Black pigment dispersion

FIELD: chemistry.

SUBSTANCE: invention refers to pigment dispersion that can find application in electrophoretic displays. The dispersion contains α) a bis-(oxodihydroindolilene)benzodifuranone colouring agent of formula I wherein R1-R10 have values specified in cl.1, β) a special polymer dispersing agent containing modified poly(meth)acrylates, and γ) a solvent applicable for dispersions used in the electrophoretic displays. There are also described new colouring agents of bis-(oxodihydroindolilene)benzodifuranone compounds, dispersing agents and the electrophoretic display comprising these agents.

EFFECT: presented colouring agents have low conductivity and using them as black pigments in the electrophoretic displays enables reducing energy consumption as compared to using state-of-art carbon black.

11 cl, 1 dwg, 1 tbl, 11 ex

 

The invention relates to the dispersion of the pigment, in particular the dispersion of black pigment comprising bis-(oxodegradable)benzopyranones the dye, special dispersing agent and an appropriate solvent to the above dispersion, coloring agents and/or dispersing funds in electrophoretic displays, as well as to new bis-(oxodegradable)benzopyranones coloring agents and dispersing agents.

In the application for U.S. patent No. 7002728 B2 presents that the electrophoretic medium, which is at present preferred, includes white particles of titanium oxide and gaseous carbon black, dispersed in a liquid hydrocarbon medium, such hydrocarbon used in its pure form or mixed with chlorinated hydrocarbons or other liquids with low dielectric constant. In the previously used electrophoretic displays, which require a black pigment, for this purpose is also served predominantly gas carbon black; such extensive use of it can be explained by the fact that this material is very cheap and easily obtained in large quantities. However, many shortcomings of the existing electrophoretic display associated with the use of gas of carbon black as a black electrophoretic particles. Him what I surface gas soot has a complex and poorly understood nature, it can be very different depending on the specifics of the source material (usually kerosene) and the specific manner in which the gas carbon black was obtained. The pigment particles of the gas soot are also poorly studied fractal aggregate structure. In addition, it is well known that the gas carbon is an effective adsorbent for gases and liquids with which it comes in contact, and these adsorbed gases and liquids can modify the physico-chemical surface properties of the gas soot. In accordance with this provision permanent surface properties of the gas soot in different batches of products is a complex task. This is especially important for electrophoretic displays, as used in electrophoretic particles usually have such a small size (about 1 micron) that their properties are determined by the properties of their surface.

Furthermore, in U.S. patent No. 7002758 shown that in the case of gas soot there are specific difficulties in obtaining particles of their own charge opposite to the other pair of particles in an electrophoretic display. In particular, it was shown that when using gas carbon black and titanium dioxide as black, and, accordingly, the white particles in an electrophoretic display with a pair of particles with opposite charges, the combination of a carrying charge of reagents and other materials which provide education for all positively charged gas particles of soot, leads to the appearance of small amounts of particles of titanium dioxide, which also have a positive charge. The resulting mixture of negatively and positively charged particles of titanium dioxide leads to a weakening of the maximum optical state of the optical medium, which in turn causes a reduction in contrast.

It is also known that gas soot has an electric conductivity of not only compact, but also in the form of a dispersion in polymers that provides them with antistatic properties (S. P. Rwei, etc.. Colloid. Polym. Sci. 2002, 280, pages 1110-1115), the same applies to the dispersion in mineral oil (J. Electroanul. Chem. 2005, 577, 67-78). This means that the electric field through the variance will be held electric current, and as a result will decrease the electric field, together with the orientation of the particles (in the case when the field was imposed once and was not supported by certain of its voltage), or as a result of this will be necessary in the expenditure of electrical energy to compensate for this effect.

Accordingly there is a need for black particles for use in electrophoretic environment that is devoid of the problems associated with the use of gas soot, for example, Tr is the required dispersion of iron particles, which has a low electrical conductivity or otherwise, which is characterized by high resistance. However, the search for such black particles is very difficult. Optical properties of many pigments known, of course, for their use in formulations of paints and similar production aspects, however, the pigment is designed for use in electrophoretic displays, must have certain properties in addition to the appropriate optical properties. This pigment must be compatible with many other components of the electrophoretic medium, including liquid medium to form a suspension, with all other present in the environment particles of pigments, with active substances intended to control charges, with the present is usually designed to form a suspension liquid of surface-active substances and the material of the capsule wall (if the wall of the capsule is present). The pigment particles should also maintain the charge in a suspended state in intended for formation of a charge of liquid, and electrokinetic potential of the particles, the formation of which is caused by these charges must be in all cases the same polarity and should not vary too widely, while electrophoretic medium can the t to acquire unwanted electro-optical properties, for example, when some particles are too low electrokinetic potential, it may be necessary for a very long action of the driving pulse in order to put such particles to the desired position in the electrophoretic medium, and this leads to increase in response time environment. It is clear that such information is related to the ability of the pigment particles to receive and store the charges could not be obtained for all pigments, which potentially can be used in electrophoretic displays, such as electrical properties irrelevant to ordinary commercial application of pigments.

The same arguments are also valid in cases where the partner of the black pigment is not white, but colored particle, and then for such displays require yellow-black, red-black, green-black and blue-black of a system of particles with the same characteristics as the above black-and-white system.

It has been unexpectedly found that a composition comprising certain specific dispersing funds and certain bis-(oxidiser-indoline)benzopyranones colorants, may be used to replace gas soot in electrophoretic displays, it called colorants described in General terms in WO 00/2473 A1 and along with them, can also be used specifically shown in example 126 of this application "purple powder". In accordance with this, in the presence of suitable additives (dispersing funds) can be obtained dispersion pure organic black pigment in an environment with low conductivity and low dielectric constant, such pigments show electrophoretic mobility under the influence of electromagnetic fields, and therefore they can be used as black pigments in electrophoretic displays, however they also have a low conductivity and accordingly to reduce the consumption of energy, as required for such a case.

Description picture

In Fig.1 shows the geometry of the three-electrode individual wells of 96-hole plate (more detailed information is presented in example 11). Large spots represent the point of contact for the electrodes. The resistance measured between the semicircular electrodes and the Central electrode for grounding.

The invention relates to the dispersion, which can be used for electrophoretic displays, in particular to a dispersion in which the dispersed particles have a diameter of from 100 to 1000 nm (nanometers), in the preferred case from 200 to 800 nm, in the most preferred case ot to 600 nm, including

α) bis-(oxodegradable)benzopyranones the dye of the formula I

,

where

R1and R6in each case, independently of one another mean a hydrogen atom, metal, triptorelin group, fluorine atoms or chlorine, in the preferred case, the hydrogen atoms or fluorine, in the most preferred case, the hydrogen atoms;

R2, R3, R4, R5, R7, R8, R9and R10in each case, independently of one another mean a hydrogen atom, halogen atoms, groups of R11, COOH, COOR11(S-, CONH2, CONHR11, CONR11R12, cyano, hydroxyl group, group, OR11, OOCR11, OOCNH2, OOCNHR11, OOCNR11R12the nitro-group, amino group, group with other11, NR11R12, NHCOR12, NR11COR12N=CH2N=CHR11N=R11R12, sulfhydryl group, group SR11, SOR11, SO2R, SO2R11, SO3H,SO3-, SO2NH2, SO2Other11or a group of SO2NR11R12; R2and R3, R3and R4, R4and R5, R7and R8, R8and R9and/or R9and R0 can also be connected together by a direct bond or a bridge of atoms of oxygen, sulfur or a group NH or NR11;

R11and R12in each case, independently of one another denote an alkyl group with the number of carbon atoms ranging from one to twelve, cycloalkyl group with the number of carbon atoms from three to twelve, alkenylphenol group with the number of carbon atoms from two to twelve, or cycloalkenyl group with the number of carbon atoms from three to twelve or alkylamino group with the number of carbon atoms from two to twelve, with each of these groups can be a continuous chain or the chain may be interrupted by oxygen atoms, NH groups, NR13and/or sulfur atoms of two or more fragments, each of which includes at least two carbon atoms and each of which may be unsubstituted or substituted by one or more groups COOH, COOR13, COO-, CONH2, CONHR13, CONR13R14, cyano groups, exography, hydroxyl groups, groups, OR13, OOCR13, OOCNH2, OOCNHR13, OOCNR13R14, NR13, amino groups, groups with other13, NR13R14, NHCOR14, NR13COR14N=CH2N=CHR13N=CR13R14, mercaptopropanol, groups SR13, SOR13, SO2R13/sup> , SO3R13, SO3H,SO3-, SO2NH2, SO2Other13, SO2NR13R14or halogen atoms; or mean arylalkyl group with the number of carbon atoms from seven to twelve, heteroaryl group with carbon atoms of from one to eleven or aryl group with the number of carbon atoms from six to twelve, with each of these groups may be unsubstituted or substituted from one up to several times the groups COOH, COOR13, COO-, CONH2, CONHR13, CONR13R14, cyano, hydroxyl group, groups, OR13, OOCR13, OOCNH2, OOCNHR13, OOCNR13R14, a nitro-group, amino group, the other groups13, NR13R14, NHCOR14, NR13COR14N=CH2N=CHR13N=R13R14, mercaptopropyl, groups SR13, SOR13, SO2R13, SOR13, SO3H,SO3-, SO2NH2, SO2Other13, SO2NR13R14or halogen atoms;

each of the groups

R13or R14independently of each other group R13or R14means alkyl group with the number at the MOU carbon from one to six, benzyl or phenyl group, each of which is unsubstituted or substituted from one to several times above substituents, provided that the total number of atoms in each of the substituents R13and R14is from one to eight; however, the pair of substituents selected from the group consisting of all residues R13and R14may be appropriate, together with a direct link or bridges from oxygen atoms, sulfur or a group NH or NR11with the formation of rings,

or CIS-TRANS isomer substances of the formula I or salt of this coloring substance or its isomer with salt-forming functional group;

β) polymer dispersing agent comprising a modified poly(meth)acrylate polymers produced by the method, which includes stage

A1) polymerization in the first stage, one or more ethylene unsaturated monomers in the presence of at least one nitroxyl ether comprising the structural element of the formula

,

where X means a group with at least one carbon atom, thus formed from the free radical X can initiate polymerization, or

A2) polymerization in the first stage, one or more ethylene unsaturated monomers in the presence of not less than one stabil the aqueous nitroxyl free radical structural element of the formula

and free-radical initiator, with at least one monomer used in stage A1) or A2) is alkilany or hydroxyalkyl ester of acrylic or methacrylic acid with the number of carbon atoms in the alkyl or hydroxyalkyl groups of from one to six;

and the second stage

b), including the modification of the polymer or copolymer obtained in stage A1) or A2), by the reaction of transesterification, amidation, hydrolysis, or by anhydrite modification or a combination of these reactions,

γ) a solvent that is suitable for dispersions used in electrophoretic displays.

What follows is a more detailed description of the component dispersions.

Bis-(oxodegradable)benzopyranones colorants

Called CIS-TRANS isomers of coloring substances of the formula I are presented in the following basic structure (without substituents)

while it is likely that TRANS-TRANS-isomer of the above formula I is the most stable, whereas CIS-CIS-isomer is probably the least stable of these isomers.

If the compound of formula (1) represents an anion, the charge can be provided by any known who owned a suitable cation, for example, such a metal cation, organic, inorganic or ORGANOMETALLIC cation, as in the preferred case, the cation of an alkaline, alkaline earth or transition metal cation ammonium, primary ammonium, secondary ammonium, tertiary ammonium, for example, a cation of trialkylamine, Quaternary ammonium compounds, for example, tetraalkylammonium, or organometallics complex.

Coloring substances of the formula (1) can pass and reflect near infrared radiation, which limits their thermal decomposition, however, the ratio of the reflectance and transmittance depends on the size of the particles. Reflectivity (including diffraction reflection) is more important for large particles, the thickness is ≥0.4 µm, whereas the transmittance becomes important for fine particles, for example, to a particle size of from 0.01 to 0.3 μm, and for the case of dyes, which are soluble in the substrate.

Synthetically soluble coloring substances of the formula (I) are obtained usually in the form of very large agglomerates and aggregates unattractive black shades and it is very difficult to get in dispersed form, as in the case of a purple powder obtained in example 126 WO 00/24736. However, it was shown that these raw powders can be easily TRANS is put in suitable colorants in the grinding in the wet state the appropriate grinding device in the presence of a solvent, which in the preferred case is an alcohol, amide, ester, a simple ester or ketone; the result is particles with a core size of ≤0.5 µm, in the preferred case from 0.01 to 0.3 μm, which unexpectedly turned out to be very beautiful shades of black, similar to gas soot. Grinding in the wet state can be performed, for example, in a mill, Dyno as®or mill Netzsch®as a device for grinding paint Skandex®or the like, for example, using glass or ceramic (e.g., Zirconia) balls with a preferred amount of from 0.1 to 3.0 mm, in particular from 0.5 to 1.0 mm. Amounts of alcohol, amide, ether complex, a simple ester or ketone is from 0.1 to 1000 parts per part of colorants, in the preferred case from 1 to 10 parts per part of the coloring matter.

Suitable solvents for grinding in the wet state and/or recrystallization is well known in this area. In this case, you can refer to the solvents represented, for example, in applications to the European patent No. 0774494, No. 0934364 and in WO 02/068541.

The substituents in formula 1 and the General terms used for their implementation, in the preferred case are presented next value.

R2, R4, R5, R7, R9 and R10in the preferred case denote hydrogen atoms, fluorine or chlorine, in particular hydrogen atoms. R3and R8in the preferred case denote hydrogen atoms, nitro, metoxygroup, ethoxypropan, bromine atoms, chlorine, methyl, ethyl group, dimethylaminopropyl, methylaminopropyl, diethylaminopropyl, α-raftiline, β-raftiline group or groups SO3-. In the preferred case, R1and R6have the same value, the same value also have R3and R8the same is also have R4and R9the same is also have R4and R9and/or have the same value R5and R10.

Alkyl group with the number of carbon atoms ranging from one to twelve is, for example, metal, ethyl, n-sawn, ISO-propyl, n-bucilina, second-bucilina, isobutylene, tert-bucilina, 2-methylbutyl group, n-pencilina, 2-pencilina, 3-pencilina. 2,2-dimethylpropylene, n-exilda, heptylene, n-aktiline, 1,1,3,3-TETRAMETHYLBUTYL, 2-ethylhexyl, Danilina, decile, angellina or Godzilla group.

Cycloalkyl group with the number of carbon atoms from three to twelve is, for example, cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentamine, tsiklogeksilnogo, cyclohexylmethyl what I trimethylcyclohexylidene, Tugela, norbornylene, bornilla, naccarella, Karelina, mental, morenilla, Pinilla, 1-adamantina or 2-adamantly group.

Alkenylphenol group with the number of carbon atoms from two to twelve is, for example, vinyl, allyl. 2-propen-2-ilen, 2-butene-1-ilen, 3-butene-1-ilen, 1,3-butadiene-2-ilen, 2-penten-1-ilen, 3-penten-2-ilen, 2-methyl-1-butene-3-ilen, 2-methyl-3-butene-2-ilen, 3-methyl-2-butene-1-ilen, 1,4-pentadien-3-ilen group or any desired isomer hextile, octenidine, moneylines, dianilino or dodecenyl group.

Cycloalkenyl group with the number of carbon atoms from three to twelve is, for example, 2-cyclobutene-1-ilen, 2-cyclopenten-1-ilen, 2-cyclohexen-1-ilen, 3-cyclohexen-1-ilen, 2,4-cyclohexadiene-1-ilen, 1-p-menthene-8-ilen, 4(10)-Tuyen-10-ilen, 2-norbornene-1-ilen, 2,5-norbornadiene-1-ilen, 7,7-dimethyl-2,4-Nicaraguan-3-ilen or campanilla group.

Salcininkai group with the number of carbon atoms from two to twelve is, for example, 1-propyne-3-ilen, 1-butyn-4-ilen, 1-penten-3-ilen, 2-methyl-3-butyn-2-ilen, 1,4-pentadien-3-ilen, 1,3-pentadien-5-ilen, 1-hexyne-6-ilen, CIS-3-methyl-2-penten-4-in-1-ilen, TRANS-3-methyl-2-penten-4-in-1-ilen, 1,3-hexadien-5-ilen, 1-octen-8-ilen, 1-nonen-9-ilen, 1-decyn-10-ilen or 1-dodec the n-12-strong group.

Arylalkyl group with the number of carbon atoms from seven to twelve is, for example, benzyl, 2-benzyl-2-through β-phenylethylene, 9-fluoroaniline, α,α-dimethylbenzyl, ω-phenylbutyrate, ω-phenylmethylene or ω-phenylhexane group. If arylalkyl group with the number of carbon atoms from seven to twelve substituted, the substituents can be located in either the alkyl and aryl structural unit arylalkyl group.

Aryl group with the number of carbon atoms from six to twelve is, for example, phenyl, naftalina or 1-biphenylene group.

The halogen represented, for example, fluorine atoms, chlorine, bromine or iodine, preferably fluorine atoms in the alkyl groups and chlorine atoms or bromine in the aryl group.

Heteroaryl group with carbon atoms of from one to eleven is an unsaturated aromatic radical with the number involved in the conjugation of π-electrons is 4n+2, for example, 2-thienyl, 2-furilla, 1-pyrazolidine, 2-perederina, 2-thiazolidine, 2-oxazolidinyl, 2-imidazolidine, isothiazolinone, triazoline, tetrataenia group or any other cyclic system consisting of thiophene, furan, thiazole, oxazole, imidazole, isothiazol, thiadiazole, triazole, pyridine, pyrazinoic, pyrimidine, PI is iasinovich and benzene rings, which may be unsubstituted or substituted ethyl substituents, the number of which varies from one to six.

Heterocyclic groups are, for example, group

,,,,,,,,,,,,,,or.

Heterocyclic groups can also be formed by connection annulirovano Deputy in the form of aryl groups, for example, this group

,,,or.

Preferred coloring agents are pigments of the formula 1

or new sulfonic acid of the formula 2A

or their salts and/or CIS-TRANS isomers presents acids or their salts.

The invention relates also to the above new sulfonic acids of formula 2A or their salts and/or qi is-TRANS-isomers of the above acids and/or their salts.

Relevant to the present invention bis-(oxodegradable)-benzopyranones colorants receive, for example, by the method presented in WO 00/24736 A1, in particular, under or by analogy with the method described in example 126 WO 00/24736 A1. Provided in this application new coloring substance of formula I, substituted functional group sulfonic acids, or their isomers or tautomers can be also obtained by the reaction of the compounds described in example 126 WO 00/24736 A1, with fuming sulfuric acid.

Special dispersing funds

Special dispersing means, mentioned above, are polymers or copolymers, in the preferred case, a modified polyacrylate or polymethacrylate polymers, in particular copolymers, including the modified polyacrylate or polymethacrylate polymers that are obtained by the method presented in WO 2006/074969 A1 (this source is included in these materials as a reference), the method includes a step

A1) polymerization in the first stage, one or more ethylene unsaturated monomers in the presence of at least one nitroxyl ether comprising the structural element of the formula

,

where X means a group with at least one atom of carbon is kind, thus formed from the free radical X can initiate polymerization, or

A2) polymerization in the first stage, one or more ethylene unsaturated monomers in the presence of not less than one stable nitroxyl free radical structural element of the formula

and free-radical initiator, with at least one monomer used in stage A1) or A2) is alkilany or hydroxyalkyl ester of acrylic or methacrylic acid with the number of carbon atoms in the alkyl or hydroxyalkyl groups of from one to six;

and the second stage

b), including the modification of the polymer or copolymer obtained in stage A1) or A2), by the reaction of transesterification, amidation, hydrolysis, or by anhydrite modification or a combination of these reactions.

On the basis stated on pages 2 and 3 WO 2006/074969 A1 obtained above method (a method to use the technology paleolibertarianism modification) dispersing means are significantly different structurally from polymers with the same composition of monomers, but is synthesized directly from the corresponding monomers without further modification. It should be noted that the distribution of mo is the Windows, which is obtained at the stage of transesterification, is determined only by the interesterification reaction, and we should expect more uniform, i.e. disordered distribution along the polymer chain, in comparison with the direct synthesis of radical polymerization.

The ethylene unsaturated monomer in stage A1) or A2) in the preferred case are selected from isoprene, 1,3-butadiene, α-alkene with the number of carbon atoms from five to eighteen, 4-vinylpyridine) - derivatives or pyridinium ion, 2-vinylpyridine) - derivatives or pyridinium ion, vinylimidazole or imidazolinium ion, dimethylacrylamide, 3-dimethylaminopropionitrile, styrene, α-methylstyrene, p-methylstyrene, p-tert-butylstyrene or compounds of the formula CH2=C(Ra)-(C=Z)-Rbwhere Rameans a hydrogen atom or a metal group, Rbmeans an amino group, a group of O-(M+), the unsubstituted alkoxygroup with the number of carbon atoms of from one to eighteen, alkoxygroup with the number of carbon atoms from two to one hundred, the chain of which is interrupted by at least one atom of nitrogen and/or oxygen, or replacement means alkoxygroup with the number of carbon atoms of from one to eighteen, the unsubstituted alkylamino with the number of carbon atoms of from one to eighteen, dialkylamino with the number of carbon atoms in each of alkalinephp from one to eighteen, replacement of alkylamines with the number of carbon atoms of from one to eighteen or replacement of dialkylamino with the number of carbon atoms in each alkyl groups of from one to eighteen, a group-O-CH2-CH2-N(CH3)2or-O-CH2-CH2-N+H(CH3)2An-while An-means a monovalent anion of an organic or inorganic acid,

M stands for a monovalent metal atom or ammonium ion.

Z means oxygen atom or sulfur.

however, as noted above, must comply with the condition, according to which at least one monomer used in the stages A1) or A2) is alkilany or hydroxyalkyl ester of acrylic or methacrylic acid with the number of carbon atoms in alkinoos or hydroxyalkyl group of from one to six.

Nitroxylenes ether with a structural element of the formula

represents, for example, the compound of the formula

Stable free radicals with a structural elementpresents, for example, in the application for the European patent No. 621878 (Xerox).

So, for example, compoundsorpresented in WO 96/24620 (Atochem).

In particular, K is changed nitroxyl ethers and nitroxyl radicals, represented by the formula

,,,,

,or.

,,,,,or.

If the selected path is received, the appropriate method A2), the preferred free radical initiator, representing ataegina (for example, azo-2,2-bis-isobutyronitrile), peroxide (for example, acetylcyclohexanone-sulfonylated), ether, nagkalat (for example, disuccinate peroxide or hydroperoxide (for example, tert-butylhydroperoxide).

In the preferred case, the first stage polymerization is carried out in accordance with the polymerization method A1).

In the preferred case, the second stage (b) is an interesterification reaction, hydrolysis or anhydrite modification. In particular, preference is given of the interesterification reaction. Preferably, when in the course of the interesterification reaction is separated by-product, representing the alcohol with the number of carbon atoms of from one to six, with the help of distillate is.

In a special embodiment, stage A1) or A2) of the above method of obtaining is carried out twice and get the block copolymers, in which the first and second stage free-radical polymerization of the monomer or mixture of monomers contain based on the total amount of monomers from 50 to 100 wt.% alilovic or hydroxyalkyl esters of acrylic or methacrylic acid with the number of carbon atoms in alilovic or hydroxyalkyl groups from one to six, and on the second or, respectively, in the first stage of radical polymerization in the composition of the ethylene unsaturated monomer there are no primary or secondary ester bonds.

Preferably, when receiving blockcopolymer in the first stage polymerization, the monomer or mixture of monomers contain based on the total amount of monomers from 50 to 100 wt.% alilovic or hydroxyalkyl esters of acrylic or methacrylic acid with the number of carbon atoms in alilovic or hydroxyalkyl groups from one to six, and in the second stage of polymerization of the ethylene unsaturated monomer is a 4-vinylpyridin or pyridinium ion, 2-vinylpyridine or pyridinium ion, vinylimidazole or imidazolinium ion, dimethylacrylamide, 3-dimethylaminopropionitrile, styrene, α-methylsterols, p-methylsterol or p-tert-butalbiral.

In special the m variant of the invention block copolymers is a gradient block copolymers.

As noted above, require that the polymer or copolymer obtained by the controlled free radical polymerization. In U.S. patent No. 4581429 Solomon et al. first described these methods using stable nitroxyl free radicals as a means to control the flow of the reaction. It is presented above in stages A1) and A2).

U.S. patent No. 4581429 relates to a method of free radical polymerization with controlled or "living" polymer chain growth, causing the oligomeric homopolymers and copolymers, including block copolymers and graft copolymers. In accordance with the patent use initiators which partially correspond to the formula R R N-O-X. In the course of polymerization is the formation of free radicals R R"N-O. and .X. At the same time .X represents a free radical group, for example, tert-botilony or sinosauropteryx radical, which can lead to polymerization of the Monomeric structural units containing ethylene group.

As was shown above, the phase method b) includes modifying obtained in stage A1) or A2) a polymer or copolymer by the reaction of transesterification, amidation, hydrolysis or anhydrite modification or as a result of a combination of these reactions.

When interesterification is replacing alcohol radika is and ester groups of the polymer or copolymer other alcohol radical. In the preferred case, the substituted alcohol radical is a structural element of methanol, ethanol, propanol or butanol. In a typical case, the interesterification reaction is carried out at elevated temperature, typically in the range from 70 to 200°C. the obtained controlled free radical polymerization of the polymer is reacted with the appropriate alcohol in the presence of such well-known catalysts, as tetraisopalmitate, tetrabutyltin, or alcoholate of an alkaline or alkaline earth metals such as sodium methylate, lithium methylate or tert-butyl lithium. Usually formed in the reaction mass interesterification alcohol, representing low-boiling by-product of the reaction, is separated through distillation. If necessary catalyst residues can be removed by adsorption or extraction, or they can be recycled or inactivated such known methods, such as hydrolysis with water or acid. The selection of a replacement of alcohol is important. Substitute alcohol determines the properties of the resulting copolymer.

Hydrolysis is the cleavage of ester bonds in alkaline or acidic conditions; it can be done in the case when the polymer or copolymer contains an ester functional group. The degree of hydrolysis may vary inthe widest limits, it depends on the duration and on the reaction conditions. So, for example, upon receipt of free acid groups can be hydrolyzed from 5 to 100%, in the preferred case from 10 to 70% of the ester functional groups; these groups can be converted into the salt form. Metal ion in the preferred case presents ion such alkali metal ion is lithium, sodium, potassium, or ammonium cation, as ammonium ion or ion NR4+where the residues R means a hydrogen atom or alkyl group with carbon atoms of from one to eighteen, if not all four of the remainder R have the same value.

Anhydrite modification can be performed in the case where the polymer or copolymer contains hydroxyl functional groups. Carriers of the hydroxyl functional groups are, for example, such monomers with hydroxyl functional groups, as hydroxyethylacrylate or hydroxyethylmethacrylate. In General, the process of modification can be any aliphatic or aromatic anhydrides. Examples of anhydrides are maleic acid anhydride, the anhydride pyromellitic acid anhydride cyclohexanedicarboxylic acid, succinic acid anhydride, camphoric anhydride acid.

In the preferred case dispergiruyushchie the funds are polymeric dispersing means, choose from modified poly(meth)acrylate polymers of the formula II

,

where

X means an oxygen atom or a group NH,

m takes the value 0 or 10 to 20,

p value is from 60 to 90,

R15means a hydrogen atom or methyl group, and

R means an alkyl group with carbon atoms to thirty, in the preferred case, up to twenty, in the preferred case, up to sixteen carbon atoms, where one or more carbon atoms may be replaced by oxygen atoms, and these groups may be unsubstituted or substituted by dimethylaminopropane or trimethylammonium groups, with group X-R should not be the same for all (b) structural units of the fragment-CH2-C(R15)(CO-X-R) in the formula II and a variety of group X-R distributed along the polymer chain in a random way,

or are salts of such polymers, including forming a salt functional group.

If m takes the value 0, then pyridylmethylene structural unit is missing.

The alkyl group R with the number of carbon atoms up to thirty, in which one or more carbon atoms replaced by oxygen atoms and which is substituted dimethylamino or trimethylammonio group presented, for example, 5-dimethylamino-3-oxapentane group is ormula (CH 3)2N-CH2-CH2-O-CH2-CH2- or 5-trimethylammonio-3-oxapentane group, while it is preferable that this group differed from the 2-dimethylaminomethylene group.

Preferably, when the alkyl group R contains from two to twenty carbon atoms, in particular from four to sixteen carbon atoms and represents, for example, n-boutelou group or a linear or branched alkyl group with the number of carbon atoms from twelve to sixteen, for example, 1-hexadecyl group.

As noted above, the group X-R should not be the same for all (b) structural units of the fragment-CH2-C(R15)(WITH-X-R) in the formula II. In the preferred case, up to 20% of the mentioned structural units of R must represent an unsubstituted alkyl group with the number of carbon atoms of from one to six, such as this 1 bucilina group, while the other structural units of R are different from unsubstituted alkyl groups with carbon atoms of from one to six and are, for example, such a linear or branched alkyl group with the number of carbon atoms from twelve to sixteen, as, for example, 1-hexadecyl group or 5-dimethylamino-3-oxapentane group of the formula (CH3)2N-CH2-CH2-O-CH2-CH2- or 5-trimethyl-ammonio-3-OK is pentelow group.

Salt-forming group in the compound of formula II is, in particular, dimethylaminopropyl, which can react with, for example, methyliodide with the formation of trimethylammonio group. Suitable counterions are, for example, tetraphenylborate or such dialkylphosphinate as deoderent.

Solvents for dispersion

Examples of suitable solvents for dispersing funds are aliphatic hydrocarbons, for example, isoparaffin solvents of high purity Isopar™ G, Isopar™ M boiling in a narrow temperature range, halogenated hydrocarbons such as tetrachloroethylene, and Halocarbon™ 0.8 (polymer chlorotrifluorethylene with low molecular weight), and silicone fluids. Preferably, when the medium for dispersion is dodecan.

Relevant to the present invention, the dispersion can be used in electrophoretic displays.

The invention relates also to the use in electrophoretic displays, bis-(oxodegradable)benzopyranones coloring substances of the formula I and/or polymeric dispersing means which are defined above, and for use in an electrophoretic display dispersion comprising bis-(oxodegradable)benzopyranones the dye of the formula I, the polymer dispersing agent, the distribution of which is given above, and a suitable solvent.

The invention relates to an electrophoretic display comprising a dispersion of bis-(oxodegradable)benzopyranones colorants of formula I, the polymer dispersing agent as defined above, and a solvent, which is suitable for dispersions used in electrophoretic displays.

The invention is illustrated in the following examples.

Examples

Reduction

DMAPMA: N,N-dimethylaminoethylmethacrylate,

DMAEE: dimethylaminoethoxide,

hyflo: Hyflo SuperCel® (Fisher Scientific, Inc.), bulk soda infusoria earth,

GPC: gel permeation chromatography,

LDI-TOF MS: time-of-flight mass spectrometry with laser desorption/ionization,

Mn: Brednikova molecular weight,

nBA: n-butyl acrylate,

PDI: polydispersity (polydispersity of the sample is determined as the result of dividing the mass-average molecular mass Mwfor Mnit is an indicator of the breadth of distribution of mass),

Ph4BNa: tetraphenylborate sodium

THF: tetrahydrofuran,

4VP: 4-vinylpyridin.

Abbreviations for NMR spectra

S.: the singlet.

so: three of a kind,

m: multiplet.

Reagents

Cetyl alcohol (1-hexadecanol 98% purity, supplied by Cognis), LIAL® 125 a: a mixture of alkanols with the number of the ω carbon atoms from twelve to fifteen with a linear chain or with one branch of the company Sasol Olefins and Surfactants GmbH

Lupragen® N 107: dimethylaminoethoxide (supplied by BASF).

General notes on the nomenclature and formulas given in this description for the polymer dispersing funds

As shown in example 6, transesterification occurs in a random order. This is not reflected adequately in many formulas, such as formula 4, in accordance with which it is possible to imagine that there are block butyl esters and block alilovic esters with the number of carbon atoms in the alkyl groups of from twelve to fifteen. However, these formulas are more illustrative than, for example, the formula 4', and therefore they are used. Unlike formulas abbreviated names better reflect which parts of polymer built in statistical order and which parts are represented by block. For example, the name of poly(nBA-co-LialA-b-DMAPMA), shown in example 7, refers to a polymer comprising the unit (it is marked with the letter "b") poly-n-butyl acrylate, in which butylene groups randomly replaced by residues of alcohols LIAL®, we are talking about a poly(nBA-co-LialA) and another block from polydimethylaminoethyl-methacrylamide. The approximate number of monomers in these blocks are shown, for example, in example 7 (11-co-60)-b-10, that is, in this case, about eleven n-butyl acrylate structural units occasionally in the m order copolymerizable with sixty-Lial-acrylate structural units and followed by the section of the ten polydimethylaminoethyl-methacrylamide (DMAPMA) structural units. However, it should be noted that the abbreviations do not say anything about the end groups at both ends of the polymer, which may represent, for example, 1-phenylethylene group.

Obtaining new and known pigments

Example 1. Obtaining the pigment of formula 1.

The synthesis of the pigment represented by the above formula 1 of babeseveryone and isatin described in example 12B on page 35 WO 00/24736 A1. As described in WO 00/24736 A1, the product is a violet powder. Although the authors of this patent application believe that the above formula 1 reflects the most probable structure of the product obtained according to example 12B, full confidence that does not exist. Concrete structure can also meet the isomer, in particular, CIS-TRANS-isomer of formula 1 or a mixture of such isomers.

The following describes a new method of synthesis, which leads to the formation of an improved form of the pigment represented by the above formula 1, the CIS-TRANS-isomer or a mixture of such isomers.

A mixture of 8.5 g of 2,5-dihydroxy-1,4-benzene-luxusni acid (0,37 mol, Aldrich company), 11 g of isatin (0,74 mol, 98%, Aldrich company) and 14 g of the monohydrate of p-toluene-sulfonic acids (brand purum, the company Fluka) in 800 ml of glacial acetic acid is stirred at 105°C for 14 hours. The reaction mixture is cooled to the room temperature and the suspension is filtered through a paper filter, for washing use 250 ml of acetic acid, 200 ml of methanol and 500 ml of water. Black powder is dried in a vacuum drying Cabinet at 70°C and a pressure of 104 PA.

Examples 2 to 5.

General procedure for examples 2 to 5.

In 30 ml of fuming sulfuric acid (content of free sulfuric anhydride is 25%) under stirring to dissolve 5,00 g of black pigment represented by the above formula 1 or its isomer (obtained by the new method described in example 1). Dark purple solution, the temperature rises to 30°C, cooled to 20°C., stirred for 4 hours, unload 500 ml of a mixture of ice water and stirred for further one hour. Within 5 minutes, add 25 g (i.e. multiple stoichiometric excess amine or ammonium salt, in certain examples 2 to 5. The black suspension is stirred 30 minutes, filtered and washed with 50 ml of water. Wet pressed the filter cake is suspended in 100 ml of water, add 5 g of amine or ammonium salt and extracted the product with methylene chloride two times in 150 ml. Two organic phases are combined and added with stirring to 1200 ml of hexane, the desired product is released in the form of small crystals. The suspension is stirred 30 minutes and filtered through a glass fiber filter. Because the product may bleed on the filter, wash it with filter 100 miltilingual and allocate the evaporation of the solvent in a rotary evaporator in vacuum at slightly elevated temperature.

According to the mass spectrum of the target product contains mainly two sulfopropyl. According to spectra1H NMR exact position of the sulfo cannot be determined.

Example 2A. Obtaining the pigment of formula 2A.

To obtain dissolvability formula 2, in which the position of the sulfo-defined it is presented on the next following formula 2A - use the following way to obtain.

In 80 ml of glacial acetic acid and 20 ml of water was stirred at 105°C for 14 hours a mixture of 2.3 g of 2,5-dihydroxy-1,4-benzodioxane acid (0,01 mol, Aldrich company), 5.7 g dihydrate sodium salt of isatin-5-sulfonic acids (0,02 mol, 98%, the company Fluka) and 0.7 g of the monohydrate of p-toluenesulfonic acid (brand Ritt, the company Fluka). The reaction mixture is cooled to 80°C. and the suspension is filtered through a paper filter for washing use 80 ml of acetic acid and 100 ml of methanol. Black powder is dried in a vacuum drying Cabinet at 70°C and a pressure of 104PA (PA means Pascal), obtain the connection formula 2A; LDI-TOF MS: m/z=608.

Example 2.

For tributylammonium salt compounds represented by the above formula 2 as an amine use tributylamine. The output of 2.1,

Example 3.

For trioctylamine salt compounds represented by the above formula 2 is used ammonium salt, a small town in alleyway a bromide of trioctylamine. The output of 1.6,

This substance is characterized by the elemental analysis data, the corresponding bis-(trioctylamine) salt.

Found (calculated): With 66,35% (67,92%); N 9,02% (cent to 8.85%); N 3,86% (4,17%); O Of 14.25% (14,29%); S 5,44% (4,77%). Residual bromide in samples not detected.

Example 4.

For octadecyltrimethylammonium salt compounds represented by the above formula 2 is used ammonium salt, representing the bromide of octadecyltrimethylammonium. The output of 8.3,

This substance is characterized by the elemental analysis data corresponding to the monohydrate mono-(octadecyltrimethylammonium) salt.

Found (calculated): 59,06% (60,18%); N 7,46% (6.34%); N 4,01% (4,48%); O each holding 21.25% (22,17%); S 6.78% (6,84%). Residual bromide in samples not detected.

Example 5.

For tetraethylammonium salt compounds represented by the above formula 2 is used ammonium salt, representing the bromide of tetraethylammonium. Output 1,2,

Obtaining reagents and copolymers used as dispersing funds

Example 6. The synthesis of compounds 4 (4'), i.e. poly(nBA-co-CetylA-b-4VP).

In a flask with a volume of 500 ml, equipped with a mechanical stirrer and distillation column, which is cooled with a mixture of acetone with dry ice, download 100.0 g of poly(nBA-b-4VP) representing a block of copolymer n-butyl acrylate and 4-vinyl-pyridine with a degree of polymerization 75-6-15, described in example A2 on page 36 WO 2006/074969 A1, 100.0 g of xylene and a 71.1 g of cetyl alcohol (molecular weight 242,5 g/mol, 45 mole.% based on n-butyl ester group) and distilled water by azeotropic distillation with xylene. For 5 hours at a temperature of 190°C. add three servings of 0.25 g of tert-butyl lithium (LiOtBu). The resulting n-butanol is distilled off under reduced pressure. Get 149,8 g of poly(nBA-co-CetylA-b-4VP) formula 4 in the form of yellowish wax. Brednikova molecular mass Mnis 15400 g/mol (polydispersity of 1.5). Analysis by gel permeation chromatography and spectrum data1H NMR show almost quantitative conversion of cetyl alcohol.

Obviously, the above formula 4 does not accurately reflect the structure of the obtained product because transesterification most likely occurs in a random order and in accordance with this more accurate representation of the structure of the obtained polymer is reflected, probably by formula 4'. A similar comment can be made in relation to the following examples 7 to 9.

Example 7. Synthesis of poly(nBA-co-LialA-b-DMAPMA) formula 6.

In a flask with a volume of 350 ml, equipped with a mechanical stirrer and distillation column, which is cooled with a mixture of acetone with dry ice, download 90,5 g of copolymer f is rmula 5 and 100.3 g of Lial 125 (80 mole. % based on n-butyl ester group), in the reactor to create an inert atmosphere, passing through the solution at room temperature for 1 hour nitrogen. The mixture is heated at a temperature of from 135 to 142°C and add the catalyst (four portions 350 mg of Tetra(isopropyl)orthotitanate every 2 hours). The resulting m-butanol is distilled off under reduced pressure (200 mbar). After 8 hours the resulting brownish polymer is cooled to room temperature, get RUB 145.1 g of the copolymer of formula 6 (Mnis 11300 g/mol, a polydispersity of 1.35 according to the analysis by gel permeation chromatography in tetrahydrofuran), a solids content of 97.3% (halogen oven, 200°C), its composition (according to spectrum1H NMR) corresponds to poly(nBA-co-LialA-b-DMAPMA) in the form (11-co-60)-b-10.

The original compound of formula 5 get below way.

Stage 7.1

In a flask with a volume of 500 ml, equipped with a mechanical stirrer and distillation column, loads of 122.5 g of poly-n-butyl acrylate [poly(nBA)] synthesized in analogy to example A1 WO 2006/074969, the degree of polymerization of 75 in accordance with the data1H NMR. Mnis 6830 g/mol, polydispersity 1,31) and 85,98 g dimethylaminopropionitrile. The mixture is heated under nitrogen atmosphere to 135°C. the Reaction is terminated after a time of 2.5 hours, mesoblastic to 100°C and distilled unreacted dimethylaminopropionitrile in high vacuum (<20 mbar) until the solids content of more than 98,0% (halogen dryer at 200°C).

Obtain 143 g of a brownish viscous blockcopolymer formula 5 with Mn7480 according to gel chromatography in tetrahydrofuran and a polydispersity of 1.32. In accordance with the analysis using the1H NMR degree of polymerization for p(nBA-b-DMAPMA) is defined as 71-b-10.

Example 8. Synthesis of copolymer salt of formula 7 [poly(nBA-co-LialA-with-DMAEE[IU-quat]A-b-DMAPMA)]+(TPB).

In a flask with a volume of 500 ml, equipped with a mechanical stirrer and distillation column, which is cooled with a mixture of acetone with dry ice, loads of 200.0 g of poly(nBA-b-4VP) formula 3 with a degree of polymerization of 75-b-15, shown in example 6 and obtained in accordance with example A2 WO 2006/074969, 203,1 g Lial 125 (about 100 mole. % based on n-butyl ester group) and 4.6 g of Lupragen N 107 (dimethylaminoethoxide, molecular weight 133,2, about 3 mole. % based on n-butyl ester group). Add a dose of 2.5 g of Tetra(isopropyl)orthotitanate and stirred the mixture in an inert atmosphere under reduced pressure for 8 hours at a temperature of 140°C, fending off the formed n-butanol. After the reaction is distilled taken in excess of the residual alcohols in high vacuum (20 mbar) until the solids content of greater than 98% (halogen oven, 200°C). Get brownish viscous polymer with an average composition (on the data 1H NMR) (5-co-1-co-70)-b-15 for poly(nBA-co-DMAEEA-co-Lial125A)-b-p(4VP) and a value of Mn17500 (according to gel permeation chromatography in tetrahydrofuran) with a polydispersity of 1.31. In a three-neck flask with a volume of 250 ml, equipped with a mechanical stirrer, download 50.0 g of this polymer and add 100 g of n-dodecane. The mixture is gently heated to 40°C. to obtain a homogeneous solution. After cooling to room temperature, the polymer solution is added to 0.29 g under the conditions (1.0 equivalent based on the amino group) and then left overnight under stirring at room temperature. Get the solution of polymer with Quaternary amine groups with a solids content of 32.1% (halogen oven, 200°C), the value of Mnpolymer is 14300 g/mol (according to gel permeation chromatography in tetrahydrofuran) at polydispersity 1,29. At the last stage in 13.2 g of dodecane dissolve 0.66 g of tetraphenylborate sodium (Ph4BNa), carefully add it to the polymer solution and stirred for 3 hours at room temperature. Obtained a hazy mixture is filtered through soda infusino land hyflo and get a yellowish solution (solids content of 31.3%) of the salt of formula 7 with Mn14300 g/mol (polydispersity 1.24). The average composition (according to1H NMR) of the cation of poly(nBA-co-DMAEE[Me-quat]A-co-Lial125A)-b-p(4VP)+ defined as (5-co-1-co-70)-b-15.

Example 9. Synthesis of dispersing funds formula 9 [poly(nBA-co-LialA-with-DMAEE[H]A)-b-DMAPMA]+(DDDP)-.

At a temperature of 50°C and 283 g of dodecane completely dissolve 50.0 g of a copolymer of formula 8. Add deoderent (DDDP, 0.64 g) of formula 10, which is obtained in accordance with stage 9.2, and stirred at 80°C for 2 hours. Ammonium salt of formula 9 obtained as a transparent brown solution in n-dodecane. Gel permeation chromatography of the polymer in tetrahydrofuran gives the value of Mn18800 g/mol (polydispersity 1.30). The average composition (according to1H NMR) of the cation of poly(nBA-co-DMAEE[H]A-co-Lial125A)-b-p(4VP)+corresponds to (7-co-1-co-66)-b-14.

Original products obtained are presented in the following ways.

Stage 9.1. Synthesis of copolymer of formula 8.

In accordance with the method described in example 8, in a flask with a volume of 500 ml, equipped with a mechanical stirrer and distillation column, which is cooled with a mixture of acetone with dry ice, obtain 175 g of the copolymer of formula 8. To do this, hold the interesterification reaction in the reaction mass formed from 103,7 g blockcopolymer poly(nBA)-b-4R(VP) average composition (according to1H NMR) 73 unit nBA and 14 units of 4-vinylpyridine) - derivatives, 110,1 g Lial 125 (about 100 mole. % based on n-butyl ester groups who), 1.0 g Lupragen N 107 (molecular weight 133,2, 1.5 mole. % based on n-butyl ester group) and 1.3 g of Tetra(isopropyl)orthotitanate (18 hours at the temperature of 140°C and a pressure of 200 mbar), getting brownish viscous copolymer of formula 8 with an average composition (according to1H NMR) (7-co-1-co-66)-b-14 for poly(nBA-co-DMAEEA-with-Lial125A)-b-p(4VP) and a value of Mn15900 g/mol (according to gel permeation chromatography in tetrahydrofuran) with a polydispersity of 1.61.

Stage 9.2. Synthesis of deoderent (DDDP) formula 10.

In a three-neck flask with a volume of 250 ml, equipped with a magnetic stirrer, 10 ml water dissolve 10.6 g of monohydrate hypophosphite sodium (molecular weight 106 g/mol, Fluka production) and cooled to 15°C. To this solution carefully added 7.51 g of concentrated sulfuric acid (97%. 0.75 equivalent) and get turbid and viscous reaction mass. Then at room temperature was added 35.4 g of 1-dodecene (2.0 equivalent) and then 2,42 g dibenzoylperoxide (C6H5CO-OO-SOS6H5production Fluka, 50% in water) in the form of a solution in 20 ml of 1,4-dioxane. Inhomogeneous mixture is heated to 80-85°C. and stirred for 2 hours, then add another 2,42 g dibenzoylperoxide (produced by Fluka. 50% in water) in 20 ml of 1,4-dioxane and stirred for 2 hours at 85°C. After cooling to room temperature ribault 50 ml of toluene, heated to 60°C. and cooled to room temperature. A two-phase system separated and the aqueous phase is extracted with twice 50 ml of toluene. The combined organic phases are washed with water and sodium chloride solution in water, close to saturation (brine), (two times 20 ml of water and, respectively, 1 times 20 ml of brine). After filtration through a soda infusino land evaporated toluene to dryness. The remaining solid is dissolved in hot hexane (60°C, 200 ml) and left to cool for crystallization. Part of the crystals are filtered, the filter cake washed with cold hexane and dried at 25°C in a rotary evaporator. Get 14,65 g (yield 36%) of the compounds of formula 10 in the form of a white crystalline mass.1H NMR (deuterochloroform, ppm): 9,8 (C., 1H, HE); 1,5-1,8 (m, 8 H, 2 R-CH2- N2), 1.2 to 1.5 (m, 36 H, 18-CH2-), and 0.9 (t, 6N, 2N3).

Example 10. Synthesis of poly(nBA-co-LialA-b-4VP) formula 11.

Into a flask of 100 ml capacity equipped with a mechanical stirrer and distillation column, which is cooled with a mixture of acetone with dry ice, download 18,77 g of poly(nBA-b-4VP) with degree of polymerization 73-b-14, obtained according to example A2, WO 2006/074969, and 20,63 g Lial 125 (80 mole. % based on n-butyl ester group) and let the mixture of gases within 60 min is t at a temperature of 65°C and a pressure of 50 mbar. For 6 hours at 142°C add three portions of 0.29 grams of bis-(acetylacetonate) bis-(isopropylate) titanium. The resulting n-butanol is distilled off under reduced pressure.

Get 28,94 g of the copolymer of formula 11 [poly(nBA-co-LialA-b-4VP)] in the form of a brownish viscous substances; Mnis 18760 g/mol (polydispersity of 1.34). Analysis by gel permeation chromatography, and spectrum data1H NMR shows almost complete conversion of the alcohol Lial 125.

Example 11. Obtaining dispersions and their properties.

This example illustrates obtaining an oil phase containing various dispersed electrophoretic particles of the black pigment. The physical characteristics of the obtained dispersions below in table 1.

A common way to obtain dispersions

In the dispersing device DAS 200 (Lau GmbH) at 25°C for 15 hours, crushed and 1.00 g of pigment substances in 9.0 g of dodecane (749,0 kg/m3) (Aldrich D22,110-4) in the presence of 0.75 g dispersing the funds specified in table 1. In the case of obtaining two-color electrophoretic dispersion according to example 11 and above the amount of 1.00 g of the pigment substance is replaced by 0.5 g of each of the pigments shown in the example 11And.

The dispersion was diluted with an additional amount of dodecane to a concentration of from 10 to 2% by weight. To determine the dynamic light scattering 20 is CL of this dispersion is again diluted with dodecane to a volume of 1 ml.

The size, diameter in nm and electrokinetic potential (ξ) [mV] particles dispersed pigment is determined using dynamic light scattering on a Malvern instrument Zetasizer Nano Series apparatus (Malvern Instruments Ltd., UK). Certain particle sizes are shown in nanometers in Size column of the following table 1, data on the electrophoretic mobility (calculated) is shown in column µ in units of 10-8m2/B·c at 40 In (electrophoretic mobility is a factor of proportionality between the velocity of the particles and the strength of the electric field), and electrokinetic potential (zetapotential) shown in the column "Zeta (mV)".

Electrophoretic mobility µ are calculated using the Smoluchowski equation (ξ=µη/ε, where µ denotes the mobility, η, equal 1,344 MPa·s, is a medium viscosity at 25°C and ε equal to 2.0, is a dielectric constant at 20°C).

Determination of resistance R

The resistance R [Ω], shown in table 1, determine the following method.

The gas dispersion carbon black (Base Carbon Black production Cabot Modified Carbon Black Toolkit; Cabot Corp.) in dodecane get the reference sample, using as dispersing funds copolymer 4 (obtained according to example 6) SP-10515 in accordance with the above General method to obtain dis is ersi".

Net dodecan, dispersion gas soot and dispersion of pigments (in all cases the concentration is 2 wt.%) put in equal amounts to the wells of 96-hole plate production Gatlik Ltd. (Basel, Switzerland; http://www.gatlik.com/) three-point geometry of the electrode for determination of low conductivity, as described in WO 2005/105292 A1 (Fig.1 in the materials of the present application). Plate made of polyimide with a flat gold electrodes in the form of a double semi-circles, as shown in Fig.1 of this patent application to individual wells. The wells have a diameter of 5 mm and a depth of 2 mm Before the measurement plate is cleaned using ethanol as long as the resistance between the electrodes will not be more than 1013Ω. The resistance is determined between the semicircular electrode, the Central electrode is used for grounding. For each sample variance definition is carried out in three different holes and drop the highest and lowest values.

µ[10-8m2/·S at 40 In]
Table 1.
ExamplePigment [formula No. / example]Dispersing tool [formula No. / example]Concentration **Size [nm]Zeta [mV]R[Ω]
11aGas soot*4/6150149-3,4×10-3-3,96of 3.53×109
11b2/44/6100551-2,32×10-2-27,15,71×109
11b2A (free disulpho-acid) / 2A6/775314-3,09×10-2-36,1of 1.09×1010
11g2A (free disulpho-acid) / 2A11/1075338-3,71×10-2-43,24,36×1010
111/1of 89.1 75511-1,32×10-2-15,44,69×109
11th1/14/675471-1,99×10-2-23,2He defined.
G1/19/975435-2,59×10-2-30,2Not determined.
S1/17/875411to 2.29×10-2-26,6Not determined.
11And1/1 + Pigment Yellow 128***6/775493-1,95×10-2-22,7Not determined.
* Base Carbon Black production Cabot Modified Carbon Black Toolkit; Cabot Corp.
** The column "Concentration" refers to the percent weight dispersing means with respect to the pigment mass.
*** CROMOPHTAL Jet Yellow 8GT production Ciba, Inc.

The resistance of the hole with clean dodecanol is more than 1013Ω (>10-3Ohms).

As shown in table 1 data, the absolute value of the electrokinetic potential and resistance dispersions of black pigments, which correspond to the present invention (examples from 11b to 11), in all cases higher than for material comparison, representing the gas soot (example 11a).

The value of the electrodynamic potential is that its absolute value (i.e. positive or negative) is a measure of the stability of colloidal dispersions. Electrodynamic potential reflects the degree of repulsion between adjacent equally charged particles in dispersion. For molecules and particles that are small enough size, for example, of the present invention the nanoparticles, the high value of the electrodynamic potential confirms their stability, i.e. their variance is not affected by aggregation. If this potential has a low value, the force of attraction of an eye yaytsa more forces of repulsion and dispersion is destroyed as a result of flocculation. In accordance with this dispersion with high electrodynamic potential (negative or positive) stable electric fields, while colloids with low value electrodynamic potential prone to coagulation or flocculation. Another role of electrodynamic potential is that the mobility of the particles under the action of the electric field is proportional to the electrodynamic potential. The higher the electrodynamic potential (its absolute value), the more likely is the movement of particles and the switching between two States.

High resistance dispersion is desirable because it corresponds to its low electrical conductivity; this reduces the power consumption of the display and a stable image is saved for a longer time in the case when the imposed electric field is maintained by the capacitor without consuming current.

1. Dispersion, which can be used in electrophoretic displays, including
α) bis-(oxodegradable)benzopyranones the dye of the formula I

where
R1and R6in each case, independently of one another mean a hydrogen atom, methyl group, triptorelin group, fluorine atoms or chlorine is a, in the preferred case, the hydrogen atoms or fluorine, in the most preferred case, hydrogen atoms,
R2, R3, R4, R5, R7, R8, R9and R10in each case, independently of one another denote hydrogen atoms, halogen, the group R11, COOH, COOR11(S-, CONH2, CONHR11, CONR11R12, cyano, hydroxyl group, group, OR11, OOCR11, OOCNH2, OOCNHR11, OOCNR11R12the nitro-group, amino group, group with other11, NR11R12, NHCOR12, NR11OR12N=CH2N=CHR11N=CR11R12mercaptopropyl, group SR11, SOR11, SO2R11, SO3R11, SO3H, SO3-, SO2NH2, SO2Other11or a group of SO2NR11R12while R2and R3, R3and R4, R4and R5, R7and R8, R8and R9and/or R9and R10can also be connected together by a direct bond or a bridge of atoms of oxygen, sulfur or a group NH or NR11,
R11and R12in each case, independently of one another denote an alkyl group with the number of carbon atoms ranging from one to twelve, cycloalkyl group with the number of carbon atoms from three to twelve, alkenylphenol group with the number of carbon atoms from TLD is up to twelve or cycloalkenyl group with the number of carbon atoms from three to twelve or alkylamino group with the number of carbon atoms from two to twelve, each of these groups can be a continuous chain, or chain perivious by oxygen atoms, NH groups, NR13and/or sulfur atoms of two or more fragments, each of which includes at least two carbon atoms and each of which may be unsubstituted or substituted by one or more groups COOH, COOR13(S-, CONH2, CONHR13, CONR13R14, cyano groups, exography, hydroxyl groups, groups, OR13, OOCR13, OOCNH2, OOCNHR13, OOCNR13R14, NR13, amino groups, groups with other13, NR13R14, NHCOR14, NR13COR14N=CH2N=CHR13N=CR13R14, mercaptopropanol, groups SR13, SOR13, SO2R13, SO3R13, SO3N, SO3-, SO2NH2, SO2Other13, SO2NR13R14or halogen atoms, or mean arylalkyl group with the number of carbon atoms from seven to twelve, heteroaryl group with carbon atoms of from one to eleven or aryl group with the number of carbon atoms from six to twelve, each of which can be unsubstituted or substituted from one up to several times the groups COOH, COOR13, COO-, CONH2, CONHR13, CONR13R14, cyano, hydroc the ilen group, groups OR13, OOCR13, OOCNH2, OOCNHR13, OOCNR13R14, a nitro-group, amino group, the other groups13, NR13R14, NHCOR14, NR13COR14N=CH2N=CHR13N=CR13R14, mercaptopropyl, groups SR13, SOR13, SO2R13, SO3R13, SO3H, SO3-, SO2NH2, SO2Other13, SO2NR13R14or halogen atoms, with each of the groups
R13or R14independently of each other group R13or R14means alkyl group with the number of carbon atoms of from one to six, benzyl or phenyl group, each of which may be unsubstituted or substituted from one to several times above substituents, provided that the total number of atoms in each of the substituents R13and R14is from one to eight, with a pair of substituents selected from the group consisting of all residues R13and R14,may be appropriate, together with a direct link or bridges from oxygen atoms, sulfur or a group NH or NR11with the formation of rings,
or including CIS-/TRANS-isomer substances of the formula I or salt of this coloring substance or its isomer with salt-forming functional group,
β) polymer disperging what it means, including the modified poly(meth)acrylate polymers produced by the method, which includes the stage
A1) polymerization in the first stage, one or more ethylene unsaturated monomers in the presence of at least one nitroxyl ether comprising the structural element of the formula

where X means a group with at least one carbon atom, thus formed from the free radical X• initiates polymerization, or
A2) polymerization in the first stage, one or more ethylene unsaturated monomers in the presence of not less than one stable nitroxyl free radical structural element of the formula

and free-radical initiator, with at least one monomer used in stage A1) or A2) is alkilany or hydroxyalkyl ester of acrylic or methacrylic acid with the number of carbon atoms in alilovic or hydroxyalkyl groups from one to six,
and the second stage
b), including the modification of the polymer or copolymer obtained in stage A1) or A2) by the reaction of transesterification, amidation, hydrolysis, or by anhydrite modification or a combination of these reactions,
and including
γ) a solvent that is suitable for dispersions, COI is lsemaj in electrophoretic displays.

2. Dispersion under item 1, where the dye is a pigment of the formula 1

3. Dispersion under item 1, where the dye is an acid of formula 2A

or its salt and/or CIS-/TRANS-isomer of this acid or salt.

4. Dispersion under item 1, where the polymeric dispersing agent selected from modified poly(meth)acrylate polymers of the formula II

where
X means an oxygen atom or a group NH,
m takes the value 0 or 10 to 20,
p value is from 60 to 90,
R15means a hydrogen atom or methyl group, and
R means an alkyl group with carbon atoms to thirty, in which one or more carbon atoms may be replaced by oxygen atoms, and this group can be unsubstituted or substituted by dimethylaminopropoxy or trimethylaminuria, while group X-R should not be the same for all (p) to structural units of the fragment of the formula-CH2-C(R15)(CO-X-R) is present in the formula II,
and of salts of such polymers, including forming a salt functional group.

5. Dispersion under item 1, where the solvent is dodecan.

6. The variance in one of the paragraphs. from 1 to 5, where dispersed particles have a diameter of from 200 to 800 nm.

7. Presented in paragraph 3 bis-(xochitonalan)benzopyranones the dye of formula 2A or its salt and/or CIS-/TRANS-isomer of this acid or salt.

8. The use of bis-(oxodegradable)benzopyranones colorants of formula I as defined in one of the paragraphs. 1 to 3, and/or polymeric dispersing means on one of the PP.1, 9 and 10 in an electrophoretic display.

9. Polymeric dispersing agent selected from modified poly(meth)acrylate polymers of the formula II

where
X means an oxygen atom or a group NH,
m takes the value 0 or 10 to 20,
p value is from 60 to 90,
R15means a hydrogen atom or methyl group, and
R means an alkyl group with carbon atoms to twenty, in which one or more carbon atoms may be replaced by oxygen atoms, and this group can be unsubstituted or substituted by dimethylaminopropoxy or trimethylaminuria, while group X-R should not be the same for all (p) to structural units of the fragment of the formula-CH2-C(R15)(CO-X-R) is present in the formula II, and a different group of X-R distributed along the polymer chain in a random way,
or salts of such polymers, including forming a salt functional group.

10. Dispersing agent for p. 9, where R up to twenty percent named p of the structural units of the fragment of the formula-CH2-C(R15)(CO-X-R)- means unsubstituted alkyl group with h the scrapping of the carbon atoms of from one to six, and other structural units of R are different from unsubstituted alkyl groups with carbon atoms of from one to six.

11. Electrophoretic display, comprising the dispersion of bis-(oxodegradable)benzopyranones colorants of formula I as defined in one of the paragraphs. 1 to 3, the polymer dispersing agent according to one of paragraphs.1, 9 and 10, and a solvent, which is suitable for dispersions used in electrophoretic displays.



 

Same patents:

FIELD: process engineering.

SUBSTANCE: invention relates to removal of excess paint at spraying in painting chamber by separation fluid. Separation fluid contains the components that follow. (a) At least 49.95 wt % of water. (b) At least one non-ionic surfactant. (c) At least 5-50 wt % of organic water-soluble film stabilising component of monomer and polymer polyols. Components (b) and (c) differ. Separation fluid viscosity complies with DIN 53211 at 23°C to make 11-25 s. Proposed method comprises the steps that follow. i) Forcing the gas flow through painting chamber. ii) Bringing excess paint in contact with gas flow the make paint-saturated gas flow. iii) Making of continuous flow of fluid film of separation fluid on gas flow surface. iv) Forcing said gas flow saturated with paint to said surface with forming of first separation fluid saturated with paint. v) Removal of first separation fluid saturated with paint and gas flow with decreased content paint.

EFFECT: efficient removal of excess paint, stable process.

15 cl, 1 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to water-dispersible polyurethane, method of obtaining thereof, thereof application and cosmetic preparation, containing polyurethane as thickening agent. Water-dispersible polyurethane contains mainly linear basic chains, consisting of alternating hydrophilic and hydrophobic sections. Polyurethane has two terminal sections (T), which are hydrophobic, and, at least, one hydrophobic terminal section (T) represents branched alkyl residue. Hydrophilic section (S) is directly attached to each section (T). At least, one hydrophobic section (D) is directly attached to, at least, one end of each of sections (S). The main polyurethane chain contains, at least, one hydrophilic section (P), and if there is more than one section (P), two sections (P) are separated with, at least, one hydrophobic section (D). Polyurethane contains, at least, three hydrophilic sections. Ratio of molecular weight of any of hydrophilic sections (S) to molecular weight of any of hydrophilic sections (P) lies within the interval from 1:1.4 to 1:70. At least, two hydrophobic sections (D) are aliphatic diisocyanate residues, and, at least, one hydrophilic section (P) represents residue of polyether with number average molecular weight, at least, 1500 g/mol. Polyurethane can represent mixture of different mentioned above polyurethanes. Polyurethanes are obtained in two steps. At the first stage interaction of, at least, one polyether diol with, at least, one aliphatic diisocyanate is realised in presence of zinc carboxylate in solvent medium. At the second stage obtained product is subjected to interaction with, at least, one ethoxylated aliphatic alcohol in solvent medium. After that, separation of solvents is performed and water is added. Polyurethanes are applied for manufacturing of water-containing cosmetic preparation.

EFFECT: invention makes it possible to increase viscosity of cosmetic preparations and their storage stability.

10 cl, 4 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: dispersant is a copolymer of (meth)acrylic acid with an alkyl oxide monomer, having a polymerisable functional group and terminated by a hydrogen atom or an alkyl group having 1-4 carbon atoms. The thickener is an associative thickener containing at least one hydrophobic group which is a polystyrylphenyl, preferably selected from distyrylphenyl, tristyrylphenyl and mixtures thereof. More preferably, the hydrophobic group is tristyrylphenyl.

EFFECT: dispersant-thickener combination enables to enhance gloss retention of a paint film over time, while providing the aqueous composition with the required rheological properties.

28 cl, 2 tbl, 18 ex

FIELD: printing.

SUBSTANCE: invention discloses a counterfeit-proof document, in which at least on one area, which is visible from the side surface, at least two different paints are applied. The said paints along the marked direction on the area have concentration curves differing from each other, so that the ratio (R(x)) of the concentrations of at least two different paints varies on the area depending on the location along the marked direction, with at least two different paints are fluorescent paints. The concentration curves are chosen so that at the excitation of fluorescence the area which leads to the appearance of the marked colour print is distinguishable; and at least two different paints have different durability. In addition, the concentration curves and the area size along the marked direction are chosen so that, after manufacturing after a preliminary determined period of validity a distinguishable shift is formed which leads to the appearance of colour print of the area.

EFFECT: invention provides increased protection against forgery of the document, and the simplicity of checking the attribute of authenticity.

35 cl, 12 dwg, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a paint composition containing a hydrophobic latex polymer component for endowing resistance to softening by water and staining of the paint film obtained from the latex paint produced from the paint composition, as well as paint, a paint film and production method thereof.

EFFECT: invention enables to obtain a latex paint film and a latex paint, which are not sensitive to water, staining, deterioration of lustre and change in rheological properties.

11 cl, 7 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to copolymer surfactants and use thereof in emulsion paints. The paint composition for colouring emulsion paints contains at least one pigment, water and a copolymer surfactant. The copolymer surfactant has average molecular weight between 400 and 200000 Da and contains the following monomers: (a) 10-80 wt % of at least one compound selected from α,β-ethylene unsaturated C3-C12 carboxylic acids or anhydride thereof, (b) 10-80 wt % of at least one α,β-ethylene unsaturated C2-C12 vinyl monomer and (c) 0.01-20 wt % of at least one surfactant. Each of the said monomers is either an acrylic or methacrylic ester with an ethoxylated fragment, having the following structure: H2C=C(X)-C(O)O-E-R, where X denotes hydrogen or methyl, E denotes ethoxylate and R denotes alkyl phenyl, monostyrene phenyl, distyrene phenyl or tristyrene phenyl. When added to a water emulsion paint, the dye composition does not lead to change in viscosity for low Stormer shearing force in a water emulsion paint obtained from a mixture containing the said dye composition, by more than approximately ±10% of the viscosity for low Stormer shearing force of the acrylic base from which the paint was prepared. The dye composition also contains at least one oxygen-containing solvent, antifoaming agent, preservative and sodium hydroxide. Described also is a water emulsion paint which is prepared from a mixture of the base of the paint and the dye composition containing at least one pigment, water and the said copolymer surfactant. The paint also contains an associative thickener which is a non-ionic hydrophobically modified ethylene oxide urethane block copolymer, hydrophobically modified polyether, hydrophobically modified alkali-soluble emulsion, hydrophobically modified poly(meth)acrylic acid, hydrophobically modified hydroxyl ethyl cellulose, hydrophobically modified poly(acrylamide) or mixture thereof.

EFFECT: paint has good fluidity properties/levelling capacity, does not change colour after rubbing.

27 cl, 9 tbl, 15 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a synthetic thickener used in compositions for making paints. The synthetic thickener contains a water-soluble or water-swellable synthetic polymer whose main chain contains terminal and/or intermediate blocks of oligomeric hydrophobic fragments. The hydrophobic fragments are selected from a group which includes alkyl or aryl fragments which contain a polymerising cyclic monomer or mixture thereof. The monomer is selected from a group which includes alkyl glycidyl ethers, aryl glycidyl ethers, alkyl epoxy and mixtures thereof. Alternatively, hydrophobic fragments are selected from a group which includes polymerising alkene or mixture thereof and derivatives thereof. The polymerising alkene monomer is selected from a group which includes styrene and styrene compounds. The main chain of the water-soluble or water-swellable synthetic polymer is selected from a group which includes polyethylene glycol, polyacetal polyethers and polyurethane. The synthetic thickener can be used as a modifier of rheological characteristics, especially in latex paints.

EFFECT: use of the synthetic thickener in water-based coatings ensures good thickening, levelling and insignificant drips.

5 cl, 23 ex, 4 tbl

FIELD: dyes.

SUBSTANCE: invention relates to stable mixtures comprising filling agents and condensing agents chosen in the indicated combinations and concentrations. These stable mixtures can be used as mixtures in a method for preparing dyes by using dye precursors or as a component in the covering material such as a dye, or for another final aim wherein pigments conferring the paints covering power are used.

EFFECT: improved and valuable properties of mixtures.

13 cl

FIELD: paint and varnish industry.

SUBSTANCE: invention proposes a flowing pigment mixture comprising titanium dioxide of universal sort or sort used in internal works with the concentration 40-100 vol.%, a thickening agent, dispersing agent and, optionally, water. The volume content of dry TiO2 is 15%, not less. As a thickening agent the mixture can comprise at least one hydrophobically modified ethyleneoxide-urethane polymer or at least one hydrophobically modified alkali-soluble emulsion, or at least one hydrophobically modified hydroxyalkylcellulose. As a dispersing agent the indicated mixture can comprise, for example, copolymers of maleic acid and diisobutylene, or butyl methacrylate and methacrylic acid, or acrylic acid and hydroxypropyl acrylate. Mixture can comprise additionally one or more additive taken among the following series: froth breaker, surface-active substance, coalescent agent, base, biocide, mildewcide agent, combined disperser, polymeric binding agent, a polymer with cellular latex particles. Proposed mixtures are stable and don't require a stirring. Invention can be used in preparing universal dyes and dyes for internal finishing.

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

20 cl, 13 tbl, 8 ex

The invention relates to petrochemical and paint industries, namely, to obtain a solvent for the paint industry

FIELD: chemistry.

SUBSTANCE: infrared-inert substrates include moulded polymer articles, films, fibres, coatings and other organic and inorganic materials. The method of producing said substrates involves adding an effective amount of dispersed bis-oxodihydroindolylene benzodifuranone dye into the substrate or onto the surface of the substrate. The resultant substrates have reflecting power and are transparent for a large part of non-reflected near-infrared radiation. A wide application is disclosed - for casings of electronic devices, garden furniture, motor car, naval or aerospace parts, laminates, artificial leather, textile materials, optical fibres and in multicolour printing processes. The obtained substrates can be laser welded. Novel bis-oxodihydroindolylene benzodifuranone compounds are also disclosed.

EFFECT: low heat build-up and high value of substrates in many fields of application.

16 cl, 5 dwg, 46 ex

FIELD: organic chemistry, dyes.

SUBSTANCE: invention relates, in particular, to new macroheterocyclic compounds that can be used as an acid dye for silk and wool. Invention describes 3,4,17,18-dicyclopenta[c,d]phenalene-2,5,6,15,16,19-tetrahydro-1H-7,10,11,14,21,24,25,28-tetraphenylene-2,2'-9,12,23,26-tetrasulfo-[c,m]-[1,6,15,20]-tetraazacyclooctacosane-[2,3,4,5,7,10,11,14,16,17,18,19,21,24,25,28] (I) as an acid dye for silk and wool. Indicated compound (I) shows affinity both to cellulose fibers and to protein and polyamide fibers and can stain mixed fabrics consisting of three fibers of different types.

EFFECT: valuable properties of dye.

2 dwg, 3 ex

FIELD: organic chemistry, dyes.

SUBSTANCE: invention relates to new arylenediamines that can be used as a direct and acid dye. Invention describes 4,4'-bis-(1-indenone-3-yl)-2,2'-disulfobiphenylene eliciting property of a direct and acid dye. Indicated compound (I) possesses property of a direct and acid dye and stains cotton, protein and polyamide fibers and mixed fabrics consisting of different fibers showing deep and intensive color.

EFFECT: valuable properties of dye.

1 dwg, 5 ex

The invention relates to organic dyes for dichroic light polarizers (DPS)

The invention relates to new compounds useful as an agent for tagging, more specifically, to new dyes, the absorption maximum of which lies at or near the red border of the visible spectrum

The invention relates to the field of chemical technology, in particular the reactions of synthesis, decomposition, addition, substitution, and may find application in the synthesis of inorganic and organic substances

FIELD: chemistry.

SUBSTANCE: method of producing amidoimides of alkenylsuccinic acid is carried out by reacting aminoamides, obtained by reacting industrial polyamines or a mixture of polyamines with butyric acid or isobutyric acid or oleic acid or stearic acid or stearine, at temperature of 160-190°C for 4-6 hours in molar ratio polyamine: acid of 1-1.1:1, with alkenylsuccinic anhydride, first at temperature of 25-29°C for 0.5 hours, then at 110-115°C for 0.5-1 hours and the obtained mixture is then held at 145-150°C for 3-4 hours. The molar ratio of alkenylsuccinic anhydride to aminoamide is equal to 1:1.1-1.4 and the process is carried out in the presence of industrial oil. The industrial polyamines are selected from diethylenetriamine or triethylenetetramine or N,N'-bis(β-ethylamino)piperazine or tetraethylenepentamine or ethylenediamine.

EFFECT: improved method of producing succinimide additives, wider range of additives and corrosion inhibitors.

5 cl, 2 tbl, 30 ex

FIELD: chemistry.

SUBSTANCE: amidoimides of alkenylsuccinic acid are produced by reacting aminoamides obtained by reacting polypropylene polyamines, selected from dipropylene triamine or tripropylene tetramine or tetrapropylene pentaamine or a mixture of polyamines or 1,2-diaminopropane, with butyric acid or isobutyric acid or oleic acid or 2-ethylhexenoic acid in molar ratio amine: acid of 1-1.15:1, with alkenylsuccinic anhydride first at temperature of 90-105°C for 1.2-1.8 hours and then at 162-165°C for 3.5-4 hours in the presence of industrial oil. Amidoimides of alkenylsuccinic acid can also be produced by reacting alkenylsuccinic anhydride with polypropylene polyamines with normal or isomeric structure, selected from dipropylene triamine or tripropylene tetramine or tetrapropylene pentaamine, or with a mixture of polyamines or with 1,2-diaminopropane in molar ratio 1:1-1.1, respectively at 140-148°C for 4-6 hours, followed by treatment of succinimide with butyric acid or isobutyric acid or oleic acid or 2-ethylhexenoic acid at 165-175°C for 6-8 hours in molar ratio succinimide: acid of 1:1, in the presence of a hydrocarbon solvent - industrial oil.

EFFECT: improved methods of producing a succinimide additive.

8 cl, 2 tbl, 34 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a technique of producing cis-1,4-polydienes by polymerising butadiene, isoprene or mixtures thereof in a medium of a hydrocarbon solvent in the presence of a rare-earth element based Ziegler-Natta catalyst. In the final stage of the polymerisation process, an α-olefin and maleic anhydride copolymer is added to the reaction mass in ratio of cis-1,4-polydiene to copolymer of 1:1·10-4 - 1·10-1.

EFFECT: improved properties of cis-1,4-polydienes, cold flow, dynamic viscosity and polydispersity.

2 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: described is a liquid graft polymer obtained using a method which involves reaction of a polymer of a C4-C7 monoolefin monomer and a C4-C14 multiolefin monomer which contains butyl rubber, in the presence of a material for conducting graft copolymerisation, which contains maleic anhydride, and a free-radical polymerisation initiator which contains an organic peroxide, wherein the liquid graft polymer has number-average molecular weight (Mn) from 150000 to 30000. Described is a vulcanised compound containing the described liquid graft polymer and a vulcanising agent based on a multi-functional amine. Described is a method of decomposing a non-liquid butyl polymer to a liquid butyl graft polymer, where the method involves reaction of a non-liquid butyl polymer of a C4-C7 monoolefin monomer and a C4-C14 multiolefin monomer which contains butyl rubber, in the presence of a material for conducting graft copolymerisation, which contains maleic anhydride, and a free-radical polymerisation initiator containing dicumyl peroxide, wherein the liquid graft polymer has number-average molecular weight (Mn) from 150000 to 30000.

EFFECT: liquid maleated butyl rubber is obtained.

16 cl, 2 tbl, 2 dwg, 10 ex

FIELD: chemistry.

SUBSTANCE: method of producing polyethylene succinimide involves a step for synthesis of alkenyl amber anhydride, a step for mixing the alkenyl amber anhydride with industrial oil, a step for mixing polyethylene polyamine with industrial oil and a step for synthesis of polyethylene succinimide. The novelty lies in that the step for synthesis of alkenyl amber anhydride, preliminary heating is carried out for 20-50 minutes, and holding at temperature 160-175°C is carried out for 50-60 minutes, the alkenyl amber anhydride is mixed with industrial oil in weight ratio 1:(0.70-0.79), polyethylene polyamine is mixed with industrial oil while heating to 100-106°C in weight ratio 1:(1.94-2.6), wherein preliminary mixing of the obtained solutions of alkenyl amber anhydride and polyethylene polyamine in industrial oil at the step for synthesis of polyethylene succinimide is carried out at temperature 90-110°C.

EFFECT: invention increases output of polyethylene succinimide and reduces power consumption of the process.

3 cl, 1 tbl, 3 ex

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