JP5824985B2 - Method for producing dicyclopentadiene resin - Google Patents

Description

  The present invention is a method for producing a dicyclopentadiene resin having excellent production stability and quality. More specifically, the present invention efficiently removes unreacted oil, particularly unreacted dicyclopentadienes, from the reaction mixture after the polymerization reaction. It is related with the method of manufacturing the dicyclopentadiene-type resin excellent in quality by doing.

  A method for producing a petroleum resin by polymerizing in the presence of a Friedel-Crafts catalyst using an unsaturated hydrocarbon-containing fraction obtained in the cracking and refining of petroleum as a raw material is well known. As the unsaturated hydrocarbon-containing fraction, two types of C5 fraction having a boiling range of 20 to 110 ° C. and C9 fraction having a boiling range of 140 to 280 ° C. are generally obtained and obtained from the C5 fraction. An aliphatic petroleum resin, an aromatic petroleum resin obtained from the C9 fraction, and an aliphatic / aromatic copolymer petroleum resin obtained by copolymerizing the C5 fraction and the C9 fraction are known. An alicyclic petroleum resin obtained by thermally polymerizing dicyclopentadiene is also known.

  Specific examples of the dicyclopentadiene used as a raw material for the alicyclic petroleum resin include dicyclopentadiene, methyldicyclopentadiene, dimethyldicyclopentadiene, and the like. When polymerization is carried out in the presence of a type catalyst, since a large amount of unsaturated bonds are present in the resin, the hue of the resin deteriorates and gel formation occurs, resulting in a problem of quality deterioration. Therefore, when producing an aliphatic petroleum resin, an aromatic petroleum resin, an aliphatic / aromatic copolymer petroleum resin, etc., it is common to produce the dicyclopentadiene by a fraction obtained by removing it by distillation or the like.

  On the other hand, from the viewpoint of utilization of unused fractions, a method of producing a petroleum resin by conducting a polymerization reaction in the presence of a Friedel-Crafts-type catalyst using dicyclopentadiene as a raw material has been studied. A method of polymerizing the C9 fraction contained in the presence of a Friedel-Crafts type catalyst (for example, see Patent Document 1), a method of polymerizing a C9 fraction and dicyclopentadiene in the presence of a Friedel-Crafts type catalyst (for example, Patent Documents 2 to 4), a method of polymerizing a C5 fraction and dicyclopentadiene in the presence of a Friedel-Crafts catalyst (for example, refer to Patent Document 5), and the like have been proposed.

JP-A-62-064811 (refer to the claims) Japanese Patent Laid-Open No. 07-033951 (refer to the claims) Japanese Patent Laid-Open No. 08-034824 (refer to the claims) Japanese Patent Laying-Open No. 2011-127006 (see claims) JP 2010-006901 A (refer to claims)

  However, in the methods proposed in Patent Documents 1 to 5, when unreacted oil after the polymerization reaction is removed by distillation, foaming occurs from the surface of the reaction mixture, and bubbles are accompanied by reaching the top of the reactor. There are problems such as clogging the exhaust gas piping with the resin, causing the device to malfunction due to adhesion of the resin, and a large amount of unreacted dicyclopentadiene remaining in the resin.

  Therefore, the present invention improves the quality by efficiently removing unreacted oil, particularly unreacted dicyclopentadiene from the reaction mixture after the polymerization reaction of dicyclopentadiene and unsaturated hydrocarbon-containing fraction. It is an object of the present invention to provide a method for producing an excellent dicyclopentadiene resin.

  As a result of diligent investigations to solve the above problems, the present inventors have found that when removing unreacted dicyclopentadiene from the reaction mixture after the polymerization reaction, an antifoaming agent is added to thereby reduce the amount of dicyclopentadiene. The present inventors have found that this is a method for producing a dicyclopentadiene resin that prevents foaming and is excellent in production stability and quality, and has completed the present invention.

That is, the present invention provides a mixture of dicyclopentadiene obtained by pyrolysis and refining of petroleum and a C9 fraction having a boiling range of 140 to 280 ° C and / or a C5 fraction having a boiling range of 20 to 110 ° C. When producing a dicyclopentadiene resin by performing a polymerization reaction in the presence of a Friedel-Crafts catalyst and removing unreacted oil from the reaction mixture after the polymerization reaction, an antifoaming agent is added to the reaction mixture after the polymerization reaction. A process for producing a dicyclopentadiene resin, characterized by adding 1 to 500 ppm and distilling off unreacted oil to obtain a dicyclopentadiene resin having a hue measured according to ASTM D-1544-63T of 12 or less It is about.

  The present invention is described in detail below.

  The process for producing a dicyclopentadiene resin of the present invention comprises dicyclopentadiene obtained by pyrolysis and purification of petroleum, a C9 fraction having a boiling range of 140 to 280 ° C, and / or a boiling range of 20 to 110 ° C. A production method in which a mixture with a C5 fraction is subjected to a polymerization reaction in the presence of a Friedel-Crafts-type catalyst, an antifoaming agent is added to the reaction mixture after the polymerization reaction of a dicyclopentadiene resin, and unreacted oil is distilled off. is there.

  The dicyclopentadiene resin feedstock in the method for producing dicyclopentadiene resin of the present invention is obtained by dicyclopentadiene obtained by pyrolysis and refining of petroleum, C9 fraction having a boiling point range of 140 to 280 ° C, and / Or a mixture with a C5 fraction having a boiling range of 20 to 110 ° C.

  Any dicyclopentadiene may be used as long as it is generally known as dicyclopentadiene obtained by pyrolysis and refining of petroleum. For example, dicyclopentadiene, methyl Examples include dicyclopentadiene such as dicyclopentadiene, dimethyldicyclopentadiene, and mixtures thereof.

  As the C9 fraction, any material can be used as long as it is known as a fraction having a boiling point range of 140 to 280 ° C. generally obtained by pyrolysis and refining of petroleum. , Α-methylstyrene, β-methylstyrene, vinyltoluene, indene, vinyl aromatic hydrocarbons having 8 to 10 carbon atoms typified by alkyl derivatives of indene; olefins having 10 or more carbon atoms; 9 or more carbon atoms Saturated aromatics of these; and mixtures thereof.

  As the C5 fraction, any substance can be used as long as it is known as a fraction having a boiling range of 20 to 110 ° C. generally obtained by pyrolysis and refining of petroleum. , Conjugated diolefinically unsaturated hydrocarbons having 4 to 6 carbon atoms represented by trans-1,3-pentadiene, cis-1,3-pentadiene, cyclopentadiene, methylcyclopentadiene, etc .; butene, 2-methyl- C 4-6 monoolefinically unsaturated hydrocarbons typified by 1-butene, 2-methyl-2-butene, 1-pentene, 2-pentene, cyclopentene and the like; cyclopentane, 2-methylpentane, 3 -Aliphatic saturated hydrocarbons such as methylpentane and n-hexane; and mixtures thereof.

  And the mixture of the dicyclopentadiene which is the raw material oil of the dicyclopentadiene resin in the present invention and the C9 fraction and / or the C5 fraction is not limited in the mixing ratio, and among them, the obtained di- Since the cyclopentadiene resin is particularly excellent in softening point and hue, it is a mixture of 10 to 90% by weight of the dicyclopentadiene and 90 to 10% by weight of the C9 fraction and / or the C5 fraction. Preferably there is.

  In the present invention, when the mixture is subjected to a polymerization reaction to obtain a dicyclopentadiene resin, the polymerization reaction is performed in the presence of a Friedel-Crafts type catalyst, and the polymerization reaction at that time is not limited. A dicyclopentadiene resin can be produced by adding a Friedel-Crafts type catalyst to the mixture and heating to polymerize. Examples of the Friedel-Crafts type catalyst include aluminum trichloride, aluminum tribromide, boron trifluoride, phenol complexes thereof, butanol complexes thereof, and the like. Among them, boron trifluoride phenol complexes, boron trifluoride, etc. A butanol complex is preferred. The polymerization temperature is preferably from 0 to 100 ° C, particularly preferably from 0 to 80 ° C. Further, the amount of the Friedel-Crafts-type catalyst added is arbitrary, and among them, the production method is particularly excellent in production efficiency, so 0.1 to 2.0 parts by weight relative to 100 parts by weight of the mixture. Preferably there is. Furthermore, the polymerization time is preferably in the range of 0.1 to 10 hours. The reaction pressure is preferably atmospheric pressure to 1 MPa.

  In the production method of the dicyclopentadiene resin of the present invention, it is also possible to remove the Friedel-Crafts-type catalyst after the polymerization reaction. In this case, neutralization treatment with a base, washing with water, distillation with a solvent, etc. It is also possible to select a conventional method.

  In the method for producing a dicyclopentadiene resin of the present invention, an antifoaming agent is added to the reaction mixture after the polymerization reaction of the mixture of the dicyclopentadiene and the C9 fraction and / or the C5 fraction. The reaction oil is distilled off. At that time, by adding a defoaming agent, it is possible to efficiently remove the unreacted oil by suppressing foaming during distillation removal of the unreacted oil, so that the production stability and quality are excellent. This is a method for producing a dicyclopentadiene resin.

  Any antifoaming agent can be used as long as it is known as an antifoaming agent, and among them, it becomes a particularly efficient method for producing a dicyclopentadiene-based resin. For example, polysiloxane, dimethylpolysiloxane, diphenylpolysiloxane, methylphenylpolysiloxane, methylvinylpolysiloxane, etc. are silicone-based antifoaming agents whose main component is defoaming effect; , Oil compound type silicone antifoaming agent as main component of defoaming effect; Emulsion type silicone antifoaming agent in which oil compound type silicone is dispersed in the presence of water together with surfactant; Perfluoroalkyl group-containing siloxane Perfluoroether group-containing siloxane, perfluoropolyether Fluorosilicone defoaming agent containing ter-group-containing organopolysiloxane as the main component of defoaming effect; Amide defoaming agent containing aliphatic amide as the main component of defoaming effect; Hydrophobic based on mineral oil Mineral oil-based antifoaming agent blended with functional silica, amide, silicone, fatty acid, and the like, and these can be used in combination.

  Specific examples of the silicone antifoaming agent include (trade name) KF-96 (manufactured by Shin-Etsu Chemical Co., Ltd.), (trade name) KF-96 ADF (manufactured by Shin-Etsu Chemical Co., Ltd.), and (trade name) KS-604 (Shin-Etsu Chemical). (Product name) KS-7708 (made by Shin-Etsu Chemical Co., Ltd.), (product name) SH200 (made by Toray Dow Corning), (product name) FS1265 (made by Toray Dow Corning), (product name) TSF451 ( Silicone oils such as Momentive Performance Materials), (trade name) THF450 (product of Momentive Performance Materials), (trade name) YSA6403 (product of Momentive Performance Materials); (trade name) KS-602A (Manufactured by Shin-Etsu Chemical), (trade name) TSA720 (manufactured by Momentive Performance Materials), (quotient Name) Silicone oil solution such as YSA02 (Momentive Performance Materials); (trade name) KS-508 (manufactured by Shin-Etsu Chemical Co., Ltd.), (trade name) KS-530 (manufactured by Shin-Etsu Chemical Co., Ltd.), (trade name) KS-531 (manufactured by Shin-Etsu Chemical), (trade name) KS-537 (manufactured by Shin-Etsu Chemical), (product name) KS-538 (manufactured by Shin-Etsu Chemical), (product name) KS-540 (manufactured by Shin-Etsu Chemical) ), (Product Name) FS Antifoam 1266 (Toray Dow Corning), (Product Name) FS Antifoam 80 (Toray Dow Corning), (Product Name) FS Antifoam 544 Compound (Toray Dow Corning) (Product name) 1308 ANTIFOAM CONCENTRATE (made by Toray Dow Corning), (Product name) DK Q1-1086 (Toray Da (Product name) DK Q1-1183 (made by Toray Dow Corning), (Product name) DK Q1-071 (made by Toray Dow Corning), (Product name) YSA6406 (made by Momentive Performance Materials) (Trade name) TSA780 (manufactured by Momentive Performance Materials) and other self-emulsifying modified silicones.

  As specific examples of the oil compound type silicone-based antifoaming agent, (trade name) KS-66 (manufactured by Shin-Etsu Chemical Co., Ltd.), KS-69 (manufactured by Shin-Etsu Chemical Co., Ltd.), (trade name) DK Q1-049 (Toray Dow) (Product name) SH 5500 COMPOUND (made by Toray Dow Corning), (product name) SC 5540 COMPOUND (made by Toray Dow Corning), (product name) 8590 ADDITIVE (made by Toray Dow Corning), (product) Name) Silica silicones such as TSA750 (made by Momentive Performance Materials), (trade name) TSA750S (made by Momentive Performance Materials), and the like.

  Specific examples of emulsion-type silicone antifoaming agents include (trade name) KM-73 (manufactured by Shin-Etsu Chemical Co., Ltd.), (trade name) KM-73A (manufactured by Shin-Etsu Chemical Co., Ltd.), and (trade name) KM-73E (Shin-Etsu). (Product name) KM-72 (manufactured by Shin-Etsu Chemical), (product name) KM-72F (manufactured by Shin-Etsu Chemical), (product name) KM-72S (manufactured by Shin-Etsu Chemical), (product name) ) KM-72FS (manufactured by Shin-Etsu Chemical), (trade name) KM-70 (manufactured by Shin-Etsu Chemical), (product name) KM-71 (manufactured by Shin-Etsu Chemical), (product name) KM-75 (Shin-Etsu Chemical) ), (Trade name) KM-7750 (manufactured by Shin-Etsu Chemical), (product name) KM-85 (manufactured by Shin-Etsu Chemical), (product name) KM-89 (manufactured by Shin-Etsu Chemical), (product name) KM -90 (manufactured by Shin-Etsu Chemical), (trade name) KM-98 (manufactured by Shin-Etsu Chemical), (Trade name) KM-7752 (manufactured by Shin-Etsu Chemical Co., Ltd.), (trade name) TSA7341 (manufactured by Momentive Performance Materials), (brand name) TSA739 (manufactured by Momentive Performance Materials), (trade name) TSA732 (momentive)・ Performance Materials), (Product Name) TSA732A (Momentive Performance Materials), (Product Name) TSA772 (Momentive Performance Materials), (Product Name) TSA730 (Momentive Performance Materials) (Product name) TSA770 (made by Momentive Performance Materials), (product name) TSA775 (made by Momentive Performance Materials), (product name) TSA737 (momentive puff) -Performance-Materials Co.'s), (trade name) TSA737F (Momentive Performance Materials Co.'s), and the like (trade name) YMA6509 (Momentive Performance Materials Co.'s).

  Specific examples of fluorosilicone antifoaming agents include fluorosilicone oils such as (trade name) FA-630 (manufactured by Shin-Etsu Chemical Co., Ltd.); fluorosilicone oil solutions such as (trade name) FA-600 (manufactured by Shin-Etsu Chemical Co., Ltd.). Etc.

  Specific examples of the amide type antifoaming agent include (trade name) Alflow H-50S (manufactured by NOF), (trade name) SN-Deformer 477 (manufactured by San Nopco), (trade name) SN-5013 (manufactured by San Nopco), and the like. Is mentioned.

  Specific examples of mineral oil-based antifoaming agents include (trade name) Pronal K-302N (manufactured by Toho Chemical Industry), (trade name) Pronal A-5066 (manufactured by Toho Chemical Industry), and (trade name) Pronal A-3540. (Manufactured by Toho Chemical Industry Co., Ltd.), (trade name) Pronal A-5044 (manufactured by Toho Chemical Industry Co., Ltd.) and the like.

  Furthermore, these antifoaming agents change the solubility and dispersibility of the components in addition to the main components of the antifoaming effect (silicone, oil compound type silicone, emulsion type silicone, fluorosilicone, amide, mineral oil, etc.). A surfactant or the like may be added to increase the foam effect. These antifoaming agents may be used alone or in combination of two or more.

  And since it becomes possible to produce a dicyclopentadiene-based resin stably even in the production at a particularly high temperature, an oil compound type silicone-based antifoaming agent, a fluorosilicone-based antifoaming agent, a mineral oil-based resin An antifoaming agent is preferred.

  There is no limit to the amount of antifoaming agent added in the method for producing a dicyclopentadiene resin of the present invention, and among them, particularly efficient production is possible. Therefore, the antifoaming effect in the antifoaming agent with respect to the mixture Is preferably 0.1 to 1000 ppm, and more preferably 1 to 500 ppm.

  The antifoaming agent may be added before the unreacted oil is removed from the reaction mixture after the polymerization reaction, and among them, when removing the unreacted dicyclopentadiene from the dicyclopentadiene resin by distillation, When heated, dicyclopentadiene decomposes into cyclopentadiene, and at the same time, the cyclopentadiene, which is a low-boiling component, tends to be abruptly foamed, resulting in a particularly excellent defoaming effect that suppresses the foaming. Therefore, it is preferable to add before the reaction mixture after the polymerization reaction reaches 160 ° C.

  In the production method of the dicyclopentadiene resin of the present invention, any method can be used as the method for distilling off the unreacted oil as long as the unreacted oil can be distilled off. A distillation method, an atmospheric distillation method, a pressure distillation method, etc. can be mentioned. Among them, the atmospheric distillation method is preferable because the apparatus can be simplified, and the temperature at that time is 130 to It is preferable that it is 260 degreeC, and it is especially preferable that it is 170-240 degreeC.

  The dicyclopentadiene resin obtained by the production method of the present invention preferably has a softening point of 60 to 160 ° C., particularly 70 to 150 ° C., and a hue of 13 or less, particularly 12 or less. Moreover, since it becomes what is excellent in workability, it is preferable that it is a thing of a weight average molecular weight (Mw) 500-5000.

  According to the production method of the present invention, unreacted dicyclopentadiene can be efficiently removed, and a dicyclopentadiene resin having excellent quality can be produced efficiently.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention does not receive a restriction | limiting at all by these Examples. In addition, the raw material oil used in the Example and the comparative example, the antifoamer, and the analysis method of the obtained resin are as follows.

(Raw oil (mixture))
C9 fraction: A fraction having a boiling range of 140 to 280 ° C. obtained by thermal decomposition of naphtha was used. The composition is shown in Table 1. In Table 1, DCPD is an abbreviation for dicyclopentadiene.
Dicyclopentadiene (DCPD): Dicyclopentadiene obtained by thermal decomposition of naphtha was used. The compositions (DCPD (A) and DCPD (B) are shown in Table 2. In Table 2, DCPD is an abbreviation for dicyclopentadiene and CPD is an abbreviation for cyclopentadiene.
C5 fraction: A fraction having a boiling range of 20 to 110 ° C. obtained by thermal decomposition of naphtha was used. The composition is shown in Table 3. In Table 3, CPD is an abbreviation for cyclopentadiene.

（消泡剤）
消泡剤Ａ：フルオロシリコーン系消泡剤（信越化学工業（株）製、商品名ＦＡ−６００）。
消泡剤Ｂ：オイルコンパウンド型シリコーン系消泡剤（信越化学工業（株）製、商品名ＫＳ−６９）
消泡剤Ｃ：鉱物油系消泡剤（東邦化学工業（株）製、商品名プロナールＫ−３０２Ｎ）。
消泡剤Ｄ：オイルコンパウンド型シリコーン系消泡剤（信越化学工業（株）製、商品名ＫＳ−６６）
消泡剤Ｅ：鉱物油系消泡剤（東邦化学工業（株）製、商品名プロナールＡ−５０４４）
消泡剤Ｆ：オイルコンパウンド型シリコーン系消泡剤（モメンティブ・パフォーマンス・マテリアルズ製、商品名ＴＳＡ７５０Ｓ）。
消泡剤Ｇ：シリコーン系消泡剤（信越化学工業（株）製、商品名ＫＳ−７７０８）。

(Defoamer)
Antifoaming agent A: Fluorosilicone antifoaming agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name FA-600).
Antifoam B: Oil compound type silicone antifoam (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KS-69)
Antifoaming agent C: Mineral oil-based antifoaming agent (manufactured by Toho Chemical Co., Ltd., trade name Pronal K-302N).
Antifoaming agent D: Oil compound type silicone antifoaming agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KS-66)
Antifoam E: Mineral oil-based antifoam (trade name Pronal A-5044, manufactured by Toho Chemical Co., Ltd.)
Antifoaming agent F: Oil compound type silicone antifoaming agent (product name TSA750S, manufactured by Momentive Performance Materials).
Antifoaming agent G: Silicone type antifoaming agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KS-7708).

(Analysis method)
(1) Content of each component of raw material oil: It analyzed using the gas chromatograph method based on JIS K-0114 (2000).
(2) Residual amount of DCPDs in the resin: The resin was dissolved in toluene and analyzed using a gas chromatograph method in accordance with JIS K-0114 (2000).
(3) Weight average molecular weight (Mw): Measured by gel permeation chromatography according to JIS K-0124 (1994) using polystyrene as a standard substance.
(4) Softening point: Measured by a method based on JIS K-2531 (1960) (ring and ball method).
(5) Hue (Gardner): Measured according to ASTM D-1544-63T as a 50 wt% toluene solution.

Example 1
A glass autoclave having an internal volume of 2 liters was charged with 150 g of a C9 fraction obtained by decomposition of naphtha as a raw material oil and 350 g of a DCPD fraction (DCPD (A)) having the composition shown in Table 2. (C9 fraction / DCPDs = 30/70 (% by weight)). Next, after heating to 40 ° C. in a nitrogen atmosphere, boron trifluoride butanol complex (Stella Chemifa Co., Ltd., boron trifluoride butanol) is used as a Friedel-Crafts type catalyst in an amount of 1. 0 part by weight was added and polymerization was carried out at 40 ° C. for 2 hours. After adding a caustic soda aqueous solution, the aqueous phase was removed to obtain a polymerization reaction liquid (hereinafter referred to as polymerization reaction liquid A). Table 4 shows the synthesis conditions for the polymerization reaction solution A.

  Then, 400 g of the polymerization reaction solution A obtained in a 0.5 liter separable flask equipped with a nitrogen introduction tube, a thermometer and a deaeration tube, and 1.4 mg of the defoaming agent A (effective component amount in the polymerization reaction solution: 3 ppm) Added. Nitrogen was introduced from the nitrogen introduction tube at a flow rate of 7 ml / min, and the temperature was raised to 240 ° C. over 30 minutes, followed by further heating for 30 minutes to distill off unreacted oil. When the unreacted oil was distilled off, no increase in the liquid level due to foaming was observed. The yield was measured by dividing the dicyclopentadiene resin remaining in the reactor after the heating and the dicyclopentadiene resin adhering to the upper lid.

  The yield of the resin remaining in the reactor was 144 g (yield: 36% by weight), no adhesion of dicyclopentadiene resin to the upper lid, and adhesion of the resin to the deaeration tube by preventing foaming was also observed. There wasn't. The remaining amount of DCPDs remaining in the dicyclopentadiene resin was 0 ppm. Table 5 shows the results of removing unreacted oil and the physical properties of the obtained dicyclopentadiene resin.

Example 2
A dicyclopentadiene resin was produced in the same manner as in Example 1, except that 3.0 mg of antifoam B (active ingredient amount in the polymerization reaction solution: 8 ppm) was added instead of 1.4 mg of antifoam A. went. When removing the unreacted oil, no increase in the liquid level due to foaming was observed.

  The yield of the dicyclopentadiene resin remaining in the reactor was 143 g (yield: 36% by weight), and no adhesion of the dicyclopentadiene resin to the top lid was observed. No adhesion was seen. The remaining amount of DCPDs remaining in the dicyclopentadiene resin was 0 ppm. Table 5 shows the results of removing unreacted oil and the physical properties of the obtained dicyclopentadiene resin.

Example 3
A dicyclopentadiene-based resin was produced in the same manner as in Example 1 except that 20 mg of antifoaming agent C (effective component amount in the polymerization reaction solution: 50 ppm) was added instead of 1.4 mg of antifoaming agent A. . When removing the unreacted oil, no increase in the liquid level due to foaming was observed.

  The yield of the dicyclopentadiene resin remaining in the reactor was 145 g (yield: 36% by weight), and no adhesion of the dicyclopentadiene resin to the upper lid was observed. No adhesion was seen. The remaining amount of DCPDs remaining in the dicyclopentadiene resin was 0 ppm. Table 5 shows the results of removing unreacted oil and the physical properties of the obtained dicyclopentadiene resin.

Comparative Example 1
An attempt was made to produce a dicyclopentadiene resin by the same method as in Example 1 except that 1.4 mg of antifoam A was not added. When the unreacted oil was removed by distillation, the liquid level increased greatly due to foaming.

  The yield of dicyclopentadiene resin remaining in the reactor was as small as 120 g (yield: 30% by weight), and defoaming was insufficient, so the deaeration tube was clogged with resin, and more resin adhered to the top lid. It was. The remaining amount of DCPDs remaining in the dicyclopentadiene resin was 40 ppm. Table 5 shows the results of removing unreacted oil and the physical properties of the obtained dicyclopentadiene resin.

Example 4
A polymerization reaction liquid A was obtained in the same manner as in Example 1.

  Then, 400 g of the polymerization reaction solution A obtained in a 0.5 liter separable flask equipped with a nitrogen introduction tube, a thermometer, and a deaeration tube and 12 mg of an antifoaming agent D (the amount of active ingredients in the polymerization reaction solution: 30 ppm) were added. . Nitrogen was introduced from the nitrogen introduction tube at a flow rate of 10 ml / min, and the temperature was raised to 170 ° C. over 60 minutes, followed by further heating for 60 minutes to remove unreacted oil by distillation. When the unreacted oil was distilled off, no increase in the liquid level due to foaming was observed. The yield was measured by dividing the dicyclopentadiene resin remaining in the reactor after the heating and the dicyclopentadiene resin adhering to the upper lid.

  The yield of the dicyclopentadiene resin remaining in the reactor was 186 g (yield: 37% by weight), and no adhesion of the dicyclopentadiene resin to the top lid was observed. No adhesion was seen. The remaining amount of DCPDs remaining in the dicyclopentadiene resin was 0 ppm. Table 5 shows the results of removing unreacted oil and the physical properties of the obtained dicyclopentadiene resin.

Comparative Example 2
An attempt was made to produce a dicyclopentadiene resin by the same method as in Example 4 except that 12 mg of antifoam D was not added. When the unreacted oil was removed by distillation, the liquid level increased greatly due to foaming.

  The yield of dicyclopentadiene resin remaining in the reactor was as low as 129 g (yield: 32% by weight), and defoaming was insufficient, so the deaeration tube was clogged with resin, and more resin adhered to the top lid. It was. The remaining amount of dicyclopentadiene remaining in the obtained dicyclopentadiene resin was 450 ppm, which was insufficiently removed. Table 5 shows the results of removing unreacted oil and the physical properties of the obtained resin.

Example 5
A glass autoclave having an internal volume of 2 liters was charged with 250 g of a C5 fraction obtained by decomposition of naphtha as a raw oil and 250 g of a DCPD fraction (DCPD (A)) having the composition shown in Table 2. (C5 fraction / DCPDs = 50/50 (% by weight)). Next, after cooling to 10 ° C. in a nitrogen atmosphere, 2. Boron trifluoride butanol complex (Stella Chemifa Co., Ltd., boron trifluoride butanol) as a Friedel-Crafts-type catalyst is added to 100 parts by weight of the feedstock. 0 part by weight was added and polymerization was carried out at 40 ° C. for 2 hours. After adding a caustic soda aqueous solution, the aqueous phase was removed to obtain a polymerization reaction liquid (hereinafter referred to as polymerization reaction liquid B). Table 4 shows the synthesis conditions for the polymerization reaction solution B.

  Then, 400 g of the polymerization reaction solution B obtained in a 0.5 liter separable flask equipped with a nitrogen introduction tube, a thermometer, and a deaeration tube, and 4 mg of an antifoaming agent (the amount of active ingredients in the polymerization reaction solution: 10 ppm) were added. . Nitrogen was introduced from the nitrogen introduction tube at a flow rate of 7 ml / min, and the temperature was raised to 240 ° C. over 30 minutes, followed by further heating for 30 minutes to distill off unreacted oil. When the unreacted oil was distilled off, no increase in the liquid level due to foaming was observed. The yield was measured by dividing the dicyclopentadiene resin remaining in the reactor after the heating and the dicyclopentadiene resin adhering to the upper lid.

  The yield of the dicyclopentadiene resin remaining in the reactor was 160 g (yield: 40% by weight). No resin was observed on the upper lid, and the resin was also adhered to the deaeration tube by preventing foaming. There wasn't. The remaining amount of DCPDs remaining in the dicyclopentadiene resin was 0 ppm. Table 5 shows the results of removing unreacted oil and the physical properties of the obtained dicyclopentadiene resin.

Comparative Example 3
An attempt was made to produce a dicyclopentadiene resin by the same method as in Example 5 except that 4 mg of the antifoaming agent E was not added. When the unreacted oil was removed, the liquid level increased significantly due to foaming.

  The yield of dicyclopentadiene resin remaining in the reactor was as small as 141 g (yield: 35% by weight), and defoaming was insufficient, so the deaeration tube was clogged with resin, and more resin adhered to the top lid. It was. The remaining amount of DCPDs remaining in the obtained dicyclopentadiene resin was 30 ppm. Table 5 shows the results of removing unreacted oil and the physical properties of the obtained dicyclopentadiene resin.

Example 6
Instead of defoaming agent E4 mg, defoaming agent F4 mg (the amount of active ingredients in the polymerization reaction solution: 10 ppm) was used, and the temperature was raised to 240 ° C. over 30 minutes, but the temperature was raised to 220 ° C. over 25 minutes. Except for the above, a dicyclopentadiene-based resin was produced in the same manner as in Example 5. When the unreacted oil was distilled off, no increase in the liquid level due to foaming was observed.

  The yield of the dicyclopentadiene resin remaining in the reactor was 162 g (yield: 41% by weight), and no adhesion of the dicyclopentadiene resin to the upper lid was observed. No adhesion was seen. The remaining amount of DCPDs remaining in the dicyclopentadiene resin was 0 ppm. Table 5 shows the results of removing unreacted oil and the physical properties of the obtained dicyclopentadiene resin.

Comparative Example 4
An attempt was made to produce a dicyclopentadiene resin by the same method as in Example 6 except that 4 mg of antifoam F was not added. When the unreacted oil was removed, the liquid level increased significantly due to foaming.

  The yield of the dicyclopentadiene resin remaining in the reactor was as low as 139 g (yield: 35% by weight), and defoaming was insufficient, so the deaeration tube was clogged with resin, and the resin adhering to the top lid increased. It was. The remaining amount of DCPDs remaining in the obtained dicyclopentadiene resin was 40 ppm. Table 5 shows the results of removing unreacted oil and the physical properties of the obtained dicyclopentadiene resin.

Example 7
In a glass autoclave having an internal volume of 2 liters, 100 g of C9 fraction obtained by decomposition of naphtha as a raw material oil, 50 g of DCPD fraction (DCPD (B)) having the composition shown in Table 2, and Table 3 350 g of the C5 fraction shown in (5) was charged (C5 fraction / C9 fraction / DCPDs = 70/20/10 (% by weight)). Next, after heating to 35 ° C. in a nitrogen atmosphere, boron trifluoride phenol complex (Stella Chemifa Co., Ltd., boron trifluoride phenol) is used as a Friedel-Crafts type catalyst in an amount of 1. 3 parts by weight was added and polymerization was carried out at 35 ° C. for 2 hours. After adding a caustic soda aqueous solution, the aqueous phase was removed to obtain a polymerization reaction liquid (hereinafter referred to as polymerization reaction liquid C). Table 4 shows the synthesis conditions for the polymerization reaction solution C.

  Then, 400 g of the polymerization reaction solution C obtained in a 0.5 liter separable flask equipped with a nitrogen introduction tube, a thermometer, and a deaeration tube, and 20 mg of an antifoaming agent G (effective component amount in the polymerization reaction solution; 50 ppm) were added. . Nitrogen was introduced from the nitrogen introduction tube at a flow rate of 10 ml / min, and the temperature was raised to 150 ° C. over 120 minutes, followed by further heating for 120 minutes to distill off unreacted oil. When the unreacted oil was distilled off, a slight increase in the liquid level due to foaming was observed, but the dicyclopentadiene resin was recovered without any problem. The yield was measured by dividing the dicyclopentadiene resin remaining in the reactor after the heating and the dicyclopentadiene resin adhering to the upper lid.

  The yield of the dicyclopentadiene resin remaining in the reactor was 153 g (yield: 38% by weight), and although the resin was slightly attached to the upper lid by preventing foaming, the resin on the deaeration tube The adhesion of was not seen. The remaining amount of DCPDs remaining in the dicyclopentadiene resin was 0 ppm. Table 5 shows the results of removing unreacted oil and the physical properties of the obtained dicyclopentadiene resin.

Comparative Example 5
An attempt was made to produce a dicyclopentadiene resin by the same method as in Example 7 except that 20 mg of antifoaming agent G was not added. When the unreacted oil was removed, the liquid level increased significantly due to foaming.

  The yield of dicyclopentadiene resin remaining in the reactor was as low as 133 g (yield: 33 wt%), and defoaming was insufficient, so the deaeration tube was clogged with resin, and the resin adhering to the top lid increased. It was. The remaining amount of DCPDs remaining in the obtained dicyclopentadiene resin was 300 ppm, which was insufficiently removed. Table 5 shows the results of removing unreacted oil and the physical properties of the obtained dicyclopentadiene resin.

  According to the method for producing a dicyclopentadiene resin of the present invention, it is possible to efficiently produce a dicyclopentadiene resin having excellent quality.

Claims (5)

A mixture of dicyclopentadiene obtained by pyrolysis and refining of petroleum and a C9 fraction having a boiling range of 140 to 280 ° C and / or a C5 fraction having a boiling range of 20 to 110 ° C is used as a Friedel-Crafts catalyst. When producing a dicyclopentadiene resin by removing the unreacted oil from the reaction mixture after the polymerization reaction in the presence of the polymerization reaction, 1 to 500 ppm of an antifoaming agent is added to the reaction mixture after the polymerization reaction. A method for producing a dicyclopentadiene resin, characterized in that a dicyclopentadiene resin having a hue measured according to ASTM D-1544-63T of 12 or less is obtained by distilling off unreacted oil. The antifoaming agent is a group consisting of a silicone antifoaming agent, an oil compound silicone antifoaming agent, an emulsion silicone antifoaming agent, a fluorosilicone antifoaming agent, an amide antifoaming agent, and a mineral oil defoaming agent. The method for producing a dicyclopentadiene resin according to claim 1, wherein at least one or more types of antifoaming agents are selected. The antifoaming agent is at least one type of antifoaming agent selected from the group consisting of an oil compound type silicone-based antifoaming agent, a fluorosilicone-based antifoaming agent and a mineral oil-based antifoaming agent. Item 3. A process for producing a dicyclopentadiene resin according to Item 1 or 2. The method for producing a dicyclopentadiene resin according to any one of claims 1 to 3, wherein the antifoaming agent is added to the reaction mixture at 160 ° C or lower. The method for producing a dicyclopentadiene resin according to any one of claims 1 to 4, wherein unreacted oil is distilled off at 130 to 260 ° C.