RESINS DERIVED FROM RENEWABLE SOURCES AND STRUCTURES MANUFACTURED FROM SAID RESINS

Abstract

In the present invention a family of preferably bio-based resins is disclosed. The resins exhibit a broad range of applicability in terms of suitable processing techniques. The resins are designed in a manner that allows the introduction of functional in the resin backbone capable of providing adhesion towards reinforcements. The invention also relates to specimen manufactured with said resin.

Claims

1. A resin comprising: a first composition comprised of: 2-99.99% by weight of monomers capable of forming cyclic monomers and/or cyclic monomers and/or oligomers and polymers from said monomers, where the monomers are capable of forming one or more of the following components: lactones, lactames, lactimes, dicyclic esters, cyclic esters, cyclic amides, cyclic aromatic sulphides, cyclic carbonates, 1,5-dioxepan-2-one or cyclic aromatic disulphides, where the oligomers are produced by of one or more of said components, and where the polymers are produced from one or more of said components or lactones, lactames, lactimes, dicyclic esters, cyclic esters, cyclic aromatic sulphides, cyclic carbonates, 1,5-dioxepan-2-one, cyclic aromatic disulphides or other molecules that are capable of undergoing ring opening polymerisation, and where hydroxy acids cannot correspond to more than 50% by mole of the first composition; and a second composition comprised of: 0.01-98% by weight of molecules capable of copolymerising with one or more of said components of the first composition and simultaneously preferably having at least one other reactive chemical group or oligomers or polymers containing said molecules.

2. A resin according to claim 1, where the first composition constitutes 10-99.99% by weight of the resin, and where the second composition constitutes 0.01-80% by weight of the resin, more preferably the first composition constitutes 25-99.99% by weight and the second composition constitutes 0.01-50% by weight, most preferably the first composition constitutes 60-99.99% by weight and the second composition constitutes 0.01-30% by weight.

3. A resin accordance to claim 1, where at least 40% by weight of the sum of the first composition and the second composition originate from a renewable origin being a naturally occurring resource which replenishes to overcome resource depletion through either biological reproduction or other natural reoccurring processes within the human time scale, more preferably at least 60% by weight originate from a renewable origin and most preferably at least 75% by weight.

4. A resin according to claim 1, where the first composition or the second composition contain one or more molecules with a melting point below 70 C.

5. A resin according to claim 1, where the second composition contain at least one molecule with at least one carbon double bond and at least one more reactive group or at least one molecule capable of undergoing ring opening polymerisation and containing at least one more reactive group.

6. A resin according to claim 1, where the resin is in a monomeric state, or in a partly polymerised state or in a fully polymerised state.

7. A resin according to claim 1, and containing monomers, oligomers, and polymers not capable of copolymerising with one or more of the components of the first composition and of the second composition.

8. A resin according to claim 1, and containing fibres or fibrous material with a fibre length of 0.001 mm to 500 mm, more preferably 0.01 mm to 50 mm, most preferably 0.05 mm to 10 mm and/or fillers with a size between 0.001 mm to 100 mm, preferably from 0.001 mm to 5 mm and/or nanofillers with a size between 1 nm and 50,000 nm, preferably from 1 nm to 10,000 nm.

9. A resin according to claim 1, and containing one or more cross linkers capable of undergoing chemical reaction with one or more chemical groups of either the first composition or the second composition or crosslink the polymer network through copolymerization.

10. A resin according to claim 1, and including one or more of antioxidants, UV absorbers, colourants, fungicides, pesticides, antibacterials, antibiotics, fillers, and/or flame retarders.

11. A structure containing the resin according to claim 1, and where the resin of the structure constitutes a sprayable adhesive.

12. A structure containing the resin according to claim 1, and where the resin is capable of being used as an adhesive in the production of fiberboards, particleboards, chipboards, or strawboards.

13. A structure containing the resin according to claim 1, and manufactured by means of resin transfer moulding or vacuum assisted resin transfer moulding or injection or extrusion moulding or pultrusion or needle punching or by airlaid processing or a process, that includes airlaid processing as one of the production steps.

14. A structure, so-called pre-preg, containing a fibrous structure wetted with unpolymerised or partly polymerised resin in accordance with the resin of claim 1.

15. A self-supporting plant receptacle containing the resin according to claim 1 and containing a growth medium, and where the resin constitutes an adhesive to the growth medium.

Description

EXAMPLE 1

[0068] A round bottomed flask equipped with a stirrer is placed in an oil bath at 110 C. and 20 g lactide and 5 g PLA are added. After 10 minutes, the temperature is elevated to 165 C. and through stirring, the PLA is dissolved in the lactide. Upon dissolution, the temperature is reduced to 130 C. and 5 g glycolide and 1 g aconitic acid are added whereupon the mixture is stirred after which the content of the flask is allowed to cool to room temperature and this constitutes one part of a two component resin system.

[0069] In another flask, 50 L of stannous octoate is mixed with 0.4 g of glycerol at room temperature. This constitutes the other part of the two component resin system.

EXAMPLE 2

[0070] A flask equipped with a stirrer is placed in an oil bath at 105 C. and 17 g L-lactide, 5 g meso lactide, 3 g glycolide, 1 g diethyl aconitate and 1.5 g aconitic anhydride are added under stirring. The content of the flask is allowed to cool to room temperature and this constitutes one part of a two component resin system.

[0071] In another flask, 20 L of zinc octoate and 40 L of stannous octoate are mixed with 0.6 g of glycerol and 0.5 g of propylene glycol with a molecular mass of 1000 Da at ambient temperature. This constitutes the other part of the two component resin system.

EXAMPLE 3

[0072] A flask equipped with a stirrer is placed in an oil bath at 105 C. and 20 g lactide, 3 g glycolide, 1 g gamma butyrolactone, 1 g ethyl cinnamate, 1.5 g aconitic anhydride, 0.2 g glycerol and 0.8 mL propylene glycol with a molecular mass of 2000 Da are added under stirring. After obtaining a homogeneous mixture, 30 L of stannous octoate and 7 L ethanol are added under stirring and the mixture is immediately cooled to provide a one component resin system.

EXAMPLE 4

[0073] A round bottomed flask equipped with a stirrer is placed in an oil bath at 110 C. and 20 g of lactide, 1 g 3-hydroxybutyrolactone, 2 g dimethyl itaconate, 0.5 g cinnamyl cinnamate and 5 g of PLA and 1 g of poly butylene succinate are added. After 20 minutes, the temperature is elevated to 165 C. and through stirring, the PLA and poly butylene succinate are dissolved in the lactide. Upon dissolution, the temperature is reduced to 130 C. and 5 g e-caprolactone and 1 g of muconic acid are added whereupon the mixture is stirred whereupon the content of the flask is allowed to cool to room temperature and this constitutes one part of a two component resin system.

[0074] In another flask, 60 L of 4-(dimethylamino)pyridine is mixed with 0.4 g of isophorone diamine at room temperature. This constitutes the other part of the two component resin system.

EXAMPLE 5

[0075] To an aluminium container is added 50 g lactide, 20 g poly (lactic-co-glycolic acid), 0.7 g talc and 60 L stannous chloride and the container is sealed and placed in an oven preheated 160 C. and is left there for 1.5 h whereupon the poly (lactic-co-glycolic acid) is dissolved in the lactide through stirring. The temperature of the oven is reduced to 140 C. and to the mixture, 1 g itaconic acid and 0.5 g fumaric are added under stirring. After 2 h at 140 C., 2 g tyrosine is added gradually under stirring. The mixture is then cooled and represents at partly polymerised one component system.

EXAMPLE 6

[0076] A flask equipped with a stirrer is placed in an oil bath at 105 C. and 15 g lactide, 2 g itaconic acid, 0.3 g lysine, 50 mg 4-pyrrolidinopyridine and 2 g jute fibre with a length between 100 and 500 m are mixed under stirring. Upon mixing, the temperature is increased to 150 C. where it is kept for 3 h. To the mixture 0.5 g of Dupont Biomax Strong 120, 0.6 g poly ethylene glycol and 0.4 g methionine are added under stirring. The mixture is allowed to cool to ambient temperature and represents at partly polymerised one component system.

EXAMPLE 7

[0077] A flask equipped with a stirrer is placed in an oil bath at 120 C. and 15 g lactide, 5 g lactic acid, 2 g cinnamic acid, 0.5 g sinapyl alcohol and 30 L stannous octoate are mixed under stirring and this temperature is kept for 3 h where after the temperature is increased to 160 C. for 2 h. 1 g tryptophan is added under stirring and after bubbling ceases, 15 mg mequinol is added as inhibitor and the reaction mixture is cooled. This part constitutes one part of a partly polymerised two component resin system.

[0078] In another flask, 40 L of zinc octoate is mixed with 0.1 g glycerol, 0.4 g isophorone diamine and 0.5 g of propylene glycol with a molecular mass of 3000 Da at room temperature. This constitutes the other part of the two component partly polymerised resin system.

EXAMPLE 8

[0079] A Teflon container equipped with stirrer is placed in an oven at 120 C. and 15 g lactide, 5 g PLA, 2 g aconitic acid, 1 g of maleic anhydride, 0.5 g methyl itaconate, 0.5 g diethyl itaconate, 50 mg hydroquinone and 0.7 g straw with a size of 250-500 m and 30 L stannous octoate are mixed under stirring. After 15 minutes, the temperature is increased to 160 C. where the PLA dissolves in the mixture through stirring and the temperature is kept for 5 h. 3.3 g of tryptophan and 2 mg Macrolex Red EG are added under stirring and the mixture is allowed to further polymerise at 160 C. for 2 h. The mixture is cooled and exemplifies a fully polymerised single component system.

EXAMPLE 9

[0080] A procedure similar to example 8 is followed except that 15 mg mequinol are added under stirring prior to cooling down the sample.

EXAMPLE 10

[0081] A flask equipped with a stirrer is placed in an oil bath at 120 C. and 5 g lactide, 2 g fumaric acid, 1 g itaconic acid, 0.8 g gallic acid and 0.2 mL glycerol are mixed under stirring. After 20 minutes, 10 g initiator containing poly lactic oligomers with a molecular weight of 1000-3000 Da are added and the temperature is increased to 170 C. where it is kept for 4 h where after 3 g PLA are added. When the PLA is dissolved by the aid of stirring the mixture is cooled.

EXAMPLE 11

[0082] A flask under nitrogen flow equipped with a stirrer is placed in an oil bath at 120 C. and 10 g lactide, 2 g glycolide, 2 g fumaric acid, 5 g aconitic acid and 20 L 4-(dimethylamino)pyridine are mixed under stirring. The mixture is allowed to react for 3 h at 120 C. before the temperature is increased to 160 C. where 1 g of Nylon 6 is added under stirring so that the Nylon 6 dissolves in the mixture. After 5 h at 160 C., the temperature is reduced to 150 C. and 2 g bis(aminophenyl)methylphosphine oxide, 0.8 g Jeffamine D230 and 0.5 g 3 mm PLA fibres are added gradually under stirring. The temperature is kept at 150 C. for 1 h and the resin is cooled. Upon cooling the resin is crushed into granulates of a size smaller than 1 cm and is placed in a vacuum oven at 70 C. for 1 h.

EXAMPLE 12

[0083] A flask equipped with a stirrer is placed in an water bath at 70 C. and 10 g lactide, 1 g glycolide, 0.6 g Novozym 435, 200 mg inhibitor free methacrylic acid and 150 mL toluene as solvent are added to the flask. The contents of the flask are allowed to react for 48 h, whereupon 0.15 g tryptophan is added under stirring. The contents of the container are cast onto a glass plate which is placed in an vacuum oven at a pressure of 50 mbar and a temperature of 60 C. to allow the toluene to evaporate. Upon evaporation of the toluene, the polymer is recovered.

EXAMPLE 13

[0084] 2 g of the resin of example 9 is at 180 C mixed with 8 g PLA resin using mechanical stirring. Upon mixing the resin is cooled.

EXAMPLE 14

[0085] In an extruder, 10 g of the resin of example 9, 10 g of poly butylene succinate and 80 g PLA are mixed and extruded into pellets.

EXAMPLE 15

[0086] In an extruder, 10 g of the resin of example 9, 10 g of poly butylene succinate, 80 g PLA and 15 g of 2 mm flax fibres are mixed and extruded into pellets.

EXAMPLE 16

[0087] A flask under nitrogen flow equipped with a stirrer is placed in an oil bath at 120 C. and 10 g lactide, 2 g glycolide, 2 g aconitic acid, 0.5 g cinnamic acid, 0.1 g sorbitol and 1 g maleic anhydride are mixed until at homogeneous liquid is obtained. Then 30 L stannous octoate and 10 mg tert-butyl peroxide are added whereupon the temperature is increased to 155 C. and this temperature is kept for 3 h.

EXAMPLE 17

[0088] A flask equipped with a stirrer is placed in an oil bath at 140 C. and 20 g lactide and 0.1 g glucono delta-lactone are mixed until a homogenous mixture is obtained. Thereupon 10 L stannous octoate are added under stirring. The mixture is allowed to react for 3.5 h.

EXAMPLE 18

[0089] A flask under nitrogen flow equipped with a stirrer is placed in an oil bath at 100 C. and 20 g L-lactide and 4 mL -caprolactone are added. When these components are molten and mixed, 30 L 1-dodecanol and 45 L stannous octoate are added whereupon the temperature is increased to 140 C. After 1 h at 140 C., 0.85 g cinnamic acid and 0.08 g dicumyl peroxide are added whereupon the temperature is increased to 165 C. 4 hours after increasing the temperature to 165 C. the resin is cast from the flask. From nuclear magnetic resonance it is found that 60% of the double bonds in cinnamic acid have reacted.

EXAMPLE 19

[0090] To a flask under nitrogen flow equipped with a stirrer in an oil batch at 165 C. is added 20 g lactide, 3 g aconitic acid 30 L dodecanol, 45 L stannous octoate and 0.31 g benzyl peroxide. The mixture is allowed to react for 12 h and is then cast from the flask. The cast resin is in this example referred to as pre-polymer.

[0091] In a new flask under nitrogen flow, 2 g of the prepolymer is mixed with 20 g lactide and 0.2 g of itaconic acid at 155 C. until a homogeneous mixtures is obtained.

EXAMPLE 20

[0092] 10 g of the prepolymer in example 19 is in an extruder mixed with 40 g of PLA and extruded into new pellets.