Guar graph-interpolymerization and other polysaccharides by electron-beam machining

FIELD: organic chemistry.

SUBSTANCE: graft method of functional group to polysaccharide polymer of galactomannan type, preferentially to guar by means of high-energy electron beams radiation with non-saturated monomer occurrence containing specified functional group. Method can contain depolymerization of graft-polymer up to specified molecular weight. Prefential galactomannan processed under this method is guar gum, guar endosperm and hydroxypropylguar. According to preferential variant of method realization guar gum is also depolymerized, preferentially to molecular weight lower than approximately 700000 daltons and the most preferentially to molecular weight from approximately 100000 daltons to approximately 250000 daltons. According to the most preferable variant depolymerized guar has polydispersity lower, approximately 3.0. Graft-polysaccharide is applied in cosmetic formulations such as moisturizing stick.

EFFECT: possibility for functional groups graft to polysaccharide polymer by means of high-energy electron beams radiation.

17 cl, 1 dwg, 6 tbl, 5 ex

 

Cross-reference to related patent application this application on the invention described advantage over the prior patent application US No. 60/391320, registered on June 25, 2002, and provisional patent application US No. 60/405547 registered 23 August 2002, according to §119 of title 35 of the code of laws of the US.

The technical field to which the invention relates.

The object of the present invention is a method for the chemical modification of the polysaccharide polymers, in particular dispersible and/or water-soluble polysaccharides and galactomannans, such as guar gum, by irradiation with high-energy electron beams. This method according to the present invention is effective for vaccinations to the polysaccharides of different functional groups in order to give certain predefined properties or characteristics of the thus obtained polymers.

Background of invention

Polysaccharides, in particular, galactomannans, such as guar, have many uses. Guar in the form of a resin mainly used in food and personal care products to impart density. Resin on its strength as a thickener exceeds the starch in five to eight times. Guar gum is also used as an excipient at break of PLA is tov during oil production.

Guar gum is a natural adhesive that is present in the seeds of leguminous plant Cyamopsis tetragonolobus. The seeds consist of a pair of viscous nelomky endospermic departments, hereafter called the endosperm of the guar. The endosperm of guar contains guar gum, but it is too viscous and it is extremely difficult to grind into powder with the aim of separating the resin. After processing of natural guar gum obtained as a yellow powder, and it has a molecular mass of between approximately 2000000 Dalton and 5000000 Dalton.

In some industries, such as food production, cosmetics and shampoos, it would be desirable to use a polysaccharide, in particular galactomannans, such as guar gum, modified by grafting thereto a functional group such as a vinyl monomer or other material. It would also be desirable to polysaccharide with grafted functional groups, galactomannan or guar gum would be dispersible and/or soluble in water and have a lower molecular weight than unvaccinated polysaccharide, galactomannan or guar.

It was reported that in the presence of cerium(IV) is grafting of acrylamide to guar. Deshmukh, S.R.; Singh, R.P. J. Appl. Polym. Sci. (1987) 33, 1963. Under the influence of gamma-irradiation occurs vaccination to guar Acrylonitrile, resulting in a gain overabsorbed water. Lokhande, .T. and others, J. Appl. Polym. Sci. (1992), 45, 2031-20-36. The use of an initiator, such as cerium(IV), it is impossible to implement on an industrial level for reasons of toxicity and cost. Although the polymerization of the grafting under the influence of gamma irradiation and is one of the ways to obtain grafted guar itself irradiation require expensive containment and radioactive source.

In the patent RO 66503 it was reported that cellulose products with improved properties, especially resistance to the action of microorganisms) were obtained by grafting to fibrous cellulosic materials (e.g. cotton) monomers (for example, methyl methacrylate, vinyl chloride or vinylidenechloride) at a temperature of 10-25°using accelerated electrons with energy 500-3000 MeV at 108-109 glad, total dose 1-3 Mrad and amperage 20-25 A. Fibrous cellulosic materials were pre-treated with NaOH at a temperature of 90°C for 60 minutes.

High-energy electron beams were used for the grafting of vinyl monomers to polysaccharides, such as starch and cellulose. Olivier, A. and others, Biomacromolecules (2001), 2, 1260-1266; Ruckert, D. and others, J. Appl. Polym. Sci. (1999), 73 409-417; Yamagishi, H., and others, J. Membr. Sci. (1993), 85, 71-81; Ratzsch, M. and others, Acta Polym. Sci. (1999), 41, 620-7. There are a number of other articles that describe how the grafting of vinyl monomers to polysaccharides, mainly to the cellulite, tighten the see and starch, with the aim of obtaining plastic composite materials and/or impart specific properties of solid surfaces such as fiber or membrane. However, as far as we know, has not previously been proposed to modify dispersible and/or water-soluble polysaccharides such as galactomannan or dispersible and/or water-soluble derivatives of cellulose with vinyl monomers with the aim of obtaining new products, preferably applied in liquid compositions. Moreover, for any previously known grafted polysaccharides in the control of molecular weight during the polymerization was not registered lower molecular weight than the original polysaccharides.

Summary of the invention

The aim of the present invention is the grafting of functional groups using containing similar groups of unsaturated monomers, for example, vinyl monomers, polysaccharides, in particular the galactomannans, such as guar, to form a product having the desired properties or characteristics.

Another objective of the present invention is the depolymerization of polysaccharides derivatives to a pre-specified range of molecular weights with the purpose of increasing the applicability of the grafted polymer.

Another objective of the present invention is the I provision of a method of grafting to the polysaccharides, the galactomannans and, in particular, the guar resin, functional groups, decreasing the formation of impurities in the final product.

Another purpose of this invention is the provision of method of inoculation and depolymerization of polysaccharides, which can be entirely implemented at approximately room temperature and without the use of radioactive materials as a source depolymerizes radiation.

Another object of the present invention to provide a grafted soluble or dispersible in water polysaccharides that are useful as additives in liquid compositions, by irradiating electron beams in the presence of vinyl monomers or polymers.

Another object of the present invention to provide a depolimerizovannogo the grafted guar resin having a predetermined molecular weight and polydispersity.

These and other objectives can be achieved through used in the present invention methods, according to which the polysaccharides, in particular modified dispersible and/or water-soluble cellulose such as hydroxyethylcellulose, galactomannan, such as the guar powder resin, the endosperm of guar, cationic guar, nonionic guar, swollen in water endosperm guar powder hydroxypropylamino, xanthan gum is xanthan gum, is exposed to irradiation by high-energy electron beams in the presence of at least one unsaturated monomer containing various functional groups, with the aim of implementation, thus, grafting of functional groups to the polysaccharide. According to the present invention galactomannans, such as guar gum, modified by grafting thereto functional groups, which leads to giving a modified product of predefined properties. In addition, guar gum having a molecular weight of not less than 2000000 Dalton, depolymerized during this process to a predetermined lower molecular weight. This predefined lower molecular weight preferably does not exceed approximately 700000 daltons, preferably should be less than around 500,000 daltons, and most preferably should be less than 300,000 daltons. The method according to the present invention is also applicable to the modification and depolymerization other galactomannans and polysaccharides.

In the scope of the present invention also includes a grafted depolimerizovannogo polysaccharide, in particular grafted polysaccharides, dispersible and/or soluble in water, such as a modified cellulose, and guar gum with grafted functional groups, obtained according to the written here. These grafted and dispersible and/or water-soluble polysaccharides are intended for use, in particular in the food industry, cosmetics and other personal care products, pharmaceuticals and other industrial sectors, such as the production of flowable pesticides, liquid nutritional supplements, compositions for shampoos, detergents, ceramics and coatings.

The type and dose of high-energy electron beams used in the implementation of the present invention will vary depending on the type of polysaccharide polymer, the desired degree of chemical modification and reduction of molecular weight and desired speed of depolymerization. When vaccination and depolymerization of the guar resin dose of radiation of the electron beam, which is irradiated guar gum, will preferably vary from about 0.5 Mrad to about 20 Mrad, but higher or lower doses of radiation of the electron beam than lying in this preferred range may also be used.

The drawing is a graph showing the decrease in molecular weight of the guar powder resin, the guar resin grafted chloride methacrylamidoethylene (MARTHA), guar resin grafted vinylphosphonate (hereinafter VPA) depending the spine from exposure to increasing doses of radiation from high-energy electron beam.

Detailed description of the invention

A. Polysaccharides

The term "polysaccharide"as used in context, refers to a polymer containing a repeating sacharine fragments, including starch, Polydextrose, lignocellulose, cellulose and their derivatives (e.g. methylcellulose, ethylcellulose, carboxymethyl cellulose, hydroxyethyl cellulose, cellulose acetate, butyrate cellulose acetate, propionate, cellulose acetate, derivatives of starch and amylase, amylopectin and its derivatives, as well as other chemically and physically modified starches and the like.

B. Galactomannan

The galactomannans are polysaccharides consisting mainly of monosaccharides mannose and galactose. Mannose links form a chain consisting of many hundreds (1→4)-β-D-mannopyranosyl residues with 1→6-related α-D-galactopyranosyl residues located at different distances depending on the source plant. The galactomannans of the present invention can be obtained from many sources. Such sources include guar gum, the endosperm of guar, cationic and nonionic guar, resin carob and the resin of cesalpinia prickly, as will be further described below. In addition, the galactomannan can be also obtained using classical synthetic methods is whether by chemical modification of natural galactomannans.

1. Guar gum

Guar gum, which after grinding to a powder, often referred to as "the guar flour"is a natural adhesive that is present in the seeds of leguminous plant Cyamopsis tetragonolobus. Water-soluble fraction (85%), referred to as "guaran" consists of linear chains of (1→4)-β-D-mannopyranosyl links with attached 1→6-links α-D-galactopyranosyl links. The ratio of D-galactose to D-mannose in guarana is approximately 1:2. Guar gum may take the form of a whitish powder that is dispersible in hot or cold water. Guar gum can be purchased, for example, from Rhodia, Inc. (Cranbury, New Jersey), Hercules, Inc. (Wilmington, delawar) and TIC Gum, Inc. (Belcamp, Maryland).

2. The endosperm of guar

The seeds of the guar consist of a pair of viscous nelomky endospermic departments, hereinafter referred to as "the endosperm of guar", which concluded brittle embryo. After peeling the seeds split, germ (43-47% of the seed) are removed during sorting, and grind the endosperm. Located in the endosperm resin contained in small cells with water-insoluble wall. In these cells the resin slowly dispersed in water, and consequently it is desirable to ensure the destruction of the walls of the cells, as well as obtaining particles of small size.

As reported the W the endosperm contains about 78-82% of the polysaccharide of galactomannan and small amounts of protein substances, inorganic salts, water-insoluble resin and cell membranes, as well as residual amounts of the seed coat and embryo. They are extremely viscous and difficult to grinding.

3. Resin carob

Resin carob or resin carob (Ceratonia green) is purified endosperm of the seeds of the carob tree, ceratonia siliqua. The ratio of galactose and mannose for this type of resin is about 1:4. Growing carob for a long time and is widely known in the industry resin. This type of resin is available commercially and can be purchased from TIC Gum, Inc. (Belcamp, Maryland), and Rhodia, Inc. (Cranbury, New Jersey).

4. Resin of cesalpinia prickly

The resin of cesalpinia prickly obtained from the purified resin seeds cesalpinia prickly. The ratio of galactose and mannose is about 1:3. In the US there is no commercial production of tar cesalpinia prickly, but the resin can be obtained from various sources outside the US.

C. Modified cellulose

Modified cellulose are cellulose containing at least one functional group such as a hydroxy-group, or hydroxycarboxylic group, or hydroxyalkyl group (for example, hydroxymethylene, hydroxyethylene, hydroxypropyl or hydroxybutyl group).

He Modified galactomannan

Other interest galactomannans are modified galactomannan, including carboxymethylate, carboxyphenoxypropane, cationic hydroxypropanoic, hydroxyalkyl, including hydroxyether, hydroxypropanoyl, hydroxybutyric and higher hydroxyalkanoate, carboxylique, including carboxymethylate, carboxypropanoyl, carboxybutyl and higher carboxylique, gidroksietilirovanny, hydroxypropylamino and karboksimetilirovaniya derivatives guarana, gidroksietilirovanny and karboksimetilirovaniya derivatives carabina (resin carob), hydroxypropylamino and karboksimetilirovaniya derivative resin Cassia Tora and modified galactomannan or galactomannans resin. Preferred modified galactomannan is hydroxypropanoic with a low degree of substitution, such as below 0.6.

D. xanthan gum

Interest xanthane are xanthan gum and gel. Xanthan gum is a polysaccharide resin produced Xathomonas campestris. Xanthan gum contains as main hexonic links of D-glucose, D-mannose and D-glucuronic acid, as well as stargetframename acid and is partially acetylated.

According to the present invention the polysaccharide polymers, in particular, galactomannan, such as solid guar gum, modified cellulose and xanthan gum, mixed with unsaturated compounds containing functional groups, preferably derived from polymerized vinyl compounds, with the aim of grafting compounds containing functional groups to the polymer. The resulting mixture is subjected to irradiation by high-energy electron beams. Irradiation leads to the formation of a mixture of modified dispersible and/or water-soluble polysaccharide, in which the functional group is grafted to the polysaccharide structure, and having a predetermined lower molecular weight. The dose and the duration of the exposure depends on the specific subject material processing. The type and dose of the applied radiation may vary depending on the specific polymer of objects to be processed according to the present invention, and functionalized unsaturated compounds used for vaccination. The method according to the present invention is applicable to a wide range of polysaccharides, but in particular, it applies to dispersible and/or water-soluble polysaccharides, galactomannans and modified galactomannans. This way obanno useful when modifying and depolymerization of the guar resin and its derivatives in the form of a powder or endosperm. Preferred functional groups grafted to the polymer, are provided with vinyl monomers containing such groups, such as carboxylate, sulphonate, phosphonate and Quaternary ammonium groups.

Typical used for grafting monomers mixed with polysaccharides order to polysaccharide vaccination functional groups are as follows:

Table 1

Properties attached to products functional groups
used for grafting monomerfunctional group
methacrylic acidcarboxylate group
acrylamidoglycolate (AMPS)sulphonate group
vinylphosphonate (VPA)phosphonate group
chloride of methacrylamidoethylene (MARTHA)Quaternary ammonium group

The polysaccharide polymer is processed according to the present invention, is in the solid phase before and during treatment. The term "solid phase" includes powders, granules, flakes, particles, and other similar forms. In the initial state of the polymer and the unsaturated monomer containing a functional group mixed other the other.

Irradiation is exposed directly to the mixture of the polymer and the unsaturated monomer in the solid phase, preferably in advance of the polymer in trays on a continuous conveyor production line. According to the present invention is designed to polymerization modification with or without solid polymer is placed in a tray with such a layer thickness that provides penetration through the solid material of high-energy electron beams. The polydispersity is reduced if all the material is penetrated by the electron beam. If low polydispersity is desired, the layer of solid material is exposed to high-energy electron beam should have a fairly uniform thickness. Designed to irradiate a mixture of a polymer and unsaturated compounds containing functional groups can be placed in a suitable container and covered with a transparent for radiation of a thin plastic film for security reasons. This coating is not necessary. After that, the container is passed, for example, by conveyor through the camera exposure. The mixture is irradiated with high energy electron beams specified dose of radiation, depending on the degree of modification of the polymer, which should be retrieved.

The dose of radiation is the amount of time that is required to ensure that the dose required for grafting functional groups to the polymer and in the optimum case for the depolymerization of the polymer to a predetermined molecular weight. This power is directly related to how much time is required to achieve the specified dose and, consequently, to the amount of time during which the polymer is irradiated with ionizing radiation. Beams of high power quickly generate radiation dose. As indicated below in table 2, even electron beam of lower power (1 kW) ensure a given dose of irradiation target 40 times faster than gamma irradiation of equivalent power. Using Vysokoe reticency electron beams allows to achieve much better performance by getting vaccinated depolimerizovannogo of galactomannan.

Table 2

Comparison of radiation doses for technology of gamma irradiation and electron beam technology
Gamma irradiationThe electron beam irradiation
The target doseKgKg
Dose (depending on technology)10 kGy/h400 kGy/h
The time required to achieve the specified dose2 h (120 min)of 0.05 hours (3 minutes)

Irradiation of polymer high voltage electron beams is preferably carried out at room temperature.

As mentioned above, the degree of depolymerization, deriving from the application of the method according to the present invention, influence of the molecular weight of the original polymer, subjected to processing, and pre-specified molecular weight depolimerizovannogo product. Guar gum has a molecular mass of more than 2000000 daltons, typically between 2000000 Dalton and 5000000 daltons. In the usual embodiment of the present invention, the polymer will depolymerized to a predetermined molecular weight, preferably below approximately 700000 daltons, more preferably up to molecular weight below when listello of 500,000 daltons, and even more preferably to molecular weight below approximately 300,000 daltons.

In the present invention, the irradiation of high-energy electrons used for inoculation of various vinyl monomers containing functional groups, polysaccharides, in particular guar and its derivatives, with their depolymerization or without it. In the exercise of this original polysaccharides disclosed various properties, such as hydrophilicity/hydrophobicity, ability to dispersion and/or solubility in water and/or cationic properties (due to the Quaternary ammonium groups) or anionic properties (thanks carboxylate, sulphonate and phosphonate groups). Thus, single-stage irradiation process not only leads to depolymerization of the polysaccharide, but also to give the polymer of various properties or characteristics for suitability for use in specific applications.

As an example, the powder of guar inflicted chloride methacrylamidoethylene (known as MARTHA) or vinylphosphonate (VPA) in a mass ratio of 10:1 by suspension of the polymer in the solution of the corresponding monomer in a suitable solvent, followed by evaporation of the solvent under vacuum. The monomer can also be applied on guar more economical method, such as spraying it in liquid form or in nerissa the certain condition, or in diluted condition in the corresponding media. The molecular weight of irradiated products was measured using gel permeation chromatography. The mass-average molecular weight shown in the drawing.

When irradiated test specimens Guara coated with the monomer was observed a slightly higher degree of depolymerization at the same dose, compared to samples without monomer, indicating that the implementation of the graft-copolymerization. It was also noted that the grafted products contain less water-insoluble material. These NMR spectroscopy showed that the selected guar were inoculated either MARTHA or vinylphosphonate.

When carrying out the present invention the preferred 1-10 MeV generator high-energy electron beam as the generated beams penetrate deeper into the material, thereby making it possible to irradiate thicker layers of material. Can be used and energy above 10 MeV, but this is not preferred, because it can cause radioactive heavy elements. High-voltage electron beam generator can be purchased from Electron Solutions Inc. and Science Research Laboratory, Somerville, Massachusetts, Ion Beam Applications, Louvan-La-Neuve, Belgium, and The Titan Corporation, San Diego, California.

Low-voltage electron beam generator (150 Kev - 1 MeV can also be used. The material is irradiated in the form of a layer by passing through the generator; the exposure can be optionally carried out after the mechanical grinding of the material to powder. Such a generator is usually cheaper and does not require concrete screen. Low-voltage electron beam generator can be purchased from Energy Sciences, Inc., Wilmington, Massachusetts, (model EZCure), Radiation Dynamics Inc., Edgewood, new York, (model Easy E-beam) and Electron Solutions Inc., Somerville, Massachusetts (model EB-APR). Traditionally this equipment is used mainly for heat treatment of surfaces by radiation.

For vaccinations/depolymerization of guar can be used electron beams with low energy (1,3 MeV) and high power (>100 kW). Power of 100 kW is able to provide vaccination/depolymerization 2400 kg/h at a dose of 15 Mrad or 12000 kg/h at a dose of 3 Mrad.

The method according to the present invention can be applied to vaccinations/depolymerization other polygalacturonases (for example, resin carob) or α-related polyglucose, such as amylose and amylopectin.

As mentioned above, depolimerizovannogo galactomannan used in the food industry, the production of cosmetics and pharmaceuticals and other industrial sectors, such as the production of flowable pesticides, liquid pittel the different additives, compositions for shampoos, detergents, ceramics and coatings.

The following examples of the invention are given for illustrative purposes only. They in no way be considered as limiting the present invention.

Example 1

The following is an example of a graft-copolymerization Guara.

Powder guar suspended in acetone and then mixed with a solution or vinylphosphonate (VPA), or chloride of methacrylamidoethylene (MARTHA) at a ratio of guar to the corresponding monomer 10:1. After that, the mixture was dried under vacuum and placed in a plastic vessel in amounts not exceeding the penetration depth of the electron beam. Then the samples were placed on a tray, passed through the camera exposure on a closed pipeline. The samples were irradiated by electron beam, obtained with the help of 4.5 MeV generator operating at a beam current of 15 milliamps, and aimed at the upper surface of the tray. The required radiation dose is provided by matching the linear speed of the conveyor.

After irradiation, the molecular weight of the sample was analyzed using gel permeation chromatography (column: Supeico Progel-TSK G3000PWXLandG6000PWXLseries-connected; mobile phase: 55 mm Na2SO4, of 0.02% NaN3; volumetric flow rate: 0.6 ml/min; detector: detector the refractive index of a Waters 410; injection volume: 200 μl; temperature: 40°). The samples were dissolved in mobile phase before reaching the mass fraction of a substance in a solution of 0.025%. A calibration curve was built using stachyose and two samples of the guar resin with a molecular mass 667, 58000 and 2000000 Dalton.

Molecular mass distribution is presented below in table 3. The molecular mass of the original sample was approximately from 2000000 to 3000000 daltons. After irradiation, the molecular weight was decreased in an exponential dependence on the radiation dose. The polydispersity of the grafted polymers guar/MARTHA varied from 2.91 in up to 3.45. Molecular weight at a given dose can be predicted with the help of the drawing. For powder coated with guar or MARTHA, or VPA, was marked by a declining rate of depolymerization.

Grafted guar was isolated by washing the corresponding homopolymer methanol. Inoculation VPA or MARTHA to the guar was confirmed by NMR spectroscopy on nuclei31R or TMR, respectively.

The decrease in molecular weight with increasing dose clearly shown by the example of three different types of samples (figure 1). The degree of depolymerization increased with increasing irradiation doses. The degree of depolymerization was similar for all materials, and no significant changes since the shka the guar resin, the endosperm of guar or powder hydroxypropranolol resin was not observed. You can find a correlation between the degree of depolymerization or molecular mass with irradiation doses (drawing) and, thus, it is possible to easily predict the decrease of molecular weight for a given dose on the condition that famous original molecular weight before irradiation.

td align="left"> Powder guar/VPA 10/1, 15 Mrad
Table 3

Molecular mass distribution of irradiated guar
SampleThe molecular weight at the maximum of the distribution (Mρ)The mass-average molecular mass (Mw)Brednikova molecular mass (Mn)The polydispersity (Mw/Mn)
Powder guar 0 rad2960000286000012000002,37
Powder guar 1 Mrad4740005710001610003,54
Powder guar 3 Mrad196000249000789003,16
Powder guar 5 Mrad110000132000418003,16
Powder guar 10 Mrad5990068100217003,13
Powder coated examination bed with the guar 15 Mrad3890046400149003,11
Powder guar/MARTHA 10/1, 1 Mrad3290004140001380003,00
Powder guar/MARTHA 10/1,3 Mradof 145,000177000555003,19
Powder guar/MARTHA 10/1, 5 Mrad111000128000410003,13
Powder guar/MARTHA 10/1, 10 Mrad6910072100209003,45
Powder guar/MARTHA 10/1, 15 Mrad4030048200166002,91
Powder guar/VPA 10/1, 1 Mrad587000663,000 forof 118,0005,61
Powder guar/VPA 10/1, 3 Mrad223000 a294000590004,99
Powder guar/VPA 10/1, 5 Mrad137000175000388004,50
Powder guar/VPA 10/1, 10 Mrad9060096600211004,57
4640058700162003,63

Example 2

50 parts of hydroxypropylamino obtained from the company Rhodia, Inc. from Cranbury, new Jersey under the trademark Jaguar 8000, mixed with 15 parts of chloride of methacrylamidoethylene (MARTHA, 50% aqueous solution) and 15 parts of methanol. The wet mixture was then dried under vacuum at a temperature of 30-40°C. thereafter, the dried powder was placed in a plastic bag with a layer thickness of below 3 see irradiation with a dose of 3.8 mrad was carried out as described in example 1. The residual amount of unreacted MARTHA was, according to analysis by HPLC, 0,39% of the sample (which corresponds to the degree of conversion of 97%). Then, the irradiated sample was vaporized together with 5 grams of 10% solution of sodium metabisulfite in a mixture of water and methanol in the ratio of 1:1, and then processed in a vacuum furnace at a temperature of 65-70°C for two hours. According again to the analysis, the residual monomer content amounted to 440 parts per million.

Since, as has been established, a homopolymer MARTHA soluble in methanol, guar inoculated with MARTHA was isolated by precipitation from aqueous solution under the action of methanol. To do this, 0.50 parts described above Guara treated metabisulfite, dissolved in 5,15 castaway. Grafted guar besieged by adding a solution of methanol and dried. The PMR spectra showed that on a dedicated hydroxypropanoate was approximately 9% MARTHA that corresponds to the degree of grafting more than 69%.

Example 3

In this example, the technique was applied, similar applied in example 2. As grafted monomer instead of MARTHA used vinylphosphonate (VPA). About 2.3% of VPA was attached to the selected hydroxypropylamino that corresponds to the degree of grafting of over 20%.

Example 4

Hydroxymethylcellulose, obtained from Dow under the trademark Cellosize CARRIED QP 100M-H, sprayed together with a 50% solution MARTHA at the ratios of active ingredients shown in table 4, and then thoroughly mixed. After that swollen Martha pulp dried on air and grind into powder for the convenience of subsequent work. Irradiation and subsequent processing was carried out according to the procedure described in example 2, the dose indicated in table 4. The residual content of MARTHA was measured using HPLC after irradiation (table 4) and after further processing (table 5). The molecular weight was determined for selected samples (table 6). Analysis by gel permeation chromatography showed the presence of small amounts or none at homopolymer MARTHA. The grafted polymer clay is allocated from a solution in water and methanol by means of precipitation with acetone. Colloidal titration of the selected polymer showed that more than 85% MARTHA was attached to the hydroxyethyl cellulose (NES).

Table 4

The percentage of MARTHA after irradiation
Dose (Mrad)0,51351020
BORE/MARTHA:

85/15
2,180,761,66to 0.0600,0440,042
70/301,960,71was 0.1380,100,0670,13
50/502,231,580,190,210,140,11

0,0027

n/a

n/a
Table 5

The percentage of MARTHA after subsequent processing
Dose (Mrad)0,51351020
BORE/MARTHA:85/15

70/30

50/50
0,13

0.021

0,0113
0,033

n/a*< / br>
n/a
0,012

n/a

n/a
n/a

n/a

n/a
n/a

n/a

n/a
*n/a - not found

Table 6

The molecular mass (Mw). determined for selected samples by the method of gel permeation chromatography
Irradiation dose(Mrad)0,510
BORE/MARTHA:

85/15
552000119000
70/30488000101000
50/50310000103000

Compositions containing grafted polysaccharide can be used as cosmetic compositions, such as lipstick, pencils, blush, etc.

The following are specific composition moisturizing pencil containing grafted polysaccharide of example 4, containing thickening resin - 2 wt.%, the polysaccharide of example 4 - 1 wt.%, sodium chloride, 1 wt.%, ethanol - 1 wt.%, polyurethane (SER-AD FX 1100) - 0.5 wt.%, water up to 100 wt.%.

While some embodiments of the present invention described and/or illustrated by the examples above, from the above disclosure of the invention the experts in this field should be obvious and various other options for its implementation. Thus, the crust is ASEE the invention is not limited to the described and/or illustrated by examples variants of implementation of the present invention, but it also implies the possibility of significant changes and modifications without departure from the scope of the claims.

1. The method of grafting an unsaturated monomer containing a functional group to the polysaccharide soluble or dispersible in water comprising the following stages:

a) preparation of a mixture consisting of an unsaturated monomer containing a functional group and a water-soluble or dispersible in water polysaccharide;

b) irradiating the mixture with radiation dose of high-energy electron beam sufficient to form a grafted copolymer of an unsaturated monomer containing functional groups, and water soluble or dispersible polysaccharide in water, depolimerizovannogo relatively unvaccinated polysaccharide.

2. The method according to claim 1, where the unsaturated monomer is a vinyl monomer containing a functional group.

3. The method according to claim 1, where the polysaccharide is selected from the group comprising guar, cationic guar, nonionic guar, resin carob, the resin of cesalpinia prickly, amylose, amylopectin, xanthan gum and xanthan resin.

4. The method according to claim 2, where the polysaccharide is guar.

5. The method according to claim 2, where the polysaccharide is a modified cellulose.

6. The method according to claim 2, where the functional group is carboxylate is, phosphonate or sulphonate group.

7. The method according to claim 2, where the vinyl monomer is a chloride of methacrylamidoethylene.

8. The method according to claim 2, where the functional group is a Quaternary ammonium group.

9. The polysaccharide grafted unsaturated monomer containing a functional group which is capable of dispersing in water, obtained by the method according to claim 1.

10. Grafted polysaccharide according to claim 9, where the polysaccharide is selected from the group comprising modified cellulose, galactomannan and xanthan gum.

11. Grafted polysaccharide of claim 10, where the polysaccharide is a modified cellulose.

12. Grafted polysaccharide according to claim 9, where the unsaturated monomer is a vinyl monomer.

13. Grafted polysaccharide indicated in paragraph 12, where the vinyl monomer is selected from the group comprising vinyl monomer containing a carboxylate group, a vinyl monomer containing a sulphonate group, a vinyl monomer containing a phosphonate group, and a vinyl monomer containing a Quaternary ammonium group.

14. Grafted polysaccharide according to item 13, where the vinyl monomer containing Quaternary ammonium functional group.

15. Grafted polysaccharide according to claim 9, where the polysaccharide is selected from the group comprising guar, cationic guar, nonionic guar, resin carob, the resin of cesalpinia prickly, can the new resin and amylose.

16. Grafted polysaccharide according to claim 9, where the polysaccharide is selected from the group comprising guar and hydroxypropanoic.

17. Cosmetic composition comprising a grafted polysaccharide according to claim 9.

Priority items:

25.06.2002 - claims 1 to 6;

25.06.2003 - 17.



 

Same patents:

FIELD: polymers, chemical technology.

SUBSTANCE: invention describes a method for synthesis of grafted copolymers of chitin and chitosan with synthetic polymers. Method involves chemical interaction of chitin or chitosan with a synthetic polymer chosen from the group comprising polyacrylamide, polylactic acid, polyvinyl acetate, polyvinyl alcohol, maleic anhydride-modified polyethylene or polypropylene or with a monomer - acrylamide or lactide (cyclic dimer of lactic acid). The reaction is carried in solid aggregate state of reagents by the reaction extrusion at temperature below melting point of synthetic reagent. Method provides excluding the used of catalysts or solvents.

EFFECT: improved method of synthesis.

18 cl, 10 ex

The invention relates to a polymer dispersion based on starch, which contains a copolymer of starch and monomer

The invention relates to fototermin derived fractions, each of which receive chemical binding photoreactive connection with glycosaminoglycans /hereinafter sometimes referred to for brevity as a "GAG"/ and stitched glycosaminoglycans having a three-dimensional netted structure which is obtained by exposing the above derived expression for the dimerization photoreactive compounds, to processes for their preparation, and, further, to a satisfactory biocompatible materials for medical use, which contain them

The invention relates to water-soluble, acid containing groups of the grafted copolymers with biological destruction based on sugars and monomethylethanolamine carboxylic acids, sulphonic acids and/or phosphonic acids or salts of these acids, and, if necessary, other monomers, and also to a method for producing these copolymers at temperatures up to 200oC using radical polymerization initiators

Antimutagen // 2101915
The invention relates to the field of genetics of agricultural plants, in particular to substances that have anti-mutagenic activity under the action of gamma radiation

FIELD: chemistry.

SUBSTANCE: method for depolymerisation of polysaccharides of galactomannan, as well as xanthan, type, preferably galactomannans, to specified molecular weight by high-energy electron beam treatment. Preferential galactomannans for the said type of treatment are guar gum, guar endosperm and hydroxypropylguar. According to preferential version of the method, guar gum is depolymerised, preferably, to molecular weight of ca. 100000 daltons to ca. 200000 daltons.

EFFECT: depolymerised guar has lower polydispersity and can be used for oil well fracturing in order to gain in oil yield.

16 cl, 15 tbl, 6 dwg

FIELD: food industry; oat enzymatic treatment.

SUBSTANCE: using this method it is possible to obtain new improved oat products containing modified starch, the products have increased glucose and β-glucan content. The present invention is also related to the food products and food compositions, including oat with modified starch or oat liquid containing modified starch.

EFFECT: use of enzymes at their optimal temperatures; efficiency and effectiveness.

24 cl, 1 dwg, 1 tbl, 3 ex

FIELD: biotechnology, microbiological industry.

SUBSTANCE: invention relates to a novel culture of microorganism producing high-molecular exopolysaccharide. Invention proposes the strain of microorganism Paracoccus denitrificans VKPM B-8617 that produces exopolysaccharide possessing cross-linking properties in aqueous and water-containing hydrocarbon systems. Exopolysaccharide is formed by residues of glucose, galactose, mannose and rhamnose in the ratio = 52:4:1, respectively, and comprises glucuronic and pyruvic acids, and acyl groups also and has molecular mass (0.5 x 106)-(2 x 107) Da. This exopolysaccharide is able to form pseudoplastic and thixotropic highly viscous solutions showing stable values of dynamic viscosity in the range of temperature from 20°C to 90°C and unstratifying emulsions. Proposed exopolysaccharide can be used in building, paper, textile, perfume-cosmetic, food, chemical, oil- and gas-extracting industry, agriculture, and in pharmaceutics and medicine.

EFFECT: valuable properties of strain and exopolysaccharide.

2 cl, 9 ex

FIELD: technology of natural substances.

SUBSTANCE: invention relates to a method for isolating pectin from vegetable raw used for production of products of prophylactic and curative designation. Invention describes a method for preparing pectin. Method involves treatment of preliminary milled vegetable raw, for example, dried sunflower heads with a mixture of chloroform and ethanol followed by extraction in water bath at 70-80°C for 30-40 min, filtration and separation of the first extract. Filtered off vegetable raw is poured with distilled water at temperature 60-70°C and extracted in water bath at temperature 90-95°C for 1 h followed by filtration and separation of the second extract. Filtered off vegetable raw is poured with 0.3-0.5% ammonium oxalate solution, extracted in water bath at temperature 75-80°C for 30-40 min, filtered and the third extract is separated. Filtered off vegetable raw is poured with a 0.4-0.5% hydrochloric acid solution, heated at temperature 75-80°C for 1 h followed by filtration and separation of the fourth extract that is mixed with prepared first, second and third extracts. Prepared solution is neutralized with ammonium hydroxide to pH 7 and precipitated with 96% ethyl alcohol, precipitate is squeezed our and dried at temperature 4-6°C. Proposed method provides increasing yield of pectin and its solubility.

EFFECT: improved preparing method.

2 cl, 1 ex

FIELD: chemical technology.

SUBSTANCE: invention relates to the inclusion complex of cyclodextrins with elemental sulfur. Complex can be prepared using different homologues of cyclodextrins, for example, beta- and gamma-cyclodextrins and hydroxypropylated forms of gamma- and beta-cyclodextrins. Proposed complex can be used as a biologically active compound for medicinal, veterinary and agricultural designation. Invention provides the possibility for further preparing true solutions of elemental sulfur in water in the concentration up to 250-300 mg/l.

EFFECT: improved preparing method, valuable properties of complex.

7 cl, 7 ex

FIELD: medicine, polymeric materials, pharmacy.

SUBSTANCE: invention describes biomaterial as a deposit comprising at least one suitable anion-active polymeric water-soluble component and amphiphilic component of ammonium type comprising a cationic surfactant. Deposit is prepared in the following steps: (1) contacting anion-active polymeric component and cyclodextrin component in aqueous medium, and (2) addition of the above said amphiphilic component of ammonium type to mixture prepared in the step (1) wherein components are taken in amounts providing formation of above said deposit. Biomaterial is used for preparing a depot-composition with regulated release and acceptable for prolonged feeding pharmaceutical substances. Also, invention describes a medicinal agent comprising biomaterial and representing a sheet material or film for closing and healing wounds, or surgery thread, and medicinal implant, or insert comprising the preliminary molded biomaterial.

EFFECT: improved preparing method, valuable properties of material.

27 cl, 34 ex

FIELD: chemistry of polymers.

SUBSTANCE: invention describes a composition for using as a conditioner and comprising water and at least one cationic polygalactomannan or derivative of cationic polygalactomannan. A lower limit of average molecular mass of these cationic substances is 5000 Da and the upper limit is 200000 Da, transparency value of 10% aqueous solution is above 80% at wavelength 600 nm. The protein content is less 1.0% as measured for polysaccharide mass and the content of aldehyde groups is at least 0.01 ml-eqiv./g. Residue for modification of cationic derivative of polygalactomannan is chosen from group comprising alkyl, hydroxyalkyl, alkylhydroxyalkyl and carboxymethyl wherein alkyl comprises in chain from 1 to 22 carbon atoms, Hydroxyalkyl is chosen from group comprising hydroxyethyl, hydroxypropyl and hydroxybutyl, and cation residue is chosen from compounds of quaternary ammonium but with exception of hydroxypropyl trimethyl ammonium chloride. Proposed compositions are used for preparing a clear final product, for example, for personal hygiene agent and household chemistry agent.

EFFECT: improved preparing method, improved and valuable properties of composition.

55 cl, 11 tbl, 14 ex

FIELD: chemical-pharmaceutical industry.

SUBSTANCE: invention relates to a method for synthesis of arabinogalactan-base sulfated biopolymers wherein arabinogalactan is the main polysaccharide from Siberian larch. Invention describes a method for preparing sulfated derivatives of arabinogalactan that involves interaction of arabinogalactant in dimethylsulfoxide medium in the ratio 1:3 with a sulfating agent representing complex SO3 - dimethylformamide in the concentration of SO3 ≥18%. The process is carried out at continuous stirring, at temperature 20°C for 30 min followed by isolation of product both in acid and saline forms. The substitution degree of biopolymer macromolecule is 8.1-12.65% as measured for the quantitative content of sulfur. Synthesized sulfated derivatives of arabinogalactan retain the structural organization, water-solubility and membranotropicity of natural polysaccharide, and elicit high physiological (anticoagulating and hypolipidemic) activity also.

EFFECT: improved method of synthesis.

2 cl, 3 dwg, 3 ex

FIELD: fish processing industry.

SUBSTANCE: invention relates to method for production of chitin from raw materials belonging to class Crustacea. Claimed method includes maxillopod grinding, enzymatic hydrolysis of proteins, hydrolyzate separation followed by drying, demineralization deproteinization. Enzymatic hydrolysis is carried out by using own maxillopod enzymes. Autoenzymolisis is carried out in aqueous medium with addition of bioconserving agents in raw/bioconserving agent solution of 1:(3-4) for 21 h at 35°C. As bioconserving agent milky whey or aloe juice is used. After protein hydrolyzate separation chitin semi-product is demineralized.

EFFECT: decreased product cost, product of improved quality, environmentally friendly method.

3 cl, 7 ex, 2 tbl

FIELD: medicine, pharmacology.

SUBSTANCE: invention relates to method for production of modified Dermathane sulfate (DS) by interaction thereof with animo-containing compounds in aqueous medium at pH 4.7-4.8 in presence of condensing agent such as 1-ethyl-3[3-(dimethylamino)propyl]carbodiimide (EDC). As animo-containing compounds substances of general formula RNH2 are used, wherein R is C6H4OH (p- or o-aminophenol residues), C6H4COOH (p-aminobenzoic or anthranilic acid residues), C6H3(OH)COOH (4- or 5-aminosalicilic acid residues), etc., such as defined in specification, in molar component ratio of DS:RNH2:EDC = 1:1:(0.75-1.50) followed by purification from low molecular components.

EFFECT: dermathane sulfate derivatives useful in medicine and pharmacology.

1 tbl, 2 ex

FIELD: organic chemistry.

SUBSTANCE: graft method of functional group to polysaccharide polymer of galactomannan type, preferentially to guar by means of high-energy electron beams radiation with non-saturated monomer occurrence containing specified functional group. Method can contain depolymerization of graft-polymer up to specified molecular weight. Prefential galactomannan processed under this method is guar gum, guar endosperm and hydroxypropylguar. According to preferential variant of method realization guar gum is also depolymerized, preferentially to molecular weight lower than approximately 700000 daltons and the most preferentially to molecular weight from approximately 100000 daltons to approximately 250000 daltons. According to the most preferable variant depolymerized guar has polydispersity lower, approximately 3.0. Graft-polysaccharide is applied in cosmetic formulations such as moisturizing stick.

EFFECT: possibility for functional groups graft to polysaccharide polymer by means of high-energy electron beams radiation.

17 cl, 1 dwg, 6 tbl, 5 ex

FIELD: technological processes.

SUBSTANCE: invention relates to single-phase production free flowing hydrophobic starches, which includes treatment of starch with siliconate and acid in a single-phase process.

EFFECT: disclosed is a method for single-phase production of free flowing hydrophobic starches.

11 cl, 1 dwg, 1 tbl

FIELD: organic chemistry.

SUBSTANCE: graft method of functional group to polysaccharide polymer of galactomannan type, preferentially to guar by means of high-energy electron beams radiation with non-saturated monomer occurrence containing specified functional group. Method can contain depolymerization of graft-polymer up to specified molecular weight. Prefential galactomannan processed under this method is guar gum, guar endosperm and hydroxypropylguar. According to preferential variant of method realization guar gum is also depolymerized, preferentially to molecular weight lower than approximately 700000 daltons and the most preferentially to molecular weight from approximately 100000 daltons to approximately 250000 daltons. According to the most preferable variant depolymerized guar has polydispersity lower, approximately 3.0. Graft-polysaccharide is applied in cosmetic formulations such as moisturizing stick.

EFFECT: possibility for functional groups graft to polysaccharide polymer by means of high-energy electron beams radiation.

17 cl, 1 dwg, 6 tbl, 5 ex

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention relates to chemistry and deals with a pharmaceutical substance based on hydroxiethylated starch, its production method and a pharmaceutical composition for production of a medication with volemic action. The invention may find application in chemistry and medicine. The pharmaceutical substance represents a water-soluble powder of amylopectin hydroxiethylated starch with ratio of substituted hydroxiethylated C2/C6 atom groups is equal to 2 - 20, average molecular weight (Mw) remaining within the range of 100-450 kDa and the substitution degree amounting to 0.25-0.75. For production of the pharmaceutical substance of hydroxiethylated starch one uses starch with amylopectin content equal to 60-98% that is hydrolysed in suspension with an acid until an inherent viscosity value [η]=0.10-0.2. The hydrolysed starch is dissolved in water at T=70-105°C, hydroxiethylated in an inert gas atmosphere an alkylating agent and a catalyst until substitution degree is 0,25-0.75. The reaction mixture is neutralised; the produced solution is cleared of low-molecular fractions of hydroxiethylated starch and impurities by ultrafiltration method, filtered in a sterile way and dried. Additionally, the invention deals with a pharmaceutical composition for production of a medication with volemic action using the above method.

EFFECT: development of a pharmaceutical substance volemic action as well as optimisation of the pharmaceutical substance production method enabling regulation of substitution degree within the interval required, obtaining a favourable ratio of substituted hydroxiethyl groups.

21 cl, 5 ex

FIELD: technological processes.

SUBSTANCE: invention relates to single-phase production free flowing hydrophobic starches, which includes treatment of starch with siliconate and acid in a single-phase process.

EFFECT: disclosed is a method for single-phase production of free flowing hydrophobic starches.

11 cl, 1 dwg, 1 tbl

FIELD: immunotherapeutic agents.

SUBSTANCE: antigenic preparations are obtained from keratinophilic fungi Trichophiton or Microsporum species or yeast species Candida by alkali hydrolysis techniques. Thus obtained preparations can be, in particular used, as vaccines and for treating allergy and modulating immune response.

EFFECT: expanded immunotherapeutic possibilities.

17 cl, 5 dwg, 12 tbl, 20 ex

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