Polycarbonate polymers having siloxane repeat units, compositions, and methods

Abstract

Polycarbonate polymers are described that contain non-aromatic cyclic groups attached with carbonate linkers. Some of the non-aromatic cyclic groups contain substituents having siloxane repeat units. Representative formulas for the substituents having siloxane repeat units include: -CH 2 -CH 2 -Si(R 4 ) 2 -(OSi(R 4 ) 2 ) m -R 5 , and -CH[Si(R 4 ) 2 -(OSi(R 4 ) 2 ) m -R 5 ]-CH 3 (wherein m is the number of siloxane repeat units, R 4 and R 5 are independently alkyl, aryl, aralkyl, or aralkylene. Polycarbonate polymers typically contain a high concentration of carbonate linking groups, for example, in an amount of at least 85 or 90 mol % based on the total linking groups of the polymer. Compositions including and methods of making the polycarbonate polymers are also described.

Description

Summary of the Invention

[0001] Described herein are polycarbonate polymers that include non-aromatic cyclic groups attached with carbonate linkers, some of which include substituents having siloxane repeat units.

[0002] Representative formulas for substituents having siloxane repeat units include: [ka] (wherein m is the number of siloxane repeat units; R 4 and R 5 are independently alkyl, aryl, aralkyl, or aralkylene. Includes:

[0003] Polycarbonate polymers typically contain a high concentration of carbonate linking groups, for example at least 85 or 90 mol % based on the total linking groups of the polymer. Thus, the amount of non-carbonate (e.g., ether) groups is typically less than 15 or 10 mol %. The high concentration of carbonate linking groups contributes to the degradability of the polycarbonate polymer. A lower thermogravimetric mass loss onset temperature may indicate improved degradability. In some embodiments, the thermogravimetric mass loss onset temperature is in the range of 220°C to 300°C.

[0004] The polycarbonate polymer has the formula: [ka] (In the formula, n is independently in the range of 1 to 5, R 1 is vinyl, R 2 is hydrogen, R 3 are independently -CH2-Si(R 4 )2-(OSi(R 4 )2) m -R 5or -[Si(R 4 )2-(OSi(R 4 )2) m -R 5 ]-CH3, m is the number of siloxane repeat units; R 4 and R 5 is independently alkyl, aryl, aralkyl, or aralkylene; u, v, w, x, y, and z are the numbers of each polymerized unit. It is expressed as:

[0005] In some embodiments, u+v+w is such that the polycarbonate polymer contains no more than 15 or 10 mol % polymerized units that contain non-carbonate (eg, ether) linking groups.

[0006] Polycarbonate polymers can be further characterized by physical properties such as molecular weight and glass transition temperature (Tg).

[0007] The inclusion of a substituent having a siloxane repeat unit typically reduces the Tg compared to the same polycarbonate polymer lacking the substituent having a siloxane repeat unit.

[0008] The inclusion of substituents having siloxane repeating units typically increases the (eg, receding) contact angle with water compared to the same polycarbonate polymer lacking substituents having siloxane repeating units.

[0009] Polycarbonate polymers, either alone or copolymerized with other ethylenically unsaturated materials, can be utilized as low surface energy films or coatings.

[0010] The inclusion of polymerized units that contain vinyl groups makes the polycarbonate polymer amenable to copolymerization with other ethylenically unsaturated materials.

[0011] In another embodiment, a composition is described that includes the reaction product of at least one ethylenically unsaturated material and a polycarbonate polymer described herein.

[0012] Methods for making the described polycarbonate polymers are also described. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] Described herein are polycarbonate polymers that include non-aromatic cyclic groups linked by carbonate linking groups. Some of the non-aromatic cyclic groups include substituents with siloxane repeat units. The non-aromatic cyclic groups can also be characterized as alicyclic groups or cycloalkane groups. The siloxane repeat units are typically linked to the non-aromatic cyclic groups by ethylene linking groups.

[0014] In one embodiment, the substituent comprising a siloxane repeat unit has the formula: -CH2-CH2-Si(R 4 )2-(OSi(R 4 )2) m -R 5 formula 1 (In the formula, R 4 and R 5 is independently alkyl, aryl, aralkyl, or aralkylene, and m is the number of siloxane repeat units. has.

[0015] When vinyl-substituted cycloalkyl epoxides or vinyl-substituted cycloalkyl cyclic carbonates are utilized in the synthesis of polycarbonate polymers, the substituents containing siloxane repeat units are primarily represented by Formula 1.

[0016] In another embodiment, the substituent is a siloxane repeat unit having the formula: -CH[Si(R 4 )2-(OSi(R 4 )2) m -R 5 ]-CH3 formula 2 (In the formula, R 4 and R5 is independently alkyl, aryl, aralkyl, or aralkylene, and m is the number of siloxane repeat units. Includes.

[0017] In some embodiments, the polycarbonate polymers described herein comprise a combination of substituents comprising siloxane repeat units according to Formula 1 and Formula 2.

[0018] The siloxane-containing repeating units may be the product of hydrosilylation of either a monomer prior to polymerization of the polycarbonate polymer or a polycarbonate copolymer containing pendant vinyl groups. Those skilled in the art understand that the inherent selectivity of the hydrosilylation reaction depends on the catalyst and method applied (Matisons, J. Hydrosilylation: A Comprehensive Review on Recent Advances. Springer, 2009). Depending on the selection of the hydrosilylation catalyst and hydrosilylation reaction conditions, siloxane repeating units of formula 2 may also be present. In some embodiments, the siloxane repeating units represented by formula 2 may be present at more than 0.2%, 1%, 5%, 10%, 25%, or 45 mol%, as represented by [mol% of formula 1 / (mol% of formula 1+mol% of formula 2)]. In other embodiments, the amount of siloxane repeating units represented by formula is less than 45, 25, 10, 5, 1, or 0.2 mol%.

[0019] The exact identity of the hydrosilylation catalyst is not important as long as selective conversion of the pendant olefin is achieved. If the monomer is hydrosilylated prior to polymerization, the preferred catalyst will not result in significant conversion of existing epoxide or cyclic carbonate functional groups. Similarly, preferred catalysts for hydrosilylation of polycarbonate precursors containing pendant vinyl groups typically do not mediate significant reduction of carbonate bonds present in the polymer. Examples of suitable hydrosilylation catalysts include Karstedt's catalyst, HPtCl, [(cod)Rh(u-OSiMe)], [(cod)Ir(Cl)], and [La(N(SiMe)) (cod = cyclooctadiene). The hydrosilylation catalyst may be homogeneous, heterogeneous, or present on a solid support.

[0020] R 4 and R 5 independently contains 12 or fewer carbon atoms. In some embodiments, R 4 and R 5 is independently an alkyl group. In an exemplary embodiment, R 4 is alkyl (e.g., methyl) or aryl (e.g., phenyl). In some embodiments, R 5 is a C1-C aryl such as methyl, propyl, or butyl. 18 It is an alkyl group.

[0021] The average number m of siloxane repeat units is typically at least about 5, 6, 7, 8, 9, or 10. In some embodiments, the average number m of siloxane repeat units is no more than 70, 60, 50, 40, 30, or 20. As the number of siloxane repeat units increases, the substituents comprising pendant siloxane repeat units, such as those represented by Formulas 1 and 2, can have a molecular weight of at least 600 g / mol. In some embodiments, the substituents comprising pendant siloxane repeat units have a molecular weight of no more than 6, 5, 4, 3, 2, or 1 kg / mol.

[0022] The polycarbonate polymers described herein can be represented by Formula 3, as follows: [ka]

[0023] In formula 3, the non-aromatic cyclic group contains at least 4 carbon atoms, i.e., n is 1. Thus, n represents the number of carbon atoms in addition to the 3 carbon atoms. Generally, n is independently in the range of 1 to 5. Thus, the total number of carbon atoms in the non-aromatic cyclic group is in the range of 4 to 8. In some embodiments, the total number of carbon atoms is 5, 6, or 8. Those skilled in the art will appreciate that "independently in the range of" means that each n is within a range, but that the n of one polymerizable group is not necessarily the same as the n of a different polymerizable group. For example, the n of the polymerizable unit having subscript x can be 3, as in cyclohexane, while the n of the polymerizable unit having subscript y can be 5, as in cyclooctane. In some embodiments, the n of the polymerizable groups having subscript x, y, or z are the same. In some embodiments, the n of the polymerizable groups of the polycarbonate polymer of formula 3 are the same. In some embodiments, n is 3 and the alicyclic is cyclohexane.

[0024] In formula 3, R 1 is vinyl. The vinyl groups can be 1-vinyl, 2-vinyl, or a combination thereof, depending on the monomers from which the polycarbonate polymer is synthesized, as described above.

[0025] In formula 3, R 2 is hydrogen. Therefore, R 2 The polymerized units where is hydrogen can be characterized as unsubstituted non-aromatic cyclic groups.

[0026] In formula 3, R 3 are independently -CH2-Si(R 4 )2-(OSi(R 4 )2) m -R 5 or -[Si(R4 )2-(OSi(R 4 )2) m -R 5 ]-CH3, where m is the number of siloxane repeat units, and R 4 and R 5 is independently alkyl, aryl, aralkyl, or aralkylene as defined above.

[0027] The subscripts u, v, w, x, y, and z represent the number of each polymerized unit.

[0028] In a preferred embodiment, the polycarbonate polymer contains significantly more carbonate linkages than non-carbonate (e.g., ether) linkages, and thus the polycarbonate polymer contains more polymerized units with subscripts x, y, z than those with u, v, and w.

[0029] The method of polycarbonate polymerization affects the amount of u+v+w relative to x+y+z. "Carbonate linkage %" can be defined as (x+y+z) / (u+v+w+x+y+z), which represents the tendency of the polymerization reaction to incorporate carbon dioxide when epoxide monomers are used as precursors, or to maintain carbonate functionality when cyclic carbonates are used as precursors. Carbon dioxide uptake or carbonate conservation can occur in competition with epoxide homopolymerization or carbon dioxide release, respectively, to form polyether linkages within the polymer backbone. The degradability of polycarbonate polymers is influenced by the % of carbonate linkages, with increased degradability favored by a high % of carbonate linkages. In general, decreasing the % carbonate linkage value increases the thermal stability of the polymer relative to the comparative polymer, with (x+y+z) / (u+v+w+x+y+z) approaching 1.

[0030] In some embodiments, the polycarbonate polymer comprises carbonate linking groups in an amount of at least 75, 80, or 85 mol % based on the total linking groups of the polymer. In this embodiment, x+y+z in formula 3 is such that the polycarbonate polymer comprises at least 75, 80, 85, or 90 mol % of such polymerized units. When the polycarbonate polymer comprises a high concentration of carbonate linkages as described above, the amount of non-carbonate linkages is less than 25, 20, 15, or 10 mol %. In this embodiment, u+v+w in formula 3 is such that the polycarbonate polymer comprises less than 25, 20, 15, or 10 mol % of such polymerized units. In some embodiments, u is zero. In some embodiments, v is zero. In some embodiments, w is zero.

[0031] The polycarbonate polymers described herein contain polymerized units of unsubstituted non-aromatic cyclic groups. These polymerized units are represented by the formula R 2 In some embodiments, the polycarbonate polymer comprises polymerized units of unsubstituted non-aromatic cyclic groups attached in the polymer backbone with non-carbonate (e.g., ether) linkages, as represented by polymerized units having subscript v in formula 3. When such units are present, the mol % is typically low, as discussed above. In a typical embodiment, the polycarbonate polymer comprises polymerized units of unsubstituted non-aromatic cyclic groups attached in the polymer backbone with non-carbonate linkages, as represented by polymerized units having subscript y in formula 3. The polycarbonate polymer typically comprises polymerized units of unsubstituted non-aromatic cyclic groups in an amount ranging from 60 mol % to 98.5 mol %.

[0032] In some embodiments, the polycarbonate polymers described herein include polymerized units that have vinyl substituents. These polymerized units include R 1In some embodiments, the polycarbonate polymer comprises a non-aromatic cyclic group that includes a vinyl substituent attached in a polymer backbone that has a non-carbonate (e.g., ether) linkage, as represented by polymerized units having subscript u in formula 3. When such units are present, the mol % is typically low, as discussed above. In some embodiments, the polycarbonate polymer comprises a non-aromatic cyclic group that includes a vinyl substituent attached in a polymer backbone that has a carbonate linkage, as represented by polymerized units having subscript x in formula 3.

[0033] The polycarbonate polymer typically comprises at least 5, 6, 7, 8, 9, or 10 mol% of polymerized units of non-aromatic cyclic groups containing vinyl substituents. In some embodiments, the amount of polymerized units of non-aromatic cyclic groups containing vinyl substituents is at least 15, 16, 17, 18, 19, or 20 mol% of the polycarbonate polymer. In some embodiments, the amount of polymerized units of non-aromatic cyclic groups containing vinyl substituents is no more than 30, 25, 20, or 15 mol% of the polycarbonate polymer. The presence of vinyl substituents can accommodate copolymerization of the polycarbonate polymer with other ethylenically unsaturated materials.

[0034] The polycarbonate polymers described herein include polymerized units having siloxane repeating units. These polymerized units are represented by the R 3 In some embodiments, the polycarbonate polymer comprises a non-aromatic cyclic group that comprises a substituent having a siloxane repeat unit attached to a polymer backbone with a non-carbonate (e.g., ether) linkage, as represented by polymerized units having subscript u in Formula 3. When such units are present, the mol % is typically low, as discussed above. In some embodiments, the polycarbonate polymer comprises a non-aromatic cyclic group that comprises a substituent having a siloxane repeat unit attached to a polymer backbone with a carbonate linkage, as represented by polymerized units having subscript x in Formula 3.

[0035] Polycarbonate polymers typically contain at least 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 mol% of polymerized units that contain a substituent with a siloxane repeat unit. In some embodiments, the amount of polymerized units with a siloxane repeat unit is no more than 10, 9, 8, 7, 6, 5, 4, or 3 mol% of the polycarbonate polymer. The presence of a substituent with a siloxane repeat unit is adapted to lower the Tg and lower the surface energy of the polycarbonate polymer compared to the same polycarbonate polymer lacking a substituent with a siloxane repeat unit. In some embodiments, the polycarbonate polymer has a higher advancing contact angle with water than the same polymer without the siloxane substituent. In some embodiments, the advancing contact angle with (deionized) water is at least 105 or 110 degrees. In some embodiments, the receding contact angle with water is at least 70, 75, 80, 85, or 90 degrees.

[0036] The amount of vinyl and siloxane groups in a polycarbonate polymer can be determined from nuclear magnetic resonance (NMR).

[0037] The molecular weight of the polycarbonate polymers described herein can be determined using gel permeation chromatography (as described in the Examples below). In some embodiments, the polycarbonate polymer can have a single peak with a normal distribution of molecular weights. In other embodiments, the polycarbonate polymer can have two or more peaks. For example, the polycarbonate polymer can have a bimodal molecular weight distribution. In some embodiments, the polycarbonate polymer is multimodal, with each peak having a polydispersity of 4, 3, 2, or 1.5, 1.3, 1.2, or 1.1 or less.

[0038] The polycarbonate polymers described herein typically have a weight average molecular weight (Mw) in the range of 5,000 g / mol to 1,500,000 g / mol (5 kg / mol to 1500 kg / mol). In some embodiments, the weight average molecular weight (Mw) is at least 10,000, 15,000, 20,000, or 25,000 g / mol. In some embodiments, the polycarbonate polymer has a weight average molecular weight (Mw) of less than 750,000, 500,000, 250,000, or 100,000 g / mol. In some embodiments, the polycarbonate polymer has a weight average molecular weight (Mw) of less than 75,000, 50,000, or 25,000 g / mol.

[0039] In some embodiments (e.g., polydispersity approaches 1), the number average molecular weight is about the same as the weight average molecular weight described immediately above. In some embodiments, the polycarbonate polymers described herein have a number average molecular weight (Mn) ranging from 5,000 g / mol to 750,000 g / mol. In some embodiments, the number average molecular weight (Mn) is at least 10,000, 15,000, 20,000, or 25,000 g / mol. In some embodiments, the polycarbonate polymers have a number average molecular weight (Mn) of less than 500,000, 250,000, or 100,000 g / mol. In some embodiments, the polycarbonate polymers have a number average molecular weight (Mn) of less than 75,000, 50,000, or 25,000 g / mol.

[0040] Lower molecular weights may be preferred for copolymerization with other ethylenically unsaturated materials, however, higher molecular weight materials may be preferred for preparing dilute coating solutions in organic solvents.

[0041] The glass transition temperature (Tg) of the polycarbonate polymer can be determined using differential scanning calorimetry (DSC) (following the method described in the Examples below). In some embodiments, the polycarbonate polymer has a Tg of at least 50, 55, or 60°C. In some embodiments, the polycarbonate polymer has a Tg of 115, 110, 100, 95, 90, 85, 80, 75, or 70°C or less. The Tg of the resulting polycarbonate polymer can be modified by the polymer backbone structure and siloxane side chains. Inclusion of a substituent with a higher concentration of siloxane repeat units can decrease the Tg. The Tg of the polycarbonate polymer can also be decreased by increasing the value of m in Formulas 1 and 2. Further modification of the Tg of the polycarbonate polymer can be achieved by judicious selection of the alicyclic group, as exemplified by the reported values ​​for cyclopentene polycarbonate (Tg ∼84.5°C) and cyclohexane polycarbonate (Tg ∼117°C, Lu et.al. Angew. Chem., 2015, 54, pg 2241 and Darensbourg et.al. ACS Catalysis, 2013, 3, pg 3050, respectively).

[0042] The polycarbonate polymers described herein can be prepared by any suitable method.

[0043] One suitable method includes providing a polycarbonate polymer containing non-aromatic cyclic groups, some of which contain vinyl moieties, and reacting at least a portion of the vinyl moieties with a material containing siloxane repeat units and a single hydride group in the presence of a metal catalyst. Suitable metal catalysts include Karstedt's catalyst (platinum-divinyl(tetra)methylsiloxane), HPtCl, [(cod)Rh(u-OSiMe)], [(cod)Ir(Cl)], and [La(N(SiMe)) (cod=cyclooctadiene). Polycarbonates containing non-aromatic cyclic groups, some of which contain vinyl moieties, can be prepared by reacting cycloalkene oxide, vinylcycloalkene oxide, and carbon dioxide in the presence of a catalyst (Coates GWet.al.Angew.Chem.2004,43,p.6618).

[0044] A variety of catalysts can be used to form vinyl-functionalized polycarbonate precursors from epoxide monomers and CO2. (See, for example, Inoue's Inoue, S.; Koinuma, H.; Tsuruta, T. Makromol. Chem 1969, 130, pp. 210-220). Examples of other suitable catalysts described in the literature include Zn-based catalysts derived from Zn(CH2CH3)2 and many alcohols or carboxylic acids, Al-based catalysts supported by porphyrin or Schiff base-type ligands, Co-based catalysts supported by porphyrin or Schiff base-type ligands, and some organoborane compounds. The reported catalysts require the addition of anionic cocatalyst salts. It is recognized that each specific catalyst has different reaction conditions to achieve the desired carbonate incorporation percentage, molecular weight, and polydispersity of the product polycarbonate. Reaction parameters such as monomer identity, concentration, CO2 pressure, reaction temperature and duration are known to affect salient properties of the resulting polycarbonate.

[0045] Thus, the alternating polycarbonate polymer is synthesized by alternating copolymerization of at least two epoxides with carbon dioxide. The at least two epoxides include at least one cycloalkene oxide, such as cyclohexene oxide (CHO), and at least one vinylcycloalkene oxide, such as 4-vinylcyclohexene oxide (VCHO). Alternative cycloalkene oxides include cyclobutene oxide, cyclopentene oxide, norbornene oxide, and cyclooctene oxide. Vinylcycloalkene oxides can be formed from selective olefin epoxidation, as known in the art.

[0046] When polycarbonate polymers are prepared by alternating copolymerization of epoxides and carbon dioxide, the structure of alternating polycarbonates differs from conventional condensation polycarbonates in that the polymer backbone contains carbon segments of exactly two methylene / methine units alternating with carbonate linkages. The two methylene / methine units are part of a non-aromatic cyclic group, as exemplified by cyclohexane polycarbonates containing pendant vinyl and siloxane substituents such as: [ka]

[0047] The structure of alternating polycarbonates influences the chemical stability of these materials. Because 2-carbon units separate adjacent carbonate moieties in the backbone, the polymers undergo a "backbiting" decomposition reaction when exposed to alkaline conditions or elevated temperatures. The kinetics of the "backbiting" decomposition reaction are influenced by the ring size of the product cyclic carbonates and thus the percentage of carbonate linkages present in the polycarbonate backbone. The polycarbonate polymers described herein preferably have a high concentration of carbonate linkages, as previously described.

[0048] Some of the polymerizable groups of the polycarbonate polymer contain vinyl substituents. The vinyl substituents can be further reacted with a siloxane oligomer having a single hydride group, such as polydimethylsiloxane (PDMS). One representative compound is shown below, where R 4 is methyl, R 5 is C4H9). [ka]

[0049] Other siloxane oligomers (e.g., polydimethylsiloxane (PDMS)) have a single hydride group and can be prepared by several methods, including anionic polymerization (Hadjichristidis, N.; Hirao, A. Anionic Polymerization: Principles, Practice, Strength, Consequences, and Applications. Springer Japan, 2015, pg. 239). For example, the anionic initiator LiR 5 can be used to initiate the anionic ring-opening polymerization of hexamethylcyclotrisiloxane (D3), followed by termination with (CH3)2SiHCl. Suitable anionic initiators are phenyllithium, sec-butyllithium, n-butyllithium, methyllithium, benzylpotassium, phenylsodium, and hexyllithium. The number of siloxane repeat units m can be controlled by the ratio of initiator to monomer as well as by the conversion of monomer.

[0050] A representative reaction scheme, not showing any groups with non-carbonate (eg ether) groups, is as follows: [ka]

[0051] In other embodiments, compositions are described that include the reaction product of at least one other ethylenically unsaturated material with a polycarbonate polymer (e.g., vinyl-containing) described herein. Various ethylenically unsaturated materials can be combined with the polycarbonate polymer. In some embodiments, the ethylenically unsaturated material is a monomer or oligomer having a molecular weight of 10,000, 5,000, 2500, 1000, 500, or 250 g / mol or less. The ethylenically unsaturated material is monofunctional, polyfunctional, or mixtures thereof. The ethylenically unsaturated material may be aromatic (e.g., phenoxyethyl acylate (PEA)), aliphatic (e.g., hexanediol acrylate (HDDA)), or mixtures thereof. The compositions can include various amounts of the polycarbonate polymer described herein. In some embodiments, the compositions include more polycarbonate polymer than the other ethylenically unsaturated material. For example, the composition may include at least 60, 70, 80, or 90% by weight of a polycarbonate polymer described herein and at least 10, 15, 20, 25, 30, 35, or 40% by weight of other ethylenically unsaturated materials.

[0052] Polycarbonate polymers, either alone or copolymerized with another ethylenically unsaturated material, can be utilized as low surface energy films or coatings, which may be characterized by their contact angle with water as described above. EXAMPLES

[0053] All parts, percentages, ratios, etc. in the examples and elsewhere herein are by weight unless otherwise stated. All other reagents, unless otherwise indicated, were obtained or available from fine chemical suppliers such as MilliporeSigma, Burlington, MA, USA, or can be synthesized by known methods. Table 1 (below) lists the materials used in the examples and their suppliers. [Table 1]

[0054] General Procedures and Test Methods Drying of reagents and reaction preparation CHO was stirred overnight over CaH2, degassed with three freeze-pump-thaw cycles, and concentrated in a flask containing n-butyllithium cooled in liquid nitrogen (the solvent was removed in vacuum). CHO was then thawed in a 0°C ice-water bath and after stirring for 30 minutes (min), the purified monomer was collected in a flask by vacuum transfer. VCHO was dried by stirring over CaH2 for 12 hours prior to vacuum distillation. (S)-(-)-α,α-diphenyl-2-pyrrolidinemethanol was freeze-dried from benzene (25 grams (g) in 50 milliliters (mL)) prior to use. [PPN]Cl was dried by recrystallization of 10 g from 50 mL of anhydrous DCM layered with 150 mL of anhydrous hexane. PDMS-H was stirred with CaH2 for 12 hours and then degassed with three freeze-pump-thaw cycles. Once degassed, the PDMS was isolated by filtration in a glove box.

[0055] All other chemicals were used as received.

[0056] Prior to polymerization, a 300 mL Parr reactor (Parr Instrument Company, Moline, IL, USA) was sealed and heated to 130° C. The heated reactor was then placed under high vacuum (ultimate pressure of approximately 10 millitorr (mtorr)) for 12 hours before being placed in a glove box for reagent charging.

[0057] CHO / VCHO polycarbonate was dried prior to hydrosilylation by lyophilization from benzene (approximately 1 g polymer / 3 mL benzene).

[0058] Gel Permeation Chromatography (GPC) The GPC instrument consisted of a 1260 Infinity LC (consisting of a quaternary pump, autosampler, column compartment, and diode array detector) manufactured by Agilent Technologies (Santa Clara, CA, USA) and was operated at a flow rate of 1.0 mL / min. The GPC column set consisted of PLgel MIXED-A (length 300 millimeters (mm) × inner diameter 7.5 mm) + PLgel MIXED-B (length 300 mm × inner diameter 7.5 mm), both manufactured by Agilent Technologies. Detection consisted of a DAWN HELEOS II 18-angle light scattering detector, a VISCOSTAR viscometer, and an OPTILAB T-REx refractive index detector, all three manufactured by Wyatt Technology Corporation (Santa Barbara, CA, USA). Data were collected and analyzed using the software ASTRA version 6 manufactured by Wyatt Technology Corporation. The column compartment, viscometer, and refractive index detector were set at 40 °C.

[0059] Solvents and eluents (or mobile phases) consisted of tetrahydrofuran (stabilized with 250 parts per million (ppm) butylated hydroxytoluene) OMNISO LV grade modified with 5% v / v triethylamine (both from MilliporeSigma, Burlington, Massachusetts). Analysis was completed using conventional GPC methods and polystyrene molecular weight standards.

[0060] Differential Scanning Calorimetry (DSC) Samples were prepared for thermal analysis by weighing the material and placing it in a DSC sample pan. Samples were analyzed using a DSC2500 (TA Instruments, New Castle, DE, USA) using the heat-cool-heat method (-50°C to 200°C at 10°C / min). After data collection, thermal transitions were analyzed using TRIOS software version 5.0 from TA Instruments. Any glass transition (Tg) or significant endothermic or exothermic peaks, if present, were evaluated based on the second heat flow curve. Glass transition temperatures were evaluated using a step change in the heat flow curve. The onset and midpoint (half height) of the transition were recorded at the glass transition. Peak area values ​​and / or peak minimum / maximum temperatures were also determined. Peak integration results were normalized by sample weight and reported in Joules per gram (J / g).

[0061] Thermogravimetric analysis (TGA) The prepared polycarbonates were analyzed in a thermogravimetric analyzer (DISCOVERY TGA from TA Instruments) under nitrogen purge using a temperature gradient of 5° C. / min from room temperature (23° C.) to 450° C. After data collection, the onset and end points of polymer decomposition were analyzed using TRIOS software version 5.0 from TA Instruments.

[0062] nuclear magnetic resonance (NMR) Portions of polymer samples were analyzed as solutions of unknown concentration (typically about 12 mg / mL) in CDCl3. NMR spectra were acquired on a Bruker AVANCE 600 MHz NMR spectrometer (Bruker, Billerica, MA, USA) equipped with an inverse cryogenic probe.

[0063] Water contact angle test The polymer samples were dissolved at 10 wt% in 1-methoxy-2-propanol. Coatings of the resulting solutions were applied to 2.5 × 7.5 cm glass microscope slides (Fisher Scientific, Hampton, NH, USA) using a #12 wire-wound rod (BYK, Inc., Wesel, Germany) and dried for 20 min in an oven held at 80 °C. Contact angles were measured using the sessile drop method with a goniometer (Rame Hart Instrument Company, Succasunna, NJ, USA). A 10 μL drop of water was applied to the surface with a needle. To determine the advancing contact angle, the drop volume was increased in 5 μL increments and the contact angle was measured as the drop spread across the surface. To determine the receding contact angle, the drop volume was decreased in 5 μL increments and the contact angle was measured as the drop receded across the surface.

[0064] Preparation Example Preparation Example 1 (PE-1): Synthesis of CHO / VCHO copolymer using boron-based catalyst A representative procedure is described below for PE-1A. In a nitrogen-filled glovebox, THF (50.0 mL), CHO (40 mL), VCHO (10 mL), [PPN]Cl (250 milligrams (mg), 0.436 millimoles (mmol)), and borinic anhydride (160 mg, 0.436 mmol) were added to a 300 mL Parr reactor. The reactor was sealed and attached to a CO2 tank via a transfer line. The transfer line was purged with CO2 by pressurization and venting (3 x 200 psi (1.38 MPa)). Stirring was started and CO2 was introduced until a constant pressure of 200 psi could be achieved. After 1 hour, the reactor was heated to 60°C and placed under 400 psi (2.76 MPa) of CO2. The polymerization was allowed to proceed at 60°C and 400 psi (2.76 MPa) of CO2 for 16 hours, after which the reactor was cooled to room temperature. Upon cooling, the viscosity of the reaction solution increased significantly. The reactor was then slowly vented with stirring. Once vented, 150 mL of THF was added to further dissolve / dilute the reaction product. The CHO / VCHO polycarbonate was precipitated from methanol (approximately 600 mL) and reprecipitated from THF / methanol before being isolated by filtration. The resulting polymer was dried under vacuum to give a colorless solid (22 g). PE-1B was prepared in a similar manner with corresponding adjustments for reactant amounts. Analytical results for PE-1A and PE-1B are shown in Table 2. The mol% of monomer incorporation was obtained by NMR analysis. Mn, Mw, and PDI were obtained by GPC analysis and reported for each individual peak of the bimodal distribution. Both samples were bimodal by GPC analysis. PE-1A contained approximately 35% by weight of the higher molecular weight polycarbonate and PE-1B contained approximately 37% of the higher molecular weight polycarbonate. Tg was obtained by DSC analysis. TGA onset temperature was obtained by TGA analysis. [Table 2]

[0065] Preparation Example 2: Synthesis of CHO / VCHO copolymer using Zn-based catalyst Polymer PE-2 was synthesized by a procedure adapted from Nozaki et.al. (J. Am. Chem. Soc., 1999, 121, 11008). The Zn catalyst was prepared in a glove box by adding ZnEt2 (3.5 mL) to a stirred solution of (S)-(-)-α,α-diphenyl-2-pyrrolidinemethanol (1.0 g) in toluene (45 mL). The heterogeneous mixture was then heated to 60 °C for 2 h before use.

[0066] In a nitrogen filled glove box, CHO (40 mL) and VCHO (10 mL) were added to a 300 mL Parr reactor equipped with a glass liner. The above Zn catalyst mixture was then added, after which the reactor was sealed and attached to a CO2 tank via a transfer line. The transfer line was purged with CO2 by pressurization and venting (3 x 200 psi, 1.38 MPa). Stirring was started and CO2 was introduced until a constant pressure of 200 psi (1.38 MPa) could be achieved. The reactor was then heated to 60°C. Once the temperature reached 60°C, the pressure of the reaction was maintained at 500 psi + / - 50 psi (3.45 + / - 0.35 MPa) for 16 hours. After approximately 12 hours, stirring could not be maintained due to the high viscosity of the reaction mixture.

[0067] Upon completion, the reactor was cooled and vented before extracting a colorless, transparent monolith. The product was dissolved in THF (~80 mL) and then precipitated from methanol (~500 mL) and isolated by filtration. Residual Zn catalyst was removed by redissolving the white polymer in DCM (~300 mL) and washing in a separatory funnel with 1 M aqueous HCl (3 x 400 mL) followed by deionized (DI) water (1 x 400 mL). The resulting polymer solution was added to methanol (~600 mL) to precipitate the white product, which could be isolated by filtration. Drying under high vacuum gave 55 g (76% yield) of alternating polycarbonate.

[0068] The analytical results of PE-2 are shown in Table 3. The mol% of monomer incorporation was obtained by NMR analysis. Mn, Mw, and PDI were obtained by GPC analysis and reported for each individual peak of the bimodal distribution. Tg was obtained by DSC analysis. TGA onset temperature was obtained by TGA analysis. [Table 3]

[0069] [Example] Examples 1-3: Hydrosilylation of CHO / VCHO Polycarbonates A representative procedure is described for EX-3. Under Ar atmosphere, the dried CHO / VCHO polymer PE-2 (50.0 g, 74.0 mmol pendant-C=C) was dissolved in toluene (150 mL) in a 350 mL sealable glass pressure vessel. Once dissolved, PDMS-H (6.5 g, 4.7 mmol Si-H) was added, followed by 5 drops of Karstedt's catalyst. The reaction was then heated to 75° C. for 16 h, during which time the color changed from light yellow to dark orange / brown. The reaction was then cooled and precipitated from methanol (400 mL) to give a viscous gummy precipitate and a cloudy supernatant, which was removed by decantation. The off-white polymer product was reprecipitated from THF / methanol and then isolated by filtration. The resulting polymer was dried under reduced pressure to give an off-white solid. All other examples in Table 4 were prepared in a similar manner. The identity and amount of precursor CHO / VCHO polymer, amount of toluene, and amount of PDMS-H used in each example are shown in Table 4. The results of NMR (mol % data) and DSC (Tg) analyses are also shown in Table 4. [Table 4]

[0070] Examples EX-1 to EX-3 were tested for advancing and receding water contact angles according to the General Procedure for Water Contact Angle Testing. The results are shown in Table 5. [Table 5]

[0071] Examples 4 and 5: Photocrosslinked coatings The polymer of Example 1 (EX-1) was dissolved in 1-methoxy-2-propanol at 20% solids. The acrylates HDDA and PEA were each dissolved in 1-methoxy-2-propanol at 20% solids. TPO was dissolved in 1-methoxy-2-propanol at 10% solids. MEHQ was dissolved in 1-methoxy-2-propanol at 1% solids. Polymer / acrylate coating solutions were then prepared by mixing 1.40 g of polycarbonate solution, 0.60 g of acrylate solution (HDDA in Example A and PEA in Example B), and 40 mg of MEHQ solution. 50 mg of each polymer / acrylate coating solution was placed in a DSC pan and the solvent was evaporated by heating in an oven held at 70° C. for 3 hours. The dried polymer / acrylate mixtures were then analyzed by DSC. The results are shown in Table 6 (EX-4 uncured and EX-5 uncured).

[0072] To a 1.50 g aliquot of the polymer / acrylate solution, 60 mg of the TPO solution was added. Coatings were then cast by drop coating 1.0 mL of these resulting solutions onto glass microscope slides (25 mm x 75 mm, Fisher Scientific, Hampton, NH, USA), then dried in an oven held at 70°C for 30 minutes. The coatings were cured using a Fusion D-valve conveyor system (Fusion Light Hammer 10, Heraeus, Hanau, Germany) at 100% intensity and a belt speed of 30 feet / min. The system was purged with flowing nitrogen, and the coatings were passed through the system three times. The coatings were tested for advancing and receding water contact angles according to the General Procedure for Water Contact Angle Testing. The results of these tests are shown in Table 7. A small amount of each coating was scraped off the glass with a razor blade and then placed into a DSC pan and analyzed. The results of this test are shown in Table 6 (EX-4 cure and EX-5 cure).

Table 6

Table 7

Claims

1. A polycarbonate polymer comprising non-aromatic cyclic groups joined by carbonate linking groups, a portion of the non-aromatic cyclic groups being siloxane repeat units having the formula: formula: 【Chemistry 1】 (where m is the number of siloxane repeat units, R ４ and R ５ are independently alkyl, aryl, aralkyl, or aralkylene. A polycarbonate polymer comprising a substituent having the formula:

2. 10. The polycarbonate polymer of claim 1, wherein the carbonate linking groups are present in an amount of at least 85 mol %, based on total linking groups of the polycarbonate polymer.

3. 10. The polycarbonate polymer of claim 1, wherein the polycarbonate polymer comprises non-carbonate linking groups in an amount less than 15 mol%, based on the total linking groups of the polymer.

4. 10. The polycarbonate polymer of claim 1, wherein the polymer comprises polymerized units of unsubstituted non-aromatic cyclic groups in an amount ranging from 60 mol % to 98.5 mol %.

5. 10. The polycarbonate polymer of claim 1, wherein the polycarbonate polymer comprises polymerized units of non-aromatic cyclic groups that include vinyl substituents in an amount ranging from 1 mol % to 30 mol %.

6. 10. The polycarbonate polymer of claim 1, wherein the polymer comprises polymerized units of non-aromatic cyclic groups that include substituents with siloxane repeat units in an amount ranging from 0.5 mol % to 10 mol %.

7. 10. The polycarbonate polymer of claim 1, wherein the polymer comprises polymerized units of unsubstituted non-aromatic cyclic groups in an amount ranging from 60 mol % to 98.5 mol %.

8. The polycarbonate polymer has the following formula: 【Chemistry 2】 wherein n independently ranges from 1 to 5; R １ is vinyl, R ２ is hydrogen, R ３ is independent, 【Transformation 3】 and R ４ and R ５ are independently alkyl, aryl, aralkyl, or aralkylene; u, v, w, x, y, and z are the numbers of each polymerized unit.

10. The polycarbonate polymer of claim 1 having the formula:

9. 9. The polycarbonate polymer of claim 8, wherein u+v+w is such that the polycarbonate polymer contains less than 15 mol % of such polymerized units.

10. 10. The polycarbonate polymer of claim 1, wherein the polycarbonate polymer has a weight average molecular weight (Mw) ranging from 5,000 g / mol to 1,500,000 g / mol.

11. 10. The polycarbonate polymer of claim 1, wherein the polycarbonate polymer has a number average molecular weight (Mn) ranging from 5,000 g / mol to 750,000 g / mol.

12. 10. The polycarbonate polymer of claim 1, wherein the polycarbonate polymer has a Tg of 50°C or greater and 100°C or less.

13. 2. The polycarbonate polymer according to claim 1, wherein the polycarbonate polymer has a mass loss onset temperature in thermogravimetric analysis in the range of 220°C to 300°C.

14. 10. The polycarbonate polymer of claim 1, wherein the polymer has a higher receding contact angle with water than the same polymer without the siloxane substituents.

15. A composition comprising the reaction product of at least one ethylenically unsaturated material and the polycarbonate polymer of claim 1.

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