Stabilized sizing formulation

Abstract

The present invention relates to sizing agent formulations, especially to stabilizing a sizing formulation by a modified non-food polysaccharide. The method for preparation of the modified non-food polysaccharide is further provided.

Claims

1. A stabilized sizing formulation, comprising a sizing agent and an anionically charged derivative of a non-food polysaccharide which comprises xylan or arabinogalactan or a mixture thereof, wherein the non-food polysaccharide is selected from the group consisting of celluloses, hemicelluloses, gums, pectins, xylans, mannans, glucans and mucilages.

2. The formulation according to claim 1, wherein the sizing agent is alkyl ketene dimer (AKD) or alkenyl succinic anhydride (ASA) or a mixture thereof.

3. The formulation according to claim 1, wherein the anionically charged derivative of the non-food polysaccharide is obtained by modifying the non-food polysaccharide with carboxymethyl reagent.

4. The formulation according to claim 3, wherein, the carboxymethyl reagent is monochloro acetic acid.

5. The formulation according to claim 4, wherein degree of substitution of the anionically charged derivative of the non-food polysaccharide from 0.03 to 1.0.

6. The formulation according to claim 1, wherein the non-food polysaccharide is xylan or arabinogalactan or mixtures thereof.

7. The formulation according to claim 1, wherein said formulation is in a form of a dispersion.

8. The formulation according to claim 7, wherein the dispersion is an emulsion.

9. The formulation according to claim 1, wherein ratio of the anionically charged derivative of the non-food polysaccharide to the sizing agent is from 0.05:1 to 0.15:1.

10. A method for preparing the stabilized sizing formulation of claim 1, wherein the sizing agent and the anionically charged derivative of the non-food polysaccharide comprising xylan or arabinogalactan or a mixture thereof are brought into contact within a solution whereby a dispersion is formed by homogenization at a pressure from 140 to 160 bar.

11. A method to sizing paper and paper products, said method comprising the steps of obtaining formulation of claim 1 and sizing paper and paper products with the formulation.

12. The method according to claim 11, wherein dosing of the stabilized sizing formulation into pulp is from 0.5 to 3 kg/t.

13. A method for preparation of the anionically charged derivative of the non-food polysaccharide of claim 1 comprising the steps of: i. providing a suspension of the non-food polysaccharide comprising xylan or arabinogalactan or a mixture thereof and an alcohol; ii. introducing aqueous base solution to the mixture of step i., and stirring the resulting mixture; iii. introducing carboxymethyl reagent to the mixture of step ii., and stirring the resulting mixture at elevated temperature; and iv. washing and filtering the resulting anionically charged derivative of the non-food polysaccharide before recovery.

Description

BRIEF DESCRIPTION OF THE FIGURES

(1) FIG. 1 shows sizing results (Cobb60) of stabilized sizing formulations of the present invention comprising a sizing agent and an anionic derivative of xylan.

(2) FIG. 2 shows sizing results (Cobb60) of stabilized sizing formulations of the present invention comprising a sizing agent and an anionic derivative of arabinogalactan.

DETAILED DESCRIPTION

(3) By non-food polysaccharides is meant polysaccharides which fail to provide a source for a nutritional diet. Unlike starch, non-food polysaccharides cannot be used for nutritional purposes.

(4) The non-food polysaccharides include indigestible non-starch polysaccharides (NSP) consisting of long chains of repeating glucose units. However, unlike starches, the glucose units in non-starch polysaccharides are joined by beta-acetal linkage bonds. The beta-acetal linkage cannot be split by the enzymes in the digestive tract. The non-starch polysaccharides include, for example, celluloses, hemicelluloses, gums, pectins, xylans, mannans, glucans and mucilages. Typical NSPs found in wheat are arabinoxylans and cellulose. Preferably, the non-food polysaccharides of the present invention are selected from xylan, arabinogalactan or mixtures thereof.

(5) In one embodiment the stabilized sizing formulation of the present invention comprises a sizing agent and a modified non-food polysaccharide which comprises xylan or arabinogalactan or mixtures thereof.

(6) Xylan (CAS number: 9014-63-5) is one example of highly complex polysaccharides that is found in plant cell wall and in certain algae. Xylan is a polysaccharide made from units of xylose which is a pentose sugar. Xylans are almost as ubiquitous as cellulose in plant cell walls and contain predominantly ?-D-xylose units linked as in cellulose. The formula of a xylan may be presented as follows:

(7) ##STR00004##
wherein n is the number of xylose units.

(8) Another specific example of a non-food polysaccharide is arabinogalactan. It is a biopolymer consisting of arabinose and galactose monosaccharides. Two classes of arabinogalactans are found in nature: plant arabinogalactan and microbial arabinogalactan. In plants, it is a major component of many gums, including gum arabic and gum ghatti. Both the arabinose and galactose exist solely in the furanose configuration. An example of a structure of an arabinogalactan is presented by the following formula:

(9) ##STR00005##

(10) An arabinogalactan from wood of the larch tree (Larix laricina) is composed of d-galactose and l-arabinose in a 6:1 molar ratio accompanied by small amounts of d-glucuronic acid. Arabinogalactans are found in a variety of plants but are more abundant in Larix occidentalis (western larch).

(11) In one aspect of the present invention a method for preparation of a modified non-food polysaccharide is provided. The properties of non-food polysaccharides may be modified by functionalizing or derivatizing with varying chemicals. The properties of the modified polysaccharides, such as hydrophobicity and/or plasticization, may be enhanced further by modifying them with esters and/or ether groups into the hemicellulose backbone. Depending on the quality of the substituents, the degree of substitutions, type of backbone, molecular weight of the remaining backbone, solubility and thermal properties can be changed remarkably and the dispersion properties enhanced even further.

(12) The disclosed method comprises modifying the non-food polysaccharide by functionalization using a functionalizing agent which is capable of charging the non-food polysaccharide. The non-food polysaccharides may be modified to exhibit cationic or anionic properties. There are several methods available for carrying out this charging.

(13) The non-food polysaccharide of the present invention is charged by rendering it anionic with a suitable anionization reagent. This method for anionic charging the non-food polysaccharide comprises the steps of i. providing a suspension of the non-food polysaccharide and an alcohol; ii. introducing aqueous base solution to the mixture of step i., and stirring the resulting mixture at room temperature; iii. introducing anionization reagent, such as carboxymethyl reagent, to the mixture of step ii., and stirring the resulting mixture at elevated temperature; and iv. washing and filtering the resulting anionically charged derivative of the non-food polysaccharide before recovery.

(14) In one embodiment of the present invention the anionic non-food polysaccharide derivative preferably contains carboxymethyl groups with a high degree of substitution. These anionically charged derivatives of non-food polysaccharides are prepared by reaction of the non-food polysaccharide preferably with monochloro acetic acid in varying reaction media. The reaction of monochloro acetic acid with the non-food polysaccharide proceeds more rapidly at higher temperatures than in room temperature.

(15) In a preferred reaction method according to the present invention the anionically charged derivatives of non-food polysaccharides are prepared by reacting the non-food polysaccharide with a carboxymethyl reagent. The non-food polysaccharide is suspended in an alcohol, preferably ethanol. Aqueous base solution is introduced into the suspension and resulting mixture is preferably vigorously stirred at room temperature, preferably at least 1 hour. To this mixture the carboxymethyl reagent is introduced and resulting mixture is stirred at elevated temperature, preferably at least 2 hours. The resulting product is poured to excess amount of water, neutralized and purified by filtration, preferably ultrafiltration (CutOff 1000).

(16) In one embodiment the non-food polysaccharide comprises xylan or arabinogalactan or mixtures thereof.

(17) Preferably, the base is metal hydroxide, more preferably NaOH or KOH, even more preferably NaOH, and most preferably 50% aqueous NaOH solution. The carboxymethyl reagent is preferably monochloro acetic acid. Preferably, the elevated temperature is from 35 to 65? C., more preferably from 45 to 55? C., such as about 50? C.

(18) The preferred non-food polysaccharides to be anionized in the present invention are xylan and arabinogalactan or a mixture thereof.

(19) The anionization reagents may be selected from commercially available reagents.

(20) In one embodiment xylan is anionized using monochloro acetic acid as anionization reagent. Xylan is suspended into ethanol. 50% aqueous NaOH solution is added to the suspension and resulting mixture is vigorously stirred at room temperature for 1 hour. Monochloro acetic acid is added to the mixture and stirred at 50?C. for two 2 hours. The resulting product is poured to excess amount of water, neutralized and purified by filtration.

(21) The reaction mechanism is the following:

(22) ##STR00006##

(23) In another embodiment arabinogalactan is anionized using monochloro acetic acid as anionization reagent. Arabinogalactan is suspended into ethanol. 50% aqueous NaOH solution is added to the suspension and resulting mixture is vigorously stirred at room temperature for 1 hour. Monochloro acetic acid is added to the mixture and stirred at 50? C. for two 2 hours. The resulting product is poured to excess amount of water, neutralized and purified by filtration.

(24) Degree of substitution (DS) of the anionically charged derivatives of non-food polysaccharides is dependent on the reagents, reagent ratios and reaction conditions. The degree of substitution may be determined by potentiometric titration know for a skilled person.

(25) The degree of substitution of the anionically charged derivatives of non-food polysaccharides is preferably from 0.03 to 1.0. The degree of substitution in the monochloro acetic acid charged xylan is preferably from 0.03 to 0.60, and more preferably from 0.06 to 0.31, whereas for monochloro acetic acid charged arabinogalactan preferably from 0.03 to 0.60, and most preferably from 0.11 to 0.42.

(26) In another aspect of the present invention a stabilized sizing formulation is provided comprising a sizing agent and an anionically charged non-food polysaccharide.

(27) The sizing agent of the formulation is preferably alkyl ketene dimer (AKD), alkenyl succinic anhydride (ASA) or mixtures thereof. The amount of ASA in the formulation is from 0.5 to 5.0 weight-%, preferably from 1.0 to 3.0% by weight, more preferably from 1.0 to 2.0% by weight, even more preferably from 1.0 to 1.50% by weight, and most preferably from 1.24 to 1.26% by weight of the formulation. weight, more preferably from 1.0 to 2.0% by weight, even more preferably from 1.0 to 1.50% by weight, and most preferably from 1.24 to 1.26% by weight of the formulation.

(28) In one embodiment the stabilized sizing formulation comprises ASA or AKD, and an anionized xylan. The polysaccharide is most advantageously anionized using carboxymethyl reagent, such as monochloro acetic acid, and preferably the degree of substitution is less than 1.0, more preferably from 0.03 to 0.60, and most preferably from 0.06 to 0.31.

(29) In another preferred embodiment the stabilized sizing formulation comprises ASA or AKD, and an anionized arabinogalactan. The polysaccharide is most advantageously anionized using carboxymethyl reagent, such as monochloro acetic acid, and preferably the degree of substitution is less than 1.0, more preferably from 0.03 to 0.60, and most preferably from 0.11 to 0.42.

(30) The amount of charged functionalized non-food polysaccharide to the sizing agent in the stabilized sizing formulation is from 0.05:1 to 0.15:1, preferably from 0.07:1 to 0.13:1, more preferably from 0.09:1 to 0.11:1. These amounts are considerably less than the corresponding amounts of starch required and tested as reference. The amount of starch required to provide the same stabilizing effect was about 20 times more.

(31) The stabilized sizing formulation according to the present invention is preferably in a form of a dispersion, more preferably an emulsion.

(32) In one embodiment the amount of ASA in the sizing emulsion formulation is 1.25% by weight and the amount of xylen anionically modified with carboxymethyl reagent, preferably monochloro acetic acid, to ASA is about 0.1:1.

(33) In another embodiment the amount of ASA in the sizing emulsion formulation is 1.25% and the amount of arabinogalactan anionically modified with carboxymethyl reagent, preferably monochloro acetic acid, to ASA is 0.1:1.

(34) The formulation according to the present invention may further contain typically used, or readily commercially available, emulsifiers or retention aids, such as e.g. Fennopol K 3400 R.

(35) The dosage of the sizing agent formulation according to the present invention to the pulp is preferably from 0.5 to 3 kg/t when the formulation comprises the charged non-food polysaccharide stabilizing agent.

(36) In a further aspect of the present invention a method for preparing the stabilized sizing formulation is provided. The sizing agent and the charged non-food polysaccharide are brought into contact within an aqueous solution whereby a dispersion is formed.

(37) In one embodiment the cationic noon-food polysaccharide is first dissolved into water or an aqueous solvent whereto the sizing agent is subsequently introduced. The mixture is then homogenized. The sizing agent is preferably mixed with an aqueous solution of the charged non-food polysaccharide to ensure efficient mixing.

(38) Preferably, the sizing formulation is formed by homogenizing the aqueous mixture. The homogenization may be carried out in high pressure, preferably at a pressure from 140 to 160 bar.

(39) In a yet further aspect of the present invention use of the stabilized sizing formulation as depicted above is provided for sizing paper and paper products. A preferred dosage amount of the sizing formulation into pulp furnish is from 0.5 to 3 kg/t.

(40) The sizing efficiency of the sizing formulation may be evaluated by preparing handsheets and measuring the Cobb value of the paper product resulting from a manufacturing process utilising the sizing formulation. The Cobb60 value determines the water absorptiveness of sized paper according to ISO 535:1991(E) standard.

(41) Using the stabilized sizing formulation according to the present invention Cobb60 values are lower to the values obtained when using starch as stabilizer. Thus, it is possible to replace starch stabilized sizing formulations with formulations comprising non-food polysaccharides without sacrificing the stabilizing ability or the quality of the final paper product.

(42) It is further noted that the amount of charged modified non-food polysaccharide may be clearly less, possibly 1/10 or even 1/20, than the amount of starch needed, to reach equal results. The amount of the stabilizing agent in the emulsions of sizing formulations could be significantly lower, such as 1/20 of that compared to starch as a stabilizer. This has a particular effect on the effluent water chemical load and to the post processing and recycling of the effluent.

(43) Hereafter, the present invention is described in more detail and specifically with reference to the examples, which are not intended to limit the present invention.

EXAMPLES

(44) Preparation of Anionic Xylan by Carboxymethylating the Xylan

(45) Three samples with varying degree of substitution are prepared from the non-food polysaccharide, xylan.

(46) Xylan was suspended in ethanol. 50% aqueous NaOH solution was added to the suspension and reaction mixture was vigorously stirred at room temperature for 1 hour. 80% monochloro acetic acid (MCAOH) was added to the reaction mixture, and temperature of the reaction bath was raised to 50? C. After 2 hours resulting product was precipitated from water, filtrated and washed with aqueous ethanol (70%) and finally washed with pure ethanol prior drying.

(47) For specific amounts of reagents, see Table 1 for details. All the reagents are commercially available.

(48) Preparation of Anionic Arabinogalactan by Carboxymethylating the Arabinogalactan.

(49) Two samples with varying degree of substitution are prepared from the nonfood polysaccharide, arabinogalactan.

(50) Arabinogalactan was suspended in ethanol. 50% aqueous NaOH solution was added to the suspension and reaction mixture was vigorously stirred at room temperature for 1 hour. 80% monochloroacetic acid (MCAOH) was added to the reaction mixture, and temperature of the reaction bath was raised to 50? C. After 2 hours resulting product was poured to excess amount of water, neutralized and purified by ultrafiltration (CutOff 1000).

(51) For specific amounts of reagents, see Table 1 for details. All the reagents are commercially available.

(52) Analysis of the Synthesized Anionic Xylans and Anionic Arabinogalactans

(53) Degree of substitution (DS) of the synthesized anionic xylans and arabinogalactans was measured by potentiometric titration. Degradation temperatures (T.sub.10%) of the samples were also measured.

(54) In table 1 are presented degrees of substitutions and degradation temperatures of the synthesized anionic xylans and anionic arabinogalactans.

(55) TABLE-US-00001 TABLE 1 DS Degradation Sample Non-food poly- MCAOH NaOH Ethanol (potentiometric temperature Code saccharide (g) (g) (g) (g) titration) (? C.) CM_X311 Xylan (30 g) 4.5 7 120 0.12 257 CM_X411 Xylan (30 g) 3.0 5 120 0.06 255 CM_X711 Xylan (30 g) 7.5 10 120 0.31 259 CM_Ag111 Arabinogalactan 7.5 10 120 0.42 228 (30 g) CM_Ag211 Arabinogalactan 2.0 3 120 0.11 213 (30 g)
Preparation of the Stabilized Sizing Formulations

(56) ASA emulsions are prepared using a kitchen blender with 2 min mixing, after which they are passed through a homogenizer at 150 bar pressure.

(57) Firstly, sizing emulsion is prepared from 1.25% ASA emulsions using anionized xylan from table 1 to ASA ratio of 0.1:1 as stabilizer.

(58) Secondly, sizing emulsion is prepared from 1.25% ASA emulsions using anionized arabinogalactan from table 1 to ASA ratio of 0.1:1 as stabilizer.

(59) As a reference sizing emulsion is prepared also from starch (Raisamyl 50021) and 1.25% ASA emulsion using starch to ASA ratio of 2:1 as stabilizer. Further reference samples are made from 1.25% ASA emulsions using xylan and arabinogalactan without anionization in ratios of 0.1:1 as stabilizers.

(60) Preparation of Laboratory Handsheets, and Sizing Results

(61) Laboratory handsheets, 80 g/m.sup.2, are prepared by introducing into 50/50 hardwood/softwood Kraft pulp furnish having a pH 8.5 the stabilized sizing formulations prepared in above example. No fillers are used in the resulting paper processing and the wet end starch amount is 5 kg/t. The stabilized size formulation dosage is 0.75 kg/t. K 3400R (200 g/t) is used as a retention aid.

(62) The results from Cobb60 testing are depicted in FIG. 1 for anionic xylan stabilized sizing agent formulation, and further depicting the reference sample results for cationic starch and xylan.

(63) The results from Cobb60 testing are depicted in FIG. 2 for anionic arabinogalactan stabilized sizing agent formulation further depicting the reference sample results for cationic starch and arabinogalactan.

(64) The smaller the Cobb60 number the better the sizing, i.e. the paper product is more hydrophobic and absorbs less water.

(65) FIG. 1 shows that the paper sheets wherein anionized xylan is used are more hydrophobic than cationic starch based sizing agent.

(66) FIG. 2 shows that the paper sheets wherein anionized arabinogalactan is used are more hydrophobic than cationic starch based sizing agent.