CN106905483A - A kind of cyclic olefine copolymer and preparation method thereof - Google Patents
A kind of cyclic olefine copolymer and preparation method thereof Download PDFInfo
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- CN106905483A CN106905483A CN201510981963.9A CN201510981963A CN106905483A CN 106905483 A CN106905483 A CN 106905483A CN 201510981963 A CN201510981963 A CN 201510981963A CN 106905483 A CN106905483 A CN 106905483A
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- YGCNHBOWEUSBBI-UHFFFAOYSA-N O=C(C=CC1=O)N1c(cc1)ccc1-c1nnc[o]1 Chemical compound O=C(C=CC1=O)N1c(cc1)ccc1-c1nnc[o]1 YGCNHBOWEUSBBI-UHFFFAOYSA-N 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
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Abstract
The invention discloses a kind of cyclic olefine copolymer, obtained through copolyreaction in the presence of metathesis polymerization catalyst by comonomer, comonomer is cycloolefin and BMI, BMI has Formulas I or the structure shown in Formula II, wherein, R1And R2It is independently each respectively the C of hydrogen atom or linear or side chain1To C6Fat alkane base, and cyclic olefine copolymer glass transition temperature TgHigher than 144 DEG C.The invention also discloses the preparation method by above-mentioned cyclic olefine copolymer.The present invention in cycloolefin monomers by adding the BMI with Formulas I or structure shown in Formula II, the heat resistance of the cyclic olefine copolymer that polymerization is obtained can be improved, and copolymer can be obtained under relatively mild conditions, the production cost of cyclic olefine copolymer is reduced.
Description
Technical field
The present invention relates to cyclic olefine copolymer field, in particular it relates to it is a kind of containing BMI with
Copolymer of cycloolefin and preparation method thereof.
Background technology
Cyclic olefine copolymer is a class by the thermoplastic engineering plastic of the high added value of cyclic olefin polymerization,
This copolymer has a high transparency, low-k, excellent heat resistance, chemical resistance, melt
Mobility, barrier and dimensional stability are preferable.Therefore, cyclic olefine copolymer can be widely used in system
Make various optics, information, electrical equipment, medical material.
The heat resistance of cyclic olefine copolymer is the important performance of this material.In making for some higher temperatures
With under environment, if the heat resistance of cyclic olefine copolymer is poor, cyclic olefine copolymer can be distorted
With deformation equidimension on change, so as to directly affect the optical property and mechanical property of cyclic olefine copolymer
Energy.Therefore, improving the heat resistance of cyclic olefine copolymer can greatly expand the use model of cyclic olefine copolymer
Enclose.The important indicator for weighing cyclic olefine copolymer heat resistance is the glass transition temperature of cyclic olefine copolymer
Degree, glass transition temperature is temperature of the copolymer from glassy state to rubber transition, when environment temperature connects
Near or when reaching the glass transition temperature of copolymer, copolymer can occur more serious deformation, and power
Learn performance to be greatly reduced, this brings totally unfavorable influence to the application of copolymer material.Therefore improve
The glass transition temperature of copolymer can effectively improve the heat resistance of copolymer.
The glass transition temperature of cyclic olefine copolymer is relatively low in the prior art, and heat resistance is poor, have impact on
The scope of application of cyclic olefine copolymer material.
The content of the invention
It is an object of the invention to provide a kind of cyclic olefine copolymer and preparation method thereof, the copolymer is than existing
The heat resistance of cyclic olefin polymer increase, the preparation method can solve the problem that in the prior art to equipment
The problem harsh with reflection condition requirement.
To achieve these goals, the present invention provides a kind of cyclic olefine copolymer, is easy by comonomer
Obtained through copolyreaction in the presence of the polymerization catalyst of position, it is characterised in that：The comonomer is ring
Alkene and BMI, the BMI have Formulas I or the structure shown in Formula II：
Wherein, R1And R2It is independently each respectively the C of hydrogen atom or linear or side chain1To C6Fat
Fat alkyl；
The glass transition temperature T of the cyclic olefine copolymergHigher than 144 DEG C.
The present invention also provides the preparation method of above-mentioned cyclic olefine copolymer, comprises the following steps：Will be above-mentioned common
Polycondensation monomer and metathesis polymerization catalyst are dissolved in solvent and are uniformly dispersed；Removal of solvent under reduced pressure, will obtain
Fluid composition be injected into pattern；Intensification carries out copolyreaction.
By above-mentioned technical proposal, span of the structure as shown in Formulas I or Formula II is added to carry out acyl in cycloolefin
Imines, introduces the structure containing heteroatomic ring in the copolymer, can make the heat-resisting of the copolymer for obtaining
Property be obviously improved, and the reaction condition for preparing of copolymer does not require height anhydrous and oxygen-free environment so that altogether
Polymers can be obtained under relatively mild conditions, reduce the production cost of copolymer.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Specific embodiment of the invention is described in detail below.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides a kind of cyclic olefine copolymer, be by comonomer metathesis polymerization catalyst effect
Lower to be obtained through copolyreaction, comonomer is cycloolefin and BMI, the BMI
With the structure shown in Formulas I or Formula II：
Wherein, R1And R2It is independently each respectively the C of hydrogen atom or linear or side chain1To C6Fat
Fat alkyl；
The glass transition temperature T of cyclic olefine copolymergHigher than 144 DEG C.By structure such as Formulas I or Formula II
Shown BMI is added in cycloolefin, can in the copolymer be introduced and be contained heteroatomic ring
Structure, obtains the copolymer with heat resistance higher.
Wherein, C1To C6Fat alkane base can include C1To C6Alkyl and C1To C6Alkenyl.
Specifically, C1To C6Alkyl can for methyl, ethyl, the propyl group of straight or branched, butyl,
Amyl group, hexyl and perhaps various other homologue groups.Specific alkyl be methyl, ethyl, n-propyl,
Isopropyl and the tert-butyl group etc.；C1To C6Alkenyl can include vinyl and straight or branched acrylic,
Cyclobutenyl, pentenyl and hexenyl.
Above-mentioned BMI can be made for example, by the method disclosed in the B of CN 101870693
It is standby.
According to the present invention, the implication of the glass transition temperature is well known to those skilled in the art, can
For weighing the performance of polymeric material, the heat resistance of polymer is characterized.
Wherein, in order to further improve the heat resistance of cyclic olefine copolymer, according to the present invention, relative to 100
The cycloolefin of molar part, the content of BMI is preferably 1-15 molar parts, metathesis polymerization catalysis
The content of agent is preferably 0.04-0.2 molar parts.
It is highly preferred that according in cyclic olefine copolymer of the present invention, relative to 100 molar parts
Cycloolefin, the content of BMI is 2-10 molar parts, and the content of metathesis polymerization catalyst is
0.05-0.125 molar parts.
Cyclic olefine copolymer of the invention, above-mentioned cycloolefin is known to those skilled in the art, is
Intramolecular has carbon-to-carbon double bond in having the ester ring type structure and the ester ring type structure being made up of carbon atom
Compound.
According to cyclic olefine copolymer of the present invention, it is preferable that cycloolefin can be 4-8 for carbon number
Substituted or unsubstituted cycloolefin, or the substituted or unsubstituted bicyclic alkene of norborneol alkenes
Hydrocarbon.The cycloolefin or bicyclic alkene of above-mentioned carbon number have ring strain preferably, can be easy
There is ring opening metathesis polymerization in the presence of the polymerization catalyst of position, obtain cycloolefin and BMI
Copolymer.
Wherein, as the cycloolefin or the substitution base of bicyclic alkene of substitution, its species is art technology
Known to personnel, such as carbon number is the alkyl of 1-10, halogen atom, be substituted with halogen atoms
Alkyl of carbon number 1-10 etc..
Specifically, as the alkyl of carbon number 1-10, can enumerate：The carbon such as methyl, ethyl, propyl group
The alkyl of atomicity 1-10；The alkenyl of the carbon number such as vinyl, acrylic 2-10；Acetenyl, alkynes
The alkynyl of the carbon number 2-10 such as propyl group, 3- butynyls；The carbon numbers such as phenyl, 1- naphthyls, 2- naphthyls
The aryl of 6-10；Cycloalkyl of the carbon number such as cyclopropyl, cyclopenta, cyclohexyl 3-10 etc..
As halogen atom, fluorine atom, chlorine atom, bromine atoms etc. can be enumerated.
As the alkyl of the carbon number 1-10 being substituted with halogen atoms, chloromethyl, 2- chloroethenes can be enumerated
Base, trifluoromethyl, pentafluoroethyl group etc..
According to the present invention, in substituted cycloolefin or bicyclic alkene, substitution base can be for one or more
Individual, under preferable case, substitution base is one.
According to cyclic olefine copolymer of the present invention, carbon number can be choosing for the cycloolefin of 4-8
One or more from cyclobutane, cyclopentene, cycloheptene and cyclo-octene, norborneol alkenes bicyclic alkene
Can be selected from ENB, dicyclopentadiene, methyldicyclopentadiene, two rings [2.2.2] oct-2-ene and
One or more in two rings [2.2.1] hept- 2,5- diene.
Above-mentioned cycloolefin and bicyclic alkene can be used alone one kind, it is also possible to make two or more combinations
With.
Contain metathesis polymerization catalyst in cyclic olefine copolymer of the invention, metathesis polymerization used is catalyzed
Agent is not particularly limited, can be used it is known those.As metathesis polymerization catalyst, can enumerate with transition
Centered on metallic atom atom and be combined with multiple ions, atom, polyatomic ion and compound etc. and
Into transition metal complex.It is usually used as transition metal atoms in the transition metal complex
The atom of 5 races, 6 races and 8 races.Atom to each race is not particularly limited, and the atom of 5 races can enumerate example
As tantalum, the atom of 6 races can enumerate such as molybdenum and tungsten, the atom of 8 races can enumerate such as ruthenium and osmium.
Cyclic olefine copolymer of the invention, under preferable case, metathesis polymerization catalyst can be ruthenium card
Guest's compound, wherein, ruthenium carbene compound be preferably two (tricyclohexyl phosphine) benzylidene dichloros close ruthenium,
[double (2,4,6- the trimethylphenyls) -2- imidazolines subunits of 1,3-] dichloro (benzylidene) (tricyclohexyl phosphine)
Conjunction ruthenium, dichloro (adjacent isopropoxy benzene methylene) (tricyclohexyl phosphine) ruthenium (II) and (1,3- pairs-(2,4,6-
Trimethylphenyl) -2- imidazolidines subunit) dichloro (adjacent isopropoxy benzylidene) close ruthenium in one kind or
It is several.Ruthenium carbene compound catalysis activity is high, can improve the ring-opening polymerization rate of cyclic olefine copolymer,
Because unreacted cyclenes hydrocarbon content is few so the copolymer peculiar smell that obtains of polymerization is smaller.Meanwhile, ruthenium Cabbeen
Compound have it is more stable relative to moisture in oxygen or air and not easy in inactivation the characteristics of.
Above-mentioned ruthenium carbene compound can be for example, by Journal of the American Chemical
Society, 1996,118 (1) volumes, 100-110 pages, or Tetrahedron Letters, 40 (12) in 1999
It is prepared by volume, the method for the record of the document such as 2247-2250 page.Can also be obtained by commercially available mode, example
Such as can be that, purchased from Shanghai crystalline substance pure reagent Co., Ltd, article number is two (tricyclohexyl phosphines) of G113747
It is [double (2,4,6- trimethylphenyls) -2- imidazoles of 1,3- of G120500 that benzylidene dichloro closes ruthenium, article number
Quinoline subunit] dichloro (benzylidene) (tricyclohexyl phosphine) closes ruthenium, article number for the dichloro of G132547 is (adjacent
Isopropoxy benzene methylene) (tricyclohexyl phosphine) ruthenium (II) and article number for G124687 (1,3- is double-
(2,4,6- trimethylphenyls) -2- imidazolidines subunit) dichloro (adjacent isopropoxy benzylidene) conjunction ruthenium.
The present invention also provides the preparation method of above-mentioned cyclic olefine copolymer, comprises the following steps：Will be above-mentioned common
Polycondensation monomer and metathesis polymerization catalyst are dissolved in solvent and are uniformly dispersed,；Removal of solvent under reduced pressure, will
To fluid composition be injected into pattern；Intensification carries out copolyreaction.
According in preparation method of the present invention, dissolving therein, dispersion and depressurization steps are to system
Temperature do not limit, as long as ensureing that comonomer and metathesis polymerization catalyst are uniformly dispersed in a solvent,
And solvent can be discharged smoothly outside system.In order to prevent comonomer and metathesis polymerization catalyst from entering
Starting reaction before entering shaping mould causes system viscosity to raise, in dissolving, dispersion and depressurization steps, body
The temperature of system is preferably -20 to 30 DEG C, and within the scope of the preferred temperature, metathesis polymerization catalyst is urged
Agent activity is relatively low, and comonomer and metathesis polymerization catalyst can be avoided to enter the premise of shaping mould
Preceding beginning ring-opening polymerization causes system viscosity to uprise, insufficient so as to avoid the solvent in system from discharging
The copolymer mechanical properties decrease for causing.
According in preparation method of the present invention, it is possible to use a small amount of solvent dissolves above-mentioned comonomer
With metathesis polymerization catalyst so that each component is well mixed, in solution polymerization process, solvent can be as
The medium of polymerisation is used.In order to avoid the moisture in solvent inactivates metathesis polymerization catalyst, preferably
In the case of, solvent can influence catalyst activity with purified treatment before to remove moisture therein etc.
Impurity, the method for above-mentioned purification process is well known to those skilled in the art, can be according to《Reagent is pure
Change handbook》Purification process is carried out to different solvents.
Wherein, do not required particularly as the species of solvent, as long as meet solvent being catalyzed to metathesis polymerization
Agent is inactive.Under preferable case, solvent can be selected from pentane, n-hexane, normal heptane,
Pentamethylene, hexamethylene, hexahydrotoluene, dimethyl cyclohexane, cyclooctane, benzene,toluene,xylene,
One or more in Anaesthetie Ether, tetrahydrofuran and dichloromethane.Wherein in order that solvent was depressurizing
Discharge system is easier in journey, under preferable case, using the relatively low solvent of boiling point, is for example, selected from
One or more in dichloromethane, Anaesthetie Ether, pentane and tetrahydrofuran.The method of dissolving does not have yet
There is special limitation, as long as ensureing that comonomer and metathesis polymerization catalyst are well mixed, Ke Yixiang
Same solvent is added in above-mentioned comonomer and metathesis polymerization catalyst, agitated or ultrasonic mixing is equal
It is even, it is also possible to dissolve metathesis polymerization catalyst, cycloolefin and BMI with a small amount of solvent respectively
Its solution is well mixed again afterwards.Above-mentioned mixing and dispersing mode can be including stirring, ultrasonic disperses etc..
After comonomer and metathesis polymerization catalyst dissolve and are well mixed, can will wherein by the way of decompression
Solvent discharge, the time of Depressor response and the pressure of system has no particular limits, as long as meeting body
Solvent emptying in system, while not causing comonomer and metathesis polymerization catalyst to start polymerisation in advance
.
According in preparation method of the present invention, in order to reduce the planted agent of the moulding material of copolymer
Power, under preferable case, shaping mould can pass through preheating before fluid composition is injected, wherein preheat
Temperature can be 30-60 DEG C.The shaping mould of preheated to above-mentioned temperature range can reduce copolymer into
The internal stress of section bar material, reduces the crackle and defect in the moulding material of copolymer, improves its mechanical property.
According in preparation method of the present invention, in order to improve the reactivity of cycloolefin ring-opening polymerisation,
Heating mode is preferably gradient increased temperature, and specifically, intensification order can be 40-70 DEG C of first stage, the
100-130 DEG C of two-stage, 140-160 DEG C of phase III, 165-185 DEG C of fourth stage, the 5th stage
190-200 DEG C, wherein, the reaction time per the stage is 2-5 hours.Using the preparation of above-mentioned intensification order
The copolymer that method is obtained, first cycloolefin can carry out ring opening metathesis polymerization in preceding three phases,
The network structure of crosslinking is formed, the unreacted carbon-carbon double bond for wherein containing in network structure can heat up
Latter two stage, with BMI in carbon-carbon double bond occur D-A reaction, formed crosslinking is total to
Polymers.
The present invention is further illustrated below by embodiment, but, therefore the present invention should not be subject to any
Limitation.In the following embodiments, to be purchased from Shanghai crystalline substance pure for used cycloolefin and metathesis polymerization catalyst
Reagent Co., Ltd
Embodiment 1
The present embodiment is used to illustrate cyclic olefine copolymer of the invention and preparation method thereof.
Take the dicyclopentadiene of 100 molar parts, 0.04 molar part dichloro (adjacent isopropoxy benzene methylene)
(tricyclohexyl phosphine) ruthenium (II), BMI (the wherein R shown in 1 molar part Formulas I1And R2
It is hydrogen atom) it is well mixed, it is placed in 50mL single-necked flasks, 5mL pentanes after purification are added,
Stirring dissolves it at 30 DEG C, vacuumizes the solvent in removing system.Reactant is changed into being incited somebody to action during thick liquid
It is poured into 30 DEG C of moulds of preheating, and gradient increased temperature carries out ring-opening polymerization, obtains copolymer p 1.
Warming temperature and time：70℃(4h)+130℃(3h)+160℃(4h)+185℃(3h)+200℃(3h).
Embodiment 2
The present embodiment is used to illustrate cyclic olefine copolymer of the invention and preparation method thereof.
Take the ENB of 40 molar parts, the methyldicyclopentadiene of 60 molar parts, 0.2 molar part [1,3-
Double (2,4,6- trimethylphenyl) -2- imidazolines subunits] dichloro (benzylidene) (tricyclohexyl phosphine) conjunction ruthenium, 15
BMI (wherein R shown in molar part Formula II1It is methyl, R2It is hydrogen atom) it is well mixed,
It is placed in 50mL single-necked flasks, adds 2mL CH after purification2Cl2, stirring dissolves it at -20 DEG C,
Vacuumize the solvent in removing system.Reactant is changed into being poured into 30 DEG C of moulds of preheating during thick liquid
Middle gradient increased temperature carries out ring-opening polymerization, obtains copolymer p 2.Warming temperature and time：40℃(3h)+
100℃(4h)+150℃(2h)+165℃(4h)+190℃(4h)。
Embodiment 3
The present embodiment is used to illustrate cyclic olefine copolymer of the invention and preparation method thereof.
Take two rings [2.2.1] hept- 2 of 85 molar parts, 5- diene, the 3- vinyl -1- cyclopentene of 10 molar parts,
The cyclo-octene of 5 molar parts, (tricyclohexyl phosphine) the benzylidene dichloro of 0.05 molar part two closes ruthenium, 2 molar parts
Bismaleimide (wherein R shown in Formulas I1It is vinyl, R2Be hydrogen atom) amine be well mixed, put
In 50mL single-necked flasks, 5mL Anaesthetie Ethers after purification are added, stirring dissolves it at 0 DEG C,
Vacuumize the solvent in removing system.Reactant is changed into being poured into 40 DEG C of moulds of preheating during thick liquid
In, gradient increased temperature carries out ring-opening polymerization, obtains copolymer p 3.Warming temperature and time：40℃(1h)+
120℃(2h)+150℃(2h)+175℃(2h)+190℃(3h)。
Embodiment 4
The present embodiment is used to illustrate cyclic olefine copolymer of the invention and preparation method thereof.
Take two rings [2.2.2] oct-2-ene of 25 molar parts, the dicyclopentadiene of 75 molar parts, 0.125 mole
Part (1,3- pairs-(2,4,6- trimethylphenyls) -2- imidazolidines subunit) dichloro (adjacent isopropoxy benzene methylene
Base) close ruthenium, BMI (the wherein R shown in 10 molar part Formula II1It is n-propyl, R2It is hydrogen
Atom) it is well mixed, it is placed in 50mL single-necked flasks, add 5mL tetrahydrofurans after purification, 0 DEG C
Lower stirring dissolves it, vacuumizes the solvent in removing system.Reactant is changed into being poured during thick liquid
Enter in 60 DEG C of moulds of preheating, gradient increased temperature carries out ring-opening polymerization, obtains copolymer p 4.Heat up
Temperature and time：60℃(2h)+125℃(2h)+150℃(3h)+170℃(3h)+195℃(2h).
Embodiment 5
The present embodiment is used to illustrate cyclic olefine copolymer of the invention and preparation method thereof.
Take the dicyclopentadiene of 70 molar parts, the 3- vinyl -1- cyclobutanes of 20 molar parts, 10 molar parts
Cycloheptene, (tricyclohexyl phosphine) the benzylidene dichloro of 0.1 molar part two close ruthenium, 8 molar part Formulas I institutes
BMI (the wherein R for showing1And R2It is hydrogen atom), it is placed in 50mL single-necked flasks, plus
Enter 2mL dichloromethane after purification, stirring dissolves it at 0 DEG C, by the metathesis polymerization in embodiment 5
(tricyclohexyl phosphine) benzylidene of catalyst two dichloro closes ruthenium and is placed in another 50mL single-necked flask,
1mL dichloromethane after purification is added, stirring dissolves it at 0 DEG C, by two parts solution at 0 DEG C
After mixing and stirring, the solvent in removing system is vacuumized.Reactant is changed into being poured during thick liquid
Enter in 50 DEG C of moulds of preheating, gradient increased temperature carries out ring-opening polymerization, obtains copolymer p 5.Heat up
Temperature and time：60℃(2h)+120℃(2h)+150℃(3h)+172℃(2h)+190℃(3h).
Embodiment 6
The present embodiment is used to illustrate cyclic olefine copolymer of the invention and preparation method thereof.
Take the dicyclopentadiene of 100 molar parts, 0.08 molar part [1,3- double (2,4,6- trimethylphenyl) -2-
Imidazoline subunit] dichloro (benzylidene) (tricyclohexyl phosphine) conjunction ruthenium, it is double shown in 5 molar part Formulas I
Maleimide (wherein R1And R2It is hydrogen atom), it is placed in 50mL single-necked flasks, add 2mL
Dichloromethane after purification, stirring dissolves it at 0 DEG C, by the metathesis polymerization catalyst in embodiment 6
[double (2,4,6- the trimethylphenyls) -2- imidazolines subunits of 1,3-] dichloro (benzylidene) (tricyclohexyl phosphine)
Close ruthenium to be placed in another 50mL single-necked flask, add 1mL dichloromethane after purification, stirred at 0 DEG C
Mixing dissolves it, by two parts solution after mixing and stirring at 0 DEG C, in vacuumizing removing system
Solvent.Reactant is changed into being poured into during thick liquid in 45 DEG C of moulds of preheating, and gradient increased temperature is opened
Cyclopolymerization is reacted, and obtains copolymer p 6.Warming temperature and time：60℃(2h)+125℃(3h)+160℃
(2h)+180℃(2h)+200℃(2h)。
Embodiment 7
The present embodiment is used to illustrate cyclic olefine copolymer of the invention and preparation method thereof.
Using preparation method and raw material same as Example 1, except that, dichloro (adjacent isopropyl oxygen
Base phenylmethylene) (tricyclohexyl phosphine) ruthenium (II) be 0.1 molar part, the bismaleimide shown in Formulas I
Amine is 5 molar parts, prepares copolymer p 7.
Comparative example 1
This comparative example is used to illustrate the polymer different from the present invention that the polymer to be without bismaleimide
Amine, remaining component and content and preparation method are same as Example 1, prepare polymer D1.
Comparative example 2
This comparative example is used for the preparation method of the cyclic olefine copolymer for illustrating different from the present invention.Using with reality
The preparation method of the identical cyclic olefine copolymer of example 1 is applied, except that solvent is removed without decompression, is opened
Cyclopolymerization temperature is 170 DEG C, is reacted 10 hours, prepares cyclic olefine copolymer D2.
Comparative example 3
This comparative example is used for the preparation method of the cyclic olefine copolymer for illustrating different from the present invention.Using with reality
The preparation method of the identical cyclic olefine copolymer of example 1 is applied, except that the span shown in Formulas I is come into acyl
Imines (wherein R1And R2It is hydrogen atom) diphenyl methane dimaleimide of equimolar part is replaced with,
Prepare cyclic olefine copolymer D3.
Testing example 1
Copolymer p 1-P6 and the D1-D2 difference that above-described embodiment 1-6 and comparative example 1-2 are prepared
Carry out dynamic mechanical analysis (DMA) and thermogravimetic analysis (TGA) (TGA), the T that test is obtainedg, it is weightless
Decomposition temperature T when 10%d 10%And carbon yield data at 800 DEG C are listed in Table 1 below.
The dynamic mechanical analysis (DMA) of sample are using the Q800 type Dynamic mechanicals of TA companies of the U.S.
Tool analyzer is tested.Using single-cantilever pattern, sample size is 40 × 7 × 2mm3.Heating rate is
3 DEG C/min, temperature elevating range is 25-220 DEG C, and loading frequency is 1Hz.
The thermogravimetic analysis (TGA) of sample is measured using TA companies of U.S. thermal gravimetric analyzer.Condition determination：
Nitrogen atmosphere, 25 DEG C of initial temperature, 800 DEG C of end temp, 20 DEG C/min of programming rate.
Table 1
| Material | Carbon yield/% at 800 DEG C | |||
| Embodiment 1 | P1 | 144.9 | 438.2 | 17.2 |
| Embodiment 2 | P2 | 155.6 | 446.1 | 34.8 |
| Embodiment 3 | P3 | 146.1 | 440.3 | 18.1 |
| Embodiment 4 | P4 | 157.2 | 444.8 | 25.3 |
| Embodiment 5 | P5 | 158.4 | 443.5 | 22.7 |
| Embodiment 6 | P6 | 161.2 | 442.6 | 20.2 |
| Embodiment 7 | P7 | 156.3 | 442.1 | 21.0 |
| Comparative example 1 | D1 | 136.5 | 432.3 | 16.2 |
| Comparative example 2 | D2 | 142.7 | 423.2 | 16.7 |
| Comparative example 3 | D3 | 140.9 | 429.2 | 16.9 |
Be can be seen that relative to the polymer D1 without BMI from the data in table 1 and
The copolymer D3 of the BMI of other structures is added, copolymer p of the invention 1 is in cycloolefin
Add the BMI of structure such as Formulas I or Formula II so that the glass transition temperature T of copolymerg、
Decomposition temperature T when weightless 10%D10%And carbon yield at 800 DEG C is all improved, illustrate that cycloolefin is total to
The heat resistance of polymer material is improved.And the Data Comparison from P7 and P1 can be seen that in the present invention
The preferred cycloolefin relative to 100 molar parts, the content of BMI is 2-10 molar parts,
The content of metathesis polymerization catalyst be 0.05-0.125 molar parts in the case of, the copolymer for obtaining it is heat-resisting
Performance is more prominent.On the other hand, be can be seen that using this from the Data Comparison of copolymer p 1 and D2
The first dissolving comonomer and metathesis polymerization catalyst of invention remove solvent again, and are allowed to using gradient increased temperature
The cyclic olefine copolymer that the method for combined polymerization is prepared has more preferable heat resistance, meanwhile, the preparation
Method reaction condition is gentle, simple and easy to operate.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in range of the technology design of the invention, can be to technical side of the invention
Case carries out various simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means.In order to avoid need not
The repetition wanted, the present invention is no longer separately illustrated to various possible combinations.
Additionally, can also be combined between a variety of implementation methods of the invention, as long as its
Without prejudice to thought of the invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of cyclic olefine copolymer, is passed through altogether in the presence of metathesis polymerization catalyst by comonomer
It is poly- to react what is obtained, it is characterised in that：The comonomer be cycloolefin and BMI, it is described
BMI has Formulas I or the structure shown in Formula II：
Wherein, R1And R2It is independently each respectively the C of hydrogen atom or linear or side chain1To C6Fat
Fat alkyl；
The glass transition temperature T of the cyclic olefine copolymergHigher than 144 DEG C.
2. cyclic olefine copolymer according to claim 1, it is characterised in that：Rubbed relative to 100
The cycloolefin of your part, the content of the BMI is 1-15 molar parts, and the metathesis polymerization is urged
The content of agent is 0.04-0.2 molar parts.
3. cyclic olefine copolymer according to claim 2, it is characterised in that：Rubbed relative to 100
The cycloolefin of your part, the content of the BMI is 2-10 molar parts, and the metathesis polymerization is urged
The content of agent is 0.05-0.125 molar parts.
4. cyclic olefine copolymer according to claim 1, it is characterised in that：The cycloolefin is
Carbon number is substituted or unsubstituted double for the substituted or unsubstituted cycloolefin or norborneol alkenes of 4-8
Cycloolefin.
5. cyclic olefine copolymer according to claim 4, it is characterised in that：The carbon number
For the cycloolefin of 4-8 be selected from one or more in cyclobutane, cyclopentene, cycloheptene and cyclo-octene,
The norborneol alkenes bicyclic alkene be selected from ENB, dicyclopentadiene, methyldicyclopentadiene,
One or more in two rings [2.2.2] oct-2-ene and two rings [2.2.1] hept- 2,5- diene.
6. cyclic olefine copolymer according to claim 1, it is characterised in that：The metathesis polymerization
Catalyst is ruthenium carbene compound, and the ruthenium carbene compound is selected from two (tricyclohexyl phosphine) benzene methylenes
Base dichloro closes ruthenium, [double (2,4,6- the trimethylphenyls) -2- imidazolines subunits of 1,3-] dichloro (benzylidene)
(tricyclohexyl phosphine) closes ruthenium, dichloro (adjacent isopropoxy benzene methylene) (tricyclohexyl phosphine) ruthenium (II)
(1,3- pairs-(2,4,6- trimethylphenyls) -2- imidazolidines subunit) dichloro (adjacent isopropoxy benzene methylene
Base) close ruthenium in one or more.
7. the preparation method of the cyclic olefine copolymer in claim 1-6 described in any one, its feature
It is：Comprise the following steps：The comonomer and metathesis polymerization catalyst are dissolved in solvent and divided
Dissipate uniform；Removal of solvent under reduced pressure, the fluid composition that will be obtained is injected into pattern；Intensification carries out copolymerization
Reaction.
8. preparation method according to claim 7, it is characterised in that：The dissolving, dispersion and
In depressurization steps, temperature is -20 to 30 DEG C, and the solvent can be selected from pentane, n-hexane, just
Heptane, pentamethylene, hexamethylene, hexahydrotoluene, dimethyl cyclohexane, cyclooctane, benzene.Toluene,
One or more in dimethylbenzene, Anaesthetie Ether, tetrahydrofuran and dichloromethane.
9. preparation method according to claim 7, it is characterised in that：The shaping mould is by pre-
Heat, preheating temperature is 30-60 DEG C.
10. preparation method according to claim 7, it is characterised in that：The intensification is gradient liter
Temperature, intensification is sequentially 40-70 DEG C of first stage, 100-130 DEG C of second stage, 140-160 DEG C of phase III,
165-185 DEG C of fourth stage, the 5th 190-200 DEG C of stage, wherein, the reaction time per the stage is 2-5
Hour.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101870693A (en) * | 2010-06-29 | 2010-10-27 | 沈阳航空航天大学 | Bismaleimide containing 1,3,4-oxadiazole structure and preparation method thereof |
| CN102942564A (en) * | 2012-11-20 | 2013-02-27 | 沈阳航空航天大学 | Asymmetric bismaleimide containing 1, 3, 4-oxadiazole structure and preparation method thereof |
-
2015
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101870693A (en) * | 2010-06-29 | 2010-10-27 | 沈阳航空航天大学 | Bismaleimide containing 1,3,4-oxadiazole structure and preparation method thereof |
| CN102942564A (en) * | 2012-11-20 | 2013-02-27 | 沈阳航空航天大学 | Asymmetric bismaleimide containing 1, 3, 4-oxadiazole structure and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 胡方圆: "聚双环戊二烯的制备及其改性研究", 《中国博士学位论文工程科技I辑》 * |
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| JP7069618B2 (en) | 2017-09-28 | 2022-05-18 | Dic株式会社 | Maleimide compounds, and compositions and cured products using them. |
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