Method of obtaining polyphenylene ether ketone oxymate
SUBSTANCE: described is a method of obtaining polyphenylene ether ketone oxymate, consisting in the interaction of dioxymate anions of 4,4'-diacetyldiphenyloxide with 4,4'-dihalogenbenzophenone at higher temperatures in the aprotonic dipolar solvent dimethylsulphoxide, characterised by the fact that the synthesis of polyphenylene ether ketone oxymate is carried out in two stages: at the first stage with the reaction of potassium dioxymate of 4,4'-diacetyldiphenyloxide with 4,4'-dichlorobenzophenone with a molar ratio of 1:0.5 and the concentration of a solution C=1 mol/l in terms of dioxymate for 1 hour at a temperature of 165°C in the presence of a solid powder-like KOH obtained is a dioxymate anion of the following structure -O-N=C(CH3)-C6H4-O-C6H4-C(CH3)=N-O-C6H4-CO-C6H4-O-N=C(CH3)-C6H4-O-C6H4-C(CH3)=N-O-, at the second terminating stage of the process a mixture of 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone and crushed and annealed K2CO3 in molar ratios of 0.5:0.005:0.15, counted per 1 mol of the initial diketoxime of 4,4'-diacetyldiphenyloxide, in a water-free DMSO, with an additional volume of the water-free DMSO being taken in such an amount that the concentration of the solution by each of the monomers at the second oligopolymer stage of the synthesis becomes equal to 0.5 mol/l, the total time of carrying out the reaction is 6 hours at a temperature of 165°C.
EFFECT: intensification, optimisation and cheapening of the process of obtaining polyphenylene ether ketone oxymate.
The invention relates to a method for simple aromatic polyesters by the reaction of nucleophilic substitution in aprotic dipolar solvents (ADPR), particularly to a method of producing polymers containing in the main chain between the phenyl nuclei ether linkages, keto groups and ketoxime fragments.
Known polyphenylenevinylene by RF patent no.2466153 simple link:
the viscosity of 0.4-0.5 DL/g, a molecular mass MW40800-51000.
It is obtained in anhydrous dimethyl sulfoxide (DMSO) in collaboration equimolar quantities (0.5 mol/l) 4,4'-diftorbenzofenon and potassium of dioxamate 4,4'-diacetyldiphenylurea at a temperature of 165°C. according to the following scheme:
The disadvantages of this method of production is the high cost 4,4'-diftorbenzofenon that affects the value of polyphenylenevinylene.
The objective of the invention is to intensify, optimization and reduce the process of getting polyphenylenevinylene based dihalogen-benzophenone (4,4'-dichloro - 4,4'-differenzierung) and potassium of dioxamate 4,4'-diacetyldiphenylurea with preservation of the physical-mechanical characteristics inherent in this is the polymer.
The method is that the reaction of interaction of potassium dioxalate 4,4'-diacetyldiphenylurea with dehalogenation in dimethyl sulfoxide (DMSO) (tKip=189°C) is conducted as a continuous process in two stages.
At the first stage of the process from digitoxin 4,4'-diacetyldiphenylurea and features of non-CON (molar ratio 1:2), we obtain the solution of potassium dioxalate 4,4'-diacetyldiphenylurea in anhydrous DMSO. The reaction of condensation of potassium dioxalate 4,4'-diacetyldiphenylurea with 4,4'-dichlorobenzophenone (molar ratio 1:0.5) with carry, when the concentration of the solution of potassium to dioxamate 4,4'-diacetyldiphenylurea 1 mol/L. After azeotropic distillation of water the reaction is finished after 1 hour at 165°C., thereby forming oximetry dianion the following structure:
-O-N=C(CH3)-C6H4-O-C6H4- (CH3)=N-O-C6H4-CO-C6H4-O-N=C(CH3)-C6H4-O-C6H4- (CH3)=N-O-.
At the second stage of the process, add a mixture of 4,4'-diftorbenzofenon, 4,4'-dichlorobenzophenone and K2CO3(crushed and calcined), in a molar ratio of 0.5:0,005:0.15 in terms of 1 mol of the original digitoxin 4,4'-diacetyldiphenylurea in anhydrous DMSO (additional volume of anhydrous DMSO is taken from the calculation that the concentration of rest the RA for each of the monomers in the second oligoprimers the synthesis phase will be equal to 0.5 mol/l). Thus, the total molar ratio digitoxin 4,4'-diacetyldiphenylurea, mixtures of 4,4'-debtor - and 4,4'-dichlorobenzophenone and CON, TO2CO3the sum of the two phases was 1:1,005:2:0,15. The formation of the polymer after azeotropic distillation of the water - 6 hours. The polymer has a reduced viscosity ηCR=0.5 to 0.6 DL/g, the molecular mass MW≈51000-56000.
The method is illustrated by the following examples:
Example 1. The synthesis was performed in chetyrehkolkoy flask, purged with dried and purified from oxygen, nitrogen, equipped with a stirrer, a thermometer, a tube for supplying nitrogen and nozzle Dean-stark for azeotropic distillation of water. In the course of the synthesis temperature was maintained with an accuracy of ±0,2°C. In the flask under vigorous stirring was dissolved 2,844 g (0.01 mol) digitoxin 4,4'-diacetyldiphenylurea in 10 ml of dimethyl sulfoxide (reagent-grade) (this corresponds to C=1.0 mol/l in digitoxin), was added 1,122 g (0.02 mol) features of non-powdered KOH (reagent-grade).
For azeotropic distillation formed during the reaction water in the flask was added dry toluene, the volume of which was taken from the calculation of its permanent return from the trap Dean-stark in the reaction flask, which leads to its economy. After azeotropic distillation of water and residues of toluene at a temperature of 150°C in flask was loaded 1,2556 g (0,005 mol) of 4,41-dichlorobenzophenone. Those which the temperature was raised to 165°C., and the reaction mixture was stirred at this temperature for 1 hour.
Further, in the second stage of the reaction flask was added a mixture of 0,2073 g (0,0015 mol) pre-calcined and crushed To2CO3(CHP), 1,091 g (0,005 mol) 4,4'-diftorbenzofenon and 0,0126 g (0,00005 mol) 4,4'-dichlorobenzophenone in 10 ml of DMSO (CHP). Thus the concentration of the reaction mixture at the second oligo-polymer phase in terms of digitoxin 4,4'-diacetyldiphenylurea was 0.5 mol/L. Total molar ratio digitoxin 4,4'-diacetyldiphenylurea, mixtures of 4,4'-debtor - and 4,4'-dichlorobenzophenone and CON, TO2CO3the sum of the two phases was 1:1,005:2:0,15. In the second stage, the temperature was maintained at 165°C with accuracy ±0.2°C. the formation of the polymer after azeotropic distillation of the water - 6 hours.
The resulting polymer was besieged in acidified distilled water, washed with distilled water, dried with a gradual increase in temperature to 100°C. the polymer was Then dried under vacuum. Received 4.4 g of polyphenylenevinylene (exit 96%) with ηCR=of 0.64 DL/g
Example 2. As in example 1, except that the reaction was carried out without adding To2CO3. Got to 4.16 g of polyphenylenevinylene (output - 90%) with a viscosity ηCR=value of 0.52 DL/g
Example 3. As in example 1, except that the reaction was conducted for 5 hours. Received 4.3 g of polyphenylenevinylene is one of (output - 93%) with a viscosity ηCR=of 0.45 DL/g
Polyphenylenevinylene dissolved in chloroform, dimethylsulfoxide, dimethylacetamide.
The structure of the synthesized polymer is confirmed by elemental analysis and IR and PMR spectroscopy.
Elemental analysis data:
Found. %: C=75,61; H=4,89; N=OF 5.92.
Calculated for C29H22N2O4IN %: C=75,32; N=4,76; N=6,06.
In the IR spectra of the polymers has an absorption band in the region of 690 cm-1(aromatic ring), 1665 cm-1(>=0), 1365 cm-1(-CH3sym.), 1406-1412 cm-1corresponding to C=N-groups, and 1242 cm-1corresponding connection (Ph O-Ph).
According to PMR-spectroscopy, for digitoxin observed signals in the region of 2.3 M. D. (6N, S., CH3C=N), 1.8 m D. (H, s, C=N-OH). In polyphenyleneoxides signal in the region of 2.3 M. D. (6N, S., CH3C=N) remains, while the signal in the region of 1.8 M. D. (H, s, C=N-OH) disappears, which indicates that the bond formation (N-O-Ph).
Thus, we propose a new method for the synthesis of polyphenylenevinylene, allowing to reduce twice the consumption of expensive 4,4'-di-fermentation, replacing it with a cheaper 4,4'-dichlorobenzophenone.
In addition, in the reaction can be used potassium hydroxide, containing approx the si carbonate, if you know the percentage. In this case, the allocation for the required amount of KOH and2CO3.
The method of receiving polyphenylenevinylene, which consists in the interaction dioxamate anions 4,4'-diacetyldiphenylurea with 4,4'-dehalogenation at elevated temperatures in an aprotic dipolar solvent, dimethyl sulfoxide, characterized in that the synthesis of polyphenylenevinylene carried out in two stages: the first stage reaction of potassium dioxalate 4,4'-diacetyldiphenylurea with 4,4'-dichlorobenzophenone at a molar ratio of 1:0.5 and the solution concentration C=1 mol/l for dioxamate for 1 hour at a temperature of 165°C. in the presence of solid powdered KOH receive dioxamate anion of the following structure:
on the second final stage of the process, add a mixture of 4,4'-diftorbenzofenon, 4,4'-dichlorobenzophenone and crushed and calcined To2CO3in a molar ratio of 0.5:0,005:0.15 in terms of 1 mol of the original digitoxin 4,4'-diacetyldiphenylurea in anhydrous DMSO, and the additional volume of anhydrous DMSO is taken from the calculation that the concentration Rast is the PR for each of the monomers in the second oligoprimers the synthesis phase will be equal to 0.5 mol/l, the total time of the reaction for 6 hours at a temperature of 165°C.
SUBSTANCE: group of inventions relates to cyanate ester-based polymer compositions which are modified with polysulphones, reinforced with fibrous filler and are used for producing structural polymer composite materials with operating temperature of up to 200°C and articles from said materials, which can be used in aviation, aerospace, motorcar, ship-building and other industries. Disclosed is a cyanate ester-based polymer composition for polymer composite materials, which comprises a thermoplastic modifier and a curing agent, wherein the modifier used is a thermoplastic selected from polysulphone, polyestersulphone, polyarylsulphone or mixtures thereof, and the curing agent used is an amine catalyst. The invention also discloses a prepreg which includes said polymer composition and fibrous filler, and an article made from said prepreg by moulding.
EFFECT: producing a thermoplastic-modified cyanate ester-based polymer composition which is characterised by homogeneity of the composition, which enables prepreg processing thereof and enables to obtain moisture-proof articles from polymer composite materials made therefrom, with improved thermomechanical properties, a coefficient of variation of physical and mechanical properties and good retention of strength properties at high temperatures.
7 cl, 12 dwg, 3 tbl
SUBSTANCE: described are compositions for hair care, containing a β-aminoether compound in a cosmetically acceptable carrier, such as a spray or cream. Described is a compound of formula
in which n represents an integer number from 1 to 100; Z and Z′ together with atoms, which they are bound to, represent acrylate, methacrylate or amino-terminal groups; R2 represents C1-C20alkyl, possibly substituted with: hydroxyl, siloxyl, C1-C20alkoxygroup, substituted with hydroxyl, amino-C1-C20alkyl, substituted with from one to two hydroxyl groups, C6-C10aryl, substituted with C1-C20alkoxygroup, or C5-C10heteroaryl, containing one nitrogen heteroatom; and A contains a rubber fragment, which has a molecular weight in the range from approximately 1000 g/mol to approximately 10000 g/mol, selected from the group, consisting of butadiene and isoprene units. Also described is a cosmetic composition for hair, containing the said compound and cosmetically acceptable carrier. The application of the said cosmetic composition for scalp care is described.
EFFECT: obtaining the cosmetic composition for hair, increasing adhesion of hairs to each other, adding volume, texture and shape to the hair.
10 cl, 4 tbl, 17 ex
SUBSTANCE: invention relates to compositions, containing an active substance. Described is a composition for the active substance delivery, which contains: a) at least, one block-copolymer, containing, at least, one poly(2-oxazoline) block A, consisting of repeating units of formula where RA stands for a hydrocarbon group, which can be optionally substituted with -OH, -SH, -COOH, -NR'2, -COOR', -CONR', -CHO, where R' stands for H or C1-3 alkyl, and RA is selected in such a way that a repeating link of formula (I) is hydrophilic; and at least one poly(2-oxazoline) block B, consisting of repeating units of formula (II), where RB stands for a hydrocarbon group, which can be optionally substituted with halogen, -OH, -SH, -COOH, -NR''2, -COOR'', -CONR'', -CHO, where R'' stands for H, alkyl or alkenyl, and RB is selected in such a way that a repeating link of formula is more hydrophobic than the repeating link of formula (I); and (b) one or more active substances. Also described is application of a copolymer for solubilisation of the active substance in water or a water solution.
EFFECT: described copolymers serve as a universal medication delivery system with high loading.
12 cl, 6 dwg
SUBSTANCE: described is a method of producing a highly purified disinfectant which contains polyhexamethylene guanidine hydrochloride, characterised by that flush water from production of polyhexamethylene guanidine hydrochloride in solid form is used. The flush water is mixed with 25% NaCl solution in ratio of 1:1 (polyhexamethylene guanidine hydrochloride solution with impurities: NaCl solution) while stirring constantly for 1 hour at temperature in the range of 50-60°C. Stirring is stopped and the mixture is cooled to 5°C, thereby dividing the mixture into two parts; the bottom part is drained, neutralised and sent for recycling and the top part containing up to 60-70% polyhexamethylene guanidine hydrochloride is further diluted to 50% with an aqueous solution of quaternary ammonium salts (QAS) to QAS concentration of not higher than 5%.
EFFECT: extracting highly purified, concentrated high-molecular weight polyhexamethylene guanidine hydrochloride from flush water, reducing the amount and toxicity of waste water, improving disinfecting properties and increasing output of the commercial-grade product when producing polyhexamethylene guanidine hydrochloride in solid form, reducing cost.
1 cl, 1 ex, 2 tbl
SUBSTANCE: method of producing a disinfectant involves first carrying out polycondensation of hexamethylenediamine and guanidine hydrochloride. Polycondensation starts with preparation of a reaction mass in form of a suspension of crystalline guanidine hydrochloride in molten hexamethylenediamine, taken in ratio of 1:(1-1.5). The suspension is obtained by gradually adding crystalline guanidine hydrochloride, preheated to temperature of 90-120°C, to molten hexamethylenediamine and then stirring. The reaction mass is then heated in steps: holding for 4 hours at 120°C, then for 8 hours at 160°C and then for 3 hours at 180°C. Temperature is then gradually raised to 210°C at a rate of 3-4°C/h. The reaction mass is then subjected to vacuum treatment and cooled.
EFFECT: method enables to reduce toxicity of the end product and obtain a polymer with the required molecular weight and sufficient purity without washing steps.
SUBSTANCE: described is a method of producing polyguanidines by polycondensation of a guanidine salt with a diamine while heating, characterised by that polycondensation is carried out in the presence of an organic acid or a mixture of organic acids and heating is carried out in steps as follows: at the first step at 120-130°C for 0.5-1 hour; at the second step at 150-160°C for 3.5-4 hours; at the third step at 170-180°C for 0.5-1.5 hours.
EFFECT: improved method.
11 cl, 2 tbl, 4 ex
SUBSTANCE: present invention relates to polyphenylene ether ketone oximates, as well as a method for production thereof. An elementary unit of said polyphenylene ether ketone oximate has the formula: [-O-N=C(CH3)-C6H4-O-C6H4-C(CH3)=N-O-C6H4-CO-C6H4]n. The polyphenylene ether ketone oximate has reduced viscosity of 0.4-0.5 dl/g and molecular weight ranging from 40800 to 51000. Polyphenylene ether ketone oximate are obtained by non-equilibrium nucleophilic polycondensation of difluorodiphenyl ketone with diacetyl diphenyl oxide diketoxime. The reaction is carried out in dimethyl sulphoxide for 6 hours at 165°C, with reaction of equimolar amounts of potassium diacetyl diphenyl oxide dioximate with 4,4'-difluorobenzophenone. The molar ratio 4,4'-difluorobenzophenone: 4,4'-diacetyl diphenyl oxide diketoxime: KOH: K2CO3 is equal to 1:1:2:0.15.
EFFECT: obtained polymer has improved mechanical properties, heat-resistance, and also has a system of properties which are characteristic for both polyether formal oximates and polyether ketones.
2 cl, 3 ex
SUBSTANCE: present invention relates to a method of producing oligo-3,3-bis(azidomethyl)oxetane which is used as a hydroxyl-containing compound for producing energy-intensive polyurethane thermoplastic elastomers. The method involves cationic polymerisation of 3,3-bis(chloromethyl)oxetane in methylene chloride at 20-35°C in the presence of 1-10 wt % boron trifluoride etherate and a diatomic alcohol in molar ratio of 1:(5-15) to 3,3-bis(chloromethyl)oxetane. Further, the intermediate oligo-3,3-bis(chloromethyl)oxetane is separated in finely dispersed form, for which at the end of polymerisation, an organic solvent is added to the reaction mass, methylene chloride is evaporated and oligo-3,3-bis(chloromethyl)oxetane is precipitated with water. Sodium azide is then added to the obtained finely dispersed oligo-3,3-bis(chloromethyl)oxetane in a medium of an organic solvent at 90-130°C in the presence of 0.5-3 wt % tetrabutylammonium bromide.
EFFECT: highly efficient method of producing oligo-3,3-bis(azidomethyl)oxetane and high output of the end product.
5 cl, 1 tbl, 7 ex
SUBSTANCE: disclosed are oligomers based on hexamethylene guanidine derivatives of formula (I), where R denotes or , n1, n2 and n3 equal 1-3, z equals 0.15-1.10; with molecular weight distribution Mw/Mn from 5.4 to 9.3, with weight-average molecular weight Mw 3800-6300 and number-average molecular weight Mn 600-1100. Disclosed also is a disinfectant containing disclosed oligomers as an active component, as well as use thereof.
EFFECT: disclosed compounds have improved and steadily reproducible disinfectant properties, low toxicity and corrosiveness.
4 cl, 1 dwg, 6 tbl, 8 ex
FIELD: medicine, pharmaceutics.
SUBSTANCE: inventions relate to field of medicine, veterinary, agriculture and pharmacology and deals with biocidal polyguanidine of formula Acid or (1), method of its obtaining and based on it biocidal composition.
EFFECT: inventions make it possible to obtain biocidal polyguanidine with high antimicrobial activity with wide spectrum of action.
4 cl, 14 tbl, 17 ex
SUBSTANCE: aromatic polyethersulfone ketones of formula , where n=1-20; z=2-100; ; ; ; , are described.
EFFECT: aromatic polyethersulfone ketones are characterised by higher indices of fire-, heat-, and thermal stability and mechanical characteristics.
SUBSTANCE: present invention relates to block-copolyesters. Described are aromatic block-copolyesters of formula where n=1-20; m=20-50; z=2-50.
EFFECT: obtaining high-strength, heat- and fire-resistant block-copolyesters.
1 tbl, 6 ex
SUBSTANCE: claimed invention relates to aromatic polyethers. Described are the aromatic polyethers of formula where
EFFECT: obtaining aromatic polyethers with high indices of fire-, heat- and thermal resistance.
1 tbl, 9 ex
SUBSTANCE: claimed invention relates to aromatic polyethers. Described are the aromatic polyethers of formula where n=2-20; z=2-100;
EFFECT: obtaining aromatic polyethers with high indices of fire-, heat- and thermal resistance.
1 tbl, 6 ex
SUBSTANCE: described are polyarylene ether ketones of formula
, where n=1-20; m=2-50.
EFFECT: obtaining polyarylene ether ketones having high heat-, fire- and chemical resistance, as well as improved mechanical properties.
3 tbl, 3 ex
SUBSTANCE: invention relates to a heat-resistant wire or cable with improved operational properties designed for use in demanding or extreme conditions, for example in well drilling or field development, in industrial, military aerospace, naval fields, as well as in the motorcar, railway and public transport. Such cables can be subjected to extreme temperatures, corrosive substances or atmospheres or fire. The wire or cable comprises a conductor and a polymer sheath consisting of an internal and an external layer. One layer is tape made of polyetheretherketone (PEEK) and has thickness of 5-150 mcm. The second layer is fire-resistant and is made of a siloxane polymer or a polymer based on silicon dioxide as a polymer matrix. The PEEK tape can be combined with a mica layer or a layer which is polymer tape with mica particles.
EFFECT: invention increases fire-resistance of the sheath, its flexibility and resistance to mechanical stress, enables to obtain a wire or cable with a lower weight and diameter.
12 cl, 5 dwg
SUBSTANCE: invention relates to polyethrketones. Claimed is fireproof unsaturated polyetherketone of formula where z=21-100.
EFFECT: fireproof unsaturated polyetherketone possesses high values of oxygen index, high mechanical and thermal properties.
SUBSTANCE: present invention relates to high-molecular weight compounds, particularly block copolyesters. Described are block copolyesters of formula where n=1-20; m=2-50; z=2-30.
EFFECT: obtaining block copolyesters with improved thermal and mechanical properties.
1 tbl, 3 ex
SUBSTANCE: claimed invention relates to block-copolyether formals. Described are the block-copolyether formals of formula
, where n=1-20; m=2-50; z=2-30.
EFFECT: obtaining the block-copolyether formals possessing high heat and thermal stability, as well as high mechanical characteristics.
1 tbl, 3 ex
SUBSTANCE: described are aromatic block-copolyethers of formula where n=1-20; m=2-50; z=2-30.
EFFECT: obtaining block-copolyethers, which possess high heat- and thermal resistance, high mechanical characteristics.
SUBSTANCE: invention relates to a redox ammoximation method, wherein a ketone or aldehyde reacts with ammonia and oxygen in the presence of a catalyst, where the catalyst is a redox catalyst based on aluminophosphate, having a qualitative general formula M1M2AlPO-5 (I), where M1 denotes at least one transition metal selected from Co(III), Mn(III), Fe(III), Cr(VI), Cu(III), V(V) and Ru(III); M2 denotes a metal selected from Ge(IV), Sn(IV), Re(IV), V(IV) and mixtures thereof; M1 and M2 are different from each other; and a certain portion of phosphorus atoms in the structure of the type M1M2AlPO-5 is substituted with atoms of M2. Also disclosed is a redox ammoximation catalyst.
EFFECT: providing a selective ammoximation method.
11 cl, 5 tbl, 6 dwg, 16 ex