CN1738843A - Polymers with new sequence distributions - Google Patents
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- CN1738843A CN1738843A CNA2003801090310A CN200380109031A CN1738843A CN 1738843 A CN1738843 A CN 1738843A CN A2003801090310 A CNA2003801090310 A CN A2003801090310A CN 200380109031 A CN200380109031 A CN 200380109031A CN 1738843 A CN1738843 A CN 1738843A
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Abstract
The invention relates to new polymerization processes including diluents including hydrofluorocarbons and their use to produce novel polymers with new sequence distributions. In particular, the invention relates to copolymers of an isoolefin, preferably isobutylene, and a multiolefin, preferably a conjugated diene, more preferably isoprene, with new sequence distributions.
Description
The cross reference of related application
The application has required the provisional application No.60/435 that submitted on December 20th, 2002,60/479,081 the rights and interests of submitting to 17,60/464,187 and 2003 on the June of submitting on April 21st, 061,2003, and their disclosure is hereby incorporated by reference.
Invention field
The new polymerization process and their production that the present invention relates to comprise the thinner that comprises hydrogen fluorine carbon have the purposes of the new polymers of new sequence distribution.Especially, the present invention relates to isoolefine, preferred iso-butylene, with polyene hydrocarbon, preferred conjugated diolefine, more preferably isoprene, have a multipolymer that new sequence distributes.
Background
Isoolefin polymer prepares in carbon cation polymerization process.Isoprene-isobutylene rubber particularly importantly, it is an iso-butylene and the multipolymer of a small amount of isoprene.Isoprene-isobutylene rubber prepares by low temperature cationic polymerization process, and its general requirement iso-butylene has＞purity and the isoprene of 99.5wt% have＞and the purity of 98.0wt% is with preparation high molecular isoprene-isobutylene rubber.
The copolymerization of the carbon cation polymerization of iso-butylene and it and comonomer such as isoprene is complicated on mechanism.Referring to, for example,
Organic Chemistry, SIXTH EDITION, Morrison and Boyd, Prentice-Hall, 1084-1085, Englewood Cliffs, New Jersey 1992, and K.Matyjaszewski, ed,
Cationic Polymerizations, Marcel Dekker, Inc., New York, 1996.This catalyst system typically is made up of two-pack: initiator and Lewis acid.Lewis acidic example comprises AlCl
3And BF
3The example of initiator comprises Bronsted acid such as HCl, RCOOH (wherein R is an alkyl), and H
2O.In polymerization process, in being called a step that causes step, iso-butylene and Lewis acid/initiator produce carbon ion to reaction.Subsequently, additional monomeric unit is added on the formed carbon ion, this is commonly referred to as growth steps.These steps are typically carried out in thinner or solvent.Temperature, thinner polarity and counter ion all influence the chemical process of growth.In the middle of these, thinner is commonly referred to be important.
Generally accepted the widespread use of the slurry phase polymerisation process (producing isoprene-isobutylene rubber, polyisobutene etc.) in the thinner methyl chloride in the industry.Typically, polymerization process generally is lower than-90 ℃ widely at low temperatures, uses the thinner of methyl chloride as reaction mixture.Methyl chloride uses because of various reasons, comprising its dissolved monomer and aluminum chloride catalyst, but solvent polymerization produce product not.Methyl chloride also has suitable freezing point and boiling point, so as to allow respectively low temperature polymerization and effectively with polymkeric substance and unreacted monomer separation.Slurry phase polymerisation process in methyl chloride provides a plurality of attendant advantages: can be implemented in the polymer concentration of about 26%-37% volume in the reaction mixture, form contrast with the concentration about only 8%-12% in solution polymerization.Obtained the acceptable of polymer material, made heat of polymerization more effectively to remove by the surface heat exchange than low viscosity.Slurry phase polymerisation process in methyl chloride is used for the production of high molecular weight polyisobutylene and isobutylene-isoprene butyl rubber polymer.Similarly, the polyreaction of iso-butylene and p-methylstyrene also uses methyl chloride to carry out.Similarly, star-branched isoprene-isobutylene rubber also uses methyl chloride production.
Yet, exist a plurality of problems relevant with the polyreaction in methyl chloride, for example polymer beads is mutually coalescent and accumulate in trend on reactor wall, heat transfer surface, agitating vane and the agitator/pump in reactor.Along with temperature of reaction raises, coalescence rate improves apace.Agglomerate particles tendency adheres to all surface such as the reactor vent pipe that they contact and any heat transfer equipment (it is crucial, because must keep the low-temp reaction condition) that is used to remove the polymeric heat release goes up and growth and hardening on these surfaces.
The reactor that is purchased that is used to make these rubber has the volume of the high cycle rate that is provided by pump impeller typically for to rise to 30 liters thorough mixing formula container greater than 10.Polymerization and pump all produce heat, and in order to keep slurry at lesser temps, reactive system needs ability and removes heat.The example of this type of Continuous Flow stirred-tank reactor (" CFSTR ") sees US patent No.5, and 417,930, this patent is hereby incorporated by reference, and below generally is called " reactor " or " butyl reactor ".In these reactors, slurry utilizes the effect of pump and cycles through the pipeline of heat exchanger, and the boiling ethene at shell-side provides cooling effect simultaneously, and slurry temp is by boiling ethylene temperature, required heat flux and heat passage total-resistance decision.In the slurry side, heat-exchanger surface is the accumulating poly compound little by little, suppresses heat passage, and it will tend to cause that slurry temp raises.This has usually limited the actual slurry concentration that can use of 26-37 volume % for slurry, thinner and unreacted monomer cumulative volume in most of reactors.The solution in several pieces of patents of the problem of accumulation of polymer (as US patent No.2,534,698, US patent No.2,548,415, US patent No.2,644,809).Yet these patents solve and the coalescent relevant variety of problems of the polymer beads of implementing required suitability for industrialized production unsatisfactorily.
US patent No.2,534,698 especially disclose a kind of polymerization process of the bonded that comprises following two steps: iso-butylene and mixture with polyene hydrocarbon of 4-14 carbon atom/molecule are dispersed in the main body (body) of the material that contains the aliphatic hydrocrbon that fluorine replaces but less than therein dissolving largely, according to ratio be two/the a aliphatic hydrocrbon that under polymerization temperature, has the fluorine replacement of 1-5 carbon atom to 10 parts for the per molecule of liquid, carry out polymerization by the dispersed mixture that under the temperature between-20 ℃ and-164 ℃, allows iso-butylene and per molecule have the polyene hydrocarbon of 4-14 carbon atom to its application Friedel-Crafts catalyzer then.Yet ' the 698 suitable fluorocarbon of instruction will cause two-phase system, and wherein monomer, comonomer and catalyzer are insoluble to basically and make their use become difficult and unsatisfactory in the fluorocarbon.
US patent No.2,548,415 especially disclose the continuous polymerization method of preparation multipolymer, and its each step comprises: carry the materials flow of being made up of the isoprene of the iso-butylene of main ratio and less ratio continuously in polymerization reactor; Inclined to one side C2H4F2 C2H4F2 diluted mixture thing with 1/2 volume to 10 volume; Come the mixture of polymerization isobutylene-isoprene by the liquid stream that in reaction mixture, adds the previously prepared polymerizing catalyst of forming by the boron trifluoride that is dissolved in the inclined to one side C2H4F2 C2H4F2 continuously, holding temperature is between-40 ℃ and-103 ℃ in whole copolymerization ... has instructed as the boron trifluoride of lewis acid catalyst and its complex compound and 1 ' 415, and the 1-C2H4F2 C2H4F2 is as the use of preferred binding substances.This binding substances provides catalyzer, monomer and comonomer all to dissolve in system wherein and has still obtained the benefit of the polymkeric substance insoluble of height with acquisition minimizing reactor fouling.Yet boron trifluoride for various reasons rather than the preferred commercial catalysts of butyl polymer.
US patent No.2,644,809 have especially instructed the polymerization process that comprises the several steps that combines: the per molecule of main ratio is had the monoolefine of 4-8 carbon atom (comprising end value) and mix with the polyene hydrocarbon that per molecule than small proportion has 4-14 carbon atom (comprising end value), with the Refrigerant 12 that is selected from 1-10 volume (calculating) according to mixed olefins, methylene dichloride, Trichloromonofluoromethane, Dichloromonofluoromethane, liquid in dichloro tetrafluoro ethane and their mixture exists down with dissolved Friedel-Crafts polymerization catalyst gained mixture, wherein monoolefine and polyene hydrocarbon are dissolved in this liquid, carry out polyreaction then under the temperature between the freezing point of-20 ℃ and liquid.' 809 disclose Chlorofluorocarbons (CFCs) keeping ideal slurry characteristic and at utmost reducing use on the reactor fouling, have also instructed the introducing by the diolefine that interpolation realized (being isoprene) of Chlorofluorocarbons (CFCs) (CFC).CFC is known to be ozone-depleting type chemical.Yet government regulations is controlled manufacturing and the distribution of CFC closely, makes these materials have no attraction for industrial operation.
In addition, Thaler, W.A., Buckley, Sr., D.J., HighMolecular-Weight, High Unsaturation Copolymers of Isobutyleneand Conjugated Dienes, 49 (4) Rubber Chemical Technology, 960 (1976), especially disclose iso-butylene and isoprene (isoprene-isobutylene rubber) and with the cation emulsion polyreaction of multipolymer in heptane of cyclopentadiene.
Therefore, seeking the blend that substitutes thinner or thinner is ideal to produce the novel polymeric system that can reduce particles coalesce and/or reduce the amount of chlorinated hydrocarbons such as methyl chloride.This type of novel polymeric system will reduce particles coalesce and reactor fouling but the ability that can not damage processing parameter, condition or component and/or not sacrifice throughput/output and/or produce high molecular polymer.In addition, find that the novel polymer relevant with aforesaid method will help to satisfy the whole world to elastomeric more demands and/or new final application also is provided.
Hydrogen fluorine carbon (HFC) is some chemical that are used as environment amenable cooling agent at present.Because the ozone-depleting potentiality that they have extremely low (even zero).Their low-ozone consumes potentiality and is considered to lack chlorine relevant.HFC also typically has low inflammableness, particularly compares with chlorinated hydrocarbons with hydrocarbon.
Iso-butylene/isoprene copolymer closes reaction to carry out under various polymerizing conditions, comprising different monomer feed ratio, temperature, catalyzer and solvent or thinners.Many these class systems have been described.Referring to, for example,
Cationic Polymerizations of Olefins: A Critical Inventory, J.P.Kennedy, (10-12 and 86-137) Wiley-Interscience, New York, 1972 and
Carbocationic Polymerization, J.P.Kennedy, E.Marechal, Wiley-Interscience, New York, 1982.
The copolymerization of iso-butylene and isoprene carries out in solution and in slurry.The mixture that solution polymerization usually uses chlorinated hydrocarbons or hydro carbons and chlorinated hydrocarbons is as the solvent of monomer, catalyzer and prepared multipolymer.Typical example is chloric ethane/hexanes mixtures.At the slurry copolymerization, hydrochloric ether, methyl chloride is used as the solvent of monomer and catalyzer usually, but the multipolymer of being produced is insoluble in the thinner.
The influence that the sequence of prepared multipolymer distributes, monomeric unit is subjected to the inherent reactivity of polymerizing condition and employed comonomer along the sign of the arrangement of main polymer chain.The sequence of multipolymer distributes and can express according to the unitary combination of adjacent structure.For example, the characterized sequence of two kinds of monomeric units is known as diad.Three monomeric unit sequences are known as triad.Four monomeric unit sequences are known as four unit groups, and are like that.Demonstrate difference on having of preparing under the different condition multipolymer that identical comonomer introduces may distribute in their sequence, this can be expressed by the mark of the diad in copolymer chain (or triad, etc.).Sequence distribution and comonomer are introduced on the mathematics gets in touch each other by probability-statistics, and this is owing to the competition character of the chemical event that is involved in copolymerization.Helping a kind of parameter of the sign of this mutual relationship is reactivity ratio, i.e. homopolymerization increases the ratio of the rate constant of (addition same monomer) and cross propagation (addition different monomers).Have identical comonomer and introduce, usually demonstrate different physicalies but have the multipolymer that different sequences distributes.Referring to, for example
Chemical Microstructure of Polymer Chains, J.L.Koenig, Wiley-Interscience, New York, 1980 and
Polymer Sequence Determination:Carbon-13 NMR Method, J.C.Randall, AcademicPress, 1977.Extreme but understandable example is random and the contrast of the physical attribute of segmented copolymer.
Be known that generally conjugated diolefine is lower than iso-butylene on reactive behavior in the carbocation copolymerization system.In the middle of known linear conjugated diene, isoprene be with the diolefine that has more reactive behavior of iso-butylene copolymerization in a kind of.Express towards distributing with the sequence of prepared multipolymer of conjugated diolefine than this trend of low reaction activity.Under given multipolymer was formed, isoprene unit did not demonstrate the tendency of following other isoprene unit in copolymer chain.Therefore, compare with system with the comonomer that has more reactive behavior, BII (B=iso-butylene, I=isoprene), IIB and III triad mark are lower.
Usually in the mixture of chlorinated hydrocarbons or hydrocarbon and chlorinated hydrocarbons, carry out because iso-butylene/isoprene copolymer closes reaction, so the degree that the sequence distribution changes is quite limited.The expression of this restriction is determined by investigating the known response reactivity ratio of isoprene for iso-butylene/isoprene copolymer closes reaction.Referring to, for example, J.E.Puskas, " CarbocationicPolymerizations " in
Encyclopedia of Polymer Science and Technology, (DOI:10.1002/0471440264.pst 040) John Wiley﹠amp; Sons, New York, 2003.Value (the r of isoprene reactivity ratio under various polymerizing conditions
IP) drop under 1.4, show the triad mark (BII, IIB and III) of the obtainable isoprene heart placed in the middle of close limit in prepared multipolymer.Find that a kind of polymerization system that the triad mark of the isoprene heart placed in the middle of different concns wherein can prepare is that some multipolymers of introducing when being suitable for crosslink sites and functional group of preparation are needed under given comonomer introducing rate.
Other reference background document comprises WO 02/34794, and it discloses by using the free radical polymerisation process of hydrogen fluorine carbon.Other reference background document comprises DE 100 61 727 A, WO02/096964, and WO 00/04061, US patent No.5,624,878, US patent No.5,527,870 and US patent No.3,470,143.
General introduction of the present invention
The invention provides the new polymerization process that comprises the thinner that comprises hydrogen fluorine carbon and they and be used to produce purposes with new polymers that new sequence distributes.Especially, the invention provides and comprise isoolefine, preferred iso-butylene, with polyene hydrocarbon, preferred conjugated diolefine, more preferably isoprene, have a multipolymer that new sequence distributes.
Provide in the present invention to comprise isoolefine, preferred iso-butylene, with polyene hydrocarbon, preferred conjugated diolefine, more preferably isoprene, multipolymer, the multipolymer sequence that this multipolymer has by the following formula definition distributes:
F＝mA/(1+mA)
2
Wherein m is a multipolymer sequence distribution parameter; A is the molar ratio of polyene hydrocarbon and isoolefine in multipolymer; With F be isoolefine-polyene hydrocarbon-polyene hydrocarbon triad mark in multipolymer; Wherein m is greater than 1.5.
In previous embodiments, m can be greater than 2.0.
In previous embodiments, m can be greater than 2.5.
In previous embodiments, m can be greater than 3.5.
In another aspect of the present invention, the invention provides and comprise isoolefine, preferred iso-butylene, with polyene hydrocarbon, preferred conjugated diolefine, more preferably isoprene, multipolymer, the multipolymer sequence that this multipolymer has by the following formula definition distributes:
F＝mA/(1+mA)
2
Wherein m is a multipolymer sequence distribution parameter; A is the molar ratio of polyene hydrocarbon and isoolefine in multipolymer; With F be isoolefine-polyene hydrocarbon-polyene hydrocarbon triad mark in multipolymer; Wherein m is 1.10-1.25.
In previous embodiments, m can be 1.15 to 1.20.
In previous embodiments, m can be 1.15 to 1.25.
In previous embodiments, m can be about 1.20.
In another aspect of the present invention, the invention provides the multipolymer of producing by a kind of method, this method comprises allows isoolefine (preferred iso-butylene), polyene hydrocarbon (preferred conjugated diolefine, more preferably isoprene), one or more Lewis acids, one or more initiators contact with the thinner that comprises one or more hydrogen fluorine carbon (HFC); The multipolymer sequence that this multipolymer has by the following formula definition distributes:
F＝mA/(1+mA)
2
Wherein m is a multipolymer sequence distribution parameter; A is the molar ratio of polyene hydrocarbon and isoolefine in multipolymer; With F be isoolefine-polyene hydrocarbon-polyene hydrocarbon triad mark in multipolymer; Wherein m be greater than 1.5 or m be 1.10-1.25.
In previous embodiments, m can be greater than 2.0.
In previous embodiments, m can be greater than 2.5.
In previous embodiments, m can be greater than 3.5.
In previous embodiments, m can be 1.15 to 1.20.
In previous embodiments, m can be 1.15 to 1.25.
In previous embodiments, m can be about 1.20.
In any one of previous embodiments, this multipolymer can be formed the halo multipolymer by halo.
In any one of previous embodiments, when existing, the halo multipolymer is by chlorine or bromine institute halo.
In any one of previous embodiments, when existing, content of halogen is greater than 0.5wt%, based on the weight of halo multipolymer.
In any one of previous embodiments, when existing, content of halogen is 0.5wt%-3.0wt%, based on the weight of halo multipolymer.
In any one of previous embodiments, this multipolymer has the Mw greater than 50,000.
In any one of previous embodiments, this multipolymer has the Mw greater than 100,000.
In any one of previous embodiments, this multipolymer has the Mw greater than 500,000.
In any one of previous embodiments, this multipolymer has greater than 1,000,000 Mw.
In any one of previous embodiments, this multipolymer has the MWD greater than 2.
In any one of previous embodiments, this multipolymer has the MWD of 2-6.
In any one of previous embodiments, this multipolymer has at least 20 ± 5 mooney viscosity (ML 1+8,125 ℃, ASTM D 1646).
In any one of previous embodiments, this multipolymer has 20 ± 5 to 60 ± 5 mooney viscosity (ML 1+8,125 ℃, ASTM D 1646).
In any one of previous embodiments, this polyene hydrocarbon, or conjugated diolefine, or isoprene, when existing, content is greater than 0.5mol%.
In any one of previous embodiments, this polyene hydrocarbon, or conjugated diolefine, or isoprene, when existing, content is greater than 1.0mol%.
In any one of previous embodiments, this polyene hydrocarbon, or conjugated diolefine, or isoprene, when existing, content is greater than 2.5mol%.
In any one of previous embodiments, this polyene hydrocarbon, or conjugated diolefine, or isoprene, when existing, content is greater than 5.0mol%.
The present invention also provides and has comprised any one multipolymer and the blend that is selected from second kind of rubber at least a following these rubber in the previous embodiments: natural rubber, polyisoprene rubber, poly-(vinylbenzene-copolymerization-divinyl) rubber (SBR), polybutadiene rubber (BR), poly-(isoprene-copolymerization-divinyl) rubber (IBR), styrene isoprene butadiene rubber (SIBR) (SIBR), ethylene-propylene rubber(EPR) (EPR), ethylene-propylene-elastoprene (EPDM), polysulphide, iso-butylene/cyclopentadiene copolymer rubber, iso-butylene/methyl cyclopentadiene copolymer rubber, paracril, epoxypropane polymer, star-branched butyl rubber and halo star-branched butyl rubber, brominated butyl rubber, chlorinated butyl rubber, star-branched polyisobutene rubber, the butyl of star-branched bromination (polyisobutene/isoprene copolymer) rubber; Poly-(iso-butylene-copolymerization-p-methylstyrene) and halo poly-(iso-butylene-copolymerization-p-methylstyrene), halo gathers (iso-butylene-copolymerization-isoprene-copolymerization-p-methylstyrene), poly-(iso-butylene-copolymerization-isoprene-copolymerization-vinylbenzene), halo gathers (iso-butylene-copolymerization-isoprene-copolymerization-vinylbenzene), poly-(iso-butylene-copolymerization-isoprene-copolymerization-alpha-methyl styrene) halo poly-(iso-butylene-copolymerization-isoprene-copolymerization-alpha-methyl styrene) and their mixture.
The invention still further relates to a kind of polymerization process, comprise allowing one or more monomers, one or more Lewis acids and one or more initiators in the presence of the thinner that comprises one or more hydrogen fluorine carbon (HFC), contact under polymerizing condition in reactor.
In another embodiment, the present invention relates to the method for production polymer of monomers, be included in and allow monomer contact in the presence of hydrogen fluorine carbon thinner with Lewis acid in the reactor, wherein Lewis acid is not by chemical formula MX
3The compound of expression, wherein M is 13 family's metals, X is a halogen.
In one embodiment, the invention provides and be suitable for the polymerisation medium that one or more monomers of polymerization form polymkeric substance, this polymerisation medium comprises one or more Lewis acids, one or more initiators and comprise the thinner of one or more hydrogen fluorine carbon (HFC).
In another embodiment, the invention provides the polymerisation medium that is suitable for one or more monomers formation polymkeric substance of polymerization, this polymerisation medium comprises one or more Lewis acids and comprises the thinner of one or more hydrogen fluorine carbon (HFC); Wherein one or more Lewis acids are not by chemical formula MX
3The compound of expression, wherein M is that 13 family's metals and X are halogens.
In preferred embodiment, the polymerization process and the medium that are described in above any embodiment are produced polymkeric substance, the latter comprises (gathering) isobutylene homo, isobutylene-isoprene (isoprene-isobutylene rubber) multipolymer, iso-butylene and alkylstyrene copolymers and star-branched butyl rubber terpolymer.
Accompanying drawing
Fig. 1 is the graphic representation of the relation between specific inductivity and temperature.
Fig. 2 is that the thinner quality is drawn and the relevant graphic representation of the volume fraction of hydrogen fluorine carbon in methyl chloride.
Fig. 3 is the peak molecular weight (M of some polymkeric substance of the present invention as described herein
p) with respect to the graphic representation of monomer conversion.
Fig. 4 is at BII triad fractional percentage value and is introduced in the diagram of the relation between the mol%IP in the multipolymer.
Be described in detail
Each specific embodiment of the present invention, version and embodiment are described now, comprising in order to understand preferred embodiment of the present invention and the definition that comes requirement as right. In order to determine aggressive behavior, the scope of " invention " refer in the claims any one or a plurality of, comprising their equivalent, and key element or with listed those restrictions that are equal to.
For the present invention and its claim, the term catalyst system refers to and comprises that (as described here) is used for any lewis acid or other metal complex of the polymerisation of catalysis olefinic monomer of the present invention, and at least a initator, and optional other a small amount of catalytic component.
In one embodiment, the invention provides and be suitable for the polymerisation medium that one or more monomers of polymerization form polymer, this polymerisation medium comprises one or more lewis acids, one or more initators, and comprises the diluent of one or more HFCs (HFC).
In another embodiment, the invention provides the polymerisation medium that is suitable for one or more monomers formation polymer of polymerization, this polymerisation medium comprises one or more lewis acids and comprises the diluent of one or more HFCs (HFC); Wherein one or more lewis acids are not by chemical formula MX3The compound of expression, wherein M is that 13 family's metals and X are halogens.
This phrase " be suitable for polymerization single polymerization monomer and form polymer " relates to, and in order to realize required polymerization the production of material according to technological parameter described here and component property, the selection of polymerizing condition and component is within those skilled in the art's the limit of power. Have a lot of changes of polymerization and the variation on polymeric component, these can be used for obtaining desirable polymer attribute. In preferred embodiments, this base polymer comprises the polyisobutene homopolymers, isobutylene-isoprene (butyl rubber) copolymer, isobutene and p-methylstyrene copolymer, and star-branched butyl rubber terpolymer.
Diluent refers to dilution or lytic agent. Diluent is defined as particularly comprising and can be used as lewis acid, the chemicals of the solvent of other metal complex, initator, monomer or other additive as described herein. In enforcement of the present invention, diluent can not change the component of polymerisation medium, i.e. the component of catalyst system, the general aspects of monomer etc. Yet, must recognize the interaction that can occur between diluent and the reactant. In preferred embodiments, diluent does not react at any significance degree with catalyst system component, monomer etc. In addition, the term diluent comprises at least mixture of two or more diluents.
Reactor is any container that chemical reaction occurs.
Slurry refers to the diluent (comprising the monomer that precipitates from diluent) of certain volume, monomer, lewis acid, and initator. Slurry concentration is that the Polymers that partially or even wholly precipitates is in the percentage by volume of slurry cumulative volume.
The new numbering plan of each family of the periodic table of elements that here uses with at CHEMICAL AND ENGINEERING NEWS, similarly use in 63 (5), 27 (1985).
Polymer can be used to refer to homopolymers, copolymer, and interpretation, terpolymer, etc. Similarly, copolymer can refer to comprise at least two kinds of monomers, the optional polymer that other monomer is arranged.
When polymer referred to comprise monomer, monomer was to be present in the polymer with the polymerized form of monomer or with the derivative form of monomer. Similarly, when catalytic component was described to comprise the component of indifferent equilibrium form, this component that those skilled in the art understand ionic species was the form that obtains polymer with monomer reaction.
Isoalkene refers to have two substituent any olefinic monomers at same carbon atom.
Polyene refers to have any monomer of two two keys. In preferred embodiments, this polyene is any monomer that comprises two conjugated double bonds.
The elastomer that here uses or elastic composition refer to any polymer consistent with ASTM D1566 definition or the composition of polymer. This term can use interchangeably with " rubber " that here uses.
Alkyl refers to seize one or more hydrogen from the structural formula of alkane and the alkane group of deriving from this alkane, for example, and methyl (CH3), or ethyl (CH3CH
2) etc.
Aryl refers to consist of for example benzene of aromatic compounds, naphthalene, and phenanthrene, the ring structure characteristic of anthracene etc., and typically in its structure, have the alkyl of two keys (" unsaturated ") alternately. Therefore aryl is the group of deriving from this aromatic compounds by seize one or more hydrogen from the structural formula of aromatic compounds, for example, and phenyl, or C6H
5。
" replacement " refers to that at least one hydrogen group is replaced by at least one substituting group, and this substituting group is selected from, for example, and halogen (chlorine, bromine, fluorine, or iodine), amino, nitro, sulphur oxygen base (sulfonate radical or alkyl azochlorosulfonate), mercaptan, alkyl hydrosulfide, and hydroxyl; Have the straight or branched alkyl of 1-20 carbon atom, it comprises methyl, ethyl, propyl group, the tert-butyl group, isopropyl, isobutyl group etc.; Alkoxyl has the straight or branched alkoxyl of 1-20 carbon atom, and comprises, for example, and methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, amoxy, isoamoxy, own oxygen base, heptan the oxygen base, octyloxy, the ninth of the ten Heavenly Stems oxygen base, and the last of the ten Heavenly stems oxygen base; Haloalkyl, it refers to the straight or branched alkyl with 20 carbon atoms of 1-that replaced by at least one halogen, and comprises, for example, chloromethyl, bromomethyl, methyl fluoride, iodomethyl, 2-chloroethyl, 2-bromoethyl, the 2-fluoro ethyl, 3-chloropropyl, 3-bromopropyl, 3-fluoropropyl, 4-chlorobutyl, 4-fluorine butyl, dichloromethyl, two bromomethyls, difluoromethyl, diiodomethyl, 2,2-Dichloroethyl, 2,2-, two bromomethyls, 2,2-two fluoro ethyls, 3,3-, two chloropropyls, 3,3-two fluoropropyls, 4,4-, two chlorobutyls, 4,4-difluoro butyl, trichloromethyl, 4,4-difluoro butyl, trichloromethyl, trifluoromethyl, 2,2, the 2-trifluoroethyl, 2,3,3-trifluoro propyl, 1,1,2,2-tetrafluoro ethyl, with 2,2,3,3-tetrafluoro propyl group. Therefore, for example, " styrene units of replacement " comprises p-methylstyrene, p-ethyl styrene etc.
In one embodiment, the present invention relates to the blend of HFC or HFC and hydrocarbon and/or chlorohydrocarbon for the production of the purposes of polymer slurries, this slurry is less scaling (namely, in reaction vessel, also observe and more resemble particle glassy, less viscosity, to chamber wall or less to the adhesion of stirrer paddle, and reduced coalescent between particle and the particle). More particularly, the blend that the present invention relates to HFC diluent or HFC diluent and hydrocarbon and/or chlorohydrocarbon is used for isoalkene and diene and/or ring-alkylated styrenes polymerization and combined polymerization significantly having reduced reactor fouling with the purposes of production isoolefin homopolymer and copolymer. In addition, the blend that the present invention relates to HFC diluent or HFC diluent and hydrocarbon and/or chlorohydrocarbon is used for isoalkene and diene polymerization and the combined polymerization purposes with the production isoolefin copolymers, compare with common system, significantly reduced reactor fouling and so that reactor has the service life of prolongation.
In another embodiment, HFC is used for tubular reactor and reduces the accumulation of polymer on stirrer paddle at the accumulation of polymer on the heat transfer tubes and/or minimizing, therefore obtains longer service life.
In another embodiment, the tubular reactor that this HFC is used for higher temperature with larger running time length (as comparing with time span possible for other halogenated hydrocarbons, greater than 15 hours, be preferably greater than 20 hours, be preferably greater than 30 hours, more preferably greater than 48 hours) the production polymer.
HFC is used for the boiling pool reactor from refrigeration in another embodiment, wherein removes heat with minimizing reactor wall incrustation by the evaporation of diluent and monomer mixture, and especially reduces agitator/blade incrustation.
In a further preferred embodiment, compare under same temperature with when using other halogenated hydrocarbons, HFC is used for polymerization and obtains more HMW.
In one embodiment, the present invention relates to use the discovery of the new paradigmatic system of the diluent that contains HFC. These diluents effectively dissolve selected catalyst system with monomer but are relative weak solvent for polymer product. The paradigmatic system of using these diluents be difficult for because polymer beads each other coalescent and they be gathered on the polymerization hardware and fouling. In addition, the present invention relate in addition these diluents in paradigmatic system under those polymerization temperatures that are equal to or higher than when using chlorohydrocarbon diluent only such as chloromethanes the purposes of preparation high molecular polymer and copolymer.
In another embodiment, the present invention relates to use the discovery of the new paradigmatic system of fluoridizing aliphatic hydrocarbon that can the catalyst-solvent system. These paradigmatic systems are also beneficial for the production of isoalkene slurry polymerization and the polymer slurries that is difficult for incrustation, allow simultaneously the dissolving of monomer, comonomer and commercial preferred aluminum alkyl halide catalyst. In addition, the present invention relates to these diluents are compared under higher polymerization temperature preparation high molecular polymer and copolymer with the paradigmatic system of only using chlorohydrocarbon diluent such as chloromethanes purposes in addition.
In another embodiment, the present invention relates to the preparation of isoolefin homopolymer and copolymer, especially need butyl rubber and the isobutene-needed polymerisation of p-alkylstyrene copolymers of production isobutylene-isoprene form. More particularly, the present invention relates to the method for blend by using HFC diluent or HFC and chlorohydrocarbon diluent (resembling chloromethanes) polymerization and combined polymerization isoalkene in slurry phase polymerisation process.
In another embodiment, paradigmatic system of the present invention is used for isomonoolefin and the p-ring-alkylated styrenes monomer that combined polymerization has 4-7 carbon atom. According to the preferred embodiments of the invention, system's production contains isoalkene such as the p-ring-alkylated styrenes of isobutene and about 0.5-20wt% such as the copolymer of p-methylstyrene of the 80-99.5wt% that has an appointment. Yet according to another embodiment, when also producing the material of glassy or plasticity, this copolymer comprises isoalkene or the isobutene of about 10-99.5wt%, and p-ring-alkylated styrenes such as the p-methylstyrene of about 0.5-90wt%.
In preferred embodiments, the present invention relates to produce the method for polymer of the monomer of cationic polymerizable, be included in and allow monomer, lewis acid and initator in the reactor in the presence of diluent, at 0 ℃ or lower, preferably-10 ℃ or lower, preferably-20 ℃ or lower, preferably-30 ℃ or lower, preferred-40 ℃ or lower, preferred-50 ℃ or lower, preferably-60 ℃ or lower, preferably-70 ℃ or lower, preferred-80 ℃ or lower, preferred-90 ℃ or lower, preferably-100 ℃ or lower, preferred 0 ℃ contacts under the freezing point temperature of polymerisation medium such as diluent and monomer mixture.
Monomer and polymer
Can be comprised by the monomer of this system's polymerization any hydrocarbon monomer that can come with the present invention polymerization. Preferred monomer comprises alkene, alpha-olefin, dibasic alkene, isoalkene, conjugated diene, non-conjugated diene, the phenylethylene of phenylethylene and/or replacement and in the vinyl ethers one or more. Phenylethylene can (on ring) by alkyl, aryl, halide or alkoxide replace. Preferably, this monomer contains 2-20 carbon atom, more preferably 2-9 carbon atom, more preferably 3-9 carbon atom. The example of preferred alkene comprises styrene, p-ring-alkylated styrenes, p-methylstyrene, AMS, divinylbenzene, di isopropenylbenzene, isobutene, 2-methyl-1-butene alkene, 3-methyl-1-butene, 2-methyl-2-amylene, isoprene, butadiene, 2,3-dimethyl-1,3-butadiene, nopinene, laurene, 6,6-dimethyl-fulvene, hexadiene, cyclopentadiene, piperylene, methyl vinyl ether, ethyl vinyl ether, and isobutylvinyl ether etc. Monomer also can be the bond of two or more monomers. SBC also can be used as monomer. Preferred block copolymer comprises phenylethylene such as styrene, p-methylstyrene, AMS, and C4-C
30Alkadienes, such as isoprene, the copolymer of butadiene etc. Particularly preferred monomer bond comprises 1) isobutene and p-methylstyrene, 2) isobutene and isoprene, and the homopolymers of isobutene.
In addition, preferred monomer comprises and is described in Cationic Polymerization of Olefins, A Critical Inventory, Joseph Kennedy, Wiley Interscience, those monomers of the cationic polymerizable of describing among the New York 1975. Monomer comprises any monomer of cationic polymerizable, if make those monomers at cationic stabilized or expansion center, because this monomer contains electron donating group. See also Cationic Polymerization of Olefins, A Critical Inventory, Joseph Kennedy, Wiley Interscience, New York 1975 for discussing in detail of cation catalysis.
This monomer is to be present in the polymerisation medium with the amount in the 75wt%-0.01wt% scope in one embodiment, 60wt%-0.1wt% additionally, 40wt%-0.2wt% additionally, 30-0.5wt% additionally, 20wt%-0.8wt% additionally, and 15wt%-1wt% in another embodiment additionally.
Preferred polymer is included in any homopolymers in those monomers of listing in this section. The example of homopolymers comprises polyisobutene, poly-p-methylstyrene, polyisoprene, polystyrene, poly alpha methylstyrene, polyvingl ether (such as polymethyl vinyl ether, poly-ethyl vinyl ether).
Preferred polymer also comprises 1) copolymer of isobutene and ring-alkylated styrenes; With 2) copolymer of isobutene and isoprene.
Butyl polymer is by allowing monomer mixture for copolymerization react to prepare in one embodiment, and this mixture has at least (1) C4-C
6Isoalkene monomer component such as isobutene and (2) polyene or conjugate diene monomer component. Isoalkene is in one embodiment in accounting for the 70-99.5wt% scope of total copolymerization monomer mixture, and in another embodiment in 85-99.5 wt% scope. This isoalkene is in the 92-99.5wt% scope in another embodiment. The conjugated diene component is with the amount of 30-0.5wt% in one embodiment, and is present in the copolymerized monomer mixture with the amount of 15-0.5wt% in another embodiment. In another embodiment, the 8-0.5wt% of monomer mixture for copolymerization is conjugated diene. C4-C
6Isoalkene can be isobutene, 2-methyl-1-butene alkene, 3-methyl-1-butene, 2-methyl-2-butene, and in the 4-methyl-1-pentene one or more. Polyene can be C4-C
14Conjugated diene, such as isoprene, butadiene, 2,3-dimethyl-1,3-butadiene, nopinene, laurene, 6,6-dimethyl-fulvene, hexadiene, cyclopentadiene and piperylene. An example of butyl rubber polymer of the present invention is by the isobutene of 85-99.5wt% and the reaction of 15-0.5wt% isoprene, or reacts to obtain by 95-99.5wt% isobutene and 5.0wt%-0.5wt% isoprene in another embodiment. Following table illustrates above referenced wt% and how to be expressed as mol%.
| Wt％IC4 a | mol％IC4 | wt％IC5 b |
|
| 70 | 73.9 | .5 | .4 |
| 85 | 87.3 | 5 | 4.2 |
| 92 | 93.3 | 8 | 6.7 |
| 95 | 95.9 | 15 | 12.7 |
| 99.5 | 99.6 | 30 | 26.1 |
The a.IC4-isobutene
The b.IC5-isoprene
For the purposes of the present invention, describe and characterized by copolymer sequence distributed constant m by copolymer sequence distribution equation formula as described below at three unit number of components of isoalkene and polyene and the relation that is introduced between the mol% of the polyene in the copolymer.
F＝mA/(1+mA)
2
Wherein: m is the copolymer sequence distributed constant,
A is the molar ratio of polyene and isoalkene in copolymer, and
F is isoalkene-polyene in copolymer-polyene three unit number of components.
This equational best fit has obtained the m value of isoalkene and the copolymerization of polyene in various diluents.
In certain embodiments, m is greater than 1.5; Additionally, greater than 2.0; Additionally, greater than 2.5; Additionally, greater than 3.0; Additionally, greater than 3.5.
In other embodiments, m is 1.10 to 1.25; Additionally, 1.15 to 1.20; Additionally, 1.15 to 1.25; Additionally, m is about 1.20.
The invention further relates to the terpolymer and the tetrapolymer that comprise above listed monomeric any binding substances.Preferred terpolymer and tetrapolymer comprise the polymkeric substance that comprises iso-butylene, isoprene and Vinylstyrene, the polymkeric substance that comprises iso-butylene, right-ring-alkylated styrenes (preferred p-methylstyrene) and isoprene, comprise cyclopentadiene, iso-butylene and to the polymkeric substance of ring-alkylated styrenes (preferred p-methylstyrene), the polymkeric substance of iso-butylene, cyclopentadiene and isoprene, the polymkeric substance that comprises cyclopentadiene, iso-butylene and methyl cyclopentadiene comprises the polymkeric substance of iso-butylene, p-methylstyrene and cyclopentadiene.
Lewis acid
Lewis acid (being also referred to as aided initiating or catalyzer) can be with the metal of the 4th, 5,13,14 and 15 families of the periodic table of elements in preferred embodiments, comprises boron, aluminium, and gallium, indium, titanium, zirconium, tin, vanadium, arsenic, antimony, and bismuth are any Lewis acid on basis.Those of skill in the art will appreciate that some elements are more suitable in enforcement of the present invention.In one embodiment, this metal is an aluminium, boron and titanium, and wherein aluminium is ideal.The example of illustrative comprises AlCl
3, (alkyl) AlCl
2, (C
2H
5)
2AlCl and (C
2H
5)
3Al
2Cl
3, BF
3, SnCl
4, TiCl
4In particularly preferred embodiments, BF
3It or not selected Lewis acid.
4,5 and 14 family's Lewis acids have formula M X
4Wherein M is 4,5 or 14 family's metals; With X is to be independently selected from fluorine, chlorine, the halogen in bromine and the iodine, preferred chlorine.X also can be a pseudohalogen.For the present invention and its claim, pseudohalogen is defined as azido-(azide), isocyano, thiocyanate ion, isosulfocyanate radical or cyanogen root.Non-limitative example comprises titanium tetrachloride, titanium tetrabromide, vanadium tetrachloride, tin tetrachloride and zirconium tetrachloride.4,5 or 14 family's Lewis acids also can contain the halogen more than a type.Non-limitative example comprises the monobromo titanous chloride, dibromo titanium dichloride, monobromo vanadium trichloride and a chlorine three Tin tetrafluoride .s.
Can be used for 4,5 and 14 family's Lewis acids of the present invention and also can have formula M R
nX
4-nWherein M is 4,5 or 14 family's metals; Wherein R is selected from C
1-C
12Alkyl, aryl, arylalkyl, the monovalence alkyl in alkylaryl and the group of naphthene base; With n be 0 to 4 just; X is independently selected from fluorine, chlorine, the halogen in bromine and the iodine, preferred chlorine.X also can be a pseudohalogen.For the present invention and its claim, pseudohalogen is defined as azido-, isocyano, thiocyanate ion, isosulfocyanate radical or cyanogen root.Term " arylalkyl " refers to contain the group of aliphatic series and aromatic structure, and base is on the alkyl position.Term " alkylaryl " refers to contain the group of aliphatic series and aromatic structure, and base is on the aryl position.These lewis acidic non-limitative examples comprise the benzyl titanous chloride, dibenzyl titanium dichloride, benzyl tri-chlorination zirconium, dibenzyl dibrominated zirconium, methyl titanous chloride, dimethyl bifluoride titanium, dimethyltin chloride and phenyl vanadium trichloride.
4,5 and 14 family's Lewis acids in can be used for inventing also can have formula M (RO)
nR '
mX
4 (m+n)Wherein M is 4,5 or 14 family's metals, and wherein RO is selected from C
1-C
30Monovalence-oxyl in alkoxyl group, aryloxy, alkoxy aryl, the alkyl-aryloxy; R ' is the C that is selected from as defined above
1-C
12Alkyl, aryl, arylalkyl, the monovalence alkyl in alkylaryl and the cycloalkyl; N is the integer of 0-4 and the integer that m is 0-4, requires the summation of n and m to be no more than 4; X is the halogen that is independently selected from fluorine, chlorine, bromine and the iodine, preferred chlorine.X also can be a pseudohalogen.For the present invention and its claim, pseudohalogen is defined as azido-, isocyano, thiocyanate ion, isosulfocyanate radical or cyanogen root.For purpose of the present invention, those of skill in the art will recognize that this term alkoxyl group and aryloxy structurally are equal to alkoxide and phenates respectively.Term " alkoxy aryl " refers to contain the group of aliphatic series and aromatic structure, and base is on the alkoxyl group position.Term " alkyl-aryloxy " refers to contain the group of aliphatic series and aromatic structure, and base is on the aryloxy position.These lewis acidic non-limitative examples comprise the methoxyl group titanous chloride, n-butoxy titanous chloride, two (isopropoxy) titanium dichloride, the phenoxy group titanium tribromide, phenyl methoxyl group zirconium trifluoride, methyl methoxy base titanium dichloride, methyl methoxy base tindichloride and benzyl isopropoxy vanadous chloride.
Can be used for 4 among the present invention, 5 and 14 family's Lewis acids also can have formula M (RC=OO)
nR '
mX
4-(m+n)Wherein M is 4,5 or 14 family's metals; Wherein RC=OO is selected from C
2-C
30Monovalence alkyl acyloxy in alkyl acyloxy, aryl acyloxy, arylalkyl acyloxy, the alkylaryl acyloxy; R ' is the C that is selected from as defined above
1-C
12Alkyl, aryl, arylalkyl, the monovalence alkyl in alkylaryl and the cycloalkyl; N is the integers that 0 to 4 integer and m are 0-4, requires the summation of n and m to be no more than 4; X is independently selected from fluorine, chlorine, the halogen in bromine and the iodine, preferred chlorine.X also can be a pseudohalogen.For the present invention and its claim, pseudohalogen is defined as azido-, isocyano, thiocyanate ion, isosulfocyanate radical or cyanogen root.Term " arylalkyl acyloxy " refers to contain the group of aliphatic series and aromatic structure, and base is on the alkyl acyloxy position.Term " alkylaryl acyloxy " refers to contain the group of aliphatic series and aromatic structure, and base is on aryl acyloxy position.These lewis acidic non-limitative examples comprise the acetoxyl group titanous chloride, benzoyloxy tribromide zirconium, benzoyloxy titanium trifluoride, different propionyloxy tin trichloride, methyl acetoxyl group titanium dichloride and benzyl benzoyloxy vanadium chloride.
The 5 family's Lewis acids that can be used among the present invention also have formula M OX
3Wherein M is 5 family's metals; Wherein X is independently selected from fluorine, chlorine, the halogen in bromine and the iodine, preferred chlorine.Non-limitative example is a vanadylic chloride.
The 13 family's Lewis acids that can be used among the present invention have formula M X
3Wherein M is that 13 family's metals and X are independently selected from fluorine, chlorine, the halogen in bromine and the iodine, preferred chlorine.X also can be a pseudohalogen.For the present invention and its claim, pseudohalogen is defined as azido-, isocyano, thiocyanate ion, isosulfocyanate radical or cyanogen root.Non-limitative example comprises aluminum chloride, boron trifluoride, gallium trichloride and indium trifluoride.
Can be used for 13 family's Lewis acids of the present invention and also can have general formula: MR
nX
3-n, wherein M is 13 family's metals; R is selected from C
1-C
12Alkyl, aryl, arylalkyl, the monovalence alkyl in alkylaryl and the cycloalkyl; With n be 0 to 3 integer; X is independently selected from fluorine, chlorine, the halogen in bromine and the iodine, preferred chlorine.X also can be a pseudohalogen.For the present invention and its claim, pseudohalogen is defined as azido-, isocyano, thiocyanate ion, isosulfocyanate radical or cyanogen root.Term " arylalkyl " refers to contain the group of aliphatic series and aromatic structure, and base is on the alkyl position.Term " alkylaryl " refers to contain the group of aliphatic series and aromatic structure, and base is on the aryl position.These lewis acidic non-limitative examples comprise ethylaluminum dichloride, methylaluminum dichloride, benzyl al dichloride, the isobutyl-gallium dichloride, diethyl aluminum chloride, dimethylaluminum chloride, ethyl aluminium sesqui chloride, aluminium trimethide sesquichloride, trimethyl aluminium and triethyl aluminum.
13 family's Lewis acids in can be used for inventing also can have formula M (RO)
nR '
mX
3-(m+n)Wherein M is 13 family's metals, and wherein RO is selected from C
1-C
30Monovalence-oxyl in alkoxyl group, aryloxy, alkoxy aryl, the alkyl-aryloxy; R ' is the C that is selected from as defined above
1-C
12Alkyl, aryl, arylalkyl, the monovalence alkyl in alkylaryl and the cycloalkyl; N is the number of 0-3 and the number that m is 0-3, requires the summation of n and m to be no more than 3; X is the halogen that is independently selected from fluorine, chlorine, bromine and the iodine, preferred chlorine.X also can be a pseudohalogen.For the present invention and its claim, pseudohalogen is defined as azido-, isocyano, thiocyanate ion, isosulfocyanate radical or cyanogen root.For purpose of the present invention, those of skill in the art will recognize that this term alkoxyl group and aryloxy structurally are equal to alkoxide and phenates respectively.Term " alkoxy aryl " refers to contain the group of aliphatic series and aromatic structure, and base is on the alkoxyl group position.Term " alkyl-aryloxy " refers to contain the group of aliphatic series and aromatic structure, and base is on the aryloxy position.These lewis acidic non-limitative examples comprise the methoxyl group al dichloride, oxyethyl group al dichloride, 2,6-two-tertiary butyl phenoxy group al dichloride, methoxymethyl aluminum chloride, 2,6-two-tertiary butyl phenoxymethyl aluminum chloride, isopropoxy gallium dichloride and phenoxymethyl indium.
13 family's Lewis acids in can be used for inventing also can have formula M (RC=OO)
nR '
mX
3-(m+n)Wherein M is 13 family's metals, and wherein RC=OO is selected from C
2-C
30Monovalence hydrocarbon acyl group in alkyl acyloxy, aryl acyloxy, arylalkyl acyloxy, the alkylaryl acyloxy; R ' is the C that is selected from as defined above
1-C
12Alkyl, aryl, arylalkyl, the monovalence alkyl in alkylaryl and the cycloalkyl; N is the number of 0-3 and the number that m is 0-3, requires the summation of n and m to be no more than 3; X is the halogen that is independently selected from fluorine, chlorine, bromine and the iodine, preferred chlorine.X also can be a pseudohalogen.For the present invention and its claim, pseudohalogen is defined as azido-, isocyano, thiocyanate ion, isosulfocyanate radical or cyanogen root.Term " arylalkyl acyloxy " refers to contain the group of aliphatics and aromatic structure, and free radical is on the alkyl acyloxy position.Term " alkylaryl acyloxy " refers to contain the group of aliphatic series and aromatic structure, and base is on aryl acyloxy position.These lewis acidic non-limitative examples comprise the acetoxyl group al dichloride, benzoyloxy aluminum dibromide, benzoyloxy bifluoride gallium, methyl acetoxyl group aluminum chloride and different propionyloxy Indium-111 chloride.
15 family's Lewis acids have formula M X
y, wherein M is that 15 family's metals and X are independently selected from fluorine, chlorine, and the halogen in bromine and the iodine, preferred chlorine and y are 3,4 or 5.X also can be a pseudohalogen.For the present invention and its claim, pseudohalogen is defined as azido-, isocyano, thiocyanate ion, isosulfocyanate radical or cyanogen root.Non-limitative example comprises six antimony chlorides, antimony hexafluoride, and arsenic pentafluoride.15 family's Lewis acids also can contain the halogen more than a type simultaneously.Non-limitative example comprises the monochlor(in)ate antimony pentafluoride, arsenous fluoride, and Trichlorobismuthine and tetrachloro are fluoridized arsenic.
Can be used for 15 family's Lewis acids of the present invention and also can have formula M R
nX
Y-nWherein M is 15 family's metals; Wherein R is selected from C
1-C
12Alkyl, aryl, arylalkyl, the monovalence alkyl in alkylaryl and the cycloalkyl; With n be 0 to 4 integer; Y 3,4 or 5 requires n less than y; X is independently selected from fluorine, chlorine, the halogen in bromine and the iodine, preferred chlorine.X also can be a pseudohalogen.For the present invention and its claim, pseudohalogen is defined as azido-, isocyano, thiocyanate ion, isosulfocyanate radical or cyanogen root.Term " arylalkyl " refers to contain the group of aliphatic series and aromatic structure, and base is on the alkyl position.Term " alkylaryl " refers to contain the group of aliphatic series and aromatic structure, and base is on the aryl position.These lewis acidic non-limitative examples comprise tetraphenylphosphonichloride chloride antimony and triphenyl antimony butter.
15 family's Lewis acids in can be used for inventing also can have formula M (RO)
nR '
mX
Y-(m+n)Wherein M is 15 family's metals, and wherein RO is selected from C
1-C
30Monovalence-oxyl in alkoxyl group, aryloxy, alkoxy aryl, the alkyl-aryloxy; R ' is the C that is selected from as defined above
1-C
12Alkyl, aryl, arylalkyl, the monovalence alkyl in alkylaryl and the cycloalkyl; N is that the integer of 0-4 and integer and y that m is 0-4 are 3,4 or 5, and the summation that requires n and m is less than y; X is the halogen that is independently selected from fluorine, chlorine, bromine and the iodine, preferred chlorine.X also can be a pseudohalogen.For the present invention and its claim, pseudohalogen is defined as azido-, isocyano, thiocyanate ion, isosulfocyanate radical or cyanogen root.For purpose of the present invention, those of skill in the art will recognize that this term alkoxyl group and aryloxy structurally are equal to alkoxide and phenates respectively.Term " alkoxy aryl " refers to contain the group of aliphatic series and aromatic structure, and base is on the alkoxyl group position.Term " alkyl-aryloxy " refers to contain the group of aliphatic series and aromatic structure, and base is on the aryloxy position.These lewis acidic non-limitative examples comprise tetrachloro methoxyl group antimony, dimethoxy trichlorine antimony, dichloro methoxyl group arsine, chlorine dimethoxy arsenic, and difluoro-methoxy arsenic.
15 family's Lewis acids in can be used for inventing also can have formula M (RC=OO)
nR '
mX
Y-(m+n)Wherein M is 15 family's metals, and wherein RC=OO is selected from C
2-C
30Monovalence alkylacyloxy in alkyl acyloxy, aryl acyloxy, arylalkyl acyloxy, the alkylaryl acyloxy; R ' is the C that is selected from as defined above
1-C
12Alkyl, aryl, arylalkyl, the monovalence alkyl in alkylaryl and the cycloalkyl; N is that the integer of 0-4 and integer and y that m is 0-4 are 3,4 or 5, and the summation that requires n and m is less than y; X is the halogen that is independently selected from fluorine, chlorine, bromine and the iodine, preferred chlorine.X also can be a pseudohalogen.For the present invention and its claim, pseudohalogen is defined as azido-, isocyano, thiocyanate ion, isosulfocyanate radical or cyanogen root.Term " arylalkyl acyloxy " refers to contain the group of aliphatic series and aromatic structure, and base is on the alkyl acyloxy position.Term " alkylaryl acyloxy " refers to contain the group of aliphatic series and aromatic structure, and base is on aryl acyloxy position.These lewis acidic non-limitative examples comprise acetate moiety four antimony chlorides, (benzoate anion) four antimony chlorides and chlorination bismuth acetate.
Particularly preferred Lewis acid can be any in those Lewis acids that can be used in the cationoid polymerisation of isobutylene copolymers, comprise: aluminum chloride, aluminium tribromo-compound, ethylaluminum dichloride, trichlorine triethyl two aluminium, diethyl aluminum chloride, methylaluminum dichloride, aluminium trimethide sesquichloride, dimethylaluminum chloride, boron trifluoride, titanium tetrachloride or the like, wherein ethylaluminum dichloride and trichlorine triethyl two aluminium are preferred.
The weak coordinate Lewis acid such as the B (C of Lewis acid such as methylaluminoxane (MAO) and specially design
6F
5)
3Also be suitable Lewis acid within the scope of the present invention.
Initiator
Can be used for initiator of the present invention is those initiators that can form title complex in suitable diluent with selected Lewis acid coordination, and it has formed the polymer chain of continuous growth apace with olefine reaction.The example of illustrative comprises Bronsted acid, as H
2O, HCl, RCOOH (wherein R is an alkyl), and alkylogen are as (CH
3)
3CCl, C
6H
5C (CH
3)
2Cl and (2-chloro-2,4,4-trimethylpentane).Recently, transition metal complex is as metallocenes and other this type of material, as can be used to cause isobutene polymerisation as the material of single site catalyst system when being activated with weak coordinate Lewis acid or lewis acid.
In one embodiment, this reactor and this catalyst system are substantially free of water.Be substantially free of water and be defined as being lower than 30ppm (based on the gross weight of catalyst system), preferably be lower than 20ppm, preferably be lower than 10ppm, preferably be lower than 5ppm, preferably be lower than 1ppm.Yet when water was selected as initiator, it was added in the catalyst system, with greater than 30ppm, was preferably greater than 40ppm and even had (based on the gross weight of catalyst system) more preferably greater than the amount of 50ppm.
In preferred embodiments, initiator comprises hydrogen halide, carboxylic acid, acid halide, sulfonic acid, alcohol, phenol, tertiary alkyl halogenide, uncle's aralkyl halide, tertiary alkyl ester, uncle's aralkyl ester, tert-alkyl ether, uncle's aralkyl ethers, alkylogen, aryl halide, alkylaryl halogen, or in the arylalkyl carboxylic acid halides one or more.
Preferred hydrogen halide initiator comprises hydrogenchloride, hydrogen bromide and hydrogen iodide.Particularly preferred hydrogen halide is a hydrogenchloride.
Preferred carboxylic acid comprises aliphatic series and aromatic carboxylic acid simultaneously.The example that can be used for carboxylic-acid of the present invention comprises acetate, propionic acid, butyric acid; Styracin, phenylformic acid, 1-Mono Chloro Acetic Acid, dichloro acetic acid, trichoroacetic acid(TCA), trifluoroacetic acid, right-chlorobenzoic acid and right-fluorobenzoic acid.Particularly preferred carboxylic-acid comprises trichoroacetic acid(TCA), trifluoroacetic acid and right-fluorobenzoic acid.
Can be used for acid halide of the present invention and structurally be similar to carboxylic acid, wherein the OH of halogen substituted acid.Halogen can be a fluorine, chlorine, and bromine or iodine, wherein chlorine is preferred.Preparing carboxylic acid halides from the parent carboxylic class is that known and those skilled in the art should be familiar with these operations in the prior art.Can be used for acid halide of the present invention and comprise Acetyl Chloride 98Min., acetyl bromide, cinnamyl chloride, Benzoyl chloride, benzoyl bromide, trichoroacetic chloride, trifluoroacetyl chloride, trifluoroacetyl chloride and right-fluorobenzoyl chloride.Particularly preferred carboxylic acid halides comprises Acetyl Chloride 98Min., acetyl bromide, trichoroacetic chloride, trifluoroacetyl chloride and right-fluorobenzoyl chloride.
Sulfonic acid as the initiator among the present invention not only comprises aliphatic sulfonic acid but also comprise aromatic sulfonic acid.The example of preferred sulfonic acid comprises methylsulfonic acid, trifluoromethayl sulfonic acid, trichloromethane sulfonic acid and tosic acid.
Can be used for sulfonic acid halide of the present invention and structurally be similar to sulfonic acid, wherein the OH of halogen substituted parent acid.Halogen can be a fluorine, chlorine, and bromine or iodine, wherein chlorine is preferred.Preparing sulfonic acid halide from parent sulfonic acid is that known and those skilled in the art should be familiar with these operations in the prior art.Can be used for preferred sulfonic acid halogen of the present invention and comprise methane sulfonyl chloride, methylsulfonyl bromine, TSC trichloromethane sulfonyl chloride, trifluoromethanesulfonyl chloride and p-toluenesulfonyl chloride.
Can be used for alcohols of the present invention and comprise methyl alcohol, ethanol, propyl alcohol, 2-propyl alcohol, 2-methyl propan-2-ol, hexalin, and benzylalcohol.Can be used for phenols of the present invention and comprise phenol; 2-cresols; 2; Right-chlorophenol; Right-fluorophenol; 2,3,4,5, the 6-Pentafluorophenol; And 2 hydroxy naphthalene.
Preferred tertiary alkyl and aralkyl initiator comprise uncle system (tertiary) compound that is expressed from the next:
Wherein X is a halogen, pseudohalogen, ether, or ester, or their mixture, preferred halogen, preferred chlorine and R
1, R
2And R
3Be alkyl, aryl or the arylalkyl of any linearity, ring-type or branching independently, preferably contain 1-15 carbon atom and more preferably 1-8 carbon atom.N is the quantity in initiator site and is number more than or equal to 1 that preferably between 1 to 30, more preferably n is 1 to 6 number.Arylalkyl can be that replace or unsubstituted.For purpose of the present invention and its any claim, arylalkyl is defined as referring to contain simultaneously the compound of aromatics and aliphatic structure.The preferred example of initiator comprises 2-chloro-2,4, the 4-trimethylpentane; 2-bromo-2,4, the 4-trimethylpentane; 2-chloro-2-methylpropane; 2-bromo-2-methylpropane; 2-chloro-2,4,4,6, the 6-five methylheptane; 2-bromo-2,4,4,6, the 6-five methylheptane; 1-chloro-1-ethyl methyl benzene; 1-chlorine diamantane; 1-chloroethyl benzene; 1, two (the 1-chloro-1-methylethyl) benzene of 4-; The 5-tertiary butyl-1, two (the 1-chloro-1-methylethyl) benzene of 3-; 2-acetoxyl group-2,4, the 4-trimethylpentane; 2-benzoyloxy-2,4, the 4-trimethylpentane; 2-acetoxyl group-2-methylpropane; 2-benzoyloxy-2-methylpropane; 2-acetoxyl group-2,4,4,6, the 6-five methylheptane; 2-benzoyl-2,4,4,6, the 6-five methylheptane; 1-acetoxyl group-1-ethyl methyl benzene; 1-acetoxyl group diamantane; 1-benzoyloxy ethylbenzene; 1, two (1-acetoxyl group-1-methylethyl) benzene of 4-; The 5-tertiary butyl-1, two (1-acetoxyl group-1-methylethyl) benzene of 3-; 2-methoxyl group-2,4, the 4-trimethylpentane; 2-isopropoxy-2,4, the 4-trimethylpentane; 2-methoxyl group-2-methylpropane; 2-benzyloxy-2-methylpropane; 2-methoxyl group-2,4,4,6, the 6-five methylheptane; 2-isopropoxy-2,4,4,6, the 6-five methylheptane; 1-methoxyl group-1-ethyl methyl benzene; 1-methoxyl group diamantane; 1-methoxy ethyl benzene; 1, two (1-methoxyl group-1-methylethyl) benzene of 4-; The 5-tertiary butyl-1, two (1-methoxyl group-1-methylethyl) benzene and 1,3 of 3-, 5-three (1-chloro-1-methylethyl) benzene.Other suitable initiator can find in US patent 4,946,899, and the document is introduced into for reference here.For the present invention and its claim, pseudohalogen is defined as belonging to trinitride, isocyanic ester, thiocyanic ester, any compound of lsothiocyanates or prussiate.
Another kind of preferred initiator is a polymkeric substance halogenide, R
1, R
2Or R
3In one be olefin polymer and residue R group as defined above.Preferred olefin polymer comprises polyisobutene, polypropylene, and polyvinyl chloride.Polymerization initiator can have the end of the chain that is positioned at polymkeric substance or along the skeleton of polymkeric substance or the halo tertiary carbon within skeleton.When this olefin polymer has that side is hung on the polymer backbone or during at the intraskeletal a plurality of halogen atom that is on the tertiary carbon, this product can contain and has comb shaped structure and/or side chain branched polymers, and this depends on the quantity and the position of halogen atom in olefin polymer.Similarly, the use of end of the chain uncle polymkeric substance halogenide initiator provides the method for producing a kind of product, and this product can contain segmented copolymer.
Particularly preferred initiator can be any those initiators that can be used in the cationoid polymerisation of isobutylene copolymers: hydrogenchloride, 2-chloro-2,4,4-trimethylpentane, 2-chloro-2-methylpropane, 1-chloro-1-ethyl methyl benzene, and methyl alcohol.
Can be used for catalyst body system: compositions of the present invention and typically comprise (1) initiator and (2) Lewis acid aided initiating or other metal complexes described here.In preferred embodiments, the Lewis acid aided initiating doubly exists to the amount between about 200 times of the mole number of existing initiator with about 0.1 mole of the mole number of existing initiator.In a further preferred embodiment, the Lewis acid aided initiating exists with the amount between about 0.8 times of to the mole number of existing initiator about 20 times of the mole number of existing initiator.This initiator arrives about 10 with about 0.1 mol in preferred embodiments
-6The amount of mol exists.Certainly can understand, initiator bigger or less amount still belongs in the scope of the invention.
Catalyst consumption will depend on the institute's molecular weight and the molecular weight distribution of the polymkeric substance of producing.Typically this scope is about 1 * 10
-6Mol to 3 * 10
-2Mol and most preferably 10
-4To 10
-3Mol.
Can be used for catalyst system of the present invention and may further include catalyst composition, the latter comprises reactive behavior positively charged ion and weak coordinate negatively charged ion (" WC negatively charged ion " or " WCA " or " NCA ").Comprise that the anionic catalyst composition of WC will comprise the reactive behavior positively charged ion and be novel catalyst system in some cases.
Weak coordinate negatively charged ion is defined as a kind of negatively charged ion, it both be not coordinated to be coordinated to positively charged ion a little less than positively charged ion or it and when negatively charged ion is used as the stabilization negatively charged ion in the present invention WCA anionic fragment or substituting group can not transferred to positively charged ion and are produced neutral by product or other neutral compound.This type of weak anionic preferred example of corrdination type comprises: alkyl three (pentafluorophenyl group) boron (RB (pfp)
3 -), four perfluorophenyl boron (B (pfp)
4 -), four perfluorophenyl aluminium carboranes, halo carborane or the like.Positively charged ion is to add to any positively charged ion that produces carbocation on the alkene.
This negatively charged ion can be by combining with positively charged ion for the known any method of those skilled in the art.For example in preferred embodiments, this WC negatively charged ion is as containing negatively charged ion simultaneously and cationic compound is introduced in the thinner in the active catalyst system of this form.In a further preferred embodiment, the composition that contains the WC anionic moiety is at first handled to obtain negatively charged ion in the presence of positively charged ion or reactive behavior cationic source, and promptly negatively charged ion is activated.Similarly this WC negatively charged ion can be activated under the situation that does not have positively charged ion or cationic source (it is introduced into subsequently) to exist.In preferred embodiments, contain anionic composition and contain the blending and react and form by product, negatively charged ion and positively charged ion mutually of cationic composition.
Weak coordinate negatively charged ion
Any metal or the metal compound that can form anionic title complex (this title complex can not be transferred to substituting group or fragment on the positively charged ion and produce neutral molecule to neutralize this positively charged ion) can be used as the WC negatively charged ion.Any metal or the metalloid that can form the co-ordination complex in the water soluble in addition also can be used for or be included in comprising this anionic composition.Suitable metal includes, but are not limited to aluminium, gold, platinum or the like.Suitable metalloid includes, but not limited to boron, phosphorus, silicon or the like.Contain anionic compound, it comprises the co-ordination complex that contains single metal or metalloid atom, and well-known and wherein many that yes especially contain this compounds of single boron atom in anionicsite, can be purchased.In view of this situation, comprise the co-ordination complex that contains single boron atom a kind of to contain anionic salt be preferred.
In general, the WC negatively charged ion can be by following general formula:
[(M’)
m+Q
1...Q
n]
d-
Wherein:
M ' is metal or metalloid;
Q
1To Q
nBe the bridging or the hydrogen foundation group of bridging not independently, dialkyl amide base, alkoxyl group and aryloxy, alkyl and substituted hydrocarbon radical, halocarbon base and replace the halocarbon base and organic metalloid group that alkyl and halocarbon base replace, and Q
1To Q
nIn any one but to be no more than one can be halogen group;
M is the integer of the form valence charge of expression M;
N be ligand q sum and
D is the integer more than or equal to 1.
What certainly can understand is, above and negatively charged ion described below can come balance with positively charged component, this component was removed before negatively charged ion and positively charged ion interaction.For the positively charged ion that is described as using with negatively charged ion is like this equally.For example, Cp
2ZrMe
2Can with comprise negatively charged ion (WCA
-R
+) composition combine R wherein
+Work with Me group one and to stay Cp
2Zr
+MeWCA
-Catalyst system.
The preferred WC negatively charged ion that comprises boron can be by following general formula:
[BAr
1Ar
2X
3X
4]
-
Wherein:
B is the boron of valence state 3;
Ar
1And Ar
2Be identical or different containing have an appointment about 20 carbon atoms of 6-aromatics or replace aromatic hydrocarbon radical and can be connected with each other by stable bridged group; With
X
3And X
4Be hydrogen independently, alkyl and substituted hydrocarbon radical, halocarbon base and replacement halocarbon base, alkyl and halocarbon base replacement-organic metalloid group, dibasic pnicogen group, the sulfur family element group and the halogen group of replacement, precondition is X
3And X
4Not halogen simultaneously.
In general, Ar
1And Ar
2Can be any aromatics or replacement aromatic hydrocarbon radical independently.Suitable aromatic group includes, but not limited to phenyl, naphthyl and anthryl.Comprise in the suitable substituent that replaces on the aromatic hydrocarbon radical, but not necessarily be limited to, alkyl, organic metalloid group, alkoxyl group and aryloxy, fluorocarbon radicals and fluorine hydrogen carbon back etc., as be used for X
3And X
4Those.This substituting group can be with respect to the neighbour who is keyed to the carbon atom on the boron atom, or contraposition.Work as X
3And X
4In any one or both when being alkyl, can be separately and Ar
1And Ar
2The same identical or different aromatics or replacement aromatic group maybe can be the alkyl of straight or branched, alkenyl or alkynyl, the cyclic hydrocarbon group that cyclic hydrocarbon group or alkyl replace.As noted before, Ar
1And Ar
2Can be connected to X
3Or X
4On any one.At last, X
3And X
4Also can be connected with each other by suitable bridged group.
Can be as the illustrative of the anionic boron component of WC but nonrestrictive example be: the quaternary boron compound, as four (phenyl) boron, four (right-tolyl) boron, four (neighbour-tolyl) boron, four (pentafluorophenyl group) boron, four (neighbours, right-3,5-dimethylphenyl) boron, four (,-3,5-dimethylphenyl) boron, (right-trifluoromethyl) boron or the like.
Can be used as the anionic suitable ingredients that contains other metal and metalloid of WC can enumerate similarly, but such enumerating do not think it must is complete.In this respect, should be noted that enumerating of front do not think exhaustive, the boron compound that other is useful and contain the useful compound of other metal or metalloid will be behind the generality discussion of reference front and general formula and in can be easily by this area those technician understood.
The preferred especially WC negatively charged ion that comprises boron can be by following general formula:
[B(C
6F
5)
3Q]
-
Wherein:
F is a fluorine, and C is a carbon, and B and Q are as defined above.Comprise the anionic illustrative of these preferred WC of boron but non-limiting instance is a boron trityl salt, wherein Q is simple alkyl such as methyl, butyl, cyclohexyl, phenyl or wherein Q be the polymkeric substance alkyl such as the polystyrene of indefinite chain length, polyisoprene, or poly-p-methylstyrene.
Polymkeric substance Q substituting group on most preferred negatively charged ion provides the advantage that can obtain highly soluble ion-exchange activator component and final catalyzer.Soluble catalyst and/or precursor are usually than insoluble wax, and oil or solid are preferred, because they can be diluted to required concentration and can easily shift by the use simple device in commercial process.
The WC negatively charged ion that contains a plurality of boron atoms can be by following general formula:
[(CS)
a(BX′)
mX″
b]
c-
Or
[[[(CX
6)
a(BX
7)
m(X
8)
b]
c-]
2T
n+]
d-
Wherein:
X, X ', X ", X
6, X
7And X
8Be hydrogen independently, halogen group, alkyl, substituted hydrocarbon radical, the halocarbon base replaces the halocarbon base, or alkyl-or the organic metalloid group of halocarbon base-replacement;
T is a transition metal, preferred 8,9 or 10 family's metals, preferred nickel, cobalt or iron;
A and b be 〉=0 integer;
C is 〉=1 integer;
The even-integral number of a+b+c=from 2 to about 8;
M is from 5 to about 22 integer;
A and b are identical or different integers 0;
C is 〉=2 integer;
The even-integral number of a+b+c=from 4 to about 8;
M is from 6 to about 12 integer;
N makes the integer of 2c-n=d; With
D is 〉=1 integer.
The anionic example of of the present invention preferred WC that comprises a plurality of boron atoms comprises:
(1) satisfy the borine or the carborane anion of following formula:
[(CH)
ax(BH)
bx]
cx-
Wherein:
Ax is 0 or 1;
Ex is 1 or 2;
ax+ex＝2；
Bx is from about integer of 10 to 12; Or
(2) borine or carborane or the neutral borine or the carborane compound of satisfied following general formula:
[(CH)
ay(BH)
my(H)
by]
cy-
Wherein:
Ay is 0 to 2 integer;
By is 0 to 3 integer;
Cy is 0 to 3 integer;
ay+by+cy＝4；
My is from about 9 to about 18 integer; Or
(3) metallo-borane or the metallocarborane negatively charged ion of satisfied following general formula:
[[[(CH)
az(BH)
mz(H)
bz]c
z-]
2M
nz+]
dz-
Wherein:
Az is 0 to 2 integer;
Bz is 0 to 2 integer;
Cz is 2 or 3;
Mz is from about integer of 9 to 11;
az+bz+cz＝4；
And nz and dz are 2 and 2 or 3 and 1 respectively.
The anionic illustrative of WC but nonrestrictive example comprise: carborane, and as ten hypoboric acid roots, ten chlorine, ten borates, ten dichloros, ten hypoboric acid roots, 1-carbon ten borates, 1-carbon ten borates, 1-trimethyl silyl-1-carbon ten borates;
The borine of borine and carborane anion and carborane title complex and salt are as decaborane (14), 7,8-two carbon decaboranes (13), 2,7-two carbon, 11 borines (13), 11 hydrogen-7,8-dimethyl-7,8-two carbon 11 borines, 6-carbon ten borates (12), 7-carbon 11-borate root, 7,8-two carbon 11-borate roots; With
The metallo-borane anionic species, as two (nine hydrogen-1,3-two carbon nine borates) cobalt acid group (III), two (11 hydrogen-7,8-two carbon 11-borate roots) ferrous acid root (III), two (11 hydrogen-7,8-two carbon 11-borate roots) cobalt acid group (III), two (11 hydrogen-7,8-two carbon 11-borate roots (unaborato)) nickel acid group (III), two (nine hydrogen-7,8-dimethyl-7,8-two carbon 11-borate roots) ferrous acid root (III), two (tribromo octahydros-7,8-two carbon 11-borate roots) cobalt acid group (III), two (11 hydrogen, two carbon, ten hypoboric acid roots) cobalt acid groups (III) and two (11 hydrogen-7-carbon 11-borate root) cobalt acid group (III).
This WC anion composition that most preferably is used to form in the method the catalyst system that uses is to contain three perfluorophenyl boron, is connected in those of four (pentafluorophenyl group) boron anions on central atom (atomic) molecule or polymer complexes or the particle and/or two or more three (pentafluorophenyl group) boron anion group with covalent linkage.
Cationic components
In each preferred embodiment of the present invention, this WC negatively charged ion combines with one or more positively charged ions in being selected from inhomogeneous positively charged ion and cationic source.
Some preferred classes are:
(A) cyclopentadienyl transition metal compounds and its derivative.
(B) have the replacement carbocation of the composition that is expressed from the next:
R wherein
1, R
2And R
3Be hydrogen, alkyl, aryl, aralkyl or their base of deriving, preferred C
1-C
30Alkyl, aryl, aralkyl or their base of deriving;
(C) silicon of Qu Daiing; Preferred those that represent by following structural formula:
R wherein
1, R
2And R
3Be hydrogen, alkyl, aryl, aralkyl or their base of deriving, preferred C
1-C
30Alkyl, aryl, aralkyl or their base of deriving;
(D) can produce the composition of proton; With
(E) germanium, tin or plumbous cation composition, wherein some are to be represented by following structural formula:
R wherein
1, R
2And R
3Be hydrogen, alkyl, aryl, aralkyl or their base of deriving, preferred C
1To C
30Alkyl, aryl, derive base and the R* of aralkyl or they are Ge, Sn or Pb.
A. cyclopentadienyl-containing metal derivative
Preferred cyclopentadienyl transition metal derivative comprise the list that belongs to 4,5 or 6 group 4 transition metals-, two-or those transistion metal compounds of three-cyclopentadienyl derivative, preferred list-cyclopentadienyl (Mono-Cp) or two-cyclopentadienyl (Bis-Cp) the 4th group 4 transition metal composition, zirconium, titanium or hafnium composition especially.
The preferred cyclopentadienyl derivative (cationic source) that can combine with weakly coordinating anion is represented by following structural formula:
(A-Cp)MX
1 +；
(A-Cp)ML
+；
With
Wherein:
(A-Cp) be (Cp) (Cp*) or Cp-A '-Cp*;
The identical or different cyclopentadienyl rings that Cp and Cp* are replaced by 0-5 substituting group S, each substituted radical S is alkyl independently, substituted hydrocarbon radical, halocarbon base, replace the halocarbon base, organic metalloid that alkyl replaces, organic metalloid that the halocarbon base replaces, dibasic boron, dibasic pnicogen, the sulfur family element or the halogen group that replace, or Cp and Cp* be cyclopentadienyl rings, and wherein any two adjacent S groups link to each other and form C
4-C
20Ring and obtain saturated or undersaturated many ring cyclopentadienyl ligands;
R is the substituting group in the middle of these cyclopentadienyls, and it also can be bonded in atoms metal;
A ' is a bridged group, and this group can be used to limit Cp and Cp* ring or (C
5H
5-y-xS
x) and JR '
(z-1-y)The rotation of group;
M is 4,5 or 6 group 4 transition metals;
Y is 0 or 1;
(C
5H
5-y-xS
x) by the cyclopentadienyl rings of 0-5 S group replacement;
X is 0-5, the expression substitution value;
JR '
(z-1-y)Be the heteroatoms ligand, wherein J is the 16 family's elements that have 15 family's elements of ligancy 3 or have ligancy 2, preferred nitrogen, phosphorus, oxygen or sulphur;
R " be alkyl, preferred alkyl;
X and X
1Be hydrogen independently, alkyl, the alkyl of replacement, the halocarbon base, the halocarbon base of replacement, and alkyl-and organic metalloid group of halocarbon base-replacements, the pnicogen group of replacement, or the sulfur family element group of replacement; With
L is an alkene, diolefine or aryne ligand, or neutral Lewis base.
The additional ring pentadiene compounds that can be used among the present invention is described in US patent No5, and in 055,438,5,278,119,5,198,401 and 5,096,867, they are hereby incorporated by reference.
B. the carbocation of Qu Daiing
The preferred source of cationic another kind is the carbocation that replaces.
Preferred examples comprises the material that is expressed from the next:
R wherein
1, R
2And R
3Be hydrogen independently, or linear, branching or ring-type aromatics or aliphatic group, preferred C
1-C
20Aromatics or aliphatic group, precondition are R
1, R
2Or R
3In only one can be hydrogen.R in preferred embodiments
1, R
2Or R
3Not H.Preferred aromatic hydrocarbon comprises phenyl, tolyl, 3,5-dimethylphenyl, xenyl or the like.Preferred aliphatic group comprises methyl, ethyl, propyl group, butyl, amyl group, hexyl, octyl group, nonyl, decyl, dodecyl, 3-methyl amyl, 3,5,5-trimethylammonium hexyl or the like.In particularly preferred embodiments, work as R
1, R
2And R
3When being phenyl, the interpolation of aliphatic series or aromatic alcohol has promoted the polymerization of iso-butylene significantly.
C. the silicon positively charged ion of Qu Daiing
In another preferred embodiment, the silicon ion composition of replacement, preferred trisubstituted silicon ion composition combines polymerization single polymerization monomer with WCA.Preferred silicon positively charged ion is those that are expressed from the next:
R wherein
1, R
2And R
3Be hydrogen independently, or linear, branching or ring-type aromatics or aliphatic group, precondition is R
1, R
2And R
3In only one can be hydrogen.Preferably, R
1, R
2And R
3Not H.Preferably, R
1, R
2And R
3Be C independently
1-C
20Aromatics or aliphatic group.More preferably, R
1, R
2And R
3Be C independently
1-C
8Alkyl.The example of useful aromatic group can be selected from phenyl, tolyl, 3,5-dimethylphenyl and xenyl.The non-limitative example of useful aliphatic group can be selected from methyl, ethyl, propyl group, butyl, amyl group, hexyl, octyl group, nonyl, decyl, dodecyl, 3-methyl amyl and 3,5,5-trimethylammonium hexyl.The replacement silicon positively charged ion of particularly preferred one group reactive behavior can be selected from trimethyl silicane, triethyl silicon and benzyl dimethyl silicon.
For the replacement silicon of stable form and its synthetic discussion, see also F.A.Cotton, G.Wilkinson, Advanced Inorganic Chemistry, John Wileyand Sons, New York 1980.Similarly for the cationic tin of stable form, germanium and plumbous composition and they synthetic sees also Dictionary of Or ganometalliccompounds, Chapman and Hall, New York 1984.
D. can produce the composition of proton
Cationic the 4th source is for producing any compound of proton when the anionic composition of coordinate combines with weak coordinate negatively charged ion or a little less than containing.Proton can obtain proton and corresponding by product (be ether and be alcohol for the situation of water for the situation of pure and mild phenol) from the reaction of the anionic Stable Carbon cationic salts that contains weak coordinate, non-nucleophilicity and existing water, alcohol or phenol and produce.This type of reaction can be preferred for following situation: the reaction of carbocation salt and protonated additive is faster than the reaction of it and alkene.Other proton generation type reactant comprises thio-alcohol, carboxylic-acid, or the like.Similarly chemical process can realize with silicon type catalyzer.In particularly preferred embodiments, work as R
1, R
2And R
3When being phenyl, the interpolation of aliphatic series or aromatic alcohol has promoted the polymerization of iso-butylene significantly.
Another method that produces proton comprises mixes 1 or 2 family's metals (preferred lithium) with water, as by in wetting thinner, do not interfering in the presence of polymeric Lewis base such as the alkene.Observe, when Lewis base such as iso-butylene exist with 1 or 2 family's metals and water, can produce proton.Weak in preferred embodiments coordinate negatively charged ion also is present in " wetting " thinner, so that produce active catalyst when adding 1 or 2 family metals.
Active catalyst system
A. cyclopentadienyl transition metal compounds
Cp transition-metal cation (CpTm
+) can be combined into active catalyst with at least two kinds of approach.First method is to comprise CpTm
+Compound with comprise WCA
-Second kind of compound combine, react then and form by product and activity " weak coordinate " is right.Similarly, CpTm
+Compound also can be directly and WCA
-Combine and form active catalyst system.Typically WCA combines with the ratio of positively charged ion/cationic source by 1: 1, however 100: 1 ratio (CpTm
+Than WCA) also be feasible in enforcement of the present invention.
The active cation catalyzer can be by transistion metal compound and some neutral lewis acids such as B (C
6F
6)
3nReaction prepares, and forms negatively charged ion after hydrolyzable ligand (X) reaction of the latter and transistion metal compound, as ([B (C
6F
5)
3(X)]
-), and this negatively charged ion can make the cationic transition metal material that is produced by reaction become stable.
Novel aspect of the present invention is that formed activated carbon cationic catalyst title complex and it are represented by following structural formula:
With
Wherein each G is hydrogen or aromatics or aliphatic group independently, preferred C
1-C
100Aliphatic group and g are the integers that expression is introduced in the number of the monomeric unit in the polymer chain of growth, and g is preferably more than or equal to 1 number, preferably from 1 to about 150,000 number.WCA
-It is aforesaid any weak coordinate negatively charged ion.All other symbol is as defined above.
The present invention in another embodiment also provides the reactive catalyst compositions of being represented by following structural formula:
With
Wherein each G is aliphatic series or aromatic group independently, preferred C
1-C
100Aliphatic series or aromatic group and g are the n integers that expression is introduced in the quantity of the monomeric unit in the polymer chain of growth, and g is preferably more than or equal to 1 number, preferably from 1 to about 50,000 number.
WCA
-It is aforesaid any weak coordinate negatively charged ion.All other symbol is as defined above.
B. carbocation of Qu Daiing and silicon compound
The cationic generation of trisubstituted carbocation and silicon can be carried out before being used for polymerization or carry out in the polymerization original position.Positively charged ion or stable being pre-formed with separating to react with the corresponding halogen of potential carbocation or silicon ion by anionic basic metal of weak corrdination type or alkaline earth salt of cationic salts are realized, are similar to method known in the prior art.The carbocation that replaces or the formation of silicon ion is according to carrying out with the similar mode original position of stable salt, but in container and under required polymerization temperature.The advantage of back one program is that it can produce carbocation or silicon positively charged ion, rather than too unstable and can't be disposed by first method.Positively charged ion or cationic precursor typically use by 1: 1 ratio with WCA, yet 1: 100 ratio (C+ or Si+ and WCA) also is feasible in enforcement of the present invention.
Novel aspect of the present invention is that formed activated carbon cationic catalyst title complex and it are represented by following structural formula:
Wherein each G is hydrogen or alkyl independently, preferred C
1-C
100Aliphatic group and g are the n integers that expression is introduced in the number of the monomeric unit in the polymer chain of growth, and g is preferably more than or equal to 1 number, preferably from 1 to about 150,000 number.WCA
-It is aforesaid any weak coordinate negatively charged ion.All other symbol is as defined above.
Another novel aspect of the present invention is that formed activated carbon cationic catalyst title complex and it are represented by following structural formula:
Wherein each G is hydrogen or aliphatics or aromatic group independently, preferred C
1-C
100Aliphatic group and g are the n integers that expression is introduced in the number of the monomeric unit in the polymer chain of growth, and g is preferably more than or equal to 1 number, preferably from 1 to about 150,000 number.WCA
-It is aforesaid any weak coordinate negatively charged ion.All other symbol is as defined above.
Ge
，Sb
，Pb
Germanium, tin or the plumbous cation composition use that can combine with WCA described here in addition.Preferred compositions comprises those that represented by following structural formula:
R wherein
1, R
2And R
3Be hydrogen, alkyl, aryl, aralkyl or their base of deriving, preferred C
1To C
30Alkyl, aryl, derive base and the R* of aralkyl or they are Ge, Sn or Pb.This R group is C in preferred embodiments
1-C
10Alkyl, preferable methyl, ethyl, propyl group, or butyl.
Hydrogen fluorine carbon
Hydrogen fluorine carbon preferably in the present invention as thinner, combines individually or with other hydrogen fluorine carbon or with other thinner.For the present invention and claim, hydrogen fluorine carbon (" HFC ' s " or " HFC ") is defined as the saturated or unsaturated compound be made up of hydrogen, carbon and fluorine basically, and precondition is to have at least one carbon, at least one hydrogen and at least one fluorine.
In certain embodiments, thinner comprises by general formula C
xH
yF
zThe hydrogen fluorine carbon of expression, wherein x is 1 to 40, additionally from 1 to 30, additionally from 1 to 20, additionally from 1 to 10, additionally from 1 to 6, additionally from 2 to 20, additionally from 3 to 10, additionally from 3 to 6, most preferably from 1 to 3 at least, and wherein y and z are integers and are at least 1.
The example of illustrative comprises methyl fuoride; Methylene fluoride; Trifluoromethane; Fluoroethane; 1, the 1-C2H4F2 C2H4F2; 1, the 2-C2H4F2 C2H4F2; 1,1, the 1-Halothane; 1,1, the 2-Halothane; 1,1,1, the 2-Tetrafluoroethane; 1,1,2, the 2-Tetrafluoroethane; 1,1,1,2, the 2-pentafluoride ethane; 1-fluoropropane; 2-fluoropropane; 1, the 1-difluoropropane; 1, the 2-difluoropropane; 1, the 3-difluoropropane; 2, the 2-difluoropropane; 1,1,1-trifluoro propane; 1,1,2-trifluoro propane; 1,1,3-trifluoro propane; 1,2,2-trifluoro propane; 1,2,3-trifluoro propane; 1,1,1, the 2-tetrafluoropropane; 1,1,1, the 3-tetrafluoropropane; 1,1,2, the 2-tetrafluoropropane; 1,1,2, the 3-tetrafluoropropane; 1,1,3, the 3-tetrafluoropropane; 1,2,2, the 3-tetrafluoropropane; 1,1,1,2, the 2-pentafluoropropane; 1,1,1,2, the 3-pentafluoropropane; 1,1,1,3, the 3-pentafluoropropane; 1,1,2,2, the 3-pentafluoropropane; 1,1,2,3, the 3-pentafluoropropane; 1,1,1,2,2, the 3-HFC-236fa; 1,1,1,2,3, the 3-HFC-236fa; 1,1,1,3,3, the 3-HFC-236fa; 1,1,1,2,2,3, the 3-heptafluoro-propane; 1,1,1,2,3,3, the 3-heptafluoro-propane; Fluorobutane; The 2-butyl fluoride; 1,1-difluoro butane; 1,2-difluoro butane; 1,3-difluoro butane; 1,4-difluoro butane; 2,2-difluoro butane; 2,3-difluoro butane; 1,1,1-trifluoro butane; 1,1,2-trifluoro butane; 1,1,3-trifluoro butane; 1,1,4-trifluoro butane; 1,2,2-trifluoro butane; 1,2,3-trifluoro butane; 1,3,3-trifluoro butane; 2,2,3-trifluoro butane; 1,1,1,2-tetrafluoro butane; 1,1,1,3-tetrafluoro butane; 1,1,1,4-tetrafluoro butane; 1,1,2,2-tetrafluoro butane; 1,1,2,3-tetrafluoro butane; 1,1,2,4-tetrafluoro butane; 1,1,3,3-tetrafluoro butane; 1,1,3,4-tetrafluoro butane; 1,1,4,4-tetrafluoro butane; 1,2,2,3-tetrafluoro butane; 1,2,2,4-tetrafluoro butane; 1,2,3,3-tetrafluoro butane; 1,2,3,4-tetrafluoro butane; 2,2,3,3-tetrafluoro butane; 1,1,1,2, the 2-3-pentafluorobutane; 1,1,1,2, the 3-3-pentafluorobutane; 1,1,1,2, the 4-3-pentafluorobutane; 1,1,1,3, the 3-3-pentafluorobutane; 1,1,1,3, the 4-3-pentafluorobutane; 1,1,1,4, the 4-3-pentafluorobutane; 1,1,2,2, the 3-3-pentafluorobutane; 1,1,2,2, the 4-3-pentafluorobutane; 1,1,2,3, the 3-3-pentafluorobutane; 1,1,2,4, the 4-3-pentafluorobutane; 1,1,3,3, the 4-3-pentafluorobutane; 1,2,2,3, the 3-3-pentafluorobutane; 1,2,2,3, the 4-3-pentafluorobutane; 1,1,1,2,2, the 3-hexafluoro butane; 1,1,1,2,2, the 4-hexafluoro butane; 1,1,1,2,3, the 3-hexafluoro butane; 1,1,1,2,3, the 4-hexafluoro butane; 1,1,1,2,4, the 4-hexafluoro butane; 1,1,1,3,3, the 4-hexafluoro butane; 1,1,1,3,4, the 4-hexafluoro butane; 1,1,1,4,4, the 4-hexafluoro butane; 1,1,2,2,3, the 3-hexafluoro butane; 1,1,2,2,3, the 4-hexafluoro butane; 1,1,2,2,4, the 4-hexafluoro butane; 1,1,2,3,3, the 4-hexafluoro butane; 1,1,2,3,4, the 4-hexafluoro butane; 1,2,2,3,3, the 4-hexafluoro butane; 1,1,1,2,2,3,3-seven fluorine butane; 1,1,1,2,2,4,4-seven fluorine butane; 1,1,1,2,2,3,4-seven fluorine butane; 1,1,1,2,3,3,4-seven fluorine butane; 1,1,1,2,3,4,4-seven fluorine butane; 1,1,1,2,4,4,4-seven fluorine butane; 1,1,1,3,3,4,4-seven fluorine butane; 1,1,1,2,2,3,3, the 4-Octafluorobutane; 1,1,1,2,2,3,4, the 4-Octafluorobutane; 1,1,1,2,3,3,4, the 4-Octafluorobutane; 1,1,1,2,2,4,4, the 4-Octafluorobutane; 1,1,1,2,3,4,4, the 4-Octafluorobutane; 1,1,1,2,2,3,3,4,4-nine fluorine butane; 1,1,1,2,2,3,4,4,4-nine fluorine butane; 1-fluoro-2-methylpropane; 1,1-two fluoro-2-methylpropanes; 1,3-two fluoro-2-methylpropanes; 1,1,1-three fluoro-2-methylpropanes; 1,1,3-three fluoro-2-methylpropanes; 1,3-two fluoro-2-(methyl fluoride) propane; 1,1,1,3-tetrafluoro-2-methylpropane; 1,1,3,3-tetrafluoro-2-methylpropane; 1,1,3-three fluoro-2-(methyl fluoride) propane; 1,1,1,3,3-five fluoro-2-methylpropanes; 1,1,3,3-tetrafluoro-2-(methyl fluoride) propane; 1,1,1,3-tetrafluoro-2-(methyl fluoride) propane; The fluorine tetramethylene; 1,1-difluoro tetramethylene; 1,2-difluoro tetramethylene; 1,3-difluoro tetramethylene; 1,1,2-trifluoro tetramethylene; 1,1,3-trifluoro tetramethylene; 1,2,3-trifluoro tetramethylene; 1,1,2,2-ptfe ring butane; 1,1,3,3-ptfe ring butane; 1,1,2,2,3-five fluorine tetramethylene; 1,1,2,3,3-five fluorine tetramethylene; 1,1,2,2,3, the 3-trans-1,1,2,2,3,4-Hexafluorocyclobutane; 1,1,2,2,3, the 4-trans-1,1,2,2,3,4-Hexafluorocyclobutane; 1,1,2,3,3, the 4-trans-1,1,2,2,3,4-Hexafluorocyclobutane; 1,1,2,2,3,3,4-seven fluorine tetramethylene; With their mixture and the mixture of aforesaid unsaturated HFC.Particularly preferred HFC comprises methylene fluoride, trifluoromethane, 1,1-C2H4F2 C2H4F2,1,1,1-Halothane, methyl fuoride and 1,1,1,2-Tetrafluoroethane.
The example of the illustrative of unsaturated hydrogen fluorine carbon comprises vinyl fluoride; Vinylidene fluoride; 1, the 2-difluoroethylene; 1,1, the 2-trifluoro-ethylene; 1-fluorine propylene; 1,1-difluoro propylene; 1,2-difluoro propylene; 1,3-difluoro propylene; 2,3-difluoro propylene; 3,3-difluoro propylene; 1,1, the 2-trifluoro propene; 1,1, the 3-trifluoro propene; 1,2, the 3-trifluoro propene; 1,3, the 3-trifluoro propene; 2,3, the 3-trifluoro propene; 3,3, the 3-trifluoro propene; 1-fluoro-1-butylene; 2-fluoro-1-butylene; 3-fluoro-1-butylene; 4-fluoro-1-butylene; 1,1-two fluoro-1-butylene; 1,2-two fluoro-1-butylene; 1,3-difluoro propylene; 1,4-two fluoro-1-butylene; 2,3-two fluoro-1-butylene; 2,4-two fluoro-1-butylene; 3,3-two fluoro-1-butylene; 3,4-two fluoro-1-butylene; 4,4-two fluoro-1-butylene; 1,1,2-three fluoro-1-butylene; 1,1,3-three fluoro-1-butylene; 1,1,4-three fluoro-1-butylene; 1,2,3-three fluoro-1-butylene; 1,2,4-three fluoro-1-butylene; 1,3,3-three fluoro-1-butylene; 1,3,4-three fluoro-1-butylene; 1,4,4-three fluoro-1-butylene; 2,3,3-three fluoro-1-butylene; 2,3,4-three fluoro-1-butylene; 2,4,4-three fluoro-1-butylene; 3,3,4-three fluoro-I-butylene; 3,4,4-three fluoro-1-butylene; 4,4,4-three fluoro-1-butylene; 1,1,2,3-tetrafluoro-1-butylene; 1,1,2,4-tetrafluoro-1-butylene; 1,1,3,3-tetrafluoro-1-butylene; 1,1,3,4-tetrafluoro-1-butylene; 1,1,4,4-tetrafluoro-1-butylene; 1,2,3,3-tetrafluoro-1-butylene; 1,2,3,4-tetrafluoro-1-butylene; 1,2,4,4-tetrafluoro-1-butylene; 1,3,3,4-tetrafluoro-1-butylene; 1,3,4,4-tetrafluoro-1-butylene; 1,4,4,4-tetrafluoro-1-butylene; 2,3,3,4-tetrafluoro-1-butylene; 2,3,4,4-tetrafluoro-1-butylene; 2,4,4,4-tetrafluoro-1-butylene; 3,3,4,4-tetrafluoro-1-butylene; 3,4,4,4-tetrafluoro-1-butylene; 1,1,2,3,3-five fluoro-1-butylene; 1,1,2,3,4-five fluoro-1-butylene; 1,1,2,4,4-five fluoro-1-butylene; 1,1,3,3,4-five fluoro-1-butylene; 1,1,3,4,4-five fluoro-1-butylene; 1,1,4,4,4-five fluoro-1-butylene; 1,2,3,3,4-five fluoro-1-butylene; 1,2,3,4,4-five fluoro-1-butylene; 1,2,4,4,4-five fluoro-1-butylene; 2,3,3,4,4-five fluoro-1-butylene; 2,3,4,4,4-five fluoro-1-butylene; 3,3,4,4,4-five fluoro-1-butylene; 1,1,2,3,3,4-hexafluoro 1-butylene; 1,1,2,3,4,4-hexafluoro 1-butylene; 1,1,2,4,4,4-hexafluoro 1-butylene; 1,2,3,3,4,4-hexafluoro 1-butylene; 1,2,3,4,4,4-hexafluoro 1-butylene; 2,3,3,4,4,4-hexafluoro 1-butylene; 1,1,2,3,3,4,4-seven fluoro-1-butylene; 1,1,2,3,4,4,4-seven fluoro-1-butylene; 1,1,3,3,4,4,4-seven fluoro-1-butylene; 1,2,3,3,4,4,4-seven fluoro-1-butylene; 1-fluoro-2-butylene; 2-fluoro-2-butylene; 1, the 1-difluoro-2-butene; 1, the 2-difluoro-2-butene; 1, the 3-difluoro-2-butene; 1, the 4-difluoro-2-butene; 2, the 3-difluoro-2-butene; 1,1,1-three fluoro-2-butylene; 1,1,2-three fluoro-2-butylene; 1,1,3-three fluoro-2-butylene; 1,1,4-three fluoro-2-butylene; 1,2,3-three fluoro-2-butylene; 1,2,4-three fluoro-2-butylene; 1,1,1,2-tetrafluoro-2-butylene; 1,1,1,3-tetrafluoro-2-butylene; 1,1,1,4-tetrafluoro-2-butylene; 1,1,2,3-tetrafluoro-2-butylene; 1,1,2,4-tetrafluoro-2-butylene; 1,2,3,4-tetrafluoro-2-butylene; 1,1,1,2,3-five fluoro-2-butylene; 1,1,1,2,4-five fluoro-2-butylene; 1,1,1,3,4-five fluoro-2-butylene; 1,1,1,4,4-five fluoro-2-butylene; 1,1,2,3,4-five fluoro-2-butylene; 1,1,2,4,4-five fluoro-2-butylene; 1,1,1,2,3,4-hexafluoro-2-butylene; 1,1,1,2,4,4-hexafluoro-2-butylene; 1,1,1,3,4,4-hexafluoro-2-butylene; 1,1,1,4,4,4-hexafluoro-2-butylene; 1,1,2,3,4,4-hexafluoro-2-butylene; 1,1,1,2,3,4,4-seven fluoro-2-butylene; 1,1,1,2,4,4,4-seven fluoro-2-butylene; With they mixture and comprise the mixture of aforesaid saturated HFC.
In one embodiment, this thinner comprises that non-perfluorochemical or this thinner are non-perfluorination thinners.Those compounds that perfluorochemical is made up of carbon and fluorine.Yet, in another embodiment, when thinner comprises blend, this blend can comprise perfluorochemical, and is preferred, this catalyzer, monomer and thinner be present in single mutually in or said components and thinner can be miscible, describe in further detail as following.In another embodiment, this blend also can comprise Chlorofluorocarbons (CFCs) (CFC ' s), or by chlorine, those compounds that fluorine and carbon are formed.
In another embodiment, (be typically greater than 10,000Mw preferably surpasses 50 when higher weight-average molecular weight (Mw), 000Mw, more preferably surpass 100,000Mw) be desireed the time, suitable diluent is included in-85 ℃ of following specific inductivity greater than 10, be preferably greater than 15, more preferably greater than 20, more preferably greater than 25, more preferably 40 or higher hydrogen fluorine carbon.(typically be lower than 10,000Mw preferably is lower than 5, and 000Mw more preferably less than 3, is in the embodiment of being desireed 000Mw), and specific inductivity can be lower than 10, or can add relatively large initiator or transfer agent when specific inductivity is higher than 10 at rudimentary molecular weight.The DIELECTRIC CONSTANT of thinner
DBe from being immersed in thinner [observed value C
D] in, have known DIELECTRIC CONSTANT
RReference fluid [observed value C
R] in and at air (ε
A=1) [observed value C
A] in the observed value of capacity of parallel plate capacitor measure.Measured capacitor C under each situation
MBe by C
M=ε C
c+ C
sProvide, wherein ε has electrical condenser immersion fluidic specific inductivity wherein, C
CBe that effective capacitance and Cs are stray capacitys.From these observed values, ε
DBe by formula ε
D=((C
D-C
A) ε
R+ (C
R-C
D))/(C
R-C
A) try to achieve.Additionally, instrument of building for specific purpose such as the BrookhavenInstrument Corporation BIC-870 specific inductivity that can be used to directly measure thinner.The contrast of the specific inductivity (ε) of several selected thinners under-85 ℃ provide below and with graphic depiction in Fig. 1.
| Thinner | ε，-85℃ |
| Methyl chloride | 18.34 |
| Methylene dichloride | 36.29 |
| 1, the 1-ethylene dichloride | 29.33 |
| 1,1, the 1-Halothane | 22.18 |
| 1,1,1, the 2-Tetrafluoroethane | 23.25 |
| 1,1,2, the 2-Tetrafluoroethane | 11.27 |
| 1,1,1,2, the 2-pentafluoride ethane | 11.83 |
In other embodiments, one or more HFC use that combines with another kind of thinner or diluent mixture.Suitable additional diluent comprises hydrocarbon, especially hexane and heptane, halohydrocarbon, especially chlorinated hydrocarbon or the like.Specific examples includes but not limited to propane, Trimethylmethane, pentane, methylcyclopentane, isohexane, the 2-methylpentane, 3-methylpentane, 2-methylbutane, 2,2-dimethylbutane, 2,3-dimethylbutane, 2-methylheptane, 3-methyl hexane, 3-ethylpentane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2, the 4-dimethylpentane, 3,3-dimethylpentane, 2-methylheptane, 3-ethyl hexane, 2,5-dimethylhexane, pure isooctane, octane, heptane, butane, ethane, methane, nonane, decane, dodecane, undecane, hexane, methylcyclohexane, cyclopropane, tetramethylene, pentamethylene, methylcyclopentane, 1, the 1-dimethylcyclopentane, suitable-1, the 2-dimethylcyclopentane, instead-1, the 2-dimethylcyclopentane, anti--1, the 3-dimethylcyclopentane, ethyl cyclopentane, hexanaphthene, methylcyclohexane, benzene, toluene, dimethylbenzene, o-Xylol, p-Xylol, m-xylene, and the halo form of all above-mentioned substances, the chlorinated forms of preferred above material, the more preferably fluorinated forms of all above-mentioned substances.The bromination form of above material also is useful.Specific examples comprises, methyl chloride, methylene dichloride, ethyl chloride, propyl chloride, Butyryl Chloride, chloroform or the like.
In another embodiment, nonreactive activity alkene can combine as thinner with HFC.Example includes, but not limited to ethene, propylene etc.
In one embodiment, the HFC use that combines with hydrochloric ether such as methyl chloride.Additional example comprises the use that combines of HFC and hexane or methyl chloride and hexane.In another embodiment, HFC and for the use that combines of one or more gases of polymerization performance inert, as carbonic acid gas, nitrogen, hydrogen, argon gas, neon, helium, krypton, zenon, and/or other rare gas element are informed in when entering in the reactor preferably liquid.Preferred gas comprises carbonic acid gas and/or nitrogen.
The HFC use that combines with one or more nitrated paraffinic hydrocarbonss in another embodiment is comprising C
1-C
40Nitrated linearity, ring-type or branched paraffin.Preferred nitrated paraffinic hydrocarbons includes, but not limited to Nitromethane 99Min., nitroethane, nitropropane, nitrobutane, nitropentane, nitro hexane, nitro heptane, the nitro octane, nitro decane, nitrononane, the nitro dodecane, nitroundecane, nitro ring methane, nitrocyclohexane, nitro cyclopropane, nitro tetramethylene, the nitro pentamethylene, nitrocyclohexane, nitro suberane, the nitro cyclooctane, nitro cyclodecane, nitro cyclononane, the nitro cyclododecane, nitro ring undecane, oil of mirbane, and two-and three-nitro form of above-mentioned substance.Preferred examples is the HFC with the Nitromethane 99Min. blending.
Based on the thinner cumulative volume, the typical amount of HFC is 1-100 volume %, additionally between 5 and 100 volume %, additionally between 10 and 100 volume %, additionally between 15 and 100 volume %, additionally between 20 and 100 volume %, additionally between 25 and 100 volume %, additionally between 30 and 100 volume %, additionally between 35 and 100 volume %, additionally between 40 and 100 volume %, additionally between 45 and 100 volume %, additionally between 50 and 100 volume %, additionally between 55 and 100 volume %, additionally between 60 and 100 volume %, additionally between 65 and 100 volume %, additionally between 70 and 100 volume %, additionally between 75 and 100 volume %, additionally between 80 and 100 volume %, additionally between 85 and 100 volume %, additionally between 90 and 100 volume %, additionally between 95 and 100 volume %, additionally between 97 and 100 volume %, additionally between 98 and 100 volume %, and additionally between 99 and 100 volume %.HFC and one or more chlorinated hydrocarbons blending in preferred embodiments.In a further preferred embodiment, HFC is selected from methylene fluoride, trifluoromethane, a fluoroethane, 1,1-C2H4F2 C2H4F2,1,1,1-Halothane, 1,1,1,2-Tetrafluoroethane and their mixture.
Thinner or diluent mixture are that the basis is selected with its solubleness in polymkeric substance in another embodiment.Some thinner dissolves in polymkeric substance.Preferable absorbent has solubleness seldom or does not have solubleness in polymkeric substance.Solubleness in polymkeric substance is by being the film of thickness between 50 and 100 microns with polymer formation, then film is soaked 4 hours down at-75 ℃ in thinner (enough mulch films).Film is taken out from thinner, at room temperature placed 90 seconds in case from the surface of film the thinner of evaporating surplus, weighing then.The increase per-cent of film weight after the quality specific absorption is defined in and soaks.Thinner or diluent mixture are selected, so that the quality absorption rate of polymkeric substance is lower than 4wt%, preferably are lower than 3wt%, preferably are lower than 2wt%, preferably are lower than 1wt%, more preferably less than 0.5wt%.
In preferred embodiments, thinner or diluent mixture are selected, and requiring in the measured glass transition temperature Tg of the polymkeric substance that any thinner, unreacted monomer and the additive that are lower than 0.1wt% are arranged is within 15 ℃ with having formed the difference of thickness between the Tg of the measured polymkeric substance of the film between the 50-100 micron (this film in thinner (enough mulch films) in-75 ℃ of immersions 4 hours down).Second-order transition temperature is measured by dsc (DSC).These technology are fully described in the literature, for example, B.Wunderlich, " The Nature of the Glass Transition and its Determination byThermal Analysis ", in Assignment of the Glass Transition, ASTM STP 1249, R.J.Seyler, Ed., American Society for Testingand Materials, Philadelphia, 1994, pp.17-31.Prepare sample as mentioned above, sealing immediately afterwards in being immersed in the DSC sample disc, and maintain under the temperature that is lower than-80 ℃, before promptly being engraved in dsc measurement.Preferred these Tg values are within each other 12 ℃, preferably within each other 11 ℃, preferably within each other 10 ℃, preferably within each other 9 ℃, preferably within each other 8 ℃, preferably within each other 7 ℃, preferably within each other 6 ℃, preferably within each other 5 ℃, preferably within each other 4 ℃, preferably within each other 3 ℃, preferably within each other 3 ℃, preferably within each other 2 ℃, preferably within each other 1 ℃.
Polymerization process
The present invention can implement continuously and in the discontinuous method.The present invention can implement in plug flow reactor and/or stirred autoclave in addition.Especially the present invention can implement in " butyl reactor ".The example of illustrative comprises any reactor that is selected from following: Continuous Flow stirred-tank reactor, plug flow reactor, travelling belt or drum reactor, shower nozzle or jet nozzle reactors, tubular reactor and self-refrigeration type boiling pool reactor.
In yet another aspect, heat can be used for removing by making of heat transfer surface, as in tubular reactor, wherein refrigerant on a side of pipe and polyblend on opposite side.Heat also can be removed by the evaporation polyblend, as can be from seeing in the refrigerating boiling pool type reactor.Another example is the plug flow reactor, and wherein when mixture passed reactor, the part of polyblend was evaporated.Another example is to remove heat by surface heat transmission in the plug flow reactor, and this realizes by use refrigerant on the opposite side of heat transfer surface.Another example is wherein to be aggregated in the reactor that carries out on travelling belt or the drum, and wherein thinner/monomer/mixed catalyst is injected into this travelling belt or drum is gone up and along with the carrying out of reaction removed heat by the evaporation of thinner.Heat can be in this type of reactor be removed (be present in as refrigerant bulging inboard or under travelling belt, and produce polymkeric substance on the opposite side of this band or drum) by surface heat transmission in addition.The reactor of another type is shower nozzle or jet nozzle reactors.These reactors have the short residence time, and wherein monomer, thinner and catalyst body tie up in shower nozzle or the nozzle and mix, and when mixture passes nozzle at a high speed polymerization take place.
Preferred reactor comprises the Continuous Flow stirred-tank reactor, no matter it is with intermittently or continuous-mode operation, no matter and it is in having the jar of agitator or operate in tubular reactor.Preferred reactor also comprises and wherein carries out polymerization on a side of heat transfer surface and refrigerant is present in the reactor on the opposite side.Example is wherein to contain the reactor that the pipe of refrigerant is walked in the inside of reactor polymerisation zone.Another example is to carry out polyreaction in pipe inside, and refrigerant is present in the outside of pipe in housing.
The present invention also can implement in batch reactor, and wherein monomer, thinner and catalyzer are added in the reactor, and polyreaction proceeds to and finishes (as by quenching) and reclaim polymkeric substance then then.
In certain embodiments, the present invention implements by using slurry phase polymerisation process.Yet other polymerization process also can be considered, as solution polymerization process.Polymerization process of the present invention can be a cationic polymerization process.
In one embodiment, this be aggregated in when catalyzer, monomer and thinner be present in single-phase in the time carry out.Preferably, this is aggregated in wherein catalyzer, monomer and thinner as single-phase and carry out in the continuous polymerization method that exists.In slurry polymerization, monomer, catalyzer and initiator all can be miscible in thinner or the diluent mixture, that is, constitute single-phasely, and separate well with thinner from the polymer precipitation thing of thinner.Ideally, as suppress by the less of polymkeric substance or the Tg that do not have at all to have demonstrated indicated polymkeric substance " swelling " that reduce or that do not have and/or as shown in Figure 2 seldom or the thinner quality that does not have absorb.Therefore, the polymerization in thinner of the present invention helps high polymers concentration to be disposed under low viscosity, have concurrently good heat passage, the reactor fouling of attenuating, the accessibility of polymerization in homogeneous phase and/or the subsequent reactions that directly carries out for the resulting polymers mixture.
The monomer that has reacted in reactor has constituted the part of slurry.In one embodiment, solids concn is equal to or greater than 10vol% in slurry.In another embodiment, solids concn is equal to or greater than 25vol% in the slurry that exists in reactor.In another embodiment, solids concn is less than or equal to 75vol% in slurry.In another embodiment, solids concn is 1-70vol% in the slurry that exists in reactor.In another embodiment, solids concn is 5-70vol% in the slurry that exists in reactor.In another embodiment, solids concn is 10-70vol% in the slurry that exists in reactor.In another embodiment, solids concn is 15-70vol% in the slurry that exists in reactor.In another embodiment, solids concn is 20-70vol% in the slurry that exists in reactor.In another embodiment, solids concn is 25-70vol% in the slurry that exists in reactor.In another embodiment, solids concn is 30-70vol% in the slurry that exists in reactor.In another embodiment, solids concn is 40-70vol% in the slurry that exists in reactor.
Typically, can use the continuous flow stirred-tank reactor.This reactor generally is equipped with abundant whipping device, as turbo mixer or arm stirrer, external cooling chuck and/or inner cooling tube and/or pipeline, or remove the miscellaneous equipment that heat of polymerization is kept desired reaction temperature, the introducing equipment (as ingress pipe) of monomer, thinner and catalyzer (mix ground or individually), temperature-sensitive equipment and with polymkeric substance, thinner and unreacted monomer be discharged to hold jar or quench tank in discharge upflow tube or outlet pipe.Preferably, this reactor is removed air and moisture by purging.Those of skill in the art understand suitable assembling and operation.
Reactor is preferably through realizing catalyzer and monomeric well blend after the design in reactor, good turbulent flow penetration heat transfer tube or pipeline are arranged or within it, and enough fluid stream is arranged in the entire reaction volume to avoid heteropolymer gathering or separate from thinner.
Operable other reactor comprises any common reactor that can carry out continuous slurry polymerization technology and its equivalent in enforcement of the present invention, and is disclosed in 930 as at US 5,417, introduces for reference here.The reactor pump impeller can be the type of upwards pumping or the type of pumping downwards.Reactor will contain the catalyst system of the present invention of q.s so that catalysis contains the polyreaction of monomeric feedstream effectively, make the polymkeric substance with desired characteristic of producing q.s.Feedstream contains greater than 5wt%, is preferably greater than the total monomer concentration (based on the gross weight of monomer, thinner and catalyst system) of 15wt%, in another embodiment greater than 30wt% in one embodiment.In another embodiment, feedstream will contain the monomer concentration of 5wt% to 50wt%, based on the gross weight of monomer, thinner and catalyst system.
In some embodiments, feed stream is substantially free of silica positively charged ion type of production material.Be substantially free of silica positively charged ion generation type material and be meant, in feedstream, do not surpass these silica positively charged ion generation type materials of 0.0005wt% based on total monomer weight.The representative instance of silica positively charged ion generation type material is to have chemical formula R
1R
2R
3SiX or R
1R
2SiX
2Deng halogen-alkyl silica compounds, wherein " R " is that alkyl and " X " are halogens.Reaction conditions should make required temperature, the pressure and the residence time keep reaction medium effectively liquid and produce the required polymkeric substance with desired characteristic.Raw material monomer stream typically is substantially devoid of under polymerizing condition unfriendly any impurity with catalyst reaction.For example, in some embodiments, this raw material monomer preferably should be substantially devoid of alkali (as caustic alkali), and the compound of sulfur-bearing is (as H
2S, COS and organic mercaptan, for example, thiomethyl alcohol, sulfur alcohol), nitrogenous alkali, oxygen containing alkali such as alcohols or the like.Yet raw material monomer can be not too pure, based on total olefin content, typically is no less than 95%, more preferably is no less than 98%, is no less than 99%.Amount at this impurity of preferred embodiment is lower than 10, and 000ppm (weight) preferably is lower than 500ppm, preferably is lower than 250ppm, preferably is lower than 150ppm, preferably is lower than 100ppm.
Normally this situation, the reaction times, temperature, concentration, the character of reactant and similar factor have determined molecular weight of product.Polymeric reaction temperature easily according to the subject polymer molecular weight and the consideration (for example speed, temperature control etc.) of the polymeric monomer of wanting and standard technology variable and economic aspect select.The polymeric temperature is lower than 0 ℃, and is preferred in one embodiment between the freezing point of-10 ℃ and slurry, and in another embodiment between-25 ℃ to-120 ℃.In another embodiment, this polymerization temperature is-40 ℃ to-100 ℃ and is-70 ℃ to-100 ℃ in another embodiment.In another ideal embodiment, temperature range is-80 ℃ to-100 ℃.Therefore, different reaction conditions is produced the product of different molecular weight.Therefore the synthetic of required reaction product can come the process (widely used in the prior art technology) of monitoring reaction to realize by the analysis by the sample that regularly takes out in reaction process.
In preferred embodiments, this polymerization temperature is within 10 ℃ above freezing of thinner, preferably within 8 ℃ above freezing of thinner, preferably within 6 ℃ above freezing of thinner, preferably within 4 ℃ above freezing of thinner, preferably within 2 ℃ above freezing of thinner, preferably within 1 ℃ above freezing at thinner.For the present invention and its claim, when using phrase " within X above freezing ℃ at thinner ", it refers to that the freezing point of thinner adds X ℃.For example, if the freezing point of thinner is-98 ℃, then 10 ℃ above freezing at thinner are-88 ℃.
Reaction pressure is, in one embodiment from 0 to 14,000kPa (wherein 0kPa is total vacuum), in another embodiment from 7kPa to 12,000kPa, in another embodiment from 100kPa to 2000kPa, in another embodiment from 200kPa to 1500kPa, in another embodiment from 200kPa to 1200kPa and in another embodiment from 200kPa to 1000kPa, in another embodiment from 7kPa to 100kPa, in another embodiment from 20kPa to 70kPa, in another embodiment from 40kPa to 60kPa, in another embodiment from 1000kPa to 14,000kPa, in another embodiment from 3000kPa to 10,000kPa and in another embodiment from 3,000kPa to 6,000kPa.
Raw material monomer stream, catalyzer, the order that initiator contacts with thinner can have nothing in common with each other to another embodiment from an embodiment.
In another embodiment, initiator and Lewis acid are injected in the flow reactor via catalyzer nozzle or injection device then by be mixed together the scheduled time of its pre-mated in 0.01 second to 10 hours scope in selected thinner.In another embodiment, Lewis acid and initiator are added in the reactor separately.In another embodiment, this initiator in being injected into reactor before with the starting monomer blending.Ideally, this monomer does not contact with Lewis acid, or Lewis acid and initiator blending before monomer enters in the reactor.
In one embodiment of the invention, before in being injected into reactor between 0.1 second and 5 minutes, preferably be lower than 3 minutes, preferably between 0.2 second and 1 minute, this initiator and Lewis acid carry out its pre-mated by mixing in selected thinner under the temperature between the freezing point temperature of-40 ℃ and thinner, wherein be duration of contact between 0.01 second and several hrs.
In another embodiment of the invention, this initiator and Lewis acid typically mix in selected thinner under the temperature between-40 ℃ and-98 ℃ and carry out its pre-mated by between 80 ℃ and-150 ℃.
Total residence time in reactor can be according to for example catalyst activity and concentration, monomer concentration, raw material injection speed, throughput rate, temperature of reaction and required molecular weight change, and generally are between several seconds and five hours, and typically between about 10 and 60 minutes.The variable that influences the residence time comprises monomer and thinner raw material rate of injection and total reactor volume.
Employed catalyzer (Lewis acid) and monomer ratio are to be generally used in the carbon cation polymerization process those in this area.In one embodiment of the invention, this monomer and catalyst molar ratio typically 500 to 10000 and in another embodiment in 2000 to 6500 scopes.In another ideal embodiment, the ratio of Lewis acid and initiator is 0.5 to 10, or 0.75 to 8.The total concn of initiator 5 to 300ppm or 10 arrives 250ppm typically in reactor.In one embodiment, initiator concentration 50 arrives 3000ppm typically in the catalysagen materials flow.Another mode that is described in the amount of catalyst reactor is its amount with respect to polymkeric substance.0.25-20 moles of polymer/mole initiator is arranged in one embodiment and 0.5-12 moles of polymer/mole initiator is arranged in another embodiment.
The catalyst system of the present invention that reactor contains q.s contains the polyreaction of monomeric feedstream with catalysis, makes the polymkeric substance with desired characteristic of producing q.s.Feedstream contains the total monomer concentration (based on monomer, the gross weight of thinner and catalyst system) greater than 20wt% in one embodiment, in another embodiment greater than 25wt%.In another embodiment, feedstream will contain the monomer concentration of 5wt% to 50wt%, based on the gross weight of monomer, thinner and catalyst system.
Molar ratio by control Lewis acid and initiator, catalyst efficiency in reactor (based on Lewis acid) maintains between 10,000 pounds of polymkeric substance/pound catalyzer and the 300 pounds of polymkeric substance/pound catalyzer and ideally between 4000 pounds of polymkeric substance/pound catalyzer to 1000 pound polymkeric substance/pound catalyzer.
In one embodiment, the monomeric polyreaction of cationic polymerizable (polyreaction as iso-butylene and isoprene forms isoprene-isobutylene rubber) comprises several steps.The reactor of the pump impeller with can make progress pumping or pumping downwards at first, is provided.Pump impeller is typically driven with measurable amperage by electric motor.Reactor typically is equipped with the parallel vertical reaction tubes in containing the chuck of liquid ethylene.The total internal volume that comprises this pipe is greater than the 30-50 liter, therefore can carry out the polyreaction of extensive volume.This reactor typically utilizes liquid ethylene to remove polymerization reaction heat from formation slurry.Pump impeller keeps slurry, thinner, catalyst system and unreacted monomer to flow through reaction tubes consistently.The feedstream of monomer (as isoprene and iso-butylene) in the polarity thinner of cationic polymerizable joined in the reactor, and feedstream contains the positively charged ion generation type silica compounds that is lower than 0.0005wt% and does not typically contain aromatic monomer.Then catalyst system is joined in the reactor, catalyst system has Lewis acid and the initiator that exists with 0.50 to 10.0 molar ratio.In reactor, the feedstream of monomer and catalyst system is in contact with one another, and therefore this reaction forms the slurry of polymkeric substance (as isoprene-isobutylene rubber), and wherein the solid in slurry has the concentration from 20vol% to 50vol%.At last, formed polymkeric substance (as isoprene-isobutylene rubber) leaves reactor via outlet or outflow pipeline, simultaneously polyreaction is proceeded in the feedstream input, has therefore constituted continuous slurry polymerization.Advantageously, the present invention improves this technology in many ways, for example, at reactor wall, heat transfer surface is on agitator and/or the paddle wheel by final minimizing, with the amount of accumulation of polymer in flowing out pipeline or outlet opening, this can utilize pressure discordance or " beating " to weigh.
In one embodiment, the polymkeric substance that obtains from one embodiment of the invention is to have about molecular weight distribution of 2 to 5, and the polyisobutene/isoprene copolymer (isoprene-isobutylene rubber) of the degree of unsaturation between 0.5-2.5 mole/100 mole of monomer.This product can carry out follow-up halogenation and obtain halogenated butyl rubber.
The present invention relates in another embodiment:
A. polymerization process comprises allowing one or more monomers that one or more Lewis acids contact in the presence of the thinner that comprises one or more hydrogen fluorine carbon (HFC) with one or more initiators;
B. the method for paragraph A, wherein thinner comprises the HFC of 1-100 volume %, based on the cumulative volume of thinner;
C. the method for paragraph A or B, wherein HFC has 21 or higher specific inductivity under-85 ℃;
D. paragraph A, any one method of B or C, wherein polymkeric substance has the thinner quality specific absorption that is lower than 4wt%;
E. paragraph A, B, the method for C or D, wherein thinner comprises hydrocarbon in addition;
F. paragraph A, B, C, the method for D or E, wherein initiator is selected from hydrogen halide, carboxylic acid, water, tertiary alkyl halogenide and their mixture;
G. paragraph A, B, C, D, the any one method of E or F, wherein monomer is selected from vinylbenzene, p-methylstyrene, alpha-methyl styrene, Vinylstyrene, di isopropenylbenzene, iso-butylene, 2-methyl-1-butene alkene, 3-methyl-1-butene, 2-methyl-2-amylene, isoprene, divinyl, 2,3-dimethyl-1,3-butadiene, beta-pinene, myrcene, 6,6-dimethyl-fulvene, hexadiene, cyclopentadiene, methyl cyclopentadiene, piperylene, methylvinylether, ethyl vinyl ether, isobutyl vinyl ether and their mixture;
H. paragraph A, B, C, D, E, any one method among F or the G, wherein styrenic block copolymer is present in the contact procedure;
I. paragraph A, B, C, D, E, F, any one method of G or H, wherein temperature is below 0 ℃ or 0 ℃;
J. paragraph A, B, C, D, E, F, G, any one method of H or I, wherein this temperature is within 10 ℃ above freezing of thinner;
K. paragraph A, B, C, D, E, F, g, H, any one method of I or J, wherein there is not water basically in slurry;
L. paragraph A, B, C, D, E, F, G, H, I, any one method of J or K, wherein this temperature is between-105 ℃ and-60 ℃, preferred-80 ℃;
M. paragraph A, B, C, D, E, F, G, H, I, any one method of J or L, wherein this method includes greater than the 30ppm water initiator of (by weight); With
N. by paragraph A, B, C, D, E, F, G, H, I, J, k, the product that any one method of L or M is produced.
Industrial application
Polymkeric substance of the present invention provides chemistry and physical property, makes them be suitable in the various application.Low-permeability to gas makes these polymkeric substance that maximum use, the i.e. inner tube of a tyre and tire flap be arranged.These performances are at air cushion, the air cushion spring, and airbag also has importance in gas-storing bag and the medicine seal box.The thermostability of polymkeric substance of the present invention makes them be used for rubber tyre-vulcanisation bladder ideally, the travelling belt that flexible pipe that high temperature uses and heat supply matter transportation are used.
This polymkeric substance demonstrates high damping properties and while uniqueness on temperature and frequency has wide damping and shock absorption scope.They can be used for molding processing rubber components and and at the automobile hanging vibroshock, auto exhaust Apparatus for hanging articles and vehicle body have been installed extensive use.
Polymkeric substance of the present invention also can be used for tire tyre sidewall and tread compound.At sidewall, polymer property is given good ozone resistants, and crackle cuts off growth, and outward appearance.Polymkeric substance of the present invention also can blend.The blend of the suitable preparation that homodiene rubber is arranged that demonstrates the cocontinuity of phase can obtain excellent sidewall.The polymkeric substance of the application of the invention can be implemented in moisture-proof, on the snow and ice sliding and the improvement on dried tractive force, but not in the wear resistance of high-performance tire and the loss on the rolling resistance.
The blend of polymkeric substance of the present invention and thermoplastic resin is used for the toughness reinforcing of these compounds.High density polyethylene(HDPE) and isotatic polypropylene usually come modification with the polyisobutene of 5-30wt%.In some applications, polymkeric substance of the present invention provides the high flexibility mixture, and it can be processed in thermoplastic plastic molded's processing units.Polymkeric substance of the present invention also can with polyamide blended other industrial application that produces.
Polymkeric substance of the present invention also can be used as tackiness agent, caulking agent, the interstitial material that sealing agent and glazing are used.They also can have isoprene-isobutylene rubber, are used as softening agent in the rubber formulation of SBR and natural rubber.In linear low density polyethylene (LLDPE) blend, they induce the adhesion to the stretch-wraps film.They also are used for lubricant and are used for canned and the cable compaction material as dispersion agent widely.
In some applications, polymkeric substance of the present invention makes them also can be used for chewing gum, and is used for medical field, as the parts of medicine stopper and paint roller.
The following example reflection embodiment of the present invention but do not think limit the scope of the invention.
Embodiment
This polymerization is undertaken by using the glass reaction container, and it is equipped with teflon turbine type impeller on by the external electric driving glass stirring shaft that agitator drove.The size of Glass Containers and design are all marked for each group of embodiment.The head of reactor comprises the opening of the reinforced usefulness of stir shaft, thermopair and initiator/aided initiating solution.In the pentane or isohexane bath of reactor immersion in loft drier, make reactor cooling arrive desired reaction temperature, as listed in table with assembling.The temperature that the hydrocarbon that stirs is bathed is controlled to ± and 2 ℃.With reaction medium realize whole devices that liquid contact before using 120 ℃ of dryings and in nitrogen atmosphere, cooling off down.Iso-butylene (Ma theson or Exxon Mobil) and methyl chloride (Air Products) are dry by allowing them flow through to contain barytic three stainless head towers, and are condensed as liquid in loft drier and collect.Change it, methyl chloride can be in addition dry by allowing gas stream cross to contain the stainless head tower of silica gel and molecular sieve.Two kinds of raw materials are condensed as liquid and are collected in the loft drier.Isoprene (Aldrich) is dry on the hydrolith and distill under argon atmospher.P-methylstyrene (Aldrich) drying and vacuum distilling on hydrolith.From 2,4, the formulations prepared from solutions TMPCl (2-chloro-2,4,4-trimethylpentane) of the HCl of 4-2,4,4-Trimethyl-1-pentene-1 and 2.0mol/L concentration in diethyl ether.TMPCl carries out distillation before using.Be dissolved in by HCl gas and reach 2-3wt% concentration among the dry MeCl and prepare HCl (Aldrich, 99% is pure) material solution aequum.The hydrogen fluorine carbon of collecting as transparent, colourless liquid under-95 ℃ is to use with received form.Keep hydrogen fluorine carbon muddy or that have visible insoluble precipitate before use, to carry out distillation down at-95 ℃.The propane (Aldrich) that uses with received form is cooled and uses as liquid.Alkyl al dichloride (Aldrich) uses as hydrocarbon solution.These solution can be purchased or prepare from purified alkyl al dichloride.
The slurry copolymerization is undertaken by monomer and comonomer are dissolved in to stir in the liquefying hydrogen fluorine carbon that is under the polymerization temperature and under the predetermined stirring velocity between 800 to 1000rpm.The use of the electric stirring motor of treater control can be controlled at stirring velocity within the 5rpm.Initiator/aided initiating solution is to make in hydrogen fluorine carbon, or for the convenience of small-scale test, makes in the methyl chloride of small volume.Prepare initiator/aided initiating solution by the 1.0M solution that initiator is dissolved in the thinner (in each embodiment specifically specify) and under mixing, add aluminum alkyl halide.Use initiator/aided initiating solution immediately.The dropping funnel of this initiator/aided initiating solution by using refrigerated glass Pasteur transfer pipet or optional strap clamp to overlap for example uses 500ml glass reaction container, is added drop-wise in the polyreaction.When specifying in an embodiment for the second time or initiator/aided initiating adds for the third time, we refer to the preparation of second batch or the 3rd batch freshly prepd initiator/aided initiating solution and be added on volume and concentration on be equal to first.The physical properties of rubber grain and the state of incrustation when the interpolation of each catalyzer batch finishes by stopping and shifting out stir shaft and detect particulate matter with chilled spatula and measure.Stirring begins once more and comes the cancellation reaction by the methyl alcohol that adds greater than 100 microlitres.Transformation efficiency is recorded as the monomeric wt% that changes into polymkeric substance.
Polymericular weight is Waters Alliance 2690 separation modules and Waters 410 differential refractometer detectors that the post well heater is housed by use, is measured by SEC (size exclusion chromatography).Tetrahydrofuran (THF) has 500,1000,2000,104, one group Waters Styragel HR 5 μ posts of 105 and 106 dust pore sizes as eluent (1ml/min, 35 ℃).Correction based on narrow molecular-weight polyisobutene standard substance (American Polymer Standards) is used to calculate molecular weight and distribution.
Polymericular weight can be by using different corrections and experiment rules to measure on other SEC instrument.The method of the SEC of characterize polymers molecular weight (also being known as GPC or gel permeation chromatography) is commented in many publications.A kind of this type of source be by L.H.Tung at Polymer Yearbook, H.-G.Elias and R.A.Pethrick, Eds., HarwoodAcademic Publishers, New York, 1984, the commentary that provides in the 93-100 page or leaf is introduced for reference here.
The introducing of comonomer be by
1The H-NMR spectrometry is measured.The NMR measuring result obtains under the strength of electric field corresponding with 400MHz or 500MHz.
1The H-NMR spectrum is to use the CDCl of polymkeric substance
3Solution at room temperature is recorded on the Bruker Avance NMR spectra system.Whole chemical shifts is with reference to TMS.
The triad sequence distribute by under the temperature of the field intensity of 125.7MHz and 50 ℃, use Varian Unity spectrophotometer from
13C NMR Zymography obtains.Polymer samples is dissolved into CDCl with the concentration of 6-8wt%
3In (acetopyruvic acid chromium (III) salt that contains 1.5%wt/v) as relaxant.Free induction decay is with 90 ° of pulses, and recirculation in 3.0 seconds postpones and collects 2.133 second capture time.Each data set is by 30, and the sweep length of 007Hz and 30,000 scanning/transitions are formed.Whole chemical shifts is benchmark with the tetramethylsilane.
Data processing is utilized from Acorn NMR, and (Livermore, the NutsProNMR Utility Transform software that CA) is purchased carries out Inc..This carbon-13 free induction decay carries out Fourier transform with 65K point and 1Hz line broadening, and the spectrum that is obtained is adjusted phase place and carries out baseline correction.In order to optimize measuring accuracy, the area of alkene resonance is measured by peak overlapping is legal, measures and can't help manual integration.The peak profile of supposing 85%Lorentzian and 15%Gaussian feature is used for calculating.Live width, highly and the position changed to obtain matched curve.
Isoprene triad resonance basis is by C.Corno, A.Proni, A.Priola and S.Cesca be at Macromolecules 1980,13, in 1092 and J.L.White, T.D.Shaffer, C.J.Ruff and J.P.Cross are at Macromolecules 1995,28, the information of report is made attribution analysis in 3290, and two documents are hereby incorporated by reference.For each triad structure, observe the resonance of quaternary carbon and tertiary carbon.Carbon (season and uncle) for each type calculates BII (B=iso-butylene, I=isoprene) alkene triad mark.For example, the BII value of tertiary carbon is calculated divided by the summation of whole tertiary carbon integrations of BIB, BII, IIB and III triad by the mean value with BII tertiary carbon integration and IIB tertiary carbon fraction.According to definition, this BII triad mark must equal IIB triad mark.In case (uncle and Ji) calculates BII triad mark for each carbon type, the amount contrast that these are worth equalization in addition and are used for and are introduced in the isoprene of multipolymer.Formed the curve of BII mark (being expressed as the percentage ratio of the triad of whole isoprene heart placed in the middle, for example 100 * BII mark), and be described below the mol% isoprene in the introducing multipolymer.
For purpose of the present invention, describe by multipolymer sequence distribution equation formula as described below in BII triad mark and the relation between the mol% isoprene in the multipolymer of being introduced in and characterize by multipolymer sequence distribution parameter m.
F
BII＝mA/(1+mA)
2
Wherein: m is a multipolymer sequence distribution parameter,
A is the molar ratio of isoprene and iso-butylene in multipolymer, [IP]/[IB] and,
F
BIIIt is the BII triad mark in multipolymer.
This equational best-fit has obtained the value of the m of iso-butylene and the copolymerization of isoprene in each thinner.
By
13The data that C NMR Zymography obtains are to obtain best-fit by the iterative solution to multipolymer sequence distribution equation formula to carry out match.Copolymerization in each thinner has obtained sequence distribution parameter m to this equational best-fit for iso-butylene and isoprene.
Various NMR methods have been used for characterizing that comonomer is introduced and distribute in the sequence of multipolymer.Many in these methods all are applicable to polymkeric substance of the present invention.The general reference of having commented the application of NMR spectrum on the sign of polymkeric substance is H.R.Kricheldorf, Polymer Yearbook, H.-G.Elias and R.A.Pethrick, Eds., HarwoodAcademic Publishers, New York, 1984, the 249-257 page or leaf is introduced for reference here.
Table 1 has been listed under-90 to-95 ℃ at hydrogen fluorine carbon and methyl chloride (CH
3Cl) the polymeric result who carries out in (embodiment 10) and the propane (embodiment 11) compares.The miniature resin kettle of 100ml glass is used for these embodiment.TMPCl (2-chloro-2,4,4-trimethylpentane) is in these embodiments as initiator.
Table 1
a
| Embodiment | Temperature (℃) | Thinner | Output (g) | Transformation efficiency (Wt.%) | Mw× 10 -3 | Mw/Mn | Mol％IP |
| 1 b | -95 | CH 3F | 0.80 | 21.1 | 225 | 2.4 | 1.2 |
| 2 c，d | -93 | CH 2F 2 | 3.28 | 83 | 305 | 3.1 | 1.7 |
| 3 | -90 | CH 2F 2 | 0.99 | 24.8 | 297 | 3.4 | 1.5 |
| 4 | -95 | CHF 3 | 1.88 | 47.1 | 390 | 4.6 | 2.2 |
| 5 c | -95 | CH 3CHF 2 | 1.48 | 37.3 | 842 | 2.5 | 1.4 |
| 6 c，d | -95 | CH 3CF 3 | 2.89 | 72.1 | 327 | 2.3 | 2.0 |
| 7 | -95 | CH 2FCF 3 | 1.48 | 37.3 | 384 | 2.5 | 1.7 |
| 8 c | -95 | CHF 2CHF 2 | 0.82 | 41.0 | 142 | 2.3 | 2.3 |
| 9 c，e | -95 | CHF 2CF 3 | 0.39 | 29.3 | 106 | 2.8 | 2.6 |
| 10 | -90 | CH 3Cl | 0.58 | 14.5 | 397 | 3.3 | 1.3 |
| 11 | -95 | Propane | 2.37 c | 59.4 | 67 | 2.4 | 2.0 |
A: when the thinner of specified polyreaction with 30ml, 5.4ml iso-butylene and the isoprene (IP) of 0.23ml carry out, initiator/aided initiating solution be the 1.0M hexane solution of the methylaluminum dichloride (MADC) of the TMPCl by using 1.6 microlitres and 11.5 microlitres in the methyl chloride of 1.3ml when preparing except.
B: add three the initiator/aided initiatings batch in the reactor to
C: add two the initiator/aided initiatings batch in the reactor to
D: the ethyl aluminum chloride (EADC) that replaces MADC
E: by the establish rules reaction of mould of the thinner of 10ml
Polymerization in any hydrogen fluorine carbon has obtained rubber grain, and it does not adhere to reactor wall or adheres to stir shaft.When stirring stopped, particle floated to the surface of liquid.These particles when when testing near temperature of reaction by with freezing spatula to their the pressurization detect to show it is hard.Polymerization in methyl chloride has obtained adhering to simultaneously the rubber grain of reactor wall and stir shaft.This particle is when obviously being elastomeric when detecting with freezing spatula when testing near temperature of reaction.Polymerization in propane causes two-phase liquid-liquid reactions.The dense polymkeric substance that obviously is rich in mutually, and the lighter propane that is rich in mutually.
Embodiment 12-14
The results are shown in the table 2 of the polyreaction of under-50 to-55 ℃, carrying out.Embodiment 13 and 14 is comparative examples.The miniature resin kettle of 100ml glass is used for these embodiment.TMPCl (2-chloro-2,4,4-trimethylpentane) is in these embodiments as initiator.
Table 2
a
| Embodiment | Temperature (℃) | Thinner | Output (g) | Transformation efficiency (Wt.%) | Mw× 10 -3 | Mw/M n | Mol％ IP |
| 12 | -55 | CH 2F 2 b | 1.1 | 29.0 | 205 | 2.2 | 1.9 |
| 13 | -50 | CH 3Cl | 1.1 | 29.0 | 52 | 1.5 | 1.1 |
| 14 | -55 | Propane b | 1.2 | 30.9 | 87 | 2.2 | 1.8 |
A: the polyreaction thinner of 30ml, 5.4ml iso-butylene and the isoprene (IP) of 0.23ml carry out, initiator/aided initiating solution is that the 1.0M hexane solution of the methylaluminum dichloride of the TMPCl by using 1.6 microlitres and 11.5 microlitres in the methyl chloride of 1.3ml prepares.
B: add two the initiator/aided initiatings batch in the reactor to
Polymerization in methylene fluoride obtains rubber grain, and it demonstrates more the rubber-like of stiffness physicals, and this can be under temperature of reaction detects with freezing spatula and verifies.On reactor wall and stir shaft, find to have a spot of fouling.By comparison, the polymerization in methyl chloride causes forming simultaneously the viscous coating of polymkeric substance on reactor wall and stir shaft.Few polymkeric substance " suspension " is in diluent medium.Polymerization experiment based on propane does not seem and experiment (table 1, the embodiment 11) difference of carrying out under-95 ℃.Two phases are obviously arranged in reactor.Fine and close is rich in polymkeric substance mutually and gently is rich in propane mutually.Has much lower viscosity at the polymkeric substance in the presence of the propane thinner than the polymkeric substance that in the methyl chloride experiment, forms.
Embodiment 15-21
Table 3 has been listed the result of the polyreaction of carrying out under-95 ℃ in hydrogen fluorine carbon/methyl chloride blend.The miniature resin kettle of 100ml glass is used for these embodiment.TMPCl (2-chloro-2,4,4-trimethylpentane) is in these embodiments as initiator.
Table 3
a
| Embodiment | Thinner | Vol％ | Output (g) | Transformation efficiency (Wt.%) | Mw× 10 -3 | Mw/ Mn | |
| 15 | CH 3Cl/CH 2FCF 3 | 95/5 | 2.97 | 74.0 | 234 | 3.5 | 1.2 |
| 16 | CH 3Cl/CH 2FCF 3 | 90/10 | 1.90 | 47.0 | 600 | 2.9 | 1.6 |
| 17 | CH 3Cl/CH 2FCF 3 | 85/15 | 2.58 | 64.0 | 435 | 2.5 | 1.3 |
| 18 | CH 3Cl/CH 2FCF 3 | 85/15 | 1.83 | 46.0 | 570 | 2.5 | 1.7 |
| 19 | CH 3Cl/CH 2FCF 3 | 80/20 | 1.85 | 46.6 | 285 | 2.7 | 1.5 |
| 20 | CH 3Cl/CH 2F 2 | 80/20 | 3.22 | 80.0 | 312 | 3.2 | 1.9 |
| 21 | CH 3Cl/CH 3CF 3 | 80/20 | 2.83 | 70.6 | 179 | 2.7 | 2.2 |
A: when the thinner of specified polyreaction with 30ml, 5.4ml iso-butylene and the isoprene (IP) of 0.23ml carry out, initiator/aided initiating solution be the 1.0M hexane solution of the ethylaluminum dichloride (EADC) of the TMPCl by using 3.2 microlitres and 23.0 microlitres in the methyl chloride of 2.6ml when preparing except.
B: use methylaluminum dichloride (MADC), replace ethylaluminum dichloride (EADC)
Embodiment 22-25
The polymeric result who carries out under-55 ℃ provides in table 4.Two batches initiator/aided initiating solution is used for each embodiment.The miniature resin kettle of 100ml glass is used for these embodiment.TMPCl (2-chloro-2,4,4-trimethylpentane) is in these embodiments as initiator.
Table 4
a
| Embodiment | Thinner | Vol％ | Output (g) | Transformation efficiency (Wt.%) | Mw× 10 -3 | Mw/M n | Mol％ IP |
| 22 | CH 3Cl/CH 2FCF 3 | 90/10 | 2.35 | 61.7 | 84 | 1.7 | 2.2 |
| 23 | CH 3Cl/CH 2FCF 3 | 85/15 | 2.96 | 77.7 | 77 | 2.2 | 2.2 |
| 24 | CH 3Cl/CH 2FCF 3 | 80/20 | 2.37 | 62.2 | 82 | 1.9 | 2.0 |
| 25 | CH 3Cl/CH 2FCF 3 | 75/25 | 2.38 | 62.5 | 88 | 2.0 | 2.2 |
A: the polyreaction thinner of 30ml, 5.4ml iso-butylene and the isoprene (IP) of 0.23ml carry out, initiator/aided initiating solution is that the 1.0M hexane solution of the methylaluminum dichloride (MADC) of the TMPCl by using 1.6 microlitres and 11.5 microlitres in the methyl chloride of 1.3ml prepares.
Embodiment 26
Polymerization is carried out under-95 ℃ with the methoxyl group al dichloride.This initiator/aided initiating solution is dissolved in the liquid 1,1,1 under-35 ℃ of being in of 2.6ml by the anhydrous methanol with 0.93 microlitre, prepares in the 2-Tetrafluoroethane.In this solution, add the concentration 1.0mol/L solution of ethylaluminum dichloride in pentane of 23 microlitres.With gained solution stirring 10 minutes.Press second kind of solution of the same manner preparation.In each solution, under agitation add the 2-chloro-2,4 of 3.2 microlitres, the 4-trimethylpentane, and be cooled to-95 ℃.With the refrigerated transfer pipet two kinds of drips of solution are added in the polymeric solution.The miniature resin kettle of 100ml glass is used for this embodiment.
Table 5
| Embodiment | Thinner | Output (g) | Transformation efficiency (Wt.%) | Mw× 10 -3 | Mw/Mn | Mol％ IP |
| 26 | CH 2FCF 3 | 2.61 | 65 | 248 | 2.6 | 2.6 |
Embodiment 27
Table 6 has been listed 1,1,1,2-Tetrafluoroethane and 1, in 85/15 (v/v) blend of 1-C2H4F2 C2H4F2 in-95 ℃ of polymeric results that carry out.This polymerization experiment thinner of 30ml, 5.4ml iso-butylene, 0.26ml isoprene, and using a kind of initiator/aided initiating solution to carry out, this solution is that the concentration 1.0M hexane solution by the methylaluminum dichloride (MADC) of TMPCl that uses 3.2 microlitres and 32.0 microlitres prepares in the 2.6ml methyl chloride.The miniature resin kettle of 100ml glass is used for this embodiment.
Table 6
| Embodiment | Output (g) | Transformation efficiency (Wt.%) | Mw×10 -3 | Mw/Mn | Mol％ IP |
| 27 | 0.28 | 7 | 772 | 2.8 | 1.8 |
Embodiment 28-31
Table 7 has been listed the result who uses the polyreaction that p-methylstyrene (pMS) carries out as comonomer in the blend of hydrogen fluorine carbon and hydrogen fluorine carbon and methyl chloride under-95 ℃.The miniature resin kettle of 100ml glass is used for these embodiment.TMPCl (2-chloro-2,4,4-trimethylpentane) is in these embodiments as initiator.
Table 7
a
| Embodiment | Thinner | Output (g) | Transformation efficiency (Wt.%) | Mw×10 -3 | Mw/Mn | Mol％ pMS |
| 28 | CH 2FCF 3 | 1.37 | 33 | 322 | 3.2 | 2.1 |
| 29 | CH 3Cl/CH 2FCF 3 80/20V/V | 0.96 | 23 | 762 | 4.2 | 2.2 |
| 30 b | CH 2FCF 3 | 3.81 | 92 | 160 | 3.3 | 3.6 |
| 31 b，c | CHFCF 3 | 1.18 | 28 | 278 | 3.2 | 1.8 |
A: when the thinner of specified polyreaction with 30ml, 5.4ml iso-butylene and the p-methylstyrene of 0.34ml carry out, initiator/aided initiating solution be the 1.0M hexane solution of the ethylaluminum dichloride (EADC) of the TMPCl by using 3.2 microlitres and 23.0 microlitres in the methyl chloride of 2.6ml when preparing except.
B: use the concentration 1.0M hexane solution of the ethylaluminum dichloride of 32.0 microlitres, replace the amount of in above (a), indicating.
C: use the 2-chloro-2-methylpropane of 1.6 microlitres, replace the TMPCl that in (a), uses.
Polymerization in any thinner of table 7 has obtained rubber grain, and it does not adhere to reactor wall or adheres to stir shaft.When stirring stopped, particle floated to the surface of liquid.When testing, prove that by particle being pressurizeed to detect particle is hard with freezing spatula near temperature of reaction.
Embodiment 32-37
Table 8 has been listed in hydrogen fluorine carbon and the result of the polyreaction of carrying out under-95 ℃ in the methyl chloride of contrast usefulness.Embodiment 36 and 37 is comparative examples.Three neck 500ml glass reactors are used for these embodiment.Before each polymerization, the monomeric raw material monomer of 10wt% that contains of 300ml is joined in the refrigerated reactor.Initiator/aided initiating molar ratio be controlled at 1/3 and concentration be set in 0.1wt%EADC among the MeCl.Initiator/aided initiating drips of solution is added in the polyblend and control interpolation rate requirement temperature of reactor is no more than 4 ℃.The amount of the initiator/aided initiating solution that adds in each test depends on required monomer conversion target.
Table 8
a
| Embodiment | Thinner | Transformation efficiency (Wt.%) | Mn× 10 -3 | Mw× 10 -3 | Mw/Mn | Mol％ IP |
| 32 | CH 2FCF 3 | 65 | 315 | 626 | 2.0 | 2.7 |
| 33 | CH 2FCF 3 | 94 | 213 | 489 | 2.3 | 3.0 |
| 34 | CH 3CHF 2 | 55 | 414 | 813 | 2.0 | 1.3 |
| 35 | CH 3CHF 2 | 100 | 197 | 558 | 2.8 | 1.8 |
| 36 | CH 3Cl | 54 | 170 | 628 | 3.7 | 2.0 |
| 37 | CH 3Cl | 97 | 135 | 517 | 3.8 | 2.4 |
A: polymerization is carried out with iso-butylene/isoprene mole raw material ratio of 95/5
Embodiment in table 8 has illustrated at CHF
2CF
3And CH
3CHF
2The production of the high molecular isoprene-isobutylene rubber that use EADC/HCl initiator system is carried out in the thinner.At CHF
2CF
3And CH
3CHF
2The molecular weight of the butyl polymer of middle preparation is significantly higher than the polymkeric substance for preparing with similar monomer conversion in MeCl under conditions of similarity.With the polymer phase ratio that in MeCl, under similar experiment condition, makes, at CH
2FCF
3And CH
3CHF
2The polymolecularity of the butyl polymer that both make (Mw/Mn) is narrower and more approach 2.0 most probable polymolecularity.Isoprene introducing rate in the multipolymer that MeCl makes is at CH
2FCF
3And CH
3CHF
2Analog value between.Compare with the polymer slurries particle that in MeCl, under conditions of similarity, makes, at CH
2FCF
3And CH
3CHF
2The polymer slurries particle that makes among both has the viscosity of much less significantly in disposal process.
Embodiment 38-44
Table 9 has been listed in hydrogen fluorine carbon and methyl chloride (contrast) in the result of the copolymerization of-95 ℃ of iso-butylenes that carry out and p-methylstyrene.Embodiment 41 and 42 is comparative examples.Three neck 500ml glass reactors are used for these embodiment.Before each polymerization, the monomeric raw material monomer of 10wt% that contains of 300ml is joined in the refrigerated reactor.Initiator/aided initiating molar ratio be controlled at 1/3 and concentration be set in 0.1wt%EADC among the MeCl.Initiator/aided initiating drips of solution is added in the polyblend and control interpolation rate requirement temperature of reactor is no more than 4 ℃.The amount of the initiator/aided initiating solution that adds in each test depends on required monomer conversion target.
Table 9
a
| Embodiment | Thinner | Transformation efficiency (Wt.%) | Mn× 10 -3 | Mw× 10 -3 | Mw/Mn | Mol％ pMS |
| 38 | CHF 2CF 3 | 22 | 91 | 298 | 3.3 | 4.3 |
| 39 | CHF 2CF 3 | 57 | 89 | 291 | 3.3 | 4.4 |
| 40 | CHF 2CF 3 | 98 | 74 | 244 | 3.3 | 4.6 |
| 41 | CH 3CHF 2 | 56 | 188 | 1,091 | 5.8 | 4.1 |
| 42 | CH 3CHF 2 | 100 | 169 | 908 | 5.4 | 4.9 |
| 43 | CH 3Cl | 57 | 97 | 443 | 4.6 | 3.8 |
| 44 | CH 3Cl | 69 | 94 | 342 | 3.6 | 4.0 |
A: polymerization is carried out with iso-butylene/p-methylstyrene mole raw material ratio of 90/10
Embodiment in table 9 shows, by at CH
2FCF
3Use the EADC/HCl initiator system in the thinner, produced iso-butylene-PMS multipolymer that suitable molecular weight is arranged with the multipolymer of producing in the MeCl thinner.At CH
3CHF
2Iso-butylene/p-methylstyrene the multipolymer of preparation demonstrates much higher molecular weight.At CH
2FCF
3In the pMS introducing rate in multipolymer that realized more much higher when similar reaction conditions than in MeCl, using identical raw material monomer to form.In addition, at CH
2FCF
3The polymer slurries particle of middle preparation shows at CH
2FCF
3Middle than in MeCl, having much lower viscosity.
Embodiment 45-47
Table 10 has been listed at CH
2FCF
3And CH
3CHF
280/20 mixture (by volume) in the result of copolymerization of iso-butylene/p-methylstyrene of under-95 ℃, carrying out and iso-butylene/isoprene.Three neck 500ml glass reactors are used for these embodiment.Before each polymerization, the monomeric raw material monomer of 10wt% that contains of 300ml is joined in the refrigerated reactor.Initiator/aided initiating molar ratio be controlled at 1/3 and concentration be set in 0.1wt%EADC among the MeCl.Initiator/aided initiating drips of solution is added in the polyblend and control interpolation rate requirement temperature of reactor is no more than 4 ℃.The amount of the initiator/aided initiating solution that adds in each test depends on required monomer conversion target.
Table 10
| Embodiment | Comonomer | Transformation efficiency (Wt.%) | Mn×10 -3 | Mw×10 -3 | Mw/ |
| 45 a | Isoprene | 87 | 309 | 676 | 2.2 |
| 46 b | pMS | 76 | 449 | 1,048 | 2.3 |
| 47 b | | 100 | 349 | 1,166 | 3.3 |
A: polymerization is carried out with iso-butylene/isoprene mole raw material ratio of 95/5
B: polymerization is carried out with iso-butylene/p-methylstyrene mole raw material ratio of 90/10
Table 10 has illustrated at the CH as polymerization diluent
2FCF
3And CH
3CHF
2Mixture in use the EADC/HCl initiator system, the production of high molecular isobutylene-isoprene copolymer and iso-butylene-pMS multipolymer.At CH
2FCF
3/ C
3CHF
2The polymer slurries particle that makes in the mixture demonstrate with as mentioned above at pure CH
2FCF
3Or CH
3CHF
2The non-sticky outward appearance that the particle that makes in the thinner is identical.
Embodiment 48-117
Embodiment 48-117 for example understands the copolymerization of iso-butylene and other comonomer.Copolymerization is carried out two kinds of temperature with in four kinds of thinners.
At the polymerization embodiment that table is listed among the 11-16 is to carry out the slurry copolymerization in by the developmental tube that the rare earth magnetic stirring bar is being housed to obtain.Monomer solution be under temperature required (indicating in the paragraph below) in developmental tube by with the liquid diluent of 20ml, the liquid iso-butylene of 5ml and the liquid copolymeric that enough reaches 3mol% comonomer raw material prepare with the monomer blending.Polymeric solution carries out magnetic agitation and causes by using the dropping of refrigerative glass Pasteur transfer pipet to stock material aided initiating/initiator solution under indicated temperature.Transformation efficiency is recorded as the monomeric wt% that changes into polymkeric substance.
Table 11 is listed in methyl chloride (as a comparison, embodiment 48,49,50,57,58,59,66,67 and 68), 1,1,1,2-Tetrafluoroethane or 1, in the 1-C2H4F2 C2H4F2 in-95 ℃ of polymeric results that carry out.Iso-butylene and right-t-butyl styrene (t-BuS) (0.36ml/ experiment), indenes (Ind) (0.23ml/ experiment) or beta-pinene (β P) (0.31ml/ takes turns experiment) carry out copolymerization, as indicated at table 18.By add 0.320ml 1,1,1, the concentration 1.0mol/L ethylaluminum dichloride solution in hexane of concentration 1.0mol/L HCl solution and 0.960ml prepares the material solution of ethylaluminum dichloride (EADC) and hydrogenchloride (HCl) in the 2-Tetrafluoroethane in methyl chloride in the methyl chloride of 100ml.Be added to by this raw material EADC/HCl drips of solution in the monomer solution of stirring and carry out polyreaction 1.5ml.The interpolation of the methyl alcohol by 0.2ml stops polymerization.Polymerization in any hydrogen fluorine carbon has obtained rubber grain, and it does not adhere to reactor wall or adheres to stirring rod.When stirring stopped, particle floated to the surface of liquid.These particles when when testing near temperature of reaction by with freezing spatula to their the pressurization detect to show it is hard.Polymerization in methyl chloride has obtained adhering to simultaneously the rubber grain of reactor wall and stir shaft.
Table 11
| Embodiment | Thinner | CoM | Output (mg) | Transformation efficiency (wt.%) | Mw× 10 -3 | Mw/Mn | mol％ CoM |
| 48 | CH 3Cl | t-BuS | 496 | 12.8 | 139 | 2.5 | 1.4 |
| 49 | CH 3Cl | t-BuS | 384 | 9.6 | 130 | 2.3 | 2.4 |
| 50 | CH 3Cl | t-BuS | 485 | 12.6 | 112 | 2.2 | 1.5 |
| 51 | CH 2FCF 3 | t-BuS | 345 | 8.9 | 128 | 2.0 | 2.0 |
| 52 | CH 2FCF 3 | t-BuS | 249 | 6.4 | 128 | 2.0 | 1.6 |
| 53 | CH 2FCF 3 | t-BuS | 295 | 7.6 | 119 | 1.9 | 1.9 |
| 54 | CH 3CHF 2 | t-BuS | 325 | 8.4 | 297 | 2.7 | 1.8 |
| 55 | CH 3CHF 2 | t-BuS | 433 | 11.2 | 217 | 2.6 | 2.3 |
| 56 | CH 3CHF 2 | t-BuS | 333 | 8.6 | 303 | 2.7 | 1.8 |
| 57 | CH 3Cl | Ind | 375 | 9.9 | 68 | 2.2 | 1.2 |
| 58 | CH 3Cl | Ind | 179 | 4.7 | 117 | 1.7 | 1.3 |
| 59 | CH 3Cl | Ind | 130 | 3.4 | 103 | 2.3 | 1.1 |
| 60 | CH 2FCF 3 | Ind | 2279 | 60.8 | 131 | 2.2 | 2.3 |
| 61 | CH 2FCF 3 | Ind | 1199 | 31.9 | 101 | 2.1 | 2.4 |
| 62 | CH 2FCF 3 | Ind | 2299 | 61.3 | 116 | 2.2 | 2.0 |
| 63 | CH 3CHF 2 | Ind | 323 | 14.0 | 141 | 2.3 | 1.8 |
| 64 | CH 3CHF 2 | Ind | 243 | 9.1 | 138 | 2.3 | 1.8 |
| 65 | CH 3CHF 2 | Ind | 526 | 8.6 | 146 | 2.3 | 1.9 |
| 66 | CH 3Cl | βp | 402 | 10.5 | 20.7 | 1.0 | 8.3 |
| 67 | CH 3Cl | βP | 406 | 10.6 | 20.5 | 1.1 | 7.8 |
| 68 | CH 3Cl | βp | 235 | 6.2 | 17.6 | 1.0 | 8.9 |
| 69 | CH 2FCF 3 | βp | 644 | 17.7 | 29.5 | 1.4 | 9.4 |
| 70 | CH 2FCF 3 | βp | 833 | 22.1 | 39.7 | 1.4 | 8.1 |
| 71 | CH 2FCF 3 | βp | 610 | 16.2 | 37.0 | 1.4 | 8.5 |
Table 12 has been listed in methyl chloride (as a comparison, embodiment 72,73,74,81,82 and 83), 1,1,1,2-Tetrafluoroethane or 1, the polymeric result who carries out under-50 ℃ in the 1-C2H4F2 C2H4F2.Iso-butylene and right-t-butyl styrene (t-BuS) (0.36ml/ experiment) or indenes (Ind) (0.23ml/ experiment) carry out copolymerization, as indicated at table 12.By add 0.320ml 1,1,1, the concentration 1.0mol/L ethylaluminum dichloride solution in hexane of concentration 1.0mol/L HCl solution and 0.960ml prepares the material solution of ethylaluminum dichloride (EADC) and hydrogenchloride (HCl) in the 2-Tetrafluoroethane in methyl chloride in the methyl chloride of 100ml.Be added drop-wise to by this EADC/HCl material solution in the monomer solution of stirring and carry out polymerization, for embodiment 72,73, except 74,81,82,83 and 87 1.5ml.At embodiment 72,73, in 74,81,82,83 and 87, use the EADC/HCl solution of 2.3ml.The interpolation of the methyl alcohol by 0.2ml stops polymerization.Polymerization in any hydrogen fluorine carbon has obtained rubber grain, and it does not adhere to reactor wall or adheres to stirring rod.When stirring stopped, particle floated to the surface of liquid.Compare these particles with the embodiment of methyl chloride preparation and be stiffness more, this can be by verifying when with freezing spatula particle being pressurizeed to detect when testing near temperature of reaction.Polymerization in methyl chloride has obtained adhering to simultaneously the rubber grain of reactor wall and stir shaft.
Table 12
| Embodiment | Thinner | CoM | Output (mg) | Transformation efficiency (wt.%) | Mw× 10 -3 | Mw/Mn | mol％ CoM |
| 72 | CH 3Cl | t-BuS | 1750 | 45.3 | 48.4 | 1.7 | 2.9 |
| 73 | CH 3Cl | t-BuS | 1917 | 49.6 | 58.0 | 1.9 | 2.9 |
| 74 | CH 3Cl | t-BuS | 2758 | 71.4 | 60.4 | 2.0 | 2.9 |
| 75 | CH 2FCF 3 | t-BuS | 500 | 12.9 | 35.3 | 1.4 | 4.1 |
| 76 | CH 2FCF 3 | t-BuS | 523 | 13.5 | 39.2 | 1.5 | 4.3 |
| 77 | CH 2FCF 3 | t-BuS | 568 | 14.7 | 39.7 | 1.5 | 4.3 |
| 78 | CH 3CHF 2 | t-BuS | 651 | 16.9 | 68.1 | 1.7 | 4.4 |
| 79 | CH 3CHF 2 | t-BuS | 733 | 19.0 | 71.9 | 1.6 | 4.1 |
| 80 | CH 3CHF 2 | t-BuS | 440 | 11.4 | 70.3 | 1.7 | 2.8 |
| 81 | CH 3Cl | Ind | 704 | 18.6 | 49.9 | 1.4 | 1.0 |
| 82 | CH 3Cl | Ind | 645 | 17.1 | 34. | 1 | 1.4 |
| 83 | CH 3Cl | Ind | 319 | 8.4 | 44.6 | 1.4 | 1.1 |
| 84 | CH 2FCF 3 | Ind | 424 | 11.3 | 36.7 | 1.4 | 1.7 |
| 85 | CH 2FCF 3 | Ind | 464 | 12.4 | 37.9 | 1.4 | 2.0 |
| 86 | CH 2FCF 3 | Ind | 496 | 13.2 | 40.8 | 1.5 | 1.9 |
| 87 | CH 3CHF 2 | Ind | 328 | 8.7 | 40.8 | 1.5 | 1.4 |
| 88 | CH 3CHF 2 | Ind | 338 | 9.0 | 42.9 | 1.5 | 13 |
Table 13 has been listed 1, and the 1-C2H4F2 C2H4F2 is 1,1,1, the polymeric result who carries out under-95 ℃ in the concentration 20wt% blend in the 2-Tetrafluoroethane.Iso-butylene and a kind of following comonomer or comonomer are to carrying out copolymerization, as as shown in the table 13: isoprene (IP) (0.20ml/ experiment), p-methylstyrene (pMS) (0.26ml/ experiment), right-t-butyl styrene (t-BuS) (0.36ml/ experiment), indenes (Ind) (0.23ml/ experiment), the 50/50mol/mol blend (IP/pMS) of beta-pinene (β P) (0.31ml/ experiment) or isoprene (0.10ml) and p-methylstyrene (0.13ml) (each experiment) is as indicated in the table 20.By add 0.320ml 1,1,1, the concentration 1.0mol/L ethylaluminum dichloride solution in hexane of concentration 1.0mol/L HCl solution and 0.960ml prepares the material solution of ethylaluminum dichloride (EADC) and hydrogenchloride (HCl) in the 2-Tetrafluoroethane in methyl chloride in the methyl chloride of 100ml.Be added drop-wise to by this EADC/HCl material solution in the monomer solution of stirring and carry out polymerization, for embodiment 98,99, except 100,101,102 and 103 1.5ml.For embodiment 98,99 and 100, use the EADC/HCl solution of 3.0ml.For embodiment 101,102 and 103, use the EADC/HCl solution of 2.3ml.The interpolation of the methyl alcohol by 0.2ml stops polymerization.Polymerization in any hydrogen fluorine carbon has obtained rubber grain, and it does not adhere to reactor wall or adheres to stirring rod.When stirring stopped, particle floated to the surface of liquid.These particles when when testing near temperature of reaction by with freezing spatula to their the pressurization detect to show it is hard.Polymerization in methyl chloride has obtained adhering to simultaneously the rubber grain of reactor wall and stir shaft.
Table 13
| Embodiment | CoM | Output (mg) | Transformation efficiency (wt.%) | Mw×10 -3 | Mw/Mn | mol％ CoM |
| 89 | IP | 1147 | 31.1 | 453 | 2.0 | 1.9 |
| 90 | IP | 2061 | 55.9 | 628 | 1.8 | 2.0 |
| 91 | IP | 2382 | 64.6 | 276 | 2.0 | 2.2 |
| 92 | pMS | 654 | 17.3 | 782 | 3.4 | 2.8 |
| 93 | pMS | 722 | 19.1 | 624 | 3.0 | 2.8 |
| 94 | pMS | 795 | 21.0 | 665 | 3.0 | 2.7 |
| 95 | t-BuS | 411 | 10.6 | 304 | 2.0 | 1.6 |
| 96 | t-BuS | 389 | 9.8 | 252 | 2.1 | 1.9 |
| 97 | t-BuS | 445 | 11.5 | 241 | 2.1 | 1.9 |
| 98 | Ind | 166 | 4.4 | 283 | 2.2 | 1.3 |
| 99 | Ind | 405 | 10.7 | 267 | 2.3 | 1.4 |
| 100 | Ind | 208 | 5.5 | 317 | 2.1 | 1.2 |
| 101 | βP | 1340 | 35.6 | 104 | 1.5 | 5.2 |
| 102 | βP | 375 | 10.0 | 79.4 | 1.4 | 8.4 |
| 103 | βP | 389 | 10.4 | 76.9 | 1.4 | 8.8 |
| 104 | IP/pMS | 331 | 8.9 | 632 | 1.8 | 0.49/1.7 |
| 105 | IP/pMS | 423 | 11.3 | 699 | 1.8 | 0.67/1.5 |
| 106 | IP/pMS | 361 | 9.7 | 989 | 2.1 | 0.71/1.5 |
Table 14 has been listed in methyl chloride (as a comparison, embodiment 107 and 108), and 1,1,1, the 2-Tetrafluoroethane, 1,1-C2H4F2 C2H4F2, or 1,1-C2H4F2 C2H4F2 be 1,1,1, the 20wt% blend (CH in the 2-Tetrafluoroethane
3CHF
2/ CH
2FCF
3) in, in the result of the copolymerization of-95 ℃ of iso-butylenes that carry out and divinyl (0.15ml/ experiment).By add 0.320ml 1,1,1, the concentration 1.0mol/L ethylaluminum dichloride solution in hexane of concentration 1.0mol/L HCl solution and 0.960ml prepares the material solution of ethylaluminum dichloride (EADC) and hydrogenchloride (HCl) in the 2-Tetrafluoroethane in methyl chloride in the methyl chloride of 100ml.Be added to by this raw material EADC/HCl drips of solution in the monomer solution of stirring and carry out polyreaction 1.5ml.The interpolation of the methyl alcohol by 0.2ml stops polymerization.Polymerization in any hydrogen fluorine carbon has obtained rubber grain, and it does not adhere to reactor wall or adheres to stirring rod.When stirring stopped, particle floated to the surface of liquid.These particles when when testing near temperature of reaction by with freezing spatula to their the pressurization detect to show it is hard.Polymerization in methyl chloride has obtained adhering to simultaneously the rubber grain of reactor wall and stir shaft.The listed shown molecular weight of polymkeric substance is higher than the exclusion limit of the SEC instrument that is used to measure molecular weight in table 14.The Mw of these polymkeric substance is higher than 1.5 * 10
6G/mol.Because high molecular is arranged, also can't determining molecular weight distribution (MWD) for these samples.
Table 14
| Embodiment | Thinner | Output (mg) | Transformation efficiency (wt.%) | mol％ CoM |
| 107 | CH 3Cl | 503 | 13.7 | 0.2 |
| 108 | CH 3Cl | 689 | 18.8 | 0.1 |
| 109 | CH 2FCF 3 | 448 | 12.2 | 0.2 |
| 110 | CH 2FCF 3 | 543 | 14.8 | 0.3 |
| 111 | CH 2FCF 3 | 404 | 11.0 | 0.3 |
| 112 | CH 3CHF 2 | 338 | 9.2 | 0.2 |
| 113 | CH 3CHF 2 | 481 | 13.1 | 0.1 |
| 114 | CH 3CHF 2 | 352 | 9.6 | 0.2 |
| 115 | CH 3CHF 2/CH 2FCF 3 | 453 | 12.4 | 0.3 |
| 116 | CH 3CHF 2/CH 2FCF 3 | 777 | 21.2 | 0.2 |
| 117 | CH 3CHF 2/CH 2FCF 3 | 573 | 15.7 | 0.2 |
Embodiment 118-141
The polymerization embodiment that lists in table 15 and 16 obtains by carrying out the slurry copolymerization in the developmental tube that the rare earth magnetic stirring bar is being housed.For the embodiment in the table 15-95 ℃ down with for the embodiment in table 16 under-35 ℃, in developmental tube, prepare monomer solution.By the refrigerated liquid diluent with 20ml, the liquid iso-butylene of 5ml and the isoprene blending of 0.20ml prepare solution.Provided the exception part of this program below.Polymeric solution carries out magnetic agitation and causes by using the dropping of refrigerative glass Pasteur transfer pipet to stock material aided initiating/initiator solution under indicated temperature.Transformation efficiency is recorded as the monomeric wt% that changes into polymkeric substance.
Table 15 has been listed the polymeric result who carries out under-95 ℃.Embodiment 118,119, and 120,123,124,125 and 126 is comparative examples, and wherein embodiment 118 and 119 is embodiments of the invention.
Be added drop-wise to by material solution in the monomer solution of stirring and carry out polymerization ethylaluminum dichloride (EADC)/hydrogenchloride (HCl).By add 0.320ml 1,1,1, in the 2-Tetrafluoroethane concentration 1.0mol/L ethylaluminum dichloride solution in hexane of concentration 1.0mol/L HCl solution and 0.960ml in the methyl chloride of 100ml, the material solution of preparation EADC and HCl in methyl chloride.The cumulative volume that adds the material solution in the polyreaction of each embodiment to is shown in Table 15.The independent material solution of ethylaluminum dichloride and hydrogenchloride is used for embodiment 125 and 126.By with 2.0ml 1,1,1, the concentration 1.0mol/L ethylaluminum dichloride solution in hexane of concentration 0.16mol/L HCl solution and 0.960ml adds in the methyl chloride of 100ml and prepares this solution in the 2-Tetrafluoroethane.It is identical preparing for the solution for two kinds in the final mol/L concentration of ethylaluminum dichloride in the material solution and hydrogenchloride.The interpolation of the methyl alcohol by 0.2ml stops polymerization.3,3, the polymerization in the 3-trifluoro propene has obtained rubber grain, and it does not adhere to reactor wall or adheres to stirring rod.When stirring stopped, particle floated to the surface of liquid.These particles when when testing near temperature of reaction by with freezing spatula to their the pressurization detect to show it is hard.Polymerization in methyl chloride has obtained adhering to simultaneously the rubber grain of reactor wall and stir shaft.1, the polymerization meeting in 1-ethylene dichloride or the vinylidene chloride obtains the solvent-swollen polymer beads, and they adhere to reactor wall and stirring rod.
Table 15
| Embodiment | Thinner | Catalyst solution (ml) | Output (mg) | Transformation efficiency (wt.%) | Mw×10 -3 | Mw/Mn | mol ％IP |
| 118 | CH 3Cl | 1.7 | 844 | 22.9 | 271 | 2.2 | 1.7 |
| 119 | CH 3Cl | 1.7 | 618 | 16.7 | 255 | 1.9 | 1.8 |
| 120 | CH 3Cl | 1.7 | 597 | 16.2 | 224 | 2.2 | 1.7 |
| 121 | H 2C＝CHCF 3 | 1.7 | 309 | 16.7 | 266 | 2.3 | 2.2 |
| 122 | H 2C＝CHCF 3 | 1.7 | 274 | 20.6 | 218 | 2.1 | 1.8 |
| 123 | H 2C＝CCl 2 | 1.7 | 118 | 3.2 | 33 | 1.4 | 1.4 |
| 124 | H 2C＝CCl 2 | 4.0 | 447 | 13.4 | 47 | 2.1 | 1.0 |
| 125 | CH 3CHCl 2 | 1.5 | 112 | 3.0 | 108 | 3.1 | 1.7 |
| 126 | CH 3CHCl 2 | 1.5 | 202 | 5.5 | 116 | 2.6 | 1.9 |
Table 16 has been listed the polymeric result who carries out under-35 ℃.Embodiment 127-136 is the comparative example, and embodiment 137-141 is embodiments of the invention.
Carry out polymerization by dripping the right material solution of aided initiating/initiator.By add 0.320ml 1,1,1, the concentration 1.0mol/L ethylaluminum dichloride solution in hexane of concentration 1.0mol/L HCl solution and 0.960ml prepares the material solution of ethylaluminum dichloride and hydrogenchloride (HCl) in the 2-Tetrafluoroethane in methyl chloride in the methyl chloride of 100ml.The independent material solution of ethylaluminum dichloride and hydrogenchloride is used for embodiment 134,135 and 136.By with 0.034ml 1,1,1, the concentration 1.0mol/L ethylaluminum dichloride solution in hexane of concentration 0.93mol/L HCl solution and 0.0960ml adds in the methyl chloride of 10ml and prepares this solution in the 2-Tetrafluoroethane.It is identical preparing for the solution for two kinds in the final mol/L concentration of ethylaluminum dichloride in the material solution and hydrogenchloride.Methylaluminum dichloride (MADC)/2-chloro-2,4, the independent material solution of 4-trimethylpentane (TMPCl) is used for embodiment 132 and 133.Add to by concentration 1.0mol/L methylaluminum dichloride solution in hexane in the methyl chloride of 10ml and prepare MADC/TMPCl solution the TMPCl of 6.6 microlitres and 0.0960ml.The cumulative volume that adds the material solution in the polyreaction of each embodiment to is shown in Table 16.
The interpolation of the methyl alcohol by 0.2ml stops polymerization.1,1-C2H4F2 C2H4F2 or 1,1,1, the polymerization in the 2-Tetrafluoroethane obtains rubber grain, and it demonstrates more the rubber-like of stiffness physicals, and this can be under temperature of reaction detects with freezing spatula and verifies.On reactor wall and stirring rod, find to have a spot of fouling.Comparatively speaking, the polymerization in methyl chloride causes forming simultaneously the viscous coating of polymkeric substance on reactor wall and stirring rod.Few polymkeric substance " suspension " is in diluent medium.1,1-two fluorobenzene or 1, the polymerization meeting in the 2-ethylene dichloride obtains the solvent-swollen polymer phase, and they adhere to reactor wall and stirring rod.Polymerization meeting in 1 is carried out in solution.By the air-dry pinching compound back and forth that desolvates that removes.
Table 16
| Embodiment | Thinner | Catalyst solution (ml) | Output (mg) | Transformation efficiency (wt.%) | Mw ×10 -3 | Mw/ Mn | mol％ IP |
| 127 | CH 3Cl | 4.0 | 1953 | 53.1 | 45 | 1.2 | 1.2 |
| 128 | CH 3Cl | 4.0 | 1678 | 45.6 | 54 | 1.3 | 1.3 |
| 129 | CH 3Cl | 4.0 | 2339 | 63.6 | 51 | 1.2 | 1.4 |
| 130 | CH 3CCl 3 | 4.0 | 3068 | 83.2 | 48 | 2.2 | 0.9 |
| 131 | CH 3CCl 3 | 5.0 | 2993 | 81.2 | 59 | 2.2 | 1.0 |
| 132 | 1,2-two fluorobenzene | 4.0 | 2033 | 55.1 | 35 | 1.6 | 1.5 |
| 133 | 1,2-two fluorobenzene | 4.0 | 1901 | 51.6 | 29 | 1.8 | 1.4 |
| 134 | CH 2ClCH 2Cl | 4.0 | 2563 | 69.5 | 29 | 1.9 | 1.3 |
| 135 | CH 2ClCH 2Cl | 4.0 | 2707 | 73.4 | 24 | 1.8 | 1.3 |
| 136 | CH 2ClCH 2Cl | 4.0 | 2683 | 72.8 | 27 | 1.9 | 1.4 |
| 137 | CH 2FCF 3 | 3.0 | 2348 | 63.8 | 76 | 1.5 | 2.3 |
| 138 | CH 2FCF 3 | 1.5 | 1024 | 27.8 | 92 | 1.5 | 2.2 |
| 139 | CH 3CHF 2 | 3.0 | 1085 | 29.5 | 78 | 1.5 | 1.6 |
| 140 | CH 3CHF 2 | 3.0 | 1104 | 30.0 | 92 | 1.4 | 1.6 |
| 141 | CH 3CHF 2 | 3.0 | 953 | 25.9 | 95 | 1.5 | 1.6 |
Embodiment 142-146
Table 17 has been listed under-95 ℃ at CH
2FCF
3In the result of copolymerization of the isobutylene-isoprene of carrying out.Change iso-butylene/isoprene charge ratio for each embodiment.Three neck 500ml glass reactors are used for these embodiment.Before each polymerization, the monomeric raw material monomer of 10wt% that contains of 300ml is joined in the refrigerated reactor.Initiator/aided initiating molar ratio be controlled at 1/3 and concentration be set in 0.1wt%EADC among the MeCl.Initiator/aided initiating drips of solution is added in the polyblend and control interpolation rate requirement temperature of reactor is no more than 4 ℃.The amount of the initiator/aided initiating solution that adds in each test depends on required monomer conversion target.
Table 17
| Embodiment | The IB/IP molar feed ratio | Transformation efficiency (Wt.%) | Mn× 10 -3 | Mw× 10 -3 | Mw/Mn | Mol％ IP |
| 142 | 98/2 | 100 | 209 | 905 | 4.3 | 1.2 |
| 143 | 97/3 | 100 | 141 | 636 | 4.5 | 1.7 |
| 144 | 95/5 | 100 | 127 | 481 | 3.8 | 2.9 |
| 145 | 93/7 | 94 | 174 | 423 | 2.4 | 3.8 |
| 146 | 90/10 | 85 | 133 | 348 | 2.6 | 5.2 |
These embodiment have illustrated the preparation of the high molecular weight copolymer that high-isoprene introducing rate is arranged.Being flocked in the hydrogen fluorine carbon of sludge particles significantly reduces.The GPC of these iso-butylene/isoprene copolymers follows the trail of and does not show gel formation or crosslinked any sign, even also is like this for the embodiment 146 that contains above the 5mol% isoprene.Homodiene content iso-butylene/isoprene copolymer prepared in accordance with the present invention can utilize standard, the ripe halogenation method of making halobutyl (halobutyl) polymkeric substance to come in addition halogenation subsequently.
Embodiment 147
For at methyl chloride and CH
2FCF
3In iso-butylene/isoprene determining molecular weight of under-95 ℃, carrying out to the dependency of transformation efficiency.This dependency is measured for two kinds of different initiators/aided initiating systems; A kind of based on TMPCl and another kind of based on HCl.Two kinds of catalyst systems all use EADC as this Lewis acid aided initiating.Three neck 500ml glass reactors are used for these embodiment.Before each polymerization, the monomeric raw material monomer of 10wt% that contains of 300ml is joined in the refrigerated reactor.The molar ratio of 95/5 iso-butylene/isoprene is used for each polymerization.Initiator/aided initiating molar ratio be controlled at 1/3 and concentration be set in 0.1wt%EADC among the MeCl.Initiator/aided initiating drips of solution is added in the polyblend and control interpolation rate requirement temperature of reactor is no more than 4 ℃.The amount of the initiator/aided initiating solution that adds in each test depends on required monomer conversion target.These polymeric data are shown among Fig. 3, as the curve of peak molecular weight (Mp) to monomer conversion (wt%).Observe along with improving transformation efficiency, the expection of molecular weight reduces.These data show that also HCl is at CH
2FCF
3The preferred initiator of middle copolymerization.
Embodiment 148
The copolymerization of iso-butylene and cyclopentadiene is at CH under-93 ℃
2FCF
3In carry out.The molar ratio of iso-butylene/cyclopentadiene of 97/3 is used at the feeding raw material monomeric this polyreaction of 10.8wt% being arranged.For this experiment, cyclopentadiene carries out new cracking (cracked).By with 200 microlitres at CH
2FCF
3Middle concentration 1.0mol/L solution chlorination hydrogen is dissolved in the precooling CH of 50ml
2FCF
3In prepare initiator/aided initiating solution.In this solution, add the concentration 1.0mol/L solution of ethylaluminum dichloride in hexane of 500 microlitres.This solution stirring 5 minutes.Begin polyreaction in the monomer solution by under agitation initiator/aided initiating drips of solution being added to.The interpolation of this solution remains in order to prevent that polymerization temperature is elevated to needed speed more than-92 ℃.Use the initiator of 35ml/aided initiating solution altogether.The miniature resin kettle of 500ml glass is used for this embodiment.
Table 18
| Embodiment | Thinner | Transformation efficiency (Wt%) | Mw×10 -3 | Mw/Mn | Mol％CPD | ％1，2 |
| 148 | CH 2FCF 3 | 50 | 527 | 1.9 | 5.3 | 15 |
The solubleness of ethylaluminum dichloride in hydrogen fluorine carbon and blend
The solubility test that is reported among the table 19-25 is undertaken by using purified ethylaluminum dichloride (EADC).Each test is carried out in the following manner.The hydrogen fluorine carbon of the condensation of 5ml is joined in the loft drier cryostat in the developmental tube that the drying that is cooled to-90 ℃ crosses.In this liquid that is under-90 ℃, add pure, the liquid ethylaluminum dichloride (EADC) of 4.1 microlitres.Check solubleness by vigorous stirring gained mixture.Mixture rises to the boiling point of thinner then, simultaneously the content of stirring test pipe.After thinner reaches its boiling point,, developmental tube mixture is cooled to-90 ℃ by being immersed in the cryostat.After the heating of finishing, carry out the observation reported.If catalyzer does not dissolve after this first heating, then add the methyl chloride of 0.5ml.Repeat this heating.The methyl chloride of follow-up interpolation 0.5ml after each heating is till observing the EADC dissolving or obtaining the 50/50V/V blend.Carry out following observation and record result.
1,1,1,2-Tetrafluoroethane (HFC-134a)
Table 19
| Preparation | Volume % methyl chloride | Observations |
| EADC+5ml HFC- | 0 | Insoluble " chip " |
| + 0.5ml methyl chloride | 9 | Trickle flocculation |
| + 0.5ml methyl chloride | 17 | Trickle flocculation |
| + 0.5ml methyl chloride | 23 | Muddy suspension; Slightly flocculation under b.p. |
| + 0.5ml methyl chloride | 29 | Muddy; Unusual fine particle |
| + 0.5ml methyl chloride | 33 | Slight muddy; No visible particle |
| + 0.5ml methyl chloride | 38 | Still slight muddy |
| + 0.5ml methyl chloride | 41 | Almost transparent |
| + 0.5ml methyl chloride | 44 | Almost transparent |
| + 0.5ml methyl chloride | 47 | Transparent |
| + 0.5 | 50 | Transparent |
In the test in table 19, after stopping, stirring flocculates from very muddy suspension." chip " at first no longer as seen.
Methylene fluoride (HFC-32)
Table 20
| Preparation | Volume % methyl chloride | Observations |
| EADC+5ml HFC-32 | 0 | Insoluble " chip " |
| + 0.5ml methyl chloride | 9 | Slight muddy |
| + 0.5ml methyl chloride | 17 | Some flocculations |
| + 0.5ml methyl chloride | 23 | Transparent |
Trifluoromethane (HFC-23)
Table 21
| Preparation | Volume % methyl chloride | Observations |
| EADC+5ml HFC-23 | 0 | Insoluble " chip " |
| + 0.5ml methyl chloride | 9 | Do not dissolve |
| + 0.5ml methyl chloride | 17 | Do not dissolve |
| + 0.5ml methyl chloride | 23 | Do not dissolve |
| + 0.5ml methyl chloride | 29 | Do not dissolve |
| + 0.5ml methyl chloride | 33 | Do not dissolve |
| + 0.5ml methyl chloride | 38 | Do not dissolve |
| + 0.5ml methyl chloride | 41 | Do not dissolve |
| + 0.5ml methyl chloride | 44 | Do not dissolve |
| + 0.5ml methyl chloride | 47 | Do not dissolve |
| + 0.5 | 50 | Do not dissolve |
1,1,1-Halothane (HFC-143a)
Table 22
| Preparation | Volume % methyl chloride | Observations |
| EADC+5ml MC- | 0 | Insoluble " chip " |
| + 0.5ml methyl chloride | 9 | Muddy suspension |
| + 0.5ml methyl chloride | 17 | Muddy suspension |
| + 0.5ml methyl chloride | 23 | Clear solution |
1,1-C2H4F2 C2H4F2 (HFC-152a)
Table 23
| Preparation | Volume % fluoromethane | Observations |
| EADC+5ml HFC- | 0 | Solvable |
The solubility test of carrying out in table 24 is that the 1.0mol/L hydrocarbon feed solution by the ethylaluminum dichloride (EADC) of using the pure EADC that at room temperature lists and hydrocarbon preparation from table carries out.The pentane pentane of making a comment or criticism.The ULB hexane refers to contain the hexane (mixture of isomers) of the ultralow benzene grade that is lower than 5ppm benzene.Final 1,1,1,2-Tetrafluoroethane (HFC-134a) solution is to add in developmental tube among the liquid HFC-134a that remains under-35 ℃ by the room temperature EADC material solution with listed volume in table to prepare.In all cases, obtain initial soln, it is transparent and colourless.Gained solution is implemented cooling by developmental tube is immersed in then in the loft drier cryostat of constant temperature under-95 ℃.By with the temperature of thermometer monitoring liquid with visually measure the muddy cloud point that begins to measure.Allow solution rise to be higher than the temperature of cloud point, solution is bleach once more.By cooling off repeatedly and this solution that heats up, in several minutes, observe near the behavior of solution cloud point.It is reproducible that this phenomenon is found.
Table 24
| Hydrocarbon | 1.0M the volume of EADC material solution (microlitre) | The volume of HFC-134a (mL) | Final EADC concentration (Wt.%) | Cloud point (℃) |
| | 100 | 10 | 0.1 | -87 |
| Pentane | 174 | 15 | 0.1 | -87 |
| The ULB hexane | 174 | 15 | 0.1 | -85 |
The alkoxyl group al dichloride is 1,1,1, and the solubility test that the solubleness in the 2-Tetrafluoroethane (HFC-134a) is reported in table 25 is undertaken by each alkoxyl group al dichloride of in-situ preparing.General procedure is as follows.By under-30 ℃, 0.0001 mol of alcohol being added to the solution for preparing correspondent alcohol among 10 milliliters the HFC-134a.In this solution, add the concentration 1.0mol/L pentane material solution of the EADC of 100 microlitres.After this last interpolation, the periodically jolting in ensuing 5 minutes of HFC-134a solution.Solution rises to-10 ℃ in encloses container, cool off in-95 ℃ loft drier cryostat at constant temperature then.By with the temperature of thermometer monitoring liquid with visually measure the muddy cloud point that begins to measure.Allow solution rise to be higher than the temperature of cloud point, solution is bleach once more.By cooling off repeatedly and this solution that heats up, in several minutes, observe near the behavior of solution cloud point.It is reproducible that this phenomenon is found.
Table 25
| CH 3OAlCl 2 | CH 3CH 2OAlCl 2 | (CH 3) 3COAlCl 2 | CF 3CH 2OAlCl 2 | |
| FW(g/mol) | 128.92 | 142.95 | 171.00 | 196.92 |
| @-40 ℃ of Wt.% Rong Ye | 0.09 | 0.10 | 0.12 | 0.14 |
| Cloud point (℃) | -85 | -85 | -85w/ solid | -87 |
Embodiment 149-151
The copolymerization of iso-butylene and isoprene is by using different iso-butylenes/isoprene copolymer monomer than carrying out under-95 ℃.Whole copolymerizations is that the iso-butylene with the thinner of 30ml and 4.0ml carries out.Carry out in three kinds of different thinners at six different on the consumption of isoprene copolymerizations.Being added to the amount that produces the isoprene of six kinds of different isoprene concentration in the monomer solution for each thinner is 0.11,0.27,0.41,0.57,0.89, and 1.27ml.The multipolymer of embodiment 149 prepares in methyl chloride, so embodiment 149 is comparative examples.The multipolymer of embodiment 150 prepares in the 2-Tetrafluoroethane 1,1,1.The multipolymer of embodiment 151 prepares in the 1-C2H4F2 C2H4F2 1.The multipolymer of embodiment 152 prepares in the 1-methylene fluoride 1.Embodiment 150,151 and 152 is embodiments of the invention.Use in each thinner of 8ml by add 12.6 microlitres at CH
2FCF
3In the 0.93mol/L hydrogen chloride solution and the prepared initiator/aided initiating solution of the 1.0mol/L ethylaluminum dichloride solution in hexane of 35.4 microlitres prepare multipolymer.Be lower than-92 ℃ by stirring monomer solution under 800rpm and dropping this initiator/aided initiating solution with holding temperature and carry out polyreaction.By with methyl alcohol cancellation polyreaction, collected polymer and dry polymer are in a vacuum at room temperature isolated multipolymer.In refrigerator, store this polymkeric substance, before analyzing till.Embodiment 149,150 and 151 fractional data (being expressed as percentage ratio) are shown among Fig. 4.
In table 26, provide with dielectric constant values by the comparison of the iterative fitting of the multipolymer sequence distribution equation formula shown in above at-95 ℃ of following thinners for the sequence distribution parameter m that these embodiment calculated.
Table 26
| Embodiment | Thinner | Productive rate wt.% | Mol％IP | ％BII | m | ε，-95℃ |
| 149 | CH 3Cl | 58.9 58.4 46.9 45.1 | 2.55 5.61 9.16 12.7 | 4.99 7.41 10.9 13.3 | 1.4 | 18.34 |
| 150 | CH 2FCF 3 | 38.3 34.1 37.8 13.1 | 3.32 6.98 10.83 15.5 | 4.01 7.88 11.3 14.0 | 1.2 | 23.25 |
| 151 | CH 3CHF 2 | 48.1 42.1 37.2 24.5 15.6 | 1.92 3.16 4.16 7.09 8.88 | 4.67 6.18 8.46 12.4 14.9 | 2.3 | 29.33 |
| 152 | CH 2F 2 | 100 | 2.4 | 4.3 | 1.9 | 36.29 |
Whole patents and the patent application here listed, test method (as the ASTM method) and other document will be introduced for reference on this type of publication degree consistent with the present invention and for all authorities that allow these introducings fully.
When providing numerical lower limits and numerical upper limits here, the scope from any lower limit to any upper limit is all considered.
Although described the embodiment of illustrative of the present invention particularly, should be appreciated that under the premise without departing from the spirit and scope of the present invention, various other improvement are conspicuous and can easily realize for those of skill in the art.Therefore, do not think that the scope of the claim that this specification sheets is appended is limited to embodiment given here and narration, but claim is believed to comprise all features of the novelty that can patent that exists in the present invention, comprising all further features of the equivalent of being thought these features by the technical staff in the technical field of the invention.
Claims (95)
1. the multipolymer sequence that the multipolymer that comprises isoolefine and polyene hydrocarbon, this multipolymer have by the following formula definition distributes:
F＝mA/(1+mA)
2
Wherein m is a multipolymer sequence distribution parameter; A is the molar ratio of polyene hydrocarbon and isoolefine in multipolymer; With F be isoolefine-polyene hydrocarbon-polyene hydrocarbon triad mark in multipolymer; Wherein m is greater than 1.5.
2. the multipolymer of claim 1, wherein m is greater than 2.0.
3. the multipolymer of claim 1, wherein m is greater than 2.5.
4. the multipolymer of claim 1, wherein m is greater than 3.5.
5. the multipolymer of any one in the aforementioned claim, wherein polyene hydrocarbon is a conjugated diolefine, preferred isoprene.
6. the multipolymer of any one in the aforementioned claim, wherein multi-olefin content is greater than 0.5mol%.
7. the multipolymer of any one in the aforementioned claim, wherein multi-olefin content is greater than 1.0mol%.
8. the multipolymer of any one in the aforementioned claim, wherein multi-olefin content is greater than 2.5mol%.
9. the multipolymer of any one in the aforementioned claim, wherein multi-olefin content is greater than 5.0mol%.
10. the multipolymer sequence that the multipolymer that comprises iso-butylene and isoprene, this multipolymer have by the following formula definition distributes:
F＝mA/(1+mA)
2
Wherein m is a multipolymer sequence distribution parameter; A is the molar ratio of isoprene and iso-butylene in multipolymer; With F be isobutylene-isoprene-isoprene triad mark in multipolymer; Wherein m is greater than 1.5.
11. the multipolymer of claim 10, wherein m is greater than 2.0.
12. the multipolymer of claim 10, wherein m is greater than 2.5.
13. the multipolymer of claim 10, wherein m is greater than 3.5.
14. the multipolymer of any one among the claim 10-13, wherein isoprene content is greater than 0.5mol%.
15. the multipolymer of any one among the claim 10-13, wherein isoprene content is greater than 1.0mol%.
16. the multipolymer of any one among the claim 10-13, wherein isoprene content is greater than 2.5mol%.
17. the multipolymer of any one among the claim 10-13, wherein isoprene content is greater than 5.0mol%.
18. comprise the multipolymer of isoolefine and polyene hydrocarbon, the multipolymer sequence that this multipolymer has by the following formula definition distributes:
F＝mA/(1+mA)
2
Wherein m is a multipolymer sequence distribution parameter; A is the molar ratio of polyene hydrocarbon and isoolefine in multipolymer; With F be isoolefine-polyene hydrocarbon-polyene hydrocarbon triad mark in multipolymer; Wherein m is 1.10-1.25.
19. the multipolymer of claim 18, wherein m is 1.15 to 1.20.
20. the multipolymer of claim 18, wherein m is 1.15 to 1.25.
21. the multipolymer of claim 18, wherein m is about 1.20.
22. the multipolymer of any one among the claim 18-21, wherein polyene hydrocarbon is a conjugated diolefine, preferred isoprene.
23. the multipolymer of any one among the claim 18-22, wherein multi-olefin content is greater than 0.5mol%.
24. the multipolymer of any one among the claim 18-22, wherein multi-olefin content is greater than 1.0mol%.
25. the multipolymer of any one among the claim 18-22, wherein multi-olefin content is greater than 2.5mol%.
26. the multipolymer of any one among the claim 18-22, wherein multi-olefin content is greater than 5.0mol%.
27. comprise the multipolymer of iso-butylene and isoprene, the multipolymer sequence that this multipolymer has by the following formula definition distributes:
F＝mA/(1+mA)
2
Wherein m is a multipolymer sequence distribution parameter; A is the molar ratio of isoprene and iso-butylene in multipolymer; With F be isobutylene-isoprene-isoprene triad mark in multipolymer; Wherein m is 1.10-1.25.
28. the multipolymer of claim 18, wherein m is 1.15 to 1.20.
29. the multipolymer of claim 18, wherein m is 1.15 to 1.25.
30. the multipolymer of claim 18, wherein m is about 1.20.
31. the multipolymer of any one among the claim 27-30, wherein isoprene content is greater than 0.5mol%.
32. the multipolymer of any one among the claim 27-30, wherein isoprene content is greater than 1.0mol%.
33. the multipolymer of any one among the claim 27-30, wherein isoprene content is greater than 2.5mol%.
34. the multipolymer of any one among the claim 27-30, wherein isoprene content is greater than 5.0mol%.
35. by the multipolymer that a kind of method is produced, this method comprises allows isoolefine, preferred iso-butylene, and polyene hydrocarbon, one or more Lewis acids, one or more initiators contact with the thinner that comprises one or more hydrogen fluorine carbon (HFC); The multipolymer sequence that this multipolymer has by the following formula definition distributes:
F＝mA/(1+mA)
2
Wherein m is a multipolymer sequence distribution parameter; A is the molar ratio of polyene hydrocarbon and isoolefine in multipolymer; With F be isoolefine-polyene hydrocarbon-polyene hydrocarbon triad mark in multipolymer; Wherein m be greater than 1.5 or m be 1.10-1.25.
36. the multipolymer of claim 10, wherein m is greater than 2.0.
37. the multipolymer of claim 10, wherein m is greater than 2.5.
38. the multipolymer of claim 10, wherein m is greater than 3.5.
39. the multipolymer of claim 18, wherein m is 1.15 to 1.20.
40. the multipolymer of claim 18, wherein m is 1.15 to 1.25.
41. the multipolymer of claim 18, wherein m is about 1.20.
42. the multipolymer of claim 35, wherein polyene hydrocarbon is a conjugated diolefine, preferred isoprene.
43. the multipolymer of any one among the claim 35-42, wherein multi-olefin content is greater than 0.5mol%.
44. the multipolymer of any one among the claim 35-42, wherein multi-olefin content is greater than 1.0mol%.
45. the multipolymer of any one among the claim 35-42, wherein multi-olefin content is greater than 2.5mol%.
46. the multipolymer of any one among the claim 35-42, wherein multi-olefin content is greater than 5.0mol%.
47. the multipolymer of any one among the claim 35-46, wherein one or more hydrogen fluorine carbon are by chemical formula C
xH
yF
zExpression, wherein x is that 1 to 40 integer and y and z are the integers more than 1 or 1.
48. the multipolymer of claim 47, wherein x is 1 to 10.
49. the multipolymer of claim 47, wherein x is 1 to 6.
50. the multipolymer of claim 47, wherein x is 1 to 3.
51. the multipolymer of claim 35, wherein one or more hydrogen fluorine carbon are independently selected from: methyl fuoride; Methylene fluoride; Trifluoromethane; Fluoroethane; 1, the 1-C2H4F2 C2H4F2; 1, the 2-C2H4F2 C2H4F2; 1,1, the 1-Halothane; 1,1, the 2-Halothane; 1,1,1, the 2-Tetrafluoroethane; 1,1,2, the 2-Tetrafluoroethane; 1,1,1,2, the 2-pentafluoride ethane; 1-fluoropropane; 2-fluoropropane; 1, the 1-difluoropropane; 1, the 2-difluoropropane; 1, the 3-difluoropropane; 2, the 2-difluoropropane; 1,1,1-trifluoro propane; 1,1,2-trifluoro propane; 1,1,3-trifluoro propane; 1,2,2-trifluoro propane; 1,2,3-trifluoro propane; 1,1,1, the 2-tetrafluoropropane; 1,1,1, the 3-tetrafluoropropane; 1,1,2, the 2-tetrafluoropropane; 1,1,2, the 3-tetrafluoropropane; 1,1,3, the 3-tetrafluoropropane; 1,2,2, the 3-tetrafluoropropane; 1,1,1,2, the 2-pentafluoropropane; 1,1,1,2, the 3-pentafluoropropane; 1,1,1,3, the 3-pentafluoropropane; 1,1,2,2, the 3-pentafluoropropane; 1,1,2,3, the 3-pentafluoropropane; 1,1,1,2,2, the 3-HFC-236fa; 1,1,1,2,3, the 3-HFC-236fa; 1,1,1,3,3, the 3-HFC-236fa; 1,1,1,2,2,3, the 3-heptafluoro-propane; 1,1,1,2,3,3, the 3-heptafluoro-propane; Fluorobutane; The 2-butyl fluoride; 1,1-difluoro butane; 1,2-difluoro butane; 1,3-difluoro butane; 1,4-difluoro butane; 2,2-difluoro butane; 2,3-difluoro butane; 1,1,1-trifluoro butane; 1,1,2-trifluoro butane; 1,1,3-trifluoro butane; 1,1,4-trifluoro butane; 1,2,2-trifluoro butane; 1,2,3-trifluoro butane; 1,3,3-trifluoro butane; 2,2,3-trifluoro butane; 1,1,1,2-tetrafluoro butane; 1,1,1,3-tetrafluoro butane; 1,1,1,4-tetrafluoro butane; 1,1,2,2-tetrafluoro butane; 1,1,2,3-tetrafluoro butane; 1,1,2,4-tetrafluoro butane; 1,1,3,3-tetrafluoro butane; 1,1,3,4-tetrafluoro butane; 1,1,4,4-tetrafluoro butane; 1,2,2,3-tetrafluoro butane; 1,2,2,4-tetrafluoro butane; 1,2,3,3-tetrafluoro butane; 1,2,3,4-tetrafluoro butane; 2,2,3,3-tetrafluoro butane; 1,1,1,2, the 2-3-pentafluorobutane; 1,1,1,2, the 3-3-pentafluorobutane; 1,1,1,2, the 4-3-pentafluorobutane; 1,1,1,3, the 3-3-pentafluorobutane; 1,1,1,3, the 4-3-pentafluorobutane; 1,1,1,4, the 4-3-pentafluorobutane; 1,1,2,2, the 3-3-pentafluorobutane; 1,1,2,2, the 4-3-pentafluorobutane; 1,1,2,3, the 3-3-pentafluorobutane; 1,1,2,4, the 4-3-pentafluorobutane; 1,1,3,3, the 4-3-pentafluorobutane; 1,2,2,3, the 3-3-pentafluorobutane; 1,2,2,3, the 4-3-pentafluorobutane; 1,1,1,2,2, the 3-hexafluoro butane; 1,1,1,2,2, the 4-hexafluoro butane; 1,1,1,2,3, the 3-hexafluoro butane; 1,1,1,2,3, the 4-hexafluoro butane; 1,1,1,2,4, the 4-hexafluoro butane; 1,1,1,3,3, the 4-hexafluoro butane; 1,1,1,3,4, the 4-hexafluoro butane; 1,1,1,4,4, the 4-hexafluoro butane; 1,1,2,2,3, the 3-hexafluoro butane; 1,1,2,2,3, the 4-hexafluoro butane; 1,1,2,2,4, the 4-hexafluoro butane; 1,1,2,3,3, the 4-hexafluoro butane; 1,1,2,3,4, the 4-hexafluoro butane; 1,2,2,3,3, the 4-hexafluoro butane; 1,1,1,2,2,3,3-seven fluorine butane; 1,1,1,2,2,4,4-seven fluorine butane; 1,1,1,2,2,3,4-seven fluorine butane; 1,1,1,2,3,3,4-seven fluorine butane; 1,1,1,2,3,4,4-seven fluorine butane; 1,1,1,2,4,4,4-seven fluorine butane; 1,1,1,3,3,4,4-seven fluorine butane; 1,1,1,2,2,3,3, the 4-Octafluorobutane; 1,1,1,2,2,3,4, the 4-Octafluorobutane; 1,1,1,2,3,3,4, the 4-Octafluorobutane; 1,1,1,2,2,4,4, the 4-Octafluorobutane; 1,1,1,2,3,4,4, the 4-Octafluorobutane; 1,1,1,2,2,3,3,4,4-nine fluorine butane; 1,1,1,2,2,3,4,4,4-nine fluorine butane; 1-fluoro-2-methylpropane; 1,1-two fluoro-2-methylpropanes; 1,3-two fluoro-2-methylpropanes; 1,1,1-three fluoro-2-methylpropanes; 1,1,3-three fluoro-2-methylpropanes; 1,3-two fluoro-2-(methyl fluoride) propane; 1,1,1,3-tetrafluoro-2-methylpropane; 1,1,3,3-tetrafluoro-2-methylpropane; 1,1,3-three fluoro-2-(methyl fluoride) propane; 1,1,1,3,3-five fluoro-2-methylpropanes; 1,1,3,3-tetrafluoro-2-(methyl fluoride) propane; 1,1,1,3-tetrafluoro-2-(methyl fluoride) propane; The fluorine tetramethylene; 1,1-difluoro tetramethylene; 1,2-difluoro tetramethylene; 1,3-difluoro tetramethylene; 1,1,2-trifluoro tetramethylene; 1,1,3-trifluoro tetramethylene; 1,2,3-trifluoro tetramethylene; 1,1,2,2-ptfe ring butane; 1,1,3,3-ptfe ring butane; 1,1,2,2,3-five fluorine tetramethylene; 1,1,2,3,3-five fluorine tetramethylene; 1,1,2,2,3, the 3-trans-1,1,2,2,3,4-Hexafluorocyclobutane; 1,1,2,2,3, the 4-trans-1,1,2,2,3,4-Hexafluorocyclobutane; 1,1,2,3,3, the 4-trans-1,1,2,2,3,4-Hexafluorocyclobutane; 1,1,2,2,3,3,4-seven fluorine tetramethylene; Vinyl fluoride; Vinylidene fluoride; 1, the 2-difluoroethylene; 1,1, the 2-trifluoro-ethylene; 1-fluorine propylene; 1,1-difluoro propylene; 1,2-difluoro propylene; 1,3-difluoro propylene; 2,3-difluoro propylene; 3,3-difluoro propylene; 1,1, the 2-trifluoro propene; 1,1, the 3-trifluoro propene; 1,2, the 3-trifluoro propene; 1,3, the 3-trifluoro propene; 2,3, the 3-trifluoro propene; 3,3, the 3-trifluoro propene; 1-fluoro-1-butylene; 2-fluoro-1-butylene; 3-fluoro-1-butylene; 4-fluoro-1-butylene; 1,1-two fluoro-1-butylene; 1,2-two fluoro-1-butylene; 1,3-difluoro propylene; 1,4-two fluoro-1-butylene; 2,3-two fluoro-1-butylene; 2,4-two fluoro-1-butylene; 3,3-two fluoro-1-butylene; 3,4-two fluoro-1-butylene; 4,4-two fluoro-1-butylene; 1,1,2-three fluoro-1-butylene; 1,1,3-three fluoro-1-butylene; 1,1,4-three fluoro-1-butylene; 1,2,3-three fluoro-1-butylene; 1,2,4-three fluoro-1-butylene; 1,3,3-three fluoro-1-butylene; 1,3,4-three fluoro-1-butylene; 1,4,4-three fluoro-1-butylene; 2,3,3-three fluoro-1-butylene; 2,3,4-three fluoro-1-butylene; 2,4,4-three fluoro-1-butylene; 3,3,4-three fluoro-I-butylene; 3,4,4-three fluoro-1-butylene; 4,4,4-three fluoro-1-butylene; 1,1,2,3-tetrafluoro-1-butylene; 1,1,2,4-tetrafluoro-1-butylene; 1,1,3,3-tetrafluoro-1-butylene; 1,1,3,4-tetrafluoro-1-butylene; 1,1,4,4-tetrafluoro-1-butylene; 1,2,3,3-tetrafluoro-1-butylene; 1,2,3,4-tetrafluoro-1-butylene; 1,2,4,4-tetrafluoro-1-butylene; 1,3,3,4-tetrafluoro-1-butylene; 1,3,4,4-tetrafluoro-1-butylene; 1,4,4,4-tetrafluoro-1-butylene; 2,3,3,4-tetrafluoro-1-butylene; 2,3,4,4-tetrafluoro-1-butylene; 2,4,4,4-tetrafluoro-1-butylene; 3,3,4,4-tetrafluoro-1-butylene; 3,4,4,4-tetrafluoro-1-butylene; 1,1,2,3,3-five fluoro-1-butylene; 1,1,2,3,4-five fluoro-1-butylene; 1,1,2,4,4-five fluoro-1-butylene; 1,1,3,3,4-five fluoro-1-butylene; 1,1,3,4,4-five fluoro-1-butylene; 1,1,4,4,4-five fluoro-1-butylene; 1,2,3,3,4-five fluoro-1-butylene; 1,2,3,4,4-five fluoro-1-butylene; 1,2,4,4,4-five fluoro-1-butylene; 2,3,3,4,4-five fluoro-1-butylene; 2,3,4,4,4-five fluoro-1-butylene; 3,3,4,4,4-five fluoro-1-butylene; 1,1,2,3,3,4-hexafluoro 1-butylene; 1,1,2,3,4,4-hexafluoro 1-butylene; 1,1,2,4,4,4-hexafluoro 1-butylene; 1,2,3,3,4,4-hexafluoro 1-butylene; 1,2,3,4,4,4-hexafluoro 1-butylene; 2,3,3,4,4,4-hexafluoro 1-butylene; 1,1,2,3,3,4,4-seven fluoro-1-butylene; 1,1,2,3,4,4,4-seven fluoro-1-butylene; 1,1,3,3,4,4,4-seven fluoro-1-butylene; 1,2,3,3,4,4,4-seven fluoro-1-butylene; 1-fluoro-2-butylene; 2-fluoro-2-butylene; 1, the 1-difluoro-2-butene; 1, the 2-difluoro-2-butene; 1, the 3-difluoro-2-butene; 1, the 4-difluoro-2-butene; 2, the 3-difluoro-2-butene; 1,1,1-three fluoro-2-butylene; 1,1,2-three fluoro-2-butylene; 1,1,3-three fluoro-2-butylene; 1,1,4-three fluoro-2-butylene; 1,2,3-three fluoro-2-butylene; 1,2,4-three fluoro-2-butylene; 1,1,1,2-tetrafluoro-2-butylene; 1,1,1,3-tetrafluoro-2-butylene; 1,1,1,4-tetrafluoro-2-butylene; 1,1,2,3-tetrafluoro-2-butylene; 1,1,2,4-tetrafluoro-2-butylene; 1,2,3,4-tetrafluoro-2-butylene; 1,1,1,2,3-five fluoro-2-butylene; 1,1,1,2,4-five fluoro-2-butylene; 1,1,1,3,4-five fluoro-2-butylene; 1,1,1,4,4-five fluoro-2-butylene; 1,1,2,3,4-five fluoro-2-butylene; 1,1,2,4,4-five fluoro-2-butylene; 1,1,1,2,3,4-hexafluoro-2-butylene; 1,1,1,2,4,4-hexafluoro-2-butylene; 1,1,1,3,4,4-hexafluoro 2-butylene; 1,1,1,4,4,4-hexafluoro-2-butylene; 1,1,2,3,4,4-hexafluoro-2-butylene; 1,1,1,2,3,4,4-seven fluoro-2-butylene; 1,1,1,2,4,4,4-seven fluoro-2-butylene; With their mixture.
52. the multipolymer of claim 35, wherein one or more hydrogen fluorine carbon are independently selected from methyl fuoride, methylene fluoride, trifluoromethane, 1,1-C2H4F2 C2H4F2,1,1,1-Halothane, 1,1,1,2-Tetrafluoroethane and their mixture.
53. the multipolymer of claim 35, wherein thinner comprises 15-100 volume %HFC, based on the cumulative volume of thinner.
54. the multipolymer of claim 35, wherein thinner comprises 20-100 volume %HFC, based on the cumulative volume of thinner.
55. the multipolymer of claim 35, wherein thinner comprises 25-100 volume %HFC, based on the cumulative volume of thinner.
56. the multipolymer of claim 35, wherein thinner further comprises hydrocarbon, nonreactive activity alkene, and/or rare gas element.
57. the multipolymer of claim 56, wherein this hydrocarbon is the halohydrocarbon except that HFC.
58. the multipolymer of claim 57, wherein halohydrocarbon is a methyl chloride.
59. the multipolymer of claim 35, wherein one or more Lewis acids are by formula MX
4Expression;
Wherein M is 4,5 or 14 family's metals; With
Each X is a halogen.
60. the multipolymer of claim 35, wherein one or more Lewis acids are by formula MR
nX
4-nExpression;
Wherein M is 4,5 or 14 family's metals; With
Each R is independently selected from alkyl, aryl, arylalkyl, the monovalence C in alkylaryl and the cycloalkyl
1-C
12Alkyl;
N is the integer of 0-4; With
Each X is a halogen.
61. the multipolymer of claim 35, wherein one or more Lewis acids are by formula M (RO)
nR '
mX
4-(m+n)Expression;
Wherein M is 4,5 or 14 family's metals; With
Each RO is selected from alkoxyl group, aryloxy, alkoxy aryl, the monovalence C in the alkyl-aryloxy
1-C
30-oxyl;
Each R ' is independently selected from alkyl, aryl, arylalkyl, the monovalence C in alkylaryl and the cycloalkyl
1-C
12Alkyl;
N is the integer of 0-4; With
M is 0 to 4 integer, and wherein the summation of n and m is no more than 4; With
Each X is a halogen.
62. the multipolymer of claim 35, wherein one or more Lewis acids are by formula M (RC=OO)
nR '
mX
4-(m+n)Expression;
Wherein M is 4,5 or 14 family's metals; With
Each RC=OO is independently selected from alkyl acyloxy, aryl acyloxy, arylalkyl acyloxy, the monovalence C in the alkylaryl acyloxy
2-C
30Alkylacyloxy;
Each R ' is independently selected from alkyl, aryl, arylalkyl, the monovalence C in alkylaryl and the cycloalkyl
1-C
12Alkyl;
N is the integer of 0-4; With
M is 0 to 4 integer, and wherein the summation of n and m is no more than 4; With
Each X is a halogen.
63. the multipolymer of claim 35, wherein one or more Lewis acids are by formula MOX
3Expression;
Wherein M is 5 family's metals; With
Each X is a halogen.
64. the multipolymer of claim 35, wherein one or more Lewis acids are by formula MX
3Expression;
Wherein M is 13 family's metals; With
Each X is a halogen.
65. the multipolymer of claim 35, wherein one or more Lewis acids are by formula MR
nX
3-nExpression;
Wherein M is 13 family's metals;
Each R is independently selected from alkyl, aryl, arylalkyl, the monovalence C in alkylaryl and the cycloalkyl
1-C
12Alkyl;
N is the integer of 1-3; With
Each X is a halogen.
66. the multipolymer of claim 35, wherein one or more Lewis acids are by formula M (RO)
nR '
mX
3-(m+n)Expression;
Wherein M is 13 family's metals;
Each RO is selected from alkoxyl group, aryloxy, alkoxy aryl, the monovalence C in the alkyl-aryloxy
1-C
30-oxyl;
Each R ' is independently selected from alkyl, aryl, arylalkyl, the monovalence C in alkylaryl and the cycloalkyl
1-C
12Alkyl;
N is the integer of 0-3;
M is 0 to 3 integer, and wherein the summation of n and m is 1-3; With
Each X is a halogen.
67. the multipolymer of claim 35, wherein one or more Lewis acids are by formula M (RC=OO)
nR '
mX
3-(m+n)Expression;
Wherein M is 13 family's metals;
Each RC=OO is independently selected from alkyl acyloxy, aryl acyloxy, arylalkyl acyloxy, the monovalence C in the alkylaryl acyloxy
2-C
30Alkylacyloxy;
Each R ' is independently selected from alkyl, aryl, arylalkyl, the monovalence C in alkylaryl and the cycloalkyl
1-C
12Alkyl;
N is the integer of 0-3;
M is 0 to 3 integer, and wherein the summation of n and m is 1-3; With
Each X is a halogen.
68. the multipolymer of claim 35, wherein one or more Lewis acids are by formula MX
yExpression;
Wherein M is 15 family's metals;
Each X is a halogen; With
Y is 3,4 or 5.
69. the multipolymer of claim 35, wherein one or more Lewis acids are by formula MR
nX
Y-nExpression;
Wherein M is 15 family's metals;
Each R is independently selected from alkyl, aryl, arylalkyl, the monovalence C in alkylaryl and the cycloalkyl
1-C
12Alkyl;
N is the integer of 0-4; With
Y is 3,4 or 5, and wherein n is less than y; With
Each X is a halogen.
70. the multipolymer of claim 35, wherein one or more Lewis acids are by formula M (RO)
nR '
mX
Y-(m+n)Expression;
Wherein M is 15 family's metals;
Each RO is selected from alkoxyl group, aryloxy, alkoxy aryl, the monovalence C in the alkyl-aryloxy
1-C
30-oxyl;
Each R ' is independently selected from alkyl, aryl, arylalkyl, the monovalence C in alkylaryl and the cycloalkyl
1-C
12Alkyl;
N is the integer of 0-4; With
M is the integer of 0-4;
Y is 3,4 or 5, and wherein the summation of n and m is less than y; With
Each X is a halogen.
71. the multipolymer of claim 35, wherein one or more Lewis acids are by formula M (RC=OO)
nR '
mX
Y-(m+n)Expression;
Wherein M is 15 family's metals;
Each RC=OO is independently selected from alkyl acyloxy, aryl acyloxy, arylalkyl acyloxy, the monovalence C in the alkylaryl acyloxy
2-C
30Alkylacyloxy;
Each R ' is independently selected from alkyl, aryl, arylalkyl, the monovalence C in alkylaryl and the cycloalkyl
1-C
12Alkyl;
N is the integer of 0-4; With
M is the integer of 0-4;
Y is 3,4 or 5, and wherein the summation of n and m is less than y; With
Each X is a halogen.
72. the multipolymer of claim 35; wherein one or more Lewis acids are independently selected from titanium tetrachloride; titanium tetrabromide; vanadium tetrachloride; tin tetrachloride; zirconium tetrachloride; the monobromo titanous chloride; the dibromo titanium dichloride; the monobromo vanadium trichloride; one chlorine, three Tin tetrafluoride .s, benzyl titanous chloride, dibenzyl titanium dichloride; benzyl tri-chlorination zirconium; dibenzyl dibrominated zirconium, methyl titanous chloride, dimethyl bifluoride titanium; dimethyltin chloride; the phenyl vanadium trichloride, methoxyl group titanous chloride, n-butoxy titanous chloride; two (isopropoxy) titanium dichloride; the phenoxy group titanium tribromide, phenyl methoxyl group zirconium trifluoride, methyl methoxy base titanium dichloride; methyl methoxy base tindichloride; benzyl isopropoxy vanadous chloride, acetoxyl group titanous chloride, benzoyl tribromide zirconium; the benzoyloxy titanium trifluoride; different propionyloxy tin trichloride, methyl acetoxyl group titanium dichloride, benzyl benzoyloxy vanadium chloride; vanadylic chloride; aluminum chloride, boron trifluoride, gallium trichloride; indium trifluoride; ethylaluminum dichloride, methylaluminum dichloride, benzyl al dichloride; the isobutyl-gallium dichloride; diethyl aluminum chloride, dimethylaluminum chloride, ethyl sesquialter aluminum chloride; methylaluminum sesquichloride; trimethyl aluminium, triethyl aluminum, methoxyl group al dichloride; the oxyethyl group al dichloride; 2,6-two-tertiary butyl phenoxy group al dichloride, methoxymethyl aluminum chloride; 2; 6-two-tertiary butyl phenoxymethyl aluminum chloride, isopropoxy gallium dichloride, phenoxymethyl indium; the acetoxyl group al dichloride; the benzoyloxy aluminum dibromide, benzoyloxy bifluoride gallium, methyl acetoxyl group aluminum chloride; different propionyloxy Indium-111 chloride; six antimony chlorides, antimony hexafluoride, arsenic pentafluoride; one chlorine antimony pentafluoride; arsenous fluoride, Trichlorobismuthine, a fluorine four arsenic chlorides; tetraphenylphosphonichloride chloride antimony; the triphenyl antimony butter, tetrachloro methoxyl group antimony, dimethoxy butter of antimony; dichloro methoxyl group arsenic; chlorine dimethoxy arsenic, difluoro-methoxy arsenic, acetate moiety close Four Modernizations antimony; (benzoate anion closes) four antimony chlorides and chlorination bismuth acetate.
73. the multipolymer of claim 35, wherein one or more Lewis acids are independently selected from aluminum chloride, alchlor, ethylaluminum dichloride, ethyl sesquialter aluminum chloride, diethyl aluminum chloride, methylaluminum dichloride, methylaluminum sesquichloride, dimethylaluminum chloride, boron trifluoride, and titanium tetrachloride.
74. the multipolymer of claim 35, wherein Lewis acid is not by formula M X
3The compound of expression, wherein M is 13 family's metals, X is a halogen.
75. the multipolymer of claim 35, wherein one or more initiators comprise hydrogen halide, carboxylic acid, acid halide, sulfonic acid, alcohol, phenol, polymerization halogenide, tertiary alkyl halogenide, uncle's aralkyl halide, tertiary alkyl ester, uncle's aralkyl ester, tert-alkyl ether, uncle's aralkyl ethers, alkylogen, aryl halide, alkylaryl halogen, or arylalkyl acyl chlorides.
76. the multipolymer of claim 35, wherein one or more initiators are independently selected from HCl, H
2O, methyl alcohol, (CH
3)
3CCl, C
6H
5C (CH
3)
2Cl, (2-chloro-2,4,4-trimethylpentane) and 2-chloro-2-methylpropane.
77. the multipolymer of claim 35, wherein one or more initiators are independently selected from hydrogenchloride, hydrogen bromide, hydrogen iodide, acetate, propionic acid, butyric acid; Styracin, phenylformic acid, 1-Mono Chloro Acetic Acid, dichloro acetic acid, trichoroacetic acid(TCA), trifluoroacetic acid, right-chloro-benzoic acid, right-fluorobenzoic acid, Acetyl Chloride 98Min., acetyl bromide, cinnamyl chloride, Benzoyl chloride, benzoyl bromide, trichoroacetic chloride, trifluoroacetyl chloride, right-fluorobenzoyl chloride, methylsulfonic acid, trifluoromethanesulfonic acid, trichlorine methylsulfonic acid, tosic acid, methylsulfonyl chloride, methylsulfonyl bromine, trichlorine methylsulfonyl chloride, trifluoromethanesulfchloride chloride, p-toluenesulfonyl chloride, methyl alcohol, ethanol, propyl alcohol, the 2-propyl alcohol, 2-methyl propan-2-ol, hexalin, benzylalcohol, phenol, 2-cresols, 2, right-chlorophenol, right-fluorophenol, 2,3,4,5,6-Pentafluorophenol, and 2 hydroxy naphthalene.
78. the multipolymer of claim 35, wherein one or more initiators are independently selected from 2-chloro-2,4, the 4-trimethylpentane; 2-bromo-2,4, the 4-trimethylpentane; 2-chloro-2-methylpropane; 2-bromo-2-methylpropane; 2-chloro-2,4,4,6, the 6-five methylheptane; 2-bromo-2,4,4,6, the 6-five methylheptane; 1-chloro-1-ethyl methyl benzene; 1-chlorine diamantane; 1-chloroethyl benzene; 1, two (the 1-chloro-1-methylethyl) benzene of 4-; The 5-tertiary butyl-1, two (the 1-chloro-1-methylethyl) benzene of 3-; 2-acetoxyl group-2,4, the 4-trimethylpentane; 2-benzoyloxy-2,4, the 4-trimethylpentane; 2-acetoxyl group-2-methylpropane; 2-benzoyloxy-2-methylpropane; 2-acetoxyl group-2,4,4,6, the 6-five methylheptane; 2-benzoyl-2,4,4,6, the 6-five methylheptane; 1-acetoxyl group-1-ethyl methyl benzene; 1-acetoxyl group diamantane; 1-benzoyloxy ethylbenzene; 1, two (1-acetoxyl group-1-methylethyl) benzene of 4-; The 5-tertiary butyl-1, two (1-acetoxyl group-1-methylethyl) benzene of 3-; 2-methoxyl group-2,4, the 4-trimethylpentane; 2-isopropoxy-2,4, the 4-trimethylpentane; 2-methoxyl group-2-methylpropane; 2-benzyloxy-2-methylpropane; 2-methoxyl group-2,4,4,6, the 6-five methylheptane; 2-isopropoxy-2,4,4,6, the 6-five methylheptane; 1-methoxyl group-1-ethyl methyl benzene; 1-methoxyl group diamantane; 1-methoxy ethyl benzene; 1, two (1-methoxyl group-1-methylethyl) benzene of 4-; The 5-tertiary butyl-1, two (1-methoxyl group-1-methylethyl) benzene and 1,3 of 3-, 5-three (1-chloro-1-methylethyl) benzene.
79. the multipolymer of claim 35, wherein one or more initiators further comprise weak coordinate negatively charged ion.
80. the multipolymer of claim 35, wherein one or more initiators comprise the water (by weight) greater than 30ppm.
81. the multipolymer of claim 35, wherein this contact comprises that further contact is independently selected from alkene, alpha-olefin, dibasic alkene, isoolefine, conjugated diolefine, non-conjugated diene, styrenic, the styrenic of replacement and one or more monomers in the vinyl ether.
82. the multipolymer of claim 35, wherein this contact comprises that further contact is independently selected from vinylbenzene, and is right-ring-alkylated styrenes, p-methylstyrene, alpha-methyl styrene, Vinylstyrene, di isopropenylbenzene, iso-butylene, 2-methyl-1-butene alkene, 3-methyl-1-butene, 2-methyl-2-amylene, isoprene, divinyl, 2,3-dimethyl-1, the 3-divinyl, beta-pinene, myrcene, 6,6-dimethyl-fulvene, hexadiene, cyclopentadiene, methyl cyclopentadiene, piperylene, methylvinylether, one or more monomers in ethyl vinyl ether and the IVE.
83. the multipolymer of any one in the aforementioned claim, wherein multipolymer can be formed the halo multipolymer by halo.
84. the multipolymer of claim 83, wherein the halo multipolymer is by chlorine or bromine institute halo.
85. the multipolymer of claim 83 or 84, wherein content of halogen is greater than 0.5wt%, based on the weight of halo multipolymer.
86. the multipolymer of claim 83 or 84, wherein content of halogen is 0.5wt% to 3.0wt%, based on the weight of halo multipolymer.
87. the multipolymer of any one in the aforementioned claim, wherein multipolymer has the Mw greater than 50,000.
88. the multipolymer of any one in the aforementioned claim, wherein multipolymer has the Mw greater than 100,000.
89. the multipolymer of any one in the aforementioned claim, wherein multipolymer has the Mw greater than 500,000.
90. the multipolymer of any one in the aforementioned claim, wherein multipolymer has greater than 1,000,000 Mw.
91. the multipolymer of any one in the aforementioned claim, wherein multipolymer has the MWD greater than 2.
92. the multipolymer of any one in the aforementioned claim, wherein multipolymer has the MWD of 2-6.
93. the multipolymer of any one in the aforementioned claim, wherein multipolymer has at least 20 ± 5 mooney viscosity (ML 1+8,125 ℃, ASTM D 1646).
94. the multipolymer of any one in the aforementioned claim, wherein multipolymer has 20 ± 5 to 60 ± 5 mooney viscosity (ML 1+8,125 ℃, ASTM D 1646).
95. comprise in the aforementioned claim multipolymer of any one and be selected from the blend of second kind of rubber at least a following rubber: natural rubber, polyisoprene rubber, poly-(vinylbenzene-copolymerization-divinyl) rubber (SBR), polybutadiene rubber (BR), poly-(isoprene-copolymerization-divinyl) rubber (IBR), styrene isoprene butadiene rubber (SIBR) (SIBR), ethylene-propylene rubber(EPR) (EPR), ethylene-propylene-dience rubber (EPDM), polysulphide, iso-butylene/cyclopentadiene copolymer rubber, iso-butylene/methyl cyclopentadiene copolymer rubber, paracril, epoxypropane polymer, star-branched butyl rubber and halo star-branched butyl rubber, brominated butyl rubber, chlorinated butyl rubber, star-branched polyisobutene rubber, the butyl of star-branched bromination (polyisobutene/isoprene copolymer) rubber; Poly-(iso-butylene-copolymerization-p-methylstyrene) and halo poly-(iso-butylene-copolymerization-p-methylstyrene), halo gathers (iso-butylene-copolymerization-isoprene-copolymerization-p-methylstyrene), poly-(iso-butylene-copolymerization-isoprene-copolymerization-vinylbenzene), halo gathers (iso-butylene-copolymerization-isoprene-copolymerization-vinylbenzene), poly-(iso-butylene-copolymerization-isoprene-copolymerization-alpha-methyl styrene) halo poly-(iso-butylene-copolymerization-isoprene-copolymerization-alpha-methyl styrene) and their mixture.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US43506102P | 2002-12-20 | 2002-12-20 | |
| US60/435,061 | 2002-12-20 | ||
| US60/464,187 | 2003-04-21 | ||
| US60/479,081 | 2003-06-17 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1738843A true CN1738843A (en) | 2006-02-22 |
| CN100577699C CN100577699C (en) | 2010-01-06 |
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| CNB2003801068675A Expired - Fee Related CN100402565C (en) | 2002-12-20 | 2003-12-19 | Polymer without long branched chain |
| CNB2003801069682A Expired - Fee Related CN100427512C (en) | 2002-12-20 | 2003-12-19 | Polymerization processes |
| CNB2003801069697A Expired - Fee Related CN100402558C (en) | 2002-12-20 | 2003-12-19 | Polymerization processes |
| CNB2003801069610A Expired - Fee Related CN100569812C (en) | 2002-12-20 | 2003-12-19 | Has the polymkeric substance that new sequence distributes |
| CNB2003801069875A Expired - Fee Related CN1332986C (en) | 2002-12-20 | 2003-12-19 | Polymerization processes |
| CN200380109031A Expired - Fee Related CN100577699C (en) | 2002-12-20 | 2003-12-19 | Polymers with new sequence distributions |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2003801068675A Expired - Fee Related CN100402565C (en) | 2002-12-20 | 2003-12-19 | Polymer without long branched chain |
| CNB2003801069682A Expired - Fee Related CN100427512C (en) | 2002-12-20 | 2003-12-19 | Polymerization processes |
| CNB2003801069697A Expired - Fee Related CN100402558C (en) | 2002-12-20 | 2003-12-19 | Polymerization processes |
| CNB2003801069610A Expired - Fee Related CN100569812C (en) | 2002-12-20 | 2003-12-19 | Has the polymkeric substance that new sequence distributes |
| CNB2003801069875A Expired - Fee Related CN1332986C (en) | 2002-12-20 | 2003-12-19 | Polymerization processes |
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| CN102372810A (en) * | 2010-08-19 | 2012-03-14 | 中国石油化工股份有限公司 | Method for preparing isomonoolefin-polyene hydrocarbon copolymer |
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| CN106574012A (en) * | 2014-04-30 | 2017-04-19 | 阿朗新科新加坡私人有限公司 | 2,3,3,3-tetrafluoro-1-propene as diluent for the preparation of novel butyl rubbers |
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- 2003-12-19 CN CNB2003801069682A patent/CN100427512C/en not_active Expired - Fee Related
- 2003-12-19 CN CNB2003801069697A patent/CN100402558C/en not_active Expired - Fee Related
- 2003-12-19 CN CNB2003801069610A patent/CN100569812C/en not_active Expired - Fee Related
- 2003-12-19 CN CNB2003801069875A patent/CN1332986C/en not_active Expired - Fee Related
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| CN106574012B (en) * | 2014-04-30 | 2019-04-19 | 阿朗新科新加坡私人有限公司 | 2,3,3,3- tetrafluoro-1-propene is used for the preparation of butyl rubber as diluent |
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| CN111094367A (en) * | 2017-07-13 | 2020-05-01 | 阿朗新科德国有限责任公司 | Process for the production of isobutene polymers with improved temperature control |
| CN113366027A (en) * | 2018-12-17 | 2021-09-07 | 阿朗新科新加坡私人有限公司 | Process for producing isoolefin polymers using tertiary ethers |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1729208A (en) | 2006-02-01 |
| CN1729215A (en) | 2006-02-01 |
| CN100402565C (en) | 2008-07-16 |
| CN1729209A (en) | 2006-02-01 |
| CN100569812C (en) | 2009-12-16 |
| CN100577699C (en) | 2010-01-06 |
| CN1332986C (en) | 2007-08-22 |
| CN1729204A (en) | 2006-02-01 |
| CN100427512C (en) | 2008-10-22 |
| CN1753918A (en) | 2006-03-29 |
| CN100402558C (en) | 2008-07-16 |
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