JPH0469163B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is a method for producing a novel hydrophilic polymer having unsaturated double bonds in its polymer structure by modifying high molecular weight 1,4-polybutadiene by a polymer reaction on its unsaturated double bonds. It is related to. Various types of water-soluble polymers have been known so far. For example, natural polymers include alginic acid (sodium alginate), carboxymethylcellulose (CMC), and methylcellulose [MC:
Methyl etherified cellulose (25-32%)]
Examples include saccharides, polysaccharides, and chemically modified products thereof, and further examples of water-soluble polysaccharides produced by microorganisms include pullulan, dextran, and xanthan gum. Examples of synthetic polymers include polyvinyl alcohol (poval), polyethylene oxide, sodium polyacrylate, and polyacrylamide. The above-mentioned water-soluble polymers are used in various ways in the field of water-soluble polymer materials, taking advantage of their respective property characteristics. For example, adhesives, paints, fiber processing agents, sizing materials, Japanese paper, paperboard, adhesives for papermaking, emulsifiers, flocculants, liquid frictional resistance reducers, thickeners, asphalt emulsifiers,
Spreading agents for agricultural chemicals, pigment dispersants, latex thickeners,
In addition to industrial fields such as soil conditioners and printing agents, we also use ice cream additives, food processing, pharmaceuticals, cosmetics,
It is also used in large quantities in biological fields such as beer foam sustaining stabilizers, diet foods, pharmaceutical tablets, and plasma expanders. The amount of water-soluble polymers used in the field of water-soluble polymer materials has reached a total of several hundred thousand tons/year (in Japan), and water-soluble polymers with special characteristics are increasingly being sought after. On the other hand, attempts have also been made to make diene polymers having unsaturated double bonds hydrophilic for use in electrodeposition coatings and the like. Originally, diene polymers such as polybutadiene are insoluble in highly polar solvents such as water and alcohols, but if these polymers can be dissolved in water and alcohols, they can be used in many fields of application. can do. Therefore, a large number of various methods have been reported for making diene polymers water-soluble, and they can be broadly classified as follows. (1) Maleation of polybutadiene or further reaction of the maleated product to increase hydrophilicity. (2) Copolymerization of butadiene with other vinyl monomers, or synthesis of butadiene derivatives by reaction of butadiene monomers and their special properties. A method of imparting hydrophilicity by polymerizing a monomer (3) A method of making the polymer hydrophilic by epoxidizing polybutadiene and then opening the oxirane ring with a carboxylic acid, secondary amine or diamine (4) A method of imparting hydrophilicity to the polymer by polymerizing the above ( Methods of making polymers hydrophilic by chemical modification (addition of sulfonic acid groups, etc.) other than methods 1) to (3) However, in the literature, polymers obtained by the above-mentioned known methods are Even if it is described as water-soluble or water-dilutable, it may actually be in the form of a latex, which is a different concept from water-soluble, or it can be diluted with water in the coexistence of a large amount of water-compatible organic solvents such as cellosolves. Most of them are water-soluble, and very few are truly water-soluble. In addition, in the above-mentioned known method, the base polybutadiene used for chemical modification is mostly low molecular weight (liquid) polybutadiene with a molecular weight of less than 10,000, and high molecular weight polymers with a molecular weight of 10,000 or more are used. There are few cases where it is used. As a result of intensive research aimed at making high molecular weight diene polymers having unsaturated double bonds hydrophilic, the present inventors discovered that the unsaturated double bonds of high molecular weight 1,4-polybutadiene were reduced in a specific proportion. The present invention was achieved based on the finding that a hydrophilic diene polymer can be obtained by epoxidizing and then heating in the presence of a tertiary amine and a carboxylic acid. The present invention was made based on the above findings, and
1,4-polybutadiene in which 85% or more of the unsaturated double bonds are 1,4-bonds and the molecular weight is 10,000 or more,
Provided is a method for producing a hydrophilic polymer, which comprises epoxidizing 5 to 60 mol% of its unsaturated double bonds, and then heating in the presence of a tertiary amine and a carboxylic acid to open the epoxy ring. to do,
The novel modified polymer obtained by the production method of the present invention is a high molecular weight polymer that is hydrophilic (in some cases water-soluble) and has an unsaturated double bond in the polymer structure, and is similar to conventional water-soluble polymers. It can be used not only in known fields of application but also by taking advantage of the characteristics of having an unsaturated double bond (photosensitivity, imparting rubbery properties, curing by thermal crosslinking, etc.). The method for producing a hydrophilic polymer of the present invention will be described in detail below based on its embodiments. The 1,4-polybutadiene used for hydrophilization in the present invention has a 1,4-bond content (sum of cis-1,4-bond and trans-1,4-bond content) of 85% or more. and the average molecular weight is
It is 1,4-polybutadiene with a high molecular weight of 10,000 or more. Therefore, the present invention processes the above-mentioned 1,4-polybutadiene in two steps: partial epoxidation of the 1,4-polybutadiene (first stage reaction) and opening of the epoxy ring of the epoxidized polybutadiene (second stage reaction). It is modified and made hydrophilic by carrying out the following reaction. First, the partial epoxidation of 1,4-polybutadiene in the first stage reaction will be explained. What is important in this first stage reaction is to reduce the proportion of unsaturated double bonds (epoxidation rate) in the 1,4-polybutadiene to be epoxidized by the partial epoxidation of the 1,4-polybutadiene to total unsaturation. 5 to 60 mol% based on double bonds, preferably 15 to 45
It is to make it into mol%. 1,4-polybutadiene that has been epoxidized in excess of the upper limit of the epoxidation rate may gel or become insoluble in the solvent in the ring-opening reaction step of the epoxy ring in the second stage reaction. In addition, 1,4-polybutadiene that has been epoxidized to a lower limit than the lower limit of the epoxidation rate may not become hydrophilic even after the epoxy ring is opened in the second stage reaction, or the hydrophilicity may be insufficient. Become something. In the present invention, the method for epoxidizing 1,4-polybutadiene is not particularly limited, and may include unsaturated A conventionally known method can be used to epoxidize a compound having a heavy bond. As an example, epoxidation of 1,4-polybutadiene by an in-situ peracid method will be described below. Epoxidation of 1,4-polybutadiene by the peracid method is carried out by adding an organic acid and hydrogen peroxide to a solution of 1,4-polybutadiene in an inert organic solvent, and the reaction formula is as follows. be. RCO ₂ H＋H ₂ O ₂ RCO ₃ H＋H ₂ O (1) That is, an organic acid reacts with hydrogen peroxide to form a peracid, which acts on the unsaturated double bonds of 1,4-polybutadiene to epoxidize the 1,4-polybutadiene. It is thought that the organic acid produced in the above reaction formula (2) repeats the same reactions as in the above reaction formulas (1) and (2). As the organic acid, formic acid, benzoic acid, acetic acid, etc. can be used, and it is particularly preferable to use formic acid because of its high peracid production rate. In addition, as an inert organic solvent for 1,4-polybutadiene, 1,4-polybutadiene is dissolved,
and those that are poorly soluble in water and inert to hydrogen peroxide (or peracid), such as hydrocarbons such as benzene, toluene, xylene, and cyclohexane; halogenated substances such as chloroform, carbon tetrachloride, and chlorobenzene. Hydrocarbons and the like can be used alone or in combination of two or more. In addition, a solution of 1,4-polybutadiene in an inert organic solvent is prepared by adding 1,4-polybutadiene to an inert organic solvent, usually at 0 to 80°C, preferably at 20 to 60°C.
A method of dissolving polybutadiene in an inert organic solvent by stirring and mixing at ℃ for 1 minute to 1 hour, or adding a polymerization terminator such as water or hydrochloric acid to the 1,4-polybutadiene polymerization solution and deashing by washing with water etc. Obtained by other methods. The reaction conditions for epoxidation, such as the concentration of 1,4-polybutadiene in the inert organic solvent solution of 1,4-polybutadiene, the amount of organic acid and hydrogen peroxide added thereto, and the method of adding them, Although the reaction conditions are not limited as they vary depending on the type of organic acid to be used and the target epoxidation rate, for example, in the case of a peracid method using formic acid as the organic acid, the following reaction conditions are usually adopted. Ru. The concentration of 1,4-polybutadiene in the inert organic solvent solution of 1,4-polybutadiene is about 1 to 30% by weight, and the amount of formic acid added is about 1,4-polybutadiene.
The amount of hydrogen peroxide added is preferably 0.01 to 2 mol per 100 g, and the amount of hydrogen peroxide added is preferably 0.1 to 4 mol per 100 g of 1,4-polybutadiene. The amounts of formic acid and hydrogen peroxide added can be varied within the above range depending on the target epoxidation rate. Further, hydrogen peroxide is preferably added to a solution of 1,4-polybutadiene in an inert organic solvent as a 20 to 60% by weight hydrogen peroxide solution. There are no particular restrictions on the method of adding formic acid and hydrogen peroxide to a solution of 1,4-polybutadiene in an inert organic solvent, but formic acid may be added to a solution of 1,4-polybutadiene in an inert organic solvent and mixed. A preferred method is to gradually add aqueous hydrogen peroxide having a concentration within the above range to the obtained solution while maintaining the solution at a temperature of 0 to 80°C. After adding formic acid and hydrogen peroxide in the above predetermined amounts to the above inert organic solvent solution of 1,4-polybutadiene, the mixed solution is heated to 0 to 80°C, preferably
The 1,4-polybutadiene is epoxidized by stirring and mixing at 20 to 60°C, preferably for 10 minutes to 10 hours. When the reaction temperature of epoxidation is lower than the above lower limit,
1,4-polybutadiene is difficult to epoxidize,
Moreover, when it is higher than the above upper limit, hydrogen peroxide and peracid are easily decomposed and it is dangerous. In addition, a small amount of a stabilizer such as 2,6-di- Tertiary-butyl-P
-Cresol (BHT) etc. can be added, and the addition of such stabilizers is a preferred method. Once the epoxidation of the first stage reaction described above is completed,
It is preferable to separate the epoxidized polybutadiene (epoxidized polybutadiene) from the reaction product liquid and then transfer it to the second stage reaction. It is also possible to proceed to a step reaction. The epoxidized polybutadiene can be separated by a conventionally known separation method, for example, by washing the reaction product liquid obtained by epoxidation with water at a relatively low temperature.
A method of pouring into a large amount of an organic solvent in which epoxidized polybutadiene is poorly soluble, such as methyl alcohol, to precipitate and separate rubber-like epoxidized polybutadiene, or washing the reaction product liquid with water and then steam distilling it. The epoxidized polybutadiene can be separated by precipitating and separating epoxidized polybutadiene by evaporating and removing low-boiling substances such as an inert organic solvent and formic acid (organic acid) in the reaction product solution. Note that the second stage reaction is performed at a relatively high temperature (40 to 40℃) as described below.
(160℃), and if a large amount of hydrogen peroxide or formic acid remains, the polymer may gel during the reaction. If possible, it is preferable to wash the reaction product liquid with water at a relatively low temperature to remove most of the hydrogen peroxide and formic acid. Next, the ring-opening reaction of the epoxy ring of the epoxidized polybutadiene, which is the second stage reaction, will be explained. The ring-opening reaction of the epoxy ring in this second stage reaction is carried out by the first stage reaction.
1,4-polybutadiene (epoxidized polybutadiene) in which mol% of 1,4-polybutadiene has been epoxidized is heated in the presence of a tertiary amine and a carboxylic acid to cause the reaction to open the epoxy ring, which undergoes this second stage reaction. By doing this, the desired hydrophilic polymer can be obtained. Note that the concept of hydrophilicity as used in the present invention is not limited to water-soluble, but also includes those soluble in lower alcohols such as methyl alcohol and ethyl alcohol. The tertiary amine used in the second stage reaction of the present invention is
It is capable of dissolving epoxidized polybutadiene at room temperature or when heated, either alone or by mixing with another tertiary amine or a solvent for a polymer other than the tertiary amine as necessary. Examples of the tertiary amine include pyridine,
Pyridines such as 2-chloropyridine; α-, β
-, γ- picolines; 3,5-lutidine,
Lutidines such as 2,4-lutidine; ethylpyridines; collidines such as 2,4,6-collidine; quinolines, isoquinolines, alkylimidazoles such as N-methylimidazole, N-
Heterocyclic type tertiary amines such as methylcarbazole, pyrazine; aliphatic tertiary amines such as triethylamine, tripropylamine, tributylamine, diethylbutylamine; trialkanolamines such as triethanolamine, tripropanolamine, tributanolamine; N, N-
dimethylaniline, N,N-diethylaniline,
Tertiary amines having an aromatic ring such as benzyl N,N-dimethylamine; or N-alkylpiperidines such as N-methylpiperidine, N-ethylpiperidine; N,N'-dimethylpiperazine, N-
Mention may be made of tertiary amines such as methylmorpholine. Among these tertiary amines, hydrophilic tertiary amines such as those soluble in water or those having high mutual solubility with water are preferred in order to obtain a more preferable hydrophilic polymer. That is, when such a tertiary amine is used, the modified polymer is less likely to precipitate during the reaction, and the reaction can be carried out in a homogeneous solution. Although it is also influenced by the reaction conditions, tertiary amines with less steric hindrance around the nitrogen atom have an advantageous nucleophilic attack of the nitrogen atom of the tertiary amine on the epoxide, resulting in faster reaction and more favorable hydrophilicity. This is preferred because a polymer can be obtained. Examples of such tertiary amines that are hydrophilic and have little steric hindrance include pyridines, picolines, lutidines, quinolines, isoquinolines, alkylimidazoles, pyrazines, and derivatives thereof. In addition, the carboxylic acid used in the second stage reaction of the present invention may be a compound having one to several carboxy groups, but in order to obtain a more preferable hydrophilic polymer, in particular, compounds with 10 carbon atoms as exemplified below are preferred. Among the following carboxylic acids, aliphatic saturated acids are preferred, and aliphatic saturated monocarboxylic acids are particularly preferred. fatty acids such as formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, valeric acid, caproic acid; hydroxy acids such as glycolic acid, lactic acid, hydroacrylic acid, 3-hydroxybutyric acid, glyceric acid, gluconic acid; fluoroacetic acid, Halogeno acids such as chloroacetic acid, chloropropionic acid, chlorobutyric acid, triclobutyric acid, trichloroacetic acid; aldehydic acids such as glyoxalic acid; keto acids such as pyruvic acid, acetoacetic acid, levulinic acid; benzoic acid, p-toluic acid, m
- Substituted benzoic acids such as chlorobenzoic acid, salicylic acid, m-hydroxybenzoic acid, and p-hydroxybenzoic acid; carboxylic acids with aromatic rings such as gallic acid, mandelic acid, and phenylacetic acid; oxalic acid, malonic acid,
Polybasic acids such as succinic acid, tartaric acid, malic acid, phthalic acid, and citric acid. The ring-opening reaction of the epoxy ring of the epoxidized polybutadiene in the second stage reaction is carried out as follows. When the epoxidized polybutadiene is separated from the reaction product liquid after the completion of the first stage reaction, first, the epoxidized polybutadiene is dissolved in a tertiary amine or a solvent containing a tertiary amine. The above-mentioned solvent is not particularly limited, but it is preferable to use an inert organic solvent such as a hydrocarbon or a halogenated hydrocarbon used in the first stage reaction because the process system will not be complicated. When reacting by using a tertiary amine as a solvent without using the above solvent, even if a poorly soluble organic solvent such as methyl alcohol used when separating the epoxidized polybutadiene remains, a small amount will cause the tertiary amine to react. There is no problem even if formic acid and hydrogen peroxide remain as long as they do not interfere with the ring reaction and a small amount of formic acid and hydrogen peroxide remain. However, if a large amount of methyl alcohol remains, the reaction temperature will not rise above its boiling point. In that case, most of the methyl alcohol may be distilled off prior to the reaction. Next, a carboxylic acid is added to a solution in which epoxidized polybutadiene is dissolved in a tertiary amine or a solvent containing a tertiary amine, and the mixture is heated and stirred to react, thereby opening the epoxy ring. The reaction temperature is preferably 40°C or higher and 160°C or lower. When the reaction temperature is lower than the above temperature, the reaction rate is slow;
Not really responding. Further, at temperatures higher than the above temperature, the polymer may gel during the reaction. Further, although the reaction time varies depending on the reaction conditions, the reaction can be carried out for 10 minutes or more and less than 10 hours. In addition, when performing the second stage reaction without separating the epoxidized polybutadiene from the reaction product liquid after the first stage reaction, it is possible to add the tertiary amine and carboxylic acid directly to the reaction product liquid and separate the epoxidized polybutadiene. It may be heated and stirred under similar reaction conditions. When hydroxycarboxylic acids are used as the carboxylic acids, some hydroxycarboxylic acids such as gluconic acid and glyceric acid are commercially available as 50 to 90% by weight aqueous solutions. If a large amount of water is present in the reaction system, epoxidized polybutadiene will not dissolve in the solvent, so when using the above-mentioned hydroxycarboxylic acid aqueous solution, add the hydroxycarboxylic acid in advance to the epoxidized polybutadiene solution. It is best to remove water by azeotropically removing water and the tertiary amine by adding an aqueous solution to a tertiary amine that can be azeotroped with water and heating it. By removing azeotropic water under reduced pressure, a homogeneous solution of the polymer can be obtained. It is not necessary to react (ring-open) all the epoxy rings of the epoxidized polybutadiene in the second stage reaction, and the ring-opening is preferably performed based on the unsaturated double bonds of the 1,4-polybutadiene before epoxidation. ~60 mol%, more preferably 15-45 mol%. That is, for example, if only 5 mol% is epoxidized, it is necessary to open the entire ring, but if 60 mol% is epoxidized, it is possible to open the entire ring, or the epoxidized The ring may be opened by 5 mol% based on the unsaturated double bonds of the 1,4-polybutadiene before the ring opening. The amount of epoxy rings remaining in the polymer after the completion of the second stage reaction can be roughly estimated by ¹ H-NMR. That is, the polymer was dissolved in a heavy water (D ₂ O) solvent [or heavy methanol (CD ₃ OD)] and ¹ H-NMR was measured, and the epoxide protons before and after the second stage reaction were measured.

It can be calculated from the amount of decrease in [Formula]. After the completion of the second stage reaction, the obtained modified polymer (hydrophilic polymer) according to the present invention can be recovered and purified from the reaction solution as follows. For example, after the second stage reaction is completed, the reaction solution is poured into a large amount of n-hexane, or the temperature of the reaction solution is lowered to around room temperature, and a poor solvent such as n-hexane is added to the reaction solution. Possibly, the modified polymer is precipitated. At this time, if the concentration of the modified polymer in the reaction solution is too dilute, even if the poor solvent is added, the solution may only become cloudy and the polymer may not precipitate. In this case, after concentrating the reaction solution under reduced pressure to remove a portion of the solvent such as the tertiary amine,
By adding the above-mentioned poor solvent, the polymer can be precipitated. Next, the modified polymer can be recovered by distilling the precipitated polymer at room temperature or heating it and distilling off the solvent under reduced pressure. The above-mentioned modified polymer has a high affinity with tertiary amines and carboxylic acids, and depending on the combination of reactions and reaction rates, it is often not possible to sufficiently remove these with a single precipitation. In such a case, if necessary, the recovered modified polymer may be further heated (heated).
It can be purified by combining reprecipitation such as dissolution in isopropanol and precipitation with n-hexane, thereby obtaining a solid modified polymer substantially free of solvents such as tertiary amines. . There are many fields in which it can be used, such as paints, even if it contains a small amount of solvent. The modified polymer according to the present invention obtained as described above is a rubber-like polymer after drying, and the degree of hydrophilicity varies depending on the reaction rate of the polymer, the type of tertiary amine used, the type of carboxylic acid, etc. However, it is soluble in water and/or methyl alcohol and ethyl alcohol at room temperature.
In addition, it dissolves in many tertiary amines such as pyridine at room temperature or when heated, and further dissolves in n-propanol,
It is a hydrophilic polymer that dissolves in isopropanol, isobutyl alcohol, tertiary butyl alcohol, isoamyl alcohol, diethylene glycol, and benzyl alcohol at room temperature or when heated. However, the above-mentioned hydrophilic polymer according to the present invention does not contain benzene, toluene, xylene, or n-hexane (the general reagent is an aliphatic polymer mainly composed of n-hexane).
_Aromatic , aliphatic, and alicyclic hydrocarbon compounds such as n-heptane, petroleum ether (mineral spirits), naphtha, and cyclohexane; and halogenated compounds such as chloroform and chlorobenzene. In addition to hydrocarbons, it is insoluble in diethyl ether, methyl isobutyl ketone, acetone, etc. That is, it is insoluble in solvents with weak or moderate hydrogen bonding properties. As mentioned above, the novel modified polymer obtained by the production method of the present invention is a high molecular weight polymer that is hydrophilic (in some cases water-soluble) and has an unsaturated double bond in the polymer structure, and has a water-soluble adhesive. agent,
It can be used in fields such as water-soluble paints, water-absorbing materials, re-wetting adhesives, electrodeposition paints, fibers, and paper applications (antistatic, water-absorbing, moisture-absorbing processing, sticky materials for papermaking, etc.), and it can be used in conventional applications. It can be used by taking advantage of special characteristics not found in known water-soluble polymers (photosensitivity, imparting rubbery properties, curability through thermal crosslinking, etc.). Examples of the present invention will be listed below along with comparative examples, and the effects of the present invention will be explained in more detail. In addition, 1 and 4 used in the examples and comparative examples
- The microstructure (content of 1,4-bonds) of polybutadiene was measured and calculated by infrared absorption spectrum (IR) or nuclear magnetic resonance spectrum (NMR). In addition, the epoxidation rate of epoxidized polybutadiene (ratio of all unsaturated double bonds in 1,4-polybutadiene before reaction converted to epoxy structure: mol%) is determined by dissolving epoxidized polybutadiene in deuterated chloroform, Calculated by measuring with NMR. Furthermore, the structure of the modified polymer obtained by the ring-opening reaction of the epoxy ring can be changed by dissolving this polymer in heavy methanol (CD ₃ OD) or heavy water (D ₂ O).
It was investigated by measuring with ¹ H-NMR. The solubility of the polymer was determined by putting about 0.1 g of the polymer into a test tube containing about 5 ml of solvent and leaving it overnight (about 12 hours). Example 1 Epoxidation Toluene was added to a 300 ml four-necked flask equipped with a stirrer, thermometer, dropping funnel, and condenser.
Then add UBEPOL #150 (cis-1,4-polybutadiene) to this as 1,4-polybutadiene.
97.4% bond, 1.3% trans-1,4-bond, 1,
2-bond 1.3%; [η] 2.1; Number average molecular weight approx.
200,000 (manufactured by Ube Industries) was added, and 10.82 g (0.2 mol monomer unit) was added, and the mixture was stirred and mixed at 45°C for 100 minutes to dissolve. Add 2.02 g of formic acid to this solution while keeping the liquid temperature at 45℃.
g (0.044 mol) and mixed. Next, 30% by weight was added to the resulting solution while keeping the liquid temperature at 45°C.
48g of hydrogen peroxide (contains 0.42 moles of hydrogen peroxide)
was added dropwise over 20 minutes. The resulting mixture was heated at 45℃ for 5 minutes.
The mixture was stirred and mixed for a period of time to epoxidize the 1,4-polybutadiene. After the reaction was completed, the reaction product solution was washed with water, and the water-washed reaction product solution was poured into 1000 ml of methyl alcohol to precipitate and separate the epoxidized polybutadiene. The separated epoxidized polybutadiene was purified by redissolving it in tetrahydrofuran (THF), precipitating it in methyl alcohol, and then drying under reduced pressure (room temperature, 2 days). (This purification was performed because it was necessary to thoroughly remove impurities for analysis, and is not necessary for the next second stage reaction.) The epoxidation rate of epoxidized polybutadiene calculated from NMR is It was 31 mol%. Ring-opening reaction of epoxy ring After the completion of the epoxidation reaction, about 6 g of the epoxidized polybutadiene (crude wet material that has not been purified or dried) separated by precipitation was dissolved in 150 ml of pyridine and stirred for 90 minutes. The temperature was raised to .degree. C., and 0.1 mol of the carboxylic acid shown in Table 1 was added, followed by a reaction for 5 hours. Then, after cooling to room temperature, n-hexane
The modified polybutadiene with the epoxy ring opened was precipitated by pouring it into 500 ml of the solution. This was redissolved in isopropyl alcohol (IPA) and the modified polybutadiene was purified by repeating n-hexane precipitation, and dried under reduced pressure at room temperature for 2 days or more to obtain ring-opened polymers (products of the present invention 1-1 to 1-6). I got it. When products 1-1 to 1-6 of the present invention were measured by ¹ H-NMR, it was confirmed that the epoxymethine protons had disappeared and the epoxy rings were completely opened. Example 2 Epoxidized polybutadiene with an epoxidation rate of 51 mol% was obtained in the same manner as in Example 1, except that 0.0066 mol of formic acid and 0.66 mol of 30% by weight hydrogen peroxide solution were used during the epoxidation reaction. Using this epoxidized polybutadiene, the ring-opening reaction of the epoxy ring was performed in the same manner as in Example 1 to obtain ring-opened polymers (products of the present invention 2-1 to 2-5). still,
The carboxylic acids used in the ring-opening reaction of the epoxy ring are shown in Table-1. When products 2-1 to 2-5 of the present invention were measured by ¹ H-NMR, it was confirmed that the epoxymethine protons had disappeared and the epoxy rings were completely opened. Example 3 Epoxidized polybutadiene with an epoxidation rate of 8 mol% was obtained in the same manner as in Example 1, except that 0.0108 mol of formic acid and 0.108 mol of 30% by weight hydrogen peroxide solution were used during the epoxidation reaction. 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 ring-opened polymers (products of the present invention 3-1 to 3-3). still,
The carboxylic acids used in the ring-opening reaction of the epoxy ring are shown in Table-1. When products 3-1 to 3-3 of the present invention were measured by ¹ H-NMR, it was confirmed that the epoxymethine proton had disappeared and the epoxy ring had completely opened. Comparative Example 1 Epoxidized polybutadiene with an epoxidation rate of 3 mol % was obtained in the same manner as in Example 1, except that 0.0108 mol of formic acid and 0.06 mol of 30% by weight hydrogen peroxide solution were used during the epoxidation reaction. Using this epoxidized polybutadiene, the epoxy ring was subjected to a ring-opening reaction in the same manner as in Example 1 to obtain ring-opened polymers (comparative products 1-1 and 1-2). The carboxylic acids used in the ring-opening reaction of the epoxy ring are shown in Table 1. Comparative Example 2 Formic acid 0.2 mol and 30% by weight during epoxidation reaction
The procedure of Example 1 was repeated except that epoxidation was carried out for 10 hours using 0.66 mol of hydrogen peroxide solution. After drying, the resulting polymer gelled (approximately
The epoxidation rate was calculated to be 63 mol % based on the oxygen content calculated based on the assumption that all oxygen was derived from epoxide. Example 4 Diene35R (cis-1,4
-bond 38.1%, trans-1,4-bond 52.2%,
Vinyl bond 9.7%; [η] 2.0; Number average molecular weight approx.
Epoxy Epoxidized polybutadiene with a conversion rate of 29 mol% was obtained. 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 ring-opened polymers (products of the present invention 4-1 to 4-5). still,
The carboxylic acids used in the ring-opening reaction of the epoxy ring are shown in Table-1. When products 4-1 to 4-5 of the present invention were measured by ¹ H-NMR, it was confirmed that the epoxymethine protons had disappeared and the epoxy rings were completely opened. Products of the present invention obtained in Examples 1 to 4, comparative products obtained in Comparative Example 1, base polymer (UBEPOL #150) (control product 1) used in Examples, and base polymer used in Example 4 The results of solubility tests on (Diene35R) (Control Product 2) in various solvents are summarized in Table 1.

【table】

[Table] Example 5 Instead of performic acid made from formic acid and hydrogen peroxide used in Example 1, commercially available m-chloroperbenzoic acid (obtained from Aldrich, purity: about 80%) was used as an epoxidizing agent at 0.09%. Epoxidized polybutadiene with an epoxidation rate of 32 mol % was obtained in the same manner as in Example 1, except that the epoxidation was performed at 30° C. using mol. Using this epoxidized polybutadiene, the ring-opening reaction of the epoxy ring was carried out in the same manner as in Example 1, except that the carboxylic acids shown in Table 2 were used as the carboxylic acids. 3) was obtained. When products 5-1 to 5-3 of the present invention were measured by ¹ H-NMR, it was confirmed that the epoxymethine protons had disappeared and the epoxy rings were completely opened. Examples 6 and 7 During the ring-opening reaction of the epoxy ring, α-picoline was used instead of the pyridine used in Example 1.
The ring-opened polymer (inventive product 6 -1,6-2,7
-1,7-2) were obtained. Invention products 6-1, 6-2, 7-1, 7-2
When measured by ¹ H-NMR, it was confirmed that the epoxymethine proton had disappeared in all cases, and the epoxy ring was completely opened. Example 8 During the ring-opening reaction of the epoxy ring, 75 ml of pyridine and 75 ml of toluene were used instead of the pyridine used in Example 1.
ml, epoxidized polybutadiene was dissolved in this mixture, and the carboxylic acid shown in Table 2 was used as the carboxylic acid. Ring-opened polymers (products of the present invention 8-1 and 8-2) were obtained. When products 8-1 and 8-2 of the present invention were measured by ¹ H-NMR, it was confirmed that the epoxymethine proton had disappeared and the epoxy ring was completely opened. Comparative Examples 3 to 6 During the ring-opening reaction of the epoxy ring, 150 toluene was used instead of the pyridine used in Example 1.
ml (Comparative Example 3), dioxane 150ml (Comparative Example 4),
Using 150 ml of o-dichlorobenzene (Comparative Example 5), 150 ml of toluene, and 0.3 g of quaternary ammonium salt (triethylbenzylammonium chloride) (Comparative Example 6) as the epoxy ring-opening catalyst, using acetic acid as the carboxylic acid, 90 ℃ for 5 hours (Comparative Examples 3, 4, 6) or 160℃ for 1 hour (Comparative Example 5)
The same procedure as in Example 1 was carried out except that heating was performed. When the polymers obtained in Comparative Examples 3, 4, and 6 (Comparative Products 3, 4, and 6) were collected and measured by ¹ H-NMR, the epoxy rings remained without being opened at all. In Comparative Example 5, the reaction system lost fluidity about 1 hour after the heating started, and the viscosity increased and gelatinized. I tried to dissolve the reactant (including the solvent) in several types of solvents, but it was insoluble, so I judged it to be gelation. Example 9 During the ring-opening reaction of the epoxy ring, 150 ml of N-methyl-2-pyrrolidone was used in place of the pyridine used in Example 1, epoxidized polybutadiene was dissolved in this, and 100 ml of triethanolamine was added as the tertiary amine. A ring-opened polymer (Product 9 of the present invention) was obtained in the same manner as in Example 1, except that 0.1 mol of acetic acid was used as the carboxylic acid, and the mixture was heated and stirred at 120° C. for 7 hours. When product 9 of the present invention was measured by ¹ H-NMR, ring opening of the epoxy ring was confirmed, but the signal overlapped with the triethanolamine signal, making it impossible to accurately calculate the ring opening rate of the epoxy ring. Nakatsuta. Comparative Example 7 The same procedure as Example 9 was carried out except that triethanolamine was not used. The obtained polymer (comparative product 7) was collected and incubated for ¹ H.
- When measured by NMR, the epoxy ring remained without being opened at all. Table 2 summarizes the results of solubility tests in various solvents for the products of the present invention obtained in Examples 5 to 9 and the comparative products obtained in Comparative Examples 3, 4, 6, and 7.

[Table] Comparative Example 8 The same procedure as in Example 1 was carried out except that no carboxylic acid was added during the ring-opening reaction of the epoxy ring. The obtained polymer (comparative product 8) was collected and incubated for ¹ H.
-As measured by NMR, the epoxy ring remained unconsumed. Example 10 A ring-opened polymer (inventive product
10). When product 10 of the present invention was measured by ¹ H-NMR,
About 50 mole percent of the epoxy rings, ie, about 15 mole percent of the total unsaturated double bonds in the original polybutadiene, remained as epoxy structures, and about 16 mole percent were open. Example 11 A ring-opened polymer (inventive product
11). When product 11 of the present invention was measured by ¹ H-NMR,
Approximately 25 mole percent of the epoxy rings, ie, approximately 8 mole percent of the total unsaturated double bonds in the original polybutadiene, remained as epoxy structures and about 23 mole percent were open. Example 12 During the epoxidation reaction, 5.04 g of polybutadiene (UBEPOL #150), 0.022 mol of formic acid and
Polybutadiene was epoxidized in the same manner as in Example 1 except that 0.22 mol of 30% by weight hydrogen peroxide solution was used. it is conceivable that). After the epoxidation reaction is completed, the reaction product liquid is washed with water,
Without isolating the epoxidized polybutadiene, add 75 ml of pyridine and 0.1 acetic acid to the reaction product solution washed with water.
A ring-opened polymer (product 12 of the present invention) was obtained in the same manner as in Example 1, except that the ring-opening reaction was carried out at 100° C. for 7 hours under stirring. When product 12 of the present invention was measured by ¹ H-NMR,
It was confirmed that the epoxymethine proton had disappeared and the epoxy ring was completely opened. Table 3 summarizes the results of solubility tests in various solvents for the products of the present invention obtained in Examples 10 to 12 and the comparative product obtained in Comparative Example 8.

[Table] Judgment, and *1, *2, *3, *5
, *7 and *8
All media are the same as in Table 1.
*Epoxidation rate (mol%)
Example 13 The same procedure as in Example 1 was carried out except that oxalic acid was used as the carboxylic acid during the ring-opening reaction of the epoxy ring.
The ring-opening reaction system became non-uniform as the polymer precipitated in a rubbery state 20 minutes after the start of the reaction. At this point, the ring-opening reaction was stopped, and the precipitated polymer was purified and dried in the same manner as in Example 1. Obtained polymer (invention product 13)
When the solubility of the compound was evaluated, it was found to be water-soluble. When product 13 of the present invention was measured by ¹ H-NMR,
It was confirmed that the epoxymethine proton had disappeared and the epoxy ring was completely opened.

Claims (1)

[Claims] 1. 1,4-polybutadiene in which 85% or more of the unsaturated double bonds are 1,4-bonds and the molecular weight is 10,000 or more, and 5 to 60 mol% of the unsaturated double bonds are epoxy 1. A method for producing a hydrophilic polymer, which comprises curing the epoxy ring by heating in the presence of a tertiary amine and a carboxylic acid to open the epoxy ring. 2. The method for producing a hydrophilic polymer according to claim 1, wherein the epoxy ring is opened in an amount of 5 to 60 mol% based on the unsaturated double bonds of 1,4-polybutadiene before epoxidation. 3. The method for producing a hydrophilic polymer according to claim 1, wherein the carboxylic acid is a carboxylic acid having 10 or less carbon atoms. 4 Claims in which the tertiary amine is one or a mixture of two or more selected from the group consisting of pyridines, picolines, lutidines, quinolines, isoquinolines, alkylimidazoles, pyrazines, and derivatives thereof. 2. A method for producing a hydrophilic polymer according to item 1.