WATER-SOLUBLE REGENERATED FIBER PRODUCTION FROM CALLUNA VULGARIS PLANT SPECIES

Abstract

The method disclosed relates to production of regenerated fiber from cellulose-containing plant species, in the textile sector. In particular, the method relates to obtaining water-soluble regenerated cellulose fiber using high or low purity cellulose raw material isolated from the wild plant species of Calluna Vulgaris.

Claims

1. Regenerated fiber obtained from Calluna Vulgaris plant.

2. A method of obtaining regenerated fiber from Calluna Vulgaris plant, characterized in that; it comprises the operation steps of: obtaining cellulose pulp from Calluna Vulgaris plant and performing lignin disintegration; performing hemicellulose disintegration in the cellulose pulp; performing bleaching; adding N-methyl morpholine-N-oxide, water, and polyethyleneglycol, respectively; and passing the obtained solution through spinning nozzles.

3. The method according to claim 2, characterized in that; the operations of obtaining cellulose pulp and lignin disintegration comprise the operation steps of: turning Calluna Vulgaris plant into chips; keeping at ambient temperature for 8 hours via NaOH; baking; grinding; and; chemical impregnation via Na.sub.2SO.sub.3 and NaOH.

4. The method according to claim 2, characterized in that; the operation of hemicellulose disintegration in the cellulose pulp comprises the operation steps of: adding xylanase enzyme into cellulose pulp; treating cellulose pulp with xylanase enzyme at 65 C. for 150 minutes; and washing cellulose pulp.

5. The method according to claim 2, characterized in that; during the operation of adding N-methyl morpholine-N-oxide, water, and polyethyleneglycol, it comprises the operation step of mixing 10-15% by weight cellulose pulp with 50-65% by weight N-methyl morpholine-N-oxide, 10-20% by weight polyethyleneglycol, and 10-20% by weight water.

6. The method according to claim 2, characterized in that, it comprises the operation step of performing fiber spinning by passing the solution obtained following addition of N-methyl morpholine-N-oxide, water, and polyethyleneglycol, respectively, to cellulose pulp, through spinning nozzles.

7. The method according to claim 6, characterized in that, before the fiber spinning operation, it comprises the operation step of mixing said solution for 20-60 minutes at 30-80 C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0098] In this detailed description, the preferred embodiments of the water-soluble regenerated fiber production from Calluna Vulgaris plant according to the invention are only disclosed for better understanding of the subject without forming any limiting effect.

[0099] The invention relates to production of water-soluble regenerated fibers from Calluna Vulgaris (L.) Hull and Ericaceae plant species that originate from the same family.

[0100] Below, the characteristics of Calluna Vulgaris plant are given.

[0101] Biological class: Plant

[0102] Branches on the family tree: Angiosperms, Eudicots, Asterids

[0103] Regnum: Ericales

[0104] Family: Ericaceae

[0105] Genus: Calluna Salisb

[0106] Species: Calluna Vulgaris

[0107] Latin name: Calluna Vulgaris (L.) Hull

[0108] Calluna Vulgaris is a wild dwarf plant growing in acidic soil in pasture areas in cold winter months. It is a plant species that may threaten biological diversity in plateaus. It is typically a 0.5-1.25 meter high, evergreen, woody, and scrubby plant. It is pretty wooly in the beginning of growth. Then it becomes bare. It has stalkless leaves that extend through the branches; grow in four vertical lines; are green in the beginning and then become brown; and have wools up to 3.5 mm long. While its bell-shaped flowers are pale blue, they may also be pink and white. The flowers grow on the narrow leaves. Its tiny seeds are 0.5 mm long and 0.7 mm wide and in the shape of four-cell round capsules. Calluna Vulgaris spreads easily and it may occupy new areas rapidly.

[0109] Calluna Vulgaris grows new leaves and shoots beginning from spring to autumn. Its flowers are necklace-shaped and stand suspended downwards, and come into blossom towards the end of autumn. It buds out towards the end of winter. Its seeds germinate all year round. But the best germination occurs during spring and autumn. After a forest fire, it becomes capable of producing seeds in 3 years in that region. Dense green offshoots of Calluna Vulgaris plant become woody and may live about 30 years. Each plant is capable of giving one million seeds per square meter by producing 3000-4000 flowers and thousands of seeds. Its weak and tiny looking seeds survive for about 100 years. They are spread by wind or contact with animals.

[0110] The seeds can even germinate only through thermal treatment without getting any light. It can also make vegetative reproduction. Calluna Vulgaris comes out in steppes, inside forest lands, and throughout tree lines. They are colonized up to 1500 meters height. They are capable of growing in wet and marsh areas; it is extremely resistant to icing.

[0111] In the below given Table 3, the development calendar of Calluna Vulgaris is given.

TABLE-US-00003 TABLE 3 Development Calendar of Calluna Vulgaris January February March April May June July August September October November December Blooming + + + + Vegetative + + + + + + + + growth Reproduction + + + + + form Seeding + + + + + Germination + + + + + + + + +

[0112] Other species covered are named in Latin as Erica Cinera, Erica Lusitanica, and Erica Manipuliflora Salisb. They are found in Giresun, Trabzon, Rize, Artvin, and Istanbul in Turkey.

[0113] The fact that this plant is capable of growing in acidic soils and winter months; each plant is capable of giving one million seeds per square meter by producing 3000-4000 flowers and thousands of seeds; and it can grow in marsh areas are the most significant characteristics of the wild plant, Calluna Vulgaris. It spreads easily and invades new areas quickly.

[0114] Cellulosic Substance Analysis in Calluna Vulgaris Plant Structure Via Chemical Methods

[0115] Lignin and Cellulose Separation Methods Via Acid-Detergent Method

[0116] Evaluation is made for grass, hay, bush, and tree via lignin acid-detergent separation method. Cellulose is hydrolyzed in isolation with 72% sulphuric acid (H.sub.2SO.sub.4). The reaction of the chemical substances used in the acid-detergent method leads to substantial dissolution of hemi-cellulose and allows calculating the amount of the remaining alpha-cellulose. [0117] CTAB (Cetyltrimethyl-ammonium bromide); 50 g of Cetyl trimethyl ammonium bromide is found in 5 litres of 0.5 Molar H.sub.2SO.sub.4.

[0118] Procedure: 100 ml of CTAB solution is added into a 250 ml beaker containing 0.500-1.000 g of dry material, and a few drops of octan-2-ol is dropped as an anti-foaming agent. The beaker is stirred for 1 hour. The obtained solution is passed through the previously weighed No. 2 sinter (W2) filter under pressure vacuum. The remaining precipitate is washed three times with boiling deionised water/acetone until it becomes colourless. The precipitate is dried at 105 C. for 2 hours, cooled in a dessicator, and weighed (W3). With this analysis method, the amount of cellulose found in C. Vulgaris plant can be determined.

% ADF=(W3W2)*100/WI [0119] Reaction chemicals: Sulphuric acid (72% W/V) 720 ml H.sub.2SO.sub.4 is added into 540 ml deionised water.

[0120] Procedure: a sample smoothly ground with 72% H.sub.2SO.sub.4 (15 C.) is mixed until it turns into a cake and placed in a suitable container. 3 hours later, it is washed with non-acidic water, vacuumed, dried for 2 hours at 105 C., cooled in a dessicator, and weighed (W4). The solid portion is combusted for 2 hours in a furnace at 550 C., cooled in a dessicator, and weighed (W5).

% LIGNIN=(W4W5)*100/WI

% CELLULOSE=(W3W4)*100/WI

[0121] With this application, % LIGNIN and % CELLULOSE amounts are determined.

[0122] In the below given Table 4, dry weight % of the cellulose found in all of the Calluna Vulgaris plant via ADF extraction is given.

[0123] Below given results are obtained with the above given two applications.

TABLE-US-00004 TABLE 4 dry weight % of the cellulose found in all of the Calluna Vulgaris plant obtained by ADF extraction Holocellulose Hemi-cellulose Alpha cellulose Genus of Plant (% Dry weight) (% Dry weight) (% Dry weight) Calluna Vulgaris 36.6 15.2 21.4

[0124] In the below given Table 5, among the chemical compounds found in the structure of Calluna Vulgaris plant, dry weights of proteins (PRO); lipid (LIP); phenol (PHE); undefined carbohydrates (TNC); and minerals (ASH) are given in mg/g.

TABLE-US-00005 TABLE 5 Chemical analysis results of Calluna Vulgaris plant PRO LIP PHE CEL LIG VAKS TNC ASH mg/g mg/g mg/g mg/g mg/g mg/g mg/g mg/g TOTAL 27 14 32 450 151 10 45 68 854

[0125] Table 5 provides the chemical analysis results of Calluna Vulgaris plant The cellulose, lignin, and fat samples forming the cellular walls are extracted in order to determine their amounts. The samples are purified by being treated in turn with the natural detergent solution formed of disodium ethylene-diaminetetra acetate dihydrate, sodium borate decahydrate, disodium hydrogen phosphate chemicals and decahydronaphthaline, acetone, and sodium sulphide.

[0126] Samples in equal amounts are treated with acid detergent solution (sulphuric acid 1 N and cetyltrimethyl ammonium bromide) so as to remove hemi cellulose. Afterwards, they are treated with potassium permanganate to remove lignin. And then, cellulose is removed by sulphuric acid (72% W/W). Remaining oils and minerals are removed by combustion in a crematorium for 3 hours at 500-550 C. The minerals are determined after keeping the material in crematorium for 5 hours at 550 C.

[0127] Protein amount (PRO): Total nitrogen amount is determined by using Kjeldahl method.

[0128] Lipid (LIP): Determined by diethyl ether extraction for 8 hours in a Soxhlet extractor. Phenols having different molecular weights are treated at 70 C. with pure methanol and 50% aqueous methanol solution, respectively. It is colorimetrically determined by using Folin-ciocalteu chemical substance.

[0129] For total anonymous amylase activation structures; the endo and exonuclease - and amylase activation is determined by using Hajedorn-jensen volumetric method following 48 hours of incubation at 37 C.

[0130] The above-mentioned methods are general analysis methods applied on Calluna Vulgaris plant and as well as used in determination of protein, oil cellulose, lignin amounts in all plants.

[0131] In Calluna Vulgaris plant, -amyrin, -amyrin, oleanolic acid, taraxerol, and ursolic acid etc. compounds determined by using super critical carbondioxide extraction method are known as triterpenoids. Below, enumerated carbon frameworks of triterpenoids are given.

##STR00009##

[0132] Moreover, below, triterpenoids found at the leaves, roots, and stems of Calluna Vulgaris plant are given in g/g dry weight.

TABLE-US-00006 TABLE 6 triterpenoids found at the leaves, roots, and stems of Calluna Vulgaris plant (g/g dry weight) Leaves Roots Stems -amyrin 35,000 370 3,900 -amyrin 13,000 550 5,700 Leupeol 19,000 0 0 Oleanolic acid 11,000 55 14,000 Taraxerol 0 610 0 Taraxer-4-1 0 490 0 Ursolic acid 52,000 130 34,000 Unnamed ursolic 26,000 20 7,500 acid

[0133] Biological activity of Calluna Vulgaris plant: Ursolic acid and oleanolic acid compounds show anti-cancer characteristics against leukaemia cells, gastritic tumors and lung tumors. Since it has triterpenoid compounds, it has antiulcerous and antimicrobial biological activity.

[0134] Below, the production method of water-soluble regenerated fibers from Calluna Vulgaris (L.) Hull according to the invention and Ericaceae plant species that originate from the same family.

[0135] The method of obtaining regenerated fiber from Calluna Vulgaris plant basically comprises the operation steps of: [0136] Obtaining cellulose pulp from Calluna Vulgaris plant and performing lignin disintegration, [0137] Performing hemicellulose disintegration in the cellulose pulp, [0138] Performing bleaching, [0139] Adding N-methyl morpholine-N-oxide, water, and polyethyleneglycol, respectively, and [0140] Passing the obtained solution through spinning nozzles.

[0141] First of all, kraft cellulose pulp is obtained from Calluna Vulgaris plant and lignin disintegration operation is performed. For obtaining this pulp, Calluna Vulgaris plant is mechanically turned into chips form. Penetration is ensured by keeping the material at ambient temperature for 8 hours with 3.0% NaOH, and then it is baked in a pressurised container for 1 hour at 125 C. Following baking operation, it is ground for 10 minutes in pressureless vapour. Chemical impregnation is made with 2-3% Na.sub.2SO.sub.3 and 1-7% NaOH, and treated for 5 minutes at 60-120 C. At the stage of obtaining kraft cellulose pulp, lignin disintegration is also performed in the same process.

[0142] Xylanase enzyme is applied on kraft cellulose pulp for disintegrating hemicellulose polymer structures. Enzyme dosage, 0.5 kg/ton; application time, 150 minutes; temperature, 65 C.; density, 10%; pH 8.5-8.7; and xylanase enzyme activity is 5000 IU/ml. The pulp treated with enzyme is then washed with distilled water.

[0143] Kraft cellulose pulp treated with xylanase enzyme is then beached with hydrogen peroxide (H.sub.2O.sub.2). Bleaching is applied on kraft cellulose pulp with 1.5% NaOH, 0.5% sodium silicate, 0.1% MgSO4, 4% H.sub.2O.sub.2, and at 90 C. and 3-5 atm pressure, for 180 minutes. The pH value and viscosity of the kraft cellulose solution (pulp) are 11 and 14.7 mPas, respectively.

[0144] The lignin amount in the pulp is found using ISO 2470 method (luminosity=51%) and TAPPI-T236 om-99 method (Kappa No.=9.72).

[0145] As the lignin amount found in wood pulp solution increases, the kappa No. rises and the luminosity is reduced. More yellowish or brownish solution pulp is obtained. It is not possible to pass such a solution through spinning nozzles under pressure and obtain fibers. Since this solution will have resistance against fluidity, high pressure is required for obtaining fiber by passing the solution through spinning nozzles; but such high pressures are not possible due to the mechanical structures of the spinning nozzles. However, a pulp solution having the below given viscosity, kappa value, and luminosity characteristics would optimally allow performing fiber spinning.

[0146] 1. Viscosity: 14.7 mPas

[0147] 2. Kappa No.=9.72

[0148] 3. Luminosity=51%

[0149] 55% amine oxide NMMO, 20% PEG, 10% water, 15% cellulose pulp mixture are prepared in a container and mixed at 30-70 C. at 40 RPM for 60 minutes. The preferred rates in said mixture are given below in table form.

TABLE-US-00007 TABLE 7 PEG/NMMO/Water/Cellulose mixing rates Preferred Usable amount by amount by Ingredient weight (%) weight (%) Cellulose pulp obtained from 15 10-15 Calluna Vulgaris plant N-methylmorpholine- 55 50-65 N-oxide (NMMO) Water 10 20-10 Polyethyleneglycol (PEG) 20 20-10

[0150] Cellulose-Amine Oxide (NMMO)-Polyethyleneglycol (PEG) solution: 10-15% cellulose, 50-65% amine oxide (NMMO), 10-20% PEG, and 10-20% water. Through the spinning nozzles; cellulose solution completes molecular orientation via wet spinning method.

[0151] With wet fiber spinning method; a solution consisting of polyethylene glycol, NMMO, cellulose pulp, and water is mixed for 20-60 minutes at 30-80 C., and then fiber spinning is performed by using spinning nozzles made of stainless steel, nickel, or platinum alloys with nozzle channel diameters ranging between 0.2-1 mm.

[0152] In the cellulose pulp obtained from Calluna Vulgaris plant, the lignin material is required to be removed completely. Viscosity of polyethylene glycol/water/cellulose/NMMO solution should be fluid such that it would not prevent formation of yarn. The fiber diameter increases as the viscosity increases.

[0153] While cellulose is mixed with 10-20% PEG and 50-65% aqueous amine oxide (NMMO) solution, cellulose activation temperature increases up to 60 C. Cellulose swells in polar media such as water. The temperature of swollen cellulose increases up to 70 C. in amine oxide (NMMO)-water mixture. If this temperature is maintained for about 60 minutes, cellulose activation is completed. In this way, good mixture and homogeneous cellulose melt are obtained. Before the formed solution turns into solid chips and granule form, subvention can be made to the spinning part. Homogeneous polymer melt or solution is a key product having smooth spinning performance and final product characteristics.

[0154] Different from the traditional raw material sources of other regenerated fibers, within the scope of the invention, regenerated fiber is obtained by using Calluna Vulgaris (L.) Hull and Ericaceae plant species from the same family. As the organic solvent, N-methyl morpholine-N-oxide is used. Polyethylene glycol polymer structure that can form amorphous groups is preferred. Viscosity is reduced by using polyethylene glycol polymer. Moreover, the hydrogen bridge bonds among the cellulose macro molecules are reduced by using a polyethylene glycol polymer structure. Polyethylene glycol polymer is water dissoluble. The yarn obtained from regenerated fibers according to the invention can be dissolved in water by using cellulose enzymes or acidic solutions. Attraction force occurs between each solution having partial electronegative charge and hydrogen atoms found in cellulose macro molecules and having partial positive + charge. Bond polarity increases with the partial attractive forces between the hydrogen groups having partial positive + charge in the solution polymer also containing the solvent substance and the oxygen or halogen groups in the solvent substance having negative charge.

[0155] Cellulose material found in Calluna Vulgaris plant is utilized as cellulose raw material source and water-soluble polymer yarn can be obtained from this raw material by using regenerated cellulose fiber obtaining methods. Hydrophilicity and softness of the final product are improved with environment-friendly water-soluble yarns.

[0156] Water-soluble fibers cannot be obtained with traditional regenerated cellulose fiber obtaining methods. Thanks to the invention, water-soluble polymer fiber can be produced via regenerating method by using renewable cellulose source. Moreover, water-soluble regenerated cellulose fibers can be re-used as cellulose polymers via recycling process. Conventional PVA polymer known as water-soluble polymer is separated into acetaldehyde or formaldehyde molecules as a result of dissolving in acetic acid or formic acid at high temperatures, and cannot be used in recycling processes.

[0157] Cellulose pulp obtained after removing lignin, pectin etc. substances from Calluna Vulgaris plant containing 21.4% cellulose is treated with N-methylmorpholine-N-oxide solvent, and thus modified fiber is obtained. Since the degree of polymerization of cellulose polymers forming these fibers are low, they dissolve in water when they are treated with cellulose enzyme. Therefore, the fibers according to the invention can be used in place of PVA (polyvinyl alcohol).

[0158] Different from natural fibers, cellulose macro molecules forming regenerated cellulose fiber have low average polymerization (OP) degrees. OP degrees of cellulose materials or linters used as raw material in obtaining regenerated cellulose fibers are actually not that low. However, as the polymerization degrees of macro molecules increase, the viscosities of their solutions also increase in parallel. Since very high pressure is required for passing high viscosity solutions smoothly through small nozzle holes, cellulose macro molecules are partially disintegrated while preparing fiber solution. The polymerization degrees of cellulose macro molecules used for obtaining fibers is required to be above 200.

[0159] As a significant result of seeing low average polymerization degrees in cellulose macro molecules that form normal regenerated cellulose fibers, these fibers have much lower wet strength compared to dry strength (wet breaking strength is about 55-65% of dry breaking strength).

[0160] Polyethyleneglycol polymer structure is formed of hydrogen bonds between cellulose macromolecules and N-methyl morpholine within fiber spinning solution. In this way, since the strength of hydrogen bonds and Vander Waals attraction forces among cellulose macro molecules would be reduced, the wet strength of obtained fibers is lower. Therefore, they are dissolved easily in water by using cellulose enzymes in dye-treatment processes.

[0161] Since polyethyleneglycol reduces viscosity, the hydrogen bonds and Vander Waals attraction forces are reduced among cellulose macro molecules. As a result, weaker macromolecular cellulose polymer is obtained. Since the amorphous region of said fibers is 30-40% more than traditional regenerated fibers and they have lower wet strength, they can easily be dissolved in cellulose enzyme solution at 50 C.-60 C. temperature. Already short cellulose macro molecules of regenerated cellulose fibers cannot be placed uniformly within the fiber. Therefore, a big portion of these fibers (about 80-85%) is formed of amorphous regions. Non-uniform arrangement of macro molecules reduces the attractive forces among these molecules as well as reducing their wet strength, and at the same time, causes their water and aqueous flottes to impact on amorphous regions in a simpler and more effective manner.

[0162] In spinning bath, polyethyleneglycol, NMMO, and cellulose solution is oriented with wet spinning method in an extruder at 30-80 C. temperature range.

[0163] Below, a reaction scheme is given, which shows that polyethyleneglycol molecule forms hydrogen bonds between NMMO and cellulose macro molecules and thus prevents formation of hydrogen bridge bonds between the solvent (N-methyl morpholine N-oxide) and cellulose macro molecules, and allows formation of amorphous structures among cellulose macro molecules.

##STR00010##

[0164] Amorphous regions are formed among cellulose macro molecules by using 10-20% polyethylene glycol polymer. During the dyeing process of this yarn having lower wet strength, its removal by using cellulose enzyme is much easier. In this way, yarns obtained from cellulose raw material with this method become water soluble. Polyethylene glycol polymer is an easily water soluble polymer. It is an organic product compared to obtaining process steps of polyvinyl alcohol yarn. Polyvinyl alcohol yarn commonly used in textile sector is used in specific processes due to is water soluble characteristics. Yet, hydrocotton products can also be referred to as organic production, since regenerated cellulose yarn obtained with polyethylene glycol process is used instead of polyvinyl alcohol yarn, the regenerated cellulose yarn is an organic product, and the process method is suitable.

[0165] Polyethylene glycol polymer forms hydrogen bonds between cellulose macro molecules during fiber spinning. By means of these hydrogen bonds, while their dry strength reaches 7-9.5 g/denier levels, their wet breaking strength is reduced down to 3-5.5 g/denier levels. Their specific weight is around 1.35-1.45 g/cm.sup.3.

[0166] During application, the yarns obtained with the method according to the invention are not required to be treated with formic acid or acetic acid at 90-100 C. temperature during additional bath before bleachery and dyeing, as in removal processes of PVA yarns from raw materials. Application of pilling operation found in dyeing process is adequate instead of this process. In the pilling operation, cellulose enzyme is applied at 2-3 g/L, pH 5-5.5, and 50-60 C. for 30 minutes.

[0167] It is possible to use polyvinylchloride polymer structure instead of polyethylene glycol. Hydrogen bridge bonds can be formed between cellulose macro molecules by forming amorphous groups with this polymer. Moreover, wet or dry spinning processes can be developed by using polyvinylchloride/NMMO/water solvents. Accordingly, following obtaining of yarn via fiber spinning from polymers that can form hydrogen bridge bonds with cellulose macro molecules, yarns that can easily be removed in water can be obtained by using enzyme or solvents.

[0168] An attraction force occurs between each polymer having partial electronegative charge and hydrogen atoms found in cellulose macro molecules and having partial positive + charge.

[0169] NMMO/H.sub.2O/PEG are used as solvents. Regenerated cellulose fiber is obtained by forming cellulose solution, NMMO determined as amine-oxide, and the yarns obtained from these fibers are made water-soluble using cellulose enzyme.