SE2150508A1 - Pinene-based polymers - Google Patents

Pinene-based polymers

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Publication number
SE2150508A1
SE2150508A1 SE2150508A SE2150508A SE2150508A1 SE 2150508 A1 SE2150508 A1 SE 2150508A1 SE 2150508 A SE2150508 A SE 2150508A SE 2150508 A SE2150508 A SE 2150508A SE 2150508 A1 SE2150508 A1 SE 2150508A1
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Sweden
Prior art keywords
acid
polymer
alkyl
hydroxyethyl
hhdc
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SE2150508A
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SE545575C2 (en
Inventor
Arne Stamm
Johannes Öhlin
Per-Olof Syrén
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Arne Stamm
Syren Per Olof
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Application filed by Arne Stamm, Syren Per Olof filed Critical Arne Stamm
Priority to SE2150508A priority Critical patent/SE545575C2/en
Priority to PCT/EP2022/060778 priority patent/WO2022223825A1/en
Publication of SE2150508A1 publication Critical patent/SE2150508A1/en
Publication of SE545575C2 publication Critical patent/SE545575C2/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/553—Acids or hydroxy compounds containing cycloaliphatic rings, e.g. Diels-Alder adducts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/137—Acids or hydroxy compounds containing cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/27—Polyhydroxylic alcohols containing saturated rings
    • C07C31/272—Monocyclic
    • C07C31/274—Monocyclic with a three to five-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/593—Dicarboxylic acid esters having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3212—Polyhydroxy compounds containing cycloaliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/28—Polyesters

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

The present invention relates to a polymer comprising repeating units of formula (I)whereinA is selected from O, NR6, -C(O)-O- and C=O;B is selected from O, NR6, -O-C(O)-, C=0, and E-C(O)-X-C(O)-, wherein E is O or NR6; R1, R2, R3, R4, R5 and R6each independently are selected from H, C1-6 alkyl, halogenated C1-6 alkyl;X is selected from C1-6 alkyl, C2-6 alkenyl, which may be mono- or diunsaturated, C3-6 cycloalkyl, C3-6 cycloalkenyl, diamino- C2-6 alkyl, diamino- C2-6 alkenyl, and a 4- to 6-membered saturated or unsaturated ring optionally containing one or more hetero atoms selected from N, O, S and Si, which 4- to 6-membered saturated or unsaturated ring is optionally substituted;and wherein any alkyl and alkenyl may be linear or branched and is optionally substituted with a halogen or an aromatic unit; andm is an integer between 10 and 10000,and a method for its preparation, as well as its use in coating, barrier, or moulding applications.

Description

PINENE-BASED POLYMERS FIELD OF THE INVENTION The present invention relates to a polymer comprising repeating units of formula (I) Rfrëßtr /\ R2 Ra u) a method for its preparation, and its use in coating, barrier, or moulding applications.
TECHNICAL BACKGROUND Today, the vast majority of all polymeric synthetic materials are fossil-based. As polymeric materials are essential for our daily life innovative technologies to generate sustainable biomaterials from renewable feedstocks are urgently needed. Paint and coating industries, as well as other chemical companies, seek to replace current petroleum-sourced products with renewable alternatives. Still, only a very small proportion of all synthetic polymers are generated from renewable resources. Growing plants only for bioplastic production raises further environnlental issues, e.g. the use of fertilizers and land reclšrectecl from food procâuction (Tabone, M. D., et al., Environ. Sci. Technol. 44, 8264-8269 (2010)). Development of sustainable polymers towards a circular materials economy would thus be favoured by the use of already existing but underutilized side streams in industrial processes.
Terpenes äs a large of srrzaåâ-rrloleczlle hydrocarboras that are produced predominantly by plants and constfitlite one of the most fišversšflefí farnllies of natural procluctza (Oldfield, E. & Lin, F.-Y. Angew. Chemie Int. Ed. 51, 1124-1137 (2012)) with a broad variety of structural and functional properties. One major source of terpenes is turpentine, a pine-tree resin emanating from the paper and pulping industry. The main component of turpentine is oL-pinene, which has a bicyclic unsaturated structure that has been shown to react cationically. However, the steric hindrance ofthe trisubstituted double bond poses an issue to the production of high molecular weight polymers (Lomelí-Rodríguez, M., et al., Polymers (Basel). 10, 600 (2018)). Lanteri et al. (Front. Chem. 8, 85 (2020)) studied the use of terpene-based diols as monomers for polyester synthesis by using the photo oxidized product of citronellol as comonomertogetherwith butanediol and dimethyl succinate. Firdaus et al. (Macromolecules 44, 7253-7262 (2011)) studied the use of functionalized, limonene-based monomers bearing both, ester and alcohol functionality. lshmuratov, G. Y., et al., (Chem. Nat. Compd. 53, 63-65 (2017)) have reported the use of ozone for the cleavage ofthe alpha pine double bond.
Thus, achieving appropriate functionalization of inert metabolites to afford activated monomers compatible with desired polymerization type and provision of scalable synthesis of bio-based materials with tuneable properties are problems that need to be solved.
SUMMARY OF THE INVENTION lt is an object of the present invention to provide a bio-based polymer, such as a polyester resin, a polyamide resin, or a polyurethane resin, with tailored properties based on terpene derived monomers solely or in combination with dicarboxylic acid or a diester thereof, and the use of said bio-based polymer as coating and green barriers.
A further object is to provide a method for preparing a bio-based polymer, such as a polyester, polyamide or polyurethane resin from a terpene-derived monomer solely or in combination with a dicarboxylic acid or diester thereof.
A still further object is to provide a coating comprising the bio-based polymer resin.
BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 presents lH-NIVIR spectra of polyesters.
Figure 2 presents molecular weight distribution curves.
Figure 3 presents TGA thermograms for (a) polyester resins and (b) cured polyester coatings. Figure 4 presents DSC thermograms for (a) polyester resins and (b) cured polyester coatings.
DETAILED DESCRIPTION OF THE INVENTION ln a first aspect the present invention relates to a polymer comprising repeating units of formula (I) R4 AÜBFQS m ,/"\ R2 RS u) wherein A is selected from O, NRG, -C(O)-O- and C=O; B is selected from O, NRG, -O-C(O)-, C=O, and E-C(O)-X-C(O)-, wherein E is O or NRG; Rl, RZ, R3, R4, R5 and R6 each independently are selected from H, CH alkyl, and halogenated CH alkyl; X is selected from CH alkyl, CH alkenyl, which may be mono- or diunsaturated, CH cycloalkyl, CH cycloalkenyl, diamino- CH alkyl, diamino- CH alkenyl, and a 4- to 6- membered saturated or unsaturated ring optionally containing one or more hetero atoms selected from N, O, S and Si, which 4- to 6-membered saturated or unsaturated ring is optionally substituted; and wherein any alkyl and alkenyl may be linear or branched and is optionally substituted with a halogen or an aromatic unit; and m is an integer between 10 and 10000.
Preferably, A and E each independently are selected from O and NRG. Also preferably, B is E-C(O)-X-C(O)-. ln one embodiment, the polymer of the present invention comprises repeating units of formula (ll) R2 Rß (n) wherein A and E each independently are selected from O and NRG; Rl, RZ, R3, R4, R5 and R6 each independently are selected from H, C14; alkyl, halogenated C14; alkyl; X is selected from C1-7 alkyl, CN alkenyl, which may be mono- or diunsaturated, C34; cycloalkyl, C34; cycloalkenyl, diamino- C24; alkyl, diamino- C24; alkenyl, and a 4- to 6- membered saturated or unsaturated ring optionally containing one or more hetero atoms selected from N, O, S and Si, which 4- to 6-membered saturated or unsaturated ring is optionally substituted; and wherein any alkyl and alkenyl may be linear or branched and is optionally substituted with a halogen or an aromatic unit; and m is an integer from 10 to 10000.
Preferably, in any one of the formulas (I) and (ll) above, Rl, RZ and R3 are each independently methyl. Preferably, X is selected from ethyl, propyl, butyl, ethenyl, propenyl, butenyl, butadienyl, pyrrolidinyl, pyrrolinyl, pyrrolyl, imidazolyl, pyrazolyl, furyl, thienyl, pyridyl, pyrazinyl, pyranyl, and phenyl. I\/|ore preferably, X is ethenyl, 2- propenyl, or furyl. ln some embodiments m is an integer from 10 to 1000, or from 10 to 100.
The polymer according to the present invention may be a polyester, a polyamide a polyurethane or a polyester resin. Preferably, the polymer is a polyester, or a polyester resin. ln one aspect, the polymer according to the present invention may be obtained by polycondensation or polyadduct formation of at least two different monomers, characterized in that a first monomer is 1-(1'-hydroxyethyl)-3-(2"-hydroxyethyl)-2,2- dimethylcyclobutane (HHDC) and that a second monomer is selected from at least one of a dicarboxylic acid, an anhydride or a diester thereof, and an isocyanate. Preferably, the second monomer is a dicarboxylic acid or a diester thereof. Preferably, the dicarboxylic acid or a diester thereof is selected from any one of malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, aspartic acid, itaconic acid, maleic acid, 2,5-furan dicarboxylic acid, dimethyl maleate (DI\/|I\/|), dimethyl itaconate (DMI), and dimethyl furandicarboxylate (DI\/I-FDCA), and mixtures thereof. I\/|ore preferably, the dicarboxylic acid or a diester thereof is selected from dimethyl maleate (DI\/|I\/|), dimethyl itaconate (DMI), and dimethyl furandicarboxylate (DM-FDCA). Preferred isocyanates are selected from methylenebis(phenyl isocyanate) (I\/|D|), toluene diisocyanate (TDI), and hexamethylene diisocyanate (HDI). ln a further aspect the present invention relates to a method for preparing a polymer of formula (I) by reacting 1-(1'-hydroxyethyl)-3-(2"-hydroxyethyl)-2,2- dimethylcyclobutane (HHDC) with a dicarboxylic acid, an anhydride or a diester thereof, or an isocyanate. Preferably, the method for preparing a polymer is made by reacting 1- (1'-hydroxyethyl)-3-(2"-hydroxyethyl)-2,2-dimethylcyclobutane (HHDC) with a dicarboxylic acid, or an anhydride or a diester thereof. The reaction may be made by polycondensation. ln one embodiment the dicarboxylic acid or diester thereof used in the method for preparing the polymer is selected from itaconic, maleic acid, 2,5-furan dicarboxylic acid, dimethyl maleate (DI\/|I\/|), dimethyl itaconate (DMI), and dimethyl furandicarboxylate (DM-FDCA), and mixtures thereof.
The method according to the present invention may comprise a step of mixing the 1-(1'- hydroxyethyl)-3-(2"-hydroxyethyl)-2,2-dimethylcyclobutane (HHDC) with a dicarboxylic acid, or an anhydride or a diester thereof, or an isocyanate to obtain a mixture. ln one embodiment, a polymerisation inhibitor is added to the mixture, such as a radical inhibitor, preferably a phenolic radical inhibitor, such as mequinol. ln a further embodiment, a catalyst is added to the mixture. The catalyst may provide for a more rapid polymerization. The method according to the present invention may also comprise a step of heating the mixture to obtain a polyester resin. Heating may provide for improved solubility of reagents or a higher reaction rate, or both.
The polymer obtained by the method of the invention may further be cured to obtain a cross-linked polymer, such as a cross-linked polyester. Thus, the method according to the present invention may further comprise a step of curing the polymer to obtain a cross-linked polymer. Curing of the polymer may be obtained by UV, preferably using cross-linkers, such as multifunctional thiols, such as trimethylolpropane tris(3- mercaptopropionate) (TMTP). The polymer can also be cured together with solvents, including styrene, methyl methacrylate, and Sobrerol methacrylate.
The monomer 1-(1'-hydroxyethyl)-3-(2"-hydroxyethyl)-2,2-dimethylcyclobutane used in the method according to the present invention may be obtained by oxidative cleavage ofthe double bond in oL-pinene, such as by using ozone, to obtain the oL-pinene-ozonide followed by reduction, such as by using sodium borohydride.
A yet further aspect ofthe present invention is the use ofan oL-pinene derived monomer, such as 1-(1'-hydroxyethyl)-3-(2"-hydroxyethyl)-2,2-dimethylcyclobutane (HHDC), for the preparation of a polymer, such as a polyester, a polyester resin, a polyurethane or a polyurethane resin. As presented herein, HHDC provides a bio-based renewable polyol in polyurethane or polyester resin synthesis resulting in a fully amorphous polyester or polyurethane with increased thermal stability, when co-polymerized with a dicarboxylic acid or diester thereof, or an isocyanate including itaconic, maleic acid and 2,5-furan dicarboxylic acid. Thus, the present invention enables synthesis of a variety of biobased polyesters and polyurethanes by reacting HHDC with different diacids or isocyanides or isocyanates. The present invention thus enables the synthesis of fully biobased polymers by using biobased comonomers like furan-, itaconic- or maleic-based substrates. By addition of further types of monomers to the polymerization system, the properties of the polymer may be further tailored.
The polymer according to the present invention can be efficiently produced from oL- pinene derived from turpentine. The cyc|ic structure of oL-pinene enables the preparation of polymers with an extent of rings in the backbone, which allows for beneficial structural and thermal properties of the generated materials. Thus, the present invention enables use of abundant renewable building blocks in industrial waste streams to generate polymers with industrially appealing properties, such as appealing glass-transition temperatures and hydrophobicities.
One application of the present invention is in formulations based on curing of the polymer. Such formulations could be used as coatings; barriers, preferably against oxygen and moisture; consumer, marine and automotive articles; as well as in sheet moulding and bulk moulding composites. Thus, in a further aspect, the present invention also relates to coatings, barriers, sheet moulding and bulk moulding composites comprising a polymer according to the present invention. Preferably, the present invention relates to coatings or barriers comprising a polymer according to the present invention.
Thus, in a further aspect, the present invention relates to the use ofa polymer according to the present invention, such as in a coating, in a barrier, in sheet moulding or in bulk moulding composites.
The present invention thus enables fully bio-based coatings exhibiting properties similar to petroleum-based counterparts. Further, through the recycling of waste streams within the pulp and paper industry, the present invention also provides a cost-effective way for pulp and paper mills to upcycle their waste and use it directly as part of the protective paper coatings, such as cardboard and food packaging with green barriers.
The invention will now be described by the following examples which do not limit the invention in any respect. All cited documents and references mentioned herein are incorporated by reference in their entireties.
EXAMPLES EXAMPLE 1 Synthesis of 1-(1'-hydroxyethyl)-3-(2"-hydroxyethyl)-2,Z-dimethylcyclobutane (HHDC) A solution of oL-pinene (50 g, 367 mmol) in I\/|e0H (100 ml) and CHZCIZ (400 ml) was stirred at -76 °C, purged with an 03/02 mixture (200 l/h, 290 mA) until 1 equivalent (367 mmol) of 03 was absorbed (indicated by colour change). The reaction was afterwards purged with oxygen, treated with NaBH4 (42.4 g, 1.12 mol) and stirred for 4 h at room temperature. Afterwards 5M hydrochloric acid was added until the pH reached 1 (about 130 ml). The organic layer was separated, and the aqueous layer was washed three times with ethyl acetate. The organic layers were combined, dried over IV|gS04 and concentrated under reduced pressure. The crude product was purified using column chromatography resulting in the diol as transparent oil with a yield of 65% (240 mmol, 41g).
EXAMPLE 2 Synthesis of polyester resins by polycondensation Four different polyester compositions were prepared by charging 2.5 g of HHDC monomer (prepared according to Example 1), dimethyl maleate (DMM), dimethyl itaconate (DMI), and dimethyl furandicarboxylate (DM-FDCA) into a round bottom flask (25 ml) according to ratios seen in Table 1 along with 2-3 ml of p-xylene and optionally a radical inhibitor, mequinol (5 wt% of total monomer weight). The reaction vessel was connected to a Dean-Stark setup and lowered into an oil bath at 160°C. Reaction was started with injection of catalyst Ti(0Bu)4 (7 mol% of total monomer amount). The attached solvent trap was filled with p-xylene. The reaction was stopped once SEC- analysis showed molecular weights in the range of 4k-8k Da. The resulting polymer was precipitated twice in ice-cold methanol and dried under vacuum.
EXAMPLE 3 Curing of HHDC-based polyester coatings HHDC-based polymers (prepared in accordance with Example 2), trimethylolpropane tris(3-mercaptopropionate) (thiol agent TI\/ITP) (1:1 molar ratio of thiol to unsaturations), UV-curing agent lrgacure 651 (1 wt% of resin weight) and solvent butyl acetate (40 wt% of resin weight) were mixed and then poured on to substrate using a box applicator (150 pm). For producing free standing film, an additional droplet of releasing agent silicone was added to the wet resin mixture. Coatings were subjected to UV-light until FT-IR showed a significant decrease in the signal originating from C=C at 1600-1680 cm'1. Successful crosslinking was further corroborated by the fact that the films were insoluble in chloroform and EtOAc, two solvents that solubilizes the uncured polyeste rs.
Characterization instrumentation and methods GC-MS (Shimadzu, GCMS-QP2010 Ultra) was performed on an Rxi®-5ms (30 m, 0.25 mm [inner diameter], 0.25 pm [film thickness], RESTEK). The temperature program was set at 70 °C, before increasing to 300 °C with a rate of 20 °C/min and finally increased to 350 °C with a rate of5 °C/min before holding at 350 °C for 10 min. For I\/IPLC, a Biotage lsolera Four system equipped with a UV detector and Biotage KP-Sil SNAP Cartridge columns was used. 1H (400 MHz) and BC (100 MHz) NMR spectra were recorded with a Bruker Avance AM 400 instrument. The signal ofthe deuterated solvent CDCI; (ó'= 7.26 ppm47) was used as reference. For SEC, a TOSOH EcoSEC HLC-8320GPC system was used equipped with an EcoSEC RI detector and three PSS PFG 5 pm columns (microguard, 100 Ã, and 300 Ã). Poly(methyl methacrylate) (PI\/|I\/IA) standards were used for calibration and toluene was used as internal standard.
DSC was performed using a I\/lettler Toledo DSC 820 module. Samples (5-10 mg) were prepared in 100 pL aluminium crucibles. The samples were subjected to heating from to 170 °C (or 160 °C), then cooled to -60 °C, and then heated again to 170 °C (or 160 °C) at a heating/cooling rate of 10 °C/min under nitrogen flow (50 mL/min). The data obtained from the second heating was used for analyses. For TGA, a I\/Iettler Toledo TGA/DSC1 instrument was used. Samples (5-7 pg) were prepared in 70 pL alumina crucibles and heated from 40 to 700 °C at a heating rate of 10 °C/min under a nitrogen flow (50 mL/min).
FTIR was performed on a Perkin-Elmer Spectrum 100 FT-IR instrument equipped with a single reflection ATR system and a I\/IIR-TGS detector using a MKII Golden Gate (Graseby Specac Ltd, Kent, England). Spectra were recorded over the range 4000-600 cm'1 and based on 16 scans at an average 4.0 cm'1 resolution.
Cobb method for determining water absorptiveness of carton coated with biobased coatings. Coated carton, ICG 280 for Cobb-testing was acquired by Iggesund Paperboard. Cobb-setup was made with inspiration from the official ISO-535 since a proper setup was not available. |nstead of a metal cylinder with clamping potential, a rubber cylinder with an inner diameter of 3.3 cm was used. |nstead of clamping, a circular metal weight was used to fixate the cylinder. To determine baseline absorptiveness, three pieces of untreated carton where subjected to Cobbm-test. Another three-set of UV-treated carton was also subjected to Cobb test to account for substrate effects on absorptiveness post curing. Lastly all four HHDC-based polyester resins were coated onto the carton and cut into three samples of each. Samples plates with a diameter 2 5 cm. Besides these ad-hoc solutions, testing procedure follows as described by ISO- standard. Absorptiveness, A is calculated by the following expression. F is the inverse of 3 the surface area in the unit m" .
A I F(mwet _ mdry) Contact angle measurements to determine wettability of the four terpene-based polyester coatings, untreated carton, and UV-treated carton (ICG 280, Iggesund Paperboard). Coated substrates used were same as for the Cobb-test. Three droplets of about 10-15 ml of each sample were measured. Contact angle of left and right side where averaged and then combined into a total average for all three droplets.
Measurements were made with an OCA20 (Data Physics).
Dynamical mechanical analysis (DMA) experiments were performed with a DMA Q800 from TA Instruments equipped with a tensile fixture. Samples of prepared coating a geometry of 30-5-0.07 mm3 strips fixated with 16-18 mm between anchoring points. Samples are initially cooled down to -100°C by nitrogen cooling. Then heated with a rate of 5°C/min up to 180°C while subdued to an oscillating axial stress to the sample to induce a periodic pre-determined strain of 7% at frequency 1 Hz. Glass-transition temperatures are reported as the temperature corresponding to the maximum value of the resulting tan-ö curve.
Composition The composition of the copolymers prepared according to Example 2 was determined by 1H NI\/IR. Respective lH-NIVIR spectra of the synthesized polymers are displayed in Figure 1. The molecular weights were calculated by the ratio of signals within the polymers 7.2 > ö > 4 ppm to signals stemming from end groups 4 > ö > 3.5 ppm. The ratio was further multiplied by the mass ofthe repeating units for respective polymer to determine molecular weights. The results are presented in Table 2. 11 Table 1 Sample "ímnmïïkïrf Reaction Charged Ratio A:Btot coïrlšïïiïign A,B,B a - = ID t|me [h] (B+B* Btot) (A:B:B*)[%] 16 HHDc, DMM 7 1.0111 49.s150.2 18 HHDc, DM| 39 1.0211 50.9149.1 HHDc DMM 20 ' ' 7 1.021 0.5 0.5 50.6123.1126.3 DM-FDcA ( J' ) 21 HHDQDIVH' 16 102- 05 05 501-239-26 DNHIDCA ..(.+.) .. .. a) A=HHDC, B=DMM Or DMI, B*=DM-FDCA The polymers were further characterized by SEC to study the molecular structure, while thermal degradation was studied using thermal gravimetric analysis (TGA). Glass transition temperatures were analyzed using differential scanning calorimetry (DSC) and DMA (dynamic mechanical analysis). The results are presented in Table 2. Molecular weight distribution curves are shown in Figure 2 of the four polyester compositions.
Thermal characterization of uncured polyesters Thermal characterization of polymers prepared according to Example 2 is shown in figure 3(a) and 4(a). The TGA thermograms presented in Figure 3(a) show two step degradation profile for all synthesized HHDC based polyesters. A partial decomposition around 100-150°C causes between 4 and 15% mass reduction. Full decomposition starts at 240-250°C for the polyesters containing FDCA, while the itaconate and maleate polyesters have slightly better thermal resistance, decomposing closer to 300°C. Decomposition temperatures (Td-5%) ofthe four polyesters are reported in Table 2. The DSC thermograms are shown in figure 4(a) and extracted values are summarized in Table 2. The polymers pHHDC-DMM and pHHDC-DMI possess glass transition temperatures below room temperature while the polymers containing FDCA display values slightly above. ltaconate-based polymers tend to have slightly lower Tg compared to the maleate based materials. One more carbon in the itaconate compared with the maleate residue facilitates chain movement, thus contributing to lower the Tg, and the endo- 12 double bond of the maleate residues further impairs chain movement due to the spz- hybridization. FDCA-moieties tend to significantly increase Tg. DSC shows no exothermic crystallization trend indicating all polyesters being fully amorphous.
Table 2 Sample ïH-NMR Mn D DSC Tg TGA Td ID Mn [g/mol] [g/mol] (Mw/Mn) [°C] [°C] 16 6384 4453 2.3 17.0 274.8 18 8445 7734 3.0 13.6 258.5 20 6105 4405 1.9 42.3 153.0 21 6242 4248 2.9 32.5 125.4 Thermal characterization of cured polyesters The four polyester coatings prepared according to Example 3, were characterized by TG- analysis and DSC to determine their thermal properties (Table 3). The TGA and DSC thermograms are presented in Figures 3(b) and 4(b), respectively. DSC-derived Tg - values are higher for all four materials compared to uncured polyesters due to the introduced cross-linkages, hindering coordinated chain movement. The two coatings containing FDCA have less amounts of unsaturated groups and thus shows decrease in Tg for the respective materials. Td-5% obtained from TG analysis are quite similar for all four materials being around 270°C. Tensile analysis is conducted by dynamical mechanical analysis (DMA) showing a storage moduli around 2 GPa for all four materials at temperatures below the softening temperature (Ty).
Cobb test and contact analysis To test the materials as protective coatings for paper applications, thin "10 um films were coated on industrial used paper (|CG280; 280g/m2, Iggesund Paper Board) and cured. Results of the Cobb test are all average absorptiveness (A) based on three measurements of each sample (Table 3). To evaluate the obtained values, non-coated carton samples were measured (non-treated and UV-treated). UV irradiated carton had the highest average A-value of 51 [g/m3] while non-treated cardboard had 37 [g/m3]. A significant decrease of water absorptiveness is experienced with all coating resins. Ever 13 so slightly does the two coatings with itaconate-moieties excel with absorptiveness below 2 [g/m3]. For comparison, disposable food service items coated with biobased polymers should have a Cobb-value smaller than 25 [g/m3].46 Contact angle of untreated ca rdboard was 72°. The contact angles ofthe two references after UV- and heat treatment were 52° and 81°, respectively. lt shows that UV irradiation has a negative impact on the paper material inherent properties.
Table 3 Sample ID Dsc rg TG? rd C24 c0b13120 Monomers(A,B) [ C] [ C] [] [] non-treated _ _ _ 72 37 UV-treated _ _ _ 52 51 16 TMTP HHDc, D|v||v| 62 270 72 2.7 18 TMTP HHDc, D|v|| 58 274 ss 1.1 20 TMTP HHDc, DMM, FDcA 47 265 62 2.1 21 TMTP HHDc, Divn, FDcA 62 267 92 1.5 14

Claims (10)

1. 1. CLAIMS 1.
2. A polymer comprising repeating units of formula (I ) R4 A R* Bïzs f \ R2 Rf* u) wherein A is selected from O, NRG, -C(O)-O- and C=O; B is selected from O, NRG, -O-C(O)-, C=O, and E-C(O)-X-C(O)-, wherein E is O or NRG; Rl, RZ, R3, R4, R5 and R6 each independently are selected from H, C14; alkyl, halogenated C14; alkyl; X is selected from C1-7 alkyl, CN alkenyl, which may be mono- or diunsaturated, C34; cycloalkyl, C34; cycloalkenyl, diamino- C24; alkyl, diamino- C24; alkenyl, and a 4- to 6-membered saturated or unsaturated ring optionally containing one or more hetero atoms selected from N, O, S and Si, which 4- to 6-membered saturated or unsaturated ring is optionally substituted; and wherein any alkyl and alkenyl may be linear or branched and is optionally substituted with a halogen or an aromatic unit; and m is an integer from 10 to A polymer according to claim 1, wherein B is E-C(O)-X-C(O)-, wherein E is O or NRG.
3. A polymer obtainable by polycondensation or polyadduct formation of at least two different monomers, characterized in that a first monomer is 1-(1'- hydroxyethyl)-3-(2"-hydroxyethyl)-2,2-dimethylcyclobutane (HHDC), and a second monomer is selected from a dicarboxylic acid, an anhydride thereof or a diester thereof, or an isocyanate.
4. The polymer according to claim 3 wherein the second monomer is selected from malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, aspartic acid, itaconic acid, maleic acid, 2,5-furan dicarboxylic acid, dimethyl maleate (DI\/|I\/|), dimethyl itaconate (DMI), and dimethyl furandicarboxylate (DI\/I-FDCA), and mixtures thereof.
5. A method for preparing the polymer according to claim 1 by reacting 1-(1'- hydroxyethyl)-3-(2"-hydroxyethyl)-2,2-dimethylcyclobutane (HHDC) with a dicarboxylic acid, an anhydride or a diester thereof, or an isocyanate.
6. The method according to claim 5, comprising a step of mixing the 1-(1'- hydroxyethyl)-3-(2"-hydroxyethyl)-2,2-dimethylcyclobutane (HHDC) with a dicarboxylic acid or a diester thereof to obtain a mixture.
7. The method according to claim 6, wherein the dicarboxylic acid or diester is selected from malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, aspartic acid, itaconic, maleic acid, 2,5-furan dicarboxylic acid, dimethyl maleate (DI\/|I\/|), dimethyl itaconate (DMI), and dimethyl furandicarboxylate (DM-FDCA), and mixtures thereof.
8. The method according to any one of claims 5 to 7, wherein the mixture may further comprise a polymerisation inhibitor, preferably a phenolic radica| inhibitor, such as mequinol.
9. The method according to any one of claims 5 to 8, comprising a step of curing the polymer to obtain a cross-linked polymer.
10. Use of a polymer according to any one of claims 1 to 4, in a coating or barrier. 16
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Citations (4)

* Cited by examiner, † Cited by third party
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US20170101488A1 (en) * 2015-10-08 2017-04-13 Northwestern University Apopinene as a Biorenewable Monomer for Ring-Opening Metathesis Polymerization
US20190002387A1 (en) * 2017-06-30 2019-01-03 The University Of North Dakota Cyclobutane-1, 3-diacid building blocks
US20190106383A1 (en) * 2017-10-06 2019-04-11 International Business Machines Corporation Pinene-derived diisocyanates
WO2020168177A1 (en) * 2019-02-14 2020-08-20 University Of Florida Research Foundation Methods and compositions for biorenewable polyesters derived from camphoric acid

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US20170101488A1 (en) * 2015-10-08 2017-04-13 Northwestern University Apopinene as a Biorenewable Monomer for Ring-Opening Metathesis Polymerization
US20190002387A1 (en) * 2017-06-30 2019-01-03 The University Of North Dakota Cyclobutane-1, 3-diacid building blocks
US20190106383A1 (en) * 2017-10-06 2019-04-11 International Business Machines Corporation Pinene-derived diisocyanates
WO2020168177A1 (en) * 2019-02-14 2020-08-20 University Of Florida Research Foundation Methods and compositions for biorenewable polyesters derived from camphoric acid

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