CN110776618A - Cycloolefin copolymer and preparation method and application thereof - Google Patents
Cycloolefin copolymer and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a cycloolefin copolymer and its preparation method and application, the said cycloolefin copolymer includes at least one constitutional unit (A) and at least one constitutional unit (B), the invention makes the cycloolefin copolymer obtained be amorphous polymer by combining these two constitutional units, compared with ordinary cycloolefin copolymer, glass transition temperature and thermal deformation temperature control range are wide, have excellent heat resistance, and the light transmittance of polymer is excellent, have appropriate water absorption and mechanical property at the same time, the raw materials are apt; the invention prepares the cycloolefin copolymer through ring-opening metathesis polymerization reaction and hydrogenation reaction, and obtains the temperature-resistant optical material meeting the actual application requirement by controlling each reaction condition.
Description
Technical Field
The invention relates to the technical field of optical materials, in particular to a cycloolefin copolymer and a preparation method and application thereof.
Background
With the development of electronics and display technologies towards high speed, high density, ultra-thin and high integration, the requirements on the properties of the polymer optical material, such as heat resistance, high temperature dimensional stability, water and oxygen resistance, are higher and higher, so researchers in the field pay attention to the research of colorless transparent high temperature resistant polymer optical materials.
Among them, cycloolefin copolymers have high transparency, low birefringence, high refractive index of light, chemical resistance, excellent heat resistance, melt flowability, dimensional stability, and the like, and are widely used for manufacturing various optical, information, electric, medical materials, and the like.
There are two main ways of polymerizing cycloolefins: the present invention relates to a method for preparing a high-temperature resistant ethylene/norbornene copolymer (COC) by ring-opening metathesis polymerization and addition polymerization, wherein the COC is a classical addition polymer material, the performance of the copolymer is excellent, the currently available commercial COC products include APEL of the japan mitsui chemical company and TOPAS of the takoner company, but the COC material still has defects in some aspects, such as the increase of the glass transition temperature (Tg) of the COC material with the increase of the norbornene content, the high Tg COC material is fragile due to the excessive rigid norbornene structural units, and the COC material is difficult to achieve high temperature resistance due to the insufficient molecular volume of norbornene, and the transparency needs to be improved. In addition, cyclic olefin Copolymer (COP) is obtained by ring-opening metathesis polymerization and hydrogenation of norbornene-type monomers, and currently commercialized COP materials include ZEONEX of japan rapes corporation, and COP materials have characteristics of uniform polymer composition, excellent optical properties, and the like, but if the glass transition temperature of COP materials obtained by ring-opening metathesis polymerization of conventional norbornene-type monomers is lower than that of COC materials.
Due to the defects, most of the cycloolefin copolymers are difficult to be applied to meet the requirements of high-grade electronic devices, such as high-grade lenses, liquid crystal display screens and the like.
CN109134755A discloses a heat-resistant cycloolefin copolymer and a preparation method thereof, in particular to a norbornene derivative 5-ethylidene-2-norbornene, 1-hexene-and 1-octene-long-chain α olefin copolymer, the preparation method of the invention has the advantages of mild reaction conditions, short period, simple operation and the like, and the used catalyst Cpket has very good catalytic activity and thermal stability for the copolymerization reaction, and has great industrial application value and good application prospect.
CN106905483B discloses a cycloolefin copolymer, which is obtained by copolymerization of comonomers under the action of a metathesis polymerization catalyst, wherein the comonomers are cycloolefin and bismaleimide, and the glass transition temperature Tg of the obtained cycloolefin copolymer is higher than 144 ℃. The invention also discloses a preparation method of the cycloolefin copolymer, which can improve the heat resistance of the cycloolefin copolymer obtained by polymerization by adding bismaleimide with a specific structure into a cycloolefin monomer, and the copolymer can be prepared under a relatively mild condition, thereby reducing the production cost of the cycloolefin copolymer. However, the reaction raw materials of the invention have complex structures and are not easy to obtain, and the glass transition temperature of more than 144 ℃ can not meet the requirements of the existing high-grade electronic equipment, so that the heat resistance is required to be further improved, and the transparency is also required to be improved.
CN109593160A discloses a preparation method of cycloolefin copolymer, belonging to the field of organic materials, the preparation steps of the invention are that inert organic solvent, cycloolefin and ethylene are respectively added into a reactor under the conditions of 40-95 ℃ and 0.1-5.0MPa pressure; wherein the molar ratio of the cycloolefin to the ethylene is 1-50: 1; then adding or not adding a chain transfer agent; finally, adding a catalyst to carry out solution polymerization reaction for 0.1-10 h. The polymerization activity of the ethylene-cycloolefin copolymer prepared by the method is high, and the prepared ethylene-cycloolefin copolymer has lower molecular weight compared with ethylene-cycloolefin copolymers prepared by other catalyst systems. But the resulting polymer has poor heat resistance and transparency.
Therefore, there is a need in the art to develop a novel cycloolefin copolymer that is easily available in raw materials, simple to prepare, and has excellent heat resistance and transparency, so as to be suitable for various high-grade electronic display devices.
Disclosure of Invention
An object of the present invention is to provide a cycloolefin copolymer which is excellent in heat resistance and transparency, and which is easily available in raw materials and simple in preparation method.
In order to achieve the purpose, the invention adopts the following technical scheme:
the present invention provides a cycloolefin copolymer comprising at least one structural unit (a) and at least one structural unit (B);
the R is
1、R
2、R
3、R
4、R
5Each independently selected from hydrogen or methyl;
m and k are each independently 0 or 1;
the dashed line marks represent the connecting bonds between the building blocks.
The invention provides a novel cycloolefin copolymer, which comprises a structural unit (A) and a structural unit (B), wherein the structural units with the two specific structures are combined to obtain the cycloolefin copolymer which is an amorphous polymer.
The cycloolefin copolymer provided by the present invention needs to contain both the structural unit (A) and the structural unit (B), wherein only one structural unit (A) may be contained, or two or more structural units (A) may be contained, and the structural units (B) are the same. Ester bonds and alicyclic groups in the structural unit (B) provide more rigid groups for the polymer, namely, the polymer is endowed with higher glass transition temperature and heat distortion temperature, but if the content of the structural unit (B) is too high, the polymer becomes brittle, so that the ratio of the two structural units is controlled within a proper range by matching with the structural unit (A), and the excellent heat resistance is endowed to the polymer, and simultaneously, the mechanical property and other properties of the polymer can be ensured not to be influenced.
Preferably, the total number of structural units in the cycloolefin copolymer is n
0The number of the structural units (A) is n
1The number of the structural units (B) is n
2N is said n
0、n
1、n
2The following conditions are satisfied: n is more than or equal to 0.6
1/n
0≤0.9，E.g., 0.61, 0.63, 0.65, 0.66, 0.68, 0.7, 0.72, 0.75, 0.8, 0.82, 0.85, 0.88, etc., 0.1. ltoreq. n
2/n
00.4, e.g., 0.12, 0.15, 0.18, 0.2, 0.22, 0.25, 0.28, 0.3, 0.32, 0.35, 0.38, etc.
The second object of the present invention is to provide a method for preparing a cycloolefin copolymer according to the first object, which comprises the steps of:
(1) subjecting a cycloolefin monomer to a ring-opening metathesis polymerization reaction to obtain a cycloolefin ring-opening polymer containing a structural unit (C) and a structural unit (D);
dashed line markers represent connecting bonds between structural units; each structural unit of the cycloolefin ring-opening polymer is connected by a double bond, and the position marked by a dotted line can be understood as a half double bond, and when the position is connected with a half double bond of another structural unit, a double bond is formed;
the cycloolefin monomer includes a monomer A
And a monomer B
The R is
1、R
2、R
3、R
4、R
5Each independently selected from hydrogen or methyl;
m and k are each independently 0 or 1;
(2) and carrying out hydrogenation reaction on the cyclic olefin ring-opening polymer under the action of hydrogen to obtain the cyclic olefin copolymer.
The invention takes the norbornene type or dimethylocta-hydrogen naphthalene type based cycloolefin monomer A and the norbornyl ester type or dimethylocta-hydrogen naphthalene type based cycloolefin monomer B as the starting raw materials, can realize the ring-opening metathesis copolymerization reaction under the action of a proper catalyst, and a large amount of double bonds are reserved on the main chain of the prepared copolymer, and the existence of the double bonds can cause the copolymer to be not resistant to yellowing and heat, so that the unsaturated double bonds need to be converted into saturated carbon-carbon bonds through further hydrogenation reaction, thereby obtaining the cycloolefin copolymer with excellent heat resistance.
With respect to the cycloolefin in the present invention
The synthesis can be carried out commercially or according to the prior art, which can be exemplified by the synthesis method of cyclic olefin monomers disclosed in CN104262074A, by a person skilled in the art.
Cyclic olefins in the invention
Can be synthesized by a Diels-Alder reaction, and the reaction formula is shown as follows:
preferably, in the step (1), the monomer A specifically comprises any one or at least two combinations of the following compounds represented by I-1 to I-6:
preferably, in the step (1), the monomer B specifically includes any one or at least two combinations of the following compounds represented by II-1 to II-16:
preferably, the reaction system of the ring-opening metathesis polymerization in the step (1) further comprises a solvent, a chain transfer agent and a catalyst 1.
Preferably, the solvent includes any one or a combination of at least two of benzene, toluene, xylene, n-hexane, and cyclohexane.
Preferably, the mass of the cycloolefin monomer is 5 to 50% of the mass of the solvent, for example, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, etc., preferably 5 to 20%.
The preferred cycloolefin monomer accounts for 5-50% of the solvent by mass, because the monomer concentration is too low, the production efficiency is too low, the monomer concentration is too high, the solution viscosity is too high after ring-opening metathesis polymerization reaction, gelation is easy to occur, and difficulty is caused to hydrogenation reaction.
Preferably, the chain transfer agent comprises α -olefinic compounds, preferably any one or a combination of at least two of 1-pentene, 1-hexene, 1-heptene and 1-octene.
Preferably, the molar ratio of the chain transfer agent to the cycloolefin monomer is 1 (100 to 1000), for example, 1:200, 1:300, 1:400, 1:500, 1:600, 1:700, 1:800, 1:900, and the like.
Preferably, the catalyst 1 comprises Grubbs 1
st、Grubbs 2
ndAnd Hoveyda-Grubbs, or a combination of at least two thereof.
The invention preferably uses the specific ruthenium catalyst to catalyze the ring-opening metathesis polymerization, the catalyst has high activity, low catalyst addition amount and high cycloolefin conversion rate, the catalytic hydrogenation reaction can be directly carried out without further treatment after the reaction, the optical-grade cycloolefin copolymer can be prepared by simple post-treatment, and the whole process is simple and easy to operate.
Preferably, the mass ratio of the catalyst 1 to the cycloolefin monomer is 1 (10)
4～10
5) For example, 1:11000, 1:15000, 1:16000, 1:17000, 1:18000, 1:20000, 1:30000, 1:40000, 1:50000, 1:60000, 1:70000, 1:80000, 1:90000 and the like.
Preferably, the ring-opening metathesis polymerization of step (1) is terminated by a chain terminator.
Preferably, the chain terminator comprises ethyl vinyl ether.
Preferably, the molar ratio of the chain terminator to the cycloolefin monomer is 1 (1000 to 10000), for example 1:2000, 1:3000, 1:4000, 1:5000, 1:6000, 1:7000, 1:8000, 1:9000 and the like.
Preferably, in step (1), the ring-opening metathesis polymerization is carried out under nitrogen protection.
Preferably, step (1) specifically comprises: mixing a cyclic olefin monomer, a solvent and a chain transfer agent, stirring for the first time, then adding a catalyst 1, stirring for the second time, adding a chain terminator, and stirring for the third time to obtain a cyclic olefin ring-opening polymer reaction liquid.
Preferably, in the step (1), the temperature is controlled to be 0 to 30 ℃ while the first stirring is performed, for example, 1 ℃, 5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 28 ℃ and the like.
Preferably, in the step (1), the catalyst 1 is firstly dissolved in the solvent and then is added dropwise into the reaction system.
Preferably, in step (1), the temperature is controlled to be less than or equal to 35 ℃ during the addition of the catalyst 1, such as 15 ℃, 16 ℃, 17 ℃, 18 ℃, 19 ℃, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃, 30 ℃, 31 ℃, 32 ℃, 33 ℃, 34 ℃ and the like.
Preferably, in the step (1), the time for the second stirring is 0.5-2 h, such as 0.6h, 0.7h, 0.8h, 0.9h, 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h and the like.
Preferably, in the step (1), the time for the third stirring is 10-30 min, such as 12min, 14min, 16min, 18min, 20min, 22min, 25min, 26min, 28min, 29min, and the like.
Preferably, step (1) specifically comprises: vacuumizing a reaction bottle, introducing nitrogen to replace air, adding a cycloolefin monomer, a solvent and a chain transfer agent under the protection of nitrogen, stirring for the first time, controlling the temperature to be 0-30 ℃, dissolving a catalyst 1 in the solvent, dropwise adding the catalyst into a reaction system at the temperature of less than or equal to 35 ℃, stirring for the second time for 0.5-2 hours after dropwise adding is finished, adding a chain terminating agent, and stirring for the third time for 10-30 minutes to obtain a cycloolefin ring-opening polymer reaction solution.
Preferably, in the step (2), the reaction system of the hydrogenation reaction further comprises a catalyst 2.
Preferably, the catalyst 2 comprises a homogeneous catalyst.
Preferably, the homogeneous catalyst comprises RuHCl (CO) (PPh)
3)
3And/or Rh (PPh)
3)
3Cl。
Preferably, the Rh (PPh)
3)
3Cl and PPh
3Used in combination, preferably PPh
3Is added in an amount of Rh (PPh)
3)
31 to 5 times, for example, 2 times, 3 times, 4 times, etc., of Cl.
Preferably, the catalyst 2 is added in an amount of 0.05 to 0.5% by mass, for example, 0.06%, 0.08%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.48% and the like, based on the mass of the cycloolefin monomer.
Preferably, in the step (2), the hydrogenation reaction is carried out in a high-pressure reaction kettle.
Preferably, the high-pressure reactor is pressurized to 5 to 10MPa, such as 5.5MPa, 6MPa, 6.5MPa, 7MPa, 7.5MPa, 8MPa, 8.5MPa, 9MPa, 9.5MPa, and the like.
Preferably, in the step (2), the temperature of the hydrogenation reaction is 80 to 140 ℃, for example, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 135 ℃ and the like.
Preferably, the step (2) specifically comprises: adding a catalyst 2 into the cycloolefin ring-opening polymer reaction liquid obtained in the step (1), uniformly stirring, putting into a high-pressure reaction kettle, replacing air in the kettle with nitrogen, pressurizing to 5-10 MPa with hydrogen, stirring for the fourth time, heating to 80-140 ℃, reacting until the pressure in the kettle is constant, stopping heating, cooling to room temperature, releasing pressure, and discharging to obtain a cycloolefin copolymer solution.
Preferably, step (3) is performed after step (2): and (3) mixing the cycloolefin copolymer solution obtained in the step (2) with a water-soluble extractant solution, stirring and heating for the fifth time, adding a peroxide aqueous solution, stirring for the sixth time, reacting at a constant temperature, cooling, and keeping a cycloolefin copolymer solution phase.
The purpose of step (3) is to remove the catalyst, a system composed of a water-soluble extracting agent/peroxide participates in the removal reaction of the catalyst together, the effect is excellent, the removal rate can reach 99.0 percent at most, and the highest recovery rate of the noble metal and the best quality of the polymer product are realized.
Preferably, in the step (3), the target temperature for raising the temperature is 80 to 110 ℃, for example, 82 ℃, 85 ℃, 88 ℃, 90 ℃, 92 ℃, 95 ℃, 98 ℃, 100 ℃, 102 ℃, 105 ℃ and the like.
Preferably, in the step (3), the isothermal reaction time is 0.5-2 h, such as 0.6h, 0.7h, 0.8h, 1h, 1.2h, 1.5h, 1.8h, and the like.
Preferably, in the step (3), the water-soluble extractant includes any one or a combination of at least two of formic acid, acetic acid, ethylenediamine, propylenediamine, monoethanolamine, diethanolamine and triethanolamine, preferably triethanolamine.
Preferably, in the step (3), the mass concentration of the water-soluble extractant in the water-soluble extractant solution is 2-20%, for example, 3%, 4%, 5%, 8%, 10%, 12%, 14%, 16%, 18%, etc.
In the step (3), the amount of the water-soluble extractant solution added is preferably 25 to 100% by mass, for example, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or the like, based on the mass of the cycloolefin copolymer solution obtained in the step (2).
Preferably, in step (3), the peroxide comprises an organic peroxide and/or an inorganic peroxide, preferably any one or a combination of at least two of hydrogen peroxide, peroxyacetic acid and ammonium persulfate, preferably hydrogen peroxide.
Preferably, in the step (3), the mass concentration of the peroxide in the peroxide aqueous solution is 5 to 30%, for example, 6%, 8%, 10%, 12%, 15%, 16%, 18%, 20%, 22%, 25%, 28%, etc.
In the step (3), the amount of the aqueous peroxide solution is preferably 25 to 100% by mass, for example, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95% or the like, based on the mass of the cycloolefin copolymer solution obtained in the step (2).
Preferably, the step (3) specifically comprises the following steps:
and (3) adding a water-soluble extractant solution into the cycloolefin copolymer solution obtained in the step (2), stirring for the fifth time, heating to 80-110 ℃, adding a peroxide aqueous solution, stirring for the sixth time, reacting for 0.5-2 h at constant temperature, cooling, and keeping a cycloolefin copolymer solution phase.
Preferably, step (4) is performed after step (3): and (4) adding a precipitator into the cycloolefin copolymer solution phase obtained in the step (3) for precipitation, filtering, collecting a solid phase, washing and drying to obtain the cycloolefin copolymer.
Preferably, the precipitating agent comprises any one or a combination of at least two of isopropanol, methanol, ethanol and acetone.
Preferably, the preparation method specifically comprises the following steps:
(1) vacuumizing a reaction bottle, introducing nitrogen to replace air, adding a cycloolefin monomer, a solvent and a chain transfer agent under the protection of nitrogen, stirring for the first time, controlling the temperature to be 0-30 ℃, dissolving a catalyst 1 in the solvent, dropwise adding the catalyst into a reaction system at the temperature of less than or equal to 35 ℃, stirring for the second time for 0.5-2 hours after dropwise adding is finished, adding a chain terminating agent, and stirring for the third time for 10-30 minutes to obtain a cycloolefin ring-opening polymer reaction solution;
(2) adding a catalyst 2 into the cycloolefin ring-opening polymer reaction liquid, stirring uniformly, putting into a high-pressure reaction kettle, replacing air in the kettle with nitrogen, pressurizing to 5-10 MPa with hydrogen, stirring for the fourth time, heating to 80-140 ℃, reacting until the pressure in the kettle is constant, stopping heating, cooling to room temperature, relieving pressure, and discharging to obtain a cycloolefin copolymer solution;
(3) adding a water-soluble extractant solution into the cycloolefin copolymer solution, stirring for the fifth time, heating to 80-110 ℃, adding a peroxide aqueous solution, stirring for the sixth time, reacting at a constant temperature for 0.5-2 h, cooling, and keeping a cycloolefin copolymer solution phase;
(4) and adding a precipitator into the cycloolefin copolymer solution phase for precipitation, filtering, collecting a solid phase, washing and drying to obtain the cycloolefin copolymer.
It is a further object of the present invention to provide a polymer optical material obtained by processing (for example, forming a film) the cycloolefin copolymer described in one of the objects.
Preferably, the method for processing the cyclic olefin copolymer into the film comprises the following steps:
taking a certain amount of cycloolefin copolymer in a sample bottle, heating and dissolving in a solvent to prepare a solution with the mass concentration of 5-15%, pouring the solution onto a clean glass plate to form a film by tape casting, heating the solution in an oven at 80 ℃ for 4-6 h, volatilizing most of the solvent, heating the solution in a vacuum drying oven at 70 ℃ for 8-12 h, naturally cooling the solution to room temperature, placing the glass plate in deionized water, removing the film, and drying the film in the oven at 100 ℃ to prepare the heat-resistant cycloolefin copolymer optical film.
The fourth object of the present invention is to provide an application of the polymer optical material of the third object, and the polymer optical material is applied to an optical device.
Preferably, the optical device comprises a lens or a liquid crystal display.
Preferably, the polymer optical material is applied to a light guide plate or a polarizing film of an optical device.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention combines two structural units with specific structures, the obtained cycloolefin copolymer is an amorphous polymer, compared with the common cycloolefin copolymer, the regulation and control range of the glass transition temperature and the thermal deformation temperature is wide, the heat resistance is excellent, the light transmittance of the polymer is excellent, the polymer has proper water absorption and mechanical properties, the raw materials are easy to obtain, the glass transition temperature of the cycloolefin copolymer is 185-210 ℃, the thermal deformation temperature is 158-178 ℃, the light transmittance reaches 91%, the PDI is 1.75-2.30, and the molecular weight distribution is uniform;
(2) the invention takes the norbornene type or dimethylocta-hydrogen naphthalene type based cycloolefin monomer A and the norbornyl ester type or dimethylocta-hydrogen naphthalene type based cycloolefin monomer B as the starting raw materials, can realize the ring-opening metathesis copolymerization reaction under the action of a proper catalyst, and a large amount of double bonds are reserved on the main chain of the prepared copolymer, and the existence of the double bonds can cause the copolymer to be not resistant to yellowing and heat, so that the unsaturated double bonds need to be converted into saturated carbon-carbon bonds through further hydrogenation reaction, thereby obtaining the cycloolefin copolymer with excellent heat resistance.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The proportions of the structural units in the cycloolefin copolymers obtained in the following examples and comparative examples are calculated on the basis of the charge of the monomers, n being for example in example 1
1/n
0＝0.6，n
2/n
0＝0.4。
Example 1
Selection of cycloolefin Compounds
(28.2g，0.3mol)、
(23.2g, 0.1mol) and
(26.0g, 0.1mol) three cycloolefin compounds are used as reaction raw materials to carry out ring-opening metathesis polymerization and hydrogenation reaction to prepare the cycloolefin copolymer, and the preparation method comprises the following steps:
(1) vacuumizing the reaction bottle, replacing air in the reaction bottle with nitrogen, repeatedly operating for 3 times, respectively adding cycloolefin monomers (I-1, II-1 and II-7), toluene 774g and 1-hexene 0.42g under the protection of nitrogen, mixing and stirring, and controlling the temperature in the reaction bottle to be 15 ℃. 7.8mg of Grubbs 1
stDissolving in 10mL of toluene, dropwise adding into a reaction system, and controlling the temperature in the reaction kettle to be not more than 35 ℃. After the dropwise addition, continuously stirring and reacting for 1h, adding 0.036g of ethyl vinyl ether, continuously stirring for 30min, finishing the reaction, preparing colorless, transparent and viscous cycloolefin ring-opening polymer solution,the iodine value of the polymer was determined to be 203.3gI
2/100g。
(2) 0.0774g of RuHCl (CO) (PPh) was charged into the cycloolefin Ring-opened polymer solution
3)
3The catalyst is put into a high-pressure reaction kettle after being stirred evenly, the air in the kettle is replaced by nitrogen, high-purity hydrogen is used for pressurizing to 8MPa, the stirring is started and the temperature is raised to 140 ℃, when the pressure in the kettle is constant, the heating is stopped, the kettle is cooled to the room temperature, the pressure is relieved, the discharging is carried out, the cycloolefin copolymer solution is obtained, and the iodine value of the polymer is tested to be 7.1gI
2The hydrogenation conversion rate reaches 96.5 percent when the catalyst is 100 g.
(3) Adding 400g of 10% triethanolamine solution into a cycloolefin copolymer solution, stirring, heating to 110 ℃, adding 400g of 10% hydrogen peroxide aqueous solution for desorption reaction for 2 hours, cooling for delamination after the reaction is finished, reserving a cycloolefin copolymer solution phase, desorbing a catalyst, and analyzing that the desorption rate of Ru is 98.5%.
(4) Adding isopropanol into the cycloolefin copolymer solution from which the catalyst is removed to precipitate a white solid, and filtering, washing and drying the white solid to obtain 73.5g of heat-resistant cycloolefin copolymer, namely the conversion rate of the cycloolefin monomer is 95.0%.
Example 2
Selection of cycloolefin Compounds
(43.2g, 0.4mol) and
(27.4g, 0.1mol) two cycloolefin compounds are used as reaction raw materials to carry out ring-opening metathesis polymerization and hydrogenation reaction to prepare the cycloolefin copolymer, and the preparation method comprises the following steps:
(1) vacuumizing the reaction flask, then replacing the air in the reaction flask with nitrogen, repeatedly operating for 3 times, respectively adding cycloolefin monomers (I-2 and II-8), toluene 1412g and 1-pentene 0.18g under the protection of nitrogen, mixing and stirring, and controlling the temperature in the reaction flask to be 15 ℃. 0.7mg of Grubbs 2
ndDissolving in 6mL of toluene, dropwise adding into a reaction system, and controlling the temperature in the reaction kettle to be not more than 35 ℃. After the dropwise addition is finishedContinuously stirring for reaction for 0.5h, adding 0.005g of ethyl vinyl ether, continuously stirring for 10min, finishing the reaction, preparing colorless transparent viscous cycloolefin ring-opening polymer solution, and testing that the iodine value of the polymer is 205.5gI
2/100g。
(2) 0.07g of RuHCl (CO) (PPh) was charged into the cycloolefin Ring-opened Polymer solution
3)
3The catalyst is put into a high-pressure reaction kettle after being stirred evenly, the air in the kettle is replaced by nitrogen, high-purity hydrogen is used for pressurizing to 5MPa, the stirring is started and the temperature is raised to 100 ℃, when the pressure in the kettle is constant, the heating is stopped, the kettle is cooled to the room temperature, the pressure is relieved, the discharging is carried out, the cycloolefin copolymer solution is obtained, and the iodine value of the polymer is tested to be 5.8gI
2The hydrogenation conversion rate reaches 97.2 percent when the catalyst is 100 g.
(3) Adding 400g of 10% triethanolamine aqueous solution into a cycloolefin copolymer solution, stirring, heating to a certain temperature, adding 400g of 10% hydrogen peroxide aqueous solution, performing desorption reaction for 1h, cooling for layering after the reaction is finished, retaining a cycloolefin copolymer solution phase, removing a catalyst, and analyzing to obtain a Ru desorption rate of 98.8%.
(4) Adding isopropanol into the cycloolefin copolymer solution from which the catalyst is removed to precipitate white solid, and filtering, washing and drying the white solid to obtain 63.5g of heat-resistant cycloolefin copolymer, namely the conversion rate of the cycloolefin monomer is 90.0%.
Example 3
Selection of cycloolefin Compounds
(42.7g, 0.35mol) and
(44.7g, 0.15mol) two cycloolefin compounds are used as reaction raw materials to carry out ring-opening metathesis polymerization and hydrogenation reaction to prepare the cycloolefin copolymer, and the preparation method comprises the following steps:
(1) vacuumizing the reaction bottle, replacing air with nitrogen, repeating the operation for 3 times, respectively adding cyclic olefin monomers (I-3 and II-9), xylene 874g and 1-octene 0.28g under the protection of nitrogen, mixing, stirring, and controllingThe temperature in the reaction flask was made to be 10 ℃. 2.6mg of Grubbs 1
stDissolving in 6mL of dimethylbenzene, dropwise adding into a reaction system, and controlling the temperature in the reaction kettle to be not more than 35 ℃. After the dropwise addition, the mixture is continuously stirred and reacted for 1 hour, 0.02g of ethyl vinyl ether is added, the mixture is continuously stirred for 20 minutes to finish the reaction, a colorless, transparent and viscous cyclic olefin ring-opening polymer solution is prepared, and the iodine value of the polymer is tested to be 170.2gI
2/100g。
(2) 0.437g of RuHCl (CO) (PPh) was put into the cycloolefin Ring-opened Polymer solution
3)
3The catalyst is put into a high-pressure reaction kettle after being stirred evenly, the air in the kettle is replaced by nitrogen, high-purity hydrogen is used for pressurizing to 10MPa, the stirring is started and the temperature is raised to 100 ℃, when the pressure in the kettle is constant, the heating is stopped, the kettle is cooled to the room temperature, the pressure is relieved, the discharging is carried out, the cycloolefin copolymer solution is obtained, and the iodine value of the polymer is tested to be 0.85gI
2Per 100g, namely the conversion rate of the hydrogenation reaction reaches 99.5 percent.
(3) Adding 250g of 10% triethanolamine aqueous solution into a cycloolefin copolymer solution, stirring, heating to a certain temperature, adding 250g of 10% hydrogen peroxide aqueous solution for desorption reaction for 0.5h, cooling for layering after the reaction is finished, retaining a cycloolefin copolymer solution phase, desorbing a catalyst, and analyzing to obtain a Ru desorption rate of 98.5%.
(4) Adding isopropanol into the cycloolefin copolymer solution from which the catalyst is removed to precipitate a white solid, and filtering, washing and drying the white solid to obtain 80.6g of heat-resistant cycloolefin copolymer, namely the conversion rate of the cycloolefin monomer is 92.2%.
Example 4
Selection of cycloolefin Compounds
(72.0g, 0.45mol) and
(15.6g, 0.05mol) two cycloolefin compounds are used as reaction raw materials to carry out ring-opening metathesis polymerization and hydrogenation reaction to prepare the cycloolefin copolymer, and the preparation method comprises the following steps:
(1) after the reaction bottle is vacuumizedThen, the atmosphere therein was replaced with nitrogen, and after repeating the operation for 3 times, the cycloolefin monomers (I-4 and II-10), 438g of cyclohexane and 0.42g of 1-hexene were charged under the protection of nitrogen, respectively, and the mixture was stirred while controlling the temperature in the reaction flask to 10 ℃. 4.4mg of Grubbs 2
ndDissolving in 8mL of cyclohexane, and then dropwise adding into a reaction system, wherein the temperature in the reaction kettle is controlled not to exceed 35 ℃. After the dropwise addition, the mixture is continuously stirred and reacted for 1h, 0.018g of ethyl vinyl ether is added, the mixture is continuously stirred for 30min to finish the reaction, colorless, transparent and viscous cycloolefin ring-opening polymer solution is prepared, and the iodine value of the polymer is tested to be 150.0gI
2/100g。
(2) 0.0876g of RuHCl (CO) (PPh) was charged into the cycloolefin Ring-opened polymer solution
3)
3The catalyst is put into a high-pressure reaction kettle after being stirred evenly, the air in the kettle is replaced by nitrogen, high-purity hydrogen is used for pressurizing to 10MPa, the stirring is started and the temperature is raised to 80 ℃, when the pressure in the kettle is constant, the heating is stopped, the kettle is cooled to the room temperature, the pressure is relieved, the discharging is carried out, the cycloolefin copolymer solution is obtained, and the iodine value of the polymer is 3.0gI through the test
2100g, namely the conversion rate of the hydrogenation reaction reaches 98.0 percent.
(3) Adding 400g of 10% triethanolamine aqueous solution into a cycloolefin copolymer solution, stirring, heating to a certain temperature, adding 400g of 10% hydrogen peroxide aqueous solution for desorption reaction for 2h, cooling for delamination after the reaction is finished, reserving a cycloolefin copolymer solution phase, desorbing the catalyst, and analyzing the desorption rate of Ru to be 98.8%.
(4) Adding isopropanol into the cycloolefin copolymer solution phase without the catalyst to precipitate white solid, and filtering, washing and drying to obtain 80.2g of heat-resistant cycloolefin copolymer, namely the conversion rate of cycloolefin monomer is 91.5%.
Example 5
Selection of cycloolefin Compounds
(52.2g，0.3mol)、
(24.6g, 0.1mol) and
(31.2g, 0.1mol) two cycloolefin compounds are used as reaction raw materials to carry out ring-opening metathesis polymerization and hydrogenation reaction to prepare the cycloolefin copolymer, and the preparation method comprises the following steps:
(1) vacuumizing the reaction flask, replacing air with nitrogen, repeating the operation for 3 times, respectively adding cycloolefin monomers (I-1, II-2 and II-11), toluene 1080g and 1-heptene 0.098g under the protection of nitrogen, mixing and stirring, and controlling the temperature in the reaction flask to be 30 ℃. 10.8mg of Grubbs 2
ndDissolving in 6mL of toluene, dropwise adding into a reaction system, and controlling the temperature in the reaction kettle to be not more than 35 ℃. After the dropwise addition, the mixture is continuously stirred and reacted for 1 hour, 0.036g of ethyl vinyl ether is added, the mixture is continuously stirred for 30 minutes to finish the reaction, a colorless, transparent and viscous cyclic olefin ring-opening polymer solution is prepared, and the iodine value of the polymer is tested to be 124.5gI
2/100g。
(2) 0.108g of Rh (PPh) was put into the cycloolefin Ring-opened polymer solution
3)
3Cl catalyst and 0.540g PPh
3Stirring uniformly, placing into a high-pressure reaction kettle, replacing air in the kettle with nitrogen, pressurizing to 5MPa with high-purity hydrogen, starting stirring, heating to 140 ℃, stopping heating when the pressure in the kettle is constant, cooling to room temperature, releasing pressure, discharging to obtain cycloolefin copolymer solution, and testing that the iodine value of the polymer is 6.2 gI
2The hydrogenation conversion rate reaches 95.0 percent when the catalyst is 100 g.
(3) Adding 300g of 10% triethanolamine aqueous solution into a cycloolefin copolymer solution, stirring, heating to a certain temperature, adding 300g of 10% hydrogen peroxide aqueous solution for desorption reaction for 2h, cooling for demixing after the reaction is finished, reserving a cycloolefin copolymer solution phase, and desorbing a catalyst, wherein the desorption rate of Ru is 98.8% and the desorption rate of Rh is 98.5% through analysis.
(4) Adding isopropanol into the cycloolefin copolymer solution from which the catalyst is removed to precipitate white solid, and filtering, washing and drying the white solid to obtain 102.0g of heat-resistant cycloolefin copolymer, namely the conversion rate of cycloolefin monomer is 94.5%.
Example 6
Selection of cycloolefin Compounds
(56.4g，0.3mol)、
(24.6g, 0.1mol) and
(32.6g, 0.1mol) three cycloolefin compounds as reaction raw materials to carry out ring-opening metathesis polymerization and hydrogenation reaction to prepare the cycloolefin copolymer, and the preparation method comprises the following steps:
(1) vacuumizing the reaction flask, replacing air with nitrogen, repeating the operation for 3 times, respectively adding cycloolefin monomers (I-6, II-5 and II-12), toluene 1136g and 1-hexene 0.42g under the protection of nitrogen, mixing and stirring, and controlling the temperature in the reaction flask to be 0 ℃. 5.7mg of Grubbs 1
stDissolving in 10mL of toluene, dropwise adding into a reaction system, and controlling the temperature in the reaction kettle to be not more than 35 ℃. After the dropwise addition, the mixture is continuously stirred and reacted for 1 hour, 0.0036g of ethyl vinyl ether is added, the mixture is continuously stirred for 30 minutes, the reaction is ended, a colorless, transparent and viscous cyclic olefin ring-opening polymer solution is prepared, and the iodine value of the polymer is tested to be 115.0gI
2/100g。
(2) 0.1136g of RuHCl (CO) (PPh) was put into the cycloolefin Ring-opened polymer solution
3)
3The catalyst is put into a high-pressure reaction kettle after being stirred evenly, the air in the kettle is replaced by nitrogen, high-purity hydrogen is used for pressurizing to 8MPa, the stirring is started and the temperature is raised to 140 ℃, when the pressure in the kettle is constant, the heating is stopped, the kettle is cooled to the room temperature, the pressure is relieved, the discharging is carried out, the cycloolefin copolymer solution is obtained, and the iodine value of the polymer is 1.2gI through testing
2Per 100g, namely the conversion rate of the hydrogenation reaction reaches 99.0 percent.
(3) Adding 350g of 10% triethanolamine aqueous solution into a cycloolefin copolymer solution, starting stirring, heating to a certain temperature, adding 350g of 10% hydrogen peroxide aqueous solution for desorption reaction for 2h, cooling for delamination after the reaction is finished, retaining a cycloolefin copolymer solution phase, desorbing a catalyst, and analyzing to obtain the catalyst with the Ru desorption rate of 99.0%.
(4) Adding isopropanol into the cycloolefin copolymer solution from which the catalyst is removed to precipitate white solid, and filtering, washing and drying the white solid to obtain 104.5g of heat-resistant cycloolefin copolymer, namely the conversion rate of cycloolefin monomer is 92.0%.
Example 7
Selection of cycloolefin Compounds
(64.0g, 0.4mol), and
(31.2g, 0.1mol) two cycloolefin compounds are used as reaction raw materials to carry out ring-opening metathesis polymerization and hydrogenation reaction to prepare the cycloolefin copolymer, and the preparation method comprises the following steps:
(1) vacuumizing the reaction flask, replacing the air with nitrogen, repeating the operation for 3 times, respectively adding cycloolefin monomers (I-4 and II-13), toluene 952g and 1-hexene 0.42g under the protection of nitrogen, mixing and stirring, and controlling the temperature in the reaction flask to be 20 ℃. 1.0mg of Hoveyda-Grubbs was dissolved in 3mL of toluene, and the solution was added dropwise to the reaction system while controlling the temperature in the reaction vessel to not more than 35 ℃. After the dropwise addition, the mixture is continuously stirred and reacted for 1 hour, 0.036g of ethyl vinyl ether is added, the mixture is continuously stirred for 30 minutes to finish the reaction, a colorless, transparent and viscous cycloolefin ring-opening polymer solution is prepared, and the iodine value of the polymer is 143.5gI by testing
2/100g。
(2) 0.0952g of RuHCl (CO) (PPh) was put into the cycloolefin Ring-opened polymer solution
3)
3The catalyst is put into a high-pressure reaction kettle after being stirred evenly, the air in the kettle is replaced by nitrogen, high-purity hydrogen is used for pressurizing to 10MPa, the stirring is started and the temperature is raised to 120 ℃, when the pressure in the kettle is constant, the heating is stopped, the kettle is cooled to the room temperature, the pressure is relieved, the discharging is carried out, the cycloolefin copolymer solution is obtained, and the iodine value of the polymer is 1.7gI through the test
2100g, namely the conversion rate of hydrogenation reaction reaches 98.8 percent.
(3) Adding 265g of 10% triethanolamine aqueous solution into a cycloolefin copolymer solution, stirring, heating to a certain temperature, adding 265g of 10% hydrogen peroxide aqueous solution to perform a removal reaction for 2 hours, cooling and layering after the reaction is finished, reserving a cycloolefin copolymer solution phase, removing a catalyst, and analyzing that the removal rate of Ru is 98.6%.
(4) Adding isopropanol into the cycloolefin copolymer solution phase without the catalyst to precipitate white solid, and filtering, washing and drying to obtain 89.0g of heat-resistant cycloolefin copolymer, namely the conversion rate of cycloolefin monomer is 93.5%.
Example 8
Selection of cycloolefin Compounds
(52.2g，0.3mol)、
(13.0g, 0.05mol) and
(48.9g, 0.15mol) three cycloolefin compounds as reaction raw materials to carry out ring-opening metathesis polymerization and hydrogenation reaction to prepare the cycloolefin copolymer, and the preparation method comprises the following steps:
(1) vacuumizing the reaction bottle, replacing air in the reaction bottle with nitrogen, repeatedly operating for 3 times, respectively adding cycloolefin monomers (I-5, II-6 and II-14), n-hexane 1141g and 1-hexene 0.42g under the protection of nitrogen, mixing and stirring, and controlling the temperature in the reaction bottle to be 10 ℃. 3.4mg of Grubbs 1
stDissolving in 6mL of normal hexane, then dropwise adding into a reaction system, and controlling the temperature in the reaction kettle to be not more than 35 ℃. After the dropwise addition, the mixture is continuously stirred and reacted for 1 hour, 0.036g of ethyl vinyl ether is added, the mixture is continuously stirred for 30 minutes to finish the reaction, a colorless, transparent and viscous cycloolefin ring-opening polymer solution is prepared, and the iodine value of the polymer is tested to be 121gI
2/100g。
(2) 0.1141g of Rh (PPh) was put into the cycloolefin Ring-opened polymer solution
3)
3Cl catalyst and 0.1141gPPh
3Stirring uniformly, putting into a high-pressure reaction kettle, replacing air in the kettle with nitrogen, pressurizing to 10MPa with high-purity hydrogen, starting stirring, heating to 100 ℃, and reacting until the pressure in the kettle is constantStopping heating, cooling to room temperature, releasing pressure, discharging to obtain cyclic olefin copolymer solution, and testing the iodine value of the polymer to be 1.2gI
2Per 100g, namely the conversion rate of the hydrogenation reaction reaches 99.0 percent.
(3) Adding 315g of 10% triethanolamine aqueous solution into a cycloolefin copolymer solution, stirring, heating to a certain temperature, adding 315g of 10% hydrogen peroxide aqueous solution to perform a desorption reaction for 2 hours, cooling and layering after the reaction is finished, reserving a cycloolefin copolymer solution phase, desorbing the catalyst, and analyzing that the desorption rate of Ru is 98.8% and the desorption rate of Rh is 99.0%.
(4) Adding isopropanol into the cycloolefin copolymer solution from which the catalyst is removed to precipitate a white solid, and filtering, washing and drying the white solid to obtain 107.3g of heat-resistant cycloolefin copolymer, namely the conversion rate of the cycloolefin monomer is 94.0%.
Example 9
Selection of cycloolefin Compounds
(56.4g，0.3mol)、
(36.9g, 0.15mol) and
(16.3g, 0.05mol) three cycloolefin compounds are used as reaction raw materials to carry out ring-opening metathesis polymerization and hydrogenation reaction to prepare the cycloolefin copolymer, and the preparation method comprises the following steps:
(1) vacuumizing the reaction flask, replacing air with nitrogen, repeating the operation for 3 times, respectively adding cycloolefin monomers (I-6, II-3 and II-15), toluene 1100g and 1-hexene 0.42g under the protection of nitrogen, mixing and stirring, and controlling the temperature in the reaction flask to be 20 ℃. 3.3mg of Grubbs 2
ndDissolving in 6mL of toluene, dropwise adding into a reaction system, and controlling the temperature in the reaction kettle to be not more than 35 ℃. After the dropwise addition, the mixture is continuously stirred and reacted for 1 hour, 0.036g of ethyl vinyl ether is added, the mixture is continuously stirred for 30 minutes to finish the reaction, and a colorless, transparent and viscous cycloolefin ring-opening polymer solution is prepared, and the solution is tested to beIodine number of polymer 120.0g I
2/100g。
(2) 0.1096g of RuHCl (CO) (PPh) was put into the cycloolefin Ring-opened polymer solution
3)
3The catalyst is put into a high-pressure reaction kettle after being stirred evenly, the air in the kettle is replaced by nitrogen, high-purity hydrogen is used for pressurizing to 10MPa, the stirring is started and the temperature is raised to 140 ℃, when the pressure in the kettle is constant, the heating is stopped, the kettle is cooled to the room temperature, the pressure is relieved, the discharging is carried out, the cycloolefin copolymer solution is obtained, and the iodine value of the polymer is tested to be 0.1gI
2Per 100g, namely the conversion rate of the hydrogenation reaction reaches 99.2 percent.
(3) Adding 305g of 10% triethanolamine aqueous solution into a cycloolefin copolymer solution, starting stirring, heating to a certain temperature, adding 305g of 10% hydrogen peroxide aqueous solution to perform a removal reaction for 2 hours, cooling and layering after the reaction is finished, retaining a cycloolefin copolymer solution phase, removing a catalyst, and analyzing to obtain a Ru removal rate of 99.0%.
(4) Adding isopropanol into the cycloolefin copolymer solution phase without the catalyst to precipitate white solid, and filtering, washing and drying to obtain 101.4g of heat-resistant cycloolefin copolymer, namely the conversion rate of cycloolefin monomer is 92.5%.
Example 10
Selection of cycloolefin Compounds
(56.4g，0.3mol)、
(26.0g, 0.1mol) and
(34.0g, 0.1mol) three cycloolefin compounds are used as reaction raw materials to carry out ring-opening metathesis polymerization and hydrogenation reaction to prepare the cycloolefin copolymer, and the preparation method comprises the following steps:
(1) vacuumizing the reaction bottle, replacing air with nitrogen, repeating the operation for 3 times, adding cycloolefin monomers (III-1, IV-1 and V-1), toluene 1164g and 1-hexene 0.42g under the protection of nitrogen, mixing, stirring, and controlling reverse reactionThe temperature in the flask should be 20 ℃. 4.3mg of Grubbs 1
stDissolving in 10mL of toluene, dropwise adding into a reaction system, and controlling the temperature in the reaction kettle to be not more than 35 ℃. After the dropwise addition, the mixture is continuously stirred and reacted for 1 hour, 0.025g of ethyl vinyl ether is added, the mixture is continuously stirred for 30 minutes, the reaction is ended, colorless, transparent and viscous cyclic olefin ring-opening polymer solution is prepared, and the iodine value of the polymer is tested to be 116.0gI
2/100g。
(2) 0.1164g of RuHCl (CO) (PPh) was put into the cycloolefin Ring-opened polymer solution
3)
3The catalyst is put into a high-pressure reaction kettle after being stirred evenly, the air in the kettle is replaced by nitrogen, high-purity hydrogen is used for pressurizing to 10MPa, the stirring is started and the temperature is raised to 140 ℃, when the pressure in the kettle is constant, the heating is stopped, the kettle is cooled to the room temperature, the pressure is relieved, the discharging is carried out, the cycloolefin copolymer solution is obtained, and the iodine value of the polymer is 1.2gI through testing
2Per 100g, namely the conversion rate of the hydrogenation reaction reaches 99.0 percent.
(3) Adding 320g of 10% triethanolamine aqueous solution into a cycloolefin copolymer solution, stirring, heating to a certain temperature, adding 320g of 10% hydrogen peroxide aqueous solution for desorption reaction for 2h, cooling for delamination after the reaction is finished, reserving a cycloolefin copolymer solution phase, desorbing the catalyst, and analyzing the desorption rate of Ru to be 98.8%.
(4) Adding isopropanol into the cycloolefin copolymer solution from which the catalyst is removed to precipitate white solid, and filtering, washing and drying the white solid to obtain 105.3g of heat-resistant cycloolefin copolymer, namely the conversion rate of the cycloolefin monomer is 90.5%.
Comparative example 1
The cycloolefin copolymer of this comparative example was TOPAS 6015, available from Taconina, USA.
Comparative example 2
The cyclic olefin copolymer of this comparative example was TOPAS 6017, available from Taconina, USA.
Comparative example 3
The difference from example 1 is that monomer II-1 and monomer II-7 were not added and monomer I-1 was added in an amount of 0.5 mol.
Performance testing
(1) Determination of the Ru or Rh content: the content of Ru or Rh metal in the extract was analyzed by an atomic absorption spectrophotometer (model: PE-5000, manufacturer: PerkinElmer, USA),
calculation of Ru or Rh removal:
(2) iodine value of the polymer: the test method is GB/T5532-2008;
calculation of the hydrogenation conversion:
(3) calculation of the polymer yield:
(4) polymer weight average molecular weight (M)
w) And molecular weight distribution (PDI) test:
a high temperature gel permeation chromatograph (model: Agilent PL gel MIXED-BLS, manufacturer: Agilent Co., USA) is used, the mobile phase is 1,2, 4-trichlorobenzene, the column temperature is 150 ℃, the flow rate is 1mL/min, the sample injection volume is 200 mu L, and the standard product is narrow distribution polystyrene.
(5) Polymer glass transition temperature (Tg): the test method is ISO 11375-1, -2, -3.
(6) Heat distortion temperature (HDT, 1.82MPa) of polymer: the test temperature was ISO 75part 2.
(7) Total light transmittance of polymer (t 120 μm): a120 μm thick sample was prepared and tested for total light transmittance in ASTM-D1003.
The test results of the performance tests (4) to (7) are shown in table 1.
TABLE 1
In Table 1, "-" indicates that the test was not performed.
As can be seen from Table 1, the cycloolefin copolymer prepared by the invention has the weight-average molecular weight of 115000-135000, the molecular weight distribution PDI of 1.75-2.30, uniform molecular weight and molecular weight distribution, the glass transition temperature of 185-210 ℃, the heat distortion temperature of 158-178 ℃, and the light transmittance of 91%, and has higher glass transition temperature and heat distortion temperature compared with two types of imported materials TOPAS 6015 (comparative example 1) and TOPAS 6017 (comparative example 2) with excellent temperature resistance, and the requirement of higher heat resistance is met.
Comparative example 3 omits only one of the monomers compared to example 1, and ensures that the total monomer addition is constant, the resulting cycloolefin copolymer has a significantly reduced glass transition temperature and a significantly reduced heat distortion temperature, thereby demonstrating that the above-mentioned excellent properties can be obtained only when the cycloolefin copolymer contains the structural units of the two specific structures of the present invention at the same time.
Catalyst removal Rate test
Taking the cycloolefin copolymer solution obtained in the step (2) in the example 1, selecting different extracting agents, peroxides and the use amounts thereof according to the catalyst removal step in the step (3), layering the aqueous solution of the extracting agents and the peroxides with the cycloolefin copolymer solution after the reaction is finished, analyzing the metal concentration of the catalyst in the aqueous solution of the extracting agents, and measuring the catalyst removal rate in the cycloolefin copolymer solution, which is specifically shown in table 2.
TABLE 2
As can be seen from Table 2, the system composed of triethanolamine/hydrogen peroxide is used together to take part in the catalyst removal reaction, and the catalyst removal effect is the best. Therefore, in each of examples 2 to 10, a triethanolamine/hydrogen peroxide system was selected for catalyst removal, so as to achieve the highest recovery rate of noble metals and the best quality of polymer products.
The present invention is illustrated in detail by the examples described above, but the present invention is not limited to the details described above, i.e., it is not intended that the present invention be implemented by relying on the details described above. 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.
Claims (10)
1. A cycloolefin copolymer, characterized in that the cycloolefin copolymer comprises at least one structural unit (a) and at least one structural unit (B);
the R is
1、R
2、R
3、R
4、R
5Each independently selected from hydrogen or methyl;
m and k are each independently 0 or 1;
the dashed line marks represent the connecting bonds between the building blocks.
2. The cycloolefin copolymer according to claim 1, characterized in that the total number of structural units in the cycloolefin copolymer is n
0The number of the structural units (A) is n
1The number of the structural units (B) is n
2N is said n
0、n
1、n
2The following conditions are satisfied: n is more than or equal to 0.6
1/n
0≤0.9，0.1≤n
2/n
0≤0.4。
3. A method for preparing a cycloolefin copolymer according to claim 1 or 2, characterized in that the preparation method comprises the following steps:
(1) subjecting a cycloolefin monomer to a ring-opening metathesis polymerization reaction to obtain a cycloolefin ring-opening polymer containing a structural unit (C) and a structural unit (D);
dashed line markers represent connecting bonds between structural units;
the cycloolefin monomer includes a monomer A
And a monomer B
The R is
1、R
2、R
3、R
4、R
5Each independently selected from hydrogen or methyl;
m and k are each independently 0 or 1;
(2) and carrying out hydrogenation reaction on the cyclic olefin ring-opening polymer to obtain the cyclic olefin copolymer.
4. The method according to claim 3, wherein in step (1), the monomer A specifically includes any one or at least two combinations of the following compounds represented by I-1 to I-6:
preferably, in the step (1), the monomer B specifically includes any one or at least two combinations of the following compounds represented by II-1 to II-16:
5. the preparation method according to claim 3 or 4, wherein the reaction system of the ring-opening metathesis polymerization of the step (1) further comprises a solvent, a chain transfer agent and a catalyst 1;
preferably, the solvent comprises any one or a combination of at least two of benzene, toluene, xylene, n-hexane and cyclohexane;
preferably, the mass of the cycloolefin monomer accounts for 5-50% of the mass of the solvent, and preferably 5-20%;
preferably, the chain transfer agent comprises α -olefinic compounds, preferably any one or a combination of at least two of 1-pentene, 1-hexene, 1-heptene and 1-octene;
preferably, the molar ratio of the chain transfer agent to the cycloolefin monomer is 1 (100-1000);
preferably, the catalyst 1 comprises Grubbs 1
st、Grubbs 2
ndAnd Hoveyda-Grubbs, or a combination of at least two thereof;
preferably, the mass ratio of the catalyst 1 to the cycloolefin monomer is 1 (10)
4～10
5)；
Preferably, the ring-opening metathesis polymerization of step (1) is terminated by a chain terminator;
preferably, the chain terminator comprises ethyl vinyl ether;
preferably, the molar ratio of the chain terminator to the cycloolefin monomer is 1 (1000 to 10000);
preferably, in step (1), the ring-opening metathesis polymerization is carried out under the protection of nitrogen;
preferably, step (1) specifically comprises: mixing a cyclic olefin monomer, a solvent and a chain transfer agent, stirring for the first time, then adding a catalyst 1, stirring for the second time, adding a chain terminator, and stirring for the third time to obtain a cyclic olefin ring-opening polymer reaction solution;
preferably, in the step (1), the temperature is controlled to be 0-30 ℃ while the first stirring is carried out;
preferably, in the step (1), the catalyst 1 is dissolved in a solvent and then is dropwise added into a reaction system;
preferably, in the step (1), the temperature is controlled to be less than or equal to 35 ℃ in the process of adding the catalyst 1;
preferably, in the step (1), the time for the second stirring is 0.5-2 h;
preferably, in the step (1), the third stirring time is 10-30 min;
preferably, step (1) specifically comprises: vacuumizing a reaction bottle, introducing nitrogen to replace air, adding a cycloolefin monomer, a solvent and a chain transfer agent under the protection of nitrogen, stirring for the first time, controlling the temperature to be 0-30 ℃, dissolving a catalyst 1 in the solvent, dropwise adding the catalyst into a reaction system at the temperature of less than or equal to 35 ℃, stirring for the second time for 0.5-2 hours after dropwise adding is finished, adding a chain terminating agent, and stirring for the third time for 10-30 minutes to obtain a cycloolefin ring-opening polymer reaction solution.
6. The preparation method according to any one of claims 3 to 5, wherein in the step (2), the reaction system of the hydrogenation reaction further comprises a catalyst 2;
preferably, the catalyst 2 comprises a homogeneous catalyst;
preferably, the homogeneous catalyst comprises RuHCl (CO) (PPh)
3)
3And/or Rh (PPh)
3)
3Cl；
Preferably, the Rh (PPh)
3)
3Cl and PPh
3Used in combination, preferably PPh
3Is added in an amount of Rh (PPh)
3)
31-5 times of Cl in mass;
preferably, the adding amount of the catalyst 2 is 0.05-0.5% of the mass of the cycloolefin monomer;
preferably, in the step (2), the hydrogenation reaction is carried out in a high-pressure reaction kettle;
preferably, the high-pressure reaction kettle is pressurized to 5-10 MPa;
preferably, in the step (2), the temperature of the hydrogenation reaction is 80-140 ℃;
preferably, the step (2) specifically comprises: adding a catalyst 2 into the cycloolefin ring-opening polymer reaction liquid obtained in the step (1), uniformly stirring, putting into a high-pressure reaction kettle, replacing air in the kettle with nitrogen, pressurizing to 5-10 MPa with hydrogen, stirring for the fourth time, heating to 80-140 ℃, reacting until the pressure in the kettle is constant, stopping heating, cooling to room temperature, releasing pressure, and discharging to obtain a cycloolefin copolymer solution.
7. The production method according to any one of claims 3 to 6, wherein step (3) is performed after step (2): mixing the cycloolefin copolymer solution obtained in the step (2) with a water-soluble extractant solution, stirring and heating for the fifth time, adding a peroxide aqueous solution, stirring for the sixth time, reacting at a constant temperature, cooling, and keeping a cycloolefin copolymer solution phase;
preferably, in the step (3), the target temperature of the temperature rise is 80-110 ℃;
preferably, in the step (3), the constant-temperature reaction time is 0.5-2 h;
preferably, in the step (3), the water-soluble extractant comprises any one or a combination of at least two of formic acid, acetic acid, ethylenediamine, propylenediamine, monoethanolamine, diethanolamine and triethanolamine, preferably triethanolamine;
preferably, in the step (3), the mass concentration of the water-soluble extractant in the water-soluble extractant solution is 2-20%;
preferably, in the step (3), the addition amount of the water-soluble extractant solution is 25-100% of the mass of the cycloolefin copolymer solution obtained in the step (2);
preferably, in the step (3), the peroxide comprises an organic peroxide compound and/or an inorganic peroxide, preferably any one or a combination of at least two of hydrogen peroxide, peroxyacetic acid and ammonium persulfate, preferably hydrogen peroxide;
preferably, in the step (3), the mass concentration of the peroxide in the peroxide aqueous solution is 5-30%;
preferably, in the step (3), the addition amount of the peroxide aqueous solution is 25-100% of the mass of the cycloolefin copolymer solution obtained in the step (2);
preferably, the step (3) specifically comprises the following steps:
adding a water-soluble extractant solution into the cycloolefin copolymer solution obtained in the step (2), stirring for the fifth time, heating to 80-110 ℃, adding a peroxide aqueous solution, stirring for the sixth time, reacting at a constant temperature for 0.5-2 h, cooling, and keeping a cycloolefin copolymer solution phase;
preferably, step (4) is performed after step (3): adding a precipitator into the cycloolefin copolymer solution phase obtained in the step (3) for precipitation, filtering, collecting a solid phase, washing and drying to obtain the cycloolefin copolymer;
preferably, the precipitating agent comprises any one or a combination of at least two of isopropanol, methanol, ethanol and acetone.
8. The preparation method according to any one of claims 3 to 7, characterized by specifically comprising the steps of:
(1) vacuumizing a reaction bottle, introducing nitrogen to replace air, adding a cycloolefin monomer, a solvent and a chain transfer agent under the protection of nitrogen, stirring for the first time, controlling the temperature to be 0-30 ℃, dissolving a catalyst 1 in the solvent, dropwise adding the catalyst into a reaction system at the temperature of less than or equal to 35 ℃, stirring for the second time for 0.5-2 hours after dropwise adding is finished, adding a chain terminating agent, and stirring for the third time for 10-30 minutes to obtain a cycloolefin ring-opening polymer reaction solution;
(2) adding a catalyst 2 into the cycloolefin ring-opening polymer reaction liquid, stirring uniformly, putting into a high-pressure reaction kettle, replacing air in the kettle with nitrogen, pressurizing to 5-10 MPa with hydrogen, stirring for the fourth time, heating to 80-140 ℃, reacting until the pressure in the kettle is constant, stopping heating, cooling to room temperature, relieving pressure, and discharging to obtain a cycloolefin copolymer solution;
(3) adding a water-soluble extractant solution into the cycloolefin copolymer solution, stirring for the fifth time, heating to 80-110 ℃, adding a peroxide aqueous solution, stirring for the sixth time, reacting at a constant temperature for 0.5-2 h, cooling, and keeping a cycloolefin copolymer solution phase;
(4) and adding a precipitator into the cycloolefin copolymer solution phase for precipitation, filtering, collecting a solid phase, washing and drying to obtain the cycloolefin copolymer.
9. A polymeric optical material obtained by molding the cycloolefin copolymer according to claim 1 or 2.
10. Use of the polymeric optical material according to claim 9 in an optical device;
preferably, the optical device comprises a lens or a liquid crystal display screen;
preferably, the polymer optical material is applied to a light guide plate or a polarizing film of an optical device.
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| CN112661640A (en) * | 2020-12-21 | 2021-04-16 | 无锡阿科力科技股份有限公司 | Cycloalkene compound and preparation method and application thereof |
| CN113354776A (en) * | 2021-07-13 | 2021-09-07 | 无锡阿科力科技股份有限公司 | Preparation method of cycloolefin copolymer and application of cycloolefin copolymer in preparation of heat-resistant optical material |
| CN113881179A (en) * | 2021-11-09 | 2022-01-04 | 无锡大诚高新材料科技有限公司 | Medical packaging material and preparation method and application thereof |
| CN114685716A (en) * | 2020-12-31 | 2022-07-01 | 江苏博睿光电股份有限公司 | Crosslinkable cycloolefin copolymer and preparation method and application thereof |
| CN117400612A (en) * | 2023-12-15 | 2024-01-16 | 河南达新源新材料有限公司 | Low-density heat-shrinkable film for labels, preparation method and application thereof |
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