阅读说明：本技术 一种热聚合成碳五碳九共聚石油树脂的方法及其应用 (Method for thermally polymerizing carbon five carbon nine copolymerized petroleum resin and application thereof ) 是由 周艳青 杨兴锴 伍家卫 马庭洲 唐蓉萍 王继元 石星丽 李薇 郑晓明 吕维华 颉 于 2021-11-02 设计创作，主要内容包括：本发明属于石油树脂合成技术领域,公开了一种热聚合成碳五碳九共聚石油树脂的方法及其应用,将原料碳五低聚物、精制的双环戊二烯和富含双环戊二烯的碳九馏分置于釜式反应器进行加热反应,先在150℃进行预聚反应2h,再在240-280℃反应3-10h,在低于1.0MPa下即可得到质量稳定、色号低于5、软化点在80-110℃的碳五碳九共聚石油树脂。本发明的原料配方中加入精制的双环戊二烯提高体系中双环戊二烯的含量,使得反应稳定进行,产品色号低；使用碳五低聚物代替碳五馏分作为原料,使得反应系统压力低,工艺更安全；在150℃左右增加预聚反应过程控制,使得反应过程副反应减少。(The invention belongs to the technical field of petroleum resin synthesis, and discloses a method for thermally polymerizing carbon five carbon nine copolymerized petroleum resin and application thereof, wherein raw materials of carbon five oligomer, refined dicyclopentadiene and carbon nine fraction rich in dicyclopentadiene are placed in a kettle type reactor for heating reaction, prepolymerization reaction is carried out for 2h at 150 ℃, then reaction is carried out for 3-10h at 280 ℃ and the carbon five carbon nine copolymerized petroleum resin with stable quality, color number lower than 5 and softening point lower than 80-110 ℃ can be obtained under the pressure lower than 1.0 MPa. According to the invention, the refined dicyclopentadiene is added into the raw material formula to improve the content of dicyclopentadiene in a system, so that the reaction is stably carried out, and the color number of a product is low; the carbon five oligomer is used as a raw material instead of the carbon five fraction, so that the pressure of a reaction system is low, and the process is safer; the control of the prepolymerization reaction process is increased at about 150 ℃, so that the side reaction in the reaction process is reduced.)

1. A method for thermally polymerizing a carbon five carbon nine copolymerized petroleum resin, which is characterized by comprising the following steps:

placing the raw materials of the carbon five oligomer, the refined dicyclopentadiene and the carbon nine fraction rich in the dicyclopentadiene into a kettle type reactor for heating, and reacting at the temperature of 240-280 ℃ after prepolymerization reaction to obtain the carbon five carbon nine copolymerized petroleum resin with stable quality.

2. The method of thermally polymerizing carbon five carbon nine copolymerized petroleum resin according to claim 1, wherein the method of thermally polymerizing carbon five carbon nine copolymerized petroleum resin comprises the steps of:

step one, adding a dicyclopentadiene-enriched carbon nine fraction, refined dicyclopentadiene and a carbon five oligomer with a boiling range of 130-;

heating to 150 ℃ for prepolymerization reaction for 2h, continuously heating to 240 ℃ and 280 ℃, keeping the reaction pressure below 1.0MPa, keeping the reaction for 3-10h, cooling to below 60 ℃, slowly opening a pressure reduction valve, and discharging when the pressure is reduced to 0;

and step three, distilling the reaction liquid under reduced pressure until no low fraction is distilled off, discharging, and cooling to obtain the C-V-C-N copolymerized petroleum resin.

3. The method for thermally polymerizing carbon five carbon nine copolymerized petroleum resin according to claim 2, wherein in the first step, the synthesis of the carbon five oligomer comprises:

separating and removing light four components and trace moisture in the carbon five generated in the ethylene cracking production to obtain a carbon five mixed component with light removal, dehydration and impurity removal and the water content of less than 50 PPM; the whole fraction with the carbon penta being removed is subjected to thermal polymerization reaction for 2 to 6 hours at the temperature of 240 ℃ and the temperature of 280 ℃ and under the pressure of 5.0 to 6.5MPa to obtain the carbon penta oligomer.

4. The method of thermally polymerizing carbon five carbon nine copolymerized petroleum resin according to claim 3, wherein the decarburized five whole fraction includes piperylene, isoprene, cyclopentadiene, and dicyclopentadiene.

5. The method for thermally polymerizing carbon five carbon nine copolymerized petroleum resin according to claim 2, wherein in the first step, the synthesis of the refined dicyclopentadiene comprises:

thermally polymerizing cyclopentadiene in the cracked C-V fraction to form dicyclopentadiene, rectifying and separating the dicyclopentadiene by a rectifying tower, and separating unreacted C-V components from the top of the rectifying tower to obtain high-purity refined dicyclopentadiene at the tower bottom.

6. The method for thermally polymerizing carbon five carbon nine copolymerized petroleum resin according to claim 5, wherein the mass percent of the refined dicyclopentadiene is higher than 85%.

7. The method for thermally polymerizing carbon five carbon nine copolymerized petroleum resin according to claim 2, wherein in the first step, the dicyclopentadiene-rich carbon nine fraction is obtained by:

separating and removing the components with more than ten carbon atoms in the carbon nine fraction of the ethylene cracking byproduct to obtain the carbon nine mixed component which is rich in dicyclopentadiene, styrene derivatives and indene and has the boiling range of 130-230 ℃.

8. The method for thermally polymerizing a carbon five carbon nine copolymerized petroleum resin according to claim 7, wherein the dicyclopentadiene component is contained in an amount of more than 30% by mass.

9. A carbon five carbon nine copolymerized petroleum resin prepared by the method of thermally polymerizing the carbon five carbon nine copolymerized petroleum resin according to any one of claims 1 to 8.

10. Use of the carbon five carbon nine copolymerized petroleum resin of claim 9 in rubber processing, road marking paint, ink and adhesive preparation.

Technical Field

The invention belongs to the technical field of petroleum resin synthesis, and particularly relates to a method for thermally polymerizing carbon five carbon nine copolymerized petroleum resin and application thereof.

Background

At present, petroleum resin is a thermoplastic resin produced by processes of pretreatment, polymerization, distillation and the like of carbon five and carbon nine fractions which are byproducts in the process of producing ethylene by cracking petroleum fractions, and is an oligomer with the molecular weight of 300-3000. It has the characteristics of low acid value, good mixing and dissolving property, low melting point, good adhesion, water resistance, chemical resistance and the like. The adhesive is widely applied to the fields of road marking paint, printing ink, rubber processing, adhesives and the like. According to the monomer and molecular structure of the resin, the resin can be divided into aromatic petroleum resin, aliphatic petroleum resin, alicyclic petroleum resin and the like.

The existing polymerization processes of petroleum resin mainly comprise two types, one is a cation catalysis low-temperature polymerization method, which is called as a cold polymerization method for short, and the other is a heating initiation free radical polymerization method, which is called as a hot polymerization method for short.

The cold polymerization method takes aluminum trichloride and the like as catalysts, has a mature process, and is a main method for industrially producing petroleum resin at present. CN102718924A adopts a cold polymerization method, takes the treated carbon five fraction and carbon nine fraction as raw materials, takes boron trifluoride as a catalyst, and reacts for 2-5 hours at the temperature of 30-65 ℃, so that the obtained petroleum resin has the color number of 4-6. CN111704684A discloses a method for modifying carbon five carbon nine copolymerized petroleum resin by peroxyacetic acid, which takes boron trifluoride, aluminum trichloride and the like as catalysts for catalytic polymerization, and the color number of the obtained petroleum resin is between 4 and 8. According to the above cases, the petroleum resin obtained by the cold polymerization method has low color number, but the cold polymerization method takes aluminum trichloride and the like as catalysts in the production process, so that a large amount of industrial wastewater can be generated, 3 tons of industrial wastewater can be generated when 1 ton of resin is produced, and the wastewater contains a large amount of aluminum ions and chloride ions, so that the treatment difficulty is high, the cost is high, and the environment is greatly polluted.

The thermal polymerization method does not use a catalyst, does not produce waste water and waste residue in the production process, accords with the guidelines of clean production, energy conservation and emission reduction and circular economy source treatment, and has higher environmental protection significance. CN107163186A mixes the carbon nine mixed components and the carbon five mixed components, cyclopentadiene is added in the mixed carbon nine and carbon five as an initiator, wherein, the active components of pentadiene, isoprene, styrene derivatives, indene derivatives and cyclopentadiene are subjected to thermal polymerization reaction at the temperature of 250-280 ℃ and under the pressure of 2.2-3.0MPa and in the presence of other saturated components in the carbon nine and carbon five as solvent oil, thus obtaining petroleum resins with various molecular weights. CN1356346A is prepared from one or more of unsaturated olefin-rich fractions such as carbon nine fraction, carbon five fraction, dicyclopentadiene fraction, etc. which are byproducts of ethylene preparation by petroleum cracking as raw materials by carrying out thermal polymerization at 280 ℃ and 0.3-3.5MPa without or with little initiator and distilling to remove low fraction. The polymer is prepared by mixing carbon five and carbon nine according to a certain mass ratio, and reacting at the temperature of 200-250 ℃ and the pressure of 0.5-0.8 MPa. The petroleum resin produced by the thermal polymerization method in the above cases has dark color, the color number is more than 5, some are even more than 12, and the distribution range of the softening point is also large. In view of the above, the conventional thermal polymerization process has problems of high product color number, many side reactions, and high risk of operation at high temperature and high pressure, and therefore, a new method for thermally polymerizing a carbon five carbon nine copolymerized petroleum resin is needed to improve the quality of the thermally polymerized petroleum resin product, reduce the occurrence of side reactions, and reduce the risk of operation.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides a method for thermally polymerizing carbon five carbon nine copolymerized petroleum resin and application thereof, and particularly relates to a novel process for producing the carbon five carbon nine copolymerized petroleum resin by using carbon five oligomer, refined dicyclopentadiene and dicyclopentadiene-rich carbon nine fraction as raw materials.

The invention is realized by a method for thermally polymerizing carbon five-carbon nine copolymerized petroleum resin, which comprises the following steps:

placing raw materials of carbon five oligomer, refined dicyclopentadiene and carbon nine fraction rich in dicyclopentadiene into a kettle type reactor for heating reaction, firstly carrying out prepolymerization reaction for 2h at 150 ℃, then carrying out reaction for 3-10h at 280 ℃ and obtaining the carbon five carbon nine copolymerized petroleum resin with stable quality, color number lower than 5 and softening point at 80-110 ℃ under the pressure lower than 1.0 MPa.

Further, the method for thermally polymerizing the carbon five-carbon nine copolymerized petroleum resin comprises the following steps:

step one, adding a dicyclopentadiene-enriched carbon nine fraction, refined dicyclopentadiene and a carbon five oligomer with a boiling range of 130-;

heating to 150 ℃ for prepolymerization reaction for 2h, continuously heating to 240 ℃ and 280 ℃, keeping the reaction pressure below 1.0MPa, keeping the reaction for 3-10h, cooling to below 60 ℃, slowly opening a pressure reduction valve, and discharging when the pressure is reduced to 0;

and step three, distilling the reaction liquid under reduced pressure until no low fraction is distilled off, discharging, and cooling to obtain the C-V-C-N copolymerized petroleum resin.

Further, in step one, the synthesis of the carbon pentaoligomer comprises:

separating and removing light carbon four components and trace moisture in the carbon five generated in the ethylene cracking production to obtain a carbon five mixed component with light removal, dehydration and impurity removal and the water content of less than 50 PPM; the whole fraction with the carbon penta being removed is subjected to thermal polymerization reaction for 2 to 6 hours at the temperature of 240 ℃ and the temperature of 280 ℃ and under the pressure of 5.0 to 6.5MPa to obtain the carbon penta oligomer.

Further, the decarburized penta whole fraction comprises piperylene, isoprene, cyclopentadiene and dicyclopentadiene.

Further, in the step one, the synthesis of the refined dicyclopentadiene comprises the following steps:

thermally polymerizing cyclopentadiene in the cracked C-V fraction to form dicyclopentadiene, rectifying and separating the dicyclopentadiene by a rectifying tower, and separating unreacted C-V components from the top of the rectifying tower to obtain high-purity refined dicyclopentadiene at the tower bottom.

Further, the mass percentage of the refined dicyclopentadiene is higher than 85%.

Further, in the first step, the method for obtaining the carbon nine fraction rich in dicyclopentadiene comprises the following steps:

separating and removing the components with more than ten carbon atoms in the carbon nine fraction of the ethylene cracking byproduct to obtain the carbon nine mixed component which is rich in dicyclopentadiene, styrene derivatives and indene and has the boiling range of 130-230 ℃.

Further, the mass percentage content of the dicyclopentadiene component is higher than 30%.

The invention also aims to provide the carbon five-carbon nine copolymerized petroleum resin prepared by the method for thermally polymerizing the carbon five-carbon nine copolymerized petroleum resin.

The invention also aims to provide application of the carbon five-carbon nine copolymerized petroleum resin in rubber processing, road marking paint, printing ink and adhesive preparation.

By combining all the technical schemes, the invention has the advantages and positive effects that: the raw materials of the method for thermally polymerizing the carbon five-carbon nine copolymerized petroleum resin comprise three parts, namely the carbon five oligomer, the refined dicyclopentadiene and the dicyclopentadiene-rich carbon nine fraction, the carbon five-carbon nine copolymerization reaction increases the control of the prepolymerization reaction process, can reduce the pressure of the thermal polymerization reaction process of the carbon five-carbon nine copolymerized petroleum resin, reduce the color number of the carbon five-carbon nine copolymerized petroleum resin and improve the quality of the carbon five-carbon nine copolymerized petroleum resin.

Compared with the existing process conditions, the refined dicyclopentadiene is added into the raw material formula of the invention to improve the content of dicyclopentadiene in the system, so that the reaction is stably carried out and the color number of the product is low; the new process uses the carbon five oligomer to replace carbon five fraction as a raw material, so that the pressure of a reaction system is low, and the process is safer; the new process increases the control of the prepolymerization reaction process at about 150 ℃, so that the side reaction in the reaction process is reduced.

The novel process can replace the production process for synthesizing the petroleum resin by copolymerizing five carbon nine in the prior art, does not use catalysts such as aluminum trichloride and boron trifluoride, omits a washing process step, does not generate industrial sewage and residues, reduces the production cost of the petroleum resin by copolymerizing five carbon nine, and meets the current national environmental protection standard. The synthesis method changes the process route of producing the carbon five-carbon nine copolymerized petroleum resin in the prior thermal polymerization synthesis technology, replaces the carbon five fraction with the carbon five oligomer, controls the concentration of dicyclopentadiene in the raw materials by adding high-purity refined dicyclopentadiene, obtains the carbon five-carbon nine copolymerized petroleum resin with stable softening point and light color at a lower pressure lower than 1.0MPa by increasing the control of the prepolymerization reaction process, and improves the product quality.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments of the present invention will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.

FIG. 1 is a flow chart of a method for thermally polymerizing a carbon five-carbon nine-copolymerized petroleum resin according to an embodiment of the present invention.

FIG. 2 is an infrared spectrum of a synthetic carbon five carbon nine copolymerized petroleum resin provided in an embodiment of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

In view of the problems of the prior art, the present invention provides a method for thermally polymerizing a carbon five carbon nine copolymerized petroleum resin, which is described in detail below with reference to the accompanying drawings.

The invention aims to provide a novel process for synthesizing carbon five-carbon nine-copolymer petroleum resin, which can reduce the pressure in the thermal polymerization process of the carbon five-carbon nine-copolymer petroleum resin, reduce the color number of the carbon five-carbon nine-copolymer petroleum resin and improve the quality of the carbon five-carbon nine-copolymer petroleum resin.

In order to realize the purpose, the novel process adopted by the invention comprises the following steps: the raw material consists of three parts of a carbon five oligomer, fine dicyclopentadiene and carbon nine fraction rich in dicyclopentadiene, and the copolymerization reaction of carbon five and carbon nine increases the control of the prepolymerization reaction process, and specifically comprises the following steps:

as shown in fig. 1, the method for thermally polymerizing a carbon five-carbon nine-copolymerized petroleum resin according to an embodiment of the present invention includes the steps of:

s101, adding a carbon nine fraction, refined dicyclopentadiene and a carbon five oligomer which are rich in dicyclopentadiene indene and have a boiling range of 130-;

s102, heating to 150 ℃, carrying out prepolymerization reaction for 2h, continuously heating to 280 ℃, keeping the reaction pressure below 1.0MPa, keeping the reaction for 3-10h, cooling to below 60 ℃, slowly opening a pressure reduction valve, and discharging when the pressure is reduced to 0;

s103, distilling the reaction liquid under reduced pressure until no low fraction is distilled off, discharging, and cooling to obtain the C-V-C-N copolymerized petroleum resin.

The embodiment of the invention provides a novel process for synthesizing carbon five-carbon nine copolymerized petroleum resin, which comprises the following steps:

the raw material consists of three parts of a carbon five oligomer, refined dicyclopentadiene and a carbon nine fraction rich in dicyclopentadiene, the raw material is heated in a kettle type reactor for reaction, firstly, the prepolymerization reaction is carried out for 2 hours at the temperature of about 150 ℃, then, the reaction is carried out for 3 to 10 hours at the temperature of 240 ℃ and 280 ℃, and the carbon five carbon nine copolymerized petroleum resin with stable quality, the color number of less than 5 and the softening point of 80 to 110 ℃ can be obtained under the pressure of less than 1.0 MPa. Compared with the existing process conditions, the new process has the advantages that the refined dicyclopentadiene is added into the raw material formula to improve the content of the dicyclopentadiene in the system, so that the reaction is stably carried out, and the color number of the product is low; the new process uses the carbon five oligomer to replace carbon five fraction as a raw material, so that the pressure of a reaction system is low, and the process is safer; the new process increases the control of the prepolymerization reaction process at about 150 ℃, so that the side reaction in the reaction process is reduced.

The synthesis method of the carbon pentaoligomer provided by the embodiment of the invention comprises the following steps: separating and removing light carbon four components and trace moisture in the carbon five generated in the ethylene cracking production to obtain a carbon five mixed component with light removal, dehydration and impurity removal and the water content of less than 50 PPM; the decarburized penta whole fraction mainly contains piperylene, isoprene, cyclopentadiene and dicyclopentadiene. The whole fraction of the carbon penta-de-doped is subjected to thermal polymerization for 2 to 6 hours at the temperature of 240 ℃ and the temperature of 280 ℃ and under the pressure of 5.0 to 6.5MPa to obtain the carbon penta-oligomer.

The method for obtaining the refined dicyclopentadiene provided by the embodiment of the invention comprises the following steps: thermally polymerizing cyclopentadiene in the cracked carbon five fraction to form dicyclopentadiene, then rectifying and separating the dicyclopentadiene through a rectifying tower, separating the unreacted rest carbon five components from the top of the rectifying tower, and obtaining high-purity refined dicyclopentadiene at the tower bottom, wherein the mass percentage content is higher than 85%.

The method for obtaining the dicyclopentadiene-enriched carbon nine fraction provided by the embodiment of the invention comprises the following steps: separating and removing components with more than ten carbon atoms in the carbon nine fraction of the ethylene cracking byproduct to obtain a carbon nine mixed component which is rich in dicyclopentadiene, styrene derivatives and indene and has a boiling range of 130-230 ℃, wherein the mass percentage of the dicyclopentadiene component is higher than 30%.

The prepolymerization reaction is carried out at about 150 ℃ for 2 hours.

According to the novel process for synthesizing the carbon five-carbon nine copolymerized petroleum resin by the thermal polymerization method, a solvent is not required to be added in the reaction process, and when the reaction raw materials, namely the carbon five oligomer, the refined dicyclopentadiene and the dicyclopentadiene-enriched carbon nine mixed fraction are subjected to thermal polymerization, other saturated components which do not participate in the reaction in the mixed components are used as solvent oil to perform thermal polymerization.

The raw material formula is suitable for synthesizing the carbon five-carbon nine copolymerized petroleum resin by a cold polymerization method and is also suitable for synthesizing the carbon five-carbon nine copolymerized petroleum resin by a hot polymerization method.

The thermal polymerization method for synthesizing the carbon five-carbon nine-copolymerized petroleum resin provided by the embodiment of the invention comprises the following specific operation steps: adding a dicyclopentadiene-rich carbon nine fraction, refined dicyclopentadiene and a carbon five oligomer with a boiling range of 130-230 ℃ into a 1L high-pressure reaction kettle, heating to 150 ℃, carrying out prepolymerization reaction for 2 hours, then continuously heating to 240-280 ℃, keeping the reaction pressure below 1.0MPa, keeping the reaction for 3-10 hours, cooling to below 60 ℃, slowly opening a pressure reduction valve, and discharging when the pressure is reduced to 0. And (3) distilling the reaction liquid under reduced pressure until no low fraction is distilled off, discharging, and cooling to obtain the C-V-C-N-C copolymerized petroleum resin.

The chromatographic analysis report of the refined dicyclopentadiene provided by the embodiment of the invention is shown in table 1, and the chromatographic analysis report of the carbon nine fraction rich in dicyclopentadiene is shown in table 2.

TABLE 1 Fine Dicyclopentadiene chromatography report

Components	Content%	Components	Content%
				Total carbon six	2.61	iP dimer	0.19
Benzene and its derivatives	0.07	Dicyclopentadiene (DCPD)	86.38
				Toluene	0	Indenes	1.65
Other dimers	1.30	More than ten carbon heavy components	0.41
				Hydrocarbyl norbornene (MB)	7.39

TABLE 2 Dicyclopentadiene-enriched C.sub.nine fraction chromatography report

The infrared spectrogram of the carbon five-carbon nine-copolymer petroleum resin synthesized by the synthesis method disclosed by the invention is as shown in fig. 2, and the characteristic absorption peak appearing in fig. 2 is the same as the characteristic absorption peak of the infrared spectrogram of the C5/C9 copolymer petroleum resin disclosed in the research on hydrogenation of C5/C9 copolymer petroleum resin at the 17 th stage of 2012, Guangdong chemical industry. As is well known, the absorption peak of C-H stretching vibration and aliphatic chain unsaturated carbon hydrogen ═ C-H stretching vibration on aromatic ring is 3100-^-1There are absorption peaks between them, there are 4 bands under the normal condition of the skeleton vibration absorption of the aromatic ring: 1600cm^-1、1585cm^-1、1500cm^-1、1450cm^-1Out-of-plane bending vibration of C-H on aromatic ring is 650cm at 900-^-1Has strong absorption peak. The synthesis method synthesizes the carbon five carbon nine copolymerized petroleum resin.

The main performance indexes of the carbon five carbon nine copolymerized petroleum resin synthesized by the synthetic method are shown in table 3.

TABLE 3 analysis of the performance index of C5/C9 copolymer resin

The hue and stability indexes of petroleum resin are directly related to the quality of resin products. After analysis, the test sample of the carbon five carbon nine copolymerized petroleum resin synthesized by the novel process of the invention obtains the main performance indexes shown in table 3, and the result shows that the performance indexes of the carbon five carbon nine copolymerized petroleum resin, such as hue, stability and the like, all accord with the characteristics of the carbon five carbon nine copolymerized petroleum resin.

The novel process can replace the production process for synthesizing the petroleum resin by copolymerizing five carbon nine in the prior art, does not use catalysts such as aluminum trichloride and boron trifluoride, omits a washing process step, does not generate industrial sewage and residues, reduces the production cost of the petroleum resin by copolymerizing five carbon nine, and meets the current national environmental protection standard. The synthetic method changes the process route of producing the carbon five carbon nine copolymerized petroleum resin in the prior thermal polymerization technology, replaces the carbon five fraction with the carbon five oligomer, controls the concentration of dicyclopentadiene in the raw materials by adding high-purity refined dicyclopentadiene, obtains the carbon five carbon nine copolymerized petroleum resin with stable softening point and light color at a lower pressure lower than 1.0MPa by increasing the control of the prepolymerization reaction process, and improves the product quality.

The technical scheme of the invention is further described by combining the reaction principle.

The polymerization reaction principle of the invention is as follows:

conjugated dienes can be subjected to 1, 4-addition reactions with certain unsaturated compounds having carbon-carbon double bonds to form cyclic compounds, a reaction known as diene synthesis and also known as diels-alder reaction. The chain or cyclic C5 monoolefins and C5 diolefins react in a thermal polymerizer to form a thermal polymer via a Diels-Alder reaction. The thermal polymerization process is a series of diene addition reactions, and polymers with different molecular weights can be obtained by controlling the polymerization temperature, controlling the thermal polymerization time, adjusting the molecular space structure and the like. In the thermal polymerization reaction, a small portion of C5 and C10 reacts to form C15 and C20. Thermal polymerization process the active mono-olefins in the carbon five fraction are: 3-methyl-1-butene, 1-pentene, cyclopentene; the active diolefins are: 2-methyl-1, 3-butadiene, 1, 4-pentadiene, 1, 3-pentadiene, cyclopentadiene, dicyclopentadiene, methyldicyclopentadiene. The active components in the mixed C-nine fraction include diolefin containing two conjugated double bonds, dicyclopentadiene and active methyl styrene. Meanwhile, dicyclopentadiene and other diolefins such as piperylene, isoprene, styrene derivatives and indene derivatives can also be subjected to polymerization reaction in a hot environment.

The technical solution of the present invention is further described below with reference to specific examples.

Example 1

200ml of dicyclopentadiene indene-rich C9 fraction with the boiling range of 130-230 ℃, 350ml of refined dicyclopentadiene and 350ml of C5 oligomer are added into a 1L high-pressure reaction kettle, the mixture is heated to 150 ℃ for prepolymerization reaction for 2 hours, then the temperature is continuously raised to 240 ℃, the reaction pressure is kept at 0.4MPa, after the reaction is maintained for 10 hours, the temperature is reduced to below 60 ℃, a pressure reducing valve is slowly opened, the pressure is reduced to 0, the material is discharged, the reactant is distilled under reduced pressure until no low fraction is distilled out, the material is discharged and cooled, and 316.8g of C5/C9 copolymerized petroleum resin is obtained.

Example 2

200ml (183.4g) of C9 fraction rich in dicyclopentadiene indene with the boiling range of 130-230 ℃, 350ml (339.1g) of refined dicyclopentadiene and 350ml (311.7g) of C5 oligomer are added into a 1L high-pressure reaction kettle, the mixture is heated to 150 ℃ for prepolymerization reaction for 2 hours, then the mixture is continuously heated to 245 ℃, the reaction pressure is kept at 0.5MPa, the temperature is reduced to below 60 ℃ after the reaction is kept for 9 hours, a pressure reducing valve is slowly opened, and the mixture is discharged after the pressure is reduced to 0. And distilling the reaction liquid under reduced pressure until no low fraction is distilled off, discharging, and cooling to obtain 509.8g of C5/C9 copolymerized petroleum resin.

Example 3

200ml (184.0g) of dicyclopentadiene indene-rich C9 fraction with the boiling range of 130-230 ℃, 350ml (335.6g) of refined dicyclopentadiene and 350ml (305.3g) of C5 oligomer are added into a 1L high-pressure reaction kettle, the mixture is heated to 150 ℃ for prepolymerization reaction for 2 hours, then the mixture is continuously heated to 250 ℃, the reaction pressure is kept at 0.55MPa, the reaction is maintained for 8 hours, the temperature is reduced to below 60 ℃, a pressure reduction valve is slowly opened, and the mixture is discharged when the pressure is reduced to 0. And distilling the reaction liquid under reduced pressure until no low fraction is distilled off, discharging, and cooling to obtain 487.2g of C5/C9 copolymerized petroleum resin.

Example 4

200ml (183.8g) of dicyclopentadiene indene-rich C9 fraction with the boiling range of 130-230 ℃, 350ml (338.6g) of refined dicyclopentadiene and 350ml (311.9g) of C5 oligomer are added into a 1L high-pressure reaction kettle, the mixture is heated to 150 ℃ for prepolymerization reaction for 2 hours, then the temperature is continuously raised to 250 ℃, the reaction pressure is kept at 0.5MPa, the reaction is maintained for 7 hours, the temperature is lowered to below 60 ℃, a pressure reduction valve is slowly opened, and the product is discharged when the pressure is reduced to 0. And (3) carrying out reduced pressure distillation on the reaction liquid until no low fraction is distilled off, discharging, and cooling to obtain 488.7g of C5/C9 copolymerized petroleum resin.

Example 5

200ml (189.9g) of C9 fraction rich in dicyclopentadiene indene with the boiling range of 130-230 ℃, 350ml (339.2g) of refined dicyclopentadiene and 350ml (311.0g) of C5 oligomer are added into a 1L high-pressure reaction kettle, the mixture is heated to 150 ℃ for prepolymerization reaction for 2 hours, then the mixture is continuously heated to 250 ℃, the reaction pressure is kept at 0.45MPa, the reaction is kept for 6 hours, then the temperature is reduced to below 60 ℃, a pressure reducing valve is slowly opened, and the mixture is discharged when the pressure is reduced to 0. And distilling the reaction liquid under reduced pressure until no low fraction is distilled off, discharging, and cooling to obtain 388.3g of C5/C9 copolymerized petroleum resin.

Example 6

200ml (184g) of dicyclopentadiene indene-rich C9 fraction with the boiling range of 130-230 ℃, 350ml (335.6g) of refined dicyclopentadiene and 350ml (305.3g) of C5 oligomer are added into a 1L high-pressure reaction kettle, the mixture is heated to 150 ℃ for prepolymerization reaction for 2 hours, then the mixture is continuously heated to 250 ℃, the reaction pressure is kept at 0.55MPa, the reaction is kept for 5 hours, then the temperature is reduced to below 60 ℃, a pressure reducing valve is slowly opened, and the mixture is discharged when the pressure is reduced to 0. And distilling the reaction liquid under reduced pressure until no low fraction is distilled off, discharging, and cooling to obtain 488.0g of C5/C9 copolymerized petroleum resin.

Example 7

200ml (183.8g) of dicyclopentadiene indene-rich C9 fraction with the boiling range of 130-230 ℃, 350ml (338.8g) of refined dicyclopentadiene and 350ml (309.8g) of C5 oligomer are added into a 1L high-pressure reaction kettle, the mixture is heated to 150 ℃ for prepolymerization reaction for 2 hours, then the temperature is continuously raised to 250 ℃, the reaction pressure is kept at 0.5MPa, the reaction is maintained for 4 hours, the temperature is lowered to below 60 ℃, a pressure reduction valve is slowly opened, and the mixture is discharged when the pressure is reduced to 0. And distilling the reaction liquid under reduced pressure until no low fraction is distilled off, discharging, and cooling to obtain 373.2g of C5/C9 copolymerized petroleum resin.

Example 8

200ml (183.8g) of dicyclopentadiene indene-rich C9 fraction with the boiling range of 130-230 ℃, 350ml (337.9g) of refined dicyclopentadiene and 350ml (308.9g) of C5 oligomer are added into a 1L high-pressure reaction kettle, the mixture is heated to 150 ℃ for prepolymerization reaction for 2 hours, then the temperature is continuously raised to 250 ℃, the reaction pressure is kept at 0.4MPa, the reaction is maintained for 3 hours, the temperature is lowered to below 60 ℃, a pressure reduction valve is slowly opened, and the product is discharged when the pressure is reduced to 0. And distilling the reaction liquid under reduced pressure until no low fraction is distilled off, discharging, and cooling to obtain 391.0g of C5/C9 copolymerized petroleum resin.

Example 9

200ml (179.9g) of dicyclopentadiene indene-rich C9 fraction with the boiling range of 130-230 ℃, 350ml (341.5g) of refined dicyclopentadiene and 350ml (312.8g) of C5 oligomer are added into a 1L high-pressure reaction kettle, the mixture is heated to 150 ℃ for prepolymerization reaction for 2 hours, then the mixture is continuously heated to 255 ℃, the reaction pressure is kept at 0.55MPa, the reaction is maintained for 7 hours, the temperature is reduced to below 60 ℃, a pressure reducing valve is slowly opened, and the mixture is discharged when the pressure is reduced to 0. And (3) carrying out reduced pressure distillation on the reaction liquid until no low fraction is distilled off, discharging, and cooling to obtain 513.3g of C5/C9 copolymerized petroleum resin.

Example 10

200ml (180.5g) of dicyclopentadiene indene-rich C9 fraction with the boiling range of 130-230 ℃, 350ml (336.7g) of refined dicyclopentadiene and 350ml (311.6g) of C5 oligomer are added into a 1L high-pressure reaction kettle, the mixture is heated to 150 ℃ for prepolymerization reaction for 2 hours, then the temperature is continuously raised to 260 ℃, the reaction pressure is kept at 0.55MPa, the reaction is maintained for 6 hours, the temperature is lowered to below 60 ℃, a pressure reduction valve is slowly opened, and the mixture is discharged when the pressure is reduced to 0. And (3) carrying out reduced pressure distillation on the reaction liquid until no low fraction is distilled off, discharging, and cooling to obtain 490.1g of C5/C9 copolymerized petroleum resin.

Example 11

200ml (188.8g) of dicyclopentadiene indene-rich C9 fraction with the boiling range of 130-230 ℃, 350ml (332.0g) of refined dicyclopentadiene and 350ml (310.1g) of C5 oligomer are added into a 1L high-pressure reaction kettle, the mixture is heated to 150 ℃ for prepolymerization reaction for 2 hours, then the temperature is continuously raised to 265 ℃, the reaction pressure is kept at 0.65MPa, the reaction is maintained for 3 hours, the temperature is lowered to below 60 ℃, a pressure reduction valve is slowly opened, and the mixture is discharged when the pressure is reduced to 0. And distilling the reaction liquid under reduced pressure until no low fraction is distilled off, discharging, and cooling to obtain 451.0g of C5/C9 copolymerized petroleum resin.

Example 12

200ml (182.4g) of dicyclopentadiene indene-rich C9 fraction with the boiling range of 130-230 ℃, 350ml (328.4g) of refined dicyclopentadiene and 350ml (305.3g) of C5 oligomer are added into a 1L high-pressure reaction kettle, the mixture is heated to 150 ℃ for prepolymerization reaction for 2 hours, then the temperature is continuously raised to 270 ℃, the reaction pressure is kept at 0.65MPa, the reaction is maintained for 3 hours, the temperature is lowered to below 60 ℃, a pressure reduction valve is slowly opened, and the product is discharged when the pressure is reduced to 0. And distilling the reaction liquid under reduced pressure until no low fraction is distilled off, discharging, and cooling to obtain 503.6g of C5/C9 copolymerized petroleum resin.

Example 13

200ml (180.6g) of dicyclopentadiene indene-rich C9 fraction with the boiling range of 130-230 ℃, 350ml (336.1g) of refined dicyclopentadiene and 350ml (301.1g) of C5 oligomer are added into a 1L high-pressure reaction kettle, the mixture is heated to 150 ℃ for prepolymerization reaction for 2 hours, then the temperature is continuously raised to 275 ℃, the reaction pressure is kept at 0.70MPa, the reaction is maintained for 3 hours, the temperature is lowered to below 60 ℃, a pressure reduction valve is slowly opened, and the product is discharged when the pressure is reduced to 0. And distilling the reaction liquid under reduced pressure until no low fraction is distilled off, discharging, and cooling to obtain 307.8g of C5/C9 copolymerized petroleum resin.

Example 14

200ml (180.6g) of dicyclopentadiene indene-rich C9 fraction with the boiling range of 130-230 ℃, 350ml (336.1g) of refined dicyclopentadiene and 350ml (308.3g) of C5 oligomer are added into a 1L high-pressure reaction kettle, the mixture is heated to 150 ℃ for prepolymerization reaction for 2 hours, then the temperature is continuously raised to 280 ℃, the reaction pressure is kept at 0.80MPa, the reaction is maintained for 3 hours, the temperature is lowered to below 60 ℃, a pressure reduction valve is slowly opened, and the product is discharged when the pressure is reduced to 0. And (3) carrying out reduced pressure distillation on the reaction liquid until no low fraction is distilled off, discharging and cooling to obtain 393.0g of C5/C9 copolymerized petroleum resin.

While the method and techniques of the present invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the art that modifications and rearrangements of the methods and techniques described herein can be made to achieve the desired results without departing from the spirit, scope, and scope of the invention. It is expressly intended that all such similar substitutes and modifications are deemed to be within the spirit, scope and content of the invention.

The above description is only for the purpose of illustrating the present invention and the appended claims are not to be construed as limiting the scope of the invention, which is intended to cover all modifications, equivalents and improvements that are within the spirit and scope of the invention as defined by the appended claims.