CN100351295C - Charge dissipation modifiers for olefinic interpolymer compositions - Google Patents
Charge dissipation modifiers for olefinic interpolymer compositions Download PDFInfo
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Abstract
Olefinic interpolymer compositions comprising the olefinic interpolymer, residuals from a transition metal catalyst and boron containing activator package, and a charge dissipation modifier and methods for making them. The compositions have dissipation factors that are at least 50% less than the corresponding olefinic interpolymer compositions which have not been treated with charge dissipation modifiers. The compositions are useful in wire and cable applications.
Description
The field of the invention
The present invention relates to comprise the reaction post-reactor residue of olefin copolymer, transition-metal catalyst and boron containing activator package (package) and the composition of olefin copolymer of charge dissipation properties-correcting agent.In yet another aspect, the present invention relates to reduce method with the dissipation factor of the prepared composition of olefin copolymer of the binding substances of transition-metal catalyst and boron containing activator package by in copolymer compositions, adding charge dissipation properties-correcting agent.In yet another aspect, the present invention relates to contain electric wire and cable (the W ﹠amp of these composition of olefin copolymer; C) product.
Background of the present invention
Transition-metal catalyst, especially metallocenes and constrained geometry catalysts, the discovery that is used for the preparation of olefin copolymer has caused having synthesized various new and useful composition of olefin copolymer.These transition-metal catalysts typically activate with the boron containing activator package.After polymer formation, catalyzer-activator system passes through to add water, methyl alcohol, or other catalyzer passivator comes deactivation.After separation, formed composition of olefin copolymer has kept the residue of catalyzer-activator system and has typically had dissipation factor greater than 0.10.Alap dissipation factor is that composition of olefin copolymer is needed in electronic application.Composition of olefin copolymer can pickling or the steam extracting to remove or to reduce catalyzer and activator residue, this further can reduce below the dissipation factor to 0.01 or 0.01 of composition of olefin copolymer, this depend on composition be how to wash or steam extractive.US 3,819, and 591 provide the example of acid elution technology and US 3,076,795 and US 3,590,026 that the example of steam extraction technique is provided.Although these technology can reduce dissipation factor effectively, increased additional step and additional manufacturing cost and considered it is undesirable but pickling and stripping are the preparation of composition of olefin copolymer, produced the additional waste liquid that must handle separately from environmental.
Find surprisingly now, by specific charge dissipation properties-correcting agent being added in the prepared composition of olefin copolymer of usefulness transition-metal catalyst and boron containing activator package, it is low at least about 50% level that dissipation factor can be reduced to the dissipation factor of the corresponding composition of olefin copolymer of handling than charge dissipation properties-correcting agent of no use, therefore obtained to be used for electricity and used fairly simple, the lower cost of (especially low-voltage and medium voltage electric wire and cable insulation layer and involucrum), the composition of olefin copolymer more friendly to environment.
The present invention's general introduction
One aspect of the present invention is to comprise olefin copolymer, the reaction post-reactor residue of transition-metal catalyst and boron containing activator package, composition of olefin copolymer with charge dissipation properties-correcting agent, the dissipation factor that said composition had is lower at least about 50% than the dissipation factor of the identical composition of olefin copolymer that does not contain charge dissipation properties-correcting agent of the present invention (charge dissipation modifier), and this charge dissipation properties-correcting agent is selected from:
A) structural formula (I) and amine compound (II):
(I)NRx
Wherein x be 3 and each R to be independently selected from linearity, branching and cyclic hydrocarbon group and hydrogen or two or more R substituting group be cyclic hydrocarbon group and each R together
1-5Be independently selected from linearity, branching and cyclic hydrocarbon group and hydrogen or R
1-5Substituent two or more be the cyclic hydrocarbon group together;
B) silicon dioxide compound; With
C) phosphoric acid
With their mixture.
Another aspect of the present invention is to improve method with the electrical property of the prepared composition of olefin copolymer of transition-metal catalyst and boron containing activator package by add charge dissipation properties-correcting agent in composition of olefin copolymer.In case reaching needed polymerization level just adds charge dissipation properties-correcting agent in the solution polymerization process to.Therefore, if charge dissipation properties-correcting agent can be added to after composition of olefin copolymer-solvent solution leaves reactor in successive soln technology in this solution or use the solution batch technology directly to be added in the reactor after polyreaction has reached the required level of finishing or discharged from reactor at this solution and be added in this solution afterwards.In addition, this charge dissipation properties-correcting agent can be added to by slurry process or gas phase process preparation and in addition in the insulating solid olefin-copolymerization composition.Charge dissipation properties-correcting agent adds by using method well known in the prior art, up hill and dale mixed olefins copolymer compositions and charge dissipation properties-correcting agent.
Another aspect of the present invention is the electric wire and cable product that contains composition of olefin copolymer of the present invention.
The narration of preferred embodiment
The composition of olefin copolymer that demonstrates improved dissipation factor after charge dissipation properties-correcting agent of the present invention adds is to prepare in the polymerization process of using transition-metal catalyst and boron containing activator package.In general, this type of polymerization can be at solution, slurry, or the gas phase process neutralization becomes known under the condition of Ziegler-Natta or Kaminsky-Sinn type polyreaction in the prior art, be 0-250 ℃, preferred 30-200 ℃ temperature, and normal atmosphere-10,000 atmospheric pressure carries out.
Olefin copolymer is from least a C
2-20'alpha '-olefin monomers and the preparation of randomly at least a multi-olefin monomer.Alpha-olefin can be an aliphatics, aromatics or ring compound, as cyclobutene, cyclopentenes, or norbornylene, comprising on 5 and 6 by C
1-20The norbornylene that alkyl replaces.Alpha-olefin is C preferably
2-20Fatty compounds, more preferably C
2-16Fatty compounds.Preferred 'alpha '-olefin monomers comprises 4 vinyl cyclohexene, vinyl cyclohexane, norbornadiene and C
2-10Aliphatics alpha-olefin (especially ethene, propylene, iso-butylene, butene-1, amylene-1, hexene-1,3-Methyl-1-pentene, 4-methyl-1-pentene, octene-1, decylene-1, dodecylene-1 and vinylbenzene) and their mixture.Most preferred monomer is an ethene, and ethene and propylene, 4-methyl-1-pentene, butene-1, hexene-1, at least a mixture in octene-1 and the vinylbenzene.
Multi-olefin monomer if use, can be cross-linking set or branch point or both.Each multi-olefin monomer is C ideally
4-40Diolefinic monomer (being also referred to as " diolefine ") and more to make us be non-conjugated diene desirably.The non-conjugated diene hydrocarbon can be C
5-15Straight chain, side chain or cyclic hydrocarbon diene.The illustrative non-conjugated diene is the acyclic diene of straight chain, as 1, and 4-hexadiene, 1,5-heptadiene and 1,6-octadiene; Side chain acyclic dienes such as 5-methyl isophthalic acid, 4-hexadiene, 2-methyl isophthalic acid, 5-hexadiene, the 6-methyl isophthalic acid, 5-heptadiene, 7-methyl isophthalic acid, 6-octadiene, 3,7-dimethyl-1,6-octadiene, 3,7-dimethyl-1,7-octadiene, 5,7-dimethyl-1, the 7-octadiene, 1, the 7-octadiene, 1, the mixed isomers of 9-decadiene and dihydromyrcene; The alicyclic diene of monocycle, as 1,1,5-cyclooctadiene and 1,5-encircle 12 carbon diene; The cyclic diolefine of many alicyclic condensed of ring and bridge joint, as tetrahydroindene, methyl tetrahydroindene, dicyclopentadiene, dicyclo (2,2,1)-heptan-2,5 diene (norbornadiene), methyl norbornadiene; Alkenyl, alkylidene group, cycloalkenyl group and cycloalkylidene norbornylene such as 5-methylene-2-norbornene (MNB), 5-ethylidene-2-norbornene (ENB), 5-vinyl-2-norbornylene (VNB), 5-propenyl 2-norbornylene, 5-isopropylidene-2-norbornylene, 5-(4-cyclopentenyl)-2-norbornylene and 5-cyclohexylidene-2-norbornylene.
When diolefine was conjugated diolefine, it can be a 1,3-pentadiene, 1,3-butadiene, 2-methyl isophthalic acid, 3-divinyl, 4-methyl isophthalic acid, 3-pentadiene, or 1.This diene preferably is selected from ENB, and 1, the non-conjugated diene in 4-hexadiene and the norbornadiene, more preferably, ENB.
Typically produce dissipation factor and be set forth in WO 98/49212, US5,965 greater than the example of the transition-metal catalyst that combines with the boron containing activator package of 0.10 composition of olefin copolymer, 756, US 6,160,066, US 6,143,682, WO 00/02891, and WO 00/02891, with US 6,127,497 (late transition metal catalysts), their content is hereby incorporated by reference.These catalyzer can separately or combine (dual catalyst system) use and in continuous or batch reactor method, use single or multiple reactors.
Transition-metal catalyst is given catalytic activity by the boron containing activator package.The activator wrapping material contain organic boron compound and optional aluminum compound.The example that can be used in the boron compound in the activator package includes, but not limited at each alkyl or fluoridizes have 1 to 10 carbon atom in the alkyl and fluoridize three (alkyl) boron compound (the perfluorination derivative that comprises it).Perfluorination three (aryl) boron compound is preferred.Three (pentafluorophenyl group) borine (below be called " FAB ") most preferably.As mentioned above, these boron compounds can be as the independent component of activator package, or preferably, they can with the aluminum compound coupling.The example of aluminum compound includes, but not limited to have trialkyl aluminium compound or the polymerization or the oligomeric aikyiaiurnirsoxan beta of 1 to 4 carbon atom in each alkyl.What preferred activator package will have a 1-20 carbon atom in each alkyl fluoridizes three (alkyl) boron compound, and most preferably FAB combines with the trialkyl aluminium compound that has 1-4 carbon atom in each alkyl.Another kind of preferred activator package (MMAO) combines FAB and triisobutyl aluminium modified methylaluminoxane (methylalumoxane).Two kinds of preferred activator packages are binding substancess, and the latter can produce the olefin copolymer that is used among the present invention effectively but formed composition of olefin copolymer typically has the dissipation factor greater than 0.10.
Boric acid ester is not to be used for the boron compound of activator package of the present invention and is not boron substance of the present invention.
When these transition-metal catalysts and activator package were used for solution methods preparation composition of olefin copolymer, the suitable inert solvents that is used for these solution polymerizations comprised, for example, straight chain and branched-chain hydrocarbon, as Trimethylmethane, butane, pentane, hexane, heptane, octane, and the mixture of paraffinic comprise kerosene and isoparaffin, ring-type and clicyclic hydrocarbon such as hexanaphthene, suberane, methylcyclohexane, methyl suberane and their mixture; With the aromatics of aromatics and alkyl replacement, as benzene, toluene, dimethylbenzene, and ethylbenzene.Suitable solvent also can comprise the liquid olefin as monomer or comonomer, comprising divinyl, and cyclopentenes, the 1-hexene, 4 vinyl cyclohexene, vinyl cyclohexane, the 3-Methyl-1-pentene, 4-methyl-1-pentene, 1, the 4-hexadiene, 1-octene, 1-decene, vinylbenzene, Vinylstyrene, allyl benzene, and Vinyl toluene (comprising independent a kind of or its mixture in whole isomer).The mixture of aforementioned substances also is suitable.If desired, common gaseous olefin can be converted to liquid and be used as inert liq by pressurization.
Charge dissipation properties-correcting agent of the present invention is added to in the prepared composition of olefin copolymer of transition-metal catalyst and boron containing activator package dissipation factor being reduced at least about 50%, and do not compare with the identical composition of olefin copolymer of charge dissipation properties-correcting agent processing of the present invention.Preferably, do not utilize pickling or stripping to carry out under the situation of aftertreatment at composition of olefin copolymer, the charge dissipation properties-correcting agent of the present invention of q.s is added to dissipation factor to be reduced in the composition of olefin copolymer and is lower than 0.12, preferably be lower than 0.10, more preferably less than 0.05 with most preferably be lower than 0.01.
Though do not wish to be subjected to any special theory, but should believe, suitably bring into play function in order to make charge dissipation properties-correcting agent, it must with physics mode with take place from the activator of polyreaction/catalyst residue to interact or contact, with the composition of olefin copolymer of formation dissipation factor than corresponding untreated composition of olefin copolymer low 50%.This interaction has only when olefin copolymer and charge dissipation properties-correcting agent and closely mixes, and for example in solution or under melted state, can take place.
The preferred method that charge dissipation properties-correcting agent is added to composition of olefin copolymer is that charge dissipation properties-correcting agent is added to from composition of olefin copolymer-solvent solution that solution polymerization process obtains.
When charge dissipation properties-correcting agent was added in composition of olefin copolymer-solvent solution, it can be used as passivator and charge dissipation properties-correcting agent simultaneously.When charge dissipation properties-correcting agent is also during this passivator, do not need additional passivator is added in composition of olefin copolymer-solvent solution.Yet, typically independent passivator such as water or methyl alcohol are added in the solution with charge dissipation properties-correcting agent.Charge dissipation properties-correcting agent can be used for continuously simultaneously and batch reactor method and being used for is used the method for a plurality of reactors of single reactor or serial or parallel connection.No matter be added as the binding substances of passivator and charge dissipation properties-correcting agent or as just charge dissipation properties-correcting agent in successive processes, charge dissipation properties-correcting agent preferably is added in the discharge materials flow of autoreactor.
When being used for single reactor successive processes and during as the binding substances of passivator/charge dissipation properties-correcting agent or as just charge dissipation properties-correcting agent, charge dissipation properties-correcting agent preferably after copolymer compositions-solvent solution leaves reactor and any time point that still is in the solution of copolymer compositions be added in this copolymer compositions-solvent solution.If use placed in-line double-reactor or a plurality of reactor successive processes, charge dissipation properties-correcting agent is added when preferably still being in the solution with copolymer compositions after copolymer compositions-solvent solution leaves final reactor.If this successive processes is the multiple reactor parallel process, then charge dissipation properties-correcting agent can be added after solution leaves each reactor or after whole reactors is discharged the materials flow merging.In the intermittence solution process, when reaction has reached desirable when finishing level, charge dissipation properties-correcting agent preferably is added in the reactor.
When using independent passivator, passivator can be added into same time point of charge dissipation properties-correcting agent and charge dissipation properties-correcting agent, before joining charge dissipation properties-correcting agent in copolymer compositions-solvent solution, be added into, in case or after charge dissipation properties-correcting agent being joined in copolymer compositions-solvent solution polyreaction be added into and preferably before solvent is removed from composition of olefin copolymer-solvent solution, be added into after reaching the required level of finishing.
When independent passivator was added in the composition of olefin copolymer, this dissipation factor was typically greater than about 0.10.By using passivator such as water and methyl alcohol, can't typically obtain to be lower than about 0.10 level.
Be noted that in general the efficient of transition-metal catalyst and activator package is high more, the dissipation factor of formed olefin copolymer is low more.For high catalyst/activator efficient (for example, the efficient of 1,000 myriagrams polymkeric substance/gram transition metal and Geng Gao) situation, the interpolation of charge dissipation properties-correcting agent is not that to be used for material that some electricity uses necessary.Yet if use charge dissipation properties-correcting agent, dissipation factor is improved probably, but this improvement does not reach 50% level.
The another kind of method that charge dissipation properties-correcting agent is added in the composition of olefin copolymer is as solid after separating from solution, slurry or gas phase process charge dissipation properties-correcting agent to be added in the composition of olefin copolymer at composition of olefin copolymer.When using this method of charge dissipation properties-correcting agent interpolation, composition of olefin copolymer must closely mix with charge dissipation properties-correcting agent so that charge dissipation properties-correcting agent realizes each other that with catalyzer/activator residue enough physics contacts so that the copolymer compositions dissipation factor reduces at least about 50%.The example of realizing the method for this purpose comprises, but be not limited to, olefin copolymer and charge dissipation properties-correcting agent in forcing machine or other melt blended device melt-mixing or olefin copolymer is dissolved in the suitable solvent again and handles the solution that contains olefin copolymer with charge dissipation properties-correcting agent.
Still, the another kind of method of charge dissipation properties-correcting agent being added in the composition of olefin copolymer is to carry out blend with excessive charge dissipation properties-correcting agent composition of olefin copolymer of handling and the composition of olefin copolymer of not handling with charge dissipation properties-correcting agent.Composition can come blend as the method for melt blending in forcing machine by method well known in the prior art.
Charge dissipation properties-correcting agent, in the time of in being added composition of olefin copolymer it that the dissipation factor of composition is reduced is about 50%, comprising:
A) structural formula (I) and amine compound (II):
(I)NRx
Wherein x be 3 and each R to be independently selected from linearity, branching and cyclic hydrocarbon group and hydrogen or two or more R substituting group be cyclic hydrocarbon group and each R together
1-5Be independently selected from linearity, branching and cyclic hydrocarbon group and hydrogen or R
1-5Substituent two or more be the cyclic hydrocarbon group together,
B) silicon dioxide compound; With
C) phosphoric acid
With their mixture.
Amine compound as charge dissipation properties-correcting agent can be any primary amine in the present invention, secondary amine, tertiary amine, or ammonia.This R and R
1-5Group can be any hydrocarbyl group, as linearity, and branching, or cyclic aliphatic or aromatics, preferred C
1-C
50Fatty compounds, more preferably C
3-C
20Fatty compounds.The example of amine compound comprises aniline, Isopropylamine, ammonia, pyridine and N most preferably, N-octadecyl methyl amine (being also referred to as " two-the tallow alkyl methylamine ").
Silicon dioxide compound as charge dissipation properties-correcting agent comprises any type of SiO in the present invention
2The preferably silicon-dioxide of surface modification and high surface area silica.Hydrophobic silica most preferably.
The amount that is added to the charge dissipation properties-correcting agent in the composition of olefin copolymer can or be determined by the amount of the boron-containing compound that is used to prepare multipolymer by the amount of transition-metal catalyst.Catalyst efficiency is low more, and is big more and reduce many more at least about 50% needed charge dissipation properties-correcting agent for the dissipation factor that makes copolymer compositions for the amount of the needed catalyzer of multipolymer for preparing specified rate.Preferably, the addition of charge dissipation properties-correcting agent enough makes this dissipation factor reduce to be lower than 0.12, more preferably less than 0.10.For the purposes of the present invention, the amount of the atoms metal of transition-metal catalyst is used for determining the amount of required charge dissipation properties-correcting agent in copolymer compositions.Preferably, transition metal atoms (for example titanium, zirconium and hafnium) is at least 1: 1000 with charge dissipation properties-correcting agent ratio, more preferably at least 1: 100 and most preferably at least 1: 10.
With the physicals of the prepared olefin copolymer of transition-metal catalyst and boron containing activator package such as the influence that as if fusing point, second-order transition temperature and molecular weight distribution are not subjected to the interpolation of charge dissipation properties-correcting agent of the present invention.The composition of olefin copolymer of handling with charge dissipation properties-correcting agent of the present invention has enough dissipation factors for use in most electric wire and cable insulation layer and involucrum application.For most low pressure applications, it is needed being less than or equal to about 0.10 dissipation factor.Use for middle pressure, it is needed being less than or equal to about 0.01 dissipation factor.These dissipation factors are not that the determinative whether absolute and concrete product can be used in low voltage and middle voltage electric wire and cable insulation layer and the involucrum is whether product has passed through long-term underwater test.Typically, do not have the product that is lower than about 0.10 dissipation factor and can't pass through this test.
The following example is used to illustrate but does not limit the present invention clearly or implicitly.Except as otherwise noted, otherwise whole part and percentage ratio is by weight, based on gross weight.Numerical range comprises end value, except as otherwise noted.Embodiments of the invention are to be by alphabetic(al) letter representation by Arabic numerals signs and comparative example.
Embodiment
Except that following specifically describing, be used for embodiment 4-7 preparation as will be used to prepare the composition of olefin copolymer-solvent solution that uses embodiments of the invention and comparative example at the continuous polymerization method described in the WO 98/49212.This method is at the continuous discharge of the continuous charging and the polymers soln of reactant, and solvent and unreacted monomeric devolatilization operation and polymer recovery design.Ethene, propylene and ENB monomer, titanium [N-(1, the 1-dimethyl ethyl)-1,1-dimethyl-1-(1,2,3,3a, 8a-eta)-1,5,6,7-tetrahydrochysene-2-methyl-s-indacen-1-yl] silanamindato (2-)-.kappa.N] [(1,2,3,4-eta)-1,3-pentadiene catalyzer (being also referred to as (tert-butylamides base) dimethyl (5-2-methyl-s-indacen-1-yl) silane titanium (II) 1,3-pentadiene catalyzer), the boron containing activator package of forming by the binding substances of FAB and MMAO, and the Isopar-E solvent is added continuously and/or is recycled in the single reactor.
In an embodiment, the charge dissipation modifier solution prepares with the Isopar-E solvent and is introduced in this solution after the composition of olefin copolymer-solvent solution of heat leaves reactor.The concentration of charge dissipation modifier solution is that manual adjustment is come on the basis with the catalyst efficiency, to keep 1: 1000 metal titanium and charge dissipation properties-correcting agent molar ratio.Before the collection of copolymer compositions, composition of olefin copolymer-solvent solution stream was kept two hours at least.Composition of olefin copolymer-the solvent solution that contains charge dissipation properties-correcting agent is pumped by static mixer and reactor post-heater.Reactor post-heater temperature maintenance is at 150 ℃.Copolymer compositions is pumped in the separator, unreacted comonomer, unreacted hydrogen, unreacted ENB and solvent volatilize therein, obtain comprising the molten copolymer composition of the residue of ethylene/propylene/diene hydrocarbon copolymer (" EPDM "), charge dissipation properties-correcting agent and catalyzer and activator.After the collection of copolymer compositions was finished, charge dissipation modifier solution stream was closed and system is cleaned the separator of any material of being handled by charge dissipation properties-correcting agent with cleaning at least 2 hours with untreated copolymer compositions.Charge dissipation properties-correcting agent additive tank before adding new charge dissipation modifier solution with fresh solvent washing, to prevent the crossed contamination of charge dissipation properties-correcting agent.After collecting, copolymer compositions under 115 ℃ in vacuum drying oven drying at least 8 hours to guarantee solvent removal completely.
Except that explain in detail the back, comparative example's composition according to paragraph in front in the same procedure described make, just add passivator and replace charge dissipation properties-correcting agent.Passivator in the comparative example is with received form and does not further purify and just use.Water and methyl alcohol are bought from Fisher Scientific International Inc.PEP-Q obtains from Cariant Corp.Tricresyl phosphate propyl diester and phosphoric acid are to obtain from AldrichChemical Company (present Sigma-aldrich Company).Silicon-dioxide (AEROSIL R 972 forges the system hydrophobic silica) is to obtain from Degussa Corp.Two-the tallow alkyl methylamine (Armeen M2HT) obtain from Akzo Nobel Inc.
By in the Haake mixing tank of cam agitating vane is housed 100 ℃ of mixing velocities of using down 55rpm with the dicumyl peroxide blend of the copolymer compositions of 50g and 1g 3 minutes, for the electric test in embodiment and comparative example prepares dry composition of olefin copolymer.Pressurization between two Mylar polyester chipss (DuPont Company) of copolymer compositions/peroxide blends in mould of 12 grams is to prepare the sheet of 3.5 inch diameters and about 0.17cm thickness.This plate is by at least 3 minute carrying out crosslinked in the following preheating of 375 (191 ℃) this compressing tablet and mould.Mould block coefficient composition, being forced into 20 tons of pressure in the Tetrahedron press kept 3 minutes, by using 240 to be cooled to 120 (49 ℃) and to keep under these conditions 3 minutes as press rate setting value (press rate setting).The crosslinked 3.5 inch diameter sheets of about 0.17cm thickness have been obtained to have.
The dissipation factor of sheet is measured by using for the used Tettex Model 2914 Test Cell of solid insulating material under 130 ℃ according to ASTM D150.Tettex Model 5283 supply transformer are Test Cell supply voltage.Tettex Model 2966 TemperatureControl Unit heating Test Cell electrode.Go up measuring resistance at Tettex Model 5476A resistance bridge (from the Tettex equipment of Tettex Corporation acquisition).
Embodiment 1-3 and Comparative Examples A-H
Prepare EPDM-1, have 70wt% ethene, 29wt% propylene, 0.5wt%ENB, the copolymer compositions of 40 mooney viscosity and 1.3 hundred myriagrams (MMg) multipolymer/g titanium.This composition is used for embodiment 1-3 and Comparative Examples A-G.At embodiment 1-3, add various charge dissipation properties-correcting agent.In Comparative Examples A, neither add charge dissipation properties-correcting agent and also do not add passivator.In comparative example B-G, add various passivators.Measure the dissipation factor of each embodiment.Table 1 has shown the type of charge dissipation properties-correcting agent (embodiment) and passivator (comparative example) and the dissipation factor of consumption and each composition.Adopted the comparative example H of EPDM-A to be also included within this table.EPDM-A is Nordel 2722E (DuPontDow Elastomers LLC), the industrial EPDM composition that is used for the electricity application, it has 72wt% ethene, the 23.6wt% propylene, 4.4wt%ENB, 27 mooney viscosity and with common Ziegler-Natta catalyst production with carried out the steam extracting.In this table and in the table of some back, charge dissipation properties-correcting agent is expressed as " CDM " and passivator is expressed as " DEA ".
Table 1
| Embodiment and comparative example | Copolymer compositions | CDM/DEA | The every 8000ml solvent of concentration C DM/DEA g 5 | Dissipation factor |
| Embodiment 1 | EPDM-1 | Two-the tallow alkyl methylamine | 48.8g | 0.031 |
| Embodiment 2 | EPDM-1 | Silicon-dioxide | 5.5g | 0.021 |
| Embodiment 3 | EPDM-1 | Phosphoric acid | 8.9g | 0.061 |
| Comparative Examples A | EPDM-1 | Do not have | - | 0.454 |
| Comparative example B | EPDM-1 | Water | 1.6g | 0.125 |
| Comparative example C | EPDM-1 | IRGANOX 1010 3And water | 2.88g/0.18g | 0.156 |
| Comparative example D | EPDM-1 | PEP-Q 4 | 94.2g | 0.341 |
| Comparative example E | EPDM-1 | Stearic acid | 25.2g | 0.195 |
| Comparative example F | EPDM-1 | Methyl alcohol | 2.9g | 0.149 |
| Comparative example G | EPDM-1 | The tricresyl phosphate propyl diester | 19.3g | 0.334 |
| Comparative example II | EPDM-1 | -- | -- | 0.003 |
3Tetramethylolmethane four (3-(3,5-di-t-butyl-4-hydroxybenzene) propionic ester) obtains from CibaSpecialty Chemicals Corp.
4Four (2, the 4-di-tert-butyl-phenyl)-4,4-biphenylene bisphosphonates
5For 454g polymkeric substance/hr throughput rate, the value of 1.3MMg polymkeric substance/g Ti catalyst efficiency and 8g/ minute modifier solution flow velocity.
All Comparative Examples A-G comprise those that handle with passivator, have than the composition of industrial use and have carried out the higher dissipation factor of contrast EPDM-A of the extractive comparative example H of steam.There is not the Comparative Examples A of passivator in all test copolymer compositions, to have the highest dissipation factor (0.454).When water was used as passivator (comparative example B), dissipation factor reduced to 0.125 from 0.454.Similarly, when methyl alcohol was used as passivator (comparative example F), dissipation factor was reduced to 0.149.Therefore, what have reduced the dissipation factor of composition of olefin copolymer effectively separately for water and methyl alcohol.Yet, these comparative examples' dissipation factor is the still high order of magnitude and make composition can't be used for most electricity to use.
IRGANOX 1010 and water add with PEP-Q as passivator in comparative example C and add as passivator in comparative example D.These passivators are usually as the additive and the stablizer that prevent polymer unwinds.IRGANOX 1010 is not a charge dissipation properties-correcting agent of the present invention.PEP-Q be contain phosphorus functionalized molecule but neither charge dissipation properties-correcting agent of the present invention.As shown in table 1, comparative example D has 0.341 the factor.Comparative example C has 0.156 the low dissipation factor.It mainly is because the effect of water that the low dissipation factor of comparative example C is considered to.Once more, fail dissipation factor with copolymer compositions of these additives is reduced to and is lower than 0.10 desired level.
With the same in comparative example D, the passivator that is used for comparative example G contains phosphorus atom, but is not charge dissipation properties-correcting agent of the present invention.Comparative example G has obtained quite high dissipation factor (0.334), is similar to the measured dissipation factor for comparative example D.The passivator of comparative example D and G contains phosphorus but be different from the phosphoric acid (embodiment 3) that belongs to charge dissipation properties-correcting agent of the present invention on chemical property.
Comparative example E has 0.195 dissipation factor.Passivator in this comparative example is a stearic acid, and it contains acid functional group but the dissipation factor of composition of olefin copolymer can't be reduced to the desired level that is used for most of electricity application.
Surprisingly, the copolymer compositions of embodiment 1-3 though very different charge dissipation properties-correcting agent is handled on being used in chemical structure and forming, has significantly improved dissipation factor for Comparative Examples A-G separately.As shown in table 1, embodiment 1-3 has 0.031,0.021 and 0.061 dissipation factor respectively.These dissipation factors almost are better than from the result of Comparative Examples A-G acquisition with the order of magnitude.In addition, embodiment 1 and 2 dissipation factor have represented on dissipation factor 93-95% to reduce and embodiment 3 has represented 87% minimizing, compares with untreated copolymer compositions (Comparative Examples A).In addition, the dissipation factor of these three embodiment has been represented 51-83% minimizing on dissipation factor, compares with the water treatment copolymer compositions of comparative example B.Though embodiment 1-3 does not have the same low dissipation factor with comparative example H, but the dissipation factor of these embodiment is enough low and can satisfy the electric requirements that most of electricity is used, this shortcoming of additional step of but not relevant with the comparative example H steam extracting and the waste treatment of steam extracting waste liquid.
Embodiment 4-8 and comparative example I
By making water prepare EPDM-2, has 70wt% ethene, 29.5wt% propylene, 0.5wt%ENB, the copolymer compositions of 22 mooney viscosity and 0.53 hundred myriagram (MMg) multipolymer/g titanium as the catalyzer passivator.This composition is used for embodiment 4-8 and comparative example I.
In embodiment 4-8, various charge dissipation properties-correcting agent and EPDM-2 blending.The EPDM-2 of each charge dissipation properties-correcting agent and 50 grams are blending 5 minutes under the stirring velocity of 70 ℃ temperature and 55rpm in the Haake mixing tank of cam agitating vane is housed.Add dicumyl peroxide (1.0g) then, this blend mixed other 3 minutes under the stirring velocity of 100 ℃ and 55rpm in the Haake mixing tank.The sample of blend is suppressed then in flakes and according to aforesaid program and is cured.Sheet is tested down at 130 ℃ according to ASTM D150.The dissipation factor of the type of the properties-correcting agent that is added and amount and blending embodiment is shown in Table 2.
Table 2
| Embodiment/comparative example | Copolymer compositions | Charge dissipation properties-correcting agent | The addition of CDM (g) | Dissipation factor |
| The comparative example 1 | EPDM-2 | Do not have | -- | 0.068 |
| 4 | EPDM-2 | Aniline | 0.261 | 0.009 |
| 5 | EPDM-2 | Pyridine | 0.281 | 0.002 |
| 6 | EPDM-2 | Isopropylamine | 0.225 | 0.008 |
| 7 | EPDM-2 | 25% ammonia and 75% water | 0.323 | 0.007 |
| 8 | EPDM-2 | Two tallow alkyl methylamine | 0.530 | 0.017 |
Embodiment 9 and 10 and comparative example J
EPDM-3, has 70wt% ethene, the 29.5wt% propylene, 0.5wt%ENB, the copolymer compositions of 22 mooney viscosity and 0.56 hundred myriagram (MMg) multipolymer/g titanium is according to preparing with the same mode of EPDM-2, just, for embodiment 9, charge dissipation properties-correcting agent is being added in the copolymer solution except that before desolvating.There is not properties-correcting agent in the EPDM-3 composition, is used for comparative example J.By using the Haake mixing tank that the EPDM-3 of 25 grams and the embodiment 9 composition blending of 25 grams were prepared the copolymer compositions of embodiment 10 in 5 minutes, use peroxide treatment subsequently and then carry out sheet to prepare.The results are shown in the table 3.
The comparison of the dissipation factor of embodiment 9 is than the composition of embodiment J, the same combination that charge dissipation properties-correcting agent of no use is handled, dissipation factor low more than 50%.By making dissipation factor reduce an order of magnitude (embodiment 10) composition of embodiment 9 and the further blending of comparative example J of same section.Therefore, the dissipation factor of copolymer compositions can reduce by allowing it contact fully with the composition that contains excessive charge dissipation properties-correcting agent.
| Embodiment/comparative example | Copolymer compositions | Charge dissipation properties-correcting agent | The amount of CDM (g) in copolymer compositions | Dissipation factor |
| Comparative example J | EPDM-3 | Do not have | - | 0.0629 |
| Embodiment 9 | EPDM-3 | Two tallow alkyl methylamine | 0.989 | 0.0300 |
| Embodiment 10 | EPDM-3 | Two tallow alkyl methylamine | 0.49 | 0.0032 |
Comparative example K and L
EPDM-4 prepares by above described at the beginning method in the embodiment part, just the boron containing activator package is N, two (the tallow alkyl)-N-ammonium methyls four (2 of N-, 3,4,5,6-pentafluorophenyl group)-binding substances of boric acid ester (Boulder Scientific Company) and MMAO (Akzo-Nobel).This method obtains having 70wt% ethene, 29.5wt% propylene, 0.5wt%ENB, the copolymer compositions of 20 mooney viscosities and 2.14MMg multipolymer/g titanium.This composition, EPDM-4 is used for comparative example K and L.In comparative example L, the charge dissipation properties-correcting agent blending of EPDM-4 and table 4, and measure dissipation factor.
As shown in the table 4, charge dissipation properties-correcting agent of the present invention can't reduce dissipation factor effectively with the interpolation among the EPDM of boric acid ester activator preparation.In fact, dissipation factor has improved.
Table 4
| The comparative example | Copolymer compositions | Charge dissipation properties-correcting agent | CDM addition (g) | Dissipation factor |
| K | EPDM-5 | Do not have | -- | 0.093 |
| L | EPDM-5 | Two tallow alkyl methylamine | 0.497 | 0.512 |
Claims (18)
1. composition of olefin copolymer comprises:
A. olefin copolymer or comprise at least a C separately
2-C
20The mixture of the olefin copolymer of 'alpha '-olefin monomers;
The polyreaction post-reactor residue of b. at least a transition-metal catalyst and boron containing activator package; With
C. be selected from following at least a charge dissipation properties-correcting agent in these:
I) general formula (I) and amine compound (II):
Wherein x be 3 and each R to be independently selected from linearity, branching and cyclic hydrocarbon group and hydrogen or two or more R substituting group be cyclic hydrocarbon group and each R together
1-5Be independently selected from linearity, branching and cyclic hydrocarbon group and hydrogen or R
1-5Substituent two or more be cyclic hydrocarbon group together because of;
Ii) silicon dioxide compound; With
Iii) phosphoric acid;
With their mixture,
Wherein this composition of olefin copolymer has the dissipation factor than the dissipation factor low at least 50% of the identical composition of olefin copolymer of not using charge dissipation properties-correcting agent to handle.
2. the composition of olefin copolymer of claim 1, wherein olefin copolymer comprises at least a polyene hydrocarbon.
3. the composition of olefin copolymer of claim 1, wherein charge dissipation properties-correcting agent is selected from aniline, isopropylamine, pyridine, and N, N-octadecyl methylamine.
4. the composition of olefin copolymer of claim 1, wherein charge dissipation properties-correcting agent is N, N-octadecyl methyl amine.
5. the composition of olefin copolymer of claim 1, wherein charge dissipation properties-correcting agent is silicon dioxide compound.
6. the composition of olefin copolymer of claim 1, wherein also lotus dissipation properties-correcting agent is phosphoric acid.
7. the composition of olefin copolymer of claim 1, wherein at least a 'alpha '-olefin monomers is to be selected from ethene, propylene, 1-butylene, 1-hexene, 1-octene, and 4-methyl-1-pentene.
8. the composition of olefin copolymer of claim 1, wherein at least a olefin copolymer comprises two kinds of 'alpha '-olefin monomers.
9. the copolymer compositions of claim 8, wherein 'alpha '-olefin monomers is ethene and octene.
10. the composition of olefin copolymer of claim 8, wherein 'alpha '-olefin monomers is ethene and butylene.
11. the composition of olefin copolymer of claim 7, it comprises the mixture of olefin copolymer, and wherein each olefin copolymer comprises two or three 'alpha '-olefin monomers that is selected from ethene, propylene, butylene and the octene.
12. the composition of olefin copolymer of claim 1, wherein at least a olefin copolymer comprises at least a polyene hydrocarbon.
13. the composition of olefin copolymer of claim 12, wherein each polyene hydrocarbon is to be selected from 5-ethylidene-2-norbornene and 5-vinyl-2-norbornylene.
14. the composition of olefin copolymer of any one among the claim 1-12, wherein composition has the dissipation factor below 0.10 or 0.10,
15. reduce the method for the dissipation factor of composition of olefin copolymer, comprising:
A. allow comprise the olefin copolymer that all is dissolved in the solvent or the mixture of olefin copolymer, the copolymer compositions-solvent solution of the polymerization post-reactor residue of at least a transition-metal catalyst and boron containing activator package be selected from following charge dissipation properties-correcting agent in these and contact:
I) general formula (I) and amine compound (II);
Wherein x be 3 and each R be independently selected from linearity, branching and cyclic hydrocarbon group and hydrogen or two or more R substituting group are cyclic hydrocarbon group and each R together
1-5Be independently selected from linearity, branching and cyclic hydrocarbon group and hydrogen or R1-5 substituent two or more be the cyclic hydrocarbon group together;
Ii) silicon dioxide compound; With
Iii) phosphoric acid;
With they mixture and
B. separate handled copolymer compositions.
16. reduce the mixture that comprises olefin copolymer or olefin copolymer, the method for the dissipation factor of the solid composition of olefin copolymer of the polymerization post-reactor residue of at least a transition-metal catalyst and boron containing activator package, this method comprises:
A. heat this composition of olefin copolymer to melted state;
B. allow composition of olefin copolymer be selected from following charge dissipation properties-correcting agent in these and contact:
I) general formula (I) and amine compound (II):
Wherein x be 3 and each R to be independently selected from linearity, branching and cyclic hydrocarbon group and hydrogen or two or more R substituting group be cyclic hydrocarbon group and each R together
1-5Be independently selected from linearity, branching and cyclic hydrocarbon group and hydrogen or R
1-5Substituent two or more be cyclic hydrocarbon group together because of;
Ii) silicon dioxide compound; With
Iii) phosphoric acid;
With their mixture;
C. allow charge dissipation properties-correcting agent and catalyzer and activator residue generation physics interact to transform dissipation factor fully; With
D. reclaim handled copolymer compositions.
17. composition of olefin copolymer by the preparation of the method for claim 15 or claim 16.
18. comprise the cable of the composition of olefin copolymer of any one among electric conductor and the claim 1-14.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US42087902P | 2002-10-24 | 2002-10-24 | |
| US60/420,879 | 2002-10-24 | ||
| US10/691,163 | 2003-10-21 |
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| CN100351295C true CN100351295C (en) | 2007-11-28 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3522183A (en) * | 1968-05-07 | 1970-07-28 | Simplex Wire & Cable Co | Solid dielectric polyolefin compositions containing various voltage stabilizers |
| DE2139599A1 (en) * | 1971-08-03 | 1973-02-15 | Siemens Ag | Insulation for electric cables - esp high-tension cables based on polyolefin and contng tert amine |
| DE2234065A1 (en) * | 1972-07-07 | 1974-01-24 | Siemens Ag | Electric cable insulation - contg a polyolefin with a tetra alkyl diamino diaryl alkane as antioxidant |
| US5883178A (en) * | 1995-02-16 | 1999-03-16 | Chisso Corporation | Crystalline polyolefin resin composition and electrical insulating part comprising said composition |
| JPH11268145A (en) * | 1998-03-20 | 1999-10-05 | Toray Ind Inc | Electrically insulating film and capacitor using the same |
-
2003
- 2003-10-24 CN CNB2003801020623A patent/CN100351295C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3522183A (en) * | 1968-05-07 | 1970-07-28 | Simplex Wire & Cable Co | Solid dielectric polyolefin compositions containing various voltage stabilizers |
| DE2139599A1 (en) * | 1971-08-03 | 1973-02-15 | Siemens Ag | Insulation for electric cables - esp high-tension cables based on polyolefin and contng tert amine |
| DE2234065A1 (en) * | 1972-07-07 | 1974-01-24 | Siemens Ag | Electric cable insulation - contg a polyolefin with a tetra alkyl diamino diaryl alkane as antioxidant |
| US5883178A (en) * | 1995-02-16 | 1999-03-16 | Chisso Corporation | Crystalline polyolefin resin composition and electrical insulating part comprising said composition |
| JPH11268145A (en) * | 1998-03-20 | 1999-10-05 | Toray Ind Inc | Electrically insulating film and capacitor using the same |
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| CN1708545A (en) | 2005-12-14 |
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