Patent Grant
10526429
The present invention relates to methods for making polyisobutylene diol. More specifically, the invention relates to methods for making a polyisobutylene diol from a polyisobutylene diallyl.
Thermoplastic elastomers based on difunctional, telechelic soft segments have exceptionally desirable properties. Examples of difunctional telechelic soft segments useful in such thermoplastic elastomers include polyisobutylene-based soft segments. There are many unique and desirable physical and mechanical properties that are offered exclusively by polyisobutylene and polyisobutylene-based materials, including thermal stability, biocompatibility and gas impermeability, among others. These properties can be tuned and further modified in copolymerization strategies with other materials, for example, to synthesize polyurethanes based on a polyisobutylene (PIB) soft segment. A process of making polyisobutylene-based soft segments by carbocationic polymerization begins with a difunctional initiator molecule and produces a polyisobutylene diol.
Some of the materials used in the process of making polyisobutylene diol are costly, hazardous, and difficult to handle. Safer and less costly materials are needed.
Example 1 is a method for making a polyisobutylene diol from a polyisobutylene diallyl. The method includes hydroborating the polyisobutylene diallyl to produce a polyisobutylene dialkyl borane, and oxidizing the polyisobutylene dialkyl borane to form the polyisobutylene diol. The polyisobutylene diallyl is hydroborated by combining in situ the polyisobutylene diallyl with a borane-coordinating solvent, an alkaline metal salt of borohydride, and an acid. The alkaline metal salt of borohydride is combined with the polyisobutylene diallyl before the acid is combined with the polyisobutylene diallyl.
Example 2 is the method of Example 1, wherein the alkaline metal salt of borohydride includes at least one of sodium borohydride, potassium borohydride, and lithium borohydride.
Example 3 is the method of either of Examples 1 or 2, wherein the acid is the strong mineral acid, the strong mineral acid including at least one of sulfuric acid, hydrochloric acid, hydroiodic acid, and hydrobromic acid.
Example 4 is the method of either of Examples 1 or 2, wherein the acid includes a strong Lewis acid, a halide, or a combinations thereof; the strong Lewis acid including at least one of boron trichloride, aluminum trichloride, and aluminum trifluoride; and the halide including at least one of iodine and bromine.
Example 5 is the method of any of Examples 1-4, wherein the borane-coordinating solvent includes at least one of tetrahydrofuran, diethyl ether, dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.
Example 6 is the method of any of Examples 1-5, wherein oxidizing the polyisobutylene dialkyl borane to form the polyisobutylene diol includes combining a base and an oxidizer with the polyisobutylene dialkyl borane.
Example 7 is the method of Example 6, wherein the oxidizer is at least one of hydrogen peroxide, peracetic acid, potassium permanganate, and benzoyl peroxide.
Example 8 is the method of either of Examples 6 or 7, wherein the base includes at least one of sodium hydroxide and potassium hydroxide.
Example 9 is a method for making a polyisobutylene diol, the method including providing a polyisobutylene dichloride, reacting the polyisobutylene dichloride with allyltrimethylsilane to produce a polyisobutylene diallyl, hydroborating the polyisobutylene diallyl to produce a polyisobutylene dialkyl borane, and combining a base and an oxidizer with the polyisobutylene dialkyl borane to form the polyisobutylene diol. The polyisobutylene diallyl is hydroborated by combining in situ the polyisobutylene diallyl with a borane-coordinating solvent, an alkaline metal salt of borohydride, and an acid. The alkaline metal salt of borohydride is combined with the polyisobutylene diallyl before the acid is combined with the polyisobutylene diallyl.
Example 10 is the method of Example 9, wherein the alkaline metal salt of borohydride includes at least one of sodium borohydride, potassium borohydride, and lithium borohydride.
Example 11 is the method of either of Examples 9 or 10, wherein the acid is the strong mineral acid, the strong mineral acid including at least one of sulfuric acid, hydrochloric acid, hydroiodic acid, and hydrobromic acid.
Example 12 is the method of either of Examples 9 or 10, wherein the acid includes a strong Lewis acid, a halide, or a combinations thereof; the strong Lewis acid including at least one of boron trichloride, aluminum trichloride, and aluminum trifluoride; and the halide including at least one of iodine and bromine.
Example 13 is the method of any of Examples 9-12, wherein the borane-coordinating solvent includes at least one of tetrahydrofuran, diethyl ether, dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.
Example 14 is the method of any of Examples 9-13, wherein the oxidizer is at least one of hydrogen peroxide, peracetic acid, potassium permanganate, and benzoyl peroxide.
Example 15 is the method of any of Examples 9-14, wherein the base includes at least one of sodium hydroxide and potassium hydroxide.
Example 16 is a method for making a polyisobutylene diol, the method including providing a polyisobutylene diallyl, hydroborating the polyisobutylene diallyl to produce a polyisobutylene dialkyl borane, and oxidizing the polyisobutylene dialkyl borane to form the polyisobutylene diol. The polyisobutylene diallyl is hydroborated by combining in situ the polyisobutylene diallyl with a borane-coordinating solvent, an alkaline metal salt of borohydride, and an acid. The alkaline metal salt of borohydride is combined with the polyisobutylene diallyl before the acid is combined with the polyisobutylene diallyl.
Example 17 is the method of Example 16, wherein the alkaline metal salt of borohydride includes at least one of sodium borohydride, potassium borohydride, and lithium borohydride.
Example 18 is the method of either of Examples 16 or 17, wherein the acid is the strong mineral acid, the strong mineral acid including at least one of sulfuric acid, hydrochloric acid, hydroiodic acid, and hydrobromic acid.
Example 19 is the method of either of Examples 16 or 17, wherein the acid includes a strong Lewis acid, a halide, or a combinations thereof; the strong Lewis acid including at least one of boron trichloride, aluminum trichloride, and aluminum trifluoride; and the halide including at least one of iodine and bromine.
Example 20 is the method of any of Examples 16-19, wherein the borane-coordinating solvent includes at least one of tetrahydrofuran, diethyl ether, dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.
Example 21 is the method of any of Examples 16-20, wherein providing the polyisobutylene diallyl includes providing a polyisobutylene dichloride, and reacting the polyisobutylene dichloride with allyltrimethylsilane to produce the polyisobutylene diallyl.
Example 22 is the method of Example 16, wherein oxidizing the polyisobutylene dialkyl borane to form the polyisobutylene diol includes combining a base and an oxidizer with the polyisobutylene dialkyl borane.
Example 23 is the method of Example 22, wherein the oxidizer is at least one of hydrogen peroxide, peracetic acid, potassium permanganate, and benzoyl peroxide.
Example 24 is the method of either of Examples 22 or 23, wherein the base includes at least one of sodium hydroxide and potassium hydroxide.
Example 25 is a method for making a polyisobutylene diol, the method including providing a polyisobutylene dichloride, reacting the polyisobutylene dichloride with allyltrimethylsilane to produce a polyisobutylene diallyl, hydroborating the polyisobutylene diallyl to produce a polyisobutylene dialkyl borane, and combining a base and an oxidizer with the polyisobutylene dialkyl borane to form the polyisobutylene diol. The polyisobutylene diallyl is hydroborated by combining in situ the polyisobutylene diallyl with a borane-coordinating solvent, an alkaline metal salt of borohydride, and an acid. The alkaline metal salt of borohydride is combined with the polyisobutylene diallyl before the acid is combined with the polyisobutylene diallyl.
Example 26 is the method of Example 25, wherein the alkaline metal salt of borohydride includes at least one of sodium borohydride, potassium borohydride, and lithium borohydride.
Example 27 is the method of either of Examples 25 or 26, wherein the acid is the strong mineral acid, the strong mineral acid including at least one of sulfuric acid, hydrochloric acid, hydroiodic acid, and hydrobromic acid.
Example 28 is the method of either of Examples 25 or 26, wherein the acid includes a strong Lewis acid, a halide, or a combinations thereof; the strong Lewis acid including at least one of boron trichloride, aluminum trichloride, and aluminum trifluoride; and the halide including at least one of iodine and bromine.
Example 29 it the method of any of Examples 25-28, wherein the borane-coordinating solvent includes at least one of tetrahydrofuran, diethyl ether, dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.
Example 30 is the method of any of Examples 25-29, wherein the oxidizer is at least one of hydrogen peroxide, peracetic acid, potassium permanganate, and benzoyl peroxide.
Example 31 is the method of any of Examples 25-30, wherein the base includes at least one of sodium hydroxide and potassium hydroxide.
Example 32 is a method for making a polyisobutylene diol, the method including providing a polyisobutylene dichloride, reacting the polyisobutylene dichloride with allyltrimethylsilane to produce a polyisobutylene diallyl, hydroborating the polyisobutylene diallyl to produce a polyisobutylene dialkyl borane, and combining hydrogen peroxide and at least one of sodium hydroxide and potassium hydroxide with the polyisobutylene dialkyl borane to form the polyisobutylene diol. The polyisobutylene diallyl is hydroborated by combining in situ the polyisobutylene diallyl with tetrahydrofuran, an alkaline metal salt of borohydride, and an acid. The alkaline metal salt of borohydride is combined with the polyisobutylene diallyl before the acid is combined with the polyisobutylene diallyl.
Example 33 is the method of Example 32, wherein the acid is the strong mineral acid, the strong mineral acid including at least one of sulfuric acid, hydrochloric acid, hydroiodic acid, and hydrobromic acid.
Example 34 is the method of Example 32, wherein the acid includes a strong Lewis acid, a halide, or a combinations thereof; the strong Lewis acid including at least one of boron trichloride, aluminum trichloride, and aluminum trifluoride; and the halide including at least one of iodine and bromine.
Example 35 is the method of any of Examples 32-34, wherein the alkaline metal salt of borohydride includes at least one of sodium borohydride, potassium borohydride, and lithium borohydride.
While multiple embodiments are disclosed, still other embodiments of the present invention will become apparent to those skilled in the art from the following detailed description, which shows and describes illustrative embodiments of the invention. Accordingly, the drawings and detailed description are to be regarded as illustrative in nature and not restrictive.
While the invention is amenable to various modifications and alternative forms, specific embodiments have been shown by way of example in the drawings and are described in detail below. The intention, however, is not to limit the invention to the particular embodiments described. On the contrary, the invention is intended to cover all modifications, equivalents, and alternatives falling within the scope of the invention as defined by the appended claims.
In embodiments of this disclosure, producing a polyisobutylene diol can require a hydroboration of a polyisobutylene diallyl followed by an oxidation step. A reagent generally employed in the art to provide borane for hydroboration is 9-borabicyclo(3.3.1)nonane (9-BBN). However, 9-BBN is a costly material that is difficult to handle and store. Additionally, 9-BBN is flammable.
Embodiments of this disclosure can employ an alkaline metal salt of borohydride combined with an acid in a borane-coordinating solvent to provide a source of borane for hydroboration. In embodiments of this disclosure, the alkaline metal salt of borohydride and the acid are combined with the polyisobutylene diallyl in situ and are added to the polyisobutylene diallyl separately from each other. That is, the alkaline metal salt of borohydride and the acid are not combined with each other before being added to the polyisobutylene diallyl. In this way, the borane is formed only in the reaction vessel containing the polyisobutylene diallyl, minimizing exposure of the borane to moisture before it can react with the polyisobutylene diallyl. This is beneficial because borane reacts readily with moisture to form boric acid, which must eventually be removed from the polyisobutylene diol, at additional cost. In addition, any borane reacting with moisture is not available for hydroboration, thus requiring additional material to generate borane and react with the polyisobutylene diallyl, which increases the cost of the hydroboration.
In contrast to 9-BBN, some alkaline metal salts of borohydride, such as sodium borohydride, are not flammable and are more easily stored. The use of sodium borohydride for hydroboration can result in about a 95% cost savings over the use of 9-BBN.
Once the polyisobutylene dichloride is produced, allyl end groups can be added to the polyisobutylene chain. In the embodiment shown in
Once the polyisobutylene diallyl is produced, an alkaline metal salt of borohydride, and a borane-coordinating solvent are added in situ to the polyisobutylene diallyl. In some embodiments, the alkaline metal salt of the borohydride is added after the borane-coordinating solvent is added. In other embodiments, the borane-coordinating solvent is added after the alkaline metal salt of the borohydride is added. Following the addition of the alkaline metal salt of borohydride and the borane-coordinating solvent, an acid is added in situ to the polyisobutylene diallyl. As noted above, the alkaline metal salt of borohydride and the acid are not combined before being added to the polyisobutylene diallyl.
In some embodiments, the alkaline metal salt of the borohydride can include sodium borohydride, potassium borohydride, and or lithium borohydride. In some embodiments, the acid can include a strong mineral acid, such as sulfuric acid, hydrochloric acid, hydroiodic acid, hydrobromic acid, or mixtures thereof. In some embodiments, the acid can include an elemental halide, such as iodine, bromine, or mixtures thereof. In some embodiments, the acid can include a strong Lewis acid, such as boron trichloride, aluminum trichloride, aluminum trifluoride, or mixtures thereof. In some embodiments, the borane-coordinating solvent can include tetrahydrofuran (THF), diethyl ether, dimethoxyethane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, or mixtures thereof.
In some embodiments, the molar ratio of the borane-coordinating solvent to the alkaline metal salt of borohydride is at least 1:1 to coordinate and stabilize the borane to prevent side reactions. In some embodiments, the molar ratio of the borane-coordinating solvent to the alkaline metal salt of borohydride is as low as 1.1:1, 1.2:1, 1.3:1, 1.4:1, or 1.5:1, or as high as 1.6:1, 1.7:1, 1.8:1, 1.9:1, or 2.:1, or between any valued defined between any two of the foregoing values, such as 1.1:1 to 2:1, 1.2:1 to 1.9:1, 1.3:1 to 1.8:1, 1.4:1 to 1.7:1, or 1.5:1 to 1.6:1.
Combining the alkaline metal salt of the borohydride and the acid in the presence of the borane-coordinating solvent can create a borane complex. For example, in some embodiments, sodium borohydride (NaBH4) and a mineral acid, such as sulfuric acid (H2SO4), are combined in situ with THF to produce a borane complex as shown in Equation 1 below:
2NaBH4+H2SO4+2THF→2BH3:THF+Na2SO4+H2. Eq. 1
The hydrogen gas (H2) produced can be diluted with an inert gas, such as nitrogen, and safely vented away. The sodium sulfate (Na2SO4) can be removed by subsequent water washing.
In some other embodiments, sodium borohydride and a Lewis acid, such as boron trichloride (BCl3), are combined in situ with THF to produce a borane complex as shown in Equation 2 below:
3NaBH4+BCl3+4THF→4BH3:THF+3NaCl. Eq. 2
As shown in
The polyisobutylene dialkyl borane can then be oxidized to form the polyisobutylene diol. In some embodiments, the polyisobutylene dialkyl borane can be oxidized by the addition of an oxidizer, for example, hydrogen peroxide, peracetic acid, potassium permanganate, or benzoyl peroxide.
Various modifications and additions can be made to the exemplary embodiments discussed without departing from the scope of the present invention. For example, while the embodiments described above refer to particular features, the scope of this invention also includes embodiments having different combinations of features and embodiments that do not include all of the described features. Accordingly, the scope of the present invention is intended to embrace all such alternatives, modifications, and variations as fall within the scope of the claims, together with all equivalents thereof.
Hindered dicumyl ether was combined with anhydrous hexane and 2,6-di-tert-butylpyridine in a reactor. Methyl chloride (MeCl) and isobutylene were added to the reactor through a cooling coil cooled to −80° C. The solution was stirred and kept at −80° C. by a liquid nitrogen-cooled jacket or coil in the reactor. Polymerization was initiated by adding titanium tetrachloride to the reactor to form polyisobutylene dichloride (
In a three-necked 2000 mL round bottomed flask equipped with magnetic stirring, a dry nitrogen blanket, an ice bath, a rubber septum, and a digital thermocouple, 10.66 g of the polyisobutylene diallyl (0.005 moles, molecular weight of 2,000 Da) was dissolved in 605 mL of anhydrous THF. Sodium borohydride in an amount of 0.605 g (0.016 moles) was added to the polyisobutylene diallyl in the flask and allowed to dissolve with the aid of stirring. After the resulting solution had equilibrated at 0° C., an aliquot of 0.8523 g (0.016 moles) of concentrated sulfuric acid was added to solution in the flask dropwise using a syringe, resulting in the liberation of hydrogen gas and the formation of polyisobutylene dialkyl borane (
Proton nuclear magnetic resonance spectroscopy of the clear, viscous oil confirmed the presence of 1-hydroxylpropyl terminated end groups, thus confirming the synthesis of polyisobutylene diol.
This application claims priority to Provisional Application No. 62/468,316, filed Mar. 7, 2017, which is herein incorporated by reference in its entirety.
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| Number | Date | Country | |
|---|---|---|---|
| 20180258196 A1 | Sep 2018 | US |
| Number | Date | Country | |
|---|---|---|---|
| 62468316 | Mar 2017 | US |
