Barbarastrasse oligoadenylate as heat monomeric basis cured compositions and anaerobic composition based on them
(57) Abstract:Use: for sealing and fixing the threaded and smooth cylindrical joints, seal flanged connections subject to prolonged exposure to elevated temperatures. The inventive anaerobic composition comprising barbarastrasse of oligoadenylate General formula
H2CFOCOCH2RCH2OCOCFCH2< / BR>where 100 hours hydropeaking initiator, and 0.2 to 5.0 hours, the polymerization accelerator is 0.2 to 5.0 hours, the stabilizer of 0.002 to 0.2 h 2 S. p. F.-ly, 3 tables. The invention relates to the chemistry of polymers, namely, the cured compositions, such as heat-resistant anaerobic compositions, which are used for sealing and fixing the threaded and smooth cylindrical joints, seal flanged connections subject to prolonged exposure to elevated temperatures (400oC for at least 50 h, and the strength of the connection shall be not less than 5 N. m), as well as to new chemical compounds-carborundorum oligoadenylates General formula
< / BR>< / BR>used as heat-resistant Monomeric basis cured compositions.Known connections (application YAP 3;4
used as a Monomeric basis anaerobic compositions and compositions for coatings, cured by heating under the action of UV radiation.Anaerobic composition based on the specified connection, after curing in a narrow metal gap (bolt, nut) for 24 h at room temperature has time unscrewing 30,0 34,0 N. m, and after exposure to 180oC for 6 h and tested at the specified temperature 26,0 32,0 N. mCoatings on steel obtained by curing a monomer basis at a temperature of 150oC for 0.5 h or under the action of UV-irradiation, have a pencil hardness H-2H.Data on thermal stability of the compositions at 400oC in the patent are not given.Closest to the present invention is an anaerobic composition containing acrylate oligomer triethyleneglycoldinitrate, hydrophilicity initiator, a polymerization accelerator, a stabilizer (patent Germany N 2802360, CL 09 To 3/10, published. 1978).This composition has a viscosity of 28 180 SDR and the time of unscrewing after curing it into the narrow metal gap (pain nut) for 24 hours at room temperature 125 350 CT cm (12,5 35,0 Nm).LASS="ptx2">The set task is solved by synthesis carborundorum of oligopyrroles General formula
< / BR>where
< / BR>and the fact that the anaerobic composition comprising barbarastrasse oligopyrroles, hydrophilicity initiator, a polymerization accelerator and a stabilizer, in contrast to the known, contains barbarastrasse oligopyrroles General formula
< / BR>where
< / BR>in the following ratio, wt. hSpecified barbarastrasse oligopyrroles 100
Hydrophilicity initiator 0,2-5,0
The polymerization accelerator 0,2-5,0
The stabilizer 0,002 0,2
Barbarastrasse oligoadenylate General formula (I) are not described in literature. They are synthesized in the Institute of polymers and are used as heat-resistant Monomeric basis cured compositions for the first time.These compounds are produced by interaction of the acid chloride of 2-tarakanovas acid 1,7-bis(oxymethyl)-meta-carboran or 1,2-bis(oxymethyl)-ortho-carboran in the medium of organic solvent in the presence of an acceptor of hydrogen chloride triethylamine (Et3N). The synthesized compounds are high-boiling substances, soluble in diethyl ether, the Mr spectra.Example 1. Synthesis of bis-(2-forcricket)-meteorburn (product 1).Charged to the reactor 81,72 g (0.4 mol) of 1,7-bis (oxymethyl)-meta-carboran (ICD), 300 ml of diethyl ether, 95,48 g (0.88 mol) of acid chloride of 2-tarakanovas acid (HAPAC) and at 0-5oC, and stirring was added dropwise 96,96 g (0,48 mol. ) Et3N within one hour. The precipitation is filtered off, the reaction mass is washed with 5% aqueous solution of hydrochloric acid and then with water until neutral. After distillation in vacuum, diethyl ether get 131,16 g (94 from theory.) light yellow product 1 with the value of kinematic viscosity 6010-6m/s, n2D0= 1,5160, which is at +5oC during the day crystallizes (tPL32-35oC). Found (%): 31,28; F 10,67; 34,32. Calculated for C10H18B10O4F2(%): 31,03; F 10,91; 34,48.Range PMR 10% R-RA in CCL4, .m.D. was 4.42 (4H, och2), 5,44 D. D. (2HACH*2,2IHAHB3,4 Hz3IHAF 12.9 Hz), 5,73 D. D. (2HBCH2,2IHAHB3,4 Hz3IHBF 42,8 Hz).IR spectrum (cm-1):B-H2600,C=01760,C=C1670.
Example 2. Synthesis of bis-(2-thoracicoabdominal)-orthocarbonate (p the ether, 47,7 g (0.44 mol) HATAK and under stirring at 0-5oC was added dropwise 48,48 g (0.48 mol) Et3N within one hour. Subsequent selection operation carried out analogously to example 1. Get 66,27 g (95 from theory.) the crystalline product 2. Tpl.36-38oC. Found (%): 31,14; F 10,78; C 34,16. Calculated for C10H18B10O4F2(%): 31,03, F 10,91; C 34,48.Range of the MRP . M. D. 4,84 (4H, och2), 5,47 D. D. (2HACH*214,2IHAHB3,6 GS3IHAF 12.9 Hz), 5,76 D. D. (2HBCH2,3IHAHB3,6 Hz3IHBF 42,6 Hz).The IR spectrum similar to the spectrum of the product 1.The synthesized compounds are used as Monomeric fundamentals of anaerobic compositions (AK).As the polymerization accelerator in AK using N, N-dimethyl-para-toluidine (DMPT), di(hydroxyethyl)-para-toluidine (DGAT), o-benzosulfimide (OBSI), dibenzosuberone (DBSI). Note: W spin system AWH
As hydroperoxide initiator use the hydroperoxide has been studied (CCP), tertiary butyl (GATB). In the stabilizer is used 2,2,6,6-tetramethyl-4-oxopiperidin-1-oxyl (TMOP), malachite green (MOH), oxalic acid (SC).From table. 2 shows that the proposed anaerobic composition has the following values of M1/MpNm (in parentheses on the prototype):
after curing of the composition on the samples of the bolt-nut at room temperature for 24 h 28,5 40,0/39,5 60,0 (39,5/55,0);
after heating the samples at 400oC for 50 and 100 hours, and tested them at 400oC 17,5-28, and testing them at room temperature 40,5 51,0/29,0 and 45,5 45,0 55,0/27,0 42,0 respectively (27,0/a 0.5, 31.0/0).Thus, the use of new synthesized carborundorum of oligopyrroles General formula (I) as a monomer basis anaerobic compositions can improve the strength of the hardened anaerobic compositions after prolonged exposure 400oC.The increase in the number hydropeaking polymerization initiator and polymerization accelerator more than 5 wt. hours at 100 wt.h. monomer leads to premature polymerization of the composition during storage.The use of these components is less than 0.2 wt. hours at 100 wt.h. monomer dramatically reduces the ability of the AK dried at room temperature in a threaded connection. Increasing the amount of stabilizer is more than 0.2 wt. am also leads to a decrease in the rate of curing and reducing its content of less than 0.002 wt. PM affects the stability of AK during storage.Below is shown the possibility of using synthesized carborundorum of oligopyrroles as heat Monomeric bases compositions for coatings, cured by heating under the action of UV-irradiation and see their properties.Example 9. 2. The composition is prepared by mixing (wt. PM): 100 product 1 and 1.0 peroxide be the Les which they receive a coating thickness of 60 Myron.Example 10. The composition prepared according to example 9, only use instead of 100 wt. including product 1 the same amount of product 2. After curing of the composition at 150oC for 1 h on aluminium receive a coating thickness of 70 μm.Example 11. The composition is prepared by mixing (wt. PM): 100 product 1 and 3.0 benzylacetone as photoinitiator. The composition applied to the glass surface and subjected to UV irradiation (lamp CES-400, the distance from the radiation source to the surface 15 cm). After 15 to get a solid coating thickness of 100 microns.Example 12. The composition is prepared by mixing (wt. PM): 66,7 product 1, 33.3 product 2 and 3.0 benzylacetone. Composition utverjdayut analogously to example 11. After 15 to get a solid coating thickness of 110 microns.For comparison, we have tested the properties of the coatings obtained by curing known carborundorum of oligopyrroles formula (III), in particular bis(acryloyloxy)-meteorburn (BAMC), when heated under the action of UV radiation.Example 13 (for comparison). The composition is prepared by mixing (wt. PM): 100 BANK and 1.0 benzoyl peroxide. The coating thickness of 70 μm was prepared as in example 9.Example 14 (comparison). Whom will gorhaut UV irradiation in example 121. After 15 second exposure, the composition remains liquid. After 60 seconds, the result is a floor with an upper liquid layer. The thickness of the coating after removal of the liquid layer by treatment with acetone 50 microns.The resulting coatings determine the adhesion method of lattice cuts (GOST 15140-78), as well as the loss of mass when heated in air in a dynamic mode (5oC/min) from 20 to 900oC derivatograph Q-1500D system Paulik-Paulik and Erdei (Hungary). The weight of the portion 50 mg.The results of the tests are presented in table. 3.From table. 3 shows (examples 9, 10 and 13 for comparison; examples 11, 12 and 14 for comparison) that the coatings obtained on the basis of the synthesized compounds of formula (I) have a higher adhesion and heat stability as compared with the coatings on the basis of known compounds of the formula (III).Thus, the synthesized barbarastrasse oligoadenylate can be used as heat-resistant Monomeric basis cured compositions. 1. Barbarastrasse oligoadenylate General formula
< / BR>where R-CB10H10C-,
< / BR>as heat Monomeric basis cured compositions.2. Anaerobic comp, trichomania the fact that as acrylate oligomer contains barbarastrasse oligopyrroles General formula
< / BR>where R-CB10H10C-,
< / BR>in the following ratio, wt.h.Barbarastrasse oligopyrroles 100
Hydrophilicity initiator 0,2 5,0
The polymerization accelerator 0,2 5,0
The stabilizer 0,002 0,2
< / BR>where n 5-29,
Me Ca, Ba, Cd, Zn, Mg, Cu, Pb
FIELD: polymerization processes.
SUBSTANCE: polymer containing at least one boronate substituent or its precursor is prepared by controlled living radical polymerization of monomers in presence of living chain growth control agent, in particular sulfur-containing compound having S-C(S)- bond, said monomers being represented by (i) at least one monomer having at least one boronate substituent or its precursor and selected from group consisting of acryloylbenzeneboronic acid, methacryloylbenzeneboronic acid, vinyl-4-benzeneboronic acid, 3-acrylamidophenylboronic acid, 3-methacrylamidophenylboronic acid, individually or in mixture, or in salt form, and (ii) at least having no boronate substituents nor their precursors. Also described is associate containing above-defined polymer with at least one compound ligand having at least one group capable of forming complex with the polymer containing at least one boronate substituent or its precursor.
EFFECT: narrowed molecular mass distribution and uniformity along the polymer chain.
FIELD: chemistry of high-molecular compounds, chemical technology.
SUBSTANCE: invention relates to a method for synthesis of polytriesters of boric acid and phenol. Proposed polytriesters of boric acid and phenol are synthesized by the complete esterification reaction of boric acid with phenol resulting to formation of a mixture containing triphenylborate followed by distillation of mixture under vacuum. Hydrocarbon forming azeotropic mixtures with water - benzene, toluene and xylene are used as solvents. Then isolated triphenylborate is polymerized with trioxymethylene or paraformaldehyde using boron trifluoride etherate as a catalyst. Also, invention claims polytriester of phenol and boric acid synthesized by a method above said. Synthesized polymers represent thermostable boron-containing phenolformaldehyde resins that are easily soluble in polar solvents. Synthesized compounds can be used in industry instead phenolic resins for conferring thermostable properties for articles.
EFFECT: improved method of synthesis, valuable properties of ester.
2 cl, 1 tbl, 2 ex
SUBSTANCE: invention concerns epoxy binding agent for obtaining fiberglass on the basis of reinforcing filler for glass fiber cloth, glass fiber blanket, glass fiber roving etc, applied mainly in construction reinforcement applied under effect of aggressive media, and in obtaining high-strength fiberglass for various engineering, shipbuilding industries etc. Binding agent includes the following components, wt %: 56.11-56.42 of ED-22 epoxy resin, 42.10-42.29 of isomethyltetrahydrophthalic anhydride, 0.79 of UP-606/2 2,4,6-tris(dimethyl)phenol, 0.50-1.00 of polytriphenyl ether of boric acid.
EFFECT: enhanced physical and mechanical properties of binding agent, chemical resistance to aggressive media, and obtaining homogeneous and pore-free monoliths after thermal hardening.
2 tbl, 3 ex
SUBSTANCE: invention relates to a method of hardening organoboron polymers used in the industry of heat-resistant composite materials. Described is a method of hardening polymethylene-p-triphenyl ether of boric acid at 185-195°C for 2-2.5 hours with a sulphur curing system, with the following composition of components, pts. wt: sulphur - 26.9 - 28.6; thiuram - 11.6-12.3; zinc oxide - 3.9-4.2 and captax - 2.0-2.3 per 100 pts. wt polymethylene-p-triphenyl ether of boric acid.
EFFECT: proposed method avoids release of gas and gaseous products of hardening and therefore improves physical and mechanical properties of the friction product.
1 cl, 6 ex
SUBSTANCE: disclosed are polyboron-phenyl siloxanes of general formula [(C6H5SiO1.5)x(BO1.5)]n, which contain repeating units: , where x ranges 2.0 to 3.6; n≥17. Disclosed also is a method of producing said polyboron-phenyl siloxanes, involving reaction of an organosilicon compound with boric acid, characterised by that the organosilicon compound used is polyphenyl siloxane, and synthesis of end products is carried out by mechanochemical activation of a mixture of polyphenyl siloxane and boric acid in molar ratio Si/B from 1:1 to 3:1, frequency of mechanochemical activation of 10 Hz, ratio of the mass of the nozzle to the mass of the payload equal to 1.8, and activation time of 1-5 minutes, followed by separation of the formed polyboron-phenyl siloxanes.
EFFECT: obtaining novel polyboron-phenyl siloxanes with a given ratio and a cheap, environmentally friendly and fast method for production thereof is provided.
9 cl, 9 dwg, 1 tbl, 14 ex
SUBSTANCE: claimed is a method of obtaining oligoborosilazanes by the interaction of oligosilazanes, which do not contain alkyl radicals at a nitrogen atom, with an aminoborane complex, which does not contain alkyl radicals at a nitrogen atom, with the ratio of silazane to a boron-containing modifier from 3 to 18, with carrying out the process at a temperature of 40-140°C in a mixture of toluene with diglyme or benzene with diethyl ether with the molar ratio from 1:1 to 1:33.
EFFECT: method makes it possible to obtain oligoborosilazanes with the given molecular weight with high output, which is reached due to the step-by-step thermal processing of the reaction mixture at an increased temperature.
2 cl, 4 tbl, 13 ex
SUBSTANCE: method is proposed for the preparation of oligobosilazanes by the interaction of oligosilazanes containing NH and Si-H groups, which are organosilicon compounds of the silazane class that do not contain alkyl radicals at the nitrogen atom and boron-containing modifiers with BH groups that do not contain alkyl radicals at the nitrogen atom, in a solvent mixture, characterized in that the oligobisilazanes are prepared in two stages, the first of which involves dissolving aminoborane in an N-methylcyclosilazane medium selected from [R1R2Si-NR3]n, where R1=H, R2=Me, H; R3=Me; n=3, 4, at molar ratios of N-methylcyclosilazane to aminoborane from 0.60 to 2.18 and a Si/B ratio of 2.40 to 6.55 at a temperature of 90-120°C for 0.5-2.0 hours to form a boron-containing composition which is an adduct of aminoborane with N-methylcyclosilazane, and in the second stage, the boron-containing composition interacts with an oligosilazane selected from oligoorganosilazanes, organocyclosilazanes and disilazanes in various ratios, by heat treatment in an inert gas atmosphere (nitrogen, argon) at 90-140°C for 3.5-8.0 h. When aminosilane is added to oligosilazane, a preliminary heat treatment of the reaction mixture is carried out at 60-80°C in an ammonia medium.
EFFECT: proposed method is carried out in a controlled mode without the use of high-temperature solvents and allows to obtain oligobosilazanes with improved thermal and oxidative stability.
2 cl, 2 dwg, 2 tbl, 8 ex
FIELD: polymer materials.
SUBSTANCE: invention relates to novel liquid molding compositions comprising water-soluble or water-foaming polymer, which can be employed to improve water and moisture resistance as well as for waterproofing operation, for instance of waterproofing of cables. Composition contains water, water-soluble or water-foaming organic polymer obtained from monomer mixture containing 25 to 90 wt % of nonomer(s) selected from group including (meth)acrylamide and (meth)acrylic acid or salts thereof; 10 to 75 wt % of nonomer(s) selected from group including C8-C30-alkylethoxylated (meth)acrylamides, C8-C0-alkyl(meth)allyl ethers and C8-C30-alkylethoxylated (meth)allyl ethers; and water-miscible organic volatile liquid. Polymer is present in the form of discrete particles with average cross dimension below 10 μm. Invention further provides a method for improving water and moisture resistance of articles and/or preventing introduction of water into interior of article by way of contacting this article with above-indicated composition. Method of imparting waterproofing to outside or internal components of a cable comprises contacting at least one internal component with liquid molding composition. Invention allows preparation of composition capable of protecting fiber-optic cable.
EFFECT: enhanced waterproofing properties.
15 cl, 2 tbl, 11 ex
FIELD: hermetic based on law molecular siloxane rubber, in particular sealing composition.
SUBSTANCE: invention relates to sealing composition vulcanized by reaction with air moisture. Claimed rubber-based composition comprising zinc oxide, ethyl silicate, and diethylaminomethyltriethoxysilane, contains additionally pulverized grinded quartz. As a variant hermetic also contains chalk and/or dolomite. Composition of present invention is useful in sealing of various conjunctions operating in wide temperature limits where oil and gasoline resistance is required.
EFFECT: hermetic with low-cost components and excellent in operating characteristic.
1 cl, 2 tbl, 7 ex
FIELD: chemical technology.
SUBSTANCE: invention relates to a cross-linking binding composition based on an aqueous base comprising (A) an aqueous dispersion of hybrid resin based on polyester-polyacrylate that comprises 50-90 wt.-% of polyester and 10-50 wt.-% of polyacrylate. Hybrid resin is prepared by grafting the composition of unsaturated monomers polymerized by radical mechanism on partially unsaturated hydroxy-functional polyester; and (B) organic polyisocyanate wherein partially unsaturated hydroxy-functional polyester prepared by reaction of mixture of polycarboxylic acid and, optionally, monocarboxylic acids with one or some (cyclo)aliphatic alcohols wherein 0.5-6 mole% of acids and/or alcohols show the unsaturation level of ethylene type. The composition of unsaturated monomers polymerized by radical mechanism comprises a mixture of hydrophobic and hydrophilic monomers. Also, invention relates to a method for preparing composition used for covers comprising above said an aqueous binding composition and substrate with applied cross-linked cover prepared by applying such composition for cover. Invention provides preparing the composition with retaining exploitation indices as result of excessive foam formation and differing with acceptable values of working life and hardening rate.
EFFECT: valuable properties of composition.
16 cl, 3 tbl, 19 ex