BIO-monomers, polymers and methods of preparing the same

Abstract

The present invention relates to bio-monomers and bio-polymers produced from said monomers. The invention also relates to methods for producing both the monomeric and polymeric compounds that are substantially optically transparent and biodegradable.

Description

[0001] BIO-MONOMERS, POLYMERS AND METHODS OF PREPARING THE SAME

[0002] Field

[0003] The present invention relates to bio-monomers and bio-polymers produced from said monomers. The invention also relates to methods for producing both the monomeric and polymeric compounds that are substantially optically transparent and biodegradable.

[0004] Background

[0005] Materials that allow the transmission of light waves to pass through are generally referred to as optically transparent. Some classic examples include undoped pure widow glass, transparent ceramics and even clear spring water. When light encounters a material, it can interact with it in several different ways. These interactions depend on the wavelength of the light and the nature of the material. Photons interact with a material by some combination of reflection, absorption and transmission. Optically transparent materials such as undoped glass and clear water, transmit much of the light and reflect very little.

[0006] Transparency within the field of optics, which is also referred to pellucidity or diaphaneity, is the physical property of allowing light to pass through the material without appreciable scattering of light. On a macroscopic scale the photons can be said to follow Snell's law. Translucency (also called translucence or translucidity') allows light to pass through, but does not necessarily follow Snell's law; the photons can be scattered at either of the two interfaces, or internally, where there is a change in index of refraction. Put another way, a translucent material is made up of components with different indices of refraction. A transparent material is made up of components with a uniform index of refraction. Transparent materials appear clear to the eye, with the overall appearance of one colour, or any combination leading up to a brilliant spectrum of every colour. The opposite property of translucency is opacity. Transparent materials possess several key characteristics that make them distinct:

[0007] • Optical Clarity: Transparent materials are known for their high level of optical clarity, which means they allow light to pass through them with minimal distortion. This property makes them ideal for applications where visual clarity is crucial, such as in windows, eyeglasses, and camera lenses.

[0008] • Refractive Index: The refractive index is a measure of how much a material bends light as it passes through it. Transparent materials typically have a higher refractive index compared to other materials, which gives them unique optical properties, such as the ability to bend or focus light. This property is utilized in lenses for optical devices like telescopes and microscopes.

[0009] • Transparency Range: Transparent materials can transmit light within a specific range of wavelengths, known as the transparency range. The transparency range can vary depending on the material, and it determines the colour or wavelength of light that can pass through the material.

[0010] • Physical Properties: Transparent materials can have varying physical properties, such as hardness, flexibility, and thermal stability, depending on the material from which they are made. For example, glass is known for its hardness and resistance to scratches, making it suitable for applications like windows and glassware. On the other hand, transparent plastics like polycarbonate are known for their flexibility and impact resistance, making them suitable for applications like safety goggles and car windows.

[0011] Transparent materials have many applications across various industries, due to varying and unique properties, including:

[0012] • Architecture and Construction: Transparent materials like glass are extensively used in the construction industry for windows, skylights, and facades to allow natural light to enter the buildings, creating a pleasant and energy-efficient environment. Transparent materials also find applications in structural components like staircases, balustrades, and canopies, where aesthetics and functionality are important.

[0013] • Electronics: Transparent materials are widely used in the electronics industry for displays, touchscreens, and optical sensors. Transparent conductive materials like indium tin oxide (ITO) are used as coatings on glass and plastics to create transparent electrodes for devices like smartphones, tablets, and LCD screens. • Automotive: Transparent materials like glass and polycarbonate are used in the automotive industry for windshields, windows, and headlights. These materials provide excellent optical clarity, impact resistance, and durability, ensuring the safety and comfort of passengers.

[0014] • Optics: Transparent materials like glass and plastics are used in the manufacturing of lenses, prisms, and optical filters for various optical devices, including cameras, microscopes, telescopes, and spectrometers. These materials enable the manipulation and control of light for imaging, magnification, and analysis.

[0015] • Packaging: Transparent plastics like PET (polyethylene terephthalate) and PVC (polyvinyl chloride) are widely used in the packaging industry for food, beverages, and consumer products. Transparent packaging allows consumers to see the contents of the package, enhancing transparency and visual appeal, while also providing protection and preservation of the contents.

[0016] • Medical and Pharmaceutical: Transparent materials are used in various medical and pharmaceutical applications, such as in the manufacturing of medical devices, drug containers, and packaging. Transparent plastics like PVC, PET, and polystyrene are commonly used due to their biocompatibility, durability, and transparency, allowing for easy visual inspection and monitoring of medical processes.

[0017] • Displays and Signage: Transparent materials are used in displays and signage applications to create eye-catching visual effects. Transparent LED displays, holographic displays, and projection screens are examples of how transparent objects are used to create unique and immersive visual experiences in advertising, retail, and entertainment.

[0018] • Art and Design: Transparent objects are also used in art and design, where their unique optical properties are creatively utilized to create sculptures, installations, and other artistic pieces. Transparent materials like glass, acrylic, and resin are used by artists and designers to create visually stunning and innovative artworks.

[0019] • Coating applications: Transparent materials may be used as durable coating materials for biosensors, as well as timber and ceramic surfaces. Furthermore transparent materials can provide the following benefits:

[0020] • Enhanced Visual Clarity: Transparent materials provide excellent optical clarity, allowing for clear and unobstructed views. This makes them ideal for applications where visual clarity is crucial, such as windows, displays, and lenses.

[0021] • Energy Efficiency: Transparent materials like glass can help in reducing energy consumption in buildings by allowing natural light to enter, reducing the need for artificial lighting during the day. This results in energy savings and a more sustainable approach to building design.

[0022] • Aesthetics and Design Flexibility: Transparent materials offer a wide range of design possibilities due to their versatility and ability to be shaped and moulded into various forms. They can add aesthetic appeal to architectural designs, displays, packaging, and art pieces, enhancing the overall visual experience.

[0023] • Durability and Impact Resistance: Transparent materials like polycarbonate offer high impact resistance, making them suitable for applications where safety and durability are critical, such as in automotive windshields, safety goggles, and protective screens.

[0024] • Customizability: Transparent materials can be customized in terms of shape, size, and colour to suit specific requirements. This makes them versatile and adaptable to different applications and industries such as 3D-printable polymers.

[0025] There is a need to develop materials, and in particular new polymeric materials which can improve upon the existing pool of commercially important transparent materials and in particular the development of optically transparent materials which are practically durable and biodegradable.

[0026] Summary of the invention

[0027] The invention is predicated (in part) by the discovery that many thiol-ene based polymers, which are derived from levoglucosenone (LGO) and Levoglucosan (LGA) based monomers, are substantially optically transparent and therefore can be suitably used in the field of optics. Levoglucosan (LGA) (1,6-anhydro-P-d-glucopyranose) is a dehydrated glucose containing a ketal functional group and is a renewable chemical obtained in high yields from pyrolysis of biomass such as cellulose and starch. Biomass is currently the largest source of renewable carbon-based energy. Lignocellulosic biomass, consisting of cellulose (40-50%), hemicellulose (15-25%) and lignin (15-30%) is the most abundant source of carbon-based molecules. Accordingly, LGA is a potentially valuable starting material for the production of other commercially important materials.

[0028] LGA can be converted to many different higher value chemicals such as levoglucosenone (1,6- Anhydro-3,4-dideoxy-p-d-g / ycero-hex-3-enopyranos-2-ulose) (LGO), levoglucosenol (LGO- OH), levulinic acid, furfural, and 5-hydroxymethylfurfural directly or through a glucose intermediate via chemical, catalytic and biochemical processes.

[0029] LGA is also found naturally in many organisms such as Lotus creticus, and Lotus filicaulis.

[0030] More than 90% of today’s synthetic polymers are derived from fossil fuels, 87% of these contribute to plastic waste. The largest source of renewable carbon is biomass waste. Cellulose accounting for up to 40-50 % of biomass streams. The pyrolysis of cellulose yields many C6 compounds including Levoglucosan (LGA). The present inventors have developed novel monomers and polymers derived from LGA and LGA analogues, such as LGO.

[0031] LGA has been underutilised as a renewable source for the synthesis of polymers and thermosets. With its chemical functionality, LGA offers the tailored modification for a specific application (tunable glass transition temperature, Tg). It is estimated to be produced from biomass at a low cost providing the ability to become a competitive alternative to petroleum- derived materials. Thermosets are a common class of polymer used in many everyday plastic applications. This is due to their high shape stability, solvent resistance and thermal stability. Currently, it is standard to synthesise thermoset materials from petroleum-derivatives. Thus, biomass derived materials present as a possible sustainable alternative to produce thermoset materials. Levoglucosenone (LGO), is an abundant platform material, most commonly used to prepare the bio-based solvent Cyrene™. LGO is prepared on an industrial scale via the Furacell process. LGO has a synthetically valuable structure, possessing stereogenic centres and providing access to a variety of natural and unnatural compounds. The 1,6-anhydro bridge locks the pyranose ring in particular conformation, sterically hindering the P-face of the molecule, resulting in excellent facial selectivity. LGO readily reacts via six different major synthetic pathways. The most common is reductive ring cleavage to synthesise deoxy sugars, followed by the well published Baeyer-Villiger reaction to generate the platform molecule ((S)- y-hydroxymethyl-a,P-butenolide, HBO) for pharmaceutical synthesis. Halogenation of the six membered ring is possible, as is hydrogenation of the double bond, producing Cyrene™. Cycloaddition to the double bond introduces various functionalities such as epoxy groups. Lastly, addition reactions (either 1,4- or 1,2-addition) provides a pathway to introduce a nucleophile into the LGO ring structure.

[0032] To prepare polymers the present inventors utilise thiol-ene chemistry which is adapted to the synthesis of thermosets, whereby a LGA or LGO derived monomer with an unsaturated carbon bond - alkenes or alkynes (for example allyl or acrylate functionality) - can be cured with stoichiometrically equivalent thiol / mercapto monomers, via UV light (with added initiator).

[0033] In one aspect, the present invention provides compounds of the general formula (I): or salts thereof, wherein:

[0034] R1is selected from H, OH, -O(CH2)nCR6CH2, -OC(X)(CH2)nCR6CH2, -OC(X)(CH2)nOC(X)CR6CH2, -N(C(O)C1-C4)( (CH2)nCR6CH2), -OC(O)(NR7)(CH2)nCR6CH2, -O-optionally substituted arylene-(CH2)nCR6CH2, -OC(X)- optionally substituted arylene- (CH2)nCR6CH2, -O(CH2)nCCH, -OC(X)(CH2)nCCH, -N(C(O)C1-C4)( (CH2)nCCH), -O- optionally substituted arylene-(CH2)nCCH, -OC(X)- optionally substituted arylene- (CH2)nCCH; -O(CH2)nCHCH2O, -OC(X)(CH2)nCHCH2O -OC(X)(CH2)nOC(X)CHCH2O, -N(C(O)C1-C4)( (CH2)nCHCH2O), -OC(O)(NR7)(CH2)nCHCH2O, -O-optionally substituted arylene-(CH2)nCHCH2O, or -OC(X)- optionally substituted arylene-(CH2)nCHCH2O;

[0035] R2is selected from H, OH, -O(CH2)nCR6CH2, -OC(X)(CH2)nCR6CH2, -OC(X)(CH2)nOC(X)CR6CH2, -N(C(O)C1-C4)( (CH2)nCR6CH2), -OC(O)(NR7)(CH2)nCR6CH2, -O- optionally substituted arylene-(CH2)nCR6CH2, -OC(X)- optionally substituted arylene- (CH2)nCR6CH2, -O(CH2)nCCH, -OC(X)(CH2)nCCH, -N(C(O)C1-C4)( (CH2)mCCH), -O- optionally substituted arylene-(CH2)nCCH, -OC(X)- optionally substituted arylene - (CH2)nCCH, -O(CH2)nCHCH2O, -OC(X)(CH2)nCHCH2O -OC(X)(CH2)nOC(X)CHCH2O, -N(C(O)C1-C4)( (CH2)nCHCH2O), -OC(O)(NR7)(CH2)nCHCH2O, -O-optionally substituted arylene-(CH2)nCHCH2O, or -OC(X)- optionally substituted arylene-(CH2)nCHCH2O;

[0036] R3is selected from -(CH2)nCR6CH2, -C(X)(CH2)nCR6CH2, -C(X)(CH2)nOC(X)CR6CH2, -optionally substituted arylene-(CH2)nCR6CH2, -C(O)(NR7)(CH2)nCR6CH2, -C(X)- optionally substituted arylene-(CH2)nCR6CH2, -(CH2)nCCH, -C(X)(CH2)nCCH, - optionally substituted arylene-(CH2)nCCH, -C(X)-optionally substituted arylene - (CH2)nCCH, -(CH2)nCHCH2O, -C(X)(CH2)nCHCH2O -C(X)(CH2)nOC(X)CHCH2O, - C(O)(NR7)(CH2)nCHCH2O,

[0037] -optionally substituted arylene-(CH2)nCHCH2O, or -C(X)- optionally substituted arylene - (CH2)nCHCH2O; n is an integer selected from 0 to 7 ; X is O or S;

[0038] - refers to an optional double bond;

[0039] R6is H or methyl;

[0040] R7is H, Cl -4 alkyl or optionally substituted phenyl; and wherein the following compounds are excluded: In particular embodiments n is an integer selected from 1 to 7.

[0041] In a further particular embodiment the - refers to a double bond.

[0042] In a further particular embodiment the > - refers to a double bond and n is an integer selected from 1 to 7.

[0043] In a particular embodiment the compounds of the formula (I) are compounds of formula (la): or salts thereof, wherein:

[0044] R1is selected from H, OH, -O(CH2)nCR6CH2, -OC(X)(CH2)nCR6CH2, -OC(X)(CH2)nOC(X)CR6CH2, -N(C(O)C1-C4)( (CH2)nCR6CH2), -OC(O)(NR7)(CH2)nCR6CH2, -O-optionally substituted arylene-(CH2)nCR6CH2, -OC(X)- optionally substituted arylene- (CH2)nCR6CH2, -O(CH2)nCCH, -OC(X)(CH2)nCCH, -N(C(O)C1-C4)( (CH2)nCCH), -O- optionally substituted arylene-(CH2)nCCH, -OC(X)- optionally substituted arylene- (CH2)nCCH, -O(CH2)nCHCH2O, -OC(X)(CH2)nCHCH2O -OC(X)(CH2)nOC(X)CHCH2O, -N(C(O)C1-C4)( (CH2)nCHCH2O), -OC(O)(NR7)(CH2)nCHCH2O, -O-optionally substituted arylene-(CH2)nCHCH2O, or -OC(X)- optionally substituted arylene-(CH2)nCHCH2O;

[0045] R2is selected from H or OH; R3is selected from -(CH2)nCR6CH2, -C(X)(CH2)nCR6CH2, -C(X)(CH2)nOC(X)CR6CH2, -optionally substituted arylene-(CH2)nCR6CH2, -C(O)(NR7)(CH2)nCR6CH2, -C(X)- optionally substituted arylene-(CH2)nCR6CH2, -(CH2)nCCH, -C(X)(CH2)nCCH, - optionally substituted arylene-(CH2)nCCH, -C(X)-optionally substituted arylene - (CH2)nCCH, -(CH2)nCHCH2O, -C(X)(CH2)nCHCH2O -C(X)(CH2)nOC(X)CHCH2O, - C(O)(NR7)(CH2)nCHCH2O,

[0046] -optionally substituted arylene-(CH2)nCHCH2O, or -C(X)- optionally substituted arylene - (CH2)nCHCH2O; n is an integer selected from 1 to 7 ;

[0047] X is O or S;

[0048] - refers to an optional double bond;

[0049] R6is H or methyl;

[0050] R7is H, Cl -4 alkyl or optionally substituted phenyl; and wherein the following compounds are excluded:

[0051]

[0052] In a particular embodiment the compounds of the formula (I) are compounds of formula (lb): or salts thereof, wherein:

[0053] R1is selected from -O(CH2)nCR6CH2, -OC(X)(CH2)nCR6CH2, -OC(X)(CH2)nOC(X)CR6CH2, -N(C(O)C1-C4)( (CH2)nCR6CH2), -OC(O)(NR7)(CH2)nCR6CH2, -O-optionally substituted arylene-(CH2)nCR6CH2, -OC(X)- optionally substituted arylene - (CH2)nCR6CH2, -O(CH2)nCCH, -OC(X)(CH2)nCCH, -N(C(O)C1-C4)( (CH2)nCCH), -O- optionally substituted arylene-(CH2)nCCH, -OC(X)- optionally substituted arylene- (CH2)nCCH, -O(CH2)nCHCH2O, -OC(X)(CH2)nCHCH2O -OC(X)(CH2)nOC(X)CHCH2O, -N(C(O)C1-C4)( (CH2)nCHCH2O), -OC(O)(NR7)(CH2)nCHCH2O, -O-optionally substituted arylene-(CH2)nCHCH2O, or -OC(X)- optionally substituted arylene-(CH2)nCHCH2O; R2is selected from H or OH;

[0054] R3is selected from -(CH2)nCR6CH2, -C(X)(CH2)nCR6CH2, -C(X)(CH2)nOC(X)CR6CH2, -optionally substituted arylene-(CH2)nCR6CH2, -C(O)(NR7)(CH2)nCR6CH2, -C(X)- optionally substituted arylene-(CH2)nCR6CH2, -(CH2)nCCH, -C(X)(CH2)nCCH, - optionally substituted arylene-(CH2)nCCH, -C(X)-optionally substituted arylene - (CH2)nCCH, -(CH2)nCHCH2O, -C(X)(CH2)nCHCH2O -C(X)(CH2)nOC(X)CHCH2O, - C(O)(NR7)(CH2)nCHCH2O,

[0055] -optionally substituted arylene-(CH2)nCHCH2O, or -C(X)- optionally substituted arylene - (CH2)nCHCH2O; n is an integer selected from 1 to 7 ;

[0056] X is O or S;

[0057] - refers to an optional double bond; and

[0058] R6is H or methyl; and

[0059] R7is H, Cl -4 alkyl or optionally substituted phenyl.

[0060] In a particular embodiment the compounds of the formula (I) are compounds of formula (Ic): or salts thereof, wherein: R1is selected from H, OH, -O(CH2)nCR6CH2, -OC(X)(CH2)nCR6CH2, -OC(X)(CH2)nOC(X)CR6CH2, -N(C(O)C1-C4)( (CH2)nCR6CH2), -OC(O)(NR7)(CH2)nCR6CH2, -O-optionally substituted arylene-(CH2)nCR6CH2, -OC(X)- optionally substituted arylene - (CH2)nCR6CH2, -O(CH2)nCCH, -OC(X)(CH2)nCCH, -N(C(O)C1-C4)( (CH2)nCCH), -O- optionally substituted arylene-(CH2)nCCH, -OC(X)- optionally substituted arylene - (CH2)nCCH, -O(CH2)nCHCH2O, -OC(X)(CH2)nCHCH2O -OC(X)(CH2)nOC(X)CHCH2O, -N(C(O)C1-C4)( (CH2)nCHCH2O), -OC(O)(NR7)(CH2)nCHCH2O, -O-optionally substituted arylene-(CH2)nCHCH2O, or -OC(X)- optionally substituted arylene-(CH2)nCHCH2O;

[0061] R2is selected from -O(CH2)nCR6CH2, -OC(X)(CH2)nCR6CH2, -OC(X)(CH2)nOC(X)CR6CH2, -N(C(O)C1-C4)( (CH2)nCR6CH2), -OC(O)(NR7)(CH2)nCR6CH2, -O- optionally substituted arylene-(CH2)nCR6CH2, -OC(X)- optionally substituted arylene- (CH2)nCR6CH2, -O(CH2)nCCH, -OC(X)(CH2)nCCH, -N(C(O)C1-C4)( (CH2)mCCH), -O- optionally substituted arylene-(CH2)nCCH, or -OC(X)- optionally substituted arylene- (CH2)nCCH, -O(CH2)nCHCH2O, -OC(X)(CH2)nCHCH2O -OC(X)(CH2)nOC(X)CHCH2O, -N(C(O)C1-C4)( (CH2)nCHCH2O), -OC(O)(NR7)(CH2)nCHCH2O, -O-optionally substituted arylene-(CH2)nCHCH2O, or -OC(X)- optionally substituted arylene-(CH2)nCHCH2O;

[0062] R3is selected from -(CH2)nCR6CH2, -C(X)(CH2)nCR6CH2, -C(X)(CH2)nOC(X)CR6CH2, -optionally substituted arylene-(CH2)nCR6CH2, -C(O)(NR7)(CH2)nCR6CH2, -C(X)- optionally substituted arylene-(CH2)nCR6CH2, -(CH2)nCCH, -C(X)(CH2)nCCH, - optionally substituted arylene-(CH2)nCCH, -C(X)-optionally substituted arylene - (CH2)nCCH; -(CH2)nCHCH2O, -C(X)(CH2)nCHCH2O -C(X)(CH2)nOC(X)CHCH2O, - C(O)(NR7)(CH2)nCHCH2O,

[0063] -optionally substituted arylene-(CH2)nCHCH2O, or -C(X)- optionally substituted arylene - (CH2)nCHCH2O; n is an integer selected from 1 to 7 ;

[0064] X is O or S; R6is H or methyl;

[0065] R7is H, Cl -4 alkyl or optionally substituted phenyl; and wherein the following compounds are excluded:

[0066] In a particular embodiment the compounds of the formula (I) are compounds of formula (Id): or salts thereof, wherein:

[0067] R1is selected from H, OH, -O(CH2)nCR6CH2, -OC(X)(CH2)nCR6CH2, -OC(X)(CH2)nOC(X)CR6CH2, -N(C(O)C1-C4)( (CH2)nCR6CH2), -OC(O)(NR7)(CH2)nCR6CH2, -O-optionally substituted arylene-(CH2)nCR6CH2, -OC(X)- optionally substituted arylene - (CH2)nCR6CH2, -O(CH2)nCCH, -OC(X)(CH2)nCCH, -N(C(O)C1-C4)( (CH2)nCCH), -O- optionally substituted arylene-(CH2)nCCH, -OC(X)- optionally substituted arylene - (CH2)nCCH, -O(CH2)nCHCH2O, -OC(X)(CH2)nCHCH2O -OC(X)(CH2)nOC(X)CHCH2O, -N(C(O)C1-C4)( (CH2)nCHCH2O), -OC(O)(NR7)(CH2)nCHCH2O, -O-optionally substituted arylene-(CH2)nCHCH2O, or -OC(X)- optionally substituted arylene-(CH2)nCHCH2O;

[0068] R2is selected from H, OH, -O(CH2)nCR6CH2, -OC(X)(CH2)nCR6CH2, -OC(X)(CH2)nOC(X)CR6CH2, -N(C(O)C1-C4)( (CH2)nCR6CH2), -OC(O)(NR7)(CH2)nCR6CH2, -O- optionally substituted arylene-(CH2)nCR6CH2, -OC(X)- optionally substituted arylene- (CH2)nCR6CH2, -O(CH2)nCCH, -OC(X)(CH2)nCCH, -N(C(O)C1-C4)( (CH2)mCCH), -O- optionally substituted arylene-(CH2)nCCH, -OC(X)- optionally substituted arylene- (CH2)nCCH, -O(CH2)nCHCH2O, -OC(X)(CH2)nCHCH2O -OC(X)(CH2)nOC(X)CHCH2O, -N(C(O)C1-C4)( (CH2)nCHCH2O), -OC(O)(NR7)(CH2)nCHCH2O, -O-optionally substituted arylene-(CH2)nCHCH2O, or -OC(X)- optionally substituted arylene-(CH2)nCHCH2O;

[0069] R3is selected from -(CH2)nCR6CH2, -C(X)(CH2)nCR6CH2, -C(X)(CH2)nOC(X)CR6CH2, -optionally substituted arylene-(CH2)nCR6CH2, -C(O)(NR7)(CH2)nCR6CH2, -C(X)- optionally substituted arylene-(CH2)nCR6CH2, -(CH2)nCCH, -C(X)(CH2)nCCH, - optionally substituted arylene-(CH2)nCCH, -C(X)-optionally substituted arylene - (CH2)nCCH, -(CH2)nCHCH2O, -C(X)(CH2)nCHCH2O -C(X)(CH2)nOC(X)CHCH2O, - C(O)(NR7)(CH2)nCHCH2O,

[0070] -optionally substituted arylene-(CH2)nCHCH2O, or -C(X)- optionally substituted arylene - (CH2)nCHCH2O; n is an integer selected from 1 to 7 ;

[0071] X is O or S;

[0072] R6is H or methyl;

[0073] R7is H, Cl -4 alkyl or optionally substituted phenyl; and wherein the following compound is excluded:

[0074] V

[0075] °vH

[0076] So. VH In another aspect the invention provides compounds of formula (II): or salts thereof, wherein: each R1is the same and is selected from H, OH, -O(CH2)nCR6CH2, - OC(X)(CH2)nCR6CH2, -OC(X)(CH2)nOC(X)CR6CH2, -N(C(O)C1-C4)( (CH2)nCR6CH2), -OC(O)(NR7)(CH2)nCR6CH2,

[0077] -O-optionally substituted arylene-(CH2)nCR6CH2, -OC(X)- optionally substituted arylene - (CH2)nCR6CH2, -O(CH2)nCCH, -OC(X)(CH2)nCCH, -N(C(O)C1-C4)( (CH2)nCCH), -O- optionally substituted arylene-(CH2)nCCH, -OC(X)- optionally substituted arylene - (CH2)nCCH, -O(CH2)nCHCH2O, -OC(X)(CH2)nCHCH2O -OC(X)(CH2)nOC(X)CHCH2O, -N(C(O)C1-C4)( (CH2)nCHCH2O), -OC(O)(NR7)(CH2)nCHCH2O, -O-optionally substituted arylene-(CH2)nCHCH2O, or -OC(X)- optionally substituted arylene-(CH2)nCHCH2O; each R2is the same and is selected from H, OH, -O(CH2)nCR6CH2, - OC(X)(CH2)nCR6CH2, -OC(X)(CH2)nOC(X)CR6CH2, -N(C(O)C1-C4)( (CH2)nCR6CH2), -OC(O)(NR7)(CH2)nCR6CH2, -O- optionally substituted arylene-(CH2)nCR6CH2, - OC(X)- optionally substituted arylene-(CH2)nCR6CH2, -0(CH2)nCCH, - OC(X)(CH2)nCCH, -N(C(O)C1-C4)( (CH2)mCCH), -O-optionally substituted arylene- (CH2)nCCH, -OC(X)- optionally substituted arylene-(CH2)nCCH, -O(CH2)nCHCH2O, - OC(X)(CH2)nCHCH2O -OC(X)(CH2)nOC(X)CHCH2O, -N(C(O)C1-C4)( (CH2)nCHCH2O), -OC(O)(NR7)(CH2)nCHCH2O,

[0078] -O-optionally substituted arylene-(CH2)nCHCH2O, or -OC(X)- optionally substituted arylene-(CH2)nCHCH2O; r is an integer selected from 0 to 7 ;

[0079] X is O or S;

[0080] R6is H or methyl; and

[0081] R7is H, Cl -4 alkyl or optionally substituted phenyl.

[0082] In an embodiment and in with reference to the above embodiment all R1and R2are H.

[0083] In another aspect the invention provides compounds of formula (III): or salts thereof, wherein:

[0084] R1is selected from H, OH, -O(CH2)nCR6CH2, -OC(X)(CH2)nCR6CH2, -OC(X)(CH2)nOC(X)CR6CH2, -N(C(O)C1-C4)( (CH2)nCR6CH2), -OC(O)(NR7)(CH2)nCR6CH2, -O-optionally substituted arylene-(CH2)nCR6CH2, -OC(X)- optionally substituted arylene - (CH2)nCR6CH2, -O(CH2)nCCH, -OC(X)(CH2)nCCH, -N(C(O)C1-C4)( (CH2)nCCH), -O- optionally substituted arylene-(CH2)nCCH, -OC(X)- optionally substituted arylene - (CH2)nCCH, -O(CH2)nCHCH2O, -OC(X)(CH2)nCHCH2O -OC(X)(CH2)nOC(X)CHCH2O, -N(C(O)C1-C4)( (CH2)nCHCH2O), -OC(O)(NR7)(CH2)nCHCH2O, -O-optionally substituted arylene-(CH2)nCHCH2O, or -OC(X)- optionally substituted arylene-(CH2)nCHCH2O;

[0085] R2is selected from H, OH, -O(CH2)nCR6CH2, -OC(X)(CH2)nCR6CH2, -OC(X)(CH2)nOC(X)CR6CH2, -N(C(O)C1-C4)( (CH2)nCR6CH2), -OC(O)(NR7)(CH2)nCR6CH2, -O- optionally substituted arylene-(CH2)nCR6CH2, -OC(X)- optionally substituted arylene- (CH2)nCR6CH2, -O(CH2)nCCH, -OC(X)(CH2)nCCH, -N(C(O)C1-C4)( (CH2)mCCH), -O- optionally substituted arylene-(CH2)nCCH, -OC(X)- optionally substituted arylene- (CH2)nCCH, -O(CH2)nCHCH2O, -OC(X)(CH2)nCHCH2O -OC(X)(CH2)nOC(X)CHCH2O, -N(C(O)C1-C4)( (CH2)nCHCH2O), -OC(O)(NR7)(CH2)nCHCH2O, -O-optionally substituted arylene-(CH2)nCHCH2O, or -OC(X)- optionally substituted arylene-(CH2)nCHCH2O; s is an integer selected from 1 to 12; t is an integer selected from 1 to 12;

[0086] X is O or S;

[0087] R6is H or methyl; and

[0088] R7is H, Cl -4 alkyl or optionally substituted phenyl.

[0089] In an embodiment and in with reference to the above embodiment all R1and R2are H.

[0090] In another aspect, the present invention provides polymers which are characterised with a structure based on the polymerisation of at least one or more compounds of formula (I) with at least one or more of the following mercapto compound of formula (IV): wherein R1, R2and R3are as defined above ; and

[0091] R4is selected from C 1-4 alkyl, or -(CH2)OC(O)(CH2)PSH; and where each p is independently an integer of from 1 to 7, excluding the following compound of Formula (I):

[0092] In another aspect, the present invention provides polymers which are characterised with a structure based on the polymerisation of at least one or more compounds of formula (I), (II) or (III) with at least one or more of the following mercapto compound of formula (IV) or (IVa): wherein R1, R2and R3are as defined above ; and

[0093] R4is selected from C 1-4 alkyl, or -(CH2)OC(O)(CH2)PSH; each where each p is independently an integer of from 1 to 7, where z is an integer of from 0 to 7, excluding the following compound of Formula (I):

[0094] In another aspect, the invention provides methods of preparing polymeric compounds of the aspects above, said method comprising:

[0095] (i) providing a mixture of at least one or more of compounds of Formula (I) and subformula thereof , (II), or (III) and at least one or more compounds of Formula (IV) or (IV a) in a suitable solvent;

[0096] (ii) subjecting the mixture of step (i) to UV light for a period time and under conditions to form the polymeric compounds; or subjecting the mixture of step (i) to epoxide ring opening polymerisation conditions to form the polymeric compounds.

[0097] In another aspect, the invention provides methods of preparing the compounds of Formula (I), and subformula thereof, (II), or (III) according to the aspects above, said method comprising:

[0098] (a) dissolving a quantity of Levoglucosan (LGA), Levoglucosenone (LGO) or Levoglucosenol (LGO-OH) in a polar aprotic solvent; and

[0099] (b) reacting the resultant solution of step (a) with an effective quantity of Br-(CH2)nC

[0100] R6CH2, Br-C(X)(CH2)mCR6CH2, Br-N(C(O)Cl-C4)((CH2)mCR6CH2), Br / I-arylene- (CH2)nCR6CH2, Br / Cl-C(X)-arylene-(CH2)mCR6CH2, Br-(CH2)nCCH, Br- C(X)(CH2)mCCH, Br-N(C(O)Cl-C4)((CH2)mCCH), Br / Cl-

[0101] OC(O)(NR7)(CH2)mCR6CH2Br / I-arylene-(CH2)nCCH, or Br / Cl-C(X)-arylene- (CH2)mCCH and a quantity of a base for a time and under conditions to form a compound of Formula (I) - (Id).

[0102] Brief Description of the Figures

[0103] Figure 1 - Depicts some exemplified LGA-derived monomers prepared with a terminal vinyl substituent to ensure participation in thiol-ene polymerisation.

[0104] Figure 2 - Depicts a representative example of the thiol-ene polymerisation according to some embodiments of the present invention.

[0105] Figure 3 - Curing rate of polymerisation reaction according to certain embodiments of the present invention based on Heat Flow (J / g) as a functional of Time (s).

[0106] Figure 4 - The DSC was used to determine the glass transition temperature (Tg) of the thermoset thiol-ene polymer materials of certain embodiments of the present invention. The Tgvalues calculated from the DSC thermograms as depicted.

[0107] Figure 5 - Chart depicting % elongation break and Young's Modulus (MPa).

[0108] Figure 6 - Square samples of polymer were exposed to a series of solvents to assess the extent of solvent swelling. The graph depicts % swelling as determined by calculating the difference between their wet and dry weights.

[0109] Figure 7 - Spectral graph depicting % transmission as a function of wavelength (nm).

[0110] Figure 8 - Photographs of polymers derived from depicted monomers of the invention. Figure 9 - (A) TGA curve of polymers obtained from Monomer 1 (LGO-A11F-4SH), Monomer 6 (LGO-Seb-4SH) and Monomer 8 (LGO-Ole-4SH). (B) First derivative obtained from TGA curve.

[0111] Figure 10- A) GPC chromatograms for the three poly(thioether) formed via bio-derived thiolene emulsion polymerizations; B) TEM image of poly(LA-DT) latex particles; C) dynamic light scattering intensity distribution of the three poly(thioether) latexes formed.

[0112] Figure 11 - (A) Schematic overview of the preparation of core-shell latex particles via seeded emulsion polymerization, using a thiol-ene seed latex (green) and second stage monomer (purple). (B) Morphological map for equilibrium morphologies of polymer nanoparticles based on seed polymer 1 (green) and second polymer 2 (purple) as a function of various interfacial tension terms between each polymer phase as well as water. The target morphology, with a thiol-ene shell, is the upper-left quadrant of the image. Predicted particle morphologies based on interfacial tensions are marked for PS (blue) and PMMA (red).

[0113] Figure 12- A) TGA analysis and B) DTG analysis of the LA-DT seed polymer and LA-DT- Sty after seeded emulsion polymerization. C)1H NMR spectrum of the polymer resulting from the seeded emulsion polymerization with styrene, with key resonances from the thiol- ene and polystyrene polymers highlighted.

[0114] Figure 13 -TEM images of A) poly(LA-DT) and B) poly(LA-DT / styrene) after seeded emulsion polymerization. C) SEM image of poly(LA-DT / styrene)

[0115] Figure 14 - A) Dynamic light scattering intensity distribution of the poly(LA-DT) seed latex (black line) in addition to after seeded emulsion polymerization with styrene (red line) and methyl methacrylate (blue line). B) GPC chromatograms of poly(LA-DT) (black), as well as after seeded emulsion polymerization with MMA (blue) and styrene (red).

[0116] Figure 15 - A) Schematic of proposed chain transfer reaction to poly(thioether) within the particle core; B) GPC chromatograms of polystyrene prepared via free radical polymerization either in the presence or absence of poly(LA-DT). Detailed Description

[0117] As used herein the term "substantially optically transparent" means that the polymeric material of the present invention allows the transmission of light waves through the material without any substantial light absorbance. Optical transparency can be determined by passing light through an object and comparing the intensity of the incident light. The measurement typical may need optical access to both sides of the material for illumination and measurement. One test uses the ASTM D -1003 (Standard Test Method for Haze and Luminous Transmission of Transparent Plastics). Based on this test light transmission over 85% are considered as "transparent". The skilled person will appreciate that the thickness of the material will effect the perceived transparency or optical clarity. In this way and in accordance with the present invention, the present polymeric materials are expected to provide an effective light transmission of greater than 60%, 70%, or greater than 80% (at a thickness of about 3mm).

[0118] "Alkyl" refers to a monovalent alkyl groups that may be straight chained or branched, and preferably have from 1 to 4 carbon atoms, or more preferably 1 to 3 carbon atoms. Examples of such groups include methyl, ethyl, n-isopropyl, iso-propyl, and n-butyl.

[0119] "Alkenyl" refers to a monovalent aliphatic carbocyclic group having at least one carbon-carbon double bond and which may be straight chained or branched, preferably having from 2 to 5 carbon atoms. Examples of such groups include a vinyl or ethenyl group (-CH=CH2), n- propenyl (-CH2CH=CH2), zso-propenyl (-C(CH3)=CH2), but-2-enyl (-CH2CH=CHCH3), and the like.

[0120] "Alkynyl" refers to a monovalent aliphatic carbocyclic group having at least one carbon-carbon triple bond and which may be straight chained or branched, preferably having from 2 to 5 carbon atoms. Examples of such groups include an acetylene or ethynyl group (-C=CH), propargyl (-CH2C=CH), and the like.

[0121] "Arylene" refers to a divalent unsaturated aromatic carbocyclic group having a single ring (e.g. phenyl) or multiple condensed rings (e.g. naphthyl, anthracenyl), preferably having from 6 to 14 carbon atoms. Examples of aryl groups include phenylene, naphthylene , anthracenylene and the like. Preferably the arylene is an optionally substituted phenylene. “Protecting group” as used herein means a temporary modification of a potentially reactive functional group which protects it from undesired chemical transformations. Examples of such protecting groups include esters of carboxylic acids, silyl ethers of alcohols, and acetals and ketals of aldehydes and ketones, respectively. The field of protecting group chemistry has been reviewed (Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991).

[0122] The term "optionally substituted" means that a group may include one or more substituents. One or more hydrogen atoms on the group may be replaced by substituent groups independently selected from halogens (for example halo alkyl such as -CF3 or -CF2H), C1-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, -(CH2)pC3-7 cycloalkyl, -(CH2)PC4-7 cycloalkenyl, -(CH2)Paryl, -(CH2)Pheterocyclyl, -(CH2)Pheteroaryl, -C6H4S(O)qCi-6 alkyl, -C(Ph)3, -CN, -OR, -O- (CH2)I-6-R, -O-(CH2)I-6-OR, -OC(O)R, -C(O)R, -C(O)OR, -OC(O)NR'R", -

[0123] NR'R", -NRC(O)R', -NRC(O)NR'R", -NRC(S)NR'R", -NRS(O)2R', -NRC(O)OR', -C(NR)NR' R", -C(=NOR')R, -C(=NOH)NR'R", -C(O)NR'R", -C(=NCN)-

[0124] NR'R", -C(=NR)NR'R", -C(=NR')SR", -NR'C(=NCN)SR", -CONRSO2R', -C(S)NR'R", - S(O)qR, -SO2NR'R", -SO2NRC(O)R', -OS(O)2R, -PO(OR)2and -NO2; where p is 0-6, q is 0-2 and each R, R' and R" is independently selected from H, C1-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, C3-7 cycloalkyl, C4-7 cycloalkenyl, aryl, heterocyclyl, heteroaryl, C1-6 alkylaryl, C1-6 alkylheteroaryl, and C1-6 alkylheterocyclyl, wherein the alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heterocyclyl, heteroaryl, C1-6 alkylaryl, C1-6 alkylheteroaryl, or C1-6 alkylheterocyclyl, may be optionally substituted with one to six of same or different groups selected from halogen, hydroxy, lower alkyl, lower alkoxy, -CO2H, CF3, CN, phenyl, NH2 and -NO2; or when R' and R" are attached to the same nitrogen atom, they may, together with the atom to which they are attached, form a 5 to 7 membered nitrogen containing heterocyclic ring. A list of optional substituents includes: halogen (in particular, Cl, Br or F), Ci-6 alkyl, Ci-6 alkoxy, C2-6 alkenyl, C2-6 alkynyl, C1-6 haloalkyl (in particular -CF3), C1-6 haloalkoxy (such as -OCF3), C1-6 alkoxy(Ci-6)alkyl, C3-6 cycloalkyl, -OH, phenyl, benzyl, phenoxy, benzyloxy, benzoyl, -NH2, -NHC1-4 alkyl, -N(CI-4alkyl)2, -CN, -NO2, mercapto, -P=O(OH)(NH2), - S(O)2NH2, -S(O)2NHCI-4 alkyl, -S(O)2N(CI-4 alkyl)2, C 1-6 alkylcarbonyl, C 1-6 alkoxycarbonyl, CO2H, -S(O)R"' (where R'" is lower alkyl or cycloalkyl) and -S(O)2R"' (where R'" is lower alkyl, cycloalkyl or OH).

[0125] Unless otherwise defined and only in respect of the ring atoms of non-aromatic carbocyclic or heterocyclic compounds, the ring atoms of such compounds may also be optionally substituted with one or two =0 groups, instead of or in addition to the above described optional substituents.

[0126] When the optional substituent is or contains an alkyl, alkenyl, alkynyl, alkoxy, alkoxyalkyl, cycloalkyl, aryl, heteroaryl or heterocyclyl group, the group may itself be optionally substituted with one to six of the same or different substituents selected from halogen, C1-6 alkyl, C1-6 alkoxy, C2-6 alkenyl, C2-6 alkynyl, C1-6 haloalkyl (in particular -CF3), C 1-6 haloalkoxy (such as - OCF3), -OH, phenyl, benzyl, phenoxy, benzyloxy, benzoyl, -NH2, -NHC1-4 alkyl, -N(CI-4 alkyl)2, -CN, -NO2, mercapto, -P=0(0H)(NH2), -S(O)2NH2, -S(O)2NHCI-4alkyl, -S(O)2N(CI- 4 alkyl)2, C 1-6 alkylcarbonyl, C 1-6 alkoxycarbonyl, CO2H, -S(O)R"' (where R'" is lower alkyl or cycloalkyl) and -S(0)2R"' (where R'" is lower alkyl, cycloalkyl or OH).

[0127] In certain embodiments:

[0128] R1and R2is independently selected from -O(CH2)nCR6CH2, -OC(X)(CH2)nCR6CH2, - 0C(X)(CH2)nOC(X)CR6CH2, -N(C(O)C1-C4)( (CH2)nCR6CH2), OC(O)(NR7)(CH2)nCR6CH2, -O-optionally substituted arylene-(CH2)nCR6CH2, -0C(X)- optionally substituted arylene-(CH2)nCR6CH2, -0(CH2)nCCH, -0C(X)(CH2)nCCH, - N(C(O)C1-C4)( (CH2)nCCH), -O-optionally substituted arylene-(CH2)nCCH, or -0C(X)- optionally substituted arylene-(CH2)nCCH; wherein each R6is H or CH3, each n is 1,2 or 3, and each X is O. R1and R2is independently selected from -O(CH2)nCCH2O, -OC(X)(CH2)nCCH2O - OC(X)(CH2)nOC(X)CCH2O, -N(C(O)C1-C4)( (CH2)nCCH2O), -OC(O)(NR7)(CH2)nCCH2O, -O-optionally substituted arylene-(CH2)nCCH2O, or -OC(X)- optionally substituted arylene - (CtDnCCtkO; wherein each n is 1,2 or 3, and each X is O.

[0129] R3is selected from -(CH2)nCR6CH2, -C(X)(CH2)nCR6CH2, -C(X)(CH2)nOC(X)CR6CH2, - optionally substituted arylene-(CH2)nCR6CH2, -C(O)(NR7)(CH2)nCR6CH2, -C(X)- optionally substituted arylene-(CH2)nCR6CH2, -(CtDnCCH, -C(X)(CH2)nCCH, -optionally substituted arylene-(CH2)nCCH, or -C(X) -optionally substituted arylene-(CH2)nCCH; wherein each R6is H or CH3, each n is 1,2 or 3 and each X is O.

[0130] R3is independently selected from -(CH2)nCCH2O, -C(X)(CH2)nCCH2O -C(X)(CH2)nOC(X)CCH2O, -C(O)(NR7)(CH2)nCCH2O,

[0131] -optionally substituted arylene-(CH2)nCCH2O, or -C(X)- optionally substituted arylene - (CtDnCCtkO; wherein, each n is 1,2 or 3, and each X is O.

[0132] In respect to all of the above aspects:

[0133] In certain embodiments R1and R2are the same.

[0134] In certain embodiments R1and R2are OH.

[0135] In certain embodiments R1and R2are H.

[0136] In certain embodiments R1is H and R2is OH.

[0137] In certain embodiments R1is OH and R2is H

[0138] In certain embodiments R1and R3are the same.

[0139] In certain embodiments R’ . R2and R3are the same.

[0140] In certain embodiments R1and R3are the same, and R2is OH.

[0141] In certain embodiments R1and R3are the same, and R2is H.

[0142] In some embodiments, and in accordance with the above aspects, one or more of the following combinations of Rx-R3may apply:

[0143] R1is H,

[0144] R1is OH,

[0145] R1is -OCH2CHCH2O, R1is -OCH2CHCH2,

[0146] R1is -OCH2CH2CHCH2,

[0147] R1is -OCH2CH2CH2CHCH2,

[0148] R1is -OCH2CH2CH2CH2CHCH2,

[0149] R1is -OCH2CCH,

[0150] R1is -OCH2CH2CCH,

[0151] R1is -OCH2CH2CH2CCH,

[0152] R1is -OCH2CH2CH2CH2CCH,

[0153] R1is -OC(O)CH2CHCH2,

[0154] R1is -OC(O)CH2CH2CHCH2,

[0155] R1is -OC(O)CH2CH2CH2CHCH2,

[0156] R1is -OC(O)CH2CH2CH2CH2CHCH2,

[0157] R1is -OC(O)CH2CCH,

[0158] R1is -OC(O)CH2CH2CCH,

[0159] R1is -OC(O)CH2CH2CH2CCH,

[0160] R1is -OC(O)CH2CH2CH2CH2CCH,

[0161] R1is -OCH2C(CH3)CH2,

[0162] R1is -OC(O)C(CH3)CH2,

[0163] R1is -OC(O)CHCH2,

[0164] R1is -OCH2CH2C(CH3)CH2,

[0165] R1is -OCH2CH2CH2C(CH3)CH2,

[0166] R1is -OCH2CH2CH2CH2C(CH3)CH2,

[0167] R1is -N(C(O)C1-C4)( (CH2)CHCH2),

[0168] R1is -N(C(O)C1-C4)( (CH2CH2)CHCH2),

[0169] R1is -N(C(O)C1-C4)( (CH2)CCH),

[0170] R1is -N(C(O)C1-C4)( (CH2CH2)CCH),

[0171] R1is -O-optionally substituted phenylene-CtkCHCtk,

[0172] R1is -O-optionally substituted phenylene-C^CtkCHCtk,

[0173] R1is -O-optionally substituted phenylene-C^CtkCtkCHCth,

[0174] R1is -O-optionally substituted phenylene-CH2CH2CH2CH2CHCH2,

[0175] R1is -O-optionally substituted phenylene-CtkCCH,

[0176] R1is -O-optionally substituted phenylene-CtkCtkCCH,

[0177] R1is -O-optionally substituted phenylene-C^CtkCtkCCH, R1is -O-optionally substituted phcnylcnc-CHiCHiCHiCHiCCH,

[0178] R1is -OC(O)-optionally substituted phcnylcnc-CHiCHCHi,

[0179] R1is -OC(O)-optionally substituted phcnylcnc-CHiCHiCHCHi,

[0180] R1is -OC(O)-optionally substituted phcnylcnc-CHiCHiCHiCHCHi,

[0181] R1is -OC(O)-optionally substituted phcnylcnc-CHiCHiCHiCHiCHCHi,

[0182] R1is -OC(O)-optionally substituted phcnylcnc-CHiCCH,

[0183] R1is -OC(O)-optionally substituted phcnylcnc-CHiCHiCCH,

[0184] R1is -OC(O)-optionally substituted phcnylcnc-CHiCHiCHiCCH,

[0185] R1is -OC(O)-optionally substituted phcnylcnc-CHiCHiCHiCHiCCH,

[0186] R1is -OC(O)(CH2)OC(O)CHCH2,

[0187] R1is -OC(O)(CH2CH2)OC(O)CHCH2, or

[0188] R1is -OC(O)(CH2CH2CH2)OC(O)CHCH2,

[0189] R2is H,

[0190] R2is OH,

[0191] R2is -OCH2CHCH2,

[0192] R2is -OCH2CH2CHCH2,

[0193] R2is -OCH2CH2CH2CHCH2,

[0194] R2is -OCH2CH2CH2CH2CHCH2,

[0195] R2is -OCH2CCH,

[0196] R2is -OCH2CH2CCH,

[0197] R2is -OCH2CH2CH2CCH,

[0198] R2is -OCH2CH2CH2CH2CCH,

[0199] R2is -OC(O)CH2CHCH2,

[0200] R2is -OC(O)CH2CH2CHCH2,

[0201] R2is -OC(O)CH2CH2CH2CHCH2,

[0202] R2is -OC(O)CH2CH2CH2CH2CHCH2,

[0203] R2is -OC(O)CH2CCH,

[0204] R2is -OC(O)CH2CH2CCH,

[0205] R2is -OC(O)CH2CH2CH2CCH,

[0206] R2is -OC(O)CH2CH2CH2CH2CCH,

[0207] R2is -N(C(O)C1-C4)( (CH2)CHCH2),

[0208] R2is -N(C(O)C1-C4)( (CH2CH2)CHCH2),

[0209] R2is -N(C(O)C1-C4)( (CH2)CCH), R2is -N(C(O)C1-C4)( (CH2CH2)CCH),

[0210] R2is -O-optionally substituted phenylene-CH2CHCH2,

[0211] R2is -O-optionally substituted phenylene-CH2CH2CHCH2,

[0212] R2is -O-optionally substituted phenylene-CH2CH2CH2CHCH2,

[0213] R2is -O-optionally substituted phenylene-CH2CH2CH2CH2CHCH2,

[0214] R2is -O-optionally substituted phenylene-CH2CCH,

[0215] R2is -O-optionally substituted phenylene-CH2CH2CCH,

[0216] R2is -O-optionally substituted phenylene-CH2CH2CH2CCH,

[0217] R2is -O-optionally substituted phenylene-CH2CH2CH2CH2CCH,

[0218] R2is -OC(O)-optionally substituted phenylene-CH2CHCH2,

[0219] R2is -OC(O)-optionally substituted phenylene-CH2CH2CHCH2,

[0220] R2is -OC(O)-optionally substituted phenylene-CH2CH2CH2CHCH2,

[0221] R2is -OC(O)-optionally substituted phenylene-CH2CH2CH2CH2CHCH2,

[0222] R2is -OC(O)-optionally substituted phenylene-CH2CCH,

[0223] R2is -OC(O)-optionally substituted phenylene-CH2CH2CCH,

[0224] R2is -OC(O)-optionally substituted phenylene-CH2CH2CH2CCH,

[0225] R2is -OC(O)-optionally substituted phenylene-CH2CH2CH2CH2CCH,

[0226] R2is -OC(O)(CH2)OC(O)CHCH2,

[0227] R2is -OC(O)(CH2CH2)OC(O)CHCH2, or

[0228] R2is -OC(O)(CH2CH2CH2)OC(O)CHCH2;

[0229] R3is -CH2CHCH2,

[0230] R3is -CH2CH2CHCH2,

[0231] R3is -CH2CH2CH2CHCH2,

[0232] R3is -CH2CH2CH2CH2CHCH2,

[0233] R3is -CH2CCH,

[0234] R3is -CH2CH2CCH,

[0235] R3is -CH2CH2CH2CCH,

[0236] R3is -CH2CH2CH2CH2CCH,

[0237] R3is -CH2C(CH3)CH2,

[0238] R3is -CH2CH2C(CH3)CH2,

[0239] R3is -CH2CH2CH2C(CH3)CH2,

[0240] R3is -CH2CH2CH2CH2C(CH3)CH2,

[0241] R3is -C(O)CH2CHCH2, R3is -C(O)CH2CH2CHCH2,

[0242] R3is -C(O)CH2CH2CH2CHCH2,

[0243] R3is -C(O)CH2CH2CH2CH2CHCH2,

[0244] R3is -CH2C(CH3)CH2,

[0245] R3is -CH2CH2C(CH3)CH2,

[0246] R3is -CH2CH2CH2C(CH3)CH2,

[0247] R3is -CH2CH2CH2CH2C(CH3)CH2,

[0248] R3is -C(O)CH2CCH,

[0249] R3is -C(O)CH2CH2CCH,

[0250] R3is -C(O)CH2CH2CH2CCH,

[0251] R3is -C(O)CH2CH2CH2CH2CCH,

[0252] R3is -optionally substituted phenylene-CH2CHCH2,

[0253] R3is -optionally substituted phenylene-CH2CH2CHCH2,

[0254] R3is -optionally substituted phenylene-CH2CH2CH2CHCH2,

[0255] R3is -optionally substituted phenylene-CH2CH2CH2CH2CHCH2,

[0256] R3is -optionally substituted phenylene-CH2CCH,

[0257] R3is -optionally substituted phenylene-CH2CH2CCH,

[0258] R3is -optionally substituted phenylene-CH2CH2CH2CCH,

[0259] R3is -optionally substituted phenylene-CH2CH2CH2CH2CCH,

[0260] R3is -C(O)-optionally substituted phenylene-CH2CHCH2,

[0261] R3is -C(O)-optionally substituted phenylene-CH2CH2CHCH2,

[0262] R3is -C(O)-optionally substituted phenylene-CH2CH2CH2CHCH2,

[0263] R3is -C(O)-optionally substituted phenylene-CH2CH2CH2CH2CHCH2,

[0264] R3is -C(O)-optionally substituted phenylene-CH2CCH,

[0265] R3is -C(O)-optionally substituted phenylene-CH2CH2CCH,

[0266] R3is -C(O)-optionally substituted phenylene-CH2CH2CH2CCH,

[0267] R3is -C(O)-optionally substituted phenylene-CH2CH2CH2CH2CCH,

[0268] R3is -C(O)(CH2)OC(O)CHCH2,

[0269] R3is -C(O)(CH2CH2)OC(O)CHCH2, or

[0270] R3is -C(O)(CH2CH2CH2)OC(O)CHCH2. Examples of monomers of formula (I) of the present invention include but are not limited to the following:

[0271] From LGA-

[0272] From LGO -

[0273]

[0274] r = 6

[0275] Examples of mercapto of formula (IV) or (IVa) of the present invention include but are not limited to the following:

[0276] It will be appreciated that the monomers disclosed herein contain one or more stereogenic centres. The invention contemplates all stereoisomers of such compounds.

[0277] In certain embodiments the invention contemplates both "enantiomeric ally enriched" and "enantiomerically pure" forms of the monomeric compounds of the present invention. As used herein, the term "enantiomerically enriched" means that the compound is in a form such that there is more of one enantiomer than its enantiomeric pair. Such enantiomerically enriched chiral compounds display optical activity.

[0278] As used herein, the term "enantiomerically pure" means that the enantiomer is substantially free of its enantiomeric pair. Enantiomeric purity is generally expressed in terms of enantiomeric excess or %ee. For a pair of enantiomers, (+) and (-), wherein the mixture of the two enantiomers is given as the mole or weight fractions F+ or F- and wherein the sum of F+and F- is 1, the enantiomeric excess is defined as the difference of F+ and F_. Accordingly, the enantiomeric excess is expressed as a percentage, i.e. (F+ - F_) x 100. As used herein, the term "enantiomerically pure" means that the %ee is greater than 70%. Preferably, the %ee is greater than about 85%, about 88%, about 90%, about 92% or about 94%. More preferably, the %ee is greater than about 95%. In certain embodiments, the compounds of general formula (I) of the present invention are utilised in enantiomerically pure form.

[0279] Examples of stereoisomeric forms are as follows:

[0280] Preparation of the Monomers

[0281] General scheme for the preparation of various monomers according to certain embodiments of the present invention:

[0282] LGO

[0283] Preparation of the Polymers

[0284] The polymers may be prepared by mixing stoichiometric quantities of monomer and mercapto compound.

[0285] The polymerisation conditions may include radical polymerisation (UV light) or epoxide ring opening polymerisation.

[0286] The reactions may be conducted using UV light activation via radical initiation using photo initiators and thermal initiators such as 2,2'-azobis(isobutyronitrile) AIBN, benzoyl peroxide (BPO), diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, di-tert-butyl peroxide, dicumyl peroxide, TBNP, + Camphorquinone, 4,4'-dihydroxybenzophenone, and the like.

[0287] In certain embodiments the polymerisation involves stoichiometric equivalent amounts of monomers and thiol / mercapto compounds.

[0288] The reactions may also involve cast polymerisation or emulsion polymerisation techniques.

[0289] Examples of polymers which may be prepared by the polymerisation methods of the present invention include but are not limited to the following:

[0290] In certain embodiments the polymers of the present invention are characterised with optical transparency and have a tunable glass transition temperature (Tg). Tg is directly related to a material's strength and capabilities in any given end-use application. The present polymers are typically characterized with a Tg range of from -20 °C to 80 °C, good for a broad range of thermal applications. In other embodiments the polymers of the present invention are characterised with optical transparency and elongation / compression with a Young's modulus of between about 4 to 10 MPa, providing tuneable flexibility (stiff or flexible depending on application).

[0291] In certain embodiments the polymers prepared are characterised with a %transmission range of between 99%-80%.

[0292] Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.

[0293] The reference in this specification to any prior publication (or information derived from it), or to any matter which is known, is not, and should not be taken as an acknowledgment or admission or any form of suggestion that that prior publication (or information derived from it) or known matter forms part of the common general knowledge in the field of endeavour to which this specification relates.

[0294] Certain embodiments of the invention will now be described with reference to the following examples which are intended for the purpose of illustration only and are not intended to limit the scope of the generality hereinbefore described.

[0295] Examples

[0296] Synthesis and Characterisation

[0297] Four LGA-derived monomers prepared as showed in Figure 1, all with a terminal vinyl substituent to ensure participation in thiol-ene polymerisation. The reactions were performed on 1-5 g scales obtaining moderate yields. Monomers 1 and 2 were synthesized via similar experimental method, however di- and tri- functionality was selected through careful stoichiometric regulation. The monomers were purified via flash chromatography prior to and13C NMR analysis. Monomers 3 and 4 were the target of this research due to unique ester linkages and ease of synthesis. It is postulated that ester linkages can play a vital role to the degradation of the thermosets at their end of life. The degradation occurs in basic solutions and is suspected to degrade the thermoset material without creating hazardous microplastics. To prepare monomers 3 and 4, N-acyl imidazole (acid chloride or other acyl donor) intermediate was first synthesized. The acyl imidazole was used to prepare monomer 3 and 4 under mild conditions. The desired monomers were also achieved through careful stoichiometric regulation. The crude monomers were purified via flash chromatography and their structure was supported by1H and13C NMR.

[0298] Preparation of thiol-ene polymer networks

[0299] Stoichiometric equivalents of LGA monomer, corresponding thiol and initiator, were weighed into a vial (Table 1). For the thiol-ene polymerisation, stoichiometric equivalents were selected to avoid an excess of thiol or allyl groups. The homogenous mixture was cured in silicone dogbond moulds, by exposure to UV light for 60 seconds.

[0300] Table 1

[0301] Monomer Eq. Thiol Sample

[0302] 1 1:2 4 SH LGA-DA-4SH

[0303] 2 (prior

[0304] 1: 1 3 SH LGA-TA-3SH art / comparator)

[0305] 3 1:2 4 SH LGA-DP-4SH

[0306] 4 1: 1 3 SH LGA-TP-3SH

[0307] Three of the resulting thermosets possess an optically transparent appearance, are solid and vary in rigidity. With the triallyl (from Monomer 2) derivative possessing a yellow colour, as observed in the literature. Each corresponding thermoset sample will be labelled as outlined in Table 1, these labels will be referred to for the remainder of the text. Photopolymerisation kinetics

[0308] The curing behaviour and reaction time of each individual thermoset was investigated using RT-FTIR spectroscopy and photo-DSC to ensure polymer samples were cured until completion. The IR spectra shows the composition before and after UV irradiation. Absorption peaks corresponding to allyl groups (3078 cm-1and 1643 cm-1) and thiol groups (2561 cm-1) disappeared, demonstrating successful curing of the sample mixtures. The carbonyl absorption peak was retained after curing, demonstrating the alkyl units have not been affected by the UV cure.

[0309] The polymerisation behaviour of the synthesized monomers was examined using photo-DSC. The curing rate and the conversion of UV curable monomers are two key parameters that are necessary to be addressed for 3D printing applications. Thus, they were examined in this study. The released heat as a functional of time (Figure 3) for all formulations demonstrated rapid curing upon switching on the UV source (at t = 0 in this figure).

[0310] Mechanical and thermal properties of thiol-ene polymer networks

[0311] To determine the strength and stability of each of the polymer samples, mechanical and thermal experiments were performed. The mechanical performance of the samples was observed to be directly influenced by the chemical functionality of the monomer materials. The tensile strength obtained for the thermosets were 1.08, 2.74, 4.82 and 3.41 MPa with the Young’s modulus increased with increasing tensile strength, 2.51, 2.20, 4.97 and 3.67. The elongation at break of the LGA-derived thermosets ranges from 40 to 100 %. The materials increase in flexibility as with decreasing functionality (di is more flexible than tri).

[0312] Polymers 3 and 4 achieved the highest tensile strength and Young’s modulus, indicating that the pentenoyl functionality presents an improvement on the tensile strength. Interestingly, difunctionality outperformed tri- functionality when comparing the elongation at break. The polymer networks presented here possess a superior flexibility when compared to Figure 5, previous literature reports (tri allyl). Previous literature reports of LG A thiolene networks reported results 1.1 MPa tensile strength and elongation at break of 35%. Similarly, other biobased thiol-ene networks reported results including Young’s modulus and tensile strength of 0.93 MPa. The mechanical data indicates that the properties of the resulting thermosets can be tailored by selecting level of chemical substitution. The thermal properties and stability of the cured networks were analysed via TGA and DSC. All samples exhibit excellent thermal stability, with an average stability until over 300 °C. Polymer 1 appears to have the highest thermal stability, however the samples are all relatively consistent. All decomposition profiles show a multi-step degradation profile.

[0313] The DSC was used to determine the glass transition temperature (Tg) of the thermoset thiolene materials. The Tgvalues calculated from the DSC thermograms lie at 25 °C.

[0314] Solvent swelling and degradation

[0315] Square samples of polymer were exposed to a series of solvents to assess the extent of solvent swelling. Each polymer sample was soaked in the individual solvents for one hour (see Figure 6). Their swelling was determined by calculating the difference between their wet and dry weights. All thermoset systems were very stable against water, methanol, and n-hexane. More drastic swelling was observed in dichloromethane, suggesting that it is an unsuitable solvent.

[0316] The hydrolytic degradability of the cured polymer networks was investigated. Previous reports indicate that the ester linkages present in the thiol monomer are susceptible to base-mediated hydrolysis. Thus, ester linkages were further introduced during monomer synthesis to encourage further degradation with the intent to investigate a fully degradable, and potentially recyclable, system. The experiments were performed through immersing each sample into a 1.0 M solution of NaOH. The samples were immersed and their degradation monitored. The polymer degradation ranged from days to months.

[0317] Optical transparency

[0318] UV-vis spectra of each of the thermosets was recorded in the range of 400-800 nm to evaluate the transparency of the coatings. The transmission spectra are given in Figure 7. All films exhibit good transparency, with transmissivity approximately 60 % at 600 nm. The thickness of the film affects the transmissivity of the material, with thinner samples achieving better results. To illustrate this transparency, polymer 4 (3 mm), was placed in front of a mobile phone camera, with the background image still visible. Surface modification

[0319] A post-polymerisation modification was performed on a sample of each of the polymer thermosets. This was to determine the tunability of the surface. The samples were placed in a mixture of dioxane, fluoro acrylate and initiator prior to exposure to UV. Water contact angle measurements were performed prior to exposure to the post modification and then compared with the surface of each sample after exposure.

[0320] Synthetic procedures for monomers

[0321] Synthesis of allyl derivatives

[0322] 1,6-Anhydro-P-D-glucopyranose or allyl -LGO-OH or LGO-OH or LGO-diol (1 eq) was dissolved in dimethylformamide, allyl bromide (2.1 or 3.1 eq) and barium oxide (2.1 or 3.1 eq) were added to the mixture and the reaction stirred at 60 °C for 12 h. A mixture of ethyl acetate / hexane (40:60) was added and the mixture was fdtered through celite. Water was added to the fdtrate and the product was extracted in ethyl acetate / hexane (40:60) (3 x 30 mL). The solvent was dried and evaporated, to obtain a yellow liquid, the product was purified by flash chromatography to give the desired monomer.

[0323] Synthesis of ester derivatives

[0324] 4-Pentenoic acid (1 eq) was dissolved in dichloromethane, under nitrogen, carbonyl diimidazole (1.1 eq) was slowly added to the reaction and stirred at RT for 15 minutes. Dichloromethane (mL) was added to the reaction and the organic extract was washed with water (3 x 50 mL) to the solvent removed under vacuum, yielding N-pentenoyl imidazole intermediate.

[0325] 1,6-Anhydro-P-D-glucopyranose (1 eq) was dissolved in dimethylformamide (or di chloromethane compound 8 and 9), the N-pentenoyl imidazole intermediate. (2.1 or 3.1 eq), obtained in the previous step was added slowly and the reaction mixture was stirred at 60 °C for 12 h. Water was added and the product was extracted with ethyl acetate / hexane (40:60) (3 x 30 mL). The solvent was dried and evaporated, to obtain a yellow oil. The crude material was purified by flash chromatography to the desired monomer. LGO-OH Synthesis

[0326] A solution of LGO (1 eq.) in methanol cooled at 0 °C was treated first with CeCh.VHiO (1.1 eq.) and then with sodium borohydride (1 eq.). After stirring for 1 hour, the reaction mixture was concentrated and directly subjected to flash chromatography (hexane / ethyl acetate elution) to obtain LGO-OH in white crystalline form.

[0327] Allyl -LGO-OH Synthesis

[0328] A solution of LGO (1 eq.) in allyl alcohol (18 eq.), triethylamine (0.5 eq.) was added, and the mixture was stirred at 30 °C for 12 hours. In the same reaction mixture water was added and cooled at 0 °C followed by addition of sodium borohydride (2 eq.). After stirring for 20 minutes, the product was extracted with ethyl acetate (3 x 30 mL) and dichloromethane (3 x 30 mL) to obtain yellow oily liquid which was further purified by flash chromatography to obtain allyl-LGO-OH.

[0329] LGO-acrylate synthesis

[0330] R= H, CH3

[0331] Levoglucosanol (0.142 g, 1.12 mmol), anhydrous dichloromethane (2 mL) and dimethylaminopyridine (1.4 mg, 0.01 mmol), were combined and cooled to 0 °C. Dried triethylamine (0.25 mL) and acryloyl chloride (0.29 mL) were then added. The reaction flask was flushed with nitrogen then sealed and the reaction mixture slowly warmed with stirring. Upon reaching 25 °C, the reaction was stirred for an additional 18 hours at room temperature. Flash chromatography with a mixture of 60:40 ethyl acetate / hexanes (300 mL), followed by flushing with methanol was used to purify the crude product. Pure acrylated levoglucosanol was obtained as a transparent oil with a yield of 66 % (134 mg, 0.734 mmol). ’ H NMR (600 MHz, CDC13): / ppm 3.84 (t, J=3.8 Hz,lH), 4.02 (d, J=8 Hz, 1H), 4.73 (s, 1H), 5.62 (s, 1H), 5.69 (d, J=15 Hz, 2H), 5.92 (d, 10 Hz, 1H), 6.23 (m, 2H), 6.50 (d, J=16 Hz, 1H).13C NMR (150 MHz, CDCI3): / ppm 30.8, 71.4, 71.8, 99.2, 124.8, 127.9, 131.8, 132.5, 165.9 (C=O).

[0332]

[0333] R=H, CH3

[0334] Levoglucosanol (1 eq), anhydrous dichloromethane and CDI (1.5 eq) were stirred for 2 hours.

[0335] HEM A (1.5 eq) was added to the reaction mixture and heated to reflux overnight. The solvent was removed under vacuum and flash chromatography was followed.

[0336] Bio-derived thioi-ene emulsion polymerisation from LGO-P and LGA-DP. Synthetic procedures

[0337] Levoglucosenol (LGO-OL) was synthesised via the sodium borohydride-based reduction of LGO. Dipentenoyl-functional monomers were synthesised as per previous literature reports. The acyl imidazole intermediates of LGA, LGO-OL and isosorbide were first synthesised, with careful stoichiometric regulation of CDI and subsequently 4-pentenoic acid (pentenoyl chloride can also be used) achieving the desired di-pentenoyl monomers based on LGA and isosorbide and the mono-pentenoyl substituted LGO-OL. The crude monomers were purified via flash chromatography (ethyl acetate / hexane, 40:60) and their structures were confirmed by 'H NMR.

[0338] Polymerisation

[0339] AZ> initio thiol-ene emulsion polymerisation

[0340] An aqueous solution of SDS (10 mL, 8 mM) solution, SI 1, was added to a round bottom flask, prior to the addition of corresponding thiol (EGBP) and alkene monomers. Stoichiometric equivalents of both monomers were added to ensure the ratio of -SH to C=C groups was 1. The mixture was stirred at 750 rpm via magnetic stirring and purged with nitrogen for 10 minutes. At the conclusion of this time, a KPS solution was added (1 mL, 5 mM), and polymerization was allowed to proceed at 60 °C for 3 hours. The resulting polymer latex was opened to the air and allowed to cool, followed by subsequent characterization.

[0341] Seeded emulsion copolymerisation

[0342] Monomer (either styrene or MMA) in an aqueous KPS solution (524 mg, 10 mL, 8 mM) was added to a sample of the seed latex (10 mL, 813 mg). The sample was left to stir overnight at room temperature to enable the seed particles to swell with monomer. Subsequently the reaction mixture was stirred and purged with nitrogen for 10 minutes, prior to the addition of an aqueous solution of KPS (5 mM). The sample was added to an oil bath at 60 °C, and polymerization was allowed to proceed for 3 hours.

[0343] Synthetic scheme:

[0344] Films dried at 25 °C

[0345] Preparation of Bio-derived thiol-ene polymers from emulsion polymerization Materials

[0346] Levoglucosan (LGA), 1,1’ -carbonyl diimidazole (CDI), isosorbide ((3R,3aR,6S,6aR)- Hexahydrofuro[3,2-b]furan-3,6-diol) were purchased from Combi Blocks. Dimethyl aminopyridine, ethylene glycol bi s(3 -mercaptopropionate) (EGBP), potassium persulfate, sodium dodecyl sulfate, sodium borohydride, cerium (III) chloride, methyl methacrylate (MMA) and styrene were purchased from Sigma-Aldrich. 4-Pentenoic acid was purchased from Arctom Chemicals. Levoglucosenone (LGO) was obtained from Circa Group.

[0347] Synthetic procedures

[0348] Levoglucosenol (LGO-OL) was synthesised via the sodium borohydride-based reduction of LGO as reported previously. Dipentenoyl-functional monomers were synthesised as per previous literature reports. The acyl imidazole intermediates of LGA, LGO-OL and isosorbide were first synthesised, with careful stoichiometric regulation of CDI and subsequently 4- pentenoic acid (pentenoyl chloride can also be used) achieving the desired di-pentenoyl monomers based on LGA and isosorbide and the mono-pentenoyl substituted LGO-OL. The crude monomers were purified via flash chromatography (ethyl acetate / hexane, 40:60) and their structures were confirmed by NMR.

[0349] Polymerisation

[0350] AZ> initio thiol-ene emulsion polymerisation

[0351] An aqueous solution of SDS (10 mL, 8 mM) solution, SI 1, was added to a round bottom flask, prior to the addition of corresponding thiol (EGBP) and alkene monomers. Stoichiometric equivalents of both monomers were added to ensure the ratio of -SH to C=C groups was 1. The mixture was stirred at 750 rpm via magnetic stirring and purged with nitrogen for 10 minutes. At the conclusion of this time, a KPS solution was added (1 mL, 5 mM), and polymerization was allowed to proceed at 60 °C for 3 hours. The resulting polymer latex was opened to the air and allowed to cool, followed by subsequent characterization. Seeded emulsion copolymerisation

[0352] Monomer (either styrene or MMA) in an aqueous KPS solution (524 mg, 10 mL, 8 mM) was added to a sample of the seed latex (10 mL, 813 mg). The sample was left to stir overnight at room temperature to enable the seed particles to swell with monomer. Subsequently the reaction mixture was stirred and purged with nitrogen for 10 minutes, prior to the addition of an aqueous solution of KPS (5 mM). The sample was added to an oil bath at 60 °C, and polymerization was allowed to proceed for 3 hours.

[0353] Characterisation

[0354] Nuclear magnetic resonance spectroscopy (NMR) spectra were acquired using a Bruker AVANCE III HD 600 MHz spectrometer. NMR spectra were obtained by placing the sample in a 5 mm NMR tube with CDCh as the solvent.

[0355] Differential scanning calorimetry (DSC) experiments were performed using a Mettler Toledo DSC 1 STARe System instrument. Samples (typically 5 mg of polymer) were sealed in an aluminium crucible during sample preparation. Three heating and cooling loops across a temperature range from -50 °C to 200 °C at a standard heating rate of 10 °C per minute were performed for each sample. The second heating loop was used to infer glass transition temperature data.

[0356] Thermogravimetric analysis (TGA) was performed using a NETZSCH STA 449 F5 Jupiter. Alumina crucibles were used to hold the sample in the furnace. The sample (~15 mg) was heated from 25 to 800 °C at a rate of 10 °C per minute in a nitrogen atmosphere.

[0357] Dynamic light scattering (DLS) measurements were measured by using a Malvern ZetaSizer Nanoseries instrument integrated with DTS software. The measurement was performed at 298 K using a 4 mW He-Ne laser with wavelength 633 nm. The scattering angle was 173°. Results were based on the average values of three independent measurements. Scanning electron microscopy (SEM) all images were taken using a Hitachi SU-70 field emission analytical scanning electron microscope, sputter coated with gold.

[0358] Transmission electron microscopy (TEM) bright field images were collected on a Tecnai TF20 at an accelerating voltage of 200 kV. High angle annular dark field (HAADF) images were acquired in STEM mode.

[0359] Gel Permeation Chromatography (GPC) was used to determine the average molecular weight and molar mass distributions of the linear polymers isolated from the latexes. An Agilent Infinity 1260 GPC system was used for analysis with a triple detector suite (refractive index, light scattering and viscosity), two PLgel MIXED-C columns in a column oven set to 30 °C, and THF as eluent (flow rate 0.8 mL min-1). All polymer samples were dissolved for at least one hour prior to analysis in the eluent at approximately 5 mg mL1, then filtered through a 450 nm nylon filter. The system was calibrated with poly(methyl methacrylate) (PMMA) standards with molecular weights of 400 to 1,944,000 g mol1.

[0360] Contact angle measurements were performed via dispensing a 5 pL droplet of water or diiodomethane onto the sample surface using manual pressure. An image of the drop was captured and apparent contact angles were measured using ImageJ software with the DropSnake plugin.

[0361]

[0362] The above scheme depicts the LGA, LGO-OL and isosorbide monomer synthesis and subsequent thiol-ene emulsion polymerization.

[0363] Monomer Synthesis

[0364] Suitable monomers for thiol-ene polymerization were synthesized from three renewable feedstocks; specifically levoglucosan (LGA), isosorbide, and levogluco send (LGO-OL). LGO-OL was produced via the sodium borohydride mediated reduction of levoglucosenone, a direct product of cellulose pyrolysis that is now available on a commercial scale. LGA and isosorbide were modified with two equivalents of pentenoic acid, as per previous literature reports (Scheme 1) in good yield (-70%); in comparison one equivalent of pentenoic acid was used with LGO-OL, taking advantage of the internal ring double bond that can participate in thiol-ene polymerizations. The structures of these monomers were confirmed by1H NMR and13C NMR (see SI 2). Previously our group has prepared allyl- and pentenoyl-substituted LGA monomers for the preparation of crosslinked thermosets via thiol-ene UV photopolymerization. In this work, we evaluated the applicability of these three diene monomers in an emulsion polymerization setting. Specifically, we performed radical mediated thiol-ene emulsion polymerization using a dithiol as shown above to create polymer latex particles consisting of linear poly(thioether) chains.

[0365] Bio-based Latex synthesis and polymer properties

[0366] For polymer latex synthesis, equimolar mixtures of EGBP and each diene monomer were prepared, ensuring stoichiometric equivalents of C=C and -SH groups. This mixture was used as the monomer phase for ab initio emulsion polymerization experiments using potassium persulfate (KPS) as initiator and sodium dodecyl sulfate (SDS) as surfactant respectively. Polymerizations were allowed to proceed for three hours at 60 °C. All resulting latexes were stable white dispersions, with little to no coagulum forming over the course of the reaction. Particle size analysis was performed using DLS, with a unimodal particle size distribution and z-average particle diameters of the order of 1-3 micrometres (see Table 2). The significant variation observed is attributed to the nature of the diene monomer used. The latex LA-DT (based on the dipentenoyl-LGA monomer) gave the smallest particle diameter of 1046 nm, through to very large particles with z-average particle diameter of 3325 nm for sample LO-DT (based on the mono-pentenoyl-LGO monomer). These average particle sizes are significantly larger than other published examples of thiol-ene emulsion polymerization. Given the mechanism of particle formation in these polymerizations is anticipated to be via homogeneous nucleation (even above the critical micelle concentration of the surfactant used) from oligomers formed in the aqueous phase, the large particle size can be attributed to the highly hydrophilic nature of our thiol and ene monomers. TEM analysis of the LA-DT latex (see Figure 10B) demonstrated the formation of soft, spherical latex particles of similar diameter to that determined by DLS, with moderate particle size dispersity.

[0367] Table 2. Z-average particle diameter and polydispersity (PDI) of bio-derived polymer latexes, in addition to thermal analysis and molar mass analysis of polymers isolated from these latexes.

[0368] Sample Z-average diameter (nm) PDI Mn(Da) B Tonset Tso

[0369] LA -DT 1046 0.302 4514 3.01 250 295

[0370] IS -DT 1614 0.241 4499 2.87 301 370

[0371] LO-DT 3325 0.220 1752 2.73 305 375 Molar mass and thermal properties of the resulting polymers were obtained by GPC, DSC and TGA respectively. Consistent with the step-growth mechanism of radical mediated thiol-ene polymerization, the number average molar mass as determined from GPC was relatively low for all polymers formed (Table 2). TGA showed that the polymers were stable up to a temperature of 250 °C, with maximum mass loss occurring at temperatures of -300-370 °C. The polymers from these latexes possessed relatively low 7g’s as determined by DSC, which was expected given the structure of these poly (thioethers) and previous work from our group looking at various LGA-based thiol-ene polymers. Due to most commercially available thiols (and the various vinyl compounds used) for thiol-ene polymerization resulting in relatively soft, low 7gpolymers, a two-stage emulsion polymerization process was used to generate latexes with both hard (i.e. high Tg) and soft phases, as discussed in the following section.

[0372] Multiphase Particles via Seeded Emulsion Polymerization Using a Thiol-Ene Seed Eatex

[0373] Seeded emulsion polymerization is a well-established route for the preparation of nano structured polymer colloids. The literature presents numerous examples where controlling the colloidal structure of multiphase latex particles offers a route to tailor the mechanical properties of dried films for their use in waterborne surface coatings. The success of bioderived thiol-ene emulsion polymerization systems described in the previous section provides a starting point for multiphase latex particles, typically prepared via a two-stage polymerization approach using a seed latex. We sought to use our bio-based thiol-ene polymer latexes to prepare latex particles with a core-shell morphology. In various coating applications, the creation of latex particles with a high 7gcore and a low 7gshell is desirable - the soft shell promotes particle coalescence and film formation, while the hard core provides mechanical strength.32As our thiol-ene latexes (in addition to other thiol-ene emulsion polymers reported in the literature) consist of low 7gpolymer, we envisaged this phase as the particle shell. To control film-forming properties, the intention was to introduce a second stage polymer with a high glass transition temperature, to act as a hard particle ‘core’ (Figure 11A). With foresight, the hard high 7gphase could also be based on bio-derived monomers (i.e. using a monomer such as vanillin methacrylate). In a binary polymer particle system consisting of seed polymer (Figure 11B, polymer 1) and the second polymer (Figure 11B, polymer 2), various particle morphologies can be predicted as the thermodynamic equilibrium morphology to minimize the Gibbs’ free energy of the system. These morphologies include core-shell, inverted core-shell, and Janus / hemispherical structures, in addition to two separate particle phases. Various authors have used a morphological mapping approach (Figure 11B) to predict particle morphology based on the interfacial tensions between polymer 1 and polymer 2, as well as the interfacial tension of each polymer with the surrounding medium (in this case water). Except for some common polymers, these interfacial tension terms are not known and various models to predict these quantities must be used. Furthermore, this mapping approach only predicts thermodynamically preferred morphologies - non-equilibrium structures can also be formed if phase migration within the particle structure is restricted.

[0374] Here we considered predicted particle morphologies using our P(LA-DT) latex as seed, with a high Tg core of either polystyrene (PS) or poly(methyl methacrylate) (PMMA). PS and PMMA were also chosen as their interfacial tension data is well known. In order to estimate various interfacial tension terms between these polymer phases, static contact angle measurements on cast films from our P(LA-DT) latex were performed and the Owens-Wendt-Rabel-Kaelble (OWRK) model was used to calculate the surface energy of this polymer. Full details are provided in the ESI. The static contact angles on a P(EA-DT) film for water and diiodomethane were 45.8 ± 1.1° and 43.9 ± 1.7° respectively, giving a surface energy for P(EA-DT) of 55.3 mN m1. This value is comparable to other thiol-ene polymeric coatings reported in the literature. Based on this value, interfacial tensions yn, yiw and pw were calculated where polymer 2 was either PS (blue circle, Figure 11B) or PMMA (red square, Figure 11B). Given the relatively hydrophilic nature of P(EA-DT) in comparison to the more hydrophobic PS and PMMA, the predicted equilibrium morphology of these systems is indeed a PS (or PMMA) core with a thiol-ene shell (Figure 11B).

[0375] To experimentally test these predicted morphologies and prepare bio-based structured colloids, a P(EA-DT) seed latex was used, prior to the addition of styrene in a surfactant solution as a second-stage polymerization. The EGBP:EA-DP seed latex was prepared in a manner equivalent to Table Sil. The seed latex was stirred overnight to enable swelling of the polymer particles with styrene prior to polymerization. Mass ratios (40:60, styrene to thiol-ene, corresponding to a mole ratio of 3.8: 1) were selected to promote optimal film forming conditions. The reaction was then purged with nitrogen, initiator was added, and the reaction flask heated to 60 °C for 3 hours. The emulsion was stable with little coagulum formed. The dried polymer was isolated from the latex, withXH NMR confirming the presence of both polystyrene and poly(thioether) due to diagnostic signals from both polymers. Specifically, the signal from the anomeric proton (marked ‘a’) of the LA-DT polymer was compared to the ortho protons in the aromatic ring of polystyrene (marked ‘b’). Integration of these signals indicated a polymer ratio of PSty:P(LA-DT) of 4: 1 , which was in good agreement with the feed ratio of styrene to seed polymer (3.8: 1). TGA analysis of LA-DT-Sty (Figure 12A) showed a slight increase in thermal stability (compared to LA-DT), with a 25 degree increase in the temperature whereby 50 % mass loss is observed (Tso = 320 °C). The derivative of the TGA trace (Figure 12B) shows two prominent mass loss events for the sample from seeded emulsion polymerization, with the second peak at elevated temperatures attributed to the polystyrene chains present in the polymer sample.

[0376] Electron microscopy analysis was performed on our P(LA-DT) / PS latexes to verify the resulting particle structure. TEM analysis of the particles after seeded emulsion polymerization supports the predicted core-shell morphology (Figure 13B); particles of approximately 1 pm diameter can be observed that possess a spherical core which is attributed to the PS phase, due to the significant contrast under the electron beam, surrounded by a more diffuse region of lower electron contrast (the thiol-ene shell). Evidence of some smaller PS particles is also present, indicative of some degree of secondary nucleation, which agrees with DLS analysis of this latex (Figure 14A). SEM analysis (Figure 13C) showed a series of spherical polymer particles in a state of partial coalescence on the SEM grid, which we attributed to the low 7gpoly(thioether) phase at the surface of these particles as a shell. The same core- shell morphology was observed when MMA was used as second monomer for seeded emulsion polymerization experiments (see SI 7 for SEM and TEM analysis).

[0377] In contrast, reversing the order of our two-stage emulsion polymerization process was unsuccessful. A polystyrene seed latex was first formed via ab initio emulsion polymerization at 60 °C with SDS as surfactant and KPS as initiator, followed by an attempt at seeded emulsion polymerization where an equimolar mixture of LA-DP and EGBP was used as the second stage monomer. Under identical conditions to those described previously, this experiment resulted in significant coagulum formation. NMR analysis of the isolated coagulum showed that it was P(LA-DT) polymer and unreacted monomer with some polystyrene, while the stable latex phase was exclusively polystyrene (see SI 8). Despite the predicted equilibrium particle morphology being identical (a polystyrene core and a poly(thioether) shell), this morphology was not achieved for several reasons. Both diene and dithiol are relatively hydrophilic compounds, and the polystyrene seed latex possesses a T&well above room temperature. This restricts the ability of the monomers to swell the polystyrene seed, and therefore polymerization in the continuous phase is more likely to occur. In contrast, a low 7gthiol-cnc seed latex is able to readily swell with the more hydrophobic styrene monomer, allowing seeded emulsion polymerization to proceed successfully. Similar behaviour was reported by Jiang et al.,31who attempted to perform thiol-ene polymerization and radical chain polymerization of styrene simultaneously; the formation of poly(thioether) “patches” on the particle surface in their work was due to the relative hydrophilicities of the monomers and significant difference in Tg_.

[0378] Table 3. Z-average particle diameters and PDI values of poly(LA-DT) before and after seeded emulsion polymerization with either styrene or MMA, in addition to molar mass distribution data of the polymers isolated from these multiphase systems.

[0379] Sample Z-average (nm) PDI Mnf)

[0380] LA-DT 1046 0.302 4514 2.50

[0381] LA-DT-Sty 536 0.25 1706 2.94

[0382] LA-DT-MMA 1003 0.422 2379 2.02

[0383] GPC analysis of the core- shell latexes performed in this work produced molar mass distributions with relatively low Afnvalues. When performing a thiol-ene polymerization, followed by the radical polymerization of a vinyl monomer, the presence of free thiols (via the end groups of the seed polymer) is present within the particle interior. It is well known that thiols are excellent chain transfer agents, opening the possibility that chain transfer to polymer may occur. This would reduce the number average molar mass of the formed poly(styrene) chains, as well as create the possibility that block copolymers may form (via the chain growth of styrene from the terminus of the poly(thioether) chains (see Figure 14A). To test this, some solution polymerization experiments were performed, Firstly, a sample of poly(LA-DT) was prepared via bulk UV photopolymerization (see SI 10 for details). This polymer was then dissolved in in 1,4-dioxane, to which styrene was added (at the same mass ratio of styrene:poly(LA-DT) as per our seeded emulsion polymerization experiments). The free radical polymerization of styrene was then performed under nitrogen at 60 °C using an azo initiator. GPC analysis of these samples was then performed, in addition to a control sample where styrene was polymerized but no poly(LA-DT) was present. The GPC chromatograms (Figure 6B) show a shift to longer elution volumes (and hence lower molar masses) for polystyrene in the presence of poly(LA-DT), suggesting the possibility of chain transfer to polymer is not insignificant.

Claims

The claims defining the invention are as follows:

1. A compound of the general formula (I):or a salt thereof, wherein:R1is selected from H, OH, -O(CH2)nCR6CH2, -OC(X)(CH2)nCR6CH2, -OC(X)(CH2)nOC(X)CR6CH2, -N(C(O)C1-C4)( (CH2)nCR6CH2), OC(O)(NR7)(CH2)nCR6CH2,-O-optionally substituted arylene-(CH2)nCR6CH2, -OC(X)- optionally substituted arylene-(CH2)nCR6CH2, -O(CH2)nCCH, -OC(X)(CH2)nCCH, -N(C(O)C1-C4)( (CH2)nCCH), -O-optionally substituted arylene-(CH2)nCCH, -OC(X)- optionally substituted arylene-(CH2)nCCH; -O(CH2)nCHCH2O, -OC(X)(CH2)nCHCH2O - OC(X)(CH2)nOC(X)CHCH2O, -N(C(O)C1-C4)( (CH2)nCHCH2O), OC(O)(NR7)(CH2)nCHCH2O,-O-optionally substituted arylene-(CH2)nCHCH2O, or -OC(X)- optionally substituted arylene-(CH2)nCHCH2O;R2is selected from H, OH, -O(CH2)nCR6CH2, -OC(X)(CH2)nCR6CH2, -OC(X)(CH2)nOC(X)CR6CH2, -N(C(O)C1-C4)( (CH2)nCR6CH2), -OC(O)(NR7)(CH2)nCR6CH2, -O- optionally substituted arylene-(CH2)nCR6CH2, -OC(X)- optionally substituted arylene- (CH2)nCR6CH2, -O(CH2)nCCH, -OC(X)(CH2)nCCH, -N(C(O)C1-C4)( (CH2)mCCH), - O-optionally substituted arylene-(CH2)nCCH, -OC(X)- optionally substituted arylene - (CH2)nCCH, -O(CH2)nCHCH2O, -OC(X)(CH2)nCHCH2O -OC(X)(CH2)nOC(X)CHCH2O, -N(C(O)C1-C4)( (CH2)nCHCH2O), -OC(O)(NR7)(CH2)nCHCH2O, -O-optionally substituted arylene-(CH2)nCHCH2O, or -OC(X)- optionally substituted arylene-(CH2)nCHCH2O;R3is selected from -(CH2)nCR6CH2, -C(X)(CH2)nCR6CH2, C(X)(CH2)nOC(X)CR6CH2, -optionally substituted arylene-(CH2)nCR6CH2, - C(O)(NR7)(CH2)nCR6CH2, -C(X)- optionally substituted arylene-(CH2)nCR6CH2, - (CH2)nCCH, -C(X)(CH2)nCCH, -optionally substituted arylene-(CH2)nCCH, -C(X)- optionally substituted arylene-(CH2)nCCH, -(CH2)nCHCH2O, -C(X)(CH2)nCHCH2O - C(X)(CH2)nOC(X)CHCH2O, -C(O)(NR7)(CH2)nCHCH2O,-optionally substituted arylene-(CH2)nCHCH2O, or -C(X)- optionally substituted arylene-(CH2)nCHCH2O; n is an integer selected from 0 to 7;X is O or S;- refers to an optional double bond;R6is H or methyl;R7is H, Cl -4 alkyl or optionally substituted phenyl; and wherein the following compounds are excluded:

2. A compound according to claim 1 wherein n is an integer selected from 1 to 7.

3. A compound according to claim 1 or 2 wherein - refers to a double bond.

4. A compound according to claim 1 or 2 wherein - refers to a single bond.

5. A compound of formula (I) according to claim 1 which is a compound of formula (la):or a salt thereof, wherein:R1is selected from H, OH, -O(CH2)nCR6CH2, -OC(X)(CH2)nCR6CH2, - OC(X)(CH2)nOC(X)CR6CH2, -N(C(O)C1-C4)( (CH2)nCR6CH2), OC(O)(NR7)(CH2)nCR6CH2,-O-optionally substituted arylene-(CH2)nCR6CH2, -OC(X)- optionally substituted arylene-(CH2)nCR6CH2, -O(CH2)nCCH, -OC(X)(CH2)nCCH, -N(C(O)C1-C4)( (CH2)nCCH), -O-optionally substituted arylene-(CH2)nCCH, -OC(X)- optionally substituted arylene-(CH2)nCCH, -O(CH2)nCHCH2O, -OC(X)(CH2)nCHCH2O - OC(X)(CH2)nOC(X)CHCH2O, -N(C(O)C1-C4)( (CH2)nCHCH2O), OC(O)(NR7)(CH2)nCHCH2O,-O-optionally substituted arylene-(CH2)nCHCH2O, or -OC(X)- optionally substituted arylene-(CH2)nCHCH2O;R2is selected from H or OH;R3is selected from -(CH2)nCR6CH2, -C(X)(CH2)nCR6CH2, C(X)(CH2)nOC(X)CR6CH2, -optionally substituted arylene-(CH2)nCR6CH2, - C(O)(NR7)(CH2)nCR6CH2, -C(X)- optionally substituted arylene-(CH2)nCR6CH2, - (CH2)nCCH, -C(X)(CH2)nCCH, -optionally substituted arylene-(CH2)nCCH, -C(X)- optionally substituted arylene-(CH2)nCCH, -(CH2)nCHCH2O, -C(X)(CH2)nCHCH2O - C(X)(CH2)nOC(X)CHCH2O, -C(O)(NR7)(CH2)nCHCH2O,-optionally substituted arylene-(CH2)nCHCH2O, or -C(X)- optionally substituted arylene-(CH2)nCHCH2O; n is an integer selected from 1 to 7 ;X is O or S;- refers to an optional double bond;R6is H or methyl;R7is H, Cl -4 alkyl or optionally substituted phenyl; andwherein the following compounds are excluded:

6. A compound of the formula (I) according to claim 1 which is a compound of formula (lb):or a salt thereof, wherein:R1is selected from -O(CH2)nCR6CH2, -OC(X)(CH2)nCR6CH2, -OC(X)(CH2)nOC(X)CR6CH2, -N(C(O)C1-C4)( (CH2)nCR6CH2), -OC(O)(NR7)(CH2)nCR6CH2, -O-optionally substituted arylene-(CH2)nCR6CH2, -OC(X)- optionally substituted arylene-(CH2)nCR6CH2, -O(CH2)nCCH, -OC(X)(CH2)nCCH, -N(C(O)C1-C4)( (CH2)nCCH), -O-optionally substituted arylene-(CH2)nCCH, -OC(X)- optionally substituted arylene-(CH2)nCCH, -O(CH2)nCHCH2O, -OC(X)(CH2)nCHCH2O - OC(X)(CH2)nOC(X)CHCH2O, -N(C(O)C1-C4)( (CH2)nCHCH2O), OC(O)(NR7)(CH2)nCHCH2O,-O-optionally substituted arylene-(CH2)nCHCH2O, or -OC(X)- optionally substituted arylene-(CH2)nCHCH2O;R2is selected from H or OH;R3is selected from -(CH2)nCR6CH2, -C(X)(CH2)nCR6CH2, C(X)(CH2)nOC(X)CR6CH2, -optionally substituted arylene-(CH2)nCR6CH2, - C(O)(NR7)(CH2)nCR6CH2, -C(X)- optionally substituted arylene-(CH2)nCR6CH2, - (CH2)nCCH, -C(X)(CH2)nCCH, -optionally substituted arylene-(CH2)nCCH, -C(X)- optionally substituted arylene-(CH2)nCCH, -(CH2)nCHCH2O, -C(X)(CH2)nCHCH2O - C(X)(CH2)nOC(X)CHCH2O, -C(O)(NR7)(CH2)nCHCH2O, -optionally substituted arylene-(CH2)nCHCH2O, or -C(X)- optionally substituted arylene-(CH2)nCHCH2O; n is an integer selected from 1 to 7 ;X is O or S;- refers to an optional double bond; andR6is H or methyl; andR7is H, Cl -4 alkyl or optionally substituted phenyl.

7. A compound of the formula (I) according to claim 1 which is a compound of formula (Ic):or a salt thereof, wherein:R1is selected from H, OH, -O(CH2)nCR6CH2, -OC(X)(CH2)nCR6CH2, -OC(X)(CH2)nOC(X)CR6CH2, -N(C(O)C1-C4)( (CH2)nCR6CH2), OC(O)(NR7)(CH2)nCR6CH2,-O-optionally substituted arylene-(CH2)nCR6CH2, -OC(X)- optionally substituted arylene-(CH2)nCR6CH2, -O(CH2)nCCH, -OC(X)(CH2)nCCH, -N(C(O)C1-C4)( (CH2)nCCH), -O-optionally substituted arylene-(CH2)nCCH, -OC(X)- optionally substituted arylene-(CH2)nCCH, -O(CH2)nCHCH2O, -OC(X)(CH2)nCHCH2O - OC(X)(CH2)nOC(X)CHCH2O, -N(C(O)C1-C4)( (CH2)nCHCH2O), OC(O)(NR7)(CH2)nCHCH2O,-O-optionally substituted arylene-(CH2)nCHCH2O, or -OC(X)- optionally substituted arylene-(CH2)nCHCH2O;R2is selected from -O(CH2)nCR6CH2, -OC(X)(CH2)nCR6CH2, -OC(X)(CH2)nOC(X)CR6CH2, -N(C(O)C1-C4)( (CH2)nCR6CH2), -OC(O)(NR7)(CH2)nCR6CH2, -O- optionally substituted arylene-(CH2)nCR6CH2, -OC(X)- optionally substituted arylene- (CH2)nCR6CH2, -O(CH2)nCCH, -OC(X)(CH2)nCCH, -N(C(O)C1-C4)( (CH2)mCCH), - O-optionally substituted arylene-(CH2)nCCH, or -OC(X)- optionally substituted arylene-(CH2)nCCH, -O(CH2)nCHCH2O, -OC(X)(CH2)nCHCH2O -OC(X)(CH2)nOC(X)CHCH2O, -N(C(O)C1-C4)( (CH2)nCHCH2O), -OC(O)(NR7)(CH2)nCHCH2O, -O-optionally substituted arylene-(CH2)nCHCH2O, or -OC(X)- optionally substituted arylene-(CH2)nCHCH2O;R3is selected from -(CH2)nCR6CH2, -C(X)(CH2)nCR6CH2, C(X)(CH2)nOC(X)CR6CH2, -optionally substituted arylene-(CH2)nCR6CH2, - C(O)(NR7)(CH2)nCR6CH2, -C(X)- optionally substituted arylene-(CH2)nCR6CH2, - (CH2)nCCH, -C(X)(CH2)nCCH, -optionally substituted arylene-(CH2)nCCH, -C(X)- optionally substituted arylene-(CH2)nCCH; -(CH2)nCHCH2O, -C(X)(CH2)nCHCH2O - C(X)(CH2)nOC(X)CHCH2O, -C(O)(NR7)(CH2)nCHCH2O,-optionally substituted arylene-(CH2)nCHCH2O, or -C(X)- optionally substituted arylene-(CH2)nCHCH2O; n is an integer selected from 1 to 7 ;X is O or S;R6is H or methyl;R7is H, Cl -4 alkyl or optionally substituted phenyl; and wherein the following compounds are excluded:

8. A compound of the formula (I) according to claim 1 which is a compound of formula (Id):or a salt thereof, wherein:R1is selected from H, OH, -O(CH2)nCR6CH2, -OC(X)(CH2)nCR6CH2, -OC(X)(CH2)nOC(X)CR6CH2, -N(C(O)C1-C4)( (CH2)nCR6CH2), OC(O)(NR7)(CH2)nCR6CH2,-O-optionally substituted arylene-(CH2)nCR6CH2, -OC(X)- optionally substituted arylene-(CH2)nCR6CH2, -O(CH2)nCCH, -OC(X)(CH2)nCCH, -N(C(O)C1-C4)( (CH2)nCCH), -O-optionally substituted arylene-(CH2)nCCH, -OC(X)- optionally substituted arylene-(CH2)nCCH, -O(CH2)nCHCH2O, -OC(X)(CH2)nCHCH2O - OC(X)(CH2)nOC(X)CHCH2O, -N(C(O)C1-C4)( (CH2)nCHCH2O), OC(O)(NR7)(CH2)nCHCH2O,-O-optionally substituted arylene-(CH2)nCHCH2O, or -OC(X)- optionally substituted arylene-(CH2)nCHCH2O;R2is selected from H, OH, -O(CH2)nCR6CH2, -OC(X)(CH2)nCR6CH2, -OC(X)(CH2)nOC(X)CR6CH2, -N(C(O)C1-C4)( (CH2)nCR6CH2), -OC(O)(NR7)(CH2)nCR6CH2, -O- optionally substituted arylene-(CH2)nCR6CH2, -OC(X)- optionally substituted arylene- (CH2)nCR6CH2, -O(CH2)nCCH, -OC(X)(CH2)nCCH, -N(C(O)C1-C4)( (CH2)mCCH), - O-optionally substituted arylene-(CH2)nCCH, -OC(X)- optionally substituted arylene- (CH2)nCCH, -O(CH2)nCHCH2O, -OC(X)(CH2)nCHCH2O -OC(X)(CH2)nOC(X)CHCH2O, -N(C(O)C1-C4)( (CH2)nCHCH2O), -OC(O)(NR7)(CH2)nCHCH2O, -O-optionally substituted arylene-(CH2)nCHCH2O, or -OC(X)- optionally substituted arylene-(CH2)nCHCH2O;R3is selected from -(CH2)nCR6CH2, -C(X)(CH2)nCR6CH2, C(X)(CH2)nOC(X)CR6CH2, -optionally substituted arylene-(CH2)nCR6CH2, - C(O)(NR7)(CH2)nCR6CH2, -C(X)- optionally substituted arylene-(CH2)nCR6CH2, - (CH2)nCCH, -C(X)(CH2)nCCH, -optionally substituted arylene-(CH2)nCCH, -C(X)- optionally substituted arylene-(CH2)nCCH, -(CH2)nCHCH2O, -C(X)(CH2)nCHCH2O - C(X)(CH2)nOC(X)CHCH2O, -C(O)(NR7)(CH2)nCHCH2O, -optionally substituted arylene-(CH2)nCHCH2O, or -C(X)- optionally substituted arylene-(CH2)nCHCH2O; n is an integer selected from 1 to 7 ;X is O or S;R6is H or methyl;R7is H, Cl -4 alkyl or optionally substituted phenyl; and wherein the following compound is excluded:

9. A compound of formula (II):or salts thereof, wherein: each R1is the same and is selected from H, OH, -O(CH2)nCR6CH2, - OC(X)(CH2)nCR6CH2, -OC(X)(CH2)nOC(X)CR6CH2, -N(C(O)C1-C4)( (CH2)nCR6CH2), -OC(O)(NR7)(CH2)nCR6CH2,-O-optionally substituted arylene-(CH2)nCR6CH2, -OC(X)- optionally substituted arylene - (CH2)nCR6CH2, -O(CH2)nCCH, -OC(X)(CH2)nCCH, -N(C(O)C1-C4)( (CH2)nCCH), -O- optionally substituted arylene-(CH2)nCCH, -OC(X)- optionally substituted arylene - (CH2)nCCH, -O(CH2)nCHCH2O, -OC(X)(CH2)nCHCH2O -OC(X)(CH2)nOC(X)CHCH2O, -N(C(O)C1-C4)( (CH2)nCHCH2O), -OC(O)(NR7)(CH2)nCHCH2O, -O-optionally substituted arylene-(CH2)nCHCH2O, or -OC(X)- optionally substituted arylene-(CH2)nCHCH2O; each R2is the same and is selected from H, OH, -O(CH2)nCR6CH2, - OC(X)(CH2)nCR6CH2, -OC(X)(CH2)nOC(X)CR6CH2, -N(C(O)C1-C4)( (CH2)nCR6CH2), -OC(O)(NR7)(CH2)nCR6CH2, -O- optionally substituted arylene-(CH2)nCR6CH2, - OC(X)- optionally substituted arylene-(CH2)nCR6CH2, -0(CH2)nCCH, - OC(X)(CH2)nCCH, -N(C(O)C1-C4)( (CH2)mCCH), -O-optionally substituted arylene- (CH2)nCCH, -OC(X)- optionally substituted arylene-(CH2)nCCH, -O(CH2)nCHCH2O, -OC(X)(CH2)nCHCH2O -OC(X)(CH2)nOC(X)CHCH2O, -N(C(O)C1-C4)( (CH2)nCHCH2O), -OC(O)(NR7)(CH2)nCHCH2O,-O-optionally substituted arylene-(CH2)nCHCH2O, or -OC(X)- optionally substituted arylene-(CH2)nCHCH2O; r is an integer selected from 0 to 7 ;X is O or S;R6is H or methyl; andR7is H, Cl -4 alkyl or optionally substituted phenyl.

10. A compound of formula (III):or salts thereof, wherein:R1is selected from H, OH, -O(CH2)nCR6CH2, -OC(X)(CH2)nCR6CH2, -OC(X)(CH2)nOC(X)CR6CH2, -N(C(O)C1-C4)( (CH2)nCR6CH2), -OC(O)(NR7)(CH2)nCR6CH2, -O-optionally substituted arylene-(CH2)nCR6CH2, -OC(X)- optionally substituted arylene - (CH2)nCR6CH2, -O(CH2)nCCH, -OC(X)(CH2)nCCH, -N(C(O)C1-C4)( (CH2)nCCH), -O- optionally substituted arylene-(CH2)nCCH, -OC(X)- optionally substituted arylene - (CH2)nCCH, -O(CH2)nCHCH2O, -OC(X)(CH2)nCHCH2O -OC(X)(CH2)nOC(X)CHCH2O, -N(C(O)C1-C4)( (CH2)nCHCH2O), -OC(O)(NR7)(CH2)nCHCH2O, -O-optionally substituted arylene-(CH2)nCHCH2O, or -OC(X)- optionally substituted arylene-(CH2)nCHCH2O;R2is selected from H, OH, -O(CH2)nCR6CH2, -OC(X)(CH2)nCR6CH2, -OC(X)(CH2)nOC(X)CR6CH2, -N(C(O)C1-C4)( (CH2)nCR6CH2), -OC(O)(NR7)(CH2)nCR6CH2, -O- optionally substituted arylene-(CH2)nCR6CH2, -OC(X)- optionally substituted arylene- (CH2)nCR6CH2, -O(CH2)nCCH, -OC(X)(CH2)nCCH, -N(C(O)C1-C4)( (CH2)mCCH), -O- optionally substituted arylene-(CH2)nCCH, -OC(X)- optionally substituted arylene- (CH2)nCCH, -O(CH2)nCHCH2O, -OC(X)(CH2)nCHCH2O -OC(X)(CH2)nOC(X)CHCH2O, -N(C(O)C1-C4)( (CH2)nCHCH2O), -OC(O)(NR7)(CH2)nCHCH2O, -O-optionally substituted arylene-(CH2)nCHCH2O, or -OC(X)- optionally substituted arylene-(CH2)nCHCH2O; s is an integer selected from 1 to 12; t is an integer selected from 1 to 12;X is O or S;R6is H or methyl; andR7is H, Cl -4 alkyl or optionally substituted phenyl.

11. A compound according to anyone of claims 1 to 10 wherein R1and R2is independently selected from -O(CH2)nCR6CH2, -OC(X)(CH2)nCR6CH2, -OC(X)(CH2)nOC(X)CR6CH2, -N(C(O)C1-C4)( (CH2)nCR6CH2), -OC(O)(NR7)(CH2)nCR6CH2, -O- optionally substituted arylene-(CH2)nCR6CH2, -OC(X)- optionally substituted arylene - (CH2)nCR6CH2, -O(CH2)nCCH, -OC(X)(CH2)nCCH, -N(C(O)C1-C4)( (CH2)nCCH), - O-optionally substituted arylene-(CH2)nCCH, or -OC(X)- optionally substituted arylene-(CH2)nCCH; wherein each R6is H or CH3, each n is 1,2 or 3, and each X is O.

12. A compound according to anyone of claims 1 to 8 wherein R3is selected from - (CH2)nCR6CH2, -C(X)(CH2)nCR6CH2, -C(X)(CH2)nOC(X)CR6CH2, -optionally substituted arylene-(CH2)nCR6CH2, -C(O)(NR7)(CH2)nCR6CH2, -C(X)- optionally substituted arylene-(CH2)nCR6CH2, -(CH2)nCCH, -C(X)(CH2)nCCH, -optionally substituted arylene-(CH2)nCCH, or -C(X)-optionally substituted arylene-(CH2)nCCH; or-(CH2)nCHCH2O, -C(X)(CH2)nCHCH2O -C(X)(CH2)nOC(X)CHCH2O, -C(O)(NR7)(CH2)nCHCH2O, -optionally substituted arylene-(CH2)nCHCH2O, or -C(X)- optionally substituted arylene-(CH2)nCHCH2O; wherein each R6is H or CH3, each n is 1,2 or 3 and each X is O,13. A compound according to anyone of claims 1 to 12 wherein R1and / or R2is - O(CH2)nCHCH2O,-OC(X)(CH2)nCHCH2O -OC(X)(CH2)nOC(X)CHCH2O, -N(C(O)C1-C4)( (CH2)nCHCH2O), -OC(O)(NR7)(CH2)nCHCH2O, -O-optionally substituted arylene-(CH2)nCHCH2O, or -OC(X)- optionally substituted arylene-(CH2)nCHCH2O.13a. A compound according to anyone of claims 1 to 13 wherein X is O.

14. A compound according to anyone of claims 1 to 13 wherein R1and R3are the same.

15. A compound according to anyone of claims 1 to 13 wherein R1and R2are OH.

16. A compound according to anyone of claims 1 to 13 wherein R1and R2are H.

17. A compound according to anyone of claims 1 to 13 wherein R1is H and R2is OH.

18. A compound according to anyone of claims 1 to 13 wherein R1is OH and R2is H.

19. A compound according to anyone of claims 1 to 13 wherein R1and R3are the same.

20. A compound according to anyone of claims 1 to 13 wherein R1, R2and R3are the same.

21. A compound according to anyone of claims 1 to 13 wherein R1and R3are the same, and R2is OH.

22. A compound according to anyone of claims 1 to 13 wherein R1and R3are the same, and R2is H.

23. A compound according to anyone of claims 1 to 13 wherein:R1 is H, orR1 is OH, orR1 is -OCH2CHCH2O, orR1 is -OCH2CHCH2, orR1 is -OCH2CH2CHCH2, orR1 is -OCH2CH2CH2CHCH2, orR1 is -OCH2CH2CH2CH2CHCH2, orR1 is -OCH2CCH, orR1 is -OCH2CH2CCH, orR1 is -OCH2CH2CH2CCH, orR1 is -OCH2CH2CH2CH2CCH, orR1 is -OC(O)CH2CHCH2, orR1 is -OC(O)CH2CH2CHCH2, orR1 is -OC(O)CH2CH2CH2CHCH2, orR1 is -OC(O)CH2CH2CH2CH2CHCH2, orR1 is -OC(O)CH2CCH, orR1 is -OC(O)CH2CH2CCH, orR1 is -OC(O)CH2CH2CH2CCH, orR1 is -OC(O)CH2CH2CH2CH2CCH, orR1 is -OCH2C(CH3)CH2, orR1 is -OC(O)C(CH3)CH2, orR1 is -OC(O)CHCH2, orR1 is -OCH2CH2C(CH3)CH2, orR1 is -OCH2CH2CH2C(CH3)CH2, orR1 is -OCH2CH2CH2CH2C(CH3)CH2, orR1 is -N(C(O)C1-C4)( (CH2)CHCH2), orR1 is -N(C(O)C1-C4)( (CH2CH2)CHCH2), orR1 is -N(C(O)C1-C4)( (CH2)CCH), orR1 is -N(C(O)C1-C4)( (CH2CH2)CCH), orR1 is -O-optionally substituted phenylene-CH2CHCH2, orR1 is -O-optionally substituted phenylene-CH2CH2CHCH2, orR1 is -O-optionally substituted phenylene-CH2CH2CH2CHCH2, orR1 is -O-optionally substituted phenylene-CH2CH2CH2CH2CHCH2, orR1 is -O-optionally substituted phenylene-CH2CCH, orR1 is -O-optionally substituted phenylene-CH2CH2CCH, orR1 is -O-optionally substituted phenylene-CH2CH2CH2CCH, orR1 is -O-optionally substituted phenylene-CH2CH2CH2CH2CCH, orR1 is -OC(O)-optionally substituted phenylene-CH2CHCH2, orR1 is -OC(O)-optionally substituted phenylene-CH2CH2CHCH2, orR1 is -OC(O)-optionally substituted phenylene-CH2CH2CH2CHCH2, orR1 is -OC(O)-optionally substituted phenylene-CH2CH2CH2CH2CHCH2, orR1 is -OC(O)-optionally substituted phenylene-CH2CCH, orR1 is -OC(O)-optionally substituted phenylene-CH2CH2CCH, orR1 is -OC(O)-optionally substituted phenylene-CH2CH2CH2CCH, orR1 is -OC(O)-optionally substituted phenylene-CH2CH2CH2CH2CCH, orR1 is -OC(O)(CH2)OC(O)CHCH2, orR1 is -OC(O)(CH2CH2)OC(O)CHCH2, orR1 is -OC(O)(CH2CH2CH2)OC(O)CHCH2.

24. A compound according to anyone of claims 1 to 13 wherein:R2is H, orR2is OH, orR2is -OCH2CHCH2, orR2is -OCH2CH2CHCH2, orR2is -OCH2CH2CH2CHCH2, orR2is -OCH2CH2CH2CH2CHCH2, orR2is -OCH2CCH, orR2is -OCH2CH2CCH, orR2is -OCH2CH2CH2CCH, orR2is -OCH2CH2CH2CH2CCH, orR2is -OC(O)CH2CHCH2, orR2is -OC(O)CH2CH2CHCH2, orR2is -OC(O)CH2CH2CH2CHCH2, orR2is -OC(O)CH2CH2CH2CH2CHCH2, orR2is -OC(O)CH2CCH, orR2is -OC(O)CH2CH2CCH, orR2is -OC(O)CH2CH2CH2CCH, orR2is -OC(O)CH2CH2CH2CH2CCH, orR2is -N(C(O)C1-C4)( (CH2)CHCH2), orR2is -N(C(O)C1-C4)( (CH2CH2)CHCH2), orR2is -N(C(O)C1-C4)( (CH2)CCH), orR2is -N(C(O)C1-C4)( (CH2CH2)CCH), orR2is -O-optionally substituted phenylene-CtkCHCtk, orR2is -O-optionally substituted phenylene-CtkCtkCHCtk, orR2is -O-optionally substituted phenylene-CH2CH2CH2CHCH2, orR2is -O-optionally substituted phenylene-CH2CH2CH2CH2CHCH2, orR2is -O-optionally substituted phenylene-CtkCCH, orR2is -O-optionally substituted phenylene-CtkCtkCCH, orR2is -O-optionally substituted phenylene-C^CtkCtkCCH, orR2is -O-optionally substituted phenylene-CH2CH2CH2CH2CCH, orR2is -OC(O)-optionally substituted phenylene-CtkCHCtk, orR2is -OC(O)-optionally substituted phenylene-C^CtkCHCtk, orR2is -OC(O)-optionally substituted phenylene-CH2CH2CH2CHCH2, orR2is -OC(O)-optionally substituted phenylene-CH2CH2CH2CH2CHCH2, orR2is -OC(O)-optionally substituted phenylene-CtkCCH, orR2is -OC(O)-optionally substituted phenylene-CtkCtkCCH, orR2is -OC(O)-optionally substituted phenylene-C^CtkCtkCCH, orR2is -OC(O)-optionally substituted phenylene-CH2CH2CH2CH2CCH, orR2is -OC(O)(CH2)OC(O)CHCH2, orR2is -OC(O)(CH2CH2)OC(O)CHCH2, orR2is -OC(O)(CH2CH2CH2)OC(O)CHCH2.

25. A compound according to anyone of claims 1 to 8 wherein:R3is -CH2CHCH2, orR3is -CH2CH2CHCH2, orR3is -CH2CH2CH2CHCH2, orR3is -CH2CH2CH2CH2CHCH2, orR3is -CH2CCH, orR3is -CH2CH2CCH, orR3is -CH2CH2CH2CCH, orR3is -CH2CH2CH2CH2CCH, orR3is -CH2C(CH3)CH2, orR3is -CH2CH2C(CH3)CH2, orR3is -CH2CH2CH2C(CH3)CH2, orR3is -CH2CH2CH2CH2C(CH3)CH2, orR3is -C(O)CH2CHCH2, orR3is -C(O)CH2CH2CHCH2, orR3is -C(O)CH2CH2CH2CHCH2, orR3is -C(O)CH2CH2CH2CH2CHCH2, orR3is -CH2C(CH3)CH2, orR3is -CH2CH2C(CH3)CH2, orR3is -CH2CH2CH2C(CH3)CH2, orR3is -CH2CH2CH2CH2C(CH3)CH2, orR3is -C(O)CH2CCH, orR3is -C(O)CH2CH2CCH, orR3is -C(O)CH2CH2CH2CCH, orR3is -C(O)CH2CH2CH2CH2CCH, orR3is -optionally substituted phenylene-CH2CHCH2, orR3is -optionally substituted phenylene-CH2CH2CHCH2, orR3is -optionally substituted phenylene-CH2CH2CH2CHCH2, orR3is -optionally substituted phenylene-CH2CH2CH2CH2CHCH2, orR3is -optionally substituted phenylene-CH2CCH, orR3is -optionally substituted phcnylcnc-CHiCHiCCH, orR3is -optionally substituted phcnylcnc-CHiCHiCHiCCH, orR3is -optionally substituted phcnylcnc-CHiCHiCHiCHiCCH, orR3is -C(O)-optionally substituted phenylene-CH2CHCH2, orR3is -C(O)-optionally substituted phcnylcnc-CHiCHiCHCHi, orR3is -C(O)-optionally substituted phcnylcnc-CHiCHiCHiCHCHi, orR3is -C(O)-optionally substituted phcnylcnc-CHiCHiCHiCHiCHCHi, orR3is -C(O)-optionally substituted phenylene-CH2CCH, orR3is -C(O)-optionally substituted phcnylcnc-CHiCHiCCH, orR3is -C(O)-optionally substituted phcnylcnc-CHiCHiCHiCCH, orR3is -C(O)-optionally substituted phcnylcnc-CHiCHiCHiCHiCCH, orR3is -C(O)(CH2)OC(O)CHCH2, orR3is -C(O)(CH2CH2)OC(O)CHCH2, orR3is -C(O)(CH2CH2CH2)OC(O)CHCH2.

26. A compound selected from one of the following:r = 627. A polymer which is characterised with a structure based on the polymerisation of at least one or more compounds of formula (I) with at least one or more of the following mercapto compound of formula (IV):wherein R1, R2and R3are as defined in anyone of claims 11-26; andR4is selected from C 1-4 alkyl, or -(CH2)OC(O)(CH2)PSH; and where each p is independently an integer of from 1 to 7, excluding the following compound of Formula (I):

28. A polymer which is characterised with a structure based on the polymerisation of at least one or more compounds of formula (I), (II) or (III) with at least one or more of the following mercapto compound of formula (IV) or (IVa):wherein R1, R2and R3are defined in claims 11-26; andR4is selected from C 1-4 alkyl, or -(CH2)OC(O)(CH2)PSH; each where each p is independently an integer of from 1 to 7, where z is an integer of from 0 to 7, excluding the following compound of Formula (I):

29. A polymer which is characterised with a structure based on the polymerisation of at least one or more compounds of formula (II) or (III) as defined in claims 9 and 10 with at least one or more of the following mercapto compound of formula (IV) or (IVa):wherein R1and R2are defined in claims 11, 13, 15-18, 23, and 24; andR4is selected from Cl -4 alkyl, or -(CH2)OC(O)(CH2)PSH; each where each p is independently an integer of from 1 to 7, where z is an integer of from 0 to 7.

30. A polymer according to claim 28 and 29 in which the mercapto compound is selected from:and each p is selected from 2-5.

31. A method of preparing polymeric compounds according to anyone of claims 26 to 30, said method comprising:(i) providing a mixture of at least one or more of compounds of Formula (I) and subformula thereof , (II), or (III) and at least one or more compounds of Formula (IV) or (IV a) in a suitable solvent;(ii) subjecting the mixture of step (i) to UV light for a period time and under conditions to form the polymeric compounds; or subjecting the mixture of step (i) to epoxide ring opening polymerisation conditions to form the polymeric compounds.

32. A method of preparing the compounds of Formula (I), and subformula thereof, (II), or(III) according to anyone of claims 26 to 30, said method comprising:(a) dissolving a quantity of Levoglucosan (LGA), Levoglucosenone (LGO) or Levoglucosenol (LGO-OH) in a polar aprotic solvent; and(b) reacting the resultant solution of step (a) with an effective quantity of Br-(CH2)nC R6CH2, Br-C(X)(CH2)mCR6CH2, Br-N(C(O)Cl-C4)((CH2)mCR6CH2), Br / I-arylene-(CH2)nCR6CH2, Br / Cl-C(X)-arylene-(CH2)mCR6CH2, Br-(CH2)nCCH, Br-C(X)(CH2)mCCH, Br-N(C(O)Cl-C4)((CH2)mCCH), Br / Cl-OC(O)(NR7)(CH2)mCR6CH2Br / I-arylene-(CH2)nCCH, or Br / Cl-C(X)-arylene- (CH2)mCCH and a quantity of a base for a time and under conditions to form a compound of Formula (I) - (Id), (II) or (III).

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