containing polymer and its derivative. <P>SOLUTION: The method comprises [process 1] and [process 2] as described below. The [process 1] comprises the following steps: a polymer formed by the polymerization of an olefin or the copolymerization of an olefin and a diene and having a (alkyl-substituted) double bond on the terminal end of the polymer chain 400-500,000 in Mw (weight-average molecular weight) is reacted in the presence of a first carboxylic acid (CA1) and hydrogen peroxide to obtain an epoxy group-containing polymer. The [process 2] comprises the following steps: a second carboxylic acid (CA2) is reacted with the epoxy group-containing polymer to produce a polymer having on the terminal end(s) hydroxy or acyloxy group(s) and having hydrogen atom(s) or hydroxy group(s) on the site(s) next to the terminal end(s). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an industrial production method for an epoxy group-containing polymer and derivatives thereof.

  Since an ethylene polymer has a non-polar molecular structure and poor affinity with other substances, it has been attempted to introduce various functional groups into the polymer. For example, epoxy group or α, β-dihydroxy group has high reactivity, and various groups such as hydroxyl group, amino group, carboxyl group, acid anhydride, acid halogen group, ester group, halogenated hydrocarbon, mercapto group, isocyanato group, etc. It is very useful because it reacts quickly with functional groups to produce corresponding chemical bonds. By utilizing the reactivity with these functional groups, it is possible to show excellent effects in adhesion between polyolefin and other substances, printability, compatibility in polymer blends, and the like. For this reason, a method of epoxidizing or α, β-dihydroxylation with a high industrial yield is particularly desired for the double bond portion of the polymer.

  So far, examples of reports in which an epoxy group or a derivative thereof has been introduced using hydrogen peroxide and an aromatic or aliphatic carboxylic acid include epoxidation of butadiene of Non-Patent Document 1 and polycyclohexane of Non-Patent Document 2. The epoxidation of pentadiene-α methylstyrene copolymer is mentioned. Here, a method of epoxidizing a double bond portion of a polymer with hydrogen peroxide and acetic acid or formic acid is described, but in both cases, the epoxidation yield is as low as 45% or less and the reaction temperature is also low. The method was limited to a polymer having a low temperature of 50 ° C. or lower and being soluble in an organic solvent near room temperature.

On the other hand, in the epoxidation of the styrene-butadiene copolymer exemplified in Patent Document 1, it is only described with respect to a method for suppressing gel by-produced from the produced epoxidized product, and in particular, dissolves polyolefins. There is no description of the reaction under the high temperature required for. Also, what is exemplified in Patent Document 2 is an epoxidation reaction in a continuous process of soybean oil, and is produced in the system particularly in the epoxidation reaction of polyolefins that require a reaction at 90 ° C. or higher. It cannot be applied due to the low thermal stability of performic acid. Moreover, although there was description about a by-product, there was no description about manufacture of (alpha), (beta) -dihydroxy body.
Polymer Papers Vol. 37, no. 3, pp. 195 Acta Polymerica 36 (1985) pp. 357 US Pat. No. 4,131,705 Japanese Examined Patent Publication No. 4-61869

  The present invention aims to provide a solution to these problems, and an industrially advantageous method that can introduce epoxy groups and derivatives thereof into polymers having a wider variety and molecular weight. It is to provide.

The method for producing an epoxy group-containing polymer and a polymer (P) which is a derivative thereof according to the present invention is characterized by sequentially performing the following [Step 1] and [Step 2].
[Step 1] The following general formula (1)

(In Formula (1), A is a group formed by polymerization of olefins having 2 to 20 carbon atoms or olefins having 2 to 20 carbon atoms and diene, and was measured by gel permeation chromatography (GPC). (The weight average molecular weight (Mw) represents 400 to 500,000, and R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.)
Is reacted in the presence of hydrogen peroxide with one or more first carboxylic acids (CA1) selected from the group consisting of aliphatic carboxylic acids and aromatic carboxylic acids. The following general formula (2)

(In formula (2), A, R ¹ and R ² each represent the same group or atom as in formula (1).)
A step of obtaining an epoxy group-containing polymer represented by:
[Step 2] The epoxy group-containing polymer represented by the formula (2) is reacted with one or more second carboxylic acids (CA2) selected from the group consisting of aliphatic carboxylic acids and aromatic carboxylic acids, Further, if necessary, it is reacted with water or alcohols in the presence of a base catalyst to give the following general formula (3)

(In the formula (3), A, R ¹ and R ² each represent the same group or atom as in the general formula (1), Q ¹ represents a hydroxyl group or an acyloxy group having 1 to 18 carbon atoms, and Q ² Represents a hydrogen atom or an acyl group having 1 to 18 carbon atoms.)
The process of manufacturing the polymer (P) represented by these.

  In the present invention, it is preferable to carry out [Step 1] and [Step 2] successively without isolating the epoxy group-containing polymer that is the product of [Step 1], and to end [Step 1]. One or more reducing agents selected from the group consisting of an organic reducing agent, preferably ascorbic acid (vitamin C), isoascorbic acid, tocopherol (vitamin E), and salts thereof after and before the implementation of [Step 2] It is preferable to further carry out [Step 1 ′] in which the residual peroxide is subjected to a reduction treatment using the above.

  In the present invention, the first carboxylic acid (CA1) in [Step 1] is preferably acetic acid or propionic acid, and the second carboxylic acid (CA2) in [Step 2] is preferably formic acid or acetic acid. . Furthermore, the reaction temperature in [Step 1] is preferably in the range of 80 to 100 ° C., and the pH of the reaction mixture is preferably in the range of 1.5 to 4.0.

  In the production method of the present invention, by changing the type of aromatic or aliphatic carboxylic acid to be used, an epoxy group-containing polymer and its derivative can be made separately, and a highly versatile functional group-containing polymer. The manufacturing method can be provided.

Hereinafter, the production method of the epoxy group-containing polymer and derivatives thereof of the present invention will be specifically described.
<Double bond-containing polymer>
The starting material of the present invention is a double bond-containing polymer represented by the following general formula (1).

  In general formula (1), A represents the group formed by superposition | polymerization of a C2-C20 olefin or a C2-C20 olefin and diene.

  Examples of the olefin having 2 to 20 carbon atoms include α-olefins such as ethylene, propylene, 1-butene and 1-hexene, and the group formed by polymerization is a homopolymer or a copolymer of these olefins, or characteristics. It may be copolymerized with other polymerizable unsaturated compounds as long as the above is not impaired. Of these, ethylene, propylene, and 1-butene are particularly preferable. Examples of the diene include butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, ethylidene norbornene, vinyl norbornene, and dicyclopentadiene. Among these, vinyl norbornene, ethylidene norbornene, dicyclopentadiene, butadiene, and isoprene are particularly preferable.

  In the general formula (1), the weight average molecular weight (Mw) measured by gel permeation chromatography (hereinafter abbreviated as GPC) of the group represented by A is 400 to 500,000, preferably 800 to 200,000. More preferably, it is 1000-100000. Here, Mw is a polystyrene equivalent value.

  The ratio of the weight average molecular weight (Mw) to the weight average molecular weight (Mn) measured by GPC of the group represented by A in the general formula (1), that is, the molecular weight distribution (Mw / Mn) is not particularly limited. Although there are 0 to several tens of materials, 4.0 or less, particularly 3.0 or less may be preferable in terms of uniformity of physical properties.

  The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the group represented by A can be measured under the following conditions using, for example, GPC-150 manufactured by Millipore.

Separation column: TSK GNH HT (column size: diameter 7.5 mm, length: 300 mm)
Column temperature: 140 ° C
Mobile phase: Orthodichlorobenzene (Wako Pure Chemical Industries, Ltd.)
Antioxidant: Butylhydroxytoluene (manufactured by Takeda Pharmaceutical Company Limited) 0.025% by mass
Movement speed: 1.0 ml / min Sample concentration: 0.1% by mass
Sample injection amount: 500 microliters Detector: Polyolefin having an unsaturated group at one end as described later as a differential refractometer
The molecular weight is measured and the molecular weight equivalent to the terminal is removed.

In the general formula (1), R ¹ and R ² are each independently hydrogen or a hydrocarbon residue having 1 to 18 carbon atoms bonded to a double bond of the olefin constituting A. Hydrogen, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, hexadecyl group and the like.

<Production of double bond-containing polymer>
Examples of the method for producing the double bond-containing polymer represented by the general formula (1), which is a raw material of the present invention, include the following.
(1) Polymerization using a transition metal compound having a salicylaldoimine ligand as a polymerization catalyst as disclosed in JP-A-2001-2731, JP-A-2003-73412 and JP-A-2000-239312 Method.
(2) A polymerization method using a Ziegler type catalyst comprising a titanium compound and an organoaluminum compound.
(3) A polymerization method using a vanadium catalyst comprising a vanadium compound and an organoaluminum compound.
(4) A polymerization method using a metallocene catalyst comprising a metallocene compound such as zirconocene and an organoaluminum oxy compound (aluminoxane).

<Production of epoxy group-containing polymer> [Step 1]
In [Step 1] of the present invention, the double bond-containing polymer represented by the general formula (1) is converted into one or more first carboxylic acids selected from the group consisting of aliphatic carboxylic acids and aromatic carboxylic acids. By reacting in the presence of acid (CA1) and hydrogen peroxide, an epoxy group-containing polymer represented by the following general formula (2) is obtained.

In general formula (2), A, R ¹ and R ² each represent the same group or atom as in general formula (1).

  In the method of the present invention, a peracid obtained from hydrogen peroxide and at least one first carboxylic acid (CA1) selected from the group consisting of an aliphatic carboxylic acid and an aromatic carboxylic acid is prepared in a reaction system. , A method of reacting with a double bond-containing polymer.

  Examples of the first carboxylic acid (CA1) include aliphatic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, and valeric acid, and aromatics such as benzoic acid, 4-methylbenzoic acid, phthalic acid, terephthalic acid, and isophthalic acid. One or more carboxylic acids are selected from the group consisting of group carboxylic acids. Of these, acetic acid or propionic acid is preferred, and acetic acid is particularly preferred from the relationship between the decomposition temperature of peracid and the reaction temperature.

  The amount of the first carboxylic acid (CA1) to be used is 0.5 mol to 10 mol, preferably 0.8 mol to 8 mol, more preferably 1.0 mol, per 1 mol of the raw material double bond-containing polymer. Mol to 5 mol.

  The hydrogen peroxide to be used is usually used as an aqueous solution, and the concentration thereof is 3% by mass to 90% by mass, preferably 5% by mass to 70% by mass, and more preferably 10% by mass to 50% by mass. The amount of hydrogen peroxide to be used is 0.5 mol to 10 mol, preferably 0.8 mol to 8 mol, more preferably 1.0 mol to 5 mol, per 1 mol of the raw material double bond-containing polymer.

  The quantity ratio between hydrogen peroxide and the first carboxylic acid (CA1) is in the range of 1: 0.01 to 1:20, preferably 1: 0.5 to 1:10.

  In [Step 1] of the present invention, a reaction solvent can be used as necessary. As the reaction solvent, a solvent that is not affected by the oxidation reaction can be used, and examples thereof include aromatic hydrocarbon solvents such as benzene, toluene, and xylene. When a reaction solvent is used, the amount used is 0.5 to 50 times by weight, preferably 1 to 10 times by weight with respect to the double bond-containing polymer.

  In a general embodiment of [Step 1] of the present invention, a solvent, a carboxylic acid, and a double bond-containing polymer are mixed in a reactor, and the mixture is heated until it is uniformly dissolved. After the reaction temperature is reached, hydrogen peroxide is slowly added dropwise. The reaction temperature is preferably a temperature at which the double bond-containing polymer to be used is melted, but it is necessary to set the reaction temperature in view of the decomposition temperature of the peracid produced in the reaction system. Also, depending on the peracid to be produced, it is explosive, so care must be taken when setting the temperature. The reaction temperature is 25 ° C to 150 ° C, preferably 50 ° C to 110 ° C, more preferably 80 ° C to 100 ° C. When reacting at 100 ° C. or higher, there is a risk of bumping due to the dropwise addition of hydrogen peroxide, so an appropriate reactor such as an autoclave is selected. The time required for the reaction varies depending on the reaction conditions such as the ratio of hydrogen peroxide and carboxylic acid, the reaction temperature, the solubility of olefins in the solvent, and the reactivity, but it is usually several minutes to 50 hours, preferably 0. It is in the range of 1 to 10 hours, more preferably 0.5 to 5 hours. The dropping rate of hydrogen peroxide is gradually dropped according to the reaction rate and the removal rate of reaction heat.

  In the method of the present invention, the reaction may be carried out by adjusting the pH of the reaction mixture. The pH is preferably between 1.0 and 5.0, preferably between 1.5 and 4.0. The pH of the reaction mixture can be adjusted by changing the carboxylic acid species used or adding an aqueous solution of an acid such as sulfuric acid or phosphoric acid.

(Analysis of epoxy group-containing polymer)
The epoxy group content of the epoxy group-containing polymer is determined by ¹ H-NMR. For example, in the case of a terminal epoxy group-containing polymer obtained by epoxidizing a single-end double bond-containing polymer consisting only of ethylene, the peak (C) for the three protons of the methyl group at the saturated terminal is 0.65 to 0. The peak (D) corresponding to 3 protons at the root of the epoxy group is observed at 2.3 to 2.4 ppm, 2.6 to 2.7 ppm, and 2.8 to 2.9 ppm for each proton. When the epoxy modification is not sufficient, a peak (E) corresponding to 3 protons of the terminal double bond is observed at 2 protons at 4.70 to 5.0 ppm and 1 proton at 5.5 to 5.8 ppm. Each peak (C), if each _S C, _{S D} and _{S E} peak areas of (D) and (E), epoxy group content (Ep (%)) is calculated by the following equation.
_{Ep (%) = S D ×} 200 / (S C + S D + S E)

Moreover, the production | generation of an epoxy group-containing polymer can be confirmed also in FT-IR. For example, in the case of a terminal epoxy group-containing polymer obtained by epoxidizing a polymer having only one terminal double bond consisting of ethylene, the peak based on C—H stretching of 991 cm ⁻¹ vinyl group disappears, and 847 cm ⁻ The formation of epoxy groups can be confirmed by the peak of C—O—C symmetrical stretching vibration near the peak of ¹ .

<Reduction treatment of residual peroxide> [Step 1 ']
In the case of production of an epoxy group-containing polymer according to [Step 1] of the present invention, the peroxide may or may not be treated after the reaction, but in order to carry out safely, after the completion of [Step 1] and It is desirable to further carry out [Step 1 ′] in which the residual peroxide is reduced before carrying out [Step 2]. Although it does not specifically limit regarding the method of a reduction process, The reduction process using an organic reducing agent or an inorganic reducing agent can be mentioned.

  Examples of the organic reducing agent include citric acid and salts thereof, ascorbic acid (vitamin C), isoascorbic acid, tocopherol (vitamin E), and salts thereof, hydrazine, formaldehyde, methanol, ethanol, hydrogen, ethylene, and the like. Examples of the inorganic reducing agent include sodium thiosulfate and sodium sulfite. Of these, one or more organic reducing agents selected from the group consisting of ascorbic acid (vitamin C), isoascorbic acid, tocopherol (vitamin E), and salts thereof are preferred, and ascorbic acid (vitamin C) or isoascorbine Acid is particularly preferred. Examples of the salt include alkali metal salts such as lithium, sodium, and potassium, and alkaline earth metal salts such as magnesium and calcium. Of these, sodium, potassium, and calcium salts are preferable.

  In [Step 1 ′], in order to reliably decompose the residual peroxide, it is preferable to use the reducing agent in excess relative to the residual peroxide. In this case, the excess reducing agent is removed. Need to do. In the present invention, it is advantageous to use the above-mentioned organic reducing agent from the viewpoint that the excess reducing agent can be easily separated and removed, and no ash derived from the inorganic salt remains.

  These reducing agents may be added to the reaction system as they are, or may be added in a state dissolved or suspended in water or an organic solvent. The amount of the reducing agent used is 0.01 mol to 10 mol, preferably 0.1 mol to 5 mol, relative to 1 mol of hydrogen peroxide used. The method of decomposition treatment is not particularly limited, but considering the decomposition temperature of the peroxide, the reaction temperature is increased to promote the decomposition of the peroxide, the addition of an acid or base, etc. to promote the decomposition of the peroxide, etc. The method is mentioned. The reaction time in the reduction treatment varies depending on the reaction conditions, but is usually from several minutes to 50 hours.

  In the production method of the present invention, since there is little production of by-products, after [Step 1] and [Step 1 ′] performed as necessary, [Step 2] described later can be carried out as it is. . If necessary, the desired epoxy group-containing polymer can be removed by simple operations such as liquid separation, crystallization, and washing, excluding carboxylic acid, water, and reaction solvent. Further, the epoxy group-containing polymer obtained as desired can be further purified.

<Polymer (P)>
The polymer (P) according to the present invention is a polymer represented by the following general formula (3).

In general formula (3), A, R ¹ and R ² each represent the same group or atom as in general formula (1).

Q ¹ represents a hydroxyl group or an acyloxy group having 1 to 18 carbon atoms, and Q ² represents a hydrogen atom or an acyl group having 1 to 18 carbon atoms.

The acyloxy group having 1 to 18 carbon atoms Q ^1, the following general formula (4)

(In the formula (4), R ³ is a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms, hydrogen, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, And a acyl group having 1 to 18 carbon atoms of Q ² is represented by the following general formula (5).

(In Formula (5), R < ³ > shows group represented by General formula (4)).

  Specifically, the polymer (P) represented by the general formula (3) is any one of the polymers of the following general formulas (6) to (9) or a mixture thereof.

(In the formulas (6) to (9), A, R ¹ and R ² are as defined in the general formula (1), and R ³ is as defined in the general formula (4).)

<Production of polymer (P)> [Step 2]
(Production of ester group-containing polymer)
In [Step 2] in the present invention, the epoxy group-containing polymer represented by the formula (2) is added to one or more second carboxylic acids (CA2) selected from the group consisting of aliphatic carboxylic acids and aromatic carboxylic acids. ) Can be reacted to produce an ester group-containing polymer represented by the general formulas (6) to (8) in the polymer (P).

  In the method for producing an ester group-containing polymer, the second carboxylic acid (CA2) to be used is not particularly limited as long as it has an acidity suitable for ring opening of an epoxy group. Formic acid, acetic acid, propion, etc. Select one or more carboxylic acids from the group consisting of aliphatic carboxylic acids such as acid, butyric acid, valeric acid, and aromatic carboxylic acids such as benzoic acid, 4-methylbenzoic acid, phthalic acid, terephthalic acid, and isophthalic acid. Use. Among these, formic acid or acetic acid is preferable, and formic acid is particularly preferable because it has an acidity suitable for ring opening of the epoxy group of the polymer and is easily available.

  In the production of the ester group-containing polymer, the amount of the second carboxylic acid (CA2) used is 0.1 mol to 50 mol, preferably 0.5 mol to 20 mol, per 1 mol of the epoxy group-containing polymer. . Moreover, the temperature of reaction is 0-200 degreeC, Preferably it is 10-150 degreeC. The time required for the reaction is in the range of 0.1 to 30 hours, preferably 0.5 to 10 hours. When a solvent is used, a solvent that is not affected by the reaction can be used, and examples thereof include aromatic hydrocarbon solvents such as benzene, toluene, and xylene.

  A catalyst can also be used in the reaction of the epoxy group-containing polymer and the second carboxylic acid (CA2). Catalysts include mineral acids such as hydrochloric acid, hydrobromic acid, phosphoric acid and sulfuric acid, tetrabutylammonium chloride, trioctylmethylammonium chloride, or quaternary ammonium salts such as bromide, iodide, sulfite or sulfate. , Lewis acid catalysts such as boron trifluoride, boron trichloride, iron (III) chloride, zinc chloride, aluminum chloride, and Lewis base catalysts such as trimethylamine, triethylamine, tributylamine, trimethylphosphine, tributylphosphine, triphenylphosphine can do. The amount of these catalysts used is in the range of 0.001 mol to 1 mol, preferably 0.01 mol to 0.5 mol, per 1 mol of the epoxy group-containing polymer.

  [Step 2] in the present invention may be carried out in one pot after [Step 1] and [Step 1 ′], which is performed as necessary, and the epoxy group-containing polymer obtained. It may be carried out after taking out and purifying it.

(Analysis of ester group-containing polymer)
Formation of the ester group-containing polymer can be confirmed by ¹ H-NMR. For example, in the case of an ester group-containing polymer obtained by ring-opening a single-end epoxy group-containing polymer consisting only of ethylene with formic acid, the peak (D) for the three protons at the root of the epoxy group disappears and is derived from the formyl group of formate 1 to 2 proton peaks of about 8.0 to 8.1 ppm, and methylene group 2 proton peaks at the base of the formate ester are around 3.6 to 4.3 ppm and 4.7 to 5.0 ppm. appear. When 1 mol of formic acid is added from the end of the epoxy group to 1 mol of epoxy group, 2 protons of the methylene group at the base of the formate ester appear in the vicinity of 3.7 ppm, and 1 proton of methine at the base of the hydroxyl group is 3 It is detected in the vicinity of .9 to 4.1 ppm. When further dehydration and esterification proceeded from this hydroxyl group and formic acid, two protons of the methylene group at the base of the terminal formate ester appeared at 4.0 to 4.2 ppm, and the methine at the base of the other ester One proton appears in the vicinity of 4.9 ppm. When the reaction is not sufficient, a peak (D) corresponding to 3 protons at the root of the epoxy group is observed.

Formation of the ester group-containing polymer can also be confirmed by FT-IR. For example, in the case of an ester group-containing polymer obtained by ring-opening a polymer having only one terminal epoxy group consisting of ethylene with formic acid, when esterification proceeds, 847 cm ^{−1 of the} symmetric contraction vibration of epoxy group C—O—C , And the C = O stretching vibration of the carbonyl group at 1733 cm ^-1 appears.

(Production of α, β-dihydroxy polymer)
Among the polymers (P) according to the present invention, the α, β-dihydroxy polymer represented by the general formula (9) is an epoxy group-containing polymer represented by the general formula (2) in [Step 2]. A polymer or an ester group-containing polymer represented by the general formulas (6) to (8) can be produced by reacting with water or alcohols, preferably in the presence of a base catalyst.

  Examples of the alcohol used for the reaction include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-2-propanol, 2-methyl-1-propanol and the like. The amount of water or alcohol used for the reaction is 1 to 100 mol, preferably 2 to 50 mol, per 1 mol of the epoxy group-containing polymer or ester group-containing polymer. The temperature of the reaction is 0 to 200 ° C, preferably 10 to 150 ° C. The time required for the reaction is in the range of 0.1 to 30 hours, preferably 0.5 to 10 hours. When a reaction solvent is used, a solvent that does not affect the reaction can be used. For example, an aromatic hydrocarbon solvent such as benzene, toluene, xylene, or water or alcohol used in the reaction can be used as the solvent. .

  Although it does not specifically limit as a base catalyst used for reaction, LiOH, NaOH, KOH, CsOH etc. are used. These basic catalysts may be used in the form of a solid, or may be added as a solution or suspension of water or alcohol. The usage-amount of a base catalyst is 0.001 mol-50 mol with respect to 1 mol of epoxy group containing polymers or ester group containing polymers, Preferably, they are 0.01 mol-10 mol.

  The α, β-dihydroxy polymer may be produced after taking out the epoxy group-containing polymer or ester group-containing polymer, or in one pot.

(Analysis of α, β-dihydroxy polymer)
The formation of α, β-dihydroxy polymer can be confirmed by ¹ H-NMR. For example, when an ethylene-containing polymer containing only one end of an epoxy group is produced from an ester-containing polymer ring-opened with formic acid, the proton peak derived from the ester group decreases, and the methylene group at the base end of the hydroxyl group decreases. Two protons appear in the vicinity of 3.4 to 3.6 ppm, and one proton of methine at the base of the internal hydroxyl group appears at 3.6 ppm. When the reaction is not sufficient, the peak of the ester group-derived proton is observed.

The production of α, β-dihydroxy polymer can be confirmed by FT-IR. For example, when a one-terminal epoxy group-containing polymer consisting only of ethylene is converted into a diol via the formate ester, the peak of contraction vibration of the carbonyl group 1733 cm ⁻¹ is reduced, and the stretching of the O—H derived from the hydroxyl group is reduced. This can be confirmed by the appearance of CO stretching vibrations of vibration 3370 cm ⁻¹ and 1122 cm ⁻¹ .

[Example]
EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.
In addition, the weight average molecular weight Mw and Mw / Mn were measured by the method described in the text using GPC. FT-IR (FT-IR6100 manufactured by JASCO) was used for tracking the reaction. The melting point (Tm) was a peak top temperature obtained by measurement using DSC.

[Synthesis Example 1]
(Synthesis of double bond-containing ethylene polymer (P-1))
The compound (I) used as the catalyst was synthesized according to Synthesis Example 6 of JP-A-2003-73412, and the single-end double bond-containing polyethylene was synthesized according to Example 9 of the same publication.
A stainless steel autoclave with an internal volume of 2000 ml sufficiently purged with nitrogen was charged with 1000 ml of heptane at room temperature, and the temperature was raised to 150 ° C. Subsequently, 30 kg / cm ² G was pressurized with ethylene in the autoclave to maintain the temperature. A hexane solution (1.00 mmol / ml in terms of aluminum atom) of MMAO (manufactured by Tosoh Finechem) was injected with 0.5 ml (0.5 mmol), and then a toluene solution (0.0002 mmol / ml) of the following compound (I) 0. 5 ml (0.0001 mmol) was injected to initiate the polymerization. After carrying out the polymerization at 150 ° C. for 30 minutes in an ethylene gas atmosphere, the polymerization was stopped by press-fitting a small amount of methanol. The obtained polymer solution was added to 3 liters of methanol containing a small amount of hydrochloric acid to precipitate a polymer. After washing with methanol, it was dried under reduced pressure at 80 ° C. for 10 hours to obtain a double bond-containing ethylene polymer (P-1).

The analysis results are as follows.
Mw: 1900, Mw / Mn: 2.24
¹ H-NMR (C ₆ D ₆ ): δ 0.81 (t, 3H, J = 6.9 Hz), 1.10-1.45 (m), 1.93 (m, 2H), 4.80 (dd, 1H, J = 9.2, 1.6 Hz ), 4.86 (dd, 1H, J = 17.2, 1.6 Hz), 5.60-5.72 (m, 1H)
IR: 4322, 4250, 2897-2848, 2634, 1642, 1463, 991, 909, 730 cm ^-1
Melting point (Tm): 123 ℃

[Synthesis Example 2]
(Synthesis of double bond-containing ethylene polymer (P-2))
450 ml of heptane was charged into a stainless steel autoclave with an internal volume of 1000 ml sufficiently purged with nitrogen, and 100 liters / hr of ethylene was circulated at room temperature for 15 minutes to saturate the liquid phase and the gas phase. Subsequently, 28 NL of propylene was introduced, the temperature was raised to 80 ° C., and then the pressure was increased to 8 kg / cm ² G with ethylene to maintain the temperature. 0.5 ml (0.5 mmol) of decane solution of triisobutylaluminum (aluminum atom conversion: 1.00 mmol / ml) was injected, and then toluene solution (0.0002 mmol / ml) of the above compound (I) 1 ml (0.0002 mmol) Was injected to initiate polymerization. The pressure was maintained while continuously supplying ethylene gas, and the polymerization was carried out at 80 ° C. for 60 minutes. Then, the polymerization was stopped by press-fitting 5 ml of methanol, and the monomer was depressurized after the temperature was lowered. The obtained polymer slurry was mixed with 2 L of methanol and stirred and then filtered. The obtained product was dried under reduced pressure at 80 ° C. for 10 hours to obtain 41.4 g of a double bond-containing ethylene polymer (P-2).
The analysis results are as follows.
Mw: 1310, Mw / Mn: 1.66
¹ H-NMR (C ₂ D ₂ Cl ₄ ): δ 0.85-0.92 (m), 1.05-1.71 (m), 2.05 (m, 2H), 4.67 (m), 4.89 (dd, 1H, J = 10.0, 1.3 Hz), 4.93 (dd, 1H, J = 11.9, 1.3 Hz), 5.40 (2H, m) 5.73-5.91 (m, 1H)
Vinyl group / vinylene group / vinylidene group = 70.6 / 24.6 / 4.8 (mol / mol) ( ¹ H-NMR)
IR: 4322, 4250, 3604-2635, 2340, 1642, 1466-1461, 1377, 991, 909, 729, 720 cm ^-1
Melting point (Tm): 97.5 ℃

[Synthesis Example 3]
(Synthesis of double bond-containing ethylene polymer (P-3))
A stainless steel autoclave with an internal volume of 2 liters that has been sufficiently purged with nitrogen is charged with 940 ml of hexane, 20 ml of propylene, and 50 ml of vinylnorbornene (5-vinylcyclo [2.2.1] hept-2-ene), and hydrogen is supplied at 0.3 MPa. It was introduced until (gauge pressure). Subsequently, after raising the temperature in the system to 150 ° C., 0.3 mmol of triisobutylaluminum, 0.004 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate, (t-butylamido) dimethyl (tetramethyl-η Polymerization was initiated by injecting 0.02 mmol of ⁵ -cyclopentadienyl) silane titanium dichloride (Sigma-Aldrich) with ethylene. Thereafter, only ethylene was continuously supplied to keep the total pressure at 2.9 MPa (gauge pressure), and polymerization was carried out at 150 ° C. for 20 minutes. After the polymerization was stopped by adding a small amount of ethanol into the system, unreacted ethylene and vinyl norbornene were purged. The resulting polymer solution was dried overnight at 100 ° C. under reduced pressure. As described above, the unsaturated group content per 1,000 carbon atoms was 11.8, and the vinyl norbornene content was 10.3% by mass (unsaturated group content (average) = 1.1 / molecule). .
The analysis results are as follows.
Mw: 3700, Mw / Mn: 2.8
IR: 4322, 4251, 3077-2635, 1637, 1467, 1377, 1303, 993, 907, 721, 718 cm ^-1
Density: 937kg / m ³
Melting point (Tm): 106 ℃
Penetration depth: 3 (10 ^-1 mm)

100 g of the above double bond-containing polymer (P-1) (Mn850 as vinyl group 108 mmol) and 300 g of toluene were charged into a four-necked 1000 ml separable flask and heated under reflux for 30 minutes with stirring to completely remove the polymer. After melting, 28.3 g (472 mmol) of acetic acid was added to bring the internal temperature to 90 ° C., and then 34.4 g (354 mmol) of 35% aqueous hydrogen peroxide was added dropwise over 3 hours. Stir at 0 ° C. for 3 hours. After confirming the disappearance of the peak at 991 cm ^{−1 by} IR, 100 g of warm water was added and allowed to stand to remove the aqueous layer. After repeating this operation twice, 15.0 g (17 mmol) of 20% aqueous ascorbic acid solution was added at 80 to 85 ° C., and after stirring for 15 minutes, the peroxide in the reaction system was completely removed with a peroxide test paper. After confirming that it was decomposed, the aqueous layer was separated after standing. The product was cooled while slowly adding 300 g of methanol from an internal temperature of 70 ° C., the product was crystallized, and the filtered solid was washed with methanol. The obtained solid was dried under reduced pressure of 1 to 2 hPa to obtain 96.3 g of a white solid of an epoxy group-containing ethylene polymer (yield 99%, olefin conversion rate 100%). The analysis results are as follows.
Mw: 2058, Mw / Mn: 1.84
¹ H-NMR (C ₂ D ₂ Cl ₄ ): δ 0.88 (3H, t, J = 6.92 Hz), 1.18-1.66 (m), 2.38 (1H, dd, J = 2.64, 5.28 Hz), 2.66 (1H , dd, J = 4.29, 5.28 Hz) 2.80-2.87 (1H, m)
IR: 4322, 4250, 2938-2839, 2635, 2839-2635, 915, 847, 730, 719 cm ^-1
Melting point (Tm): 121 ℃
Penetration depth: 0 (10 ^-1 mm)
Softening point: 129.5 ℃
Melt viscosity (140 ℃): 189 mPa ・ s
5% weight loss temperature: 344 ℃ (TGA)

Except that the raw material double bond-containing polymer (P-1) was changed to (P-2) synthesized in Synthesis Example 2, the same treatment as in Example 1 was carried out, and the corresponding epoxy group-containing polymer. 87.6 g (olefin conversion 100%, yield 89%) was obtained.
The analysis results are as follows.
Mw: 1470, Mw / Mn: 1.54
¹ H-NMR (C ₂ D ₂ Cl ₄ ): δ 0.80-0.88 (m), 0.9-1.6 (m), 2.37-2.40 (1H, dd, J = 2.97, 5.28 Hz), 2.50 (m), 2.66 (1H, dd, J = 3.96, 5.28 Hz) 2.80-2.86 (1H, m), 2.95 (m)
IR: 4322, 4250, 3603, 3036-2635, 2343, 1468-1459, 1259, 915, 848, 724, 717 cm ^-1
Melting point (Tm): 73.6 ℃
Melt viscosity (140 ℃): 19 mPa ・ s
Softening point 101.5 ℃
5% weight loss temperature: 322 ℃ (TGA)

Except that the raw material double bond-containing polymer (P-1) was changed to (P-3) synthesized in Synthesis Example 3, the same treatment as in Example 1 was carried out, and the corresponding epoxy group-containing polymer. 96.3 g of a white solid was obtained (yield 99%, olefin conversion 100%).
The analysis results are as follows.
¹ H-NMR (C ₂ D ₂ Cl ₄ ): δ 0.88 (t, 3H, J = 5.94 Hz), 0.25-2.25 (m), 2.28-2.50 (m, 1H), 2.57-2.78 (m, 1H) 2.80-3.15 (m, 1H)
IR: 4319, 4253, 3371, 2976-2905, 1474-1456, 1377, 1255, 876, 823, 732, 720, 715 (cm ^-1 )
Mw: 4870, Mw / Mn: 2.7
Density: 961kg / m ³
Melting point (Tm): 113 ℃
Penetration depth: 2 (10 ^-1 mm)

The above double bond-containing polymer (P-1) 100 g (Mn850, vinyl group 108 mmol) and toluene 300 g were charged and heated to reflux with stirring for 30 minutes to completely melt the polymer, and then 28.3 g of acetic acid. (472 mmol) was added to bring the internal temperature to 90 ° C., and 34.4 g (354 mmol) of 35% aqueous hydrogen peroxide was added dropwise over 3 hours, followed by stirring at an internal temperature of 90 to 92 ° C. for 3 hours. After confirming the disappearance of the peak at 991 cm ^{−1 by} IR, 100 g of warm water was added and allowed to stand to remove the aqueous layer. After repeating this operation twice, 32.7 g (1.09 mol) of formic acid was slowly added at an internal temperature of 90 to 92 ° C., and the esterification reaction was further carried out for 10 hours. After confirming the disappearance of the epoxy peak at 847 cm ^{−1 by} IR, 300 g of acetonitrile was slowly added to crystallize the product polymer. The solid collected by filtration was washed with methanol, and the obtained solid was dried under reduced pressure of 1 to 2 hPa, whereby 97.0 g (yield 97%, conversion 100%) of an ester group-containing ethylene polymer was obtained. Obtained.
¹ H-NMR (C ₂ D ₂ Cl ₄ ): δ 0.87 (t, 3H, J = 6.59 Hz), 1.03-1.71 (m), 2.28-2.50 (m, 1H), 4.05 (2H, J = 6.92, 11.21 Hz), 5.14 (1H, m), 8.06 (2H, m)
IR: 4322, 4250, 2924-2841, 1733, 1473, 1463, 1177, 730, 719 (cm ^-1 )
Melting point (Tm): 121 ℃

100 g of the ester group-containing ethylene polymer obtained in Example 4 and 200 g of toluene were charged into a four-necked 1000 ml separable flask and the internal temperature was adjusted to 105 ° C., and then 75 g of a 5% KOH n-butanol solution (66.66). 8 mmol) was added slowly and stirred at this temperature for 3 hours. After confirming the disappearance of the peak at 1733 cm ^{−1 by} IR, the product was cooled to 60 ° C., 300 g of methanol was slowly added and the product was crystallized while cooling, and the solid collected by filtration was washed with methanol. The obtained solid was dried at 60 ° C. under reduced pressure of 1 to 2 hPa to obtain 99.0 g of a white solid of an α, β-dihydroxy group-containing ethylene polymer (yield 99%, conversion rate 100%).
The analysis results are as follows.
Mw: 2788, Mw / Mn: 2.03
¹ H-NMR (C ₂ D ₂ Cl ₄ ): δ 0.89 (3H, t, J = 6.92 Hz), 1.05-1.84 (m), 3.41 (1H, dd, J = 5.94, 9.89 Hz) 3.57- 3.63 ( 1H, m).
IR: 4322, 4250, 3370, 2950-2345, 2635, 1581, 1462-1377, 1122, 730-718, 619 cm ^-1
Melting point (Tm): 122 ℃
Penetration depth: 0 (10 ^-1 mm)
Softening point: 129.0 ℃
Melt viscosity (140 ℃): 214 mPa ・ s
5% weight loss temperature: 297 ℃ (TGA)

100 g of the above double bond-containing polymer (P-2) (Mn 690, vinyl group 137 mmol) and toluene 100 g were charged into a four-necked 1000 ml separable flask and the internal temperature was set to 90 ° C. to completely melt the polymer. After that, 34.9 g (582 mmol) of acetic acid was added and 35.3 g (363 mmol) of 35% aqueous hydrogen peroxide was added dropwise over 3 hours, followed by stirring at an internal temperature of 90 to 92 ° C. for 3 hours. After confirming the disappearance of the peak at 991 cm ^{−1 by} IR, 100 g of warm water was added and allowed to stand to remove the aqueous layer. After repeating this operation twice, 32.7 g (1.09 mol) of formic acid was slowly added at an internal temperature of 90 to 92 ° C., and the esterification reaction was further carried out for 10 hours. After confirming the disappearance of the epoxy peak at 847 cm ^{−1 by} IR, 100 g of warm water was added and allowed to stand to remove the aqueous layer. This operation was repeated twice, followed by cooling, cooling from an internal temperature of 70 ° C. while slowly adding 300 g of methanol, the product was crystallized, and the filtered solid was washed with methanol. The obtained solid was dried under reduced pressure of 1 to 2 hPa to obtain 87 g (yield 87%, conversion rate 100%) of an α, β-dihydroxy group-containing ethylene polymer.
The analysis results are as follows.
¹ H-NMR (C ₂ D ₂ Cl ₄ ): δ 0.87 (m), 1.0-1.8 (m), 3.39 (1H, dd, J = 7.58, 11.2 Hz) 3.40- 3.45 (2H, m)
IR: 4322, 4250, 3370, 2973-2840, 2635, 1472, 1464, 1377, 1072,730, 719 (cm ^-1 )
Melting point (Tm): 108 ℃

The same procedure as in Example 6 was conducted except that the raw material double bond-containing polymer (P-2) was changed to (P-3), and 93 g (yield) of an α, β-dihydroxy group-containing ethylene polymer was obtained. Conversion rate 95%, conversion rate 100%).
The analysis results are as follows.
Mw: 4870, Mw / Mn: 2.76
¹ H-NMR (C ₂ D ₂ Cl ₄ ): δ 0.55-2.14 (m), 3.32-3.67 (m)
IR: 4322, 4250, 3370, 3976-2830, 1616, 1472, 1377, 1349, 1081, 730, 723, 717, 620 (cm-1)
Melting point (Tm): 113 ℃
Density: 962kg / m ³

  According to the method for producing an epoxy group-containing polymer and derivatives thereof of the present invention, epoxy groups can be efficiently introduced into polymers having a wide variety and molecular weights, and epoxy group-containing polymers and derivatives thereof are made separately. In addition, since a highly versatile functional group-containing polymer can be produced, it is extremely industrially valuable.

Claims (9)

A process for producing a polymer (P) represented by the following general formula (3), wherein the following [Step 1] and [Step 2] are sequentially performed.
[Step 1] The following general formula (1)

(In Formula (1), A is a group formed by polymerization of olefins having 2 to 20 carbon atoms or olefins having 2 to 20 carbon atoms and diene, and was measured by gel permeation chromatography (GPC). (The weight average molecular weight (Mw) represents 400 to 500,000, and R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.)
Is reacted in the presence of hydrogen peroxide with one or more first carboxylic acids (CA1) selected from the group consisting of aliphatic carboxylic acids and aromatic carboxylic acids. The following general formula (2)

(In formula (2), A, R ¹ and R ² each represent the same group or atom as in formula (1).)
A step of obtaining an epoxy group-containing polymer represented by:
[Step 2] The epoxy group-containing polymer represented by the formula (2) is reacted with one or more second carboxylic acids (CA2) selected from the group consisting of aliphatic carboxylic acids and aromatic carboxylic acids, Further, if necessary, it is reacted with water or alcohols in the presence of a base catalyst to give the following general formula (3)

(In the formula (3), A, R ¹ and R ² each represent the same group or atom as in the general formula (1), Q ¹ represents a hydroxyl group or an acyloxy group having 1 to 18 carbon atoms, and Q ² Represents a hydrogen atom or an acyl group having 1 to 18 carbon atoms.)
The process of manufacturing the polymer (P) represented by these.   The polymer (P) according to claim 1, wherein [Step 1] and [Step 2] are carried out successively without isolating the epoxy group-containing polymer which is the product of [Step 1]. Manufacturing method.   2. The method according to claim 1, wherein [Step 1 ′] is further performed after the completion of [Step 1] and before performing [Step 2], in which a residual peroxide is reduced using an organic reducing agent. 2. A process for producing the polymer (P) according to 2.   The organic reducing agent in [Step 1 ′] is one or more reducing agents selected from the group consisting of ascorbic acid (vitamin C), isoascorbic acid, tocopherol (vitamin E), and salts thereof. The method for producing a polymer (P) according to claim 3.   The method for producing a polymer (P) according to any one of claims 1 to 4, wherein the first carboxylic acid (CA1) in [Step 1] is acetic acid or propionic acid.   The method for producing a polymer (P) according to any one of claims 1 to 5, wherein the second carboxylic acid (CA2) in [Step 2] is formic acid or acetic acid.   The first carboxylic acid (CA1) in [Step 1] is acetic acid, and the second carboxylic acid (CA2) in [Step 2] is formic acid. The manufacturing method of the polymer (P) of description.   The process for producing a polymer (P) according to any one of claims 1 to 7, wherein the reaction temperature in [Step 1] is in the range of 80 to 100 ° C.   The method for producing the polymer (P) according to any one of claims 1 to 8, wherein the pH of the reaction mixture in [Step 1] is in the range of pH 1.5 to 4.0.