JPS6045630B2 - Oligomer manufacturing method - Google Patents

Description

[Detailed description of the invention] The present invention relates to a novel method for producing oligomers.

More specifically, the present invention relates to a method for producing an oligomer obtained by thermally polymerizing di(dihydrodicyclopentanenyl) maleate and/or di(dihydrodicyclopentanenyl) fumarate represented by formula (1).・・・
・(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 synchropentadiene at 220 to 300'C. It is also known to introduce a polar group into the polydicyclopentadiene by reacting an α,β monounsaturated carboxylic acid or its anhydride (for example, Japanese Patent Publication No. 49-455).

Another method for introducing polar groups into polydicyclopentadiene is to use syncropentadiene and a polymerizable monomer having a polar group, such as α, β monounsaturated carboxylic acid, or unsaturated alcohol vinylphenol vinyl ester, before starting polymerization. This method is a method in which the mixture is thermally copolymerized at 200 to 350° C., and this method is 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 at a high yield. The goal is to provide a way to do so.

As a result of intensive research into a method for producing oligomers suitable for the above purpose, the present inventors found that di(dihydrodicyclopentanenyl) maleate and/or di(dihydrodidiclopentadienyl) fumarate was The inventors have discovered that the above oligomer can be obtained by thermal polymerization without using a catalyst, leading to the present invention.

The present invention provides di(dihydrodicyclopentadienyl) maleate and/or di(dihydrodicyclopentadienyl) fumarate in the absence of a catalyst between 220 and 300'.
The number average molecular weight to be polymerized by heating to C is 500 to 200
01 Softening point is 50-180℃, iodine value is 75-134
The present invention relates to a method for producing oligomers soluble in aromatic hydrocarbon solvents, ketone solvents, and ester solvents.
The oligomer obtained by the production method of the present invention exhibits good compatibility with rubber and synthetic resins because molecules of di(dihydrodicyclopentadienyl) maleate and/or di(dihydrodicyclopentadienyl) fumarate This is thought to be due to the presence of an ester bond within. Furthermore, in the present invention, the oligomer does not form a gel during polymerization and is obtained in high yield, which is thought to be because the oligomer is thermally polymerized in a specific temperature range in the absence of a catalyst. For example, in the presence of a radical catalyst, It is difficult to obtain oligomers due to the formation of gels during polymerization. Furthermore, the oligomer obtained by the production method of the present invention is presumed to contain ester bonds not only in the side chains 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. Di(dihydrodidicyclopentadienyl) 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 or maleic acid in a ratio of 2 moles to 1 mole of the former to the latter. It can be obtained by carrying out an esterification reaction.

Alternatively, it can 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. . That is, in the present invention, di(dihydrodicyclopentadienyl) fumarate can be used in exactly the same manner as di(dihydrodicyclopentadienyl) maleate. Di(dihydrodicyclopentadienyl) fumarate can be obtained by an esterification reaction between hydroxylated dicyclopentadiene and fumaric acid. Next, the properties of the oligomer obtained by the production method of the present invention will be explained.

The number average molecular weight of the oligomer is 500 to 2000,
Preferably it is 550-1500. Number average molecular weight is 5
If it is less than 0, it is inappropriate because there are many low molecular weight components and a bad odor is generated, and the product has a viscous liquid state.
On the other hand, if the number average molecular weight exceeds 2000, it is unsuitable because the compatibility with rubbers, synthetic resins, etc. and the solubility in solvents decrease. The softening point of the oligomer is 50 to 180°C,
Preferably it is 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 iodine value of the oligomer obtained by the production method of the present invention is 75 to 134, and if the iodine value is less than 75, 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 134 corresponds to the iodine value of the raw material monomers di(dihydrodicyclopentadiel) maleate and di(dihydrodicyclopentadienyl) fumarate, and in the oligomer of the present invention, the upper limit is 134.
Iodine numbers above 34 are virtually unattainable. Furthermore, the oligomer obtained by the production method of the present invention is soluble in aromatic hydrocarbon solvents, ketone solvents and ester solvents, and does not produce insoluble substances.

Specific examples of these solvents include benzene, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cycloh7xanone, methyl acetate, ethyl acetate, r-valerolactone, and benzyl acetate. In the present invention, the polymerization temperature is 220-3
00'C, more preferably 230-2
A temperature within the range of 80'C is good. If the reaction temperature is lower than 220° C., it takes a long time to obtain an oligomafu with a desired molecular weight, and the reaction is not stable, so that only a viscous liquid low molecular weight product is often produced.

On the other hand, temperatures exceeding 300°C are unsuitable because the product becomes markedly colored and an insoluble gel is formed. No radical or non-radical catalyst is required during the polymerization reaction. The reaction time is preferably between 0.5 and 2 (b), but is not particularly limited. In addition, the polymerization reaction proceeds without using a solvent, and the boiling point of the raw material monomers di(dihydrodicyclopentadienyl) maleate and di(dihydrodicyclopentadiel) fumarate is 25
Since the temperature is 0°C or higher, the polymerization reaction can be carried out even under atmospheric pressure. If necessary, it may be carried out using a solvent such as toluene or xylene in a closed container under self-generated pressure based 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 oligomers produced. After the polymerization reaction is completed, unreacted substances, low molecular weight substances, and solvents can be removed by distillation or other polymer purification means to obtain the desired oligomer.

The oligomers obtained as described above can be used for various purposes. For example, it is extremely useful as a compounding agent for rubbers, paints, printing inks, pressure sensitive adhesives, adhesives, etc. 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 JIS K253l.

Iodine value: Measured according to JIS KOO7O. Number average molecular weight: Measured by vapor pressure equilibrium method. (Solvent: Acetone) Solubility in solvent: Oligomer concentration is 3% by volume.
The solution was stirred at 25°C for 3 minutes to determine the solubility of the oligomer.

Example 1 A stainless steel autoclave having an internal volume of 11 was charged with 500 Da of di(dihydrodicyclopentadienyl)maleate, 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 150°C, the reactant was taken out, and transferred to a 11-4-hole flask equipped with a stirrer, a thermometer, and a nitrogen inlet tube. The temperature was raised to 0.degree. C., and low molecular weight components were distilled off under reduced pressure in a nitrogen stream to obtain an oligomer. The properties of this oligomer are shown in Table 1. Example 2 400 y of di(dihydrodicyclopentadienyl) maleate and 20 y of xylene were placed in the same autoclave as in Example 1.
After reacting at 240°C for 5 hours in the same manner as in Example 1, the autoclave was cooled to room temperature, and the reaction solution was transferred to a 11-4-hole flask similar to Example 1.
Xylene was distilled off at .degree. C., then the temperature was raised to 180.degree. C., and low molecular weight components were distilled off under reduced pressure in a nitrogen stream to obtain oligomers with the properties shown in Table 1.

Example 3 600 y of di(dihydrodicyclopentadienyl) maleate was charged into a 11-4-hole flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube, and the temperature was raised to 230°C while stirring under a nitrogen stream. After reacting for 2 hours, the temperature was further raised to 245°C, and the reaction was continued at this temperature for 3 hours.

Thereafter, 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 obtained oligomer. Comparative Example 1 After the reaction was carried out in the same manner as in Example 1 except that the reaction temperature was changed to 200'C, the same post-treatment as in Example 1 was carried out to distill off low molecular weight components, and the residue was cooled to room temperature. However, the residue did not solidify and took on a viscous liquid form.

The number average molecular weight of this product was 430, and virtually no polymerization occurred. Comparative Example 2 400 y of di(dihydrodicyclopentadienyl) maleate, 4 d of dicumyl peroxide, and 200 y of xylene were charged into the same apparatus as in Example 1, 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 part and dissolved in benzene to prepare 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. The polymer substances used are as follows. Ethylene-vinyl acetate copolymer:
Evaflex 210 manufactured by Mitsui Polychemicals Vinyl chloride-vinyl acetate copolymer: Denka Vinyl 1000MT2 manufactured by Denki Kagaku Kogyo Natural rubber Ni Mooney viscosity 55 Styrene-isoprene block copolymer: Kaliflex TR-1107 manufactured by Ciel Chemical Epoxy resin: manufactured by Ciel Chemical Epicote 828 compatibility test results are shown in Table 2.

(Note) O mark: Good compatibility and no turbidity.

The oligomer obtained by the production method of the present invention is useful as a modifier for rubber and synthetic resins, and is currently used in rosin,
It can be used in fields where natural resins such as rosin esters and polyterpenes and synthetic resins such as polar group-containing hydrocarbon resins are used, such as in the fields of rubber, paints, printing inks, pressure sensitive adhesives, and adhesives.

Claims (1)

[Claims] 1 Di(dihydrodicyclopentadienyl) maleate and/or di(dihydrodicyclopentadienyl)
Fumarate is polymerized by heating to 220 to 300°C in the absence of a catalyst, and has a number average molecular weight of 500.
~2000, softening point 50~180℃, iodine value 75
-134 and is soluble in aromatic hydrocarbon solvents, ketone solvents and ester solvents.