Functionalization and reinforcement in the dry state and in the wet state of a cellulosic material by an oxidized polysaccharide

Abstract

Disclosed are compounds, in particular based on polysaccharides, that are adsorbed on a cellulosic material, and relates in particular to the application of such compounds as reinforcing agent for cellulosic materials, in the wet and/or dry state. The compounds include a combination of at least one polysaccharide adsorbed on a cellulosic material, the polysaccharide including at least two different monosaccharide units, forming first and second monosaccharide units, the second monosaccharide units being branched on a chain including at least the first monosaccharide units, at least some of the second monosaccharide units being non-cyclic and bearing aldehyde functions, the aldehyde functions possibly forming hemiacetal functions with hydroxy functions of the cellulosic material.

Claims

1. A compound comprising an association of at least one polysaccharide adsorbed on a cellulosic material, said polysaccharide being an oxidized xyloglucan comprising at least two different monosaccharide units, forming first and second monosaccharide units, said second monosaccharide units being branched on a chain comprising at least said first monosaccharide units, at least some of the second monosaccharide units being non-cyclic and bearing aldehyde functions, said aldehyde functions possibly forming hemiacetal functions with hydroxy functions of the cellulosic material.

2. The compound according to claim 1, wherein the branched monosaccharides are at least on of xyloses, galactoses, fucoses and arabinoses.

3. The compound according to claim 1, wherein the polysaccharide bearing non-cyclic branched monosaccharides bearing aldehyde functions are oxidized xyloses.

4. The compound according to claim 1, wherein the adsorbed polysaccharide is selected from the group composed of a tamarind seed xyloglucan (TXG), a pea xyloglucan, and any of the mixtures thereof.

5. The compound according to claim 1, wherein the polysaccharide is oxidized by a periodate.

6. The compound according to claim 1, wherein the polysaccharide has a degree of oxidation higher than 0% and lower than or equal to 50%, expressed in number of oxidized saccharide units out of the total number of saccharide units.

7. The compound according to claim 1, wherein the polysaccharide is covalently bonded to the cellulosic material by hemiacetal functions between aldehyde functions of branched monosaccharides and hydroxy functions of the cellulosic material.

8. The compound according to claim 1, wherein the polysaccharide is also covalently bonded by one or more reactive molecules reacting with aldehyde functions of the polysaccharide.

9. The compound according to claim 1, wherein the polysaccharide is also covalently bonded by at least two reactive molecules reacting with aldehyde functions of the polysaccharide.

10. A method for covalently binding a cellulosic material with a polysaccharide, said method comprising the adsorption of a polysaccharide on a cellulosic material to form a compound according to claim 1, and the reaction of aldehyde functions of the polysaccharide with hydroxy functions of the cellulosic material to form hemiacetal functions.

11. The method according to claim 10, wherein adsorption is conducted with the cellulosic material in an aqueous medium.

12. The method according to claim 10, wherein the compound is formed and dried in the form of paper, fibres, or nonwovens.

13. The method according to claim 10, wherein the polysaccharide is covalently bonded to the cellulosic substrate and caused to react with one or more reactive molecules reacting with aldehyde functions of the polysaccharide.

14. The method according to claim 13, wherein the polysaccharide is used as additive to reinforce the strength in the wet state of a cellulosic material comprising hydroxy functions.

15. The method according to claim 13, wherein the polysaccharide is used as additive to reinforce the strength in the dry state of a cellulosic material comprising hydroxy functions.

16. A method of forming the compound of claim 1, comprising adding a polysaccharide as reinforcing additive of a cellulosic material comprising hydroxy functions, said polysaccharide being an oxidized xyloglucan comprising non-cyclic branched monosaccharides bearing aldehyde functions, wherein some aldehyde functions possibly form hemiacetal functions with hydroxy functions of the cellulosic material, said polysaccharide being able to adsorb on the cellulosic material.

17. A method of imparting a new functionality to the compound of claim 1, comprising adding one of more reactive molecules that react with aldehyde functions of the compound, wherein the one or more functions are selected from the group consisting of antiseptic, colouring, and increasing the mechanical properties of the material thus formed, and wherein said reactive molecules are selected from the group consisting of amines, polyamines, hydroxylamines, imines, hydrazide, and any combinations thereof.

Description

(1) In the Figures:

(2) FIG. 1 illustrates a branched structure of a compound of the invention with a backbone of D-glucopyranose units linked together by 1.fwdarw.4 bonds and branched;

(3) FIG. 2 gives the weight yield of the reaction in Example 2 for different degrees of oxidation on 1.42 g of xyloglucan in 0.8% solution;

(4) FIG. 3 illustrates the trend in adsorption of oxidized xyloglucan as a function of its degree of oxidation for weight proportions of xyloglucan and celluloses in 0.2% solution of 1 per 1 (.circle-solid.) and 1 per 3 ();

(5) FIG. 4 illustrates the impact of the proportion of xyloglucan (white), XgOx11 (grey) and XgOx23 (shaded) on the ultimate tensile strength of NFC films;

(6) FIG. 5 illustrates the impact of the proportion of xyloglucan (white), XgOx11 (grey) and XgOx23 (shaded) on the ultimate tensile strength of wet NFC films;

(7) FIG. 6 shows the impact of the weight proportion of xyloglucan (white) and XgOx12 (grey) and XgOx23 (shaded) on the ultimate tensile strength of NFC films post-treated in a 0.3 weight % solution of adipic hydrazide.

(8) FIG. 7 illustrates the ultimate tensile strength of NFC films and xyloglucan (white, left column), XgOx12 (shaded, second column from the left) and XgOx23 without (grey, third column from the left) and with post-treatment (shaded, right column) with adipic dihydrazide, for different compositions;

(9) FIG. 8 schematically illustrates a method for producing paper or paperboard.

(10) Other objectives, characteristics and advantages of the invention will become clearly apparent to those skilled in the art on reading the explanatory description referring to examples given solely as illustration and which cannot in any manner be construed as limiting the scope of the invention.

(11) The examples are an integral part of the present invention and any characteristic appearing to be novel, compared with any prior state of the art, from the description taken as a whole including the examples, forms an integral part of the invention with regard to the function and generality thereof.

(12) Therefore, the scope of each example is general.

(13) Also, in the examples, all percentages are given in weight unless otherwise stated, temperature is expressed in degrees Celsius unless otherwise stated, and pressure is atmospheric pressure unless otherwise stated.

(14) The degrees of oxidation of xyloglucan given in the examples are evaluated by oxime-formation assay.

EXAMPLES

Example 1: Preparation of XgOx

(15) 1.1. Oxidation of Xyloglucan.

(16) TABLE-US-00001 Equipment: Flaw materials: 2 1 L beakers. 10 g of tamarind Xyloglucan. Balance. Q.S. NaIO4. 2 magnetic stirrers. About 650 mL distilled water. Magnetic plate.

(17) Operating Mode:

(18) Weigh about 10 g of tamarind Xyloglucan in a 1L beaker.

(19) In a 1L beaker, weigh the desired equivalent of sodium periodate which is solubilized under stirring in about 650 mL of distilled water.

(20) Pour the solubilized periodate solution into the beaker containing the xyloglucan.

(21) Leave the beaker under stirring (about 700 rpm), until the mixture does not become too viscous and the stirrer no longer rotates.

(22) Cover the beaker with a parafilm and leave to stand overnight.

(23) 1.2. Purification of the Solution

(24) Principle:

(25) For purification of the solution, dialysis is performed allowing the salts and small molecules to pass through a membrane and into a basin of water. The water must therefore be changed often since, when equilibrium between the ions in the solution and pure water is reached, purification no longer occurs.

(26) Dialysis is completed when the conductivity of the water is less than10 S/cm.

(27) A purified, oxidized xyloglucan is recovered.

Example 2: Impact of Oxidation on the Oxidized Xyloglucan

(28) Yields

(29) The weight yield of the reaction was examined for different degrees of oxidation on 1.42 g of xyloglucan in 0.8% solution. The final weight was calculated after dialysis by gravimetry, and the results are given in FIG. 2. The reaction gives a good yield of about 95% for moderate oxidation rates of up to about 30%. The low loss of matter in this case is the result of the different operating phases. On the other hand, for higher oxidation rates, the yield is decreased since it drops to 82% for 49% oxidation, then to 77.5% for 62% oxidation. Loss of matter here is due to purification via dialysis. The cut-off threshold of the equipment used is 14000 g/mol. Therefore, after chain rupturing, a large amount of matter of lower molecular weight can be evacuated. These phenomena are examined in the following paragraphs.

(30) Molecular Weights

(31) Oxidation of the polysaccharides is systematically accompanied by a drop in molecular weight. Oxidation was performed on 1 g of xyloglucan in 0.4% solution. Different degrees of oxidation were performed and the molecular weights of the products obtained were controlled. The measured results are given in Table 1.

(32) TABLE-US-00002 TABLE 1 Trend in weight average (Mw) and number average (Mn) molar mass and in the polydispersity index (PDI) of Xg as a function of oxidation rate. Mw (kDa) Mn (kDa) PDI Xyloglucan 863 5.4 652 15.9 1.32 0.03 XgOx9 376 1.9 283 4.9 1.33 0.02 XgOx21 130 1.8 99 1.4 1.31 0.02 XgOx30 155 2.5 108 1.3 1.44 0.007 XgOx46 133 4.8 103 4.4 1.29 0.01 XgOx59 28 1.1 23 1.0 1.25 0.01

(33) Oxidation can have a significant impact on the molecular weight of the polysaccharide.

(34) For example, under the preparation conditions of Example 1, at 10% oxidation, the molecular weight was largely modified since it is divided by two. It further decreases by a factor of 2 at 20%, then appears to stabilise up to about 50%. However, it drops to 23 kDa at 60% oxidation i.e. just twice the value of the cut-off threshold of the membranes used for purifications which is 14 kDa. This last drop occurs at a degree of oxidation which necessarily involves oxidation of the glucoses which form the backbone of the molecule, and degradation thereof can account for said decrease in molecular weight.

(35) Impact on Adsorption

(36) The impact of the oxidation reaction on the molecular weights and structure of the polymer can modify the physicochemical properties thereof. The adsorption properties of XgOx were therefore controlled: the solution of XgOx and suspension of NFC were left under stirring for 1 h. The equivalent dry weights added were 0.3 g of XgOx and 0.3 g or 0.9 g of NFC according to study. Different concentrations were examined. After centrifugation at 11200 rpm at 10 C. for 30 minutes, the supernatant was removed and the residue redispersed in deionized water. After a second centrifugation under the same conditions, the residue was placed in an oven and weighed. The difference between the weight obtained and the initial dry weight of NFC gives the amount of adsorbed XgOx.

(37) FIG. 3 shows the trend in the amount of adsorbed Xg for a 0.2 weight concentration in solution, as a function of degree of oxidation, for 2 proportions of different nanofibrillated cellulose (circle: 1 per 1; triangle: 1 per 3). The adsorption capacity of Xg is not affected up to the region of 30% oxidation. Thereafter, a major decrease is observed in adsorption properties which become practically zero after 50%. At this degree of oxidation, the glucose backbone of the chain responsible for Xg adsorption starts to be oxidized thereby modifying the behaviour thereof. The presence of the aldehydes and rupture of a carbon-carbon bond will gradually increase the flexibility of the chain and modify its capacity to form hydrophobic interactions and hydrogen bonds. XgOx must therefore preferably be used at degrees of oxidation of about 0 to 25%, to ensure the maintained adsorption capacity of the product.

Example 4: Use as Reinforcing Additive

(38) Oxidized xyloglucans were used as paper reinforcing additives in both the dry and wet states.

(39) Different formulations were tested with different degrees of oxidation DO, different concentrations, different sources of paper pulp and different molar masses.

(40) 1. Variations in Cellulose Sources.

(41) i. NFC Films

(42) NFC and XgOx films were prepared by tape casting: the NFC suspension at 2.23 weight % is added to obtain the desired quantity, followed by addition of xyloglucan in solution, and the total volume is adjusted to 50 ml with deionized water. The final dry weights of the films are 0.5 g, with Xg/XgOx proportions of 0, 1, 5, 10 and 25 weight % of the dry film. The mixture is stirred 2 h at room temperature then poured into a Petri dish. Tape casting is carried out under a hood at room temperature to complete dryness. The films are then subjected to tensile tests.

(43) FIG. 4 shows the trend in the properties of the dry films as a function of the proportion of XgOx and for different degrees of oxidation.

(44) Xyloglucan and oxidized xyloglucan reinforce NFC films in the dry state in similar manner with a gain of about 50% in yield strength, the proportions and degree of oxidation not displaying any significant impact.

(45) The same experiment was reproduced on wet films, after immersion for 1 h in water. The results are given in FIG. 5.

(46) The reinforcing effect is pronounced for the two different degrees of oxidation, whereas it is nil for the non-oxidized Xg. ii. Flax Fibre

(47) The role of the additive was also tested on flax fibres. Technical bundles were soaked in about 20% oxidized XgOx solution, concentrated to 1 weight % (XgOx22 indicating 22% oxidized xyloglucan. This denoting system is used in the other examples by analogy). After rinsing and drying, these fibres were subjected to tensile testing, first in the dry state (Table 2).

(48) TABLE-US-00003 TABLE 2 Mechanical properties of treated technical fibres, standard deviations are given in brackets. Yield strength Young's (MPa) modulus (GPa) /E Non-treated 813 (270) 58 (13) 1.38 (0.21) fibres XgOx22 755 (157) 55 (5.6) 1.37 (0.24)

(49) No significant difference in property is noted between the treated and non-treated fibres. On the other hand, Table 3 gives the results obtained on wet fibres:

(50) TABLE-US-00004 TABLE 3 Mechanical properties of the wet technical fibres, standard deviations are given in brackets. Young's Yield strength modulus Deformation Max (MPa) (GPa) max (%) Non-treated 159 (81) 27 (8) 0.60 (0.33) fibres XgOx22 375 (185) 23 (9) 1.28 (0.42)

(51) A significant increase is observed in the yield strength of the fibres, despite large standard deviations. iii. Paper Pulp

(52) Paper samples of handsheet type were prepared from different pulps: Kraft pulp, a sulfite and cotton linters. Suspensions containing 2 g/l cellulose and 0.01% XGOX20 (XgOx20) were prepared, filtered and dried on handsheet moulds to obtain paper of about 60 g/m.sup.2. The samples were subjected to tensile testing before and after 48h immersion in water. The results are detailed in Table 4.

(53) TABLE-US-00005 TABLE 4 Effect of XGOX20 additive on papers derived from different types of pulp. Wet/Dry ratio Dry (MPa) Wet (MPa) Ref Kraft Ref. 22 0.05 10% XGOX20 40 2.5 Sulfite Ref. 6.15 0.15 20% XGOX20 10.13 1.25 Cotton Ref. 4.7 0.12 30% XGOX20 10.1 1.25

(54) Significant strengthening is observed with XGOX20 in the dry state of up to about 100% of initial strength. Strengthening is also noted in the wet state of 10 to 30% depending on pulp and under these conditions.

(55) 2. Effect of Concentrations.

(56) XGOX20 was directly added to the paper stock before forming. XgOx was therefore fixed onto the fibres by adsorption. Different concentrations of additive in the stock were tested, and the properties of the papers prepared as follows are given in Table 5:

(57) 1 L of fibrous suspension at 2 g/L+1 L water were added to a Bchner flask containing 3 paper filters stacked on a nylon filtration fabric of porosity 215 m and 18.5 cm in diameter. Filtration was performed under the vacuum of a water pump and the paper obtained was dried at room temperature (25 C.) for 24 h, then in an oven at 60 overnight.

(58) Ref. Solution: 100% Kraft pulp in tap water.

(59) 0.001 XGOX20: XgOx20 in 0.001% solution in the Kraft pulp suspension.

(60) 0.01 XGOX20: XgOx20 in 0.01% solution in the Kraft pulp suspension.

(61) 0.5 XGOX20: XgOx20 in 0.5% solution in the Kraft pulp suspension.

(62) TABLE-US-00006 TABLE 5 Trend in the effect of XGOX20 additive as a function of its weight concentration in the paper pulp (Kraft). 0% 0.001% 0.01% 0.5% XGOX20 XGOX20 XGOX20 XGOX20 Ultimate dry 6.53 (1.2) 12.76 (0.6) 14.68 (2.5) 18.80 (2.78) strength wet 0.00 0.98 (0.1) 1.25 (0.2) 2.28 (0.3) (MPa) Standard deviations are given in brackets.

(63) Very distinct gains in yield strength are ascertained, both in the dry and wet states, on and after 0.001 weight % of XGOX20 in the starting fibrous suspension (2 g/l). However, the effect appears to increase with concentration.

(64) 3. Effect of Degree of Oxidation (DO)

(65) Xyloglucan was used as additive for different degrees of oxidation.

(66) 1 L of fibrous suspension at 2 g/L containing 0.1 weight % of XgOx+1 L water were added to a Bchner flask containing 3 paper filters stacked on a nylon filtration fabric of 215 m porosity and 18.5 cm in diameter. Filtration was performed under the vacuum of a water pump and the paper obtained was dried at room temperature for 24 h, then in an oven at 60 overnight.

(67) The degree of oxidation will impact both adsorption capacity and crosslinking density.

(68) TABLE-US-00007 TABLE 6 Impact of degree of oxidation of xyloglucan on the mechanical properties of treated papers. Ref % Ox = 1% % Ox = 12% % Ox = 20% % Ox = 35% % Ox = 47% Ultimate dry 6.53 (1.2) 13.06 (1.9) 13.9 (2.9) 13.8 (1.6) 8.3 (1.8) 11.04 (2.7) strength wet 0 0.012 (0.09) 0.9 (0.09) 1.48 (0.19) 0.36 (0.13) 0.54 (0.09) (MPa) Standard deviations are given in brackets.

(69) It is therefore noted that at very low % Ox (1%), the product is adsorbed and reinforces the paper in the dry state via the network of H bonds formed by the presence of xyloglucan. On the other hand, in the wet state, no reinforcement is observed due to disappearance of the H bonds and absence of covalent bonds of hemiacetal type. At average degrees of oxidation (10<% Ox<25), the equilibrium is optimal between adsorption of the product and crosslinking density. Beyond 25%, the glycose backbone will be oxidized and adsorption capacity decreases. This translates as a reduction in mechanical properties in the dry state and in the wet state. A certain percentage of reinforcement is observed however which can be accounted for by the adsorption of a fraction of the chains which maintain a structure compatible with adsorption, and by bulk deposition of the product during the production method by filtration. In this case, the high proportion of aldehyde functions present on the chains allows significant crosslinking, the effects of which are mechanically translated.

(70) 4. Conclusion

(71) Synthesis of the product was controlled, in particular by controlling the degree of oxidation.

(72) Physicochemical characterization of adsorption shows the formation of the XgOx-cellulose complex.

(73) Different applications have demonstrated the efficacy of the product on various cellulosic substrates.

Example 5: Over-Crosslinking

(74) i. Mechanical Properties of NFC Fims

(75) NFC films containing different proportions of XgOx were subjected to post-treatment in an aqueous solution of adipic dihydrazide. After drying, tensile tests were applied to the films. The results given in FIG. 6 show the impact of the weight proportion of xyloglucan, XgO12 and XgO23 on the ultimate tensile strength of post-treated NFC films.

(76) The post-treated films were tested after soaking in water. The yield strengths of the wet post-treated films are compared in FIG. 7 with those of NFC-XgOx films.

(77) In a wet medium, XgOx allows maintained cohesion of the film through the formation of hemiacetals. The addition of dihydrazide further reinforces mechanical properties, all the more so if DO and the proportion of XgOx are high. For example, at 25% XgOx23, the film displays an average strength of 0.4 MPa, which increases up to 17 MPa after post-treatment, i.e. 40% of the value of a dry NFC film. ii. Mechanical Properties of Papers

(78) The effect of this over-crosslinking was tested on papers. Chitosan, a biosourced amino polymer, was used to obtain a 100% bio-sourced additive system. Non-Pressed Papers

(79) A first test phase was conducted on papers designed as follows: 1 L of 2 weight % Kraft fibre suspension was prepared, with the concentrations of XgOx 20 specified in the table below. Just before filtration, the volume was increased to 2 L under vigorous stirring after which the suspension was vacuum filtered. After extraction of water, the vacuum was maintained and a 0.01 weight % solution of chitosan was sprayed onto the cake. The papers obtained were dried at room temperature.

(80) The mechanical properties given in Table 7 were obtained.

(81) TABLE-US-00008 TABLE 7 Yield strengths of additive-containing papers in the dry and wet states (standard deviations on 5 samples given in brackets) treated by impregnation with chitosan. dry (MPa) wet (MPa) Ref. 7.1 (0.82) 0.1 (0.06) 0.001% XgOx20 12.8 (0.6) 1 (0.1) 0.01% XgOx20 14.7 (2.5) 1.25 (0.22) 0.5% XgOx20 18.8 (2.82) 2.28 (0.33) 0.001% XgOx20 + chitosan 19.8 (2.5) 2.3 (0.51) 0.01% XgOx20 + chitosan 16.2 (3.48) 3 (0.49) 0.5% XgOx20 + chitosan 19.7 (3.7) 4 (0.35)

(82) In similar manner, papers treated with XgOx35 were over-crosslinked after drying. Paying heed to the same protocol, the papers were dried after filtration, soaked in 0.01 weight % solution of chitosan before further drying. The mechanical properties are given in Table 8.

(83) TABLE-US-00009 TABLE 8 Yield strengths of additive-containing papers in the dry and wet states (standard deviations on 5 samples given in brackets), post-treated with chitosan. (Mpa) dry (Mpa) wet Ref. 6.9 (1.2) 0.1 (0.02) 0.1% XgOx20 12 (1.9) 1.9 (0.14) 0.1% XgOx20 + chitosan 10.3 (2.25) 2.7 (0.62) 0.01% XgOx20 13.1 (0.18) 1.6 (0.22) 0.01% XgOx20 + chitosan 11.6 (1.33) 2.9 (0.33)

Papers Prepared on Franck Handsheet Moulds

(84) Additive-containing papers were prepared on Franck handsheet moulds from 1 L of fibrous suspension at 2 g/l and 0.01 weight % of XgOx20. After filtration, a 0.01 weight solution of chitosan was sprayed onto the filter cakes before vacuum drying at 90 for 7 min. The results are given in Table 9.

(85) TABLE-US-00010 TABLE 9 Yield strengths of additive-containing papers in the dry and wet states (standard deviations on 5 samples given in brackets) treated by spraying with chitosan. XgOx20 + Classic Paper XgOx 20 chitosan dry 20.1 (0.6) 38.6 (1.9) 37.2 (4.0) wet 0.09 (0.06) 4.0 (0.07) 6.73 (0.29)

(86) Over-crosslinking with chitosan, irrespective of initial XgOx content or treatment method, systematically gave a very significant increase in wet state properties.

Example 6: Use of Another Oxidized Polysaccharide

(87) Synthesis:

(88) 10 g of polymers were dissolved in 1 L of water under vigorous stirring. The periodate was added and the reaction conducted for 12 h at room temperature away from light. A solution of 1 weight % oxidized polysaccharide was obtained. Table 10 gives the stoichiometry conditions.

(89) TABLE-US-00011 TABLE 10 Weight of added Stoichiometry polysaccharide Weight of added (NaIO4/Polym) Denomination (g) periodate (g) Locust bean 0.10 LOx10 10.00 1.32 gum 0.19 LOx20 10.43 2.64 Guar gum 0.10 GOx10 9.96 1.32 0.20 GOx20 10.12 2.64

(90) The cellulose was purified to prevent parallel effects of residual periodate and to allow analysis of the products obtained. Dialysis was therefore performed until conductivity was obtained equalling that of laboratory deionized water.

(91) After dialysis, the concentrations were measured as dry matter content. The additives were then used as such.

(92) Paper Characterization:

(93) The oxidized polysaccharides were added to a 2 g/l fibrous suspension of Kraft pulp to reach an additive concentration of 0.01 weight %. After 1 h under agitation, handsheets were prepared by filtration.

(94) The papers obtained were subjected to tensile testing in the dry state after 48 h immersion in deionized water. The different polysaccharides are compared with XGOX20 and with a reference paper not containing additives in Table 11 (below).

(95) Conclusion:

(96) Under the test conditions, the performance of the oxidized polysaccharides derived from guar gum and locust bean gum are far removed from that of the oxidized xyloglucan. The differences are striking both in the dry and wet states.

(97) TABLE-US-00012 TABLE 11 Paper 0.01% 0.01% 0.01% 0.01% 0.01% Ref. XGOX20 GOx10 GOx20 LOx10 LOx20 Ultimate dry 6.53 (1.2) 14.68 (2.5) 9.60 (1.36) 8.66 (0.95) 8.85 (0.32) 7.10 (1.01) strength wet 0 1.25 (0.2) 0.03 (0.02) 0.06 (0.04) 0.10 (0.06) 0.14 (0.03) (MPa)

Example 7: Functionalization Test with a Colouring Agent

(98) To show the reactivity of the remaining available aldehyde functions, a Kraft paper not containing additives was prepared as follows: 1 L of Kraft fibre suspension at 2 g/l was vacuum filtered and dried at room temperature.

(99) Papers to which were added XgOx20, XgOx44, Oxidized Guar (GOx44) or oxidized locust bean gum (Cox44), oxidized as in the preceding protocol, were prepared as follows: 1 l of Kraft fibre suspension at 2 g/l containing 0.1% or 0.01 weight % of XgOx20 or XgOx44 or GOx44 or Cox44 were vacuum filtered and dried at room temperature.

(100) A sample was taken measuring 1 cm.sup.2 of each of the papers containing or not containing additives, and immersed in 2,4-Dinitrophenylhydrazine (DNPH) prepared as follows: 0.19813 of DNPH is weighed and dissolved in a mixture of 3 ml of 37% HCl, 20 ml of ethanol and 20 ml of water, in a 100 ml volumetric flask. After completing the volume with ethanol up to the marking, a 0.01 mol/l DNPH solution is obtained. The samples were left in the DNPH solution for 48 h. After thorough rinsing, the papers without additives displayed a pale-yellow colour whereas the papers containing additives displayed a very pronounced orange colouring (particularly 0.1% Cox44, 0.1 and 0.01% XgOx44) indicating grafting of DNPH onto the aldehydes of the oxidized polysaccharide in the paper according to proportion and type of additive, as per the following reaction:

(101) ##STR00001##
In a photograph (not illustrated) it can be seen that the paper with additives and the paper without additives, after being placed in contact with the DNPH solution and rinsed, display different colours with a pale-yellow paper for the paper without additives and orange coloured paper for the paper containing additives.