Hydrogenation of polyester oligomers containing terephthalic and isophthalic acid residues

FIELD: polymer production.

SUBSTANCE: invention provides a method for hydrogenation of polyester oligomers containing terephthalic and isophthalic acid residues, which are thereby converted into 1,4-cyclohexanedicarboxylic acid residues. Also proposed is a method for preparing polyesters containing 1,4-cyclohexanedicarboxylic acid residues by hydrogenating first polyester oligomer containing terephthalic acid residues followed by reacting thus obtained oligomer with one or several polyester-forming reagents to form higher molecular weight polyester. Another embodiment of invention involves hydrogenation of polyester oligomers containing isophthalic acid residues, which residues are converted into 1,3-cyclohexanedicarboxylic acid residues.

EFFECT: expanded synthetic possibilities.

13 cl, 1 tbl, 15 ex

 

The technical FIELD

This invention relates to a method for hydrogenation of oligomer complex polyester containing residues of terephthalic acid, where the residues of terephthalic acid into the residues of 1,4-cyclohexanedicarboxylic acid. This invention also relates to a method for producing polyesters containing residues of 1,4-cyclohexanedicarboxylic acid, by first hydrogenation oligomer complex polyester containing residues of terephthalic acid, and then carrying out the interaction of the obtained oligomer with one or more forming a complex of the polyester reactants with more complex macromolecular polyester.

Prior art

Complex sobolifera containing residues of terephthalic acid and ethylene glycol and the remains of one or more saturated dibasic carboxylic acids, form a growing market polyesters special purpose. Introduction to the structure of polyethylene terephthalate (PET) saturated co monomer, such as 1,4-cyclohexanecarbonyl acid (CHDA), can give the obtained complex polyester desirable properties, for example, a lower crystallization rate. Complex sobolifera typically obtained through the interaction of purified dibasic carboxylic acid, such as CHDA, with dialami in terms of polymerise the AI. Complex sobolifera obtained from CHDA or complex diapir, much more expensive, due to the amount of the monomer CHDA. For example, 1,4-CHDA on a commercial scale is usually derived from terephthalic acid (TPA) catalyzed by ruthenium hydrogenation disodium salt TRA, followed by neutralization and separation CHDA obtained from aqueous sodium salts. The present invention relates to a method for producing complex sobolifera containing residues CHDA, by hydrogenation of oligomers of polyesters, containing the remains of TRA.

Methods of hydrogenation containing terephthalic acid esters derived from poly(ethyleneterephthalate), is known. U.S. patent 3501420 describes the depolymerization of waste from poly(ethyleneterephthalate) in alcohol to obtain a solution of esters of terephthalic acid. The resulting solution was subjected to hydrogenation with the removal of coloring substances. In this method, poly(ethyleneterephthalate) before entering into contact with hydrogen is transformed into a predominantly Monomeric esters. Discolored solution of esters TRA can be used to obtain high-quality poly(ethyleneterephthalate).

U.S. patent 3487100 describes the possibility of discoloration bis-hydroxyethylacrylate (NO)is obtained from crude TPA and ethylene glycol, by processing gorodom in the presence of a hydrogenation catalyst. The NO is dissolved in water and filtered to remove oligomeric compounds (insoluble in water). The filtered solution is treated with hydrogen in the temperature range 50-100°C. Despite the fact that the hydrogenation treatment reduces the content fluorenone impurities, NO need to be in solution, and the product has yet to crystallize from the solution prior to use. Another disadvantage is that the oligomers polyesters used in this method to process impossible. Japanese document JP Kokai 50-142537 describes a method of obtaining cyclohexanedimethanol (CHDM) by depolymerization and hydrogenation waste of poly(ethyleneterephthalate). In this way waste of PET subjected to depolymerization at 7-fold excess of ethylene glycol in the presence of hydrogen and hydrogenation catalyst to the transformation of poly(ethyleneterephthalate) in a solution of esters of ethylene glycol and cyclohexanedicarboxylic acid. The product of this stage is separated from the catalyst and again subjected to treatment with hydrogen at high pressure in the presence of a second hydrogenation catalyst. The aim of the second stage is the transformation of esters cyclohexanedicarboxylic acid in solution CHDM.

SUMMARY of INVENTION

Applicants have developed a method by which oligomer the complex polyester, that is, low molecular weight complex of the polyester containing the remains of TRA and one or more diols, can under certain conditions be subjected to the hydrogenation of a transformation, at least 1 mole percent of the residues of the TRA in the remains of the CHDA. Accordingly, one variation of the present invention is a method, where the oligomer complex polyester containing residues of terephthalic acid, in contact with hydrogen in the presence of supported on a carrier or suspended hydrogenation catalyst at a hydrogen pressure of at least approximately 60 bar gauge pressure (Bari; approximately 870 pounds per square inch gauge pressure - lb/in2(and)), and at a temperature in the range from about 180 to 280°where at least 1 mole percent of the residues of terephthalic acid converted into the residues of 1,4-cyclohexanedicarboxylic acid. The second implementation of the present invention is a method including steps:

1) contacting the oligomer complex polyester containing residues of terephthalic acid, with hydrogen in the presence of supported on a carrier or suspended hydrogenation catalyst at a hydrogen pressure of at least approximately 60 bar g and at a temperature in the range when listello from 180 to 280° With transformation, at least 1 mole percent of the residues of terephthalic acid residues of 1,4-cyclohexanedicarboxylic acid; and

2) interaction of the oligomeric product of stage (1) with one or more forming a complex of the polyester reactants in the presence of the polymerization catalyst and the conditions of polymerization under pressure and temperature to obtain a complex of the polyester containing residues of 1,4-cyclohexanedicarboxylic acid.

The present invention relates to an economical method for producing a complex sobolifera containing the remains of TRA and CHDA. The obtained oligomer formed from the comonomers can be polimerizuet the usual way of obtaining complex spoliation of saturated and unsaturated monomers. Polyesters which can be obtained in accordance with the present invention, finds diverse application in various fields such as adhesives, packaging materials for foodstuffs and compositions for coating.

DETAILED description of the INVENTION

The oligomer used in the invention are usually obtained by the esterification of terephthalic acid or its complex diapir, such as terephthalate, with one or more dialami, such as ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-cyclohexanedimethanol and the like. Product is t the esterification reaction is a mixture of oligomers, characterized by the degree of polymerization (DP)in the range from approximately 2 to 20. The oligomer preferably is characterized by the value of DP in the range from about 2 to 10, most preferably from about 3 to 5, where DP is defined as srednekamennogo molecular weight of the oligomer, divided by the molecular weight of the repeating unit. Oligomers that can be used in the present invention can also be characterized by the General formula:

BUT-[Diol]x-[-TRA-Diol-]y-H

where the Diol is a divalent residue of a component formed diola or a glycol such as ethylene glycol, diethylene glycol, 1,2 - and 1,3-propandiol, 2-methyl-1,3-propandiol, 2,2-dimethyl-1,3-propandiol, 1,4-butanediol, 1,4-cyclohexanedimethanol and the like, TRA represents the bivalent residue of terephthalic acid, x is 0 or 1, and the average value is in the range from approximately 2 to 20. Oligomeric raw materials in a new way applicants insoluble in water, and thus it differs from the NO, which is subjected to hydrogenation in accordance with the description in U.S. patent 3487100.

The oligomer can be obtained by the use of crude terephthalic acid, purified terephthalic acid, or forming a complex of the polyester is derived, this ka is the exporter. The crude terephthalic acid (CTA), obtained by oxidation of para-kisslola usually contains 4-carboxybenzene (IAS) as the main impurity, and a smaller, but significant number of colored impurities. Colored impurities identify as a mixture of mainly isomers decarboxylation (with smaller amounts of mono - and three-carboxyfluorescein) and dicarboxyethyl. Data intensely colored derivatives carboxyfluorescein can be subjected to hydrogenation to obtain a colorless derivatives carboxyfullerene. In low concentrations have been identified other compounds, such as decarboxylation and dicarboximides. Despite the fact that upon receipt of the oligomers used as starting materials for the method of the present invention, essentially you can use any brand of one HUNDRED, used a HUNDRED typically contains less than about 4000 ppm IAS, preferably less than 700 ppm IAS, and most preferably from about 50 to 250 ppm CBA.

One HUNDRED is usually injected into the reaction, at least one diola at a temperature in the range from about 200 to about 280°obtaining the oligomer, which can be gidrirovanii in accordance with the present invention. Suitable for the esterification of pressure include, but are not limited the tsya only them: pressure up to approximately 27,6 Bari (400 lb/in 2(and)), and preferably up to about 13,8 Bari (200 lb/in2(and)). The reaction can occur under acidic samostalna, or it can be accelerated using a suitable esterification catalyst, such as titanium or an organic or inorganic acid. A mixture of oligomers typically receive continuously in the sequence of one or more reactors. In a commercial way often use two reactors. Alternatively, the mixture of monomers and oligomers can be obtained in one or more reactors of periodic action. Suitable for the esterification reactors at the present prior art, and there is no need to describe them here. In General, the esterification is carried out in a period of time ranging from about 1 to about 4 hours, you Need to understand that in General the smaller the reaction temperature, the greater the duration of the reaction time. The oligomer obtained from a HUNDRED, usually characterized by the value of b*at least equal to 3, usually being in the range from approximately 4 to 7, as defined by the measurement for the color b* color scale L, a, b using the color test ASTM spectrometer Hunter Ultra Scan 8000.

The method of the invention applicants can implement through in the edenia molten oligomer, containing terephthalic acid, into contact with hydrogen in the presence of supported on a carrier or suspended catalyst at a temperature in the range from about 180 to 280°With (depending on the content of ethylene glycol), and at a pressure of hydrogen of at least approximately 60 Bari. Preferred conditions include a temperature in the range from about 240 to 270°With, in some implementations, more preferably from about 250 to 260°C and hydrogen pressures in the range from approximately 70 to 170 Bari (approximately 1016 to 2467 lb/in2(and)), more preferably from about 100 to 140 Bari (from about 1450 until 2031 lb/in2(and)). Suitable duration of time of hydrogenation include values up to approximately three hours. You must understand that the duration of hydrogenation will vary depending on the number and activity of the selected catalyst, but also on the partial pressure of hydrogen and mode of operation. The method of hydrogenation can be performed in a periodic, semi-continuous or continuous mode of operation using a slurry or a fixed catalyst layer. The method preferably is carried out in a continuous mode of operation used with the em reactor including a catalyst layer, where the molten oligomer at elevated temperature and pressure flows along the surface and through the thickness of one or more layers deposited on the carrier of the catalyst for hydrogenation. The hydrogenation can be carried out in the presence of a diluent, such as a diol, such as ethylene glycol used in the preparation of the oligomer. The amount of diluent used can be in the range from approximately 5 to 50 mass% based on the weight of oligomer.

Examples of hydrogenation catalysts that can be used in a new way applicants include platinum group metals such as ruthenium, rhodium, palladium, platinum and osmium. You can also use and Nickel. Suitable catalysts are commercially available in companies Englehard and Sud Chemie. Preferred hydrogenation catalysts include palladium, platinum and Nickel catalysts, especially supported on a carrier catalyst containing from about 0.1 to 10 weight percent palladium or platinum on the material of the catalyst carrier. Suitable materials catalyst carrier include, but are not limited to them: ZrO2, carbon, silica, alumina, zeolites, TiO2and mixtures thereof, with the preferred carbon. The oligomer, which is subjected to hydrogenation in accordance with anastasimatarion, characterized by the values of b*less than about 3, preferably less approximately 2, and it contains less than 250 ppm of the IAS. The method of the present invention leads to the transformation of at least 1 mole%, more often from about 10 to 50 mole percent of the residues of terephthalic acid present in the oligomeric mixtures, residues of 1,4-cyclohexanedicarboxylic acid.

Subjected to the hydrogenation of a mixture of oligomers can be polimerizuet on commonly used ways to obtain a complex of the polyester. The composition and properties of the final complex of the polyester may vary as a result of the reaction or polymerization subjected to the hydrogenation of a mixture of oligomers with other copolymerizable compounds or substances, such as, for example, the oligomer complex polyester, which has not been subjected to hydrogenation or was subjected to hydrogenation under other conditions obtaining oligomeric product containing more or less of the residues of 1,4-cyclohexanedicarboxylic acid. Subjected to the hydrogenation of a mixture of oligomers can also be introduced into the reaction with dibasic carboxylic acids and/or dialami, different from that which was obtained oligomer.

The polymerization or polycondensation is carried out in commonly used reactors, which are known at the present level is ehniki in continuous or batch modes. Suitable polycondensation catalysts include compounds of titanium, gallium, germanium, tin, antimony, aluminum, bismuth, silicon, zirconium, preferred compounds of antimony, germanium, titanium or mixtures thereof. The amount of catalyst is in the range from about 5 to about 400 ppm, and preferably from about 20 to about 300 ppm in the case of germanium or antimony. A mixture of oligomers undergoes polycondensation in the melt phase with obtaining the polymer precursor, the degree of polymerization is in the range from approximately 20 to approximately 120. Complex polyester precursor receive in sequence from one or more reactors operating at elevated temperatures. To facilitate the removal of excess glycols, water, alcohols and other products of the reaction, the polycondensation reactors operate under vacuum or inert purge gas. The inert gas is any gas which does not cause the passage of unwanted reactions or undesired characteristics of the product. Suitable gases include, but are not limited to: CO2, argon, helium and nitrogen.

Complex polyester is the reaction product of a polycondensation often granularit to facilitate R the bots with him. If kristallizuetsya complex polyesters polyester then crystallized and additionally polymerized in the solid phase, using the equipment and conditions that state of the art known. However kristallizuetsya polyesters of the present invention can also directly apply to the equipment for molding without granulation or transfer in the solid state, using methods such as those described in U.S. patents 5597891 and 5648032, but not limited to.

The method of hydrogenation of the present invention is usually carried out for oligomer, which is formed in the process of producing high molecular weight polyesters. However, it may be possible and use the present invention in other parts of the production process complicated polyester, while the feed material, subject to hydrogenation, will be in a liquid state, allowing the transfer pump through the selected hydrogenation reactor and enter into contact with the catalyst by passing the desired reaction. For example, fed to the hydrogenation of the raw material can also be a prepolymer. Stage hydrogenation can be conducted in the first reactor for the production of the oligomer, when using granular hydrogenation catalyst, and already between the first and second reactor and to obtain oligomer when using a reactor with a fixed and/or irrigated catalyst bed. Stage hydrogenation may be possible to spend between esterification and polycondensation, after polycondensation or at any intermediate point. In implementations in which the selected polycondensation catalyst reacts with the catalytic hydrogenation may be the preferred carrying out hydrogenation prior to the introduction of a polycondensation catalyst.

Polyesters derived from oligomers subjected to hydrogenation in accordance with the present invention include homopolymers and copolymers of polyesters that are suitable for a wide range of applications including packaging material, film, sheet, coating, adhesives, molded articles and the like. Packaging material for food products is a particularly preferred usage for some polyesters of the present invention. Polyesters containing component formed by the remnants of the dibasic carboxylic acid containing residues of 1,4-cyclohexanedicarboxylic acid and optionally residues of one or more other dibasic carboxylic acids, such as terephthalic acid and/or isophthalic acid, preferably from about 1 to 50 mole percent of the residues of 1,4-cyclohexanedicarboxylic acid, and more preferably from about 2 to 10 mole percent of the residues of 1,4-cyclohexanedicarboxylic acid, and the component formed by residues of diols containing residues of at least one diol, such as divalent residues of ethylene glycol, 1,4-cyclohexanedimethanol, diethylene glycol, butanediol and mixtures thereof. Polyesters can also contain residues of comonomers in amounts up to about 50 mole percent of one or more of various dibasic carboxylic acids and/or up to about 50 mole percent of one or more diols per 100 molar percent of the dibasic carboxylic acid and 100% (mol.) diol. In certain implementations it may be preferable modification of the comonomers in the component formed by the dibasic carboxylic acid component formed by the glycol, or each of them individually in the amount of up to about 25 mole percent, or up to about 15 molar percent. More specifically, suitable comonomers which are dibasic carboxylic acids include aromatic dibasic carboxylic acid, preferably containing from 12 to 14 carbon atoms, or aliphatic dibasic carboxylic acid, preferably containing from 4 to 12 carbon atoms. Examples of comonomers which are dibasic carboxylic acids include CFT left acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, cyclohexadecane acid, diphenyl-4,4'-dicarboxylic acid, diphenyl-3,4'-dicarboxylic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sabotinova acid, mixtures thereof and the like.

Suitable comonomers, which dialami include cycloaliphatic diols, preferably containing from 6 to 20 carbon atoms or aliphatic diols, preferably containing from 3 to 20 carbon atoms. Examples of such diols include triethylene glycol, propane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, neopentylglycol, 3-methylpentan-2,4-diol, 2-methyl-1,4-pentanediol, 2,2,4-trimethylpentanediol-(1,3), 2-ethylhexane-1,3-diol, 2,2-diethylpropane-(1,3), hexanediol-(1,3), 1,4-di(hydroxyethoxy)benzene, 2,2-bis(4-hydroxycyclohexyl)propane, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane, 2,2,4,4-tetramethylcyclobutane, 2,2-bis(3-hydroxyethoxyphenyl)propane, 2,2-bis(4-hydroxytamoxifen)propane, isosorbide, hydroquinone, mixtures thereof and the like. Polyesters can be obtained from two or more of the above diols.

Polyesters of the present invention can also contain small amounts of trifunctional or tetrafunctional of comonomers, such as trimellitic anhydride, trimethylolpropane, pyromellitic Giang grid, the pentaerythritol and other forming a complex polyester, polyacid or polyol, generally known state of the art. In addition, although not required, if desired, it is possible to use additives that are commonly used in complex polyesters. Such additives include, but are not limited to: dyes, toners, pigments, carbon black, glass fiber, fillers, modifying additives that increase the impact strength, antioxidants, stabilizers, flame retardants, additives, contributing to the re-heating, compounds that reduce the content of acetaldehyde, connections, aktseptiruya oxygen, additives that improve the tightness, such as particles in the form of plates, and the like. Polyesters derived from oligomers subjected to hydrogenation in accordance with the present invention, preferably produced by polymerization subjected to hydrogenation mixture of oligomers, and they contain:

(i) the remains of dibasic acids comprising residues of 1,4-cyclohexanedicarboxylic acid and residues of terephthalic acid; and

(ii) residues of diols comprising residues of ethylene glycol.

In accordance with a use case adopted in the description and the claims, the remainder refers to a group, which is a chemical product is connected to the I in a particular reaction scheme or subsequent preparation of the composition, or chemical product, regardless of whether the group is actually obtained from the chemical compounds. For example, the residue of ethylene glycol in a complex polyester refers to one or more repeating units

-Och2CH2About the complex polyester regardless of whether to obtain a complex of the polyester used ethylene glycol. Similarly, the balance sabatinovka acid complex polyester refers to one or more of the groups- (CH2)8WITH - in the complex polyester, regardless of whether in the synthesis of complex polyester residue obtained by reaction sabatinovka acid or its ether complex.

Copolymers of terephthalic acid and 1,3-cyclohexanedicarboxylic acid can be obtained from the crude isophthalic acid without first obtaining the purified 1,3-cyclohexanedicarboxylic acid as isophthalic acid can also be converted into the corresponding cyclohexanecarbonyl acid by treatment with hydrogenation. Process similar to that described for method in the case of 1,4-cyclohexanedicarboxylic acid, are removed or become redundant for the method in the case of 1,3-cyclohexanedicarboxylic acid. Thus, another variant of the embodiment of the present invention relates to a method involving the introduction of the oligomer is false polyester, containing residues of isophthalic acid (IPA), in contact with hydrogen in the presence of supported on a carrier or suspended hydrogenation catalyst at a hydrogen pressure of at least approximately equal to 60 bar gauge pressure (Bari), and at a temperature in the range from about 180 to 280°where at least 1 mole percent, preferably from about 10 to 50 mole percent of the residues of terephthalic acid into the remains of 1,3-cyclohexanedicarboxylic acid. In the method of hydrogenation of oligomer complex polyester containing residues of terephthalic acid, you can use the above-described preferred conditions and oligomers, where the residues of terephthalic acid substituted residues of isophthalic acid, conversion of at least 1 mole percent, preferably from about 10 to 50 mole percent of the residues of isophthalic acid residues of 1,3-cyclohexanedicarboxylic acid.

EXAMPLES

The methods presented in this invention will also be illustrated using the following examples. Unless other specified, all percentages given in the examples are mass.

EXAMPLES 1-15

In an autoclave made of titanium with a volume of 300 ml, equipped with a glass liner was loaded Oli the Omer poly(ethyleneterephthalate) (100 g), the degree of polymerization of which was equal to 5.1. The oligomer was obtained by reaction of ethylene glycol and a HUNDRED at a molar ratio of 1.3/1, respectively, at 260°C for 2 hours was Added to the hydrogenation catalyst (8 g), and the resulting mixture was subjected to excess pressure to 34.3 Bari (approximately 500 lb/in2(and)), the generated hydrogen. The mixture was heated to 210-260°C for 180 minutes while maintaining the pressure at the level 68,9-124 Bari (approximately 1000-1800 lb/in2(and)by hydrogen. After cooling the mixture from the autoclave were removed and were used to obtain the powder (after removal of large catalyst particles). Examples 1, 4 and 7 included the introduction of 17% ethylene glycol before hydrogenation in order to lower the melting range of the oligomer.

A sample of the oligomer subjected to hydrogenation in each example, umalali under the action of methanol and analyzed by the method of gas chromatography for the presence of methyl esters cyclohexanedicarboxylic acid. Examples of total shown in the table, where the pressure is a pressure of hydrogen (Bari), temperature represents the temperature (° (C)and the value listed for CHDA, represents an approximate mole percent of residues of the dibasic acid oligomer represented the remnants of 1,4-cyclohexanedicarboxylic acid.

TABLENumber exampleCatalystTemperaturePressureCHDA11% Pd + 0,1% Ni on alumina21070221% Pd + 0,1% Ni on alumina230701231% Pd + 0,1% Ni on alumina2301247241% Pd + 0,1% Ni on alumina2301243551% Pd + 0,1% Ni on alumina260705661% Pd + 0,1% Ni on alumina2601244373% Pd on silica2101241583% Pd on silica2301244493% Pd on silica23012416103% Pd on silica26012415113% Pd on silica260 12420121% Pd on titanium oxide23012423131% Pd on titanium oxide26012412141% Ru on carbon2307012151% Pd on carbon2301244

The invention has been described in detail with particular reference to its preferred options for implementation, but you must understand that without deviating from the essence and scope of the invention can be implemented variations and modifications.

1. The method of hydrogenation of oligomer complex polyester, which comprises the contacting of the oligomer complex polyester containing residues of terephthalic acid, with hydrogen in the presence of supported on a carrier or suspended hydrogenation catalyst at a hydrogen pressure of at least approximately 60 to 200 bar gauge pressure (Bari), and at a temperature in the range from about 180 to 280°where at least 1 mol.% residues of terephthalic acid is converted into the residues of 1,4-cyclohexanedicarboxylic acid.

2. The method according to claim 1, where the oligomer complex of the polyester containing the mod and terephthalic acid, the degree of polymerization is in the range from approximately 2 to 20, in contact with hydrogen at a hydrogen pressure of at least being in the range from approximately 70 to 170 Bari, and at a temperature in the range from about 240 to 270°C.

3. The method according to claim 1, where the oligomer complex polyester containing residues of terephthalic acid, the degree of polymerization is in the range from approximately 2 to 10, in contact with hydrogen in the presence of supported on a carrier or suspended hydrogenation catalyst selected from catalysts containing from about 0.1 to 10 wt.% palladium or platinum on the material of the catalyst carrier, when the hydrogen pressure, at least in the range from approximately 70 to 170 Bari, and at a temperature in the range from about 240 to 270°C.

4. The method according to claim 3, where the degree of polymerization of the oligomer complex of the polyester is in the range from approximately 2 to 10.

5. The method of hydrogenation of oligomer complex polyester, which comprises the contacting of the oligomer complex of the polyester described by the formula

BUT-[Diol]x-[-TRA-Diol-]y-N,

where the Diol is a divalent residue of a component formed diola, TRA represents a divalent is a residue of terephthalic acid, x is 0 or 1, and the average value y is in the range from approximately 2 to 20 with hydrogen in the presence of supported on a carrier or suspended hydrogenation catalyst selected from catalysts containing from about 0.1 to 10 wt.% palladium or platinum on the material of the catalyst carrier, when the hydrogen pressure, at least in the range from approximately 70 to 170 Bari, and at a temperature in the range from about 240 to 270°where at least 1 mol.% residues of terephthalic acid is converted into the residues of 1,4-cyclohexanedicarboxylic acid.

6. The method according to claim 5, where the Diol is a divalent residue of a component formed diola selected from ethylene glycol, diethylene glycol, 1,2 - and 1,3-propane diol, 2-methyl-1,3-propane diol, 2,2-dimethyl-1,3-propane diol, 1,4-butanediol and 1,4-cyclohexanedimethanol, and from about 10 to 50 mol.% residues of terephthalic acid into the residues of 1,4-cyclohexanedicarboxylic acid.

7. The method of obtaining complex polyester, which includes stage

(1) hydrogenation of oligomer complex polyester according to claim 1 by contacting the oligomer complex polyester containing residues of terephthalic acid, with hydrogen in the presence of supported on a carrier or suspended catalyst, gidrirovanie is at a pressure of hydrogen, at least approximately 60 to 200 bar g and at a temperature in the range from about 180 to 280°With conversion of at least 1 mol.% residues of terephthalic acid residues of 1,4-cyclohexanedicarboxylic acid; and

(2) the interaction of the oligomeric product of stage (1) with one or more forming a complex of the polyester reactants in the presence of the polymerization catalyst and the conditions of polymerization under pressure and temperature to obtain a complex of the polyester containing residues of 1,4-cyclohexanedicarboxylic acid.

8. The method according to claim 7, which includes stages

(1) contacting the oligomer complex of the polyester described by the formula

BUT-[Diol]x-[-TRA-Diol-]y-N,

where the Diol is a divalent residue of a component formed diola, TRA represents the bivalent residue of terephthalic acid, x is 0 or 1, and the average value y is in the range from approximately 2 to 20 with hydrogen in the presence of supported on a carrier or suspended hydrogenation catalyst selected from catalysts containing from about 0.1 to 10 wt.% palladium or platinum on the material of the catalyst carrier, when the hydrogen pressure, at least in the range from approximately 70 to 170 Bari, is at a temperature in the range from about 240 to 270°where at least 1 mol.% residues of terephthalic acid is converted into the residues of 1,4-cyclohexanedicarboxylic acid; and

(2) the interaction of the oligomeric product of stage (1) with one or more forming a complex of the polyester reactants in the presence of the polymerization catalyst and the conditions of polymerization under pressure and temperature to obtain a complex of the polyester containing residues of 1,4-cyclohexanedicarboxylic acid.

9. The method of claim 8, where at stage (1) Diol represents a divalent residue of a component formed diola selected from ethylene glycol, diethylene glycol, 1,2 - and 1,3-propane diol, 2-methyl-1,3-propane diol, 2,2-dimethyl-1,3-propane diol, 1,4-butanediol and 1,4-cyclohexanedimethanol, and from about 10 to 50 mol.% residues of terephthalic acid into the residues of 1,4-cyclohexanedicarboxylic acid.

10. The method of obtaining complex polyester, which includes stage

(1) hydrogenation of oligomer complex polyester according to claim 5 by contacting the oligomer complex of the polyester described by the formula

BUT-[Diol]x-[-TRA-Diol-]y-N,

where the Diol is a divalent residue of ethylene glycol, TRA represents the bivalent residue of terephthalic acid, x is 0 or 1,and the average value y is in the range from approximately 2 to 20, with hydrogen in the presence of supported on a carrier or suspended hydrogenation catalyst selected from catalysts containing from about 0.1 to 10 wt.% palladium or platinum on the material of the catalyst carrier, when the hydrogen pressure, at least in the range from approximately 70 to 170 Bari, and at a temperature in the range from about 240 to 270°where from about 10 to 50 mol.% residues of terephthalic acid into the residues of 1,4-cyclohexanedicarboxylic acid; and

(2) polymerization of the oligomeric product of stage (1) in the presence of the polymerization catalyst and the conditions of polymerization under pressure and temperature to obtain a complex of the polyester containing residues of 1,4-cyclohexanedicarboxylic acid.

11. The method of hydrogenation of oligomer complex polyester, comprising the contacting of the oligomer complex polyester containing residues of terephthalic acid, with hydrogen in the presence of supported on a carrier or suspended hydrogenation catalyst at a hydrogen pressure of at least approximately equal to 60 bar gauge pressure (Bari), and at a temperature in the range from about 180 to 280°where at least 1 mol.% residues of isophthalic acid is transformed into the remains of 1,3-cyclohex addicabadaway acid.

12. Osposobljavanja oligomer complex polyester, which comprises the contacting of the oligomer complex of the polyester described by the formula

BUT-[Diol]x[-IPA-Diol-]y-N,

where the Diol is a divalent residue of a component formed diola, IPA represents the bivalent residue of isophthalic acid, x is 0 or 1, and the average value is in the range from approximately 2 to 20, with hydrogen in the presence of supported on a carrier or suspended hydrogenation catalyst selected from catalysts containing from about 0.1 to 10 wt.% palladium or platinum on the material of the catalyst carrier, when the hydrogen pressure, at least in the range from approximately 70 to 170 Bari, and at a temperature in the range from about 240 to 270°where at least 1 mol.% residues of isophthalic acid is transformed into the remains of 1,3-cyclohexanedicarboxylic acid.

13. The method according to item 12, where the Diol is a divalent residue of a component formed diola selected from ethylene glycol, diethylene glycol, 1,2 - and 1,3-propane diol, 2-methyl-1,3-propane diol, 2,2-dimethyl-1,3-propane diol, 1,4-butanediol and 1,4-cyclohexanedimethanol, and from about 10 to 50 mol.% residues of terephthalic acid into the remains of 1,3-cyclohexa the dicarboxylic acid.



 

Same patents:

FIELD: chemical technology.

SUBSTANCE: invention relates to technology for preparing alkyde resin that can be used as a base in preparing paint and varnish materials. Method for preparing alkyde resin involves interaction of vegetable oil, phthalic anhydride, pentaerythritol in heating followed by azeotropic distilling off of reaction water. Distilled tall oil is used as vegetable oil and maleic anhydride are added additionally in the following regimen and charging components: firstly, distilled tall oil, maleic and phthalic anhydride are charged, the mixture is heated to 170-180°C and kept up to the complete binding maleic anhydride. Then pentaerythritol and xylene are charged for azeotropic distilling off of water and the reaction mixture is heated to 240-250°C until acid number value of resin will be 10-15 mg of KOH/g and viscosity value of 53% resin solution in white spirit 60-80 s. Components for synthesis are taken in the following ratio, wt.-%: distilled tall oil, 70-78; phthalic anhydride, 1-7; maleic anhydride, 3-5, and pentaerythritol, the balance. Coatings made in using the proposed resin show high impact strength and prolonged working life.

EFFECT: improved preparing method.

3 tbl, 5 ex

FIELD: polymer production.

SUBSTANCE: alkyd-siloxane resin is prepared via interaction of alkyd resin with polyorganosiloxane on heating. Method is distinguished by that polyorganosiloxane is notably polyphenylethoxysiloxane with weight proportion of ethoxy groups 17-40%, which is first treated with butyl alcohol at 130-150°C for 1-2 h until content of ethoxy groups achieves 10-13%, after which resulting modifier is brought into cocondensation with low-viscosity alkyd resin having acid number 5-15 mg KOH/g and viscosity of its 60% xylene solution 40-60 s at 160-170 and alkyd resin-to-modifier ratio (65-85):(20-35). Alkyd resin utilized is based on vegetable oils, pentaerythritol, and phthalic anhydride.

EFFECT: reduced increase in viscosity of alkyd-siloxane resin and enhanced protective properties of coatings based on this resin.

2 tbl, 5 ex

FIELD: polymer production.

SUBSTANCE: invention relates to production of modified alkyd resins widely used in varnish-and-paint industry as well as to lacquer materials based thereon for use as indoor and outdoor painting operations. Alkyd resin is obtained through alcoholysis of vegetable oils and optionally colophony with polyhydric alcohol (glycerol or pentaerythritol) in presence of catalyst, in particular mixture of lead and cadmium salts of saturated or unsaturated aliphatic C6-C18-monocarboxylic acid in the form of solution, in white spirit on heating, quantity of catalyst constituting 0.009-0.02% on the weight of components. Alcoholysis is followed by polycondensation of phenol resin based on alkylphenol and formaldehyde (at their ratio from 1:1 to 1:2) with dicarboxylic acid anhydride and modifier or using aromatic monocarboxylic acid in mixture with substituted aromatic monocarboxylic acid taken in specified proportions. Modified alkyd resins thus obtained serve as base for production of lacquer material containing a variety of fillers, pigments, siccatives, organic solvent, and, if necessary, thickener as well as various special additives (fire retardants, corrosion inhibitors, and the like). Resulting resins ate clear, with elevated content of volatiles, low acid number, rapidly drying, which enable manufacture of lacquer materials based thereon.

EFFECT: improved physicochemical properties of lacquer materials (hardness, elasticity).

3 cl, 4 tbl

The invention relates to the condensation copolymers, are able to absorb oxygen, which can be used for the manufacture of films, containers, packaging, bottles, etc

-hydroxyethylamino group, and the method of production thereof" target="_blank">

The invention relates to amorphous and/or semicrystalline the copolymers of esters containing-hydroxyethylamino group, and the way they are received, which are used as components forming cross-links in the powdered water-soluble and solvent-based varnishes

The invention relates to compositions for coatings, in particular for re-finishing cars, to a method of curing compositions for coatings

The invention relates to a method for producing polyesters of high molecular weight

The invention relates to the chemistry of polymers, namely the synthesis of thermotropic liquid crystal spoliation in the melt, which can be used to obtain high-strength fibers and construction materials

FIELD: chemistry of metalloorganic compounds.

SUBSTANCE: invention relates to novel compounds representing metallic salt of compound corresponding to the formula (I): wherein both M1 and M2 mean lithium or combined to form one cation of metal calcium, strontium or aluminum monohydroxide and wherein R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 are similar or different and chosen separately from group consisting of hydrogen atom, (C1-C9)-alkyl, and two carboxy-fragments are in cis-configuration if metal cation represents aluminum monohydroxide. Proposed compounds can be used as priming and/or clearing agents for thermoplastics. Such compounds provide required crystallization temperature, rigidity and compatibility of an acid absorbing agent in synthesized polyolefins, and they show low hygroscopicity and therefore good stability in storing as powdery or granulated compositions. Also, invention relates to an article made of thermoplastic polymer and thermoplastic composition and comprising at least one claimed compound.

EFFECT: valuable properties of compounds.

9 cl, 6 tbl, 8 ex

FIELD: chemistry of metalloorganic compounds.

SUBSTANCE: invention relates to novel compounds representing metallic salt of compound corresponding to the formula (I): wherein both M1 and M2 mean lithium or combined to form one cation of metal calcium, strontium or aluminum monohydroxide and wherein R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 are similar or different and chosen separately from group consisting of hydrogen atom, (C1-C9)-alkyl, and two carboxy-fragments are in cis-configuration if metal cation represents aluminum monohydroxide. Proposed compounds can be used as priming and/or clearing agents for thermoplastics. Such compounds provide required crystallization temperature, rigidity and compatibility of an acid absorbing agent in synthesized polyolefins, and they show low hygroscopicity and therefore good stability in storing as powdery or granulated compositions. Also, invention relates to an article made of thermoplastic polymer and thermoplastic composition and comprising at least one claimed compound.

EFFECT: valuable properties of compounds.

9 cl, 6 tbl, 8 ex

FIELD: polymer production.

SUBSTANCE: invention provides a method for hydrogenation of polyester oligomers containing terephthalic and isophthalic acid residues, which are thereby converted into 1,4-cyclohexanedicarboxylic acid residues. Also proposed is a method for preparing polyesters containing 1,4-cyclohexanedicarboxylic acid residues by hydrogenating first polyester oligomer containing terephthalic acid residues followed by reacting thus obtained oligomer with one or several polyester-forming reagents to form higher molecular weight polyester. Another embodiment of invention involves hydrogenation of polyester oligomers containing isophthalic acid residues, which residues are converted into 1,3-cyclohexanedicarboxylic acid residues.

EFFECT: expanded synthetic possibilities.

13 cl, 1 tbl, 15 ex

FIELD: polymer production.

SUBSTANCE: invention provides a method for hydrogenation of polyester oligomers containing terephthalic and isophthalic acid residues, which are thereby converted into 1,4-cyclohexanedicarboxylic acid residues. Also proposed is a method for preparing polyesters containing 1,4-cyclohexanedicarboxylic acid residues by hydrogenating first polyester oligomer containing terephthalic acid residues followed by reacting thus obtained oligomer with one or several polyester-forming reagents to form higher molecular weight polyester. Another embodiment of invention involves hydrogenation of polyester oligomers containing isophthalic acid residues, which residues are converted into 1,3-cyclohexanedicarboxylic acid residues.

EFFECT: expanded synthetic possibilities.

13 cl, 1 tbl, 15 ex

FIELD: polymer production.

SUBSTANCE: invention relates to production of modified alkyd resins widely used in varnish-and-paint industry as well as to lacquer materials based thereon for use as indoor and outdoor painting operations. Alkyd resin is obtained through alcoholysis of vegetable oils and optionally colophony with polyhydric alcohol (glycerol or pentaerythritol) in presence of catalyst, in particular mixture of lead and cadmium salts of saturated or unsaturated aliphatic C6-C18-monocarboxylic acid in the form of solution, in white spirit on heating, quantity of catalyst constituting 0.009-0.02% on the weight of components. Alcoholysis is followed by polycondensation of phenol resin based on alkylphenol and formaldehyde (at their ratio from 1:1 to 1:2) with dicarboxylic acid anhydride and modifier or using aromatic monocarboxylic acid in mixture with substituted aromatic monocarboxylic acid taken in specified proportions. Modified alkyd resins thus obtained serve as base for production of lacquer material containing a variety of fillers, pigments, siccatives, organic solvent, and, if necessary, thickener as well as various special additives (fire retardants, corrosion inhibitors, and the like). Resulting resins ate clear, with elevated content of volatiles, low acid number, rapidly drying, which enable manufacture of lacquer materials based thereon.

EFFECT: improved physicochemical properties of lacquer materials (hardness, elasticity).

3 cl, 4 tbl

FIELD: polymer production.

SUBSTANCE: alkyd-siloxane resin is prepared via interaction of alkyd resin with polyorganosiloxane on heating. Method is distinguished by that polyorganosiloxane is notably polyphenylethoxysiloxane with weight proportion of ethoxy groups 17-40%, which is first treated with butyl alcohol at 130-150°C for 1-2 h until content of ethoxy groups achieves 10-13%, after which resulting modifier is brought into cocondensation with low-viscosity alkyd resin having acid number 5-15 mg KOH/g and viscosity of its 60% xylene solution 40-60 s at 160-170 and alkyd resin-to-modifier ratio (65-85):(20-35). Alkyd resin utilized is based on vegetable oils, pentaerythritol, and phthalic anhydride.

EFFECT: reduced increase in viscosity of alkyd-siloxane resin and enhanced protective properties of coatings based on this resin.

2 tbl, 5 ex

FIELD: chemical technology.

SUBSTANCE: invention relates to technology for preparing alkyde resin that can be used as a base in preparing paint and varnish materials. Method for preparing alkyde resin involves interaction of vegetable oil, phthalic anhydride, pentaerythritol in heating followed by azeotropic distilling off of reaction water. Distilled tall oil is used as vegetable oil and maleic anhydride are added additionally in the following regimen and charging components: firstly, distilled tall oil, maleic and phthalic anhydride are charged, the mixture is heated to 170-180°C and kept up to the complete binding maleic anhydride. Then pentaerythritol and xylene are charged for azeotropic distilling off of water and the reaction mixture is heated to 240-250°C until acid number value of resin will be 10-15 mg of KOH/g and viscosity value of 53% resin solution in white spirit 60-80 s. Components for synthesis are taken in the following ratio, wt.-%: distilled tall oil, 70-78; phthalic anhydride, 1-7; maleic anhydride, 3-5, and pentaerythritol, the balance. Coatings made in using the proposed resin show high impact strength and prolonged working life.

EFFECT: improved preparing method.

3 tbl, 5 ex

FIELD: polymer production.

SUBSTANCE: invention provides a method for hydrogenation of polyester oligomers containing terephthalic and isophthalic acid residues, which are thereby converted into 1,4-cyclohexanedicarboxylic acid residues. Also proposed is a method for preparing polyesters containing 1,4-cyclohexanedicarboxylic acid residues by hydrogenating first polyester oligomer containing terephthalic acid residues followed by reacting thus obtained oligomer with one or several polyester-forming reagents to form higher molecular weight polyester. Another embodiment of invention involves hydrogenation of polyester oligomers containing isophthalic acid residues, which residues are converted into 1,3-cyclohexanedicarboxylic acid residues.

EFFECT: expanded synthetic possibilities.

13 cl, 1 tbl, 15 ex

FIELD: chemistry.

SUBSTANCE: method of obtaining alkyd resin includes the operation of mixing in a capacity reactor, connected to a flowing tubular reactor, vegetable oils and polyatomic alcohol in the presence of a catalyst - 10% solution 2-ethylhexanate lead and while heating and the subsequent poly-etherification in the presence of dicarboxylic acid and xylene. Supply of the catalyst is carried out through a measuring hopper, connected at the inlet of the flow reactor, at a speed of not more than 10 l/min. at the poly-etherification stage to the reaction mass is added 10% paratoluenesulfonic acid solution to the xylene at a speed of not more than 10 l/min. Loading of this solution is also carried out through the measuring hopper of the flow reactor.

EFFECT: colour reduction of alkyd resin solution and acceleration of drying of coatings based on it while using reactors of large volumes and increasing the quality of varnish obtained from alkyd resin.

1 cl, 1 dwg

FIELD: oil and gas industry.

SUBSTANCE: here is disclosed application of polycarbonates produced by interaction of organic carbonate (A) of formula RO(CO)OR with aliphatic alcohol (B) and with one or several bi-atomic alcohols (B'); alcohols ROH are detached and one or several products of condensation (K) are formed; upon further inter-molecular interaction of products of condensation (K) ready product is generated. Also there is disclosed application of complex poly-ethers produced by interaction of aliphatic dicarboxylic acid (A2) or it derivative with monooleate of glycerine or monostearate of glycerine (B2) and triatomic alcohol (Cx); notably, molar ratio of hydroxyl groups to carboxyl groups or their derivatives is from 5:1 to 1:5.

EFFECT: disclosed hyper-branched polymers are ready available, do not require considerable expenditures for synthesis and are suitable for dewatering oil emulsions of any deposit.

7 cl, 2 tbl, 17 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of modifying a biodegradable polymer or copolymer. Described is a method of modifying a polymer or copolymer, having the structure of one or more repeating units (1), where n is an integer, m is an integer between 0 and 6, and R is selected from hydrogen, substituted or unsubstituted C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 aralkyl and C7-C20 alkaryl, where said groups may include straight or branched alkyl fragments; optionally one or more substitutes are selected from a group comprising hydroxyl groups, alkoxy groups, straight or branched alk(en)yl, aryloxy, halogen, carboxylic acid, ester, carboxy, nitrile and amido, involving bringing the polymer or copolymer into contact with a cyclic organic peroxide under conditions where at least a certain amount of the said peroxide decomposes. The invention also describes a modified polymer or copolymer obtained using said method.

EFFECT: obtaining a (co)polymer characterised by high degree of branching without formation of gel.

7 cl, 4 ex, 8 tbl, 3 dwg

FIELD: chemistry.

SUBSTANCE: composition contains a radiation-curable olibomer, having glass transition temperature Tg and/or melting point Tm lower than 30°C. The radiation-curable oligomer is obtained through reactionof one or more carboxyl functional polyesters with one or more monoepoxides modified with a (meth)acrylic compound, and/or one or more polyepoxides and one or more α, β-unsaturated carboxylic acids.

EFFECT: obtaining coating compositions, having good chemical resistance, solvent resistance, scratch resistance and surface hardness coupled with improved flexibility, adhesion and scratching during flexure and fast deformation, improved corrosion resistance and improved heat resistance and good electrical insulation properties.

12 cl, 2 tbl, 29 ex

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