JPH0593008A - Production of new polymer having epoxy group - Google Patents

Abstract

PURPOSE:To obtain a new polymer having high reactivity with cation and containing an epoxy group capable of smoothly controlling the reaction with cation by epoxidizing a polymer having a specific cyclic olefin group. CONSTITUTION:The objective polymer can be produced by epoxidizing a polymer having a cycloolefin group on side chain and produced by polymerizing 1-99wt.% of a composition expressed by formula (R<1> to R<3>, Ra and Rb are H or 1-9C alkyl; (c) is integer of 4-8; (n) is integer of >=0). The vinyl monomer copolymerizable with the above composition is e.g. (meth)acrylic acid (ester), maleic acid, itaconic acid, vinyl ethers and styrene derivatives.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a novel polymer having an epoxy group in its side chain. Since the novel polymer of the present invention has an epoxy group in the side chain,
It is a substance that can be used by reacting with an initiator that generates a cation by light or heat or an epoxy curing agent such as an acid anhydride, phenol or amine, and is useful as a resin for paints or a resin for adhesives.

[0002]

2. Description of the Related Art Conventionally, as a copolymer having an epoxy group in a side chain, a polymerizable monomer such as butyl acrylate or styrene, glycidyl (meth) acrylate or 3,4-epoxycyclohexylmethyl (meth) is used. ) It is known to use an acrylate or the like, and a polymer having a glycidyl group or a 3,4-epoxycyclohexylmethyl group in its side chain is used to apply it to a new paint using a cationic curing reaction. Is being considered. However, with glycidyl groups, the reaction is often too slow.
Furthermore, since glycidyl (meth) acrylate uses epichlorohydrin for production, chlorine ions and the like may be mixed in the product, which may adversely affect the cured product and coating film.

[0003]

OBJECT OF THE INVENTION The present invention has high reactivity with cations,
It is an object of the present invention to provide a novel polymer having an epoxy group capable of controlling the reaction with a cation.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventors have found a novel polymer having an epoxy group in its side chain, which is suitable for this purpose.

That is, the present invention provides a novel polymer having a cyclic olefin in the side chain obtained by polymerizing the composition (A) represented by the general formula (I), and an aromatic vinyl monomer. 1 to A with respect to 99 to 1% by weight of at least one vinyl-based monomer selected from the group consisting of a vinyl cyanide-based monomer, and a (meth) acrylic acid ester-based monomer.
The present invention relates to a method for producing a polymer having an epoxy group, which is obtained by further epoxidizing a polymer having a cyclic olefin obtained by copolymerizing 99 to 99% by weight. It also has a vinyl group obtained by reacting a compound having one or more vinyl groups and one epoxy group in one molecule with either an unsaturated carboxylic acid or an unsaturated carboxylic acid ester having a hydroxyl group. A polymer having a vinyl group in the side chain obtained by polymerizing the unsaturated carboxylic acid ester composition (B), an aromatic vinyl-based monomer, a vinyl cyanide-based monomer, and (meth) acrylic acid A polymer having a vinyl group formed by copolymerizing 1 to 99% by weight of B with respect to 99 to 1% by weight of at least one vinyl monomer selected from the group consisting of ester monomers, The present invention also relates to a method for producing a novel polymer having an epoxy group obtained by epoxidation.

Next, the present invention will be described in more detail.

In the general formula (I), R ¹ , R ² and R ³ can be simultaneously replaced by hydrogen or an alkyl group generally containing 1 to 9 carbon atoms for each group. .. For example, in the case of acrylic acid ester, R ¹ is a hydrogen atom, and in the case of methacrylic acid ester, R ¹ is a methyl group. Further, R ² and R ³ depend on the raw material alcohol. For example, when 1,2,3,6-tetrahydrobenzyl alcohol is used as a raw material, R ² and R ³ are all hydrogen atoms. Also, 2-methyl-1,
When 2,3,6-tetrahydrobenzyl alcohol is used as a raw material, R ² is a hydrogen atom and R ³ is a methyl group.

R ^a and R ^b are hydrogen atoms or alkyl groups generally containing from 1 to 9 carbon atoms,
This depends on the starting lactone.

For example, when ε-caprolactone is used as a raw material, R ^a and R ^b are all hydrogen atoms. Also,
When β-methyl-δ-valerolactone is used, R ^a and R ^b are a methyl group and a hydrogen atom, and when 3-ethylcaprolactone is used, R ^a and R ^b are an ethyl group and a hydrogen atom. ..

Further, c is an integer of 4 to 8, which is also determined by the starting lactone. For example, c = 5 for ε-caprolactone, c = 4 for valerolactone, and c = 7 for cyclooctanone lactone. n represents an integer of 0 or more and is the number of moles of the added lactone. For example, n = 0, 5 when no lactone is added.
In the case of molar addition, n = 5.

Further, in the composition represented by the general formula (I), n does not have to be a single integer, and the composition represented by the general formula (I) may be a mixture of different n. ..

The composition represented by the general formula (I) is disclosed in Japanese Patent Application No.
It can be synthesized by the synthetic method shown in No. 320320. Further, examples of commercially available products thereof include CYCLOMER AF manufactured by Daicel Chemical Industries, Ltd.
-200, CYCLOMERMF-100, CYCLO
There are MER MF-101 and the like, and they can be used. Furthermore, the composition represented by the general formula (I) is
You may use only 1 type or 2 or more types simultaneously. The composition represented by the general formula (I) is radical-polymerized by using a radical polymerization initiator, and further epoxidized to obtain the novel polymer having an epoxy group of the present invention. Moreover, a solvent is used if necessary.

Only the composition represented by the general formula (I) may be radically polymerized, or if necessary, the composition represented by the general formula (I) and a vinyl monomer may be copolymerized. Good.

As the vinyl-based monomer copolymerizable with the composition represented by the general formula (I), unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid and itaconic acid, acrylic acid esters and methacrylic acid are used. Examples include unsaturated carboxylic acid esters such as acid esters, vinyl ethers, and styrene derivatives. At least one of these
One or more compounds can be copolymerized.

On the other hand, the compound having one epoxy group and one or more vinyl groups in one molecule used in the present invention is represented by the general formula (XI).

[0016] [I is an integer of 1 to 5, R ⁴ is a hydrogen atom or an alkyl group having 1 to 50 carbon atoms, R ⁵ and R ⁶ are hydrogen atoms, an alkyl group having 1 to 50 carbon atoms or a substituted phenyl group, R ⁵ and R ⁶ may have a ring wound thereon.] Examples of the compound represented by the general formula (XI) are the following compounds.

4-vinylcyclohexene-1-oxide, 5-vinylbicyclo [2.2.1] hept-2-ene-2-oxide, limonene monoxide, trivinylcyclohexane monoxide, divinylbenzene monoxide, butadiene mono. Oxide and 1,2-epoxy-
Compounds represented by general formula (IV) such as 9-decene, compounds represented by general formula (V) such as allylglycidyl ether, represented by general formula (VI) such as glycidylstyryl ether Such as compounds.

Further, the compounds represented by Chemical formulas 4, 5 and 6 can also be used.

[0019]

[Chemical 4]

[0020]

[Chemical 5]

[0021]

[Chemical 6]

[0022] These may be used alone or in combination of two or more.

If necessary, ethylene oxide,
Monoepoxides such as propylene oxide, cyclohexene oxide, styrene oxide and α-olefin oxide, and diepoxides such as vinylcyclohexene dioxide and 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate, etc. You may use together with the compound which has one epoxy group and one or more vinyl groups in a molecule.

The unsaturated carboxylic acid used in the present invention includes unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid, maleic acid, fumaric acid, itaconic acid, and their acid anhydrides. is there.

The unsaturated carboxylic acid ester having a hydroxyl group is represented by the general formula (XII). CR ⁰ ₂ = CR ¹ COOR ⁰ OH (XII) Examples of the compound represented by the general formula (XII) are the following compounds.

2-hydroxyethyl (meth) acrylate
2-hydroxypropyl (meth) acrylate and 4
-General formula such as hydroxybutyl (meth) acrylate
The compound represented by (VII) 4, a caprolactone-modified 2-
Hydroxyethyl (meth) acrylate and other general formula (V
Examples thereof include compounds represented by III), caprolactone-modified 4-hydroxybutyl (meth) acrylate, ethylene oxide of unsaturated carboxylic acids such as maleic acid, fumaric acid and itaconic acid, or caprolactone-modified products thereof. These may be used alone or in combination of two or more.

The unsaturated carboxylic acid ester composition having a vinyl group used in the novel polymer of the present invention has 1 in 1 molecule in the presence of an esterification or etherification catalyst.
It is obtained by reacting a compound having one epoxy group and one or more vinyl groups with the unsaturated carboxylic acid or unsaturated carboxylic acid ester having a hydroxyl group.

The unsaturated carboxylic acid ester composition having a vinyl group obtained as a result of the above reaction is an unsaturated carboxylic acid ester having a hydroxyl group as an initiator, for example, 2
When -hydroxyethyl acrylate is used, it has the following structure.

CH ₂ ═CHCOOCH ₂ CH ₂ (Y) _r OH (XIII) [wherein, in the general formula (XIII), r is a natural number of 1 to 100 and is used for the reaction. It depends on the usage ratio of ethyl acrylate and a compound having one epoxy group and one or more vinyl groups in one molecule.
Y is an ether generated by ring-opening of an epoxy group of a compound having one epoxy group and one or more vinyl groups in one molecule.
It is a unit structure of a product bound by a tel bond portion] Further, for an unsaturated carboxylic acid or an unsaturated carboxylic acid ester having a hydroxyl group, one epoxy group and one or more vinyl groups are contained in one molecule. The compounds are reacted in a molar ratio of 0.1 to 100 times, preferably 1 to 5 times. If the molar ratio is 0.1 times or less, the functional properties characteristic of the present invention are not exhibited, and if it is 100 times or more, the vinyl group-containing monomer is present.
Not as useful as

The novel polymer of the present invention is obtained by polymerizing the above-described unsaturated carboxylic acid ester composition having a cyclic olefin or vinyl group and epoxidizing a polymer having a cyclic olefin or vinyl group, or 99 to 1% by weight of at least one vinyl monomer selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, and (meth) acrylic acid ester monomers.
And 1 to 99% by weight of the unsaturated carboxylic acid ester composition having a cyclic olefin or vinyl group described above are epoxidized. The proportion of the monomers used, the polymerization reaction conditions and the like can be arbitrarily determined according to the desired polymer, and are not different from the known seed polymerization reaction.

As an example of such a polymerization reaction, each monomer component is dissolved or dispersed in a solvent-free or organic solvent and polymerized while stirring at a temperature of about 60 to 180 ° C. in the presence of a radical polymerization initiator. How to do it. The reaction time is usually about 1 to 40 hours.
As the organic solvent, hydrocarbon solvents such as heptane, toluene, xylene, octane and mineral split, ester solvents such as ethyl acetate, n-butyl acetate, isobutyl acetate, methyl cellosolve acetate and butyl carbitol acetate. Solvents, ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethanol, n-butanol, sec-butanol
Alcohol-based solvents such as alcohol and isobutanol, ether-based solvents such as n-butyl ether, dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and the like can be used.

These solvents can be used alone or in appropriate combination. Further, as the radical polymerization initiator, any of those usually used can be used. As one example, benzoyl peroxide, peroxides such as t-butylperoxy-2-ethylhexanoate,
Examples thereof include azo compounds such as azoisobutyl nitrile and azobisdimethylvaleronitrile.

The polymer having a cyclic olefin or vinyl group thus synthesized is reacted with an epoxidizing agent to synthesize the polymer having an epoxy group of the present invention. Examples of the agent include peracids and hydroperoxides. Examples of peracids include formic acid, peracetic acid, perbenzoic acid, and trifluoroperacetic acid. Of these, peracetic acid is a preferred epoxidizing agent because it is industrially produced in large quantities, is inexpensively available, and has high stability. Examples of the hydroperoxides include hydrogen peroxide, tertiary butyl hydroperoxide, cumeneper oxide and the like.

In the epoxidation, a catalyst can be used if necessary.

For example, in the case of peracid, an alkali such as sodium carbonate or an acid such as sulfuric acid can be used as a catalyst. In the case of hydroperoxides, a mixture of tungstic acid and caustic soda is used with hydrogen peroxide, an organic acid is used with hydrogen peroxide, or molybdenum hexacarbonyl is used in combination with tert-butyl hydroperoxide. A catalytic effect can be obtained.

The epoxidation reaction is carried out by adjusting the presence or absence of a solvent and the reaction temperature according to the physical properties of the equipment and raw materials. The reaction temperature range that can be used depends on the reactivity of the epoxidizing agent used. With respect to peracetic acid, which is a preferable epoxidizing agent, 0 to 70 ° C. is preferable. The reaction is slow below 0 ° C,
Decomposition of peracetic acid occurs at 70 ° C. In the tertiary butyl hydroperoxide / molybdenum dioxide diacetylacetonate system, which is an example of hydroperoxide, the temperature is preferably 20 ° C to 150 ° C for the same reason. The solvent can be used for the purpose of reducing the viscosity of the raw material and stabilizing it by diluting the epoxidizing agent. In the case of peracetic acid, aromatic compounds, ethers, esters and the like can be used.

The charged molar ratio of the epoxidizing agent to the unsaturated bond can be changed according to the purpose such as the amount of the unsaturated bond to be left.

When a compound having a large number of epoxy groups is intended, the epoxidizing agent is preferably added in an equimolar amount or more with respect to the unsaturated group. However, it is usually disadvantageous in excess of 2 times the molar amount in view of economical efficiency and side reaction, and in the case of peracetic acid, 1 to 1.5 times the molar amount is preferable. The epoxidation reaction is carried out continuously or batchwise, but in the case of continuous reaction, the piston flow type is preferred. At this time, each of the polymerization inhibitors may be charged individually, but it is preferable that the powdery one is dissolved in a solvent and then charged. Alternatively, it may be dissolved in the raw material ester and charged. Further, the same applies to the batch method, but it is desirable to use the semi-batch method in which the oxidizing agent is sequentially charged.

The composition of interest can be taken out from the reaction crude liquid by chemical engineering means such as concentration, but it is preferable to wash the reaction crude liquid with water or neutralization water before concentration.

Further, even when not concentrated, it is preferable to wash the reaction crude liquid with water or neutralized water. Particularly when an organic peracid is used as the oxidizing agent, it is preferable to wash the reaction crude liquid with neutralized water. This is because if a low boiling point component such as a solvent is attempted to be removed without neutralization, polymerization is extremely easy.

The alkaline aqueous solution used for neutralization includes, for example, NaOH, KOH, K ₂ CO ₃ and Na ₂ C.
_{O 3, NaHCO 3, KHCO 3} , an aqueous solution of an alkaline substance such as NH ₃ can be used. The concentration used can be freely selected within a wide range. From the viewpoint of liquid separation, it is preferable to use a NaOH aqueous solution, a Na ₂ CO ₃ aqueous solution, or a NaHCO ₃ aqueous solution. Neutralization and washing with water are preferably carried out in the temperature range of 10 to 90 ° C, preferably 10 to 50 ° C. In the neutralization washing step, it is important to remove the residual organic peracid together with the neutralization and removal of the organic acid. In order to stably operate the subsequent low boiling point component removing step, the residual organic peracid content in the neutralization upper layer liquid is repeatedly neutralized and washed with water until it becomes 0.1% or less, preferably 0.01% or less. There is a need. Therefore, when washing with neutralized water in a continuous manner, a multi-stage method is used, but if the number of steps is usually 3 to 5, the organic peracid concentration can be lowered to a specified value or less.

In the case of a multi-stage system, it is preferable to use complete washing with water or use an aqueous solution of about 1% at most in the final stage. This is because when the bottom liquid after removing low-boiling components is used as a product as it is, alkali metals are mixed into the product and affect the quality. This is also the case when the neutralization is repeated in a batch. In the case of continuous neutralization water washing, it is no problem to use the lower layer water in the countercurrent type for pre-neutralization, and it is more economical.

The amount of alkali used for the neutralization water washing is 0. 1 in an equivalent ratio to the total amount of the organic peracid and the organic acid in the reaction crude liquid.
The amount is preferably 5 to 3 times, preferably 1.1 to 1.5 times, and it is not economical to increase the amount more than necessary. Further, if the equivalent ratio is lowered more than necessary, a large amount of water is required to remove the organic peracid or organic acid, which is not a good idea, and the loss of dissolution of the solvent in the lower layer water also increases. A thin film evaporator or the like is preferably used to remove low boiling point components from the reaction crude liquid which has been neutralized or washed with water.
The heating temperature at the time of removing low boiling point is 50 to 180 from the viewpoint of preventing polymerization.
C., preferably 60 to 100.degree. C. The pressure can be arbitrarily selected depending on the physical properties of the low boiling point component, but it is common to operate under reduced pressure in relation to the heating temperature. If the first low boiling point does not sufficiently concentrate, perform the second low boiling point again. This step completely removes the remaining low-boiling point component, and is performed in the same manner as the first deboiling step, but it is generally performed under a high vacuum by further increasing the pressure reduction degree.

[0044]

INDUSTRIAL APPLICABILITY Since the novel polymer of the present invention has an epoxy group in its side chain, it can be used as an initiator which produces a cation by light or heat, or an epoxy curing agent such as acid anhydride, phenol or amine. It is a substance that can be used by reacting and is useful in various fields. Further, the novel polymer of the present invention has an epoxy group having a reactivity different from that of the glycidyl group, and is a useful substance as a resin for paints and a resin for adhesives.

Examples of the present invention will be shown below.

[0046]

[Synthesis Example 1] To a flask equipped with a stirrer, an air introduction tube and a dropping funnel, 300 g of toluene and 14 g of benzyltriethylammonium chloride as a catalyst are placed, and the temperature is set to 80 ° C.
Heated to. Also, 1,2-epoxy-9-decene 20
0 g, methacrylic acid 112 g and p-methoxypheno-
0.1 g of the mixed solution was placed in a dropping funnel and added dropwise to the previous flask at a reaction temperature of 80 ° C. for 10 hours for reaction.
The reaction was terminated when the conversion of epoxide was 95%, and pure water was added to 200
The resulting organic layer was concentrated by a thin film evaporator to obtain 310 g of an unsaturated carboxylic acid ester composition having a vinyl group.

Oxirane oxygen concentration (%) 0.54 Acid value (mgKOH / g) 15.4

[0048]

[Synthesis Example 2] In a flask equipped with a stirrer, a nitrogen gas introducing tube and a cooling tube, 67 g of xylene and perbutyl Z2.5 were added.
g was taken and heated to 110 to 120 ° C. Under a nitrogen atmosphere, a mixture of the following monomers and an initiator was added dropwise thereto over 3 hours, and the mixture was further reacted for 7 hours to obtain 165 g of a target copolymer solution.

Synthesis Example 1 Synthetic product 50 g Methyl methacrylate 38 g Ethylhexyl acrylate 12 g Perbutyl O 2.5 g The obtained copolymer solution had a number average molecular weight of 7500 and an iodine value of 31.1 g / It was a transparent liquid with 100 g and a solid content of 61%.

[0050]

[Synthesis Example 3] 130 g (1.0 mol) of 2-hydroxyethyl methacrylate was placed in a jacketed 2 liter reactor equipped with a condenser, a dropping funnel and a nitrogen gas introducing tube.
4-vinylcyclohexene-1-oxide 372 g
(3.0 mol) was charged. Subsequently, 3.6 g of BF ₃ ether was added dropwise as a 10% ethyl acetate solution over 2 hours for reaction. During the dropping, the inside of the system was kept at 50 ° C. After completion of the dropwise addition, when analyzed by gas chromatography,
It was confirmed that 4-vinylcyclohexene-1-oxide had almost disappeared.

Subsequently, 480 g of ethyl acetate was added to the reaction crude liquid and washed twice with 500 g of pure water to obtain 958 g of an ethyl acetate solution having a solid content of 46.3%. The 2-hydroxyethyl methacrylate contained in the obtained ethyl acetate solution was
It was 2.1% by gas chromatography. Further, the obtained ethyl acetate layer was concentrated by a thin film evaporator,
Unsaturated carboxylic acid ester composition having vinyl group 44
0 g was obtained. Gel permeation chromatography-
As a result of the analysis, 2-hydroxyethyl methacrylate without addition of 4-vinylcyclohexene-1-oxide (n = 0), one added (n = 1), two added (n = 2) ,. ． ． It was a mixture with a distribution of. MN = 564 (polystyrene conversion), MW / MN =
It was 1.35. ^From the result of ¹ H-NMR spectrum, the average number of moles of 4-vinylcyclohexene-1-oxide added to 2-hydroxyethyl methacrylate was about 3.7 moles.

[0052]

[Synthesis Example 4] 70 g of xylene and 3 g of perbutyl Z were placed in a flask equipped with a stirrer, a nitrogen gas introducing tube and a cooling tube, and the mixture was heated and stirred at 110 to 120 ° C. While maintaining this reaction temperature, a mixture of the following monomers and an initiator was added dropwise under a nitrogen atmosphere over 3 hours, and the mixture was further reacted for 10 hours to obtain 168 g of a target polymer xylene solution.

Synthesis Example 3 Synthetic product 50 g Styrene 50 g Perbutyl O 2.5 g This has a number average molecular weight of 5600 and an iodine value of 46.9 g / 1.
It was a transparent liquid with 00 g and a solid content of 59%.

[0054]

[Synthesis Example 5] 70 g of xylene and perbutyl Z were placed in a flask equipped with a stirrer, a nitrogen gas introducing tube and a cooling tube.
3.0 g was taken and heated to 120 ° C. Under a nitrogen atmosphere, a mixture of the following monomers and an initiator was added dropwise thereto over 3 hours, and the mixture was further reacted for 3 hours to obtain 167 g of a target copolymer solution.

Cyclic olefin-containing methacrylate [A] ^* 100 g Perbutyl O 3 g The obtained copolymer solution was transparent with a number average molecular weight of 3500, an iodine value of 83.0 g / 100 g and a solid content of 62%. It was a liquid.

* The cyclic olefin-containing methacrylate [A] has n = 0 in the general formula III.

[0057]

[Synthesis Example 6] 70 g of xylene and 0.5 parts of perbutyl Z were placed in a flask equipped with a stirrer, a nitrogen gas introducing tube and a cooling tube.
g was taken and heated to 100 ° C. To this, under a nitrogen atmosphere, a mixture of the following monomers and an initiator was added dropwise over 2 hours, and the mixture was further reacted for 5 hours to obtain the target copolymer solution 1
68 g were obtained.

Cyclic olefin-containing acrylate [B] ^** 50 g Methyl methacrylate 38 g 2-Ethylhexyl acrylate 2 g Styrene 10 g Perbutyl O 2.0 g The obtained copolymer solution had a number average molecular weight. It was a transparent liquid of 8000, iodine value 45.0 g / 100 g, and solid content 60%.

** The cyclic olefin-containing acrylate [B] has the general formula II of n = 0.

..

[Synthesis Example 7] 70 g of xylene and perbutyl Z3.0 were placed in a flask equipped with a stirrer, a nitrogen gas introducing tube and a cooling tube.
g, and heated to 120 ° C. Under a nitrogen atmosphere, a mixture of the following monomers and an initiator was added dropwise thereto over 3 hours, and the mixture was further reacted for 3 hours to obtain the target copolymer solution 1
69 g were obtained.

Cyclic olefin-containing methacrylate [C] ^*** 50 g Methyl methacrylate 38 g 2-Ethylhexyl acrylate 2 g Styrene 10 g Perbutyl O 3.0 g The resulting copolymer solution had a number average. It was a transparent liquid having a molecular weight of 4000, an iodine value of 25.4 g / 100 g, and a solid content of 60%.

*** The cyclic olefin-containing methacrylate [C] has n = 1 (average) in the general formula III.

[0063]

Example 1 150 g of the vinyl group-containing polymer solution obtained in Synthesis Example 2 was placed in a jacketed 2 liter reactor equipped with a condenser, a peracetic acid charging port, and a nitrogen inlet tube.
2-ethylhexyl sodium tripolyphosphate 0.02
50 g of a solution of ethyl peracetate in which g was dissolved (concentration of peracetic acid: 30%) was added dropwise over about 1 hour while maintaining the reaction temperature at 50 ° C., followed by aging for 8 hours for epoxidation. Next, 200 g of pure water was added, the mixture was stirred for 30 minutes, and then allowed to stand at 50 ° C. After 30 minutes, the separated lower layer was gradually extracted. Next, 100 g of ethyl acetate was added, and 250 g of pure water was further added.
After stirring for 30 minutes and standing still (50 ° C.) for 30 minutes, the lower layer was extracted. Further, 200 g of pure water was added and the mixture was stirred at 50 ° C for 30 minutes. Then, the mixture was left standing for 30 minutes at 50 ° C., and the lower layer was extracted.
The obtained organic layer was concentrated to obtain 94 g of a polymer having a desired epoxy group.

The properties were as follows:

Oxirane oxygen concentration (%) 2.96 Acid value (mgKOH / g) 2.2

[0066]

Example 2 150 g of the vinyl group-containing polymer solution obtained in Synthesis Example 4 was charged into a jacketed 2 liter reactor equipped with a condenser, a peracetic acid charging port, and a nitrogen introducing tube. To this, 80 g of peracetic acid (30%, ethyl acetate solution)
2-ethylhexyl sodium tripolyphosphate 0.0
A peracetic acid solution in which 4 g was added and dissolved was added dropwise over about 4 hours while maintaining the reaction temperature of 50 ° C., and the mixture was aged for 5 hours for epoxidation. Next, 250 g of pure water was added, the mixture was stirred for 30 minutes, and then allowed to stand at 50 ° C. After 30 minutes, the separated lower layer was gradually extracted. Next, 100 g of ethyl acetate was added, 300 g of pure water was added, and the mixture was stirred for 30 minutes and allowed to stand (50 ° C.) for 30 minutes to extract the lower layer. Further, add 300 g of pure water to 50 ° C
It was stirred for 30 minutes. Then, the mixture was allowed to stand at 50 ° C. for 30 minutes and the lower layer was extracted to obtain 252 g of a polymer solution having an epoxy group with a solid content of 36.7%.

The properties were as follows:

APHA 10 Oxirane oxygen concentration (%) 1.70 Acid value (mgKOH / g) 0.4 Viscosity (cp / 25 ° C.) 2100

[0069]

Example 3 150 g of the vinyl group-containing polymer solution obtained in Synthesis Example 5 was placed in a jacketed 2 liter reactor equipped with a condenser, a peracetic acid charging port, and a nitrogen introducing tube.
2-Ethylhexyl sodium tripolyphosphate 0.06
130 g (peracetic acid concentration 30%) of ethyl acetate solution in which g was dissolved was added dropwise to carry out epoxidation in the same manner as in Example 2 to obtain 285 g of a polymer solution having an epoxy group with a solid content of 35.0%. It was The properties were as follows.

APHA 20 Oxirane oxygen concentration (%) 2.54 Acid value (mgKOH / g) 0.6 Viscosity (cp / 25 ° C.) 1600

[0071]

Example 4 150 g of the vinyl group-containing polymer solution obtained in Synthesis Example 6 was placed in a jacketed 2 liter reactor equipped with a condenser, a peracetic acid charging port, and a nitrogen inlet tube.
2-Ethylhexyl sodium tripolyphosphate 0.03
70 g of an ethyl peracetate solution in which g was dissolved (concentration of peracetic acid: 30%) was added dropwise to carry out epoxidation in the same manner as in Example 2 to obtain 234 g of a polymer solution having an epoxy group with a solid content of 40.1%. It was

The properties were as follows:

APHA 15 Oxirane oxygen concentration (%) 1.68 Acid value (mgKOH / g) 0.3 Viscosity (cp / 25 ° C.) 3500

[0074]

Example 6 150 g of the vinyl group-containing polymer solution obtained in Synthesis Example 7 was placed in a jacketed 2 liter reactor equipped with a condenser, a peracetic acid charging port, and a nitrogen inlet tube.
2-ethylhexyl sodium tripolyphosphate 0.02
40 g of an ethyl peracetate solution in which g was dissolved (concentration of peracetic acid: 30%) was added dropwise to carry out epoxidation in the same manner as in Example 2 to obtain 192 g of a polymer solution having an epoxy group having a solid content of 47.8%. It was

The properties were as follows:

APHA 35 Oxirane oxygen concentration (%) 1.17 Acid value (mgKOH / g) 1.1 Viscosity (cp / 25 ° C.) 3200

Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display area C08F 220/68 MMG 7242-4J 299/02 MRT 7442-4J

Claims (19)

[Claims] 1. The following general formula 1 (I) << R < ¹ >, R < ² >, R < ³ >, Ra, and Rb can be simultaneously replaced by a hydrogen atom or an alkyl group generally containing 1 to 9 carbon atoms for each group. c is 4-8
Of the novel polymer having a cyclic olefin obtained by polymerizing the composition (A) represented by Production method. 2. At least one vinyl monomer selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, and (meth) acrylic acid ester monomers. 1% by weight of the composition represented by Chemical Formula 1
A process for producing a novel polymer having an epoxy group, which is obtained by epoxidizing a novel polymer having a cyclic olefin copolymerized by 99% by weight. 3. A vinyl obtained by reacting a compound having one or more vinyl groups and one epoxy group in one molecule with either an unsaturated carboxylic acid or an unsaturated carboxylic acid ester having a hydroxyl group. A process for producing a novel polymer having an epoxy group, which is obtained by epoxidizing a vinyl group-containing polymer obtained by polymerizing a group-containing unsaturated carboxylic acid ester composition (B). 4. At least one vinyl monomer 99 to selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, and (meth) acrylic acid ester monomers. Obtained by reacting a compound having one or more vinyl groups and one epoxy group in one molecule with one of unsaturated carboxylic acid or unsaturated carboxylic acid ester having a hydroxyl group per 1% by weight. A process for producing a novel polymer having an epoxy group, which is obtained by epoxidizing a polymer having a vinyl group, which is obtained by copolymerizing 1 to 99% by weight of an unsaturated carboxylic acid ester composition having a vinyl group. 5. A part or all of the composition represented by the general formula (I) is represented by the general formula (2) The method for producing a novel polymer having an epoxy group according to claim 1, which is a composition represented by the formula (1). 6. A part or all of the composition represented by the general formula (I) is represented by the general formula (3): The method for producing a novel polymer having an epoxy group according to claim 1, which is a composition represented by the formula (1). 7. A novel epoxy group-containing compound according to claim 3, wherein the compound having one or more vinyl groups and one epoxy group in one molecule is B which is 4-vinylcyclohexene-1-oxide. Method for producing polymer. 8. A compound having one or more vinyl groups and one epoxy group in one molecule is 5-vinylcyclo [2.
2.1] A method for producing a novel polymer having an epoxy group according to claim 3 or 4, which comprises B which is hept-2-ene-2-oxide. 9. A process for producing a novel polymer having an epoxy group according to claim 3 or 4, wherein the compound having one or more vinyl groups and one epoxy group in one molecule is B which is limonene monoxide. 10. A compound having one or more vinyl group and one epoxy group in one molecule is represented by the following general formula (IV): The method for producing a novel polymer having an epoxy group according to claim 3 or 4, which comprises B which is a compound represented by << n0 is an integer of 0 to 30 >>. 11. A compound having one or more vinyl group and one epoxy group in one molecule is represented by the following general formula (V): << however, n1 and n2 are integers from 0 to 30 >>, which is a compound represented by B, and a process for producing a novel polymer having an epoxy group according to claim 3 or 4. 12. A compound having at least one vinyl group and one epoxy group in one molecule is represented by the following general formula (VI): A method for producing a novel polymer having an epoxy group according to claim 3 or 4, which is a compound represented by << Ph is a substituted phenyl group >>. 13. The method for producing a novel polymer having an epoxy group according to claim 3, wherein the unsaturated carboxylic acid is B which is (meth) acrylic acid. 14. An unsaturated carboxylic acid ester having a hydroxyl group is represented by the following general formula (VII) CH ₂ ═CR ¹ CO (O (CR ² R ³ ) _m ) _n OH (VII) << where m Is a compound represented by an integer of 1 to 10>, The process for producing a novel polymer having an epoxy group according to claim 3 or 4. 15. An unsaturated carboxylic acid ester having a hydroxyl group is represented by the following general formula (VIII) CH ₂ ═CR ¹ COOCH ₂ CH ₂ (OCO (CH ₂ ) ₅ ) _m OH (VIII) A method for producing a novel polymer having an epoxy group according to claim 3 or 4, which is a compound. 16. An unsaturated carboxylic acid ester having a hydroxyl group is represented by the following general formula (IX) R ⁰ OCOCH═CHCO (O (CR ² R ³ ) _m1 ) _m2 OH (IX) << where m1, The method for producing a novel polymer having an epoxy group according to claim 3 or 4, wherein m2 is an integer of 1 to 10 and R ⁰ is a compound represented by an organic compound residue. 17. An unsaturated carboxylic acid ester having a hydroxyl group is represented by the following general formula (X) R ⁰ OCOCH═CHCOOCH ₂ CH ₂ (OCO (CH ₂ ) ₅ ) _m OH (X) A process for producing a novel polymer having an epoxy group according to claim 3 or 4, which is a compound. 18. The method according to claim 1, wherein the epoxidizing agent is a peracid. 19. The method according to claim 1, 2 or 3 or 4, wherein the epoxidizing agent is peracetic acid or hydrogen peroxide.