CN102731721A - Cycloolefin copolymer and preparation method thereof - Google Patents
Cycloolefin copolymer and preparation method thereof Download PDFInfo
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- CN102731721A CN102731721A CN201210140493XA CN201210140493A CN102731721A CN 102731721 A CN102731721 A CN 102731721A CN 201210140493X A CN201210140493X A CN 201210140493XA CN 201210140493 A CN201210140493 A CN 201210140493A CN 102731721 A CN102731721 A CN 102731721A
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Abstract
The invention discloses a cycloolefin copolymer with a structure shown in the formula (I), wherein m and n are polymerization degrees, m:n>=1.5, and R1 and R2 are independently selected from hydrogen or C1-C10 saturated aliphatic hydrocarbon. According to the invention, a cycloolefin monomer with a structure shown in the formula (II) and alpha-alkene are adopted as polymerization monomers; the copolymerization monomers are subjected to a polymerization reaction under the existence of a catalyst and in an inert solvent, such that the cycloolefin copolymer with the structure shown in the formula (I) is obtained. According to the invention, the cycloolefin monomer with the structure shown in the formula (II) is large-volume cycloolefin. Because of a stereospecific blockade effect, under the condition of a low insertion rate, the cycloolefin copolymer with high glass transition temperature and with the structure of the formula (I) is obtained. The flexible alpha-alkene units in the copolymer are increased, such that the rigidity of the cycloolefin copolymer chains is reduced, the entanglement among the chains is enhanced, such that the anti-tearing performance of the cycloolefin copolymer is improved, and the brittleness of the copolymer is ameliorated.
Description
Technical field
The present invention relates to technical field of polymer, relate in particular to a kind of cyclic olefine copolymer and preparation method thereof.
Background technology
Cyclic olefine copolymer (COC) is that the addition copolymerization prepared in reaction by terminal olefin and cycloolefin obtains, and it has excellent properties such as, transparency height little such as density, Heat stability is good, optical index height and chemical resistance be strong.Since 20th century, be synthesized the nineties first, COC had become one of important engineering plastics, was applied in heat-resisting and the optical material.At present, the Mitsui Chemicals company (Mitsui) of Japan and the Ticona company (Ticona) of the U.S. have released business-like COC, and trade(brand)name is respectively APEL and Topas.
The disclosed result of study of prior art shows: as the second-order transition temperature (T of COC
g) during greater than 150 ℃, the COC that obtains just has higher utility.In order to obtain T
gCOC greater than 150 ℃; Prior art is through improving the second-order transition temperature that the insertion rate of cycloolefin in multipolymer improves the cyclic olefine copolymer that obtains; For example the multipolymer of the disclosed ethylene-norbornene of prior art (NB) just can obtain T when the insertion rate of norbornylene surpasses 50mol%
gCyclic olefine copolymer greater than 150 ℃.Yet under high cycloolefin insertion rate, the rigidity of the COC molecule that obtains is stronger, makes that the fragility of multipolymer is more serious, and this shortcoming has hindered the application of COC.
In order under the prerequisite that keeps than high glass transition temperature, to improve the fragility of COC molecule, prior art discloses more method.Like nineteen ninety-five, Germany scientist Kaminsky utilizes metallocene catalyst catalyzed ethylene and dimethano-octahydro naphthalene (DMON) copolymerization, has synthesized T
gBe up to 143 ℃ COC, wherein the insertion rate of DMON is 44mol% (Angew.Chem., Int.Ed.1995,34,2273.).Yet the catalytic activity of luxuriant ferrous metal catalyzer in the method is lower, makes that the activity of polyreaction is 4.0 * 10
-10～0.94 * 10
-6G/mol
ZrH, and to obtain multipolymer be the hemihedral crystal structure, and using value is not high.In order to obtain having the COC of higher using value, Korea S scientist Lee in 2010 as comonomer, utilizes the catalyzer of the constrained geometry configuration of phenylene bridging with three cyclopentadiene (TCPD), has prepared T
gBe up to 177 ℃ COC, wherein the insertion rate of TCPD is 45mol% (Macromolecules 2010,43,725.), the COC that obtains is carried out the Elongation test result show, and be 37mol%, T in TCPD insertion rate
gWhen being 154 ℃, its elongation at break is 2.8%, and the fragility of the COC that obtains is improved not obvious, still has more serious fragility, is unfavorable for its application.
Summary of the invention
The object of the present invention is to provide a kind of cyclic olefine copolymer and preparation method thereof, cyclic olefine copolymer provided by the invention has higher elongation at break, and its fragility is significantly improved, and helps its application.
The present invention provides a kind of cyclic olefine copolymer, has formula (I) structure:
Wherein, m and n are the polymerization degree, m:n >=1.5;
R
1And R
2Be independently selected from hydrogen or carbonatoms and be 1 ~ 10 representative examples of saturated aliphatic alkyl.
Preferably, 20 >=m:n >=2.3.
Preferably, said R
1And R
2Be independently selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-or hydrogen.
The present invention provides the preparation method of the described cyclic olefine copolymer of a kind of technique scheme, may further comprise the steps:
In inert solvent, cycloolefin monomers and the terminal olefin that will have formula (II) structure carry out polyreaction under the condition that catalyzer exists, the cyclic olefine copolymer of (I) structure that obtains having formula;
In the formula (I), m and n are the polymerization degree, m:n >=1.5;
R
1And R
2Be independently selected from hydrogen or carbonatoms and be 1 ~ 10 representative examples of saturated aliphatic alkyl.
Preferably, said terminal olefin and said mol ratio with cycloolefin monomers of formula (II) structure are (2.3 ~ 20): 1.
Preferably, said terminal olefin is ethene, propylene, 1-butylene, iso-butylene, 1-amylene, 2-methyl isophthalic acid-butylene, 3-methyl-1-butene, 1-hexene, 2-Methyl-1-pentene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-butylene.
Preferably, said catalyzer and said mol ratio with cycloolefin monomers of formula (II) structure are 1: (1 ~ 20).
Preferably, said catalyzer comprises Primary Catalysts and promotor;
Said Primary Catalysts is (tertiary butyl amido)-dimethyl--(tetramethyl--η
5-cyclopentadienyl moiety)-the silane titanium dichloride;
Said promotor is triisobutyl aluminium and triphen carbon four-(pentafluorophenyl group) borate.
Preferably, the mol ratio of the triisobutyl aluminium in said Primary Catalysts and the said promotor is 1: (200 ~ 2500);
Triphen carbon four in said Primary Catalysts and the said promotor-(pentafluorophenyl group) boratory mol ratio is 1: (1 ~ 10).
Preferably, said inert solvent is straight chain hydrocarbon compound, cyclic hydrocar-bons compound or arene compounds;
The temperature of said polyreaction is 0 ℃ ~ 100 ℃;
The time of said polyreaction is 1 minute ~ 60 minutes.
The present invention provides a kind of cyclic olefine copolymer, has formula (I) structure, and wherein m and n are the polymerization degree, m:n>=1.5; R
1And R
2Be independently selected from hydrogen or carbonatoms and be 1 ~ 10 representative examples of saturated aliphatic alkyl.The present invention is polymerization single polymerization monomer with terminal olefin with the cycloolefin monomers with formula (II) structure, and it is carried out polyreaction under the effect of catalyzer He in the inert solvent, the cyclic olefine copolymer of (I) structure that obtains having formula.The cycloolefin monomers that the present invention adopts has formula (II) structure, and it is big volume cycloolefin, in polymerization process; Because sterically hindered effect, under the insertion rate of lower cycloolefin monomers, the cyclic olefine copolymer that obtains has high glass transition; Flexible terminal olefin unit increases in this multipolymer; Thereby make the cyclic olefine copolymer chain rigidity reduce, the entanglement between the chain strengthens, thereby has improved the tear resistance of cyclic olefine copolymer; Make its fragility improve, obtained having the improved cyclic olefine copolymer of higher glass transition temperature and fragility.Experimental result shows that the insertion rate≤30.0mol% of the cycloolefin monomers in the cyclic olefine copolymer provided by the invention, its second-order transition temperature can reach 207.0 ℃, and high glass transition makes cyclic olefine copolymer have advantages of high practicability; Elongation test is the result show, when its second-order transition temperature was 160.4 ℃, its elongation at break was 7.6%, and tensile strength is 55.0MPa.
And the cyclic olefine copolymer that the present invention obtains has higher transparency and MWD preferably, and among the preparation method of cyclic olefine copolymer provided by the invention, the polyreaction of cycloolefin monomers and terminal olefin has high reaction activity and high.Experimental result shows that the molecular weight of the cyclic olefine copolymer that the present invention obtains is 173kg/mol ~ 439kg/mol, and molecular weight distributing index is 1.67 ~ 2.80; Cyclic olefine copolymer provided by the invention is at transmittance＞80% of visible region; Reactive behavior is (6.0 * 10
6~ 20.0 * 10
6) g/mol
TiH.
Description of drawings
The cyclic olefine copolymer that Fig. 1 obtains for the embodiment of the invention 2 and embodiment 8
13C NMR spectrogram;
The DSC curve of the cyclic olefine copolymer that Fig. 2 obtains for the embodiment of the invention 5 ~ 8;
The stress-strain curve of the cyclic olefine copolymer that Fig. 3 obtains for the embodiment of the invention 6 ~ 8;
The light transmittance curve in the ultraviolet-visible spectrum district of the cyclic olefine copolymer that Fig. 4 obtains for the embodiment of the invention 7 ~ 8;
The cyclic olefine copolymer that Fig. 5 obtains for the embodiment of the invention 8
1H NMR spectrogram.
Embodiment
The present invention provides a kind of cyclic olefine copolymer, has formula (I) structure:
formula (I);
Wherein, m and n are the polymerization degree, m:n >=1.5;
R
1And R
2Be independently selected from hydrogen or carbonatoms and be 1 ~ 10 representative examples of saturated aliphatic alkyl.
The present invention provides a kind of cyclic olefine copolymer, has formula (I) structure, and wherein m and n are the polymerization degree, and m:n>=1.5 are preferably 2.3≤m:n≤20, more preferably 3≤m:n≤15; The weight-average molecular weight of the cyclic olefine copolymer that the present invention obtains is preferably 150kg/mol ~ 800kg/mol, more preferably 170kg/mol ~ 500kg/mol.In cyclic olefine copolymer provided by the invention; The value of n is less; The content of this explanation cycloolefin monomers is less, and having the unitary ratio of flexible alpha-olefine polymerizing accordingly increases, thereby cyclic olefine copolymer molecule chain flexibility is provided; Improved its tear resistance, made its fragility obtain improving significantly.
In said formula (I), said R
1And R
2Be independently selected from hydrogen or carbonatoms and be 1 ~ 10 representative examples of saturated aliphatic alkyl, preferably be independently selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-or hydrogen, most preferably be hydrogen.
Cycloolefin monomers in the cyclic olefine copolymer provided by the invention has formula (II) structure; It is big volume comonomer, with the process of alpha-olefin copolymer in because space steric effect makes the content of the terminal olefin in the cyclic olefine copolymer chain increase; Make the polymkeric substance chain rigidity reduce; Entanglement between the chain strengthens, thus the cyclic olefine copolymer that has obtained having higher flexibility, and under the insertion rate of the lower cycloolefin monomers with formula (II) structure; The cyclic olefine copolymer that obtains has high glass transition, has higher utility.Experimental result shows, in cyclic olefine copolymer provided by the invention, have the insertion rate of formula (II) structure ring olefinic monomer can be between 0mol% ~ 30.4mol% adjustable, its second-order transition temperature can reach 207.0 ℃; T when cyclic olefine copolymer
gWhen being 164.0 ℃, its elongation at break is 7.6%, and tensile strength is 55.0MPa, and tensile modulus is 2590MPa; T when cyclic olefine copolymer
gWhen being 154.0 ℃, its elongation at break is 2.8%, and tensile modulus is 2100MPa, has successfully obtained having under the high glass-transition temperature cyclic olefine copolymer of superior performance.
The present invention provides the preparation method of the described cyclic olefine copolymer of a kind of technique scheme, may further comprise the steps:
In inert solvent, cycloolefin monomers and the terminal olefin that will have formula (II) structure carry out polyreaction under the condition that catalyzer exists, the cyclic olefine copolymer of (I) structure that obtains having formula;
In the formula (I), m and n are the polymerization degree, m:n >=1.5;
R
1And R
2Be independently selected from hydrogen or carbonatoms and be 1 ~ 10 representative examples of saturated aliphatic alkyl.
The preparation method of cyclic olefine copolymer provided by the invention carries out in inert solvent, and said inert solvent is preferably straight chain hydrocarbon compound, cyclic hydrocar-bons compound or arene compounds, and more preferably benzene-like compounds most preferably is toluene.
In said inert solvent, the present invention will have cycloolefin monomers and the terminal olefin of formula (II) structure under the condition that catalyzer exists, and carry out polyreaction, the cyclic olefine copolymer of (I) structure that obtains having formula.The present invention does not have special limitation to said source with cycloolefin monomers of formula (II) structure, can be the commercial goods, can be the self-control product yet.The present invention does not have special limitation to said preparation method with cycloolefin monomers of formula (II) structure; In the present invention; Said cycloolefin monomers with formula (II) structure preferably prepares according to the described method of following technical paper: Michael N.Paddon-Row and Robert Hartcher.Orbital Interactions.7.The birch reduction as a tool for exploring orbital interactions through bonds.Through-Four-;-Five-, and-Six-Bond Interactions
1.Journal of the American Chenzicul Society, 1980,102:671 ~ 678. are specially:
Under the protection of rare gas element, with the reaction of anthracene and norbornadiene, the cycloolefin monomers of (II) structure that obtains having formula.The mol ratio of said in the present invention anthracene and said norbornadiene is preferably (0.1 ~ 0.5): 1, more preferably (0.15 ~ 0.3): 1; Said rare gas element is preferably nitrogen; The present invention is preferably in autoclave, with anthracene and norbornadiene reaction; The temperature of reaction of said anthracene and norbornadiene is preferably 150 ℃ ~ 200 ℃, more preferably 160 ℃ ~ 190 ℃; The reaction times of said anthracene and norbornadiene is preferably 20 h ~ 40 hours, and more preferably 25 h ~ are 30 hours.
After said anthracene and the reaction of said norbornadiene were accomplished, the present invention preferably reduced to room temperature with reaction system, then unreacted norbornadiene is distilled out, and obtains reaction product, and said reaction product is a faint yellow solid.After obtaining reaction product, the present invention preferably with said reaction product extract, recrystallization, filtration and drying, the cycloolefin monomers of (II) structure that obtains having formula.The present invention does not have special limitation to said extraction, recrystallization, filtration and exsiccant method, adopts extraction well known to those skilled in the art, recrystallization, filtration and exsiccant technical scheme to get final product.The present invention preferably is solvent with the sherwood oil; With apparatus,Soxhlet's extracting 20 h ~ 30 hours; The concentrated extract that will obtain then carries out recrystallization, separates out white crystal, and the product that then recrystallization is obtained filters; The solid that obtains is preferably carried out vacuum-drying under 40 ℃ ~ 60 ℃, the monomer of the cycloolefin of (II) structure that obtains having formula.
The preparation method of the cycloolefin monomers that the present invention adopts with formula (II) structure, its synthesizing and purifying is simple, and productive rate is high.Experimental result shows that the yield of the cycloolefin monomers with formula (II) structure that the preparation method that the present invention adopts obtains is up to 80.0%.
Behind the cycloolefin monomers of (II) structure that obtains having formula; The present invention carries out polyreaction with said cycloolefin monomers with formula (II) structure and terminal olefin under the condition that the inert solvent catalyst neutralisation exists, the cyclic olefine copolymer of (I) structure that obtains having formula.The present invention preferably provides the inert solvent dissolved to have the cycloolefin monomers solution and the catalyst solution of formula (II) structure; Have in the cycloolefin monomers solution of formula (II) structure, said catalyst solution and the terminal olefin adding inert solvent said; After carrying out polyreaction, the cyclic olefine copolymer of (I) structure that obtains having formula.In the present invention; Said terminal olefin is preferably ethene, propylene, 1-butylene, iso-butylene, 1-amylene, 2-methyl-1-butene alkene, 3-methyl-1-butene, 1-hexene, 2-Methyl-1-pentene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-butylene; More preferably ethene, propylene, 1-butylene, iso-butylene, 1-amylene, 3-methyl-1-butene, 1-hexene, 3-Methyl-1-pentene most preferably are ethene; Said terminal olefin and said mol ratio with cycloolefin monomers of formula (II) structure are preferably (2.3 ~ 20): 1, and, more preferably (3.0 ~ 15): 1; Said catalyzer and said mol ratio with cycloolefin monomers of formula (II) structure are preferably 1: (1 ~ 20), more preferably 1: (5 ~ 10).In the present invention; When said terminal olefin is ethene; Because ethene is gaseous phase, the present invention is preferably with being full of ethylene gas in the reaction soln, and continues in said reactor drum, to feed ethylene gas; Keep the pressure of ethene to be preferably 0.5 normal atmosphere ~ 2 normal atmosphere, more preferably 1 normal atmosphere ~ 1.5 normal atmosphere;
In the present invention; Said catalyzer can be cycloolefin monomers and the alpha-olefin copolymer catalyst for reaction of being used for well known to those skilled in the art; Preferably include Primary Catalysts and promotor, said Primary Catalysts comprises but is not limited to (tertiary butyl amido)-dimethyl--(tetramethyl--η
5-cyclopentadienyl moiety)-and silane titanium dichloride (CGC), said promotor comprises but is not limited to triisobutyl aluminium (TIBA) and triphen carbon four-(pentafluorophenyl group) borate [Ph
3CB (C
6F
5)
4]; The mol ratio of the triisobutyl aluminium in said Primary Catalysts and the said promotor is preferably 1: (200 ~ 2500), more preferably 1: (250 ~ 2000); Triphen carbon four in said Primary Catalysts and the said promotor-(pentafluorophenyl group) boratory mol ratio is preferably 1: (1 ~ 10), more preferably 1: (3 ~ 6).
The present invention preferably carries out according to following order when said cycloolefin monomers, terminal olefin and catalyzer with (II) structure mixed in inert solvent:
The present invention at first adds the solution of inert solvent of solution, terminal olefin and the said promotor of said cycloolefin monomers with (II) structure in inert solvent; The solution that in the mixing solutions that obtains, adds the inert solvent of said Primary Catalysts then, after the polyreaction, the cyclic olefine copolymer of (I) structure that obtains having formula.In the present invention, said volumetric molar concentration with cycloolefin monomers solution of formula (II) structure is preferably 0.1mol/L ~ 5mol/L, more preferably 1.0mol/L ~ 3mol/L; The volumetric molar concentration of triisobutyl aluminum solutions is preferably 0.1mol/L ~ 5mol/L in the said promotor, and more preferably 0.3mol/L ~ 3mol/L most preferably is 0.5mol/L ~ 1mol/L; The volumetric molar concentration of triphen carbon four in the said promotor-(pentafluorophenyl group) borate solution is preferably 1 μ mol/mL ~ 10 μ mol/mL, more preferably 5 μ mol/mL ~ 8 μ mol/mL; The volumetric molar concentration of said Primary Catalysts solution is preferably 0.1 μ mol/mL ~ 5 μ mol/mL, more preferably 0.5 μ mol/mL ~ 2 μ mol/mL.In the present invention, the temperature of said polyreaction is preferably 0 ℃ ~ 100 ℃, more preferably 20 ℃ ~ 90 ℃, most preferably is 40 ℃ ~ 80 ℃; The time of said polyreaction is preferably 1 minute ~ and 60 minutes, more preferably 5 minutes ~ 30 minutes.
In the process of carrying out polyreaction, said cycloolefin monomers volume with formula (II) structure is bigger, because the influence of space steric effect; Under the insertion rate of lower cycloolefin monomers; Obtain having the high glass transition cyclic olefine copolymer, have formula (I) structure, the unitary ratio of flexible terminal olefin increases in this multipolymer; Thereby the cyclic olefine copolymer chain rigidity that obtains is reduced; Entanglement between the chain strengthens, thereby has improved the tear resistance of cyclic olefine copolymer, makes its fragility improve.Further, the present invention is with (tertiary butyl amido)-dimethyl--(tetramethyl--η
5-cyclopentadienyl moiety)-and the silane titanium dichloride is a Primary Catalysts, in the process of carrying out polyreaction, and the bridged group (SiMe on this Primary Catalysts substituted-cyclopentadienyl
2) limited atoms metal spatial geometric configuration; Thereby make the atoms metal avtive spot in the Primary Catalysts more exposed; Make it have excellent copolymerization catalytic capability; Impel the cycloolefin monomers of (II) structure that has formula and the copolyreaction of terminal olefin, thereby make polyreaction of the present invention have high reaction activity and high.
After polyreaction was accomplished, the present invention preferably carried out aftertreatment to the reaction solution that said polyreaction obtains, and is specially:
The present invention can mix said reaction solution with the ethanolic soln of hydrochloric acid, stop the growth of polymeric chain, obtains reaction product; Said reaction product is carried out carrying out drying after the solid-liquid separation, obtain cyclic olefine copolymer.The method that among the present invention said termination polymeric chain is increased does not have particular restriction, can adopt above-mentioned ethanolic soln blended mode with reaction solution and hydrochloric acid, and the volume(tric)fraction of the ethanolic soln of said hydrochloric acid is preferably 5% ~ 15%; The present invention preferably adopts filtering mode that said reaction product is carried out solid-liquid separation, and said filtering product is washed, and in the present invention, the reagent of said washing is preferably acetone, and the number of times of said washing is preferably 2 times ~ 5 times; The present invention does not have special limitation to said exsiccant method; Adopt exsiccant technical scheme well known to those skilled in the art to get final product, in the present invention, said drying is vacuum-drying; Said exsiccant temperature is 50 ℃ ~ 80 ℃, and the said exsiccant time is preferably 20 h ~ 30 hours.
After obtaining cyclic olefine copolymer, the present invention carries out the evaluation and the performance test of structure to said cyclic olefine copolymer, and detailed process is following:
The present invention carries out nucleus magnetic resonance (NMR) with the cyclic olefine copolymer that obtains and detects, and comprises
1H NMR spectrum,
13C NMR spectrum and undistorted polarization transfer strengthen (DEPT) spectrum; The result shows; Cyclic olefine copolymer provided by the invention has formula (I) structure, and the insertion rate of said cycloolefin monomers with formula (II) structure is between 0mol% ~ 30.4mol%, and the insertion rate with formula (II) structure ring olefinic monomer reduces; Reduce the rigidity of the cyclic olefine copolymer that obtains, thereby improved the tear resistance of cyclic olefine copolymer;
The present invention carries out Elongation test to the cyclic olefine copolymer that obtains, and the result shows that the elongation at break of the cyclic olefine copolymer that the present invention obtains is between 2.1% ~ 7.6%; Tensile strength is between 44MPa ~ 63.3MPa; Tensile modulus is at 2390MPa ~ 2680MPa, and this shows that cyclic olefine copolymer provided by the invention has higher stretch-proof performance; Its tear resistance is improved, thereby makes that its fragility has obtained improving significantly;
The present invention adopts differential scanning calorimetry (DSC) that the second-order transition temperature of the cyclic olefine copolymer that obtains is measured; The result shows; The second-order transition temperature of cyclic olefine copolymer provided by the invention can reach 207 ℃; This shows that the present invention has prepared to have than high glass transition temperature and the improved cyclic olefine copolymer of fragility, and the cyclic olefine copolymer that the present invention obtains has advantages of high practicability;
The present invention has measured the molecular weight of cyclic olefine copolymer; The result shows; The weight-average molecular weight of the cyclic olefine copolymer thing of embodiment of the invention preparation is 173kg/mol ~ 439kg/mol, and molecular weight distributing index is 1.60 ~ 2.80, has good molecular weight controllability;
The present invention has measured the light transmission of cyclic olefine copolymer, and the result shows that the transparency of cyclic olefine copolymer provided by the invention is high, at transmittance＞80% of visible region.
The present invention provides a kind of cyclic olefine copolymer and preparation method thereof, and cycloolefin copolymerization provided by the invention has formula (I) structure, and wherein m and n do, m:n>=1.5; R
1And R
2Be independently selected from hydrogen or carbonatoms and be 1 ~ 10 representative examples of saturated aliphatic alkyl.The present invention is polymerization single polymerization monomer with terminal olefin with the cycloolefin monomers with formula (II) structure, and it is carried out polyreaction under the effect of catalyzer, the cyclic olefine copolymer of (I) structure that obtains having formula.The cycloolefin monomers that the present invention selects has formula (II) structure, and it is big volume cycloolefin, in polymerization process; Because space steric effect under the insertion rate of lower cycloolefin monomers, obtains having the high glass transition cyclic olefine copolymer; Flexible terminal olefin unit increases in this cyclic olefine copolymer; Thereby make the cyclic olefine copolymer chain rigidity reduce, the entanglement between the chain strengthens, thereby has improved the tear resistance of cyclic olefine copolymer; Make its fragility improve, obtained having the improved cyclic olefine copolymer of higher glass transition temperature and fragility.And the cyclic olefine copolymer that the present invention obtains has higher transparency and MWD preferably, and among the preparation method of cyclic olefine copolymer provided by the invention, the polyreaction of cycloolefin monomers and terminal olefin has high reaction activity and high.Experimental result shows, the insertion rate≤30.0mol% of the cycloolefin monomers in the cyclic olefine copolymer provided by the invention, and its second-order transition temperature can reach 207.0 ℃, and high glass transition makes cyclic olefine copolymer have advantages of high practicability; Elongation test is the result show, when its second-order transition temperature was 160.4 ℃, its elongation at break was that 7.6% tensile strength is 55.0MPa; The molecular weight of the cyclic olefine copolymer that the present invention obtains is 173kg/mol ~ 439kg/mol, and molecular weight distributing index is 1.67 ~ 2.80; Cyclic olefine copolymer provided by the invention is at transmittance＞80% of visible region; Reactive behavior is up to 2.0 * 10
7G/mol
TiH.
In order to further specify the present invention, below in conjunction with embodiment cyclic olefine copolymer provided by the invention and preparation method thereof is carried out detailed description, but can not they be interpreted as the qualification to protection domain of the present invention.
In the autoclave of 150mL, add 42g anthracene and 108g norbornadiene successively.Under nitrogen atmosphere, with anthracene and norborneol 180 ℃ of following reacting by heating 27 hours.Reaction is reduced to room temperature with the temperature of reaction system after accomplishing, and steams unreacted norbornadiene, gets faint yellow solid.With the sherwood oil is solvent, with resulting faint yellow solid, with apparatus,Soxhlet's extracting 24 hours, obtains concentrating extract.Said concentrated extract is carried out recrystallization, separate out white crystal, filter then, the solid that obtains is carried out vacuum-drying under 50 ℃, must have cycloolefin monomers.
The cycloolefin monomers that the present invention obtains is a white crystal, and the quality of the cycloolefin monomers that weighing obtains is 50.2g, and calculating yield is 80.0%.
The present invention carries out structural characterization with the cycloolefin monomers that obtains, and the result shows that the cycloolefin monomers of the present invention's preparation has formula (II) structure.
Under ethene atmosphere, the toluene solution, toluene solution and the 3mL volumetric molar concentration of TIBA that the 1.5mL volumetric molar concentration is 0.5mol/L of the cycloolefin monomers with formula (II) structure that in the exsiccant reactor drum, adds 21.5mL dry toluene, 1mL volumetric molar concentration successively and be embodiment 1 preparation of 2mol/L is the [Ph of 6 μ mol/mL
3CB (C
6F
5)
4] toluene solution; The mixing solutions that obtains after stirring 10 minutes under 40 ℃, to wherein adding the toluene solution that the 3mL volumetric molar concentration is the CGC of 1 μ mol/mL, is continued in said reactor drum, to feed ethene; And to keep the pressure of ethene be 1 normal atmosphere, polyreaction 5 minutes.After polyreaction is accomplished, the reaction solution that obtains is poured in the ethanolic soln that volume(tric)fraction is 10% hydrochloric acid into the evolution reaction product; The reaction product that obtains is filtered, and with behind the washing with acetone 3 times, the product that obtains is placed vacuum drying oven, drying is 24 hours under 60 ℃, obtains white cyclic olefine copolymer.
The present invention carries out proton nmr spectra to the cyclic olefine copolymer that obtains and detects, and the result is as shown in Figure 1, the cyclic olefine copolymer that Fig. 1 obtains for the embodiment of the invention 2 and embodiment 8
13C NMR spectrogram, wherein (a) cyclic olefine copolymer of obtaining for embodiment 2
13C NMR spectrogram can find out that by Fig. 1 (a) cyclic olefine copolymer provided by the invention has structure shown in (I); By cyclic olefine copolymer
1The HNMR spectrogram calculates can know that in the present embodiment, the insertion rate with cycloolefin monomers of formula (II) structure is 7.60mol%.
The present invention adopts differential scanning calorimetry (DSC) that the second-order transition temperature of the cyclic olefine copolymer that obtains is detected, and the result shows that the second-order transition temperature of the cyclic olefine copolymer of present embodiment preparation is 70.8 ℃.
The present invention carries out the Elongation test experiment to the cyclic olefine copolymer that obtains, and the result shows that the cyclic olefine copolymer of present embodiment preparation has elongation at break, tensile strength and tensile modulus preferably.
The quality that weighing of the present invention obtains the cyclic olefine copolymer of present embodiment preparation is 3.70g; The relative weight-average molecular weight that adopts the GPC detection to obtain the cyclic olefine copolymer of present embodiment preparation is 173kg/mol, and the relative molecular weight dispersion index is 2.50.
The present invention detects the catalytic activity of polyreaction, and the result shows that the catalytic activity of polyreaction is 14.0 * 10 in the present embodiment
6G/mol
TiH.
The present invention has detected the transmittance of cyclic olefine copolymer, obtains the light transmittance curve in its ultraviolet-visible spectrum district, and the result shows that the cyclic olefine copolymer of present embodiment preparation has higher transmittance.
Under ethene atmosphere, in the exsiccant reactor drum, add 21.5mL dry toluene, 1.5mL volumetric molar concentration successively and be [the Ph of 6 μ mol/mL of toluene solution and 3mL volumetric molar concentration of toluene solution, TIBA that the 1.5mL volumetric molar concentration is 0.5mol/L of cycloolefin monomers of embodiment 1 preparation of 2mol/L with formula (II) structure
3CB (C
6F
5)
4] toluene solution; The mixing solutions that obtains after stirring 10 minutes under 60 ° of C, to wherein adding the toluene solution that the 3mL volumetric molar concentration is the CGC of 1 μ mol/mL, is continued in said reactor drum, to feed ethene; And to keep the pressure of ethene be 1.2 normal atmosphere, polyreaction 5 minutes.After polyreaction is accomplished, the reaction solution that obtains is poured in the ethanolic soln that volume(tric)fraction is 10% hydrochloric acid into the evolution reaction product; The reaction product that obtains is filtered, and with behind the washing with acetone 3 times, the product that obtains is placed vacuum drying oven, drying is 24 hours under 60 ° of C, obtains white cyclic olefine copolymer.
The present invention carries out proton nmr spectra to the cyclic olefine copolymer that obtains and detects, by cyclic olefine copolymer
13C NMR spectrogram can find out that cyclic olefine copolymer provided by the invention has structure shown in (I); By cyclic olefine copolymer
1H NMR spectrogram calculates and can obtain, and the insertion rate with cycloolefin monomers of formula (II) structure is 9.50mol%.
The quality that weighing of the present invention obtains the cyclic olefine copolymer of present embodiment preparation is 5.40g; The relative weight-average molecular weight that adopts the GPC detection to obtain the cyclic olefine copolymer of present embodiment preparation is 205kg/mol, and the relative molecular weight dispersion index is 1.84.
The present invention carries out the Elongation test experiment to the cyclic olefine copolymer that obtains, and the result shows that the cyclic olefine copolymer of present embodiment preparation has elongation at break, tensile strength and tensile modulus preferably.
The present invention adopts differential scanning calorimetry (DSC) that the second-order transition temperature of the cyclic olefine copolymer that obtains is detected, and the result shows that the second-order transition temperature of the cyclic olefine copolymer of present embodiment preparation is 78.0 ℃.
The present invention detects the catalytic activity of polyreaction, and the result shows that the catalytic activity of polyreaction is 21.6 * 10 in the present embodiment
6G/mol
TiH.
The present invention has detected the transmittance of cyclic olefine copolymer, obtains the light transmittance curve in its ultraviolet-visible spectrum district, and the result shows that the cyclic olefine copolymer of present embodiment preparation has higher transmittance.
Under ethene atmosphere, the toluene solution, toluene solution and the 3mL volumetric molar concentration of TIBA that the 1.5mL volumetric molar concentration is 0.6mol/L of the cycloolefin monomers with formula (II) structure that in the exsiccant reactor drum, adds 21.5mL dry toluene, 2mL volumetric molar concentration successively and be embodiment 1 preparation of 2mol/L is the [Ph of 7 μ mol/mL
3CB (C
6F
5)
4] toluene solution; The mixing solutions that obtains after stirring 10 minutes under 80 ° of C, to wherein adding the toluene solution that the 3mL volumetric molar concentration is the CGC of 1 μ mol/mL, is continued in said reactor drum, to feed ethene; And to keep the pressure of ethene be 1.1 normal atmosphere, polyreaction 15 minutes.Polyreaction is poured the reaction solution that obtains in the ethanolic soln that volume(tric)fraction is 10% hydrochloric acid into the evolution reaction product after accomplishing; The reaction product that obtains is filtered, and with behind the washing with acetone 3 times, the product that obtains is placed vacuum drying oven, drying is 24 hours under 60 ° of C, obtains white cyclic olefine copolymer.
The present invention carries out proton nmr spectra to the cyclic olefine copolymer that obtains and detects, by cyclic olefine copolymer
13C NMR spectrogram can find out that cyclic olefine copolymer provided by the invention has structure shown in (I); By cyclic olefine copolymer
1H NMR spectrogram calculates and can draw, and the insertion rate with cycloolefin monomers of formula (II) structure is 11.40mol%.
The present invention adopts differential scanning calorimetry (DSC) that the second-order transition temperature of the cyclic olefine copolymer that obtains is detected, and the result shows that the second-order transition temperature of the cyclic olefine copolymer of present embodiment preparation is 80.0 ℃.
The present invention carries out the Elongation test experiment to the cyclic olefine copolymer that obtains, and the result shows that the cyclic olefine copolymer of present embodiment preparation has elongation at break, tensile strength and tensile modulus preferably.
The quality that weighing of the present invention obtains the cyclic olefine copolymer of present embodiment preparation is 1.55g; The relative weight-average molecular weight that adopts the GPC detection to obtain the cyclic olefine copolymer of present embodiment preparation is 173kg/mol, and the relative molecular weight dispersion index is 1.67.
The present invention detects the catalytic activity of polyreaction, and the result shows that the catalytic activity of polyreaction is 6.0 * 10 in the present embodiment
6G/mol
TiH.
The present invention has detected the transmittance of cyclic olefine copolymer, obtains the light transmittance curve in its ultraviolet-visible spectrum district, and the result shows that the cyclic olefine copolymer of present embodiment preparation has higher transmittance.
Under ethene atmosphere, the toluene solution, toluene solution and the 3mL volumetric molar concentration of TIBA that the 1.5mL volumetric molar concentration is 0.7mol/L of the cycloolefin monomers with formula (II) structure that in the exsiccant reactor drum, adds 20.5mL dry toluene, 2mL volumetric molar concentration successively and be embodiment 1 preparation of 3mol/L is the [Ph of 6.5 μ mol/mL
3CB (C
6F
5)
4] toluene solution; The mixing solutions that obtains after stirring 10 minutes under 60 ° of C, to wherein adding the toluene solution that the 3mL volumetric molar concentration is the CGC of 1 μ mol/mL, is continued in said reactor drum, to feed ethene; And to keep the pressure of ethene be 1 normal atmosphere, polyreaction 20 minutes.After polyreaction is accomplished, the reaction solution that obtains poured into contain in the ethanolic soln that volume(tric)fraction is 10% hydrochloric acid the evolution reaction product; The reaction product that obtains is filtered, and with behind the washing with acetone 3 times, the product that obtains is put into vacuum drying oven, drying is 24 hours under 60 ° of C, obtains white cyclic olefine copolymer.
The present invention carries out proton nmr spectra to the cyclic olefine copolymer that obtains and detects, by cyclic olefine copolymer
13C NMR spectrogram can find out that cyclic olefine copolymer provided by the invention has structure shown in (I); By cyclic olefine copolymer
1H NMR spectrogram calculates, and the insertion rate with cycloolefin monomers of formula (II) structure is 12.40mol%.
The present invention adopts differential scanning calorimetry (DSC) that the second-order transition temperature of cyclic olefine copolymer is detected; The result is as shown in Figure 2; The DSC curve of the cyclic olefine copolymer that Fig. 2 obtains for the embodiment of the invention 5 ~ 8, wherein, the DSC curve of the cyclic olefine copolymer that curve a obtains for embodiment 5; Curve a by among Fig. 2 can find out that the second-order transition temperature of the cyclic olefine copolymer of present embodiment preparation is 83.5 ℃.
The present invention carries out the Elongation test experiment to the cyclic olefine copolymer that obtains, and the result shows that the cyclic olefine copolymer of present embodiment preparation has elongation at break, tensile strength and tensile modulus preferably.
The quality that weighing of the present invention obtains the cyclic olefine copolymer of present embodiment preparation is 3.10g; The relative weight-average molecular weight that adopts the GPC detection to obtain the cyclic olefine copolymer of present embodiment preparation is 330kg/mol, and the relative molecular weight dispersion index is 2.25.
The present invention detects the catalytic activity of polyreaction, and the result shows that the catalytic activity of polyreaction is 12.4 * 10 in the present embodiment
6G/mol
TiH.
The present invention has detected the transmittance of cyclic olefine copolymer, obtains the light transmittance curve in its ultraviolet-visible spectrum district, and the result shows that the cyclic olefine copolymer of present embodiment preparation has higher transmittance.
Under ethene atmosphere, the toluene solution, toluene solution and the 3mL volumetric molar concentration of TIBA that the 1.5mL volumetric molar concentration is 0.5mol/L of the cycloolefin monomers with formula (II) structure that in the exsiccant reactor drum, adds 18.75mL dry toluene, 3.75mL volumetric molar concentration successively and be embodiment 1 preparation of 2mol/L is the [Ph of 6 μ mol/mL
3CB (C
6F
5)
4] toluene solution; The mixing solutions that obtains after stirring 10 minutes under 60 ° of C, to wherein adding the toluene solution that the 3mL volumetric molar concentration is the CGC of 1 μ mol/mL, is continued in said reactor drum, to feed ethene; And to keep the pressure of ethene be 1 normal atmosphere, polyreaction 5 minutes.After polyreaction is accomplished, the reaction solution that obtains is poured in the ethanolic soln that volume(tric)fraction is 10% hydrochloric acid into the evolution reaction product; The reaction product that obtains is filtered, and with behind the washing with acetone 3 times, the product that obtains is put into vacuum drying oven, drying is 24 hours under 60 ° of C, obtains white cyclic olefine copolymer.
The present invention carries out proton nmr spectra to the cyclic olefine copolymer that obtains and detects, by cyclic olefine copolymer
13C NMR spectrogram can find out that cyclic olefine copolymer provided by the invention has structure shown in (I); By cyclic olefine copolymer
1H NMR spectrogram calculates, and the insertion rate with cycloolefin monomers of formula (II) structure is 15.0mol%.
The present invention adopts differential scanning calorimetry (DSC) that the second-order transition temperature of cyclic olefine copolymer is detected; The result is as shown in Figure 2; The DSC curve of the cyclic olefine copolymer that Fig. 2 obtains for the embodiment of the invention 5 ~ 8, wherein, curve b is the DSC curve of the cyclic olefine copolymer of embodiment 6 preparations; Curve b by among Fig. 2 can find out that the second-order transition temperature of the cyclic olefine copolymer of present embodiment preparation is 125.5 ℃.
The present invention carries out the Elongation test experiment to the cyclic olefine copolymer that obtains, and the result is as shown in Figure 3, the stress-strain curve of the cyclic olefine copolymer that Fig. 3 obtains for the embodiment of the invention 6 ~ 8; Wherein, Curve a is the stress-strain curve of the cyclic olefine copolymer of embodiment 6 preparations, can be found out by the curve a among Fig. 3, and the elongation at break of the cyclic olefine copolymer of present embodiment preparation is 14.0%; Tensile strength is 63.3MPa, and tensile modulus is 2680MPa.
The quality that weighing of the present invention obtains the cyclic olefine copolymer of present embodiment preparation is 3.75g; The relative weight-average molecular weight that adopts the GPC detection to obtain the cyclic olefine copolymer of present embodiment preparation is 360kg/mol, and the relative molecular weight dispersion index is 1.97.
The present invention detects the catalytic activity of polyreaction, and the result shows that the catalytic activity of polyreaction is 15.0 * 10 in the present embodiment
6G/mol
TiH.
The present invention has detected the transmittance of cyclic olefine copolymer, obtains the light transmittance curve in its ultraviolet-visible spectrum district, and the result shows that the transmittance of the cyclic olefine copolymer of present embodiment preparation is 78%.
Under ethene atmosphere, the toluene solution, toluene solution and the 3mL volumetric molar concentration of TIBA that the 1.5mL volumetric molar concentration is 0.5mol/L of the cycloolefin monomers with formula (II) structure that in the exsiccant reactor drum, adds 17.5mL dry toluene, 5.0mL volumetric molar concentration successively and be embodiment 1 preparation of 2mol/L is the [Ph of 6 μ mol/mL
3CB (C
6F
5)
4] toluene solution; The mixing solutions that obtains after stirring 10 minutes under 60 ℃, to wherein adding the toluene solution that the 3mL volumetric molar concentration is the CGC of 1 μ mol/mL, is continued in said reactor drum, to feed ethene; And to keep the pressure of ethene be 1 normal atmosphere, polyreaction 25 minutes.After polyreaction is accomplished, the reaction solution that obtains is poured in the ethanolic soln that volume(tric)fraction is 10% hydrochloric acid into the evolution reaction product; The reaction product that obtains is filtered, and with behind the washing with acetone 3 times, the product that obtains is placed vacuum drying oven, drying is 24 hours under 60 ℃, obtains white cyclic olefine copolymer.
The present invention carries out proton nmr spectra to the cyclic olefine copolymer that obtains and detects, by cyclic olefine copolymer
13C NMR spectrogram can find out that cyclic olefine copolymer provided by the invention has structure shown in (I); By cyclic olefine copolymer
1H NMR spectrogram calculates, and the insertion rate with cycloolefin monomers of formula (II) structure is 20.2mol%.
The present invention adopts differential scanning calorimetry (DSC) that the second-order transition temperature of the cyclic olefine copolymer that obtains is detected; The result is as shown in Figure 2; The DSC curve of the cyclic olefine copolymer that Fig. 2 obtains for the embodiment of the invention 5 ~ 8; Wherein, curve c is the DSC curve of the cyclic olefine copolymer of embodiment 7 preparations, can be found out that by the curve c among Fig. 2 the second-order transition temperature of the cyclic olefine copolymer of present embodiment preparation is 160.4 ℃.
The present invention carries out the Elongation test experiment to the cyclic olefine copolymer that obtains; The result is as shown in Figure 3, the stress-strain curve of the cyclic olefine copolymer that Fig. 3 obtains for the embodiment of the invention 6 ~ 8, wherein; The stress-strain curve of the cyclic olefine copolymer that curve b obtains for embodiment 7; The elongation at break that can be found out the cyclic olefine copolymer of present embodiment preparation by the curve b among Fig. 3 is 7.6%, and tensile strength is 55.0MPa, and tensile modulus is 2590MPa.
The quality that weighing of the present invention obtains the cyclic olefine copolymer of present embodiment preparation is 4.70g; The relative weight-average molecular weight that adopts the GPC detection to obtain the cyclic olefine copolymer of present embodiment preparation is 407kg/mol, and the relative molecular weight dispersion index is 2.80.
The present invention detects the catalytic activity of polyreaction, and the result shows that the catalytic activity of polyreaction in the present embodiment is 18.8 * 10
6G/mol
TiH.
The present invention has detected the transmittance of cyclic olefine copolymer; The result is as shown in Figure 4; The light transmittance curve in its ultraviolet-visible spectrum district of the cyclic olefine copolymer that Fig. 4 obtains for the embodiment of the invention 7～8, wherein, curve A is the light transmittance curve in ultraviolet-visible spectrum district of the cyclic olefine copolymer of embodiment 7 preparation; Can find out transmittance＞80% of the cyclic olefine copolymer of present embodiment preparation by the curve A among Fig. 4.
Under ethene atmosphere, the toluene solution, toluene solution and the 3mL volumetric molar concentration of TIBA that the 1.5mL volumetric molar concentration is 0.5mol/L of the cycloolefin monomers with formula (II) structure that in the exsiccant reactor drum, adds 12.5mL dry toluene, 10.0mL volumetric molar concentration successively and be embodiment 1 preparation of 2mol/L is the [Ph of 6 μ mol/mL
3CB (C
6F
5)
4] toluene solution; The mixing solutions that obtains after stirring 10 minutes under 60 ℃, to wherein adding the toluene solution that the 3mL volumetric molar concentration is the CGC of 1 μ mol/mL, is continued in said reactor drum, to feed ethene; And to keep the pressure of ethene be 1 normal atmosphere, polyreaction 30 minutes.After polyreaction is accomplished, the reaction solution that obtains is poured in the ethanolic soln that volume(tric)fraction is 10% hydrochloric acid into the evolution reaction product; The reaction product that obtains is filtered, and with behind the washing with acetone 3 times, the product that obtains is placed vacuum drying oven, drying is 24 hours under 60 ℃, obtains white cyclic olefine copolymer.
The present invention carries out proton nmr spectra to the cyclic olefine copolymer that obtains and detects, the cyclic olefine copolymer that result such as Fig. 1 and shown in Figure 5, Fig. 1 obtain for the embodiment of the invention 2 and embodiment 8
13C NMR spectrogram, wherein curve b is the cyclic olefine copolymer of embodiment 8 preparation
13C NMR spectrogram, curve c are that the undistorted polarization transfer of the cyclic olefine copolymer of embodiment 8 preparations strengthens (DEPT) spectrum, can find out that by curve b among Fig. 1 and curve c cyclic olefine copolymer provided by the invention has structure shown in (I); The cyclic olefine copolymer that Fig. 5 obtains for the embodiment of the invention 8
1H NMR spectrogram is by shown in Figure 5
1The HNMR spectrogram calculates, and the insertion rate with cycloolefin monomers of formula (II) structure is 30.4mol%.
The present invention adopts differential scanning calorimetry (DSC) that the second-order transition temperature of the cyclic olefine copolymer that obtains is detected; The result is as shown in Figure 2; The DSC curve of the cyclic olefine copolymer that Fig. 2 obtains for the embodiment of the invention 5 ~ 8, wherein, curve d is the DSC curve of the cyclic olefine copolymer of the embodiment of the invention 8 preparations; Curve d by among Fig. 2 can find out that the second-order transition temperature of the cyclic olefine copolymer of present embodiment preparation is 207.0 ℃.
The present invention carries out the Elongation test experiment to the cyclic olefine copolymer that obtains, and the result is as shown in Figure 3, the stress-strain curve of the cyclic olefine copolymer that Fig. 3 obtains for the embodiment of the invention 6 ~ 8; Wherein, Curve c is the stress-strain curve of the cyclic olefine copolymer of the embodiment of the invention 8 preparations, can be found out by curve c among Fig. 3, and the elongation at break of the cyclic olefine copolymer of present embodiment preparation is 2.4%; Tensile strength is 44.2MPa, and tensile modulus is 2390MPa.
The quality that weighing of the present invention obtains the cyclic olefine copolymer of present embodiment preparation is 5.00g; The relative weight-average molecular weight that adopts the GPC detection to obtain the cyclic olefine copolymer of present embodiment preparation is 439kg/mol, and the relative molecular weight dispersion index is 1.97.
The present invention detects the catalytic activity of polyreaction, and the result shows that the catalytic activity of polyreaction is 20.0 * 10 in the present embodiment
6G/mol
TiH.
The present invention has detected the transmittance of cyclic olefine copolymer; The result is as shown in Figure 4; The light transmittance curve in its ultraviolet-visible spectrum district of the cyclic olefine copolymer that Fig. 4 obtains for the embodiment of the invention 7 ~ 8, wherein, curve B is the light transmittance curve in ultraviolet-visible spectrum district of the cyclic olefine copolymer of embodiment 8 preparation; Can find out transmittance＞85% of the cyclic olefine copolymer of present embodiment preparation by the curve B among Fig. 6.
The present invention provides a kind of cyclic olefine copolymer, has formula (I) structure, and wherein m and n are the polymerization degree, m:n>=1.5; R
1And R
2Be independently selected from hydrogen or carbonatoms and be 1 ~ 10 representative examples of saturated aliphatic alkyl.The present invention is polymerization single polymerization monomer with terminal olefin with the cycloolefin monomers with formula (II) structure, and it is carried out polyreaction under the effect of catalyzer He in the inert solvent, the cyclic olefine copolymer of (I) structure that obtains having formula.The cycloolefin monomers that the present invention selects has formula (II) structure, and it is big volume cycloolefin, in polymerization process; Because the influence of sterically hindered effect under the situation of low insertion rate, obtains the cyclic olefine copolymer of high second-order transition temperature; Flexible terminal olefin unit increases in this multipolymer; Thereby make the cyclic olefine copolymer chain rigidity reduce, the entanglement between the chain strengthens, thereby has improved the tear resistance of cyclic olefine copolymer; Make its fragility improve, the improved cyclic olefine copolymer of higher glass transition temperature that obtains and fragility.Experimental result shows, the insertion rate≤30.0mol% of the cycloolefin monomers in the cyclic olefine copolymer provided by the invention, and its second-order transition temperature can reach 207.0 ℃, and high glass transition makes cyclic olefine copolymer have advantages of high practicability; Elongation test is the result show, when its second-order transition temperature was 160.4 ℃, its elongation at break was 7.6%, and tensile strength is 55.0MPa.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; Can also make some improvement and retouching, these improvement and retouching also should be regarded as protection scope of the present invention.
Claims (10)
1. cyclic olefine copolymer has formula (I) structure:
Wherein, m and n are the polymerization degree, m:n >=1.5;
R
1And R
2Be independently selected from hydrogen or carbonatoms and be 1 ~ 10 representative examples of saturated aliphatic alkyl.
2. cyclic olefine copolymer according to claim 1 is characterized in that, 20 >=m:n >=2.3.
3. cyclic olefine copolymer according to claim 1 is characterized in that, said R
1And R
2Be independently selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-or hydrogen.
4. the preparation method of any described cyclic olefine copolymer of claim 1 ~ 3 may further comprise the steps:
In inert solvent, cycloolefin monomers and the terminal olefin that will have formula (II) structure carry out polyreaction under the condition that catalyzer exists, the cyclic olefine copolymer of (I) structure that obtains having formula;
In the formula (I), m and n are the polymerization degree, m:n >=1.5;
R
1And R
2Be independently selected from hydrogen or carbonatoms and be 1 ~ 10 representative examples of saturated aliphatic alkyl.
5. preparation method according to claim 4 is characterized in that, said terminal olefin and said mol ratio with cycloolefin monomers of formula (II) structure are (2.3 ~ 20): 1.
6. preparation method according to claim 4; It is characterized in that said terminal olefin is ethene, propylene, 1-butylene, iso-butylene, 1-amylene, 2-methyl-1-butene alkene, 3-methyl-1-butene, 1-hexene, 2-Methyl-1-pentene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-butylene.
7. preparation method according to claim 4 is characterized in that, said catalyzer and said mol ratio with cycloolefin monomers of formula (II) structure are 1: (1 ~ 20).
8. preparation method according to claim 4 is characterized in that said catalyzer comprises Primary Catalysts and promotor;
Said Primary Catalysts is (tertiary butyl amido)-dimethyl--(tetramethyl--η
5-cyclopentadienyl moiety)-the silane titanium dichloride;
Said promotor is triisobutyl aluminium and triphen carbon four-(pentafluorophenyl group) borate.
9. preparation method according to claim 4 is characterized in that, the mol ratio of the triisobutyl aluminium in said Primary Catalysts and the said promotor is 1: (200 ~ 2500);
Triphen carbon four in said Primary Catalysts and the said promotor-(pentafluorophenyl group) boratory mol ratio is 1: (1 ~ 10).
10. preparation method according to claim 4 is characterized in that, said inert solvent is straight chain hydrocarbon compound, cyclic hydrocar-bons compound or arene compounds;
The temperature of said polyreaction is 0 ℃ ~ 100 ℃;
The time of said polyreaction is 1 minute ~ 60 minutes.
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| CN113444206B (en) * | 2021-07-22 | 2022-03-11 | 苏州来奇祥生物科技有限公司 | Ternary polymerization catalyst and preparation method of ternary polymerization |
| CN115819656A (en) * | 2021-09-16 | 2023-03-21 | 华为技术有限公司 | Cycloolefin copolymer, process for producing the same and use thereof |
| CN114805654A (en) * | 2022-05-16 | 2022-07-29 | 中国科学院长春应用化学研究所 | Cycloolefin copolymer and preparation method thereof |
| CN114805654B (en) * | 2022-05-16 | 2023-04-07 | 中国科学院长春应用化学研究所 | Cycloolefin copolymer and preparation method thereof |
| CN115028763A (en) * | 2022-07-28 | 2022-09-09 | 中国科学院长春应用化学研究所 | Cycloolefin copolymer and preparation method thereof |
| CN115850581A (en) * | 2022-12-01 | 2023-03-28 | 无锡阿科力科技股份有限公司 | Cycloolefin copolymer and preparation method and application thereof |
| CN115850581B (en) * | 2022-12-01 | 2024-03-19 | 无锡阿科力科技股份有限公司 | Cycloolefin copolymer and preparation method and application thereof |
| CN116217772A (en) * | 2023-01-10 | 2023-06-06 | 中国科学院长春应用化学研究所 | Cycloolefin copolymer and preparation method thereof |
| CN116217772B (en) * | 2023-01-10 | 2024-05-28 | 中国科学院长春应用化学研究所 | Cycloolefin copolymer and preparation method thereof |
| CN117089005A (en) * | 2023-08-21 | 2023-11-21 | 天津大学 | Ultralow dielectric copolymer and preparation method and application thereof |
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