CN115028763B - Cycloolefin copolymer and preparation method thereof - Google Patents
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Abstract
The invention provides a cycloolefin copolymer and a preparation method thereof, belonging to the field of functionalized polyolefin. The copolymer has a structure shown in a formula (I), wherein X, Y and Z are polymerization degrees, wherein X is more than or equal to 20, Y is more than or equal to 1, and X is more than or equal to 200, and Z is more than or equal to 5; m is the length of the monomer chain, and m is more than or equal to 1 and less than or equal to 10. In an inert solvent, a cycloolefin monomer with a structure shown in a formula (II), a polar olefin monomer with a structure shown in a formula (III) or an aryl substituted olefin monomer, ethylene or alpha-olefin are used as a polymerization monomer, and the polymerization reaction is carried out in the inert solvent in the presence of a catalyst, so that the cycloolefin copolymer with the structure shown in the formula (I) is obtained. The cycloolefin copolymer has good toughness and excellent refractive index and hydrophilicity.
Description
Technical Field
The invention belongs to the field of functionalized polyolefin, and particularly relates to a cycloolefin copolymer and a preparation method thereof.
Background
Cycloolefin copolymers (COC) are generally prepared by addition copolymerization of ethylene or alpha-olefin and cycloolefin, and have excellent properties such as low density, high transparency, good thermal stability, low water absorption, high optical refractive index, and strong chemical resistance. Since the first synthesis in the 90 s of the 20 th century, COC has become one of the important engineering plastics, being applied in heat-resistant and optical materials. When the glass transition temperature (T) g ) When the temperature is more than 130 ℃, the obtained COC has higher practical value. To obtain T g COC at more than 130℃and the prior art increases the glass transition temperature of the cycloolefin copolymer obtained by increasing the insertion rate of cycloolefins into the copolymer, for example the copolymers of ethylene-Norbornene (NB) disclosed in the prior art, cycloolefin copolymers having a Tg of more than 150℃being obtained only when the insertion rate of norbornene exceeds 50 mol%. However, at high cycloolefin insertion rates, the resulting COC molecules are relatively stiff, such that co-moleculesThe brittleness of the polymer is severe, which prevents the use of COC. Currently, commercial COCs have been proposed by Mitsui, japan, and Bao's, japan (polymers), under the trade names APEL and Topas, respectively.
The research results disclosed in the prior art show that: COC can be applied in the fields of optics, medical applications and low dielectric materials, and the development direction is beginning to be changed into a high-end applicable material. However, most of the prior art is usually prepared from ethylene or α -olefin and nonpolar cycloolefin monomers, which greatly limits the application of this type of polyolefin material; however, ethylene or α -olefin and cyclic olefin monomer having polar groups generally exhibit poor activity, insertion rate, etc. in preparing cyclic olefin resin, resulting in the lack of application of such functional materials.
Disclosure of Invention
The invention aims to provide a cycloolefin copolymer and a preparation method thereof, wherein the cycloolefin copolymer not only has good toughness, but also has excellent refractive index and hydrophilicity.
The invention firstly provides a cycloolefin copolymer which has a structure shown in a formula (I):
wherein, X is more than or equal to 20, Y is more than or equal to 1, X is more than or equal to 200, and Z is more than or equal to 5; m is more than or equal to 1 and less than or equal to 10, n is more than or equal to 50 and less than or equal to 5000;
R 1 and R is 2 Is independent hydrogen or saturated aliphatic hydrocarbon group with 1-10 carbon atoms;
R 3 and R is 4 Is independently hydrogen or alkyl or cycloalkyl containing less than 20 carbons, aryl, alcohol, acid, ester, halogen, alkoxy, trifluoromethyl, nitro or azomethine;
R 5 is diphenylamino, diphenylmethyl, di-p-tolylmethyl, phenol, p-tolylthiophenol, o-phenylphenol, fluorenyl, dimethylfluorenyl, diphenylfluorenyl, carbazolyl or benzocarbazolyl.
Preferably, it isThe R is 1 And R is 2 Is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or hydrogen;
the R is 3 And R is 4 Is independently selected from hydrogen, methyl, ethyl, cyclohexyl, alcohol, acid, ester, fluorine, chlorine, bromine or norbornene.
Preferably, the cycloolefin copolymer specifically includes polymers of the following formulae a to o:
wherein, X is more than or equal to 20, Y is more than or equal to 1, X is more than or equal to 200, and Z is more than or equal to 5; n is more than or equal to 50 and less than or equal to 5000.
The invention also provides a preparation method of the cycloolefin copolymer, which comprises the following steps:
in an inert solvent, carrying out polymerization reaction on cycloolefin monomers with a structure shown in a formula (II), polar or aryl substituted olefin monomers with a structure shown in a formula (III) and ethylene or alpha-olefin in the presence of a catalyst to obtain cycloolefin copolymers with a structure shown in a formula (I);
in the formula (I), X, Y and Z are polymerization degrees, wherein 20 is more than or equal to X, Y is more than or equal to 1,200 is more than or equal to X, and Z is more than or equal to 5; m is more than or equal to 1 and less than or equal to 10, n is more than or equal to 50 and less than or equal to 5000;
R 1 and R is 2 Is independent hydrogen or saturated aliphatic hydrocarbon group with 1-10 carbon atoms;
R 3 and R is 4 Is independently hydrogen or alkyl or cycloalkyl containing less than 20 carbons, aryl, alcohol, acid, ester, halogen, alkoxy, trifluoromethyl, nitro or azomethine;
R 5 is diphenylamino, diphenylmethyl, di-p-tolylmethyl, phenol, p-tolylthiophenol, o-phenylphenol, fluorenyl, dimethylfluorenyl, diphenylfluorenyl, carbazolyl or benzocarbazolyl.
Preferably, the alpha-olefin is propylene, 1-butene, isobutylene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene or 2-ethyl-1-butene.
Preferably, the polar or aryl substituted olefin monomer is an olefin monomer bearing a diphenylamino group, a diphenylmethyl group, a di-p-tolylmethyl group, a phenol group, a p-tolylthiophenol group, an o-phenylphenol group, a fluorenyl group, a dimethylfluorenyl group, a diphenylfluorenyl group, a carbazolyl group, or a benzocarbazolyl group.
Preferably, the catalyst is a metallocene catalyst.
Preferably, the metallocene catalyst comprises a non-bridged zirconocene dichloride catalyst, an isopropylidene-bridged indene zirconocene dichloride catalyst, an isopropylidene-bridged fluorenocene dichloride catalyst, an isopropylidene-bridged tert-butyl fluorenocene dichloride catalyst, a diphenyl-bridged fluorenocene dichloride catalyst or a dimethylsilyl-bridged fluorenocene dichloride catalyst.
Preferably, the molar ratio of the catalyst to the cycloolefin monomer having the structure of formula (II) is 1:500-6000; the molar ratio of the catalyst to the polar or aryl-substituted olefin monomer having the structure of formula (iii) is preferably 1:50-2000; the molar ratio of the ethylene or alpha-olefin to the cycloolefin monomer having the structure of formula (II) is (1.2-18): 1; the molar ratio of the ethylene or alpha-olefin to the polar or aryl substituted olefin monomer having the structure of formula (III) is (5-200): 1.
Preferably, the polymerization reaction temperature is 30-150 ℃ and the polymerization reaction time is 30-240 minutes.
The beneficial effects of the invention are that
The invention provides a cycloolefin copolymer, which has a structure shown in a formula (I), wherein X, Y and Z are polymerization degrees, wherein 20 is more than or equal to X, Y is more than or equal to 1,200 is more than or equal to X, and Z is more than or equal to 5; m is more than or equal to 1 and less than or equal to 10. In an inert solvent, carrying out polymerization reaction on cycloolefin monomers with a structure shown in a formula (II), polar or aryl substituted olefin monomers with a structure shown in a formula (III) and ethylene or alpha-olefin in the presence of a catalyst to obtain cycloolefin copolymers with a structure shown in a formula (I);
the cycloolefin copolymer provided by the invention has the advantages that the cycloolefin monomer exists, meanwhile, the olefin monomer with high refractive groups is additionally introduced, and the cycloolefin resin with high activity and adjustable molecular weight and glass transition temperature is prepared by adjusting reaction conditions. Wherein, the introduced polar olefin monomer with high refractive index polar group not only improves the toughness of the cycloolefin resin, but also improves the refractive index and the hydrophilicity of the cycloolefin resin. A series of ternary copolymerized cycloolefin polymers are obtained by adjusting the reaction conditions using classical metallocene catalysts. The cycloolefin copolymer has higher activity, wherein the molecular weight and the glass transition temperature are controllable, the structure with the formula (II) and the structure with the formula (III) have certain insertion rate, and the introduction of the polar group with high refractive index can improve the refractive index and toughness of the cycloolefin resin to a certain extent and increase the hydrophilicity. The experimental results show that: the cycloolefin resin has an insertion rate of 8.9 to 35.8% of the structure of formula (II), an insertion rate of 0.56 to 6.57% of the structure of formula (III), a refractive index of 1.5500 to 1.6000, a glass transition temperature of 18.7 to 167.2 ℃, a weight average molecular weight of 17kg/mol to 346kg/mol, a molecular weight distribution of 1.45 to 2.77, and an elongation at break of 3.0 to 7.4%.
Meanwhile, the cycloolefin copolymer obtained by the method has higher transparency, and in the preparation method of the cycloolefin copolymer, the ternary polymerization reaction has higher reaction activity. Experimental results show that the cycloolefin copolymer provided by the invention has light transmittance in the visible light region>90%; the reactivity is 1.5-9.3x10 5 g.mol -1 h -1 。
The cycloolefin copolymer with polar groups obtained by the invention can increase the hydrophilicity of cycloolefin resin, and the water contact angle is 81-106 degrees.
Drawings
FIG. 1 is a schematic illustration of a terpolymer of example 25 of the present invention 1 H-NMR spectrum;
FIG. 2 is a schematic representation of a terpolymer of example 21 of the present invention 13 C-NMR spectrum;
FIG. 3 is a DSC graph of the terpolymer of example 18 of the present invention;
FIG. 4 is a graph showing the tensile fracture profile of a terpolymer according to example 28 of the present invention;
FIG. 5 is a graph comparing optical properties of terpolymers of examples 18, 20, 24, 25, 27, 28, 30, 32, 33 of the present invention;
FIG. 6 is a graph showing the visible light transmittance of the terpolymer of example 28 of the present invention.
Detailed Description
The invention provides a cycloolefin copolymer, which has a structure shown in a formula (I):
wherein X, Y and Z are polymerization degrees, wherein X is more than or equal to 20, Y is more than or equal to 1, and X is more than or equal to 200, and Z is more than or equal to 5; m is more than or equal to 1 and less than or equal to 10, n is more than or equal to 50 and less than or equal to 5000; preferably 18 to or more than X, Y to or more than 3,180 to or more than X, Z to or more than 12; m is more preferably more than or equal to 2 and less than or equal to 6, and is more preferably more than or equal to 15 and more than or equal to X, Y is more than or equal to 3,160 and is more than or equal to X and Z is more than or equal to 12; m is more than or equal to 2 and less than or equal to 4;
R 1 and R is 2 Is independent hydrogen or saturated aliphatic hydrocarbon group with 1-10 carbon atoms; preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or hydrogen;
R 3 and R is 4 Is independently hydrogen or alkyl or cycloalkyl containing less than 20 carbons, aryl, alcohol, acid, ester, halogen, alkoxy, trifluoromethyl, nitro or azomethine; preferably hydrogen, methyl, ethyl, cyclohexyl, alcohol, acid, ester, fluorine, chlorine, bromine or norbornene;
R 5 is a high refractive group selected from diphenylamino, diphenylmethyl, di-p-tolylmethyl, phenol, p-tolylthiophenol, o-phenylphenol, fluorenyl, dimethylfluorenyl, diphenylfluorenyl,carbazolyl or benzocarbazolyl.
According to the invention, the cycloolefin copolymers described include in particular polymers of the following formulae a to o:
the cycloolefin copolymer obtained in the present invention preferably has a weight average molecular weight of 17kg/mol to 346kg/mol, more preferably 58kg/mol to 346kg/mol. In the cycloolefin copolymer provided by the invention, the polar or aryl substituted olefin monomer with a high refractive group is introduced, so that the toughness of the cycloolefin copolymer is improved, the refractive index of the cycloolefin resin is improved, the application of the cycloolefin resin is expanded, and the applicability of the cycloolefin polymer resin is further improved.
The cycloolefin monomer in the cycloolefin copolymer provided by the invention has a structure shown in a formula (II), is a single-ring or multi-ring cycloolefin monomer, can provide rigidity characteristics in the process of copolymerizing with ethylene or alpha-olefin, and has higher glass transition temperature and higher practical value; the polar or aryl substituted olefin monomer in the cycloolefin copolymer provided by the invention has a structure shown in a formula (III), is an olefin monomer with a high refractive group, can provide a flexible characteristic on one hand, and can further improve the refractive index of the prepared cycloolefin resin on the other hand. Experimental results show that in the cycloolefin copolymer provided by the invention, the insertion rate of cycloolefin monomers with the structure shown in the formula (II) can be adjusted between 8.9% and 35.8%, the insertion rate of polar or aryl substituted olefin monomers with the structure shown in the formula (III) can be adjusted between 0.56% and 6.57%, and the highest glass transition temperature can reach 167.2 ℃; when the glass transition temperature of the cycloolefin copolymer is 114.8 ℃, the elongation at break of the cycloolefin copolymer is 7.4%, the tensile strength is 60.5MPa, the tensile modulus is 1200MPa, and the refractive index is 1.5674, so that a series of novel high-performance cycloolefin copolymers containing high refractive groups in the molecules with certain glass transition temperature are successfully obtained.
The invention provides a preparation method of a cycloolefin copolymer, which is characterized by comprising the following steps:
in an inert solvent, taking cycloolefin monomer with a structure shown in a formula (II), olefin monomer with a structure shown in a formula (III) and polar or aryl substituted olefin monomer and ethylene or alpha-olefin as polymerization monomers, and carrying out polymerization reaction in the inert solvent in the presence of a catalyst to obtain cycloolefin copolymer with a structure shown in a formula (I);
in the formula (I), X, Y and Z are polymerization degrees, wherein 20 is more than or equal to X, Y is more than or equal to 1,200 is more than or equal to X, and Z is more than or equal to 5; m is more than or equal to 1 and less than or equal to 10, n is more than or equal to 50 and less than or equal to 5000;
R 1 and R is 2 Is independent hydrogen or saturated aliphatic hydrocarbon group with 1-10 carbon atoms;
R 3 and R is 4 Is independently hydrogen or alkyl or cycloalkyl containing less than 20 carbons, aryl, alcohol, acid, ester, halogen, alkoxy, trifluoromethyl, nitro or azomethine;
R 5 is diphenylamino, diphenylmethyl, di-p-tolylmethyl, phenol, p-tolylthiophenol, o-phenylphenol, fluorenyl, dimethylfluorenyl, diphenylfluorenyl, carbazolyl or benzocarbazolyl.
The preparation method of the cycloolefin copolymer provided by the invention is carried out in an inert solvent, wherein the inert solvent is preferably a straight-chain hydrocarbon compound, a cyclic hydrocarbon compound or an aromatic hydrocarbon compound, more preferably a benzene compound, and most preferably toluene.
The polar olefin monomer or aryl substituted olefin monomer with the structure shown in the formula (III) is preferably shown in the formula 1-28:
the source of the cycloolefin monomer with the structure of the formula (II) is not particularly limited, and the cycloolefin monomer can be a commercial product or a self-made product. The method for preparing the cycloolefin monomer having the structure of the formula (II) is not particularly limited in the present invention, and in the present invention, the cycloolefin monomer having the structure of the formula (II) is preferably prepared according to the following reaction scheme. The cycloolefin monomer having the structure of formula (II) is preferably tetracyclododecene.
According to the invention, the catalyst is a metallocene catalyst, preferably as shown in the following figure: there are respectively Cat1 (non-bridged zirconocene dichloride catalyst), cat2 (isopropylidene bridged indene zirconocene dichloride catalyst), cat3 (isopropylidene bridged fluorenocene dichloride catalyst), cat4 (isopropylidene bridged tert-butyl fluorenocene dichloride catalyst), cat5 (diphenyl bridged fluorenocene dichloride catalyst), cat6 (dimethylsilyl bridged fluorenocene dichloride catalyst). The specific structure is as follows:
the invention preferably provides an inert solvent-dissolved cycloolefin monomer solution with a structure of formula (II), a polar or aryl-substituted olefin monomer solution with a structure of formula (III) and a catalyst solution, wherein the cycloolefin monomer solution with a structure of formula (II), the polar or aryl-substituted olefin monomer solution with a structure of formula (III) and the catalyst solution and ethylene or alpha-olefin are added into an inert solvent for polymerization reaction, and then the cycloolefin copolymer with a structure of formula (I) is obtained. In the present invention, the ethylene or α -olefin is preferably ethylene, propylene, 1-butene, isobutylene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-butene, more preferably ethylene, propylene, 1-butene isobutylene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, most preferably ethylene;
the molar ratio of the catalyst to the cycloolefin monomer having the structure of formula (II) is 1:500-6000, more preferably 1:1000-5000; the molar ratio of the catalyst to the polar or aryl-substituted olefin monomer having the structure of formula (iii) is preferably 1:50 to 2000, more preferably 1:80 to 1000; the molar ratio of the ethylene or alpha-olefin to the cycloolefin monomer having the structure of formula (II) is (1.2-18): 1, more preferably (3-15): 1; the molar ratio of the ethylene or alpha-olefin to the polar or aryl substituted olefin monomer having the structure of formula (III) is (5-200): 1, more preferably (10-150): 1.
In the present invention, when the ethylene or α -olefin is ethylene, since the ethylene is in a gaseous state, the present invention preferably fills the reaction solution with ethylene gas and continuously introduces ethylene gas into the reactor, maintaining the ethylene pressure preferably from 1 atmosphere to 10 atmospheres, more preferably 1 atmosphere;
in the polymerization reaction, the polar or aryl substituted olefin monomer with the structure shown in the formula (III) is provided with a high refractive index group at the tail end, and due to the influence of the high refractive index group, a high refractive index cycloolefin copolymer with certain toughness is obtained under the condition of lower insertion rate of the polar or aryl substituted olefin monomer, and the rigidity of the obtained cycloolefin copolymer chain is reduced, the entanglement among chains is enhanced, and the tear resistance of the cycloolefin copolymer is improved, so that the brittleness of the cycloolefin copolymer is improved. Furthermore, the invention uses the metallocene catalyst as the main catalyst, and the main catalyst has better tolerance to polar groups and the like in the process of polymerization reaction, so that the main catalyst has excellent copolymerization catalytic capability, and promotes the copolymerization of cycloolefin monomers with a structure of formula (II) and polar or aryl substituted olefin monomers with a structure of formula (III) and ethylene or alpha-olefin, thereby leading the polymerization reaction of the invention to have higher reactivity.
After the polymerization reaction is completed, the reaction liquid obtained by the polymerization reaction is preferably subjected to post-treatment, and the post-treatment specifically comprises the following steps: the invention can mix the reaction solution with ethanol or solution of hydrochloric acid to stop the growth of the polymerization chain and obtain a reaction product; and (3) carrying out solid-liquid separation on the reaction product, and then drying to obtain the cycloolefin copolymer. The method for terminating the polymerization chain growth in the present invention is not particularly limited, and the above-mentioned method of mixing the reaction solution with an ethanol solution of hydrochloric acid, the volume fraction of which is preferably 5% to 15%; the reaction product is preferably subjected to solid-liquid separation by adopting a filtering mode, and the filtered product is washed, wherein the washing reagent is preferably acetone, and the washing times are preferably 2 times; the method of drying is not particularly limited and a drying method known to those skilled in the art may be adopted, and in the present invention, the drying is vacuum drying, the drying temperature is 50 to 80 ℃, and the drying time is preferably 16 to 24 hours.
After the cycloolefin copolymer is obtained, the structure of the cycloolefin copolymer is identified and the performance of the cycloolefin copolymer is tested, and the specific process is as follows:
in the process of detecting the prepared high-performance cycloolefin copolymer, nuclear magnetic resonance spectroscopy is adopted to measure the molecular structure of the copolymer; measuring the melting temperature of the polymer by adopting a differential thermal analysis method; the molecular weight and molecular weight distribution index of the polymer were determined by gel permeation chromatography. Wherein nuclear magnetic resonance spectrum refers to the polymer 1 H and 13 the C NMR spectrum was measured by a Varian Unity-400 nuclear magnetic resonance spectrometer at 25℃with TMS as the internal standard and deuterated chloroform as the solvent (high temperature 110℃with deuterated tetrachloroethane as the solvent). Differential thermal analysis (DSC) refers to the measurement of the glass transition temperature of a polymer by a Perkin-ElmerPyris 1 DSC differential scanning calorimeter, the rising and falling temperature rate is 20 ℃/min, and the secondary scanning is performed. Thermal weight loss (TGA) was determined by a Perkin-Elmer Pyris type 1 instrument. The light transmittance is measured by using a Shimadzu UV-3600 ultraviolet-visible light-near infrared spectrophotometer, and the measurement wavelength is 400-800 nm. Stretching experiment: the mechanical property characterization of the polymer is carried out on INSTRON 1121, canton, MA instruments, with GB/T1040-1992 as standard, the spline clamping distance is 20.0mm, and the test is carried outThe rate was 5mm/min and each sample was tested at least 8 times to ensure data reliability. Gel Permeation Chromatography (GPC) refers to the molecular weight and molecular weight distribution index of a polymer as determined by a waters1525 type gel permeation chromatograph; the RI-Laser detector is adopted, the solvent is trichlorobenzene, the test temperature is 150 ℃, the flow rate is 1.0mL/min, and PLEasiCal PS-1 is adopted as a standard sample.
In order to further illustrate the present invention, the cycloolefin copolymer and the process for preparing the same according to the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
EXAMPLE 1 preparation of tetracyclododecene
1.5L dicyclopentadiene, 2L norbornene and 1g 2, 6-di-tert-butyl-p-methylphenol are sequentially added into a 5L autoclave, and the operation of vacuumizing and then filling nitrogen into the single-port bottle is repeated for 3 times; the single-necked flask was heated to 200℃and the contents of the autoclave were allowed to react for 3 hours with stirring.
After the reaction is finished, the obtained reaction product is cooled to 25 ℃, 1100 g of low-boiling unreacted product is obtained through reduced pressure distillation, 1800 g of target product is obtained through continuous heating and reduced pressure distillation, and the yield of the product prepared by the method provided by the embodiment 1 of the invention is 88%.
Example 2 preparation of polar monomer 5 having Structure of formula (III)
6-bromo-1-hexene (10.0 g,61.3 mmol) and phenol (5.0 g,53.1 mmol) and anhydrous potassium carbonate (22.0 g,160 mmol) were added to N, N-dimethylformamide (250 ml). The mixture was heated under reflux for about 24 hours. The solvent was removed and the crude product purified by silica gel chromatography eluting with a 0-30% ethyl acetate/hexanes gradient to give white liquid monomer 5 (8.9 g, 95%). The structural formula is as follows:
example 3 preparation of polar monomer 1 having Structure of formula (III)
6-bromo-1-hexene (10.0 g,61.3 mmol) and p-toluene thiophenol (5.0 g,40.3 mmol) and anhydrous potassium carbonate (16.7 g,120 mmol) were added to N, N-dimethylformamide (250 ml). The mixture was heated under reflux for about 24 hours. The solvent was removed and the crude product purified by silica gel chromatography eluting with a 0-30% ethyl acetate/hexanes gradient to give monomer 1 as a white liquid (7.8 g, 94%).
The structural formula is as follows:
example 4 preparation of polar monomer 17 having Structure of formula (III)
6-bromo-1-hexene (10.0 g,61.3 mmol) and carbazole (5.0 g,29.9 mmol) and anhydrous potassium carbonate (12.0 g,86.8 mmol) were added to N, N-dimethylformamide (250 ml). The mixture was heated under reflux for about 24 hours. The solvent was removed and the crude product purified by silica gel chromatography eluting with a 0-30% ethyl acetate/hexanes gradient to give monomer 17 (7.1 g, 95%) as a pale yellow solid. The structural formula is as follows:
comparative example 1 preparation of a binary cycloolefin copolymer
A75 mL glass pressure reactor connected to a gas line was first dried in vacuo at 90℃for at least 1h. 50mL of toluene and 50mmol of tetracyclododecene were then added to the reactor under an inert atmosphere, and then 10. Mu.mmol of the metallocene catalyst Cat3 (isopropylidene-bridged fluorenes-cyclopentadienyl zirconium dichloride catalyst) was dissolved in 2mL of toluene and injected into the polymerization system via a syringe. Ethylene was introduced under rapid stirring (750 revolutions) and maintained at 1bar. After 1h, the pressure reactor was vented, the polymerization quenched by addition of 200mL ethanol HCl, the polymer filtered and dried in a vacuum oven to constant weight.
Examples 5-13 Effect of polar alpha-olefin monomers containing different heteroatom high refractive groups on ethylene and cycloolefin terpolymers
A75 mL glass pressure reactor connected to a gas line was first dried in vacuo at 90℃for at least 1h. 50mL of toluene, 10mmol of tetracyclododecene and various concentrations and types of polar olefin monomers were then added to the reactor under an inert atmosphere, and then 10. Mu.mmol of Cat3 (isopropylidene-bridged fluorenocene zirconium dichloride catalyst) metallocene catalyst was dissolved in 2mL of toluene and injected into the polymerization system via a syringe. Ethylene was introduced under rapid stirring (750 revolutions) and maintained at 1bar. After 1h, the pressure reactor was vented, the polymerization quenched by addition of 200mL ethanol HCl, the polymer filtered and dried in a vacuum oven to constant weight. The specific reaction conditions and results are shown in table 1.
TABLE 1
Note that: all data are based at least on the results of two parallel experiments (unless otherwise indicated). Activity: at 10 3 g mol -1 h -1 In units of. M is M w 、M w /M n : weight average molecular weight, polymer dispersibility index, respectively, as determined by GPC in 1,2, 4-trichlorobenzene at 150℃relative to polystyrene standards.
The data in table 1 illustrates: the concentration of cycloolefin monomer is kept unchanged, the concentration of polar olefin monomer is increased, and the insertion rate is gradually increased. The different polar olefin monomers have different influences on the molecular weight and the glass transition temperature of the obtained polymer.
Examples 14 to 20 Effect of different reaction conditions on the preparation of cycloolefin resins
A75 mL glass pressure reactor connected to a gas line was first dried in vacuo at 90℃for at least 1h. 50mL of toluene and various concentrations of tetracyclododecene, various concentrations of polar monomer 17 were then added to the reactor under an inert atmosphere, and then 10. Mu. Mmol of Cat3 (isopropylidene-bridged fluorenocene zirconium dichloride catalyst) metallocene catalyst was dissolved in 2mL of toluene and injected into the polymerization system via a syringe. Ethylene was introduced under rapid stirring (750 revolutions) and maintained at 1bar. After 1h, the pressure reactor was vented, the polymerization quenched by addition of 200mL ethanol HCl, the polymer filtered and dried in a vacuum oven to constant weight. The specific reaction conditions and results are shown in table 2.
TABLE 2
Note that: all data are based at least on the results of two parallel experiments (unless otherwise indicated). Activity: at 10 3 g mol -1 h -1 In units of. M is M w 、M w /M n : weight average molecular weight, polymer dispersibility index, respectively, as determined by GPC in 1,2, 4-trichlorobenzene at 150℃relative to polystyrene standards. The DSC curve of the terpolymer obtained in example 18 is shown in FIG. 3.
Table 2 data illustrates: the polar monomer concentration is kept unchanged, and as the cycloolefin monomer concentration increases, the cycloolefin monomer insertion rate gradually increases and the polar monomer insertion rate gradually decreases. The concentration of cycloolefin monomer is kept unchanged, the concentration of polar monomer is increased, and the insertion rate is gradually increased. The cycloolefin monomer concentration is 1.0M, and the terpolymer with molecular weight of 5.75 ten thousand and glass temperature of 153.7 ℃ can be obtained when the polar monomer concentration is 0.16M.
EXAMPLES 21-33 Effect of different polarity alpha-olefin monomers and reaction conditions on the preparation of cycloolefin resins
A75 mL glass pressure reactor connected to a gas line was first dried in vacuo at 90℃for at least 1h. 50mL of toluene, tetracyclododecene (40 mmol in examples 23-33, 50mmol in examples 21, 22), various types and concentrations of alpha-olefin monomer were then added to the reactor under an inert atmosphere, and then 10. Mu.mmol of Cat3 (isopropylidene-bridged fluorenocene zirconium dichloride catalyst) metallocene catalyst was dissolved in 2mL of toluene and injected into the polymerization system via a syringe. Ethylene was introduced under rapid stirring (750 revolutions) and maintained at 1bar. After 1h, the pressure reactor was vented, the polymerization quenched by addition of 200mL ethanol HCl, the polymer filtered and dried in a vacuum oven to constant weight. The specific reaction conditions and results are shown in Table 3.
TABLE 3 Table 3
Note that: all data are based at least on the results of two parallel experiments (unless otherwise indicated). Activity: at 10 3 g mol -1 h -1 In units of. M is M w 、M w /M n : weight average molecular weight, polymer dispersibility index, respectively, as determined by GPC in 1,2, 4-trichlorobenzene at 150℃relative to polystyrene standards. Wherein, the terpolymer of example 21 13 The C-NMR spectrum is shown in FIG. 2, which shows a terpolymer of example 25 1 The H-NMR spectrum is shown in FIG. 1.
Table 3 data illustrates: the polymerization temperature affects the polymerization activity, the monomer insertion rate, the polymer molecular weight, and the glass transition temperature. The length of the alpha-olefin monomer chain has a certain influence on the polymerization activity, the monomer insertion rate, the polymer molecular weight and the glass transition temperature. When the cycloolefin concentration was 0.8M, monomer 19 was selected and kept at a concentration of 0.08M at a polymerization temperature of 50℃a terpolymer having a molecular weight of 26.9 ten thousand and a glass transition temperature of 141.6 ℃was obtained.
Table 4: influence of the insertion Rate of the monomers on the optical and mechanical Properties of the resin in the different examples
Note that: all data are based at least on the results of two parallel experiments (unless otherwise indicated). Activity: at 10 3 g mol -1 h -1 In units of. M is M w 、M w /M n : weight average molecular weight, polymer dispersibility index, respectively, as determined by GPC in 1,2, 4-trichlorobenzene at 150℃relative to polystyrene standards. Wherein the drawing breaking curve spectrum of the terpolymer of example 28 is shown in FIG. 4, and the visible light transmission curve of the terpolymer of example 28 is shown in FIG. 6Shown.
Table 4 data illustrates: different concentrations of cycloolefin monomers and concentrations and chain lengths of alpha-olefin monomers affect the optical and mechanical properties of the resulting terpolymers, and FIG. 5 is a graph showing the comparison of the optical properties of the terpolymers of examples 18, 20, 24, 25, 27, 28, 30, 32, 33 of the present invention; when the concentration of cycloolefin is 0.8M, monomer 18 is selected, the concentration of the monomer is kept at 0.16M, and the polymerization temperature is 50 ℃, the terpolymer with the molecular weight of 24.18 ten thousand, the glass transition temperature of 114.8 ℃, the refractive index of 1.5674 and the elongation at break of 7.4 percent can be obtained, and the properties of the terpolymer are far higher than those of a commercial product Mitsui APEL5014CL.
Claims (10)
1. A cycloolefin copolymer characterized by having a structure represented by the formula (I):
wherein, X is more than or equal to 20, Y is more than or equal to 1, X is more than or equal to 200, and Z is more than or equal to 5; m is more than or equal to 1 and less than or equal to 10, n is more than or equal to 50 and less than or equal to 5000, and p is 0 and 1;
R 1 and R is 2 Is independent hydrogen or saturated aliphatic hydrocarbon group with 1-10 carbon atoms;
R 3 and R is 4 Is independently hydrogen or alkyl or cycloalkyl containing less than 20 carbons, aryl, alcohol, acid, ester, halogen, alkoxy, trifluoromethyl, nitro or azomethine;
R 5 is diphenylamino, diphenylmethyl, di-p-tolylmethyl, phenol, p-tolylthiophenol, o-phenylphenol, fluorenyl, dimethylfluorenyl, diphenylfluorenyl, carbazolyl or benzocarbazolyl.
2. The cycloolefin copolymer according to claim 1, characterized in that R is 1 And R is 2 Is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or hydrogen;
the R is 3 And R is 4 Is independently selected from hydrogen, methyl, ethyl, cyclohexyl, and alcoholAcid, ester, fluorine, chlorine, bromine or norbornene.
3. The cyclic olefin copolymer according to claim 1, wherein the cyclic olefin copolymer comprises a polymer of the following formula a-o:
wherein, X is more than or equal to 20, Y is more than or equal to 1, X is more than or equal to 200, and Z is more than or equal to 5; n is more than or equal to 50 and less than or equal to 5000.
4. The process for preparing cycloolefin copolymers according to claim 1, characterized in that it comprises the following steps:
in an inert solvent, carrying out polymerization reaction on cycloolefin monomers with a structure shown in a formula (II), polar or aryl substituted olefin monomers with a structure shown in a formula (III) and ethylene or alpha-olefin in the presence of a catalyst to obtain cycloolefin copolymers with a structure shown in a formula (I);
in the formula (I), X, Y and Z are polymerization degrees, wherein 20 is more than or equal to X, Y is more than or equal to 1,200 is more than or equal to X, and Z is more than or equal to 5; m is more than or equal to 1 and less than or equal to 10, n is more than or equal to 50 and less than or equal to 5000, and p is 0 and 1;
R 1 and R is 2 Is independent hydrogen or saturated aliphatic hydrocarbon group with 1-10 carbon atoms;
R 3 and R is 4 Is independently hydrogen or alkyl or cycloalkyl containing less than 20 carbons, aryl, alcohol, acid, ester, halogen, alkoxy, trifluoromethyl, nitro or azomethine;
R 5 is diphenylamino, diphenylmethyl, di-p-tolylA methylal group, a phenol group, a p-tolylthiophenol group, an o-phenylphenol group, a fluorenyl group, a dimethylfluorenyl group, a diphenylfluorenyl group, a carbazolyl group, or a benzocarbazolyl group.
5. The process for producing a cycloolefin copolymer according to claim 4, characterized in that the α -olefin is propylene, 1-butene, isobutylene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene or 2-ethyl-1-butene.
6. The method for producing a cycloolefin copolymer according to claim 4, characterized in that the polar or aryl-substituted olefin monomer is an olefin monomer having a diphenylamino group, a diphenylsilyl group, a di-p-tolylmethyl group, a phenol group, a p-tolylthiophenol group, an o-phenylphenol group, a fluorenyl group, a dimethylfluorenyl group, a diphenylfluorenyl group, a carbazolyl group or a benzocarbazolyl group.
7. The process for preparing cycloolefin copolymer according to claim 4, characterized in that the catalyst is a metallocene catalyst.
8. The method for preparing a cycloolefin copolymer according to claim 7, wherein the metallocene catalyst comprises a non-bridged zirconocene dichloride catalyst, an isopropylidene-bridged indene zirconocene dichloride catalyst, an isopropylidene-bridged fluorenocene dichloride catalyst, an isopropylidene-bridged tert-butyl fluorenocene dichloride catalyst, a diphenyl-bridged fluorenocene dichloride catalyst or a dimethylsilyl-bridged fluorenocene dichloride catalyst.
9. The process for preparing cycloolefin copolymer according to claim 4, characterized in that the molar ratio of the catalyst to the cycloolefin monomer having the structure of the formula (II) is from 1:500 to 6000; the molar ratio of the catalyst to the polar or aryl-substituted olefin monomer having the structure of formula (iii) is preferably 1:50-2000; the molar ratio of the ethylene or alpha-olefin to the cycloolefin monomer having the structure of formula (II) is (1.2-18): 1; the molar ratio of the ethylene or alpha-olefin to the polar or aryl substituted olefin monomer having the structure of formula (III) is (5-200): 1.
10. The process for preparing cycloolefin copolymers according to claim 4, characterized in that the polymerization is carried out at a temperature of from 30℃to 150℃for a period of from 30 minutes to 240 minutes.
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