CN100369944C - Linear triene compound and copolymer - Google Patents
Linear triene compound and copolymer Download PDFInfo
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- CN100369944C CN100369944C CNB991094948A CN99109494A CN100369944C CN 100369944 C CN100369944 C CN 100369944C CN B991094948 A CNB991094948 A CN B991094948A CN 99109494 A CN99109494 A CN 99109494A CN 100369944 C CN100369944 C CN 100369944C
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Abstract
A novel and useful linear triene compound represented by the following formula (1) is co-polymerized with an alpha -olefin to obtain an ethylenically unsaturated copolymer which is superior in weatherability, heat resitance and fastness to ozone, together with superior scorch stability and vulcanizability at high velocity, wherein R<1>, R<2>, R<3>, R<4>, R<5>, R<6>, R<7> and n are defined in the specification.
Description
The present invention relates to new and useful chain triene compound and its preparation method.
The invention still further relates to new with useful ethylene/alpha-olefin/three alkene copolymers, contain the composition of this analog copolymer and the moulded products that makes by this based composition.
In general, the hydrocarbon compound that has two or more carbon-to-carbon double bonds in the molecule is called polyenoid, and known this compounds comprises for example 1,3-butadiene, 1,3-pentadiene, 1,4-hexadiene, ethylidene-2-norbornylene (ENB), Dicyclopentadiene (DCPD) or the like.With this class diene and for example ethene, propylene or the like copolymerization of alpha-olefin, just can obtain having the vulcanizable unsaturated copolymer of unsaturated link(age).Because its good performance, for example weathering resistance, thermotolerance and anti-ozone stable, it is found that this class ethylene linkage unsaturated copolymer can be widely used in for example auto parts machinery, industrial rubber product, electrically insulating material, structure and goods for building and such as the rubber product of rubber lining cloth etc., and can also as and for example polypropylene, polystyrene etc. form the raw material of polymer blend.In these ethylene/alpha-olefin/diene multipolymers, to compare with other ethylene linkage unsaturated copolymer, ethylene/propene/5-ethylidene-2-norbornene multipolymer shows higher vulcanization rate especially, thereby is widely used in the practical application especially.
Yet, with those normally used elastoprenes-for example natural rubber, styrene/butadiene rubbers, synthetic polyisoprene, divinyl rubber and paracril-compare, the vulcanization rate of this ethylene/propene/5-ethylidene-2-norbornene multipolymer is low, and the ability of itself and elastoprene covulcanization.
The vulcanization rate of common ethylene/alpha-olefin/diene multipolymer is lower, therefore, when reducing curing time in order to reduce energy consumption or reducing curing temperature, is difficult to reach high yield in the process of preparation vulcanized rubber products.
Therefore, if a kind of polyenic compounds by with alpha-olefin-as ethene-copolymerization, the ethylene linkage unsaturated copolymer that obtains vulcanizing at a high speed and having simultaneously good weathering resistance, thermotolerance and ozone resistance, then this polyenic compounds have huge industrial value.
On the other hand, people generally believe: as general aspects, but the sulfide polymer with higher vulcanization rate trends towards having poor incipient scorch stability.This be because: except the sulfuration production stage in, for example, before sulfuration, in the procedure of processing of the storing step of compounded rubber and rubber, have the polymkeric substance and polymer phase ratio of higher vulcanization rate with low sulfuration speed, easier cause crosslinked, thereby caused scorching.Therefore, the incompatibility of high-speed vulcanization and incipient scorch stability, thus be difficult to be had simultaneously the polymkeric substance of these two kinds of character.Therefore,, when attempting to increase iodine number, when sacrificing incipient scorch stability, can increase vulcanization rate by the ratio that increases ENB when in the production of ethylene/propene/ENB multipolymer, thus the processing characteristics when having reduced the processing blended rubber.That is,, in actually operating, easily produce trouble, for example extrude output reduction, motor load increase and machine barrel or punch die filling etc. because the speed of viscosity increase improves.On the contrary, when attempting to reduce iodine number,,, thereby make the productive rate of vulcanized rubber reduce because the retardance sulfuration is inevitable though improved the incipient scorch stability of multipolymer on the whole and therefore improved its processing characteristics.
The purpose of this invention is to provide a kind of new and the useful chain triene compound that can form the ethylene linkage unsaturated copolymer, described multipolymer can be vulcanized at a high speed, the incipient scorch excellent in stability, and have good weathering resistance, thermotolerance and ozone resistance simultaneously.
Another object of the present invention provides a kind of effective ways that prepare above-claimed cpd.
Another purpose of the present invention provides a kind of new and useful alpha-olefin/three alkene copolymers with high vulcanization rate and good incipient scorch stability.
A further object of the invention provides a kind of composition that contains above-mentioned multipolymer.
A further object of the present invention provides a kind of moulded products that is made by above-mentioned composition.
Chain triene compound of the present invention is represented by following formula (1):
Wherein, R
1, R
2, R
3, R
4, R
5And R
6Be hydrogen atom or alkyl separately independently of each other with 1-3 carbon atom, R
7Be the alkyl with 1-3 carbon atom, n is the integer of 0-5, prerequisite be when n be 2 or when bigger, each R
4Or R
5Can be identical or different respectively.
According to the present invention, the method for the chain triene compound of preparation formula (1) expression comprises:
With the triene compound with conjugated diolefine structure and the ethylene reaction of following formula (3) expression,
Wherein, R
1, R
2, R
3, R
4, R
5And R
6Be hydrogen atom or alkyl separately independently of each other with 1-3 carbon atom, R
7Be the alkyl with 1-3 carbon atom, n is the integer of 0-5, prerequisite be when n be 2 or when bigger, each R
4Or R
5Can be identical or different.
First kind of multipolymer of the present invention { alpha-olefin/three olefinic random copolymers (I-1) } contains:
Be derived from the structural unit (U of alpha-olefin (A) with 2-20 carbon atom
A) and
Be derived from the structural unit (U of the chain triene compound (B-1) of following formula (1) expression
B-1), wherein,
At structural unit (U
A) add structural unit (U
B-1) the overall texture unit in, structural unit (U
B-1) ratio be 0.1-30mol%, and
In 135 ℃ of limiting viscosities of measuring in naphthalane [η] is 0.1-10dl/g.
First kind of composition of the present invention (composition that contains alpha-olefin/three olefinic random copolymers) contains above-mentioned alpha-olefin/three olefinic random copolymers (I-1), vulcanizing agent (II) and/or filler (III).
Moulded products of the present invention comprises extrusion molding moulded product, injection mould goods or transfer mould goods or the foamed products that is made by above-mentioned first kind of composition.
" chain triene compound "
In following formula (1) by R
1-R
6And R
7The specific examples of the alkyl with 1-3 carbon atom of expression comprises methyl, ethyl, n-propyl and sec.-propyl.N is the integer of 0-5, is preferably 1-4.
For the chain triene compound { chain triene compound (B-1) hereinafter referred to as } by formula (1) expression of the present invention, preferred n=1 and R
4And R
5Be the compound of hydrogen atom, wherein preferred especially R
4And R
5Be hydrogen atom and R
6And R
7Be the compound of methyl or ethyl separately independently of each other.When with above-mentioned chain triene compound (B-1) as with the comonomer of alpha-olefin copolymer the time, during especially for synthetic hereinafter described second kind or the third multipolymer, can obtain the multipolymer that between vulcanization rate and incipient scorch curve, has excellent balance.
In chain triene compound of the present invention (B-1), the compound of preferred formula (2) expression { hereinafter is called chain triene compound (B-2) },
Corresponding with formula (1) expression, n=1 and R
3, R
4And R
5Be the compound of hydrogen atom separately independently of each other.In chain triene chemical combination (B-2), preferred R
6And R
7Be the compound of methyl or ethyl separately independently of each other.When synthesizing hereinafter described second kind or the third multipolymer as comonomer, can obtain the multipolymer that between vulcanization rate and incipient scorch curve, has excellent balance with this chain triene compound (B-2).
Chain triene compound (B-1) specific examples of formula of the present invention (1) expression comprises following compound:
Chain triene compound (B-2) specific examples of formula (2) expression comprises following compound:
The molecular structure of chain triene compound of the present invention (B-1) can with mass spectrum for example, IR absorption spectrum and
1The technical measurement of H-NMR spectrum.
Chain triene compound of the present invention (B-1) comprises the common steric isomer listed in the scope of the invention (trans-and cis-isomer).
When chain triene compound of the present invention (B-1) and alpha-olefin-such as ethene or propylene-copolymerization, can obtain can be by high speed sulfurized ethylene linkage unsaturated copolymer.This multipolymer also has good weathering resistance, thermotolerance and anti-ozone stable.
When using chain triene compound (B-1) the preparation ethylene linkage unsaturated copolymer of formula of the present invention (1) expression, chain triene compound (B-1) can be its cis-and trans-mixture of isomers or its cis of separating-or trans-compound.And, when chain triene compound (B-1) the preparation ethylene linkage unsaturated copolymer that uses, be positioned at and be connected R
6And R
7Number of hydrogen atoms on the relevant allylic positions of two keys between the carbon atom of group preferably is at least 3, more preferably is at least 6.
" method for preparing chain triene compound "
Through type (3) but chain triene compound (B-1) that the triene compound with conjugated diolefine structure and the ethylene reaction preparation formula (1) of expression are represented.
In formula (3) by R
1-R
6And R
7The expression alkyl with in formula (1) by R
1-R
6And R
7The alkyl of expression is identical, and its specific examples comprises methyl, ethyl, n-propyl and sec.-propyl.
The specific examples of the triene compound with conjugated diolefine structure of formula (3) expression comprises as follows:
Through type (4) but chain triene compound (B-2) that the triene compound with conjugated diolefine structure and the ethylene reaction preparation formula (2) of expression are represented,
Wherein, R
1, R
2, R
6And R
7With the same meaning in the formula (2).The specific examples of the triene compound with conjugated diolefine structure of formula (4) expression is as follows:
The available following reaction formula of reaction (5) expression of the triene compound with conjugated diolefine structure of formula (3) expression and ethene:
In above-mentioned reaction formula (5), R
1-R
7Identical with in the meaning of n and formula (1) or (3).
According to above-mentioned reaction (5), chain triene compound of the present invention (B-1) normally with cis-and the formation of trans-isomer mixture obtain.According to the molecular structure of chain triene compound (B-1), can be by distillation with cis-and trans-isomer separation.
In the reaction of the triene compound with conjugated diolefine structure of formula (3) expression and ethene, the side chain triene compound of representing with chain triene compound of the present invention (B-1) the by-product formula (6) of expection sometimes,
Wherein, R
1, R
2, R
3, R
4, R
5And R
6Be hydrogen atom or alkyl separately independently of each other with 1-3 carbon atom, R
7Be the alkyl with 1-3 carbon atom, n is the integer of 0-5, prerequisite be when n be 2 or when bigger, each R
4Or R
5Can be identical or different.If necessary, adopt known technology, for example distillation can be isolated by product from required chain triene compound of the present invention (B-1).
In production method of the present invention, be chosen as 30-200 ℃ usually in temperature, preferred 50-150 ℃, and ethylene partial pressure is chosen as 0.05-9.8MPa (0.5-100kgf/cm usually
2, gauge pressure), be preferably 0.2-6.9MPa (2-70kgf/cm
2, gauge pressure) condition under, having the triene compound of conjugated diolefine structure and the reaction of ethene can carry out smoothly, certainly, every kind of triene compound with conjugated diolefine structure according to concrete use can change above-mentioned reaction conditions.Though the reaction times has no particular limits, tend to usually in 0.5-30 hour scope, select.For reaction atmosphere, can use ethene itself, also can be with rare gas element-as argon gas and nitrogen-use with ethene.
In above-mentioned reaction, though allow to use solvent, the use of any reaction solvent is not necessary especially.In the present invention, can use for example hydrocarbon solvent of hexane, heptane, octane, nonane, decane, undecane, tridecane, toluene and dimethylbenzene, but be not limited thereto.
The triene compound with conjugated diolefine structure of formula (3) expression and the reaction of ethene are carried out in the presence of catalyzer usually.Normally used catalyzer is the catalyzer that for example contains transistion metal compound (a) or transition metal complex (b) and organo-aluminium compound (c).
As transistion metal compound (a), the included transition metal of specifiable those compounds comprises the transition metal of 10 families in the transition metal of 9 families in the iron of the transition metal that is selected from 8 families in the periodictable-for example and ruthenium, the periodictable-for example cobalt, rhodium and iridium and the periodictable-for example nickel and palladium; Transistion metal compound (a) is thiocyanate-, prussiate, muriate, bromide, iodide, carbonate, vitriol, nitrate, phosphoric acid salt, acetate and the acetylacetonate of for example above-mentioned transition metal.For transistion metal compound (a), thiocyanate-of these transition metal (a-1) and prussiate (a-2) are preferred.
As the thiocyanate-(a-1) of above-mentioned transition metal, concrete specifiable be the thiocyanate-of the transition metal of the nickel of transition metal-for example of 10 families in transition metal-for example cobalt, rhodium and the iridium of 9 families in the iron of the transition metal that for example is selected from 8 families in the periodictable-for example and ruthenium, the periodictable and the periodictable and palladium.For the thiocyanate-(a-1) of above-mentioned transition metal, preferred cobaltous thiocyanate (II) and ferric thiocyanide (II).
As the prussiate of above-mentioned transition metal, concrete specifiable be the prussiate of the transition metal of the nickel of transition metal-for example of 10 families in transition metal-for example cobalt, rhodium and the iridium of 9 families in the iron of the transition metal that for example is selected from 8 families in the periodictable-for example and ruthenium, the periodictable and the periodictable and palladium.For this class prussiate (a-2) of transition metal, the prussiate of preferred cobalt (II) and iron (II), the prussiate of preferred especially cobalt (II).
As catalyzer, also can use the catalyzer that contains transistion metal compound (a), thiocyanogen compound (e) and organo-aluminium compound (c), the contained transition metal of transistion metal compound (a) is selected from the transition metal of 10 families in the transition metal of 9 families in the iron of the transition metal of 8 families in the periodictable-for example and ruthenium, the periodictable-for example cobalt, rhodium and iridium and the periodictable-for example nickel and palladium.For transistion metal compound (a) as used herein, preferably use the compound except that transition metal thiocyanate-and transition metal prussiate.
As catalyzer, also can use the catalyzer that contains transistion metal compound (a), cyano compound (e) and organo-aluminium compound (c), the contained transition metal of transistion metal compound (a) is selected from the transition metal of 10 families in the transition metal of 9 families in the iron of the transition metal of 8 families in the periodictable-for example and ruthenium, the periodictable-for example cobalt, rhodium and iridium and the periodictable-for example nickel and palladium.For transistion metal compound (a) as used herein, preferably use the compound except that transition metal thiocyanate-and transition metal prussiate.
As mixing the transistion metal compound (a) that uses with thiocyanogen compound (d) or cyano compound (e), its concrete specifiable example is muriate, bromide, iodide, carbonate, vitriol, nitrate, phosphoric acid salt, acetate and the acetylacetonate of the transition metal of the nickel of transition metal-for example of 10 families in transition metal-for example cobalt, rhodium and the iridium of 9 families in the iron of the transition metal that for example is selected from 8 families in the periodictable-for example and ruthenium, the periodictable and the periodictable and palladium.Wherein, preferred acetylacetone cobalt (II), ferric acetyl acetonade (III), nitric acid (II), cobalt chloride (II) and cobaltous acetate (II) or the like, wherein, preferred especially acetylacetone cobalt (II), Xiao Suangu (II), cobalt chloride (II) and cobaltous acetate (II).
As mixing the thiocyanogen compound (d) that uses with transistion metal compound of the present invention (a), its concrete specifiable example is for example thiocyanate-, for example Sodium Thiocyanate 99, potassium sulfocyanate and ammonium thiocyanate; Thiocyanic ester, for example methylthiocyanide methylthiocyanate, Thiocyanic Acid Ethyl ester and thiocyanic acid phenyl ester.Wherein, preferred thiocyanate-, preferred especially potassium sulfocyanate.
As mixing the cyano compound (e) that uses with transistion metal compound of the present invention (a), its concrete specifiable example is for example ion cyano compound, for example sodium cyanide, potassium cyanide and ammonium cyanide; Nitrile (e-1), for example acetonitrile, vinyl cyanide, benzonitrile, phthalonitrile and adiponitrile.Wherein, preferred nitrile (e-1), preferred especially acetonitrile and benzonitrile.
Transistion metal compound (a) itself can be used for Preparation of catalysts.Yet, according to the present invention, in the Preparation of catalysts process, be favourable with the form hybrid transition metal compound (a) of transition metal complex (b), wherein organic ligand and transition-metal coordination.Therefore, preferably prepare catalyzer by forming transition metal complex (b), perhaps in by the process of transistion metal compound (a) preparation catalyzer, can form transition metal complex (b) as the organic compound of ligand transition metal-it is coexisted in system, perhaps form transition metal complex (b) by the step of separating that makes transition metal complex (b) by transistion metal compound (a) and coordination compound in advance by add coordination compound (f)-promptly adding to reaction system.
As coordination compound (f), that is, can be as the organic compound of ligand transition metal, its specifiable example is for example oxygenatedchemicals, for example methyl ether, ether, propyl ether, tetrahydrofuran (THF) and methyl ethyl diketone; Nitrogenous compound, for example methylamine, dimethylamine, Trimethylamine 99, ethamine, diethylamine, triethylamine, hexahydroaniline, dicyclohexyl amine, aniline, pentanoic, pyridine, picoline, 2,2 '-two pyridines and 1,10-phenanthroline; P contained compound, for example triethyl phosphine, tripropyl phosphine, tributylphosphine, tripropyl phosphine, tri-o-tolyl phosphine, two (diphenylphosphino) methane, 1, two (diphenylphosphino) ethane, 1 of 2-, two (diphenylphosphino) propane, 1 of 3-, two (diphenylphosphino) butane of 4-, triphenyl phosphite, oxidation tripropyl phosphine and triphenylphosphate.
Wherein, preferred P contained compound particularly preferably is the tri-o-tolyl phosphine.
As the organo-aluminium compound (c) that catalyst component is sneaked into, its specifiable example is, for example, and trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, chlorodimethylalumiu, diethylaluminum chloride, ethylaluminium dichloride and ethoxyquin diethyl aluminum.Wherein, preferred triethyl aluminum.This organo-aluminium compound (c) can itself be sneaked into or sneak into the formation of its solution in toluene or hexane.
According to the present invention, the triene compound with conjugated diolefine structure of formula (3) expression and the reaction of ethene are preferably carried out in the presence of following arbitrary catalyzer, can effectively make the chain triene compound of above-mentioned formula (1) or (2) expression whereby.
1) catalyzer of forming by transition metal thiocyanate-(a-1) and organo-aluminium compound (c);
2) catalyzer of forming by transistion metal compound (a), thiocyanogen compound (d) and organo-aluminium compound (c);
3) catalyzer of forming by transition metal prussiate (a-2) and organo-aluminium compound (c);
4) catalyzer of forming by transistion metal compound (a), cyano compound (e) and organo-aluminium compound (c);
5) catalyzer of forming by transistion metal compound (a), nitrile compound (e-1) and organo-aluminium compound (c);
6) catalyzer of forming by transistion metal compound (a), acetonitrile or benzonitrile and organo-aluminium compound (c);
7) a kind of catalyzer, wherein above-mentioned 1)-6) any one catalyzer in, use and one or more coordination compoundes (f) coordinate transition metal complex (b) replaces transistion metal compound (a), transition metal thiocyanate-(a-1) or transition metal prussiate (a-2).
Among the preparation method of the present invention, with respect to the amount of the triene compound with conjugated diolefine structure, catalyst consumption generally is that transistion metal compound (a) is 0.001-10mol%, is preferably 0.01-1mol%.Organic compound (f)-promptly, as the coordination compound of ligand transition metal-general consumption be 20 times of transistion metal compound (a) molar weight or still less, be preferably 0.1-10 doubly.The consumption of organo-aluminium compound (c) is 1-200 a times of transistion metal compound (a) molar weight, is preferably 3-100 doubly.
Behind triene compound with conjugated diolefine structure and ethylene reaction, adopt routine techniques-for example by distillation etc.-remove reaction solvent, by product or the like, can from reaction mixture, isolate product, i.e. the chain triene compound (B-1) of formula (1) expression.When in reaction, using catalyzer, preferably carry out the demetalization processing by for example washing reaction mixture with water.
" first kind of multipolymer (I-1): alpha-olefin/three olefinic random copolymers "
First kind of multipolymer of the present invention (I-1) will be described now, i.e. alpha-olefin/three olefinic random copolymers.
For forming first kind of multipolymer of the present invention (I-1), it is the alpha-olefin with 2-20 carbon atom (A) of alpha-olefin/three olefinic random copolymers, its specifiable example is an ethene for example, propylene, 1-butylene, the 1-amylene, the 1-hexene, 3-methyl-1-butene, the 3-Methyl-1-pentene, 3-ethyl-1-amylene, 4-methyl-1-pentene, 4-methyl isophthalic acid-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-amylene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, the 1-octene, 1-decene, the 1-dodecylene, tetradecene, cetene, 1-vaccenic acid and 1-eicosylene.They or use or use its two or more mixture separately.In these alpha-olefins (A), preferably has the alpha-olefin (A) of 1-8 carbon atom, for example ethene, propylene, 1-butylene, 1-hexene and 1-octene.
In the chain triene compound (B-1) of formula (1) expression, preferred n=1 and R
4And R
5Be the compound of hydrogen atom separately independently of each other.Still in these chain triene compounds (B-1), more preferably R
6And R
7Be the compound of methyl or ethyl separately independently of each other.The first kind of multipolymer of the present invention (I-1) that uses chain triene compound (B-1) to obtain as raw material, promptly alpha-olefin/three olefinic random copolymers have good balance between vulcanization rate and incipient scorch curve.
The chain triene compound (B-1) of formula (1) expression have usually steric isomerism (as cis-or trans-isomer).As the chain triene compound (B-1) of starting monomer can be its cis-and trans-mixture of isomers or its single-cis-isomer or trans-isomer.
First kind of multipolymer of the present invention (I-1), promptly, in alpha-olefin/three olefinic random copolymers, be derived from the structural unit of alpha-olefin (A) and the structural unit of the chain triene compound (B-1) that is derived from formula (1) expression and in random distribution, interconnect with 2-20 carbon atom.First kind of multipolymer (I-1) has the unsaturated link(age) of inheriting from the chain triene compound (B-1) of formula (1) expression.First kind of multipolymer of the present invention (I-1), promptly the main chain of alpha-olefin/three olefinic random copolymers has linear structure basically.With this compound dissolution in organic solvent the time without any the fact of insoluble residue, confirmed that on this multipolymer is substantially be linear and hypothesis that be substantially devoid of crosslinked colloidal state molecular structure.For example, above-mentioned hypothesis can promptly when measuring its limiting viscosity [η] for 135 ℃ in naphthalane, find that this multipolymer can be dissolved in the naphthalane (naphthane) fully by following true the confirmation.
First kind of multipolymer of the present invention (I-1), be that the purposes of alpha-olefin/three olefinic random copolymers comprises raw material and the modifier as various rubber products, and can be used as preparation extrusion molding moulded product, for example glass-run channel, wiper blade and weather strip sponge as the rubber starting raw material well; Injection mould goods, for example foam-in-mould sponge and transfer mould goods.
First kind of multipolymer of the present invention (I-1) promptly in alpha-olefin/three olefinic random copolymers, is derived from the structural unit (U of the chain triene compound (B-1) of formula (1) expression
B-1) content is 0.1-30mol%, is preferably 0.5-10mol%.As the single (U of the structure of the chain triene compound (B-1) that is derived from formula (1) expression
B-1) content when being above-mentioned scope, first kind of multipolymer of the present invention (I-1), promptly alpha-olefin/three olefinic random copolymers have high vulcanization rate and good incipient scorch stability.
In naphthalane, measure first kind of multipolymer of the present invention (I-1)-promptly at 135 ℃, alpha-olefin/three olefinic random copolymers-limiting viscosity [η] be 0.1-10dl/g, be preferably 0.5-5dl/g, more preferably 1.0-4.5dl/g.When limiting viscosity during in above-mentioned scope, first kind of multipolymer (I-1) of invention, promptly alpha-olefin/three olefinic random copolymers have high vulcanization rate and good incipient scorch stability.
First kind of multipolymer of the present invention (I-1) promptly in alpha-olefin/three olefinic random copolymers, is derived from the structural unit (U of chain triene compound (B-1)
B-1) molecular structure represent by following formula (1-a) basically:
Wherein, R
1, R
2, R
3, R
4, R
5And R
6Be hydrogen atom or alkyl separately independently of each other with 1-3 carbon atom, R
7Be the alkyl with 1-3 carbon atom, n is the integer of 0-5, prerequisite be when n be 2 or when bigger, each R
4And R
5Can be identical or different respectively,
By
13C-NMR spectroscopic measurement first kind of multipolymer of the present invention (I-1), i.e. alpha-olefin/three olefinic random copolymers, susceptible of proof are derived from the structural unit (U of the chain triene compound (B-1) of formula (1) expression
B-1) have a molecular structure of above-mentioned formula (1-a) expression.
Be used to prepare first kind of multipolymer of the present invention (I-1), be that the alpha-olefin (A) of alpha-olefin/three olefinic random copolymers preferably contains ethene (A-1) and another has the alpha-olefin (A-2) of 3-20 carbon atom, and be derived from the structural unit (U of ethene (A-1)
A-1) with respect to the structural unit (U that is derived from above-mentioned alpha-olefin (A-2)
A-2) mol ratio, i.e. (U
A-1)/(U
A-2) be 99/1-30/70, be preferably 90/10-50/50.As (U
A-1)/(U
A-2) when above-mentioned scope, first kind of multipolymer of the present invention (I-1), promptly alpha-olefin/three olefinic random copolymers have good rubbery material character.
Be used to prepare first kind of multipolymer of the present invention (I-1), the alpha-olefin (A) that is alpha-olefin/three olefinic random copolymers preferably contains the alpha-olefin (A-2) with 3-20 carbon atom, if necessary, also contain the alpha-olefin with 2-20 carbon atom (A-3) different with alpha-olefin (A-2), and, be derived from the structural unit (U of the alpha-olefin (A-2) of the above-mentioned 3-20 of a having carbon atom
A-2) content be 70-99.9mol%, be preferably 75-95%mol%, be derived from the structural unit (U of the alpha-olefin (A-3) of the above-mentioned 2-20 of a having carbon atom
A-3) content be 0-29.9mol%, be preferably 1-25mol%, wherein, suppose (U
A-2)+(U
A-3)+(U
B-1)=100mol% then is derived from the structural unit (U of chain triene compound (B-1)
B-1) content be 0.1-30mol%, be preferably 0.2-10mol%.When the content of every kind of structural unit during in above-mentioned scope separately ,-kind of multipolymer (I-1) of the present invention, promptly alpha-olefin/three olefinic random copolymers have good rubbery material character.
Except the chain triene compound (B-1) of alpha-olefin (A) with 3-20 carbon atom and formula (1), first kind of multipolymer of the present invention (I-1) promptly also can have the compound as other copolymerization of comonomer in alpha-olefin/three olefinic random copolymers.To other comonomer of this class, specifiable example is non-conjugated diene and cyclenes.With respect to the total mole number of all structural units that are derived from all comonomers, the content that is derived from the structural unit of above-mentioned other comonomer is generally 30mol% or still less, is preferably 0.5-10mol%.Above-mentioned other comonomer can adopt the comonomer example that is used for preparing second kind of multipolymer of the present invention described below.
First kind of multipolymer (I-1) of invention, promptly alpha-olefin/three olefinic random copolymers can vulcanize at a high speed, and have good incipient scorch stability and good weathering resistance, thermotolerance and ozone resistance.
First kind of multipolymer (I-1) of invention, be that alpha-olefin/three olefinic random copolymers in actual applications, can not only use with the unvulcanised state of itself, and can adopt technology hereinafter described that its sulfuration back is used with the form of sulphided state, can more effectively improve the characteristic of multipolymer (I-1) by sulfuration.When heterophasic copolymer,, obtained high vulcanization rate though do not reduce described incipient scorch stability.
First kind of multipolymer (I-1) of invention, promptly alpha-olefin/three olefinic random copolymers can particularly advantageously be used as the raw material and the modifier of various rubber products.
For rubber product, it specifically can be goods and the rubber lining cloth that uses in auto parts machinery, industrial rubber product, electrically insulating material, the building structure.Concrete example comprises glass-run channel, Wiper blade, weather strip, sponge, water pipe, buttonhole, sidewall and cable sheath and lock packing.
When first kind of multipolymer of the present invention (I-1), being alpha-olefin/three olefinic random copolymers joins resin for example in acrylic resin, polyvinyl resin, polybutene resin and the polystyrene time as modifier, can significantly improve the shock resistance and the anti-stress cracking of resin.
First kind of multipolymer of the present invention (I-1), but i.e. alpha-olefin/three olefinic random copolymer individual curings or with other elastomeric material covulcanization.
Compare with conventional unsaturated copolymer based on alkene, because first kind of multipolymer of the present invention (I-1), be that alpha-olefin/three olefinic random copolymers have high vulcanization rate, so under the situation of not using a large amount of vulcanizing agents, can under shorter curing time or lower curing temperature, vulcanize.First kind of multipolymer of the present invention (I-1), promptly alpha-olefin/three olefinic random copolymers have good incipient scorch stability, therefore can adopt the foamed moulded method processing with stable rate of expansion, and can improve the productivity of foaming product whereby.Delicate balance between the rate of decomposition of the initial viscosity by material resin, speed that the moulding process medium viscosity increases and whipping agent can determine foam overrun.Because the speed that viscosity increases is high more, the variation of viscosity rate of change is big more, therefore controls the rate of expansion difficulty.But because have good incipient scorch stability, so first kind of multipolymer of the present invention (I-1), i.e. the viscosity increase of alpha-olefin/three olefinic random copolymers is lower, therefore can prepare foaming mould product effectively under stable rate of expansion.Because first kind of multipolymer of the present invention (I-1), be that alpha-olefin/three olefinic random copolymers have good incipient scorch stability, therefore also has good processing stability in its process of on forcing machine, processing, so just can avoid using such as the phenomenon that extrudes any trouble that causes owing to the viscosity increase in the mach process, the phenomenon of these troubles is for example to increase owing to the sulfuration in the forcing machine causes viscosity, thus feasible output reduction, motor load increase and machine barrel and/or punch die filling or the phenomenon of blocking extruded.
When keeping above-mentioned excellent characteristic, first kind of multipolymer of the present invention (I-1), promptly another favourable feature of alpha-olefin/three olefinic random copolymers is to have good thermotolerance.
" first kind of multipolymer (I-1), the i.e. preparation of alpha-olefin/three olefinic random copolymers "
First kind of multipolymer of the present invention (I-1), promptly alpha-olefin/three olefinic random copolymers can be used the method preparation identical with following second kind of multipolymer of the present invention.Therefore, under identical condition and in the presence of the same catalyst of enumerating in the preparation of following second kind of multipolymer, the chain triene compound (B-1) of the alpha-olefin by having 2-20 carbon atom, formula (1) expression and-if necessary-copolymerization of other comonomer of optional adding, can prepare first kind of multipolymer of the present invention (I-1).
The first kind of multipolymer of the present invention (I-1) that obtains with aforesaid method, be that alpha-olefin/three olefinic random copolymers can be vulcanized at a high speed, and have good incipient scorch stability and good weathering resistance, thermotolerance and ozone resistance, so it can be used as for example raw material and the modifier of various rubber products.By vulcanizing first kind of multipolymer of the present invention (I-1), promptly the vulcanized rubber products that alpha-olefin/three olefinic random copolymers obtain not only has good weathering resistance, thermotolerance and ozone resistance, and has good caoutchouc elasticity.Using first kind of multipolymer of the present invention (I-1), i.e. alpha-olefin/when three olefinic random copolymers prepare vulcanized rubber products,, therefore can obtain high yield owing to can vulcanize at a high speed.
First kind of composition of the present invention contains first kind of multipolymer of the present invention (I-1), i.e. alpha-olefin/three olefinic random copolymers, vulcanizing agent (II) and/or filler (III).First kind of composition of the present invention is made up of compositions of vulcanize rubbers, though have more favourable characteristic when first kind of multipolymer of the present invention uses with sulfurized form, also can use itself unvulcanised state in actual applications.
Not only have good weathering resistance, thermotolerance, ozone resistance and dynamic fatigue resistance by vulcanizing the vulcanized rubber products that first kind of composition of the present invention obtain, and have good caoutchouc elasticity and rubbing property of low temperature.Because first kind of multipolymer of the present invention (I-1), promptly alpha-olefin/three olefinic random copolymers can be vulcanized at a high speed, so when using first kind of preparation of compositions vulcanized rubber products of the present invention, can obtain high productivity.The amount of the vulcanization accelerator that also can reduce vulcanizing agent (II) and sneak into is so that obtain the good vulcanized rubber products of the lower outward appearance of bloom degree.
First kind of composition of the present invention can be with vulcanizing with second kind of following identical method of composition.Therefore, by with the compound that constitutes vulcanization system-for example vulcanizing agent (II), vulcanization accelerator and vulcanization aid or the like-mix being incorporated in the sulfuration of carrying out mixture under the condition identical with following second composition, just can vulcanize first kind of composition of the present invention.
When in first kind of composition of the present invention, adding filler (III), can use with second following composition in identical toughener and tenderizer.The amount that is blended into these tougheners in the composition and tenderizer also can be identical with the amount in following second composition.
Except that said components, first kind of composition of the present invention also can mix with other component and chemical, it comprises the compound that constitutes foaming system, for example, and whipping agent and frothing aid, oxidation inhibitor (stablizer), processing aid, softening agent, colorant and other rubber component.The kind of these other components and consumption can be selected according to various requirement.
When first kind of composition of the present invention contains the compound that constitutes foaming system-for example whipping agent and frothing aid-time, first kind of composition of the present invention can adopt foamed moulded method processing.Identical mode is carried out in second foamed moulded also available with following composition.Therefore, the whipping agent and the frothing aid that use in whipping agent and frothing aid and following second composition are identical, and its consumption is also identical.
Remove first kind of multipolymer (I-1), promptly outside alpha-olefin/three olefinic random copolymers, do not influencing under realization the object of the invention condition, first kind of composition of the present invention can contain other known rubber component.Described other rubber component is identical with rubber component in following second composition, and its consumption is also identical, can develop the compounded rubber with better material character whereby.
First kind of composition of the present invention preferably contains first kind of multipolymer of the present invention (I-1), i.e. alpha-olefin/three olefinic random copolymers are benchmark with the gross weight of composition, and its content is at least 20%, and preferably at least 25%.When first kind of multipolymer (I-1), when promptly the content of alpha-olefin/three olefinic random copolymers is in above-mentioned scope, can develop compounded rubber with better material character.
First kind of composition of the present invention can be used for rubber product as raw material, for example auto parts machinery, thump damping rubber, industrial rubber product, electrically insulating material, building structure be with the raw material of goods and rubber lining cloth, in particular as preparation extrudate-for example seal gum, glass-run channel, wiper blade and rubber sponge weather strip-initial rubber raw materials; Be used for the injection mould goods, for example foam-in-mould latex foam products and automotive door seal with rubber sponge; And the robber materials that is used for the transfer mould goods as initial rubber raw materials.The specific examples of caulking gum comprises those that enumerate in second following composition.
When first kind of composition of the present invention is used as the raw material of preparation above-mentioned seal gum, glass-run channel, Wiper blade, rubber sponge weather strip and foam-in-mould goods, they can make by vulcanizing at a high speed with high yield, and have good caoutchouc elasticity, weathering resistance, thermotolerance, ozone resistance and rubbing property of low temperature.For example, by vulcanizing the green product that extrudes at short notice, just can make the rubber sponge weather strip with high yield.At this moment, can carry out tight cure in the short period of time, thereby the finished product with good caoutchouc elasticity can be provided.
Except adding first kind of multipolymer (I-1), promptly outside alpha-olefin/three olefinic random copolymers, second kind of identical method of multipolymer of available with following the present invention prepares first kind of multipolymer of the present invention.
By various forming techniques, usually use such as the forming mill of extrusion molding moulding press, calender roll, press, injection molding machine or die casting mold machine and in advance unvulcanized composition is made the shape that needs, and in the preformed while or after green product being imported in the sulfuration container, hot briquetting green product or with electron beam irradiation moulding green product can make the vulcanizate (sulfurized rubber product) of first kind of composition of the present invention.For foaming product, with method same as described above the not vulcanising composition that contains whipping agent to be vulcanized, foaming is carried out simultaneously with sulfuration, thereby obtains foaming product.Identical in the situation of technology and described second kind of composition hereinafter as used herein.
Identical with aforesaid method moulding and sulfurized vulcanized rubber products with the purposes of following second composition.
When the moulding product that is made by first kind of composition of the present invention is sheet or film, moulding product can be a laminate, wherein the other tab laminate that will be made by other rubber or resin is on the thin slice that is made by first kind of composition of the present invention, thereby made composite sheet or laminated film.The material that is used for preparing described other thin slice is for example based on the rubber of conjugated diolefine, copolymer rubber, polyethylene, polypropylene or polybutene based on ethylene/alpha-olefin.
By with mixed with resin, for example with polyolefin resin-for example polyethylene, polypropylene and polybutene-mix or with mixed with resin such as AES and ABS, form that can resin combination is used first kind of multipolymer of the present invention (I-1), i.e. alpha-olefin/three olefinic random copolymers.At this moment, the blending ratio of employing, other the softening component of additive-for example etc.-identical with the situation of following second composition of the present invention.The linking agent that adopts and cross-linking method also can be identical with the situation of following second composition of the present invention.
In first multipolymer of the present invention, following second multipolymer that provides { ethylene/alpha-olefin/three olefinic random copolymers (I-2) } and the 3rd multipolymer { alpha-olefin/three olefinic random copolymers (I-3) } are preferred.
In first composition of the present invention, following second composition that provides (composition that contains ethylene/alpha-olefin/three olefinic random copolymers) and the 3rd composition (composition that contains alpha-olefin/three olefinic random copolymers) are preferred.
Second multipolymer of the present invention (I-2) is ethylene/alpha-olefin/three olefinic random copolymers, and it contains:
Structural unit (the U that obtains by ethene (A-1)
A-1),
Structural unit (the U that obtains by the alpha-olefin that contains 3-20 carbon atom (A-2)
A-2) and
Structural unit (the U that the chain triene compound of being represented by formula (2) (B-2) obtains
B-2), the structural unit (U that obtains by ethene (A-1) wherein
A-1) with respect to the structural unit (U that obtains by the alpha-olefin that contains 3-20 carbon atom (A-2)
A-2) mol ratio, i.e. (U
A-1)/(U
A-2) be 99/1-30/70, the limiting viscosity of measuring in 135 ℃ naphthane [η] is 0.1-10dl/g, wherein structural unit (the U that is obtained by the chain triene compound (B-2) of formula (2) expression
B-2) content be 0.1-30mol%.
Second composition of the present invention (composition that contains ethylene/alpha-olefin/three olefinic random copolymers) contains above-mentioned ethylene/alpha-olefin/three olefinic random copolymers (I-2), vulcanizing agent (II) and/or filler (III).
The 3rd multipolymer of the present invention (I-3), the i.e. structural unit (U that obtains by the alpha-olefin with 3-20 carbon atom (A-2) in alpha-olefin/three olefinic random copolymers
A-2) content be 70-99.9mol%, the content of the structural unit that is obtained by the alpha-olefin with 2-20 carbon atom (A-3) is 0-30mol% and the structural unit (U that obtained by the chain triene compound (B-2) of formula (2) expression
B-2) content be 0.1-30mol%, its prerequisite is the content summation (U of these structural units
A-2)+(U
A-3)+(U
B-2) reach 100mol%, wherein the limiting viscosity of measuring in 135 ℃ naphthane [η] is 0.1-10dl/g.
The 3rd composition of the present invention (composition that contains alpha-olefin/three olefinic random copolymers) contains above-mentioned alpha-olefin/three olefinic random copolymers (I-3), vulcanizing agent (II) and/or filler (III).
Describe second multipolymer now, it is the preferred copolymer in the multipolymer of the present invention.
As constituting second multipolymer (I-2), it is the alpha-olefin with 3-20 carbon atom of ethylene/alpha-olefin/three olefinic random copolymers, the example comprises propylene, 1-butylene, 1-amylene, 1-hexene, 3-methyl-1-butene, 3-Methyl-1-pentene, 3-ethyl-1-amylene, 4-methyl-1-pentene, 4-methyl isophthalic acid-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-amylene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid and 1-eicosylene.The alpha-olefin that wherein preferably contains 3-8 carbon atom, for example propylene, 1-butylene, 1-hexene and 1-octene.
In chain triene compound (B-2) by formula (2) expression, preferred R wherein
3And R
4The compound of all representing methyl.Second multipolymer of the present invention (I-2) that uses this chain triene compound (B-2) to obtain as initial monomers is especially outstanding aspect the balance of ethylene/alpha-olefin/three olefinic random copolymers between vulcanization rate and incipient scorch curve promptly.
As the chain triene compound (B-2) of formula (2) expression, preferred 4,8-dimethyl-1,4,8-triolefin in the last of the ten Heavenly stems (being abbreviated as DMDT hereinafter sometimes).
The chain triene compound (B-2) of formula (2) expression has steric isomer (cis-and trans-isomer) usually.As the chain triene compound (B-2) of comonomer can be cis-and trans-mixture of isomers or cis-or the individual isomer of trans-isomer.
At second multipolymer of the present invention (I-2), be in ethylene/alpha-olefin/three olefinic random copolymers, the structural unit that is obtained by ethene (A-1), the alpha-olefin that contains 3-20 carbon atom and chain triene compound (B-2) exists with stochastic distribution, and the unsaturated link(age) that wherein exists the chain triene compound (B-2) by formula (2) expression to bring.Second multipolymer of the present invention (I-2), promptly the main chain of ethylene/alpha-olefin/three olefinic random copolymers has the structure of substantial linear.This multipolymer is dissolved in the organic solvent and does not show that the fact of any undissolved resistates has confirmed second multipolymer (I-2), and promptly ethylene/alpha-olefin/three olefinic random copolymers have the structure of substantial linear and are substantially devoid of the hypothesis of crosslinked colloidal molecular structure.For example, this can be dissolved in fully when measuring its limiting viscosity [η] in 135 ℃ the naphthane by multipolymer (I-2) and be confirmed.
At second multipolymer of the present invention (I-2), promptly in ethylene/alpha-olefin/three olefinic random copolymers, the structural unit (U that obtains by ethene (A-1)
A-1) with respect to the structural unit (U that obtains by alpha-olefin (A-2)
A-2) mol ratio, i.e. (U
A-1)/(U
A-2) be 99/1-30/70, preferred 90/10-50/50, it can be expressed as " ethylene/alpha-olefin " sometimes hereinafter.When this mol ratio is in above-mentioned scope, second multipolymer of the present invention (I-2), promptly ethylene/alpha-olefin/three olefinic random copolymers show good elastomeric material character.
Second multipolymer of the present invention (I-2), be that ethylene/alpha-olefin/three olefinic random copolymers can be used for following application, it comprises the raw material as various rubber products and modifier, also can be advantageously used for and be used for the extrusion mode goods, for example the raw material of the rubber of glass-run channel, Wiper blade and weather strip sponge; With acting on the injection-molded product, the raw material of the rubber of mould inner foam sponge product and transfer mould goods for example.
For second multipolymer of the present invention (I-2) as the initial rubber of the production of glass-run channel, be ethylene/alpha-olefin/three olefinic random copolymers, the mol ratio of ethylene/alpha-olefin is at 85/15-50/50, and especially 80/20-65/35 is especially favourable.When this mol ratio is in above-mentioned scope, can obtain especially outstanding glass-run channel aspect caoutchouc elasticity and low temperature flexibility.
For second multipolymer of the present invention (I-2) of the initial rubber of producing as Wiper blade, i.e. ethylene/alpha-olefin/three olefinic random copolymers, the mol ratio of ethylene/alpha-olefin is at 80/20-60/40, and especially 80/20-70/30 is especially favourable.When this mol ratio is in above-mentioned scope, can obtain especially outstanding Wiper blade aspect caoutchouc elasticity and low temperature flexibility.
Second multipolymer of the present invention (I-2) for the initial rubber of producing as the rubber sponge weather strip, be ethylene/alpha-olefin/three olefinic random copolymers, the mol ratio of ethylene/alpha-olefin is at 85/15-60/40, and especially 80/20-65/35 is especially favourable.When this mol ratio is in above-mentioned scope, can obtain especially outstanding weather strip aspect caoutchouc elasticity and low temperature flexibility.
For second multipolymer of the present invention (I-2) as the initial rubber that uses injection moulding machine or transfer moIding machine production rubber sponge mould inner foam plastic shaping goods, be ethylene/alpha-olefin/three olefinic random copolymers, the mol ratio of ethylene/alpha-olefin is at 80/20-60/40, and especially 80/20-70/30 is especially favourable.When this mol ratio is in above-mentioned scope, can obtain especially outstanding latex foam products aspect caoutchouc elasticity and low temperature flexibility.
Second multipolymer of the present invention (I-2), the i.e. structural unit (U that obtains by the chain triene compound (B-2) of formula (2) expression in ethylene/alpha-olefin/three olefinic random copolymers
B-2) content be 0.1-30mol%, preferred 0.5-10mol%.As the structural unit (U that obtains by chain triene compound (B-2)
B-2) content in above-mentioned scope the time, second multipolymer of the present invention (I-2), promptly ethene alkene/alpha-olefin/three olefinic random copolymers show high vulcanization rate and outstanding incipient scorch stability.
For second multipolymer of the present invention (I-2) as the initial rubber of producing glass-run channel, be ethylene/alpha-olefin/three olefinic random copolymers, wherein the content of the structural unit (UB-2) that is obtained by chain triene compound (B-2) especially is especially favourable in the 1.3-3.3mol% scope at 0.5-3.7mol%.As the structural unit (U that obtains by chain triene compound (B-2)
B-2) content in above-mentioned scope the time, can obtain especially outstanding glass-run channel aspect caoutchouc elasticity and low temperature flexibility.As the structural unit (U that obtains by chain triene compound (B-2)
B-2) content in above-mentioned scope the time, iodine number is usually at 10-50, in the scope of preferred 20-45.
For second multipolymer of the present invention (I-2) as the initial rubber of producing Wiper blade, i.e. ethylene/alpha-olefin/three olefinic random copolymers, the wherein structural unit (U that obtains by chain triene compound (B-2)
B-2) content at 0.3-2.8mol%, especially be especially favourable in the 0.5-2.8mol% scope.As the structural unit (U that obtains by chain triene compound (B-2)
B-2) content in above-mentioned scope the time, can obtain especially outstanding Wiper blade aspect caoutchouc elasticity and low temperature flexibility.As the structural unit (U that obtains by chain triene compound (B-2)
B-2) content in above-mentioned scope the time, iodine number is usually at 5-40, in the scope of preferred 10-40.For second multipolymer of the present invention (I-2) as the initial rubber of producing the rubber sponge weather strip, i.e. ethylene/alpha-olefin/three olefinic random copolymers, the wherein structural unit (U that obtains by chain triene compound (B-2)
B-2) content at 0.5-3.7mol%, especially be especially favourable in the 1.3-3.3mol% scope.As the structural unit (U that obtains by chain triene compound (B-2)
B-2) content in above-mentioned scope the time, can obtain especially outstanding weather strip aspect caoutchouc elasticity and low temperature flexibility.As the structural unit (U that obtains by chain triene compound (B-2)
B-2) content in above-mentioned scope the time, iodine number is usually at 10-50, in the scope of preferred 20-45.
For second multipolymer of the present invention (I-2) as the initial rubber that uses injection moulding machine or transfer moIding machine production rubber sponge mould inner foam plastic shaping goods, be ethylene/alpha-olefin/three olefinic random copolymers, the structural unit (U that obtains by chain triene compound (B-2) wherein
B-2) content at 0.5-3.7mol%, especially be especially favourable in the 1.3-3.3mol% scope.As the structural unit (U that obtains by chain triene compound (B-2)
B-2) content in above-mentioned scope the time, can obtain rubber sponge mould inner foam goods especially outstanding aspect caoutchouc elasticity and low temperature flexibility.As the structural unit (U that obtains by chain triene compound (B-2)
B-2) content in above-mentioned scope the time, iodine number is usually at 10-50, in the scope of preferred 20-45.
Second multipolymer of the present invention (I-2), the limiting viscosity [η] that promptly ethene a-alkene/three olefinic random copolymers are measured in 135 ℃ naphthane is 0.1-10dl/g, preferred 0.5-5dl/g.When limiting viscosity [η] is in above-mentioned scope, second multipolymer of the present invention (I-2), promptly ethylene/alpha-olefin/three olefinic random copolymers show high vulcanization rate and outstanding incipient scorch stability.
For second multipolymer of the present invention (I-2) as the initial rubber of producing glass-run channel, that is, ethylene/alpha-olefin/three olefinic random copolymers, limiting viscosity [η] is that 1.2-4.5dl/g, especially 2.0-3.5dl/g are particularly advantageous.When limiting viscosity [η] is in above-mentioned scope, can obtain outstanding equilibrated glass-run channel between processing characteristics and intensity.
For second multipolymer of the present invention (I-2) as the initial rubber of producing Wiper blade, i.e. ethylene/alpha-olefin/three olefinic random copolymers, limiting viscosity [η] is that 0.7-4.5dl/g, especially 1.5-3.3dl/g are particularly advantageous.When limiting viscosity [η] is in above-mentioned scope, can obtain outstanding equilibrated Wiper blade between processing characteristics and intensity.
For second multipolymer of the present invention (I-2) as the initial rubber of producing the rubber sponge weather strip, i.e. ethylene/alpha-olefin/three olefinic random copolymers, limiting viscosity [η] is that 1.2-5.0dl/g, especially 2.0-4.5dl/g are particularly advantageous.When limiting viscosity [η] is in above-mentioned scope, can obtain outstanding equilibrated weather strip between processing characteristics and intensity.
For second multipolymer of the present invention (I-2) as the initial rubber that uses injection moulding machine or transfer moIding machine production rubber sponge mould inner foam plastic shaping goods, be ethylene/alpha-olefin/three olefinic random copolymers, limiting viscosity [η] is that 0.5-2.0dl/g, especially 0.7-1.4dl/g are particularly advantageous.When limiting viscosity [η] is in above-mentioned scope, can obtain mobile outstanding mould inner foam plastic shaping goods in model.
At second multipolymer of the present invention (I-2), promptly in ethylene/alpha-olefin/three olefinic random copolymers, the structural unit (U that obtains by chain triene compound (B-2)
B-2) have basically by structure as shown in the formula (2-a) expression:
R wherein
1And R
2Represent hydrogen atom, methyl or ethyl, R respectively independently of each other
3And R
4Represent methyl or ethyl respectively independently of each other.
Structural unit (the U that obtains by chain triene compound (B-2)
B-2) having can be by using by the structure of following formula (2-a) expression
13The C-NMR spectrum detects second multipolymer and confirms.
Second multipolymer of the present invention (I-2), be that ethylene/alpha-olefin/three olefinic random copolymers can contain the structural unit that is obtained by other compound as comonomer, described comonomer can with ethene (A-1), the alpha-olefin (A-2) that contains 3-20 carbon atom and chain triene compound (B-2) copolymerization.For this other comonomer, the example can be non-conjugated diene and cycloolefin.With respect to the entire infrastructure unit of all comonomers, the content of the structural unit that is obtained by this other comonomer is 30mol% or still less, preferred 0.5-10mol%.
As the non-conjugated diene hydrocarbon of this other comonomer, specifiable is that those exist the material of two polymerisable carbon-to-carbon double bonds (C=C) or those only to have the material of a polymerisable carbon-to-carbon double bond in molecule in whole carbon-to-carbon double bonds in molecule in whole carbon-to-carbon double bonds." polymerisable carbon-to-carbon double bond " is meant in the presence of catalyzer and promptly can be used for the polymeric carbon-to-carbon double bond in the production of ethylene/alpha-olefin/three olefinic random copolymers at second multipolymer of the present invention (I-2) herein.
By copolymerization non-conjugated diene hydrocarbon, may command vulcanization rate.When in molecule, containing the non-conjugated diene hydrocarbon copolymerization of two polymerisable carbon-to-carbon double bonds, introduced the long-chain side chain, thereby increased moldability.The specific examples that is used as the non-conjugated diene hydrocarbon that contains two polymerizable carbon-to-carbon double bonds in molecule of other comonomer comprises 5-alkenyl-2-norbornylene, for example 5-vinyl-2-norbornylene and 5-allyl group-2-norbornylene; The cyclic aliphatic diolefine, for example 2,5-norbornadiene, Dicyclopentadiene (DCPD) and Fourth Ring [4.4.0.1
25.1
7.10] last of the ten Heavenly stems-3, the 8-diene; And α, ω-diolefine, for example 1,7-octadiene and 1,9-decadiene.5-alkenyl-2-norbornylene, 2 wherein, 5-norbornadiene, Dicyclopentadiene (DCPD) and 1,7-octadiene are preferred, wherein especially preferred 5-alkenyl 2-norbornylene and 2,5-norbornadiene.
As the non-conjugated diene that only contains a polymerizable carbon-to-carbon double bond in molecule as other comonomer, preferably those ends at molecule only exist a carbon-to-carbon double bond as vinyl (CH
2=CH-) and other carbon-to-carbon double bond be present in material in the molecular chain (comprising main chain and side chain) with the form of internal olefin structure.As the non-conjugated diene hydrocarbon that only contains a polymerisable carbon-to-carbon double bond, the example is the aliphatic diolefine hydrocarbon and contains the alicyclic part that has a carbon-to-carbon double bond and wherein have the alicyclic diolefine of the linear fraction of internal olefin carbon-to-carbon double bond.Wherein preferred alicyclic diolefine.
The specific examples that only contains the aliphatic diolefine hydrocarbon that is used as other comonomer of a polymerisable carbon-to-carbon double bond in molecule is 1, the 4-hexadiene, 1, the 6-octadiene, the 3-methyl isophthalic acid, the 4-hexadiene, the 4-methyl isophthalic acid, the 4-hexadiene, the 5-methyl isophthalic acid, the 4-hexadiene, 4-ethyl-1, the 4-hexadiene, 3-methyl 1, the 5-hexadiene, 3,3-dimethyl-1, the 4-hexadiene, the 5-methyl isophthalic acid, the 4-heptadiene, 5-ethyl-1, the 4-heptadiene, the 5-methyl isophthalic acid, the 5-heptadiene, the 6-methyl isophthalic acid, the 5-heptadiene, 5-ethyl-1, the 5-heptadiene, the 4-methyl isophthalic acid, the 4-octadiene, the 5-methyl isophthalic acid, the 4-octadiene, 4-ethyl-1, the 4-octadiene, 5-ethyl-1, the 4-octadiene, the 5-methyl isophthalic acid, the 5-octadiene, the 6-methyl isophthalic acid, the 5-octadiene, 5-ethyl-1, the 5-octadiene, 6-ethyl-1, the 5-octadiene, the 6-methyl isophthalic acid, the 6-octadiene, the 7-methyl isophthalic acid, the 6-octadiene, 6-ethyl-1, the 6-octadiene, 6-propyl group-1, the 6-octadiene, 6-butyl-1, the 6-octadiene, the 4-methyl isophthalic acid, the 4-nonadiene, the 5-methyl isophthalic acid, the 4-nonadiene, 4-ethyl-1, the 4-nonadiene, 5-ethyl-1, the 4-nonadiene, the 5-methyl isophthalic acid, the 5-nonadiene, the 6-methyl isophthalic acid, the 5-nonadiene, 5-ethyl-1, the 5-nonadiene, 6-ethyl-1, the 5-nonadiene, the 6-methyl isophthalic acid, the 6-nonadiene, the 7-methyl isophthalic acid, the 6-nonadiene, 6-ethyl-1, the 6-nonadiene, 7-ethyl-1, the 6-nonadiene, the 7-methyl isophthalic acid, the 7-nonadiene, the 8-methyl isophthalic acid, the 7-nonadiene, 7-ethyl-1, the 7-nonadiene, the 5-methyl isophthalic acid, the 4-decadiene, 5-ethyl-1, the 4-decadiene, the 5-methyl isophthalic acid, the 5-decadiene, the 6-methyl isophthalic acid, the 5-decadiene, 5-ethyl-1, the 5-decadiene, 6-ethyl-1, the 5-decadiene, the 6-methyl isophthalic acid, the 6-decadiene, 6-ethyl-1, the 6-decadiene, the 7-methyl isophthalic acid, the 6-decadiene, 7-ethyl-1, the 6-decadiene, the 7-methyl isophthalic acid, the 7-decadiene, the 8-methyl isophthalic acid, the 7-decadiene, 7-ethyl-1, the 7-decadiene, 8-ethyl-1, the 7-decadiene, the 8-methyl isophthalic acid, the 8-decadiene, the 9-methyl isophthalic acid, the 8-decadiene, 8-ethyl-1, the 8-decadiene, the 6-methyl isophthalic acid, 6-11 carbon diene and 9-methyl isophthalic acid, 8-11 carbon diene.
The specific examples that only contains the alicyclic diolefine that is used as other comonomer of a polymerizable carbon-to-carbon double bond in molecule comprises norbornene derivative, for example 5-ethylidene-2-norbornene, 5-propylidene-2-norbornylene and 5-butylidene-2-norbornylene; With the norbornadiene derivative, 2-methyl-2 for example, 5-norbornadiene and 2-ethyl-2,5-norbornadiene.Wherein 5-ethylidene-2-norbornene is preferred.
Can only add a kind of perhaps multiple this non-conjugated diene hydrocarbon as other comonomer.
As the cycloolefin of other comonomer, specifiable is by following formula (7-1) and the compound (7-2) represented:
In above-mentioned formula (7-1), n is 0 or 1, and m is 0 or positive integer, and q is 0 or 1, R
1-R
18And R
aAnd R
bRepresent atom or group respectively independently of each other, it is selected from hydrogen, halogen atom and alkyl, wherein R
15And R
16Can be combined together to form the monocycle that can contain two keys or encircle or radicals R more
15And R
16Or radicals R
17And R
18Can form alkylidene group.Equal at q under 0 the situation, key can condense and form 5 yuan of rings together.
In above-mentioned formula (7-2), m is 0 or positive integer, and h is 0 or positive integer, and j and k are respectively 0,1 or 2, R
7-R
15And R
17And R
18Be respectively atom or group, it is selected from hydrogen atom, halogen atom and alkyl, wherein R
19-R
27Represent atom or group respectively, it is selected from hydrogen atom, halogen atom, alkyl and alkoxyl group.
In above-mentioned formula (7-1), R
1-R
18And R
aAnd R
bRepresent atom or group respectively, it is selected from hydrogen atom, halogen atom and alkyl.
In this article, halogen atom is fluorine, chlorine, bromine or iodine.
As alkyl, specifiablely be, for example, contain 1-20 carbon atom alkyl, contain 1-20 carbon atom haloalkyl, contain the cycloalkyl of 3-15 carbon atom and contain the aromatic hydrocarbon group of 6-20 carbon atom.More particularly, alkyl can be for example methyl, ethyl, propyl group, sec.-propyl, amyl group, hexyl, octyl group, decyl, dodecyl and octadecyl.
Haloalkyl can be the group that the hydrogen atom in those alkyl is replaced to small part by fluorine atom, chlorine atom, bromine atoms or iodine atom.
Cycloalkyl can comprise, for example cyclohexyl etc.Aromatic hydrocarbon group can comprise, for example phenyl, naphthyl etc.
Can also by in (each other) formula (7-1) each to R
15And R
16, R
17And R
18, R
15And R
17, R
16And R
18, R
15And R
18And R
16And R
17Form monocycle or many rings respectively, wherein the monocycle that forms by this way or many rings can contain two keys.As formed monocycle or many rings, specifiable example is as follows:
Above-mentioned for example in, the carbon atom that marks with numerical value 1 or 2 is represented the R of itself and formula (7-1)
15(R
16) or R
17(R
18) combination.
In addition, by in conjunction with R
15With R
16Or R
17With R
18Also can form alkylidene group.This alkylidene group can contain 2-20 carbon atom usually, and specific examples comprises ethylidene, propylidene and isopropylidene.
As preferred cycloolefin, can enumerate material by following formula (7-3) expression by formula (7-1) expression:
Wherein n, m and R
1-R
18Identical with the definition in the formula (7-1).
In formula (7-2), m and h are 0 or positive integer, and j and k are respectively 0,1 or 2, R
7-R
15And R
17-R
18Identical with the definition in the formula (7-1), R
19-R
27Represent atom or group respectively, it is selected from hydrogen atom, halogen atom, alkyl and alkoxyl group.
Identical in halogen atom herein and the formula (7-1).
R as formula (7-2)
19-R
27Alkyl, can enumerate the alkyl, the haloalkyl that contains 1-20 carbon atom that contain 1-20 carbon atom, contain the cycloalkyl of 3-15 carbon atom and contain the aromatic hydrocarbon group of 6-20 carbon atom.The specific examples of alkyl comprises methyl, ethyl, propyl group, sec.-propyl, amyl group, hexyl, octyl group, decyl, dodecyl and octadecyl; The example of haloalkyl can be the group that the hydrogen atom in the above-named alkyl is replaced to small part by fluorine atom, chlorine atom, bromine atoms or iodine atom.
For cycloalkyl, can comprise cyclohexyl etc., aromatic hydrocarbon group can comprise aryl, aralkyl etc., its specific examples comprises phenyl, tolyl, naphthyl, benzyl and styroyl.For alkoxyl group, can enumerate methoxyl group, oxyethyl group and propoxy-.In conjunction with R
17And R
18Carbon atom can directly connect or be connected in conjunction with R by the alkylidene group that contains 1-3 carbon atom
21Carbon atom or in conjunction with R
19Carbon atom on.Therefore, under the situation that above-mentioned two carbon atoms connect by alkylidene group, respectively by R
17And R
21The expression group or respectively by R
18And R
19The group of expression will form alkylidene group together, and it is selected from methylene radical (CH
2-), ethylidene-CH
2CH
2-) and trimethylene (CH
2CH
2CH
2-).
In addition, when j=k=0, group is to R
23With R
20Or R
23With R
27Can be bonded to each other and form monocycle or many cyclophanes ring.When at j=k=0, at group to R
23With R
20Form under the situation of aromatic ring, the example of monocycle or many cyclophanes ring comprises the following group that provides.
In the above-mentioned formula of enumerating, symbol h is identical with the definition in the formula (7-2).
By formula (7-1) and (7-2) specific examples of cycloolefin of expression be:
Dicyclo [2.2.1] hept-2-ene" or derivatives thereof,
Fourth Ring [4.4.0.1
25.1
7.10]-3-dodecylene or derivatives thereof,
Six ring [6.6.1.1
3.6.1
10.13.0
2.70
9.14]-4-heptadecene or derivatives thereof,
Eight ring [8.8.0.1
2.9.1
4.7.1
11.18.1
13.16.0
3.6.0
12.17]-5-two dodecylene or derivatives thereofs,
Five rings [6.6.1.1
3.6.0
2.7.0
9.14]-4-cetene or derivatives thereof,
Seven ring-5-eicosylene or derivatives thereofs,
Seven ring-5-heneicosene or derivatives thereofs,
Three ring [4.3.0.1
2.5]-3-decene or derivatives thereof,
Three ring [1.4.0.1
2.5]-3-undecylene or derivatives thereof,
Five rings [6.5.1.1
3.5.0
2.7.0
3.13]-4-15 carbene or derivatives thereofs,
Five rings 15 carbon diene or derivatives thereofs,
Five rings [7.4.0.1
2.5.1
9.12.0
8.13]-3-15 carbene or derivatives thereofs,
Seven ring [8.7.0.1
3.6.1
10.17.1
12.15.0
2.7.0
11.16]-4-eicosylene or derivatives thereof,
Nine ring [10.9.1.1
4.7.1
13.20.1
15.18.0
3.8.0
2.10.0.
12.21.0
14.19]-5-ppentacosene or derivatives thereof,
Five rings [8.4.0.1
2.5.1
9.12.0
8.13]-3-cetene or derivatives thereof,
Seven ring [8.8.0.1
4.7.1
11.18.1
13.16.0
3.8.0
12.17]-5-heneicosene or derivatives thereof,
Nine ring [10.10.1.1
5.8.1
14.21.1
16.19.0
2.11.0
4.9.0
13.22.0
15.20]-5-cerotene or derivatives thereof,
1,4-methylene radical-1,4,4a, 9a-tetrahydrochysene fluorenes or derivatives thereof,
1,4-methylene radical-1,4,4a, 5,10,10a-six hydrogen anthracene or derivatives thereofs and
Cyclopentadiene-acenaphthene adducts.
By general formula (7-1) and (7-2) expression cycloolefin can carry out the Diels-Alder prepared in reaction by the olefin(e) compound that makes cyclopentadiene and corresponding molecular structure.
These cycloolefins can be single ground or two or more be used in combination.
Second multipolymer of the present invention (I-2), the speed sulfuration that promptly ethylene/alpha-olefin/three olefinic random copolymers can be high is being outstanding aspect the incipient scorch stability and is being superior aspect weathering resistance, the heat-resisting and anti-ozone.
Second multipolymer of the present invention (I-2), be that ethylene/alpha-olefin/three olefinic random copolymers can unvulcanized form or vulcanize and be used for practical application with the sulfurized form by following technology, promoted the generation of the favourable characteristic of the present invention's second multipolymer by sulfuration.In sulfidation, can obtain high vulcanization rate, and incipient scorch character does not reduce yet simultaneously.
Second multipolymer of the present invention (I-2), promptly ethylene/alpha-olefin/three olefinic random copolymers can especially be advantageously used for the starting material of various rubber products and be used as modifier.
As rubber product, can enumerate auto parts machinery, industrial rubber product, electrically insulating material, goods for building and rubber lining cloth.Specific examples comprises glass-run channel, Wiper blade, weather strip, sponge, hose, grommet, sidewall, cable sheath and gasket.
When second multipolymer of the present invention (I-2), promptly ethylene/alpha-olefin/three olefinic random copolymers adds resin, for example in polypropylene, polyethylene, polybutene and the polystyrene during as modifier, can increase the shock resistance and the anti-stress of resin greatly.
Second multipolymer of the present invention (I-2), promptly ethylene/alpha-olefin/three olefinic random copolymers can vulcanize or individually with other elastomeric material covulcanization.
Second multipolymer of the present invention (I-2), be that ethylene/alpha-olefin/three olefinic random copolymers are because its high vulcanization rate, therefore compare based on the unsaturated copolymer of alkene with routine, can or under lower curing temperature, vulcanize in short curing time, and not need to use a large amount of vulcanizing agents.Second multipolymer of the present invention (I-2), promptly ethylene/alpha-olefin/three olefinic random copolymers have outstanding incipient scorch stability, therefore, can be by foaming with stable foam expansion rate processing, the productive rate of the foam article that can obtain increasing.Therefore the initial viscosity of foam expansion rate by the material resin material, the delicate balance between the degradation rate of the rising speed of moulding process medium viscosity and whipping agent are determined, thereby the control rate of expansion is difficult, because viscosity rising speed is high more, the change of viscosity rate of change is big more.Yet incipient scorch stability is outstanding, and therefore, at second multipolymer of the present invention (I-2), promptly ethylene/alpha-olefin/three olefinic random copolymer medium viscosities rising is lower, therefore allows with stable foam expansion rate effectively to produce foam molded article.Second multipolymer of the present invention (I-2), be that ethylene/alpha-olefin/three olefinic random copolymers are because its outstanding incipient scorch stability, thereby when to add man-hour on extruding machine be outstanding aspect processing stability, therefore can avoid on extrusion machine in the course of processing because any trouble that the increase of viscosity produces, for example the reducing of the extruding output that causes along with the making the viscosity rising of sulfidation in extrusion machine in the extrusion machine, the increase of motor load and the obstruction of machine barrel and/or mould.
Second multipolymer of the present invention (I-2), promptly another advantage feature of ethylene/alpha-olefin/three olefinic random copolymers heat-resisting be outstanding aspect rotten, and keep above-mentioned outstanding feature simultaneously.
" second multipolymer (I-2), the i.e. preparation method of ethylene/alpha-olefin/three olefinic random copolymers "
Second multipolymer of the present invention (I-2), be chain triene compound (B-2) that ethylene/alpha-olefin/three olefinic random copolymers can be by ethene (A-1), the alpha-olefin (A-2) that contains 3-20 carbon atom, formula (2) expression and, as required, other comonomer copolymerization in the presence of catalyzer that randomly adds.As catalyzer, can use and contain transition metal, for example the catalyzer of the compound (G) of vanadium (V), zirconium (Zr) or titanium (Ti) and organoaluminum or Organoaluminoxy compound (H) and/or ionization ionic compound (J).
The specific examples of catalyzer comprises:
(1) titanium catalyst of forming by solid titanium-containing catalyst component (g-1) and organo-aluminium compound (h-1),
(2) vanadium catalyst of forming by soluble vanadium compound (g-2) and organo-aluminium compound (h-1) and
(3) metalloscene catalyst of forming by the metallocenes of the transition metal that is selected from periodictable the 4th family and Organoaluminoxy compound (h-2) and/or ionization ionic compound (j-1).
Wherein, preferable alloy cyclopentadienyl catalyst.Metalloscene catalyst has high catalytic activity, the height that can prepare the chain triene compound (B-2) with narrow molecular weight distributions and formula (2) expression transforms second multipolymer of the present invention (I-2) of the structure distribution of ratio, i.e. ethylene/alpha-olefin/three olefinic random copolymers.
Solid titanium catalyst component (g-1) is by making titanium compound, magnesium compound and electron donor(ED) contact preparation as described below.
As titanium compound, adopt trivalent or tetravalent titanium compound, wherein preferred tetravalent titanium compound.As tetravalent titanium compound, can enumerate for example by Ti (OR)
jX
4-jThe tetravalent titanium compound (wherein R is an alkyl, and X is halogen atom and 0≤j≤4) of expression.The titanium compound that wherein contains halogen is preferred, wherein preferred titanium tetrahalide, especially titanium tetrachloride.
Be used to prepare magnesium compound that solid contains titanium component (g-1) and can be and show or the magnesium compound of show reduction not,, can enumerate the compound that for example has magnesium-carbon bond and magnesium-hydrogen bond as the magnesium compound of show reduction.As the magnesium compound of show reduction not, can adopt material that obtains by above-mentioned reducible magnesium compound or the magnesium compound that produces in the catalyst component preparation process.The mixture that can also use title complex, complex chemical compound or form by this magnesium compound and other metal or metallic compound.Can also adopt the mixture of two or more magnesium compounds.As magnesium compound, the preferred not compound of show reduction, preferred halogen contained compound, especially magnesium chloride, chlorination alkoxyl magnesium and chlorination aryloxy magnesium.
As the electron donor(ED) that is used to prepare solid titanium-containing catalyst component (g-1), can enumerate the ester of organic carboxyl acid and the ester of polycarboxylic acid.
Solid titanium-containing catalyst component (g-1) can be by making titanium compound, magnesium compound (or MAGNESIUM METAL) and aforesaid electron donor(ED) contact preparation.For preparation solid titanium-containing catalyst component (g-1), can adopt the currently known methods for preparing high reactivity titanium-containing catalyst component by titanium compound, magnesium compound and electron donor(ED).In above-mentioned three kinds of component contact processes, they can for example contact under the existence of silicon, phosphorus or aluminum compound at other reaction reagent.
As the organo-aluminium compound (h-1) of preparation, can adopt the compound that in molecule, contains at least one aluminium-carbon bond based on the catalyzer of titanium.
This examples for compounds comprises the organo-aluminium compound by formula (8-1) expression:
(R
1)
mAl(OR
2)
nH
pX
q ……(8-1)
R wherein
1And R
2Expression contains and contains 1-15 carbon atom usually, the alkyl of preferred 1-4 carbon atom, and it can be identical or different, X is a halogen atom, 0＜m≤3,0≤n＜3,0≤p＜3 and 0≤q＜3, m+n+p+q=3; With the alkylation title complex by the metal of the aluminium of formula (8-2) expression and periodictable the 1st family:
(M
1)Al(R
1)
4 …(8-2)
M wherein
1Be lithium, sodium or potassium and R
1Have with formula (8-1) in identical implication.
For the preparation Ti-base catalyst, can add electron donor(ED) as required.For this electron donor(ED), can adopt silicoorganic compound as shown in the formula (9) or (10) expression:
R
nSi(OR’)
4-n …(9)
SiR
1R
2 m(OR
3)
3-m …(10)
In formula (9), R and R ' represent alkyl respectively, and n is the numerical value that satisfies 0＜n＜4 conditions.
In formula (10), R
1Representative ring amyl group or contain the cyclopentyl of alkyl, R
2Be alkyl, cyclopentyl or the cyclopentyl that contains alkyl, R
3Be alkyl, m is the numerical value of 0≤m≤2 of satisfying condition.
As the cyclopentyl R that contains alkyl in the formula (10)
1Can enumerate for example 2-methylcyclopentyl, 3-methylcyclopentyl, 2-ethyl cyclopentyl and 2, the 3-dimethylcyclopentyl.
In the catalyst component of preparation Ti-base catalyst of the present invention, can in pre-polymerization process, add alpha-olefin.Prepolymerization can be used the 0.1-500 gram by per 1 gram olefin polymerization catalysis, preferred 0.3-300 gram, and most preferably 1-100 gram alpha-olefin desirably carries out.Prepolymerization preferably can be undertaken by mixing alpha-olefin and catalyst component in unreactive hydrocarbons solvent, so that carry out prepolymerization under soft condition.The alpha-olefin that in pre-polymerization process, uses can be used to prepare second multipolymer (I-2), promptly the alpha-olefin of ethylene/alpha-olefin/three olefinic random copolymers is identical or different.
Be used for the soluble vanadium compound (g-2) of catalytic component based on vanadium of the present invention as preparation, can be as shown in the formula the compound of (11) and (12) expression:
VO(OR)
aX
b …(11)
V(OR)
cX
d …(12)
In formula (11) and (12), R is an alkyl, and X is halogen atom and symbol a, b, c and d represent to satisfy condition the respectively numerical value of 0≤a≤3,0≤b≤3,2≤a+b≤3,0≤c≤4,0≤d≤4 and 3≤c+d≤4.
As soluble vanadium compound (g-2), can adopt by making electron donor(ED) contact the electron donor(ED) adducts of the soluble vanadium compound that obtains with soluble vanadium compound.
Organo-aluminium compound (h-1) as the preparation catalytic component based on vanadium can adopt and the above-mentioned identical organo-aluminium compound (h-1) that is used to prepare Ti-base catalyst.
The metallocenes (g-3) that is used to prepare metallocenyl catalyzer of the present invention is the metallocenes of transition metal that is selected from the element of periodictable the 4th family.Its specific examples comprises the material as shown in the formula (13) expression:
ML
x …(13)
Wherein M is the transition metal that is selected from periodictable the 4th family, and x is the valency of expression transition metal M, and L represents ligand.
The specific examples of the transition metal of being represented by M in formula (13) comprises zirconium, titanium and hafnium.
L in the formula (13) represents the ligand with transition-metal coordination.Wherein at least one ligand L has and can contain substituent cyclopentadienyl skeleton.
For ligand L, can enumerate, for example cyclopentadienyl with cyclopentadienyi skeleton; Alkyl-or the cyclopentadienyl of cycloalkyl-replacement, for example methyl cyclopentadienyl, ethyl cyclopentadienyl, just or the sec.-propyl cyclopentadienyl, just, different, second month in a season or tertiary butyl cyclopentadienyl, dimethyl cyclopentadienyl, methyl-propyl cyclopentadienyl, methyl butyl cyclopentadienyl and methyl-benzyl cyclopentadienyl; Indenyl; 4,5,6,7-tetrahydroindenyl and fluorenyl.
The group that contains above-mentioned cyclopentadienyi skeleton can contain substituting group, for example halogen atom or trialkylsilkl.
Two or morely has the group of cyclopentadienyi skeleton if contain as ligand L by the compound of formula (13) expression, two such groups that then contain cyclopentadienyi skeleton can pass through abutment, alkylidene group for example, as ethylidene or propylidene, the alkylidene group that replaces, for example isopropylidene or phenylbenzene methylene radical, silylene, for example phenylbenzene silylene or aminomethyl phenyl silylene link together.
For the ligand L except that containing cyclopentadienyi skeleton, promptly for the ligand L that does not contain cyclopentadienyi skeleton, can enumerate the alkyl that for example contains the 1-12 carbon atom, alkoxyl group, aryloxy, contain methylthio group (SO
3R
a, R wherein
aThe aryl that alkyl, aryl or halogen that expression alkyl, halogen replace or alkyl replace), halogen atom and hydrogen atom.
For the alkyl that contains 1-12 carbon atom of ligand L, can enumerate for example alkyl, cycloalkyl, aryl and aralkyl.More particularly, they comprise alkyl, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, hexyl, octyl group, decyl and dodecyl; Cycloalkyl, for example cyclopentyl and cyclohexyl; Aryl, for example phenyl and tolyl; And aralkyl, for example benzyl and neophyl.
As the alkoxyl group of ligand L, can enumerate for example methoxyl group, oxyethyl group and positive propoxy.As aryloxy, can enumerate for example phenoxy group etc.As sulfur-containing group (SO
3R
a) for example can enumerate the first sulfo group, to toluene sulfo group, fluoroform sulfo group with to the chlorobenzene sulfo group.As halogen atom, can enumerate for example fluorine, chlorine, bromine and iodine.
More particularly, wherein the valency of transition metal is that the metallocenes of 4 formula (13) expression is represented by following formula (14):
R
2 kR
3 lR
4 mR
5 nM …(14)
Wherein, M is the transition metal of definition in the formula (13), R
2Be group (ligand), R with cyclopentadienyi skeleton
3, R
4And R
5Expression contains or does not contain the group (ligand) of cyclopentadienyi skeleton respectively, and k is at least 1 integer, k+l+m+n=4.
Following is that wherein M is zirconium and contains at least two examples with metallocenes (g-3) of cyclopentadienyl skeleton ligand:
-one chlorine one hydrogen two (cyclopentadienyl) closes zirconium
-dichloro two (cyclopentadienyl) closes zirconium
-two (trifluoromethanesulfonic acid roots) two (1-methyl-3-butyl cyclopentadienyl) close zirconium
-dichloro two (1,3-dimethyl cyclopentadienyl) closes zirconium.
According to the present invention, can use wherein above-mentionedly 1, the dibasic cyclopentadienyl of 3-is by 1, the dibasic cyclopentadienyl alternate of 2-compound.
For metallocenes (g-3), can also use at least two R in its Chinese style (14)
2, R
3, R
4And R
5, R for example
2And R
3Be the metallocenes of the bridge joint of the group (ligand) that contains cyclopentadienyi skeleton, wherein said at least two groups are by abutment, and for example the silylene of the alkylidene group of alkylidene group, replacement, silylene or replacement links together.In this case, radicals R
4And R
5Being identical, is respectively the ligand L of the above-mentioned formula (13) except that containing cyclopentadienyi skeleton.
The specific examples of the metallocenes of this bridge joint (g-3) comprising:
-ethylenebis (indenyl) dimethyl closes zirconium,
-dichloro ethylenebis (indenyl) is closed zirconium,
-dichloro isopropylidene (cyclopentadienyl-fluorenyl) closes zirconium,
-dichloro phenylbenzene silylene two (indenyls) close zirconium and
-dichloromethyl phenyl silylene two (indenyl) closes zirconium.
Equally, as metallocenes (g-3), can enumerate by what represent and disclose disclosed metallocenes among the flat 4-268307 (corresponding to US5243001) at Japanese Patent as shown in the formula (15).
In formula (15), M
1The metal of indication cycle's table the 4 families, for example titanium, zirconium or hafnium.
In formula (15), R
1And R
2Be respectively hydrogen, contain 1-10 carbon atom, the alkyl of preferred 1-3 tool carbon atom, contain 1-10 carbon atom, the alkoxyl group of preferred 1-3 carbon atom, contain 6-10 carbon atom, the aryl of preferred 6-8 carbon atom, contain 6-10 carbon atom, the aryloxy of preferred 6-8 carbon atom, contain 2-10 carbon atom, the alkenyl of preferred 2-4 carbon atom, contain 7-40 carbon atom, the aralkyl of preferred 7-10 carbon atom, contain 7-40 carbon atom, the alkaryl of preferred 7-12 carbon atom or contain 8-40 carbon atom, the virtue of preferred 8-12 carbon atom is for alkenyl, maybe can also be halogen atom, preferred chlorine atom.Among the present invention, R
1And R
2Can be identical or different.
In formula (15), R
3And R
4Can represent hydrogen atom, halogen atom respectively, preferred fluorine, chlorine or bromine atom, contain 1-10 carbon atom, preferred 1-4 carbon atom can be by halogenated alkyl, to contain 6-10 individual, preferably aryl, group-N (R of 6-8 carbon atom
10)
2,-SR
10,-OSi (R
10)
3,-Si (R
10)
3Or-P (R
10)
2Wherein R10 is a halogen atom, preferred chlorine atom, contains 1-10 carbon atom, the alkyl of preferred 1-3 carbon atom or contain 6-10 carbon atom, the preferably aryl of 6-8 carbon atom.R
3And R
4Can be same to each other or different to each other especially preferred R
3And R
4All be hydrogen.
In formula (15), R
5And R
6Can with R
3And R
4Identical, except hydrogen.R
5And R
6Can be identical or different, but preferably identical.R
5And R
6Can preferably contain 1-4 carbon atom, and preferably by halo, its specific examples is methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-and trifluoromethyl, wherein preferable methyl especially.
In formula (15), R
7Can represent:
And=BR
11,=AlR
11,-Ge-,-Sn-,-O-,-S-,=SO ,=SO
2,=NR
11,=CO ,=pR
11Or=P (O) R
11In above-mentioned, R
11, R
12And R
13Can represent hydrogen atom separately; Halogen atom; Containing 1-10 carbon atom, preferably contain the alkyl of 1-4 carbon atom, more preferably is methyl; The fluoro-alkyl that contains 1-10 carbon atom is preferably-CF
3Contain 6-10 carbon atom, preferably contain the aryl of 6-8 carbon atom; Contain the fluorinated aryl of 6-10 carbon atom, be preferably pentafluorophenyl group; Containing 1-10 carbon atom, preferably contain the alkoxyl group of 1-4 carbon atom, especially is methoxyl group; Contain 2-10 carbon atom, preferably contain the alkenyl of 2-4 carbon atom; Contain 7-40 carbon atom, preferably contain the aralkyl of 7-10 carbon atom; Contain 8-40 carbon atom, preferably contain the arylalkenyl of 8-12 carbon atom; Or contain 7-40 carbon atom, preferably contain the alkaryl of 7-12 carbon atom." R
11With R
12" or " R
11With R
13" form ring with atom with its bonding.R
11, R
12And R
13Each other can be identical or different.
M
2Can represent silicon, germanium or tin are preferably silicon or germanium.
In formula (15), R
7Preferred representative=CR
11R
12,=SiR
11R
12,=GeR
11R
12,-O-,-S-,=SO ,=pR
11Or=P (O) R
11
In formula (15), R
8And R
9Separately can with R
11Identical, R wherein
8And R
9Each other can be identical or different.
In formula (15), m and n represent 0,1 or 2 separately, are preferably 0 or 1, and wherein m+n is 0,1 or 2, is preferably 0 or 1.M and n each other can be identical or different.
Example as the metallocenes (g-3) of formula (15) representative can be following compound:
-dichloride rac-ethylidene (2-methyl isophthalic acid-indenyl)-2-zirconium
Silica-based (2-methyl isophthalic acid-indenyl)-2-zirconium of-dichloride rac-dimethylated methylene
The metallocenes of formula (15) representative can be by known method preparation (for example, Japanese Patent discloses flat 4-268307).
The compound that also can use following formula (16) representative is as metallocenes (g-3).
In above-mentioned formula (16), M represents the periodic table of elements the 4th group 4 transition metal atom, and object lesson is a titanium, zirconium or hafnium.
In formula (16), R
1And R
2Represent hydrogen atom respectively, halogen atom contains the alkyl of 1-20 carbon atom, contains halo alkyl, silicon-containing group, oxy radical, sulfur-containing group, nitrogen-containing group or the phosphorus-containing groups of 1-20 carbon atom.R
1And R
2Specific examples comprise:
-halogen atom, for example, fluorine, chlorine, bromine or iodine;
-contain 1-20 carbon atom alkyl for example, methyl, ethyl, propyl group, butyl, hexyl, cyclohexyl, octyl group, nonyl, dodecyl, eicosyl, norcamphyl or adamantyl, alkenyl for example, vinyl, propenyl or cyclohexenyl, aralkyl for example, benzyl, styroyl or hydrocinnamyl, perhaps aryl for example, phenyl, tolyl, 3,5-dimethylphenyl, trimethylphenyl, ethylbenzene base, propyl phenyl, xenyl, naphthyl, first naphthyl, anthryl or phenanthryl;
-containing the halo alkyl of 1-20 carbon atom, wherein above-mentioned alkyl is that halogen replaces;
-silicon-containing group, the silyl that for example single alkyl replaces, as methyl-silicane base or phenyl silyl, the silyl that dialkyl replaces, as dimetylsilyl or diphenylmethyl silylation, the silyl that trialkyl replaces, as trimethyl silyl, triethylsilyl, the tripropyl silyl, the thricyclohexyl silyl, the triphenyl silyl, the 3,5-dimethylphenyl silyl, methyldiphenyl base silyl, trimethylphenyl silyl or three naphthyl silyls, alkyl replaces the silicomethane ether of silyl, as the trimethyl silyl ether; The alkyl that silicon replaces, as the alkyl such as the trimethyl silyl methyl of silicon replacement, or the aryl such as the trimethyl silyl phenyl of silicon replacement;
-oxy radical, hydroxyl for example, alkoxyl group such as methoxyl group, oxyethyl group, propoxy-or butoxy, aryloxy such as phenoxy group, methylphenoxy, dimethyl phenoxy or naphthyloxy, perhaps aralkoxy such as phenyl methoxyl group or phenyl ethoxy;
-sulfur-containing group, the group that Sauerstoffatom is replaced by sulphur atom in for example above-mentioned oxy radical;
-nitrogen-containing group, for example amino, alkylamino such as methylamino-, dimethylamino, diethylin, dipropyl amino, dibutylamino or dicyclohexylamine base, aryl or alkaryl are amino as phenyl amino, diphenyl amino, xylyl amino, dinaphthyl amino or aminomethyl phenyl amino; And
-phosphorus-containing groups, for example phosphino-such as dimethyl phosphino-or diphenylphosphino.
At R
1Above-mentioned group in, preferred alkyl particularly preferably is the alkyl that contains 1-3 carbon atom, as methyl, ethyl or propyl group.R
2Also preferably represent hydrogen atom or alkyl, wherein particularly preferably be hydrogen atom and the alkyl that contains 1-3 carbon atom, as methyl, ethyl or propyl group.
In formula (16), R
3, R
4, R
5And R
6Represent hydrogen atom respectively, halogen atom contains the alkyl of 1-20 carbon atom or contains the halo alkyl of 1-20 carbon atom.Wherein preferred hydrogen atom, alkyl and halogenated alkyl.At R
3With R
4, R
4With R
5And R
5With R
6In the middle of the group, at least one group can form single aromatic ring with the carbon atom with its bonding.If in other do not form the group of aromatic ring, contain two or more alkyl or during the halo alkyl, they can be combined together to form ring.Preferably, R
6Be hydrogen atom, as long as it is not an aromatic substituent.
As the R in the formula (16)
3, R
4, R
5And R
6, specific examples and R
1And R
2The group of expression is identical, can be halogen atom, contain the alkyl of 1-20 carbon atom and contain the halo alkyl of 1-20 carbon atom.
In formula (16), X
1And X
2Represent hydrogen atom, halogen atom respectively, contain the alkyl of 1-20 carbon atom or contain halo alkyl, oxy radical or the sulfur-containing group of 1-20 carbon atom.
As enumerating halogen atom, contain the alkyl of 1-20 carbon atom and containing the specific examples of halo alkyl, oxy radical and the sulfur-containing group of 1-20 carbon atom, can enumerate R
1And R
2Those examples.
As sulfur-containing group, can enumerate above-mentioned R
1And R
2Group is cited; And sulfonate, as mesylate, fluoroform sulphonate, benzene sulfonate, benzyl sulfonic acid salt, tosilate, tri-methyl p-toluenesulfonate salt, triisobutyl benzene sulfonate, closilate and penta fluoro benzene sulfonate; And-sulfinate, as methyl-sulfinic acid salt, benzene sulfinate, benzene sulfinate, to toluenesulfinate, Three methyl Benzene-sulfinate and penta fluoro benzene-sulfinate.
In formula (16), Y represents to contain the bivalent hydrocarbon radical of 1-20 carbon atom, contains the divalence halo alkyl of 1-20 carbon atom, the divalence silicon-containing group, and the germanic group of divalence, divalence contains tin group ,-O-,-CO-,-S-,-SO-,-SO
2-,-NR
7-,-P (R
7)-,-P (O) (R
7)-,-BR
7-or-AlR
7-, R wherein
7For hydrogen atom, halogen atom, contain the alkyl of 1-20 carbon atom or contain the halo alkyl of 1-20 carbon atom.
The specific examples of Y comprises in the formula (16):
-contain the bivalent hydrocarbon radical of 1-20 carbon atom, for example, alkylidene group such as methylene radical, dimethylated methylene base, ethylene, dimethyl-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylidene and 1,4-cyclohexylidene; And arylmethylene alkyl such as phenylbenzene methylene radical and phenylbenzene-ethylene;
-divalence halo the alkyl that derived through halo by the bivalent hydrocarbon radical that contains 1-20 carbon atom is as the chlorine methylene radical etc.;
-siliceous divalent group, for example silene, alkaryl silylene and aryl silylene, as the methyl silylene, dimethylated methylene is silica-based, the diethyl silylene, the di silylene, the di-isopropyl silylene, dicyclohexyl silylene, tolyl silylene, the phenylbenzene silylene, di-p-tolyl silylene and two rubigan silylenes; Alkyl two silylenes, alkaryl two silylenes and aryl two silylenes, as tetramethyl--1,2-two silylenes and tetraphenyl-1,2-two silylenes etc.;
-germanic divalent group wherein replaces silicon in the above-mentioned siliceous divalent group with germanium; And
-stanniferous divalent group wherein replaces silicon in the above-mentioned siliceous divalent group with tin.
In the formula of above-mentioned divalent group, R
7Represent halogen atom, contain the alkyl of 1-20 carbon atom and contain the halo alkyl of 1-20 carbon atom.
In the above-mentioned Y group of enumerating, be preferably siliceous divalent group, germanic divalent group and stanniferous divalent group, wherein preferred siliceous divalent group particularly preferably is silene, aralkyl silylene and aryl silylene.
In formula (16), the part as metal M wherein contains by R
3With R
4, R
4With R
5And R
5With R
6In the group at least-single aromatic ring that group forms, specific examples is as following formula (17)-(19) representative:
Wherein Y is identical with the definition in the formula (16).
According to the present invention, the transistion metal compound that also can use following formula (20) representative is as metallocenes (g-3),
Wherein M, R
1, R
2, R
3, R
4, R
5And R
6Identical with the definition in the formula (16).
In formula (20), preferably, at R
3, R
4, R
5And R
6In, comprise R
3Two kinds of groups alkyl of respectively doing for oneself, wherein preferred R
3And R
5Or R
3And R
6Represent alkyl separately.These alkyl are preferably the second month in a season or tertiary alkyl.In addition, these alkyl can be replaced by halogen atom or silicon-containing group, wherein as halogen atom and silicon-containing group, can enumerate front R
1And R
2Those examples.
Preferably, the R in the formula (20)
3, R
4, R
5And R
6Group is not above-mentioned alkyl but hydrogen atom.As the alkyl that contains 1-20 carbon atom, form the alkyl or cycloalkyl of main chain, for example, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, hexyl, cyclohexyl, heptyl, octyl group, nonyl, dodecyl, eicosyl, norcamphyl or adamantyl; Or aralkyl, as benzyl, styroyl, hydrocinnamyl or tolyl methyl, wherein they can contain two keys and/or triple bond.
Two kinds are selected from R in the formula (20)
3, R
4, R
5And R
6Group by-rise in conjunction with forming the monocycle except that aromatic ring or encircling more.
As for halogen atom, can enumerate R
1And R
2Those that enumerate.
As for X
1, X
2And Y group, identical example in the enumerative (16).
The following specific examples of having listed the metallocenes (g-3) of formula (20) representative.
-dichloride rac-dimethylated methylene silica-based-two (4,7-dimethyl-1-indenyl) zirconium
-dichloride rac-dimethylated methylene silica-based-two (2,4,7-trimethylammonium-1-indenyl) zirconium
-dichloride rac-dimethylated methylene silica-based-two (2,4,6-trimethylammonium-1-indenyl) zirconium
According to the present invention, also can use the transistion metal compound of zirconium in the compound that replaces providing above with titanium or hafnium.
The transistion metal compound that provides above uses its racemic modification usually, although can use R-or compound-s.
Metallocenes (g-3) as formula (20) representative also can use compound given below.
R
1Be preferably alkyl, wherein particularly preferably be the alkyl that contains 1-4 carbon atom, as methyl, ethyl, propyl group or butyl.
X
1And X
2Be preferably halogen atom separately or contain the alkyl of 1-20 carbon atom.
R
3Expression contains the aryl of 6 carbon atoms of 6-1, and wherein specific examples comprises phenyl, Alpha-Naphthyl, betanaphthyl, anthryl, phenanthryl, pyrenyl, acenaphthenyl, phenalenyl (all naphthyls) and aceanthrylenyl.Preferred phenyl and naphthyl in the middle of them.These aryl can be replaced by halogen atom, the halo alkyl that contains the alkyl of 1-20 carbon atom or contain 1-20 carbon atom, as R
1Defined such.
The specific examples of transistion metal compound (metallocenes) is as follows:
-dichloride rac-dimethylated methylene silica-based-two (4-phenyl-1-indenyl) zirconium
-dichloride rac-dimethylated methylene silica-based-two (2-methyl-4-phenyl-1-indenyl) zirconium
-dichloride rac-dimethylated methylene silica-based-two { 2-methyl-4-(Alpha-Naphthyl)-1-indenyl } zirconium
-dichloride rac-dimethylated methylene silica-based-two { 2-methyl-4-(betanaphthyl)-1-indenyl } zirconium
-dichloride rac-dimethylated methylene silica-based two { 2-methyl-4-(1-anthryl-1-indenyl } zirconium
Also can use the transistion metal compound of zirconium in the compound that replaces providing above with titanium or hafnium.
According to the present invention, the compound that also can use following formula (21) representative is as metallocenes (g-3):
L
aMX
2…(21)
Wherein M is the 4th family or a lanthanide series metal in the periodic table of elements, L
aExpression produces the derivative of non-localized π-key group of geometric configuration of the restriction of metal M active part, and X represent hydrogen atom, halogen atom individually, contain 20 or still less carbon atom alkyl, contain 20 or still less Siliciumatom silyl or contain 20 or the germyl of germanium atom still less.
In the compound of formula (21) representative, preferably by those of following general formula (22) representative:
Wherein M represents titanium, zirconium or hafnium, X is identical with the definition in the formula (21), the Cp representative is connected and contains the cyclopentadienyl of the replacement of substituting group Z with metal M by π-key, Z represents the element (silicon for example of the 14th family in the early stage table of oxygen, sulphur, boron or element, germanium or tin), that Y represents is nitrogenous, the part of phosphorus, oxygen or sulphur, and wherein Z and Y can form condensed ring together.
As the compound of formula (22) representative, specific examples can be a dichloride { dimethyl (tertiary butyl-amide group)-(tetramethyl--η
5-cyclopentadienyl) silane } titanium and dichloride { (tert-butylamides base) (tetramethyl--η
5-cyclopentadienyl)-1,2-di-methyl } titanium.
Also can use those compounds of titanium in the metallocenes that replaces providing above with zirconium or hafnium.
As the metallocenes (g-3) of formula (21) or (22) representative, preferably use central metal atom as zirconium and comprise at least two zirconocenes that contain the cyclopentadienyi skeleton part.
As metallocenes (g-3), also can use the transistion metal compound of the periodic table of elements group-4 metal of following formula (23) representative:
Wherein M is the transition metal in the periodic table of elements the 4th family, and specific examples is titanium, zirconium or hafnium, is preferably zirconium.
R in the formula (23)
1Each other can be identical or different, wherein at least one is the aryl that contains 11-20 carbon atom, contains the aralkyl of 12-40 carbon atom, contains the arylalkenyl of 13-40 carbon atom, contains the alkaryl or the silicon-containing group of 12-40 carbon atom, perhaps these R
1In at least two adjacent R
1Can form single or many aromatic ring or alicyclic ring with the carbon atom that connects with them.Here, remove and R
1Outside the carbon atom that connects, the total number of carbon atoms of the ring that forms is 4-20.
At least two adjacent R in the formula (23)
1With same R
1The example that the carbon atom that connects constitutes together, one or more aromatic rings or alicyclic ring comprise condensed phenyl, condensed cyclohexyl, condensed cyclopentadienyl, condensed dihydro cyclopentadienyl, condensed indenyl, condensed tetrahydro indenyl, condensed fluorenyl, condensed tetrahydrofluorenyl and condensed octahydrofluorenyl.These groups can be by straight chained alkyl, cycloalkyl, and halogen, the alkaryl that halogen replaces, silicon-containing group, oxy radical, nitrogen-containing group and/or phosphorus-containing groups replace.
Do not form the R of aryl, aralkyl, arylalkenyl, alkaryl or aromatic ring or alicyclic ring
1Hydrogen atom, halogen atom be can represent, the alkyl or the silicon-containing group of 1-10 carbon atom contained.
As the aryl that contains 11-20 carbon atom, the example can be xenyl, anthryl and phenanthryl.As the aralkyl that contains 12-40 carbon atom, the example can be the phenanthryl methyl, phenanthryl ethyl and phenanthryl propyl group.As the arylalkenyl that contains 13-40 carbon atom, the example can be a vinyl phenanthryl etc.As the alkaryl that contains 12-40 carbon atom, the example can be methyl phenanthryl, ethyl phenanthryl and propyl group phenanthryl.As halogen atom, the example is fluorine, chlorine, bromine and iodine.As the alkyl that contains 1-10 carbon atom, the example can be methyl, ethyl, propyl group, butyl, hexyl, cyclohexyl, octyl group and nonyl.As silicon-containing group, the example can be methyl-silicane base, phenyl silyl, dimetylsilyl, diethylsilane base, diphenylmethyl silylation, trimethyl silyl, triethylsilyl, tripropyl silyl, thricyclohexyl silyl, triphenyl silyl, 3,5-dimethylphenyl silyl, methyldiphenyl base silyl, trimethylphenyl silyl and three naphthyl silyls.
These alkyl, aryl, aralkyl, arylalkenyl and alkaryl can be replaced by halogen.
In formula (23), R
2Each other can be identical or different, can represent hydrogen atom, halogen atom, contain 1-10 carbon atom alkyl, contain 6-20 carbon atom aryl, contain 2-10 carbon atom alkenyl, contain 7-40 carbon atom aralkyl, contain 8-40 carbon atom arylalkenyl, contain 7-40 carbon atom alkaryl, silicon-containing group, oxy radical, sulfur-containing group, nitrogen-containing group or phosphorus-containing groups.R in formula (23)
2The representative group in, have at least two adjacent groups with these two R
2The carbon atom that connects forms one or more aromatic rings or alicyclic ring together.Here, remove and these R
2Outside the carbon atom that connects, the total number of carbon atoms of the ring that forms is 4-20 and does not form aromatic ring or the R of alicyclic ring
2Can represent hydrogen atom separately, halogen atom, the alkyl that contains 1-10 carbon atom or silicon-containing group.。
The such group that is formed by the fluorenyl as shown in the formula (24) representative also belongs to by two R in the formula (23)
2By forming the group that one or more aromatic rings or alicyclic ring are formed.
As alkyl that contains 1-10 carbon atom and halogen atom, the example with provide above identical.
As the aryl that contains 6-20 carbon atom, the example can be phenyl, xenyl, α-and betanaphthyl, anthryl and phenanthryl.As the aralkyl that contains 7-40 carbon atom, the example can be benzyl, styroyl, hydrocinnamyl, phenanthryl methyl, phenanthryl ethyl and phenanthryl propyl group.As the arylalkenyl that contains 8-40 carbon atom, the example can be styryl and vinyl phenanthryl.
As the alkaryl that contains 7-40 carbon atom, the example can be tolyl, 3,5-dimethylphenyl, trimethylphenyl, ethylphenyl, propyl group phenyl, methyl naphthyl, methyl phenanthryl, ethyl phenanthryl and propyl group phenanthryl.As the alkenyl that contains 2-10 carbon atom, the example can be vinyl, propenyl and cyclohexenyl.As silicon-containing group, the example with provide previously identical.As oxy radical, the example can be a hydroxyl, alkoxyl group such as methoxyl group, oxyethyl group, propoxy-and butoxy; Aryloxy such as phenoxy group, methylphenoxy, dimethyl phenoxy and naphthyloxy; And aralkoxy such as phenyl methoxyl group and phenyl ethoxy.
As sulfur-containing group, the example can be those and the sulfonate that replaces Sauerstoffatom in the above-mentioned oxy radical with sulphur atom; As mesylate, fluoroform sulphonate, benzene sulfonate, benzyl sulfonic acid salt, tosilate, tri-methyl p-toluenesulfonate salt, triisobutyl benzene sulfonate, closilate and penta fluoro benzene sulfonate; And-sulfinate, as methyl-sulfinic acid salt, benzene sulfinate, benzene sulfinate, to toluenesulfinate, Three methyl Benzene-sulfinate and penta fluoro benzene-sulfinate.
As nitrogen-containing group, the example can be amino; Alkylamino such as methylamino-, dimethylamino, diethylin, dipropyl amino, dibutylamino and dicyclohexylamine base; Arylamino such as phenyl amino, diphenyl amino, xylyl amino, dinaphthyl amino or aminomethyl phenyl amino; And alkaryl amino.
As phosphorus-containing groups, the example can be dimethyl phosphino-or diphenylphosphino.
R
2Preferably represent hydrogen atom or alkyl, wherein particularly preferably be hydrogen atom and the alkyl that contains 1-3 carbon atom, as methyl, ethyl or propyl group.
As containing such R
2Substituent fluorenyl, the example preferably that can enumerate is 2,7-dialkyl group fluorenyl preferably contains the alkyl of 1-5 carbon atom.
Above-mentioned R
1And R
2Each other can be identical or different.
R in the formula (23)
3And R
4Each other can be identical or different, wherein with top similar, they represent hydrogen atom, halogen atom separately, contain the alkyl of 1-10 carbon atom, contain 6-20 carbon atom aryl, contain 2-10 carbon atom alkenyl, contain 7-40 carbon atom aralkyl, contain 8-40 carbon atom arylalkenyl, contain 7-40 carbon atom alkaryl, silicon-containing group, oxy radical, sulfur-containing group, nitrogen-containing group or phosphorus-containing groups.
In the middle of them, R preferably
3And R
4In at least one is the alkyl that contains 1-3 carbon atom.
X in the formula (23)
1And X
2Each other can be identical or different, can be hydrogen atom separately, halogen atom, the alkyl that contains 1-20 carbon atom, the halo alkyl that contains 1-20 carbon atom, oxy radical, sulfur-containing group or nitrogen-containing group, perhaps they form conjugated diene together, wherein the specific examples of halogen atom, oxy radical, sulfur-containing group and nitrogen-containing group comprise above-named those.
As the alkyl that contains 1-20 carbon atom, the example can be an alkyl, as methyl, ethyl, propyl group, butyl, hexyl, cyclohexyl, octyl group, nonyl, dodecyl, eicosyl, norcamphyl or adamantyl, alkenyl for example, vinyl, propenyl or cyclohexenyl, aralkyl for example, benzyl, styroyl or hydrocinnamyl, perhaps aryl for example, phenyl, tolyl, 3,5-dimethylphenyl, trimethylphenyl, the ethylbenzene base, propyl phenyl, α-or betanaphthyl, the first naphthyl, anthryl, phenanthryl, benzyl phenyl, the pyrenyl aceanthrenyl, phenalenyl, aceanthrenyl, tetralyl, 2,3-indanyl and xenyl.As the halo alkyl that contains 1-20 carbon atom, the example is the alkyl that contains the above-mentioned 1-20 of containing carbon atom of halogenic substituent.
As by X
1And X
2The conjugated diene that forms, the example can be η
4-1,4-phenylbenzene-1,3-butadiene, η
4-1,3-butadiene, η
4-1,4-dibenzyl-1,3-butadiene, η
4-1-phenyl-1,3-pentadiene, η
4-3-methyl isophthalic acid, 3-pentadiene, η
4-1,4-two (trimethyl silyl)-1,3-butadiene, 2,3-dimethylbutadiene, η
4-2,4-hexadiene and isoprene.As by X
1And X
2The conjugated diene that forms is preferably 1,3-butadiene, and 2, the 4-hexadiene, 1-phenyl-1,3-pentadiene and 1, the 4-diphenyl diethylene, wherein these groups can also be contained the alkyl replacement of 1-10 carbon atom.
In the middle of them, X preferably
1And X
2The halogen atom of respectively doing for oneself contains the alkyl or the sulfur-containing group of 1-20 carbon atom.
In formula (23), Y represents to contain the bivalent hydrocarbon radical of 1-20 carbon atom, contains the divalence halo alkyl of 1-20 carbon atom, the divalence silicon-containing group, and the germanic group of divalence, divalence contains tin group ,-O-,-CO-,-S-,-SO-,-SO
2-,-NR
5-,-P (R
5)-,-P (O) (R
5)-,-BR
5-or-AlR
5-, R wherein
5For hydrogen atom, halogen atom, contain the alkyl of 1-20 carbon atom or contain the halo alkyl of 1-20 carbon atom.
The specific examples of Y comprises in the formula (23):
-contain the bivalent hydrocarbon radical of 1-20 carbon atom, for example, alkylidene group such as methylene radical, dimethylated methylene base, ethylene, dimethyl-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylidene and 1,4-cyclohexylidene; And arylmethylene alkyl such as phenylbenzene methylene radical and phenylbenzene-ethylene;
-halo the alkyl that derived through halo by the bivalent hydrocarbon radical that contains 1-20 carbon atom is as the chlorine methylene radical etc.;
-siliceous divalent group, for example silene, alkaryl silylene and aryl silylene, as the methyl silylene, dimethylated methylene is silica-based, the diethyl silylene, the di silylene, the di-isopropyl silylene, dicyclohexyl silylene, tolyl silylene, the phenylbenzene silylene, di-p-tolyl silylene and two rubigan silylenes; Alkyl two silylenes, alkaryl two silylenes and aryl two silylenes, as tetramethyl--1,2-two silylenes and tetraphenyl-1,2-two silylenes etc.;
-germanic divalent group wherein replaces silicon in the above-mentioned siliceous divalent group with germanium; And
-stanniferous divalent group wherein replaces silicon in the above-mentioned siliceous divalent group with tin.
In the middle of them, preferably, the shortest-Y-bridged bond as the formula (23) is made up of one or two carbon atom.
In the formula of the above-mentioned divalent group of enumerating, R
5Same as described above, represent halogen atom, contain the alkyl and the halo alkyl that contains 1-20 carbon atom of 1-20 carbon atom.
In the above-mentioned Y group of enumerating, be preferably divalence C
1-C
5Alkyl, siliceous divalent group, germanic divalent group, wherein preferred siliceous divalent group particularly preferably is silene, aralkyl silylene and aryl silylene.
As metallocenes (g-3), also can use the transistion metal compound of following formula (25) representative:
Wherein M is the transition metal in the periodic table of elements the 4th family, specifically represents titanium, zirconium or hafnium, is preferably zirconium.
In formula (25), R
6Each other can be identical or different, can represent hydrogen atom, halogen atom, contain the alkyl of 1-10 carbon atom, the aryl that contains 6-10 carbon atom, the alkenyl that contains 2-10 carbon atom, silicon-containing group, oxy radical, sulfur-containing group, nitrogen-containing group or phosphorus-containing groups, wherein working as them is halogen atom or C
1-C
10During alkyl, specifically can represent the R that provides in the formula (23)
1Group, and as silicon-containing group, oxy radical, sulfur-containing group, nitrogen-containing group and phosphorus-containing groups, the example is same as the R that provides in the formula (23)
2Group.
As the aryl that contains 6-10 carbon atom, the example can be phenyl and α-and betanaphthyl.As the alkenyl that contains 2-10 carbon atom, the example can be vinyl, propenyl and cyclohexenyl.These alkyl and alkenyl can be replaced by halogen.
In the middle of them, R
6Be preferably alkyl, aryl or hydrogen atom, wherein especially preferably contain the alkyl of 1-3 carbon atom, as methyl, ethyl, n-propyl and sec.-propyl, and aryl such as phenyl, Alpha-Naphthyl and betanaphthyl, and hydrogen atom.
In formula (25), R
7Each other can be identical or different, can represent hydrogen atom, halogen atom, contain 1-10 carbon atom alkyl, contain 6-20 carbon atom aryl, contain 2-10 carbon atom alkenyl, contain 7-40 carbon atom aralkyl, contain 8-40 carbon atom arylalkenyl, contain 7-40 carbon atom alkaryl, silicon-containing group, oxy radical, sulfur-containing group, nitrogen-containing group or phosphorus-containing groups.Specifically, they can be the R that provides in the formula (23)
2Group.
These alkyl, aryl, alkenyl, aralkyl, arylalkenyl and alkaryl can be replaced by halogen.
In the middle of them, R
7Be preferably hydrogen atom or alkyl separately, wherein particularly preferably be hydrogen atom and the alkyl that contains 1-4 carbon atom, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl and the tertiary butyl.
R
6And R
7Each other can be identical or different.
R in the formula (25)
8And R
9One of for containing the alkyl of 1-5 carbon atom, another is hydrogen atom, halogen atom, contain the alkyl of 1-10 carbon atom, contain alkenyl, silicon-containing group, oxy radical, sulfur-containing group, nitrogen-containing group or the phosphorus-containing groups of 2-10 carbon atom, suc as formula R given in (23)
2Group.
As the alkyl that contains 1-5 carbon atom, the example can be methyl, ethyl, propyl group, butyl and amyl group.
In the middle of them, preferably, R
8And R
9One of be the alkyl that contains 1-3 carbon atom, as methyl, ethyl or propyl group, another is a hydrogen atom.
In formula (25), X
1And X
2Each other can be identical or different, suc as formula the X in (23)
1And X
2, represent hydrogen atom, halogen atom respectively, contain 1-20 carbon atom alkyl, contain halo alkyl, oxy radical, sulfur-containing group or the nitrogen-containing group of 1-20 carbon atom, perhaps they can constitute conjugated diene together.
In the middle of them, preferred halogen atom and the alkyl that contains 1-20 carbon atom.
In formula (25), as in the formula (23), Y represents to contain the bivalent hydrocarbon radical of 1-20 carbon atom, contains the divalence halo alkyl of 1-20 carbon atom, the divalence silicon-containing group, and the germanic group of divalence, divalence contains tin group ,-O-,-CO-,-S-,-SO-,-SO
2-,-NR
5-,-P (R
5)-,-P (O) (R
5)-,-BR
5-or-AlR
5-, R wherein
5For hydrogen atom, halogen atom, contain the alkyl of 1-20 carbon atom or contain the halo alkyl of 1-20 carbon atom.
In the middle of them, Y is preferably the bivalent hydrocarbon radical that contains 1-5 carbon atom, siliceous divalent group or germanic divalent group, and wherein preferred especially siliceous divalent group, its specific examples is silene, alkaryl silylene and aryl silylene.
Metallocenes (g-3) can use separately or two or more mixes use.Can use the metallocenes (g-3) that in solvent such as hydrocarbon or halohydrocarbon, dilutes.Also can use the solid-state metallocenes (g-3) that contacts with the particulate vector compound.
As the carrier compound of loaded metal luxuriant (g-3), can use mineral compound, as SiO
2, Al
2O
3, B
2O
3, MgO, ZrO
2, CaO, TiO
2, ZnO, SnO
2, BaO and ThO, and resin for example polyethylene, polypropylene, poly-1-butylene, poly--4-methyl-1-pentene and vinylbenzene/divinyl benzene copolymer.These carrier compounds can use separately or two or more mixes use.
Now, for being used to prepare the Organoaluminoxy compound (h-2) of the luxuriant catalyzer of loaded metal and the ionic compound (j-1) of ionizing is described.
The Organoaluminoxy compound (h-2) that the present invention uses can be itself known aikyiaiurnirsoxan beta or those benzene-insoluble compounds.
Above-mentioned known aikyiaiurnirsoxan beta is specifically by following formula (26) or (27) expression:
Wherein the R representation hydrocarbyl as methyl, ethyl, propyl group or butyl, is preferably methyl or ethyl, is preferably methyl especially, and m is 2 or bigger integer, is preferably 5-40.
In formula (26) or (27), aikyiaiurnirsoxan beta can be made up of blended alkyl oxygen aluminium unit, and this mixed cell is by formula OAl (R
1) representative alkyl oxygen aluminium unit and formula OAl (R
2) the alkyl oxygen aluminium unit of representative forms, R wherein
1And R
2Representative limits those groups of R respectively, and R
1Be different from R
2
It is not other organo-metallic component of organoaluminum that the Organoaluminoxy compound (h-2) that the present invention uses can contain on a small quantity.
As ionizing ionic compound (j-1), be sometimes referred to as " ionic ionizing compound " or simply be called " ionic compound ", its specific examples can be Lewis acid, ionic compound, borine and carborane.
As Lewis acid, can use those to use BR
3Expression, wherein R represents fluorine or contains substituting group such as the phenyl of fluorine, methyl or trifluoromethyl.This lewis acidic specific examples comprises trifluoro boron, triphenyl-boron, three (4-fluorophenyl) boron, three (3, the 5-difluorophenyl) boron, three (4-toluene fluoride base) boron, three (pentafluorophenyl group) boron, three (p-methylphenyl) boron, three (o-tolyl) boron and (3, the 5-xylyl) boron.
As above-mentioned ionic compound, what can enumerate is, the ammonium salt, the N that replace of trialkyl for example, N-dialkyl benzene ammonium salt, dialkyl ammonium salt and triaryl phosphonium salt.As the ammonium salt that the trialkyl of ionic compound replaces, the example can be triethyl ammonium four (phenyl) boron, tripropyl ammonium four (phenyl) boron and three (normal-butyl) ammonium four (phenyl) boron.As the dialkyl ammonium salt of ionic compound, the example can be two (1-propyl group) ammonium four (pentafluorophenyl group) boron and dicyclohexyl ammonium four (phenyl) boron.
As above-mentioned ionic compound, the example can be triphenylcarbenium father-in-law four (pentafluorophenyl group) borate, N, N-dimethyl puratized agricultural spray four (pentafluorophenyl group) borates and four (pentafluorophenyl group) boric acid iron.
As above-mentioned borine, the example can be the metallo-borane anion salt, for example Decaboron tetradecahydride, two [three (normal-butyl) ammonium] borate in the ninth of the ten Heavenly Stems, two [three (normal-butyl) ammonium] borate in the last of the ten Heavenly stems and two [three (normal-butyl) ammoniums], two (ten dihydride-Dodecaborate salt) nickel acid (III) salt.
As above-mentioned carborane, the example can be the metallocarborane anion salt, 4-carbon borine in the ninth of the ten Heavenly Stems (9), 1 for example, 3-two carbon borines in the ninth of the ten Heavenly Stems (8), two [three (normal-butyl) ammonium] two (11 hydride-7-carbon 11-borate salt) nickel acid (IV) salt.
Ionizing ionic compound (j-1) can use separately or two or more mixes use.The ionic compound (j-1) of Organoaluminoxy compound (h-2) and ionizing can use with the above-mentioned form that loads on the carrier compound.
In preparation loaded metal cyclopentadienyl catalyst, above-mentioned organo-aluminium compound (h-1) can use with the ionic compound (j-1) of Organoaluminoxy compound (h-2) or ionizing.
In order to prepare second multipolymer (I-2) among the present invention, be ethylene/alpha-olefin/three olefinic random copolymers, usually in liquid phase in the presence of the catalyzer of load titanium, load vanadium or the above-mentioned metallocenes of load, with ethene (A-1), alpha-olefin (A-2), straight chain triene compound (B-2) and as need and another kind of comonomer carries out copolymerization.Here, use varsol usually, use alpha-olefin as solvent although also allow.
The copolyreaction of ethene (A-1), alpha-olefin (A-2) and straight chain triene compound (B-2) can be carried out with intermittence or successive mode.When carrying out copolymerization with intermittent mode, spendable catalyst concentration is as follows:
For being substrate with the titanium, containing the catalyzer that titanium component (g-1) and organo-aluminium compound (h-1) are formed by solid, calculate according to titanium atom, in every liter of copolyreaction volume, be generally the about 1.0mmol of about 0.001-admittedly contain the consumption of titanium component (g-1), preferably about 0.005-0.5mmol.Calculate according to the atoms metal in the organo-aluminium compound, promptly the every mole of titanium that contains in the titanium component (g-1) by solid calculates, and the consumption of organo-aluminium compound (h-1) is generally about 10-500 mole, is preferably the 20-200 mole.Under the situation of using electron donor(ED), press every mole metal atom calculating in the organo-aluminium compound (h-1), its consumption is generally about 0.001-10 mole, is preferably the 0.01-2 mole, is preferably the 0.05-1 mole especially.
Under using with the situation of vanadium as substrate, the catalyzer formed by soluble vanadium compound (g-2) and organo-aluminium compound (h-1), in every liter of copolyreaction volume, the concentration of solvable vanadium compound (g-2) is generally 0.01-5mmol in the copolymerization system, is preferably 0.05-3mmol.Preferably solvable vanadium compound (g-2) is added in the copolymerization system, its concentration is in the copolymerization system 10 times of the existing concentration of solvable vanadium compound or still less, is preferably 1-7 doubly, more preferably be 1-5 times.Organo-aluminium compound (h-1) can be added in the copolymerization system, and wherein the mol ratio of aluminium and vanadium (A1/V) is 2 or more in the copolymerization system, is preferably 2-50, more preferably is 3-20.
Usually under the situation of in the liquid mixture of varsol and/or ethene and straight chain triene compound (B-2), diluting, soluble vanadium compound (g-2) and organo-aluminium compound (h-1) are added in the copolymerization system.Here, preferably organo-aluminium compound (h-1) is added in the copolymerization system, it has any concentration of 50 times of concentration to its concentration adjustment in copolymerization system to for example being lower than, and is added to wherein under the weaker concn that preferably solvable vanadium compound (g-2) is provided in front.
Under using with the situation of metallocenes as substrate, the catalyzer formed by the ionic compound (j-1) of metallocenes (g-3) and Organoaluminoxy compound (h-2) or ionizing, in every liter of copolyreaction volume, the concentration of metallocenes in the copolymerization system (g-3) is generally 0.00005-0.1mmol, is preferably 0.0001-0.05mmol.Organoaluminoxy compound (h-2) can be added in the copolymerization system, and wherein the mol ratio of the transition metal vanadium in aluminium and the metallocenes (A1/ transition metal) is 1-10000, is preferably 10-5000.
For ionizing ionic compound (j-1), it is added in the copolymerization system, wherein the mol ratio of ionizing ionic compound and metallocenes (g-3) { ionic compound (j-1)/metallocenes (g-3) } is 0.5-20, is preferably 1-10.
Under the situation that is mixed with machine aluminium compound (h-1), adopt such amount to make that its concentration is about 0-5mmol in every liter of copolyreaction volume, is preferably about 0-2mmol in every liter of copolyreaction volume usually.
According to the present invention, above-mentioned with the titanium be substrate catalyzer in the presence of, comonomer be ethene (A-1), alpha-olefin (A-2) and formula (2) representative straight chain triene compound (B-2) copolyreaction usually temperature range for-20 ℃-+150 ℃, be preferably 0-120 ℃, more preferably for 0-100 ℃ and pressure range for greater than 0-7.8MPa (80Kgf/cm at the most
2Gauge pressure), be preferably more than 0-4.9MPa (50Kgf/cm at the most
2Gauge pressure) finishes under the condition.
According to the present invention, above-mentioned with the vanadium be substrate catalyzer in the presence of comonomer, i.e. the copolyreaction of the straight chain triene compound (B-2) of ethene (A-1), alpha-olefin (A-2) and formula (2) representative can temperature range for-50 ℃-+100 ℃, be preferably-30 ℃-+80 ℃, more preferably for-20 ℃-+60 ℃ and pressure range for greater than 0-4.9MPa (50Kgf/cm at the most
2Gauge pressure), be preferably more than 0-2.0MPa (20Kgf/cm at the most
2Gauge pressure) carries out under the condition.
According to the present invention, above-mentioned with the catalyzer at the bottom of the metallocenyl in the presence of comonomer, i.e. the copolyreaction of the straight chain triene compound (B-2) of ethene (A-1), alpha-olefin (A-2) and formula (2) representative can temperature range for-20 ℃-+150 ℃, be preferably 0-120 ℃, more preferably for 0-100 ℃ and pressure range for greater than 0-7.8MPa (80Kgf/cm at the most
2Gauge pressure), be preferably more than 0-4.9MPa (50Kgf/cm at the most
2Gauge pressure) carries out under the condition.
According to the present invention, straight chain triene compound (B-2) and other comonomer that can add arbitrarily of ethene (A-1), alpha-olefin (A-2), formula (2) representative can be added in the copolymerization system, wherein every kind of feasible second multipolymer (I-2) that can obtain containing above-mentioned definition component of monomeric consumption.In copolyreaction, can use molecular weight regulator such as hydrogen.
By the straight chain triene compound (B-2) of copolymerization of ethylene (A-1), alpha-olefin (A-2) and formula (2) representative, second multipolymer (I-2) that obtains, promptly ethylene/alpha-olefin/three olefinic random copolymers are generally the liquid polymerization mixture that contains multipolymer.Should the liquid state copolymerization product carry out aftertreatment according to method commonly used and obtain second multipolymer (I-2), be i.e. ethylene/alpha-olefin/three olefinic random copolymers.
Second multipolymer of the present invention (I-2) that obtains according to the method, be ethylene/alpha-olefin/three olefinic random copolymers, can cure with fast speeds, and have fabulous incipient scorch stability and fabulous weathering resistance, thermotolerance and ozone resistance, therefore it can be used for many application, as the raw material of multiple rubber product with as modifier.By vulcanizing second multipolymer of the present invention (I-2), i.e. ethylene/alpha-olefin/three olefinic random copolymers and the rubber product of the sulfuration that obtains also has superiority not only aspect weathering resistance, thermotolerance and ozone resistance, and aspect caoutchouc elasticity.Use second multipolymer of the present invention (I-2), promptly in ethylene/alpha-olefin/three olefinic random copolymer production vulcanized rubber products, can carry out the high speed sulfuration, therefore can obtain high yield.
Second composition of the present invention comprises second multipolymer of the present invention (I-2), i.e. ethylene/alpha-olefin/three olefinic random copolymers, vulcanizing agent (II) and/or filler (III).Second composition of the present invention is made up of vulcanizable rubber components, and this component can not produce practical application under the sulfided state yet, although when using with sulfur form, it can produce how favourable characteristic.Sulfuration can be finished according to several different methods, for example, and by using vulcanizing agent (II) or not using under the situation of vulcanizing agent (II) by the irradiation of electron beam and heat.As filler, the example can be toughener and tenderizer.
By vulcanizing the rubber product of the sulfuration that second composition of the present invention obtains, not only aspect weathering resistance, thermotolerance, ozone resistance and anti-dynamic fatigue, and also has superiority aspect caoutchouc elasticity and the low temperature flexibility.In using the second composition production vulcanized rubber products of the present invention, can obtain high yield, because second multipolymer of the present invention (I-2), promptly ethylene/alpha-olefin/three olefinic random copolymers can carry out the high speed sulfuration.Also can reduce vulcanizing agent (II) and mix the consumption of vulcanization accelerator, therefore can obtain to have the fabulous vulcanized rubber products of low frosting outward appearance.
For by baking second composition of the present invention, can be incorporated in second composition as vulcanizing agent (II), vulcanization accelerator and vulcanization aid forming the compound of vulcanization system.
In second composition of the present invention, can mix sulphur, sulphur compounds and organo-peroxide as vulcanizing agent (II).
Form to sulphur there is no special restriction, for example can adopt powdered sulphur, sedimentary sulphur, colloid sulphur, surface-treated sulphur and insoluble sulphur.
In sulphur compounds mentioned above, concrete example can be sulfur subchloride, sulfur dichloride, high poly-polysulfide, morpholine disulfide, curing alkylphenol tetramethyl-thiuram disulfide and Selenium dimethyl dithiocarbamate.
The specific examples of organo-peroxide mentioned above can be an alkyl peroxide, for example dicumyl peroxide, ditertiary butyl peroxide, di-t-butyl peroxide-3,3,5-trimethyl-cyclohexane, tertiary butyl cumyl peroxide, two t-amyl peroxy things, 2,5-dimethyl-2,5-di-t-butyl peroxide-hexin-3,2,5-dimethyl-2,5-two (benzoyl peroxide) hexane, 2,5-dimethyl-2,5-two (t-butyl peroxy) hexane, α, α '-two (t-butyl peroxy--sec.-propyl) benzene and tert-butyl hydroperoxide; Peroxyester, for example t-butyl peroxy acetic ester, t-butyl peroxy isobutyrate, t-butyl peroxy pivalate, t-butyl peroxy maleic acid ester, t-butyl peroxy neodecanoic acid ester, t-butyl peroxy benzoic ether and di-t-butyl peroxide phthalic ester and ketone peroxide, for example bicyclohexanone superoxide etc.They can be used with two or more combining form.
Therein, it preferably is 1 minute organo-peroxide 130-200 ℃ of half-life, for example dicumyl peroxide, ditertiary butyl peroxide, di-t-butyl peroxide-3,3,5-trimethyl-cyclohexane, tertiary butyl cumyl peroxide, two t-amyl peroxy thing and tert-butyl hydroperoxides.
According to the present invention, in above-mentioned vulcanizing agent (II), the compound, particularly sulphur of preferred sulphur and sulphur are because can obtain having the rubber combination of good characteristic with this.
When vulcanizing agent (II) is the compound of sulphur or sulphur, be that ethylene/alpha-olefin/three olefinic random copolymers calculate by per 100 weight parts second multipolymers of the present invention (I-2), its consumption is the 0.1-10 weight part, preferred 0.5-5 weight part.
When vulcanizing agent (II) is organo-peroxide, be that ethylene/alpha-olefin/three olefinic random copolymers calculate by per 100 weight parts second multipolymers of the present invention (I-2), its consumption is the 0.05-15 weight part, preferred 0.15-5 weight part.
When the compound of sulphur or sulphur uses as vulcanizing agent, preferably use vulcanization accelerator simultaneously.
The concrete example of vulcanization accelerator can be the sulfinyl amine compounds, for example N-cyclohexyl-2-[4-morpholinodithio sulfinyl amine (CBS), N-oxidation divinyl-2-[4-morpholinodithio sulfinyl amine and N, N-di-isopropyl-2-[4-morpholinodithio sulfinyl amine; Thiazole compound, for example 2-mercaptobenzothiazole (MBT), 2-(2,2, 4-dinitrophenol) mercaptobenzothiazole, 2-(2,6-diethyl-4-morpholino sulfo-) benzothiazole, 2-(4 '-morpholino dithio benzothiazole) and dibenzothiazyl disulfide; Guanidine compound, for example vulkacit D, triphenyl guanidine, two adjacent nitrile guanidines (diorthonitrileguanidine), adjacent nitrile two guanidines (orthonitrile biguanide) and vulkacit D phthalic ester; Aldehyde amine or aldehyde ammonia compounds, for example condensation product of the reaction product of acetaldehyde and aniline, butyraldehyde and aniline, vulkacit H and aldamine; Imidazolines, for example 2-mercaptoimidazoline etc.; Thiourea, for example thiocarbanilide, diethyl thiourea, dibutyl thiourea, trimethyl thiourea and di-o-tolyl thiocarbamide; Thiuram compound, for example single sulfuration tetra methylthiuram, tetramethyl-thiuram disulfide (TMTD), tetraethylthiuram disulfide, tetrabutylthiuram disulfide, four sulfuration pentamethylene thiuram and dipentamethylene thiuram tetrasulfides (DPTT); Dithionic acid salt compounds, for example ziram, zinc diethyldithiocarbamate, di-t-butyl zinc dithiocarbamate, ethylphenyl thiocarbamate zinc, butyl phenyl zinc dithiocarbamate, Sodium dimethyldithiocarbamate 40min, Selenium dimethyl dithiocarbamate and tellurium dimethyldithiocarbamate; Xanthogenate compounds, for example dibutyl xanthogenic acid zinc (zinc dibutyl-xantogenate); And zinc white.
By per 100 weight parts second multipolymers of the present invention (I-2) is that ethylene/alpha-olefin/three olefinic random copolymers calculate, and the better consumption of vulcanization accelerator is the 0.1-20 weight part, preferred 0.2-10 weight part.
When the vulcanizing agent that uses (II) during as organo-peroxide, calculate by every mole of organo-peroxide, preferably with the vulcanization aid of 0.5-2 mole, the preferably auxiliary agent of about equimolar amount while use together.
Specific examples as vulcanization aid can be sulphur, quininie dioxime, and for example paraquinonedioxime etc. also has polyfunctional monomer, for example (methyl) acrylate, for example three vinylformic acid trishydroxymethyl propyl ester, polyethylene glycol dimethacrylate etc.; Allylic compound, for example diallyl phthalate and triallyl cyanurate; The maleimide compounds, for example between-phenylene bismaleimides etc.; And Vinylstyrene.
Be used as the toughener of the filler (III) of the present invention's second composition, can use the carbon black product, for example SRF, GPF, FEF, MAF, HAF, ISAF, SAF, FT and MT; With silane coupling agent above-mentioned carbon black product is carried out the surface-treated carbon black product that surface treatment obtains; Mineral filler, for example silica, treated carbonates, light calcium carbonate, water-ground limestone, fine talc powder, talcum powder, thin silicic acid powder and clay.
By per 100 weight parts second multipolymers of the present invention (I-2) is that ethylene/alpha-olefin/three olefinic random copolymers calculates, and the consumption of toughener can be 300 weight parts or still less, preferred 10-300 weight part, more preferably 10-200 weight part.
Use contains the composition of the toughener of such amount, can access its mechanical property, for example the vulcanized rubber products that all increases of tensile strength, tear strength and wear resistance.Also can under the situation of other material property that does not damage vulcanized rubber, increase its intensity, reduce production cost simultaneously.
As the tenderizer of the filler (III) of second composition of the present invention, commonly used can obtain using widely with rubber product bonded tenderizer.Concrete example comprises the petroleum-type tenderizer, for example process oil, lubricating oil, paraffin, whiteruss, petroleum pitch and Vaseline; Coal tar oil-softener, for example coal tar and coal-tar pitch; Fatty oils tenderizer, for example Viscotrol C, oleum lini, rape oil, plam oil; Wax class, for example Yatall MA, factice, beeswax, carnauba wax and lanolin; Lipid acid and soap, for example ricinoleate acid, palmitinic acid, barium stearate, calcium stearate and zinc laurate; Lipid is made softening agent, for example dioctyl phthalate (DOP); Octyl adipate and dioctyl sebacate; And synthetic superpolymer, for example petroleum resin, Atactic Polypropelene and coumarone indeneresin.In these materials, preferred petroleum-type tenderizer, and special preferred operations oil.
By per 100 weight parts second multipolymers of the present invention (I-2) is that ethylene/alpha-olefin/three olefinic random copolymers calculates, and the consumption of tenderizer can be 200 weight parts or still less, preferred 10-200 weight part, more preferably 10-150 weight part.
Second composition of the present invention contains other component except that said components.For example can mix the compound of forming foaming system, for example whipping agent and frothing aid, antioxidant (stablizer), processing material, softening agent, tinting material, other rubber accelerator and number of chemical material.The kind of these other components and consumption can be selected arbitrarily according to each special application.
Second composition of the present invention can be under foaming molding, if it contains the compound of forming foaming system, for example whipping agent and frothing aid.
As whipping agent, those whipping agents that are applied to spongy rubber usually can be widely used.Its concrete example comprises inorganic foaming agent, for example sodium bicarbonate, yellow soda ash, bicarbonate of ammonia, volatile salt and ammonium nitrate; The nitroso-group mixture, N for example, N '-dimethyl-N, N '-dinitroso terephthaloyl ammonium and N, N '-dinitroso penta tetramine; Azo-compound, for example azodicarbonamide, Diisopropyl azodicarboxylate, azo cyclohexanenitrile, azoaniline and barium azodicarboxylate; The sulfonyl hydrazide compound, for example benzol sulfohydrazide, toluene sulfonyl hydrazide, p, p '-oxygen is two-(benzol sulfohydrazide) and sulfobenzide-3,3 '-disulfonyl hydrazide; And triazo-compound, nitrine calcium, 4 for example, 4-phenylbenzene disulfonyl triazo-compound and p-toluene sulfonyt azide compound.In these compounds, preferred nitroso compound azo-compound and triazo-compound.
By per 100 weight parts second multipolymers of the present invention (I-2) is that ethylene/alpha-olefin/three olefinic random copolymers calculate, and the consumption of whipping agent can be the 0.5-30 weight part, preferred 1-20 weight part.From the composition of the whipping agent that contains above-mentioned scope amount, can generate apparent density is 0.03-0.8g/cm/
3Foamed product.
Frothing aid also can use with whipping agent.The useful influence of using frothing aid to produce simultaneously is: reduce foaming agent decomposition temperature, promote the decomposition of whipping agent and make foam even.The example of frothing aid has, organic acid, and for example Whitfield's ointment, phthalic acid, stearic acid and oxalic acid also can adopt urea and derivative thereof.
By per 100 weight parts second multipolymers of the present invention (I-2) is that ethylene/alpha-olefin/three olefinic random copolymers calculate, and the consumption of frothing aid can be the 0.01-10 weight part, preferred 0.1-5 weight part.
In second composition of the present invention, mix antioxidant, can prolong the life-span of product preferably.The concrete example of antioxidant comprises secondary aromatic amine class stablizer, phenyl naphthyl amines, 4 for example, 4 '-(α, alpha, alpha-dimethyl benzyl) pentanoic and N, N '-two-2-naphthyl-Ursol D; Phenol stablizer, for example 2,6 di tert butyl 4 methyl phenol and four-{ methylene radical-3-(3 ', 5 '-di-t-butyl-4 '-hydroxyphenyl) propionic acid } methane; Thioether class stablizer, for example two { 2-methyl-4-(the positive alkyl propane thioic acid of 3-base)-5-tert-butyl-phenyl } thioethers etc.; Benzimidazoles stablizer, for example 2-mercaptobenzimidazole etc.; Dithiocarbamate(s) stablizer, for example nickel dibutyl dithiocarbamate etc.; And the quinoline stablizer, for example 2,2,4-trimethylammonium-1,2-dihydroxyl quinoline polymkeric substance.They also can use with two or more combining form.
By per 100 weight parts second multipolymers of the present invention (I-2) is that ethylene/alpha-olefin/three olefinic random copolymers calculates, and the consumption of antioxidant can be 5 weight parts or still less, preferred 3 weight parts or still less.
As processing material, those processing materials that are applied to rubber usually can be widely used.Concrete example comprises acid for example ricinoleate acid, stearic acid, palmitinic acid and lauric acid; The salt of these higher fatty acid, for example barium stearate, Zinic stearas and calcium stearate; And ester class.
By per 100 weight parts second multipolymers of the present invention (I-2) is that ethylene/alpha-olefin/three olefinic random copolymers calculates, and the consumption of processing material can be 10 weight parts or still less, preferred 5 weight parts or still less.
Second composition of the present invention contains the known rubber components of its itself, gets final product in not hindering enforcement purpose scope of the present invention.
Can list these other rubber components, natural rubber (NR) for example, isoprenoid rubber, for example synthetic polyisoprene (IR) etc.; Conjugated diene rubber, for example divinyl rubber (BR), styrene-butadiene rubber(SBR) (SBR), acrylonitrile-butadiene rubber (NBR) and neoprene (CR); And hydrogenant NBR.
Also can combine with other known ethylene/alpha-olefin hydro carbons copolymer rubber.For example can adopt ethylene/propylene olefinic random copolymer (EPR) and ethylene/alpha-olefin/polyene copolymer, for example EPDM.
By these other rubber and second multipolymer, i.e. the total of ethylene/alpha-olefin/three olefinic random copolymers, these other rubber mix consumptions preferably make the consumption of the present invention's second multipolymer (I-2) be at least 10 weight %, preferably at least 20 weight %.As second multipolymer (I-2), promptly the content of ethylene/alpha-olefin/three olefinic random copolymers is in this scope, and rubber combination can demonstrate material property preferably.
Press the total of composition, second multipolymer that preferably contains in second composition of the present invention, promptly the content of ethylene/alpha-olefin/three olefinic random copolymers is at least 20 weight %, is preferably at least 25 weight %.When second multipolymer, promptly the content of ethylene/alpha-olefin/three olefinic random copolymers is in this scope, and rubber combination can demonstrate material property preferably.
Second composition of the present invention can be widely used as the starting material into rubber product, the goods of auto parts, automatic buffer rubber, industrial rubber product, electronic body, construction use and rubber lining cloth for example, can be used as the raw material of rubber especially, be used for the extrusion molding goods, for example sealing material, the glass blade and the sponge rubber that ooze groove, scraper blown the rain bar; And annotate pressing mold and mould and the transfer molding goods, the rubber sponge sealed strip of moulded foam rubber sponge and automotive door for example.
The object lesson of rubber packing material comprises the sealing element of sealing element, vehicle window frame and restoring cylinder between cover cap, window glass and the window frame of the sealing element of cover cap, brake fluid pressure controller of cover cap, the brake wheel cylinder of brake master cylinder in the Thrustor and O-ring, clutch cylinder.
When second composition of the present invention is used to prepare said products, when for example caulking gum, the glass rubber, the blade of scraper, the sponge rubber that ooze groove blown rain bar, moulded foam rubber sponge, they can vulcanize by two-forty, produce and have excellent material characteristic, for example caoutchouc elasticity, weathering resistance, heat impedance, anti-ozone and a low temperature flexibility with high yield.For example, a spongiform rubber weather strip can be by finishing sulfuration with the goods of extrusion molding and producing efficiently in the very short time.Here, sulfuration is enough carried out very satisfactoryly in the so short time and the finished product have good caoutchouc elasticity.
Second composition of the present invention can be with second multipolymer of the present invention, i.e. ethylene/alpha-olefin/three olefinic random copolymers and above-mentioned other component are by the usual way preparation of preparation rubber compound.For example, second composition (I-2), be ethylene/alpha-olefin/three olefinic random copolymers and other with combined component in 80-170 ℃ in internal mixer, for example mediate in Bumbury mixing tank, the kneader and mixed 3-10 minute, and after mixing, if necessary, can mix vulcanizing agent (II), vulcanization accelerator, vulcanization aid and whipping agent, the compound that obtains in 40-80 ℃ at cylinder, further mediated 5-30 minute in for example uncovered cylinder or in kneader, and then segmentation is discharged.Adopt this method, can obtain being generally ribbon shape or flaky rubber combination (compounded rubber).If the kneading temperature of internal mixer is lower, can simultaneously composition be mediated with vulcanizing agent (II), sulphur promotor and whipping agent.
The sulfur product of second composition (vulcanized rubber product) can pass through not vulcanising composition former commonly used, for example overflow mould molding machine, calendering rod, pressing machine, notes pressing mold molding machine or transfer molding machine adopt different forming techniques to make required shape and produce.The sulfuration of the fresh prod of making like this can by be heated-in the process of carrying out or with it, transfer to after the sulfuration container-or realize with electron beam radiating method.
Foaming product can contain the initial rubber stock of not vulcanizing of whipping agent and by the technology that provides above its sulfuration obtained by use, wherein simultaneously rubber stock is foamed the goods that are shaped thus and vulcanized in sulfuration.
The heating of sulfuration preferably under 150 ℃-270 ℃, with warm air, granulated glass sphere sulfuration bed, UHF (ultra-high frequency radiowave), steam or LCM (heat fusing salt container), was heated in heating container 1-30 minute.
Under the situation of not using vulcanizing agent (II) sulfidation is carried out electron beam irradiation, can use the electron beam of the energy of 0.1-10MeV, preferred 0.3-2MeV makes that absorption dose is 0.5-35Mrad, preferred 0.5-10Mrad.
Can use or not use metal pattern to the sulfurized molding.Under the situation of not using metal pattern, rubber components carries out molding in the mode of continuously moulding to sulfuration usually.
Serve many purposes through above-mentioned molding and sulfurized rubber product, the part that comprises automotive industry, for example weather strip, door glass ooze groove, window frame, radiator tube, brake part, wiping device blade, brake cap, top board parts, pneumatic tyre lid, dashboard, trim, controller handle and seat belt housing; The yielding rubber product of automobile, for example tyre tread, sidewall and start machine frame; Industrial rubber product, for example rubber cylinder, belt, wrapping material and rubber tubing; Electronic body is used for anode cap, packing ring and cable; Building and construction material, filler for example for building, surperficial cover plate and roof sheet material; And other rubber sleeve cloth, for example electric guide rubber, high durometer rubber and outer drop cloth.
The foaming vulcanizate that obtains by the rubber combination heat-foaming that will contain whipping agent can be used for preparation example such as weather strip, and thermal isolation effect, damping and sealing.
When the shaping prod by the present invention's second composition manufacturing was sheet or film like, it can be by carry out the thin slice that lamination formation composition sheet or film are made on the layer of the present invention's second composition and one or more other rubber or resin composition.For these other materials, what can adopt is for example above-mentioned conjugated diene rubber, ethylene/alpha-olefin copolymer rubber, polyethylene, polypropylene and polybutene.
Second multipolymer of the present invention, promptly ethylene/alpha-olefin/three olefinic random copolymers can be by with itself and resin, for example polyolefin resin, for example polyethylene, polypropylene, polybutene; AES and ABS blend are as resin combination.Press the total weight of resin and second multipolymer (I-2), blending ratio preferably makes second multipolymer (I-2), and promptly the content of ethylene/alpha-olefin/three olefinic random copolymers is 10 weight % or more, preferred 20 weight % or more.For-blend carried out, except second multipolymer, be ethylene/alpha-olefin/three olefinic random copolymers and blending resin, for example outside polyethylene, polypropylene and the polybutene, also can blast blending, for example butyl type rubber softening agent or polypropylene, oils and styrene/ethylene/butylene/styrene block copolymer (SEBS) and styrene/ethylene/propylene/styrene segmented copolymer (SEPS) class softening agent.
Above-mentioned by second multipolymer (I-2), be in the resin combination formed of the polyolefin resin etc. of ethylene/alpha-olefin/three olefinic random copolymers and blend, by with second multipolymer (I-2), it is crosslinked to be that ethylene/alpha-olefin/three olefinic random copolymers carry out, and rubber property is improved can to make it have preferably as rubber combination.For example can adopt superoxide, sulphur compound, phenolic resin and quinonoid compound as linking agent.In order in crosslinked, to mediate, preferably adopt dynamic crosslinking as crosslinking technological with forcing machine etc.
" the 3rd multipolymer { alpha-olefin/three olefinic random copolymers (I-3) } "
Now, to the 3rd multipolymer of the present invention (I-3), promptly alpha-olefin/three olefinic random copolymers carry out concrete description.
From forming the present invention's the 3rd multipolymer (I-3), promptly the alpha-olefin derived structural unit that goes out of alpha-olefin/three olefinic random copolymers is by having at least 3, the structural unit (U that the alpha-olefin (A-2) of preferred 3-20 carbon atom derives
A-2) and from another by having at least 2, the alpha-olefin (A-3) of preferred 2-20 carbon atom derives is different from first described structural unit (U
A-2) structural unit (U
A-3).
As deriving structural unit (U
A-2) and (U
A-3) alpha-olefin, concrete example can be for example ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 3-methyl-1-butene, 3-Methyl-1-pentene, 3-ethyl-1-amylene, 4-methyl-1-pentene, 4-methyl isophthalic acid-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-amylene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid and 1-eicosylene.Certainly, structural unit (U
A-2) do not go out from ethylene derivative.
Below (U-I) and (U-II) provided structural unit (U
A-2) and (U
A-3) preferred combination.
(U-I): the structural unit (U that derives from propylene or 4-methyl-1-pentene
A-2) and from ethene, 1-butylene, 1-amylene, 1-hexene or have the alpha-olefin derived structural unit (U that goes out of 7-20 carbon atom
A-3) combination.Be preferably used as structural unit (U here,
A-3) alpha-olefin be ethene, 1-butylene, 1-hexene and 1-octene, wherein preferred construction unit (U
A-3) be those linear units.
(U-II): from having the alpha-olefin derived structural unit (U that goes out of 6-20 carbon atom
A-2) and the structural unit (U that derives from ethene, propylene or 4-methyl 1-amylene
A-3) combination.Be preferably used as structural unit (U here,
A-2) preferably alpha-olefin be 1-hexene, 1-octene and 1-decene, wherein preferred construction unit (U
A-2) be those linear units.
As structural unit (U
A-2) and (U
A-3) combination when belonging to (U-I), can obtain having high strength and can be by two-forty sulfurized multipolymer.
As structural unit (U
A-2) and (U
A-3) combination when belonging to (U-II), can obtain having low strength and can be by low rate sulfurized multipolymer.
The present invention's the 3rd multipolymer (I-3), promptly alpha-olefin/three olefinic random copolymers are the structural unit (U that derived by the chain triene compound (B-2) shown in the general formula (2)
B-2) further form.
In the chain triene compound shown in the general formula (2), preferred R
3And R
4Be methyl.With the present invention's the 3rd multipolymer (I-3) that such chain triene compound (B-2) obtains as monomer, promptly alpha-olefin/three olefinic random copolymers are superior especially aspect the balance of vulcanization rate and incipient scorch curve.
Chain triene compound (B-2) shown in the general formula (2), preferred 4,8-dimethyl-1,4,8-triolefin in the last of the ten Heavenly stems (DMDT).
Chain triene compound (B-2) shown in the general formula (2) has stereoisomerism (anti--and along isomer) usually.As monomeric chain triene compound (B-2) can be trans-and cis-mixture of isomers or single trans-or cis-constitutional isomer.
At the present invention's the 3rd multipolymer (I-3), promptly in alpha-olefin/three olefinic random copolymers, structural unit (U
A-2), (U
A-3) and (U
B-2) with the mutual bonding of random distribution, and structural unit (U
B-2) have a unsaturated link(age) that derives by chain triene compound shown in the general formula (2).
The present invention's the 3rd multipolymer (I-3), promptly the main chain of alpha-olefin/three olefinic random copolymers is essentially linear structure.According to the 3rd multipolymer (I-3), be that alpha-olefin/three olefinic random copolymers are dissolved in this fact of organic solvent (because not having insoluble resistates to exist basically), the supposition that this multipolymer is had linear structure on substantially and is substantially free of crosslinked micelle structure is confirmable.For example, can be according in the detection of its limiting viscosity [η], this is true and determine to be insoluble to naphthalane fully at 135 ℃ of following multipolymers (I-3).
The present invention's the 3rd multipolymer (I-3), i.e. structural unit (U in alpha-olefin/three olefinic random copolymers
A-2) content in the scope of 70-99.9 mole %, preferred 75-95 mole %, structural unit (U
A-3) content in the scope of 0-29.9 mole %, preferred 1-25 mole %, and structural unit (U
B-2) content in the scope of 0.1-30 mole %, as long as preferred 0.2-10 mole % is (U
A-2), (U
A-3) and (U
B-2) the content summation of these structural units is that 100 moles of % get final product.
When the content of these structural units is in above-mentioned scope, such the 3rd multipolymer (I-3), promptly alpha-olefin/three olefinic random copolymers demonstrate good elastomeric material characteristic.
The 3rd multipolymer (I-3) can have multiple application, comprise the raw material of multiple rubber product and as the properties-correcting agent of various kinds of resin, specifically, also can be used for extruding-moulded parts as raw material preferably, for example glass oozes groove, wipes device blade and rubber sponge shelves wind and rain bar, be used to annotate pressing mold and mould goods and transfer molding goods, for example inner mold foaming-molding sponge product.
At the 3rd multipolymer of the present invention (I-3), promptly in alpha-olefin/three olefinic random copolymers, the structural unit (U that derives from chain triene compound (B-2)
B-2) have basically by the molecular structure shown in the general formula (2-a).Can be by using
13C-NMR spectrometry the 3rd multipolymer (I-3), promptly alpha-olefin/three olefinic random copolymers prove that the structural unit that derives from chain triene compound (B-2) has this fact of structure shown in the general formula (2-a).
Compare the 3rd multipolymer (I-3), the i.e. structural unit that alpha-olefin/three olefinic random copolymers can other copolymerisable monomers of copolymerization with the comonomer of chain triene compound (B-2) shown in the general formula (2) with those alpha-olefins.For other comonomer, can list non-conjugated diene and cycloolefin.Calculate by the total mole number of all structural units, the content of the structural unit that derives from other such monomers is preferably 30 moles of % or still less, preferred 0.5-10 mole %.For other such monomers, can adopt those examples identical with second multipolymer.
The 3rd multipolymer of the present invention (I-3), promptly alpha-olefin/three olefinic random copolymers can two-forty sulfuration, and aspect incipient scorch stability excellence, also excellent aspect weathering resistance, thermotolerance and ozone resistance simultaneously.
The 3rd multipolymer of the present invention (I-3), be that alpha-olefin/three olefinic random copolymers are used under the not sulfided state that not only shows such on the border in fact, show that too wherein sulfuration has promoted its excellent characteristic by it being carried out the sulfur form behind the following sulfuration process.In sulfuration,, still obtain higher vulcanization rate although the incipient scorch effect does not weaken in the meantime.
The 3rd multipolymer of the present invention (I-3), promptly alpha-olefin/three olefinic random copolymers are particularly suitable as the raw material of multiple rubber product and as modifier.
The example of rubber product has, auto parts, industrial rubber product, electronic body, product for building and rubber drop cloth.Concrete example comprises that glass oozes groove, wipes device blade, weather strip, sponge, hose, rubber neck, sidewall, cable joint-box and packing ring.
When the 3rd multipolymer of the present invention (I-3), being alpha-olefin/three olefinic random copolymers joins resin for example in polypropylene, polyethylene, polybutene and the polystyrene time as the properties-correcting agent of resin, and the shock resistance of resin and the performance of anti-stress cracking are greatly improved.
As structural unit (U
A-2) and (U
A-3) combination when belonging to (U-I), such multipolymer intensity height, and can curing with very high speed.
As structural unit (U
A-2) and (U
A-3) combination when belonging to (U-II), such multipolymer intensity is low, and can cure with very high speed.
The 3rd multipolymer of the present invention (I-3), promptly alpha-olefin/three olefinic random copolymers can individual curing or with other elastomeric material covulcanization.
Because two-forty sulfuration, compare with traditional alkene unsaturated copolymer, the 3rd multipolymer of the present invention (I-3), promptly alpha-olefin/three olefinic random copolymers can cure in the short period of time or with lower curing temperature need not to use under the situation of a large amount of vulcanizing agents.The 3rd multipolymer of the present invention (I-3), promptly alpha-olefin/three olefinic random copolymers have excellent incipient scorch stability, so it can be with the frothing mold operation with stable rate of expansion, and can obtain the increase of foaming product productive rate.Like this, initial viscosity by being present in resin raw material, the viscosity in the molding advance the speed and the rate of decomposition of whipping agent between the foaming and intumescing of balance detection accurately ratio, so be difficult to the control rate of expansion, high more because viscosity is advanced the speed, the scope of viscosity rate of change is just big more.But incipient scorch stability is still excellent, so the 3rd multipolymer of the present invention (I-3), i.e. the increase of the viscosity of alpha-olefin/three olefinic random copolymers is less, so can make the moulded parts of foaming with stable rate of expansion effectively.Operational stability aspect in operation, the 3rd multipolymer of the present invention (I-3), be that alpha-olefin/three olefinic random copolymers are also very excellent, this is because it has excellent incipient scorch stability, therefore the trouble that the viscosity increase in can preventing to operate brings, for example in forcing machine, as the filling or the obstruction of the increase of the minimizing of forcing machine output, engine loading and cylinder and/or in forcing machine, vulcanize, viscosity is increased and the deadlock that causes.
The 3rd multipolymer of the present invention (I-3), promptly another advantage of alpha-olefin/three olefinic random copolymers is in the characteristic that keeps above-mentioned excellence, and is also very superior aspect the heat resistanceheat resistant reduction.
" the 3rd multipolymer (I-3), the i.e. preparation of alpha-olefin/three olefinic random copolymers "
The 3rd multipolymer of the present invention (I-3), promptly alpha-olefin/three olefinic random copolymers can be by preparing with the above-mentioned identical method of the present invention's second multipolymer for preparing.So, it can be under above-mentioned identical condition, in the presence of the cited identical catalyzer of preparation second multipolymer, by copolymerization have 2-20 carbon atom alpha-olefin, the chain triene compound (B-2) shown in the general formula (2) and-mix other monomers if necessary-arbitrarily to make.
The 3rd multipolymer of the present invention (I-3) that obtains by such method, be that alpha-olefin/three olefinic random copolymers can cure with two-forty, and excellence aspect incipient scorch stability, also excellent aspect weathering resistance, heat impedance and anti-ozone simultaneously, so it can be applied to, the properties-correcting agent of the raw material of multiple rubber item and resin for example.With the 3rd multipolymer of the present invention (I-3), i.e. the vulcanized rubber products that alpha-olefin/three olefinic random copolymers sulfuration obtains is excellence aspect weathering resistance, heat impedance and anti-ozone not only, simultaneously also excellence aspect caoutchouc elasticity.Using the 3rd multipolymer of the present invention (I-3), i.e. alpha-olefin/when three olefinic random copolymers prepare vulcanized rubber products, can therefore can obtain high yield with high vulcanization rate operation.
The present invention's the 3rd composition contains the 3rd multipolymer of the present invention (I-3), i.e. alpha-olefin/three olefinic random copolymers, vulcanizing agent (II) and/or filler (III).The 3rd composition of the present invention is made up of vulcanizate compositions, and it can be in practical application under the sulphur state not, although when using with sulfur form, have more advantage.
The excellence of the vulcanized rubber products that obtains by sulfuration the present invention the 3rd composition not only shows weathering resistance, heat impedance, anti-ozone and anti-dynamic fatigue aspect, also shows caoutchouc elasticity and low temperature flexibility aspect simultaneously.When using the present invention's the 3rd preparation of compositions vulcanized rubber products, can obtain high yield, because the 3rd multipolymer of the present invention (I-3), promptly alpha-olefin/three olefinic random copolymers can vulcanize with two-forty.Also can reduce vulcanizing agent (II) and mix the consumption of vulcanization accelerator, can obtain the vulcanized rubber products with excellent appearance of low frosting like this.
The 3rd composition of the present invention can adopt the method sulfuration identical with aforementioned second composition.So, by with itself and the compound of forming vulcanization system, for example mixing such as vulcanizing agent (II), vulcanization accelerator, vulcanization aid, and under the condition identical, carry out the blended sulfuration with above-mentioned second composition.
As the filler that mixes the present invention's the 3rd composition (III), can enumerate toughener and the softening agent identical with aforementioned second composition.The consumption of these tougheners and the softening agent that mixes the also consumption with above-mentioned second composition is identical.
Can with the present invention's the 3rd composition blended except that said components, also have other components and chemical substance, comprise the compound of forming foaming system, for example whipping agent and frothing aid, antioxidant (stablizer), processing material, softening agent, tinting material and other rubber components.The kind of these other components and consumption can be selected according to requiring separately.
When the 3rd multipolymer of the present invention contains the compound of forming foaming system, for example when whipping agent and frothing aid, can carry out the frothing mold operation to it.Frothing mold can the mode identical with above-mentioned second composition carry out.So it is used that whipping agent and frothing aid are equal to above-mentioned second composition, its consumption is also identical.
As other Synergist S-421 95s and the 3rd composition bonded antioxidant (stablizer) and processing material of the present invention, can adopt those identical with second composition, its consumption is also identical.
Except containing the 3rd multipolymer (I-3), promptly outside alpha-olefin/three olefinic random copolymers, the 3rd composition of the present invention can also contain other, and oneself knows rubber components, and its scope does not hinder implements purpose of the present invention.These other rubber components can with above-mentioned second composition provide identical, its consumption also can be identical, so compounded rubber can reach material behavior preferably.
The 3rd composition of the present invention preferably contains the 3rd multipolymer (I-3), i.e. alpha-olefin/three olefinic random copolymers, and in the gross weight of composition, its content is at least 20%, preferably at least 25%.As the 3rd multipolymer (I-3), when promptly alpha-olefin/three olefinic random copolymers and content were in above-mentioned scope, combination rubber can reach better property of raw material.
The 3rd composition of the present invention can be used as the raw material of rubber articles, for example auto parts, automobile shock rubber, industrial rubber product, electronic body, product for building and rubber drop cloth.Particularly as the rubber raw materials of pressure moulding goods, for example seal gum, glass ooze groove, wipe device blade, sponge weather strip, annotate pressing mold and mould and the transfer molding goods, for example the rubber sponge sealed strip of inner mold foam sponge rubber item and car door.The object lesson of caulking gum comprises those and the identical example of above-mentioned second composition.
Ooze groove when the 3rd composition of the present invention is used for above-mentioned seal gum, glass, when wiping device blade, sponge weather strip and inner mold foaming product, they can be produced with high yield by high vulcanization rate, and aspect caoutchouc elasticity, weathering resistance, heat impedance, ozone resistants and low temperature flexibility excellence.For example, can promptly can high yield produce the rubber sponge weather strip by vulcanizing the fresh prod of extruding in a short period of time., carry out competent sulfuration here in very short time, the finished product of producing has excellent caoutchouc elasticity.
The 3rd composition of the present invention can the mode identical with the invention described above second composition carry out, and preparation is except mixing the 3rd multipolymer (I-3), promptly outside alpha-olefin/three olefinic random copolymers.
Use multiple foaming technique, normally used foam device, for example overflow mould molding machine, kneading cylinder, pressing machine, injection press or transfer molding machine not vulcanising composition make required sheet, and in film-making, fresh prod is heated, or, obtain the vulcanizate (vulcanized rubber products) of the present invention's the 3rd composition fresh prod being imported the sulfuration container or the original product of film-making being carried out electron beam irradiation with after vulcanizing.For foaming product, the not vulcanising composition that will contain whipping agent vulcanizes by method same as described above, and wherein foaming is carried out simultaneously with sulfuration, and therefore obtains foamed products.The operation here also can be with above-mentioned second composition identical.
The application that this method is shaped and sulfurized vulcanized rubber products and sulfur foam goods can be same with having of above-mentioned second composition.
At the finished product that is made by the present invention's the 3rd composition is sheet or film like, by other rubber or resin manufacture the layer can with by the present invention's the 3rd composition manufacturing the layer carry out lamination, make compound sheet or film.For example can adopt, conjugated diene rubber, ethylene/alpha-olefin copolymer class rubber, polyethylene, polypropylene or polybutene are as the material of other such layers.
The present invention's the 3rd multipolymer (I-3), promptly alpha-olefin/three olefinic random copolymers can be used with the form of resin combination by with itself and resin alloy, wherein for example polyolefin resin, for example polyethylene, polypropylene and polybutene of resin; And resin, for example AES and ABS.Here, the condition of the blend ratio of employing, other additives, for example softening agent etc. can be identical with the invention described above second composition.The linking agent that adopts and cross-linking method also can with the invention described above second composition in identical.
Based on above detailed description, the invention provides a kind of new and useful chain triene compound with and production technique.When with alpha-olefin copolymer, chain triene compound of the present invention can prepare the unsaturated copolymer of ethylene linkage, and it is aspect weathering resistance, heat impedance and ozone resistants, and the while is excellent quality aspect incipient scorch stability also, and can cure with two-forty.By technology of the present invention, simply method prepares above-mentioned chain triene compound with high yield.
According to the present invention, also can obtain novel and useful alpha-olefin/three olefinic random copolymers, it can cure with two-forty, and aspect incipient scorch stability excellent quality.By vulcanizing vulcanized rubber that alpha-olefin of the present invention/three olefinic random copolymers obtain not only in excellent quality aspect weathering resistance, heat impedance and the ozone resistants, its advantage also shows on the caoutchouc elasticity.
Composition of the present invention contains above-mentioned multipolymer and linking agent and/or filler, and can cure with two-forty, excellent quality aspect incipient scorch stability.Not only in excellent quality aspect weathering resistance, heat impedance and the ozone resistants, its advantage also shows on the caoutchouc elasticity by the vulcanized rubber that obtains of the sulfuration present composition.
The product that the present invention forms is to be made by above-mentioned composition, thus their excellent quality aspect incipient scorch stability, and can prepare by the two-forty sulfuration.Vulcanized article is excellent quality aspect weathering resistance, heat impedance and ozone resistants not only, and its advantage also shows on the caoutchouc elasticity.
Optimum implementation of the present invention
Hereinafter set forth the present invention in more detail, should notice that wherein the present invention should not be subjected to the restriction of these embodiment by embodiment.In an embodiment, calculate the transformation efficiency of initial triene compound, wherein C with following equation with conjugated diolefine structure
0Expression has the initial mole of feed amount of the triene compound of conjugated diolefine structure, and C represents its final molar weight of reaction back.
Transformation efficiency (%)={ (C
0-C)/C
0} * 100
With the productive rate of following equation calculating target compound, wherein P represents the molar weight of target product.
Productive rate (%)=(P/C
0) * 100
Embodiment 1-1
At capacity is in stainless steel (SUS 316) autoclave of 50ml, under nitrogen atmosphere, add 0.257g (1.47mmol) cobaltous thiocyanate (II), 0.893g (2.93mmol) tri-o-tolyl phosphine, 5ml toluene and 7.56g (55.5mmol) 2,6-dimethyl-1,3, the 6-sarohornene.Mixture at room temperature stirred 30 minutes.Subsequently, to the toluene solution that wherein adds 15.5ml (14.4mmol) triethyl aluminum (0.95 mol), close autoclave.Subsequently the ethene bottle directly is connected with autoclave, ethene is fed in the autoclave, in reaching, press to be 1MPa (10kgf/cm
2, gauge pressure), then autoclave is heated down at 80 ℃.While is the consumption of make-up ethylene off and on, makes the pressure of ethene remain on 0.9-1MPa (9-10kgf/cm
2, gauge pressure), be reflected at 80 ℃ and carried out 5 hours.
After the reaction, cool off and open autoclave, subsequently with in the reaction mixture impouring 50ml water, mixture is separated and is organic layer and water layer.Filter organic layer to remove solid, the promoting the circulation of qi analysis of hplc of going forward side by side.Find target product 4,8-dimethyl-1,4, the productive rate of 8-triolefin in the last of the ten Heavenly stems are 53% (2,6-dimethyl-1,3, the transformation efficiency of 6-sarohornene are 79%).
Contain 4,8-dimethyl-1,4, the organic layer of 8-triolefin in the last of the ten Heavenly stems under reduced pressure carry out rectifying in the distillation tower of 30 stage number.Obtain 3.3g target compound 4,8-dimethyl-1,4,8-triolefin in the last of the ten Heavenly stems.
Analyze resulting product 4,8-dimethyl-1,4,8-triolefin in the last of the ten Heavenly stems, its result is as follows:
(1) boiling point: 91 ℃/20mm Hg
(2) mass spectrum: m/z 164 (M
+Molecular ion peak), 149,135,123,108,95,79,67,55,41
(3)
1H-NMR composes (solvent: CDCl
3) absorption peak:
ppm(δ)
(1.55 3H, bimodal)
(1.65 6H, bimodal)
(2.05 4H, multimodal)
(2.75 2H, bimodal)
(4.95 2H, multimodal)
(5.2 2H, multimodal)
(5.7 1H, multimodal)
Obtain 4,8-dimethyl-1,4, the molecular structure of 8-triolefin in the last of the ten Heavenly stems as follows:
Embodiment 1-2
At capacity is in stainless steel (SUS 316) autoclave of 50ml, under nitrogen atmosphere, add 0.128g (0.44mmol) cobalt nitrate hexahydrate (II), 0.082g (0.84mmol) potassium thiocyanate, 10ml toluene and 3.0g (22mmol) 2,6-dimethyl-1,3, the 6-sarohornene.Mixture at room temperature stirred 30 minutes.Subsequently, to the toluene solution that wherein adds 2.2ml (2.1mmol) triethyl aluminum (0.95 mol), close autoclave.Subsequently the ethene bottle directly is connected with autoclave, ethene is fed in the autoclave, in reaching, press 2MPa (20kgf/cm
2, gauge pressure), then autoclave is heated down at 80 ℃.While is the consumption of make-up ethylene off and on, makes the pressure of ethene remain on 1.9-2MPa (19-20kgf/cm
2, gauge pressure), be reflected at 80 ℃ and carried out 5 hours.
After the reaction, adopt the method identical to carry out gas chromatographic analysis with embodiment 1-1.Find target product 4,8-dimethyl-1,4, the productive rate of 8-triolefin in the last of the ten Heavenly stems are 72% (2,6-dimethyl-1,3, the transformation efficiency of 6-sarohornene are 97%).
Embodiment 1-3
In the stainless steel autoclave (SUS 316) of capacity 50ml, under nitrogen atmosphere, add 0.123g (0.42mmol) acetylacetone cobalt (II) dihydrate, 0.082g (0.84mmol) potassium sulfocyanate, 10ml toluene and 3.0g (22mmol) 2,6-dimethyl-1,3, the 6-sarohornene, mixture was stirring at room 30 minutes.Add the toluene solution (0.95mol/l) of 2.2ml (2.1mmol) triethyl aluminum then, close autoclave.Subsequently the ethene bottle directly is connected with autoclave, ethene is fed in the autoclave, in reaching, press 1MPa (10kgf/cm
2, gauge pressure), so with autoclave 100 ℃ of heating.While is the consumption of make-up ethylene off and on, and the pressure that keeps ethene is at 0.9-1MPa (9-10kgf/cm
2, gauge pressure) in the scope, be reflected at 100 ℃ and carried out 5 hours.
After the reaction, adopt the methods analyst reaction product identical with embodiment 1-1 with gas-chromatography.Find target product 4,8-dimethyl-1,4, the yield of 8-triolefin in the last of the ten Heavenly stems are 66% (2,6-dimethyl-1,3, the transformation efficiency of 6-sarohornene are 79%).
Embodiment 1-4
In the stainless steel autoclave (SUS 316) of capacity 50ml, under nitrogen atmosphere, add 0.109g (0.42mmol) acetylacetone cobalt (II), 0.059g (0.81mmol) methylthiocyanide methylthiocyanate, 10ml toluene and 3.0g (22mmol) 2,6-dimethyl-1,3, the 6-sarohornene, mixture was stirring at room 30 minutes.Add the toluene solution (0.95mol/l) of 4.5ml (4.2mmol) triethyl aluminum then, close autoclave.Subsequently the ethene bottle directly is connected with autoclave, ethene is fed in the autoclave, in reaching, press 1MPa (10kgf/cm
2, gauge pressure), so with autoclave 100 ℃ of heating.While is the consumption of make-up ethylene off and on, and the pressure that keeps ethene is at 0.9-1MPa (9-10 kgf/cm
2, gauge pressure) in the scope, be reflected at 100 ℃ and carried out 1 hour.
After the reaction, adopt the methods analyst reaction product identical with embodiment 1-1 with gas-chromatography.Find target product 4,8-dimethyl-1,4, the yield of 8-triolefin in the last of the ten Heavenly stems are 61% (2,6-dimethyl-1,3, the transformation efficiency of 6-sarohornene are 97%).
Embodiment 1-5
In the stainless steel autoclave (SUS 316) of capacity 50ml, under nitrogen atmosphere, add 0.0041g (0.016mmol) cobaltous acetate (II) tetrahydrate, 0.322g (7.84mmol) acetonitrile, 10ml toluene and 3.0g (22mmol) 2,6-dimethyl-1,3, the 6-sarohornene, mixture was stirring at room 30 minutes.Add the toluene solution (0.95mol/l) of 1.38ml (1.31mmol) triethyl aluminum then, close autoclave.Subsequently the ethene bottle directly is connected with autoclave, ethene is fed in the autoclave, in reaching, press 2MPa (20kgf/cm
2, gauge pressure), so with autoclave 110 ℃ of heating.While is the consumption of make-up ethylene off and on, and the pressure that keeps ethene is at 1.9-2MPa (19-20kgf/cm
2, gauge pressure) in the scope, be reflected at 110 ℃ and carried out 6 hours.
After the reaction, adopt the methods analyst reaction product identical with embodiment 1-1 with gas-chromatography.Find target product 4,8-dimethyl-1,4, the yield of 8-triolefin in the last of the ten Heavenly stems are 68% (2,6-dimethyl-1,3, the transformation efficiency of 6-sarohornene are 99%).
Embodiment 1-6
In the stainless steel autoclave (SUS 316) of capacity 50ml, under nitrogen atmosphere, add 0.0124g (0.052mmol) cobalt chloride (II) hexahydrate, 0.064g (1.56mmol) acetonitrile, 10ml toluene and 3.0g (22mmol) 2,6-dimethyl-1,3, the 6-sarohornene, mixture was stirring at room 30 minutes.Add the toluene solution (0.95mol/l) of 1.69ml (1.61mmol) triethyl aluminum then, close autoclave.Subsequently the ethene bottle directly is connected with autoclave, ethene is fed in the autoclave, in reaching, press 2MPa (20kgf/cm
2, gauge pressure), so with autoclave 100 ℃ of heating.While is the consumption of make-up ethylene off and on, and the pressure that keeps ethene is at 1.9-2MPa (19-20kgf/cm
2, gauge pressure) in the scope, be reflected at 100 ℃ and carried out 17 hours.
After the reaction, adopt the methods analyst reaction product identical with embodiment 1-1 with gas-chromatography.Find target product 4,8-dimethyl-1,4, the yield of 8-triolefin in the last of the ten Heavenly stems are 64% (2,6-dimethyl-1,3, the transformation efficiency of 6-sarohornene are 85%).
Embodiment 1-7
In the stainless steel autoclave (SUS 316) of capacity 50ml, under nitrogen atmosphere, add 0.109g (0.42mmol) acetylacetone cobalt (II), 0.218g (2.11mmol) benzonitrile, 10ml toluene and 3.0g (22mmol) 2,6-dimethyl-1,3, the 6-sarohornene, mixture was stirring at room 30 minutes.Add the toluene solution (0.95mol/l) of 4.5ml (4.2mmol) triethyl aluminum then, close autoclave.Subsequently the ethene bottle directly is connected with autoclave, ethene is fed in the autoclave, in reaching, press 1MPa (10kgf/cm
2, gauge pressure), so with autoclave 80 ℃ of heating.While is the consumption of make-up ethylene off and on, and the pressure that keeps ethene is at 0.9-1MPa (9-10kgf/cm
2, gauge pressure) in the scope, be reflected at 80 ℃ and carried out 1 hour.
After the reaction, adopt the methods analyst reaction product identical with embodiment 1-1 with gas-chromatography.Find target product 4,8-dimethyl-1,4, the yield of 8-triolefin in the last of the ten Heavenly stems are 34% (2,6-dimethyl-1,3, the transformation efficiency of 6-sarohornene are 71%).
Embodiment 1-8
Two methyl silylene-two { 1-(2-methyl-4-the phenyl indenyl) } zirconium dichlorides of aluminium trimethide oxidative ethane (aluminium trimethide oxidative ethane (methylaluminoxane)) and 0.0025mM R-are dissolved in to prepare in the toluene and are used for the polymeric catalyst solution---in the aluminium atom---with 0.75mM.
Subsequently, at 23 ℃, assembled agitating vane and inner capacity of fully having replaced with nitrogen be add in the autoclave that is equipped with of 2 liters SUS steel that 17ml embodiment 1-1 obtains 4,8-dimethyl-1,4,8-triolefin in the last of the ten Heavenly stems (DMDT) and 883ml heptane.Then, in this autoclave, rise propylene at the ice-cooled 16N that adds down, stir simultaneously, autoclave is heated to 50 ℃ at the most subsequently, feeds ethene and reaches 0.8MPa (8kgf/cm until stagnation pressure
2, gauge pressure).In autoclave, press and reach 0.8MPa (8kgf/cm
2, gauge pressure) time, the hexane solution 1.0ml of adding 1.0mM/ml triisobutyl aluminium (TIBA) is blown into compressed nitrogen simultaneously.Subsequently, the polymerizing catalyst 3ml adding autoclave with as above preparation is blown into the beginning polymerization simultaneously with compressed nitrogen.Polymerization was carried out 30 minutes, simultaneously the internal temperature of autoclave was adjusted to 50 ℃, and simultaneously directly to the autoclave make-up ethylene to keep internal pressure at 0.8MPa (8kgf/cm
2, gauge pressure).After polymerization reacted 30 minutes from beginning, with pump 5ml ethanol is joined and to stop polymerization in the autoclave, the pressure with autoclave drops to normal atmosphere then.Under agitation in autoclave, add 2 liters of methyl alcohol subsequently.The polymer product of generation that contains reaction solvent subsequently and be the spherical formula of rubber like under 80kPa (600 holder) in 130 ℃ of dryings 13 hours, thereby obtain ethylene/propene/DMDT multipolymer (hereinafter being expressed as copolymer A).Its characteristic is as shown in table 1-1.
The ethylene/propene mol ratio of this copolymer A is 69/31, is 2.2dl/g in 135 ℃ of limiting viscosities of measuring in naphthalane [η], 4, and 8-dimethyl-1,4, the content of 8-triolefin in the last of the ten Heavenly stems (DMDT) they are 1.5 moles of %.
Embodiment 1-9 and 1-10
Use the method identical with embodiment 1-8, except the alpha-olefin of change use as shown in table 1 and the consumption and the kind of polymerizing catalyst, obtain ethylene/propene/DMDT multipolymer (hereinafter being expressed as multipolymer B) and ethene/1-octene/DMDT multipolymer (hereinafter being expressed as multipolymer C).Its characteristic is as shown in table 1-1.
Comparative example 1-1 and 1-2
Use the method identical, except using EMND or ENB (all not in the triene compound scope of formula (1)) to replace DMDT and, preparing multipolymer D and multipolymer E as showing to change shown in the 1-2 consumption and the kind of polymerizing catalyst with embodiment 1-8.The characteristic of these multipolymers is as shown in table 1-2.
Table 1-1
| Embodiment 1-8 | Embodiment 1-9 | Embodiment 1-10 | |
| Copolymer A | Multipolymer B | Multipolymer C | |
| The promotor that the catalyzer that uses uses | *1 *2 | *1 *2 | *3 *4 |
| The mol ratio of alpha-olefin comonomer ethylene/alpha-olefin | Propylene 69/31 | 1-octene 57/43 | Propylene 69/31 |
| The triolefin comonomer *5 moles of % content | DMDT 1.5 | DMDT 2.8 | DMDT 1.6 |
| Limiting viscosity [η] (dl/g) | 2.2 | 1.8 | 3.4 |
Table 1-2
| Comparative example 1-1 | Comparative example 1-2 | |
| Multipolymer D | Multipolymer E | |
| The promotor that the catalyzer that uses uses | *1 *2 | *3 *4 |
| The mol ratio of alpha-olefin comonomer ethylene/alpha-olefin | Propylene 69/31 | Propylene 69/31 |
| The triolefin comonomer *5 moles of % content | EMND 1.5 | ENB 2.6 |
| Limiting viscosity [η] (dl/g) | 2.3 | 3.3 |
The note of table 1-1 and 1-2:
*The 1R-dimethylated methylene is silica-based-two { 1-(2-methyl-4-phenyl indenyl) } zirconium dichloride
*2 methylaluminoxane (methyl aluminoxane)
*3{ dimethyl (tert-butyl-carboxamide) (tetramethyl--η
5-cyclopentadienyl) silane } titanium dichloride
*4 triphenylcarbenium are (four pentafluorophenyl groups) borate just
*5DMDT=4,8-dimethyl-1,4,8-triolefin in the last of the ten Heavenly stems
EMND=4-ethylidene-8-methyl isophthalic acid, the 7-nonadiene
The ENB=5-ethylidene norbornene
Embodiment 1-11
With copolymer A, 2 grades of zinc oxide of 5 weight parts, the 1 weight part stearic acid of 100 weight part embodiment 1-8 gained, (SHEEST 3 for 80 weight part N330 carbon blacks, trade mark, the product of Tokai Carbon K.K), (SUNPAR 2280 for 50 weight part paraffin process oils, trade mark, the product of Nippon Sun Sekiyu K.K.), 0.5 weight part sulphur, 1.5 weight part MBT vulcanization accelerators and (F/B=50/50 ℃) kneading on 6 inches cylinders of 1.0 weight part TMTD vulcanization accelerators, obtain a kind of sheet rubber.
For resulting sheet rubber, at 160 ℃ of location parameter tc (90) and t10.The vulcanization rate of parametric t c (90) sign rubber, the incipient scorch stability of parametric t 10 expression rubber, they are measured with following method: continue instrument (Curelastmeter) (Japan Sythetic Rubber Co. with 3 sulfurations of JSR type, Ltd. provide) prepare a vulcanization curve figure at 160 ℃, pre-estimate the poor ME (ME=MH-ML) between maximum twist value MH and the minimum value of reversing ML, wherein reaching with minute used time representation of 90%ME of expression is tc (90).This time tc (90) is the parameter of expression vulcanization rate.The value of this parameter is more little, and the vulcanization rate of rubber is high more.Reaching with minute used time representation of 10%ME of expression is t10, and it is the parameter of expression incipient scorch stability.The value of this parameter is big more, and the incipient scorch stability of rubber is high more.
In addition, carry out the press vulcanization test with sheet rubber at 160 ℃.The time of setting press vulcanization is that tc (90) adds 5 minutes.The observations of the material property of rubber and vulcanized rubber sheet is shown in table 1-3.
Comparative example 1-3 and 1-4
Repeat the process of embodiment 1-11, except the multipolymer D of usefulness comparative example 1-1 or 1-2 acquisition respectively or the copolymer A among the multipolymer E replacement embodiment 1-11.The result is shown in table 1-3.
Table 1-3
| Embodiment 1-11 | Comparative example 1-3 | Comparative example 1-4 | |
| Multipolymer | Copolymer A | Multipolymer D | Multipolymer E |
| The performance of rubber | |||
| Tc (90) (minute) | 4.6 | 4.8 | 10.8 |
| T10 (minute) | 2.4 | 1.9 | 2.9 |
| The performance of vulcanized rubber | |||
| Tensile strength during fracture (MPa) *1 | 14.5 | 15.2 | 15.8 |
| Unit elongation during fracture (%) *2 | 480 | 450 | 470 |
| Hardness JIS A *3 | 66 | 67 | 67 |
Note:
*1 measures according to JIS K6301
*2 measure according to JISK6301
*3 measure according to JISK6301
From table 1-3 as can be known, the rubber of embodiment 1-11 has short tc (90), except tc (90) is shorter, and long t10 is arranged.This shows that vulcanization rate is higher and incipient scorch stability is preeminent.
Opposite with it, the rubber of comparative example 1-3 has long tc (90) and short t10, shows poor than embodiment 1-11 of vulcanization rate and incipient scorch stability.The rubber of comparative example 1-4 has very long tc (90), shows that the balance between vulcanization rate and the incipient scorch stability is relatively poor.
Though the difference of t10 is 0.5 minute between the rubber of embodiment 1-11 shown in the table 1-3 and comparative example 1-3, corresponding real time difference is very large.That is,, therefore, in the actual sulfuration that the difference of the t10 of 160 ℃ of mensuration value is carried out, should show as the longer time about 100 ℃ for handling the determined actual extrusion temperature of rubber usually about 100 ℃.Like this, can prevent from for example adding man-hour because the trouble that the viscosity increase causes on the extrusion machine, such as making squeezing prod minimizing, motor load increase and cylinder obstruction or obstruction and/or viscosity increase cause stopping working, so the stability in Rubber processing has improved because sulfuration takes place in the extrusion machine.
Embodiment 1-1-1
" 4,8-dimethyl-1,4,8-triolefin in the last of the ten Heavenly stems (DMDT) synthetic "
In the stainless steel autoclave of capacity 1500ml, under nitrogen atmosphere, add 257g (1.89mol) 2,6-dimethyl-1,3,6-sarohornene, 500ml toluene, 6.18g (35.2mmol) cobaltous thiocyanate, 21.4g (70.4mmol) three p-methylphenyl phosphines and 200ml concentration are the toluene solution (triethyl aluminum 200mmol) of the triethyl aluminum of 1mol/l, close autoclave.Subsequently the ethene bottle directly is connected with autoclave, ethene is fed in the autoclave, in reaching, press 1MPa (10kgf/cm
2, gauge pressure), so autoclave was carried out polymerization 5 hours 120 ℃ of heating, the while is the consumption of make-up ethylene off and on.
After the reaction, cool off and open autoclave, subsequently with in the reaction mixture impouring 500ml water, mixture is separated and is organic layer and water layer.Isolating organic layer under reduced pressure carries out rectifying in the distillation tower of 80 column plates, thus the target compound 4 shown in the formula of obtaining (28), 8-dimethyl-1,4,8-triolefin in last of the ten Heavenly stems 108g (yield=36%).
Analyze resulting product 4,8-dimethyl-1,4,8-triolefin in the last of the ten Heavenly stems, the result is as follows:
(1) boiling point: 91 ℃/20mm Hg
(2) mass spectrum: m/z164 (M
+Molecular ion peak), 149,135,123,108,95,79,67,55,41
(3)
1H-NMR composes (solvent: CDCl
3) absorption peak:
ppm(δ)
(1.55 3H, bimodal)
(1.65 6H, bimodal)
(2.05 4H, multimodal)
(2.75 2H, bimodal)
(4.95 2H, multimodal)
(5.2 2H, multimodal)
(5.7 1H, multimodal)
Embodiment 2-1
Two methyl silylene-two { 1-(2-methyl-4-the phenyl indenyl) } zirconium dichlorides of methylaluminoxane (methyl aluminoxane) and 0.0025mM R-are dissolved in to prepare in the toluene and are used for the polymeric catalyst solution---in the aluminium atom---with 0.75 mM.
Subsequently, at 23 ℃, be to add embodiment 1-1-1 synthetic 4,8-dimethyl-1,4,8-triolefin in the last of the ten Heavenly stems (DMDT) 17ml and 883ml heptane in the autoclave that is equipped with of 21 SUS steel having assembled agitating vane and inner capacity of fully having replaced with nitrogen.Then, in this autoclave, rise propylene at the ice-cooled 16N that adds down, stir simultaneously, autoclave is heated to 50 ℃ at the most subsequently, feeds ethene until reaching 0.8MPa (8kgf/cm
2, gauge pressure) stagnation pressure.When pressure in the autoclave reaches 0.8MPa, add the hexane solution 1.0ml of 1.0mM/ml triisobutyl aluminium (TIBA), be blown into compressed nitrogen simultaneously.Subsequently, the polymerizing catalyst 3ml with as above preparation is blown into autoclave with the while compressed nitrogen, the beginning polymerization.Polymerization was carried out 30 minutes, simultaneously the internal temperature of autoclave was adjusted to 50 ℃, simultaneously directly to the autoclave make-up ethylene to keep internal pressure at 0.8MPa (8kgf/cm
2, gauge pressure).After polymerization reacted 30 minutes from beginning, use 5ml ethanol joined to stop polymerization in the autoclave, the pressure with autoclave drops to normal atmosphere then.Under agitation in autoclave, add 2 liters of methyl alcohol subsequently.Contain reaction solvent and be the spherical formula of rubber like generation polymer product in 130 ℃ dry 13 hours of 80kPa (600 holder), thereby obtain ethylene/propene/DMDT multipolymer (hereinafter being expressed as multipolymer 2A).Its characteristic is as shown in table 2-1.
The ethylene/propene mol ratio of this multipolymer 2A is 69/31, is 2.2dl/g in 135 ℃ of limiting viscosities of measuring in naphthalane [η], 4, and 8-dimethyl-1,4, the content of 8-triolefin in the last of the ten Heavenly stems (DMDT) they are 1.5 moles of %.By using
1H-NMR and
13C-NMR detects this copolymer A, determines that its molecular structure is that formula (1-a) is represented.
Embodiment 2-2 and 2-3
Use the method identical with embodiment 2-1, except shown in table 2-1, changing the alpha-olefin of use and the consumption and the kind of polymerizing catalyst, obtain ethylene/propene/DMDT multipolymer (hereinafter being expressed as multipolymer 2B) and ethene/1-octene/DMDT multipolymer (hereinafter being expressed as multipolymer 2C).Its characteristic is as shown in table 2-1.
Comparative example 2-1 and 2-2
Use the method identical, except using EMND or ENB (not in the triene compound scope of formula (1)) to replace DMDT and, preparing multipolymer 2D and multipolymer 2E as showing to change shown in the 2-2 consumption and the kind of polymerizing catalyst with embodiment 2-1.The characteristic of these multipolymers is as shown in table 2-2.
Table 2-1
| Embodiment 2-1 | Embodiment 2-2 | Embodiment 2-3 | |
| Multipolymer 2A | Multipolymer 2B | Multipolymer 2C | |
| The promotor that the catalyzer that uses uses | *1 *2 | *1 *2 | *3 *4 |
| The mol ratio of alpha-olefin comonomer ethylene/alpha-olefin | Propylene 69/31 | 1-octene 57/43 | Propylene 69/31 |
| The triolefin comonomer *5 moles of % content | DMDT 1.5 | DMDT 2.8 | DMDT 1.6 |
| Limiting viscosity [η] (dl/g) | 2.2 | 1.8 | 3.4 |
Table 2-2
| Comparative example 2-1 | Comparative example 2-2 | |
| Multipolymer 2D | Multipolymer 2E | |
| The promotor that the catalyzer that uses uses | *1 *2 | *3 *4 |
| The mol ratio of alpha-olefin comonomer ethylene/alpha-olefin | Propylene 69/31 | Propylene 69/31 |
| The triolefin comonomer *5 moles of % content | EMND 1.5 | ENB 2.6 |
| Limiting viscosity [η] (dl/g) | 2.3 | 3.3 |
The note of table 2-1 and 2-2:
*The 1R-dimethylated methylene is silica-based-two { 1-(2-methyl-4-phenyl indenyl) } zirconium dichloride
*2 methylaluminoxane (methyl aluminoxane)
*3{ dimethyl (tert-butyl-carboxamide) (tetramethyl--η
5-cyclopentadienyl) silane } titanium dichloride
*4 triphenylcarbenium are (four pentafluorophenyl groups) borate just
*5DMDT=4,8-dimethyl-1,4,8-triolefin in the last of the ten Heavenly stems
EMND=4-ethylidene-8-methyl isophthalic acid, the 7-nonadiene
The ENB=5-ethylidene norbornene
Embodiment 2-4
With multipolymer 2A, 2 grades of zinc oxide of 5 weight parts, the 1 weight part stearic acid of 100 weight part embodiment 2-1 gained, (SHEEST 3 for 80 weight part N330 carbon blacks, trade mark, the product of Tokai Carbon K.K.), (SUNPAR 2280 for 50 weight part paraffin process oils, trade mark, the product of Nippon Sun Sekiyu K.K.), 0.5 weight part sulphur, 1.5 weight part MBT vulcanization accelerators and (F/B=50/50 ℃) kneading on 6 inches cylinders of 1.0 weight part TMTD vulcanization accelerators, obtain a kind of sheet rubber.
For resulting sheet rubber,, carry out the press vulcanization test at 160 ℃ with following method location parameter tc (90) and t10.The time of setting press vulcanization is that tc (90) adds 5 minutes.For sulfurized and rubber sheet rubber, carry out sheet rubber material performance test.The result is shown in table 2-3.
" test of rubber material property (determining vulcanization rate and incipient scorch stability) "
Continue instrument (Curelastmeter) (Japan Sythetic Rubber Co., Ltd. provides) with 3 sulfurations of JSR type and measure vulcanization rate.So prepare a vulcanization curve figure at 160 ℃, pre-estimate the poor ME (ME=MH-ML) between maximum twist value MH and the minimum value of reversing ML, wherein reaching with minute used time representation of 90%ME of expression is tc (90).As measuring of vulcanization rate.The value of tc (90) is more little, and the vulcanization rate of rubber is high more.On the other hand, reaching with minute used time representation of 10%ME of expression is t10, as the parameter of incipient scorch stability.The value of t10 is big more, and the incipient scorch stability of rubber is high more.
" performance of vulcanized rubber "
Tensile strength (T when measuring the fracture of vulcanized rubber sheet according to JIS K6301
B), the unit elongation (E in when fracture
B) and hardness.
Comparative example 2-3 and 2-4
Repeat the technology of embodiment 2-4, except the multipolymer 2D of usefulness comparative example 2-1 or 2-2 acquisition respectively or the multipolymer 2A among the multipolymer 2E replacement embodiment 2-4.The result is shown in table 2-3.
Table 2-3
| Embodiment 2-4 | Comparative example 2-3 | Comparative example 2-4 | |
| Multipolymer | Multipolymer 2A | Multipolymer 2D | Multipolymer 2E |
| The performance of rubber | |||
| Tc (90) (minute) | 4.6 | 4.8 | 10.8 |
| T10 (minute) | 2.4 | 1.9 | 2.9 |
| The performance of vulcanized rubber | |||
| Tensile strength during fracture (MPa) | 14.5 | 15.2 | 15.8 |
| Unit elongation during fracture (%) | 480 | 450 | 470 |
| Hardness JIS A | 66 | 67 | 67 |
From table 2-3 as can be known, the rubber of embodiment 2-4 has short tc (90), except tc (90) is shorter, and long t10 is arranged.This shows that vulcanization rate is higher and incipient scorch stability is preeminent.
Opposite with it, the rubber of comparative example 2-3 has long tc (90) and short t10, shows poor than embodiment 2-4 of vulcanization rate and incipient scorch stability.The rubber of comparative example 2-4 has very long tc (90), shows that the balance between vulcanization rate and the incipient scorch stability is relatively poor.
Though the difference of t10 is 0.5 minute between the rubber of embodiment 2-4 shown in the table 2-3 and comparative example 2-3, corresponding real time difference is very large.That is,, therefore, in the actual sulfuration that the difference of the t10 of 160 ℃ of mensuration value is carried out, should show as the longer time about 100 ℃ for handling the determined actual extrusion temperature of rubber usually about 100 ℃.Like this, can prevent from for example adding man-hour because the trouble that the viscosity increase causes on the extrusion machine, such as making squeezing prod minimizing, motor load increase and cylinder obstruction or obstruction and/or viscosity increase cause stopping working, so the stability in Rubber processing has improved because sulfuration takes place in the extrusion machine.
Embodiment 2-5
With the method identical,, obtain showing the multipolymer 2F shown in the 2-4 except changing the amount and the kind of comonomer used under the reaction conditions with embodiment 2-1.
With 100 weight parts as above multipolymer 2F, 2 grades of zinc oxide of 5 weight parts, the 90 weight part SRF carbon black (ASAHI#50 of gained, trade mark, the product of ASAHI Carbon K.K.), 60 weight part paraffin process oils and 1 weight part polyoxyethylene glycol are kneading 6 minutes in 1.7 liters the Bumbury stirrer (Kobe Steel, Ltd. provides) at volume.In the material of the kneading that obtains, add 1.5 weight part sulphur (vulcanizing agent), 0.8 weight part 2-mercaptobenzothiazole (vulcanization accelerator), 12 weight part 2-(4 '-morpholine, two sulphur) benzothiazole (vulcanization accelerator), 2.0 weight part di-n-butyl two thiocarbamate zinc (vulcanization accelerator), 1.0 weight part 2-mercaptoimidazoline (vulcanization accelerator), 3.5 weight part p, p '-oxygen is two-(benzol sulfohydrazide) (whipping agent) and 5.0 weight part defoamers, mixture (F/B=40/40 ℃) on 8 inches cylinders integrates 15 minutes, prepares a kind of rubber combination (blended rubber) that is used for the sponge rubber extrudate.The extrusion machine that tubular mold (10mm internal diameter, 1mm wall thickness) is housed with 50mm is clamp-oned this rubber combination in the pipe under the condition of 60 ℃ of mould temperature 80 ℃, tin temperature.The moulded product that obtains vulcanized 6 minutes in 220 ℃ hot-air heated sulfuration container, obtained sulfurized sponge rubber tubular body.Measure their performance with following method for unvulcanized initial blended rubber before resulting sulfurized sponge rubber tubular body and the sulfuration.The result is shown in table 2-5.
" test of rubber material property (determining vulcanization rate and incipient scorch stability) "
Carry out test according to JIS K 6300 methods, continue instrument (Curelastmeter) (Japan Sythetic Rubber Co., Ltd. provides) with 3 sulfurations of JSR type and measure vulcanization rate the material property of rubber.Like this, prepare a vulcanization curve figure at 180 ℃, pre-estimate the poor ME (ME=MH-ML) between maximum twist value MH and the minimum value of reversing ML, wherein usefulness reaches with measure (hereinafter be expressed as tc (90)) of used time of the 90%ME that minute represents as vulcanization rate.The value of tc (90) is more little, and the vulcanization rate of rubber is high more.In addition, with reaching with measure (hereinafter being expressed as t10) of used time of the 10%ME that minute represents as incipient scorch stability.The value of t10 is big more, and the incipient scorch stability of rubber is high more.
" vulcanization characteristics "
Tensile strength (T when measuring the fracture of vulcanized rubber sheet according to JIS K6301
B), the unit elongation (E in when fracture
B) and hardness (Hs).
" permanent compression tension test "
Downcut the long ring test sample of 30mm from sulfurized tubulose sponge rubber (extrusion molding sponge rubber goods), be placed in the sponge rubber permanent compression tension test container, to lower compression up to 50% of height of specimen, promptly, the diameter of sponge tube, subsequently sample and test chamber are together transferred in the gear stove, sample is carried out thermal treatment in 100 hours at the state of pressurization at 70 ℃, (SRIS-0101) measure its permanent compression tension force (CS) according to " physical test method of swollen rubber " then.
" surfaceness "
Use pin to touch surface roughness instruments, the projection of the upper surface by the sponge rubber that will observe and the data conversion of depression become numerical value to determine the surface irregularity of sponge rubber.In the practice, sulfurized tubulose sponge rubber is cut into the ring-type sample of 50mm length respectively, therefrom take out some and detect surface irregularity, wherein have scope and be expressed as h1 from the summation of the rat value of 10 samples of the tenth-largest top rat that is up to the back, the summation of surface depression value with 10 samples of the ten low minimum level surface depression of scope from minimum to the back is expressed as h2, its poor (h1-h2) is by 10 merchants except that gained, promptly, (h1-h2)/10, be set at the surfaceness of sponge rubber.
Embodiment 2-6 and 2-8
With the method identical, except changing monomer, its consumption and the reaction conditions that uses, obtain showing multipolymer 2G shown in the 2-4 and multipolymer 2I with embodiment 2-1.
Then, repeat the process of embodiment 2-5, except replacing multipolymer 2F with multipolymer 2G-2I, preparation sponge rubber goods.The result is shown in table 2-5.
Comparative example 2-5 to 2-8
Repeat the process of embodiment 2-5, except the multipolymer 2J-2M with table 2-4 replaces multipolymer 2F, preparation sponge rubber goods.The result is shown in table 2-6.
Table 2-4
| Multipolymer | Alkene *1) | The ethylene/olefin mol ratio | Polyenoid *2)Mole % | Iodine number | Limiting viscosity (dl/g) |
| 2F | Propylene | 70/30 | DMD/1.5 | 23 | 2.2 |
| 2G | Propylene | 71/29 | DMD/1.4 | 22 | 2.3 |
| 2H | 1-butylene | 75/25 | DMD/1.6 | 25 | 2.8 |
| 2I | The 1-octene | 74/26 | DMD/1.4 | 22 | 3.0 |
| 2J | Propylene | 70/30 | EMN/1.4 | 22 | 2.2 |
| 2K | Propylene | 68/32 | EMN/0.8 | 12 | 2.2 |
| 2L | Propylene | 71/29 | ENB/3.1 | 23 | 2.1 |
| 2M | Propylene | 70/30 | ENB/1.5 | 12 | 2.2 |
Note:
*1) Prop.=polypropylene
*2) DMD=4,8-dimethyl-1,4,8-triolefin in the last of the ten Heavenly stems
EMN=4-ethylidene-8-methyl isophthalic acid, the 7-nonadiene
EN=5-ethylidene-2-norbornylene
Table 2-5
| Embodiment | ||||
| 2-5 | 2-6 | 2-7 | 2-8 | |
| Multipolymer | 2F | 2G | 2H | 2I |
| The performance of rubber | ||||
| Tc (90) (minute) | 64 | 6.5 | 6.8 | 7.0 |
| T10 (minute) | 2.7 | 2.8 | 2.9 | 3.1 |
| The performance of vulcanized rubber | ||||
| Proportion | 0.51 | 0.50 | 0.56 | 0.49 |
| Surfaceness (μ m) | 8 | 7 | 8 | 7 |
| T B(MPa) | 2.6 | 2.7 | 2.4 | 2.6 |
| E B(％) | 260 | 270 | 280 | 320 |
| CS(％) *1) | 18 | 19 | 16 | 17 |
Note:
*1): 70 ℃ keep 100 hours after permanent compression tension force
Table 2-6
| The comparative example | ||||
| 2-5 | 2-6 | 2-7 | 2-8 | |
| Multipolymer | 2J | 2K | 2L | 2M |
| The performance of rubber | ||||
| Tc (90) (minute) | 6.5 | 9.5 | 12 | 17 |
| T10 (minute) | 1.9 | 2.6 | 2.8 | 3.7 |
| The performance of vulcanized rubber | ||||
| Proportion | 0.55 | 0.48 | 0.45 | 0.47 |
| Surfaceness (μ m) | 7 | 8 | 9 | 11 |
| T B(MPa) | 2.7 | 2.3 | 2.0 | 2.1 |
| E B(％) | 280 | 340 | 290 | 300 |
| CS(％) *1) | 18 | 19 | 25 | 29 |
Note:
*1): 70 ℃ keep 100 hours after permanent compression tension force
Embodiment 2-9
With the method identical,, obtain showing the multipolymer 2N shown in the 2-7 except changing used monomer, its consumption and reaction conditions with embodiment 2-1.
With 100 weight parts as above multipolymer 2N, 2 grades of zinc oxide of 5 weight parts, 2 weight part stearic acid, the 60 weight part SRF carbon black (ASAHI#50 of gained, trade mark, the product of ASAHI Carbon K.K.), 30 weight part FEF carbon black (ASAHI#60, trade mark, the product of ASAHI Carbon K.K.), 60 weight part paraffin process oils and 2 weight part calcium oxide are kneading 5 minutes in 1.7 liters the Bumbury stirrer (KobeSteel, Ltd. provides) at volume.In the material of the kneading that obtains, add 1.5 weight part sulphur (vulcanizing agent), 2.5 weight part 2-(4 '-morpholine, two sulphur) benzothiazole (vulcanization accelerator), 1.0 weight part di-n-butyl two thiocarbamate zinc (vulcanization accelerator), 0.5 weight part ethylene thiourea (vulcanization accelerator), 7.0 weight part diazonium carboxamide (whipping agent) and 2.0 weight part urea base defoamers, mixture (F/B=40/40 ℃) on 8 inches cylinders integrates 15 minutes, prepares a kind of rubber combination (blended rubber) that is used for (in mold foaming-molded) goods of sponge rubber internal mold foaming.Use a kind of injection moulding vulcanizing agent,, this rubber combination is made the tubulose sulfuration sponge rubber of internal diameter 11mm, external diameter 15mm, length 25cm 180 ℃ molding temperature sulfurations 4 minutes.The result is shown in table 2-8.
" test of rubber material property (determining vulcanization rate and incipient scorch stability) "
Test and given identical of embodiment 2-5.
" water-absorbent "
The test sample of 20mm * 20mm and weighing under the top punching press of tubulose sponge rubber (sponge rubber of internal mold foaming).Then, in the water layer in this sample immersion moisture eliminator, the moisture eliminator jar has the gas suction outlet, and the height of stored water has 100mm at least from the moisture eliminator bottom.Then, the gas in the extraction moisture eliminator is until the 635mm Hg that reduces pressure, and the moisture eliminator jar kept 3 minutes in this reduced pressure, and emptying subsequently kept 3 minutes with this understanding to normal atmosphere again.From moisture eliminator, take out sample, wipe the water of surface attachment,, calculate water-intake rate with following arithmetic equation once more to samples weighing:
Water-intake rate (weight %)=(W2-W1)/W1} * 100
In this equation, W1 represents to immerse water example weight before, represents that with gram W2 is illustrated in the weight of soaking the back sample in the water, represents with gram.
" permanent compression tension test "
According to JIS K6301 method tubulose sulfurized sponge rubber (sponge rubber of internal mold foaming) is carried out the permanent compression tension test.Thereby be determined at the permanent compression tension force (CS) after 70 ℃ * 100 hours.
Embodiment 2-10
With the method identical, except changing monomer, its consumption and the reaction conditions that uses, obtain showing the multipolymer 2O shown in the 2-7 with embodiment 2-1.
Then, repeat the process of embodiment 2-9,, be used to prepare the sponge rubber goods except replacing multipolymer 2N with multipolymer 2O.The result is shown in table 2-8.
Comparative example 2-9 and 2-10
Repeat the process of embodiment 2-9,, be used to prepare the sponge rubber goods except multipolymer 2P and 2Q with table 2-7 replace multipolymer 2N.The result is shown in table 2-7.
Table 2-7
| Multipolymer | Alkene *1) | The ethylene/olefin mol ratio | Polyenoid *2)Mole % | Iodine number | Limiting viscosity (dl/g) |
| 2N | Propylene | 72/28 | DMD/1.2 | 19 | 1.0 |
| 2O | The 1-octene | 76/24 | DMD/1.3 | 21 | 1.1 |
| 2P | Propylene | 70/30 | EMN/1.1 | 17 | 1.0 |
| 2Q | Propylene | 72/28 | ENB/2.9 | 22 | 1.0 |
Note:
*1) Prop.=polypropylene
*2) DMD=4,8-dimethyl-1,4,8-triolefin in the last of the ten Heavenly stems
EMN=4-ethylidene-8-methyl isophthalic acid, the 7-nonadiene
ENB=5-ethylidene-2-norbornylene
Table 2-8
| Embodiment | The comparative example | |||
| 2-9 | 2-10 | 2-9 | 2-10 | |
| Multipolymer | 2N | 2O | 2P | 2Q |
| The performance of rubber | ||||
| Tc (90) (minute) | 1.9 | 2.0 | 1.9 | 2.7 |
| T10 (minute) | 1.1 | 1.0 | 0.6 | 1.1 |
| The performance of vulcanized rubber | ||||
| Proportion | 0.59 | 0.55 | 0.64 | 0.60 |
| Water-intake rate (weight %) | 10 | 8 | 12 | 22 |
| CS(％) *1) | 21 | 20 | 23 | 37 |
Note:
*1): 70 ℃ keep 100 hours after permanent compression tension force
Embodiment 3-1
" preparation catalyzer "
Fully replace the internal space of glass flask with nitrogen, add then 4.8mg R-dimethylated methylene silica-based-two { 1-(2-methyl-4-phenyl indenyl) } zirconium dichloride, and (be evaporated to dry and again the exsiccant solid be dissolved in the toluene by conventional products and prepare the methylaluminoxane (methylaluminoxane) of Witco company to the toluene solution that wherein adds 2.8ml methylaluminoxane (methyl aluminoxane) again; Al concentration=1.1 mol) and 4.8ml toluene, thus prepare catalyst solution.
" polymerization "
Add the DMDT that 900ml hexane, 1mmol triisobutyl aluminium, 70gl-butylene and 15ml embodiment 1-1-1 obtain in the stainless steel autoclave of the capacity 21 of fully having replaced with nitrogen in inside, the temperature of polymerization system rises to 70 ℃.The polymerization catalyzed agent solution 2ml (0.002mmol Zr) of as above preparation is pressed into autoclave, started copolymer with the compression propylene.Be aggregated in 70 ℃ and carried out 30 minutes, only stagnation pressure is remained on 1.4MPa (14kgf/cm by infeed propylene to it
2, gauge pressure).Stop polymerization by in polymerization system, adding small amount of ethanol, remove unreacted comonomer then.With precipitation polymers in the big excessive methyl alcohol of polymers soln impouring that generates.By this polymkeric substance of filtering separation.In the polymkeric substance of gained, add stablizer, that is, 25mg IRGANOX 1010 (trade mark, the product of Ciba-Geigy company) and 25mg MARK329K (trade mark, the product of Asahi Denka Kogyo K.K.), blend under reduced pressure 80 ℃ of dried overnight.
In this way, obtain 23.6g propylene/1-butene/DMDT random copolymers (multipolymer 3A), limiting viscosity [η] is 2.3dl/g, the content of propylene structural unit is 87.6 moles of %, the content of 1-butylene structural unit is 10.9 moles of %, the content of DMDT structural unit is 1.5 moles of %, and iodine number is 17.
Embodiment 3-2
" preparation solid titanium catalyst component "
Reacted 2 hours 130 ℃ of mixture heating up 95.2g Magnesium Chloride Anhydrous, 442ml decane and 390.6g2-ethylhexyl alcohol, thereby obtain homogeneous solution, to wherein adding the 21.3g Tetra hydro Phthalic anhydride, under agitation made its dissolving in 1 hour at 130 ℃ of heated mixt.With the homogeneous phase solution cool to room temperature of gained, then this solution of 75ml was added drop-wise to during 1 hour in the 200ml titanium tetrachloride that remains on-20 ℃.After dropwising, during 4 hours, the mixture that generates is warmed up to 110 ℃.After reaching 110 ℃, add the 5.22g diisobutyl phthalate therein, mixture under agitation remained on this temperature 2 hours then.After the reaction, with the filter of reaction mixture heat, separate and the collection solid product, severe slurry in the 275ml titanium tetrachloride was reacting 110 ℃ of heating in 2 hours then.After the reaction, solid product is collected in the reusable heat filter, with the solid product of 110 ℃ decane and the generation of hexane thorough washing, up to not detecting the free titanium compound.The solid titanium catalyst component of above-mentioned gained stores with the form of decane slurry.Dry a part of this solid titanium catalyst component is used for the chemical ingredients inspection.The composition of finding this solid titanium catalyst component is the titanium of 2.5 weight %, the chlorine of 65 weight %, magnesium and the 13.5 weight % diisobutyl phthalates of 19 weight %.
" polymerization "
Add the DMDT that 560ml decane, 400ml 1-octene and 40ml embodiment 1-1-1 obtain in the stainless steel autoclave of the capacity 2L that has fully replaced with nitrogen in inside, the temperature of polymerization system rises to 50 ℃ then.In autoclave, feed hydrogen and nitrogen with the speed of 3 liters/hour and 50 liters/hour respectively subsequently.Add 3mmol triisobutyl aluminium, 1mmol trimethylethoxysilane and 0.06mmol then---in titanium atom---catalyzer of above-mentioned preparation, started copolymer.Polymerization was carried out 30 minutes, and the temperature that keeps polymerization system simultaneously stops polymerization at 50 ℃ by add small amount of ethanol in polymerization system, removes unreacted comonomer then.With precipitation polymers in the big excessive methyl alcohol of polymers soln impouring that generates.Collect this polymkeric substance by filtering.In the polymkeric substance of gained, add stablizer, that is, 50mg IRGANOX 1010 (trade mark, the product of Ciba-Geigy company) and 50mg MARK 329K (trade mark, the product of Asahi Denka KogyoK.K.), blend under reduced pressure 120 ℃ of dried overnight.
In this way, obtain 41.6gl-octene/DMDT random copolymers (multipolymer 3B), limiting viscosity [η] is 5.0dl/g, and the content of 1-octene structural unit is 95.7 moles of %, and the content of DMDT structural unit is 4.3 moles of %, and iodine number is 21.
Embodiment 3-3
" polymerization "
Add 900ml hexane, 20ml DMDT and 1ml triisobutyl aluminium in the stainless steel autoclave that the capacity of fully having replaced with nitrogen in inside is 2 liters, the temperature of polymerization system rises to 60 ℃.Infeeding propylene subsequently makes autoclave be up to the interior 0.25MPa of pressure (2.5kgf/cm
2, gauge pressure), the polymerization catalyzed agent solution 1.5ml (0.0015mmol Zr) of embodiment 3-1 preparation is pressed into autoclave by the propylene that is blown into pressurization, started copolymer.Be aggregated in 60 ℃ and carried out 15 minutes, stagnation pressure is remained on 0.8MPa (8kgf/cm by only infeeding propylene continuously to it
2, gauge pressure).Thereafter identical among process and the embodiment 3-1.
In this way, obtain 28.0g propylene/ethylene/DMDT random copolymers (multipolymer 3C), limiting viscosity [η] is 2.0dl/g, the content of propylene structural unit is 90.1 moles of %, the content of ethene structural unit is 8.0 moles of %, and the content of DMDT structural unit is 1.9 moles of %, and iodine number is 22.
Embodiment 3-4
" preparation solid titanium catalyst component "
Reacted 2 hours 130 ℃ of mixture heating up 95.2g Magnesium Chloride Anhydrous, 442ml decane and 390.6g 2-ethylhexyl alcohol, thereby obtain homogeneous solution, to wherein adding the 21.3g Tetra hydro Phthalic anhydride, under agitation made its dissolving in 1 hour at 130 ℃ of heated mixt.With the homogeneous phase solution cool to room temperature of gained, then this solution of 75ml was added drop-wise to during 1 hour in the 200ml titanium tetrachloride that remains on-20 ℃.After dropwising, during 4 hours, the mixture that generates is warmed up to 110 ℃.After reaching 110 ℃, add the 5.22g diisobutyl phthalate therein, mixture under agitation remained on this temperature 2 hours then.After the reaction, with reaction mixture heat filter, separate and also collect solid product, severe slurry in the 275ml titanium tetrachloride then heats once more at 110 ℃ and to react in 2 hours.After the reaction, solid product is collected in the reusable heat filter, with the solid product of 1 10 ℃ decane and the generation of hexane thorough washing, up to not detecting the free titanium compound.The solid titanium catalyst component of above-mentioned gained stores with the form of decane slurry.Dry a part of this solid titanium catalyst component is used for the chemical ingredients inspection.The composition of finding this solid titanium catalyst component is the titanium of 2.5 weight %, the chlorine of 65 weight %, magnesium and the 13.5 weight % diisobutyl phthalates of 19 weight %.
" polymerization "
Add 500ml4-Methyl-1-pentene, 10ml 1-decene, 10mlDMDT and 1N in the stainless steel autoclave of the capacity 11 of fully having replaced with nitrogen in inside and rise hydrogen, the temperature of polymerization system rises to 50 ℃ then.Add 1mmol triethyl aluminum, 1mmol trimethylammonium methoxy silane and 0.005mmol then---in titanium atom---catalyzer of above-mentioned preparation, cause copolymerization.Polymerization was carried out 15 minutes, and the temperature that keeps polymerization system simultaneously stops polymerization at 50 ℃ by add small amount of ethanol in polymerization system.With precipitation polymers in the big excessive methyl alcohol of polymers soln impouring that generates.Collect this polymkeric substance by filtering.In the polymkeric substance of gained, add stablizer, that is, 30mg IRGANOX 1010 (trade mark, the product of Ciba-Geigy company) and 30mg MARK 329K (trade mark, the product of Asahi Denka Kogyo K.K.), blend under reduced pressure 80 ℃ of dried overnight.
Obtain 40.8g 4-methyl-1-pentene/1-decene/DMDT random copolymers (multipolymer 3D) like this, limiting viscosity [η] is 2.5dl/g, the content of 4-methyl-1-pentene structural unit is 94.7 moles of %, the content of 1-decene structural unit is 3.0 moles of %, the content of DMDT structural unit is 2.3 moles of %, and iodine number is 13.
The chemical constitution of multipolymer 3A-3D is like shown in the table 3-1.
Table 3-1
| Embodiment | 3-1 | 3-2 | 3-3 | 3-4 |
| Multipolymer | 3A | 3B | 3C | 3D |
| The content of ethylene unit (mole %) | - | - | 8.0 | - |
| The content of propylene units (mole %) | 87.6 | - | 90.1 | - |
| The unitary content of 1-butylene (mole %) | 10.9 | - | - | - |
| The unitary content of 1-octene (mole %) | - | 95.7 | - | - |
| The unitary content of 4MP-1 (mole %) | - | - | - | 94.7 |
| The unitary content of 1-decene (mole %) | - | - | - | 3.0 |
| The unitary content of DMDT (mole %) | 1.5 | 4.3 | 1.9 | 2.3 |
| Iodine number | 17 | 21 | 22 | 13 |
| Limiting viscosity [η] (dl/g) | 2.3 | 5.0 | 2.0 | 2.5 |
Note:
DMDT=4,8-dimethyl-1,4,8-triolefin in the last of the ten Heavenly stems
The 4MP-1=4-Methyl-1-pentene
Embodiment 3-5
With multipolymer 3B, 2 grades of zinc oxide of 5 weight parts, the 1 weight part stearic acid of 100 weight part embodiment 3-2 gained, (SHEEST 3 for 80 weight part N330 carbon blacks, trade mark, the product of Tokai Carbon K.K), (SUNPAR 2280 for 50 weight part paraffin process oils, trade mark, the product of Nippon Sun Sekiyu K.K.), 0.5 weight part sulphur, 1.5 weight part MBT vulcanization accelerators and (F/B=50/50 ℃) kneading on 6 inches cylinders of 1.0 weight part TMDT vulcanization accelerators, obtain a kind of sheet rubber.
For resulting sheet rubber,, carry out the press vulcanization test at 160 ℃ with following method location parameter tc (90) and t10.The timed interval of setting press vulcanization is that tc (90) adds 5 minutes.For sulfurized and rubber sheet rubber, carry out sheet rubber material performance test.The result is shown in table 3-2.
" test of rubber material property (determining vulcanization rate and incipient scorch stability) "
Continue instrument (Curelastmeter) (Japan Sythetic Rubber Co., Ltd. provides) with 3 sulfurations of JSR type and measure vulcanization rate.Obtain a vulcanization curve figure at 160 ℃ like this, determine the poor ME (ME=MH-ML) between maximum twist value MH and the minimum value of reversing ML, from reaching with minute used time of 90%ME of expression, that is, tc (90) determines vulcanization rate then.On the other hand, from reaching with minute used time of 10%ME of expression, that is, t10 determines incipient scorch stability.
" performance of vulcanized rubber "
Tensile strength (T when measuring the fracture of vulcanized rubber sheet according to JIS K6301
B), the unit elongation (E in when fracture
B) and hardness.
Embodiment 3-6
Repeat the process of embodiment 3-5, except the multipolymer 3B among the multipolymer 3C replacement embodiment 3-3 that obtains with embodiment 3-5.The result is shown in table 3-2.
Comparative example 3-1
Repeat the process of embodiment 3-5, except the multipolymer 3B among the embodiment 3-5 is replaced with ethylene/propene/ethylidene norbornene multipolymer (multipolymer 3E), the content of ethene is 65 moles of % among the multipolymer 3E, the content of propylene is 32 moles of %, the content of ethylidene norbornene is 3 moles of %, limiting viscosity [η] is 2.2dl/g, and iodine number is 23.The result is shown in table 3-2.
Table 3-2
| Embodiment 3-5 | Embodiment 3-6 | Comparative example 3-1 | |
| Multipolymer | Multipolymer 3B | Multipolymer 3C | Multipolymer 3E |
| The performance of rubber | |||
| Tc (90) (minute) | 5.2 | 5.5 | 10.9 |
| T10 (minute) | 3.0 | 2.9 | 3.0 |
| The performance of vulcanized rubber | |||
| Tensile strength during fracture (MPa) | 12.3 | 22.1 | 14.6 |
| Unit elongation during fracture (%) | 250 | 210 | 430 |
| Hardness JISA | 38 | 85 | 67 |
From table 3-2 as can be known, the rubber of embodiment 3-5 and 3-6 also has long t10 except short tc (90) is arranged.This shows that vulcanization rate is higher and incipient scorch stability is preeminent.
Claims (12)
1. alpha-olefin/three olefinic random copolymers, it contains the structural unit (U that is derived from the alpha-olefin (A) with 2-20 carbon atom
A) and be derived from the structural unit (U of the chain triene compound (B-1) of following formula (1) expression
B-1),
Wherein, R
1, R
2, R
3, R
4, R
5And R
6Be hydrogen atom or alkyl separately independently of each other with 1-3 carbon atom, R
7Be the alkyl with 1-3 carbon atom, n is the integer of 0-5, prerequisite be when n be 2 or when bigger, each R
4And R
5Can be identical or different respectively,
Wherein, at structural unit (U
A) add structural unit (U
B-1) the overall texture unit in, structural unit (U
B-1) ratio be 0.1-30mol%,
In 135 ℃ of limiting viscosities of measuring in naphthalane [η] is 0.1-10dl/g.
2. according to alpha-olefin/three olefinic random copolymers of claim 1, wherein, be derived from the structural unit (U of the chain triene compound (B-1) of formula (1) expression
B-1) represent by following formula (1-a):
Wherein, R
1, R
2, R
3, R
4, R
5And R
6Be hydrogen atom or alkyl separately independently of each other with 1-3 carbon atom, R
7Be the alkyl with 1-3 carbon atom, n is the integer of 0-5, prerequisite be when n be 2 or when bigger, each R
4And R
5Can be identical or different respectively.
3. according to alpha-olefin/three olefinic random copolymers of claim 1, wherein, in formula (1), n is 1, R
4And R
5Be respectively hydrogen atom.
4. according to alpha-olefin/three olefinic random copolymers of claim 3, wherein in formula (1), R
6And R
7Be methyl or ethyl separately independently of each other.
5. according to alpha-olefin/three olefinic random copolymers of claim 1, wherein alpha-olefin (A) comprises two or more alpha-olefins.
6. according to alpha-olefin/three olefinic random copolymers of claim 1, wherein alpha-olefin (A) comprises ethene (A-1) and has the alpha-olefin (A-2) of 3-20 carbon atom, and is derived from the structural unit (U of ethene (A-1)
A-1) with respect to the structural unit (U that is derived from alpha-olefin (A-2)
A-2) mol ratio (U
A-1)/(U
A-2) be 99/1-30/70.
7. according to alpha-olefin/three olefinic random copolymers of claim 1, wherein alpha-olefin (A) is drawn together alpha-olefin (A-2) with 3-20 carbon atom and the other alpha-olefin with 2-20 carbon atom (A-3), and wherein multipolymer contains:
Structural unit (the U that is derived from alpha-olefin (A-2) of 70-99.9mol% with 3-20 carbon atom
A-2),
Structural unit (the U that is derived from alpha-olefin (A-3) of 0-29.9mol% with 2-20 carbon atom
A-3),
Structural unit (the U that is derived from chain triene compound (B-1) of 0.1-30mol%
B-1);
Structural unit (U wherein
A-2), (U
A-3) and (U
B-1) and, must be 100mol%.
8.-and kind of composition, contain:
Alpha-olefin/three olefinic random copolymers (I-1),
Vulcanizing agent (II) and/or
Filler (III),
Wherein, described alpha-olefin/three olefinic random copolymers (I-1) contain:
Be derived from the structural unit (U of alpha-olefin (A) with 2-20 carbon atom
A),
Be derived from the structural unit (U of the chain triene compound (B-1) of following formula (1) expression
B-1),
Wherein, R
1, R
2, R
3, R
4, R
5And R
6Be hydrogen atom or alkyl separately independently of each other with 1-3 carbon atom, R
7Be the alkyl with 1-3 carbon atom, n is the integer of 0-5, prerequisite be when n be 2 or when bigger, each R
4And R
5Can be identical or different respectively,
Wherein, at structural unit (U
A) add structural unit (U
B-1) the overall texture unit in, structural unit (U
B-1) ratio be 0.1-30mol%,
In 135 ℃ of limiting viscosities of measuring in naphthalane [η] is 0.1-10dl/g.
9. moulded products that makes by the described composition of claim 8.
10. according to the moulded products of claim 9, wherein, moulded products is the overflow mould goods.
11. according to the moulded products of claim 9, wherein, moulded products is injection mould goods or transfer mould goods.
12. according to the moulded products of claim 9, wherein, moulded products is a foamed products.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP147942/98 | 1998-05-28 | ||
| JP14794298 | 1998-05-28 | ||
| JP147942/1998 | 1998-05-28 | ||
| JP147943/98 | 1998-05-28 | ||
| JP147943/1998 | 1998-05-28 | ||
| JP323222/98 | 1998-11-13 | ||
| JP323222/1998 | 1998-11-13 | ||
| JP31947/99 | 1999-02-09 | ||
| JP31947/1999 | 1999-02-09 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200510109911 Division CN1821191A (en) | 1998-05-28 | 1999-05-28 | Chain triene compound and copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1240201A CN1240201A (en) | 2000-01-05 |
| CN100369944C true CN100369944C (en) | 2008-02-20 |
Family
ID=36922791
Family Applications (2)
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|---|---|---|---|
| CN 200510109911 Pending CN1821191A (en) | 1998-05-28 | 1999-05-28 | Chain triene compound and copolymer |
| CNB991094948A Expired - Fee Related CN100369944C (en) | 1998-05-28 | 1999-05-28 | Linear triene compound and copolymer |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1135491A (en) * | 1994-03-14 | 1996-11-13 | 三井石油化学工业株式会社 | Vinyl unsaturated copolymer and preparation method thereof |
| US5744566A (en) * | 1995-12-29 | 1998-04-28 | Mitsui Chemicals, Inc. | Unsaturated copolymer based on olefin and produciton and use thereof |
-
1999
- 1999-05-28 CN CN 200510109911 patent/CN1821191A/en active Pending
- 1999-05-28 CN CNB991094948A patent/CN100369944C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1135491A (en) * | 1994-03-14 | 1996-11-13 | 三井石油化学工业株式会社 | Vinyl unsaturated copolymer and preparation method thereof |
| US5744566A (en) * | 1995-12-29 | 1998-04-28 | Mitsui Chemicals, Inc. | Unsaturated copolymer based on olefin and produciton and use thereof |
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|---|---|
| CN1240201A (en) | 2000-01-05 |
| CN1821191A (en) | 2006-08-23 |
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