JPH0649729B2 - Method for producing hydrophilic diene-based modified polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to high molecular weight crystalline syndiotactic 1,2.
A method for producing a novel hydrophilic diene-modified polymer having an unsaturated double bond in the polymer structure, which is substantially gel-free by modifying polybutadiene by a polymer reaction with respect to the unsaturated double bond. The hydrophilic polymer according to the present invention is used in various other fields including adhesives and paints.

[Problems to be Solved by Prior Art and Invention]

Conventionally, various types of water-soluble polymers are known. For example, natural polymers include alginic acid (sodium alginate) and carboxymethyl cellulose (CM
C), saccharides such as methylcellulose [MC: methyl etherification product of cellulose (25 to 32%)], and polysaccharides, and chemically modified products thereof. Further, as water-soluble polysaccharides by microorganisms, pullulan, dextran, xanthan gum, etc. Can also be mentioned. Examples of synthetic polymers include polyvinyl alcohol (poval), polyethylene oxide, sodium polyacrylate, and polyacrylamide.

These water-soluble polymers have no unsaturated bonds in their polymer structure.

The water-soluble polymer has been used in various ways in the field of water-soluble polymer materials while making use of the characteristics of each property.

For example, adhesives, paints, fiber processing agents, paste materials, Japanese paper / paperboard / papermaking viscous agents, emulsifiers, flocculants, liquid friction resistance reducers, thickeners, asphalt emulsifiers, thickener spreading agents, pigments In addition to industrial fields such as dispersants, latex thickeners, soil conditioners, and printing pastes, ice cream additives, food processing,
It is also used in large quantities in bio-related fields such as pharmaceuticals / cosmetics, beer foam continuous stabilizer, diet foods, pharmaceutical tablets, and plasma expanders.

The total amount of water-soluble polymers used in these water-soluble polymer materials has reached several hundred thousand tons / year (Japan), and there is a demand for water-soluble polymers with more and more special characteristics.

On the other hand, hydrophilicization of a diene-based polymer having an unsaturated double bond has also been attempted for the purpose of electrodeposition coating.

Originally, diene polymers represented by polybutadiene are insoluble in highly polar solvents such as water and alcohols, but if these polymers can be dissolved in water, alcohol, etc., they will be used in many fields of application. can do.

Therefore, various methods have been reported for making the diene polymer water-soluble, and they are roughly classified as follows.

(1) Maleization of polybutadiene or a method of further reacting the maleated product to increase hydrophilicity (2) Copolymerization of butadiene with other vinyl monomer or reaction of butadiene monomer to synthesize butadiene derivative (3) Epoxidizing polybutadiene and then opening the oxirane ring with carboxylic acid, secondary amine or diamine to make the polymer hydrophilic (4) Above ( A method of making a polymer hydrophilic by chemical modification (addition of a sulfonic acid group, etc.) other than the methods 1) to 3) However, the polymer obtained by the above-mentioned known method is water-soluble in the literature. Or, even though it is described as water-dilutable, it is actually in the form of a latex that differs from the concept of being water-soluble, or a large amount of water such as cellosolves. Most of them are water-dilutable in the presence of an organic solvent that is compatible with, and few are truly water-soluble.

In the known method described above, the base polybutadiene to be chemically modified has a molecular weight of 10,0.
Most of the polybutadiene has a low molecular weight (liquid) of less than 00, a high molecular weight polymer having a molecular weight of 10,000 or more is rarely used, and a high molecular weight crystalline 1,2-
No polybutadiene was used.

High-molecular-weight polybutadiene is produced in a much larger amount than low-molecular-weight polybutadiene, is used in many fields, and has many characteristics in terms of use.

However, the high molecular weight crystalline 1,2-polybutadiene is
It is insoluble in lower alcohols such as methyl alcohol and ethyl alcohol, and is usually relatively well dissolved in aromatic hydrocarbon solvents such as benzene, toluene and xylene, or halogen solvents such as chloroform, carbon tetrachloride and chlorobenzene. However, all of these solvents are highly toxic. Therefore, the use of crystalline 1,2-polybutadiene is greatly limited in applications such as coating, coating, and painting as a polymer solution.

Therefore, it is an object of the present invention to provide a novel modified polymer having the hydrophilicity of high molecular weight crystalline syndiotactic 1,2-polybutadiene.

[Means for solving problems]

As a result of intensive studies, the present inventors have found that unsaturated double bonds of high molecular weight crystalline syndiotactic 1,2-polybutadiene are epoxidized at a specific ratio, and then heated in the presence of a secondary amine to form an epoxy resin. By opening the ring at a specific ratio, a hydrophilic diene-based modified polymer that achieves the above-mentioned object can be obtained, and at that time, the reaction proceeds smoothly without gelation of the polymer during the reaction, The inventors have found that the modified polymer obtained does not have a substantial gel content, and have reached the present invention.

The present invention has been made based on the above findings, and 75% or more of unsaturated double bonds are 1,2-bonds and have a melting point of 60 to 1
70 ° C. and reduced viscosity (ηsp / c) (200 mg / 100
A crystalline syndiotactic 1,2-polybutadiene having a concentration of 0.2 ml or more of tetralin solution at 100 ° C.,
24-41% of the unsaturated double bonds are epoxidized and the epoxidized polybutadiene is then heated in the presence of a secondary amine to bring the epoxy ring into the unsaturated double bonds of the crystalline syndiotactic 1,2-polybutadiene. The present invention provides a method for producing a hydrophilic diene-based modified polymer, characterized in that the above-mentioned amine is introduced by ring-opening 20 to 31% based on the above.

The novel modified polymer obtained by the production method of the present invention is
It is a high molecular weight polymer that is hydrophilic and has an unsaturated double bond in the polymer structure, and is not limited to the conventionally known fields of use of water-soluble polymers, but also has the characteristics of having an unsaturated double bond (photosensitive, rubbery It can be used by making the best use of properties imparting, curing by thermal crosslinking, etc., and the conventionally known cis-1,4
-Because its properties are slightly different from those of polybutadiene (for example, the same hydrophilicity is exhibited even if the reaction rate (degree of modification) is slightly lower than that of cis-1,4-polybutadiene. Moreover, when it is formed into a coating film, the properties are good, etc.], cis-1,4-
It is possible to provide a water-soluble adhesive, a water-soluble paint, a water-absorbent material, a rewetting adhesive, an electrodeposition paint, and the like having properties different from those of the modified polybutadiene polymer.

The method for producing the hydrophilic diene-based modified polymer of the present invention will be described in detail below.

In the present invention, the crystalline syndiotactic 1,2-polybutadiene used as a target for hydrophilization is 1,2-
It has a bond content of 75% or more, a melting point of 60 to 170 ° C., and a reduced viscosity (ηsp / c) (200 mg / 100 ml concentration of tetralin solution, 100 ° C.) of 0.2 or more, preferably a reduced viscosity of 0. 0.5-3.0 syndiotactic-
1,2-polybutadiene, more preferably one having an average molecular weight of 50,000 or more. Crystalline syndiotactic 1,2-polybutadiene having a melting point higher than the above range is practically unusable because it is difficult to dissolve in a reaction solvent under the reaction conditions of epoxidation during epoxidation.

The above-mentioned crystalline syndiotactic 1,2-polybutadiene is, for example, Japanese Patent Publication No. 47-19893, Japanese Patent Publication No. 56-
No. 18005, Japanese Patent Publication No. 54-5436, Japanese Patent Publication No. 56-
No. 18128, Japanese Patent Publication No. 56-18129, Japanese Patent Publication No. 56
It can be produced by the method described in Japanese Patent Publication No. -18130 and Japanese Patent Publication No. 53-39917.

Thus, the present invention provides the 1,2-polybutadiene described above,
It modifies and hydrophilizes by performing a two-step reaction of partial epoxidation of 1,2-polybutadiene (first step reaction) and ring opening of the epoxy ring of epoxidized polybutadiene (second step reaction). .

First, the partial epoxidation of 1,2-polybutadiene in the first stage reaction will be described.

What is important in this first-stage reaction is that the ratio of the unsaturated double bonds of 1,2-polybutadiene that is epoxidized by the partial epoxidation of 1,2-polybutadiene (epoxidation ratio) to the total unsaturated double bond. 24 to 41% of the bond.

Epoxidized exceeding the upper limit of the epoxidation rate 1,
2-Polybutadiene gels or becomes insoluble in the solvent at the next stage of the ring-opening reaction step of the epoxy ring in the second reaction.

In addition, 1,2-polybutadiene epoxidized with a ratio lower than the lower limit of the above epoxidation rate does not become hydrophilic even if the epoxy ring is opened in the next second step reaction, or the hydrophilicity is insufficient. It becomes a thing.

In the present invention, the method for epoxidizing 1,2-polybutadiene is not particularly limited, and it is possible to use unsaturated dicarboxylic acid such as chlorhydrin method, direct oxidation method, hydrogen peroxide method, alkylhydroperoxide method, and peracid method. Any conventionally known method can be used as a method for epoxidizing a compound having a heavy bond.

The epoxidation of 1,2-polybutadiene by the above-mentioned peracid method (in situ-peracid method) will be further described. This epoxidation involves adding an organic acid and hydrogen peroxide to a solution of 1,2-polybutadiene in an inert organic solvent. Is added, and the reaction formula is as follows.

That is, the organic acid reacts with hydrogen peroxide to become a peracid, which acts on the unsaturated double bond of 1,2-polybutadiene to epoxidize the 1,2-polybutadiene. The above reaction formula
It is considered that the organic acid generated in (2) repeats the same reactions as in the above reaction formulas (1) and (2).

As the organic acid, formic acid, benzoic acid, acetic acid and the like can be used, and formic acid is particularly preferable since the epoxidation reaction rate is high.

Further, as the above-mentioned inert organic solvent, those which dissolve 1,2-polybutadiene, are sparingly soluble in water and inactive to hydrogen peroxide (or peracid), for example, benzene, toluene, xylene, cyclohexane Such hydrocarbons; halogenated hydrocarbons such as chloroform, carbon tetrachloride and chlorobenzene can be used alone or in admixture of two or more.

The solution of 1,2-polybutadiene in an inert organic solvent is obtained by adding 1,2-polybutadiene to the inert organic solvent and stirring and mixing at 0 to 80 ° C., preferably 20 to 60 ° C. for 1 minute to 1 hour. By dissolving the polybutadiene in an inert organic solvent, or by adding a polymerization terminator such as water or hydrochloric acid to the 1,2-polybutadiene polymerization solution to terminate the polymerization and deashing by washing with water. .

The epoxidation reaction conditions such as the concentration of 1,2-polybutadiene in the solution of the 1,2-polybutadiene in an inert organic solvent, the amounts of the organic acid and hydrogen peroxide added thereto, and the addition method thereof are used. It is not limited because it varies depending on the type of organic acid used and the target epoxidation rate, but is not limited, for example, in the case of the peracid method using formic acid as the organic acid, the following reaction conditions are usually adopted.

1,2-polybutadiene in an inert organic solvent solution
-The concentration of polybutadiene is about 1 to 30% by weight, and the addition amount of formic acid is 0.1 per 100 g of 1,2-polybutadiene.
The amount of hydrogen peroxide added is preferably 0.2 to 4 mol per 100 g of 1,2-polybutadiene. The addition amounts of these formic acid and hydrogen peroxide can be changed depending on the target epoxidation rate.

Further, hydrogen peroxide is preferably added to the solution of 1,2-polybutadiene in an inert organic solvent as 20-60 wt% hydrogen peroxide solution.

The method of adding formic acid and hydrogen peroxide to a solution of 1,2-polybutadiene in an inert organic solvent is not particularly limited,
Formic acid is added to a solution of 1,2-polybutadiene in an inert organic solvent and mixed to obtain a solution, which is then added to the solution at 0 to 80 ° C.
A method of gradually adding a hydrogen peroxide solution having a concentration within the above range while maintaining the above value is preferable.

After adding formic acid and hydrogen peroxide in the above-mentioned predetermined amount to the above-mentioned 1,2-polybutadiene solution in an inert organic solvent, the mixture is heated at 0 to 80 ° C, preferably 20 to 60 ° C, preferably 10 The 1,2-polybutadiene is epoxidized by stirring and mixing for 1 minute to 10 hours.

When the reaction temperature of epoxidation is lower than the above lower limit, 1,2-
Polybutadiene is difficult to epoxidize, and if it is higher than the above upper limit, hydrogen peroxide and peracid are likely to be decomposed, which is dangerous.

In the epoxidation reaction system of the first step reaction or in the epoxy ring opening reaction system of the second step reaction described later, a small amount of a stabilizer such as 2,6-di-
Tertiary-butyl-P-cresol (BHT) and the like can be added and the addition of such stabilizers is the preferred method.

Next, the ring opening reaction of the epoxy ring of the epoxidized polybutadiene in the second stage reaction will be described.

In the ring-opening reaction of the epoxy ring in the second-step reaction, 1,2-polybutadiene (epoxidized polybutadiene) in which 5-45 mol% of the unsaturated double bond is epoxidized by the first-step reaction is added to the second step. It is heated in the presence of an amine and reacted to open the epoxy ring, and the desired hydrophilic polymer is obtained by going through the second step reaction after the first step reaction. The term "hydrophilic" as used in the present invention means that the polymer is dissolved in at least lower alcohols such as methyl alcohol and ethyl alcohol, or cellosomes such as butyl cellosolve.

In the second-step reaction, after the first-step reaction, epoxidized polybutadiene is separated from the reaction product solution and dissolved in a secondary amine or a reaction solvent containing a secondary amine, or the epoxidized polybutadiene is removed from the reaction product solution. Can be carried out by directly adding the secondary amine to the reaction product solution following the first stage reaction without separation.

Separation of the epoxidized polybutadiene from the reaction product solution of the first-stage reaction is carried out by a conventionally known separation method, for example, after washing the reaction product solution with water at a relatively low temperature, a large amount of epoxidized polybutadiene such as methyl alcohol. Into a sparingly soluble organic solvent, a method of depositing and separating a rubber-like epoxidized polybutadiene, after washing the reaction product solution with water, an inert organic solvent in the reaction product solution by steam distillation, For example, a low boiling point substance such as formic acid (organic acid) may be removed by evaporation to deposit and separate the epoxidized polybutadiene.

The second-stage reaction is carried out at a relatively high temperature (40 to 180
℃), if a large amount of hydrogen peroxide or formic acid remains,
In some cases, the polymer may gel during the reaction. Therefore, even when the epoxidized polybutadiene is transferred to the second stage reaction without being separated, the reaction product solution is washed with water at a relatively low temperature to remove hydrogen peroxide or formic acid. It is preferred to remove most of the.

The secondary amine used in the second-stage reaction has 10 carbon atoms.
The following are preferred. Examples of the secondary amine having 10 or less carbon atoms include dimethylamine, diethylamine,
Di-n-propylamine, di-n-butylamine, di-
Aliphatic secondary amines such as n-pentylamine, morpholine, 2,6-dimethylmorpholine, cyclic aliphatic secondary amines such as piperidine, 1-methylpiperazine and pyrrolidine, N-methylaniline, N-ethylaniline and the like. In addition to the mixed secondary amine, N-methylbenzylamine, N-methylcyclohexylamine, diallylamine and the like can be mentioned.

Among the above-mentioned secondary amines, those having a small steric hindrance in the reaction with the epoxy ring, for example, a linear aliphatic secondary amine and a cycloaliphatic secondary amine are preferable. The use of these secondary amines makes it difficult for the polymer to gel during the reaction or after treatment. In addition, linear aliphatic secondary amines and cyclic aliphatic secondary amines are particularly preferable because they react quickly with the epoxy ring and a polymer having more excellent hydrophilicity can be obtained.

The preferable amount of the secondary amine used is 200 g to 10 kg per 100 g of epoxidized polybutadiene.

The reaction solvent that can be used in the second stage reaction is a solvent in which the epoxidized polybutadiene and the produced polymer are well dissolved,
And, a solvent that does not react with any of them and with a secondary amine, and examples thereof include dimethylformamide,
Dimethyl acetamide, hexamethylphosphoramide, dimethyl sulfoxide, N-methylpyrrolidone,
Tetrahydrofuran, dioxane and the like can be mentioned.

The second-step reaction can also be carried out by using the above-mentioned secondary amine as the reaction solvent without using the above-mentioned reaction solvent, and this is often preferable because the process becomes simpler.

It is also possible to use water as an auxiliary solvent.

The concentration of the epoxidized polybutadiene in the reaction solvent solution of the epoxidized polybutadiene is preferably 1 to 50% by weight.

Further, in the second-stage reaction, it is particularly preferable to use an additive such as phenols, acids, water, alcohols (hereinafter referred to as catalyst) as a reaction catalyst in order to increase the reaction rate.

Examples of the phenols include phenol and cresol, and examples of the acids include p-toluenesulfonic acid, salicylic acid, formic acid, benzoic acid, lactic acid, oxalic acid, acetic acid, n-butyric acid, and the alcohol. Examples of the class include methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, cyclohexyl alcohol and the like.

The preferred addition amount of these catalysts is 0.05 to 5 mol per 100 g of epoxidized polybutadiene.

Of these catalysts, substances that easily give protons have a remarkable reaction acceleration effect. Also, the effect of adding phenol is excellent.

The ability of these catalysts is considered to be proportional to their acid strength, and the reaction acceleration effect is considered to be proportional to the amount of catalyst added.

The reaction conditions for the second stage reaction are usually such that the reaction temperature is 40 to 18
The reaction time is 0 ° C. and 1 to 30 hours.

When the above catalyst is used, the reaction temperature can be lowered, and as a result, the high temperature gelation of high molecular weight polybutadiene can be prevented. The addition of this catalyst is also important for obtaining a polymer having a more hydrophilic property.

Although the catalyst itself may cause an electronic ring-opening of the epoxide of the epoxidized polybutadiene, the new electronic ring-opening by the catalyst can be substantially ignored in the amine-rich reaction system.

It is not necessary to react (open) all the epoxy rings of the epoxidized polybutadiene by the second step reaction, and 20 to 31% based on the unsaturated double bond of 1,2-polybutadiene before the epoxy ring is epoxidized. Open the ring.

The residual amount of the epoxy ring in the produced polymer after completion of the second stage reaction can be roughly estimated by ¹ H-NMR. That is, the produced polymer was dissolved in deuterated-chloroform (CDCl ₃ ) to prepare ¹ H-NM.
R was measured and the epoxymethine proton and the epoxymethylene proton before and after the second step reaction Can be calculated from the amount of decrease.

After the completion of the second stage reaction, the modified polymer (hydrophilic polymer according to the present invention) thus produced can be recovered and purified from the reaction solution as follows.

For example, after the completion of the second-step reaction, the reaction solution is put into a large amount of n-hexane, or after the addition, washing with water is combined to remove a small amount of the secondary amine remaining, or the temperature of the reaction solution is adjusted. By lowering the temperature to around room temperature and adding a poor solvent such as n-hexane to the reaction solution, the modified polymer is precipitated. At this time, if the concentration of the modified polymer in the reaction solution is too dilute, the modified polymer may not be precipitated even if the poor solvent is added, because the white turbidity does not occur.
In this case, the modified polymer can be deposited by concentrating the reaction solution under reduced pressure to remove a part of the solvent such as the secondary amine and then adding the poor solvent.

Next, the precipitated and precipitated modified polymer can be collected in a solvent-free lump by a method such as vacuum drying.

The modified polymer of the present invention obtained as described above,
Although there is a difference in the degree of hydrophilicity depending on the reaction rate of the polymer and the type of secondary amine used, at least one of lower alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol or cellosolves such as butyl cellosolve at room temperature or It is a hydrophilic polymer that dissolves when heated and is dissolved in these alcohols or cellosolves, and even if it is subsequently diluted with water, precipitation hardly occurs unless the dilution ratio is high.

However, the above-mentioned hydrophilic polymer according to the present invention includes benzene, toluene, xylene, and n-hexane (general reagents are n
- hexane many mixtures of aliphatic C ₆ hydrocarbons mainly containing), n-heptane, aromatic petroleum ether (mineral spirits), naphtha, cyclohexane, aliphatic, each hydrocarbon compounds alicyclic It is difficult to dissolve. That is,
It is difficult to dissolve in a solvent with weak hydrogen bonding.

Hereinafter, the present invention will be described more specifically with reference to Examples of the present invention together with Comparative Examples.

The microstructure of 1,2-polybutadiene used in Examples and Comparative Examples was calculated by measuring the infrared absorption spectrum (IR) or the magnetic resonance spectrum (NMR). Further, the melting point of the crystalline 1,2-polybutadiene was shown by the peak temperature of the endothermic curve by a self-recording differential calorimeter (DSC).

The epoxidation rate of the epoxidized polybutadiene (ratio of the total unsaturated double bonds of the 1,2-polybutadiene before the reaction converted to an epoxy structure:%) is determined by dissolving the epoxidized polybutadiene in chloroform and Or by quantifying the epoxy by the hydrochloric acid-dioxane method.

In addition, the structure of the modified polymer obtained by the ring-opening reaction of the epoxy ring shows that this polymer is deuterated with chloroform (CDC).
was dissolved in l ^_3), it was determined by measuring with 1 H-NMR.

Further, the solubility of the polymer is determined by placing about 0.1 g of the polymer in a test tube containing about 5 ml of a solvent and allowing it to stand overnight (about 12 hours).

Example 1 Epoxidation In a 2 l four-necked flask equipped with a stirrer, thermometer, dropping funnel and condenser, 1000 ml of chloroform was added.
, Then having a 1,2-bond content of 86%,
Melting point is 139 ° C and reduced viscosity (ηsp / c) (200mg
/ 100ml tetralin solution, 100 ℃) is 1.1
80 g (1.48 mol monomer unit) of 9 high molecular weight crystalline syndiotactic-1,2-polybutadiene (manufactured by Ube Industries, Ltd.) was added and dissolved by stirring and mixing at 45 ° C. for 3 hours. 48 g (1.04 mol) of formic acid was added to this solution and mixed. Then, the solution temperature is set to 45 in the obtained solution.
While maintaining the temperature at 85 ° C., 85 g of a 30% by weight hydrogen peroxide solution (containing 0.75 mol of hydrogen peroxide) was added dropwise over 30 minutes. The resulting mixed solution was stirred and mixed at 45 ° C. for 8 hours to obtain crystalline 1,2
-Epoxidized polybutadiene.

After completion of the reaction, the reaction product liquid was washed with water, and the washed reaction product liquid was put into methyl alcohol (3). The formed precipitate was redissolved in tetrahydrofuran (THF), and this was put into methyl alcohol again. The formed precipitate was collected by filtration and then dried under reduced pressure at room temperature (18 ° C.) for 2 days to obtain a partially solidified partially epoxidized polybutadiene as a white solid. The epoxidation rate of this epoxidized polybutadiene was 37%.

Ring-opening reaction of epoxy ring After completion of the epoxidation reaction, 6 g of the epoxidized polybutadiene obtained by the above epoxidation is placed in a four-necked flask having a capacity of 300 ml equipped with a stirrer, a thermometer, a dropping funnel and a condenser. 100 ml of morpholine was added to dissolve the epoxidized polybutadiene, and the mixture was stirred for 120 hours.
The temperature was raised to ℃, and then 3.33 g of lactic acid (0.0
(37 mol) was added and reacted for 5 hours.

Then, after cooling the reaction solution to room temperature, n-hexane 5
The modified polymer in which the epoxy ring was opened was poured into 00 ml to precipitate and precipitate. This was re-dissolved in THF, n-hexane precipitation and washing of the precipitated polymer were repeated to purify the modified polymer, and the modified polymer was dried at room temperature under reduced pressure for 2 days or more and then the hydrophilic polymer according to the present invention (Product 1 of the present invention). Got

When the product 1 of the present invention was measured by ¹ H-NMR, it was about 85% or more of the epoxy ring, that is, the crystallinity 1 before epoxidation was 1.
About 3 based on the unsaturated double bond of 2-polybutadiene
1% or more had an open ring.

Example 2 A flask having a volume of 1 was used in the epoxidation reaction,
Example except that 500 ml of chloroform, 30 g of crystalline syndiotactic-1,2-polybutadiene (0.555 mol monomer unit), 0.2 mol of formic acid and 0.25 mol of 30% by weight hydrogen peroxide solution were used. An epoxidized polybutadiene having an epoxidation rate of 29% was obtained in the same manner as in 1.

Using this epoxidized polybutadiene, the ring-opening reaction of the epoxy ring was carried out in the same manner as in Example 1 to obtain the hydrophilic polymer according to the present invention (Product 2 of the present invention).

The product 2 of the present invention was measured by ¹ H-NMR, and as a result, about 85% or more of the epoxy ring, that is, crystallinity 1 before epoxidation
About 2 based on the unsaturated double bond of 2-polybutadiene
More than 5% of the rings were open.

Comparative Example 1 A ring-opening polymer (Comparative Product 1) was obtained in the same manner as in Example 2 except that the epoxy ring-opening reaction time was 0.3 hours.

When the comparative product 1 was measured by ¹ H-NMR, about 10% of the epoxy rings, that is, about 3% based on the unsaturated double bond of the crystalline 1,2-polybutadiene before epoxidation was found to be ring-opened. It was

Example 3 As crystalline 1,2-polybutadiene, a high molecular weight low-crystalline 1,2 having a 1,2-bond content of 92% and a melting point of 80 ° C.
An epoxidized polybutadiene having an epoxidation rate of 24% was obtained in the same manner as in Example 2 except that polybutadiene (manufactured by Japan Synthetic Rubber Co., Ltd.) was used.

Using this epoxidized polybutadiene, the ring-opening reaction of the epoxy ring was carried out in the same manner as in Example 2 to obtain the hydrophilic polymer of the present invention (Product 3 of the present invention).

The product 3 of the present invention was measured by ¹ H-NMR, and as a result, about 85% or more of the epoxy ring, that is, the crystallinity 1 before epoxidation
About 2 based on the unsaturated double bond of 2-polybutadiene
0% or more had an open ring.

Example 4 High molecular weight crystalline 1,2-polybutadiene having a 1,2-bond content of 81% as a crystalline 1,2-polybutadiene, a melting point of 114 ° C. and a reduced viscosity of 1.1 (manufactured by Ube Industries) An epoxidized polybutadiene having an epoxidation rate of 41% was obtained in the same manner as in Example 2 except that was used.

Using this epoxidized polybutadiene, the ring-opening reaction of the epoxy ring was carried out in the same manner as in Example 2 to obtain the hydrophilic polymer according to the present invention (Product 4 of the present invention).

When the product 4 of the present invention was measured by ¹ H-NMR, it was about 85% or more of the epoxy ring, that is, the crystallinity 1 before epoxidation was 1.
About 3 based on the unsaturated double bond of 2-polybutadiene
More than 5% of the rings were open.

Example 5 As crystalline 1,2-polybutadiene, a high molecular weight crystalline 1,2-polybutadiene having a 1,2-bond content of 87%, a melting point of 153 ° C. and a reduced viscosity of 1.2 (manufactured by Ube Industries) An epoxidized polybutadiene having an epoxidation rate of 27% was obtained in the same manner as in Example 2 except that was used.

Using this epoxidized polybutadiene, the ring-opening reaction of the epoxy ring was carried out in the same manner as in Example 2 to obtain the hydrophilic polymer according to the present invention (Product 5 of the present invention).

When the product 5 of the present invention was measured by ¹ H-NMR, it was found to be about 85% or more of the epoxy ring, that is, the crystallinity 1 before epoxidation was 1.
About 2 based on the unsaturated double bond of 2-polybutadiene
Over 3% were open.

Comparative Example 2 As crystalline 1,2-polybutadiene, a high melting point (202
Epoxidation was carried out in the same manner as in Example 2 except that the crystalline 1,2-polybutadiene of (° C.) Was used, but the polybutadiene was not dissolved in the solvent. Therefore, the dissolution temperature was raised to 50 ° C., but the degree of swelling was large and partial dissolution was observed, and it was judged that it was not suitable for solution reaction such as epoxidation reaction because it was not completely dissolved. did.

Comparative Example 3 During the epoxidation reaction, crystalline syndiotactic-1,
The epoxidation rate was about 2 except that 25 g of 2-polybutadiene (0.462 mol monomer unit), 0.1 mol of formic acid and 0.05 mol of 30% by weight hydrogen peroxide were used. 0.8% of epoxidized polybutadiene was obtained.

Using this epoxidized polybutadiene, the ring-opening reaction of the epoxy ring was performed in the same manner as in Example 2 to obtain a ring-opening polymer (Comparative Product 3).

Example 6 Instead of the formic acid formed from formic acid and hydrogen peroxide used in Example 2, commercially available m-chloroperbenzoic acid (manufactured by Aldrich, purity: about 80%) was used as an epoxidizing agent.
3 mol used and crystalline syndiotactic-1,2
An epoxidized polybutadiene having an epoxidation rate of 28% was obtained in the same manner as in Example 2 except that 25 g (0.462 mol monomer unit) of polybutadiene was used for epoxidation.

Using this epoxidized polybutadiene, the ring-opening reaction of the epoxy ring was carried out in the same manner as in Example 2 to obtain the hydrophilic polymer of the present invention (Product 6 of the present invention).

When the product 6 of the present invention was measured by ¹ H-NMR, it was found to be about 90% of the epoxy ring, that is, crystalline 1,2-before epoxidation.
About 25% based on the unsaturated double bond of polybutadiene
Was open.

Example 7 The same procedure as in Example 1 was carried out except that 100 ml of piperidine was used in place of the morpholine used in Example 1 during the ring-opening reaction of the epoxy ring, and the reaction was carried out at a reflux temperature of about 106 ° C. for 8 hours. As a result, the hydrophilic polymer according to the present invention (Product 7 of the present invention) was obtained.

The product 7 of the present invention was measured by ¹ H-NMR and found to be about 80% of the epoxy ring, that is, the crystalline 1,2-
About 30% based on unsaturated double bond of polybutadiene
Was open.

Example 8 Except that the morpholine used in Example 1 was replaced with 60 ml of di-n-butylamine and 40 ml of 1,4-dioxane as a reaction solvent during the ring-opening reaction of the epoxy ring, and the reaction was carried out for 8 hours. The hydrophilic polymer according to the present invention (Product 8 of the present invention) was obtained in the same manner as in Example 1.

When the product 8 of the present invention was measured by ¹ H-NMR, it was found to be about 60% of the epoxy ring, that is, crystalline 1,2-before epoxidation.
About 22% based on unsaturated double bond of polybutadiene
Was open.

Example 9 During the ring-opening reaction of the epoxy ring, 3.48 g (0.037) of phenol was used as a catalyst instead of the lactic acid used in Example 1.
Was carried out in the same manner as in Example 1 except that the hydrophilic polymer according to the present invention (Product 9 of the present invention) was obtained.

When the product 9 of the present invention was measured by ¹ H-NMR, it was about 85% or more of the epoxy ring, that is, the crystallinity 1 before epoxidation was 1.
About 3 based on the unsaturated double bond of 2-polybutadiene
1% or more had an open ring.

Example 10 1.74 g of lactic acid as a catalyst during ring-opening reaction of epoxy ring
A hydrophilic polymer according to the present invention (Product 10 of the present invention) was obtained in the same manner as in Example 1 except that (0.019 mol) was used and the reaction was carried out for 8 hours.

When the product 10 of the present invention was measured by ¹ H-NMR, about 85% or more of the epoxy rings, that is, about 31% or more based on the unsaturated double bond of the crystalline 1,2-polybutadiene before epoxidation were opened. It was ringing.

Example 11 A hydrophilic polymer (Product 11 of the invention) according to the invention was obtained in the same manner as in Example 1 except that the ring-opening reaction of the epoxy ring was carried out at 105 ° C. for 8 hours.

When the product 11 of the present invention was measured by ¹ H-NMR, it was found to be about 60% of the epoxy ring, that is, crystallinity 1 and 2 before epoxidation.
About 22 based on the unsaturated double bonds of the polybutadiene
% Was open.

The products of the present invention obtained in Examples 1 to 11, the comparative products obtained in Comparative Examples 1 and 3, and Examples 1, 3, 4 and 5
Table 1 shows the results of the solubility tests of the base polymers (crystalline 1,2-polybutadiene) (control products 1, 2, 3 and 4) used in each of Examples 1 to 3 in various solvents.

[Effect of the Invention] According to the production method of the present invention, a novel hydrophilic diene-based modified polymer can be obtained. This modified polymer is hydrophilic and
Methyl alcohol, ethyl alcohol, which was conventionally considered as a precipitant for crystalline 1,2-polybutadiene,
It has a completely different property from that of crystalline 1,2-polybutadiene before modification such as being dissolved in alcohols such as isopropyl alcohol, and it is an aroma usually used as a solvent for crystalline 1,2-polybutadiene. Since it dissolves in the above alcohols, which are less toxic than group hydrocarbon solvents and halogen-based solvents, its application is not limited in applications such as coating, coating and painting as polymer solutions. Paint, water absorbent material,
It can be used in the fields of rewetting adhesives, electrodeposition paints, fibers, and applications to paper (antistatic, water absorption, moisture absorption processing, paper-making adhesives, etc.), and the conventionally known cis-1,4-polybutadiene. Since its properties are slightly different from the modified polymer of cis-1,4-polybutadiene, it is possible to provide a water-soluble adhesive having properties different from those of the modified polymer of cis-1,4-polybutadiene. (Photosensitivity, imparting rubber-like properties, curability by thermal cross-linking, etc.) can be used effectively.

Continuation of the front page (56) Reference JP-A-55-98202 (JP, A) JP-A-54-87791 (JP, A) JP-B-56-9924 (JP, B2)

Claims (3)

[Claims] 1. An unsaturated double bond having 75% or more of 1,2-bonds, a melting point of 60 to 170 ° C. and a reduced viscosity (ηsp /
c) (200 mg / 100 ml concentration of tetralin solution, 1
Crystalline syndiotactic 1, with a temperature of 00 ° C) of 0.2 or more
2-polybutadiene with 24 to 4 of its unsaturated double bonds
1% epoxidized, then the epoxidized polybutadiene is heated in the presence of a secondary amine to open the epoxy ring to 20-31% ring opening based on the unsaturated double bond of the crystalline syndiotactic 1,2-polybutadiene. A method for producing a hydrophilic diene-based modified polymer, wherein the above amine is introduced. 2. The method for producing a hydrophilic diene-based modified polymer according to claim 1, wherein the amine is a secondary amine having 10 or less carbon atoms. 3. The method for producing a hydrophilic diene-based modified polymer according to claim (2), wherein the amine is a linear aliphatic secondary amine.