Composition comprising furfuryl alcohol

Abstract

Composition including a first component, including furfuryl alcohol and humins and a second component including an acidic polymerization initiator. The composition can be oligomerized to a resin, which has a viscosity in the range of 0.1 to 10,000 Pa.Math.s at 25 C., determined according to ISO3219. The resin, or a blend of furfuryl alcohol and humins as a component A and an acidic polymerization initiator as a component B, separated from each other, may form a kit for an adhesive or impregnation agent.

Claims

1. A composition including a first component, comprising furfuryl alcohol and humins and a second component comprising an acidic polymerization initiator.

2. The composition according to claim 1, wherein the humins have been obtained from the dehydration of carbohydrates.

3. The composition according to claim 1, wherein the weight ratio of furfuryl alcohol to humins in the first component is in the range of 1:10 to 10:1.

4. The composition according to claim 1, wherein the second component comprises an acidic polymerization initiator which has a pK.sub.a at 25 C. of at least 3.

5. The composition according to claim 1, wherein the acidic initiator is selected from maleic anhydride, phthalic anhydride, formic acid, maleic acid, malic acid, phthalic acid, furoic acid, benzoic acid, furan-dicarboxylic acid, citric acid, levulinic acid and combinations thereof.

6. The composition according to claim 1, wherein the amount of acidic initiator as second component is in the range of 0.5 to 10% wt, based on furfuryl alcohol and humins.

7. The composition according to claim 1, wherein the first component, the second component or both the first and the second component comprise(s) one or more additional compounds, optionally selected from additional monomers, co-catalysts, diluents, fillers and combinations thereof.

8. The composition according to claim 7, wherein the additional monomers have been selected from 5-hydroxymethylfurfural, 2-(2-hydroxyacetyl)furan, 5-alkoxymethylfurfural, formaldehyde, methyl formate, levulinic acid, alkyl levulinates, 2,5-diformyl-furan, carbohydrates, furfural, prepolymer of furfuryl alcohol and combinations thereof.

9. The composition according to claim 7, wherein the co-catalyst is comprised in the second component and is optionally selected from the group consisting of aluminium trihalide, boron trihalide, zinc halide, iron halide, chromium halide, iodine and combinations thereof.

10. The composition according to claim 7, wherein the diluent has been selected from water, alcohols, ketones, esters, dimethyl sulphoxide, dimethyl formamide and combinations thereof.

11. The composition according to claim 7, wherein the filler has been selected from plasticizers, talc, lime, dyestuffs, wood flour, saw dust, bone flour clay and combinations thereof.

12. A resin obtainable by the oligomerization of the composition according to claim 1, which resin has a viscosity in the range of 0.1 Pa.Math.s to 10,000 Pa.Math.s at 25 C., determined according to ISO 3219.

13. A composition comprising: a resin obtainable by the oligomerization of the composition according to claim 1, which has a viscosity in the range of 0.1 to 10,000 Pa.Math.s at 25 C., determined according to ISO 3219; and an acidic polymerization initiator.

14. A kit for an adhesive or impregnating agent containing, separated from each other, a first component comprising a blend of furfuryl alcohol and humins, or a resin obtainable by the oligomerization of the composition according to claim 1, which has a viscosity in the range of 0.1 to 10,000 Pa.Math.s at 25 C., determined according to ISO 3219, as a component A, and an acidic polymerization initiator as a component B.

15. The kit according to claim 14, which comprises additional compounds, optionally selected from additional monomers, co-catalysts, diluents, fillers, and combinations thereof, that have been packaged separately from the component A and component B.

16. The kit according to claim 14, wherein the acidic initiator of Component B is selected from the group consisting of strong acids with a pK.sub.a at 25 C. of less than 3.

17. The kit according to claim 16, wherein the acidic initiator is selected from the group consisting of p-toluene sulphonic acid, methane sulphonic acid, mineral acids, and combinations thereof.

18. The kit according to claim 14, wherein the acidic initiator of Component B is selected from the group consisting of weak acids with a pK.sub.a at 25 C. of at least 3.

19. A process for manufacturing reinforced objects comprising providing a composition according to claim 1; impregnating the object with the composition; and heating the thus impregnated object to obtain a reinforced object.

20. The process according to claim 19, wherein the object is a wooden object, suitably selected from softwood, hardwood, plywood, wooden hardboard, strand board, fibre board, particle board or wood chips.

21. The process according to claim 19, wherein the object is selected from the group consisting of glass fibres, carbon fibres, natural fibres, polymer fibres and combinations thereof.

22. The process for binding an article to a substrate by providing a composition according to claim 12; comprising: applying a coating of the composition to at least a part of at least one of the article and the substrate; contacting the article and the substrate to obtain a structure; and heating the structure to obtain a bonded structure.

23. The process according to claim 22, wherein at least one of the article and the substrate is made of wood.

24. The process according to claim 22, wherein the article, the substrate, or both are selected from the group consisting of veneer, shelves, softwood, hardwood, plywood, wooden hardboard, strand board, fibre board, particle board, wood chips and combinations thereof.

25. A process for coating a substrate, comprising: providing a composition according to claim 12; applying a coating of the composition to at least a part of the substrate; and heating the coated substrate.

Description

BRIEF DESCRIPTION OF THE DRAWING

(1) The FIGURE shows the thermograms that were determined by Differential Scanning calorimetry (DSC) for the polymerization of several polymerizable compositions.

DETAILED DESCRIPTION OF THE INVENTION

(2) The FIGURE shows the thermogram for a composition A, comprising 98% wt of furfuryl alcohol and 2% wt of maleic anhydride as acidic initiator. It further shows the thermograms for the polymerization of mixtures of 70 parts by weight (pbw) furfuryl alcohol and 30 pbw humins with different amounts of maleic anhydride as acidic initiator. Composition B contained 2.5% wt maleic anhydride, Composition C contained 5% wt maleic anhydride and Composition D contained 7.5% wt maleic anhydride, all percentages based on the combined amount of maleic acid and the mixture of furfuryl alcohol and humins.

(3) The FIGURE shows that the heat flux of the polymerization of furfuryl alcohol takes place at a sharp peak, indicating that the increase of the heat flux is significant.

(4) The thermogram for Compositions C and D are more flat and thus show that the polymerization takes place at a lower temperature and lower rate, so that the reactions are better controllable.

(5) The thermograms for Compositions C and D show that up to a temperature of about 90 C. the polymerization does not occur. At higher temperature the polymerization only takes place at a very slow rate. The FIGURE further shows that the Compositions C and D can be excellently used for the preparation of a prepolymer or oligomer because the shelf lives for compositions C and D are excellent. Composition B does not cure until at more elevated temperature. The thermogram of this composition shows that the components can well be added together without significant reaction.

(6) The invention will be further illustrated by means of the following examples.

EXAMPLE 1

One-Step Preparation of Resin

(7) Furfuryl alcohol, humins (Table 1, Composites 1-4) and 2% wt maleic anhydride based on the amount of acid, furfuryl alcohol and humins or lignin, were mixed in one pot and heated at 125 C. for 30 minutes, subsequently heated for 30 minutes at 145 C.

(8) In another experiment furfuryl alcohol and humins (Table 1, Composite 5) were mixed at 105 C. for 20 minutes with 5% wt maleic anhydride, based on the amount of acid, furfuryl alcohol and humins. The temperature was retained for 10 minutes. After the period of heating, the mixtures were cooled down to room temperature and resins were obtained that could be stored for weeks. The viscosities of the resulting resins were between 1 Pa.Math.s. and 5000 Pa.Math.s at 25 C.

(9) TABLE-US-00001 TABLE 1 Furfuryl Maleic alcohol, Humins, anhydride, Composite % wt % wt % wt 1 78.4 19.6 2 2 68.6 29.4 2 3 59 39 2 4 49 49 2 5 66.5 28.5 5

EXAMPLE 2

Two-Step Preparation of Resin

(10) In a two-step resin formulation procedure furfuryl alcohol and humins (Table 2, Composites 6-7) were mixed at 105 C. during 20 minutes. Maleic anhydride (2.5% by weight) was added and the mixture was heated at 120-130 C. for 30 to 60 minutes. After this step, the reaction mixture was cooled down to 80 C. and a second addition of acid initiator (2.5% wt, based on the amount of acid, furfuryl alcohol and humins) was made and at this temperature stirring was continued for 5 minutes. Subsequently, the resin was cooled down to room temperature. The viscosity thereof was determined at two temperatures. It could be stored for weeks without significant increase of the viscosity.

(11) TABLE-US-00002 TABLE 2 Furfuryl Maleic Viscosity Viscosity alcohol, Humins, anhydr, at 25 C. at 50 C. Composite % wt % wt % wt (Pa .Math. s) (Pa .Math. s) 6 40 55 2.5 * 2 627 26.2 7 20 75 2.5 * 2 2260 59.1

EXAMPLE 3

(12) Resins of furfuryl alcohol and maleic anhydride were prepared using the method of Example 1 or 2. In an experiment (Table 3, Composite B and F) furfuryl alcohol was heated to 90 C. and 2% wt or 5% wt, respectively, of maleic anhydride, based on the amount of acid and furfuryl alcohol, was added and stirred for 60 min. After the period of heating, the mixtures were cooled down to room temperature and resins were obtained.

(13) In another experiment (Table 3, Composite G) furfuryl alcohol and maleic anhydride (2.5% by weight) were mixed at 110 C. for 40 minutes. Thereafter the second addition of acid initiator (2.5% by weight) was made in the same way as for the experiment with furfuryl alcohol and humins, described in Example 2. The resin obtained was at room temperature.

(14) A further experiment was conducted using a humins component that was enriched with additional monomers, viz. 5-hydroxymethyll furfural (HMF), 5-methoxymethyl furfural (MMF) and levulinic acid (LA) (Table 3, Composite L). In other aspects it was the same as Composite H.

(15) Also resins with different amounts of furfuryl alcohol, humins and maleic anhydride were made using the procedures of Example 1 or 2. One resin (Table 3, Composite K) was prepared similar to the procedure of Example 2, but the second addition of acid initiator was accomplished by the addition of 1% wt sulphuric acid in stead of 2.5% wt of maleic acid.

(16) Finally, one resin was prepared using furfuryl alcohol, lignin and maleic anhydride (Table 3, Composite J). For the lignin formulation, the maleic anhydride addition was carried out at 80 C. and then the resin was cooled down immediately to room temperature in a water bath.

(17) The amounts of the components are shown in Table 3.

(18) Composites were made using Whatman 40 filter paper and resin at 50/50% by weight. The composites obtained were cured at 160 or 170 C. for 3 hours. Composites strips with 40100.25 mm as dimensions were made for each resin formulation. The mechanical properties (tensile strength and modulus) of the cured composites using different humins ratios and different curing conditions are presented in Table 3. For comparison reasons the tensile strength and modulus for the untreated filter paper were also determined (Composite A).

(19) TABLE-US-00003 TABLE 3 Furfuryl Maleic Preparation Curing Curing Tensile alcohol, Humins, anhydride, according to Temp. Time Strength Modulus Composite % wt % wt % wt Example ( C.) (hour) (MPa) (GPa) A 9.1 1.4 B 98 2 1 170 3 26.2 3.3 C 78.4 19.6 2 1 170 3 28.7 2.7 D 68.6 29.4 2 1 170 3 26.5 4.0 E 49 49 2 1 170 3 31.8 4.2 F 95 5 1 160 3 13.4 3.2 G 95 5 2 160 3 14.8 3.5 H 40 55 5 2 160 3 29.3 4.0 I 20 75 5 2 160 3 31.1 3.1 J 40 .sup.55.sup.b 5 1 160 3 16.1 3.9 K 40 55 2.5.sup.c 2 160 3 23.7 3.7 L.sup.a 40 55 5 2 160 3 30.0 4.2 .sup.aHumins in Composite L contained humins enriched with monomers MMF, HMF and LA. In other aspects it was the same as Composite H. .sup.bOrganosolv lignin was used instead of humins. .sup.cIn 2 step formulation first step was with 2.5% wt maleic anhydride, second step with 1% wt H.sub.2SO.sub.4.

(20) The experiments show that the formulations that contained furfuryl alcohol and humins had a higher tensile strength and modulus than the corresponding resins containing furfuryl alcohol only. The results of composite J show that humins also perform better than lignin.