BINDERS AND ASSOCIATED PRODUCTS

Abstract

The present invention relates to a water-soluble binder composition comprising at least one carbohydrate component and at least one carbon dioxide reaction product comprising at least the reaction product(s) of carbon dioxide with at least one nitrogen-containing compound. It further relates to a method of its manufacture, its use, a method of manufacturing a collection of matter bound by said polymeric binder, as well as a binder solution or dispersion comprising said binder composition.

Claims

1. A water-soluble, curable, thermosetting binder composition, comprising: at least one carbohydrate component and at least one carbon dioxide reaction product comprising at least the reaction product(s) of carbon dioxide with at least one nitrogen-containing compound.

2. The binder composition according to claim 1, in which the viscosity of an aqueous solution containing 70 wt.-% of said binder composition does not increase by more than 500 cP when left to stand at 20° C. for 12 hours.

3. The binder composition according to claim 1, wherein said binder composition is capable of reacting with a crosslinker to yield one or more melanoidins as a water-insoluble composition, under relevant curing conditions.

4. The binder composition according to claim 1, wherein the ratio of total carbonyl groups in the carbohydrate component(s) to total reactive nitrogen-containing groups in the nitrogen-containing component(s) is 5:1 to 1:5.

5. The binder composition according to claim 1, wherein the at least one carbohydrate component is selected from the group consisting of monosaccharides, disaccharides, polysaccharides or a reaction product thereof.

6. The binder composition according to claim 1, wherein the at least one carbohydrate component is selected from the group consisting of reducing sugars, ribose, arabinose, xylose, lyxose, glucose (dextrose), mannose, galactose, allose, altrose, talose, gulose, idose, fructose, psicose, sorbose, dihydroxyacetone, sucrose and tagatose, as well as mixtures thereof.

7. The binder composition according to claim 1, wherein the at least one nitrogen-containing component is NH.sub.3, an inorganic amine or an organic amine comprising at least one primary amine group, as well as salts thereof.

8. The binder composition according to claim 7, wherein the at least one nitrogen-containing component is a primary polyamine having the formula H.sub.2N—Q—NH.sub.2, wherein Q is a C6 alkyl or cyclohexyl, cyclopentyl or cyclobutyl, or benzyl, each of which being optionally substituted with amino, aminoalkyl, hydroxyl, halo, or thiol, wherein alkyl is selected from the group consisting of C.sub.2-C.sub.24 alkyl, C.sub.2-C.sub.9 alkyl, and C.sub.3-C.sub.7 alkyl.

9. The binder composition according to claim 1, wherein the weight ratio between the carbohydrate component and the carbon dioxide reaction product with nitrogen-containing component is 0.5:1 to 30:1.

10. A method of manufacturing a binder composition comprising the steps of: (i) providing at least one carbohydrate component, (ii) providing at least one nitrogen-containing component, (iii) providing carbon dioxide, (iv) mixing in a solvent the carbohydrate component(s) and the nitrogen-containing component(s), and optionally cooling at room temperature, and (v) bubbling carbon dioxide into the mixture obtained in step (iv); or (i′) providing at least one carbohydrate component, (ii′) providing at least one nitrogen-containing component, (iii′) providing carbon dioxide, (iv′) reacting the carbon dioxide with the nitrogen-containing component, and (v′) mixing in a solvent the carbohydrate component(s) and the reaction product of (iv′).

11. The method according to claim 10, wherein 0.5 to 50 w % CO.sub.2 based on the total weight of the binder composition, is bubbled into the reaction mixture.

12. (canceled)

13. A water-soluble binder composition obtainable by the method according to claim 10.

14. (canceled)

15. A method of manufacturing a collection of matter bound by a polymeric binder comprising the steps: (i) providing a collection of matter, (ii) providing a binder composition according to claim 1, or a binder composition obtained by the method according to claim 10, in a solvent to obtain a solution or dispersion, (iii) applying the solution or dispersion obtained in step (ii) to the collection of matter, and (iv) applying energy to the collection of matter containing said solution or dispersion to cure the binder composition.

16. The method according to claim 15, wherein in step (ii) a crosslinker is added to the binder composition according to claim 1, or the binder composition obtained by the method according to claim 10, or the solution or dispersion thereof. U.S. Nationalization of PCT/EP2018/085579 P0461/US HAMPSON, Carl and JONES, Gareth

17. The method of manufacturing a collection of matter according to claim 15 or 16, wherein prior to the step of applying the solution or dispersion obtained in step (ii) to the collection of matter, the collection of matter is substantially free of binder.

18. A binder solution or dispersion comprising in a solvent the binder composition according to any one of claims 1 to 9 and a crosslinker.

Description

[0112] The accompanying Figures show:

[0113] FIG. 1: the impact of CO.sub.2 injection on the viscosity of a binder composition of the invention.

[0114] FIG. 2: the effect of CO.sub.2 injection on the browning of a binder composition of the invention.

[0115] FIG. 3 the addition of CO.sub.2 has no significant effect on the cure rates of binder compositions.

[0116] FIG. 4 the addition of CO.sub.2 has no significant effect on the bond strength.

[0117] The present invention will be further illustrated in the following examples, without limitation thereto.

EXAMPLE 1

Binder Composition of Glucose/Fructose and HMDA (75%/25%) and Carbon Dioxide

[0118] A carbohydrate component composed of 50 w % glucose and 50 w % fructose was dissolved in water and mixed with a corresponding amount of HMDA (hexamethylenediamine) in aqueous solution, under atmospheric pressure, in order to produce 500 g binder solution comprising 75%w carbohydrate and 25%w HMDA, and 37.5 solids (pure glucose required: 70.3125 g, pure fructose required: 70.3125 g, pure HMDA required: 46.875 g). Whilst under mild agitation, the pH is constantly monitored for the first 20 minutes. The pH dropped from 11.82 to 11.4 of its own accord. A first 50 g samples is taken at that point in time.

[0119] Carbon dioxide was then bubbled into the remaining 450 g binder solution at a slow rate for approx. 30 min. Further 50 gram samples were removed and bottled when the binder solution showed a pH of 11, 10, 9 and 8.5, respectively. An increase in binder temperature of 3-4° C. was observed during the experiment.

TABLE-US-00001 CO2 efficiency CO2 used Binder weight % CO2 pH (g) increase (g) utilized Starting pH 11.58 pH 11 11 9.5 7.19 75.68% pH 10 10 21.89 15.08 68.89% pH 9.5 9.5 31 18.54 59.81%

[0120] All five samples were left in a water bath at 30° C. and tested over the course of 3 weeks to monitor changes in shelf life, by way of cure rate, viscosity, browning and bond strength.

[0121] Viscosity was measured using an LV-Torque Brookfield Viscosimeter, spindle LV-63 at 60 rpm (for example).

[0122] FIG. 1 clearly shows that for the samples treated with carbon dioxide the viscosity increases significantly later than for the sample that has not been treated with carbon dioxide. From these results, it can be concluded that self-curing leading to increased viscosity is significantly delayed, in this test by more than 2 weeks. Shelf-life hence is increased concomitantly.

[0123] Browning was measured by IR absorbance (visible) at 470 nm.

[0124] FIG. 2 clearly shows that browning of 002-treated samples is significantly slower than non-treated sample.

[0125] Curing of binders: To follow cure rates, drops of binder were placed on glass fibre filters and cured for various times. The cured spots were extracted into water and the absorbance of the leachate measured using a spectrophotometer. Absorbance rose initially owing to the formation of soluble coloured compounds. The absorbance then fell due to the cross linking of these soluble compounds. The cure speed is considered to be the time taken for the absorbance to fall to the minimum value.

[0126] As shown in FIG. 3, the cure rate of all samples is essentially unaffected by the carbon dioxide treatment of the binder samples.

[0127] Bonding strength was measured via a standard glass veil tensile test method.

[0128] As can be seen in FIG. 4, the bonding strength is not substantially affected or may even be slightly improved when the invention binder samples are treated with carbon dioxide.

EXAMPLE 2

Binder Composition of Dextrose and HMDA Carbamate

[0129] Further work has been carried out on a binder composition based on dextrose and a commercial carbamate of HMDA (Vucofac HMDAC by Safic Alcan). The HMDA carbamate was dissolved in water until saturation (approx. 30%wt) before adding the carbohydrate component (a high fructose corn syrup at a glucose:fructose ratio of 58:42 by Cargill) 1 to form a 37.5% solids aqueous binder composition comprising 75 wt % carbohydrate and 25 wt % HMDA carbamate. Shelf live was tested as per Example 1 in comparison with a standard HMDA binder composition at 37.5 (:)/0 solids (same carbohydrate component but HMDA instead of HMDA carbamate, at same ratio).

TABLE-US-00002 Standard HMDA binder HMDA carbamate binder 34 days 229 days

[0130] Clearly, the carbamate derivative of the amine component in the binder composition significantly improves shelf live of the composition, meaning self-polymerization being significantly delayed.

EXAMPLE 3

Binder Composition of HFCS and Tri-Amino Nonane Carbamate

[0131] The carbohydrate component (high fructose corn syrup with a glucose:fructose ratio of 58:42) was dissolved in water and mixed with a corresponding amount of 4-(aminomethyl)-1,8-octanediamine (TAN) in aqueous solution, under atmospheric pressure, to form a 37.5 solids composition comprising 75 wt % carbohydrate and 25 wt % TAN. Whilst under mild agitation, the pH is constantly monitored for the first 20 minutes. The pH dropped to 11.59 of its own accord. A first 50 g samples is taken at that point in time.

[0132] Carbon dioxide was then bubbled through the remaining binder solution at a slow rate for approx. up to 178 minutes. Further 50 gram samples were removed and bottled when the binder solution showed a pH of 11, 10, and 9, respectively. No significant increase in binder temperature was observed during the experiment.

TABLE-US-00003 pH Time (min) Temperature (C. °) CO.sub.2 used 11.59 0 25 0 g 11 65 24 15.03 g 10 98 24 41.40 g 9 178 24 91.97 g

[0133] It has been found that the cure rates were not significantly affected by the carbamate formation. The completion of cure occurred between 5 and 6 minutes and the curing curves were very similar for all pH values. For the test method, refer to Example 1.

[0134] The relevant samples were left in humidity cabinet set at 30° C. and shelf live was monitored over time, in accordance with the methodology of Example 1.

TABLE-US-00004 Sample 1 sample 2 sample 3 sample 4 pH 11.59 pH 11 pH 10 pH 9 6 days 9 days 23 days 49 days