CN109134755A - 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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- CN109134755A CN109134755A CN201811022017.1A CN201811022017A CN109134755A CN 109134755 A CN109134755 A CN 109134755A CN 201811022017 A CN201811022017 A CN 201811022017A CN 109134755 A CN109134755 A CN 109134755A
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- 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 belongs to novel polycyclic alkene polymer synthesis techniques fields, provide a kind of heat-resisting cyclic olefine copolymer and preparation method thereof, more particularly to norbornene derivative 5- ethylidene -2- norbornene and the long-chains alpha olefin copolymer such as 1- hexene (1-Hexene) and 1- octene (1-Octene), preparation method of the invention is with reaction condition is mild, the period is short, simple operation and other advantages.And used catalyst Cpket has extraordinary catalytic activity and thermal stability for this copolyreaction, has great industrial application value and good application prospect.
Description
Technical field
The invention belongs to novel polycyclic alkene technical field of polymer, and in particular to a kind of heat-resisting norbornene derivative
5- ethylidene -2- norbornene and α-cycloolefin copolymer and its preparation method and application.
Background technique
Due to social and science and technology increasingly developed, for traditional polyolefin such as polyethylene (HDPE, LLDPE) and polypropylene
(PP) etc. performance, shape and other characteristics for the polyolefin product of representative suffer from various requirements, need by
Its every field for being applied to the national economy such as daily life, health care, industrial or agricultural and aerospace and defense military is worked as
In, therefore the synthesis of the novel polymer with specific function is considered as one of the target of most attraction.
Wherein, with cyclic olefine copolymer (COCs) due to its glass transition temperature TgIt can be made from it that (cycloolefin contains
Amount etc.) and their microstructure (including steric regularity etc.) be more favored adjusting.Cyclic olefine copolymer (COCs)
With the excellent optical property such as the UV-visible region high grade of transparency, low birefringence, high Abbe number, low water absorbable, dimensionally stable
Property, stable optical property, low-gravity, high-fire resistance, high fluidity, precise forming performance are excellent transferability and mainly answer
For the optical applications of camera lens and liquid crystal display light guide plate, optical thin film etc., medical treatment, detecting instrument field, electronic device
Field etc..However, the successful examples for being effectively synthesized the random high molecular weight copolymer of heat-resisting high ENB content nevertheless suffer from limit
System.
This patent mainly inquires into norbornene derivative 5- ethylidene -2- norbornene and α-cyclenes hydrocarbon type copolymer system
Standby and application.A kind of Typical Representative of norbornene and its derivative polymer as cycloolefin polymer is a kind of novel
Unformed thermoplastic.Polynorbornene and its derivative are a kind of to be used as the novel organic high of rubber as elastomer
Polymers.Its product is mainly used for soundproof plate, anti-vibration, protecting against shock and improvement road holding etc..It also has good oil suction simultaneously
Property, with the infiltration of oil product, polymer beads generate swelling and form bonding plate, and it is easy to clean, it can be applied to tire, shoes
In the fields such as bottom, toy, medical apparatus.Research and develop the high glass-transition temperature T with Autonomy intellectual propertyg's
Random high molecular weight copolymer oneself become the responsibility and realistic task of scientific research personnel.
Summary of the invention
The present invention provides a kind of heat-resisting cyclic olefine copolymer, and the copolymer is norbornene derivative 5- ethylidene-
2- norbornene and the long-chains alhpa olefin such as 1- hexene (1-Hexene) and 1- octene (1-Octene) carry out the production of copolyreaction
Object.Comprise the following structure unit:
Wherein, long-chain alhpa olefin mainly includes the case where n >=1.
Preferably, n=1, that is, 1- hexene (1-Hexene), n=3, that is, 1- octene (1-Octene) etc.；
The copolymer includes unsaturated double-bond, increases main chain rigidity, can also be polymerize by double bond
The functionalization of object, to realize the preparation of various functionalized polymers.
The present invention also provides a kind of preparation methods of cyclic olefine copolymer, it is characterised in that uses catalyst (I)
(Cpket), catalyst (II) (tBuCpket), catalyst (III) (IndOAr) has carried out norbornene derivative 5- ethylidene-
2- norbornene and the long-chains alhpa olefin such as 1- hexene (1-Hexene) and 1- octene (1-Octene) carry out copolyreaction.
The catalyst structure is as follows:
The general formula of the copolyreaction are as follows:
Preferably, it is all experiment drying, anaerobic atmosphere of inert gases under carry out.All chemicals used are
SILVER REAGENT, and purified by standard purification procedures.Anhydrous grade toluene used is first transitioned to contains molecular sieve in drying box
In the bottle of (mixture of 3A and 4A, 1/16 and 13X), without being used after being further purified.Reagent grade 5- ethylidene -2- drop
Bornylene (ENB), 1- hexene and 1- octene, by alumina, are then stored in the bottle in glove box using preceding.
Co-catalyst aikyiaiurnirsoxan beta can be selected from commercially available methylaluminoxane (MAO), be dried under reduced pressure at 50 DEG C for remove contained toluene and
AlMe3(or n-hexane) obtains white solid in glove box case after then heating 1 hour in the case where 100 DEG C of >.
Compared with prior art, the present invention provides a kind of heat-resisting cyclic olefine copolymer and preparation method thereof, the present invention
The cyclic olefine copolymer of offer can be by changing the content of monomer in polymer reaction to select specific structure, so that originally
The glass transition temperature for inventing the cyclic olefine copolymer provided can be regulated and controled accordingly, and reaction process is simple, efficient, institute
Obtain copolymer good thermal stability.
In addition, the present invention also provides a kind of preparation method of above-mentioned heat-resisting cyclic olefine copolymer, it is provided by the invention
Preparation method uses the drop with the long-chain alpha olefin monomers with formula (2) structure and the carbon-carbon double bond group with formula (3) structure
Bornylene derivatives monomer carries out combined polymerization, and reaction rate is fast, and reactivity is high, and compared with ring-opening polymerisation, without the later period plus
Hydrogen reaction treatment, reaction process are efficiently convenient.
Beneficial effects of the present invention:
1. the present invention provides the copolymerization of norbornene derivative 5- ethylidene -2- norbornene and 1- hexene, 1- octene
A series of researchs of object, the screening including condition, the test of polymer, and the copolymerisation of several classical catalyst is carried out greatly
Measure experimental study and comparison.Preparation method has many advantages, such as that reaction condition is mild, the period is short, operating condition is simple.
2. the present invention provides the copolymerization of norbornene derivative 5- ethylidene -2- norbornene and 1- hexene, 1- octene
The purposes of object, the product are a kind of high added value polythene materials, have preferable prospects for commercial application.To sum up, of the invention
The copolymer of norbornene derivative 5- ethylidene -2- norbornene and 1- hexene, 1- octene prepares polyolefin in catalytic polymerization
Aspect has great industrial application value.
Detailed description of the invention
Fig. 1 is the carbon-13 nmr spectra figure for the product that the embodiment of the present invention 1 obtains.
Fig. 2 is the carbon-13 nmr spectra figure for the product that the embodiment of the present invention 2 obtains.
Fig. 3 is the carbon-13 nmr spectra figure for the product that the embodiment of the present invention 3 obtains.
Specific embodiment
The present invention provides a kind of cyclic olefine copolymers, have the structure as shown in formula (1),
Wherein, long-chain alhpa olefin mainly includes the case where n >=1.
Preferably, n=1, that is, 1- hexene (1-Hexene), n=3, that is, 1- octene (1-Octene) etc.；
The present invention also provides a kind of preparation methods of cyclic olefine copolymer, comprising: will have the compound of formula (2) structure
Polymerization reaction is carried out under catalyst (I), (II), (III) effect with the compound of formula (3) structure, obtains polymer:
Preferably, used catalyst is classical catalyst (I) (Cpket), the catalyst (II) of oneself following existing report
(tBuCpket), catalyst (III) (IndOAr).
Preferably, according to the present invention, all experiments are in the glove box of drying, the nitrogen of anaerobic or atmosphere of inert gases
It carries out.The present invention does not have the inert gas special limitation, using inert gas well known to those skilled in the art
?.The present invention preferably carries out the polymerization reaction under conditions of magnetic stirrer, and the present invention is for the stirring
Method does not have special limitation, using agitating mode well known to those skilled in the art.
Preferably, according to the present invention, the temperature of all polymerization reactions is preferably 20 DEG C -50 DEG C, all polymerization reactions when
Between preferably 10min-60min.
In the present invention, all chemicals used are SILVER REAGENT, and are purified by standard purification procedures.The present invention couple
Be not particularly limited in the type of solvent for use, using solvent well known to those skilled in the art, the present invention preferably, institute
It is anhydrous grade toluene with toluene, and is transferred into glove box and contains molecular sieve (mixture of 3A and 4A, 1/16 He
In bottle 13X), without being used after being further purified.Reagent grade 5- ethylidene -2- norbornene (ENB), 1- hexene and 1-
Octene, by alumina, is then stored in the bottle in drying box using preceding.Kind of the present invention for co-catalyst
Class is not particularly limited, using co-catalyst well known to those skilled in the art.The preferably commercially available methylaluminoxane of the present invention
(MAO), it is dried under reduced pressure at 50 DEG C for removing contained toluene and AlMe3(or n-hexane), then in the case where 100 DEG C of >, heating 1 is small
When after white solid is obtained in glove box.
In the present invention, after the completion of the polymerization reaction, present invention preferably employs stop stirring and to pour into hydrochloric acid methanol molten
The reaction regular hour is terminated in liquid.By being filtered, washed, be dried to obtain polymerization reactant.The present invention for being filtered, washed,
The method of drying and other steps is not particularly limited, using step scheme well known to those skilled in the art.In the present invention, institute
Stating the termination time is preferably 15min, and washing times are preferably 3-5 times, and drying means used is preferably the vacuum drying at 25 DEG C
It is 24 hours dry in device.
The present invention is polymerize when carrying out later period test characterization to polymeric reaction product using NMR spectrum detection assay
Object molecular structure；Wherein, own1H and13C NMR spectra be measured at 70 DEG C by 500 spectrometer of BrukerAV (for1H
For 500.13MHz；For13C is 125.77MHz), tetramethylsilane (TMS) is internal standard, 1,1,2,2- tetrachloroethanes-d2It is molten
Agent.
The present invention uses gel permeation chromatography test polymer when carrying out later period test characterization to polymeric reaction product
Molecular weight distribution sum number average molecular weight.Wherein, gel permeation chromatography GPC) it tests and is detected at 40 DEG C using RID-10A
Device (Shimadzu Co.Ltd.) is tested, and solvent is 1.0mL/min, the tertiary fourth of 2,6- bis- containing 0.03wt% using flow velocity
The THF of base paracresol.GPC column uses ShimPAC GPC-806,804 and 802,30cm × 8.0mm diameter, by styrene/diethyl
Spherical porous gel made of alkenyl benzene copolymer, range from < 102 to 2 × 107MW, and using polystyrene standard sample into
Row calibration.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are only section Example,
Instead of all the embodiments, it is only illustrative of the invention and is not intended to limit the scope of the invention.Furthermore, it is to be understood that readding
After having read documented content of the invention, those skilled in the art can make various modifications or changes to the present invention, these etc.
Valence form equally falls within limited range of the present invention.
Experimental method used in following embodiments is conventional method unless otherwise specified.
The materials, reagents and the like used in the following examples is commercially available unless otherwise specified.
Concentration in following embodiments is molar concentration unless otherwise instructed.
The molecular weight of resulting polymers and molecular weight distribution are according to the above-mentioned side GPC in following olefinic polymerization embodiments
Method is measured and is obtained, and the polymerization activity of polymer is calculated according to following formula and obtained: polymerization activity=polymer output/(catalysis
Agent dosage × polymerization time).
The compound of following all synthesis is confirmed by nuclear-magnetism, infrared and elemental analysis.
Embodiment 1
In the glove box of nitrogen atmosphere, 1mmol is sequentially added into the screw socket bottle for being placed in the 30mL on magnetic stirring apparatus
That is 0.058g methylaluminoxane (MAO) solid (toluene or n-hexane AlMe3It is dried under reduced pressure at 50 DEG C for removing, then
Obtain white solid in glove box case after heating 1 hour in the case where 100 DEG C of >), the 5- ethylidene -2- norbornene of 5mL
(ENB), the 1- hexene of 4.5mL, 0.25mL toluene, after mixing evenly, then it is 4 μ that 0.25mL molar concentration, which is added, into reactor
The toluene solution of catalyst (I) Cpket of mol/mL is stirred at room temperature 60 minutes progress polymerization reaction experiments, is reacted
Product.
The reaction product is poured into the methanol hydrochloride solution for being 10% containing percentage by volume outside glove box, stirring 15
Minute to terminate polymerization and precipitated product is obtained by filtration, is placed in vacuum drying after the precipitated product is sufficiently washed with methanol
It is 24 hours dry in device, obtain final polymerizate.
Polymerizate obtained above is subjected to carbon-13 nmr spectra detection, the nuclear magnetic resonance of testing result such as Fig. 1 product
Shown in carbon spectrogram, as shown in Figure 1, the obtained polymerizate of the embodiment of the present invention 1 is the chemical combination with structure shown in formula (1)
Object.
Gel permeation chromatography test is carried out to the cyclic olefine copolymer that the embodiment of the present invention 1 obtains, test result is this hair
The number average molecular weight for the cyclic olefine copolymer that bright embodiment 1 obtains is 2.49 × 10-4, molecular weight distribution 1.82.
Embodiment 2
In the glove box of nitrogen atmosphere, 2mmol is sequentially added into the screw socket bottle for being placed in the 30mL on magnetic stirring apparatus
That is 0.116g methylaluminoxane (MAO) solid (toluene or n-hexane AlMe3It is dried under reduced pressure at 50 DEG C for removing, then exists
Obtain white solid in glove box case after heating 1 hour at 100 DEG C of >), the 5- ethylidene -2- norbornene (ENB) of 5mL,
The 1- hexene of 2.5mL, 2.25mL toluene, after mixing evenly, then it is 4 μm of ol/mL that 0.25mL molar concentration, which is added, into reactor
Catalyst (I) Cpket toluene solution, 30 minutes progress polymerization reaction experiments are stirred at room temperature, obtain reaction product.
The reaction product is poured into the methanol hydrochloride solution for being 10% containing percentage by volume outside glove box, stirring 15
Minute to terminate polymerization and precipitated product is obtained by filtration, is placed in vacuum drying after the precipitated product is sufficiently washed with methanol
It is 24 hours dry in device, obtain final polymerizate.
Polymerizate obtained above is subjected to carbon-13 nmr spectra detection, the nuclear magnetic resonance of testing result such as Fig. 2 product
Shown in carbon spectrogram, as shown in Figure 2, the obtained polymerizate of the embodiment of the present invention 2 is the chemical combination with structure shown in formula (1)
Object.Gel permeation chromatography test is carried out to the cyclic olefine copolymer that the embodiment of the present invention 2 obtains, test result is that the present invention is implemented
The number average molecular weight for the cyclic olefine copolymer that example 2 obtains is 1.1 × 10-4, molecular weight distribution 3.13.
Embodiment 3
In the glove box of nitrogen atmosphere, 2mmol is sequentially added into the screw socket bottle for being placed in the 30mL on magnetic stirring apparatus
That is 0.116g methylaluminoxane (MAO) solid (toluene or n-hexane AlMe3It is dried under reduced pressure at 50 DEG C for removing, then exists
Obtain white solid in glove box case after heating 1 hour at 100 DEG C of >), the 5- ethylidene -2- norbornene (ENB) of 5mL,
The 1- hexene of 4.5mL, 0.25mL toluene, after mixing evenly, then it is 4 μm of ol/mL that 0.25mL molar concentration, which is added, into reactor
Catalyst (I) Cpket toluene solution, 30 minutes progress polymerization reaction experiments are stirred at room temperature, obtain reaction product.
The reaction product is poured into the methanol hydrochloride solution for being 10% containing percentage by volume outside glove box, stirring 15
Minute to terminate polymerization and precipitated product is obtained by filtration, is placed in vacuum drying after the precipitated product is sufficiently washed with methanol
It is 24 hours dry in device, obtain final polymerizate.
Polymerizate obtained above is subjected to carbon-13 nmr spectra detection, the nuclear magnetic resonance of testing result such as Fig. 3 product
Shown in carbon spectrogram, from the figure 3, it may be seen that the obtained polymerizate of the embodiment of the present invention 3 is the chemical combination with structure shown in formula (1)
Object.Gel permeation chromatography test is carried out to the cyclic olefine copolymer that the embodiment of the present invention 3 obtains, test result is that the present invention is implemented
The number average molecular weight for the cyclic olefine copolymer that example 3 obtains is 2.36 × 10-4, molecular weight distribution 1.94.
Above embodiments are only illustrated embodiments of the present invention.It should be pointed out that the present invention is not limited to upper
Embodiment is stated, it to those of ordinary skill in the art, without departing from the principle of the present invention, can also be to this
Some improvement and modification can also be carried out for invention.All within the spirits and principles of the present invention, any modification for being made, changes equivalent replacement
Into etc., it should all fall within the scope of protection of the claims of the present invention.
Claims (8)
1. a kind of cyclic olefine copolymer, it is characterised in that the copolymer comprises the following structure unit (n >=1):
2. a kind of cyclic olefine copolymer according to claim 1, which is characterized in that the copolymer includes unsaturated double
Key increases main chain rigidity, and the functionalization of polymer can be also carried out by double bond, to realize various functionalization polymerizations
The preparation of object.
3. the preparation method of cyclic olefine copolymer described in claim 1, it is characterised in that by norbornene derivative 5- ethylidene-
2- norbornene carries out copolymerization catalysis with alhpa olefin and reacts obtained.
4. the preparation method of copolymer according to claim 3, it is characterised in that the copolyreaction uses catalyst (I)
(Cpket), catalyst (II) (tBuCpket) or catalyst (III) (IndOAr) carries out catalyzed copolymerization.
5. according to the preparation method of the copolymer of claim 3 or 4, it is characterised in that copolymerization catalysis reaction is also using helping
Catalyst, the co-catalyst are methylaluminoxane (MAO).
6. according to the preparation method of the copolymer of claim 3 or 4, it is characterised in that it is described reaction under an inert atmosphere into
Row.
7. according to the preparation method of the copolymer of claim 3 or 4, it is characterised in that condition of the reaction in anhydrous and oxygen-free
Lower progress.
8. all chemicals used are SILVER REAGENT, and are passed through according to the preparation method of the copolymer of claim 3 or 4
Standard purification procedures purifying.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4634542A (en) * | 1985-11-26 | 1987-01-06 | Exxon Research And Engineering Company | Novel interpolymer complexes of sulfonated octene-1 copolymer |
| CN108250340A (en) * | 2016-12-28 | 2018-07-06 | 北京引发科技有限公司 | A kind of method of metallocene catalyst system and its catalysis in olefine polymerization |
| CN108440700A (en) * | 2011-11-25 | 2018-08-24 | 维尔萨利斯股份公司 | The method for being used to prepare the copolymer of ethylene |
-
2018
- 2018-09-03 CN CN201811022017.1A patent/CN109134755A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4634542A (en) * | 1985-11-26 | 1987-01-06 | Exxon Research And Engineering Company | Novel interpolymer complexes of sulfonated octene-1 copolymer |
| CN108440700A (en) * | 2011-11-25 | 2018-08-24 | 维尔萨利斯股份公司 | The method for being used to prepare the copolymer of ethylene |
| CN108250340A (en) * | 2016-12-28 | 2018-07-06 | 北京引发科技有限公司 | A kind of method of metallocene catalyst system and its catalysis in olefine polymerization |
Non-Patent Citations (1)
| Title |
|---|
| 李红春 等: "茂金属催化5-亚乙烯基-2-降冰片烯与乙烯的共聚"", 《高分子材料科学与工程》 * |
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