JPS625162B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel method for producing acidic oligomers. More specifically, the present invention relates to a method for producing an acidic oligomer obtained by thermally polymerizing mono(dihydrodicyclopentadienyl) maleate and/or mono(dihydrodicyclopentadienyl) fumarate represented by formula (1). It is known from U.S. 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, and the polydicyclopentadiene obtained has α and β- It is also known to introduce a polar group into the polydicyclopentadiene by reacting an unsaturated carboxylic acid or its anhydride (for example, Japanese Patent Publication No. 49-1989).
Publication No. 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 the start of 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 the compatibility with polymeric substances such as rubber and synthetic resins, and to improve the pigment dispersibility, fluidity, and adhesion properties that hydrocarbon resins originally have. The point is to improve difficult-to-understand characteristics. Therefore, the first object of the present invention is to provide an oligomer that has excellent compatibility with polymeric substances such as rubber and synthetic resins and has good solubility in various organic solvents. The second objective is to provide a method for producing the oligomer in an industrially easy manner and in high yield. The present inventors have conducted extensive research into methods for producing oligomers suitable for the above purpose, and have found that mono(dihydrodicyclopentadienyl)maleate and/or
or mono(dihydrodicyclopentadienyl)
The inventors have discovered that an acidic oligomer that meets the first and second objectives described above can be obtained by thermally polymerizing fumarate at a specific temperature range without using a catalyst, leading to the present invention. The present invention is characterized in that mono(dihydrodicyclopentadienyl) maleate and/or mono(dihydrodicyclopentadienyl) fumarate are polymerized by heating to 220 to 300°C in the absence of a catalyst. Average molecular weight is 400-2000, softening point is
The present invention relates to a method for producing acidic oligomers having an iodine value of 60 to 102 at 50 to 180°C and soluble in ketone solvents, ester solvents, and monohydric alcohol solvents having 1 to 8 carbon atoms. In the present invention, the acidic oligomer is mono(dihydrodicyclopentadienyl) maleate and/or mono(dihydrodicyclopentadienyl) fumarate in the absence of a catalyst.
It is produced by heating to ℃ and polymerizing it. The acidic oligomers obtained by the production method of the present invention exhibit good compatibility with highly polar rubbers and synthetic resins, and are soluble in polar solvents such as mono(dihydrodicyclopentadienyl) maleate and/or Alternatively, it is considered that this is due to the carboxyl group of mono(dihydrodicyclopentadienyl) fumarate. In addition, the reason why this acidic oligomer does not form a gel during polymerization and can be obtained in high yield is thought to be because it is thermally polymerized in a specific temperature range in the absence of a catalyst. It is difficult to obtain oligomers due to the formation of gels. Furthermore, this acidic oligomer is presumed to contain an ester bond in its main chain, and in this respect is essentially different from conventionally known hydrocarbon resins and modified hydrocarbon resins. The mono(dihydrodicyclopentadienyl) maleate used in the present invention is, for example, 5- or 6-hydroxy-3a.4.5.6.7.7a-hexahydro-4.7-methanoindene (hydroxylated dicyclopentadiene). and maleic anhydride through a ring-opening esterification reaction. Alternatively, it can be obtained by an acid addition reaction between dicyclopentadiene and maleic acid. 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. . That is,
In the present invention, mono(dihydrodicyclopentadienyl) fumarate can be used in exactly the same manner as mono(dihydrodicyclopentadienyl) maleate. Next, the properties of the acidic oligomer obtained by the present invention will be explained. The number average molecular weight of the acidic oligomer is 400 to 2000, preferably 500 to 1500
It is. If the number average molecular weight is less than 400, it is unsuitable because it contains many low molecular weight components and produces a bad odor, and the product becomes waxy and has a non-uniform composition. It is unsuitable because its compatibility with synthetic resins and solubility in solvents decreases. The softening point of this acidic oligomer is 50-180°C, preferably 60-150°C. The reason why the softening point is limited to this range is the same as the reason for limiting the number average molecular weight described above. The acidic oligomer obtained by the production method of the present invention has an iodine value of 60 to 102, and if the iodine value is less than 60, the number of reactive unsaturated bonds decreases, so the effect of modifying rubber or synthetic resin becomes small. Furthermore, it is not suitable because it tends to form a gel during polymerization. On the other hand, the upper limit of the iodine value of 102 corresponds to the iodine value of the raw material monomers mono(dihydrodicyclopentadienyl) maleate and mono(dihydrodicyclopentadienyl) fumarate, and in the acidic oligomer of the present invention. Iodine above 102 is virtually unattainable. Furthermore, the acidic oligomer obtained by the present invention contains a ketone solvent, an ester solvent, and a carbon number 1.
It is soluble in monohydric alcohol solvents of ~8 and does not produce insoluble substances. Specific examples of these solvents include:
Examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, γ-valerolactone, benzyl acetate, methanol, ethanol, isopropanol, n-butanol, and 2-ethylhexanol. In particular, being soluble in methanol is one of the remarkable characteristics of the acidic oligomer obtained by the present invention. Next, in the method for producing acidic oligomers according to the present invention, the polymerization temperature is limited to a range of 220 to 300°C, more preferably a range of 230 to 280°C. When the polymerization temperature is lower than 220°C, it takes a long time to obtain an acidic oligomer of the desired molecular weight, and the reaction is not stable, so that only a wax-like low molecular weight product is often produced. On the other hand, temperatures exceeding 300°C are unsuitable because the product becomes significantly colored and forms an insoluble gel. No radical or non-radical catalyst is required during the polymerization reaction. The reaction time is preferably 0.5 to 20 hours, but is not particularly limited. In addition, the polymerization reaction proceeds without using a solvent, and the boiling point of mono(dihydrodicyclopentadienyl) maleate and/or mono(dihydrodicyclopentadienyl) fumarate, which is the raw material monomer, is 250.
Since the temperature is above 0.degree. C., the polymerization reaction can be carried out even under atmospheric pressure. If necessary, the reaction may be carried out using a solvent such as 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 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., and can also be used as a raw material for various synthetic resins as a polycarboxylic acid. 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 acidic 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 JIS K 2531. 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.
(Solvent: Acetone) 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. Example 1 500 g of mono(dihydrodicyclopentadienyl)maleate was charged into a stainless steel autoclave having an internal volume of 1, the autoclave was sealed, and the inside of the container was purged with nitrogen. Then autoclave
The mixture was heated to 250°C and reacted for 5 hours with shaking, then cooled to 150°C, the reaction product was taken out, transferred to a four-necked flask equipped with a stirrer, thermometer, and nitrogen inlet tube, and raised to 180°C. Low molecular weight components were distilled off under reduced pressure under a heated nitrogen stream to obtain an oligomer. The properties of this oligomer are shown in Table 1. Example 2 400 g of mono(dihydrodicyclopentadienyl)maleate was placed in the same autoclave as in Example 1.
and 200 g of methyl isobutyl ketone were charged and reacted at 240°C for 6 hours in the same manner as in Example 1. The autoclave was then cooled to room temperature, and the reaction solution was transferred to a four-necked flask in the same manner as in Example 1. ℃
Methyl isobutyl ketone was distilled off at 180
The temperature was raised to .degree. C., and low molecular weight components were distilled off under reduced pressure under a nitrogen stream to obtain oligomers having the properties shown in Table 1. Example 3 600 g of mono(dihydrodicyclobentadienyl) maleate was placed in a 14-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen inlet tube, and the temperature was raised while stirring under a nitrogen stream. 210
After reacting at ℃ for 3 hours, the temperature was further raised to 240℃,
The reaction was allowed to proceed at this temperature for 5 hours. After that, it was cooled to 180℃, and the reflux condenser was replaced with a vacuum distillation receiver.
Low molecular weight components were distilled off under reduced pressure. Table 1 shows the properties of the obtained oligomer.

【table】

[Table] *○ mark: Comparative example forming a transparent solution with good solubility 1 The reaction was carried out in the same manner as in Example 1 except that the reaction temperature was 200°C, and then the same treatment as in Example 1 was carried out to reduce the When the molecular weight components were distilled off and the residue was cooled to room temperature, the residue became cloudy and appeared in the form of a sticky slurry, and a transparent oligomer like that in Example 1 could not be obtained. The number average molecular weight of this thing is 290
, and virtually no polymerization occurs. Comparative Example 2 Into the same apparatus as in Example 1, 400 g of mono(dihydrodicyclopentadienyl) maleate, 4 g of dicumyl peroxide, and methyl isobutyl ketone were added.
200g 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 produced, and soluble oligomers like those in Examples were not obtained. Reference example: In order to evaluate the compatibility with various polymeric substances, the obtained oligomer and polymeric substance were mixed at a ratio of 1/1, and benzene/methyl ethyl ketone = 2/1.
to create a 10% solution. This solution was applied onto a transparent glass plate, and after drying the solvent, the turbidity of the film was visually determined. Table 2 shows the results.
Shown below. 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 Butadiene-acrylonitrile rubber: Nippor 1432J manufactured by Nippon Zeon Natural rubber: Mooney viscosity 55 Epoxy resin: Ciel Chemical Epicote 828

[Table] (Note) ○ mark: Good compatibility and no turbidity.
× mark: The coating film becomes extremely cloudy due to poor compatibility.
The acidic oligomer obtained by the present invention is particularly useful as a modifier for highly polar rubbers and synthetic resins, and can be used in fields where rosin, rosin ester, polyterpene, etc. are currently used, such as rubber, paints, and printing inks. , can be used in the fields of pressure sensitive adhesives, adhesives, etc. Furthermore, the acidic oligomer obtained by the present invention can be used as an alicyclic polycarboxylic acid, for example, as a synthetic raw material for synthetic resins such as alkyd resins, polyester resins, and polyamide resins, or as a blending material, and is extremely useful. It can be applied to a wide range of fields.

Claims (1)

[Claims] 1 Mono(dihydrodicyclopentadienyl) maleate and/or mono(dihydrodicyclopentadienyl) fumarate in the absence of a catalyst.
Characterized by polymerization by heating to 220-300℃, number average molecular weight 400-2000, softening point 50-180
°C, iodine value is 60-102, ketone solvent,
A method for producing an acidic oligomer soluble in an ester solvent and a monohydric alcohol solvent having 1 to 8 carbon atoms.