CN1342173A - Polymerization process - Google Patents

Polymerization process Download PDF

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CN1342173A
CN1342173A CN99811375A CN99811375A CN1342173A CN 1342173 A CN1342173 A CN 1342173A CN 99811375 A CN99811375 A CN 99811375A CN 99811375 A CN99811375 A CN 99811375A CN 1342173 A CN1342173 A CN 1342173A
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group
atom
monomer
aryl
cyclenes
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E·德伦特
W·斯雅迪恩
J·苏伊克尔布伊克
K·万宁格
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Basell Technology Co BV
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Montell Technology Co BV
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene

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Abstract

The invention relates to a process for the polymerization of ethene and optionally one or more other olefin monomers by contacting the monomers under polymerization conditions with a catalyst system obtainable by combining: (a) a palladium, nickel or platinum ion, (b) an anion derived from an acid having a pK a of less than 3, and containing an atom of Group V A of the Periodic Table of Elements, wherein the Group V A atom is substituted with at least one aryl group, said aryl groups being substituted with a polar group on the ortho position. The invention also relates to a novel class of cyclic olefin copolymers, containing functional groups, which are obtainable with the above process.

Description

Polymerization process
The present invention relates to ethene and choose any one kind of them or the polymerization process of multiple other olefinic monomer.This invention is particularly related to ethene, (functionalization) cyclenes monomer and the optional more polymerization process of multi-olefin monomer, and this method has prepared cyclenes copolymer or cyclenes terpolymer.This invention also relates to the new kind of the functionalization cyclenes copolymer that can pass through this method preparation.In addition, the present invention relates to the various uses of the new kind of functionalization cyclenes copolymer that obtains by this method.
The polymerization process of the cyclenes terpolymer of the cyclenes copolymer of preparation ethene known in the art or ethene; Yet what often obtain is low-molecular-weight oligomer product or the product that the small number cyclic monomer is only arranged.The term of this specification sheets " COC " or " COCs " refer to be cyclenes copolymer be again the cyclenes terpolymer; Term " COC " or " COCs " also refer to four or more a plurality of monomeric different monomers of cyclenes that comprises.
Another shortcoming of prior art method is the functionalization COCs that they do not allow the high number-average molecular weight of preparation, comprises heteroatoms such as halogen, oxygen, nitrogen, phosphorus or sulphur atom.With prior art method polymerizable functional monomer is difficult, because these monomers will influence catalyzer, makes catalytic activity reduce and obtain the polymkeric substance of low number-average molecular weight.
The demand that the substituent COCs of function is arranged on the hydrocarbon polymer main chain and the difficult both of preparation thereof are for example had description in WO-A-9720871, this patent is described (gathering) cyclenes addition polymer that preparation has side group silyl functional group.Yet these polymkeric substance are prepared by the addition homopolymerization by described cyclenes monomer, and non-cyclic monomer is mainly as the transfer agent quid pro quo.The synthetic polymkeric substance almost only is made up of cyclic monomer, therefore a high second-order transition temperature will be arranged, and this makes polymkeric substance be difficult to processing.
JP-A-10007736 discloses preparation and has had the method for the cyclenes copolymer of improved surface property (as bond properties).This method comprises that acquisition has good chemically reactive polymer polymerizing step and subsequent step, as graft modification.The shortcoming of this method is that the product with required surface property need obtain through two steps.Another shortcoming is to have to use complicated cyclic monomer in order to obtain to have required chemically reactive cyclenes copolymer.
US-A-4,855,399 have described the copolymerization of carbon monoxide and alkene hydrocarbon polymer (for example ethene), and used catalyst system is made up of palladium and part neighbour-(diphenyl phosphine) Phenylsulfonic acid.To specifications, described phenyl can further be replaced.This article does not illustrate that the catalyzer of this further replacement may be suitable olefin polymerization catalysis.
European patent application EP-A-589,527 have described in the presence of by palladium and catalyzer that the neighbour-the diphenyl phosphine Phenylsulfonic acid is formed, ethene and 5-norbornylene-2, the copolymerization of 3-dicarboxylic anhydride, the product that obtains is the product of oligopolymer, number-average molecular weight is 2700, and the cyclenes monomer of embedding has only 5mol%.
Therefore, be used for the catalyst system of the production of ethene and cyclenes copolymer, preferably with the polar group functionalization, have acceptable number-average molecular weight and acceptable cyclenes unit content is desirable.
A target of the present invention is ethene and chooses any one kind of them or the polymerization process of multiple other olefinic monomer, wherein obtained the polymerisate of higher number average molecular weight, and polymerization is to finish with higher rate.This target realizes by polymerization process described below.
Therefore, a target of the present invention is ethene and chooses any one kind of them or the polymerization process of multiple other olefinic monomer, is included under the polymerizing condition monomer whose is contacted with catalyst system, and catalyst system can pass through below in conjunction with acquisition:
(a) palladium, nickel or platinum ion,
(b) derive from the atom of pKa less than VA family in the negatively charged ion of 3 acid and the containing element periodictable, the atom of wherein said VA family is replaced by an aryl at least, and described aryl is replaced by polar group at the ortho position.
In this manual, the explanation of " polar functional group " and " polar group " is commonly used to illustrate the big key that the ratio of dipole moment C-H is arranged between functional group and molecule residuum, the general as key between carbon atom and heteroatoms such as nitrogen, oxygen or sulphur atom.
We find that method used according to the present invention can prepare the polymerisate of high number-average molecular weight with high speed.
Unless do not allude to, otherwise the explanation of " number-average molecular weight " is meant number-average molecular weight (Mn).Here " high number-average molecular weight " meaning is that number-average molecular weight is greatly more than 10,000 (Mn).
The further benefit of method of the present invention is that it does not need to use a large amount of promotors or expensive non-coordination anion, and this anionoid uses in Z-N known in the art or metallocene catalysis polymerization process usually.
We find that also can be advantageously used in ethene, cyclenes monomer and optional the third olefinic monomer according to polymerization process of the present invention is cyclenes copolymer or the cyclenes terpolymer that feedstock production has higher number average molecular weight.
The special feature of the present invention is the COCs that comprises heteroatoms (for example halogen, oxygen, nitrogen, phosphorus or sulphur atom) that can adopt this polymerization process preparation to have high number-average molecular weight.With above already mentioned the same, rely on polymerization process known in the art can not prepare the COCs of high number-average molecular weight functionalization.
The catalyst system that is used for the inventive method comprises palladium, nickel or platinum ion, preferably uses palladium ion.It is corresponding salt or acid that these ionic are fit to the source; The palladium positively charged ion that is fit to is for example at EP-A-0, describes in 589,527.To describe in detail below for preferred metal palladium catalyst; Obviously, by palladium, nickel and/or platinum are appreciated that equally.
As b) definition the preferred anionic surfactants type, can pass through general formula (1) and illustrate:
Q-R 1-An -(1) wherein Q is the group that comprises the atom of periodictable VA family, and the atom of wherein said VA family is further replaced by one or two aryl, and described aryl is replaced by polar group at the ortho position; An -It is anionicsite; R 1Be to connect described VA family's atom and described An -Bridging group.
Anionicsite-the An that is fit to -For for example-SO 3 -,-COO -,-PO 3 -With-AsO 3 -Group.In all these-SO 3 -Group is particularly preferred.
In order to satisfy pKa, improve tart bridging group An in some cases less than 3 requirement -For for example halo alkylene group or halogenated aryl, specifically be-CCl 2 -Group ,-CF 2-group or the divalence phenyl group that is replaced by fluorine atom.The example that comprises the acid that improves acidic-group is the acid of formula (1), wherein R 1An -Be-CCl 2-COO -,-CF 2-SO 3 -,-CClF-SO 3 -, 2-carboxylate salt-3,4,5,6-tetrafluoro-phenyl and-CF 2-COO -
As top b) definition, described negatively charged ion comprises the atom of the VA family in the periodictable, and suitable have nitrogen, phosphorus, arsenic or antimony; Preferred anionic surfactants comprises phosphorus atom.If desired, can use and contain the negatively charged ion that surpasses 1 VA family atom, for example contain a phosphorus and a nitrogen-atoms, or two phosphorus atom; It is necessary that yet described negatively charged ion comprises a VA family atom, make it catalyst system can with the palladium coordination, and preferably another VA family atom can not with a metallic palladium ion coordination.
VA family atom (specifically being phosphorus atom) is by bridging group R 1Be connected with An.For satisfy VA family atom catalyst system really can with palladium coordinate needs, we have found that bridging group R 1Size and structure very important.To be further described negatively charged ion (wherein VA family atom is a phosphorus) below.Obviously, by phosphorus, nitrogen, arsenic and antimony are appreciated that equally.
Recommendation is according to the bridging group R in the negatively charged ion of formula (1) 1In bridge joint, contain 1 to 3 atom, preferably two atoms at the most.Here the meaning of using " bridge joint " is to connect anionicsite An -The shortest atomchain with phosphorus atom.The concrete bridging group of recommending comprises one or two carbon atom in bridge joint, suitable bridging group for example :-CH 2-,-CH 2-CH 2-,-CF 2-,-CHCl-,-CCl 2-,-C (CH 3) 2-,-CH 2-CF 2-and-CF 2-CF 2-group.
The bridged bond atom, if special one or more bridged bond atoms may form the part ring texture when being carbon atom, for example cycloalkyl, heterocyclic radical or preferred aryl groups, for example phenyl, naphthyl, indenyl or fluorenyl.Preferred bridging group R 1Be aryl, wherein sulphur generation (sulphomato) group to encircle last two first may with R 1A replacement in the carbon atom adjacent with the key between the phosphorus atom (Q).Because can make phosphorus atom (Q) and sulphur like this for group (An -) in catalyst system easily with a palladium Atomic coordinate.Work as R 1When being phenylene group, sulphur preferably replaces at the ortho position for group like this; Work as R 1When being naphthyl, like this sulphur for group preferably at 8 or more preferably 2 replacements.Bridging group R 1May further be replaced, for example used C 1-C 12Alkyl or C 1-C 12Alkoxyl group replaces.
Anionic phosphorus atom according to formula (1) is replaced by one or two aryl, and described aryl is replaced by polar group at the ortho position.These aryl can be called R in addition 2And R 2, suitably contain 6-18 carbon atom.Exemplary aryl is phenyl, naphthyl, phenanthryl or anthryl.Preferred R 2And/or R 3Be phenyl or naphthyl.
If phosphorus is only replaced by the aryl of a polar substitution, another group can be the aryl of corresponding nothing replacement or for example is the organic group that comprises nitrogen, phosphorus, arsenic and/or antimony atoms, and condition is the metallic palladium ion coordination that these atoms can not be identical with described anionic phosphorus atom (Q).Preferred described phosphorus atom (Q) is replaced by the aryl that two ortho positions are all replaced by polar group, and the meaning at " ortho position " is two first positions that may be close to the carbon atom of phosphorus atom (Q) bonding on ring here.For example, when using phenyl, described polar group with respect to the ortho position of phosphorus atom on replace; When using naphthyl, polar group may be 8, preferably replacement on 2.
Preferably in radicals R 2And/or R 3The polar group of last replacement is hydroxy, cyano group, amino, alkylamino, alkoxyl group, thioether group or carbonyl (for example carboxyl).Above-mentioned organic group suitably comprises 1-10 carbon atom, more preferably preferably contains the alkoxyl group of 1-10 carbon atom.Example has methoxyl group, oxyethyl group, propoxy-and isopropoxy, and most preferred polar group is a methoxyl group.
Preferred group R 1, R 2And R 3Can further be replaced, for example with having the alkyl of 1-20 carbon atom or replacing with polar group.The example of possible alkyl has methyl, ethyl, sec.-propyl and dodecyl.The example of the polar group that is fit to is the polar group of early describing.
Preferred catalyst system according to the inventive method comprises palladium and has formula An --R 1R 2R 3The negatively charged ion of P, wherein R 1Be the phenyl that the azochlorosulfonate acid anion group replaces, R 2And R 3Be the phenyl that the ortho position replaces, or the naphthyl of 2 or 8 replacements, wherein substituting group is a polar group, preferably methoxyl group.
Particularly suitable anionic example is two (neighbour-methoxyphenyl) phosphino--benzene sulfonates and two (neighbour-p-methoxy-phenyl) phosphino--p-methylphenyl sulfonate.Other example comprises:
Method preparation known to described negatively charged ion can pass through generally.
According to the catalyst system of the inventive method can be aptly by before the polymeric monomer is carried out in supply with palladium cationic source or its precursor and above b) negatively charged ion of definition is combined into salt or acid preparation, can in the presence of solvent, be prepared if desired.By introducing catalyst component to reactor, add monomer and any compound that other will exist simultaneously in reaction medium, also may prepare described catalyzer in position.
The example that is fit to source metal has palladium (II), capric acid palladium (II), chlorine (1, the 5-cyclooctadiene) methyl-palladium (II), (1, the 5-cyclooctadiene) dimethyl-palladium (II), three (dibenzalacetone) palladium (0) or nickel acetate (II), two (1, the 5-cyclooctadiene) nickel (0) and three (tetramethyl--divinyl disiloxane)-two-palladiums.
Suitable palladium, nickel or platinum ion and anionic mol ratio are between 1: 1 to 1: 100, more preferably between 1: 1 to 1: 5.
Can be used for the polymerization of ethene according to method of the present invention.Optimal ethylene and one or more other olefinic monomer polymerizations (optional featureization).The example of described olefinic monomer propylene, butylene, vinylbenzene, 4-methoxy styrene and 3-butene-1-alcohol arranged.
According to the preferred embodiment of the inventive method, ethene is and the cyclenes monomer polymerization.In most preferred embodiment of the present invention, the cyclenes monomer of ethene and functionalization and optional the third olefinic monomer polymerization.Described the third olefinic monomer can be as propylene or butylene, the cyclenes of preferred NOT-functionization; Preferred described NOT-function cyclenes is corresponding with described functionalization cyclenes, and does not have functional group.An example of NOT-function cyclenes is a norbornylene.
As the prior art specification sheets has been reported, be difficult to the functionalization monomer polymerization with the prior art method, because these monomers will exert an influence to catalyzer, cause catalyst activity to reduce and obtain the polymkeric substance of low number-average molecular weight.
The applicant finds that now ethene and functionalization cyclic monomer and the third optional monomer alkene polymerizable obtain high number-average molecular weight cyclenes copolymer product, and do not have the reduction of such catalyst activity aspect.Use method of the present invention, can obtain the functionalized polymer product that comprises heteroatoms (for example halogen, oxygen, nitrogen, phosphorus or sulphur atom) of high number-average molecular weight.
The preferred functionalization cyclenes monomer that uses in the method for the invention can be described by following formula (6) and (7):
Figure A9981137500111
R wherein 4, R 5, R 6And R 7(being same to each other or different to each other) is to comprise hydrogen, hydrocarbon or heteroatomic group, wherein in formula (6), and R at least 4, R 5, R 6And R 7In a group be to comprise heteroatomic group.
The hydrocarbyl group that is fit to is C 1-C 20Alkyl or C 6-C 12Aryl.
The described heteroatom group that comprises can contain halogen, oxygen, nitrogen, phosphorus or sulphur atom as heteroatoms.The example that is fit to that comprises heteroatom group is a polar group, as ester group, ether, carboxyl, acidic group, alcohol radical, ketone group, carbonyl, cyano group, amido or amide group or halogen atom.
Described (functionalization) cyclenes can prepare ([4+2] cycloaddition) by diels-Alder reaction, wherein is used as diene with CPD (cyclopentadiene).The cyclenes of functionalization prepares with similar method, and the cycloaddition by CPD and assorted dienophile (heterodienophiles) just prepares.The example of assorted dienophile like this has azo-2-carboxylic acid's divinyl vinegar, acetaldehyde, maleic anhydride, dihydrofuran, vinylpyridine, acrylic acid alkyl vinegar or substituted olefine as mentioned above (with reference to " heterocyclic chemistry ", TL Gilchrist work, 4.3.3 chapters and sections, 1985).Following formula (8a-8h) is the example of the functionalization cyclenes that is fit to, n=1-20 wherein, and R is the alkyl that has 1-20 carbon atom.
Figure A9981137500121
Figure A9981137500131
If desired, method of the present invention can be finished in the presence of suitable solvent, and the example that is fit to solvent has hydrocarbon, aromatic hydrocarbons, alcohol, ether, ester and ketone.Wherein measure a many monomer and also can be used as solvent, condition is that this monomer is liquid phase under the reaction conditions of the inventive method.
The preferred polar solvent that uses, the COCs of Chan Shenging has high relatively number-average molecular weight like this.Particularly suitable solvent is dme, diethyl ether, toluene, hexanaphthene and the tetramethylene sulfone of ethylene glycol.
The scope of the number of suitable of the catalyzer that uses according to method of the present invention is (wanting the polymeric cycloalkene compound for every mole) 10 -8-10 -2Gram atoms metal (palladium).
Method of the present invention can be finished under medium reaction conditions.The range of reaction temperature that is fit to is at 20-180 ℃, preferably 40-130 ℃ of scope.
Usually use the reaction pressure of superatmospheric pressure,, do not get rid of pressure outside stated limit for example in the scope of 1-100bar.The pressure of advantageous applications is in the 2-60bar scope.
Another target of the present invention is new COC, form by ring texture that has at least two carbon atoms on the main chain of this polymkeric substance and non-annularity structure, its number-average molecular weight is greater than 10,000, the monomeric content of functional group supporting ring-type has 0.1% (mole) at least, and wherein COC is the polymerization acquisition by ethene, functional group supporting cyclic monomer and optional the third olefinic monomer.We find that described COC does not contain successive monomer ring texture.Preferred described COC comprises the functionalization cyclic monomer of 0.1-50% (mole), the ethene of 50-99.9% (mole) and the third monomer of 0-49.9% (mole).
The third possible monomer is described in the above.
According to embodiment of the present invention, be ethene and the monomeric multipolymer of functional group supporting ring-type according to the COCs of suitable type of the present invention, wherein the latter exists with low levels, and suitable scope is 0.1% (mole)-10% (mole).Because described functional group is combined on the main chain of described polymkeric substance, this analog copolymer provides surface property improved polyethylene based polymers.
Preferred described COC comprises most of sequence according to following formula (9):
Figure A9981137500141
Wherein n is 1-10, and the monomer olefin(e) compound of 000, at least 0.1% (mole) is a ring texture, and wherein hydrogen is by polar group R 4, R 5, R 6And/or R 7Replace.The value of n and m is high enough at least, makes number-average molecular weight surpass 10,000 (Mn).R 4, R 5, R 6And/or R 7Can with top formula (6) describe the same.Most preferably described COC comprises the sequence of formula (9 '):
Figure A9981137500151
Wherein m, n, R 4, R 5, R 6And R 7Meaning with above-reported.
Monomeric unit along the sequence at least 0.1% (mole) of formula (9 ') is the monomer with ring texture, wherein R 4, R 5, R 6And R 7In the group at least one is polar group.The COCs of preferred new functionalization obtains by above-described polymerization process.In the course of processing of the present invention, the monomeric ring texture of cyclenes not (or basically not) is influenced.Therefore, the content with cyclic monomer in synthetic COC is identical basically for the content of ring texture.
The effectiveness that should understand COCs depends on its number-average molecular weight of functionalization degree of product.COCs can compare with polymethylmethacrylate or polycarbonate in their application in theory.
The function COCs that uses method of the present invention to obtain can be used for various application.Because the surperficial bonding and surface reaction performance of their improvement, be particularly suitable for optical disc applications according to the COCs of functionalization of the present invention, for example as the articulamentum between polarity and the non-polar polymer surface, expanding material or as top coat.
COCs of the present invention also can be used for electronics and microelectronic applications, and for example planar dielectric layer, the passivation layer in IC produces made compound as supercoat and pottery, as tackiness agent, in printed circuit board (PCB) is made as polymkeric substance.
COCs of the present invention can be transparent and can be used for optical application.Transparency depends on the content and the performance of the functionalization group in described COC.They can be used as the coating in optical fiber, eyeglass or other optical device.
Described COCs can be used as lead coating, lead packing film and conduct protection and erosion shield.Described COCs also can form fiber by methods known in the art, for example wet spinning silk, dry-spinning silk, gel spinning and extruding spinning.
Further the present invention will be described by following infinite embodiment.Use following abbreviation:
Pd (OAc) 2Palladium
DPBS 2-diphenyl phosphine Phenylsulfonic acid
DOMPBS 2-(two-2-anisole phosphino-) Phenylsulfonic acid
Synthesizing of embodiment 12-/two (2-p-methoxy-phenyl) phosphino-/Phenylsulfonic acid
In water and toluene mixture, prepare the Phenylsulfonic acid lithium by lithium hydroxide and Phenylsulfonic acid.By removing among the THF that described water is suspended in 8.37g (0.051mol) Phenylsulfonic acid lithium 120ml (THF=tetrahydrofuran (THF)) (under nitrogen) and be cooled to 0 ℃ with methylbenzene azeotropic distillation.In 1 hour, adding 32ml n-Butyl Lithium (16mol/l) under 0 ℃.Make mixture reach room temperature, stirred subsequently 18 hours.Mixture is cooled to-30 ℃, slowly adds the solution of the 30ml THF that contains 14.5g (0.05mol) two (2-p-methoxy-phenyl)-methoxyl group phosphine.Make mixture reach room temperature, stirred subsequently 18 hours.Add 20ml water, under vacuum, remove THF, remaining xanchromatic oil.Add methylene dichloride and (10%) hydrochloric acid, generation is separated.With 10% hydrochloric acid soln washing organic phase, use dried over mgso then.Product is dissolved in water/acetone mixture (1: 1).Extract this mixture with 5ml toluene, then by vacuum concentration and be cooled to 4 ℃ and make the product crystallization.The product of purifying contains water.Therefore be dissolved in methylene dichloride once more, with dried over mgso and filtration.Then in solvent removed in vacuo.Productive rate: 7.01g (33%).
Embodiment 22-[two (2-p-methoxy-phenyl) phosphino-]-right-toluenesulphonic acids synthetic
As described in embodiment 1, by 0.03mol right-toluenesulphonic acids, 19ml n-Butyl Lithium (1.6mol/l) and 8.7g two (2-p-methoxy-phenyl) methoxyl group phosphine prepare described compound.Productive rate: 3.8g (30%).Embodiment 3-7
Description as embodiment 1 prepares 2-[two (2-p-methoxy-phenyl) phosphino-] Phenylsulfonic acid, the pd (OAc) that under nitrogen atmosphere, table 1 is reported 2, phosphine part and the ring-type comonomer magnetic that is incorporated into the solvent (outgasing in advance by nitrogen bubble) that table 1 report is housed of 250ml continuously stirs in the Hastelloy C autoclave.The sealing autoclave is pressurized to required pressure with ethene, and postheating is to temperature of reaction.Condition, compound and the result of used quantity, processing have been reported at table 1.
The product that obtains gel permeation chromatography (GPC) analyzing molecules amount (M w) and use 1H and 13The content of C-NMR assay determination ethene and cyclic monomer.Comparative experiments A
Except using negatively charged ion 2-diphenyl phosphine Phenylsulfonic acid, all the other repeat the experiment of embodiment 3.Condition, compound and the result of used quantity, process have been reported at table 1.
Table 1
Embodiment Catalyzer (mmol) Temperature (℃) Time (hrs) Quantity of solvent (ml) Ethylene pressure (bar) Cyclic monomer (g) Polymer yield (g) ?M w * Cyclic monomer in polymkeric substance (% (mole))
????A ??Pd(OAc) 2??(0.025) ??DPBS(0.05) ??90 ??7 Diglyme 50 ??40 5-norbornylene-2 methyl alcohol (5g) ??2 ?2,500 ??2
????3 ??Pd(OAc) 2??(0.025) ??DOMPBS ??(0.05) ??90 ??3 Diglyme 50 ??40 5-norbornylene-2 methyl alcohol (5g) ??29 ?30,000 ??10
????4 The same ??90 ??0.25 Toluene 50 ??10 Acetic acid 5-norborneol-2-alkene ester (10g) ??8 ?80,000 ??35
????5 The same ??90 ??1 Toluene 50 ??5 Norbornylene (20g) ??14 ?90,000 ??48
????6 The same ??90 ??0.5 Toluene 50 ??30 Norbornylene (20g) ??26 ?85,000 ??35
????7 The same ??75 ??1.5 Neighbour-dichlorobenzene 50 ??30 5-norbornylene-2 methyl alcohol (10g) ??14 ?90,000 ??14
*M w(molecular weight) measured with GPC, uses polystyrene to make standard substance and make solvent with THF.Embodiment 8-11
Under nitrogen atmosphere, to contain the 20g norbornylene (with norbornene derivative in embodiment 10-11 as the third monomer, see Table 2) the toluene solution of 100ml join 20mg 2-[two (2-p-methoxy-phenyl) phosphino-is housed] Phenylsulfonic acid (0.05mmol) and 5mgPd (OAc) 2In the autoclave of 250ml (0.025mmol), maintain under the nitrogen.Described mixture is with the pressurization of 5bar ethene and be heated to 90 ℃.After arriving temperature of reaction, make pressure remain on following 1 hour of the pressure constant of setting by continuous adding ethene.Then with autoclave decompress(ion) and cool to room temperature.With toluene described toluene solution is diluted to 300ml, injects methyl alcohol by spout and make polymer precipitation.The polymkeric substance that obtains leached and dry down 200mbar and 75 ℃.Table 2 has been reported used quantity, treatment condition, compound and result.
Embodiment 12
Except making solvent with 100ml THF; 17g norbornylene and 6.5g are as outside the third monomeric carbic anhydride, and all the other repeat the experiment of embodiment 11.Table 2 has been reported used quantity, treatment condition, compound and result.
Embodiment 13
With 2-[two (2-p-methoxy-phenyl) phosphino-]-(as the preparation of the report of embodiment 2) repeats the experiment of embodiment 8 to right-toluenesulphonic acids as negatively charged ion.Result who obtains and embodiment's 8 is closely similar.
Table 2
Embodiment Solvent (ml) Ethylene pressure (bar) Cyclic monomer (g) The third monomer of ring-type (g) Polymer yield (g) ???M w * ???Tg ??(℃) Cyclic monomer in polymkeric substance **(% (mole)) The third monomer of ring-type in polymkeric substance (% (mole))
???8 Toluene (100) ????12 Norbornylene (20g) Do not have ???19 ??90,400 ??109 ?????2 Do not have
???9 Toluene (100) ????5.5 Norbornylene (20g) Do not have ???2.9 ??94,000 ??141 ?????10 Do not have
???10 Toluene (100) ????12 Norbornylene (20g) 5-norbornylene-2-methyl alcohol-tetradecyl ester (1.5g) ???8 ??71,000 ??80 ?????35 ??????～3
???11 Toluene (100) ????12 Norbornylene (20g) 5-norbornylene-2-methyl alcohol (1.2g) ???7 Do not survey ??113 ?????48 ??????～1
???12 ????THF ????(100) ????12 Norbornylene (17g) Carbic anhydride (6.5g) ???3.7 Do not survey ??101 ?????35 ??????5
*M w(molecular weight) measured with GPC, makes standard substance and with the cyclohexane give solvent with divinyl. *Comprise described the third monomer.Embodiment 14-16
The first step is with 2-[two (2-p-methoxy-phenyl) phosphino-] Phenylsulfonic acid is suspended in the water and is 7 with the TBAH solution pH value that neutralizes.Toluene is joined in this solution, remove by component distillation and anhydrate.Vacuum is removed toluene then, produces 2-[two (2-p-methoxy-phenyl) phosphino-] Phenylsulfonic acid 4-butyl ammonium Bu 4N (DOMPBS).
Second step is according to document (J.Krause, K.J.Haack, G.Cestaric, R.Goddard, K.-R.Poerschke, Chem.Commun.1998,226) preparation Pd 2(tetramethyl--divinyl disiloxane) 3
100mg (0.25mmol) 2-[two (2-p-methoxy-phenyl) phosphino-of in having 2 liters of autoclaves of mechanical stirrer and catalyst injection device, packing into then] toluene solution of 1100ml of Phenylsulfonic acid and norbornylene, norbornene derivative and 0.25mmol acetic acid.This mixture is full of with 5bar ethene.Temperature is raised to 90 ℃ and final polymerization pressure is transferred to 12bar always.Under nitrogen atmosphere, separately with 96mg (0.125mmol) Pd 2(tetramethyl--divinyl disiloxane) 3Be dissolved in cold (30 ℃) toluene of 8ml and remain under-30 ℃.Then under nitrogen with 174mg (0.25mmol) Bu 4N (DOMPBS) is dissolved in the 10ml toluene, and joins Pd under-30 ℃ 2(tetramethyl--divinyl disiloxane) 3In the solution.Make this 18ml catalyst solution within 15 minutes, arrive room temperature, inject 2 liters of autoclaves then.Ethene by supply consumes makes pressure remain on 12bar and assigned 1 hour.Then with reactor decompress(ion) and cool to room temperature.With the described solution of dilution with toluene, filter by Celite.Separate described polymkeric substance by ethanol sedimentation, and in 200mbar and 75 ℃ of following dryings.More multidata about used quantity, treatment condition, compound and result sees Table 3.
Table 3
Embodiment Cyclic monomer (g) The third monomer of ring-type (g) Polymer product productive rate (g) Molecular weight (M w) ???(1) Second-order transition temperature-Tg (℃) The molecular fraction of the cyclic monomer in polymer product (comprising the third monomer) Monomeric molecular fraction in the ring-type the 3rd in mixing cyclic monomer
???14 Norbornylene (160) 5-norbornylene-2-methyl alcohol (52) ????130 ??38000 ??????105 ????????38 ?????????10
???15 Norbornylene (160) Acetic acid 5-norborneol-2-alkene ester (64) ????49 ??117000 ??????113 ????????40 ?????????10
???16 Norbornylene (190) Carboxylic acid 5-norbornylene-2 ester (14.5) ????142 ??68000 ??????114 ????????42 ????????～2.5
(1) M wMeasure with GPC, make standard substance and make solvent with THF with polystyrene

Claims (21)

1. be used for ethene and choose any one kind of them or the polymerization process of multiple other olefinic monomer, this method is included under the polymerizing condition monomer is contacted with catalyst system, and described catalyst system can pass through below in conjunction with acquisition:
(a) palladium, nickel or platinum ion,
(b) derive from the atom of pKa less than VA family in the negatively charged ion of 3 acid and the containing element periodictable, the atom of wherein said VA family is replaced by at least one aryl, and described aryl is replaced by polar group at the ortho position.
2. according to the process of claim 1 wherein that ion described as (a) definition is a palladium ion.
3. according to the method for claim 1 or 2, wherein said as negatively charged ion (b) definition has general formula (1):
Q-R 1-An -(1) wherein Q is the group that comprises the atom of periodictable VA family, and wherein said VA family atom is replaced by one or two aryl, and described aryl is replaced by polar group at the ortho position; An -It is anionicsite; R 1Be to connect described VA family's atom and described An -Bridging group.
4. according to the method for claim 3, wherein said anionicsite An -Be-SO 3 -Group.
5. according to any one the method for claim 1-4, wherein said VA family atom is a phosphorus.
6. according to any one the method for claim 3-5, wherein said bridging group R 1Be aryl, wherein sulphur generation (sulphomato) group to encircle last two first may with R 1A replacement in the carbon atom adjacent with the key between the phosphorus atom (Q).
7. according to any one the method for claim 1-6, wherein said VA family atom is replaced by two aryl, and described aryl is replaced by polar group at the ortho position.
8. according to any one the method for claim 1-7, wherein said polar group is ester group, ether, carboxylic acid group, acidic group, alcohol radical, ketone group, carbonyl, cyano group, amido or amide group or halogen atom, and described aryl is a phenyl or naphthyl.
9. method according to Claim 8, wherein said polar group is the alkoxyl group with 1-10 carbon atom.
10. according to the method for claim 9, wherein said polar group is a methoxyl group.
11. according to any one the method for claim 1-10, wherein said negatively charged ion is two (neighbour-p-methoxy-phenyl) phosphino-benzene sulfonate or two (neighbour-p-methoxy-phenyl) phosphino--right-tosylate.
12. according to the process of claim 1 wherein that the molar ratio range of described palladium, nickel or platinum ion (a) and described negatively charged ion (b) was from 1: 1 to 1: 100.
13. according to the method for claim 12, wherein said molar ratio range was from 1: 1 to 1: 5.
14. according to the process of claim 1 wherein ethene and functionalization cyclenes monomer and optional the third olefinic monomer polymerization.
15. according to the method for claim 14, wherein said functionalization cyclenes monomer has formula (6) or (7):
Figure A9981137500031
R wherein 4, R 5, R 6And R 7Being same to each other or different to each other, is to comprise hydrogen, hydrocarbon or heteroatomic group, wherein in formula (6), and R at least 4, R 5, R 6And R 7In a group be to comprise heteroatomic group.
16. cyclenes copolymer, described cyclenes copolymer contains and has ring texture and the non-annularity structure of two carbon atoms on the main chain of described polymkeric substance at least, its number-average molecular weight is greater than 10,000 and have the functional group supporting cyclic monomer of at least 0.1% (mole) content, described multipolymer is by the polymerization acquisition of ethene, various functional group supporting cyclic monomer and optional the third olefinic monomer.
17. according to the cyclenes copolymer of claim 16, described multipolymer comprises functional group supporting cyclic monomer, the ethene of 50-99.9% (mole) and the third olefinic monomer of 0-49.9% (mole) of 0.1-50% (mole).
18. according to the cyclenes copolymer of claim 17, described multipolymer contains most of sequence according to following formula (9):
Figure A9981137500041
Wherein n is 1-10,000, and m and n are high enough at least and make number-average molecular weight surpass 10,000; R 4, R 5, R 6And R 7, be same to each other or different to each other, be to comprise hydrogen, hydrocarbon or heteroatomic group; The monomer olefin(e) compound of at least 0.1% (mole) is a ring texture, and wherein hydrogen is by polar group R 4, R 5, R 6And/or R 7Replace.
19. according to any one the cyclenes copolymer of claim 16-18, described multipolymer can obtain by any one the method for claim 1-15.
20. according to any one the cyclenes copolymer of claim 16-19 as articulamentum, between different polymkeric substance as expanding material or as the purposes of top coat.
21. according to any one the cyclenes copolymer of claim 16-19 as the purposes of optics.
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