Binder Compositions and Uses Thereof

Abstract

The present invention relates to a new aqueous curable binder composition comprising a polyphenolic macromolecular compound which bears a multitude of catechol radicals (dihydroxybenzene), preferably lignosulfonate salts and condensed tannins and mixtures thereof, and a polyamine functional compound comprising primary and/or secondary and/or tertiary and/or quaternary amine functional groups, suitable for bonding particulate matter, such as fibers, more particularly mineral wool fibers, or particles, such as wood particles.

Claims

1. An aqueous curable binder composition comprising (i) a polyphenolic macromolecular compound which bears a multitude of phenol or polyhydroxybenzene radicals or catechol radicals (dihydroxybenzene), selected from lignosulfonate salts and condensed tannins and mixtures thereof, and (ii) a polyamine functional compound comprising primary and/or secondary and/or tertiary and/or quaternary amine functional groups, and/or reaction product of (i) and (ii), the ratio of polyphenolic macromolecular compound to polyamine functional compound ranging from 98:2 to 50:50 w %.

2. The aqueous curable binder composition of claim 1 wherein the lignosulfonate salt is selected from calcium lignosulfonate, sodium lignosulfonate, ammonium lignosulfonate, magnesium lignosulfonate and mixtures thereof.

3. The aqueous curable binder composition of claim 1 wherein the polyamine functional compound is selected from diamines, triamines, tetramines, pentamines and polymeric polyamines or polyimines, such as hexamethylenediamine, diethylenetetramine, diethylenetriamine, polyethyleneimine (PEI), polyvinyl amine, polyether amine, polylysine, ethylene diamine, 1,3-diaminopropane, cadaverine, spermidine, spermine, putrescine, tetraethylmethylenediamine, and triethylenetetramine, different types of polyethylenimines, such as linear polyethylenimines, branched polyethylenimines and dendrimer type polyethylenimine, and polyetheramines in linear and branched form.

4. The aqueous curable binder composition of claim 2 comprising a lignosulfonate salt, selected from ammonium lignosulfonate or calcium lignosulfonate or magnesium lignosulfonate, and a diamine in the form of hexamethylenediamine (HMDA).

5. The aqueous curable binder composition of claim 1 further comprising a matrix polymer selected from naturally derived polymers, such as polysaccharides, such as cellulose, starch, alginate, hyaluronic acid, and their derivatives, carboxymethyl cellulose (CMC), sodium carboxymethyl cellulose (NaCMC), hydroxypropyl cellulose (HPC), 2-hydroxyethyl cellulose (HEC), oligosaccharides, synthetically derived polymers, such as polyvinyls (PVA, PVAc, PAN), polyacrylics, polyacrylate, polymethacrylate, polyacrylamide, polymethacrylamides, polyurethanes, polyesters, aliphatic isocyanate oligomers, azetidinium containing polymer, chitosan and its derivatives, copolymers thereof and mixtures thereof.

6. The aqueous curable binder composition of claim 5 wherein the polyphenolic macromolecular compound makes from 50 up to 98 w % based on the total of the three components; the polyamine functional compound makes from 1 up to 40 w % based on the total of the three components; and the polymer content ranges from 1 to 20 w % based upon the total of the three components.

7. The aqueous curable binder composition of claim 1 further comprising dyes, antifungal agents, antibacterial agents, hydrophobes, silicone containing coupling agents and/or other additives such as silane, dedust oil, hydrophobic polymers, and/or combinations thereof.

8. An assembly of fibers or particles bonded with an aqueous binder composition according to claim 1 or with a binder resulting from the curing of a binder composition according to claim 1.

9. The assembly of fibers according to claim 8 being an insulation product, such as a mineral wool mat.

10. The assembly of particles according to claim 8 being a composite wood board, such as a wood fiber board, wood particle board, plywood or similar board.

11. A process for the manufacturing an assembly of fibers or particles characterized in that a combination of (i) an aqueous composition of a polyphenolic macromolecular compound which bears a multitude of phenol or polyhydroxybenzene radicals or catechol radicals (dihydroxybenzene), selected from lignosulfonate salts and condensed tannins and mixtures thereof, and (ii) an aqueous composition of a polyamine functional compound comprising primary and/or secondary and/or tertiary and/or quaternary amine functional groups, is applied sequentially or simultaneously onto a collection of fibers or particles such that the ratio of polyphenolic macromolecular compound to polyamine functional compound ranges from 98:2 to 50:50 w %, or an aqueous binder composition according to claim 1 is applied onto a collection of fibers or particles, in that the coated fibers or particles are gathered in an assembly and subjected to curing conditions whereby the polyphenolic macromolecular compound and the polyamine functional compound are caused to react to form a macromolecular binder and water is evaporated.

12. The process according to claim 11 wherein the polyamine functional compound is selected from diamines, triamines, tetramines, pentamines and polymeric plolyamines or polyimines, such as hexamethylenediamine, diethylenetetramine, diethylenetriamine, polyethyleneimine (PEI), polyvinyl amine, polyether amine, polylysine, ethylene diamine, 1,3-diaminopropane, cadaverine, spermidine, spermine, putrescine, tetraethylmethylenediamine, and triethylenetetramine, different types of polyethylenimines, such as linear polyethylenimines, branched polyethylenimines and dendrimer type polyethylenimine, and polyetheramines in linear and branched form.

13. The process according to claim 11 characterized in that curing is performed at a temperature ranging from 90° C.-200° C.

14. The process of claim 11 wherein the aqueous binder composition is applied by spraying onto the collection of fibers or particles.

15. The process of claim 11 wherein the assembly is a wood fiber board or wood particle board or similar wood board, subjected to pressing during curing.

Description

[0053] The invention will be explained in more details in the examples below with reference to the attached Figures, in which:

[0054] FIG. 1 shows the cure rate at 160° C. for various ammonium-lignosulfonate compositions;

[0055] FIG. 2-4 show the cure rate at 180° C., 160° C. and 140° C., respectively, of various binder compositions;

[0056] FIG. 5-10 show the mechanical strength of several binder compositions;

[0057] FIG. 11-12 give an indication of weathering stability by comparison of autoclaved and non-autoclaved composite binder compositions.

EXAMPLE 1: PREPARATION OF BINDER COMPOSITIONS COMPRISING LIGNOSULFONATES, POLYAMINES AND POLYMER

[0058] Calcium lignosulfonate (Borrement CA 2120) was provided by Borregaard LignoTech. Sodium lignosulfonate was purchased from Aldrich, and ammonium lignosulfonate was obtained from TemBac.

[0059] Sodium carboxymethylcellulose (NaCMC), hydroxypropylcellulose (HPC) and hydroxyethylcellulose (HEC) were obtained from Aldrich and showed a Mw of approx. 250 kDa, 100 kDa and 100 kDa, respectively.

[0060] The amine functional material such as hexamethylene diamine (HMDA) and diethylenetriamine (DETA) were obtained from Aldrich. Different types of polyethylenimines (Lupasol® EO, Lupasol® PS, Lupasol® P and Lupasol® G100), polyvinyl amines (Luredur® VM, Luredur® VH and Luredur® VI), were obtained from BASF Chemical Company, and polyetheramines (JeffamineED600, JeffamineEDR148, JeffamineT403) from Huntsman Holland BV.

[0061] The required amounts of polymer and lignosulfonate (LS) were dissolved in water individually. The required amount of polyamine functional compound was added to the LS solution followed by homogenization. The polymer solution and LS-amine solution were then combined at ambient temperature and stirred at 500 rpm for 30 minutes.

EXAMPLE 2: BINDER WEIGHT LOSS DETERMINATION

[0062] The 2-5% (solids content) binder solutions were prepared as described above and poured into a petri dish. Weight was determined. The Petri dish was then kept for 2 hours in an oven at 140° C. and weighted again. Weight loss was determined; results are shown in the Table below.

TABLE-US-00001 TABLE 1 Evaluation of binder weight loss, at 140° C. for 2 hours. Formulations Binder Weight Loss (%) 70% Am LS + 15% HMDA + 15% PVA 1.765 70% Am LS + 15% HMDA + 15% HPC 2.40 70% Am LS + 15% HMDA + 15% Na 2.60 CMC 70% Ca LS + 15% HMDA + 15% PVA 4.54 70% Ca LS + 15% HMDA + 15% HPC 6.533 70% Ca LS + 15% HMDA + 15% Na 8.517 CMC

EXAMPLE 3: CURE RATE STUDY

[0063] A 50 μl fraction of the binder solution was applied onto a spot of glass microfiber filter (Whatman™) surface. Samples were cured from 1 min up to 20 minutes at different temperatures in an appropriate oven. After curing, each glass filter sample was cut and fully immersed in 50 ml cold water contained in a 150 ml glass beaker, and sonicated for 15 min at room temperature. The extract solution filtered and the absorbance of the extract was measured with a spectrometer at 470 nm. The absorbance was then plotted as a function of cure time.

[0064] The cure rate at 160° C. was determined for various compositions comprising ammonium-LS and HMDA (10-20 w %). Results are shown in FIG. 1.

[0065] The test was repeated at three different cure temperatures (140° C., 160° C. and 180° C.) for various binder compositions of the invention. Results are shown in FIGS. 2-4. It appears from the results that the three way compositions show a faster curing.

EXAMPLE 4: BOND STRENGTH ANALYSIS

[0066] In order to determine the bond strength of binders, initially impregnated glass veils (non-woven glass fibers) of A4 size were placed into a muffle furnace for 30 minutes at 600° C. in order to ensure burnout of impregnation material and thereafter cooled for 30 min. Approx. 400 g of the prepared binder solutions were poured into separate dip trays and the burnout veils were carefully totally immersed into the relevant binder solutions. The thus impregnated veils were then cured at desired temperatures (e.g. 180° C.) and during relevant periods of time (up to 20 minutes).

[0067] The bond strength analysis was performed using a testometric machine (M350-10CT) of the binder impregnated cured veils. For each test a cured binder impregnated A4 veil was cut into 8 equal strips. Each strip was tested separately using a 50 Kg load cell (DBBMTCL-50 kg) with a test speed of 10 mm/min, controlled by winTest Analysis software. Glass veil tensile plates were attached to the testometric machine to ensure a 100 mm gap between plates. The samples were placed vertically in the grippers, within the rubber grip area, and the force tared to zero. Further, onscreen instructions were followed, and generated data reported as herein below. Various parameters such as maximum load at peak, stress at peak and modulus at peak were evaluated by the software, and data presented as an average for 8 samples with standard deviation. The average maximum load at peak/stress at peak is considered as the bond strength.

[0068] The mechanical strengths, force at peak, is presented in FIG. 5 for ammonium-lignosulfonate (AmLS) per se, AmLS/HMDA/HPC (70/15/15), AmLS/HMDA/CMC (70/15/15), AmLS/HMDA/PVA (70/15/15), AmLS/HMDA/HPC (65/15/20) and AmLS/HMDA/HPC (65/15/20) with 2% HDI (hexamethylene diisocyanate oligomer).

[0069] The mechanical strengths, force at peak is presented in FIG. 6 for calcium-lignosulfonate (CaLS) per se, CaLS/HMDA/HPC (70/15/15), CaLS/HMDA/CMC (70/15/15), CaLS/HMDA/PVA (70/15/15) and CaLS/HMDA/HEC (70/15/15).

[0070] Corresponding data is shown in FIG. 7 for Na-lignosulfonate (NaLS) per se, NaLS/HMDA/HPC (70/15/15) and NaLS/HMDA/CMC (70/15/15); and in FIG. 8 for Magnesium-lignosulfonate (MgLS) per se and MgLS/HMDA/NaCMC (70/15/15).

[0071] Further data has been generated with CaLS, various polyamines selected from diethylenetriamine, polyethylenimine and polyvinylamine (PVAm), and polymers, more specifically CaLS/DETA/NaCMC (70/15/15), CaLS/DETA/PVA (70/15/15), CaLS/PEI-EO/NaCMC (70/15/15), CaLS/PEI-EO/PVA (70/15/15) and CaLS/PVAm/PVA (70/15/15)—see FIG. 9.

[0072] FIG. 10 shows further force at peak data generated for AmLS/JeffamineED600/NaCMC (70/15/15), AmLS/JeffamineEDR148/NaCMC (70/15/15), AmLS/JeffamineT403/NaCMC (70/15/15), AmLS/PLL/NaCMC (70/15/15) and AmLS/PLL/PVA (70/15/15).

EXAMPLE 5: WEATHERING STABILITY

[0073] Dry and weathered tensile strength provide an indication of the durability of a glass fiber mat. Binder impregnated cured veils (non-woven glass fibers) were placed in an autoclave (J8341, Vessel: PV02626). The samples were subjected to 90% humidity atmosphere, in a temperature range of from 40° C. to 110° C. (full cycle), under a pressure of up to 2.62 bar for 3 hours. The samples were subsequently dried completely such that no moisture remains on the veil samples. These autoclave treated samples were tested using testometric machine (M350-10CT) for bond strength analysis (see example 4 above), and the results were compared with those from samples that have not been subjected to the humidity treatment (autoclave).

[0074] FIG. 11 compares force at peak data for AmLS/HMDA/HPC (65/15/20) before and after sterilization and AmLS/HMDA/HPC (65/15/20)+HDI (2%) before and after autoclave.

[0075] FIG. 12 compares force at peak data for CaLS/HMDA/HPC (70/15/15) before and after sterilization, CaLS/HMDA/NaCMC (70/15/15) before and after autoclave and compares force at peak data for AmLS/HMDA/HPC (65/15/20) before and after autoclave and CaLS/HMDA/PVA (70/15/15) before and after autoclave.

[0076] No significant loss of mechanical strength has been noticed. Some samples even show increased mechanical strength after autoclave weathering.

[0077] Interestingly, the polymerization reaction generates little or no water, thus reducing the energy required for production of the final insulation product.

EXAMPLE 6: PREPARATION OF A COMPOSITE WOOD BOARD

[0078] Wood in the form of assorted pine wood shavings was purchased and used as received. The wood was placed in a plastic container and a binder solution prepared in accordance with Example 6, at 80 w % solids (determined as bake out solids after drying at 140° C. for 2 hours), was sprayed onto the wood sample, during which the wood was gently tumbled in order to become uniformly coated. Samples of resinated wood were placed in a collapsible frame and compressed between heatable plates at approx. 2000 kPa, during 25 to 30 minutes, and maintained at about 80° C. The obtained board sample was well-bonded internally, smooth surfaced, mechanically strong and relatively water-resistant in the absence of any hydrophobic or other additive other than the main binder components. Estimated binder content: approx. 13 w %.