The invention provides a brand-new preparation method of the tetracyclododecene compound as shown above, and the preparation method does not introduce any solvent, reduces the energy consumption in the distillation process, and increases the output of the product; ethylene gas or other olefins are not used, so that the investment of equipment is reduced; meanwhile, the preparation method improves the conversion rate of the reaction, the obtained product has high yield and high purity, and the economy of the whole process is improved. The reaction process is as follows:

wherein dicyclopentadiene is cracked at 170 ℃ or above to generate cyclopentadiene, and the D-A reaction is carried out at 230-260 ℃, so that dicyclopentadiene serving as a reaction raw material can be directly reacted with norbornene or derivatives thereof without being separately cracked, and a target product can be obtained.

The compounds of formula (ii) can be prepared by one skilled in the art by reference to synthetic methods disclosed in the prior art, which may be exemplified by CN 104262074A.

In the present invention, the tetracyclododecene compound is selected from any one of the following structures:

preferably, the molar ratio of the cyclopentadiene monomer in the cyclopentadiene or dicyclopentadiene to the compound represented by the formula (II) is 1 (1-10), such as 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10, and other specific values within the above numerical range can be selected, and are not described in detail herein.

The molar ratio of the cyclopentadiene monomer and the compound shown in the formula (II) in the cyclopentadiene or the dicyclopentadiene is selected to be in a numerical range of 1 to 10, because the relative amount of the cyclopentadiene monomer is further reduced, the treatment amount of the compound shown in the formula (II) in one distillation after the reaction is finished is too large, the actually generated product is too small, the production efficiency is influenced, and the relative amount of the cyclopentadiene monomer is further increased, so that the cyclopentadiene can generate a self-polymerization reaction to generate the tricyclopentadiene or a byproduct with higher molecular weight.

Preferably, the mixing of cyclopentadiene or dicyclopentadiene and the compound represented by formula (ii) is performed at 45-50 ℃, for example, 45 ℃, 46 ℃, 47 ℃, 48 ℃, 49 ℃ or 50 ℃, and other specific values within the above numerical range can be selected, and thus detailed description thereof is omitted.

The cyclopentadiene or dicyclopentadiene and the compound shown in the formula (II) are mixed and then are subjected to heat preservation at the temperature of 45-50 ℃, so that the dicyclopentadiene or dicyclopentadiene

Is solid at normal temperature, keeps the temperature above the melting point of the solid, and is convenient for feeding.

Preferably, the cyclopentadiene or dicyclopentadiene and the compound represented by the formula (II) are subjected to a preheating treatment before the Diels-Alder addition reaction is carried out.

Preferably, the preheating temperature is 170-.

The purpose of the preheating treatment is to accelerate the reaction raw material to reach the reaction temperature so as to improve the reaction conversion rate.

Preferably, the addition reaction is carried out under the protection of a protective gas.

Preferably, the addition reaction is performed at a temperature of 230-260 ℃, such as 230 ℃, 235 ℃, 240 ℃, 245 ℃, 250 ℃, 255 ℃ or 260 ℃, and other specific values within the above numerical range can be selected, and are not described in detail herein.

Preferably, the addition reaction is performed under a pressure of 0.5MPa to 3.0MPa, such as 0.5MPa, 1.0MPa, 1.5MPa, 2.0MPa, 2.5MPa, or 3.0MPa, and other specific values within the above numerical range can be selected, and are not described in detail herein.

Preferably, the feeding space velocity of the addition reaction is 5-10h^-1E.g. 5h^-1、6h^-1、7h^-1、8h^-1、9h^-1Or 10h^-1And other specific point values in the above numerical range can be selected, and are not described in detail herein.

Preferably, the reaction product is subjected to a primary distillation after the end of the addition reaction.

Preferably, the temperature of the primary distillation is 96-130 ℃, such as 96 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃ or 130 ℃, etc.

Preferably, the second distillation is carried out after the first distillation is finished.

Preferably, the temperature of the secondary distillation is 65-100 ℃, such as 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃ or 100 ℃ and the like, the vacuum degree is 100-1000Pa, such as 100Pa, 200Pa, 300Pa, 400Pa, 500Pa, 700Pa, 800Pa, 1000Pa and the like, the reflux ratio is 1-50, such as 1, 5, 10, 20, 25, 30, 40 or 50 and the like, and other specific values in the above numerical range can be selected, and are not repeated herein.

The primary distillation is carried out in order to distill off the excess of unreacted compound of formula (II) during the reaction and the secondary distillation is carried out in order to obtain the compound of formula (I).

As a preferred technical scheme of the invention, the preparation method of the tetracyclododecene compound specifically comprises the following steps:

(1) mixing cyclopentadiene or dicyclopentadiene and a compound shown in a formula (II) according to the mol ratio of cyclopentadiene monomer to the compound shown in the formula (II) of 1 (1-10), and preserving the temperature at 45-50 ℃;

(2) preheating the mixture of cyclopentadiene or dicyclopentadiene and the compound shown in the formula (II), wherein the preheating temperature is 170-200 ℃;

(3) the preheated product is put under the protection of nitrogen, under the temperature condition of 230-^-1Carrying out Diels-Alder addition reaction at the feeding airspeed of (1);

(4) carrying out primary distillation on the reaction product at the temperature of 96-130 ℃;

(5) and carrying out secondary distillation on the primary distillation product under the conditions of vacuum degree of 100-1000Pa, temperature of 65-100 ℃ and reflux ratio of 1-50 to obtain the tetracyclododecene compound shown in the formula (I).

More specifically, the preparation method of the tetracyclododecene compound is carried out by matching with reaction equipment shown in figure 1, wherein 1 is a preheater, 2 is a reactor, 3 is a distillation tower, 4 is a rectifying tower, and 5,6, 7, 8, 9 and 10 are pipelines.

In another aspect, the present invention provides a use of the product obtained by the above method for preparing tetracyclododecenes in the preparation of a cyclic olefin copolymer, wherein the cyclic olefin copolymer is prepared by the addition copolymerization reaction of the tetracyclododecenes and alpha-olefin.

Especially, the material is subjected to addition copolymerization with ethylene under the action of a metallocene catalyst to prepare the cycloolefin copolymer material with good heat resistance.

In another aspect, the invention provides an application of a product prepared by the above method for preparing a tetracyclododecene compound in preparing a double-bridge structure acrylate compound, wherein the double-bridge structure acrylate compound is prepared by performing an esterification reaction on the tetracyclododecene compound and an acrylic compound.

In the application, the acrylate compound with the double bridge ring structure is used for preparing high-solid low-viscosity acrylic resin or UV coating.

The prepared resin or coating has high glass transition temperature and good mechanical property, glossiness and other properties.

Compared with the prior art, the invention has the following beneficial effects:

the invention provides a brand-new preparation method of tetracyclododecene compounds, which does not introduce any solvent, reduces the energy consumption in the distillation process and increases the output of products; ethylene gas or other olefins are not used, so that the investment of equipment is reduced; meanwhile, the preparation method improves the conversion rate of the reaction, the obtained product has high yield and high purity, and the economy of the whole process is improved.

Drawings

FIG. 1 is a schematic view of the apparatus used in examples 1 to 9 for the preparation of tetracyclododecenes, wherein 1 is a preheater, 2 is a reactor, 3 is a distillation column, 4 is a rectification column, and 5,6, 7, 8, 9 and 10 are pipes.

Detailed Description

To further illustrate the technical means and effects of the present invention, the following further describes the technical solution of the present invention with reference to the preferred embodiments of the present invention, but the present invention is not limited to the scope of the embodiments.

The tetracyclododecenes were prepared in the apparatus shown in FIG. 1, wherein 1 is a preheater, 2 is a reactor, 3 is a distillation column, 4 is a rectification column, and 5,6, 7, 8, 9 and 10 are pipes.

Example 1

The invention provides a

The preparation method of (2) is as follows:

(1) mixing dicyclopentadiene and norbornene according to the mol ratio of 1:10 of the cyclopentadiene monomers to the norbornene, and keeping the temperature at 50 ℃;

(2) introducing the mixture of dicyclopentadiene and norbornene into apreheater 1 through apipeline 5, wherein the temperature of the preheater is 170 ℃;

(3) introducing the mixture of dicyclopentadiene and norbornene into areactor 2 through apreheater 1, introducing nitrogen into thereactor 2 at the same time, keeping the temperature of 230 ℃ in thereactor 2, the pressure of 0.5MPa and the feeding space velocity of 5h^-1；

(4) After the reaction is finished, the mixed solution enters adistillation tower 3 through a pipeline 6, the distillation temperature is 96 ℃, and unreacted norbornene returns to thepreheater 1 through a pipeline 8 to be recycled;

(5) the recombined fraction obtained after distillation in thedistillation tower 3 enters a rectifyingtower 4 through apipeline 7, and the product tetracyclododecene is obtained under the conditions of the vacuum degree of 100Pa, the rectifying temperature of 65 ℃ and the reflux ratio of 1, wherein the conversion rate of the dicyclopentadiene reaches 90 percent.

Characterization of the compounds:

gas chromatography GC: GC-2014C, Shimadzu corporation, Japan, column DB-5, was tested to have a product content of 98.70%.

Elemental analysis: CE-440 model organic carbon, hydrogen, nitrogen, oxygen, sulfur element analyzer, Calif. USA, tested that the elements are C: 89.93% (89.93%), H: 10.08% (10.06%).

¹H-NMR analysis: AVANCE-400 NMR spectrometer, Bruker, Germany, CDCl₃Is a deuterated reagent, tetramethylsilane is an internal standard, and the test result is as follows: 6.23ppm (2H), 2.58ppm (2H), 2.13ppm (1H), 1.90ppm (1H), 1.60ppm (2H), 1.43-1.44ppm (4H), 1.35ppm (2H), 0.97ppm (1H), 0.70ppm (1H).

Example 2

The invention provides a

The preparation method of (1) is as followsShown in the figure:

(1) mixing dicyclopentadiene and norbornene according to the mol ratio of 1:8 of the cyclopentadiene monomers to the norbornene, and keeping the temperature at 50 ℃;

(2) introducing a mixture of dicyclopentadiene and norbornene into apreheater 1 through apipeline 5, wherein the temperature of the preheater is 200 ℃;

(3) introducing the mixture of dicyclopentadiene and norbornene into areactor 2 through apreheater 1, introducing nitrogen into thereactor 2 at the same time, keeping the temperature of 260 ℃ in thereactor 2, the pressure of 1.5MPa and the feeding airspeed of 10h^-1；

(5) the recombined component obtained after distillation in thedistillation tower 3 enters a rectifyingtower 4 through apipeline 7, and the product tetracyclododecene is obtained under the conditions of vacuum degree of 500Pa, rectifying temperature of 80 ℃ and reflux ratio of 5, wherein the conversion rate of dicyclopentadiene reaches 92 percent.

Characterization of the compounds:

gas chromatography GC: GC-2014C, Shimadzu corporation, Japan, column DB-5, was tested to have a product content of 99.0%.

¹H-NMR analysis: AVANCE-400 NMR spectrometer, Bruker Germany, CDCl3 is deuterated reagent, tetramethylsilane is internal standard, and the test result is: 6.23ppm (2H), 2.58ppm (2H), 2.13ppm (1H), 1.90ppm (1H), 1.60ppm (2H), 1.43-1.44ppm (4H), 1.35ppm (2H), 0.97ppm (1H), 0.70ppm (1H).

Example 3

The invention provides a

The preparation method of (2) is as follows:

(1) mixing dicyclopentadiene and norbornene according to the mol ratio of 1:1 of the cyclopentadiene monomers to the norbornene, and keeping the temperature at 50 ℃;

(3) introducing the mixture of dicyclopentadiene and norbornene into areactor 2 through apreheater 1, introducing nitrogen into thereactor 2 at the same time, keeping the temperature of 250 ℃ in thereactor 2, the pressure of 3.0MPa and the feeding airspeed of 5h^-1；

(4) After the reaction is finished, the mixed solution enters adistillation tower 3 through a pipeline 6, the distillation temperature is 100 ℃, and unreacted norbornene returns to thepreheater 1 through a pipeline 8 to be recycled;

(5) the recombined component obtained after distillation in thedistillation tower 3 enters a rectifyingtower 4 through apipeline 7, and the product tetracyclododecene is obtained under the conditions of vacuum degree of 250Pa, rectifying temperature of 75 ℃ and reflux ratio of 10, wherein the conversion rate of dicyclopentadiene reaches 90 percent.

Characterization of the compounds:

gas chromatography GC: GC-2014C, Shimadzu corporation, Japan, column DB-5, was tested to have a product content of 98.0%.

Example 4

The invention provides 2-methyl-tetracyclododecene

The preparation method of (2) is as follows:

(1) mixing dicyclopentadiene and 5-methylnorbornene according to the mol ratio of 1:8 of cyclopentadiene monomers to 5-methylnorbornene, and keeping the temperature at 45 ℃;

(3) introducing the mixture of dicyclopentadiene and norbornene into areactor 2 through apreheater 1, introducing nitrogen into thereactor 2 at the same time, keeping the temperature of 250 ℃ in thereactor 2, the pressure of 0.5MPa and the feeding airspeed of 5h^-1；

(4) After the reaction is finished, the mixed solution enters adistillation tower 3 through a pipeline 6, the distillation temperature is 110 ℃, and unreacted 5-methylnorbornene returns to thepreheater 1 through a pipeline 8 to be recycled;

(5) the recombined component obtained after distillation in thedistillation tower 3 enters a rectifyingtower 4 through apipeline 7, and under the conditions of a vacuum degree of 100Pa, a rectifying temperature of 90 ℃ and a reflux ratio of 50, a 2-methyltetracyclododecene product is obtained, and the conversion rate of dicyclopentadiene reaches 90 percent.

Characterization of the compounds:

gas chromatography GC: GC-2014C, Shimadzu corporation, Japan, column DB-5, was tested to have a product content of 99.9%.

Elemental analysis: CE-440 model organic carbon, hydrogen, nitrogen, oxygen, sulfur element analyzer, Calif., the elements tested were C89.58% (89.59%) and H10.41% (10.41%).

¹H-NMR analysis: AVANCE-400 NMR spectrometer, Bruker Germany, CDCl3 is deuterated reagent, tetramethylsilane is internal standard, and the test result is: 6.10ppm (2H), 2.58ppm (2H), 2.13ppm (1H), 1.87ppm (1H), 1.60ppm (1H), 1.40-1.44ppm (4H), 1.49ppm (1H), 1.24ppm (1H), 0.94-0.96ppm (4H), 0.70ppm (1H).

Example 5

The invention provides 2-methyl-tetracyclododecene

The preparation method of (2) is as follows:

(3) introducing the mixture of dicyclopentadiene and norbornene into areactor 2 through apreheater 1, introducing nitrogen into thereactor 2 at the same time, keeping the temperature of 250 ℃ in thereactor 2, the pressure of 3.0MPa and the feeding airspeed of 10h^-1；

(5) the recombined component obtained after distillation in thedistillation tower 3 enters a rectifyingtower 4 through apipeline 7, and under the conditions of a vacuum degree of 100Pa, a rectifying temperature of 90 ℃ and a reflux ratio of 20, a 2-methyltetracyclododecene product is obtained, and the conversion rate of dicyclopentadiene reaches 90 percent.

Characterization of the compounds:

Example 6

The invention provides 2-methyl-tetracyclododecene

The preparation method of (2) is as follows:

(1) mixing dicyclopentadiene and 5-methylnorbornene according to the mol ratio of 1:2 of cyclopentadiene monomers to 5-methylnorbornene, and keeping the temperature at 45 ℃;

(2) introducing the mixture of dicyclopentadiene and norbornene into apreheater 1 through apipeline 5, wherein the temperature of the preheater is 190 ℃;

(3) introducing the mixture of dicyclopentadiene and norbornene into areactor 2 through apreheater 1, introducing nitrogen into thereactor 2 at the same time, keeping the temperature of 260 ℃ in thereactor 2, the pressure of 2.5MPa and the feeding airspeed of 5h^-1；

(4) After the reaction is finished, the mixed solution enters adistillation tower 3 through a pipeline 6, the distillation temperature is 115 ℃, and unreacted 5-methylnorbornene returns to thepreheater 1 through a pipeline 8 to be recycled;

(5) the recombined component obtained after distillation in thedistillation tower 3 enters a rectifyingtower 4 through apipeline 7, and under the conditions of a vacuum degree of 100Pa, a rectifying temperature of 90 ℃ and a reflux ratio of 10, a 2-methyltetracyclododecene product is obtained, and the conversion rate of dicyclopentadiene reaches 92%.

Characterization of the compounds:

gas chromatography GC: GC-2014C, Shimadzu corporation, Japan, column DB-5, was tested to have a product content of 98.5%.

Example 7

The invention provides 2, 3-dimethyl tetracyclododecene

The preparation method of (2) is as follows:

(1) mixing dicyclopentadiene and 5, 6-dimethylnorbornene according to the molar ratio of 1:5 of cyclopentadiene monomers to 5, 6-dimethylnorbornene, and keeping the temperature at 45 ℃;

(3) introducing the mixture of dicyclopentadiene and norbornene into areactor 2 through apreheater 1, introducing nitrogen into thereactor 2 at the same time, keeping the temperature of 230 ℃ in thereactor 2, the pressure of 3.0MPa and the feeding space velocity of 5h^-1；

(4) After the reaction is finished, the mixed solution enters adistillation tower 3 through a pipeline 6, the distillation temperature is 130 ℃, and unreacted 5, 6-dimethyl norbornene returns to thepreheater 1 through a pipeline 8 for recycling;

(5) the recombined component obtained after distillation in thedistillation tower 3 enters a rectifyingtower 4 through apipeline 7, and under the conditions of the vacuum degree of 1000Pa, the rectifying temperature of 100 ℃ and the reflux ratio of 5, a 2, 3-dimethyl tetracyclododecene product is obtained, and the conversion rate of dicyclopentadiene reaches 90 percent.

Characterization of the compounds:

Elemental analysis: model CE-440 organic carbon, hydrogen, nitrogen, oxygen, sulfur element analyzer, Calif., the elements were 29.28% (89.29%) C and 10.72% (10.71%) H.

¹H-NMR analysis: AVANCE-400 NMR spectrometer, Bruker Germany, CDCl3 is deuterated reagent, tetramethylsilane is internal standard, and the test result is: 6.05ppm (2H), 2.60ppm (2H), 2.10ppm (1H), 1.90ppm (1H), 1.60ppm (2H), 1.40-1.44ppm (4H), 0.94-0.96ppm (7H), 0.70ppm (1H).

Example 8

The invention provides 2, 3-dimethyl tetracyclododecene

The preparation method of (2) is as follows:

(1) mixing dicyclopentadiene and 5, 6-dimethylnorbornene according to the mol ratio of 1:8 of cyclopentadiene monomers to 5, 6-dimethylnorbornene, and keeping the temperature at 45 ℃;

(3) dicyclopentadieneIntroducing the mixture with norbornene into areactor 2 through apreheater 1, introducing nitrogen into thereactor 2 at the same time, keeping the temperature of 260 ℃ in thereactor 2, the pressure of 1.0MPa and the feeding airspeed of 5h^-1；

(5) the recombined component obtained after distillation in thedistillation tower 3 enters a rectifyingtower 4 through apipeline 7, and under the conditions of a vacuum degree of 100Pa, a rectifying temperature of 90 ℃ and a reflux ratio of 2, a 2, 3-dimethyltetracyclododecene product is obtained, and the conversion rate of dicyclopentadiene reaches 91%.

Characterization of the compounds:

gas chromatography GC: GC-2014C, Shimadzu corporation, Japan, column DB-5, was tested to have a product content of 98.8%.

Example 9

The invention provides 2, 3-dimethyl tetracyclododecene

The preparation method of (2) is as follows:

(1) mixing dicyclopentadiene and 5, 6-dimethylnorbornene according to the molar ratio of 1:10 of cyclopentadiene monomers to 5, 6-dimethylnorbornene, and keeping the temperature at 45 ℃;

(3) the mixture of dicyclopentadiene and norbornene is passed through a preheater 1In thereactor 2, nitrogen is simultaneously introduced into thereactor 2, the temperature in thereactor 2 is kept at 250 ℃, the pressure is 1.5MPa, and the feeding airspeed is 5h^-1；

(5) the recombined component obtained after distillation in thedistillation tower 3 enters a rectifyingtower 4 through apipeline 7, and under the conditions of a vacuum degree of 100Pa, a rectifying temperature of 90 ℃ and a reflux ratio of 10, a 2, 3-dimethyltetracyclododecene product is obtained, and the conversion rate of dicyclopentadiene reaches 92%.

Characterization of the compounds:

¹H-NMR analysis: AVANCE-400 NMR spectrometer, Bruker, Germany, CDCl₃Is a deuterated reagent, tetramethylsilane is an internal standard, and the test result is as follows: 6.05ppm (2H), 2.60ppm (2H), 2.10ppm (1H), 1.90ppm (1H), 1.60ppm (2H), 1.40-1.44ppm (4H), 0.94-0.96ppm (7H), 0.70ppm (1H).

Application example 1

The tetracyclododecenes prepared in examples 1, 4 and 7 are used for preparing cycloolefin copolymer materials, and the method comprises the following steps:

the copolymerization reaction is carried out in a 2L reaction kettle, high-purity nitrogen is firstly used for pumping and discharging four times, and the air in the kettle is discharged. Then, 900mL of toluene, 100mL of the product obtained in examples 1, 4 and 7, and 240. mu. mol of Methylaluminoxane (MAO) were added under nitrogen atmosphere while stirring, and finally 30. mu. mol of a catalyst was added

Quickly heating to 80 ℃, continuously introducing ethylene gas to keep the ethylene pressure at 0.4MPa, and stopping stirring after reacting for 3 hours. Polymerization reaction knotAfter the end, the reaction is stopped by acidified ethanol, white powdery solid is precipitated, washed by ethanol, filtered, dried in vacuum at 70 ℃ for 8 hours and tested.

The method for testing the molar content of the cycloolefin comprises the following steps: determination of the molar content of cycloolefins in the polymer by Bruker AMX 500 NMR¹³C-NMR，CDCl₃Is a deuterated reagent.

Glass transition temperature Tg test method: a Diamond DSC822 of Mettlerlatid company of Switzerland is adopted, the sample amount is 5-10mg, the sample is heated in a nitrogen atmosphere, the heat history is eliminated by a method of heating, cooling and re-heating, the heating rate is 20 ℃/min, the cooling rate is 20 ℃/min, the balance is 2min, and the scanning range is 20-300 ℃.

The method for testing the molecular weight and the molecular weight distribution of the polymer comprises the following steps: trichlorobenzene is used as a solvent to prepare a polymer sample, the sample is injected at 140 ℃ at a sample injection speed of 1.0mL/min, and polystyrene is used as a standard sample.

The results are shown in table 1:

TABLE 1

Application example 2

The tetracyclododecenes prepared in examples 1, 4 and 7 were used to prepare coatings by:

into a four-necked glass flask, 1.2mol of acrylic acid, 1mol of the products obtained in examples 1, 4 and 7 and BF as a catalyst were charged₃·Et₂O2.0 g and hydroquinone as polymerization inhibitor 0.1160g, mixing and stirring, heating to 80 ℃, reacting until the acid value is unchanged, and stopping heating. Reduced pressure distillation, collecting the distillate at the distillation temperature of 150 ℃ and the vacuum degree of 50-300Pa, and obtaining the product of the acrylate with the double bridge structure and the double bridge structure

The solvent is put into a reactor provided with a mechanical stirrer, a thermometer, a reflux condenser tube, a temperature controller and a dropping funnel: c327 parts of propylene glycol methyl ether propionate, stirred and heated to the reflux temperature (namely the boiling point temperature of propylene glycol methyl ether propionate), and 1.5 parts of methacrylic acid, 11.0 parts of methyl acrylate, 10.0 parts of methyl methacrylate, 9.0 parts of hexyl methacrylate, 25.0 parts of styrene, 5.0 parts of hydroxyethyl acrylate, and double-bridge structure acrylate are put into a dropping funnel

10.0 parts of initiator and 1.5 parts of di-tert-amyl peroxide are stirred, the uniform dropping is completed within 3 hours, and the reflux temperature is kept and the stirring is continued for 4 hours after the dropping is completed. Cooling and discharging after the reaction is finished. The prepared acrylic resin and Desmodur N-3390 are taken as curing agents, paint is prepared according to the molar ratio of OH to NCO being 1:1, and the following paint film performance evaluation is carried out:

gloss: the test method is the national standard GB/T9754.

Distinctness of image: the measurement was carried out by using a portable distinctness of image measuring apparatus (PDG).

Weather resistance: the test method is the national standard GB/T1865-2009.

The paint film properties are shown in Table 2.

TABLE 2

And (4) surface note: gamma-poor, delta-good, good quality.

Comparative example 1 is a composition containing

The formulation of (1).

The applicant states that the preparation method and application of the tetracyclododecene compound of the present invention are illustrated by the above examples, but the present invention is not limited to the above examples, i.e. the present invention is not limited to the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.

Claims

1. A method for preparing a tetracyclododecene compound, comprising: mixing cyclopentadiene or dicyclopentadiene with a compound shown in a formula (II) to carry out Diels-Alder addition reaction to prepare the tetracyclododecene compound shown in the formula (I):

wherein R is₁，R₂Independently selected from H or CH₃。

2. The method of preparing a tetracyclododecene compound according to claim 1, wherein said tetracyclododecene compound is selected from any of the following structures:

3. the method for producing a tetracyclododecene compound according to claim 1 or 2, wherein the molar ratio of the cyclopentadiene monomer to the compound represented by the formula (II) in the cyclopentadiene or dicyclopentadiene is 1 (1-10);

preferably, the mixing of cyclopentadiene or dicyclopentadiene and the compound represented by formula (II) is carried out at 45-50 ℃;

preferably, the mixture of cyclopentadiene or dicyclopentadiene and the compound represented by the formula (II) is subjected to a preheating treatment before the Diels-Alder addition reaction;

preferably, the temperature of the preheating is 170-.

4. The method for producing tetracyclododecenes according to any one of claims 1 to 3, wherein said addition reaction is carried out under protection of a protective gas;

preferably, the addition reaction is carried out at a temperature of 230-260 ℃;

preferably, the addition reaction is carried out at a pressure of from 0.5MPa to 3.0 MPa;

preferably, the feeding space velocity of the addition reaction is 5-10h^-1。

5. The process for preparing tetracyclododecenes according to any of claims 1 to 4, wherein said addition reaction is followed by a primary distillation of the reaction product;

preferably, the temperature of the primary distillation is 96-130 ℃.

6. The method for producing tetracyclododecenes according to claim 5, wherein said primary distillation is followed by a secondary distillation;

preferably, the temperature of the secondary distillation is 65-100 ℃, the vacuum degree is 100-1000Pa, and the reflux ratio is 1-50.

7. The method of preparing a tetracyclododecene compound according to any one of claims 1 to 6, in particular comprising the steps of:

8. Use of the products of the process for the preparation of tetracyclododecenes according to any of claims 1 to 7 for the preparation of cycloolefin copolymers obtained by addition copolymerization of tetracyclododecenes with α -olefins according to any of claims 1 to 7.

9. Use of the product of the method for preparing tetracyclododecenes according to any of claims 1 to 7 for the preparation of double-bridged-ring-structured acrylates according to any of claims 1 to 7, wherein said double-bridged-ring-structured acrylates are obtained by esterification of a tetracyclododecenes according to any of claims 1 to 7 with an acrylic compound.

10. The use of claim 9, wherein the acrylate compound with double bridge structure is used for preparing acrylic resin with high solid content and low viscosity or UV paint.