JPS624049B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel method for producing acidic oligomers. It is known from US Pat. No. 3,084,147 that a yellow resin with a high concentration of unsaturated bonds can be obtained by heating dicyclopentadiene at 220 to 300°C. , β-unsaturated carboxylic acid or its anhydride to introduce a polar group into the polydicyclopentadiene (for example, Japanese Patent Publication No. 49-4552). Another method for introducing polar groups into polydicyclopentadiene is to combine dicyclopentadiene with a polymerizable monomer having a polar group such as α,β-unsaturated carboxylic acid, unsaturated alcohol, or vinylphenol before starting polymerization. This method is a method of mixing and thermally copolymerizing this mixture at 200 to 350° C., and is a method widely adopted in the industry along with the above-mentioned method. The purpose of introducing polar groups into hydrocarbon resins such as polydicyclopentadiene is to improve compatibility with polymeric substances such as rubber and synthetic resins, and to improve pigment dispersibility, fluidity, adhesion, etc. The point is to improve characteristics that are difficult to demonstrate. Therefore, the object of the present invention is to produce oligomers that are highly compatible with polymeric substances such as rubber and synthetic resins and have good solubility in various organic solvents by an industrially easy method and in high yield. The goal is to provide a way to do so. As a result of extensive research into the method for producing oligomers suitable for the above purpose, the present inventors discovered that mono(dihydrodicyclopentadienyl) maleate and/or mono(dihydrodicyclopentadienyl) fumarate and di(dihydrodicyclopentadienyl) maleate and/or mono(dihydrodicyclopentadienyl) fumarate An acidic oligomer is obtained by thermally polymerizing dicyclopentadienyl) maleate and/or di(dihydrodicyclopentadienyl) fumarate and optionally a maleic acid derivative at a specific temperature range without using a catalyst. The present invention was based on the discovery that the present invention is possible. The present invention relates to mono(dihydrodicyclopentadienyl) maleate and/or mono(dihydrodicyclopentadienyl) fumarate represented by formula (1) and di(dihydrodicyclopentadienyl) represented by formula (2). (enyl) maleate and/or di(dihydrodicyclopentadienyl) fumarate and optionally a maleic acid derivative represented by formula (3) or formula (4) are heated to 220 to 300°C in the absence of a catalyst. The present invention relates to a method for producing acidic oligomers by polymerizing them. Formula (1)

[Formula] Formula (2) Formula (3)

[Formula] Formula (4) R ₁ OOCCH=CHCOOH ₂ (However, R ₁ and R ₂ represent hydrogen or an alkyl group) The above mono(dihydrodicyclopentadienyl) maleate used in the present invention is, for example, 5 or 6-hydroxy-3a,4,5,6,7,
It can be obtained by ring-opening esterification reaction between 7a-hexahydro-4,7-methanoindene (hydroxylated dicyclopentadienine) and maleic anhydride, and also by acid addition reaction between dicyclopentadiene and maleic acid. Obtainable. The above mono(dihydrodicyclopentadienyl) fumarate can be obtained by fumarizing the above mono(dihydrodicyclopentadienyl) maleate by a known method, and there are no restrictions on the conditions for fumarization. . Further, the above di(dihydrodicyclopentadienyl) maleate can be obtained, for example, by esterifying hydroxylated dicyclopentadiene and maleic anhydride or maleic acid at a ratio of 2 moles to 1 mole, It can also be obtained by transesterification of hydroxylated dicyclopentadiene and dialkyl maleate. In addition, during these reactions, the cis-type maleoyl group may be isomerized to the trans-type fumaroyl group, but the presence or absence of this isomer and the mixing ratio of the isomers do not affect the present invention in any way. . The above di(dihydrodicyclopentadienyl)
Fuyate can be obtained by an esterification reaction between hydroxylated dicyclopentadiene and fumaric acid. In addition, maleic acid derivatives include maleic anhydride, maleic acid, monobutyl maleate, dimethyl maleate, diethyl maleate, fumaric acid,
Diethyl fumarate and the like can be used. The above-mentioned maleate, fumarate, and optionally maleic acid derivatives may be produced separately and polymerized, but a mixture obtained from these raw materials may be reacted at 220 to 220 °C in the absence of a catalyst. Polymerization may be carried out by heating to 300°C. In the present invention, the polymerization temperature is limited to a range of 220 to 300°C, preferably a range of 230 to 280°C. 220
At temperatures below 300°C, the polymerization reaction does not proceed smoothly, often producing only a waxy low-molecular-weight product, while at temperatures above 300°C, organisms are markedly colored and an insoluble gel is formed, making it unsuitable. . It is desirable to monitor the polymerization reaction by measuring the softening point of the product. During the polymerization reaction, radical catalysts such as peroxides or ionic catalysts such as organometallic compounds are unnecessary. The reaction time is preferably 0.5 to 20 hours, but is not particularly limited. The polymerization reaction proceeds without using a solvent, and the raw material monomers mono(dihydrocyclopentadienyl) maleate and/or mono(dihydrodicyclopentadienyl) fumarate and di(dihydrodicyclopentadienyl) maleate and Since the boiling point of di(dihydrodicyclopentadienyl) fumarate is 250°C or higher, the polymerization reaction can be carried out even under atmospheric pressure. If necessary, the reaction may be carried out using a solvent such as toluene or methyl ethyl ketone in a closed container under self-generated pressure depending on the polymerization reaction temperature. During the polymerization reaction, it is desirable to purge the reaction system with an inert gas such as nitrogen in order to prevent coloring and decomposition of the acidic oligomers produced. After the polymerization reaction is completed, unreacted substances, low molecular weight substances, and solvents are removed by distillation or other polymer purification methods.
The desired acidic oligomer can be obtained. The acidic oligomer thus obtained generally has the following properties. That is, the number average molecular weight is 450-2000, the softening point is 50-200℃, and the iodination is 60.
~134, but does not necessarily have to be limited to these ranges. In addition, the acid value and solubility of the acidic oligomer in solvents can be adjusted arbitrarily by changing the blending ratio of raw material monomers. It is possible to manufacture products that are soluble in non-polar solvents such as. This is one of the remarkable features of the present invention. The reason why the acidic oligomer of the present invention exhibits good compatibility with highly polar rubbers and synthetic resins is the carboxyl group contained in mono(dihydrodicyclopentadienyl) maleate and/or mono(dihydrodicyclopentadienyl) fumarate. This is thought to be due to the ester bond and the ester bond of di(dihydrodicyclopentadienyl) maleate and/or di(dihydrodicyclopentadienyl) fumarate. Furthermore, the reason why the acidic oligomer obtained by the production method of the present invention does not form a gel during polymerization and is obtained in high yield is thought to be because it is thermally polymerized in a specific temperature range in the absence of a catalyst. In the presence of radical catalysts, it is difficult to obtain oligomers because gels are formed during polymerization. Furthermore, the acidic oligomer obtained by the production method of the present invention is presumed to contain ester bonds not only in the side chain but also in the main chain, and in this respect, it is different from conventionally known hydrocarbon resins and modified hydrocarbon resins. It is essentially different. The acidic oligomer obtained as described above can be used for various purposes. For example, it is useful as a compounding agent for highly polar rubbers such as nitrile rubber, paints, printing inks, pressure-sensitive adhesives, adhesives, etc. It can also be used as a polycarboxylic acid as a raw material for various synthetic resins. The present invention will be explained below with reference to Examples, but the present invention is not limited thereto. In addition, the properties of the oligomers obtained in the following examples were measured by the following method. Hue: The hue of the molten oligomer was measured by the Gardner method. Softening point: Measured by the ring and ball method according to JISK2531. Acid value: Measured according to JIS K 0070. Iodine value: Measured according to JIS K 0070. Number average molecular weight: Measured by vapor pressure equilibrium method using acetone as a solvent. Solubility in solvent: A solvent was added so that the oligomer concentration was 30% by weight, and the mixture was shaken at 25°C for 30 minutes to determine the solubility of the oligomer. Mono(dihydrodicyclopentadienyl)maleate and the like used in Examples 1 to 5 were obtained by the following manufacturing method. 1 Production of mono(dihydrodicyclopentadienyl)maleate 98 parts of maleic anhydride (parts by weight, same hereinafter) and hydroxylated dicyclopentadiene (sidecanol manufactured by Hitachi Chemical Co., Ltd.) were placed in a reactor equipped with a stirrer and a reflux condenser. Add 150 parts and react at 120℃ for 3 hours to form mono(dihydrodicyclopentadienyl).
Got maleate. The acid value of this product was 224. 2. Production of mono(dihydrodicyclopentadienyl)furamate The mono(dihydrodicyclopentadienyl) maleate obtained above was heated at 180°C for 7 hours in the same reaction vessel as above to fumarate, and mono(dihydrodicyclopentadienyl) A mixture containing dicyclopentadienyl) fumarate as the main component was obtained. When the fumarization rate of this product was measured, it was 81%. 3 Production of di(dihydrodicyclopentadienyl) maleate 98 parts of maleic anhydride and 300 parts of hydroxylated dicyclopentadiene (sidecanol manufactured by Hitachi Chemical Co., Ltd.) were placed in a reaction vessel equipped with a stirrer, a partial condensation tube, and a nitrogen introduction tube. and heated at 120°C for 2 hours at 175°C under a nitrogen stream while removing by-product water by fractional distillation.
The reaction was carried out at ℃ for 15 hours. The acid value of the product is 16.4, which suggests that the purity of the compound represented by formula (2) is approximately 94 mol%. Although the fumarization rate of this product was 62%, this product will be referred to as di(dihydrodicyclopentadienyl) maleate for convenience. 4 Production of di(dihydrodicyclopentadienyl) fumarate Put 116 parts of fumaric acid and 300 parts of hydroxylated dicyclopentadiene (Sidecanol, manufactured by Hitachi Chemical Co., Ltd.) into a reaction vessel equipped with a stirrer, a partial condensation tube, and a nitrogen introduction tube. , at 150℃ for 1 hour while removing by-product water by fractional distillation under a nitrogen stream, then at 180℃
The mixture was allowed to react for 15 hours. The acid value of the product is 17.5, which suggests that the purity of di(dihydrodicyclopentadienyl) fumarate is approximately 94 mol%. Example 1 124 g of mono(dihydrodicyclopentadienyl) maleate and 380 g of di(dihydrodicyclopentadienyl) maleate were charged into a stainless steel autoclave with an internal volume of 1, the autoclave was sealed, and the inside of the container was purged with nitrogen. . Next, the autoclave was heated to 250°C and reacted for 5 hours with shaking, then cooled to 160°C, the reactant was taken out, and transferred to a four-necked flask equipped with a stirrer, thermometer, and nitrogen inlet tube. The temperature was raised to 180°C, and low molecular weight components were distilled off under reduced pressure in a nitrogen stream to obtain an acidic oligomer. The properties of this oligomer are shown in Table 1. Example 2 Mono(dihydrodicyclopentadienyl)maleate 248 was placed in an autoclave similar to Example 1.
g, di(dihydrodicyclopentadienyl) fumarate, 228 g, and toluene 200 g, and reacted at 260°C for 5 hours in the same manner as in Example 1. The autoclave was then cooled to room temperature, and the reaction solution was added to Example 1.
The toluene was distilled off at 140°C, then the temperature was raised to 180°C, and the low molecular weight components were distilled off under reduced pressure under a nitrogen stream to obtain acidic oligomers with the properties shown in Table 1. Obtained. Example 3 In an autoclave similar to Example 1, 25 g of mono(dihydrodicyclopentadienyl)maleate,
380 g of di(dihydrodicyclopentadienyl) maleate and 23 g of maleic acid were charged and reacted at 240°C for 7 hours in the same manner as in Example 1, then cooled to 160°C and the reaction product was taken out. Similar 1
The mixture was transferred to a four-necked flask, heated to 180°C, and low molecular weight components were distilled off under reduced pressure under a nitrogen stream to obtain acidic oligomers having the properties shown in Table 1. Example 4 496 g of mono(dihydrodicyclopentadienyl) maleate and di(dihydrodicyclopentadienyl) maleate were placed in a four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen inlet tube.
228g was charged, heated while stirring under a nitrogen stream, reacted at 210℃ for 3 hours, and then further heated to 250℃.
The temperature was raised to 1, and the reaction was continued at this temperature for 4 hours. after that
The mixture was cooled to 180°C, the reflux condenser was replaced with a vacuum distillation receiver, and low molecular weight components were distilled off under reduced pressure. Table 1 shows the properties of the acidic oligomer obtained. Example 5 Mono(dihydrodicyclopentadienyl)maleate 248 was placed in an autoclave similar to Example 1.
g, 248 g of di(dihydrodicyclopentadienyl) maleate, 23 g of dibutyl maleate, and 150 g of xylene were reacted in the same manner as in Example 1 at 250°C for 4 hours, then cooled to room temperature, and the reaction solution was taken out. The mixture was transferred to a four-neck flask similar to that used in Example 1, and the same post-treatment as shown in Example 2 was performed to obtain an acidic oligomer. The properties of this product are shown in Table 1. Example 6 Dicyclopentadiene was added to the same apparatus as in Example 4.
Prepare 396g, maleic anhydride 294g, and water 54g and make 80
After keeping the temperature at 130°C for 1 hour, the temperature was raised to 130°C over 1 hour, and the temperature was kept at this temperature for 3 hours. 50 samples for analysis
After the sample was collected, the temperature was raised to 245°C over 3 hours, the reaction was continued at this temperature for 6 hours, and then cooled to 180°C, and the same operation as in Example 4 was carried out to distill off low molecular weight components. Table 1 shows the properties of the acidic oligomer obtained. When the above analysis sample was analyzed, unreacted maleic acid was found to be 3.6% by weight, but unreacted dicyclopentadiene was not detected. Therefore, the above analytical sample contained 84.6% by weight of mono(dihydrodicyclopentadienyl)maleate and 11.8% by weight of di(dihydrodicyclopentadienyl)maleate.
Contains weight%.

[Table] *○ mark: Good solubility and forms a transparent solution.
x mark: Comparative example that does not dissolve completely 1 After reacting in the same manner as in Example 1 except that the reaction temperature was 200°C, the same post-treatment as in Example 1 was carried out to distill off low molecular weight components. When the residue was cooled to room temperature, the residue did not solidify and appeared as a viscous liquid. The number average molecular weight of this product was 310, and virtually no polymerization occurred. Comparative Example 2 In the same apparatus as in Example 1, 248 g of mono(dihydrodicyclopentadienyl) maleate and 228 g of di(dihydrodicyclopentadienyl) fumarate were added.
g, dicumyl peroxide 4.8g, toluene 200g
g was charged and reacted at 180°C for 5 hours. When the inside of the autoclave was examined after cooling, a large amount of gel was formed, and soluble oligomers like those in Examples were not obtained. Reference Example To ensure compatibility with various polymeric substances, the obtained oligomer and polymeric substance were mixed at a weight ratio of 1/1, and dissolved in benzene to create a 10% by weight solution. This solution was applied onto a transparent glass plate, and after drying the solvent, the turbidity of the film was visually determined. The results are shown in Table 2. The polymer substances used are as follows. Ethylene-vinyl acetate copolymer: Evaflex 210, manufactured by Mitsui Polychemicals Vinyl chloride-vinyl acetate copolymer: Denka Vinyl 1000MT, manufactured by Denki Kagaku Kogyo ₂ Natural rubber: Mooney viscosity 55 Butadiene-acrylonitrile rubber: Naipol 1432J, manufactured by Nippon Zeon Epoxy resin : Ciel Chemical Epicote 828

[Table] The acidic oligomer obtained by the production method of the present invention is useful as a modifier for rubbers and synthetic resins, especially highly polar rubbers and synthetic resins, and rosin, rosin ester, polyterpene, etc. are currently used. It can be used in various fields such as rubber, paints, printing inks, pressure sensitive adhesives, adhesives, etc. Furthermore, the acidic oligomer obtained by the production method of the present invention can be used as a polycarboxylic acid, for example, as a raw material for synthetic resins such as alkyd resins, polyester resins, and polyamide resins, or as a blending material. It can be applied to an extremely wide range of fields.

Claims (1)

[Scope of Claims] 1 Mono(dihydrodicyclopentadienyl) maleate and/or mono(dihydrodicyclopentadienyl) fumarate represented by formula (1) and the formula
Di(dihydrodicyclopentadienyl) maleate and/or di(dihydrodicyclopentadienyl) fumarate represented by (2) and, if necessary, a maleic acid derivative represented by formula (3) or formula (4); A method for producing acidic oligomers, which comprises polymerizing by heating to 220 to 300°C in the absence of a catalyst. Formula (1) [Formula] Formula (2) Formula (3) [Formula] Formula (4) R ₁ OOCCH=CHCOOR ₂ (However, R ₁ and R ₂ represent hydrogen or an alkyl group)