CN104250332A - Ternary Elastomeric Copolymer Comprising Diene And Method For Preparing Same - Google Patents
Ternary Elastomeric Copolymer Comprising Diene And Method For Preparing Same Download PDFInfo
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Abstract
The present invention relates to a ternary elastomeric copolymer having a long-chain branch, obtained in the presence of a group IV transition metal catalyst, and capable of achieving both excellent processability and excellent elasticity (flexibility), and a method for preparing the same. The ternary elastomeric copolymer is a copolymer of 40-70% by weight of ethylene, an 15-55% by weight of alpha-olefin having 3 to 20 carbon atoms, and a 0.5-20% by weight of diene, and i) has a weight average molecular weight of 100,000 to 500,000, measured by GPC; and ii) is characterized in that the Mooney viscosity ML and a Mooney relaxation area MLR measured by a Mooney viscometer(1+4+2@125 DEG C) can satisfy a specific relationship.
Description
Technical field
The present invention relates to a kind of three-dimensional elasticity multipolymer and preparation method thereof, described three-dimensional elasticity multipolymer is the multipolymer of ethene, alpha-olefin and diene.In more detail, the present invention relates to one and can have elasticity terpolymer of processibility and elasticity (flexibility) and preparation method thereof simultaneously.
Background technology
EPDM rubber is the three-dimensional elasticity multipolymer of the diene such as the alpha-olefin such as ethene, propylene and the norbornylene containing ethylidene, it has molecular structure main chain not having unsaturated link(age), and has the feature that weathering resistance, chemical resistant properties and thermotolerance etc. be better than conventional conjugated diolefine.Owing to having this feature, described EPDM rubber-like three-dimensional elasticity multipolymer is widely used in the Industrial materials such as various auto parts material, electric wire material, building and various flexible pipe, packing ring, travelling belt, collision bumper or mixed plastic.
In the past, the three-dimensional elasticity multipolymers such as this EPMD rubber mainly used the catalyzer containing vanadium compound, such as vanadium system Ziegler-Natta catalyst, were made by three kinds of monomer copolymerizations.But because the catalytic activity of this vanadium system Ziegler-Natta catalyst is lower, need to use excessive catalyzer, result causes the residual metal content in multipolymer to uprise.Therefore, need after preparing multipolymer to carry out catalyzer removal and decolorization etc., and because catalyst residue is in resin, there will be thermotolerance and be deteriorated, produce impurity or hinder the problems such as vulcanization reaction.In addition, when using the described catalyzer containing vanadium compound to prepare three-dimensional elasticity multipolymer, due to low polymerization activity and low temperature polymerization condition, wayward temperature of reaction, and the absorbed dose of the comonomer such as wayward propylene and diene, and then be difficult to the molecular structure controlling multipolymer.Therefore, when using vanadium series catalyst, the elastocopolymer that preparation has various physical properties has limitation.For this reason, a kind of IV group 4 transition metal catalyzer of metallocene system that uses of research and development substitutes vanadium system Ziegler-Natta catalyst to prepare the method for the three-dimensional elasticity multipolymers such as EPDM rubber recently.
This IV group 4 transition metal catalyzer demonstrates high polymerization activity in olefin polymerization, the polymkeric substance that molecular weight is larger can not only be prepared, and be easy to control the molecular weight distribution of multipolymer and composition etc., also there is the advantage that various comonomer can be made to close.Such as, disclose the multiple metallocene class IV group 4 transition metal catalyzer using and obtained by parts such as cyclopentadienyl, indenyl or fluorenyls in No. 5229478th, United States Patent (USP), No. 6545088th, United States Patent (USP) and No. 0488833rd, Korean granted patent etc., the three-dimensional elasticity multipolymer with macromolecule can be obtained with outstanding polymerization activity.
But, if use this IV group 4 transition metal catalyzer in the past to carry out copolymerization to three kinds of monomers, just there will be because alpha-olefin is to the hyperergy of comonomer, by the repeating unit of each monomer derived shortcoming pockety in copolymer chain.As a result, the three-dimensional elasticity multipolymers such as the EPDM rubber with outstanding elasticity and flexibility etc. are difficult to obtain.
Therefore, need to continue research and development a kind of can meet outstanding processibility, mechanical-physical character and elasticity (flexibility) simultaneously three-dimensional elasticity multipolymer and can with high productivity and the preparation method preparing three-dimensional elasticity multipolymer with high yield.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of three-dimensional elasticity multipolymer that simultaneously can meet outstanding processibility and elasticity (flexibility).
The present invention also aims to provide a kind of method can preparing described three-dimensional elasticity multipolymer with high productivity.
The invention provides a kind of three-dimensional elasticity multipolymer, this three-dimensional elasticity multipolymer be IV group 4 transition metal catalyzer exist under obtain acetate unit content be 40 to 70 % by weight, C3 ~ C20 alpha-olefin unit content be 15 to 55 % by weight and diene units content be 0.5 to 20 % by weight multipolymer
I) with GPC measure weight-average molecular weight be 100000 to 500000;
Ii) multipolymer crystallization enthalpy (Δ Hc, the J/g) y that when acetate unit content (% by weight) x and acetate unit content are x, DSC measures meets relational expression 1.55x-80.00≤y≤1.55x-75.00.
The present invention also provides a kind of three-dimensional elasticity multipolymer, this three-dimensional elasticity multipolymer be IV group 4 transition metal catalyzer exist under obtain acetate unit content be 40 to 70 % by weight, C3 ~ C20 alpha-olefin unit content be 15 to 55 % by weight and diene units content be 0.5 to 20 % by weight multipolymer
I) with GPC measure weight-average molecular weight be 100000 to 500000;
Ii) the mooney viscosity ML measured with mooney's viscosimeter (1+4+2125 DEG C) and Mooney relaxation area MLR 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 multipolymer, comprising:
Under catalyst composition exists, monomer composition is supplied to reactor and carries out copolymerization, wherein said catalyst composition comprises the First Transition metallic compound represented by following chemical formula 1 and the Second Transition compound represented by following chemical formula 2, described monomer composition comprise the ethene of 40 to 70 % by weight, C3 ~ C20 alpha-olefin of 15 to 55 % by weight and 0.5 to 20 % by weight diene
[chemical formula 1]
[chemical formula 2]
In described chemical formula 1 and 2,
R
1to R
13being same to each other or different to each other, is separately hydrogen, C1 ~ C20 alkyl, C2 ~ C20 thiazolinyl, C6 ~ C20 aryl, silyl, C7 ~ C20 alkylaryl, C7 ~ C20 arylalkyl or the metalloid base of IV race metal that replaced by alkyl, and described R
1to R
13in two adjacent different groups be connected to each other by the alkylidene group comprising C1 ~ C20 alkyl or C6 ~ C20 aryl and form cycloaliphatic ring or aromatic nucleus;
M is IV group 4 transition metal;
Q
1and Q
2mutually the same or different, be separately halogen, C1 ~ C20 alkyl, C2 ~ C20 thiazolinyl, C6 ~ C20 aryl, C7 ~ C20 alkylaryl, C7 ~ C20 arylalkyl, C1 ~ C20 alkylamino, C6 ~ C20 arylamino or C1 ~ C20 alkylidene.
Below, will describe in detail according to three-dimensional elasticity multipolymer of specific embodiment of the invention scheme and preparation method thereof.
First, when not having other to illustrate, in this specification sheets, term " three-dimensional elasticity multipolymer " refers to any elastocopolymer (such as, crosslinkable random copolymers) of ethene, C3 ~ C20 alpha-olefin and diene three kinds of monomer copolymerizables.As the exemplary of this " three-dimensional elasticity multipolymer ", such as, the multipolymer EPDM rubber of ethene, propylene and diene.Just, this " three-dimensional elasticity multipolymer " not only refers to the multipolymer of three kinds of monomers, and can comprise described ethene, belongs to more than one monomers of alpha-olefin category and belong to any elastocopolymer of more than one monomer copolymerizables of diene category.Such as, ethene, comprise propylene and 1-butylene two kinds of alpha-olefins and containing the norbornylene and 1 of ethylidene, the elastocopolymer of two kinds of diene copolymerization of 4-hexadiene, namely ethene and belong to the multipolymer of three kinds of monomer copolymerizables of alpha-olefin and diene category respectively, therefore belongs to the category of described " three-dimensional elasticity multipolymer ".
First scheme of the present invention provides a kind of three-dimensional elasticity multipolymer, this three-dimensional elasticity multipolymer be IV group 4 transition metal catalyzer exist under obtain acetate unit content be 40 to 70 % by weight, C3 ~ C20 alpha-olefin unit content be 15 to 55 % by weight and diene units content be 0.5 to 20 % by weight multipolymer
I) with GPC measure weight-average molecular weight be 100000 to 500000;
Ii) multipolymer crystallization enthalpy (Δ Hc, the J/g) y that when acetate unit content (% by weight) x and acetate unit content are x, DSC measures meets relational expression 1.55x-80.00≤y≤1.55x-75.00.
Alternative plan of the present invention provides a kind of three-dimensional elasticity multipolymer, this three-dimensional elasticity multipolymer be IV group 4 transition metal catalyzer exist under obtain acetate unit content be 40 to 70 % by weight, C3 ~ C20 alpha-olefin unit content be 15 to 55 % by weight and diene units content be 0.5 to 20 % by weight multipolymer
I) with GPC measure weight-average molecular weight be 100000 to 500000;
Ii) the mooney viscosity ML measured with mooney's viscosimeter (1+4+2125 DEG C) and Mooney relaxation area MLR meets following general expression 1,
[general expression 1]
[MLR/(ML)
2]×100≥8。
The three-dimensional elasticity multipolymer of described first and second schemes is ethene, alpha-olefin and diene three kinds of monomers form with the copolymerization of regulation content range, there is larger weight-average molecular weight, be about 100000 to 500000 or be about 150000 to 400000 by the weight-average molecular weight that GPC measures.Weight-average molecular weight large is like this based on IV group 4 transition metal catalyzer (such as, belong to first and second transistion metal compound of the following chemical formula 1 and 2 of metallocene system) outstanding activity reach, the three-dimensional elasticity multipolymer of the first and second schemes is owing to having this macromolecule, described three-dimensional elasticity multipolymer, such as EPDM rubber can demonstrate outstanding mechanical-physical character.
And, in these embodiments, multipolymer crystallization enthalpy (the Δ Hc that when acetate unit content (% by weight) x of the three-dimensional elasticity multipolymer of first scheme and acetate unit content are x, DSC measures; J/g) y such as meets relational expression 1.55x-80.00≤y≤1.55x-75.00, can meet relational expression y ≈ 1.55x-78.06 further particularly.
Meet the three-dimensional elasticity multipolymer of the first scheme of described relational expression, its degree of crystallinity is not too high relative to comprised acetate unit content, can be in optimum range.As mentioned above, due to first scheme three-dimensional elasticity multipolymer be in optimum range relative to the degree of crystallinity of acetate unit content, described three-dimensional elasticity multipolymer can have outstanding mechanical-physical character and the elasticity improved further and flexibility etc. simultaneously.Therefore, the three-dimensional elasticity multipolymer of described first scheme, such as can make with the distinctive outstanding productivity of IV group 4 transition metal catalyzer of metallocene system and yield, not only there is macromolecule and consequent outstanding mechanical-physical character, and solve the problem had with EPDM rubber in the past prepared by the IV group 4 transition metal catalyzer of metallocene system, thus outstanding elasticity and flexibility can be had simultaneously.
Relation between the described acetate unit content x of the three-dimensional elasticity multipolymer of first scheme and crystallization enthalpy y measures by following methods.First, in the content range of described each monomer, be polymerized and prepare the two or more three-dimensional elasticity multipolymers that acetate unit content is different, then utilize for each multipolymer the dsc measurement devices such as the DSC6000 of PerkinElmer company to derive DSC curve data.This DSC curve data such as can be derived with the form of Fig. 6.When deriving this DSC curve data, by each copolymer sample with the heating rate of about 0 DEG C to 20 DEG C/minute extremely about 100 DEG C, keep about 2 minutes at such a temperature, be then cooled to-150 DEG C with the speed of about-10 DEG C/minute and carry out dsc analysis.Described crystallization enthalpy can be tried to achieve by the DSC curve data of so deriving, and average crystallization temperature (Tc can be calculated; DEG C).
Using the acetate unit content that comprises in each multipolymer as x-axis, and using the crystallization enthalpy that measures for these each multipolymers as y-axis, indicate the data for each multipolymer, then linear regression analysis is carried out to these data, to derive the relation of described acetate unit content x and crystallization enthalpy y.The relation of described x and y as shown in Figure 7.
Relation between x and y being derived the three-dimensional elasticity multipolymer of first scheme by this method, result show this three-dimensional elasticity multipolymer with the EPDM rubber phase ratio using IV group 4 transition metal catalyst preparing in the past, be in lower level relative to the crystallization enthalpy of acetate unit content, relational expression y≤1.55x-75.00 can be met.The three-dimensional elasticity multipolymer confirming described first scheme thus can have the mechanical-physical character of the excellence based on macromolecule, outstanding elasticity and flexibility etc. simultaneously.Therefore, described three-dimensional elasticity multipolymer uses IV group 4 transition metal catalyzer to be prepared into have outstanding productivity, yield and mechanical-physical character, and the more outstanding elasticity shown needed for EPDM rubber and flexibility etc., be suitable as very much described EPDM rubber etc.Moreover, described three-dimensional elasticity multipolymer meets relational expression 1.55x-80.00≤y≤1.55x-75.00, meet relative to the crystallization enthalpy more than minimum level of acetate unit content, thus the suitable mechanical-physical character that can show needed for EPDM rubber and thermotolerance etc.Therefore, the three-dimensional elasticity multipolymer of described first scheme is very suitable for preparing with IV group 4 transition metal catalyzer.
In a preferred approach, the three-dimensional elasticity multipolymer of described first scheme is as EPDM rubber etc., within the scope of the total content of monomeric unit that can show suitable physical properties, such as ethylene unit is about 40 to 70 % by weight or about 50 to 70 % by weight, C3 ~ C20 alpha-olefin unit be about 15 to 55 % by weight or about 25 to 45 % by weight and diene units be within the scope of the total content of about 0.5 to 20 % by weight or about 2 to 10 % by weight, described acetate unit content and the particular kind of relationship of crystallization enthalpy can be met.Thus, described three-dimensional elasticity multipolymer can have more outstanding elasticity and flexibility etc. as EPDM rubber.If exceed the content range of this each monomer, just cannot have the suitable physical properties as EPDM rubber, or described acetate unit content and the particular kind of relationship of crystallization enthalpy cannot be met.
In addition, the three-dimensional elasticity multipolymer of alternative plan, its mooney viscosity ML measured with mooney's viscosimeter (1+4+2125 DEG C) and Mooney relaxation area MLR can meet following general expression 1, and the predetermined relationship between the acetate unit content of first scheme described in not according to and crystallization enthalpy.
[general expression 1]
[MLR/(ML)
2]×100≥8
In described general expression 1, ML is mooney viscosity, and MLR is the integrated value starting the Mooney stress relaxation within 2 minutes after rotor stops 1 second, and its calculating formula can be represented by following general expression 2.
[general expression 2]
Meet the three-dimensional elasticity multipolymer of the described alternative plan of these relations, especially can demonstrate high levels of long chain branching ratio.As mentioned above, described three-dimensional elasticity multipolymer comprises a large amount of long-chain branchs, thus can have outstanding mechanical-physical character, the elasticity improved further and flexibility etc. simultaneously.
Therefore, the three-dimensional elasticity multipolymer of described alternative plan also can be prepared with distinctive outstanding productivity and yield under the existence of IV group 4 transition metal catalyzer belonging to metallocene system, not only there is macromolecule and consequent outstanding mechanical-physical character, and solve in the past by the problem that the EPDM rubber of metallocene system IV group 4 transition metal catalyst preparing has, thus outstanding elasticity and flexibility can be had simultaneously.Therefore, according to the three-dimensional elasticity multipolymer of alternative plan, the EPDM rubber of IV group 4 transition metal catalyst preparing is also suitable as.
Described mooney viscosity (ML) and the Mooney relaxation area (MLR) of the three-dimensional elasticity multipolymer of this alternative plan measure by following method.First, be polymerized and prepare three-dimensional elasticity multipolymer, then for each multipolymer, such as, the mooney's viscosimeters such as the MV2000 of Monsanto company can be used to measure mooney viscosity ML and Mooney relaxation area MLR, and these relation chart can be derived, as Mooney relaxation curve etc.This chart can be the form as shown in Fig. 1 and Fig. 2 etc.
Particularly, described mooney viscosity ML, Mooney relaxation area MLR and relation chart thereof, measure by following method and derive.Utilize pressing mold to make test piece with each multipolymer of oxidation inhibitor process, the condition with 1+4+2 at 125 DEG C processes test piece, to measure mooney viscosity ML and Mooney relaxation area MLR.That is, by test piece preheating 1 minute, then measuring the mooney viscosity ML time is 4 minutes, and to measure the Mooney relaxation area MLR time be 2 minutes, thus can derive the relation chart of mooney viscosity ML and Mooney relaxation area MLR.
In the multipolymer of alternative plan, the content of long-chain branch can be evaluated with described mooney viscosity ML and the ratio of Mooney relaxation area MLR, and time of relaxation and the MLR of stress relaxation (stress relaxation) are subject to the high molecular impact in polymkeric substance with high molecular.Usually, low-molecular-weight polymer is lax rapidly causes MLR to reduce, and the polymer of high molecular is comparatively slowly lax, and MLR can be made to increase.Equally, the single side chain in polymer is lax rapidly causes MLR to reduce, and the long-chain branch in polymer significantly increases molecular weight, thus can increase MLR.Therefore, the ratio of ML and MLR can be used as the yardstick of the levels of long chain branching evaluated in olefines elastocopolymer.
In this way be derived the mooney viscosity ML of the three-dimensional elasticity multipolymer of described alternative plan and the relation of Mooney relaxation area MLR, confirm the EPDM rubber etc. of described its levels of long chain branching of three-dimensional elasticity multipolymer higher than the IV group 4 transition metal catalyst preparing used in the past, the relation of described general expression 1 can be met.
Especially, the three-dimensional elasticity multipolymer meeting described general expression 1 comprises a large amount of long-chain branchs, is thus applicable to extrusion processing, and has outstanding mechanical-physical character, the elasticity improved further and flexibility etc. simultaneously.On the one hand, as [MLR/ (ML) in described general expression 1
2the value of] × 100, as general expression 1 does not reach more than 8 but significantly low numerical value, such as lower than 5 time, can be considered that multipolymer has the linear structure substantially not comprising side chain, and there is multipolymer elasticity and the flexibility deficiency of this linear structure, therefore there is the problem of not easily processing.
In addition, its MLR/ML value of three-dimensional elasticity multipolymer of described alternative plan can be more than 3.As mentioned above, the ratio of ML and MLR can be used as the yardstick of the levels of long chain branching evaluating multipolymer, MLR/ML value be more than 3 multipolymer processibility outstanding, be suitable for extrusion molding, if and MLR/ML value is lower than 3, be then the multipolymer of linear structure, its processibility may be poor.
Namely, the three-dimensional elasticity multipolymer of described alternative plan is the same with the three-dimensional elasticity multipolymer of first scheme, use IV group 4 transition metal catalyst preparing, to make it have outstanding productivity, yield and mechanical-physical character, and comprise specific diene, thus there is the ratio of the weight-average molecular weight of certain limit, mooney viscosity and mooney viscosity ML and Mooney relaxation area MLR, and then more outstanding processibility, elasticity and the flexibility etc. that demonstrate needed for EPDM rubber, be suitable as EPDM rubber.
On the one hand, the three-dimensional elasticity multipolymer of described first scheme and alternative plan has the mooney viscosity ML scope meeting suitable physical properties as EPDM rubber etc.Such as, the mooney viscosity of more than 20MU can be had, or the mooney viscosity of about 20MU to 150MU or about 20MU to 130MU.If the mooney viscosity of described three-dimensional elasticity multipolymer, lower than 20MU, there will not be the processibility difference that long-chain branch etc. causes, if more than 150MU, multipolymer display high viscosity, cause the productivity of resin to reduce, therefore economy can be deteriorated.
In addition, the three-dimensional elasticity multipolymer of described first scheme and alternative plan can meet Re × Rc and be less than 1, such as, be about 0.60 to 0.99 or about 0.80 to 0.95.Wherein, Re is the reactive specific ray constant of the ethylene distribution state in display multipolymer, and Rc shows the reactive specific ray constant of the alpha-olefin distribution in multipolymer.
In this characteristic value, described Re=k11/k12, Rc=k22/k21, wherein k11 is the growth response rate constant in copolymer chain after ethylene unit during ethene bonding, k12 is the growth response rate constant in the copolymer after ethylene unit during alpha-olefin bonding, k21 is the growth response rate constant in copolymer chain after alpha-olefin unit during ethene bonding, and k22 is the growth response rate constant in copolymer chain after alpha-olefin unit during alpha-olefin bonding.
By using
13c-NMR analyzes each multipolymer, can measure each growth response rate constant of k11, k12, k21 and k22.Such as, [Journal of Polymer Science:Polymer Physics edition, 1973 are analyzed by the Triad Sequence based on Randall method, 11,275 ~ 287] and Kakugo method [Macromolecules1982,15,1150] etc., by described
13the analytical results of C-NMR can calculate the value of described Re × Rc.
The value of described Re × Rc is less than 1, and illustrate that the probability of alpha-olefin bonding after ethylene unit in described copolymer chain is high, after alpha-olefin unit, the probability of ethene bonding is high, and then described copolymer chain can have being alternately distributed between ethene and alpha-olefin.Unlike this, if the value of described Re × Rc is about 1, described copolymer chain can have the random distribution between ethene and each monomer of alpha-olefin, if the value of Re × Rc is greater than 1, same monomers bonds together, and then described copolymer chain has the form of segmented copolymer.
The value of the described Re × Rc of the three-dimensional elasticity multipolymer of described first scheme and alternative plan is less than 1, be such as about 0.60 to 0.99 or about 0.80 to 0.95, therefore this multipolymer can demonstrate the characteristic that each monomer is alternately arranged equably, and then described multipolymer degree of crystallinity is not high, required more outstanding elasticity and the flexibilities etc. such as EPDM rubber can be demonstrated.
On the one hand, described first scheme and alternative plan three-dimensional elasticity multipolymer its with DSC measure Tc Tc can be about-55 to 30 DEG C or about-40 to 15 DEG C.Now, described Tc is by measuring with the method calculating average crystallization temperature after method derivation DSC curve data as above.Because described multipolymer has the Tc of this scope, outstanding elasticity, flexibility, the processibility improved further and the thermotolerance as EPDM rubber etc. can be demonstrated.If Tc becomes too low, the thermotolerance of described three-dimensional elasticity multipolymer will reduce.On the contrary, if Tc is too high, the elasticity etc. of described three-dimensional elasticity multipolymer just may reduce.
In addition, the three-dimensional elasticity multipolymer of described first scheme and alternative plan can have the molecular weight distribution PDI of 2 to 6, more specifically can have the molecular weight distribution of 2 ~ 4.Described molecular weight distribution PDI represents the ratio Mw/Mn of weight-average molecular weight Mw and number-average molecular weight Mn, if described molecular weight distribution is lower than 2, then be difficult to import long-chain branch, processibility can reduce, if molecular weight distribution is more than 6, although processibility is outstanding but comprise low-molecular-weight polymkeric substance, adding, man-hour low-molecular-weight polymkeric substance is separated, and thus surface property may reduce.
Such as, and the three-dimensional elasticity multipolymer of described first scheme and alternative plan can have the density range that can meet suitable physical properties as EPDM rubber etc., can have about 0.840 to 0.895g/cm
3or about 0.850 to 0.890g/cm
3density range.
In addition, in the three-dimensional elasticity multipolymer of described first scheme and alternative plan, more than one C3 ~ C20 alpha-olefins can be used as described alpha-olefin, described C3 ~ C20 alpha-olefin is propylene, 1-butylene, 1-octene, 1-amylene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-decene, 1-undecylene, 1-dodecylene, 1-tridecylene, tetradecene, 1-15 carbene, cetene, 1-heptadecene, 1-19 carbene, 9-methyl isophthalic acid-decene, 11-methyl isophthalic acid-dodecylene, 12-ethyl-tetradecene etc., suitably can select C wherein
3~ C
10alpha-olefin, typical example is propylene, 1-butylene, 1-hexene or 1-octene.
In addition, described diene can use non-conjugated diene class monomer.Particularly, such as, Isosorbide-5-Nitrae-hexadiene, 1,5-heptadiene, 1,6-octadiene, 1,7-nonadiene, 1,8-decadiene, 1,12-14 carbon diene, 3-methyl isophthalic acid, 4-hexadiene, 4-methyl isophthalic acid, 4-hexadiene, 5-methyl isophthalic acid, 4-hexadiene, 4-ethyl-Isosorbide-5-Nitrae-hexadiene, 3,3-dimethyl-Isosorbide-5-Nitrae-hexadiene, 5-methyl isophthalic acid, 4-heptadiene, 5-ethyl-Isosorbide-5-Nitrae-heptadiene, 5-methyl isophthalic acid, 5-heptadiene, 6-methyl isophthalic acid, 5-heptadiene, 5-ethyl-1,5-heptadiene, 4-methyl isophthalic acid, 4-octadiene, 5-methyl isophthalic acid, 4-octadiene, 4-ethyl-Isosorbide-5-Nitrae-octadiene, 5-ethyl-Isosorbide-5-Nitrae-octadiene, 5-methyl isophthalic acid, 5-octadiene, 6-methyl isophthalic acid, 5-octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene, 6-methyl isophthalic acid, 6-octadiene, 7-methyl isophthalic acid, 6-octadiene, 6-ethyl-1,6-octadiene, 6-propyl group-1,6-octadiene, 6-butyl-1,6-octadiene, 7-methyl isophthalic acid, 6-octadiene, 4-methyl isophthalic acid, 4-nonadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-(2-propenyl)-2-norbornylene, 5-(3-butenyl)-2-norbornylene, 5-(1-methyl-2-propenyl)-2-norbornylene, 5-(4-pentenyl)-2-norbornylene, 5-(1-methyl-3-butenyl)-2-norbornylene, 5-(5-hexenyl)-2-norbornylene, 5-(1-methyl-4-pentenyl)-2-norbornylene, 5-(2,3-dimethyl-3-butenyl)-2-norbornylene, 5-(2-ethyl-3-butenyl)-2-norbornylene, 5-(6-heptenyl)-2-norbornylene, 5-(3-methyl-hexene base)-2-norbornylene, 5-(3,4-dimethyl-4-pentenyl)-2-norbornylene, 5-(3-ethyl-4-pentenyl)-2-norbornylene, 5-(7-octenyl)-2-norbornylene, 5-(2-methyl-6-heptenyl)-2-norbornylene, 5-(1,2-dimethyl-5-hexenyl)-2-norbornylene, 5-(5-ethyl-5-hexenyl)-2-norbornylene, 5-(1,2,3-trimethylammonium-4-pentenyl)-2-norbornylene, 5-propylidene-2-norbornylene, 5-isopropylidene-2-norbornylene, 5-butylidene-2-norbornylene, 5-isobutylidene-2-norbornylene, 2,3-bis-isopropylidene-5-norbornylene, 2-ethylidene-3-isopropylidene-5-norbornylene, or 2-propenyl-2,2-norbornadiene etc., and more than one diene being selected from these can be used.
Especially, in these diene, suitably use 5-ethylidene-2-norbornene, 5-methylene-2-norbornene or 4-hexadiene, the three-dimensional elasticity multipolymer of the characteristic meeting described first scheme and alternative plan can be prepared.On the one hand, in the preparation of three-dimensional elasticity multipolymer, be used as diene 5-vinyl-2-norbornylene (VNB) or dicyclopentadiene (DCPD) comprise two double bonds in the past, described two double bonds participate in polyreaction and demonstrate the macromolecular structure of cross-linked form, therefore form gel particle in polymerization process, or there is the molecular weight and the restriction being difficult to control polyreaction that are difficult to control multipolymer.
In addition, third program of the present invention provides the preparation method of the three-dimensional elasticity multipolymer of a kind of described first scheme or alternative plan, comprise: under catalyst composition exists, monomer composition is supplied to reactor and carry out copolymerization, wherein said catalyzer comprises the First Transition metallic compound represented by following chemical formula 1 and the Second Transition compound represented by following chemical formula 2, described monomer composition comprise the ethene of 40 to 70 % by weight, C3 ~ C20 alpha-olefin of 15 to 55 % by weight and 0.5 to 20 % by weight diene.
[chemical formula 1]
[chemical formula 2]
In described chemical formula 1 and 2,
R
1to R
13being same to each other or different to each other, is separately hydrogen, C1 ~ C20 alkyl, C2 ~ C20 thiazolinyl, C6 ~ C20 aryl, silyl, C7 ~ C20 alkylaryl, C7 ~ C20 arylalkyl or the metalloid base of IV race metal that replaced by alkyl, and described R
1to R
13in two adjacent different groups be connected to each other by the alkylidene group comprising C1 ~ C20 alkyl or C6 ~ C20 aryl and form cycloaliphatic ring or aromatic nucleus;
M is IV group 4 transition metal;
Q
1and Q
2mutually the same or different, be separately halogen, C1 ~ C20 alkyl, C2 ~ C20 thiazolinyl, C6 ~ C20 aryl, C7 ~ C20 alkylaryl, C7 ~ C20 arylalkyl, C1 ~ C20 alkylamino, C6 ~ C20 arylamino or C1 ~ C20 alkylidene.
Can be confirmed by following examples, use the monomer of certain content, the i.e. ethene of about 40 to 70 % by weight or about 50 to 70 % by weight, C3 ~ C20 alpha-olefin of about 15 to 55 % by weight or about 25 to 45 % by weight and the diene of about 0.5 to 20 % by weight or about 2 to 10 % by weight, and under two kinds of specific transitions metal catalysts of described chemical formula 1 and 2 exist, described each monomer is polymerized with continuous polymerization technique, just can obtain with high yield and high productivity and meet described high molecular weight range, and the three-dimensional elasticity multipolymer of the characteristic of first scheme and alternative plan.
This is mainly because described two kinds of special catalysts have outstanding catalyst activity and the reactivity with comonomer.First and second transistion metal compound special catalyst described demonstrates the outstanding catalyst activity as IV group 4 transition metal catalyzer, especially can demonstrate outstanding selectivity and copolymerization to the comonomer such as alpha-olefin and diene.Moreover, owing to using this two kinds of special catalysts, diene can be made to be uniformly distributed in macromolecular chain with higher content and to carry out copolymerization.This is because the special catalyst of described chemical formula 1 and 2 makes very stably to keep 5 firm side rings and 6 side ring structures around metallic site by quinoline amino, so there is the structural performance that structurally monomer is easy to close.Namely, the special catalyst of described chemical formula 1 and 2 is based on the structural performance of described catalyzer, the macromonomer of the double bond with long-chain branch form can be formed during ethene and alpha-olefin copolymer close, this macromonomer carries out copolymerization with catalyzer again, thus can form three-dimensional elasticity multipolymer.
Moreover, owing to using these two kinds first and second transistion metal compound special catalysts, and the monomer composition comprising each monomer is fed to polymerization reactor and carries out described copolymerization continuously, therefore described comonomer particularly diene can more uniformly be distributed in macromolecular chain.
As a result, can prepare that molecular weight is large and the three-dimensional elasticity multipolymer that each monomer is evenly alternately distributed, degree of long chain branching is contour with high productivity and high yield.And, the three-dimensional elasticity multipolymer so obtained can meet described first scheme and alternative plan characteristic, therefore, it is possible to have outstanding processibility and flexibility simultaneously.
Further, each monomer content controls at optimum range, ethene is about 40 to 70 % by weight or about 50 to 70 % by weight, alpha-olefin be about 15 to 55 % by weight or about 25 to 45 % by weight and diene be about 0.5 to 20 % by weight, or about 2 to 10 % by weight, therefore each monomer more uniformly can be alternately arranged in macromolecular chain, thus effectively can prepare the three-dimensional elasticity multipolymer of the characteristic meeting described first scheme and alternative plan.
Therefore, preparation method according to described third program can prepare described three-dimensional elasticity multipolymer with high productivity and high yield, and this three-dimensional elasticity multipolymer is applicable to IV group 4 transition metal catalyst preparing, the elasticity etc. that can meet outstanding mechanical-physical character simultaneously and improve further.
Just, if do not use described two kinds of special catalysts, or only use a kind of catalyzer, or exceed the suitable content range of described each monomer, especially the content range etc. of diene, the three-dimensional elasticity multipolymer so finally prepared would not have described high molecular weight range, or can not meet the characteristic of first scheme and/or alternative plan.
On the one hand, in the preparation method of the three-dimensional elasticity multipolymer of described third program, first and second transistion metal compound represented by described chemical formula 1 and 2 is more specifically described below.
First, in described chemical formula 1 and 2, alkyl (hydrocarbyl) can refer to the 1 valency residue from hydrocarbon polymer removing hydrogen atom, the aryl such as alkyl or phenyl such as such as ethyl.
And, in chemical formula 1 and 2, metalloid be there is metal and nonmetal between the element of middle character, such as can refer to arsenic, boron, silicon or tellurium etc.Such as, and described M, can refer to the IV group 4 transition metal elements such as titanium, zirconium or hafnium.
In these first and second transistion metal compounds, as the First Transition metallic compound of described chemical formula 1, can suitably select by more than one in the compound of following chemical formulation.
In described chemical formula, R
2and R
3mutually the same or different, be separately hydrogen or methyl, M is IV group 4 transition metal, Q
1and Q
2mutually the same or different, be separately methyl, dimethyliminio or chlorine atom.
And, as the Second Transition compound of chemical formula 2, can suitably select in the compound represented by following chemical formula formula more than one:
In described formula, R
2and R
3mutually the same or different, be separately hydrogen or methyl, M is IV group 4 transition metal, Q
1and Q
2mutually the same or different, be separately methyl, dimethyliminio or chlorine atom.
On the one hand, the catalyst composition used in the preparation method of described third program, except first and second transistion metal compound described, more than one the cocatalyst compound being selected from and being represented by following chemical formula 3, chemical formula 4 and chemical formula 5 can be comprised further.
[chemical formula 3]
-[Al(R)-O]
n-
In described chemical formula 3,
R is mutually the same or different, and the C1 ~ C20 alkyl being separately halogen, C1 ~ C20 alkyl or being optionally substituted by halogen, n is the integer of more than 2.
[chemical formula 4]
D(R)
3
In described chemical formula 4, to the definition of R as described in chemical formula 3, D be aluminium or boron.
[chemical formula 5]
[L-H]
+[ZA
4]
-or [L]
+[ZA
4]
-
In described chemical formula 5, L is neutral or positively charged ion Lewis acid, H is hydrogen atom, Z is group III A element, A is mutually the same or different, is separately unsubstituted or one of them above hydrogen atom is replaced C6 ~ C20 aryl or C1 ~ C20 alkyl by halogen, C1 ~ C20 alkyl, alkoxyl group or phenoxy group.
In this cocatalyst compound, as the compound represented by described chemical formula 3 be, such as methylaluminoxane, ethylaluminoxane, isobutyl aluminium alkoxide or butyla-luminoxane etc.
In addition, as the compound represented by described chemical formula 4 be, such as, trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-propyl aluminum, tri-butyl aluminum, dimethyl chloride is for aluminium, triisopropylaluminiuand, three sec-butyl aluminium, three cyclopentyl aluminium, triisopentyl aluminium, three hexyl aluminium, trioctylaluminum, ethyl dimethyl aluminium, methyl diethyl aluminum, triphenyl aluminum, three p-methylphenyl aluminium, dimethyl aluminum methoxide (dimethyl aluminium methoxide), dimethyl aluminum ethoxide, trimethyl-boron, triethyl-boron, tri-isobutyl-boron, tripropylborane or tri butyl boron etc., wherein, suitably can use trimethyl aluminium, triethyl aluminum or triisobutyl aluminium.
And the compound represented by described chemical formula 5 comprises the negatively charged ion be combined with the non-coordinated of Bu Shi acid cationic-compatible.Preferred negatively charged ion is the negatively charged ion with large-size, and comprises containing metalloid single coordinate bond complex compound.Especially, conventional is the compound at anion site with single boron atom.Based on this, represent that compound is preferably the salt containing negatively charged ion by described chemical formula 5, described negatively charged ion comprises the coordinate bond complex compound with single boron atom.
As the specific examples of this compound, when trialkyl ammonium salts, comprise trimethyl ammonium four (pentafluorophenyl group) borate, triethyl ammonium four (pentafluorophenyl group) borate, tripropyl ammonium four (pentafluorophenyl group) borate, three (normal-butyl) ammonium four (pentafluorophenyl group) borate, three (2-butyl) ammonium four (pentafluorophenyl group) borate, DMA four (pentafluorophenyl group) borate, DMA normal-butyl three (pentafluorophenyl group) borate, DMA benzyl three (pentafluorophenyl group) borate, DMA four (4-(t-butyldimethylsilyl)-2,3,5, 6-tetrafluoro phenyl) borate, DMA four (4-(triisopropyl silyl)-2, 3,5,6-tetrafluoro phenyl) borate, DMA penta fluoro benzene oxygen base three (pentafluorophenyl group) borate, N, N-Diethyl Aniline four (pentafluorophenyl group) borate, N, N-dimethyl-2，4，6-trimethyl aniline four (pentafluorophenyl group) borate, trimethyl ammonium four (2,3,4,6-tetrafluoro phenyl) borate, triethyl ammonium four (2,3,4,6-tetrafluoro phenyl) borate, tripropyl ammonium four (2,3,4,6-tetrafluoro phenyl) borate, three (normal-butyl) ammonium four (2,3,4,6-tetrafluoro phenyl) borate, dimethyl (tertiary butyl) ammonium four (2,3,4,6-tetrafluoro phenyl) borate, DMA four (2,3,4,6-tetrafluoro phenyl) borate, N, N-Diethyl Aniline four (2,3,4,6-tetrafluoro phenyl) borate, N, N-dimethyl-2，4，6-trimethyl aniline four (2,3,4,6-tetrafluoro phenyl) borate, dimethylammonium four (pentafluorophenyl group) borate, dodecyl dimethyl ammonium four (pentafluorophenyl group) borate, dodecyldimethylamine base ammonium four (pentafluorophenyl group) borate, hexadecyldimethyl benzyl ammonium 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, methyl two (dodecyl) ammonium four (pentafluorophenyl group) borate, methyl two (tetradecyl) ammonium four (pentafluorophenyl group) borate, methyl two (hexadecyl) ammonium four (pentafluorophenyl group) borate, methyl two (octadecyl) ammonium four (pentafluorophenyl group) borate, methyl two (eicosyl) ammonium four (pentafluorophenyl group) borate, three decyl ammonium four (pentafluorophenyl group) borates, three (dodecyl) ammonium four (pentafluorophenyl group) borate, three (tetradecyl) ammonium four (pentafluorophenyl group) borate, three (hexadecyl) ammonium four (pentafluorophenyl group) borate, three (octadecyl) ammonium four (pentafluorophenyl group) borate, three (eicosyl) ammonium four (pentafluorophenyl group) borate, decyl two (normal-butyl) ammonium four (pentafluorophenyl group) borate, dodecyl two (normal-butyl) ammonium four (pentafluorophenyl group) borate, octadecyl two (normal-butyl) ammonium four (pentafluorophenyl group) borate, N, N-bis-(dodecyl) anilino four (pentafluorophenyl group) borate, N-methyl-N-dodecyl anilino four (pentafluorophenyl group) borate or methyl two (dodecyl) ammonium four (pentafluorophenyl group) borate etc.
In addition, as dialkyl ammonium salt, such as, two-(sec.-propyl) ammonium four (pentafluorophenyl group) borates or dicyclohexyl ammonium four (pentafluorophenyl group) borate etc.
And, as carbon salt, such as, Zhuo Si (pentafluorophenyl group) borate, trityl group carbon four (pentafluorophenyl group) borate or benzene (diazo) four (pentafluorophenyl group) borate etc.
In addition, in the preparation method of described three-dimensional elasticity multipolymer, the catalyst composition comprising described first and second transistion metal compounds and optionally comprise cocatalyst compound is prepared by the method comprised the steps: make the cocatalyst compound contact comprising described first and second transistion metal compounds and represented by described chemical formula 3 or chemical formula 4, to obtain mixture; And in described mixture, add the cocatalyst compound represented by described chemical formula 5.
In addition, in described catalyst composition, the mol ratio of described First Transition metallic compound and Second Transition compound can be about 10:1 to 1:10, first and second transistion metal compound described total transistion metal compound is altogether about 1:5 to 1:500 with the mol ratio of the cocatalyst compound represented by described chemical formula 3 or chemical formula 4, and described total transistion metal compound is about 1:1 to 1:10 with the mol ratio of the cocatalyst compound represented by described chemical formula 5.
In the preparation method of described three-dimensional elasticity multipolymer, described catalyst composition also can comprise reaction solvent, as described reaction solvent is, such as, and the hydrocarbon solvents such as pentane, hexane or heptane; The aromatic solvent such as benzene or toluene etc., but be not limited thereto.
As mentioned above, as the alpha-olefin being included in described monomer composition, propylene, 1-butylene, 1-octene, 1-amylene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-decene, 1-undecylene or 1-dodecylene etc. can be used, can non-conjugative monomer be used as described diene.Wherein, as being generally used for the monomer preparing EPDM rubber, such as alpha-olefin suitably can use propylene, and described diene suitably can use the non-conjugated diene class monomers such as 5-ethylidene-2-norbornene, 5-methylene-2-norbornene or 4-hexadiene.
In the preparation method of the multipolymer of described third program, described copolymerization step the temperature of about 100 to 170 DEG C, or can be carried out at the temperature of about 100 to 160 DEG C.If described co-polymerization temperature is too low, will be difficult to synthesis three kinds of monomers alternatively distributed three-dimensional elasticity multipolymer equably, if polymeric reaction temperature is too high, monomer or prepared multipolymer will pyrolysis.And this copolymerization can with solution polymerization process, and particularly continuous solution polymerization method is carried out.Now, described catalyst composition can use with the homogeneous catalyst form being dissolved in this solution.
In order to carry out this continuous solution polymerization, described monomer composition and the catalyst composition that comprises first, second transistion metal compound and optionally comprise cocatalyst compound are supplied to reactor with solution state, to carry out described copolymerization step, and discharged continuously from reactor by the three-dimensional elasticity multipolymer after copolymerization, thus described copolymerization step can be carried out continuously.
By carrying out this continuous solution polymerization, the three-dimensional elasticity multipolymer of the characteristic meeting described first scheme and alternative plan more effectively can be obtained with high productivity and high yield.
As mentioned above, can prepare the three-dimensional elasticity multipolymer with outstanding processibility and the elasticity improved further and flexibility etc. with IV group 4 transition metal catalyzer according to the present invention, this three-dimensional elasticity multipolymer is suitable as EPDM rubber etc.
And, according to the invention provides a kind of multipolymer preparation method that can prepare this three-dimensional elasticity multipolymer with high productivity and high yield.
The three-dimensional elasticity multipolymer with long-chain branch obtained according to the present invention overcomes the suffered restriction such as the EPDM rubber of known metallocene system IV group 4 transition metal catalyst preparing, outstanding elasticity and flexibility and other physical propertiess can be had simultaneously, therefore can play the inherent characteristics of IV group 4 transition metal catalyzer, and be suitable as EPDM rubber etc.
Accompanying drawing explanation
Fig. 1 is the Mooney relaxation curve of embodiment 3 to 6 and comparative example 1 to 3.
Fig. 2 is the chart of the Mooney relaxation area MLR relative to mooney viscosity ML of embodiment 1 to 7 and comparative example 1 to 3.
Fig. 3 is the surface picture of the multipolymer prepared in embodiment 1 being carried out to the extrudate that Jia Weimo extruding (Garvey die extrusion) obtains with the rotor revolution number of 60rpm.
Fig. 4 is the surface picture of the multipolymer prepared in comparative example 1 being carried out to the extrudate that Jia Weimo extruding obtains with the rotor revolution number of 60rpm.
Fig. 5 shows the DSC curve data of the three-dimensional elasticity multipolymer of preparation in comparative example 1.
Fig. 6 shows the DSC curve data of the three-dimensional elasticity multipolymer of preparation in embodiment 9.
The chart of the acetate unit content x in the three-dimensional elasticity multipolymer of Fig. 7 prepared by display embodiment 1 to 6, comparative example 1 and 4 and the relation of crystallization enthalpy y.
Embodiment
In the examples below that invention is described in more detail.But the following example is exemplary, the content of invention is not limited to the following example.
The following example and comparative example are under the nitrogen atmosphere cutting off air and contact with moisture, employing standard Xi Laike (Schlenk) technology and glove box (Glove-box) technology are carried out, and the organic solvent for reacting adopts standard method to purify.Synthesized part and catalyzer use 400MHz nuclear magnetic resonance analyser NMR and X-ray spectrograph to add their confirmation.
The synthesis > of < part and transistion metal compound
In the examples below that, by [(1, 2, 3, 4-tetrahydroquinoline-8-base) 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-base) tetramethyl-ring pentadiene-η 5, κ-N] dimethyl titanium ([(2-Methylindolin-7-yl) tetramethylcyclopentadienyl-eta5, kapa-N] titanium dimethyl) be used separately as first and second transistion metal compound, by N, accelerine four (pentafluorophenyl group) borate and triisobutyl aluminium are used as cocatalyst compound.First and second transistion metal compound described adopts the method identical with the embodiment 2 and 14 of No. 0976131st, Korean granted patent to prepare, and described cocatalyst compound adopts the method identical with the embodiment 9 of No. 0820542nd, Korean granted patent to prepare.
The preparation of the three-dimensional elasticity multipolymer of < embodiment 1 to 7> ethene, propylene and 5-ethylidene-2-norbornene
2L pressure reactor is used to carry out the terpolymerization reaction of ethene, propylene and 5-ethylidene-2-norbornene continuously.Hexane is added with the supply rate of 6.7kg per hour by described reactor lower part continuously as polymer solvent, and extracts polymeric solution out continuously from reactor top.
By described [(1,2,3,4-tetrahydroquinoline-8-base) tetramethyl-ring pentadiene-η 5, κ-N] dimethyl titanium and [(2 methyl indole-7-base) tetramethyl-ring pentadiene-η 5, κ-N] dimethyl titanium is used as first, second transistion metal compound with the state being dissolved in hexane, and adds reactor with the speed of 24 to 60 μm of ol per hour.And, DMA four (pentafluorophenyl group) borate is used as cocatalyst compound with the state being dissolved in toluene, and adds reactor with the speed of 105 to 270 μm of ol per hour.In addition, described triisobutyl aluminium is used as additional cocatalyst compound with the state being dissolved in hexane, and adds reactor with the speed of 1800 to 3200 μm of ol per hour.
Vinyl monomer is supplied to reactor with the speed of 450 to 550g per hour and 5-ethylidene-2-norbornene monomer with the speed of 80 to 250g per hour with the speed of 890 to 900g per hour, propylene monomer, and carries out described copolymerization.
When co-polymerization temperature in reactor reaches about 160 DEG C, control to be 130 to 160 DEG C by the method that the supply rate of 5-ethylidene-2-norbornene is once increased 0.5mL/min from 1mL/min.
Under the described conditions, copolymerization is carried out by continuous solution polymerization, thus the three-dimensional elasticity multipolymer of embodiment 1 to 7 is gone out with uniform solution state continuous production, and after adding ethanol termination polyreaction, the polymeric solution of discharging continuously from reactor top is carried out drying under reduced pressure in the vacuum oven of 60 DEG C, finally makes the multipolymer of embodiment 1 to 7.
The conventional three-way elastocopolymer of < comparative example 1 to 3> ethene, propylene and 5-ethylidene-2-norbornene
Using the conventional EPDM rubber DOW Nordel4570 for preparing with the metallocene catalyst three-dimensional elasticity multipolymer as comparative example 1, using the three-dimensional elasticity multipolymer of DOW Nordel4640 as comparative example 2, using the three-dimensional elasticity multipolymer of DOW Nordel4725 as comparative example 3.
In the multipolymer of described embodiment and comparative example, the weight-average molecular weight of the content of each unit, the activity of catalyzer, multipolymer and molecular weight distribution (PDI), as shown in table 1 below.Now, the weight-average molecular weight of each multipolymer is the PL-GPC220 being provided with three linear mixed bed columns using Polymer Laboratory company, at 160 DEG C of temperature, 1,2,4-trichlorobenzene is used as solvent and carries out with the flow velocity that 1.0ml/ divides measuring.
[table 1]
< test example 1> mooney viscosity and MLR measure
Mooney viscosity and MLR use mooney's viscosimeter (the MV2000E model of Monsanto company) to measure by the following method according to ASTM D1646-04.The multipolymer pressing mold processed with oxidation inhibitor (Irganox 1076) is made test piece with the condition preheating one minute of 1+4+2 at 125 DEG C, then measuring the mooney viscosity time is 4 minutes, and to measure the MLR time be 2 minutes.
MLR is the integrated value starting the Mooney stress relaxation within 2 minutes after rotor stops 1 second, and its calculating formula can be represented by following general expression 2.
[general expression 2]
For each multipolymer of described embodiment and comparative example, Mooney relaxation curve and MLR/ML pictorialization at Fig. 1,2 for ML, the ratio of mooney viscosity and MLR, MLR/ML, the value etc. of general expression 1 are shown in table 2
[table 2]
As shown in Figure 1, the Mooney relaxation curve that can confirm embodiment 3 to 6 slowly successively decreases, and comparative example 1 to 3 falls suddenly.It can thus be appreciated that the multipolymer of embodiment has the viscosity of the multipolymer being similar to comparative example, and chart bottom area and Mooney relaxation area increase to some extent, can guess this is because the degree of long chain branching in polymer high and produce phenomenon.
Especially, as above shown in table 2, although the Mooney relaxation display approximation and have similar viscosity of embodiment 1,3,6 and comparative example 1,3, its Mooney relaxation area of the multipolymer prepared in an embodiment MLR value is significantly higher than comparative example, thus degree of long chain branching in known polymer is high.
And from the MLR value for ML of Fig. 2 and table 2, for identical ML, embodiment 1 to 7 demonstrates MLR and the MLR/ML value higher than comparative example 1 to 3, especially, [(MLR)/(ML) of embodiment 1 to 7
2the value of] × 100 is more than 10, and the value of comparative example 1 to 3 is less than 4, has very big-difference.
By this for the MLR/ML value of ML and the result of general expression 1, the three-dimensional elasticity multipolymer that can confirm described embodiment is the EPDM structure with long-chain branch comprising specific diene made under special catalyst exists, molecular weight distribution is also less than 3.5 have narrower scope, and processibility is outstanding, be suitable for extrusion molding, and mechanical-physical character is also very outstanding.
< test example 2> Jia Weimo squeeze test
Press workability is have rated by Jia Weimo (Garvey Die) pressing method according to ASTM2230.As follows for the preparation of the sample of Jia Weimo squeeze test.Relative to copolymer 1 00 weight part of preparation in embodiment 1,2 and comparative example 1,2, use paraffin oil 75 weight part, carbon black 125 weight part, ZnO5 weight part, stearic acid 1 weight part, and with the 1.6L Banbury of Farrel company with the rotor revolution number of 60rpm at 100 to 120 DEG C mixing 6 minutes.And, mixing title complex is extruded with the rotor revolution number of 45 or 60rpm by Jia Weimo extrusion machine under the mould temperature of 105 DEG C, and evaluates surface and local edge according to ASTM2230.The Jia Weimo test-results of embodiment 1,2 and comparative example 1,2 is shown in table 3, and the surface picture of the Jia Weimo extrudate of each multipolymer of embodiment 1 and comparative example 1 is shown in Fig. 3, Fig. 4.
[table 3]
When ﹡ die swelling index is extruding, the volume change of per minute is removed in the value of the length variations of per minute.
Described embodiment 1,2 and comparative example 1,2 have similar composition and the sample of mooney viscosity, when carrying out Jia Weimo squeeze test to this, as above extrusion production shown in table 3 and die swelling index similar, but the surface property embodiment 1,2 of extrudate is significantly better than comparative example 1,2.
And, can confirm by extrudate photo Fig. 3, Fig. 4 of embodiment 1 and comparative example 1, the surface property of embodiment 1 with edge configuration compared with comparative example 1 evenly and smooth.
Namely, the three-dimensional elasticity multipolymer of described embodiment 1 and 2 comprises specific diene, and use specific IV group 4 transition metal catalyzer of the present invention to import long-chain branch equably, therefore demonstrate outstanding press workability and surface property with comprised the multipolymer of 5-ethene-2-norbornylene as diene compared with in the past.
< embodiment 8 to 13> prepares the three-dimensional elasticity multipolymer of ethene, propylene and 5-ethylidene-2-norbornene
2L pressure reactor is used to carry out the terpolymerization reaction of ethene, propylene and 5-ethylidene-2-norbornene continuously.Hexane is added with the supply rate of 7.6kg per hour by described reactor lower part continuously as polymer solvent, and extracts polymeric solution out continuously from reactor top.
By described [(1,2,3,4-tetrahydroquinoline-8-base) tetramethyl-ring pentadiene-η 5, κ-N] dimethyl titanium and [(2 methyl indole-7-base) tetramethyl-ring pentadiene-η 5, κ-N] dimethyl titanium is used as first, second transistion metal compound with the state being dissolved in hexane, and adds reactor with the speed of 51 to 54 μm of ol per hour.And, DMA four (pentafluorophenyl group) borate is used as cocatalyst compound with the state being dissolved in toluene, and adds reactor with the speed of 255 to 270 μm of ol per hour.In addition, described triisobutyl aluminium is used as additional cocatalyst compound with the state being dissolved in hexane, and adds reactor with the speed of 4080 to 4200 μm of ol per hour.
Vinyl monomer is supplied to reactor with 820 to 950g speed per hour and 5-ethylidene-2-norbornene monomer with the speed of 86 to 129g per hour with the speed of 950g per hour, propylene monomer, and carries out described copolymerization.
When co-polymerization temperature in reactor reaches about 140 DEG C, control to be 120 to 140 DEG C by the method that the supply rate of 5-ethylidene-2-norbornene is once increased 0.5mL/min from 1mL/min.
Under the described conditions, copolymerization is carried out by continuous solution polymerization, thus the three-dimensional elasticity multipolymer of embodiment 8 to 13 is gone out with uniform solution state continuous production, and after adding ethanol termination polyreaction, the polymeric solution of discharging continuously from reactor top is carried out drying under reduced pressure in the vacuum oven of 60 DEG C, finally makes the multipolymer of embodiment 8 to 13.
In the multipolymer of acquisition like this, the weight-average molecular weight of the content of each unit, the activity of catalyzer and multipolymer is as following table 4.Now, the weight-average molecular weight of each multipolymer is the PL-GPC220 being provided with three linear mixed bed columns using Polymer Laboratory company, at 160 DEG C of temperature, 1,2,4-trichlorobenzene is used as solvent and carries out with the flow velocity that 1.0ml/ divides measuring.
[table 4]
The conventional three-way elastocopolymer of < comparative example 1 and 4> ethene, propylene and 5-ethylidene-2-norbornene
Employ the elastocopolymer DOW Nordel4570 of described comparative example 1, another conventional EPDM rubber Mitsui3702 is used as the three-dimensional elasticity multipolymer of comparative example 4.
The physical properties (density and mooney viscosity) of < test example 3> multipolymer is evaluated
The multipolymer press mold processed with oxidation inhibitor (Irganox1076) is made thickness is 3mm, radius is the test piece of 2mm, and measured the density of the multipolymer obtained in embodiment and comparative example with plum Teller scale.And, by the method that the test example 1 with described is identical, use mooney's viscosimeter (the MV2000E model of Monsanto company) at 125 DEG C, determine the mooney viscosity of described multipolymer.Each physical properties of mensuration like this is as following table 5.
< test example 4> measures crystallization enthalpy and derives the relational expression of acetate unit content and crystallization enthalpy
For the multipolymer of described embodiment and comparative example, the DSC device of DSC 6000 model of Perkin Elmer company is used to be derived DSC curve data.More specifically, each copolymer sample is heated to about 100 DEG C with the speed of 20 DEG C/minute from about 0 DEG C, keep about 2 minutes at about 100 DEG C after, is cooled to about-150 DEG C with the speed of about-10 DEG C/minute and carries out dsc analysis.The comparative example 1 of derivation like this and the DSC curve data of embodiment 9 are as illustrated in figures 5 and 6.
Crystallization enthalpy and the average crystallization temperature (Tc of each multipolymer is calculated by this DSC curve data; DEG C), and using the Tc of described average crystallization temperature as each multipolymer.The Tc of each multipolymer and crystallization enthalpy are shown in following table 5.
Using the content of ethene that comprises in each multipolymer of embodiment as x-axis, using the crystallization enthalpy that measures for each multipolymer as y-axis, data to each multipolymer are shown, then linear regression are carried out to these data, thus derive the relation of described acetate unit content x and crystallization enthalpy y.As shown in Figure 7, in order to compare with embodiment, the data of comparative example 1 and 4 are also shown in Figure 7 for this relation.
The mensuration of < test example 5>Re × Rc
Use
13c-NMR analyzes each multipolymer of embodiment and comparative example, measures each growth response rate constant of k11, k12, k21 and k22.Now, the Bruke DRX600 that the determinator used is 600MHz, is dissolved in each multipolymer in orthodichlorobenzene-d4 solvent, and analyzes at 100 DEG C.
[Journal of Polymer Science:Polymer Physics edition, 1973,11 are analyzed by the Triad Sequence based on Randal method, 275 ~ 287] and Kakugo method [Macromolecules 1982,15,1150] etc., by described
13the analytical results of C-NMR obtains each growth response rate constant, and has calculated Re × Rc based on formula Re=k11/k12, Rc=k22/k21 thus.Re × Rc the value calculated for each multipolymer is also shown in following table 5.
[table 5]
Can confirm from described table 5 and Fig. 7, the relation of the multipolymer of embodiment 8 to 13 its acetate unit content x and crystallization enthalpy y meets 1.55x-80.00≤y≤1.55x-75.00, especially meets y=1.55x-78.06 (R
2, and Re × Rc value is less than 1=0.907).
Compared with embodiment, the multipolymer with identical acetate unit content of comparative example 1 and 4 demonstrates higher crystallization enthalpy, does not meet 1.55x-80.00≤y≤1.55x-75.00, and Re × Rc value is greater than 1.The each monomer of three-dimensional elasticity multipolymer of embodiment 8 to 13 is alternately arranged and is uniformly distributed in macromolecular chain thus, therefore low relative to acetate unit content degree of crystallization, has outstanding elasticity and flexibility compared with comparative example.
Claims (18)
1. a three-dimensional elasticity multipolymer, this three-dimensional elasticity multipolymer be IV group 4 transition metal catalyzer exist under obtain acetate unit content be 40 to 70 % by weight, C3 ~ C20 alpha-olefin unit content be 15 to 55 % by weight and diene units content be 0.5 to 20 % by weight multipolymer
I) with GPC measure weight-average molecular weight be 100000 to 500000;
Ii) multipolymer crystallization enthalpy (Δ Hc, the J/g) y that when acetate unit content (% by weight) x and acetate unit content are x, DSC measures meets relational expression 1.55x-80.00≤y≤1.55x-75.00.
2. a three-dimensional elasticity multipolymer, this three-dimensional elasticity multipolymer be IV group 4 transition metal catalyzer exist under obtain acetate unit content be 40 to 70 % by weight, C3 ~ C20 alpha-olefin unit content be 15 to 55 % by weight and diene units content be 0.5 to 20 % by weight multipolymer
I) with GPC measure weight-average molecular weight be 100000 to 500000;
Ii) the mooney viscosity ML measured with mooney's viscosimeter (1+4+2125 DEG C) and Mooney relaxation area MLR meets following general expression 1,
[general expression 1]
[MLR/(ML)
2]×100≥8。
3. three-dimensional elasticity multipolymer according to claim 1, wherein,
Be met within the scope of the whole acetate unit content that described pass ties up to 40 to 70 % by weight.
4. three-dimensional elasticity multipolymer according to claim 2, wherein, MLR/ML is more than 3.
5. the three-dimensional elasticity multipolymer according to claims 1 or 2, wherein,
Product Re × the Rc of the reactive specific ray constant Re representing the ethylene unit distribution in multipolymer and the reactive specific ray constant Rc representing the alpha-olefin cell distribution state in multipolymer is less than 1,
Now, Re=k11/k12, Rc=k22/k21,
K11 is the growth response rate constant in copolymer chain after ethylene unit during ethene bonding, k12 is the growth response rate constant in the copolymer after ethylene unit during alpha-olefin bonding, k21 is the growth response rate constant in copolymer chain after alpha-olefin unit during ethene bonding, and k22 is the growth response rate constant in copolymer chain after alpha-olefin unit during alpha-olefin bonding.
6. three-dimensional elasticity multipolymer according to claim 5, wherein,
Described Re × Rc is 0.60 to 0.99.
7. the three-dimensional elasticity multipolymer according to claims 1 or 2, wherein,
With DSC measure Tc Tc be-55 to 30 DEG C.
8. the three-dimensional elasticity multipolymer according to claims 1 or 2, wherein,
Described mooney viscosity ML is more than 20MU.
9. the three-dimensional elasticity multipolymer according to claims 1 or 2, it has 0.840 to 0.895g/cm
3density.
10. the three-dimensional elasticity multipolymer according to claims 1 or 2, it has the molecular weight distribution of 2 to 4.
11. three-dimensional elasticity multipolymers according to claim 1, wherein,
Described alpha-olefin be selected from propylene, 1-butylene, 1-hexene and 1-octene more than one, described diene be selected from 5-ethylidene-2-norbornene, 5-methylene-2-norbornene and 4-hexadiene more than one.
The preparation method of 12. 1 kinds of three-dimensional elasticity multipolymers according to claims 1 or 2, comprising:
Under catalyst composition exists, monomer composition is supplied to reactor and carries out copolymerization, wherein said catalyst composition comprises the First Transition metallic compound represented by following chemical formula 1 and the Second Transition compound represented by following chemical formula 2, described monomer composition comprise the ethene of 40 to 70 % by weight, C3 ~ C20 alpha-olefin of 15 to 55 % by weight and 0.5 to 20 % by weight diene
[chemical formula 1]
[chemical formula 2]
In described chemical formula 1 and 2,
R
1to R
13being same to each other or different to each other, is separately hydrogen, C1 ~ C20 alkyl, C2 ~ C20 thiazolinyl, C6 ~ C20 aryl, silyl, C7 ~ C20 alkylaryl, C7 ~ C20 arylalkyl or the metalloid base of IV race metal that replaced by alkyl, and described R
1to R
13in two adjacent different groups be connected to each other by the alkylidene group comprising C1 ~ C20 alkyl or C6 ~ C20 aryl and form cycloaliphatic ring or aromatic nucleus;
M is IV group 4 transition metal;
Q
1and Q
2mutually the same or different, be separately halogen, C1 ~ C20 alkyl, C2 ~ C20 thiazolinyl, C6 ~ C20 aryl, C7 ~ C20 alkylaryl, C7 ~ C20 arylalkyl, C1 ~ C20 alkylamino, C6 ~ C20 arylamino or C1 ~ C20 alkylidene.
The preparation method of 13. three-dimensional elasticity multipolymers according to claim 12, wherein,
Described First Transition metallic compound is selected from by more than one in the compound of following chemical formulation,
In described chemical formula, R
2and R
3mutually the same or different, be separately hydrogen or methyl, M is IV group 4 transition metal, Q
1and Q
2mutually the same or different, be separately methyl, dimethyliminio or chlorine atom.
The preparation method of 14. three-dimensional elasticity multipolymers according to claim 12, wherein,
Described Second Transition compound is selected from by more than one in the compound of following chemical formulation,
In described chemical formula, R
2and R
3mutually the same or different, be separately hydrogen or methyl, M is IV group 4 transition metal, Q
1and Q
2mutually the same or different, be separately methyl, dimethyliminio or chlorine atom.
The preparation method of 15. three-dimensional elasticity multipolymers according to claim 12, wherein,
Described catalyst composition also comprises more than one the cocatalyst compound being selected from and being represented by following chemical formula 3, chemical formula 4 and chemical formula 5,
[chemical formula 3]
-[Al(R)-O]
n-
In described chemical formula 3,
R is mutually the same or different, the C1 ~ C20 alkyl being separately halogen, C1 ~ C20 alkyl or being optionally substituted by halogen, and n is the integer of more than 2;
[chemical formula 4]
D(R)
3
In described chemical formula 4, to the definition of R as described in chemical formula 3, D be aluminium or boron;
[chemical formula 5]
[L-H]
+[ZA
4]
-or [L]
+[ZA
4]
-
In described chemical formula 5, L is neutral or positively charged ion Lewis acid, H is hydrogen atom, Z is IIIA race element, A is mutually the same or different, separately for not replacing or C6 ~ C20 aryl that one of them above hydrogen atom is replaced by halogen, C1 ~ C20 alkyl, alkoxyl group or phenoxy group or C1 ~ C20 alkyl.
The preparation method of 16. three-dimensional elasticity multipolymers according to claim 12, wherein,
Described alpha-olefin be selected from propylene, 1-butylene, 1-hexene and 1-octene more than one, described diene be selected from 5-ethylidene-2-norbornene, 5-methylene-2-norbornene and Isosorbide-5-Nitrae-hexadiene more than one.
The preparation method of 17. three-dimensional elasticity multipolymers according to claim 15, wherein,
Described monomer composition, the first and second transistion metal compounds and cocatalyst compound are supplied to reactor with solution state and carries out copolymerization.
The preparation method of 18. three-dimensional elasticity multipolymers according to claim 17, wherein,
The three-dimensional elasticity multipolymer of copolymerization is discharged continuously from reactor, and carries out described copolymerization step continuously.
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| KR1020130086216A KR101585206B1 (en) | 2013-07-22 | 2013-07-22 | Elastic diene terpolymer and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108137739A (en) * | 2016-02-24 | 2018-06-08 | Lg化学株式会社 | Olefin polymer and preparation method thereof |
| CN109641990A (en) * | 2016-07-13 | 2019-04-16 | 埃克森美孚化学专利公司 | Dual metallocene catalyst copolymer compositions |
| CN113195560A (en) * | 2019-02-20 | 2021-07-30 | Lg化学株式会社 | Olefin-based polymers |
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 preparation of terpolymer of ethylene, alpha-olefin and diene |
| 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 preparation of terpolymer of ethylene, alpha-olefin and diene |
| 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 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108137739A (en) * | 2016-02-24 | 2018-06-08 | Lg化学株式会社 | Olefin polymer and preparation method thereof |
| CN109641990A (en) * | 2016-07-13 | 2019-04-16 | 埃克森美孚化学专利公司 | Dual metallocene catalyst copolymer compositions |
| CN109641990B (en) * | 2016-07-13 | 2022-08-19 | 埃克森美孚化学专利公司 | Dual metallocene catalyst copolymer compositions |
| CN113195560A (en) * | 2019-02-20 | 2021-07-30 | Lg化学株式会社 | Olefin-based polymers |
| CN113195560B (en) * | 2019-02-20 | 2024-02-06 | Lg化学株式会社 | Olefin-based polymers |
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