Low-fluoride, reactive polyisobutylene

Abstract

A method of making a low-fluoride reactive PIB composition includes (a) providing a modified C4 feedstock by way of blending a mixed C4 feedstock with a second feedstock having a lower LB/IsoB ratio; or providing a C4 feedstock with an LB/IsoB index of less than 10%; (b) feeding the modified C4 feedstock or the C4 feedstock with an LB/IsoB index of less than 10% to a CSTR with a homogeneous catalyst comprising BF.sub.3 and a modifier selected from alcohols, ethers and mixtures thereof; (c) polymerizing the modified C4 feedstock or the C4 feedstock with an LB/IsoB index of less than 10% in the reactor while maintaining the reactor at a temperature above 15 C. and utilizing a residence time less than 45 minutes to produce a crude PIB composition in a polymerization mixture; and (d) recovering a purified PIB composition from the polymerization mixture having a molecular weight, Mn, from 250 to 5000 Daltons and an alpha vinylidene content of at least 50 mol %. The crude PIB composition suitably has a fluoride content of less than 100 ppm and the purified PIB composition has a fluoride content of less than 20 ppm in preferred embodiments. In the most preferred embodiments, ammonium salts are used to neutralize the catalyst and fluoride salts are sublimed from the product at elevated temperatures.

Claims

1. A method of making a low-fluoride reactive PIB composition comprising: (a) providing a modified C4 feedstock by way of blending a mixed C4 feedstock with a second feedstock having a lower LB/IsoB ratio; or providing a C4 feedstock with an LB/IsoB index of less than 10%; (b) feeding the modified C4 feedstock or the C4 feedstock with an LB/IsoB index of less than 10% to a CSTR provided with cooling together with a homogeneous catalyst comprising BF.sub.3 and a modifier selected from alcohols, ethers and mixtures thereof; (c) polymerizing the modified C4 feedstock or the C4 feedstock with an LB/IsoB index of less than 10% in the reactor while maintaining the reactor at a temperature above 15 C. and utilizing a residence time less than 45 minutes to produce a crude PIB composition in a polymerization mixture; and (d) recovering a purified PIB composition from the polymerization mixture having a molecular weight, Mn, from 250 to 5000 Daltons and an alpha vinylidene content of at least 50 mol %.

2. The method according to claim 1, wherein the residual fluoride content of the crude PIB composition is less than 200 ppm.

3. The method according to claim 1, wherein the residual fluoride content of the purified PIB composition is less than 30 ppm.

4. The method according to claim 3, wherein the residual fluoride content of the purified PIB composition is less than 20 ppm.

5. The method according to claim 1, wherein the residual organic fluoride content of the purified PIB composition is less than 10 ppm.

6. The method according to claim 5, wherein the residual organic fluoride content of the purified PIB composition is less than 5 ppm.

7. The method according to claim 1, wherein the reactor is maintained at a temperature of 10 C. or above.

8. The method according to claim 1, wherein the reactor is maintained at a temperature of 0 C. or above.

9. The method according to claim 1, wherein the residence time is 20 minutes or less.

10. The method according to claim 1, wherein the catalyst complex comprises a modifier selected from methanol, ethanol, tertiary butanol, isopropyl ether, diethyl ether and mixtures thereof.

11. The method according to claim 1, further comprising: (e) withdrawing the crude PIB composition from the reactor; (f) neutralizing the crude PIB composition with a quenching agent; and (g) treating the crude PIB composition at a temperature of from 150 C. to 300 C. to separate oligomers from the crude PIB composition.

12. The method according to claim 11, further comprising washing the neutralized crude PIB composition with water and decanting the washed PIB composition to provide an aqueous phase and an organic phase containing PIB polymer.

13. The method according to claim 12, comprising treating the organic phase containing PIB polymer at a temperature of from 150 C. to 300 C. and a pressure of from 0.25 psia to 10 psia to remove PIB oligomers from the composition.

14. The method according to claim 13, wherein the purified PIB composition has less than 10% by weight C8 to 24 oligomers.

15. The method according to claim 1, wherein step (a) includes providing the modified C4 feedstock by way of blending a mixed C4 feedstock with a second feedstock having a lower LB/IsoB ratio, step (b) includes feeding the modified C4 feedstock to a CSTR provided with cooling together with a homogeneous catalyst comprising BF.sub.3 and a modifier selected from alcohols, ethers and mixtures thereof and step (c) includes polymerizing the modified C4 feedstock while maintaining the reactor at a temperature above 15 C. and utilizing a residence time less than 45 minutes to produce a crude PIB composition in a polymerization mixture.

16. The method according to claim 15, wherein the first mixed C4 feedstock comprises raffinate or dehydro effluents.

17. The method according to claim 15, wherein the second feedstock has an LB/IsoB index of less than 1%.

18. A method of making a low-fluoride reactive PIB composition comprising: (a) providing a C4 feedstock with an LB/IsoB index of less than 10%; (b) feeding the C4 feedstock with an LB/IsoB index of less than 10% to a CSTR provided with cooling together with a homogeneous catalyst comprising BF.sub.3 and a modifier selected from alcohols, ethers and mixtures thereof; (c) polymerizing the feedstock with an LB/IsoB index of less than 10% in the reactor while maintaining the reactor at a temperature above 15 C. and utilizing a residence time less than 45 minutes to produce a crude PIB composition in a polymerization mixture; and (d) recovering a purified PIB composition from the polymerization mixture having a molecular weight, Mn, from 250 to 5000 Daltons and an alpha vinylidene content of at least 50 mol %.

19. A method of making a low-fluoride reactive PIB composition comprising: (a) providing a modified C4 feedstock by way of blending a mixed C4 feedstock with a second feedstock having a lower LB/IsoB ratio; or providing a C4 feedstock with an LB/IsoB index of less than 10%; (b) feeding the modified C4 feedstock or the C4 feedstock with an LB/IsoB index of less than 10% to a CSTR provided with cooling together with a homogeneous catalyst comprising BF.sub.3 and a modifier selected from alcohols, ethers and mixtures thereof; (c) polymerizing the modified C4 feedstock or the C4 feedstock with an LB/IsoB index of less than 10% in the reactor while maintaining the reactor at a temperature above 15 C. and utilizing a residence time less than 45 minutes to produce a crude PIB composition in a polymerization mixture; and (d) recovering a purified PIB composition from the polymerization mixture having a molecular weight, Mn, from 250 to 5000 Daltons and an alpha vinylidene content of at least 50 mol %, wherein the feed composition and reaction conditions are selected such that the residual fluoride content of the crude PIB composition is less than 200 ppm.

20. The method according to claim 19, wherein the residual fluoride content of the crude PIB composition is less than 100 ppm.

21. The method according to claim 19, wherein the residual fluoride content of the crude PIB composition is less than 50 ppm.

22. The method according to claim 19, utilizing a residence time of 15 minutes or less.

23. The method according to claim 13, wherein the quenching agent used to neutralize the crude PIB composition is an ammonium quenching agent.

24. The method according to claim 23, wherein the quenching agent is ammonium hydroxide.

Description

BRIEF DESCRIPTION OF DRAWING

(1) The invention is described in detail below with reference to the various Figures, wherein:

(2) FIG. 1 is a schematic diagram illustrating a CSTR suitable for use in connection with the present invention; and

(3) FIG. 2 is a block diagram illustrating a wash and distillation system for purifying PIB product.

DETAILED DESCRIPTION OF INVENTION

(4) The invention is described in detail below with reference to several embodiments and numerous examples. Such discussion is for purposes of illustration only. Modifications to examples within the spirit and scope of the present invention, set forth in the appended claims, will be readily apparent to one of skill in the art. Terminology used throughout the specification and claims herein is given its ordinary meaning, for example, psi refers to pressure in lbs/inch.sup.2 and so forth. Terminology is further defined below.

(5) Blending and like terminology refers to intimate mixing of two or more feedstocks and includes simultaneously feeding two feedstocks to a reactor (in situ combination).

(6) Catalyst turnover number and like terminology refers to the weight of polymer produced per unit weight of BF.sub.3 catalyst employed in the process.

(7) Consisting essentially of and like terminology refers to the recited components and excludes other ingredients which would substantially change the basic and novel characteristics of the mixture or composition. Unless otherwise indicated or readily apparent, a composition or mixture consists essentially of the recited components when the composition or mixture includes 95% or more by weight of the recited components. That is, the terminology excludes more than 5% unreacted components.

(8) Conversion of the reaction mixture to polymer is expressed in weight percent and calculated as the weight of polymer produced less the weight of isobutylene fed to the reaction system divided by the weight of isobutylene fed to the reaction system times 100%.

(9) Crude PIB product and like terminology means PIB as recovered from the reaction mixture, by washing the crude product to remove highly water-soluble salts, and by evaporating unreacted monomer, catalyst modifier, solvent and the like but otherwise not purifying the product by distillation to promote high purity. A crude PIB product is suitably one after initial work-up where at least 95% by weight of monomer and solvent from the reactor effluent is removed and at least 75% by weight of the water soluble fluoride salts have been removed. This may be achieved by using the wash process disclosed in U.S. Pat. No. 6,858,188. The crude PIB is then analyzed for fluorides as noted below and is compared with the reactor effluent to verify soluble salt removal. The crude PIB is also compared with reactor effluent to verify solvent and monomer removal.

(10) Purified PIB and like terminology refers to PIB product recovered from the reaction mixture by washing the reactor effluent with water to remove salts and flashing to remove unreactive monomer, catalyst modifier solvent and the like, including distillation at elevated temperature to substantially remove all oligomers, The purified PIB is then analyzed for fluorides as noted below.

(11) As used herein, diluents, like terminology refers to solvent components unreactive under reaction conditions and includes aliphatic hydrocarbon compounds such as butane, propane, hexane and so forth, specifically, for example, I-butane, n-butane, n-hexane and hexane isomers, as well as mixtures thereof. Diluents also include relatively unreactive alkenes such as 1-butenes and the like which are present in the reaction mixture but do not polymerize under reaction conditions.

(12) Residual fluoride (or total) content of a product is reported in ppm fluorine by weight of the composition and is determined by combustion/ion chromotography in accordance with test method ASTM D 7359 entitled Standard Test Method for Total Fluorine, Chlorine and Sulfur in Aromatic Hydrocarbons and Their Mixtures by Oxidative Pyrohydrolytic Combustion followed by Ion Chromatography Detection (Combustion Ion Chromatography-CIC).

(13) Residual inorganic fluoride and residual organic fluoride are reported in ppm F by weight of the composition and is determined as by washing a sample of product to remove fluoride salts and measuring the total fluoride content before and after washing as noted above. Results are confirmed measuring the amount of fluorine in the wash water and mass balance. A known amount of polymer, typically 10 grams is diluted in 100 ml of hexanes in a glass bottle. Once it formed a homogenous mixture in hexane, 20 ml of ethyl alcohol and 100 ml of water is added into the mixture. This solution is heated to 80 C. for 20 minutes and then vortexed for 10 minutes. After vortexing the whole mixture is poured in a separating funnel. The bottom layer which is a mixture of water and ethyl alcohol is transferred in a beaker and used for measurement of fluorine content using a fluoride ion probe or ASTM D7359 standard test method. The remaining organic content was washed 5-7 times in excess of water. After washing, the organic layer the hexanes were evaporated under reduced pressure in Rotavap. After all the hexanes were evaporated, PIB was collected in a vial and sent for total fluoride measurement by CIC (ASTM D7359). Total fluoride content in PIB samples before wash and after wash were recorded. Results are confirmed by mass balance on fluorine content of the water/alcohol mixture.

(14) Residual inorganic fluorides present are inorganic salts typically those arising from quenching the BF.sub.3 catalyst. These species are relatively easy to extract with water and/or alcohol as seen in the procedure above.

(15) Residual organic fluorides are compounds which contain a carbon-fluorine bond and are likely to arise from incorporation of fluorine with active species in the reaction mixture. These species may be most prevalent as adducts fluorinated at tertiary carbons in the oligomer product. The contaminants are insoluble in water and thus difficult to remove after the product is synthesized. Thus, in preferred embodiments of the invention, the purified product contains less than 50 ppm by weight fluorine in the product corresponding to fluorinated compounds of the formula:

(16) ##STR00001##

(17) Unless otherwise specified, molecular weight herein is reported as number average molecular weight, M.sub.n, in Daltons, and is measured by gel permeation chromatography (GPC). GPC measurements may be carried out using a Viscotek GPCmax instrument (Malvern instruments, Worcestershire, UK) employing a 3-column set-up (5 m (particle size) 100 Angstrom (pore size), 5 m 500 Angstrom, 5 m 10.sup.4 Angstrom) and a Refractive Index (RI) detector. Polyisobutylene standards are used to construct the calibration curve using this technique.

(18) Percent, percent, % or like terminology refers to mole percent unless otherwise indicated.

(19) Polydispersity or PDI is defined as the ratio of the weight average molecular weight divided by the number average molecular weight of the polymer.

(20) Residence time is calculated as the volume of the reactor divided by the volumetric feed rate at steady state.

(21) Polyisobutylene, PIB and like terminology refers to polymers made up of repeat units derived from isobutene, also referred to as isobutylene.

(22) ##STR00002##
Such polymers are derived from feedstocks made up of purified isobutenes and hydrocarbon diluents, from isobutene concentrate, dehydro effluent, or from raffinate streams. The PIB polymer consists essentially of repeat units derived from isobutylene, but may contain minor amounts of material derived from 1-butenes, butadiene or other C.sub.4 olefins, 2-butenes (cis and/or trans) depending on the feedstock composition. Typically, the polymer is more than 99% by weight derived from isobutylene monomer. Particular compositions of interest in connection with the present invention have a number average molecular weight of from 500 to 4000 Daltons and in preferred embodiment's significant amounts of alpha vinylidene terminated molecules:

(23) ##STR00003##

(24) Highly reactive (HR) PIB polymer compositions typically include more than 75 or 80 mole % alpha molecules, while mid-range vinylidene content PIB products contain less alpha and more beta olefin isomers (1,1,2-trisubstituted or 1,2,2-trisubstituted cis or trans isomer):

(25) ##STR00004##

(26) ##STR00005##
Optionally present are internal vinylidene isomers (disubstituted internal vinylidene isomers) which also have relatively high reactivity, for example:

(27) ##STR00006##
Other structures which may be present include tetrasubsituted structures, other trisubstituted structures with a double bond in the internal gamma position, structures with other internal double bonds and aliphatic structures, for example:

(28) ##STR00007##

(29) ##STR00008##

(30) ##STR00009##

(31) When calculating endgroup percentages, all PIB molecules found in the PIB compositions having a significant presence (more than half a percent or so) are included in endgroup calculations. The endgroup content is determined by nuclear magnetic resonance .sup.13C NMR as is well known in the art.

(32) The linear alkene/isobutylene index or LB/IsoB index of a feedstock is calculated as the weight percentage of linear butenes and butadienes based on the combined weight of linear butenes, C4 dienes and isobutylene in a particular composition. For the isobutylene concentrate in Table1 the LB/IsoB index is calculated as (1.3+0.8+0.4+0.2)/(89+1.3+0.8+0.4+0.2)*100%=2.9%.

(33) TABLE-US-00001 TABLE 1 Isobutylene Concentrate Ingredient Weight % C.sub.3 component 0.00 I-butane 6.5 n-butane 1.7 1-butene 1.3 Isobutene 89 trans-2-butene 0.8 cis-2-butene 0.4 1,3-butadiene 0.2

LB/IsoB Index: 2.9%

(34) High purity isobutylene, has a still lower LB/IsoB index, about 0.30% max as is seen from the following Table 2:

(35) TABLE-US-00002 TABLE 2 High Purity Isobutylene Ingredient Value Isobutene >99.8 1-Butene plus cis-2- <0.15 butene and trans-2-butene 1,3-Butadiene <0.10 Butane <0.15 C.sub.3 components <0.10

Max LB/IsoB Index: 0.30%

(36) Mixed C4 feedstock compositions are reported in Tables 3, 4:

(37) TABLE-US-00003 TABLE 3 Dehydro Effluent Ingredient Weight % C.sub.3 components 0.4 I-butane 43 n-butane 1.3 1-butene 0.80 Isobutene 52.5 trans-2-butene 1 cis-2-butene 0.7 1,3-butadiene 0.20

LB/IsoB Index: 4.9%

(38) TABLE-US-00004 TABLE 4 Raff-1 Ingredient Weight % C.sub.3 components 0.4 I-butane 4.5 n-butane 16 1-butene 37 Isobutene 30 trans-2-butene 8.5 cis-2-butene 2.3 1,3-butadiene 0.4 Other 0.6

LB/IsoB Index: 61.9%

(39) For a discussion of mixed C4 feedstocks, see U.S. Pat. No. 9,034,998 to Faust et al., Col. 4, lines 14 and following. As referred to herein, isobutylene concentrate is a C4 composition with 80% by weight or more isobutylene and high purity isobutylene contains more than 98% by weight isobutylene. Dehydro effluent and raffinate refer to compositions having the components substantially as seen in Tables 3 and 4, wherein the various components may be +/40% by weight based on the weight of that component.

(40) The PIB polymer of the invention consists essentially of repeat units derived from isobutylene, but may contain minor amounts of material derived from 1-butenes, butadiene or other C.sub.4 olefins, 2-butenes (cis and/or trans) depending on the feedstock composition. Preferably, the polymer is more than 99% by weight derived from isobutylene monomer. Optionally, the use of a Chain transfer Agent (CTA) facilitates the production of low molecular weight, highly reactive PIB in the polymerization reaction. Suitable CTAs are known in literature. Note WO 2012/170411, citing as well as J. P. Kennedy et al, Carbocationic Polymerization (1982), page 229, John Wiley & Sons, New York which lists several chain transfer agents and their transfer coefficients. A suitable CTA for use in connection with the present invention is selected from the group consisting of 2,4,4-Trimethyl-1-pentene (-DIB), 2.4.4.-Trimethyl-2-pentene (-DIB), 2-ethyl-1-hexene, 2-methyl-1-pentene and mixtures thereof. Of these, -DIB, -DIB, or mixtures thereof are preferred. The structures of -DIB and -DIB are shown below:

(41) ##STR00010##

(42) The feedstock is optionally purified to remove water and oxygenates such as alcohols, ethers and so forth to avoid adverse effects on the catalyst. Typical media for removal of impurities from hydrocarbon feed streams use molecular sieves, activated alumina and other hybrid adsorbents in the form of an absorber bed. Suitable adsorbents include Aluminum oxides, aluminum halides, calcium oxides, zirconium oxides, titanium oxides, silicates, aluminosilicates, zeolites or mixtures thereof. Post treatment, prior to feeding to the reactor, the feed stream preferably has less than 3 ppm of oxygenates and less than 1 ppm of water.

(43) The catalyst employed is a BF.sub.3 catalyst together with a modifier, sometimes referred to as a cocatalyst or complexing agent. The modifier for the BF.sub.3 catalyst may be any compound containing a lone pair of electrons, such as, for example, an alcohol, ether, an ester or an amine or mixtures thereof. The alcohol compound used as the cocatalyst may be a primary, secondary or tertiary alcohol having 1 to 8 carbon atoms, such as, for example, methanol, ethanol, isopropanol, n-propanol, isobutanol, t-butanol, hexyl alcohol and the like. The ether compound used as the cocatalyst may be a primary, secondary or tertiary ether having 2 to 8 carbon atoms, such as, for example, dimethyl ether, diethyl ether, diisopropyl ether, methylpropyl ether, methylisopropyl ether, methylethyl ether, methylbutyl ether, methyl-t-butyl ether, ethylpropyl ether, ethylisopropyl ether, ethylbutyl ether, ethylisobutyl ether, ethyl-t-butyl ether and the like. In forming a complex of the cocatalyst and boron trifluoride, the cocatalyst alone or in combination with at least one of other cocatalysts is added into a tank, and a boron trifluoride gas is then provided to produce a complex.

(44) In one embodiment, the polymerization reaction is carried out in the presence of a catalyst system comprising secondary alkylether, tertiary alcohol, and boron trifluoride, the amount of boron trifluoride is 0.05-1.0 weight part per 100 weight part of isobutylene, the mole ratio of a co-catalyst including secondary alkylether and tertiary alcohol:boron trifluoride is 1.0-2.0:1, and the mole ratio of secondary alkylether:tertiary alcohol is 0.5-1.2:1.

(45) In many embodiments, the molar ratio of modifier to BF.sub.3 in the catalyst composition is generally in the range of from approximately 0.5-3.5 to 1, desirably within the range of from approximately 0.5:1 to approximately 2:1, and in some cases within the range of from approximately 1.5:1 to approximately 1:1. In some cases, the catalyst composition may simply be a 1:1 molar complex of BF.sub.3 and alcohol and ether mixtures In other preferred embodiments of the invention, the molar ratio of complexing agent:BF.sub.3 in said complex may be approximately 1.3:1.

(46) The temperature in the reaction zone may preferably be maintained at a constant level at a temperature of 25 C. or above; more typically 10 C. or above or wherein the reactor is maintained at a temperature of 0 C. or above. Temperatures in the range of above 20 C. to 40 C. are typical. The residence time is most preferably 45 minutes or less, such as 20 minutes or less, 15 minutes or less or 10 minutes or less. Suitable pressures may be anywhere from 2-20 bar to maintain a liquid phase.

(47) In some embodiments, it is desirable to use one or more inert diluents such as an alkane (e.g., isobutane, n-butane, hexane and the like) are used.

(48) The present invention is practiced in a CSTR, as shown schematically In the FIG. 1. CSTR apparatus 10 includes a pressurized reaction vessel 12 provided with a cooling jacket 14, a feed port 16, one or more baffles 18, 20, an outlet port 22, as well as an agitator 24, driven by a motor 26 via shaft 28.

(49) In operation, the isobutylene feedstock, together with catalyst and modifier, is fed continuously to vessel 12 in the liquid phase through feed port 16, while motor 26 drives agitator 24 via shaft 28 to keep the reaction mixture thoroughly mixed. The feed rate, cooling jacket temperature and catalyst concentration are manipulated to keep the reactor at the desired temperature and to achieve target conversion as product is continuously withdrawn from outlet port 22 after a characteristic steady state residence time in the reactor.

(50) The residence time and temperature in all cases are important features towards achieving low fluoride. Preferably, at least a relatively high temperature and/or a short residence time is employed.

(51) Catalyst productivity (efficiency) is remarkably improved at higher temperatures and lower residence times as compared to prior art systems with lower reaction temperatures and longer residence times. In Table 5, high temperature/low residence time processes as described in WO2013/062758 are compared with selected prior art reaction systems.

(52) TABLE-US-00005 TABLE 5 Comparison of Catalyst Productivity TON - BF.sub.3 lbs polymer/ Mn Source Ex. lbs BF.sub.3 Daltons WO2013/062758 35 2896.61 3118 WO2013/062758 46 3028.36 3560 WO2013/062758 16 1476.1 1087 WO2013/062758 23 1153.9 2419 U.S. Pat. No. 7,038,008 1 888.07 2387 7,038,008 2 318.45 956 7,217,773 comp 321.21 980 7,217,773 1 405.06 930 7,485,764 1 407.52 1150 7,485,764 2 407.52 1070 7,485,764 3 407.52 1030

(53) Following withdrawal from the reactor, the reaction mixture is quenched to deactivate the catalyst, preferably with an inorganic base such as sodium hydroxide or ammonium containing catalyst deactivator such as ammonium hydroxide. The effluent is then washed with water to remove salts as described in U.S. Pat. No. 6,858,188. Following washing, the processed effluent is flashed or distilled to remove oligomers in order to provide a purified product as is discussed herein.

(54) Salts may be carried downstream from a washing vessel. Thus, the use of an ammonium catalyst deactivator is particularly preferred since ammonium salts such as ammonium tetrafluoroborate sublime at elevated temperatures. Preferred ammonium quenching agents may include a variety of ammonium salts such as ammonium carbonate, ammonium bicarbonate and the like; especially preferred is ammonium hydroxide.

(55) Suitably, after washing the product is heated to a temperature of 150 C. or above as part of the purification processes to further remove fluorides. Suitable treating temperatures may be from 150 C. to 300 C. or so, optionally at lower than atmospheric pressure (taking care not to overheat the polymer), will further remove quench products of ammonium hydroxide while removing oligomers. Suitable combination of temperature and pressure can be readily estimated by a person skilled in the art on the basis of the known value of sublimation temperature of ammonium tetrafluoroborate which is 210 C. or so at 1 atm. A particularly preferred range is from 200 C. to 250 C. A suitable post-reactor purification methodology is illustrated in connection with FIG. 2.

(56) In FIG. 2 there is illustrated schematically a process and apparatus 100 for purifying PIB produced in reactors such as reactor 12 described above. The reactor outlet (for example, outlet 22) feeds line 102 which is connected to a washing and decanting system 104. Line 106 provides a quenching agent such as aqueous ammonium hydroxide in excess of the amount needed to quench the catalyst. At 104, the quenched mixture is washed with water provided by way of line 108 and separated into two phases, an aqueous phase containing catalyst residual and ammonium hydroxide and a hydrocarbon phase containing polymer, unreacted monomer and solvents. The aqueous phase exits 104 via line 110 for further processing and recycle, while the organic phase exits 104 via line 112 and is heated and flashed at 114 under positive pressure at temperatures of 120-200 C. to remove monomer and light oligomers, usually up to C12 oligomers which exit via line 116 for further processing.

(57) The partially purified PIB is forwarded via line 118 to a vacuum flash or distillation unit 120, where the product is further purified by distillation to remove oligomers, especially C8 to C24 oligomers at temperatures of from 150 C.-300 C. and pressures of from 0.25 psia to 10 psia or so. Alternatively, a wipe film evaporator or like apparatus can be employed to eliminate oligomers from the composition. The purified PIB product is removed at 122.

Example 1

(58) Utilizing the apparatus shown in FIG. 1, isobutylene feedstock having the composition shown in Table 2 is diluted in a 1:1 weight ratio with isobutene and is polymerized in the liquid phase at a temperature of 10 C. and an average residence time of less than 15 minutes. BF.sub.3 and methanol catalyst modifier are added in a methanol:BF.sub.3 ratio of 1.6:1. 1 millimole BF.sub.3 is used per mole of isobutylene introduced into the reactor. The crude product has a residual fluoride content of less than 200 ppm F by weight. Following withdrawal from the reactor, the reaction mixture is quenched to deactivate the catalyst, washed with water to remove salts and distilled to remove oligomers as discussed in connection with FIG. 2. The purified product has a total fluoride content of less than 10 ppm by weight fluoride, a molecular weight, Mn of 2100 Daltons and an alpha content of 79 mol. %.

Example 2

(59) Isobutylene feedstock having the composition of Table 2 is blended in a 1:1 weight ratio with the isobutylene raffinate-1 feedstock of Table 4. The blend is then diluted in a 1:1 weight ratio with isobutane and is polymerized in the liquid phase utilizing the apparatus shown in FIG. 1 at a temperature of 10 C. and an average residence time of about 20 minutes. BF3 and isopropanol catalyst modifier are added in a isopropanol:BF.sub.3 ratio of 1.8:1. 1 millimole BF.sub.3 is used per mole of isobutylene introduced into the reactor. The crude product has a residual fluoride content of less than 200 ppm F by weight. Following withdrawal from the reactor, the reaction mixture is quenched to deactivate the catalyst, washed with water to remove salts and distilled to remove oligomers as discussed in connection with FIG. 2. The purified product has a total fluoride content of less than 8 ppm by weight fluoride, a molecular weight, Mn of 1050 Daltons and an alpha content of 83 mol. %.

Examples 3-6

(60) These examples illustrate the surprising and profound effect of LB/IsoB index on the fluoride ride content of purified PIB polymer recovered from a reactor under a given set of conditions.

(61) Isobutylene feedstock was fed to a reactor and was polymerized in the liquid phase utilizing the feed and process features shown in Table 6. Following withdrawal from the reactor, the reaction mixture was quenched to deactivate the catalyst, washed with water to remove salts and distilled to remove oligomers as discussed in connection with FIG. 2. Examples 3-6 had a molecular weight, Mn of about 1050 Daltons. Product 1, Examples 3,4 (higher modifier/BF.sub.3 ratio) had an alpha content of about 85 mol. %, while Product 2, Examples 5, 6 had an alpha content of less than 75 mol. % and greater than 50 mol. %.

(62) The purified products had a fluoride content as indicated in Table 6, wherein it is seen that the fluoride content of the purified products correlated closely with the LB/IsoB index of the feedstock.

(63) TABLE-US-00006 TABLE 6 Effect of LB/IsoB Index on Fluoride Content at a given set of Conditions Units; LB/IsoB Product Product Feature: Index 1 2 Isobutane Content of feed Wt. % from GC 10 4 Reaction temp C. 20 30 Residence Time min <10 <15 alcohols:BF.sub.3 ratio molar ratio 1.8 1.0 Reactor Pressure (psig) 140 140 PPM Fluoride (total in Final LB/IsoB = 0.30% 1 1 Product) LB/IsoB = 2.94% 4 4 at Given LB/IsoB Index

Comparative Example 1

(64) This Example appears as Example 1 of Publication WO 2015/030489 and illustrates the effects of feed quality, residence time and temperature on fluoride content. A raffinate-1 feed was polymerized in a reactor with a BF.sub.3/isopropanol catalyst and polymerized at a temperature of 29 C. for an average residence time of 45 minutes. The crude polymer product had a fluorine content of 299 ppm.

Comparative Example 2

(65) This Example appears as Example 1 of U.S. Pat. No. 5,962,604 to Rath and illustrates the effect of temperature and feed quality on fluoride content. Isobutylene in a steam cracker refined feedstock was polymerized in a homogeneous reactor at a temperature of 13 C. over approximately 14 minutes residence time. The PIB product had an alpha content of 90 mol % and a molecular weight, Mn, of 1005. Fluorine content after extraction was 114 ppm and fluorine content after distillation was 65 ppm.

Example 7

(66) This Example illustrates the removal of oligomers from the PIB product and the surprisingly low fluoride content of the product following ammonium hydroxide quench followed by distillation under vacuum 2 psia at elevated temperature, 220 C.

(67) Following generally the procedure according to Example 1, a crude PIB product was produced and fed to the purification process of FIG. 2 and purified as described above. The product had low oligomer content and surprising low residual fluoride content as is seen in Table 7 and below. Without intending to be bound by any particular theory, the low oligomer content and sublimation of residual fluoride ammonium salts are believed to contribute substantially to the low residual fluoride content of the product.

(68) TABLE-US-00007 TABLE 7 Purified PIB Composition After Vacuum Distillation Component Wt. % Main Polymer 92.61% C32 2.33% C28 2.07% C24 1.56% C20 0.96% C16 0.41% C12 0.05% Total Oligomer 7.39%
Residual fluoride content: 1-2 ppm by weight.

Embodiments of the Invention

(69) There is thus provided in Embodiment No. 1 a method of making a low-fluoride reactive PIB composition comprising (a) providing a modified C4 feedstock by way of blending a mixed C4 feedstock with a second feedstock having a lower LB/IsoB ratio; or providing a C4 feedstock with an LB/IsoB index of less than 10%; (b) feeding the modified C4 feedstock or the C4 feedstock with an LB/IsoB index of less than 10% to a CSTR with a homogeneous catalyst comprising BF.sub.3 and a modifier selected from alcohols, ethers and mixtures thereof; (c) polymerizing the modified C4 feedstock or the C4 feedstock with an LB/IsoB index of less than 10% in the reactor while maintaining the reactor at a temperature above 15 C. and utilizing a residence time less than 45 minutes to produce a crude PIB composition in a polymerization mixture; and (d) recovering a purified PIB composition from the polymerization mixture having a molecular weight, Mn, from 250 to 5000 Daltons and an alpha vinylidene content of at least 50 mol %.

(70) Embodiment No. 2 is the method according to Embodiment No. 1, wherein step (a) includes providing the modified C4 feedstock by way of blending a mixed C4 feedstock with a second feedstock having a lower LB/IsoB ratio, step (b) includes feeding the modified C4 feedstock to a CSTR with a homogeneous catalyst comprising BF.sub.3 and a modifier selected from alcohols, ethers and mixtures thereof and step (c) includes polymerizing the modified C4 feedstock while maintaining the reactor at a temperature above 15 C. and utilizing a residence time less than 45 minutes to produce a crude PIB composition in a polymerization mixture.

(71) Embodiment No. 3 is the method according to Embodiment No. 2, wherein the first mixed C4 feedstock has an LB/IsoB index of greater than 3%.

(72) Embodiment No. 4 is the method according to Embodiment Nos. 3, wherein the first mixed C4 feedstock has an LB/IsoB index of greater than 4.5%.

(73) Embodiment No. 5 is the method according to any of Embodiment Nos. 2 to 4, wherein the first mixed C4 feedstock has an LB/IsoB index of greater than 10%.

(74) Embodiment No. 6 is the method according to any of Embodiment Nos. 2 to 5, wherein the first mixed C4 feedstock has an LB/IsoB index of greater than 25%.

(75) Embodiment No. 7 is the method according to any of Embodiment Nos. 2 to 6, wherein the first mixed C4 feedstock has an LB/IsoB index of greater than 40%.

(76) Embodiment No. 8 is the method according to Embodiment No. 2, wherein the first mixed C4 feedstock comprises raffinate or dehydro effluent.

(77) Embodiment No. 9 is the method according to any of Embodiment Nos. 2 to 8, wherein the second feedstock has an LB/IsoB index of less than 3%.

(78) Embodiment No. 10 is the method according to any of Embodiment Nos. 2 to 9, wherein the second feedstock has an LB/IsoB index of less than 1%.

(79) Embodiment No. 11 is the method according to Embodiment No. 9, wherein the second feedstock comprises isobutylene concentrate or highly purified isobutylene.

(80) Embodiment No. 12 is the method of making a low-fluoride reactive PIB composition comprising: (a) providing a C4 feedstock with an LB/IsoB index of less than 10%; (b) feeding the C4 feedstock with an LB/IsoB index of less than 10% to a CSTR with a homogeneous catalyst comprising BF.sub.3 and a modifier selected from alcohols, ethers and mixtures thereof; (c) polymerizing the feedstock with an LB/IsoB index of less than 10% in the reactor while maintaining the reactor at a temperature above 15 C. and utilizing a residence time less than 45 minutes to produce a crude PIB composition in a polymerization mixture; and (d) recovering a purified PIB composition from the polymerization mixture having a molecular weight, Mn, from 250 to 5000 Daltons and an alpha vinylidene content of at least 50 mol %.

(81) Embodiment No. 13 is the method according to Embodiment No. 12, wherein the C4 feedstock has an LB/IsoB index of less than 5%.

(82) Embodiment No. 14 is the method according to Embodiment Nos. 12 or 13, wherein the C4 feedstock has an LB/IsoB index of less than 3%.

(83) Embodiment No. 15 is the method according to any of Embodiment Nos. 12 to 14, wherein the C4 feedstock has an LB/IsoB index of less than 2.5%.

(84) Embodiment No. 16 is the method according to any of Embodiment Nos. 12 to 15, wherein the C4 feedstock has an LB/IsoB index of less than 1%.

(85) Embodiment No. 17 is the method according to any of Embodiment Nos. 12 to 16, wherein the C4 feedstock has an LB/IsoB index of less than 1% and an isobutylene content of more than 50 wt. %.

(86) Embodiment No. 18 is the method according to Embodiment No. 12, wherein the C4 feedstock comprises isobutylene concentrate, highly purified isobutylene or dehydro effluent, each of which is optionally diluted with an alkane diluent.

(87) Embodiment No. 19 is the method according to any of Embodiment Nos. 12 to 18, wherein the C4 feedstock contains 50% by weight or more isobutylene and 5% by weight or less 1-butene and 2-butene and more than 5% alkane diluent.

(88) Embodiment No. 20 is the method of making a low-fluoride reactive PIB composition comprising: (a) providing a C4 feedstock containing isobutylene; (b) feeding the C4 feedstock to a CSTR with a homogeneous catalyst comprising BF.sub.3 and a modifier selected from alcohols, ethers and mixtures thereof; (c) polymerizing the modified C4 feedstock or the C4 feedstock in the reactor while maintaining the reactor at a temperature above 40 C. and utilizing a residence time less than 45 minutes to produce a crude PIB composition in a polymerization mixture; and (d) recovering a purified PIB composition from the polymerization mixture having a molecular weight, Mn, from 250 to 5000 Daltons and an alpha vinylidene content of at least 50 mol % wherein the C4 feedstock is a modified C4 feedstock produced by way of blending a mixed C4 feedstock with a second feedstock having a lower LB/IsoB ratio; or the C4 feedstock is a C4 feedstock with an LB/IsoB index of less than 5% and with an isobutylene content of at least 60 wt. % and less than 85%.

(89) Embodiment No. 21 is the method according to Embodiment No. 20, wherein the C4 feedstocks have an LB/IsoB index of less than 3%.

(90) Embodiment No. 22 is the method according to Embodiment Nos. 20 or 21, wherein the C4 feedstocks have an LB/IsoB index of less than 2.5%.

(91) Embodiment No. 23 is the method according to any of Embodiment Nos. 20 to 22, wherein the C4 feedstocks have an LB/IsoB index of less than 1%.

(92) Embodiment No. 24 is the method according to Embodiment No. 20, wherein the reactor is maintained at a temperature of 30 C. or above.

(93) Embodiment No. 25 is the method according to Embodiment No. 20, wherein the reactor is maintained at a temperature of 25 C. or above.

(94) Embodiment No. 26 is the method according to Embodiment No. 20, wherein the reactor is maintained at a temperature of 20 C. or above.

(95) Embodiment No. 27 is the method according to any of the foregoing Embodiments, wherein the residual fluoride content of the crude PIB composition is less than 200 ppm.

(96) Embodiment No. 28 is the method according to any of the foregoing Embodiments, wherein the residual fluoride content of the crude PIB composition is less than 100 ppm.

(97) Embodiment No. 29 is the method according to any of the foregoing Embodiments, wherein the residual fluoride content of the crude PIB composition is less than 50 ppm.

(98) Embodiment No. 30 is the method according to Embodiment No. 29, wherein the residual fluoride content of the purified PIB composition is less than 25 ppm.

(99) Embodiment No. 31 is the method according to Embodiment No. 30, wherein the residual fluoride content of the purified PIB composition is less than 20 ppm.

(100) Embodiment No. 32 is the method according to Embodiment No. 31, wherein the residual fluoride content of the purified PIB composition is less than 15 ppm.

(101) Embodiment No. 33 is the method according to Embodiment No. 32, wherein the residual fluoride content of the purified PIB composition is less than 10 ppm.

(102) Embodiment No. 34 is the method according to Embodiment No. 33, wherein the residual fluoride content of the purified PIB composition is less than 5 ppm.

(103) Embodiment No. 35 is the method according to Embodiment No. 34, wherein the residual fluoride content of the purified PIB composition is less than 3 ppm.

(104) Embodiment No. 36 is a method according to Embodiment No. 35, wherein the residual fluoride content of the purified PIB composition is 2 ppm or less.

(105) Embodiment No. 37 according to any of Embodiment Nos. 1 to 29, wherein the residual organic fluoride content of the purified PIB composition is less than 40 ppm.

(106) Embodiment No. 38 according to Embodiment No. 37, wherein the residual organic fluoride content of the purified PIB composition is less than 25 ppm.

(107) Embodiment No. 39 is the method according to Embodiment No. 38, wherein the residual organic fluoride content of the purified PIB composition is less than 20 ppm.

(108) Embodiment No. 40 is the method according to Embodiment No. 39, wherein the residual organic fluoride content of the purified PIB composition is less than 10 ppm.

(109) Embodiment No. 41 is the method according to Embodiment No. 40, wherein the residual organic fluoride content of the purified PIB composition is less than 5 ppm.

(110) Embodiment No. 42 is the method according to Embodiment No. 41, wherein the residual organic fluoride content of the purified PIB composition is less than 3 ppm.

(111) Embodiment No. 43 is a method according to Embodiment No. 42, wherein the residual organic fluoride content of the purified PIB composition is 2 ppm or less.

(112) Embodiment No. 44 is the method according to Embodiment No. 29, wherein the residual organic fluoride content of the purified PIB composition contains less than 40 ppm by weight fluorine in the product corresponding to fluorinated compounds of the formula:

(113) ##STR00011##

(114) Embodiment No. 45 is the method according to Embodiment No. 44, wherein the residual organic fluoride content of the purified PIB composition contains less than 25 ppm by weight fluorine in the product corresponding to fluorinated compounds of the formula:

(115) ##STR00012##

(116) Embodiment No. 46 is the method according to Embodiment No. 45, wherein the residual organic fluoride content of the purified PIB composition contains less than 20 ppm by weight fluorine in the product corresponding to fluorinated compounds of the formula:

(117) ##STR00013##

(118) Embodiment No. 47 is the method according to Embodiment No. 46, wherein the residual organic fluoride content of the purified PIB composition contains less than 10 ppm by weight fluorine in the product corresponding to fluorinated compounds of the formula:

(119) ##STR00014##

(120) Embodiment No. 48 is the method according to Embodiment No. 47, wherein the residual organic fluoride content of the purified PIB composition contains less than 5 ppm by weight fluorine in the product corresponding to fluorinated compounds of the formula:

(121) ##STR00015##

(122) Embodiment No. 49 is the method according to Embodiment No. 48, wherein the residual organic fluoride content of the purified PIB composition contains less than 3 ppm by weight fluorine in the product corresponding to fluorinated compounds of the formula:

(123) ##STR00016##

(124) Embodiment No. 50 is the method according to any of the foregoing Embodiments, wherein the reactor is maintained at a temperature of 15 C. or above.

(125) Embodiment No. 51 is the method according to any of the foregoing Embodiments, wherein the reactor is maintained at a temperature of 10 C. or above.

(126) Embodiment No. 52 is the method according to any of the foregoing Embodiments, wherein the reactor is maintained at a temperature of 0 C. or above.

(127) Embodiment No. 53 is the method according to any of the foregoing Embodiments, wherein the reactor is maintained at a temperature of 10 C. or above.

(128) Embodiment No. 54 is the method according to any of the foregoing Embodiments, wherein the reactor is maintained at a temperature of 20 C. or above.

(129) Embodiment No. 55 is the method according to any of the foregoing Embodiments, wherein the temperature is maintained at a temperature of from 0 C. to 40 C.

(130) Embodiment No. 56 is the method according to any of the foregoing Embodiments, wherein the residence time is 30 minutes or less or 20 minutes or less.

(131) Embodiment No. 57 is the method according to any of the foregoing Embodiments, wherein the residence time is 15 minutes or less.

(132) Embodiment No. 58 is the method according to any of the foregoing Embodiments, wherein the residence time is 10 minutes or less.

(133) Embodiment No. 59 is the method according to any of the foregoing Embodiments, wherein the residence time is 7.5 minutes or less.

(134) Embodiment No. 60 is the method according to any of the foregoing Embodiments, wherein the reactor is operated with a catalyst turnover number of from 750 to 3500 lbs. polymer/lb BF.sub.3.

(135) Embodiment No. 61 is the method according to Embodiment No. 60, wherein the reactor is operated with a catalyst turnover number of at least 1000 lbs polymer/lb BF.sub.3.

(136) Embodiment No. 62 is the method according to Embodiment No. 60, wherein the reactor is operated with a catalyst turnover number of at least 1250 lbs polymer/lb BF.sub.3.

(137) Embodiment No. 63 is the method according to Embodiment No. 60, wherein the reactor is operated with a catalyst turnover number of at least 2000 lbs polymer/lb BF.sub.3.

(138) Embodiment No. 64 is the method according to any of the foregoing Embodiments, wherein the modifier comprises a mixture of alcohol and ether.

(139) Embodiment No. 65 is the method according to any of the foregoing Embodiments, wherein the catalyst complex comprises a modifier selected from methanol, ethanol, tertiary butanol, isopropyl ether, diethyl ether and mixtures thereof.

(140) Embodiment No. 66 is the method according to Embodiment No. 63, wherein the modifier consists of methanol.

(141) Embodiment No. 67 is the method according to Embodiment No. 63, wherein the modifier comprises at least one of isopropyl ether or diethyl ether.

(142) Embodiment No. 68 is the method according to any of the foregoing Embodiments, wherein the molar ratio of modifier to BF.sub.3 is in the range of 0.5:1 to 3.5:1.

(143) Embodiment No. 69 is the method according to any of the foregoing Embodiments, wherein the molar ratio of modifier to BF.sub.3 is in the range of 0.5:1 to 3:1.

(144) Embodiment No. 70 is the method according to any of the foregoing Embodiments, wherein the molar ratio of modifier to BF.sub.3 is in the range of 0.5:1 to 2:1.

(145) Embodiment No. 71 is the method according to any of the foregoing Embodiments, wherein the molar ratio of modifier to BF.sub.3 is in the range of 1:1 to 1.8:1.

(146) Embodiment No. 72 is the method according to any of the foregoing Embodiments, wherein the modifier comprises a mixture of an alcohol and an ether wherein the molar ratio of alcohol to BF.sub.3 is from 0-2:1 and the molar ratio of ether to BF.sub.3 is from 0-3:1.

(147) Embodiment No. 73 is the method according to any of the foregoing Embodiments, wherein the purified PIB composition has an alpha vinylidene content of at least 60 mole %.

(148) Embodiment No. 74 is the method according to any of the foregoing Embodiments, wherein the purified PIB composition has an alpha vinylidene content of at least 70 mole %.

(149) Embodiment No. 75 is the method according to any of the foregoing Embodiments, wherein the purified PIB composition has an alpha vinylidene content of at least 75 mole %.

(150) Embodiment No. 76 is the method according to any of Embodiment Nos. 1 to 72, wherein the purified PIB composition is characterized in that a first portion of the PIB molecules have alpha position double bonds and a second portion of the molecules have beta position double bonds, wherein said first and second portions together include at least 80 mole % of the PIB molecules of the composition, wherein said first portion includes less than 75 mole % of the PIB molecules of the composition, and wherein no more than 10 mole % of the PIB molecules of the composition have tetra-substituted double bonds.

(151) Embodiment No. 77 is the method according to any of the foregoing Embodiments, wherein the purified PIB composition includes from 0.05 mole % to 5 mole % of molecules with internal vinylidene bonds.

(152) Embodiment No. 78 is the method according to any of the foregoing Embodiments, wherein the molecular weight, Mn, of the purified PIB composition is from 300 to 5000 Daltons.

(153) Embodiment No. 79 is the method according to any of the foregoing Embodiments, wherein the molecular weight, Mn, of the purified PIB composition is from 300 to 3500 Daltons.

(154) Embodiment No. 80 is the method according to any of the foregoing Embodiments, wherein the molecular weight, Mn, of the purified PIB composition is from 500 to 3000 Daltons.

(155) Embodiment No. 81 is the method according to any of the foregoing Embodiments, wherein the molecular weight, Mn, of the purified PIB composition is from 750 to 1500 Daltons.

(156) Embodiment No. 82 is the method according to any of the foregoing Embodiments, wherein the purified PIB composition has a polydispersity index (PDI) of less than 2.5.

(157) Embodiment No. 83 is the method according to any of the foregoing Embodiments, wherein the purified PIB composition has a polydispersity index (PDI) of less than 2.

(158) Embodiment No. 84 is the method according to any of the foregoing Embodiments, wherein the purified PIB composition has a polydispersity index (PDI) of no more than 1.5.

(159) Embodiment No. 85 is the method according to any of the foregoing Embodiments, wherein the process further comprises quenching the reaction using ammonium hydroxide.

(160) Embodiment No. 86 is the method according to Embodiments No. 85, wherein salts of the quenched product include ammonium tetrafluoroborate which is removed from the PIB at temperature above 150 C. and at reduced pressure, below 15 psia.

(161) Embodiment No. 87 is a method according to any of Embodiment Nos. 1 to 85, further comprising treating the crude PIB composition at a temperature of from 150 C. to 300 C. to separate oligomers from the crude composition to produce the purified PIB composition.

(162) Embodiment No. 88 is the method according to any of the foregoing embodiments, further comprising: (i) withdrawing the crude PIB composition from the reactor; (ii) neutralizing the crude PIB composition with an ammonium salt; and (iii) treating the crude PIB composition at a temperature of from 150 C. to 300 C. to separate oligomers from the crude PIB composition.

(163) Embodiment No. 89 is a method according Embodiment No. 88, further comprising washing the neutralized crude PIB composition with water and decanting the washed PIB composition to provide an aqueous phase and an organic phase containing PIB polymer.

(164) Embodiment No. 90 is a method according to Embodiment No. 89, comprising treating the organic phase containing PIB polymer at a temperature of from 150 C. to 300 C. and a pressure of from 0.25 psia to 10 psia to remove PIB oligomers from the composition.

(165) Embodiment No. 91 is a method according to Embodiment No. 90, comprising treating the organic phase containing PIB polymer at a temperature of from 200 C. to 250 C. and a pressure of from 0.5 psia to 5 psia to remove PIB oligomers from the composition.

(166) Embodiment No. 92 is a method according to any of the foregoing Embodiments, wherein the purified PIB composition has less than 10% by weight C8 to C24 oligomers.

(167) Embodiment No. 93 is a method according to any of the foregoing Embodiments, wherein the purified PIB composition has less than 5% by weight C8 to C24 oligomers.

(168) Embodiment No. 94 is a method according to any of the foregoing Embodiments, wherein the purified PIB composition has less than 3% by weight C8 to C24 oligomers.

(169) In any of the foregoing embodiments, it is preferred in general that no more than 15 mole % of the PIB molecules of the composition have tetra-substituted double bonds. More preferably in all cases, less than 10 mole % of the PIB molecules of the composition have tetra-substituted double bonds and still more preferably in all of the foregoing embodiments, no more than 5 mole % of the PIB molecules of the composition have tetra-substituted double bonds.

(170) While the invention has been described in detail, modifications within the spirit and scope of the invention will be readily apparent to those of skill in the art. Such modifications are also to be considered as part of the present invention. In view of the foregoing discussion, relevant knowledge in the art and references discussed above in connection with the Background of the Invention, the disclosures of which are all incorporated herein by reference, further description is deemed unnecessary. In addition, it should be understood that aspects of the invention and portions of various embodiments may be combined or interchanged either in whole or in part. Furthermore, those of ordinary skill in the art will appreciate that the foregoing description is by way of illustration only and is not intended to limit the invention.