Compositions comprising polyester and modified hardwood lignin

Abstract

The present invention discloses a composition that can be extruded or injection molded, comprising chemically modified hardwood lignin and a polyester. The chemically modified hardwood lignin comprises 10 to 50 weight percent of the total weight of the composition.

Description

Technical Field

[0001] The present invention relates to a composition comprising polyester and chemically modified hardwood lignin. The composition can be injection molded. Background Art

[0002] More renewable plastic materials are needed, and lignin is a potential natural polymer to be used.

[0003] Lignin is the most readily available natural polymer after cellulose. Along with cellulose and hemicellulose, lignin is present in the cell walls of fibrous plants and wood. Lignin serves as the matrix material for polysaccharides, microfibrils, and fibers, and provides strength to plant stems. It is a high-molecular-weight phenolic macromolecule composed of three different types of monolignols: p-coumaryl alcohol, coniferyl alcohol, and sinapyl alcohol.

[0004] In recent years, have paid a lot of efforts to develop new plastic materials, these plastic materials are the mixtures of well-known synthetic polymers, such as for example polyolefins, polyesters and polynitrile, and various forms of xylogen.So, the consumer goods part that for example is made of such mixture is made of xylogen.Therefore, compared with the corresponding product that is made of synthetic polymer as unique main component, they can be considered to be more environmentally friendly, and synthetic polymer is derived from non-recyclable fossil source usually.The problem that this type of mixture will overcome comprises that the overall miscibility of xylogen and various synthetic polymers is relatively low, and the thermal stability of tight xylogen is relatively low, and the undesirable characteristic of gained mixture, for example relatively low fracture strain or tensile strength.Paid effort to solve such problem by modification xylogen used, for example by adjusting production parameters and by producing back chemical modification.

[0005] Polyester is a natural or synthetic polymer consisting of repeating units linked by ester groups (-OC[=O]-). Examples of thermoplastic synthetic polyesters include polyethylene terephthalate (PET), for example used as fibers in textile applications, polybutylene adipate terephthalate (PBAT), for example used as a biodegradable alternative to polyethylene in, for example, plastic bags; and polybutylene succinate (PBS), often the material of choice for biodegradable plastic films. Further examples of thermoplastic polyesters include polylactic acid (PLA), used as, for example, a plastic filament material, polycaprolactone (PCL), which can be used as, for example, an impact-reinforcing additive, and polybutylene terephthalate (PBT), often used as, for example, an electrical insulator.

[0006] WO2018 / 111183A1 discloses a polymer material comprising a first polymer and modified lignin. It teaches that the first polymer can be a natural or synthetic polymer. Separate embodiments related to the first polymer include a polymer selected from the group consisting of polyolefins, polyesters, and polynitriles. Disadvantages of this type of polymer material include a significant reduction in tensile strength and elongation at break compared to the first polymer alone.

[0007] In the Journal of the American Association of Pulp and Paper Engineers (Tappi Journal), March 2017, Vol. 3, pp. 111-121, Glasser et al. disclose compostable films comprising a biodegradable polyester and modified kraft lignin. The modified kraft lignin is obtained by O-alkylating the corresponding lignin using propylene oxide as an alkylating agent. Disadvantages of this type of compostable film include unstable bubbles during melt processing of 12-14 μm films when the modified kraft lignin content exceeds 30%.

[0008] US 9,000,075 B2 discloses a composition comprising a reaction product obtained by a transesterification reaction between hydroxypropyl lignin and a polyester. Disadvantages of such compositions include the need for special conditions, such as the use of a catalyst, suitable for forming a covalent bond at a stage in the manufacturing process when the hydroxypropyl lignin and the polyester are in close proximity.

[0009] In ACS Sustainable Chem. Eng. 2020, 8, 5338-5346, Xiong et al. disclose biodegradable PBAT / lignin composites comprising modified eucalyptus hydrothermal lignin. The lignin therein is modified by methylation or in the process of grafting PBAT with maleic anhydride as a compatibilizer. In the resulting composite material comprising 40 wt% of the corresponding lignin, a decrease in tensile strength and elongation at break of 21.6% and 33.2%, respectively, was observed compared to PBAT. The disadvantages of this type of composite material having a lignin content of at least 40 wt% compared to PBAT include a significant decrease in both tensile strength and elongation at break. Summary of the Invention

[0010] The present invention discloses one or several solutions on how to overcome one or several disadvantages of the above-mentioned prior art.

[0011] It is an object of the present invention to provide a composition comprising modified lignin, wherein the composition can be processed using conventional techniques such as extrusion, kneading, film blowing and injection molding.

[0012] Another object of the present invention is to disclose a composition comprising modified lignin and polyester, which composition has such physical properties that products made therefrom can be used as substitutes for corresponding products made only from polyester.

[0013] Yet another object of the present invention is to disclose a composition comprising modified lignin and polyester, which composition has a fracture strain or toughness that is comparable to or exceeds, respectively, the corresponding fracture strain or toughness of the polyester itself.

[0014] In a first aspect, the present invention relates to a composition comprising a chemically modified hardwood lignin and a polyester, wherein the chemically modified hardwood lignin carries one or several O-substituents selected from the group consisting of substituents of formulae IS to VI-S.

[0015]

[0016] The hydroxyl groups of the hardwood lignin are substituted and thus carry one or more substituents of formulae 1S to VI-S via covalent bonds, indicated by dashed lines, which are derived from the hydroxyl oxygen atoms of the softwood lignin. R comprises at least 2 carbon atoms. The polyester is one or more of PET, PLA, PCL, PBT, PEF, PHA, PHB, PBS, and PBAT. The chemically modified hardwood lignin represents 2 to 90 wt.-% of the total weight of the composition.

[0017] In a second aspect, the invention relates to a product which comprises the composition and which can be extruded and / or injection moulded.

[0018] In a third aspect, the present invention is directed to a method of extruding a composition, comprising the steps of: mixing chemically modified hardwood lignin and a polyester and, optionally, a compatibilizer to form a mixture; extruding the mixture at a temperature of at least 100°C to form an extruded material; optionally cutting the extruded material into pellets; and optionally drying the extruded material.

[0019] In a fourth aspect, the present invention relates to a method of injection molding a composition, the method comprising the steps of: providing pellets or powder of the composition; and injection molding the pellets or powder into a desired shape at a temperature of at least 100°C.

[0020] All embodiments herein are applicable in all respects. DETAILED DESCRIPTION

[0021] In this application, the term "lignin" means a polymer comprising coumarin, coniferyl and sinapyl alcohol monomers.

[0022] In this application, the terms "linker" or "linker group" are used interchangeably and refer to any group that can link lignin to a chemical group (e.g., a chemical group comprising an alkyl or alkylene fragment). It should be understood that a portion of the linker (e.g., an oxygen atom) can be derived from lignin and, after a precursor (e.g., a synthetic intermediate) is attached to the lignin, forms part of the linker itself.

[0023] In this application, the term "compatibilizer" means a compound that promotes adhesion between polymers that are otherwise poorly compatible. Compatibilizers are widely used to increase the miscibility of originally immiscible polymers or polymers that do not mix so well.

[0024] In the present application, the term "hardwood lignin" (HWL) is understood as lignin derived from hardwood, ie derived from hardwoods (angiosperms).

[0025] The botanical distinction between softwoods and hardwoods lies in their reproduction, not their end use or appearance. All trees reproduce by producing seeds, but the seed structure differs. Generally speaking, hardwoods come from deciduous trees that shed their leaves annually, while softwoods come from coniferous trees that generally remain evergreen. Hardwoods tend to grow slower and, therefore, are generally denser. Softwood trees are known as gymnosperms. Gymnosperms reproduce by forming cones, which release pollen that is carried by the wind to other trees. Hardwoods are angiosperms, a type of plant that produces seeds or fruits with some kind of covering, such as a shell.

[0026] Examples of hardwood trees include, but are not limited to, trees of the genus Triplochiton, hardwood Abachi (Triplochiton scleroxylon), trees of the genus Acacia, such as Acacia acuminate, Acacia amythethophylla, Acacia catechu, Acacia confusa, Acacia erioloba, Acacia galpinii, Acacia goetzii, Acacia karoo, Acacia leucophloea, Acacia melanoxylon, Acacia mellifera subsp. mellifera, Acacia nilotica, Acacia adstringens subsp. nilotica subsp. adstringens), Acacia nilotica subsp. nilotica, Acacia polyacantha subsp. Campylacantha, Silver wattle (Acacia dealbata), Paper thorn (Acacia sieberiana), and Robinia pseudoacacia, trees from the genus Alder (Alnus), such as Black alder (Alnus glutinosa) and Red alder (Alnus rubra), trees from the genus Ash (Fraxinus), such as Black ash (Fraxinus nigra), Blue ash (Fraxinus quadrangulata), Common ash (Fraxinus excelsior), Green ash (Fraxinus truncatum), and White ash (Fraxinus truncatum). ash) (Fraxinus pennsylvanica), Oregon ash (Fraxinus latifolia), Pumpkin ash (Fraxinus profunda), and White ash (Fraxinus truncatum)ash) (Fraxinus americana), trees from the genus Aspen (Populus), such as Bigtooth aspen (Populus gradidentata), European aspen (Populus tremula), Quaking aspen (Populus tremuloides), trees from the genus Distemonanthus, such as Ayan, Movingui (Distemonanthus benthamianus), trees from the genus Ochroma, such as Balsa (Ochroma pyramidale), trees from the genus Beech (Fagus), such as American beech (Fagus grandifolia), (Fagus chienii), Siebold's beech (Fagus crenata), Chinese beech (Fagus engleriana), Taiwan beech (Fagus hayatae), Japanese beech or Japanese blue beech (Fagus japonica), South Chinese beech (Fagus longipetiolata), Shining beech (Fagus lucida), Oriental beech (Fagus orientalis), European beech (Fagus sylvatica), and Crimean beech (Fagus × taurica), trees from the genus Basswood or linden family (Tilia), such as American basswood (Tilia americana) and white basswood (Tilia heterophylla), and trees from the genus Birch (Betula), such as red birch (Betula albosinensis), Betula alnoides, Betula ashburneri, Betulabaschkirica, Betula baschkirica, Betula baschkirica, Betula baschkirica, Betula calcicole, Betula celtiberica, Betula chichibuensis, Betula chinensis, Betula paperbark birch, Betula corylifolia, Betula costata, Betula cylindrostachya, Betula dahurica, Betula delavayi, Betula ermanii, Betula falcata, Betula fargesii, Betula fruticosa, Betula globispica, Betula gmelinii, Betula grossa, Betula gynoterminalis, Betula honanensis, Betula dahurica, Betula baschkirica, Betula baschkirica, Betula baschkirica, Betula baschkirica, Betula baschkirica, Betula baschkirica, Betula baschkirica, Betula baschkirica, Betula baschkirica, Betula baschkirica, Betula baschkirica, Betula baschkirica, Betula baschkirica, Betula baschkirica humilis), Fragrant Birch (Betulainsignis), Betula karagandensis, Betula klokovii, Betula kotulae, Bright-leaved Birch (Betula luminifera), Black Birch (Betula maximowiczii), Caucasian Birch (Betula medwediewii), Betula megerlica, Small-leaved Birch (Betula microphylla), Dwarf Arctic Birch (Betula nana), Weeping Birch (Betulapendula), White Birch (Betula platyphylla), Betula potamophila, Dwarf Birch (Betula potaninii), Betula psammophila, European Birch (Betula pubescens), Betula raddeana, Betula saksarensis, Betula saviczii, Black Birch (Betula schmidtii), Sunan Birch (Betula sunanensis), Sichuan Birch (Betula szechuanica), Tianshan Birch (Betula tianshanica), Betula utilis, Betula wuyiensis, Betulazinserlingii, Canada yellow birch (Betula alleghaniensis), paper birch (Betula cordifolia), glandular birch (Betula glandulosa), hard birch (Betula lenta), Newfoundland dwarf birch (Betula michauxii), small white birch (Betula minor), Murray birch (Betula murrayana), bog birch (Betula nana), Alaskan birch (Betula neoalaskana), river birch (Betula nigra), water birch (Betula occidentalis), North American white birch (Betula papyrifera), gray birch (Betula populifolia), Betula pumila, and Virginia round-leaved birch (Betula uber), trees from the genus Castanospermum, such as blackbean (Castanospermum australe), trees from the genus Brosimum, such as bloodwood (Brosimum rubescens, trees from the genus Acer, such as Boxelder (Acer negundo), trees from the genus Buxus, such as Boxwood, common box (Buxus sempervirens), trees from the genus Ocotea, such as Brazilian walnut (Ocotea porosa), trees from the genus Caesalpinia, such as Brazilwood (Caesalpinia echinata), trees from the genus Aesculus, such as Horse-chestnut (Aesculus hippocastanum), Ohiobuckeye (Aesculus glabra) and Yellow buckeye (Aesculus flava), trees from the genus Juglans, such as Butternut (Juglans cinerea, trees from the genus Umbellularia, such as California bay laurel (Umbellularia californica), trees from the genus Cinnamomum, such as Camphortrees from the genus Cherry (Prunus), such as Black cherry (Prunus serotina), Red cherry (Prunus pensylvanica) and Wild cherry (Prunus avium); trees from the genus Chestnut (Castanea spp.), such as European chestnut (Castanea sativa) and American chestnut (Castanea spp.). dentata), trees from the genus Ceratopetalum, such as Coachwood (Ceratopetalum apetalum), trees from the genus Leitneria, such as Corkwood (Leitneria floridana), trees from the genus Magnolia, such as Cucumbertree (Magnolia acuminata), trees from the genus Dipteryx, such as Dipteryxalata, trees from the genus Dogwood (Cornus), such as Flowering dogwood (Cornus florida) and Pacific dogwood (Cornus nuttallii), trees from the genus Ebony (Diospyros), such as Andaman marblewood (Diospyros kurzii), Ebènemarbre (Diospyros truncatum), and more. melanida), African ebony (Diospyros crassiflora), and Ceylon ebony (Diospyrosebenum, trees from the genus Elm (Ulmus), such as American elm (Ulmus americana), English elm (Ulmus procera), Rock elm (Ulmus thomasii), Slippery elm, red elm (Ulmus rubra), and Wych elm (Ulmus glabra), trees from the genus Eucalyptus (Eucalyptus), such as the Lyptus mixture of Flooded gum (Eucalyptus grandis) and Timor white gum (Eucalyptus urophylla), White mahogany (Eucalyptus acmenoides), Brown mallet (Eucalyptus astringens), Banglay, southern mahogany (Eucalyptus botryoides), River red gum (Eucalyptus camaldulensis), Karri (Eucalyptus diversicolor), Blue gum (Eucalyptus globulus), Flooded gum or rose gum (Eucalyptus grandis), York gum (Eucalyptus loxophleba), Jarrah (Eucalyptus marginata), Tallowwood (Eucalyptus microcorys), Grey ironbark (Eucalyptus paniculata), Blackbutt (Eucalyptus pilularis), Mountain ash (Eucalyptus regnans), Australian oak (Eucalyptus obliqua), Alpine ash (Eucalyptus delegatensis), Red mahogany (Eucalyptus resinifera), Swampmahogany (Eucalyptus robusta), Sydney bluegum (Eucalyptus saligna), Mugga or red ironbark (Eucalyptus sideroxylon), Redwood (Eucalyptus transcontinentalis) and Wandoo (Eucalyptus wandoo), trees from the genus Malus, such as the European crabapple (Malus sylvestris), trees from the genus Pyrus, such as the European pear (Pyrus communis), trees from the genus Pyrus ( alves (Astronium), such as Astronium balansae, Astronium concinnum, Astronium conzattii, Astronium fraxinifolium, Astronium gardneri, Astronium glaziovii, Astronium graveolens, Astronium lecointei, Astronium mirandae, Astronium nelson-rosae, Astronium obliquum and Astronium ulei, Astronium urundeuva), trees from the genus Chlorocardium, such as Greenheart (Chlorocardium rodiei), trees from the genus Dalbergia, such as Grenadilla (Dalbergia melanoxylon), Jacarandá de Brasil (Dalbergia nigra), Kingwood (Dalbergia cearensis), Cocobolo (Dalbergia retusa) and Thailand rosewood (Dalbergia cochinchinensis), trees from the genus Calophyllum, such as Guanandi (Calophyllum brasiliense), trees from the genus Bursera, such as Gumbo limbo (Bursera simaruba), trees from the genus Celtis, such as Hackberry (Celtis occidentalis), trees from the genus Hickory (Carya), such as Pecan (Carya illinoinensis), Pignut hickory (Carya glabra), Shagbark hickory (Carya ovata) and Shellbark hickory (Carya laciniosa), from the tree of the genus Hornbeam (Carpinus),For example, American hornbeam (Ostrya virginiana), from the genus Campanula, Trees from the genus Handroanthus, Handroanthus albus, Handroanthus billbergii, Handroanthus chrysanthus, Handroanthus chrysotrichus, Handroanthus guayacan, Handroanthus heptaphyllus, Handroanthus impetiginosus, Handroanthus incanus, Handroanthus lapacho, Handroanthus ochraceus, Handroanthus serratifolius, Handroanthus subtilis, Handroanthus umbellatus, and Handroanthus vellosoi, trees from the genus Milicia, African teak (Milicia excelsa), trees from the genus Carpinus, for example, American hornbeam (Carpinus caroliniana), trees from the genus Casuarina, for example, Polynesian ironwood (Casuarina equisetifolia), trees from the genus Choricarpia, for example, Giantironwood (Choricarpia subargentea), trees from the genus Copaifera, for example, Diesel tree (Copaifera langsdorffii), trees from the genus Eusideroxylon, for example, Borneo ironwood (Eusideroxylon zwageri), trees from the genus Guaiacum, for example, Guaiacwood (Guaiacum officinale and Holywood (Guaiacum sanctum), trees from the genus Hopea, such as Takian (Hopea odorata), trees from the genus Krugiodendron,For example, black ironwood (Krugiodendronferreum), trees from the genus (Olea), such as black ironwood (Oleacapensis), trees from the genus (Androstachys), such as Lebombo ironwood (Androstachysjohnsonii), trees from the genus (Lyonothamnus), such as Catalina ironwood (Lyonothamnus floribundus), trees from the genus (Mesua), such as Ceylonironwood (Mesua ferrea), trees from the genus (Olneya), such as Desertironwood (Olneya tesota), trees from the genus (Parrotia), such as Persian ironwood (Parrotia persica, trees from the genus Caesalpinia, such as the Brazilian ironwood (Caesalpinia ferrea), trees from the genus Tabebuia, such as the Yellowlapacho (Tabebuia serratifolia), trees from the genus Jacaranda, such as the Brazilian Jacaranda (Jacaranda brasiliana), trees from the genus Hymenaea, such as the Jatobá (Hymenaea courbaril), trees from the genus Cardwellia, such as the Northern silky oak (Cardwellia sublimis), trees from the genus Platanus, such as the American sycamore (Platanus occidentalis) and the London plane tree (London plane tree). plane) (Platanus × acerifolia), trees from the genus Terminalia, for example Limba (Terminalia superba), trees from the genus Locust (Robina), for example Black locust (Robinia pseudoacacia), trees from the genus Gleditsia,For example, honey locust (Gleditsia triacanthos), trees from the genus Swietenia, such as West Indies mahogany (Swietenia mahagoni), Bigleaf mahogany (Swietenia macrophylla), Pacific Coast mahogany (Swietenia humilis), trees from the genus African mahogany (Khaya), such as Khaya anthotheca, Khaya grandifoliola, Khaya ivorensis, Khaya madagascariensis, and Khaya senegalensis, trees from the genus Toona, such as Chinese mahogany (Toona sinensis), Australian mahogany (Toona sinensis), and redcedar (Toona ciliata) and Philippine mahogany (Toona calantas), Indonesian mahogany (Toona sureni), trees from the genus Sapele (Entandrophragmacylindricum), Sipo (Entandrophragma utile), Tiama (Entandrophragma angolense), Kosipo (Entandrophragma candollei), Mountain mahogany (Entandrophragma caudatumi), trees from the genus Chukrasia, such as Indian mahogany (Chukrasia velutina), trees from the genus Cedrela, such as Spanish Cedar or Brazilian mahogany (Cedrela odorata), from the tree of the genus Guarea,For example, Light bosse (Guarea cedrata), Dark bosse (Guarea thompsonii) and American muskwood (Guarea grandifolia), trees from the Meliaceae family (Carapa), such as Carapa (Carapa guianensis), trees from the genus Melia, such as Bead-tree (Melia azedarach), trees from the genus Maple (Acer), such as Sugar maple (Acer saccharum), Black maple (Acer nigrum), Boxelder (Acer negundo), Red maple (Acer rubrum), Silver maple (Acersaccharinum) and Sycamore maple (Acer pseudoplatanus, trees from the genus Marmaroxylon, for example Marblewood (Marmaroxylon racemosum), trees from the genus Corymbia, for example Red gum (Corymbia calophylla), trees from the genus Shorea, for example Shorea robusta and Shorea argentifolia, trees from the genus Intsia, for example Merbau (Intsia bijuga), trees from the genus Colophospermum, for example Mopane (Colophospermum mopane), trees from the genus Oak (Quercus),Examples include white oak (Quercus alba), bur oak (Quercus macrocarpa), post oak (Quercus stellata), swamp white oak (Quercus bicolor), southern live oak (Quercus virginiana), swamp chestnut oak (Quercus michauxii), chestnut oak (Quercus prinus), chinkapin oak (Quercus muhlenbergii), canyon live oak (Quercus chrysolepis), overcup oak (Quercus lyrata), English oak (Quercus robur), northern red oak (Quercus rubra), eastern black oak (Quercus velutina), laurel oak (Quercus laurifolia), southern red oak (Quercus falcata), Water oak (Quercus nigra), Willow oak (Quercus phellos) and Nuttall's oak (Quercus texana), trees from the genus Aucoumea, for example Okoumé (Aucoumea klaineana), trees from the genus Olea, for example Olive (Olea europaea), trees from the genus Berchemia, for example Pink ivory (Berchemia zeyheri), trees from the genus Poplar (Populus),For example, Eastern cottonwood (Populus deltoides), Swamp cottonwood (Populusheterophylla), Balsam poplar (Populus balsamifera), Black poplar (Populus nigra), Hybrid black poplar (Populus × canadensis), Black poplar and American black poplar (Populus deltoides), trees from the genus Purpleheart (Peltogyne), such as Peltogyne altissima, Peltogyne angustiflora, Peltogyne campestris, Peltogynenecatingae, Peltogyne confertiflora, Peltogyne discolor, Peltogyne excelsa, Peltogyne floribunda, Peltogyne gracilipes, Peltogyne heterophylla, Peltogyne lecointei, Peltogyne maranhensis, Peltogyne mattosiana, Mexican purpleheart (Peltogyne mexicana), Peltogyne paniculata, Peltogyne paradoxa, Peltogyne parvifolia, Peltogyne pauciflora, Peltogyne prancei, Peltogyne purpurea, Peltogyne recifensis, Peltogyne subsessilis and Peltogyne venosa, trees from the genus Flindersia, for example Queensland maple (Flindersia brayleyana), trees from the genus Endiandra, for example Queensland walnut (Endiandra palmerstonii), trees from the genus Ramin (Gonystylus),For example, Gonystylus acuminatus, Gonystylus affinis, Gonystylus areolatus, Gonystylus augescens, Gonystylus bancanus, Gonystylus borneensis, Gonystylus brunnescens, Gonystyluscalophylloides, Gonystylus calophyllus, Gonystylus confuses, Gonystylusconsanguineous, Gonystylus costalis, Gonystylus decipiens, Gonystylus eximius, Gonystylus forbesii, Gonystylus glaucescens, Gonystylus keithii, Gonystylus lucidulus, Gonystylus macrocarpus), Gonystylusmacrophyllus, Gonystylus maingayi, Gonystylus micranthus, Gonystylus nervosus, Gonystylus nobilis, Gonystylus othmanii, Gonystyluspendulus, Gonystylus punctatus, Gonystylus reticulatus, Gonystylus spectabilis, Gonystylus stenosepalus, Gonystylus velutinus and Gonystylus xylocarpus, trees from the genus Erythroxylon, for example Redheart, chakté-coc (Erythroxylon mexicanum), trees from the genus Liquidambar, for example Sweetgum (Liquidambar styraciflua), trees from the genus Sandalwood (Santalum), for example Indian Sandalwood ( sandalwood) (Santalumalbum), from trees of the genus Sassafras, for example Sassafras albidum,from the genus Atherosperma, for example Southern sassafras (Atherosperma moschatum), from the genus Brosimum, for example Satiné, red satinwood (Brosimum rubescens), from the genus Grevillea, for example Silky oak (Grevillea robusta), from the genus Oxydendrum, for example Sourwood (Oxydendrum arboretum), from the genus Cedrela, for example Spanish-cedar (Cedrela odorata), from the genus Cordia, for example Spanish elm (Cordia alliodora), from the genus Spirostachys, for example Tamboti (Spirostachys africana), trees from the genus Tectona, such as Teak (Tectonagrandis), trees from the genus Tupelo (Nyssa), such as Black tupelo (Nyssasylvatica), trees from the genus Liriodendron, such as Tulip tree (Liriodendron tulipifera), trees from the genus Syncarpia, such as Turpentine (Syncarpia glomulifera), trees from the genus Juglans, such as Eastern black walnut (Juglans nigra), Common walnut (Juglans regia), trees from the genus Willow (Salix), such as Black willow (Salix nigra), Cricket-bat willow)(Salix alba 'Caerulea'), White willow(Salix alba) and Weeping willow(Salix babylonica), from the genus Microberlinia,For example, African zebrawood (Microberlinia brazzavillensis).

[0027] In the present application, the term "hardwood kraft lignin" (HWKL) is to be understood as a subset of HWL, wherein HWKL is produced by withdrawing black liquor from the kraft process and precipitating the lignin by lowering the pH, as is familiar to the skilled person, for example according to the Lignoboost process, the SLRP process or the LignoForce process.

[0028] In the present application, the term "hardwood organosolv lignin" (HWOL) is understood to be a subset of HWL, wherein HWOL is produced by extracting lignin and hemicellulose from wood with the aid of an organic solvent, such as, for example, acetone, methanol, ethanol, butanol, ethylene glycol, formic acid or acetic acid, as is well known to the skilled person. The wood can be pretreated with alkali, acid or enzymes (cellulases). Lignin can be separated from the solvent and hemicellulose by precipitation, for example by adding water and sometimes also by simultaneously lowering the pH.

[0029] In the present application, the term "hardwood alkaline pulp lignin" (HWSPL) is to be understood as a subset of HWL, wherein HWSPL is produced by precipitation of black liquor from an alkaline pulping process and lowering the pH, e.g. according to the Lignoboost process, the SLRP process or the LignoForce process, as is well known to the skilled person.

[0030] Lignin

[0031] Lignin useful in producing the compositions of the present invention may be obtained from any suitable form of hardwood, such as, for example, sawdust or wood chips. An illustration of lignin including the text "LIG" is depicted below (hydroxyl groups not shown).

[0032]

[0033] Hardwoods are preferred because they contain as much lignin as possible. The Kappa number estimates the amount of chemicals required during pulp bleaching to achieve a pulp with a given brightness. Because the amount of bleaching agent required is related to the lignin content in the pulp, the Kappa number can be used to monitor the effectiveness of the lignin extraction stage of the process. It is roughly proportional to the residual lignin content of the pulp.

[0034] K≈c*l

[0035] K: Kappa number; c: constant ≈6.57 (depending on the method); l: lignin content, expressed as a percentage. The Kappa number is determined according to ISO 302:2004. The Kappa number may be 20 or higher, 40 or higher, or 60 or higher. In one embodiment, the Kappa number is from 10 to 100.

[0036] The hardwood material can be a mixture of hardwood materials, and in one embodiment, the hardwood material is black liquor or red liquor, or a material obtained from black liquor or red liquor. Black liquor and red liquor contain cellulose, hemicellulose, and lignin and derivatives thereof. The HWL that can be used to produce the compositions of the present invention can include black liquor or red liquor, or lignin obtained from black liquor or red liquor.

[0037] Black liquor consists of four main organic substances: approximately 30-45% by weight of woody material, 25-35% by weight of saccharinic acid, approximately 10% by weight of formic and acetic acid, 3-5% by weight of extractives, approximately 1% by weight of methanol, and various inorganic elements and sulfur. The exact composition of the liquor varies and depends on the cooking conditions and the raw materials used in the production process. Red liquor includes ions from the sulfite process (calcium, sodium, magnesium, or ammonium), sulfonated lignin, hemicellulose, and low-molecular-weight resins.

[0038] The lignin that can be used to produce the composition of the present invention is essentially HWL, such as, for example, HWKL. In one embodiment, the lignin can be a HWL selected from the group of HWL consisting of: Lignin, precipitated lignin, filtered lignin, acetosolv lignin, lignin from alkaline pulping, or organosolv lignin. In one embodiment, the lignin can be HWKL, acetosolv lignin, or organosolv lignin. In another embodiment, the lignin can be HWKL. In another embodiment, the lignin can be organosolv lignin. In another embodiment, the lignin can be obtained as residual material from ethanol production. The lignin can be in the form of particles having a particle size of 5 mm or less or 1 mm or less.

[0039] Native lignin or kraft lignin is insoluble in most organic solvents, fatty acids or oils. Instead, the prior art has proposed various techniques to depolymerize and convert the depolymerized lignin into components that are soluble in the desired medium.

[0040] The weight average molecular weight (mass) (M) of the lignin that can be used to produce the composition of the present invention w) can be 30,000 g / mol or less, such as no more than 20,000 g / mol, or no more than 10,000 g / mol, or no more than 5,000 g / mol, or no more than 2,000 g / mol, but is preferably higher than 1,000 g / mol, or higher than 1,200 g / mol, or higher than 1,500 g / mol. In one embodiment, the number average molecular weight of the lignin is between 1,000 and 4,000 g / mol, or between 1,500 and 3,500 g / mol.

[0041] Modified or derivatized lignin

[0042] The lignin that can be used to produce the composition of the present invention is essentially modified or derivatized with a chemical group R comprising at least 2 carbon atoms, such as at least 4 carbon atoms. The group R can be, but is not limited to, an alkyl group, such as, for example, C 10 -C 20 -alkyl or C 12 -C 17 -alkyl; an aryl group such as phenyl; or -(CH2CH2O) n CH2CH2O-alk, wherein n is 1 to 180 and alk is H, methyl or ethyl.Group R can be saturated, unsaturated, straight chain, branched, cyclic, and it can be further substituted by little substituent, such as for example OH, NH2, COOH, COO-alkyl or methyl.Group R is basically connected to lignin by the linking group L comprising 0 to 3 carbon atoms, 1 to 3 oxygen atoms and 0 to 1 nitrogen atoms.Linking group L can be derived from the hydroxyl group of lignin.Therefore, linking group L can comprise oxygen atoms, which can usually derive from original lignin.According to schematic chemical structures 1 and 2, linking group L can be connected to the aryl group or the aliphatic moiety on the lignin:

[0043]

[0044] In Formulas 1 and 2 above, lignin is schematically represented by R" and an aromatic or aliphatic group, respectively, L is a linker and R is a chemical group mentioned and explained herein. Since lignin has aliphatic hydroxyl groups and aromatic hydroxyl groups, the linker L can be attached to the aliphatic portion of the lignin (Structure 2). The linker L can also be directly attached to the aromatic group in the lignin (Structure 1). R" can be a hydrogen, an alkyl, an aromatic or alkoxy group or any other group found in lignin. The aromatic group of lignin can include more than one R". Therefore, the composition of the present invention essentially includes HWL, which is derivatized by covalent bonding to a substituent R, which is attached to HWL via a linker L, wherein the substituent R includes at least 2 carbon atoms, such as at least 4 carbon atoms.

[0045] The degree of modification of the hydroxyl group of the lignin that can be used for producing composition of the present invention can be expressed as the equivalent number (eq / ru) of lignin repeating unit.Equivalent number can be 0.01 or higher, 0.05 or higher, 0.1 or higher, 0.2 or higher, or 0.4 or higher, or 0.6 or higher or 0.8 or higher.In the application, it is assumed that the repeating unit of lignin has a molecular weight of 180g / mol.When lignin is chemically modified, the degree of modification of lignin can be very low and still miscible with the first polymer.In one embodiment, equivalent number can be 0.01-0.2, such as 0.02-0.1, 0.03-0.1 or 0.03-0.06.

[0046] The lignin that can be used to produce the composition of the invention is essentially HWL, such as for example HWKL, HWOL or HWSPL.

[0047] According to one embodiment, linking group L can be a chemical group including 3 carbon atoms and 3 oxygen atoms.For example, lignin (such as HWKL, HWOL or HWSPL) can be connected to the group R of lignin by alkylene glycol linking key, i.e. as described in formula I-OCH2CH (OH) CH2O-group or as described in formula II-OCH2CH (CH2OH) O-group modification.The linking group L of modified lignin can be replaced by O- by group R at one of oxygen atoms.The oxygen atom of linking group L (being bonded to the lignin in modified lignin or its part) can be derived from original lignin, i.e., the lignin before any modification producing modified lignin. Alternatively, the oxygen atom of linking group L (being bonded to the lignin in modified lignin or its part) can be derived from chemical reactant, and linking group L is formed by the chemical reactant with the chemical reaction of lignin.

[0048]

[0049] The modified lignin of formula I or II can be produced or synthesized as described below by the reaction between the compound according to formula SM2 and lignin (hydroxyl groups are not shown). According to the compound of formula SM2, it can be directly synthesized by reacting the compound according to formula SM1 with epichlorohydrin, or alternatively, by the corresponding epoxide ring-opening product, then the intramolecular reformation of epoxide by displacement intermediate chloride is synthesized, as known in the art and described below. According to the compound of formula SM2, it can also be synthesized by the O-allylation of the compound of formula SM1, for example, with allyl bromide, then oxidized, for example, with peracid, as known in the art. When producing or synthesizing the modified lignin of formula I or II of the present invention, according to the compound of formula SM2, in situ generation can be carried out under the existence of lignin.

[0050]

[0051] The R group of the modified HWL of Formula I or Formula II according to the present invention can be a linear, cyclic, branched, saturated, or unsaturated alkyl group comprising 4 to 36 carbon atoms, such as, for example, 4 to 25, 14 to 18, 12 to 15, or 12 to 14 carbon atoms. The R group of the modified HWL of Formula I or Formula II according to the present invention can be independently selected from the group consisting of a saturated alkyl group, an unsaturated alkyl group, a linear alkyl group, a branched alkyl group, and a cyclic alkyl group. Such an alkyl group can be further substituted with a substituent independently selected from the group consisting of -OH, an aryl group, and a phenyl group. Such an alkyl group can further be combined with one or more fragments selected from the group consisting of -COO-, -S-, and -O-. The R group of the modified HWL of Formula I or Formula II according to the present invention can be independently selected from the group consisting of a phenyl group, an o-methylphenyl group, a p-methylphenyl group, a cyclohexyl group, a 4-tert-butylphenyl group, a 2-ethylhexyl group, a cardanyl group, and a nonylphenyl group. The R groups of the modified HWL of formula I or formula II according to the present invention can be independently selected from the group consisting of compounds of formula S1, S2, S3, S4, S5 and S6 as depicted below. The integer n of the compounds of formula S1, S2, S3, S4, S5 and S6 can be 1-180, 1-100, 1-50, 1-25, 1-10, 1-5 or 1-2.

[0052]

[0053] The R groups of the modified HWL of Formula I or Formula II according to the present invention may include a plurality of different R groups. For example, such modified lignin may be prepared as taught herein by reacting 2 to 20% (such as 6%) of cresyl glycidyl ether and 2 to 15% (such as 6%) of C 12 -C 14 - prepared by reaction of glycidyl ether.

[0054] According to one embodiment, linking group L can include 1 carbon atom, a nitrogen atom and 2 oxygen atoms, such as for example when it is a carbamate group.For example, lignin (such as HWKL, HWOL or HWSPL) can be modified with a group R connected to lignin by a carbamate moiety, i.e. -NHC(=O)O- group as described in formula III. The oxygen atom of linking group L (bonded to the lignin in the modified lignin or a part thereof) can be derived from original lignin, i.e. the lignin before any modification to produce the modified lignin. Alternatively, the oxygen atom of linking group L (bonded to the lignin in the modified lignin or a part thereof) can be derived from a chemical reactant, and linking group L is formed by the chemical reactant by a chemical reaction with lignin.

[0055]

[0056] Modified lignin of formula III can be produced or synthesized as depicted below by reaction between isocyanate according to formula SM3 and lignin (hydroxyl groups not shown). US3072634(A) discloses a detailed description example of the synthesis of compounds according to formula III.

[0057]

[0058] The R groups of the modified HWL of Formula III according to the present invention can be linear, cyclic, branched, saturated, or unsaturated alkyl groups, benzyl and phenyl groups, with the alkyl groups comprising 4 to 36 carbon atoms, such as, for example, 4 to 25, 14 to 18, 12 to 15, or 12 to 14 carbon atoms. Such R groups can be further substituted with substituents independently selected from the group consisting of aryl, phenyl, and ester. Such R groups can further be combined with one or more moieties selected from the group consisting of -COO-, -S-, and -O-. The R groups of the modified HWL of Formula III according to the present invention can be independently selected from the group consisting of phenyl, cyclohexyl, and octadecyl. The R groups of the modified HWL of Formula III according to the present invention can be independently selected from the group consisting of compounds of Formulas S1, S2, S3, S4, S5, and S6 as described above. The integer n of the compounds of Formula S1, S2, S3, S4, S5 and S6 can be 1-180, 1-100, 1-50, 1-25, 1-10, 1-5 or 1-2.

[0059] The R groups of the modified HWL of Formula III according to the present invention can include a plurality of different R groups. Such a plurality can be selected from two, three or more R groups selected from the list consisting of: saturated alkyl, unsaturated alkyl, linear alkyl, branched alkyl and cyclic alkyl. The alkyl group can be further substituted with substituents independently selected from the group consisting of: aryl and phenyl. The alkyl group can be combined with one or more fragments selected from the group consisting of -COO-, -S- and -O-.

[0060] According to one embodiment, linking group L can be an oxygen atom.For example, lignin (such as HWKL, HWOL or HWSPL) can be connected to the group R of lignin by an oxygen atom, i.e., the -O- group modification as described in Formula IV. The oxygen atom of linking group L (bonded to the lignin in the modified lignin or a part thereof) can be derived from original lignin, i.e., the lignin before any modification of the modified lignin. Alternatively, the oxygen atom of linking group L (bonded to the lignin in the modified lignin or a part thereof) can be derived from a chemical reactant, and linking group L is formed by the chemical reactant by a chemical reaction with lignin.

[0061]

[0062] Modified lignin of formula IV can be produced or synthesized as depicted below by the reaction between an electrophile according to formula SM4 carrying a leaving group X, such as chloride, bromide, mesylate, etc., and lignin (hydroxyl groups not shown). The synthesis of compounds of formula IV is disclosed in Ind. Eng. Chem. Res. 2012, 51, 51, 16713-16720.

[0063]

[0064] The R group of the modified HWL of Formula IV according to the present invention can be a linear, cyclic, branched, saturated, or unsaturated alkyl group comprising 4 to 36 carbon atoms, such as, for example, 4 to 25, 14 to 18, 12 to 15, or 12 to 14 carbon atoms. The R group of the modified HWL of Formula IV according to the present invention can be a saturated alkyl group, an unsaturated alkyl group, a linear alkyl group, a branched alkyl group, or a cyclic alkyl group. Such an R group can be further substituted with a substituent independently selected from the group consisting of an aryl group and a phenyl group. Such an R group can further be combined with one or more moieties selected from the group consisting of -COO-, -S-, and -O-. The R group of the modified HWL of Formula IV according to the present invention can be independently selected from the group consisting of benzyl, o-methylbenzyl, p-methylbenzyl, cyclohexyl, 4-tert-butylbenzyl, 2-ethylhexyl, and nonylphenyl. The R groups of the modified HWL of formula IV according to the present invention can be independently selected from the group consisting of compounds of formula S1, S2, S3, S4, S5 and S6 as described above. The integer n of the compounds of formula S1, S2, S3, S4, S5 and S6 can be 1-180, 1-100, 1-50, 1-25, 1-10, 1-5 or 1-2.

[0065] The R groups of the modified HWL of Formula IV according to the present invention can include a plurality of different R groups. Such a plurality can be selected from two, three or more R groups selected from the list consisting of: saturated alkyl, unsaturated alkyl, linear alkyl, branched alkyl and cyclic alkyl. The alkyl group can be further substituted with substituents independently selected from the group consisting of: aryl, phenyl, benzyl and allyl. The alkyl group can be combined with one or more fragments selected from the group consisting of -COO-, -S- and -O-.

[0066] According to one embodiment, the linking group L can include 1 carbon atom and two oxygen atoms, such as, for example, when it is an ester group. For example, lignin (such as HWKL, HWOL or HWSPL) can be modified with a group R that is connected to the lignin through an ester moiety, i.e., a -C(=O)O- group as depicted in Formula V. The oxygen atom of the linking group L (bonded to the lignin or a portion thereof in the modified lignin) can be derived from the original lignin, i.e., the lignin before any modification to produce the modified lignin. Alternatively, the oxygen atom of the linking group L (bonded to the lignin or a portion thereof in the modified lignin) can be derived from a chemical reactant, and the linking group L is formed by the chemical reactant by a chemical reaction with the lignin.

[0067]

[0068] The modified lignin of formula V can be produced or synthesized by the reaction between a compound according to formula SM5, SM6 or SM7 and lignin (hydroxyl groups not shown) as depicted below. In US2016355535A, it is taught how to synthesize a compound according to formula V from the corresponding lignin.

[0069]

[0070] The R group of the modified HWL of Formula V according to the present invention can be a linear, cyclic, branched, saturated, or unsaturated alkyl group comprising 4 to 36 carbon atoms, such as, for example, 4 to 25, 14 to 18, 12 to 15, or 12 to 14 carbon atoms. The R group of the modified HWL of Formula V according to the present invention can be a saturated alkyl group, an unsaturated alkyl group, a linear alkyl group, a branched alkyl group, or a cyclic alkyl group. Such an alkyl group can be further substituted with a substituent independently selected from the group consisting of an aryl group, a phenyl group, a benzyl group, and an allyl group. Such an R group can be further substituted with a substituent independently selected from the group consisting of an aryl group and a phenyl group. Such an R group can further be combined with one or more moieties selected from the group consisting of -COO-, -S-, and -O-. The R group of the modified HWL of Formula V according to the present invention can be independently selected from the group consisting of a phenyl group, an o-methylphenyl group, a p-methylphenyl group, a cyclohexyl group, a 4-tert-butylphenyl group, a 2-ethylhexyl group, an octadecyl group, and a benzyl group. The R groups of the modified HWL of formula V according to the present invention can be independently selected from the group consisting of compounds of formula S1, S2, S3, S4, S5 and S6 as described above. The integer n of the compounds of formula S1, S2, S3, S4, S5 and S6 can be 1-180, 1-100, 1-50, 1-25, 1-10, 1-5 or 1-2.

[0071] The R groups of the modified HWL of Formula V according to the present invention can include a plurality of different R groups. Such a plurality can be selected from two, three or more R groups selected from the list consisting of: saturated alkyl, unsaturated alkyl, linear alkyl, branched alkyl and cyclic alkyl. The alkyl group can be further substituted with substituents independently selected from the group consisting of: aryl, phenyl, benzyl and allyl. The alkyl group can be combined with one or more fragments selected from the group consisting of -COO-, -S- and -O-.

[0072] According to one embodiment, linking group L can include 2 carbon atoms and an oxygen atom, such as for example when it is a dimethylsiloxy group.For example, lignin (such as HWKL, HWOL or HWSPL) can be used with the group R being connected to lignin by dimethylsiloxy moiety, i.e. -Si(Me) 2O- group modification as described in Formula VI. The oxygen atom of linking group L (being bonded to the lignin in the modified lignin or its part) can be derived from original lignin, i.e. the lignin before any modification producing the modified lignin. Alternatively, the oxygen atom of linking group L (being bonded to the lignin in the modified lignin or its part) can be derived from chemical reactant, and linking group L is formed by the chemical reactant with the chemical reaction of lignin.

[0073]

[0074] Modified lignin of formula VI can be produced or synthesized by reacting a compound according to formula SM8 (wherein X can be a halogen, such as, for example, Cl) with lignin (hydroxyl groups not shown) as depicted below. In ACS Sustainable Chem. Eng. 2016, 4, 10, 5212-5222, it is taught how compounds of formula VI can be synthesized from the corresponding lignin.

[0075]

[0076] The R group of the modified HWL of Formula VI according to the present invention can be a linear, cyclic, branched, saturated, or unsaturated alkyl group comprising 4 to 36 carbon atoms, such as, for example, 4 to 25, 14 to 18, 12 to 15, or 12 to 14 carbon atoms. The R group of the modified HWL of Formula VI according to the present invention can be a saturated alkyl group, an unsaturated alkyl group, a linear alkyl group, a branched alkyl group, or a cyclic alkyl group. Such an alkyl group can be further substituted with a substituent independently selected from the group consisting of an aryl group, a phenyl group, a benzyl group, and an allyl group. Such an R group can be further substituted with a substituent independently selected from the group consisting of an aryl group and a phenyl group. Such an R group can further be combined with one or more moieties selected from the group consisting of -COO-, -S-, and -O-. The R group of the modified HWL of Formula VI according to the present invention can be independently selected from the group consisting of a phenyl group, an o-methylphenyl group, a p-methylphenyl group, a tert-butyl group, a methyl group, a cyclohexyl group, a 4-tert-butylphenyl group, a 2-ethylhexyl group, an octadecyl group, a dodecyl group, and a benzyl group. The R groups of the modified HWL of formula VI according to the present invention can be independently selected from the group consisting of compounds of formula S1, S2, S3, S4, S5 and S6 as described above. The integer n of the compounds of formula S1, S2, S3, S4, S5 and S6 can be 1-180, 1-100, 1-50, 1-25, 1-10, 1-5 or 1-2.

[0077] The R groups of the modified HWL of formula VI according to the present invention can include a plurality of different R groups. Such a plurality can be selected from two, three or more R groups selected from the list consisting of: saturated alkyl, unsaturated alkyl, linear alkyl, branched alkyl and cyclic alkyl. The alkyl group can be further substituted with a substituent independently selected from the group consisting of: aryl, phenyl, benzyl and allyl. The alkyl group can be combined with one or more fragments selected from the group of fragments selected from -COO-, -S- and -O-.

[0078] Composition according to the present invention can be by first preparing by linking group L with group R modification or derivatized lignin, then the modified lignin is mixed with polyester to prepare, this polyester is such as for example PET, PBAT, PLA, PCL, PBT, polyethylene 2,5-furandicarboxylate (PEF), polyhydroxyalkanoate (PHA), polyhydroxybutyrate (PHB) or PBS.Can be modified in a suitable solvent.Modified lignin can be separated from the modified reaction mixture, or when mixing with polyester such as for example PET, PBAT, PLA, PCL, PBT, PEF, PHA, PHB or PBS, modified lignin can be stayed in the reaction mixture.Can be mixed by stirring or shaking or in any other suitable manner, and then can heat slurry.Any suitable technology can be used to remove any catalyst and any other undesirable component afterwards.

[0079] The composition according to the invention may alternatively be prepared by reacting lignin with a suitable reagent to link groups R via linkers L as taught herein while mixing with a polyester such as, for example, PET, PBAT, PLA, PCL, PBT, PEF, PHA, PHB or PBS.

[0080] The chemical modification of lignin (e.g., HWL or HWKL) can be carried out at 60°C and 250°C, such as 60°C or higher, 80°C or higher, or 100°C or higher, or 120°C or higher, or 150°C or higher, or 160°C or higher, or 180°C or higher, but preferably not higher than 250°C.

[0081] Compositions comprising chemically modified HWL and polyester

[0082] The present invention relates to a composition comprising a polyester and a chemically modified HWL. The composition is essentially a mixture of a polyester (e.g., PET, PLA, PCL, PBT, PEF, PHA, PHB, PBS, or PBAT) and a chemically modified HWL (e.g., HWKL, according to Figures I, II, III, IV, V, VI, or mixtures thereof). Modification to produce the modified HWL can be accomplished by reacting the HWL with a suitable reagent as taught elsewhere herein.

[0083] Surprisingly, it has been found that the compositions of the present invention have one or several advantageous physicochemical properties, such as, for example, tensile strength, toughness, film-forming properties, such as, for example, film-forming properties of less than or equal to 20 μm or 12 μm, and elongation at break, compared to the corresponding pure polyester itself or to corresponding compositions of the prior art, such as, for example, compositions based on lignin from softwood. According to the current prior art, as detailed further herein above, one or several such physicochemical properties of mixtures of chemically modified lignin and polyester would be expected to be less advantageous compared to the corresponding pure polyester.

[0084] The optimal range of chemically modified HWL in the composition of the present invention may be 2 to 90 wt-%, such as 5 to 80 wt-%, 5 to 70 wt-%, 10 to 60 wt-%, 20 to 60 wt-%, 30 to 60 wt-%, 30 to 50 wt-% or 40 to 60 wt-% of the composition of the present invention.

[0085] In the composition of the present invention, the polyester can generally constitute substantially the remainder of the total weight of the composition, after deducting the weight of the chemically modified HWL. The sum of the polyester(s) and the chemically modified HWL(s) can constitute more than 90 wt.-%, such as more than 95, 98, or 99 wt.-%, of the total weight of the composition. The remaining 10, 5, 2, and 1 wt.-%, respectively, can be constituted by one or more suitable fillers, compatibilizers, and the like.

[0086] Advantageous physicochemical properties of the compositions of the present invention may include, but are not limited to, one or more of the group consisting of: strain at break, Young's modulus, film-forming properties, and toughness.

[0087] According to one embodiment, the composition of the present invention may comprise a chemically modified HWL and a polyester, wherein the chemically modified HWL is a mixture of compounds according to formula I and II, wherein the polyester is selected from the group consisting of polyesters: PET, PLA, PCL, PBT, PEF, PHA, PHB, PBS and PBAT. The substituent R of formula I and II may be selected from C4-C 25 -alkyl, CH[(CH2) m CH3]CH(OH)(CH2) m C(=O)OC 1-3 Alkyl, CH[CH(OH)(CH2) m CH3](CH2) m C(=O)OC 1-3 Alkyl, phenyl, o-methylphenyl, p-methylphenyl, cyclohexyl, 4-tert-butylphenyl, 2-ethylhexyl, cashew, nonylphenyl and compounds of formula S1, S2, S3, S4, S5 and S6, wherein the integer m can be 3 to 10 and the integer n can be 1 to 180. The composition can include 2 to 90 wt-%, such as 5 to 80 wt-%, 5 to 70 wt-%, 10 to 60 wt-%, 20 to 60 wt-%, 30 to 60 wt-% or 40 to 60 wt-% HWL. Advantages of such compositions include improved strain at break compared to the polyester itself.

[0088] According to one embodiment, the composition of the present invention may comprise a chemically modified HWL, such as HWKL, derived from a tree from the genus Eucalyptus, such as, for example, Eucalyptus globulus, and a mixture of compounds according to formula I and II, the polyester being selected from the group of polyesters consisting of: PET, PLA, PCL, PBT, PEF, PHA, PHB, PBS and PBAT. The substituent R of formula I and II may be selected from C4-C 25 -alkyl, CH[(CH2) m CH3]CH(OH)(CH2) mC(=O)OC 1-3 Alkyl, CH[CH(OH)(CH2) m CH3](CH2) m C(=O)OC 1-3 Alkyl, phenyl, o-methylphenyl, p-methylphenyl, cyclohexyl, 4-tert-butylphenyl, 2-ethylhexyl, cashew, nonylphenyl and compounds of formula S1, S2, S3, S4, S5 and S6, wherein the integer m can be 3 to 10 and the integer n can be 1 to 180. The composition can include 2 to 90 wt-%, such as 5 to 80 wt-%, 5 to 70 wt-%, 10 to 60 wt-%, 20 to 60 wt-%, 30 to 60 wt-% or 40 to 60 wt-% HWL. Advantages of such compositions include improved strain at break compared to the polyester itself.

[0089] According to one embodiment, the composition of the present invention may comprise a chemically modified HWL, such as HWKL, derived from a tree from the genus Eucalyptus, such as, for example, Eucalyptus globulus, and a mixture of compounds according to formula I and II, the polyester being selected from the group of polyesters consisting of: PBS and PBAT. The substituent R of formula I and II may be selected from C4-C 25 -alkyl groups, such as, for example, C 12 -C 14 -alkyl. The composition may comprise 20 to 60 wt-%, such as for example 35 to 45 wt-% or 40 wt-% HWL. Advantages of such a composition include improved strain at break compared to the polyester itself.

[0090] According to one embodiment, the composition of the present invention may include a chemically modified HWL and a polyester, wherein the chemically modified HWL is a compound according to formula III, wherein the polyester is selected from the group consisting of PET, PLA, PCL, PBT, PEF, PHA, PHB, PBS and PBAT. The substituent R of formula III may be selected from C4-C 25 -alkyl, CH[(CH2) m CH3]CH(OH)(CH2) m C(=O)OC 1-3 Alkyl, CH[CH(OH)(CH2) m CH3](CH2) m C(=O)OC 1-3Alkyl, phenyl, o-methylphenyl, p-methylphenyl, cyclohexyl, 4-tert-butylphenyl, 2-ethylhexyl, cashew, nonylphenyl and compounds of formula S1, S2, S3, S4, S5 and S6, wherein the integer m can be 3 to 10 and the integer n can be 1 to 180. The composition can include 2 to 90 wt-%, such as 5 to 80 wt-%, 5 to 70 wt-%, 10 to 60 wt-%, 20 to 60 wt-%, 30 to 60 wt-% or 40 to 60 wt-% HWL. Advantages of such compositions include improved strain at break compared to the polyester itself.

[0091] According to one embodiment, the composition of the present invention may include a chemically modified HWL and a polyester, wherein the chemically modified HWL is a compound according to formula IV, wherein the polyester is selected from the group consisting of PET, PLA, PCL, PBT, PEF, PHA, PHB, PBS and PBAT. The substituent R of formula IV may be selected from C4-C 25 -alkyl, CH[(CH2) m CH3]CH(OH)(CH2) m C(=O)OC 1-3 Alkyl, CH[CH(OH)(CH2) m CH3](CH2) m C(=O)OC 1-3 Alkyl, phenyl, o-methylphenyl, p-methylphenyl, cyclohexyl, 4-tert-butylphenyl, 2-ethylhexyl, cashew, nonylphenyl and compounds of formula S1, S2, S3, S4, S5 and S6, wherein the integer m can be 3 to 10 and the integer n can be 1 to 180. The composition can include 2 to 90 wt-%, such as 5 to 80 wt-%, 5 to 70 wt-%, 10 to 60 wt-%, 20 to 60 wt-%, 30 to 60 wt-% or 40 to 60 wt-% HWL. Advantages of such compositions include improved strain at break compared to the polyester itself.

[0092] According to one embodiment, the composition of the present invention may comprise a chemically modified HWL, such as HWKL, derived from a tree from the genus Eucalyptus, such as, for example, Eucalyptus globulus, and a compound according to formula IV, the polyester being selected from the group of polyesters consisting of: PBS and PBAT. The substituent R of formula IV may be selected from CH[(CH2) m CH3]CH(OH)(CH2) m C(=O)OC 1-3 Alkyl, CH[CH(OH)(CH2) m CH3](CH2) m C(=O)OC 1-3Alkyl, phenyl, o-methylphenyl, p-methylphenyl, cyclohexyl, 4-tert-butylphenyl, 2-ethylhexyl, cardanyl, nonylphenyl and compounds of formula S1, S2, S3, S4, S5 and S6, wherein the integer m can be 3 to 10 and the integer n can be 1 to 180. The composition can include 20 to 60 weight-%, such as, for example, 35 to 45 weight-% or 40 weight-% HWL. Advantages of such a composition include improved break strain compared to the polyester itself.

[0093] According to one embodiment, the composition of the present invention may comprise a chemically modified HWL and a polyester, wherein the chemically modified HWL is a compound according to formula V, wherein the polyester is selected from the group consisting of polyesters: PET, PLA, PCL, PBT, PEF, PHA, PHB, PBS and PBAT. The substituent R of formula V may be selected from C4-C 25 The composition may comprise 2 to 90 wt-%, such as 5 to 80 wt-%, 5 to 70 wt-%, 10 to 60 wt-%, 20 to 60 wt-%, 30 to 60 wt-%, or 40 to 60 wt-% HWL. Advantages of such compositions include improved strain at break compared to the polyester itself.

[0094] According to one embodiment, the composition of the present invention may comprise a chemically modified HWL and a polyester, wherein the chemically modified HWL is a compound according to formula VI, wherein the polyester is selected from the group consisting of polyesters: PET, PLA, PCL, PBT, PEF, PHA, PHB, PBS and PBAT. The substituent R of formula VI may be selected from C4-C 25 The composition may comprise 2 to 90 wt-%, such as 5 to 80 wt-%, 5 to 70 wt-%, 10 to 60 wt-%, 20 to 60 wt-%, 30 to 60 wt-%, or 40 to 60 wt-% HWL. Advantages of such compositions include improved strain at break compared to the polyester itself.

[0095] According to one embodiment, the composition of the present invention may comprise a chemically modified HWL and a polyester, wherein the chemically modified HWL is a compound according to formula I, II or IV, and the polyester is selected from the group consisting of polyesters: PBS and PBAT. The substituent R of the compound according to formula I, II or IV may be selected from C4-C 25 -alkyl, CH[(CH2) m CH3]CH(OH)(CH2) m C(=O)OC1-3 Alkyl, CH[CH(OH)(CH2) m CH3](CH2) m C(=O)OC 1-3 Alkyl, phenyl, o-methylphenyl, p-methylphenyl, cyclohexyl, 4-tert-butylphenyl, 2-ethylhexyl, cashew, nonylphenyl and compounds of formula S1, S2, S3, S4, S5 and S6, wherein the integer m can be 3 to 10 and the integer n can be 1 to 180. The composition can include 2 to 90 wt-%, such as 5 to 80 wt-%, 5 to 70 wt-%, 10 to 60 wt-%, 20 to 60 wt-%, 30 to 60 wt-% or 40 to 60 wt-% HWL. Advantages of such compositions include improved strain at break compared to the polyester itself.

[0096] According to one embodiment, the composition of the present invention may comprise a chemically modified HWL and a polyester, wherein the chemically modified HWL is a compound according to formula I or II or a mixture thereof, wherein the polyester is selected from the group consisting of polyesters: PBS and PBAT. The substituent R of the compound according to formula I or II may be selected from C4-C 25 The composition may comprise 2 to 90 wt-%, such as 5 to 80 wt-%, 5 to 70 wt-%, 10 to 60 wt-%, 20 to 60 wt-%, 30 to 60 wt-%, or 40 to 60 wt-% HWL. Advantages of such compositions include improved strain at break compared to the polyester itself.

[0097] According to one embodiment, the composition of the present invention may comprise a chemically modified HWL and a polyester, wherein the chemically modified HWL is a compound according to formula IV, wherein the polyester is selected from the group consisting of PBS and PBAT. The substituent R of the compound according to formula IV may be selected from CH[(CH2) m CH3]CH(OH)(CH2) m C(=O)OC 1-3 Alkyl and CH[CH(OH)(CH2) m CH3](CH2) m C(=O)OC 1-3 alkyl, wherein the integer m can be 3 to 10. The composition can include 2 to 90 wt-%, such as 5 to 80 wt-%, 5 to 70 wt-%, 10 to 60 wt-%, 20 to 60 wt-%, 30 to 60 wt-%, or 40 to 60 wt-% HWL. Advantages of such compositions include improved strain at break compared to the polyester itself.

[0098] According to one embodiment, the composition of the present invention may comprise a chemically modified HWL, such as, for example, HWKL, which HWL is derived from a tree from the genus Eucalyptus. Non-limiting examples of such suitable trees consist of: Eucalyptus grandis, Eucalyptus urophylla, Eucalyptus alba, Eucalyptus astringent, Eucalyptus vinifera, Eucalyptus camaldulensis, Eucalyptus californica, Eucalyptus globulus, Eucalyptus grandis, Eucalyptus obliquus, Eucalyptus rubrum, Eucalyptus serrata, Eucalyptus paniculate, Eucalyptus ramospermum, Eucalyptus almond, Eucalyptus obliquus, Eucalyptus dligertii, Eucalyptus rubrum, Eucalyptus leucanthemum, Eucalyptus lanceolata, Eucalyptus lanceolata, Eucalyptus rubrum, Eucalyptus radiata and Eucalyptus tannicum.

[0099] Studies have shown that the compositions of the present invention can be processed by extrusion and injection molding even without the addition of any compatibilizer. The modified HWL can be blended with polyester and then extruded at a sufficiently high temperature, such as above 100°C, for example, 110-250°C, 130-240°C, 140-220°C, 140-200°C, 140-190°C, or 140-180°C. Extrusion can be performed using a twin-screw extruder. The resulting extruded product can be pelletized or powdered, which can then be dried using any suitable technique.

[0100] Injection molding of the present composition can also be performed at temperatures above 100°C, such as above 110°C or even at 200°C or higher, without any increase in viscosity or pressure. In one embodiment, the temperature is 110-250°C. The starting material for injection molding can be pellets or powders obtained by extrusion as described above. Injection molding is advantageous in that more complex shapes and structures can be produced from existing materials.

[0101] According to one embodiment, the composition of the present invention can be extruded or injection molded to obtain a physical product. Such a physical product can have a predetermined shape, depending on its production and well understood by the skilled person. Such a physical product can be produced by extruding a mixture by mixing the polyester further described herein, the modified lignin of the present invention, and optionally a compatibilizer to form a mixture. The mixture can be extruded at a temperature of at least 100° C., preferably at least 170° C. or at least 250° C., to form an extruded material. The extruded material can then be optionally cut before drying.

[0102] According to one embodiment, the composition of the present invention can be injection molded. For example, powder or pellets of the composition can be molded into a desired shape at a temperature of at least 100°C, or preferably at least 180°C or at least 250°C.

[0103] According to one embodiment, the modified HWL of the present invention may be thermally stable at temperatures up to 150°C, or up to 180°C, or up to 200°C, or up to 220°C, or up to 240°C.

[0104] According to one embodiment, the modified HWL of the present invention can be used as the sole component or one of the components of a compatibilizer. For example, the modified HWL can be mixed with a polymer (such as polyester) or a mixture of polymers (such as a mixture of polyesters) in solution, dry state or melt.

[0105] According to one embodiment, the composition of the present invention may comprise chemically modified hardwood lignin carrying one or several O-substituents selected from the group consisting of substituents of formulae IS and II-S, wherein R may be independently selected from C4-C 25 The polyester of the composition of the present invention can be PBAT (polybutylene adipate terephthalate), PCL (polycaprolactone) or a mixture thereof. The chemically modified hardwood lignin can comprise 10 to 50 weight % of the total weight of the composition, such as 10 to 45 weight % or 10 to 40 weight %.

[0106] According to one embodiment, the composition of the present invention may comprise chemically modified hardwood lignin carrying one or several O-substituents selected from the group consisting of substituents of formulae IS and II-S, wherein R may be independently selected from C4-C 25 The polyester of the composition of the present invention can be PBAT (polybutylene adipate terephthalate), PCL (polycaprolactone) or a mixture thereof. The chemically modified hardwood lignin can comprise 10 to 50 weight % of the total weight of the composition, such as 10 to 45 weight % or 10 to 40 weight %.

[0107] According to one embodiment, the composition of the present invention may comprise chemically modified hardwood lignin carrying one or several O-substituents selected from the group consisting of substituents of formulae IS and II-S, wherein R may be independently selected from C4-C 25 The polyester of the composition of the present invention can be PBAT (polybutylene adipate terephthalate). The chemically modified hardwood lignin can comprise 10 to 50 weight-%, such as 10 to 45 weight-% or 10 to 40 weight-%, of the total weight of the composition.

[0108] According to one embodiment, the composition of the present invention may comprise chemically modified hardwood lignin carrying one or several O-substituents selected from the group consisting of substituents of formulae IS and II-S, wherein R may be independently selected from C4-C 25The polyester of the composition of the present invention may be PCL (polycaprolactone). The chemically modified hardwood lignin may comprise 10 to 50 wt-%, such as 10 to 45 wt-% or 10 to 40 wt-%, of the total weight of the composition.

[0109] According to one embodiment, the composition of the present invention may comprise chemically modified hardwood lignin carrying one or several O-substituents selected from the group consisting of substituents of formulae IS and II-S, wherein R may be independently selected from C4-C 25 -alkyl. The polyester of the composition of the present invention may be PBAT (polybutylene adipate terephthalate). The chemically modified hardwood lignin may comprise 10 to 45 weight-% of the total weight of the composition.

[0110] According to one embodiment, the composition of the present invention may comprise chemically modified hardwood lignin carrying one or several O-substituents selected from the group consisting of substituents of formulae IS and II-S, wherein R may be independently selected from C4-C 25 -alkyl and o-methylphenyl. The polyester of the composition of the present invention may be PCL (polycaprolactone). The chemically modified hardwood lignin may represent 10 to 40 weight-% of the total weight of the composition.

[0111] Example

[0112] Material

[0113] The source of HWL is from Eucalyptus globulus, and the softwood lignin used is derived from a mixture of 50-60% spruce (Picea abies) and 40-50% pine (Pinus sylvestris). The lignin used in this example was processed from black liquor from the Kraft process, where the lignin was precipitated by the Ligno Boost process and then dried to produce lignin powder (96% dry content). 12 -C 14 - Glycidyl ether oil (Cas# 68609-97-2) was purchased from AL.PAS LLC.

[0114] Preparation of chemically modified HWL and softwood lignin (Examples 1:1 to 1:4)

[0115] Example 1:1 Chemically modified HWKL according to formula I and II was prepared by reaction in a Winkworth Laboratory Zigma-paddle kneader, wherein the degree of substitution was 12 wt%, i.e. 0.032 eq / ru, wherein R is C 12 -C 14 -alkyl.

[0116] First, 880g of lignin powder and 120g (0.032eq) C 12 -C 14 -Glycidyl ether oil (Cas#68609-97-2) are mixed together at ambient temperature, which gives a powder of lignin-oil mixture in which the oil is well dispersed with the lignin. 1 kg of lignin-oil mixture that has been preheated to 160-190° C. in the mixing chamber is added to a Winkworth Laboratory Zigma-paddle kneader (working volume of 7 liters, total volume of 10 liters). The oil heating circulator (Huber CC304b) is set to 200° C. (due to energy loss). The rotation speed of the stirring paddle is set to the lowest setting, and a vacuum is applied to about 800 mbar to discharge moisture and volatiles. The machine is stopped every 10 minutes, and the black rubbery viscous material (product) is scraped off the wall for better heat exchange with the lignin-oil powder, and the machine is shut down again and a vacuum is reapplied and the machine is run for another 10 minutes, and the procedure is repeated. After kneading for 45 minutes, all the lignin-oil powder has been converted into a uniform black viscous material. A black, viscous product was removed from the reactor, with a total yield of 946 g of the title product.

[0117] Example 1:2 Chemically modified HWKL according to formula I and II was prepared by reaction in a Winkworth Laboratory Zigma-paddle kneader, wherein the degree of substitution was 20 wt%, i.e. 0.058 eq / ru, wherein R is C 12 -C 14 -alkyl.

[0118] First, 800g lignin powder and 200g (0.058eq) C 12 -C 14-Glycidyl ether oil (Cas#68609-97-2) are mixed together at ambient temperature, which gives a powder of lignin-oil mixture in which the oil is well dispersed with the lignin. 1 kg of lignin-oil mixture that has been preheated to 160-190° C. in the mixing chamber is added to a Winkworth Laboratory Zigma-paddle kneader (working volume of 7 liters, total volume of 10 liters). The oil heating circulator (Huber CC304b) is set to 200° C. (due to energy loss). The rotation speed of the stirring paddle is set to the lowest setting, and a vacuum is applied to about 800 mbar to discharge moisture and volatiles. The machine is stopped every 10 minutes, and the black rubbery viscous material (product) is scraped off the wall for better heat exchange with the lignin-oil powder, and the machine is shut down again and a vacuum is reapplied and the machine is run for another 10 minutes, and the procedure is repeated. After kneading for 45 minutes, all the lignin-oil powder has been converted into a uniform black viscous material. A black, viscous product was removed from the reactor with a total yield of 933 g of product having a structure according to Structures I and II, wherein R is C12-C14.

[0119] Example 1:3 Chemically modified SWKL (softwood kraft lignin) according to formula I and II was prepared by reaction in a Winkworth Laboratory Zigma-paddle kneader, wherein the degree of substitution was 12 wt%, i.e. 0.032 eq / ru, wherein R is C 12 -C 14 -alkyl.

[0120] Prepared using the same procedure as Example 1:1 except that softwood kraft lignin (SWKL) was used.

[0121] Example 1:4 Chemically modified SWKL according to formula I and II was prepared by reaction in a Winkworth Laboratory Zigma-paddle kneader, wherein the degree of substitution was 20 wt%, i.e. 0.058 eq / ru, wherein R is C 12 -C 14 -alkyl.

[0122] Prepared by the same procedure as Example 1:2 except using SWKL.

[0123] Example 1:5 Chemically modified HWKL according to formula I and II was prepared by reaction in a Winkworth Laboratory Zigma-paddle kneader, wherein the degree of substitution was 20 wt %, ie 0.274 eq / ru, wherein R is o-methylphenyl, ie o-tolyl.

[0124] At first, 800g lignin powder and 200g (0.274eq) o-cresyl glycidyl ether oil (Cas#2210-79-9) are mixed together at ambient temperature, and this obtains lignin-oil mixture powder, and wherein oil and lignin disperse well.To be preheated to 160-190 ℃ 1kg lignin-oil mixture in the mixture chamber is added in Winkworth LaboratoryZigma-paddle kneader (working volume is 7 liters, and cumulative volume is 10 liters).Oil heating circulator (Huber CC304b) is set to 230 ℃ (due to energy loss).The rotational speed of stirring paddle is set to the lowest setting, and vacuum is applied to about 800 millibars to discharge moisture and volatile matter.Stop machine every 10 minutes, and black rubbery viscous material (product) is scraped off from wall, so that better carry out heat exchange with lignin-oil powder, and reclose machine and reapply vacuum and machine is run 10min again, and repeat this program. After 45 minutes of kneading, all the lignin-oil powder had been converted into a uniform black, sticky material. A black, sticky product was taken out of the reactor with a total yield of 933 g of a product having a structure according to structures I and II, wherein R is o-methylphenyl, i.e., o-tolyl.

[0125] Production of compositions comprising chemically modified HWL or softwood lignin and polyester

[0126] Example 2:1 Production of a composition comprising 40 wt.-% of a chemically modified HWKL according to formulas I and II wherein the degree of substitution is 12 wt.-% (0.032 eq / ru) and 60 wt.-% of a polyester which is PBAT

[0127] Polybutylene adipate terephthalate (PBAT) (Ecoworld TM 003) was blended with 40% of the compound from experiment 1:1. 30 g of PBAT and 20 g of the compound from experiment 1:1 were added to an internal mixer set at 165°C and a paddle speed of 60 rpm. The internal mixer was run for 10 minutes.

[0128] Example 2:2 Production of a composition comprising 40 wt-% of a chemically modified HWKL according to formulas I and II wherein the degree of substitution is 20 wt % (0.058 eq / ru) and 60 wt-% of a polyester which is PBAT

[0129] Polybutylene adipate terephthalate (PBAT) (Ecoworld TM003) was blended with 40% of the compound from experiment 1:2. 30 g of PBAT and 20 g of the compound from experiment 1:2 were added to an internal mixer set at 165°C and a paddle speed of 60 rpm. The internal mixer was run for 10 minutes.

[0130] Example 2:3 Production of 100% polyester PBAT as a reference

[0131] Polybutylene adipate terephthalate (PBAT) (Ecoworld TM 003) Blending in a Brabender Internal Mixer: Add 50 g of PBAT to the internal mixer set at 165°C and a paddle speed of 60 rpm. The internal mixer is run for 10 minutes.

[0132] Example 2:4 Production of a composition comprising 40 wt.-% of a chemically modified SWKL according to formulas I and II wherein the degree of substitution is 12 wt.-% (0.032 eq / ru) and 60 wt.-% of a polyester which is PBAT

[0133] Polybutylene adipate terephthalate (PBAT) (Ecoworld TM 003) was blended with 40% of the compound from experiment 1:3. 30 g of PBAT and 20 g of the compound from experiment 1:3 were added to an internal mixer set at 165°C and a paddle speed of 60 rpm. The internal mixer was run for 10 minutes.

[0134] Example 2:5 Production of a composition comprising 40 wt.-% of a chemically modified SWKL according to formulas I and II wherein the degree of substitution is 20 wt.-% (0.058 eq / ru) and 60 wt.-% of a polyester which is PBAT

[0135] Polybutylene adipate terephthalate (PBAT) (Ecoworld TM 003) was blended with 40% of the compound from experiment 1:4. 30 g of PBAT and 20 g of the compound from experiment 1:4 were added to an internal mixer set at 165°C and a paddle speed of 60 rpm. The internal mixer was run for 10 minutes.

[0136] Example 2:6 Production of a composition comprising 50 wt-% of a chemically modified HWKL according to formulas I and II wherein the degree of substitution is 20 wt % (0.058 eq / ru) and 50 wt-% of a polyester that is PBAT

[0137] Polybutylene adipate terephthalate (PBAT) (Ecoworld TM003) was blended with 50% of the compound from experiment 1:2. 25 g of PBAT and 25 g of the compound from experiment 1:2 were added to an internal mixer set at 165°C and a paddle speed of 60 rpm. The internal mixer was run for 10 minutes.

[0138] Example 2:7 Production of a composition comprising 45 wt-% of a chemically modified HWKL according to formulas I and II wherein the degree of substitution is 20 wt-% (0.058 eq / ru) and 55 wt-% of a polyester which is PBAT

[0139] Polybutylene adipate terephthalate (PBAT) (Ecoworld TM 003) was blended with 45% of the compound from experiment 1:2. 27.5 g of PBAT and 22.5 g of the compound from experiment 1:2 were added to an internal mixer set at 165°C and a paddle speed of 60 rpm. The internal mixer was run for 10 minutes.

[0140] Example 2:8 Production of a composition comprising 10 wt-% of a chemically modified HWKL according to formulas I and II wherein the degree of substitution is 20 wt % (0.058 eq / ru) and 90 wt-% of a polyester which is PBAT

[0141] Polybutylene adipate terephthalate (PBAT) (Ecoworld TM 003) was blended with 10% of the compound from Experiment 1:2. 45 g of PBAT and 5 g of the compound from Experiment 1:2 were added to an internal mixer set at 165°C and a paddle speed of 60 rpm. The internal mixer was run for 10 minutes.

[0142] Example 2:9 Production of 100% polyester PCL As a reference, polycaprolactone (PCL) (Ingevity TM CAPA6500) were blended in a Brabender internal mixer. 50 g of PCL was added to the internal mixer set at 165°C and a paddle speed of 60 rpm. The internal mixer was run for 10 minutes.

[0143] Example 2:10 A composition comprising 40 wt.-% of a chemically modified HWKL according to formula I and II (wherein the degree of substitution is 20 wt.%) (0.058 eq / ru) and 60 wt.-% of a polyester which is polycaprolactone (PCL) was produced. TMCAPA 6500) was blended with 40% of the compound from experiment 1:2 in a LabTech twin-screw extruder (screw diameter = 20 mm, L / D = 60; screw profile with conveying elements from barrels 1-3, conveying and kneading elements from barrels 4 to 13, and conveying elements from barrels 14-15 to build up pressure to the die; motor power = 11 kW). The total feed rate of the materials was set to 4 kg / h, and the screw speed was set to 350 rpm. In barrel 1, 40% of the compound from experiment 1:2 was fed via a side feeder. In barrel 10, PCL was fed via a side feeder. The processing temperature was set as follows: 80°C (lignin feed) in the first barrel section equipped with a side feeder, 150°C in the second-third barrel sections, 190°C in the fourth-ninth barrel sections, 170-100°C (gradient) in the tenth-fifteenth barrel sections, and 95°C in the die section. Both strands from the die were cooled on an air-cooled conveyor (2.6 m, 8 fans, wire mesh conveyor belt) and then pelletized in a strand pelletizer.

[0144] Example 2: 11 Production of a composition comprising 10 wt-% of a chemically modified HWKL according to formula I and II (wherein the degree of substitution is 20 wt%) (0.058 eq / ru) and 90 wt-% of a polyester that is polycaprolactone (PCL). TM CAPA 6500) was blended with 10% of the compound from experiment 1:2 in a LabTech twin-screw extruder (screw diameter = 20 mm, L / D = 60; screw profile with conveying elements from barrels 1-3, conveying and kneading elements from barrels 4 to 13, and conveying elements from barrels 14-15 to build up pressure to the die; motor power = 11 kW). The total feed rate of the materials was set to 4 kg / h, and the screw speed was set to 350 rpm. In barrel 1, 10% of the compound from experiment 1:2 was fed via a side feeder. In barrel 10, PCL was fed via a side feeder. The processing temperature was set as follows: 80°C (lignin feed) in the first barrel section equipped with a side feeder, 150°C in the second-third barrel sections, 190°C in the fourth-ninth barrel sections, 170-100°C (gradient) in the tenth-fifteenth barrel sections, and 95°C in the die section. Both strands from the die were cooled on an air-cooled conveyor (2.6 m, 8 fans, wire mesh conveyor belt) and then pelletized in a strand pelletizer.

[0145] Example 2:12 A composition comprising 40 wt.-% of a chemically modified HWKL according to formula I and II (wherein the degree of substitution is 20 wt.%) (0.274 eq / ru) and 60 wt.-% of a polyester which is polycaprolactone (PCL) was produced. TMCAPA 6500) was blended with 40% of the compound from experiment 1:5 in a LabTech twin-screw extruder (screw diameter = 20 mm, L / D = 60; screw profile with conveying elements from barrels 1-3, conveying and kneading elements from barrels 4 to 13, and conveying elements from barrels 14-15 to build up pressure to the die; motor power = 11 kW). The total feed rate of the materials was set to 4 kg / h, and the screw speed was set to 350 rpm. In barrel 1, 40% of the compound from experiment 1:5 was fed via a side feeder. In barrel 10, PCL was fed via a side feeder. The processing temperatures were set as follows: 80°C (lignin feed) in the first barrel section equipped with a side feeder, 150°C in the second-third barrel sections, 190°C in the fourth-ninth barrel sections, 170-100°C (gradient) in the tenth-fifteenth barrel sections, and 95°C in the die section. Both strands from the die were cooled on an air-cooled conveyor (2.6 m, 8 fans, wire mesh conveyor belt) and then pelletized in a strand pelletizer.

[0146] Example 2:13 A composition comprising 10 wt-% of a chemically modified HWKL according to formula I and II (wherein the degree of substitution is 20 wt%) (0.274 eq / ru) and 90 wt-% of a polyester that is polycaprolactone (PCL) was produced. TM CAPA 6500) was blended with 10% of the compound from experiment 1:5 in a LabTech twin-screw extruder (screw diameter = 20 mm, L / D = 60; screw profile with conveying elements from barrels 1-3, conveying and kneading elements from barrels 4 to 13, and conveying elements from barrels 14-15 to build up pressure to the die; motor power = 11 kW). The total feed rate of the materials was set to 4 kg / h, and the screw speed was set to 350 rpm. In barrel 1, 10% of the compound from experiment 1:5 was fed via a side feeder. In barrel 10, PCL was fed via a side feeder. The processing temperatures were set as follows: 80°C (lignin feed) in the first barrel section equipped with a side feeder, 150°C in the second-third barrel sections, 190°C in the fourth-ninth barrel sections, 170-100°C (gradient) in the tenth-fifteenth barrel sections, and 95°C in the die section. Both strands from the die were cooled on an air-cooled conveyor (2.6 m, 8 fans, wire mesh conveyor belt) and then pelletized in a strand pelletizer.

[0147] Physicochemical properties of the compositions of the present invention and comparison with corresponding polyesters

[0148] The materials from Examples 2:1, 2:2, 2:3, 2:4, 2:5, 2:6, 2:7, 2:8, 2:9, 2:10, 2:11, 2:12, and 2:13 were each hot-pressed into films. The materials were placed in a hot melt press preheated to 150° C. and subjected to a pressure of 4 tons for 3 minutes, which was then increased to 50 tons for 1 minute. The film thickness target was approximately 1 mm.

[0149] The dog-bone profile was obtained by cutting the film using a manual punching machine (Elastocon EP 08) equipped with a cutting die for tensile testing (Elastocon EP 04 ASTM D638-14). The dog-bone profile had the following dimensions: total length = 85 mm, "reduced" cross-section = 25 mm, width = 4 mm. The test speed was selected to be 3 mm / min, which corresponds to a "reduced" cross-section of 10% according to the standard method ASTM D638.

[0150]

[0151] Note 1: Modified lignin derived from softwood.

[0152] The results in the table above show that, surprisingly, compositions comprising polyester and chemically modified HWL (Examples 2.1 and 2.2) at least have strains at break that significantly exceed the strains at break of corresponding compositions based on softwood lignin (Examples 2.4 and 2.5). Furthermore, surprisingly, compositions comprising 40% by weight of the modified HWL according to the invention have tensile strengths comparable to those of the corresponding polyesters themselves (compare Examples 2.1 and 2.2 with Example 2.3), while corresponding compositions based on softwood lignin have significantly lower tensile strengths than the same pure polyesters themselves (compare Examples 2.4 and 2.5 with Example 2.3). Furthermore, surprisingly, compositions comprising 10, 45, or 50% by weight of the modified HWL according to the invention have strains at break that are at least comparable to those of the corresponding polyesters themselves (compare Examples 2:8, 2:7, and 2:6 with Example 2:3 and compare Examples 2:11, 2:13, 2:10, and 2:12 with Example 2:9). Furthermore, surprisingly, it can be noted that compositions comprising 10 or 40 wt.-% of the modified HWL according to the invention have a tensile strength greater than that of the corresponding polyester itself (compare Examples 2:13, 2:10 and 2:11 with Example 2:9).

[0153] Itemized list of implementation methods

[0154] 1. A composition comprising chemically modified hardwood lignin and polyester, wherein:

[0155] - said chemically modified hardwood lignin carries one or several O-substituents selected from the substituents of formulae IS to VI-S,

[0156]

[0157] -R comprises at least 2 carbon atoms;

[0158] - the polyester is one or more of PET, PLA, PCL, PBT, PEF, PHA, PHB, PBS and PBAT; and

[0159] - the chemically modified hardwood lignin represents 2 to 90 weight-% of the total weight of the composition.

[0160] 2. The composition according to claim 1, wherein

[0161] - the O-substituent is selected from the group consisting of substituents of formulae IS, II-S and IV-S; and

[0162] -R is independently selected from C4-C 25 -alkyl, CH[(CH2) m CH3]CH(OH)(CH2) m C(=O)OC 1-3 Alkyl, CH[CH(OH)(CH2) m CH3](CH2) m C(=O)OC 1-3 Alkyl, phenyl, o-methylphenyl, p-methylphenyl, cyclohexyl, 4-tert-butylphenyl, 2-ethylhexyl, cardanyl, nonylphenyl, and substituents of formula S1, S2, S3, S4, S5, and S6, wherein the integer m is 3 to 10 and the integer n is 1 to 180

[0163]

[0164] 3. The composition according to claim 2, wherein

[0165] - the O-substituent is a mixture of substituents of formula I and II or a substituent of formula IV;

[0166] - When the O-substituent is a mixture of substituents of formula IS and II-S, R is independently selected from C4-C 25 -alkyl, and substituents of formula S1, S2, S3, S4, S5 and S6, wherein the integer n is 1 to 180; and

[0167] - When the O-substituent is a substituent of formula IV-S, R is independently selected from CH[(CH2)m CH3]CH(OH)(CH2) m C(=O)OC 1-3 Alkyl, CH[CH(OH)(CH2) m CH3](CH2) m C(=O)OC 1-3 Alkyl groups and substituents of formula S1, S2, S3, S4, S5, and S6, wherein the integer m is 3 to 10 and the integer n is 1 to 180.

[0168] 4. The composition according to claim 3, wherein

[0169] - the O-substituent is a mixture of substituents of formula I and II; and

[0170] -R is selected from C4-C 25 -alkyl.

[0171] 5. The composition of any one of the preceding claims, wherein the polyester is selected from PBS and PBAT or mixtures thereof.

[0172] 6. A composition according to any one of the preceding claims, wherein the chemically modified hardwood lignin is derived from a tree of the genus Eucalyptus.

[0173] 7. A composition according to any one of the preceding claims, wherein the chemically modified hardwood lignin represents 20 to 60 wt-%, such as 30 to 50 wt-%, of the total weight of the composition, and substantially the remainder of the total weight of the composition is the polyester.

[0174] 8. A product which is extruded and / or injection moulded and comprises the composition according to any one of claims 1 to 7.

[0175] 9. A method of extruding the composition according to any one of claims 1 to 7, comprising the steps of:

[0176] - mixing the chemically modified hardwood lignin and the polyester and optionally a compatibilizer to form a mixture;

[0177] - extruding the mixture at a temperature of at least 100° C. to form an extruded material;

[0178] - optionally cutting the extruded material into pellets; and

[0179] - optionally drying the extruded material.

[0180] 10. A method of injection molding the composition according to any one of claims 1 to 7, comprising the steps of:

[0181] - providing granules or powder of the composition; and

[0182] - Injection moulding the pellets or powder into the desired shape at a temperature of at least 100°C.

Claims

1. A composition comprising chemically modified hardwood lignin and polyester, wherein: - said chemically modified hardwood lignin carries one or several O-substituents selected from the substituents of formulae IS and II-S, -R is independently selected from C4-C 25 -alkyl, phenyl, o-methylphenyl, p-methylphenyl, cyclohexyl, 4-tert-butylphenyl, 2-ethylhexyl, cardanyl and nonylphenyl; - the polyester is PBAT (polybutylene adipate terephthalate), PCL (polycaprolactone) or a mixture thereof; and - the chemically modified hardwood lignin accounts for 10 to 50 weight percent of the total weight of the composition -％。 2. The composition according to claim 1, wherein R is independently selected from C4-C 25 -alkyl, phenyl and o-methylphenyl.

3. A composition according to any one of the preceding claims, wherein The polyester is PBAT (polybutylene adipate terephthalate), and the chemically modified hardwood lignin comprises 10 to 45 weight-%, based on the total weight of the composition.

4. A composition according to any one of the preceding claims, wherein The polyester is PCL (polycaprolactone) and the chemically modified hardwood lignin comprises 10 to 40 wt-% of the total weight of the composition.

5. A composition according to any one of the preceding claims, wherein The chemically modified hardwood lignin is derived from trees of the genus Eucalyptus.

6. A composition according to any one of the preceding claims, wherein In addition to the chemically modified hardwood lignin, substantially the remainder of the total weight of the composition is the polyester.

7. A product which is extruded and / or injection moulded and comprises the composition according to any one of claims 1 to 6.

8. A method of extruding the composition according to any one of claims 1 to 6, comprising the steps of: - mixing the chemically modified hardwood lignin and the polyester and optionally a compatibilizer to form a mixture; - extruding the mixture at a temperature of at least 100° C. to form an extruded material; - optionally cutting the extruded material into pellets; and - optionally drying the extruded material.

9. A method of injection molding the composition according to any one of claims 1 to 6, comprising the steps of: - providing pellets or powder of the composition; and - Injection moulding the pellets or powder into the desired shape at a temperature of at least 100°C.

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