RU2799800C2 - Synthesis of building blocks and starting substances for obtaining renewable polymers - Google Patents

Abstract

FIELD: renewable starting materials production.

SUBSTANCE: invention relates to methods for producing renewable starting materials for producing polymers, the methods comprising obtaining a lactone derivative from CO₂ according to the following reaction

;

and processing the CO₂ derived lactone to form a renewable starting material, wherein the processing of the CO₂ derived lactone comprises selectively hydrogenating the CO₂ derived lactone to form a hydrogenated CO₂ lactone derivative according to the following reaction:

.

Further, the hydrogenated derivative from CO₂ lactone is processed using systems of homogeneous and heterogeneous hydrogenation, alkene metathesis. The process may also include alkoxycarbonylation of the CO₂ derivative of the lactone to form a diester and hydrogenation of the diester.

EFFECT: methods have been developed for the synthesis of starting materials for the production of polymers, including renewable polymers, from renewable resources such as CO₂ in high yields.

11 cl, 8 dwg, 4 tbl

Pd-катализатор - Pd-accelerator

Фосфин - phosphine

Description

CROSS REFERENCES TO RELATED APPLICATIONS

[0001] This application asserts the priority of Provisional Patent Application No. 62/518,400, filed June 12, 2017, the contents of which are incorporated herein by reference.

BACKGROUND OF THE INVENTION

[0002] One of the most important challenges for scientists in the 21st century is to identify practical ways to replace fossil-based raw materials with renewable sources. In this context, an important challenge for organic chemistry and the chemical industry is the efficient use of carbon dioxide. Indeed, this area is of particular current interest, and many attempts have been made in the past decades to develop synthetic methodologies using CO ₂ as a raw material. Of course, one promising way to use CO ₂ is to incorporate it into polymers. As one example, processes based on the reaction of CO ₂ and epoxides to form polycarbonates and polyether carbonates have been commercialized in recent years. Until now, they are the only polymers that contain CO ₂ and are of practical and commercial interest.

SUMMARY OF THE INVENTION

[0003] The present inventors recognized the need for methods or processes for synthesizing building blocks and starting materials to produce a wide variety of polymers, including renewable polymers from renewable resources such as CO ₂ .

[0004] In one embodiment, a method for producing a renewable raw material for forming polymers includes derivatizing a CO ₂ lactone and processing a derivative of CO ₂ lactone to form a renewable raw material. In one embodiment, processing the CO ₂ derived lactone comprises hydrogenating the CO ₂ lactone derivative to form a hydrogenated CO ₂ lactone derivative.

[0005] In one embodiment, the process for making a renewable polymer precursor comprises derivatizing a CO ₂ lactone and alkoxycarbonylating the CO ₂ derived lactone to form a diester. In one embodiment, the method further comprises hydrogenating the diester to form a renewable feedstock.

BRIEF DESCRIPTION OF THE DRAWINGS

[0006] FIG. 1 shows ¹ H-NMR spectrum (400 MHz, C ₆ D ₆ ) of δ-lactone 1.

[0007] FIG. 2 shows ¹³ C-NMR spectrum (125 MHz, C ₆ D ₆ ) of δ-lactone 1.

[0008] FIG. 3 shows the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of dimethyl 2-ethylidenoctanedioate 3.

[0009] FIG. 4 shows ¹³ C-NMR spectrum (75 MHz, CDCl ₃ ) of dimethyl 2-ethylidenodoctandioate 3.

[0010] FIG. 5 shows ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of dimethyl 2-ethyl octanedioate 4.

[0011] FIG. 6 shows the ¹³ C-NMR spectrum (75 MHz, CDCl ₃ ) of dimethyl 2-ethyl octanedioate 4.

[0012] FIG. 7 shows ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of 2-ethyloctane-1,8-diol 5.

[0013] FIG. 8 shows ¹³ C-NMR spectrum (75 MHz, CDCl ₃ ) of 2-ethyloctane-1,8-diol 5.

DETAILED DESCRIPTION OF THE INVENTION

[0014] The present invention provides methods or processes for synthesizing building blocks and starting materials to produce a wide variety of polymers, including renewable polymers, from renewable resources such as CO ₂ . For example, the present inventors unexpectedly discovered a successful catalyst system for the alkoxycarbonylation of δ-lactone 1 formed by telomerization of CO ₂ and butadiene and the _subsequent synthesis of useful unsaturated diesters 2 from the CO ₂ derivative δ-lactone 1. ami from such δ-lactones. In one embodiment, the present inventors have also investigated the catalytic hydrogenation of such resulting diesters to their saturated forms and to diols, where the recovered diesters and diols are important building blocks for polyester synthesis. According to one embodiment, the regioselective hydrogenation of δ-lactone 1 while maintaining the lactone ring structure is further provided, and the synthesis of important polymeric building blocks from it. The following is a further description of the present invention according to one embodiment.

Synthesis of a derivative from CO ₂ δ-lactone

[0015] The synthesis of polymers or monomers formed by the reaction between CO ₂ and olefins makes it possible to obtain materials based on CO ₂ with different physical and mechanical properties. Although it is known that various olefins react with carbon dioxide in the presence of specific metal complexes, in almost all cases, the isolation of the CO ₂ -olefin adduct requires the use of additional reagents in stoichiometric ratios, resulting in a large amount of waste. Thus, the direct polymerization of an olefin with CO ₂ or the synthesis of monomers derived from them in a rational and economical way is a very difficult task.

[0016] An exception to the above reactivity is the reaction of catalytic telomerization of 1,3-dienes with carbon dioxide. Using a tertiary monophosphine and a Pd(0) precursor, δ-lactone (3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one) can be obtained with good selectivity (Scheme 1). The main source of 1,3-butadiene is a by-product of the steam cracking process for producing ethylene, and can also be obtained from renewable raw materials.

Scheme 1: Synthesis of δ-lactone 1 by telomerization of butadiene and CO ₂

Regioselective hydrogenation of δ-lactone and synthesis of polymer building blocks from it

[0017] The following describes the regioselective hydrogenation of δ-lactone 1 while maintaining the lactone ring structure. Examples and embodiments of this regioselective hydrogenation of δ-lactone 1 and the synthesis of important polymer building blocks from it are described below.

[0018] In some embodiments, δ-lactone 1 can be selectively hydrogenated with 100% regioselectivity control for terminal carbon-carbon bonds. This regioselective hydrogenation of δ-lactone 1 while maintaining the lactone ring structure is unprecedented.

[0019] In some embodiments, such reactions are carried out in an oxygen-free atmosphere filled with dry nitrogen glove box (new technology). In some embodiments, solvents (including deuterated ones) are dehydrated and stored over molecular sieves (granules with 4Å-pores, 3.2 mm in diameter) under nitrogen before use. B(C ₆ F ₅ ) ₃ is commercially available from Boulder Scientific Chemicals. In some embodiments, H ₂ (grade 5.0) was purchased from Linde and dried through a Nanochem Weldassure purge column before use. In some embodiments, nuclear magnetic resonance (NMR) spectra are recorded on a Bruker Avance III 400 MHz or Agilent DD2 500 MHz spectrometer. In some embodiments, a Perkin-Elmer analyzer is used for elemental analysis for carbon, hydrogen, and nitrogen.

[0020] In some glove box embodiments, Compound 1 (219 mg, 1.44 mmol) is weighed into a 2 drachma tube. B(C ₆ F ₅ ) ₃ (36.8 mg, 0.072 mmol) dissolved in 3 ml of diethyl ether is introduced into the test tube. In some embodiments, the reaction vessel is fitted with a magnetic stir bar, loosely sealed, and placed inside a Parr high pressure reactor. In some embodiments, the reactor is purged ten times with hydrogen gas compressed at 15 atm (1.52 MPa). The reactor is sealed, removed from the glovebox and connected to a hydrogen gas purge line. The reactor was then pressurized by supplying hydrogen gas at a pressure of 60 atm (6.1 MPa), and placed in an oil bath for 12 hours at a temperature of 70° C. with stirring at a speed of 540 rpm. The reactor is slowly vented and the mixture is filtered through a pad of silica and the volatiles are removed in vacuo. NMR of the raw sample, FIG. 1-2 shows the complete regioselective conversion of the starting lactone 1 to lactone 1a (Scheme 2).

Scheme 2: Complete regioselective conversion of starting lactone 1 to lactone 1a

[0021] Partially hydrogenated δ-lactone can be converted to C8-C14 building blocks, carbonyl compounds, esters, amine building blocks, chemical reagent, polyols, esters, organic building blocks, monomers, food additives, grafting compounds, dendrimers, biomedical device coatings, polyurethane building blocks.

[0022] For example, a hydrogenated δ-lactone can be converted to 2-ethylideneenanthic acid using a homogeneous and/or heterogeneous hydrogenation system (Scheme 3). Similar reactions using Rh/phosphine biphasic hydrogenation systems can lead to ring opening in greater than 92% overall yield to form numerous isomers.

Scheme 3: hydrogenation of δ-lactone

[0023] Hydrogenated δ-lactone can be converted to building block molecules and polymers using amination and hydroaminomethylation methodologies. The hydrogenated δ-lactone can be regioselectively polymerized using ring-maintaining and/or ring-opening techniques.

[0024] Hydrogenated δ-lactone can be regioselectively polymerized using thiol click reaction (thiol addition according to Michael) to obtain regioselective polymers with predetermined properties (Scheme 4). The thiol comonomer may be selected from the group of suitable monomers containing one, two, three and/or four SH groups.

Scheme 4: Copolymerization of hydrogenated δ-lactone by Michael addition reaction of thiols

[0025] δ-Lactone can be converted to new molecules using catalysts for alkene metathesis and related processes, examples of which include: a) δ-lactone self-metathesis (Scheme 5) and b) δ-lactone cross-metathesis (Scheme 6), as shown below.

Scheme 5: Building blocks obtained by δ-lactone self-metathesis

Scheme 6: Building blocks obtained by δ-lactone cross-metathesis

[0026] The δ-lactone can be converted to new lactam molecules by metal-catalyzed lactone conversion, examples of which are shown in Scheme 7 below.

Scheme 7: Transition metal catalyzed conversion of δ-lactone to lactam building blocks

Synthesis of polymeric building blocks by alkoxycarbonylation of δ-lactone and hydrogenation of its products

[0027] In addition, interesting opportunities to directly increase the value of δ-lactone open up by converting it into other monomers, polymers and plasticizers using CO ₂ . δ-Lactone has been investigated in a variety of reactions such as hydrogenation, hydroformylation, hydroaminomethylation, hydroamination, alcoholysis and hydrolysis to form carboxylic acids and esters, diols as well as functionalized lactones. Some of these compounds are of interest for the production of polymers and polymer-related materials. In particular, diols and hydroxycarboxylic acids are potential monomers for polyester and polyurethane chemistry, while monocarboxylic acids and alcohols can be used to make plasticizers. The synthesis of polymers, either by polymerization of δ-lactone or by one-pot/two-stage co/terpolymerization of carbon dioxide and 1,3-dienes via lactone intermediates, has also been investigated. The following describes examples and embodiments of the synthesis of valuable building blocks by alkoxycarbonylation of δ-lactone and subsequent hydrogenation of its products.

[0028] δ-Lactone can be introduced into carbonylation reactions, and di- and triesters formed by carbonylation of δ-lactone become building blocks that are potentially of great interest to the polymer materials industry. However, attempts to carry out alkoxycarbonylation of δ-lactone using Pd(OAc) ₂ /triphenylphosphine as a catalyst and p-toluenesulfonic acid (PTSA) as a promoter unexpectedly only led to its alcoholysis, but not to the carbonylation product.

[0029] Sometimes in catalytic olefin hydroesterification reactions, lactone opening to form various esters cannot be avoided without an acid promoter if a palladium/phosphine catalyst is present. This may be due to the general reactivity of δ-lactone when interacting with H-Y-type substances such as water, alcohols, amines or silanes. It is difficult to prevent non-selective alcoholysis of δ-lactone. For example, when δ-lactone is heated in toluene in the presence of a primary alcohol and an acid, alcoholysis can occur in the absence of palladium to form a mixture of non-cyclic isomeric products.

[0030] The present inventors have developed a procedure for the direct synthesis of diesters by selective alcoholysis of δ-lactone, including the synthesis of useful unsaturated diesters 2 from δ-lactone 1, as described in more detail below according to one embodiment. The key factor in the successful selective domino sequence of the conversion of δ-lactone 1 in esterification/allyl substitution/alkoxycarbonylation is the use of special palladium catalysts based on PdCl ₂ and chelated diphosphines substituted with electron withdrawing groups. The resulting unsaturated diesters can be selectively hydrogenated under mild conditions to monounsaturated diesters or to saturated diesters, which in both cases are important building blocks for the synthesis of functional materials or plasticizers. Moreover, such diesters can also be hydrogenated to 2-ethyloctane-1,8-diol 5, which opens up new possibilities for polymer synthesis. All in all, the method constitutes a new approach to building blocks from δ-lactone 1 as a derivative of CO ₂ and butadiene, and thus a new step towards renewable polymers.

[0031] Typically, the synthesis of 2-ethylidenoctanedioic acid, an α,ω-unsaturated dicarboxylic acid related to 7-ethylidenoct-3-enedioic acid esters 2, from δ-lactone requires a three-step procedure: an initial rhodium/phosphine-catalyzed hydrogenolysis of δ-lactone to form a mixture of isomeric unsaturated C ₉ -carboxylic acids, followed by catalyzed rhodium/phosphine catalyst isomerization/hydroformylation of the double bond in the presence of synthesis gas, and finally the oxidation of the resulting aldehyde. However, the authors of the present invention unexpectedly found a more efficient method for the direct methoxycarbonylation of δ-lactone to dimethyl-7-ethylidenoct-3-enedioate 2a (Scheme 8).

Scheme 8: Formation of 7-ethylidenoct-3-enedioic acid esters 2 by alkoxycarbonylation of δ-lactone 1

[0032] In some embodiments, catalytic δ-lactone hydroesterification reactions are carried out using a palladium compound (such as Pd(OAc) ₂ , PdCl ₂ , Pd(dba) ₂ )) in combination with a mono- or diphosphine, alcohol and/or acid promoter.

[0033] In some embodiments, the diester may be synthesized by a domino alcoholysis/allylic substitution/carbonylation reaction. In some embodiments, alcoholysis of the δ-lactone and subsequent allyl substitution can result in a mixture of esters containing an allyl ether moiety that can be further carbonylated to an unsaturated diester.

Scheme 9: Palladium catalyzed alkoxycarbonylation of the allyl position of the δ-lactone 1. Study of various phosphine ligands. Reaction conditions: 1 (1.0 mmol), PdCl ₂ (1 mol%), monodentate ligand (4 mol%) or bidentate ligand (2 mol%), PTSA (5 mol%) toluene (2 ml), MeOH (0.25 ml, 6 mmol), CO (40 bar (4 MPa)), 120°C for 5 hours; yields determined by gas chromatographic (GC) analysis using hexadecane as an internal standard; the number in brackets indicates the exit after 20 hours. The yield is given as the sum of the E- and Z-isomers.

[0034] In some embodiments, various phosphines, such as L1-L17 in Scheme 9, are used in combination with PdCl ₂ as a catalyst precursor and PTSA as an acid promoter. In some embodiments, the reaction proceeds even in the absence of phosphine. In some embodiments, palladium metal may be present at the end and therefore the ligand may be required to stabilize the catalyst system. In some embodiments, monodentate phosphines such as (L1 and L2) result in a 20%-39% yield of 2a, but only a small amount of palladium black may be detected at the end of the reaction.

[0035] In some embodiments, diphosphines such as L3-L8 resulted in a 20%-39% yield of 2a. In some embodiments, 2a was obtained in 51% yield using a high capture angle Xantphos ligand such as L10 when the reaction was run for 5 hours. In some embodiments, the yield of 2a decreases as the reaction time is extended to 20 hours, possibly due to additional carbonylation of the double bonds in 2a. In some embodiments, phosphines from the Xantphos families such as L9-L13 and the NaPhos families such as L14-L17 are used. Ligands substituted with electron withdrawing groups such as L12, L15 and L17 resulted in yields in excess of 70%. An Iphos ligand such as L15 provided an 83% yield with a short reaction time. In particular, in this case, when the reaction was extended to 20 hours, the yield did not decrease and could reach up to 85%.

[0036] In some embodiments, the δ-lactone methoxycarbonylation is carried out using L15 as a ligand under various conditions. The conditions and results of some examples are shown in Table 1. In some examples, PTSA was used. For example, in runs 1-4 of Table 1, when the amount of PTSA is from 1 mol.% to 15 mol.%, the output of 2a first increases and reaches a plateau. In some examples, methanesulfonic acid (MSA) was used. For example, in experiment 5, the yield is 84%. In some examples, hydrochloric acid was used. For example, in run 6, the yield is 33%. Perhaps this is due to its volatility. In some examples, sulfuric acid was used. For example, Run 7 uses 5 mole % sulfuric acid and yields 89%.

Table 1. Palladium-catalyzed methoxycarbonylation of δ-lactone 1 to 2a: optimization of reaction conditions ^a . Experience Catalyst Precursor (mole%) Solvent Acid (mol.%) CO (bar) t (hours) Y ^b (%) 1 PdCl ₂ (1) toluene PTSA (1) 40 5 58 2 PdCl ₂ (1) toluene PTSA (5) 40 5 83 3 PdCl ₂ (1) toluene PTSA (10) 40 5 89 4 PdCl ₂ (1) toluene PTSA (15) 40 5 90 5 PdCl ₂ (1) toluene MSA (5) 40 5 84 6 PdCl ₂ (1) toluene HCl (5) 40 5 33 7 PdCl ₂ (1) toluene _{H2SO4 (} 5) 40 5 89 8 PdCl ₂ (CH ₃ CN) ₂ (1) toluene _{H2SO4 (} 5) 40 5 88 9 Pd(dba) ₂ (1) toluene _{H2SO4 (} 5) 40 5 16 10 Pd(OAc) ₂ (1) toluene _{H2SO4 (} 5) 40 5 19 eleven PdCl ₂ (1) CH ₃ CN H ₂ SO (5) 40 5 37 12 PdCl ₂ (1) tetrahydro-furan (THF, THF) _{H2SO4 (} 5) 40 5 45 13 PdCl ₂ (1) MeOH _{H2SO4 (} 5) 40 5 39 14 ^s PdCl ₂ (0.5) toluene _{H2SO4 (} 5) 40 3 86 15 PdCl ₂ (0.5) toluene _{H2SO4 (} 5) 40 3 89 ^16d PdCl ₂ (0.5) toluene _{H2SO4 (} 5) 40 3 87 17 PdCl ₂ (0.5) toluene _{H2SO4 (} 5) thirty 3 89 18 PdCl ₂ (0.5) toluene _{H2SO4 (} 5) 20 3 87 ^19e PdCl ₂ (0.5) toluene H ₂ SO ₄ (7.5) thirty 3 ^{91f 20g} PdCl ₂ (0.17) toluene H ₂ SO ₄ (1.7) thirty 5 80

^a Reaction conditions: 1 (1.0 mmol), [Pd] (x mol%), L15 (2x mol%), solvent (2 ml), MeOH (0.25 ml, 6 mmol), CO. ^b Determined by GC analysis using hexadecane as an internal standard. The yield is given as the sum of the E- and Z-isomers. The E/Z ratio varies from 3.6 to 4.2. ^from 130°C. ^d 110°С. ^f MeOH (0.50 ml, 12 mmol), isolated product yield 90%. ^g 1 (3.0 mmol), MeOH (0.75 ml, 18 mmol).

[0037] The present inventors have found that the source of palladium can be critical to the outcome of the reaction. In some embodiments, some commonly used palladium (0) and (II) precursors were used, for example, in runs 8-10, [Pd(dba) ₂ ], Pd(OAc) ₂ and PdCl ₂ (CH ₃ CN _{) 2} were used instead of PdCl 2 . The results are shown in Table 1. The presence of chloride ion can help to ensure that sufficiently stable catalytically active particles are formed. In some embodiments, the reaction medium may include toluene, an aprotic polar solvent, or a protic polar solvent. In some embodiments, the temperature of the reaction mixture may be between 110°C and 130°C. In some embodiments, the CO pressure may be between 20 and 40 bar (2-4 MPa).

[0038] In some embodiments, increasing the amounts of both sulfuric acid and methanol can result in a 91% yield. In some examples, such as Run 20, the amounts of lactone and MeOH are increased, good catalytic activity can still be achieved at 0.17 mole %.

[0039] In some embodiments, various alcohols are used. Some examples are shown in Table 2. In some embodiments, primary aliphatic alcohols are used, giving yields of 90% or more, such as in experiments 1-2. Notably, the alcohol most commonly used in the preparation of plasticizers, 2-ethylhexanol, gave diester 2c in substantially quantitative yield. In some embodiments, benzyl and isopropyl alcohols are used, leading to the corresponding diesters (such as 2d and 2e in runs 3-4) in 73% and 64% yields. However, tert-butanol and phenol did not lead to the desired product at all (in cases such as runs 5-6). The lack of selectivity in these cases is not surprising, given that the first step of the process involves an alcoholysis reaction, which is often slow with tertiary alcohols or phenols.

Table 2 Palladium catalyzed alkoxycarbonylation of δ-lactone 1 to 2 using various alcohols ^a .
Experience Alcohol Acid (mol.%) Product Yield (%) ^b 1 n-BuOH _{H2SO4 (} 5) 2b 90 (E/Z=3.8) 2 2-ethylhexanol _{H2SO4 (} 5) 2c 99 (E/Z=4.2) 3 _PhCH2OH PTSA (10) 2d 73 (E/Z=4.5) 4 iso-PrOH _{H2SO4 (} 5) 2e 64 (E/Z=2.3) 5 tert-BuOH PTSA (10) 2f - 6 PhOH PTSA (10) 2g -

^a Reaction conditions: 1 (1.0 mmol), [Pd] (0.5 mol%), L15 (1 mol%), ROH (6 mmol), 30 bar (3 MPa) CO in toluene (2 ml) for 5 hours. ^b Determined by GC analysis using hexadecane as an internal standard. The yield is given as the sum of the E- and Z-isomers.

[0040] In some embodiments, the 1-3 millimolar alkoxycarbonylation is carried out in a 4 ml tube placed inside a 300 ml stainless steel Parr autoclave. The molar ratios and experimental conditions used in some embodiments are shown in Scheme 8, in Table 1 and in Table 2. In some embodiments, the palladium precursor (0.01 mmol, 1 mol.%), ligand (0.02 mmol, 2 mol.%), δ-lactone (152 mg, 1.0 mmol) and the magnetic stir bar are placed in a 4 ml tube. In some embodiments, when the catalyst content is less than 1 mole %, a mother liquor is obtained from PdCl ₂ and L15 by mixing them in toluene and stirring the mixture overnight. In some embodiments, the vial is then stoppered, vented to atmosphere through a needle and evacuated, and filled three times with argon. In some embodiments, a solvent (eg, 2.0 ml) and a solution of the acid promoter in the appropriate alcohol are injected into the tube using a syringe. In some embodiments where phenol and tert-butanol are used, alcohol and acid are added by weight. In some embodiments, the autoclave is purged with CO three times, pressurized to the desired level, and then placed in a preheated aluminum block. In some embodiments, after the reaction time has elapsed, the autoclave is cooled with ice water to room temperature and the pressure is carefully reduced. In some embodiments, the reaction mixture is analyzed by gas chromatography using hexadecane as an internal standard. In some embodiments, the resulting products are isolated from the reaction mixture by column chromatography and analyzed.

[0041] In some embodiments, the reaction is carried out in a 100 ml Hastelloy-C Parr autoclave. PdCl ₂ (16.1 mg, 9.1×10 ^-2 mmol), L15 (215 mg, 0.18 mmol) and δ-lactone (9.11 g, 60 mmol) are weighed into a Schlenk flask. In some embodiments, the flask is purged with argon. In some embodiments, toluene (40 ml) and a solution of H ₂ SO ₄ (95 mg) in MeOH (15 ml) are added. In some embodiments, the mixture is stirred for 1 hour under argon and then transferred to an autoclave pre-purged with argon. In some embodiments, the autoclave is purged with CO three times, pressurized to 50 bar (5 MPa), and then heated to 120° C. for 7 hours. In some embodiments, the autoclave is then cooled with ice water and the gas is vented. In some embodiments, the volatiles are evaporated using a rotary evaporator and the crude residue is distilled under vacuum (0.25-0.20 mbar (0.18-0.15 mm Hg), collecting a fraction with a boiling point between 80-85 ° C. In some embodiments, the purity is checked using gas chromatography. In some embodiments, product 2a is obtained with an 81% yield.

[0042] In some embodiments, the reagents are commercially available from Alfa Aesar, Aldrich, TCI, or Strem. Unless otherwise specified, commercial reagents are used without purification. In some embodiments, the δ-lactone is synthesized as previously reported and stored under Ar after distillation. In some embodiments, PTSA is used as the monohydrate. In some embodiments, Pd/C, 10 wt.%, purchased from Aldrich (product no. 205699). In some embodiments, [Ru(Triphos)(TMM)] is synthesized as previously described in the literature. In some embodiments, the toluene, THF, and methanol recovered from the M BRAUN Solvent Purification System are used in standard Schlenk technology. In some embodiments, acetonitrile, n-butanol, 2-ethylhexanol, benzyl alcohol, and isopropanol are dried using standard methods and stored under an Ar atmosphere. Analytical data of compounds known in the literature coincide with the data described. In some embodiments, the NMR spectra were recorded on a Bruker AV-300, Bruker Fourier 300, or Bruker AV-400 NMR spectrometer. Signal multiplicity is denoted as s (singlet, s), d (doublet, d), t (triplet, t), dd (doublet of doublets, dd), m (multiplet, m) and br.s (broadened singlet, br.s.). FIG. 3-8 show NMR spectral data of diesters derived from δ-lactone 1.

[0043] In some embodiments, measurements are taken at room temperature. In some embodiments, mass spectra are recorded on an Agilent 6890/5973 GC-MS instrument. In some embodiments, high-resolution mass spectra (HRMS) are recorded on an Agilent 6210 instrument with a time-of-flight (Time-of-Flight) liquid chromatography/mass spectrometry (LC/MS) camera (Agilent) with electric field spray ionization (ESI). Data are given in units of mass-to-charge ratio (m/z), and signal intensities are given in brackets. In some embodiments, an Agilent HP-7890A chromatograph equipped with a flame ionization (FID) detector and an HP-5 column (polydimethylsiloxane with 5% phenyl groups, 30 m, id 0.32 mm, film thickness 0.25 µm) was used for gas chromatographic (GC) analyzes. In some embodiments, the products are isolated from the reaction mixture by column chromatography on silica gel 60, 0.063-0.2 mm, (Merck), using a gradient elution from heptane to heptane/AcOEt=8:2.

[0044] In some embodiments, GC analyzes are performed according to Table 3 using the following methods: oven temperature program: 50°C; at a rate of 15°C/minute to 260°C for 6 minutes; injection volume 1 μl with flow division (split) 50:1; and with an inlet temperature of 200°C.

Table 3 Experience Compound Hold time (minutes) 1 11.20 2 10.68 3 10.31

[0045] In some embodiments, the scalability of the method has been demonstrated. In some embodiments, the methoxycarbonylation of compound 2a (Scheme 10) is performed on a multi-gram scale. For example, using a low catalyst load (PdCl ₂ =0.15 mol%, L15=0.3 mol%) and at the concentrations of other reagents used in run 22, Table 1, dimethyl 7-ethylidenoct-3-enedioate 2a was obtained with an isolated yield of 81%.

Scheme 10: Multigram synthesis of 2a from δ-lactone 1

[0046] The unsaturated esters obtained by alkoxycarbonylation of δ-lactone 1 are valuable basic chemistry, and the corresponding saturated esters and the resulting diols are also of interest for a wide variety of applications according to one embodiment.

[0047] To convert unsaturated diesters of 2 δ-lactone to saturated esters or diols, catalytic hydrogenation reactions are performed. In some embodiments, commercial grade Pd/C (10% by weight) is used as the hydrogenation catalyst for the unsaturated diester 2a. In some embodiments, mild reaction conditions (10 bar (1 MPa) H ₂ , 60° C.) were used to reduce δ-lactone 1 to form 3,6-diethyltetrahydro-2H-pyran-2-one.

Scheme 11: hydrogenation of diester 2a

[0048] In some embodiments, diesters, such as δ-lactone 1-derived dimethyl-7-ethylidenoct-3-enedioate 2a, can be chemoselectively hydrogenated in toluene in high yields to form partially hydrogenated diesters 3 while retaining double bonds at the C-2 carbon (Scheme 11A).

[0049] In some embodiments, Pd/C, 10 wt.%, (2.8 mg), dimethyl-7-ethylidenoct-3-enedioate 2a (113 mg, 0.5 mmol) and a magnetic stir bar were placed in a 4 ml tube. In some embodiments, the tube is then sealed with a septum (Septa, styrene-butadiene rubber with a polytetrafluoroethylene (PTFE) surface) and a phenolic cap. In some embodiments, the test tube is connected to the atmosphere through a needle. In some embodiments, the tube is evacuated and filled three times with argon. In some embodiments, toluene (2.0 ml) is injected into the test tube with a syringe. In some embodiments, the tube is placed inside a 300 ml stainless steel Parr autoclave. In some embodiments, the autoclave is purged with nitrogen three times, pumped with hydrogen to a pressure of 10 bar (1 MPa), and then heated to 60° C. for 3 hours. In some embodiments, the autoclave is cooled in an ice bath and the gas is vented. In some embodiments, the completeness of the conversion is checked by GC analysis. In some embodiments, the reaction mixture is filtered through celite, the solvent is evaporated, and the crude product is purified by column chromatography (gradient elution from heptane to heptane/AcOEt=8:2) to give (E)-dimethyl-2-ethylidenodectandioate 3 as a colorless liquid in 96% yield.

[0050] Partially hydrogenated diesters 3 can be considered as analogues of acrylates (Scheme 12). Examples of such polymerization methods include the synthesis of long and short chain polymerization products using chain transfer polymerization (CTP), controlled radical polymerization such as ATRP, RAFT and NMP methodologies.

Scheme 12: radical polymerization of acrylates

[0051] Diester 3 can also be used as a comonomer for copolymerization processes using ethylene, propylene, or alpha-olefins (Scheme 13).

Scheme 13: copolymerization processes using ethylene, propylene or alpha-olefins

[0052] Diester 3 can also be used as a starting material for metathesis reactions to form polyesters and polyols (Scheme 14).

Scheme 14: Metathesis reactions to form polyesters and polyols

[0053] In some embodiments, diesters, such as δ-lactone 1-derived dimethyl-7-ethylidenoct-3-enedioate 2a, can be chemoselectively hydrogenated in tetrahydrofuran (THF) in high yields to form fully hydrogenated diesters 4 (Scheme 11B).

[0054] In some embodiments, Pd/C, 10 wt.%, (3.1 mg), dimethyl-7-ethylidenoct-3-enedioate 2a (1.4 mmol) and a magnetic stir bar were placed in a 4 ml tube. In some embodiments, the tube is then sealed with a septum (styrene butadiene rubber with a PTFE surface) and a phenolic cap. In some embodiments, the test tube is connected to the atmosphere through a needle. In some embodiments, the tube is evacuated and filled three times with argon. In some embodiments, THF (3 ml) is added to the vial and the vial is placed inside a 300 ml stainless steel Parr autoclave. In some embodiments, the autoclave is purged with nitrogen three times, pumped with hydrogen to a pressure of 10 bar (1 MPa), and then heated to 60° C. for 2.5 hours. In some embodiments, the autoclave is cooled in an ice bath and the gas is vented. In some embodiments, the completeness of the conversion is checked by GC analysis. In some embodiments, the reaction mixture is filtered through celite and the solvent is evaporated to give pure dimethyl 2-ethyl octanedioate 4 as a colorless liquid in >99% yield.

[0055] The authors of the present invention noted the marked effect of the solvent on the chemoselectivity of hydrogenation. In some embodiments, the reaction is carried out in toluene and reduction of the disubstituted double bond is achieved within 3 hours. However, the conjugated trisubstituted double bond is not restored even after 16 hours, as in Scheme 11A. In some embodiments, complete reduction of olefin bonds in compound 2a with the formation of product 4 is performed within 2.5 hours using THF as a solvent, as in Scheme 11B. Diester 4 is of potential industrial interest for applications as a plasticizer and as a comonomer in combination with diamines and diols to form the corresponding polyamides and polyesters. On the other hand, the presence of a single unsaturation makes compound 3 comparable to α,β-unsaturated esters, for example, derivatives of acrylic and tiglinic acids, which are of interest for the preparation of various functional materials.

[0056] To further illustrate the versatility of compound 2 as building blocks for polymers, the present inventors investigated its hydrogenation to diol 5 (Scheme 11C). Typically, the synthesis of diol 5 can be performed by reduction of compound 4 using LiAlH ₄ as a reagent in a stoichiometric ratio. However, when using this traditional reaction, it is difficult to isolate and purify 5 from side products. Such a methodology is clearly inconsistent with environmental requirements, and is not currently applicable to large-scale industrial production. On the other hand, fragments of esters and carboxylic acids are functional groups difficult for hydrogenation reactions. In industrial production processes, their hydrogenation is usually carried out over heterogeneous catalysts at high pressures and temperatures. The present inventors have investigated the homogeneous catalyst catalyzed hydrogenation of dimethyl 7-ethylidenoct-3-enedioate 2a, which can be used as a valuable base chemical for diols in the polymer materials industry either as feedstock or as alcohol-based plasticizers.

[0057] In some embodiments, the reduction of 2a to 5 uses two different commercially available ruthenium-based catalysts. A Noyori-type ruthenium catalyst for the hydrogenation of esters (c1, Table 3) and a PNP ruthenium chelate complex in tetrahydroborate form with the designation Ru-MACHO™ (c2, Table 3) were used in runs 1 and 2. Unfortunately, even after 22 hours, only traces of diol were present when using c1 as a catalyst, and using c2, the product was only obtained in 8% yield.

[0058] However, promising results can be obtained using ruthenium complexes of 1,1,1-tris-(diphenylphosphinomethyl)ethane (Triphos). The effects of water, MSA and zinc, and solvent in the reduction of diesters isolated from natural oil were studied. In addition, the strong dependence of biogenic acid recovery selectivity on changing ionic or acid additives was also investigated. [Ru(Triphos)(TMM)] as c3 (TMM=trimethylenemethane) and the in situ formed system from [Ru(acac) ₃ ]/Triphos (c4 in Table 3, acac=acetylacetonate) were investigated and, interestingly, it was found that the addition of acid additives reduced the selectivity for benzyl alcohol in the hydrogenation of benzoic acid. The use of Lewis acids as promoters in the reductive esterification of esters has also been studied.

[0059] In some embodiments, the metal complex or catalyst precursor and ligand, e.g., [Ru(acac) ₃ ] (e.g., 4.0 mg, 0.01 mmol), Triphos (e.g., 12.5 mg, 0.02 mmol), and zinc (e.g., 1.6 mg, 2.5×10 ^-2 mmol), are rapidly weighed in air into a 4 ml tube. In some embodiments, the tube is then stoppered, vented to atmosphere through a needle, and evacuated and filled three times with argon. In some embodiments, 2a (eg, 0.5 mmol) and a solvent stock containing the appropriate additive, eg, HNTf ₂ (7.0 mg, 2.5×10 ^-2 mmol) in methanol, are added to the tube. In some embodiments, the tube is placed inside a 300 ml stainless steel Parr autoclave and the autoclave is purged with nitrogen three times, pressurized with hydrogen and heated. In some embodiments, after the reaction time has elapsed, the autoclave is cooled with ice water and the gas is vented. In some embodiments, the crude product is analyzed by gas chromatography. In some embodiments, the yield of isolated product is obtained after purification on silica gel (gradient elution from CH ₂ Cl ₂ to CH ₂ Cl ₂ /MeOH 9:1).

[0060] Some embodiments use c4 in combination with MSA in methanol (Test 4, Table 4). For comparison, c3 in THF is used in the absence of any additive (Test 3, Table 4). In the first case, diol 5 was obtained in 35% yield, while in the latter case, mainly a mixture of esters 3 and 4 was formed. In some embodiments, sodium methoxide is used as a solvent, and bis(trifluoromethane)sulfonimide (HNTf ₂ ) is used as an additive. In some embodiments, the use of HNTf ₂ (10 mol.%) led to the product 5 with a yield of 69% (experiment 5, table 4). In some embodiments, the desired complete reduction of 2a to diol 5 is obtained under relatively mild conditions in 91% yield (80% isolated product) by reducing the amount of HNTf ₂ to 5 mol% and adding 5 mol% zinc metal, for example, in run 7, Table 4.

Experience Catalyst Solvent Additive (mole%) CO (bar) T (°C) t (hours) Yield 6 (%) 1 c1 THF MeONa (10) 50 120 22 footprints 2 c2 THF - 50 120 22 8 3 c3 THF - 70 150 22 2 4 с4 Meon MSA (10) 70 150 22 35 5 с4 Meon HNTf ₂ (10) 70 150 22 69 6 с4 Meon MSA(5)/Zn
(5) 70 150 24 42 7 с4 Meon HNTf ₂ (5)/Zn
(5) 70 150 24 91 8 с4 Meon MeONa (10) 70 150 22 17 9 с4 dioxane HNTf ₂ (5) 70 150 22 24

Table 4. ^a Reaction conditions: 3 (0.5 mmol), metal complex (0.01 mmol), ligand when added (0.02 mmol), solvent (2 ml). Conversion 3 was complete in all cases. Yields were determined by GC analysis using hexadecane as an internal standard. MSA=methanesulfonic acid. HNTf ₂ =bis(trifluoromethane)sulfonimide.

[0061] The reactions in the experiments in Table 4 are detailed as follows:

[0062] Trial 1: C1 (6.0 mg, 0.01 mmol) and a magnetic stir bar were placed in a 4 ml tube. The tube was placed in a Schlenk tube, evacuated and purged with argon three times, and then CH ₃ ONa (2.6 mg, 0.05 mmol, 10 mol%) was added. The tube was then sealed with a septum (styrene butadiene rubber with a PTFE surface) and a phenolic cap. The test tube was connected to the argon supply line by means of a needle. Compound 3 (113 mg, 0.5 mmol) and THF (2.0 ml) were injected into the tube with a syringe. The tube was placed in an alloy plate, which was transferred to a 4760 series autoclave (300 ml) from Parr Instruments under argon. After purging the autoclave three times with nitrogen, the hydrogen pressure was increased to 50 bar (5 MPa) at room temperature. The reaction was carried out for 22 hours at 120°C. After the reaction time, the autoclave was cooled to room temperature and the pressure was carefully reduced. Then hexadecane (0.100 ml) was injected as an internal standard. Yield was measured by GC analysis.

[0063] Experiment 2: C2 (5.4 mg, 0.01 mmol) and a magnetic stir bar were placed in a 4 ml tube. The tube was then sealed with a septum (styrene butadiene rubber with a PTFE surface) and a phenolic cap. The tube was connected to the atmosphere through a needle. The tube was evacuated and filled three times with argon. Compound 3 (113 mg, 0.5 mmol) and THF (2.0 ml) were injected into the tube with a syringe. The tube was placed in an alloy plate, which was transferred to a 4760 series autoclave (300 ml) from Parr Instruments under argon. After purging the autoclave three times with nitrogen, the hydrogen pressure was increased to 50 bar (5 MPa) at room temperature. The reaction was carried out for 22 hours at 120°C. After the reaction time, the autoclave was cooled to room temperature, and the pressure was carefully reduced. Then hexadecane (0.100 ml) was injected as an internal standard. Yield was measured by GC analysis.

[0064] Trial 3: C3 (7.8 mg, 0.01 mmol) and a magnetic stir bar were placed in a 4 ml tube. The tube was then sealed with a septum (styrene butadiene rubber with a PTFE surface) and a phenolic cap. The tube was connected to the atmosphere through a needle. The tube was evacuated and filled three times with argon. Compound 3 (113 mg, 0.5 mmol) and THF (2.0 ml) were injected into the tube with a syringe. The tube was placed in an alloy plate, which was transferred to a 4760 series autoclave (300 ml) from Parr Instruments under argon. After purging the autoclave three times with nitrogen, the hydrogen pressure was increased to 70 bar (7 MPa) at room temperature. The reaction was carried out for 22 hours at 150°C. After the reaction time, the autoclave was cooled to room temperature and the pressure was carefully reduced. Then hexadecane (0.100 ml) was injected as an internal standard. Yield was measured by GC analysis.

[0065] Experiment 4: Ru(acac) ₃ (4.0 mg, 0.01 mmol), 1,1,1-tris-(diphenylphosphinomethyl)ethane (11.5 mg, 0.02 mmol) and a magnetic stir bar were placed in a 4 ml tube. The tube was then sealed with a septum (styrene butadiene rubber with a PTFE surface) and a phenolic cap. The tube was connected to the atmosphere through a needle. The tube was evacuated and filled three times with argon. Compound 3 (113 mg, 0.5 mmol), 0.05M solution of methanesulfonic acid in MeOH (1.0 ml, 10 mol%) and MeOH (1.0 ml) was injected into the tube with a syringe. The tube was placed in an alloy plate, which was transferred to a 4760 series autoclave (300 ml) from Parr Instruments under argon. After purging the autoclave three times with nitrogen, the hydrogen pressure was increased to 70 bar (7 MPa) at room temperature. The reaction was carried out for 22 hours at 150°C. After the reaction time, the autoclave was cooled to room temperature and the pressure was carefully reduced. Then hexadecane (0.100 ml) was injected as an internal standard. Yield was measured by GC analysis.

[0066] Experiment 5: Ru(acac) ₃ (4.0 mg, 0.01 mmol), 1,1,1-tris-(diphenylphosphinomethyl)ethane (11.5 mg, 0.02 mmol) and a magnetic stir bar were placed in a 4 ml tube. The tube was then sealed with a septum (styrene butadiene rubber with a PTFE surface) and a phenolic cap. The tube was connected to the atmosphere through a needle. The tube was evacuated and filled three times with argon. Compound 3 (113 mg, 0.5 mmol), a 0.05M solution of HNTf ₂ in MeOH (1.0 ml, 10 mol%) and MeOH (1.0 ml) was injected into the tube with a syringe. The tube was placed in an alloy plate, which was transferred to a 4760 series autoclave (300 ml) from Parr Instruments under argon. After purging the autoclave three times with nitrogen, the hydrogen pressure was increased to 70 bar (7 MPa) at room temperature. The reaction was carried out for 22 hours at 150°C. After the reaction time, the autoclave was cooled to room temperature and the pressure was carefully reduced. Then hexadecane (0.100 ml) was injected as an internal standard. Yield was measured by GC analysis.

[0067] Experiment 6: Ru(acac) ₃ (4.0 mg, 0.01 mmol), 1,1,1-tris-(diphenylphosphinomethyl)ethane (11.5 mg, 0.02 mmol), zinc metal powder (1.7 mg, 0.025 mmol, 5 mol.%) and a magnetic stir bar were placed in a 4 ml tube. The tube was then sealed with a septum (styrene butadiene rubber with a PTFE surface) and a phenolic cap. The tube was connected to the atmosphere through a needle. The tube was evacuated and filled three times with argon. Compound 3 (113 mg, 0.5 mmol), 0.54M solution of methanesulfonic acid in MeOH (0.050 ml, 5 mol%) and MeOH (2.0 ml) was injected into the tube with a syringe. The tube was placed in an alloy plate, which was transferred to a 4760 series autoclave (300 ml) from Parr Instruments under argon. After purging the autoclave three times with nitrogen, the hydrogen pressure was increased to 70 bar (7 MPa) at room temperature. The reaction was carried out for 24 hours at 150°C. After the reaction time, the autoclave was cooled to room temperature and the pressure was carefully reduced. Then hexadecane (0.100 ml) was injected as an internal standard. Yield was measured by GC analysis.

[0068] Experiment 7: Ru(acac) ₃ (4.0 mg, 0.01 mmol), 1,1,1-tris-(diphenylphosphinomethyl)ethane (11.5 mg, 0.02 mmol), zinc metal powder (1.7 mg, 0.025 mmol, 5 mol.%) and a magnetic stir bar were placed in a 4 ml tube. The tube was then sealed with a septum (styrene butadiene rubber with a PTFE surface) and a phenolic cap. The tube was connected to the atmosphere through a needle. The tube was evacuated and filled three times with argon. Compound 3 (113 mg, 0.5 mmol), 0.025M solution of HNTf ₂ in MeOH (1.0 ml, 5 mol %) and MeOH (1.0 ml) was injected into the tube with a syringe. The tube was placed in an alloy plate, which was transferred to a 4760 series autoclave (300 ml) from Parr Instruments under argon. After purging the autoclave three times with nitrogen, the hydrogen pressure was increased to 70 bar (7 MPa) at room temperature. The reaction was carried out for 24 hours at 150°C. After the reaction time, the autoclave was cooled to room temperature and the pressure was carefully reduced. Then hexadecane (0.100 ml) was injected as an internal standard. Yield was measured by GC analysis. The product was purified by column chromatography on silica gel (gradient wash from CH ₂ Cl ₂ to CH ₂ Cl ₂ /MeOH 9:1).

[0069] Experiment 8: Ru(acac) ₃ (4.0 mg, 0.01 mmol), 1,1,1-tris-(diphenylphosphinomethyl)ethane (11.5 mg, 0.02 mmol) and a magnetic stir bar were placed in a 4 ml tube. The tube was then sealed with a septum (styrene butadiene rubber with a PTFE surface) and a phenolic cap. The tube was connected to the atmosphere through a needle. The tube was evacuated and filled three times with argon. Compound 3 (113 mg, 0.5 mmol), a 0.5M solution of CH ₃ ONa in MeOH (1.0 ml, 10 mol%) and MeOH (1.0 ml) was injected into the tube with a syringe. The tube was placed in an alloy plate, which was transferred to a 4760 series autoclave (300 ml) from Parr Instruments under argon. After purging the autoclave three times with nitrogen, the hydrogen pressure was increased to 70 bar (7 MPa) at room temperature. The reaction was carried out for 22 hours at 150°C. After the reaction time, the autoclave was cooled to room temperature and the pressure was carefully reduced. Then hexadecane (0.100 ml) was injected as an internal standard. Yield was measured by GC analysis.

[0070] Experiment 9: Ru(acac) ₃ (4.0 mg, 0.01 mmol), 1,1,1-tris-(diphenylphosphinomethyl)ethane (11.5 mg, 0.02 mmol) and a magnetic stir bar were placed in a 4 ml tube. The tube was then sealed with a septum (styrene butadiene rubber with a PTFE surface) and a phenolic cap. The tube was connected to the atmosphere through a needle. The tube was evacuated and filled three times with argon. Compound 3 (113 mg, 0.5 mmol), 0.025 M solution of HNTf ₂ in dioxane (1.0 ml, 5 mol%) and dioxane (1.0 ml) were injected into the test tube with a syringe. The tube was placed in an alloy plate, which was transferred to a 4760 series autoclave (300 ml) from Parr Instruments under argon. After purging the autoclave three times with nitrogen, the hydrogen pressure was increased to 70 bar (7 MPa) at room temperature. The reaction was carried out for 22 hours at 150°C. After the reaction time, the autoclave was cooled to room temperature and the pressure was carefully reduced. Then hexadecane (0.100 ml) was injected as an internal standard. Yield was measured by GC analysis.

[0071] It should be clear that those skilled in the art will recognize numerous changes and modifications to the currently preferred embodiments described herein. Such changes and modifications may be made without departing from the spirit and scope of the subject matter of the present invention, and without prejudice to its intended advantages. Therefore, such changes and modifications are intended to be covered by the appended claims.

Claims (43)

1. A method for producing a renewable raw material for producing polymers, and the method includes: obtaining a derivative from CO ₂ lactone according to the following reaction: ; And processing the CO ₂ lactone derivative to form a renewable starting material, wherein the processing of the CO ₂ lactone derivative comprises selectively hydrogenating the CO ₂ lactone derivative to form a hydrogenated CO ₂ lactone derivative according to the following reaction: , wherein the hydrogenated CO ₂ derivative lactone is treated to form 2-ethylidene enanthic acid using one or both of a homogeneous hydrogenation system and a heterogeneous hydrogenation system according to the following reaction: . 2. A method for producing a renewable raw material for producing polymers, the method comprising: obtaining a derivative from CO ₂ lactone according to the following reaction: ; And processing the CO ₂ lactone derivative to form a renewable starting material, wherein the processing of the CO ₂ lactone derivative comprises selectively hydrogenating the CO ₂ lactone derivative to form a hydrogenated CO ₂ lactone derivative according to the following reaction: , and wherein the hydrogenated CO ₂ derivative lactone is treated with an Rh/phosphine biphasic hydrogenation system to form 2-ethylideneenanthic acid. 3. A method for producing a renewable raw material for producing polymers, the method comprising: obtaining a derivative from CO ₂ lactone according to the following reaction: ; And processing the CO ₂ lactone derivative to form a renewable starting material, wherein the processing of the CO ₂ lactone derivative comprises selectively hydrogenating the CO ₂ lactone derivative to form a hydrogenated CO ₂ lactone derivative according to the following reaction: , and wherein the hydrogenated CO ₂ derivative lactone is treated using alkene metathesis, the alkene metathesis comprising a self-metathesis reaction as follows: or alkene metathesis includes cross-metathesis as follows: R=H, CH ₃ , alkyl, cycloalkyl, lactone, phenyl and substituted phenyl. 4. A method for producing a renewable raw material for producing polymers, the method comprising: obtaining a derivative from CO ₂ lactone according to the following reaction: ; And processing the CO ₂ lactone derivative to form a renewable starting material, wherein the processing of the CO ₂ lactone derivative comprises selectively hydrogenating the CO ₂ lactone derivative to form a hydrogenated CO ₂ lactone derivative according to the following reaction: ; And treatment of the hydrogenated CO ₂ lactone derivative which involves a metal catalyzed reaction as follows: R=H, CH ₃ , alkyl, cycloalkyl, phenyl and substituted phenyl. 5. A method for producing a renewable raw material for producing polymers, the method comprising: obtaining a derivative from CO ₂ lactone according to the following reaction: ; And alkoxycarbonylation of a derivative from CO₂ lactone to form a diester, where alkoxycarbonylation of the derivative from CO₂ lactone includes the use of a palladium compound catalyst, wherein the palladium compound catalyst comprises Pd(OAc)₂, PdCl₂ or Pd(dba)₂, where the alkoxycarbonylation of the derivative from CO₂ lactone involves a methoxycarbonylation reaction as follows: , wherein R is methyl, n-butyl, 2-ethylhexyl, PhCH ₂ , isopropyl. 6. The process of claim 5, further comprising hydrogenating the diester to form a renewable feedstock. 7. The method of claim 5 wherein the alkoxycarbonylation comprises the use of a phosphine ligand. 8. The method of claim 5 wherein the alkoxycarbonylation comprises the use of an alcohol. 9. The method of claim 5 wherein the alkoxycarbonylation comprises the use of a solvent. 10. The method of claim 5 wherein the alkoxycarbonylation comprises the use of an acid. 11. The method of claim 1 wherein the CO ₂ -derived lactone is selectively hydrogenated with 100% regioselectivity control for terminal carbon-carbon bonds.

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