JP2011195823A - Method for producing acrylic-modified (hydrogenated) polybutadiene - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for efficiently producing a (meth)acrylic-modified (hydrogenated) polybutadiene.SOLUTION: In the method for producing a (meth)acrylic-modified (hydrogenated) polybutadiene represented by formula (IV), a hydroxyl group-containing (hydrogenated) polybutadiene and a (meth)acrylic acid ester are reacted with each other by heating them at 30°C or higher in the presence of a polymerization inhibitor, and then, adding a catalytic amount of a tin compound. In the formula (IV), P is a polybutadiene, Xand Xare each independently an oxygen atom or a 1-20C ligand which may include a nitrogen atom, Yis a hydrogen atom, a hydroxy group, a carboxy group or a (meth)acrylic group.

Description

  The present invention relates to a method for producing a polybutadiene having a (meth) acryloyl group or a hydrogenated product thereof.

  As a method for producing polybutadiene having a (meth) acryloyl group, a method of condensing a polymer having a hydroxyl group and (meth) acrylic acid using p-toluenesulfonic acid as a catalyst (see Patent Document 1), (meth) acrylic A method of transesterifying acid ester and oligomer chain terminal alcohol using a titanium-based catalyst (see Patent Document 2), and a polymer in which 80% or more of the butadiene units constituting the polymer chain are composed of 1,2 bonds A method of transesterifying a hydroxyl group-containing polybutadiene having a hydroxyl group at at least one end of a chain with a (meth) acrylic acid ester using a tin-based catalyst (see Patent Document 3) is known.

Special Table 2007-505184 JP 2006-045284 A JP 2007-2111240 A

  However, in the method described in Patent Document 1, there is a possibility that the product is gelled. In the method described in Patent Document 2, there is a problem that the method for removing the catalyst is complicated. In the method described in Patent Document 3, There was a problem that a polymer of (meth) acrylic acid ester was by-produced.

  This invention makes it a subject to provide the method of manufacturing a (meth) acryl modified | denatured (hydrogenated) polybutadiene efficiently in view of the said problem.

  As a result of diligent research to solve the above problems, the present inventors have mixed and heated a hydroxyl group-containing (hydrogenated) polybutadiene, a (meth) acrylic acid ester, and a polymerization inhibitor, and then added an organotin catalyst. Thus, the present inventors have found that the above-mentioned problems can be solved by performing a transesterification reaction, and have completed the present invention.

  That is, the present invention provides (1) Formula (I)

[P is the formula (II)

(Wherein the double line portion of the solid line and the dotted line represents a single bond or a double bond) and / or the formula (III)

(Wherein, the double line portion of the solid line and the dotted line represents a single bond or a double bond) and represents a polymer containing a repeating unit, and X ¹ and X ² are each independently an oxygen atom or a nitrogen atom Represents a C _{1 to} C ₂₀ linking group which may contain a hydroxyl group-containing (hydrogenated) polybutadiene and (meth) acrylic acid ester represented by Y ¹ represents a hydrogen atom, a hydroxyl group or a carboxyl group. After heating to 30 ° C. or higher in the presence of an agent, a catalytic amount of a tin compound is added and reacted,

(Wherein R ¹ , X ¹ , X ² and P are the same as defined in formula (I). Y ² represents a hydrogen atom, a hydroxyl group, a carboxyl group or a (meth) acryl group). (Meth) acryl-modified (hydrogenated) polybutadiene production method, (2) P of (meth) acryl-modified (hydrogenated) polybutadiene represented by formula (IV) is the number of moles of formula (III) / formula (II The production method according to (1) above, wherein (3) the degree of dispersion of (meth) acryl-modified (hydrogenated) polybutadiene represented by formula (IV) In the range of 1.01 to 2.00, or (4) The gas is bubbled into the reaction vessel (1) ) To (3).

  According to the production method of the present invention, when (meth) acryl-modified (hydrogenated) polybutadiene is produced by a transesterification reaction, it is possible to prevent the formation of a polymer other than the intended polymer. Moreover, it can prevent that a reaction liquid gelatinizes.

The (meth) acryl-modified (hydrogenated) polybutadiene obtained by the production method of the present invention is not particularly limited as long as (meth) acrylic acid is directly ester-bonded to at least one end.
The acrylic-modified (hydrogenated) polybutadiene obtained by the production method of the present invention can be used as a paint, a casting resin, a molding resin, an adhesive or the like. In the present invention, (meth) acrylic acid means acrylic acid and methacrylic acid. Further, (hydrogenated) polybutadiene means polybutadiene and its hydrogenated product.

(Compound represented by formula (I))
In formula (I), X ¹ and X ² each independently represent a C _{1 to} C ₂₀ bonding group that may contain an oxygen atom and / or a nitrogen atom, and R ¹ represents a hydrogen atom or a methyl group. .
Specific examples of the C _{1 to} C ₂₀ bonding group that may contain an oxygen atom and / or a nitrogen atom include a divalent C ₁ -C ₂₀ alkylene group having a straight chain or a branched chain, and an ether bond. linear or branched divalent alkylene group having a carbon number of _C 2 _{-C 20} with having the formula (V)

(In the formula, each of R ^{4 to} R ⁶ independently has a linear or branched divalent C _{1 to} C ₁₀ alkylene group or a C _{1 to} C ₆ alkyl group as a substituent. Or a C _{3 to} C ₈ cycloalkylene group, a C _{1 to} C ₆ alkyl group optionally having a C _{5 to} C ₈ aromatic group, or a complex group thereof). And the group represented.

Examples of the “divalent C ₁ -C ₂₀ alkylene group having a linear or branched chain” include methylene, ethylene, propylene, methylethylene, butylene, 1,2-dimethylethylene, pentylene, 1-methylbutylene, Examples include 2-methylbutylene, hexaethylene, heptaethylene, octaethylene, nonaethylene, decaethylene, and the like, “a divalent C ₂ -C ₂₀ alkylene having a linear or branched chain having an ether bond. As the “group”, — (CH ₂ O) _a (CH ₂ ) — [a represents an integer of 1 to 19], — (CH ₂ CH ₂ O) _b (CH ₂ CH ₂ ) — [b is 2 to 2 represents an integer of _{9], - (CH 2 CH} 2 CH 2 O) c (CH 2 CH 2 CH 2) - [c can be exemplified the like] represents an integer of 1 to 5.

Examples of the “divalent C ₁ -C ₁₀ alkylene group having a straight chain or branched chain” in the formula (V) can include the same examples as in the specific example of the formula (I), and “C ₁ -C ₆ As the C _{3 to} C ₈ cycloalkylene group optionally having an alkyl group as a substituent ”, cyclopropylene, 2-methylcyclopropylene, cyclobutylene, 2,2-dimethylcyclobutylene, cyclopentylene, 2,3-dimethylcyclopentylene, cyclohexylene, 1,3,3-trimethylcyclohexylene, cyclooctylene and the like can be mentioned, and “C ₁ -C ₆ alkyl group optionally having C as a substituent” Examples of the “ _5- C ₈ aromatic group” include a 1,4-phenylene group and a 2-methyl-1,4-phenylene group.

  Examples of the “complexed group” include methylene-cyclopropylene, methylene-cyclopentylene, methylene-2,3-dimethylcyclopentylene, methylene-1,3,3-trimethylcyclohexylene, ethylene-cyclopropylene, Examples include ethylene-cyclohexylene, ethylene-3,3, -dimethylcyclohexylene, methylene-cyclopropylene-methylene, ethylene-cyclohexylene-methylene, hexylene-cyclohexylene-methylene and the like. Further, a group in which these orders are changed may be used.

  As formula (V), for example,

(* Represents a connecting position).

P in the formula (I) is a polybutadiene chain or a hydrogenated polybutadiene chain having the formula (II) and / or the formula (III) as a repeating unit, and is not present when the double line portion of the solid line and the dotted line is a double bond. Hydrogenated polybutadiene, and in the case of a single bond, means hydrogenated polybutadiene.
When the 1,4-bond repeating unit represented by the formula (II) has a double bond, a trans isomer, a cis isomer, or a mixture thereof may exist.

  The ratio of the repeating unit due to the 1,4-bond represented by the formula (II) and the repeating unit due to the 1,2-bond represented by the formula (III) is 0-100 mol%, respectively. ) Is preferably 80% or more, more preferably 85% or more, and more preferably 90% or more according to the measurement by the Morero method. Preferably, it is 95% or more.

The number average molecular weight of the (meth) acryl-modified (hydrogenated) polybutadiene of the present invention is usually about 500 to 15,000 according to a GPC (gel filtration) method using polystyrene as an index, and 2,000 to It is preferable that it is 10,000.
The value obtained by dividing the weight average molecular weight of the polymer by the number average molecular weight represents the degree of dispersion. As the degree of dispersion is smaller, it means that the dispersion is narrower, that is, it is composed of a polymer having a relatively close molecular weight. All polymers having the same molecular weight have a dispersity of 1. Moreover, when the value of the degree of dispersion is large, it means that the dispersion is wide, that is, it is composed of a mixture of a polymer having a small molecular weight to a polymer having a large molecular weight. When (meth) acryl-modified (hydrogenated) polybutadiene having a high degree of dispersion is cured, the strength of the cured product becomes weak or the curing temperature becomes wide. For this reason, (meth) acryl-modified (hydrogenated) polybutadiene having a low degree of dispersion is preferred. The degree of dispersion of the (meth) acryl-modified (hydrogenated) polybutadiene obtained by the production method of the present invention is 1.01 to 2.00, preferably 1.01 to 1.70.
Y ¹ in formula (I) may be unsubstituted (hydrogen atom) or may have a substituent. Examples of the substituent include a hydroxyl group or a carboxyl group.

(Compound represented by formula (IV))
In formula (IV), R ¹ , X ¹ , X ² and P are the same as defined in formula (I), and the same groups can be exemplified.
Y ² may be unsubstituted (hydrogen atom) or may have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, and a (meth) acryloyloxy group, and a (meth) acryloyloxy group is preferable.

(Method for producing (meth) acryl-modified (hydrogenated) polybutadiene represented by formula (IV))
The hydroxyl group-containing polybutadiene represented by the formula (I) of the present invention is prepared, for example, by polymerizing butadiene in a solution in the presence of a sodium catalyst, and preparing an epoxy compound such as ethylene oxide or propylene oxide. It can be obtained by the addition method. In this production method, hydroxyl groups can be introduced into the terminals of polybutadiene at a ratio of 80% or more, preferably 90% or more. Specific examples of such a hydroxyl group-containing polybutadiene include a trade name: G-3000 manufactured by Nippon Soda Co., Ltd. Furthermore, a hydroxyl group-containing hydrogenated polybutadiene can be produced by reducing the double bond of the hydroxyl group-containing polybutadiene with hydrogen. Specific examples include trade names: GI-1000 and GI-3000 manufactured by Nippon Soda Co., Ltd.

In the production method of the present invention, the hydroxyl group-containing (hydrogenated) polybutadiene represented by the formula (I) and (meth) acrylic acid ester are heated to 30 ° C. or higher in the presence of a polymerization inhibitor, and then the catalyst amount The tin compound is added and reacted.
Although the addition amount of (meth) acrylic acid ester is not particularly limited, it is preferably 9 to 200% by weight, and 14 to 100% by weight based on the hydroxyl group-containing (hydrogenated) polybutadiene. Is more preferable. Thereby, the (meth) acryloyl group can be introduced into the terminal at a ratio of 50% or more, preferably 70% or more, more preferably 90% or more, and still more preferably 95% with respect to the terminal hydroxyl group.
The hydroxyl group-containing hydrogenated polybutadiene used in the production method of the present invention can be produced by reducing the double bond of the hydroxyl group-containing polybutadiene with hydrogen. The hydrogenation rate of the hydroxyl group-containing hydrogenated polybutadiene is 80% or more of the total double bonds, preferably 90% or more, more preferably 99% or more, and further preferably 99.5%. The remaining double bond can be quantitatively analyzed by addition reaction of iodine (hereinafter referred to as “iodine value”). The iodine value is 100 or less, preferably 50 or less, more preferably 25 or less. More preferably, it is 15 or less.

  In addition, the hydroxyl group-containing (hydrogenated) polybutadiene used in the production method of the present invention preferably has a hydroxyl group at at least one end and preferably has a hydroxyl group at both ends. ) A (meth) acryl-modified (hydrogenated) polybutadiene having an ester bond with acrylic acid can be produced. Examples of the (meth) acrylic acid ester to be reacted with the hydroxyl group-containing (hydrogenated) polybutadiene include methyl (meth) acrylate and ethyl (meth) acrylate, and preferably methyl methacrylate.

The transesterification reaction between the hydroxyl group-containing (hydrogenated) polybutadiene and the (meth) acrylic acid ester can be carried out without solvent or in a suitable inert solvent in the presence of a suitable catalyst.
Examples of the transesterification reaction include dialkyltin dicarboxylates such as dibutyltin dilaurate and dioctyltin dilaurate, and organic tin compounds containing dialkyltin oxide such as dibutyltin oxide and dioctyltin oxide, preferably dibutyltin dilaurate, Dialkyltin dicarboxylates such as dioctyltin dilaurate. The catalyst is used in an amount of 0.01 to 100 parts by weight (phr) per 100 parts by weight of a hydroxyl group-containing (hydrogenated) polybutadiene, preferably 0.1 parts by weight ( phr) to 10 parts by weight (phr), more preferably 0.3 parts by weight (phr) to 5 parts by weight (phr). By using in this range, the (meth) acryl-modified (hydrogenated) polybutadiene of the present invention can be produced efficiently.

  The polymerization inhibitor may be mixed before starting the reaction or after starting the reaction, but is preferably mixed before starting the reaction. The polymerization inhibitor is not particularly limited, and examples thereof include 2,6-di-tert-butyl-4-hydroxytoluene, 2,6-di-tert-butyl-4-methylphenol, 2,2′-methylenebis (4- Methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 3,9-bis [2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) -propionyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro (5 5) Undecane, triethylene glycol-bis-3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate, n-octadecyl-3- (3,5-di-t-butyl-4- Loxyphenyl) propionate, i-octyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, hexamethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) ) Propionate, 4,6-bis (octylthiomethyl) -o-cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, pentaerythryltetrakis [3- (3,5-di-t-butyl) -4-hydroxyphenyl) propionate], tris (3,5-di-t-butylhydroxybenzyl) isocyanurate, tris (4-t-butyl-2,6-dimethyl-5-hydroxybenzyl) isocyanurate, 2, 6-di-t-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) Nord, thiodiethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N′-hexane-1,6-diylbis [3- (3,5-di-t- Butyl-4-hydroxyphenylpropionamide, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-t-butyl-a, a ′, a ″-(mesitylene-2,4,6 -Triyl) tri-p-cresol, phenols such as calcium diethylenebis [[[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate]; p-benzoquinone, anthraquinone, naphthoquinone Phenanthraquinone, p-toluquinone, 2,6-dichloroquinone, 2,5-diphenyl-p-benzoquinone, 2,5-diacetoxy-p-benzoquinone, 2,5 -Quinones such as dicaproxy-p-benzoquinone, 2,5-diacyloxy-p-benzoquinone; hydroquinone, pt-butylcatechol, 2,5-di-t-butylhydroquinone, mono-t-butylhydroquinone, monomethylhydroquinone Hydroquinones such as 2,5-di-t-amylhydroquinone; phenyl-β-naphthylamine, parabenzylaminophenol, di-β-naphthylparaphenylenediamine, dibenzylhydroxylamine, phenylhydroxylamine, diethylhydroxylamine, etc. Amines; nitro compounds such as dinitrobenzene, trinitrotoluene and picric acid; oximes such as quinonedioxime and cyclohexanone oxime; phenothiazines, organic and inorganic copper salts, etc. Or 2,6-di-t-butyl-4-hydroxytoluene.

  The reaction between the hydroxyl group-containing (hydrogenated) polybutadiene and (meth) acrylic acid ester is to remove (evaporate) alcohol, such as methanol, which is a by-product, from the target (meth) acryl-modified (hydrogenated) polybutadiene. Therefore, it is preferable to bias the equilibrium to promote the reaction.

  In addition, the reaction may be performed without a solvent or in a solvent. When the reaction is carried out in a solvent, the solvent used is not particularly limited as long as it is inert to the reaction, but it is necessary to select it in consideration of the compatibility between the raw material (hydrogenated) polybutadiene and the solvent. Specific solvents that can be used include aromatic hydrocarbons such as benzene, toluene and xylene; ether solvents such as diethyl ether, tetrahydrofuran and 1,2-dimethoxyethane; nitrile solvents such as acetonitrile and benzonitrile; dimethyl sulfoxide and the like Among these, aromatic hydrocarbons such as benzene, toluene and xylene are preferable.

As reaction temperature, it is 0-130 degreeC normally, and it is preferable that it is the range of room temperature-120 degreeC. The reaction is usually completed in a few minutes to a few hours. After completion of the reaction, when unreacted (meth) acrylic acid ester, by-product alcohol and solvent are used from this reaction solution, the solvent is removed to remove the (meth) acryl-modified (hydrogenated) polybutadiene ( Can be obtained.
The temperature at which the catalyst for the transesterification reaction is added to the reaction solution needs to be 30 ° C or higher in advance, and is preferably 35 ° C to 100 ° C.
The (meth) acryl introduction ratio of the (meth) acryl-modified (hydrogenated) polybutadiene obtained by the transesterification reaction is a value representing the ratio of the substituents that are (meth) acryl-modified based on all hydroxyl groups, expressed as a percentage. The (meth) acryl introduction rate of the (meth) acryl-modified hydrogenated polybutadiene of the present invention is 80% or more, preferably 90% or more, and more preferably 95% or more.

The transesterification reaction may be further performed while bubbling gas.
The gas used for bubbling is not particularly limited as long as it does not react with (meth) acryl-modified (hydrogenated) polybutadiene. When oxygen is bubbled, the polybutadiene may be oxidized, but when no oxygen is present, the polybutadiene may be oxidized without being able to trap radical substances generated in the reaction solution. In addition, when water is present in the gas to be bubbled, hydrogen peroxide is generated, which may oxidize polybutadiene. Therefore, as a gas used for bubbling, oxygen from which moisture is removed through silica gel or the like is preferable. The amount to be bubbled is not particularly limited, and an optimum amount can be selected depending on the volume of the reaction solution, the size and shape of the reaction apparatus. The size of the bubble in the bubbling is not particularly limited, and the size varies depending on conditions such as the nozzle shape and gas blowing pressure, but it is preferably smaller. The bubbling position may be any position in the reaction solution, but is preferably the lower layer of the reaction solution, and more preferably directly under the stirrer.

  Since the acrylic-modified (hydrogenated) polybutadiene obtained by the production method of the present invention can produce a transparent liquid without turbidity, an adhesive for articles that require transparency such as optical instruments, It is also useful as a coating material, and since it has a low dielectric constant, it is also a useful material as a high-frequency polymer material such as an electronic material or an antenna material.

  Hereinafter, the recording material of the present invention will be described in detail with reference to examples, but the present invention is not necessarily limited thereto.

(Example 1) Production method of acrylic-modified hydrogenated polybutadiene Hydroxyl-containing hydrogenated polybutadiene (product name: GI-3000, manufactured by Nippon Soda Co., Ltd.) 3080 g, 2,6-di-t-butyl in a 5000 ml glass reaction vessel Charge 8 g of -4-hydroxytoluene and 813 g of ethyl acrylate, heat up, add 17.6 g of dioctyltin dilaurate at 36 ° C., and heat to 115 ° C. The reaction was continued for 3 hours at 115 to 120 ° C. under normal pressure while gradually removing the distillate, and the reaction was further continued at about 120 ° C. for 2 hours. Thereafter, the pressure was gradually reduced at 95 to 105 ° C., and the pressure was reduced to 3.8 kPa to obtain 3183 g of acrylic-modified hydrogenated polybutadiene.

(Example 2) Method for producing methacryl-modified hydrogenated polybutadiene A methacryl-modified hydrogenated polybutadiene was obtained by the method described in Example 1 except that methyl methacrylate was used instead of ethyl acrylate in Example 1.

(Example 3)
A 5000 ml glass reaction vessel is charged with 2250 g of hydroxyl-containing polybutadiene (product name: G-2000, manufactured by Nippon Soda Co., Ltd.), 5.93 g of 2,6-di-t-butyl-4-hydroxytoluene and 1186 g of methyl methacrylate. Then, the temperature is raised and at 90 ° C., 13.2 g of dioctyltin dilaurate is added and further heated to 105 ° C. The reaction was continued for 7 hours while gradually removing the distillate at 105 to 110 ° C. and normal pressure to obtain acrylic modified polybutadiene. When the molecular weight of the reaction solution was confirmed by GPC, formation of a high molecular weight substance other than the target compound was not confirmed.

(Comparative Example 1)
The reaction was carried out under the following conditions based on the method for introducing a methacryloyl group by transesterification described in Example 1 of JP-A-49-77991.
A 500 ml glass reaction vessel is charged with 100 g of hydroxyl-containing hydrogenated polybutadiene (product name: GI-2000, manufactured by Nippon Soda Co., Ltd.), 0.5 g of tetra-n-butyl titanate and 10 g of methyl methacrylate at 100 to 150 ° C. Reacted for 5 hours. A methacryl-modified hydrogenated polybutadiene was obtained.

(Comparative Example 2)
In a 3000 ml glass reaction vessel, 1350 g of hydroxyl-containing polybutadiene (product name: G-2000, manufactured by Nippon Soda Co., Ltd.), 1.35 g of 2,6-di-t-butyl-4-hydroxytoluene, 720 g of methyl methacrylate and dioctyl Tin dilaurate 8.0g was added and reaction was started at about 120 degreeC. Sampling was performed immediately after the start and the molecular weight was confirmed by GPC. As a result, a peak corresponding to a number average molecular weight of 400,000 was detected.

(Analysis example 1)
The analysis results of the polymers of Examples 1 and 2 and Comparative Example 1 are shown in Table 1. In addition, the measuring method of each analysis item is described below.
(Resin content) 1.5 g of resin is placed in an oven at 105 to 110 ° C. and heated for 3 hours. The weight ratio of components other than volatile components was calculated from the weight before and after heating by the following formula and used as the resin content.
Resin content (%) = (weight before heating−weight after heating) ÷ weight before heating × 100
(Viscosity) Viscosity at 45 ° C. was measured with a B-type viscometer (Tokyo Keiki B-type viscometer).
(Hue) Measured according to the hue measurement method described in JIS K1557.
(Molecular weight) The molecular weight in terms of polystyrene was measured by GPC.
(Dispersion degree) The ratio of the weight average molecular weight to the number average molecular weight was calculated and used as the dispersion degree.
((Meth) acrylic introduction rate) In ¹ H-NMR (manufactured by JEOL Ltd., ECP-500), 3.6 ppm (—CH ₂ —OH) and 4.1 ppm (—CH ₂ —O-meth (acryloyl) ) Group) was measured for proton integration ratio and calculated by the following formula to obtain (meth) acryl introduction rate.
(Meth) acrylic introduction ratio (%) = 4.1 ppm proton integration ratio ÷ (3.6 ppm proton integration ratio + 4.1 ppm proton integration ratio) × 100

From the results in Table 1, when Examples 1-2 and Comparative Example 1 were compared, it was shown that the present invention introduced (meth) acryloyl groups in a sufficient ratio.
Further, comparing Example 3 with Comparative Example 2, it was shown that a polymer other than the target product was not produced by adding a catalyst after heating the reaction solution.

Example 4
Into a 5 L reaction vessel equipped with a pressure reducing valve and a bubbling tube, 1500 g of hydroxyl group-containing hydrogenated polybutadiene (GI-1000 manufactured by Nippon Soda Co., Ltd.), 3.90 g of methoquinone, and 397 g of ethyl acrylate were added and heated to 90 ° C. After adding 8.62 g of dioctyltin dilaurate, the temperature was further raised, and the reaction was allowed to proceed for 3 hours at 115 to 118 ° C. while gradually removing the distillate at normal pressure, and further for 2 hours at about 118 to 123 ° C. Subsequently, terminal acrylic-modified 1,2-polybutadiene was produced. The solution was concentrated under reduced pressure at about 4 KPa while gradually reducing the pressure at 95 to 105 ° C. with a vacuum pump.
When the physical properties were measured by the above methods, the resin content: 99.1%, viscosity: 23P (45 ° C.), hue (APHA): 50, molecular weight (Mn): 2691, molecular weight (Mw): 4499, dispersity : 1.67.

(Example 5)
In a 5 L reaction vessel equipped with a pressure reducing valve and a bubbling tube, 1500 g of hydroxyl group-containing hydrogenated polybutadiene (GI-1000 manufactured by Nippon Soda Co., Ltd.), 3.90 g of 2,6-di-t-butyl-4-hydroxytoluene, ethyl acrylate 396 g was added, heated up and added with dioctyltin dilaurate 8.58 g at 90 ° C., then further heated up and reacted for 3 hours at 115 to 118 ° C. while gradually removing the distillate under normal pressure. The reaction was further continued at about 118 to 123 ° C. for 2 hours to produce terminal acrylic-modified 1,2-polybutadiene. The solution was concentrated under reduced pressure at about 4 KPa while gradually reducing the pressure at 95 to 105 ° C. with a vacuum pump.
When the physical properties were measured by the above methods, the resin content: 99.4%, the viscosity: 24P (45 ° C.), the hue (APHA): 10, the molecular weight (Mn): 2750, the molecular weight (Mw): 4385, the degree of dispersion. : 1.59.

(Example 6)
In a 5 L reaction vessel equipped with a pressure reducing valve and a bubbling tube, 1500 g of hydroxyl group-containing hydrogenated polybutadiene (GI-1000 manufactured by Nippon Soda Co., Ltd.), 4,6-bis (octylthiomethyl) -o-cresol (product name: HP-400) , Manufactured by Kawaguchi Chemical Industry Co., Ltd.) 3.91 g of ethyl acrylate 396 g was added, and the temperature was raised, 8.56 g of dioctyltin dilaurate was added at 90 ° C., and the temperature was further raised to 115 to 118 ° C. under normal pressure. The reaction was continued for 3 hours while gradually removing the distillate at 1, and further the reaction was continued at about 118 to 123 ° C. for 2 hours to produce terminal acrylic-modified 1,2-polybutadiene. The solution was concentrated under reduced pressure at about 4 KPa while gradually reducing the pressure at 95 to 105 ° C. with a vacuum pump.
When the physical properties were measured by the above method, resin content: 99.3%, viscosity: 24P (45 ° C.), hue (APHA): 10, molecular weight (Mn): 2767, molecular weight (Mw): 4571, dispersity : 1.65.

Claims (4)

Formula (I)

[P is the formula (II)

(Wherein the double line portion of the solid line and the dotted line represents a single bond or a double bond) and / or the formula (III)

(Wherein, the double line portion of the solid line and the dotted line represents a single bond or a double bond) and represents a polymer containing a repeating unit, and X ¹ and X ² are each independently an oxygen atom or a nitrogen atom Represents a C _{1 to} C ₂₀ linking group which may contain a hydroxyl group-containing (hydrogenated) polybutadiene and (meth) acrylic acid ester represented by Y ¹ represents a hydrogen atom, a hydroxyl group or a carboxyl group. After heating to 30 ° C. or higher in the presence of an agent, a catalytic amount of a tin compound is added and reacted,

(Wherein R ¹ , X ¹ , X ² and P are the same as defined in formula (I). Y ² represents a hydrogen atom, a hydroxyl group, a carboxyl group or a (meth) acryl group). A method for producing (meth) acryl-modified (hydrogenated) polybutadiene.   The P of the (meth) acryl-modified (hydrogenated) polybutadiene represented by the formula (IV) is such that the number of moles of the formula (III) / the number of moles of the formula (II) ≧ 85/15. 2. The production method according to 1.   The production method according to claim 1 or 2, wherein the degree of dispersion of the (meth) acryl-modified (hydrogenated) polybutadiene represented by the formula (IV) is in the range of 1.01 to 2.00.   The production method according to claim 1, wherein gas is bubbled into the reaction vessel.