CN113354775A - Preparation method of cycloolefin copolymer and application of cycloolefin copolymer in preparation of heat-resistant optical material - Google Patents
Preparation method of cycloolefin copolymer and application of cycloolefin copolymer in preparation of heat-resistant optical material Download PDFInfo
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- CN113354775A CN113354775A CN202110791194.1A CN202110791194A CN113354775A CN 113354775 A CN113354775 A CN 113354775A CN 202110791194 A CN202110791194 A CN 202110791194A CN 113354775 A CN113354775 A CN 113354775A
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- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
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Abstract
The invention relates to a preparation method of a cycloolefin copolymer and application of the cycloolefin copolymer in preparation of a heat-resistant optical material, wherein the preparation method comprises the following steps: and (3) performing addition copolymerization reaction on the cycloolefin monomer and ethylene under the catalysis of a catalyst and a cocatalyst to obtain the cycloolefin copolymer. The catalyst system selected by the invention has higher catalytic activity and higher conversion rate of the cycloolefin monomer.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method of a cycloolefin copolymer and application of the cycloolefin copolymer in preparation of a heat-resistant optical material, in particular to a preparation method of a cycloolefin copolymer with high heat resistance and application of the cycloolefin copolymer in preparation of a heat-resistant optical material.
Background
Cycloolefin copolymers or cycloolefin polymers (COC) are a class of high value-added thermoplastic engineering plastics prepared by copolymerizing cycloolefins and alpha-olefins. COC materials have high transparency, extremely low dielectric constant, excellent water resistance, heat resistance, chemical stability and dimensional stability, and are widely used in the manufacture of optical lenses, automobile headlamps, electronic and electrical parts, pharmaceutical and food packaging materials. COC is generally a non-polar copolymer obtained by copolymerizing a non-misshapen substituted cyclic olefin with an alpha-olefin, and has poor adhesion to inorganic materials such as metal or glass substrates, thereby limiting the application thereof to some extent.
The disadvantage of the material can be improved by carrying out functional modification on COC, and the commonly used method is to select cycloolefins or olefin monomers with special structures as raw materials and prepare the COC material with improved functionality through an addition polymerization process or a ring-opening metathesis polymerization process.
For example, CN1659205A reports a composition containing
The norbornene ring-opening polymer of the repeating unit, the polymer and the hydrogenation product thereof have good heat resistance and electrical property, but the monomer structure used in the patent is complex, the raw material is not easy to obtain, and the hydrogenation process is needed, so that the process is complex.
For example, CN101319020 reports a cycloolefin polymer used in optical materials, polarizing plates and liquid crystal displays, by using two monomers
Copolymerization to obtain a copolymer containing
And
the cycloolefin polymer of (2) is, however, a monomer used therefor is complicated in structure and raw materials are not readily available.
Metallocene catalyst systems used in the methods disclosed in the prior art for preparing cycloolefin polymers, particularly high heat-resistant cycloolefin copolymers, such as [ { Me2C (fluo) (Cp) } ZrCl2]/MAO, [ { Ph2C (fluo) (Cp) } ZrCl2]/MAO, [ { Ph2C (ind) (Cp) } ZrCl2]/MAO, [ { Me2C (fluo) (Cp) } HfCl2]/MAO, etc. (A Tailor-Made Metallocene for the polymerization of ethylene with bulk cyclakkeys, Angew. chem. int. Engl.1995,34, No.20) have low catalytic activities, and thus addition Copolymerization cannot be achieved or polymerization activity is very low, which is not suitable for industrialization. There is therefore a need to develop a highly efficient catalytic system for the preparation of cycloolefin copolymers.
Disclosure of Invention
In view of the defects of the prior art, the present invention aims to provide a preparation method of a cycloolefin copolymer and an application thereof in the preparation of a heat-resistant optical material, and particularly provides a preparation method of a cycloolefin copolymer with high heat resistance and an application thereof in the preparation of a heat-resistant optical material.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a cycloolefin copolymer, the method comprising: performing addition copolymerization reaction on a cycloolefin monomer and ethylene under the catalysis of a catalyst and a cocatalyst to obtain the cycloolefin copolymer; the structure of the cycloolefin monomer is shown as the formula (I):
wherein R is1、R2、R3Independently selected from hydrogen or methyl;
k is selected from 0 or 1.
The cycloolefin monomer related by the invention is a norbornene with a single-bridge or double-bridge ring ester structure, has a substituent group with larger volume compared with a common cycloolefin compound, and after the cycloolefin monomer is copolymerized with ethylene, a copolymer shows higher glass transition temperature and better heat resistance under the same intercalation rate of the cycloolefin monomer.
The cycloolefin monomer according to the present invention can be synthesized by a Diels-Alder reaction, and illustratively, the reaction formula thereof is as follows:
wherein R is1、R2、R3Independently selected from hydrogen or methyl.
The structure of the cycloolefin copolymer related by the invention is shown as the formula (III):
wherein R is1、R2、R3Independently selected from hydrogen or methyl;
k is selected from 0 or 1;
the ratio of x to x + y is 0.60-0.85, such as 0.60, 0.65, 0.70, 0.75, 0.80 or 0.85, and other specific values within the numerical range can be selected, and are not described in detail herein; the ratio of y to x + y is 0.15-0.40, such as 0.15, 0.20, 0.25, 0.30, 0.35, or 0.40, and other specific values within the range can be selected, which is not described herein again.
The preparation method provided by the invention takes the cycloolefin monomer and the ethylene as the starting materials, and can prepare the cycloolefin copolymer through addition copolymerization reaction more efficiently under the co-catalysis of the catalyst and the cocatalyst, so that the reaction efficiency is obviously improved.
The prepared cycloolefin copolymer is an amorphous polymer, has low hygroscopicity, high light transmittance, high refractive index, chemical resistance and excellent mechanical strength, has higher glass transition temperature and thermal deformation temperature and better heat resistance compared with the common cycloolefin copolymer, can be used as a heat-resistant optical material after being processed and formed, and has the advantages of easily obtained raw materials and low cost.
Preferably, the cycloolefin monomer has a structure represented by the following formulae (1) to (16):
preferably, the structure of the catalyst is shown as formula (II):
wherein R is1Selected from hydrogen, C1-C4 linear or branched alkyl (e.g., methyl, ethyl, linear propyl, branched propyl, linear butyl, branched butyl).
The above catalysts are commercially available or synthesized according to the prior art, which may be exemplified by the method disclosed in CN106008766A, to a person skilled in the art.
Preferably, the amount of the catalyst added is 0.005-0.1% of the mass of the cycloolefin monomer, such as 0.005%, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, or 0.1%, and other specific values within the numerical range can be selected, and are not described in detail herein.
Preferably, the cocatalyst comprises a combination of an organoboron compound and an aluminum alkyl.
The invention creatively uses the combination of the organic boron compound and the alkyl aluminum as the cocatalyst component of the synthesis process, and the catalyst has more efficient catalytic efficiency by matching with the catalyst. The combination of organoboron compound and aluminum alkyl has better catalytic efficiency than other cocatalysts or organoboron compound alone and aluminum alkyl alone.
Preferably, the organoboron compound comprises B (C)6F5)3And/or (Ph)3CB(C6F5)4)。
B (C) in contrast to other types of organoboron compounds6F5)3And/or (Ph)3CB(C6F5)4) As one of the promoters, has higher catalytic efficiency.
Preferably, the aluminum alkyl comprises any one of triisobutylaluminum, trimethylaluminum or triethylaluminum or a combination of at least two thereof. The combination of at least two of the above-mentioned compounds, for example, the combination of triisobutylaluminum and trimethylaluminum, the combination of trimethylaluminum and triethylaluminum, the combination of triisobutylaluminum and triethylaluminum, etc., may be selected from any other combination, and thus, the details thereof are not repeated herein.
Preferably, the organic boron compound is added in an amount of 2 to 10 times, for example, 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times or 10 times, etc. of the molar amount of the catalyst, and other specific values in the numerical range can be selected, and are not repeated herein.
Preferably, the addition amount of the aluminum alkyl is 20-200 times of the molar amount of the catalyst, for example, 20 times, 50 times, 80 times, 100 times, 120 times, 150 times or 200 times, and other specific values in the numerical range can be selected, and are not repeated herein.
Meanwhile, when the organoboron compound and the aluminum alkyl are used in amounts satisfying the above-specified numerical ranges, the catalytic efficiency is further improved.
As a preferred technical solution of the present invention, the preparation method comprises: and mixing a cycloolefin monomer with a solvent, heating, mixing with a catalyst and a cocatalyst, adding ethylene, and performing addition copolymerization reaction to obtain the cycloolefin copolymer.
Preferably, the solvent includes any one or a combination of at least two of an aliphatic hydrocarbon solvent, an alicyclic hydrocarbon solvent, an aromatic hydrocarbon solvent, a halogenated aromatic hydrocarbon solvent, and an ether solvent.
The combination of at least two of the above solvents, for example, the combination of an aliphatic hydrocarbon solvent and an alicyclic hydrocarbon solvent, the combination of an alicyclic hydrocarbon solvent and an aromatic hydrocarbon solvent, the combination of a halogenated aromatic hydrocarbon solvent and an ether solvent, and the like, may be selected in any combination manner, and will not be described in detail herein.
Preferably, the aliphatic hydrocarbon solvent comprises n-hexane and/or heptane.
Preferably, the alicyclic hydrocarbon solvent includes any one or a combination of at least two of cyclopentane, cyclohexane, methylcyclohexane, or dimethylcyclohexane.
The combination of at least two of the compounds, such as the combination of cyclopentane and cyclohexane, the combination of methylcyclohexane and dimethylcyclohexane, the combination of cyclohexane and methylcyclohexane, etc., any other combination mode can be selected, and thus, the details are not repeated.
Preferably, the aromatic hydrocarbon solvent includes any one of benzene, toluene, or xylene, or a combination of at least two thereof.
The combination of at least two of the above-mentioned compounds, such as the combination of benzene and toluene, the combination of toluene and xylene, etc., can be selected in any other combination manner, and will not be described herein again.
Preferably, the halogenated aromatic hydrocarbon solvent comprises chlorobenzene and/or dichlorobenzene.
Preferably, the ether solvent includes diethyl ether and/or tetrahydrofuran.
Preferably, the mass of the solvent is 50-95% of the total mass of the solvent and the cycloolefin monomer, for example, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95%, and other specific values within the numerical range can be selected, and are not described in detail herein.
Preferably, the temperature rise refers to a temperature rise to 50-120 ℃, for example, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 95 ℃, 100 ℃, 110 ℃, 115 ℃ or 120 ℃, and other specific values in the numerical range can be selected, and are not described in detail herein.
Preferably, the pressure of the reaction system is maintained at 0.1-2.0MPa, such as 0.1MPa, 0.2MPa, 0.5MPa, 0.8MPa, 1.0MPa, 1.2MPa, 1.5MPa, 1.8MPa or 2.0MPa, and other specific values in the numerical range can be selected, and are not described in detail herein.
Preferably, the reaction time is 1 to 10 hours, for example, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours or 10 hours, and other specific values within the numerical range can be selected, and are not described in detail herein.
Preferably, the reaction is terminated with acidified ethanol.
Preferably, the precipitate is separated after the reaction is finished, washed and dried.
In a second aspect, the present invention provides a use of the cyclic olefin copolymer prepared by the method for preparing a cyclic olefin copolymer according to the first aspect in preparing a heat-resistant optical material.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method provided by the invention takes the cycloolefin monomer and the ethylene as the initial raw materials, and can prepare the cycloolefin copolymer through addition copolymerization reaction more efficiently under the co-catalysis of the catalyst and the cocatalyst, so that the reaction efficiency is obviously improved, the catalytic activity is high, and the monomer conversion rate is high. Since the cycloolefin monomers of the invention are more bulky than norbornene, meaning that the catalyst is affected by the great steric hindrance of the cycloolefin monomers when copolymerized with ethylene, the metallocene catalyst systems commonly used are, for example, [ { Me2C(fluo)(Cp)}ZrCl2]/MAO、[{Ph2C(fluo)(Cp)}ZrCl2]/MAO、[{Ph2C(ind)(Cp)}ZrCl2]/MAO、[{Me2C(fluo)(Cp)}HfCl2]The catalytic activity of MAO and the like is low, so that addition copolymerization cannot be realized or the polymerization activity is low, and the method is not suitable for industrialization.
The prepared cycloolefin copolymer is an amorphous polymer, has low hygroscopicity, high light transmittance, high refractive index, chemical resistance and mechanical strength, has high glass transition temperature and thermal deformation temperature and good heat resistance compared with the common cycloolefin copolymer, can be used for optical lenses and medical packaging materials after being processed and molded, and has easily obtained raw materials.
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 following method for calculating the catalytic activity of the catalyst is as follows: the ratio of the amount of product to the amount of catalyst charge.
The following calculation method of the conversion rate of the cycloolefin monomer was performed: the amount of the cycloolefin monomer participating in the reaction is calculated according to the insertion rate of the cycloolefin in the product and the mass of the product, and the ratio of the amount of the cycloolefin monomer to the charge amount of the cycloolefin monomer is calculated. Wherein, the detection method of the insertion rate of the cycloolefins in the product comprises the following steps: determining the molar content of cycloolefin monomer in the polymer by Bruker AMX 500 NMR spectrometer13C-NMR，C6D6In the case of the deuterated reagent, tetramethylsilane is used as an internal standard, and the insertion rate is calculated by calculating the ratio of characteristic peaks.
The following glass transition temperature Tg test methods are involved: a DSC differential scanning calorimeter (model: DSC 200F3, manufacturer: German Chinesemedicine Co., Ltd.) is adopted, the sample amount is weighed to be 10mg, and the test temperature interval is 30-300 ℃.
Molecular weight M referred to belowwAnd a molecular weight distribution (PDI) test method: 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.
Example 1
This example provides a cycloolefin copolymer prepared by the following process:
pumping out the polymerization reaction kettle for four times by using high-purity nitrogen, discharging the air in the polymerization reaction kettle, and then adding 2088g of toluene and cycloolefin monomer under the protection of nitrogen
232g (1.0mol), stirring was started and the temperature was raised to 80 ℃ and 99mg (0.5mmol) of triisobutylaluminum and 11.6mg (25. mu. mol) of catalyst were added in this order
And organoboron Compound B (C)6F5)325.6mg (50. mu. mol), ethylene gas was continuously introduced to maintain the ethylene pressure at 2.0MPa, and the reaction was stopped for 3 hours and cooled to 25 ℃. After the polymerization reaction is finished, the reaction mixture is stirred,terminating with acidified ethanol, precipitating to obtain white powdery solid, washing with ethanol, vacuum filtering to obtain cyclic olefin copolymer A1, and vacuum drying at 70 deg.C for 8 hr.
Example 2
This example provides a process for preparing a cycloolefin copolymer, which differs from that of example 1 only in that no organoboron compound B (C) is added6F5)3The other conditions were kept consistent. A cycloolefin copolymer A2 was obtained.
Example 3
This example provides a process for preparing a cycloolefin copolymer, which differs from example 1 only in that triisobutylaluminum is not added and the other conditions are kept the same. A cycloolefin copolymer A3 was obtained.
Example 4
This example provides a process for preparing a cycloolefin copolymer, which differs from that of example 1 only in that no organoboron compound B (C) is added6F5)3And triisobutylaluminum, the other conditions being identical. A cycloolefin copolymer A4 was obtained.
Example 5
This example provides a process for preparing a cycloolefin copolymer, which differs from that of example 1 only in that an organoboron compound B (C) as a cocatalyst is used6F5)3And triisobutylaluminum was replaced with 2500. mu. mol of Methylaluminoxane (MAO), and the other conditions were kept the same. A cycloolefin copolymer A5 was obtained.
Example 6
This example provides a method for preparing a cycloolefin copolymer, which is different from example 1 only in that triisobutylaluminum as a cocatalyst is replaced with trimethylaluminum in an equimolar amount, and other conditions are kept the same. A cycloolefin copolymer A6 was obtained.
Example 7
This example provides a process for preparing a cycloolefin copolymer, which is different from example 1 only in that triisobutylaluminum as a cocatalyst is replaced with triethylaluminum in an equimolar amount, and other conditions are kept the same. A cycloolefin copolymer A7 was obtained.
Example 8
This example provides a cycloolefin copolymer prepared by the following process:
pumping out the polymerization reaction kettle for four times by using high-purity nitrogen, discharging the air in the polymerization reaction kettle, and then adding 2214g of toluene and cycloolefin monomer under the protection of nitrogen
246g (1.0mol), with stirring and with heating to 80 ℃ were added 213mg (1.1mmol) of triisobutylaluminum and 24.6mg (53.8. mu. mol) of catalyst in that order
And organoboron Compound B (C)6F5)355.1mg (0.11mmol) of ethylene gas was continuously introduced at the end to maintain the ethylene pressure at 0.5MPa, and the reaction was stopped for 10h and cooled to 25 ℃. After the polymerization reaction is finished, terminating with acidified ethanol, precipitating white powdery solid, washing with ethanol, filtering to obtain a cyclic olefin copolymer B1, and drying in vacuum at 70 ℃ for 8 h.
Example 9
This example provides a process for preparing a cycloolefin copolymer, which differs from that of example 9 only in that no organoboron compound B (C) is added6F5)3The other conditions were kept consistent. A cycloolefin copolymer B2 was obtained.
Example 10
This example provides a process for preparing a cycloolefin copolymer, which differs from example 9 only in that triisobutylaluminum is not added and the other conditions are kept the same. A cycloolefin copolymer B3 was obtained.
Example 11
This example provides a process for preparing a cycloolefin copolymer, which differs from that of example 9 only in that no organoboron compound B (C) is added6F5)3And triisobutylaluminum, the other conditions being identical. A cycloolefin copolymer B4 was obtained.
Example 12
This example provides a process for preparing a cycloolefin copolymer, which differs from that of example 9 only in that an organoboron compound B (C) as a cocatalyst is used6F5)3And triisobutylaluminum was replaced with 2700. mu. mol of Methylaluminoxane (MAO), the other conditions were kept the same. A cycloolefin copolymer B5 was obtained.
Example 13
This example provides a cycloolefin copolymer prepared by the following process:
pumping out the polymerization reaction kettle for four times by using high-purity nitrogen, discharging the air in the polymerization reaction kettle, and then adding 4674g of toluene and cycloolefin monomer under the protection of nitrogen
246g (1.0mol), the mixture was heated to 100 ℃ with stirring, and 1.1g (5.4mmol) of triisobutylaluminum and 12.3mg (27. mu. mol) of catalyst were added thereto in this order
And organoboron compound (Ph)3CB(C6F5)4)249mg (0.27mmol), ethylene gas was finally continuously introduced to maintain the ethylene pressure at 2.0MPa, and the reaction was stopped for 1h and cooled to 25 ℃. After the polymerization reaction is finished, acidified ethanol is used for stopping, white powdery solid is precipitated, the white powdery solid is washed by ethanol and is filtered by suction, the cyclic olefin copolymer C1 is obtained, and the cyclic olefin copolymer is dried for 8 hours in vacuum at 70 ℃.
Example 14
This example provides a cycloolefin copolymer prepared by the following process:
pumping out the polymerization reaction kettle for four times by using high-purity nitrogen, discharging the air in the polymerization reaction kettle, and then adding 2340g of toluene and 2340g of cyclic olefin monomer under the protection of nitrogen
260g (1.0mol), stirring was started and the temperature was raised to 80 ℃ and 555mg (2.8mmol) of triisobutylaluminum and 13mg (28. mu. mol) of catalyst were added in this order
And organoboron compound (Ph)3CB(C6F5)4)129mg (140. mu. mol), ethylene gas was continuously introduced to maintain the ethylene pressure at 2.0MPa, and the reaction was stopped for 5 hours and cooled to 25 ℃. After the polymerization reaction is finished, terminating with acidified ethanol, precipitating white powdery solid, washing with ethanol, filtering to obtain a cyclic olefin copolymer D1, and vacuum drying at 70 ℃ for 8 h.
Example 15
This example provides a cycloolefin copolymer prepared by the following process:
pumping out the polymerization reaction kettle for four times by using high-purity nitrogen, discharging the air in the polymerization reaction kettle, and then adding 984g of dimethylbenzene and cycloolefin monomer under the protection of nitrogen
246g (1.0mol), the temperature was raised to 120 ℃ with stirring, and 107mg (0.54mmol) of triisobutylaluminum and 12.3mg (27. mu. mol) of catalyst were added in this order
And organoboron compound (Ph)3CB(C6F5)4)49.8mg (54. mu. mol), and finally, ethylene gas was continuously introduced to maintain the ethylene pressure at 1.0MPa, and the reaction was stopped for 5 hours and cooled to room temperature. After the polymerization reaction is finished, acidified ethanol is used for stopping, white powdery solid is precipitated, the white powdery solid is washed by ethanol and is filtered by suction, the cycloolefin copolymer E1 is obtained, and the cycloolefin copolymer is dried for 8 hours in vacuum at 70 ℃.
Example 16
This example provides a cycloolefin copolymer prepared by the following process:
pumping out the polymerization reaction kettle for four times by using high-purity nitrogen, discharging the air in the polymerization reaction kettle, and then adding 4940g of toluene and cycloolefin monomer under the protection of nitrogen
260g (1.0mol), stirring was started and the temperature was raised to 50 ℃ and 116mg (0.586mmol) of triisobutylaluminum and 13.0mg (29.3. mu. mol) of catalyst were added in this order
And organoboron Compound B (C)6F5)330.7mg (60. mu. mol), and finally, ethylene gas was continuously introduced to maintain the ethylene pressure at 0.1MPa, and the reaction was stopped after 10 hours and cooled to 25 ℃. After the polymerization reaction is finished, acidified ethanol is used for stopping, white powdery solid is precipitated, the white powdery solid is washed by ethanol and is filtered by suction, the cyclic olefin copolymer F1 is obtained, and the cyclic olefin copolymer is dried for 8 hours in vacuum at 70 ℃.
Example 17
This example provides a cycloolefin copolymer prepared by the following process:
pumping out the polymerization reaction kettle for four times by using high-purity nitrogen, discharging the air in the polymerization reaction kettle, and then adding 4940g of toluene and cycloolefin monomer under the protection of nitrogen
260g (1.0mol), stirring was started and the temperature was raised to 80 ℃ and 116mg (0.586mmol) of triisobutylaluminum and 13.0mg (29.3. mu. mol) of catalyst were added in this order
And organoboron Compound B (C)6F5)330.7mg (60. mu. mol), ethylene gas was continuously introduced to maintain the ethylene pressure at 1.0MPa, and the reaction was stopped after 8 hours and cooled to 25 ℃. After the polymerization reaction is finished, acidified ethanol is used for stopping, white powdery solid is precipitated, the white powdery solid is washed by ethanol and is filtered by suction, the cyclic olefin copolymer G1 is obtained, and the cyclic olefin copolymer G1 is dried for 8 hours in vacuum at 70 ℃.
Example 18
This example provides a cycloolefin copolymer prepared by the following process:
pumping out the polymerization reactor with high purity nitrogen four times to exhaust the air in the reactor, and adding 2466g cyclohexane and cycloolefin monomer under the protection of nitrogen
274g (1.0mol), starting stirring, heating to 80 ℃, and then adding three123mg (0.62mmol) of isobutylaluminum and 13.7mg (31. mu. mol) of catalyst
And organoboron Compound B (C)6F5)333.3mg (65. mu. mol), ethylene gas was continuously introduced to maintain the ethylene pressure at 0.5MPa, and the reaction was stopped after 8 hours and cooled to 25 ℃. After the polymerization reaction is finished, acidified ethanol is used for stopping, white powdery solid is precipitated, the white powdery solid is washed by ethanol and is filtered by suction, the cyclic olefin copolymer is recorded as H1, and the cyclic olefin copolymer is dried for 8 hours in vacuum at 70 ℃.
Example 19
This example provides a cycloolefin copolymer prepared by the following process:
pumping out the polymerization reaction kettle for four times by using high-purity nitrogen, discharging the air in the polymerization reaction kettle, and then adding 2700g of toluene and cycloolefin monomer under the protection of nitrogen
300g (1.0mol), stirring was started and the temperature was raised to 80 ℃ and, subsequently, 669mg (3.38mmol) of triisobutylaluminum and 15mg (33.8. mu. mol) of catalyst were added
And organoboron compound (Ph)3CB(C6F5)4)62.3mg (67.6. mu. mol), ethylene gas was continuously introduced to maintain the ethylene pressure at 2.0MPa, and the reaction was stopped after 8 hours and cooled to 25 ℃. After the polymerization reaction is finished, terminating with acidified ethanol, precipitating white powdery solid, washing with ethanol, filtering to obtain a cyclic olefin copolymer I1, and vacuum drying at 70 ℃ for 8 h.
Example 20
This example provides a cycloolefin copolymer prepared by the following process:
pumping out the polymerization reaction kettle for four times by using high-purity nitrogen, discharging the air in the polymerization reaction kettle, and then adding 2088g of toluene and cycloolefin monomer under the protection of nitrogen
312g (1.0mol), the temperature was raised to 80 ℃ with stirring, and 159mg (0.8mmol) of triisobutylaluminum and 15.6mg (35.2. mu. mol) of catalyst were added in this order
And organoboron compound (Ph)3CB(C6F5)4)73.8mg (80. mu. mol), ethylene gas was continuously introduced to maintain the ethylene pressure at 2.0MPa, and the reaction was stopped after 8 hours and cooled to 25 ℃. After the polymerization reaction is finished, acidified ethanol is used for stopping, white powdery solid is precipitated, the white powdery solid is washed by ethanol and is filtered by suction, the cyclic olefin copolymer is recorded as J1, and the cyclic olefin copolymer is dried for 8 hours in vacuum at 70 ℃.
Example 21
This example provides a cycloolefin copolymer prepared by the following process:
pumping out the polymerization reaction kettle for four times by using high-purity nitrogen, discharging the air in the polymerization reaction kettle, and then adding 2808g of toluene and cycloolefin monomer under the protection of nitrogen
312g (1.0mol), stirring was started and the temperature was raised to 80 ℃ and 0.719g (3.63mmol) of triisobutylaluminum and 15.6mg (36.3. mu. mol) of catalyst were added in this order
And organoboron Compound B (C)6F5)338.4mg (75. mu. mol), ethylene gas was continuously introduced to maintain the ethylene pressure at 1.0MPa, and the reaction was stopped after 10 hours and cooled to 25 ℃. After the polymerization reaction is finished, acidified ethanol is used for stopping, white powdery solid is precipitated, the white powdery solid is washed by ethanol and is filtered by suction, and the cyclic olefin copolymer K1 is obtained and is dried for 8 hours in vacuum at 70 ℃.
Example 22
This example provides a cycloolefin copolymer prepared by the following process:
pumping out the polymerization reaction kettle for four times by using high-purity nitrogen, discharging the air in the polymerization reaction kettle, and then adding 652g of toluene and cycloolefin monomer under the protection of nitrogen
652g (2.0mol), with stirring and heating to 80 ℃ and then 3.0g (15.2mmol) of triisobutylaluminum and 32.6mg (76.0. mu. mol) of catalyst were added in the stated order
And organoboron Compound B (C)6F5)3389mg (760. mu. mol), ethylene gas was continuously introduced to maintain the ethylene pressure at 2.0MPa, and the reaction was stopped after 6 hours and cooled to 25 ℃. After the polymerization reaction is finished, acidified ethanol is used for stopping, white powdery solid is precipitated, the white powdery solid is washed by ethanol and is filtered by suction, and the cyclic olefin copolymer L1 is obtained and is dried for 8 hours in vacuum at 70 ℃.
Example 23
This example provides a cycloolefin copolymer prepared by the following process:
pumping out the polymerization reaction kettle for four times by using high-purity nitrogen, discharging the air in the polymerization reaction kettle, and then adding 5928g of toluene and cycloolefin monomer under the protection of nitrogen
312g (1.0mol), the mixture was heated to 80 ℃ with stirring, and 2.883g (14.5mmol) of triisobutylaluminum and 312mg (727. mu. mol) of catalyst were added in this order
And organoboron Compound B (C)6F5)3744mg (1.454mmol), ethylene gas was continuously introduced to maintain the ethylene pressure at 0.5MPa, the reaction was stopped for 8h and cooled to 25 ℃. After the polymerization reaction is finished, acidified ethanol is used for stopping, white powdery solid is precipitated, the white powdery solid is washed by ethanol and is filtered by suction, the cycloolefin copolymer M1 is obtained, and the cyclic olefin copolymer is dried for 8 hours in vacuum at 70 ℃.
Example 24
This example provides a cycloolefin copolymer prepared by the following process:
pumping out the polymerization reaction kettle for four times by using high-purity nitrogen, discharging the air in the polymerization reaction kettle, and then adding 2934g of toluene and cycloolefin monomer under the protection of nitrogen
326g (1.0mol), the temperature was raised to 80 ℃ with stirring, and 159mg (0.8mmol) of triisobutylaluminum and 16.3mg (38.0. mu. mol) of catalyst were added in this order
And organoboron compound (Ph)3CB(C6F5)4)73.8mg (80. mu. mol), ethylene gas was continuously introduced to maintain the ethylene pressure at 1.0MPa, and the reaction was stopped for 6 hours and cooled to 25 ℃. After the polymerization reaction is finished, acidified ethanol is used for stopping, white powdery solid is precipitated, the white powdery solid is washed by ethanol and is filtered by suction, the cycloolefin copolymer is recorded as N1, and the cycloolefin copolymer is dried for 8 hours in vacuum at 70 ℃.
Example 25
This example provides a cycloolefin copolymer prepared by the following process:
pumping out the polymerization reaction kettle for four times by using high-purity nitrogen, discharging the air in the polymerization reaction kettle, and then adding 2934g of toluene and cycloolefin monomer under the protection of nitrogen
326g (1.0mol), the temperature was raised to 100 ℃ with stirring, and 159mg (0.8mmol) of triisobutylaluminum and 11.6mg (38.0. mu. mol) of catalyst were added in this order
And organoboron compound (Ph)3CB(C6F5)4)73.8mg (80. mu. mol), ethylene gas was continuously introduced to maintain the ethylene pressure at 0.8MPa, and the reaction was stopped after 10 hours and cooled to 25 ℃. After the polymerization reaction is finished, acidified ethanol is used for stopping, white powdery solid is precipitated, the white powdery solid is washed by ethanol and is filtered by suction, the cyclic olefin copolymer is recorded as O1, and the cyclic olefin copolymer is dried for 8 hours in vacuum at 70 ℃.
Example 26
This example provides a cycloolefin copolymer prepared by the following process:
the polymerization reaction kettle is firstly pumped and discharged by high-purity nitrogenSecondly, the air in the kettle is discharged, and 1360g of toluene and cycloolefin monomer are added under the protection of nitrogen
340g (1.0mol), stirring was started and the temperature was raised to 80 ℃ and 159mg (0.8mmol) of triisobutylaluminum and 17.0mg (39.6. mu. mol) of catalyst were added in this order
And organoboron compound (Ph)3CB(C6F5)4)73.8mg (80. mu. mol), ethylene gas was continuously introduced to maintain the ethylene pressure at 2.0MPa, and the reaction was stopped after 10 hours and cooled to 25 ℃. After the polymerization reaction is finished, acidified ethanol is used for stopping, white powdery solid is precipitated, the white powdery solid is washed by ethanol and is filtered by suction, the cyclic olefin copolymer P1 is obtained, and the cyclic olefin copolymer is dried for 8 hours in vacuum at 70 ℃.
Comparative example 1
This comparative example provides a cycloolefin copolymer prepared as follows:
pumping out the polymerization reaction kettle for four times by using high-purity nitrogen, discharging the air in the polymerization reaction kettle, and then adding 1692g of toluene and cycloolefin monomer under the protection of nitrogen
188g (2.0mol), stirring was started, the temperature was raised to 80 ℃ and 81.5mg (0.4mmol) of triisobutylaluminum and 9.4mg (20.5. mu. mol) of catalyst were added in this order
And organoboron Compound B (C)6F5)321.0mg (41. mu. mol), ethylene gas was continuously introduced to maintain the ethylene pressure at 2.0MPa, and the reaction was stopped for 3 hours and cooled to 25 ℃. After the polymerization reaction is finished, acidified ethanol is used for stopping, white powdery solid is precipitated, the white powdery solid is washed by ethanol and is filtered by suction, and the cyclic olefin copolymer Q1 is obtained and is dried for 8 hours in vacuum at 70 ℃.
Comparative example 2
This comparative example provides a cycloolefin copolymer prepared as follows:
pumping out the polymerization reaction kettle for four times by using high-purity nitrogen, discharging the air in the polymerization reaction kettle, and then adding 2880g of toluene and cycloolefin monomer under the protection of nitrogen
320g (2.0mol), stirring was started and the temperature was raised to 80 ℃ and 138.8mg (0.7mmol) of triisobutylaluminum and 16mg (35. mu. mol) of catalyst were added in this order
And organoboron Compound B (C)6F5)335.8mg (70. mu. mol), ethylene gas was continuously introduced to maintain the ethylene pressure at 2.0MPa, and the reaction was stopped for 3 hours and cooled to 25 ℃. After the polymerization reaction is finished, acidified ethanol is used for stopping, white powdery solid is precipitated, the white powdery solid is washed by ethanol and is filtered by suction, and the cyclic olefin copolymer Q2 is obtained and is dried for 8 hours in vacuum at 70 ℃.
Evaluation test:
the data of the glass transition temperature Tg, molecular weight Mw, molecular weight distribution PDI, cyclic olefin monomer insertion rate, catalytic activity of the catalyst, conversion rate of cyclic olefin monomer of 28 cyclic olefin copolymers prepared in examples 1 to 26 and comparative examples 1 to 2 are shown in Table 1:
TABLE 1
As can be seen from the data in Table 1:
the insertion rate of the monomer of the cycloolefin copolymer prepared by the preparation method is 15-40 mol%, and compared with the common cycloolefin copolymer, the heat resistance of the cycloolefin copolymer is obviously improved. Meanwhile, the catalytic system provided by the invention has very high catalytic activity and monomer conversion rate, can be used for preparing the cycloolefin copolymer more efficiently through addition copolymerization reaction, and obviously improves the reaction efficiency.
The applicant states that the present invention is illustrated by the above examples to a method for preparing a cyclic olefin copolymer of the present invention and its application in the preparation of heat-resistant optical materials, but the present invention is not limited to the above examples, i.e., it does not mean that the present invention must be practiced by relying on 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 (10)
1. A method for preparing a cycloolefin copolymer, characterized in that the method comprises: performing addition copolymerization reaction on a cycloolefin monomer and ethylene under the catalysis of a catalyst and a cocatalyst to obtain the cycloolefin copolymer; the structure of the cycloolefin monomer is shown as the formula (I):
wherein R is1、R2、R3Independently selected from hydrogen or methyl;
k is selected from 0 or 1.
2. The method of preparing a cycloolefin copolymer according to claim 1, wherein the cycloolefin monomer has a structure represented by the following formulae (1) to (16):
3. the method for preparing a cycloolefin copolymer according to claim 1 or 2, characterized in that the catalyst has a structure represented by the formula (II):
wherein R is1Selected from hydrogen, C1-C4 linear or branched alkyl;
preferably, the amount of the catalyst added is 0.005-0.1% by mass of the cycloolefin monomer.
4. The process for producing a cycloolefin copolymer according to any one of claims 1 to 3, wherein the co-catalyst comprises a combination of an organoboron compound and an aluminum alkyl;
preferably, the organoboron compound comprises B (C)6F5)3And/or (Ph)3CB(C6F5)4)；
Preferably, the aluminum alkyl comprises any one of triisobutylaluminum, trimethylaluminum or triethylaluminum or a combination of at least two thereof.
5. The process for producing a cycloolefin copolymer according to claim 4, wherein the organoboron compound is added in an amount of 2 to 10 times by mol based on the catalyst;
preferably, the addition amount of the aluminum alkyl is 20 to 200 times of the molar amount of the catalyst.
6. The method for preparing a cycloolefin copolymer according to any one of claims 1 to 5, characterized in that the preparation method comprises: and mixing a cycloolefin monomer with a solvent, heating, mixing with a catalyst and a cocatalyst, adding ethylene, and performing addition copolymerization reaction to obtain the cycloolefin copolymer.
7. The method for preparing a cycloolefin copolymer according to claim 6, wherein the solvent comprises any one or a combination of at least two of an aliphatic hydrocarbon solvent, an alicyclic hydrocarbon solvent, an aromatic hydrocarbon solvent, a halogenated aromatic hydrocarbon solvent, and an ether solvent;
preferably, the aliphatic hydrocarbon solvent comprises n-hexane and/or heptane;
preferably, the alicyclic hydrocarbon solvent includes any one or a combination of at least two of cyclopentane, cyclohexane, methylcyclohexane, or dimethylcyclohexane;
preferably, the aromatic hydrocarbon solvent includes any one or a combination of at least two of benzene, toluene, or xylene;
preferably, the halogenated aromatic hydrocarbon solvent comprises chlorobenzene and/or dichlorobenzene;
preferably, the ether solvent includes diethyl ether and/or tetrahydrofuran;
preferably, the mass of the solvent is 50-95% of the total mass of the solvent and the cycloolefin monomer.
8. The method for preparing cycloolefin copolymers according to claim 6 or 7, wherein the temperature rise is a temperature rise to 50 to 120 ℃;
preferably, the pressure of the reaction system is maintained at 0.1 to 2.0 MPa.
9. The process for preparing cycloolefin copolymers according to one of claims 6 to 8, characterized in that the reaction time is from 1 to 10 h;
preferably, the reaction is terminated with acidified ethanol;
preferably, the precipitate is separated after the reaction is finished, washed and dried.
10. Use of the cycloolefin copolymer produced by the process according to any one of claims 1 to 9 for producing a heat-resistant optical material.
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| CN115779858A (en) * | 2022-12-06 | 2023-03-14 | 无锡阿科力科技股份有限公司 | Refining agent of cycloolefin copolymer and preparation method and application thereof |
| CN115947892A (en) * | 2022-11-30 | 2023-04-11 | 宁夏清研高分子新材料有限公司 | high-Tg high-temperature-resistant COC material and preparation method thereof |
| CN116217807A (en) * | 2023-03-27 | 2023-06-06 | 歌尔光学科技有限公司 | Cycloolefin copolymer, optical product and electronic device |
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| CN116217807A (en) * | 2023-03-27 | 2023-06-06 | 歌尔光学科技有限公司 | Cycloolefin copolymer, optical product and electronic device |
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