CN104250332B - Three-dimensional elasticity copolymer containing diene and preparation method thereof - Google Patents
Three-dimensional elasticity copolymer containing diene and preparation method thereof Download PDFInfo
- Publication number
- CN104250332B CN104250332B CN201410307132.9A CN201410307132A CN104250332B CN 104250332 B CN104250332 B CN 104250332B CN 201410307132 A CN201410307132 A CN 201410307132A CN 104250332 B CN104250332 B CN 104250332B
- Authority
- CN
- China
- Prior art keywords
- copolymer
- dimensional elasticity
- chemical formula
- weight
- olefin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention relates to a kind of three-dimensional elasticity copolymer can simultaneously with outstanding mechanical-physical character and elasticity (flexibility) and preparation method thereof.The three-dimensional elasticity copolymer is the copolymer that the acetate unit content obtained in the presence of group iv transition metals catalyst is 40 to 70 weight %, C3~C20 alhpa olefin unit contents are 15 to 55 weight % and diene units content is 0.5 to 20 weight %, and weight average molecular weight i) determined with GPC is 100000 to 500000；Ii the Mooney viscosity ML and Mooney relaxation area MLR) determined with mooney's viscosimeter (125 DEG C of 1+4+2@) can meet particular kind of relationship.
Description
Technical field
The present invention relates to a kind of three-dimensional elasticity copolymer and preparation method thereof, the three-dimensional elasticity copolymer be ethene, α-
The copolymer of alkene and diene.In more detail, can have processability and elastic (flexibility) simultaneously the present invention relates to one kind
Elastic terpolymer and preparation method thereof.
Background technology
EPDM rubber is the three-dimensional elasticity copolymerization of the diene such as alpha-olefin and the ENB containing ethylidene such as ethene, propylene
Thing, it has the molecular structure for not having unsaturated bond on main chain, and is better than with weatherability, chemical resistance and heat resistance etc.
The feature of conventional conjugated diene.Because with this feature, the EPDM rubber class three-dimensional elasticity copolymer is widely used in various
The industrial material such as auto parts material, electric wire material, building and various flexible pipes, packing ring, conveyer belt, bumper or mixed plastic
Material.
In the past, the three-dimensional elasticity copolymer such as this EPMD rubber mainly used the catalyst containing vfanadium compound, such as vanadium
It is Ziegler-Natta catalyst, three kinds of monomer copolymerizations is made.However, due to this vanadium system Ziegler-Natta catalyst
Catalytic activity is relatively low, it is necessary to using excessive catalyst, as a result cause the residual metal content in copolymer to uprise.Therefore, make
Need to carry out catalyst removal and decolorization etc. after standby copolymer, and because catalyst is remained in resin, it may appear that it is resistance to
The problems such as hot variation, generation impurity or obstruction vulcanization reaction.In addition, being made using the catalyst containing vfanadium compound
During standby three-dimensional elasticity copolymer, due to low polymerization activity and low temperature polymerization condition, reaction temperature, and whard to control third are difficult to control
The uptake of the comonomer such as alkene and diene, and then it is difficult to control to the molecular structure of copolymer.Therefore, using vanadium series catalyst
When, preparing the elastocopolymer with various physical properties has limitation.Therefore, research and development recently are a kind of to use metallocene system
Group iv transition metals catalyst substitute vanadium system's Ziegler-Natta catalyst and prepare the three-dimensional elasticity copolymer such as EPDM rubber
Method.
This group iv transition metals catalyst shows high polymerization activity in olefin polymerization, can not only prepare point
The larger polymer of son amount, and molecular weight distribution and composition of easily controllable copolymer etc., also with various copolymerization lists can be made
The advantage of body combined polymerization.For example, U.S. Patent No. 5229478, U.S. Patent No. 6545088 and Korean granted patent
Disclosed in No. 0488833 grade using a variety of metallocene class Group IVs obtained by parts such as cyclopentadienyl group, indenyl or fluorenyls
Transition-metal catalyst, can obtain the three-dimensional elasticity copolymer with macromolecule with outstanding polymerization activity.
If, will however, carry out combined polymerizations to three kinds of monomers using this conventional group iv transition metals catalyst
Occur due to high response of the alpha-olefin to comonomer, by the repeat unit skewness of each monomer derived in copolymer chain
Even shortcoming.As a result, it is difficult to obtain the three-dimensional elasticity copolymers such as the EPDM rubber with outstanding elasticity and flexibility etc..
Can be while to meet outstanding processability, mechanical-physical character and elasticity (soft accordingly, it would be desirable to continue that research and development are a kind of
Property) three-dimensional elasticity copolymer and the preparation method of three-dimensional elasticity copolymer can be prepared with high production rate and in high yield.
The content of the invention
In view of this, outstanding processability and elasticity (flexibility) can be met simultaneously it is an object of the invention to provide a kind of
Three-dimensional elasticity copolymer.
The present invention also aims to provide a kind of method that the three-dimensional elasticity copolymer can be prepared with high production rate.
The present invention provides a kind of three-dimensional elasticity copolymer, and the three-dimensional elasticity copolymer is in group iv transition metals catalyst
In the presence of the acetate unit content that obtains be 40 to 70 weight %, C3~C20 alpha-olefin unit contents be 15 to 55 weight %, with
And the copolymer that diene units content is 0.5 to 20 weight %,
I) weight average molecular weight determined with GPC is 100000 to 500000；
Ii the copolymer crystallization enthalpy (Δ determined when) acetate unit content (weight %) x and acetate unit content are x with DSC
Hc, J/g) y meets relational expression 1.55x-80.00≤y≤1.55x-75.00.
The present invention also provides a kind of three-dimensional elasticity copolymer, and the three-dimensional elasticity copolymer is in group iv transition metals catalysis
The acetate unit content obtained in the presence of agent be 40 to 70 weight %, C3~C20 alpha-olefin unit contents be 15 to 55 weight %,
And the copolymer that diene units content is 0.5 to 20 weight %,
I) weight average molecular weight determined with GPC is 100000 to 500000；
Ii the Mooney viscosity ML and Mooney relaxation area MLR) determined with mooney's viscosimeter (125 DEG C of 1+4+2@) meets following
General expression 1,
[general expression 1]
[MLR/(ML)2]×100≥8。
The present invention also provides a kind of preparation method of three-dimensional elasticity copolymer, including：
In the presence of carbon monoxide-olefin polymeric, monomer composition is supplied into reactor and combined polymerization is carried out, wherein institute
Carbon monoxide-olefin polymeric is stated comprising the First Transition metallic compound that is represented by formula 1 below and is represented by formula 2 below
Second Transition compound, ethene of the monomer composition comprising 40 to 70 weight %, 15 to 55 weight % C3~C20
The diene of alpha-olefin and 0.5 to 20 weight %,
[chemical formula 1]
[chemical formula 2]
In the chemical formula 1 and 2,
R1To R13Be same to each other or different to each other, be separately hydrogen, C1~C20 alkyl, C2~C20 alkenyls, C6~C20 virtue
Base, silicyl, C7~C20 alkylaryls, the metalloid of C7~C20 aryl alkyls or the Group IV metal replaced by alkyl
Base, and the R1To R13In adjacent two different groups can pass through the alkylene comprising C1~C20 alkyl or C6~C20 aryl
Base is connected to each other and forms cycloaliphatic ring or aromatic rings；
M is group iv transition metals；
Q1And Q2Mutually the same or difference is separately halogen, C1~C20 alkyl, C2~C20 alkenyls, C6~
C20 aryl, C7~C20 alkylaryls, C7~C20 aryl alkyls, C1~C20 alkyl aminos, C6~C20 arylaminos or C1
~C20 alkylidene.
Below, it will be described according to three-dimensional elasticity copolymer of specific embodiments of the present invention and preparation method thereof.
First, in the case of other special instructions, in this specification term " three-dimensional elasticity copolymer " refer to ethene,
Any elastocopolymer (for example, crosslinkable random copolymer) of three kinds of monomer copolymerizables of C3~C20 alpha-olefins and diene.Make
For the exemplary of this " three-dimensional elasticity copolymer ", for example, the copolymer EPDM rubber of ethene, propylene and diene.Simply, this
Plant " three-dimensional elasticity copolymer " and refer not only to the copolymer of three kinds of monomers, and may include the ethene, belong to alpha-olefin category
More than one monomers and belong to diene category more than one monomer copolymerizables any elastocopolymer.For example, second
Two kinds of diene of alkene including propylene and two kinds of alpha-olefins of 1- butylene and the ENB containing ethylidene and 1,4- hexadienes
The elastocopolymer of combined polymerization, that is, ethene and three kinds of monomer copolymerizations for being belonging respectively to alpha-olefin and diene category
The copolymer closed, is consequently belonging to the category of " the three-dimensional elasticity copolymer ".
The first scheme of the present invention provides a kind of three-dimensional elasticity copolymer, and the three-dimensional elasticity copolymer is in Group IV transition
The acetate unit content obtained in the presence of metallic catalyst be 40 to 70 weight %, C3~C20 alpha-olefin unit contents be 15 to
55 weight % and the copolymer that diene units content is 0.5 to 20 weight %,
I) weight average molecular weight determined with GPC is 100000 to 500000；
Ii the copolymer crystallization enthalpy (Δ determined when) acetate unit content (weight %) x and acetate unit content are x with DSC
Hc, J/g) y meets relational expression 1.55x-80.00≤y≤1.55x-75.00.
The alternative plan of the present invention provides a kind of three-dimensional elasticity copolymer, and the three-dimensional elasticity copolymer is in Group IV transition
The acetate unit content obtained in the presence of metallic catalyst be 40 to 70 weight %, C3~C20 alpha-olefin unit contents be 15 to
55 weight % and the copolymer that diene units content is 0.5 to 20 weight %,
I) weight average molecular weight determined with GPC is 100000 to 500000；
Ii the Mooney viscosity ML and Mooney relaxation area MLR) determined with mooney's viscosimeter (125 DEG C of 1+4+2@) meets following
General expression 1,
[general expression 1]
[MLR/(ML)2]×100≥8。
The three-dimensional elasticity copolymer of first and second scheme is ethene, three kinds of monomers of alpha-olefin and diene to provide to contain
Measure scope combined polymerization, with larger weight average molecular weight, the weight average molecular weight determined with GPC be about 100000 to
500000 or about 150000 to 400000.So big weight average molecular weight is to be based on group iv transition metals catalyst (example
Such as, belong to first and second transistion metal compound of the following chemical formula 1 and 2 of metallocene system) outstanding activity and reach
Into, the three-dimensional elasticity copolymer of the first and second schemes is due to this macromolecule, the three-dimensional elasticity copolymer, example
As EPDM rubber can show outstanding mechanical-physical character.
Moreover, in these embodiments, acetate unit content (weight %) x of the three-dimensional elasticity copolymer of first scheme
Copolymer crystallization enthalpy (the Δ Hc determined during with acetate unit content for x with DSC；J/g) y for example meets relational expression 1.55x-
80.00≤y≤1.55x-75.00, specifically can further meet relational expression y ≈ 1.55x-78.06.
The three-dimensional elasticity copolymer of the first scheme of the relational expression is met, its crystallinity is relative to the ethene list included
First content is less high, can be in optimum range.As noted previously, as the three-dimensional elasticity copolymer of first scheme relative to second
The crystallinity of alkene unit content is in optimum range, and the three-dimensional elasticity copolymer can have outstanding mechanical-physical simultaneously
Matter and the elasticity and flexibility etc. further improved.Therefore, the three-dimensional elasticity copolymer of the first scheme, for example can be with cyclopentadienyl
The distinctive outstanding productivity ratio of group iv transition metals catalyst and yield of metal system are made, not only with macromolecule and
Resulting outstanding mechanical-physical character, and solve the group iv transition metals catalyst with metallocene system to make
The problem of standby conventional EPDM rubber has, so as to which there is outstanding elasticity and flexibility simultaneously.
Relation between the acetate unit content x and crystallization enthalpy y of the three-dimensional elasticity copolymer of first scheme can pass through
Following methods are determined.First, in the content range of each monomer, polymerize and prepare acetate unit content different two kinds with
Upper three-dimensional elasticity copolymer, is then led for each copolymer using the dsc measurement device such as DSC6000 of PerkinElmer companies
Go out DSC curve data.This DSC curve data can for example be exported in the form of Fig. 6., will when exporting this DSC curve data
Each copolymer sample is heated to about 100 DEG C with about 0 DEG C to 20 DEG C/minute of speed, keeps about 2 minutes at such a temperature, then with
About -10 DEG C/minute of speed is cooled to -150 DEG C and carries out dsc analysis.The knot can be tried to achieve by such derived DSC curve data
Brilliant enthalpy, and average crystallization temperature (Tc can be calculated；℃).
Using the acetate unit content included in each copolymer as x-axis, and it will be determined for these each copolymers
Crystallization enthalpy indicates the data for each copolymer as y-axis, then carries out linear regression analysis to these data, to export
The relation of the acetate unit content x and crystallization enthalpy y.The relation of the x and y are as shown in Figure 7.
The relation between the x and y of the three-dimensional elasticity copolymer of first scheme is derived by this method, as a result shows this
Three-dimensional elasticity copolymer with the past with the EPDM rubber of group iv transition metals catalyst preparation compared with, relative to ethylene unit
The crystallization enthalpy of content is in reduced levels, disclosure satisfy that relational expression y≤1.55x-75.00.Thereby confirm that the first scheme
Three-dimensional elasticity copolymer can have the excellent mechanical-physical character based on macromolecule, outstanding elastic and softness simultaneously
Property etc..Therefore, the three-dimensional elasticity copolymer can be prepared into outstanding production using group iv transition metals catalyst
Rate, yield and mechanical-physical character, and more outstanding elasticity and flexibility needed for EPDM rubber etc. are shown, it is especially suitable for using
Make described EPDM rubber etc..Moreover, the three-dimensional elasticity copolymer meets relational expression 1.55x-80.00≤y≤1.55x-
75.00, meet relative to the crystallization enthalpy more than floor level of acetate unit content, it is suitable needed for EPDM rubber so as to show
When mechanical-physical character and heat resistance etc..Therefore, the three-dimensional elasticity copolymer of the first scheme is very suitable for iv
It is prepared by group 4 transition metal catalyst.
In a preferred approach, the three-dimensional elasticity copolymer of the first scheme is suitable that can show as EPDM rubber etc.
When physical property monomeric unit total content in the range of, such as ethylene unit is about 40 to 70 weight % or about 50 to 70
Weight %, C3~C20 alpha-olefin units are about 15 to 55 weight % or about 25 to 45 weight % and diene units are about
In the range of 0.5 to 20 weight % or about 2 to 10 weight % total content, described acetate unit content and crystallization enthalpy can be met
Particular kind of relationship.Thus, the three-dimensional elasticity copolymer can have more excellent elastic and flexibility etc. as EPDM rubber.Such as
Fruit exceeds the content range of this each monomer, can not just have the appropriate physical property as EPDM rubber, or can not expire
The particular kind of relationship of acetate unit content and crystallization enthalpy described in foot.
In addition, the three-dimensional elasticity copolymer of alternative plan, its Mooney determined with mooney's viscosimeter (125 DEG C of 1+4+2@) glues
Degree ML and Mooney relaxation area MLR can meet following general expression 1, and the acetate unit content and knot of first scheme described in not according to
Predetermined relationship between brilliant enthalpy.
[general expression 1]
[MLR/(ML)2]×100≥8
In the general expression 1, ML is Mooney viscosity, and MLR is that the Mooney started after rotor stops 1 second within 2 minutes should
The integrated value of power relaxation, its calculating formula can be represented by following general expression 2.
[general expression 2]
The three-dimensional elasticity copolymer of the alternative plan of these relations is met, high levels of long chain branching can be especially shown
Than.As described above, the three-dimensional elasticity copolymer includes substantial amounts of long-chain branch, thus there can be outstanding mechanical-physical simultaneously
Matter, the elasticity further improved and flexibility etc..
Therefore, the three-dimensional elasticity copolymer of the alternative plan can also belong to the Group IV transition gold of metallocene system
Prepared, not only produced with macromolecule and thus with distinctive outstanding productivity ratio and yield in the presence of metal catalyst
Raw outstanding mechanical-physical character, and solve EPDM in the past with metallocene system group iv transition metals catalyst preparation
The problem of rubber has, so as to which there is outstanding elasticity and flexibility simultaneously.Therefore, according to the ternary bullet of alternative plan
Property copolymer, is also suitable for the EPDM rubber of group iv transition metals catalyst preparation.
The Mooney viscosity (ML) and Mooney relaxation area (MLR) of the three-dimensional elasticity copolymer of this alternative plan can lead to
Following method is crossed to determine.First, it polymerize and prepares three-dimensional elasticity copolymer, then for each copolymer, for example, can be used
The mooney's viscosimeters such as the MV2000 of Monsanto companies determine Mooney viscosity ML and Mooney relaxation area MLR, and can lead
Go out these relationship graph, such as Mooney relaxation curve.This chart can be the form as shown in Fig. 1 and Fig. 2 etc..
Specifically, the Mooney viscosity ML, Mooney relaxation area MLR and its relationship graph, can be determined by the following method
And export.Each copolymer is handled with antioxidant and test piece is made using pressing mold, with 1+4+2 condition to test piece at 125 DEG C
Handled, to determine Mooney viscosity ML and Mooney relaxation area MLR.That is, test piece is preheated 1 minute, then determines Mooney and glue
It is 4 minutes to spend the ML times, and determines the Mooney relaxation area MLR times for 2 minutes, so as to export Mooney viscosity ML and Mooney pine
Relaxation area MLR relationship graph.
In the copolymer of alternative plan, the content of long-chain branch can be with the Mooney viscosity ML and Mooney relaxation area
The ratio between MLR is evaluated, and slack time of stress relaxation (stress relaxation) and MLR are by having high score in polymer
The high molecular influence of son amount.Generally, relaxation causes MLR to reduce to the macromolecule of low molecule amount rapidly, and the high score of HMW
Son is more slowly loose, can increase MLR.Equally, in macromolecule relaxation causes MLR to reduce to single side chain rapidly, and high score
Long-chain branch in son dramatically increases molecular weight, so as to increase MLR.Therefore, the ratio between ML and MLR can be elastic as olefines is evaluated
The yardstick of levels of long chain branching in copolymer.
Mooney viscosity ML and the Mooney relaxation face of the three-dimensional elasticity copolymer of the alternative plan are derived in this way
MLR relation is accumulated, described its levels of long chain branching of three-dimensional elasticity copolymer is confirmed and is higher than the conventional group iv transition metals of use
EPDM rubber of catalyst preparation etc., can meet the relation of the general expression 1.
Especially, meet the general expression 1 three-dimensional elasticity copolymer include substantial amounts of long-chain branch, thus be adapted to extruding plus
Work, while with outstanding mechanical-physical character, the elasticity further improved and flexibility etc..On the one hand, when described one
As [MLR/ (ML) in formula 12The value of] × 100, such as general expression 1 do not reach more than 8 but notable low numerical value, when such as less than 5,
It can be considered that copolymer has the linear structure for containing substantially no side chain, and the copolymer with this linear structure is elastic and soft
Property it is not enough, therefore the problem of there is not easy processing.
In addition, its MLR/ML value of the three-dimensional elasticity copolymer of the alternative plan can be more than 3.As described above, ML and MLR
The ratio between can as the levels of long chain branching for evaluating copolymer yardstick, MLR/ML values are outstanding for more than 3 copolymer processability, suitable
In extrusion forming, and then it is the copolymer of linear structure, its processability may be poor if MLR/ML values are less than 3.
That is, the three-dimensional elasticity copolymer of described alternative plan uses as the three-dimensional elasticity copolymer of first scheme
IV group 4 transition metal catalyst preparations, to make it have outstanding productivity ratio, yield and mechanical-physical character, and include specific two
Alkene, so that with the ratio between a range of weight average molecular weight, Mooney viscosity and Mooney viscosity ML and Mooney relaxation area MLR
Value, and then the more outstanding processability needed for EPDM rubber, elasticity and flexibility etc. are shown, it is suitable as EPDM rubber.
On the one hand, the three-dimensional elasticity copolymer of the first scheme and alternative plan has expiring as EPDM rubber etc.
The Mooney viscosity ML scopes of the appropriate physical property of foot.For example, can have more than 20MU Mooney viscosity, or about 20MU is extremely
150MU or about 20MU to 130MU Mooney viscosity.If the Mooney viscosity of the three-dimensional elasticity copolymer is less than 20MU, will not
There is processability difference caused by long-chain branch etc., if it exceeds then copolymer shows high viscosity to 150MU, cause the productivity ratio of resin
Reduce, therefore economy can be deteriorated.
In addition, the three-dimensional elasticity copolymer of the first scheme and alternative plan can meet Re × Rc less than 1, it is, for example, about
0.60 to 0.99 or about 0.80 to 0.95.Wherein, Re is the reactive specific ray constant for showing the ethylene distribution state in copolymer,
Rc shows the reactive specific ray constant of the alpha-olefin distribution in copolymer.
In this characteristic value, Re=k11/k12, the Rc=k22/k21, wherein k11 are the ethene in copolymer chain
Growth response speed constant when ethene is bonded after unit, when k12 is bonded for alpha-olefin after ethylene unit in the copolymer
Growth response speed constant, k21 is normal for growth response speed when ethene is bonded after alpha-olefin unit in copolymer chain
Number, k22 is the growth response speed constant in copolymer chain when alpha-olefin after alpha-olefin unit is bonded.
By using13C-NMR analyzes each copolymer, and each growth response speed that can measure k11, k12, k21 and k22 is normal
Number.For example, analyzing [Journal of Polymer Science by the Triad Sequence based on Randall methods:
Polymer Physics edition, 1973,11,275~287] and Kakugo methods [Macromolecules1982,15,
1150] etc., by described13C-NMR analysis result can calculate the value of the Re × Rc.
The value of the Re × Rc is less than 1, illustrate in the copolymer chain the several of after ethylene unit alpha-olefin bonding
Rate is high, and the probability that ethene is bonded after alpha-olefin unit is high, and then the copolymer chain can have between ethene and alpha-olefin
It is alternately distributed.Unlike this, if the value of the Re × Rc is about 1, the copolymer chain can have each of ethene and alpha-olefin
Random distribution between monomer, if Re × Rc value is more than 1, same monomers bond together, and then the copolymer chain has
The form of block copolymer.
Re × the Rc of the three-dimensional elasticity copolymer of the first scheme and alternative plan value is less than 1, is, for example, about
0.60 to 0.99 or about 0.80 to 0.95, therefore this copolymer can show the characteristic that each monomer is equably alternately arranged, and enter
And the copolymer crystallinity is not high, more outstanding elasticity and flexibility needed for EPDM rubber etc. etc. can be shown.
On the one hand, its crystallization temperature Tc for being determined with DSC of the three-dimensional elasticity copolymer of the first scheme and alternative plan
It can be about -55 to 30 DEG C or about -40 to 15 DEG C.Now, the crystallization temperature can be by exporting DSC in method as described above
The method of average crystallization temperature is calculated after curve data to determine.Because the copolymer has the crystallization temperature of this scope,
It can show as the outstanding elasticity of EPDM rubber etc., flexibility, the processability and heat resistance further improved.If crystallization
Temperature becomes too low, and the heat resistance of the three-dimensional elasticity copolymer will be reduced.If described on the contrary, crystallization temperature is too high
Elasticity of three-dimensional elasticity copolymer etc. may be reduced.
In addition, the three-dimensional elasticity copolymer of the first scheme and alternative plan can have 2 to 6 molecular weight distribution PDI,
Can more specifically have 2~4 molecular weight distribution.The molecular weight distribution PDI represents weight average molecular weight Mw and number-average molecular weight
The ratio between Mn Mw/Mn, if the molecular weight distribution is less than 2, are difficult to import long-chain branch, processability can be reduced, if molecular weight
Distribution is more than 6, although processability is outstanding but includes the polymer of low molecule amount, and in processing, the polymer of low molecule amount is divided
From, thus surface characteristic may reduce.
Moreover, the three-dimensional elasticity copolymer of the first scheme and alternative plan can have as EPDM rubber etc. can
The density range of appropriate physical property is met, for example, can have about 0.840 to 0.895g/cm3Or about 0.850 to
0.890g/cm3Density range.
In addition, in the three-dimensional elasticity copolymer of the first scheme and alternative plan, can be used as the alpha-olefin
More than one C3~C20 alpha-olefins, C3~C20 alpha-olefins be propylene, 1- butylene, 1- octenes, 1- amylenes, 4- methyl isophthalic acids-
Amylene, 1- hexenes, 1- heptene, 1- decene, 1- endecatylenes, 1- dodecylenes, 1- tridecylenes, tetradecene, 1- 15
Carbene, cetene, 1- heptadecenes, the carbenes of 1- 19,9- methyl isophthalic acids-decene, 11- methyl isophthalic acids-dodecylene, 12- second
Base-tetradecene etc., can suitably select C wherein3~C10Alpha-olefin, typical example be propylene, 1- butylene, 1- hexenes
Or 1- octenes.
In addition, non-conjugated diene class monomer can be used in the diene.Specifically, for example, Isosorbide-5-Nitrae-hexadiene, 1,5- heptan two
Alkene, 1,6- octadienes, 1,7- nonadienes, 1,8- decadinene, the carbon diene of 1,12- 14,3- methyl isophthalic acids, 4- hexadienes, 4- methyl-
1,4- hexadienes, 5- methyl isophthalic acids, 4- hexadienes, 4- ethyl -1,4- hexadienes, 3,3- dimethyl -1,4- hexadienes, 5- methyl -
1,4- heptadiene, 5- ethyl -1,4- heptadiene, 5- methyl isophthalic acids, 5- heptadiene, 6- methyl isophthalic acids, 5- heptadiene, 5- ethyls -1,5-
Heptadiene, 4- methyl isophthalic acids, 4- octadienes, 5- methyl isophthalic acids, 4- octadienes, 4- ethyl -1,4- octadienes, 5- ethyls -1,4- pungent two
Alkene, 5- methyl isophthalic acids, 5- octadienes, 6- methyl isophthalic acids, 5- octadienes, 5- ethyl -1,5- octadienes, 6- ethyl -1,5- octadienes, 6-
Methyl isophthalic acid, 6- octadienes, 7- methyl isophthalic acids, 6- octadienes, 6- ethyl -1,6- octadienes, 6- propyl group -1,6- octadienes, 6- butyl -
1,6- octadienes, 7- methyl isophthalic acids, 6- octadienes, 4- methyl isophthalic acids, 4- nonadienes, 5- ethylidene -2- ENBs, 5- methylene -
2- ENBs, 5- (2- acrylic) -2- ENBs, 5- (3- cyclobutenyls) -2- ENBs, 5- (1- methyl -2- propylene
Base) -2- ENBs, 5- (4- pentenyls) -2- ENBs, 5- (1- methyl -3- cyclobutenyls) -2- ENBs, 5- (5- oneself
Alkenyl) -2- ENBs, 5- (1- methyl -4- pentenyls) -2- ENBs, 5- (2,3- dimethyl -3- cyclobutenyls) -2- drop
Bornylene, 5- (2- ethyl -3- cyclobutenyls) -2- ENBs, 5- (6- heptenyls) -2- ENBs, 5- (3- methyl-hexenes
Base) -2- ENBs, 5- (3,4- dimethyl -4- pentenyls) -2- ENBs, 5- (3- ethyl -4- pentenyls) -2- drop ice
Piece alkene, 5- (7- octenyls) -2- ENBs, 5- (2- methyl -6- heptenyls) -2- ENBs, 5- (1,2- dimethyl -5-
Hexenyl) -2- ENBs, 5- (5- ethyl -5- hexenyls) -2- ENBs, 5- (1,2,3- trimethyl -4- pentenyls) -
2- ENBs, 5- propylidene -2- ENBs, 5- isopropylidene -2- ENBs, 5- butylidene -2- ENBs, 5- are sub-
Isobutyl group -2- ENBs, the isopropylidene -5- ENBs of 2,3- bis-, 2- ethylidene -3- isopropylidene -5- ENBs or
Person's 2- acrylic -2,2- norbornadienes etc., and can be used selected from these more than one diene.
Especially, in these diene, it is appropriate using 5- ethylidene -2- ENBs, 5- methylene -2- ENBs or
4- hexadienes, can prepare the three-dimensional elasticity copolymer for the characteristic for meeting the first scheme and alternative plan.On the one hand, in the past
It is used as the 5- vinyl -2- ENBs (VNB) or dicyclopentadiene of diene in the preparation of three-dimensional elasticity copolymer
(DCPD) two double bonds are included, described two double bonds participate in polymerisations and show the macromolecular structure of cross-linked form, therefore
It is difficult to control to the molecular weight of copolymer in polymerization process formation gel particle, or presence and is difficult to control to the limit of polymerisation
System.
In addition, the third program of the present invention provides the three-dimensional elasticity copolymer of a kind of first scheme or alternative plan
Preparation method, including：In the presence of carbon monoxide-olefin polymeric, monomer composition is supplied into reactor and carries out combined polymerization,
Wherein described catalyst is represented comprising the First Transition metallic compound that is represented by formula 1 below and by formula 2 below
Second Transition compound, ethene of the monomer composition comprising 40 to 70 weight %, 15 to 55 weight % C3~C20
The diene of alpha-olefin and 0.5 to 20 weight %.
[chemical formula 1]
[chemical formula 2]
In the chemical formula 1 and 2,
R1To R13Be same to each other or different to each other, be separately hydrogen, C1~C20 alkyl, C2~C20 alkenyls, C6~C20 virtue
Base, silicyl, C7~C20 alkylaryls, the metalloid of C7~C20 aryl alkyls or the Group IV metal replaced by alkyl
Base, and the R1To R13In adjacent two different groups can pass through the alkylene comprising C1~C20 alkyl or C6~C20 aryl
Base is connected to each other and forms cycloaliphatic ring or aromatic rings；
M is group iv transition metals；
Q1And Q2Mutually the same or difference is separately halogen, C1~C20 alkyl, C2~C20 alkenyls, C6~
C20 aryl, C7~C20 alkylaryls, C7~C20 aryl alkyls, C1~C20 alkyl aminos, C6~C20 arylaminos or C1
~C20 alkylidene.
By following examples it has been confirmed that using the monomer of certain content, i.e. about 40 to 70 weight % or about 50 to
C3~C20 the alpha-olefins and about 0.5 to 20 weight of 70 weight % ethene, about 15 to 55 weight % or about 25 to 45 weight %
% or about 2 to 10 weight % diene is measured, and is existed in two kinds of specific transitions metallic catalysts of the chemical formula 1 and 2
Under, each monomer is polymerize with continuous polymerization technique, it becomes possible to meet the macromolecule to be obtained in high yield with high production rate
Measure the three-dimensional elasticity copolymer of scope and first scheme and the characteristic of alternative plan.
This, which is primarily due to described two special catalysts, has outstanding catalyst activity and the reaction with comonomer
Property.First and second described transistion metal compound special catalyst is shown as the outstanding of group iv transition metals catalyst
Catalyst activity, outstanding selectivity and copolymerization can be especially shown to comonomers such as alpha-olefin and diene.
Furthermore, due to using both special catalysts, diene can be made to be uniformly distributed in macromolecular chain with higher content and be total to
Polymerization.Because the special catalyst of the chemical formula 1 and 2 makes very stably to protect around metallic site by quinoline amino
Firm 5 side rings and 6 side ring structures are held, so with the easily accessible architectural characteristic of the monomer in structure.That is, described chemical formula
Architectural characteristic of 1 and 2 special catalyst based on described catalyst, tool can be formed during ethene and alpha-olefin copolymer conjunction
There is the macromonomer of the double bond of long-chain branch form, the macromonomer carries out combined polymerization with catalyst again, so as to be formed
Three-dimensional elasticity copolymer.
Moreover, due to using both first and second transistion metal compound special catalysts, and each list will be included
The monomer composition of body is fed to polymer reactor and is carried out continuously the combined polymerization, therefore the comonomer particularly diene energy
Enough it is more equally distributed in macromolecular chain.
As a result, it is possible to prepare with high production rate and in high yield, molecular weight is big and each monomer is uniformly alternately distributed, long-chain branch
The contour three-dimensional elasticity copolymer of change degree.Moreover, the three-dimensional elasticity copolymer so obtained disclosure satisfy that the first scheme and
The characteristic of alternative plan, therefore, it is possible to which there is outstanding processability and flexibility simultaneously.
Further, each content of monomer control is in optimum range, and ethene is about 40 to 70 weight % or about 50 to 70 weights
% is measured, alpha-olefin is that either about 25 to 45 weight % and diene are about 0.5 to 20 weight % or about 2 to about 15 to 55 weight %
To 10 weight %, therefore each monomer can be more uniformly alternately arranged in macromolecular chain, and institute is met so as to effectively prepare
State the three-dimensional elasticity copolymer of first scheme and the characteristic of alternative plan.
Therefore, the ternary bullet can be prepared with high production rate and in high yield according to the preparation method of the third program
Property copolymer, and this three-dimensional elasticity copolymer be adapted to group iv transition metals catalyst preparation, can meet outstanding simultaneously
Mechanical-physical character and the elasticity that further improves etc..
Simply, if without using described two special catalysts, or a kind of catalyst is only used, or beyond described
The appropriate content range of each monomer, especially content range of diene etc., then the three-dimensional elasticity copolymer finally prepared
There would not be the high molecular weight range, or first scheme and/or the characteristic of alternative plan can not be met.
On the one hand, in the preparation method of the three-dimensional elasticity copolymer of the third program, for by the chemical formula 1 and
2 first and second transistion metal compound represented are more specifically described below.
First, in the chemical formula 1 and 2, alkyl (hydrocarbyl) may refer to remove hydrogen atom from hydrocarbon
1 valency residue, the aryl such as the alkyl such as ethyl or phenyl.
Moreover, in chemical formula 1 and 2, metalloid be with metal and it is nonmetallic between middle property element, for example
It may refer to arsenic, boron, silicon or tellurium etc..Moreover, the M, the group iv transition metals element such as may refer to titanium, zirconium or hafnium.
In these first and second transistion metal compounds, as the First Transition metallic compound of the chemical formula 1,
Can be suitably from one or more of compound represented by below formula.
In the chemical formula, R2And R3Mutually the same or difference, is separately hydrogen or methyl, M is Group IV
Transition metal, Q1And Q2Mutually the same or difference is separately methyl, dimethyliminio or chlorine atom.
Moreover, as the Second Transition compound of chemical formula 2, can be suitably from the change represented by below formula formula
One or more of compound：
In the formula, R2And R3Mutually the same or difference, is separately hydrogen or methyl, and M is Group IV transition
Metal, Q1And Q2Mutually the same or difference is separately methyl, dimethyliminio or chlorine atom.
On the one hand, the carbon monoxide-olefin polymeric used in the preparation method of the third program, except described first and
Outside two transistion metal compounds, it can further include selected from the one kind represented by formula 3 below, chemical formula 4 and chemical formula 5
Cocatalyst compound above.
[chemical formula 3]
-[Al(R)-O]n-
In the chemical formula 3,
R is mutually the same or difference, is separately halogen, C1~C20 alkyl or the C1~C20 being optionally substituted by halogen
Alkyl, n is more than 2 integer.
[chemical formula 4]
D(R)3
In the chemical formula 4, to R definition chemical formula 3 as described, D is aluminium or boron.
[chemical formula 5]
[L-H]+[ZA4]-Or [L]+[ZA4]-
In the chemical formula 5, L is neutral or cation lewis acid, and H is hydrogen atom, and Z is group III A element, A
Mutually the same or difference is separately unsubstituted or one of hydrogen atom above by halogen, C1~C20 hydrocarbon
Base, alkoxy or phenoxy group substitution C6~C20 aryl or C1~C20 alkyl.
In this cocatalyst compound, it is as the compound represented by the chemical formula 3, such as methyl alumina
Alkane, ethylaluminoxane, isobutyl aluminium alkoxide or butyla-luminoxane etc..
In addition, being as the compound represented by the chemical formula 4, for example, trimethyl aluminium, triethyl aluminum, triisobutyl
Aluminium, tri-propyl aluminum, tri-butyl aluminum, dimethyl chloride are for aluminium, triisopropylaluminiuand, three sec-butyl aluminium, three cyclopenta aluminium, triisopentyl
Aluminium, three hexyl aluminium, trioctylaluminum, ethyl dimethyl aluminium, methyl diethyl aluminum, triphenyl aluminum, three p-methylphenyl aluminium, dimethyl methyl
Epoxide aluminium (dimethyl aluminium methoxide), dimethyl aluminum ethoxide, trimethyl borine, boron triethyl, three isobutyls
Base boron, tripropylborane or tri butyl boron etc., wherein, it can suitably use trimethyl aluminium, triethyl aluminum or triisobutyl aluminium.
Moreover, the compound represented by the chemical formula 5 includes the moon with the noncoordinating combination of the sour cationic-compatibles of Bu Shi
Ion.It is preferred that anion be the anion with large-size, and comprising containing metalloid single coordinate bond complex compound.Especially
It, conventional is the compound for having single boron atom in anion site.Based on this, compound is represented by the chemical formula 5
The preferably salt containing anion, the anion includes the coordinate bond complex compound with single boron atom.
As the instantiation of this compound, in the case of trialkyl ammonium salts, including (the phenyl-pentafluoride of trimethyl ammonium four
Base) borate, triethyl ammonium four (pentafluorophenyl group) borate, tripropyl ammonium four (pentafluorophenyl group) borate, three (normal-butyl) ammoniums
Four (pentafluorophenyl group) borates, three (2- butyl) ammonium four (pentafluorophenyl group) borates, N, accelerine four (pentafluorophenyl group)
Borate, N, accelerine normal-butyl three (pentafluorophenyl group) borate, N, accelerine benzyl three (pentafluorophenyl group)
Borate, N, accelerine four (4- (t-butyldimethylsilyl) -2,3,5,6- tetrafluoros phenyl) borate, N, N-
Dimethylaniline four (4- (triisopropylsilyl) -2,3,5,6- tetrafluoros phenyl) borate, N, the fluorine of accelerine five
Phenoxy group three (pentafluorophenyl group) borate, N, N- diethylanilines four (pentafluorophenyl group) borate, N, N- dimethyl -2,4,6- three
Methylaniline four (pentafluorophenyl group) borate, trimethyl ammonium four (2,3,4,6- tetrafluoros phenyl) borate, triethyl ammonium four (2,3,
4,6- tetrafluoros phenyl) borate, tripropyl ammonium four (2,3,4,6- tetrafluoros phenyl) borate, three (normal-butyl) ammoniums four (2,3,4,
6- tetrafluoros phenyl) borate, dimethyl (tert-butyl group) ammonium four (2,3,4,6- tetrafluoros phenyl) borate, N, accelerine four
(2,3,4,6- tetrafluoros phenyl) borate, N, N- diethylanilines four (2,3,4,6- tetrafluoros phenyl) borate, N, N- dimethyl-
2,4,6- trimethylanilines four (2,3,4,6- tetrafluoros phenyl) borate, dimethylammonium four (pentafluorophenyl group) borate, ten
Dialkyl dimethyl ammonium four (pentafluorophenyl group) borate, dodecyldimethylamine base ammonium four (pentafluorophenyl group) borate, cetyl
Dimethyl Ammonium four (pentafluorophenyl group) borate, octadecyldimethyl ammonium four (pentafluorophenyl group) borate, eicosyl dimethyl
Ammonium four (pentafluorophenyl group) borate, methyl didecyl ammonium four (pentafluorophenyl group) borate, (five fluorine of methyl two (dodecyl) ammonium four
Phenyl) borate, (pentafluorophenyl group) borate of methyl two (myristyl) ammonium four, (the phenyl-pentafluoride of methyl two (cetyl) ammonium four
Base) borate, (pentafluorophenyl group) borate of methyl two (octadecyl) ammonium four, methyl two (eicosyl) ammonium four (pentafluorophenyl group)
Borate, three decyl ammonium four (pentafluorophenyl group) borates, three (dodecyl) ammonium four (pentafluorophenyl group) borates, the three (tetradecanes
Base) ammonium four (pentafluorophenyl group) borate, three (cetyl) ammonium four (pentafluorophenyl group) borates, three (octadecyl) ammoniums four (five
Fluorophenyl) borate, three (eicosyl) ammonium four (pentafluorophenyl group) borates, (pentafluorophenyl group) boron of decyl two (normal-butyl) ammonium four
Hydrochlorate, (pentafluorophenyl group) borate of dodecyl two (normal-butyl) ammonium four, octadecyl two (normal-butyl) ammonium four (pentafluorophenyl group)
Borate, N, (pentafluorophenyl group) borate of N- bis- (dodecyl) anilino- four, N- methyl-N-dodecyls anilino- four (five
Fluorophenyl) borate or (pentafluorophenyl group) borate of methyl two (dodecyl) ammonium four etc..
In addition, as dialkyl ammonium salt, for example, (pentafluorophenyl group) borate of two-(isopropyl) ammonium four or dicyclohexyl
Ammonium four (pentafluorophenyl group) borate etc..
Moreover, as carbon salt, for example, Zhuo Si (pentafluorophenyl group) borate, (phenyl-pentafluoride of trityl group carbon four
Base) borate or benzene (diazo) four (pentafluorophenyl group) borate etc..
In addition, in the preparation method of described three-dimensional elasticity copolymer, including first and second transition metal
Compound and the carbon monoxide-olefin polymeric for optionally including cocatalyst compound can be prepared by the method comprised the following steps：
Make comprising first and second transistion metal compound and the co-catalyst represented by the chemical formula 3 or chemical formula 4
Compound is contacted, to obtain mixture；And the co-catalyst chemical combination represented by the chemical formula 5 is added in the mixture
Thing.
In addition, in the carbon monoxide-olefin polymeric, the First Transition metallic compound and Second Transition compound
Mol ratio can be about 10：1 to 1：10, by the total transition metal compound of first and second described transistion metal compound altogether
The mol ratio of thing and the cocatalyst compound represented by the chemical formula 3 or chemical formula 4 is about 1：5 to 1：500, it is described
The mol ratio of total transistion metal compound and the cocatalyst compound represented by the chemical formula 5 is about 1：1 to 1：10.
In the preparation method of the three-dimensional elasticity copolymer, the carbon monoxide-olefin polymeric can also include reaction dissolvent, make
It is for the reaction dissolvent, for example, the hydrocarbon solvent such as pentane, hexane or heptane；Arsol such as benzene or toluene etc., but not office
It is limited to this.
As described above, as the alpha-olefin included in the monomer composition, propylene, 1- butylene, 1- octenes, 1- can be used
Amylene, 4-methyl-1-pentene, 1- hexenes, 1- heptene, 1- decene, 1- endecatylenes or 1- dodecylenes etc., are used as described two
Non-conjugated monomer can be used in alkene.Wherein, as the monomer for being commonly used for preparing EPDM rubber, for example alpha-olefin can suitably use third
Alkene, the diene can be suitably non-using 5- ethylidene -2- ENBs, 5- methylene -2- ENBs or 4- hexadienes etc.
Conjugated diene monomer.
In the preparation method of the copolymer of the third program, the combined polymerization step can be in about 100 to 170 DEG C of temperature
Degree, or carried out at a temperature of about 100 to 160 DEG C.If the co-polymerization temperature is too low, three kinds of monomers of synthesis will be difficult to uniform
The alternatively distributed three-dimensional elasticity copolymer in ground, if polymeric reaction temperature is too high, monomer or prepared copolymer will be pyrolyzed.
Moreover, this combined polymerization can be carried out with solution polymerization process, particularly continuous solution polymerization method.Now, the catalyst combination
Thing can be used in the homogeneous catalyst form for being dissolved in this solution.
In order to carry out this continuous solution polymerization, by the monomer composition and first, second transition metal compound is included
Thing and the carbon monoxide-olefin polymeric for optionally including cocatalyst compound supply to reactor with solution state, to carry out institute
Combined polymerization step is stated, and the three-dimensional elasticity copolymer after combined polymerization is continuously discharged from reactor, so as to be carried out continuously
State combined polymerization step.
By carrying out this continuous solution polymerization, it can more effectively obtain with high production rate and in high yield and meet described the
The three-dimensional elasticity copolymer of one scheme and the characteristic of alternative plan.
As described above, can be prepared with outstanding processability according to present invention group iv transition metals catalyst and
The three-dimensional elasticity copolymer of the elasticity and flexibility that further improve etc., the three-dimensional elasticity copolymer is suitable as EPDM rubber
Deng.
Moreover, provided according to the present invention a kind of can prepare this three-dimensional elasticity copolymer with high production rate and in high yield
Copolymer preparation method.
The use metallocene system the according to known to overcoming the three-dimensional elasticity copolymer with long-chain branch that obtains of the present invention
Limitation suffered by EPDM rubber of IV group 4 transition metal catalyst preparations etc., can have outstanding elasticity and flexibility and its simultaneously
His physical property, therefore the inherent characteristicses of group iv transition metals catalyst can be played, and it is suitable as EPDM rubber etc..
Brief description of the drawings
Fig. 1 is the Mooney relaxation curve of embodiment 3 to 6 and comparative example 1 to 3.
Fig. 2 is the Mooney relaxation area MLR relative to Mooney viscosity ML of embodiment 1 to 7 and comparative example 1 to 3 chart.
Fig. 3 is with 60rpm rotor revolution number progress Jia Weimo extruding (Garvey to the copolymer prepared in embodiment 1
Die extrusion) obtained from extrudate surface picture.
Fig. 4 is that the copolymer prepared in comparative example 1 is carried out with 60rpm rotor revolution number to squeeze obtained from Jia Weimo extruding
Go out the surface picture of thing.
Fig. 5 shows the DSC curve data of the three-dimensional elasticity copolymer prepared in comparative example 1.
Fig. 6 shows the DSC curve data of the three-dimensional elasticity copolymer prepared in embodiment 9.
Fig. 7 is the acetate unit content x in the three-dimensional elasticity copolymer prepared by display embodiment 1 to 6, comparative example 1 and 4
With the chart of crystallization enthalpy y relation.
Embodiment
Invention is described in more detail in the examples below that.But, the following example be it is exemplary, invention
Content is not limited to the following example.
The following example and comparative example are under the nitrogen atmosphere of cut-out air and contact with moisture, using standard Xi Laike
(Schlenk) technology and glove box (Glove-box) technology are carried out, and for the organic solvent reacted are to use standard
What method was purified.Synthesized part and catalyst is given really using 400MHz NMR NMR and X-ray spectrometers
Recognize.
<The synthesis of part and transistion metal compound>
In the examples below that, by [(1,2,3,4- tetrahydroquinoline -8- bases) tetramethyl-ring pentadiene-η 5, κ-N] dimethyl
Titanium ([(1,2,3,4-Tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl-eta5, kapa-N]
Titanium dimethyl) and [(2 methyl indole -7- bases) tetramethyl-ring pentadiene-η 5, κ-N] dimethyl titanium ([(2-
Methylindolin-7-yl) tetramethylcyclopentadienyl-eta5, kapa-N] titanium dimethyl)
First and second transistion metal compound is used separately as, by (pentafluorophenyl group) borate of DMA four and triisobutyl
Aluminium is used as cocatalyst compound.First and second described transistion metal compound is used and Korean granted patent the 0976131st
Number the identical method of embodiment 2 and 14 prepare, and the cocatalyst compound use and Korean granted patent the 0820542nd
Number the identical method of embodiment 9 prepare.
<Embodiment 1 to 7>The preparation of the three-dimensional elasticity copolymer of ethene, propylene and 5- ethylidene -2- ENBs
The terpolymerization for being carried out continuously ethene, propylene and 5- ethylidene -2- ENBs using 2L pressure reactors is anti-
Should.It is continuously added to hexane as polymer solvent by the reactor lower part with the supply rate of 6.7kg per hour, and from reaction
Continuously extract polymeric solution out in device top.
[(1,2,3,4- tetrahydroquinoline -8- bases) tetramethyl-ring pentadiene-η 5, κ-N] dimethyl titanium and [(2- first by described in
Base indoles -7- bases) tetramethyl-ring pentadiene-η 5, κ-N] dimethyl titanium be dissolved in hexane state be used as first, second transition
Metallic compound, and reactor is added with the speed of 24 to 60 μm of ol per hour.Moreover, by (five fluorine of DMA four
Phenyl) borate is used as cocatalyst compound with the state for being dissolved in toluene, and with the speed of 105 to 270 μm of ol per hour
Add reactor.In addition, the triisobutyl aluminium is used as additional cocatalyst compound to be dissolved in the state of hexane, and
Reactor is added with the speed of 1800 to 3200 μm of ol per hour.
By vinyl monomer with per hour 890 to 900g speed, propylene monomer with per hour 450 to 550g speed, with
And 5- ethylidene -2- norbornene monomers supply to reactor with per hour 80 to 250g speed, and carry out described common
Polymerization.
When co-polymerization temperature in reactor reaches 160 DEG C or so, by the way that the supply of 5- ethylidene -2- ENBs is fast
The method control that degree once increases 0.5mL/min from 1mL/min is 130 to 160 DEG C.
Under the described conditions, combined polymerization is carried out by continuous solution polymerization, so as to continuously be made with uniform solution state
It is standby go out embodiment 1 to 7 three-dimensional elasticity copolymer, and add ethanol and terminate after polymerisation, will be continuous from reactor top
The polymeric solution of discharge is dried under reduced pressure in 60 DEG C of vacuum oven, is finally made the copolymer of embodiment 1 to 7.
<Comparative example 1 to 3>The conventional three-way elastocopolymer of ethene, propylene and 5- ethylidene -2- ENBs
Using the conventional EPDM rubber DOW Nordel4570 prepared with metallocene catalyst as comparative example 1 three-dimensional elasticity
Copolymer, using DOW Nordel4640 as the three-dimensional elasticity copolymer of comparative example 2, regard DOW Nordel4725 as comparative example
3 three-dimensional elasticity copolymer.
In the copolymer of the embodiment and comparative example, the content of each unit, the activity of catalyst, copolymer weight it is equal
Molecular weight and molecular weight distribution (PDI), it is as shown in table 1 below.Now, the weight average molecular weight of each copolymer is to use Polymer
The PL-GPC220 for being provided with three linear mixed bed columns of Laboratory companies, by 1 at a temperature of 160 DEG C, 2,4- trichloro-benzenes
It is measured as solvent and with 1.0ml/ points of flow velocity.
[table 1]
<Test example 1>Mooney viscosity and MLR are determined
Mooney viscosity and MLR are to use the mooney's viscosimeter (MV2000E of Monsanto companies according to ASTM D1646-04
Model) determine by the following method.Examination is made of pressing mold for the copolymer treated with antioxidant (Irganox 1076)
Piece is preheated one minute at 125 DEG C with 1+4+2 condition, and it is 4 minutes then to determine the Mooney viscosity time, and determines the MLR times
For 2 minutes.
MLR be rotor stop 1 second after start 2 minutes within Mooney stress relaxation integrated value, its calculating formula can by with
Lower general expression 2 is represented.
[general expression 2]
For the embodiment and each copolymer of comparative example, Mooney relaxation curve chart and the MLR/ML for ML figure
Table is shown in Fig. 1,2, and Mooney viscosity and MLR, MLR/ML ratio, value of general expression 1 etc. are shown in table 2
[table 2]
As shown in figure 1, the Mooney relaxation curve chart for confirming embodiment 3 to 6 slowly successively decreases, and comparative example 1 to 3 is steep
Drop.It follows that the copolymer of embodiment has the viscosity of the copolymer similar to comparative example, and chart bottom area is Mooney
Relaxation area increased, can guess because degree of long chain branching in macromolecule is high and the phenomenon that produces.
Especially, as shown in upper table 2, although the Mooney relaxation of embodiment 1,3,6 and comparative example 1,3 shows approximation and had
Similar viscosity, but the copolymer prepared in embodiment its Mooney relaxation area MLR value is significantly higher than comparative example, so as to
Know that the degree of long chain branching in macromolecule is high.
Moreover, from Fig. 2 and table 2 the MLR values for ML, for identical ML, embodiment 1 to 7, which is shown, to be higher than
MLR the and MLR/ML values of comparative example 1 to 3, especially, [(MLR)/(ML) of embodiment 1 to 72The value of] × 100 is more than 10, and
The value of comparative example 1 to 3 is less than 4, there is very big difference.
By this MLR/ML values for ML and the result of general expression 1, the three-dimensional elasticity of the embodiment can confirm that
Copolymer is that what is be made in the presence of special catalyst include the EPDM structures with long-chain branch of specific diene, molecular weight distribution
Also there is narrower scope for less than 3.5, and processability is outstanding, be suitable for extrusion forming, and mechanical-physical character is also very outstanding.
<Test example 2>Jia Weimo squeeze tests
Press workability have rated by Jia Weimo (Garvey Die) pressing method according to ASTM2230.It is following to prepare
Sample for Jia Weimo squeeze tests.Relative to the parts by weight of copolymer 1 00 prepared in embodiment 1,2 and comparative example 1,2,
Using the parts by weight of paraffin oil 75, the parts by weight of carbon black 125, ZnO5 parts by weight, the parts by weight of stearic acid 1, and with Farrel companies
1.6L Banburies are kneaded 6 minutes with 60rpm rotor revolution number at 100 to 120 DEG C.Moreover, by the cooperation kneaded
Thing is extruded by Jia Weimo extruders under 105 DEG C of mould temperature with 45 or 60rpm rotor revolution number, and according to
ASTM2230 evaluates surface and local edge.The Jia Weimo result of the tests of embodiment 1,2 and comparative example 1,2 are shown in table 3, and will
The surface picture of the Jia Weimo extrudates of each copolymer of embodiment 1 and comparative example 1 is shown in Fig. 3, Fig. 4.
[table 3]
Volume Changes per minute are removed in the value of length change per minute when ﹡ die swellings index is extruding.
The embodiment 1,2 is the sample with similar composition and Mooney viscosity with comparative example 1,2, is added when to this
When tieing up mould squeeze test, extruding production is similar with die swelling index as shown in upper table 3, but the surface characteristic embodiment of extrudate
1st, 2 it is significantly better than comparative example 1,2.
Moreover, can be confirmed by extrudate photo Fig. 3, Fig. 4 to embodiment 1 and comparative example 1, the surface characteristic of embodiment 1
With edge configuration compared with comparative example 1 it is evenly and smooth.
That is, the three-dimensional elasticity copolymer of described embodiment 1 and 2 includes specific diene, and uses the specific iv of the present invention
Group 4 transition metal catalyst equably imports long-chain branch, therefore with including being total to for 5- ethene -2- ENBs as diene in the past
Polymers, which is compared, shows outstanding press workability and surface characteristic.
<Embodiment 8 to 13>Prepare the three-dimensional elasticity copolymer of ethene, propylene and 5- ethylidene -2- ENBs
The terpolymerization for being carried out continuously ethene, propylene and 5- ethylidene -2- ENBs using 2L pressure reactors is anti-
Should.It is continuously added to hexane as polymer solvent by the reactor lower part with the supply rate of 7.6kg per hour, and from reaction
Continuously extract polymeric solution out in device top.
[(1,2,3,4- tetrahydroquinoline -8- bases) tetramethyl-ring pentadiene-η 5, κ-N] dimethyl titanium and [(2- first by described in
Base indoles -7- bases) tetramethyl-ring pentadiene-η 5, κ-N] dimethyl titanium be dissolved in hexane state be used as first, second transition
Metallic compound, and reactor is added with the speed of 51 to 54 μm of ol per hour.Moreover, by (five fluorine of DMA four
Phenyl) borate is used as cocatalyst compound with the state for being dissolved in toluene, and with the speed of 255 to 270 μm of ol per hour
Add reactor.In addition, the triisobutyl aluminium is used as additional cocatalyst compound to be dissolved in the state of hexane, and
Reactor is added with the speed of 4080 to 4200 μm of ol per hour.
By vinyl monomer with the speed of 950g per hour, propylene monomer with the sub- second of per hour 820 to 950g speed and 5-
Base -2- norbornene monomers supply to reactor with per hour 86 to 129g speed, and carry out the combined polymerization.
When co-polymerization temperature in reactor reaches 140 DEG C or so, by the way that the supply of 5- ethylidene -2- ENBs is fast
The method control that degree once increases 0.5mL/min from 1mL/min is 120 to 140 DEG C.
Under the described conditions, combined polymerization is carried out by continuous solution polymerization, so as to continuously be made with uniform solution state
It is standby go out embodiment 8 to 13 three-dimensional elasticity copolymer, and add ethanol and terminate after polymerisation, will be continuous from reactor top
The polymeric solution of discharge is dried under reduced pressure in 60 DEG C of vacuum oven, is finally made the copolymer of embodiment 8 to 13.
In the copolymer so obtained, the weight average molecular weight of the content of each unit, the activity of catalyst and copolymer is as follows
Table 4.Now, the weight average molecular weight of each copolymer is mixed using three line styles that are provided with of Polymer Laboratory companies
The PL-GPC220 of column, by 1 at a temperature of 160 DEG C, 2,4- trichloro-benzenes are used as solvent and are measured with 1.0ml/ points of flow velocity
's.
[table 4]
<Comparative example 1 and 4>The conventional three-way elastocopolymer of ethene, propylene and 5- ethylidene -2- ENBs
The elastocopolymer DOW Nordel4570 of the comparative example 1 are used, by another conventional EPDM rubber
Mitsui3702 is used as the three-dimensional elasticity copolymer of comparative example 4.
<Test example 3>The physical property (density and Mooney viscosity) of copolymer is evaluated
It is that 3mm, radius are 2mm that thickness will be made of press mold with the treated copolymer of antioxidant (Irganox1076)
Test piece, and measured with plum Teller scale the density of the copolymer obtained in embodiment and comparative example.Moreover, by with it is described
The identical method of test example 1, determined using mooney's viscosimeter (the MV2000E models of Monsanto companies) at 125 DEG C
The Mooney viscosity of the copolymer.Each physical property such as table 5 below so determined.
<Test example 4>Determine the relational expression of crystallization enthalpy and export acetate unit content and crystallization enthalpy
For the embodiment and the copolymer of comparative example, the models of DSC 6000 of Perkin Elmer companies are used
DSC devices are derived DSC curve data.More specifically, each copolymer sample is heated to 20 DEG C/minute of speed from about 0 DEG C
About 100 DEG C, kept at about 100 DEG C after about 2 minutes, be cooled to about -150 DEG C with about -10 DEG C/minute of speed and carry out DSC and divide
Analysis.The DSC curve data of so derived comparative example 1 and embodiment 9 are as illustrated in figures 5 and 6.
The crystallization enthalpy and average crystallization temperature (Tc of each copolymer are calculated by this DSC curve data；DEG C), and will be described flat
Equal crystallization temperature as each copolymer crystallization temperature.Crystallization temperature and crystallization enthalpy for each copolymer are shown in table 5 below.
Using the content of the ethene included in each copolymer of embodiment as x-axis, the knot that will be determined for each copolymer
Brilliant enthalpy shows the data to each copolymer as y-axis, then linear regression is carried out to these data, so as to export the ethene
Unit content x and crystallization enthalpy y relation.This relation as shown in fig. 7, in order to be compared with embodiment, comparative example 1 and 4
Data are also depicted in Fig. 7.
<Test example 5>Re × Rc measure
Use13C-NMR analyzes each copolymer of embodiment and comparative example, and each growth for measuring k11, k12, k21 and k22 is anti-
Answer speed constant.Now, used analyzer is 600MHz Bruke DRX600, and each copolymer is dissolved in into adjacent dichloro
In benzene-d4 solvents, and analyzed at 100 DEG C.
[Journal of Polymer Science are analyzed by the Triad Sequence based on Randal methods:
Polymer Physics edition, 1973,11,275~287] and Kakugo methods [Macromolecules 1982,15,
1150] etc., by described13C-NMR analysis result obtains each growth response speed constant, and be hereby based on formula Re=k11/k12,
Rc=k22/k21 has calculated Re × Rc.Table 5 below is also depicted in for Re × Rc values that each copolymer is calculated.
[table 5]
It can confirm from the table 5 and Fig. 7, copolymer its acetate unit content x and crystallization enthalpy y of embodiment 8 to 13 pass
System meets 1.55x-80.00≤y≤1.55x-75.00, especially meets y=1.55x-78.06 (R2=0.907), and Re ×
Rc values are less than 1.
Compared with embodiment, the copolymer with identical acetate unit content of comparative example 1 and 4 shows higher crystallization
Enthalpy, is unsatisfactory for 1.55x-80.00≤y≤1.55x-75.00, and Re × Rc values are more than 1.Thus the ternary of embodiment 8 to 13
Each monomer of elastocopolymer is alternately arranged in macromolecular chain to be uniformly distributed, therefore relative to acetate unit content degree of crystallization
It is low, there is outstanding elasticity and flexibility compared with comparative example.
Claims (12)
1. a kind of method for preparing three-dimensional elasticity copolymer, the three-dimensional elasticity copolymer is deposited in group iv transition metals catalyst
It is that 40 to 70 weight %, C3~C20 alpha-olefin unit contents are 15 to 55 weight % and two in the acetate unit content of lower acquisition
Alkene unit content is 0.5 to 20 weight % copolymer, and methods described includes：
In the presence of carbon monoxide-olefin polymeric, monomer composition is supplied into reactor and combined polymerization is carried out, wherein described urge
Agent composition includes the First Transition metallic compound represented by formula 1 below and represented by formula 2 below second
Transistion metal compound, the monomer composition includes 40 to 70 weight % ethene, 15 to 55 weight % C3~C20 α-alkene
The diene of hydrocarbon and 0.5 to 20 weight %,
[chemical formula 1]
[chemical formula 2]
In the chemical formula 1 and 2,
R1To R13Be same to each other or different to each other, be separately hydrogen, C1~C20 alkyl, C2~C20 alkenyls, C6~C20 aryl,
Silicyl, C7~C20 alkylaryls, the metalloid base of C7~C20 aryl alkyls or the Group IV metal replaced by alkyl,
And the R1To R13In adjacent two different groups by the alkylidene comprising C1~C20 alkyl or C6~C20 aryl that
This connects and forms cycloaliphatic ring or aromatic rings；
M is group iv transition metals；
Q1And Q2Mutually the same or difference is separately halogen, C1~C20 alkyl, C2~C20 alkenyls, C6~C20 virtue
Base, C7~C20 alkylaryls, C7~C20 aryl alkyls, C1~C20 alkyl aminos, C6~C20 arylaminos or C1~C20
Alkylidene,
I) weight average molecular weight determined with GPC is 100000 to 500000；
Ii the copolymer crystallization enthalpy y determined when) acetate unit content x and acetate unit content are x with DSC meets relational expression
1.55x-80.00≤y≤1.55x-75.00,
Wherein, the unit of the acetate unit content is that weight %, the copolymer crystallization enthalpy Δ Hc unit are J/g,
In the elastic terpolymer, the reactive specific ray constant Re and table of the ethylene unit distribution in copolymer are represented
Show that the reactive specific ray constant Rc of the alpha-olefin cell distribution state in copolymer product Re × Rc is less than 1,
Now, Re=k11/k12, Rc=k22/k21,
Growth response speed constant when k11 is bonded for ethene after the ethylene unit in copolymer chain, k12 is in the copolymer
Growth response speed constant when alpha-olefin is bonded after ethylene unit, k21 is second after the alpha-olefin unit in copolymer chain
Growth response speed constant when ethylene linkage is closed, k22 is the life in copolymer chain when alpha-olefin after alpha-olefin unit is bonded
Long reaction rate constant, and
Wherein, with 10:1 to 1:10 mol ratio uses the First Transition metallic compound and Second Transition compound.
2. the method according to claim 1 for preparing three-dimensional elasticity copolymer, wherein,
The relation is met in the range of 40 to 70 weight % whole acetate unit content.
3. the method according to claim 1 for preparing three-dimensional elasticity copolymer, wherein,
The crystallization temperature Tc of the three-dimensional elasticity copolymer determined with DSC is -55 to 30 DEG C.
4. the method according to claim 1 for preparing three-dimensional elasticity copolymer, wherein,
The Mooney viscosity ML of the three-dimensional elasticity copolymer is more than 20MU.
5. the method according to claim 1 for preparing three-dimensional elasticity copolymer, the three-dimensional elasticity copolymer has 0.840
To 0.895g/cm3Density.
6. the method according to claim 1 for preparing three-dimensional elasticity copolymer, the three-dimensional elasticity copolymer has 2 to 4
Molecular weight distribution.
7. the method according to claim 1 for preparing three-dimensional elasticity copolymer, wherein,
The First Transition metallic compound is selected from one or more of compound for being represented by below formula,
In the chemical formula, R2And R3Mutually the same or difference, is separately hydrogen or methyl, and M is Group IV transition
Metal, Q1And Q2Mutually the same or difference is separately methyl, dimethyliminio or chlorine atom.
8. the method according to claim 1 for preparing three-dimensional elasticity copolymer, wherein,
The Second Transition compound is selected from one or more of compound for being represented by below formula,
In the chemical formula, R2And R3Mutually the same or difference, is separately hydrogen or methyl, and M is Group IV transition
Metal, Q1And Q2Mutually the same or difference is separately methyl, dimethyliminio or chlorine atom.
9. the method according to claim 1 for preparing three-dimensional elasticity copolymer, wherein,
The carbon monoxide-olefin polymeric also include be selected from represented by formula 3 below, chemical formula 4 and chemical formula 5 more than one
Cocatalyst compound,
[chemical formula 3]
-[Al(R)-O]n-
In the chemical formula 3,
R is mutually the same or difference, is separately halogen, C1~C20 alkyl or the C1~C20 hydrocarbon being optionally substituted by halogen
Base, n is more than 2 integer；
[chemical formula 4]
D(R)3
In the chemical formula 4, to R definition chemical formula 3 as described, D is aluminium or boron；
[chemical formula 5]
[L-H]+[ZA4]-Or [L]+[ZA4]-
In the chemical formula 5, L is neutral or cation lewis acid, and H is hydrogen atom, and Z is Group IIIA element, A phases each other
Same or difference is separately the hydrogen atom more than unsubstituted or one of by halogen, C1~C20 alkyl, alcoxyl
Base or the C6~C20 aryl or C1~C20 alkyl of phenoxy group substitution.
10. the method according to claim 1 for preparing three-dimensional elasticity copolymer, wherein,
The alpha-olefin is that, selected from one or more of propylene, 1- butylene, 1- hexenes and 1- octenes, the diene is sub- selected from 5-
One or more of ethyl -2- ENBs, 5- methylene -2- ENBs and 1,4- hexadienes.
11. the method according to claim 9 for preparing three-dimensional elasticity copolymer, wherein,
The monomer composition, the first and second transistion metal compounds and cocatalyst compound are connected with solution state
It is continuous to be fed to reactor and carry out combined polymerization.
12. the method according to claim 11 for preparing three-dimensional elasticity copolymer, wherein,
The three-dimensional elasticity copolymer of combined polymerization is continuously discharged from reactor, and is carried out continuously the combined polymerization step.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020130075873A KR101585204B1 (en) | 2013-06-28 | 2013-06-28 | Elastic diene terpolymer and preparation method thereof |
| KR10-2013-0075873 | 2013-06-28 | ||
| KR1020130086216A KR101585206B1 (en) | 2013-07-22 | 2013-07-22 | Elastic diene terpolymer and preparation method thereof |
| KR10-2013-0086216 | 2013-07-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104250332A CN104250332A (en) | 2014-12-31 |
| CN104250332B true CN104250332B (en) | 2017-07-25 |
Family
ID=52185602
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410307132.9A Active CN104250332B (en) | 2013-06-28 | 2014-06-30 | Three-dimensional elasticity copolymer containing diene and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104250332B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101950462B1 (en) * | 2016-02-24 | 2019-02-20 | 주식회사 엘지화학 | Olefin polymer and preparation method thereof |
| CN109641990B (en) * | 2016-07-13 | 2022-08-19 | 埃克森美孚化学专利公司 | Dual metallocene catalyst copolymer compositions |
| KR102419481B1 (en) * | 2019-02-20 | 2022-07-12 | 주식회사 엘지화학 | Olefin based polymer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0521908B1 (en) * | 1990-03-20 | 1996-07-03 | Exxon Chemical Patents Inc. | Catalyst system of enhanced productivity |
| CN1224433A (en) * | 1996-05-03 | 1999-07-28 | Dsm有限公司 | Process for preparing terpolymers of ethylene, alpha-olefins and diolefins |
| CN1254350A (en) * | 1997-04-30 | 2000-05-24 | 唐化学原料公司 | Ethylene/alpha-olefin/diene interpolymers and their preparation |
| CN102482366A (en) * | 2009-07-01 | 2012-05-30 | Lg化学株式会社 | Method for producing an elastomer using a transition metal catalyst |
-
2014
- 2014-06-30 CN CN201410307132.9A patent/CN104250332B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0521908B1 (en) * | 1990-03-20 | 1996-07-03 | Exxon Chemical Patents Inc. | Catalyst system of enhanced productivity |
| CN1224433A (en) * | 1996-05-03 | 1999-07-28 | Dsm有限公司 | Process for preparing terpolymers of ethylene, alpha-olefins and diolefins |
| CN1254350A (en) * | 1997-04-30 | 2000-05-24 | 唐化学原料公司 | Ethylene/alpha-olefin/diene interpolymers and their preparation |
| CN102482366A (en) * | 2009-07-01 | 2012-05-30 | Lg化学株式会社 | Method for producing an elastomer using a transition metal catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104250332A (en) | 2014-12-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5133050B2 (en) | Catalyst composition comprising a shuttling agent for forming an ethylene multiblock copolymer | |
| CN1954005B (en) | Catalyst composition comprising shuttling agent for ethylene multi-block copolymer formation | |
| JP5159302B2 (en) | Catalyst composition comprising a shuttling agent for forming an ethylene copolymer | |
| KR100738851B1 (en) | Process for producing olefin polymers | |
| JP5587279B2 (en) | Catalyst composition comprising a shuttling agent for forming an ethylene multiblock copolymer | |
| WO2014209085A1 (en) | Ternary elastomeric copolymer comprising diene and method for preparing same | |
| JP7238116B2 (en) | Olefin polymerization catalyst | |
| KR101585206B1 (en) | Elastic diene terpolymer and preparation method thereof | |
| KR101391692B1 (en) | Elastic terpolymer and preparation method thereof | |
| WO2014209084A1 (en) | Trinary elastic copolymer comprising diene and method for preparing same | |
| KR20180033008A (en) | Olefin based copolymer and preparation method thereof | |
| CN112105655A (en) | Adhesive compositions comprising ethylene/alpha-olefin copolymers | |
| CN104250332B (en) | Three-dimensional elasticity copolymer containing diene and preparation method thereof | |
| KR20130046408A (en) | Polyolefin with multi-modal molecular weight distributions and pipe comprising the same | |
| KR20150121595A (en) | Elastic diene terpolymer and preparation method thereof | |
| KR101585204B1 (en) | Elastic diene terpolymer and preparation method thereof | |
| KR20190025438A (en) | Ethylene/alpha-olefin copolymer and method for preparing the same | |
| KR20190073264A (en) | Olefin polymer, method for preparing olefin polymer, and film using the same | |
| KR101792934B1 (en) | Olefin-based elastomer | |
| KR20210070816A (en) | Catalyst composition and process for preparation of polyethylene using the same | |
| KR101476374B1 (en) | Elastic diene terpolymer and preparation method thereof | |
| WO2014209082A1 (en) | Trinary elastic copolymer comprising diene and method for preparing same | |
| KR101680831B1 (en) | Elastic diene terpolymer and preparation method thereof | |
| KR20190029064A (en) | Ethylene/alpha-olefin copolymer | |
| KR101660480B1 (en) | Elastic diene terpolymer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |