Spatial employed phenols with antioxidant properties, methods for their preparation and method of producing polyolefins

 

(57) Abstract:

Usage: the polymerized antioxidants, introduced into the main chain of the polymer, based on the spatial difficult phenols. The inventive spatial zatrudnienie phenols with antioxidant properties formula I, where R1and R2the substituents mentioned below: R3a hydrogen atom or lower alkyl, with n from 0 to 3, or A (R1R2), where R1and R2spatial employed substituents, and R1has the formula II and R2identical to R1or is formula III, in each formula, X and X is an oxygen atom. R4, R5, R6, R7each independently alkyl (C1-C8or optionally, R4and R6can be hydrogen, and R8hydrogen or methyl, or ethyl same or different. Antioxidants produced by interaction disubstituted phenol with the appropriate beta or gamma unsaturated norbornene or base catalysis in an environment of alcohol. These phenolic antioxidants are used in obtaining polyolefins by polymerization of alpha-olefins or copolymerization of them with each other and/or with denami in the presence of catalysis type Ziglio carried out until the content of phenolic antioxidant, chemically associated with the (co)polymer, from 0.05 to 20 wt. 100 (co)polymer. The structure of the compounds of formulas I, II and III are indicated in the text description. 4 C. and 4 h. p. F.-ly, 1 Il. 13 table.

The invention relates to antioxidants, which can be polymerized with other monomers to form copolymers, giving the antioxidative properties of polymers, and to oxidizing agents and methods for use in the creation of such polymers.

The invention relates to a polyolefin having antioxidant properties and prepared by polymerization by Ziegler polymerized Monomeric antioxidant with alpha-olefins. In addition, this invention provides a method of introducing functional linkages in polyolefins via catalysis by Ziegler without excessive use of the joint catalysts or pestivirus agents. The development of a well-known catalytic systems according to the Ziegler has made it possible for the polymerization of alpha-olefins to the widely used polymers and copolymers.

One of the principal disadvantages of the catalytic system according to Ziegler is that it cannot be used for monomers containing functional groups, which are inherently nami catalytic system according to Ziegler, reducing, thus, the actual concentration of these components.

It is also well known that virtually all of the polyolefins require stabilization in order to avoid uncontrolled oxidation, which tends to cause undesirable changes in the polymer, including decay chains, stitching and discoloration, and thus adversely modifies the mechanical and physical properties of the polymer. In the field of stabilization were undertaken extensive research was the creation of a number of antioxidants, which give the polyolefins, including elastomeric polyolefins, more stability. The main class of antioxidants that have been developed over the years, is a difficult class of phenols.

Although molecular antioxidants type obstructed phenols have been widely used for stabilizing a significant amount of polyolefins, they have a tendency under certain conditions to migrate out of the polymer, which leads to depletion of the antioxidant in the polymer and, consequently, to the fact that the polymer has a tendency to decompose during oxidation. Application related antioxidants, which remain in the polymer under conditions that promote migration is their polymerized antioxidants for emulsified rubber. Chemistry and technology of rubber, 46,96 (1973); (2) Meyer, E. Kavchak R. W. and Naples F. J. Emulsified rubber, copolymerizable with Monomeric antioxidants. Chemistry and technology of rubber, 46,106 (1973); (3) Horvath, J. Century Associated antioxidant, stabilizing NBR. Application in the automotive industry. Elastic polymers, August 1979, S. 19; (4) Kuczkowski j.And gillik j. Polymer-bound antioxidants. Chemistry and technology of rubber, 57, 621 (1984); (5) Engels, H. C., and others the Effectiveness of new alkyl-acrylic-p-phenylendiamine, which may be associated with polymers by chemical means. The research model. Chemistry and technology of rubber, 62, 609 (1989); (6) Parker D. K., and Schulz, O. Curable amine antioxidant N-(4-anilinophenol)methacrylamide. Synthesis, copolymerization, the properties of the copolymer and characteristics. Chemistry and technology of rubber, 62, 732 (1989); (7) Gandek Etc., Hatton T. A. and Reid R. K. Single extraction and reaction: the migration of phenolic antioxidants from polyolefins in the water. Results and discussion the experiment. Independent journal of engineering chemical research. 28, 1036 (1989); (8) Miller, D. E. and other strong antioxidants for polymers in contact with extractive environments. World rubbers, August 1989, S. 13. Such antioxidants features Ibuki, or by copolymerization with olefinic monomers during the preparation of the actual polymer.

The resulting copolymerization with other monomers of the polymer-bound antioxidants limited polimerization free radicals, in particular by emulsion copolymerization of free radicals butadiene and Acrylonitrile in the production of nitrile rubbers. Conventional monomers of polymer-bound antioxidants include amide or derivatives of esters of acrylic or methacrylic acid, which can be copolymerizable through the formation of free radicals with butadiene and acrylnitrile. Although such polymer-bound antioxidants are suitable as monomers for the technologies of free radical polymerization, they are not suitable for use in polymerization catalyzed by using a Ziegler catalyst, because of their polar groups tend to act as a substance that reduces the activity of the catalyst.

In U.S. patent N 3748316, 3796687 and 4017669 proposed to carry out the copolymerization of polar monomers with a catalyst of Ziegler. Characteristically, in these earlier patents proposed defined ropylene on the Ziegler catalyst. The General principles used in patents, to which reference is made, include the specified compound having the following General formula

where R1either R or OR, and R is alkyl, acrylic or cycloalkyl containing 1-18 carbon atoms or hydrogen.

In these three patents describe methods by which the compounds of this type can be obtained, and does not describe the polymerization of such monomer. Therefore, these patents do not provide information about these compounds and polymers derived from them. In addition, it is important to note that in these patents is proposed to overcome the poisoning of the catalyst polar groups by applying together with the polar monomer (this is not the monomer, which was discussed above) is equal to the number of molar solution of alkyl aluminum solution is very expensive and very impractical from the point of view of environmental protection and safety used in modern industry production of rubber and plastics. Moreover, there is the idea of the polar monomer phenolic type to impart antioxidant properties obtained by means described in these patents ways polar copolymer.

In U.S. patent N communication and thereby being polymerized.

However, this patent did not specify how to use reactive norbornene phenolic compound in the polymerization, or as to demonstrate that after polymerization, the copolymer thus obtained has antioxidant properties.

The above norbornene monophenols compounds have been the subject invention in the U.S. patent N 4355148 describing the polymerization disclosure of rings and the exchange of the catalyst, which was obtained polymer composition of the antioxidant containing norbornylene phenolic compound with Dicyclopentadiene, norbornene or norbornene substituted with atoms and may therefore olefin such as 1-hexene.

The purpose of the invention is to create a curable antioxidants and methods of their preparation, and curable antioxidant may copolymerisate with another monomer or mixture of monomers, to give the resulting the copolymer antioxidant properties.

A more specific object of this invention is to provide a curable antioxidant compounds that can be prepared in a simple and inexpensive methods and coteries poisoning catalysis.

In accordance with the above, another objective of this invention is to obtain polyolefins having antioxidant properties and are prepared by conventional polymerization processes according to Ziegler, in which registergui antioxidant lightly copolymerized with an alpha olefin or mixture of olefins and is directly embedded in the main chain of the polymer.

Another objective of this invention is to introduce a functional relationship in polyolefins directly through catalysis by Ziegler and without the use of such special technologies, like the use of passivating groups and costly application alumoorganic catalyst for joint action.

The principles underlying the present invention consists in the application of the polymerized by Ziegler antioxidant compounds in the form of a norbornene substituted with atoms, in which Deputy contains alkalemia group, giving the connection antioxidant properties. Among giving the antioxidant properties of the substituents are preferred associated replacement of the aromatic group, and most preferred related alkyl substituted phenols.


(I) in which n is 0-3, R1arrowy radical, giving the antioxidant properties; R2either a hydrogen atom or arrowy radical, giving the antioxidant properties; R3either a hydrogen atom or Akilova group:

or compounds having the formula

where R1and R2each are allowin radical, giving antioxidant properties.

In a preferred example implementation of the invention R1has the formula

R (II) R2has the formula

R (III)

In each of these formulas, X and X1selected from divalent oxygen atom and a divalent sulfur atom; R4, R5, R6and R7each individually are independent alkilani containing 1-8 carbon atoms, such as methyl, ethyl, isopropyl, butyl, tert-butyl, pentyl, isopentyl etc. or, in addition, R4and R5can be hydrogen, R8hydrogen or stands, or ethyl, or a mixture of these compounds, and R3in the above formula is either hydrogen or an alkyl, like methyl, ethyl, propyl, etc.

Acceptable to the progress of the synthesis monopoly olefin containing antioxidant and the corresponding present invention, zvesdnuy reaction Diels-Adler, to form 2-norbornene substituted in the 5-th position alkalinous or alkylenediamine group through the interaction of cyclopentadiene 4-alkenylphenol, as shown below.

< / BR>
Particularly preferred examples of implementation of the present invention should include the following structure

< / BR>
Among mentioned above besttransport preferred are the compounds shown in the drawing.

Corresponding to this invention bisphenol curable antioxidants can be prepared from the reaction catalyzed condensation disubstituted phenol and/or disubstituted of thiophenol 2-norbornene-carboxylic compound according to the following equation

< / BR>
Suitable 2-norbornene-carboxylic compounds should include those in which R3is hydrogen or such Akilova group as methyl, ethyl, propyl, etc., with carboxyl substitution in any of the provisions of the norbornene ring, except the carbon atoms with double bonds.

Beta, gamma-unsaturated norbornene type those structures that are depicted below

also should be suitable as starting materials for the condensation reaction with phenols or thiophenol is subramania in practice disubstituted phenols and/or the disubstituted thiophenol must have as each of the groups R4and R5such independent alkyl containing 1-8 carbon atoms, like methyl, ethyl propyl, isopropyl, butyl, tert-butyl, pentyl, isopentyl etc.

The characteristic product of the reaction between 2-norbornene-5-carboxyaldehyde and two equivalents of 2,6-di-tert-butylphenol was called bisphenol-N and is represented as follows

< / BR>
When two phenolic and/or thiophenolate groups are substituted on the same molecule of norbornene, the corresponding curable antioxidant can be prepared by using a suitable mixture, usually equimolar mixture of two phenols, thiophenols or a mixture of phenol with thiophenols to form properly mixed product.

The reaction can be conducted by dissolving the phenol or thiophenol in a solvent such as lower alcohol as methyl alcohol, and then adding potassium hydroxide dissolved. Then added 2-norbornene-5-carboxyaldehyde, followed by neutralization and isolation of target compounds or mixtures of compounds.

Specialists in the art will appreciate the use of a mixture of phenol, a mixture of thiophenols or a mixture of phenol and thiophenol, pascalle and thiophenolate.

Corresponding to the present invention is polymerized by Ziegler antioxidants usually find particular application as copolymers in catalyzed by Ziegler polymerization reactions of olefins. Thus, corresponding to this invention, the antioxidant may copolymerisate with such alpha-olefins as ethylene, propylene, butene or hexene, such danami with conjugated double bonds, or without them, as butadiene, isoprene and 1,4-hexadiene, and styrene. In addition, corresponding to the present invention, the antioxidants can be used as a copolymer in the polymerization reaction mixtures of olefins upon receipt of trimers, tetramers, etc. of the Resulting polymers containing antioxidants may be crystalline or amorphous and are widely used from plastics to elastomers.

Typical Ziegler catalysts used for the implementation of the present invention consist of a compound of the transition metal, and the metal is selected from groups IV to VI of the periodic Table of elements (as published in the Catalog of chemistry and physics" by the company "see chemical rubber end company, Cleveland, PCs Ohio, USA) and used in conjunction with the alkylate Il is a metal selected from groups I-III of the periodic Table of elements. Examples of commonly used transition metals should include vanadium, titanium, zirconium, cobalt, chromium and Nickel. Examples of commonly used alkylates base metals are different alumoorganic compounds, aluminum-halodurans connection tsinkorganicheskih connection or magyarkanizsa connection. Compounds of the transition metal can be homogeneous or heterogeneous and can be complex or in combination with such electrondonor chemicals as complex organic ethers, amines, phosphines, silicates and other substances. Alternatively, the transition metal may be deposited on such an inert carrier, as MgO, Mgl2, silicon dioxide or aluminum oxide. For the implementation in practice of the present invention, in particular for the preparation of linked polyethylene with antioxidant acceptable when CrO3deposited on the activated aluminosilicate, i.e., the catalyst, also known as the catalyst "Phillips".

The reaction of polymerization by Ziegler with Monomeric olefin containing antioxidant, not limited by the process conditions and can be performed in solution, slurry, gas phase or in any combination of such processes. As eskay catalytic system of the Ziegler.

Active Ziegler catalyst is not adversely affected by monomer polymerized antioxidant. You can use the standard methods of polymerization by Ziegler, including ways to control molecular weight, well known to experts in the art, to obtain polymers with the associated antioxidant at the same molecular weight, distribution of molecular weight, the same stereospecificity and the same levels of comonomers as standard polymers. The molar ratio of the catalyst components of the alkylate base metal and the transition metal does not change. Not required stage of adding the catalyst components. The preliminary reaction of alkyl of base metal with a monomer polymerized antioxidant and is not required, and spam.

A useful example of polymerization by Ziegler antioxidant suitable for the invention, with a mixture of alpha-olefins is the preparation of ethylene-propylene-copolymer rubber and trimerization of polyethylene, alpha-olefin with 3-18 carbon atoms and diene without conjugated double bonds at the time of receipt of ternary ethylene-propylene-diene copolymer rubbers. noticecookie the polyene and the polycyclic polyene. Representatives of such compounds are dechlorination, octadiene, cyclo-(2,2,1)-hepta-2,5-diene, alkylguanine norbornene in which alkilany group contains from one to twenty carbon atoms and preferably from one to eight carbon atoms, the olefin norbornene and, in particular, 5-alkenyl-2-norbornene in which alkenilovyh group contains from three to twenty carbon atoms. Other suitable polyene having a ring with an inner bridges are polyunsaturated derivatives of bicyclo-(2,2,2)-hexane, such as bicyclo-(3,2,1)-hexane, polyunsaturated derivatives of bicyclo-(3,3,1)-nonane and polyunsaturated derivatives of bicyclo-(3,3,1)-nonane and polyunsaturated derivatives of bicyclo-(3,2,2)-nonane.

Examples of preferred compounds having rings with internal bridges are 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-n-propylidene-2-norbornene, 5-isobutylidene-2-norbornene, 5-n-butylidene-2-norbornene, Dicyclopentadiene,5-(2-methyl-2-butenyl)-2-norbornene, 5-(3-methyl-2-butenyl)-2-norbornene and 5-(3,5-dimethyl-2-hexenyl)-2-norbornene.

Copolymer of ethylene-propylene/ethylene-propylene-diene rubbers containing curable antioxidants that corresponds to the Lena (or another monoolefinic, containing 3-16 carbon atoms), varying from 95:1 to 5:90 (ethylene, propylene) and preferably from 85:15 to 55: 45. Polian or substituted Polian chemically bound in the ternary ethylene-propylene-diene rubber, and the amount of 0-30% by weight. Monomer polymerized antioxidant that corresponds to this invention, is connected in the main chain of the polyolefin in an amount of 0.001-20% by weight, which depends, in particular, for any specific application is intended polymer. The same amount of the polymerized antioxidant can be used in the other above-described polymers.

Such polymers are produced by copolymerization in the presence of a catalyst of Ziegler, well known to specialists. Methods of production of such ethylene-propylene or ethylene-propylene-diene copolymers are well known and are described in U.S. patent N 2933480, 3093621, 3211709, 3645168, 3790519, 3884993, 3894999 and 4059654, as well as in many other patents.

Described here, the monomers are polymerized antioxidant generally applicable and when copolymerized with ethylene to create high-density polyethylene, including polyethylene ultra-high molecular weight, and the ethylene and such alpha-olefins, how bout undertim conditions, which are well known to experts in the art, adding monomer polymerized antioxidant in the form of a solution of hexane, toluene, in the form of a liquid monomer or alkenovich hydrocarbons.

The copolymerization of the monomers polymerized antioxidant suitable for the invention, with propylene or mixtures of propylene and alpha-olefins at a level of 0.01 to 1.0% by weight gives thermoplastic polymers of propylene, resistant to auto-oxidation and thus suitable for processing under less severe conditions it compared to the usual polypropylene type thermoplastics.

Thus, the corresponding present invention curable antioxidant lightly copolymerized with an alpha olefin or mixture of alpha-olefins and is used to make the polymer antioxidant properties. One advantage of this invention is that unlike antioxidants that are physically mixed with the polymer composition and tends to migrate through the polymer matrix, the polymerized antioxidants, corresponding to the present invention, is not affected by this migration, because they are chemically bonded to the polymer matrix. When you implement this image is karnego products when the liquid contact is maintained until the end of the reaction. Introduction in the main chain of the polyolefin polymerized antioxidant in an amount of 0.1 to 2.0% by weight manifests itself in resistance to oxidation upon receipt, transportation and storage. Introduction in the main chain of the polyolefin polymerized antioxidant in the amount of 0.5-20% by weight provides the resistance to oxidation for high temperature processing of the polyolefin. At such high levels copolymerizing antioxidant polyolefin is also suitable for mixing with the polyolefin and/or polymers, which do not possess antioxidant properties.

Consider the following examples which are given for illustration and not for limitation, and discusses possible ways to implement the present invention upon receipt of the polymerized antioxidants, corresponding to this invention, and their use in the reaction of copolymerization of different monomers.

P R I m e R 1. Preparation and characterization of the condensation product of 2,6-di-tert-butylphenol, 2-norbornene-5-carboxyaldehyde, called bis-phenol N(N).

Synthesis of bisphenol.

Ranitelei funnel, refrigerator and indirect heating. In a flask loaded reagent methanol containing 5.2 g of dilute KOH, that is 0.08 mol of KOH. After that add by 41.2 g (0.2 mol) of 2,6-di-tert-butylphenol. The mixture is placed in a nitrogen atmosphere, carefully load and stirred until then, until you dissolve the phenol. A solution of 9.8 g (0.08 mol) of 5-norbornene-2-carboxaldehyde (mixture of isomers) in 20 ml of methanol is added dropwise through an additional funnel, stirring. The mixture of reactants is heated at the temperature of reflux distilled for 16 h, then allowed to cool to room temperature. Residue that can be collected by filtration and washed with fresh methanol. The product is a white powder having a melting point of 203-205aboutC. is Obtained the product yield in the amount of 20.0 g, which corresponds to 48% of theoretical yield.

Characterization of bisphenol

Bisphenol N is a colorless crystalline solid, having a melting point 204-205aboutC. the infrared spectrum of bisphenol a N detects the absorption bands are given in table. 1.

Peaks of the mass spectrum (the study of solids, m) are listed in table. 2.

Spectra of proton and nuclear (13(C) magnetic resonance bisfe what about N is a mixture of Exo - and endosomes. This is confirmed by liquid chromatography.

Elementary analysis:

Calculated for C36H52ABOUT2:C 83,65; N 10,16; TO 6.19.

Found (according to the results of counting experiment): 83,85, N 10,16, 5,99.

P R I m m e R 2. The copolymerization of bisphenol N with ethylene and propylene.

During typical for the case of polymerization of 2.0 ml of a solution of 4.09 g of recrystallized bisphenol N in 8,61 g of toluene is added to the dispenser Sutherland containing 3.8 mmol of sesquichloride ethylamine, 0.4 mmol of chloride vanadyl, 0.3 mmol of pyridine and 0.05 mmol of butylperoxybenzoate in 900 ml of hexane, and copolymerized with ethylene and propylene. The temperature in the dispenser is 38aboutC and a total pressure of 0.3 MPa. The pressure in the dispenser is maintained during the entire period of operation by adding a mixture of 60% ethylene and 40% propylene. After 20 min after starting the reaction is stopped by inhibiting the catalyst and 1.0 g of isopropyl alcohol, and the resulting polymer (19,0 g) precipitated by adding reacting a mixture of isopropyl alcohol.

Obtained in example 2, the polymer allocate using cyclohexane acetone to remove any residues of the monomer, and then checking means is 0 cm-1.

P R I m e R 3. A generalized procedure for copolymerization of ethylene, propylene and ethylidenenorbornene.

In the we cork the bottle is placed 150 g of hexane, 0.8 mmol of sesquichloride ethylamine, 0,065 mmol chloride vanadyl, 0.02 mmol of butylperoxybenzoate, 0.3 g of ethylidenenorbornene and 0.05 mmol of pyridine. When the reaction support the pressure of 0.31 MPa by adding a mixture containing 60% ethylene and 40% propylene. The reaction is conducted at room temperature and stopped after 20 min after the start by adding isopropyl alcohol.

The following examples illustrate the copolymerization of bisphenol a with ethylene, propylene and etilendiaminom.

P R I m e R s 4-8. The polymerization reactions were carried out as described in example 3, with the addition of various amounts of bisphenol N in 30% solution of the toluene. The weight of the total amount of reacted mixture is determined after the reaction, and analysis solution for residual bisphenol N carried out by liquid chromatography under high pressure. The results of the analysis are summarized in table.3. During the chromatographic analysis, it was noted that the standard solutions of monomer bisphenol N found two peaks that can achie the residual bisphenol a N a larger value of the specified ratio shows that both isomers are polymerized to varying degrees.

The data table.3 show that the polymer yield and lifetime of the catalyst is not very affected with the increasing content of bisphenol N in the polymerized substance. In each of the polymers 5-7 percent of the chemical conversion of bisphenol N is approximately 90-95, and its behavior is similar to behavior of ethylidenenorbornene, whose percentage of copolymerization is not concentration dependent.

P R I m e R 9A. General procedure for the synthesis of an analog of bisphenol N-alpha, alpha-bis(2,6-dimethylphenol)-5-methylene-2-norbornene.

The reaction is performed in a round bottom flask with three necks with a capacity of 200 ml equipped with a fridge, a mechanical stirrer and a rubber diaphragm. In the flask is charged with 50 ml of reagent methanol, 5,2 g (0.08 mol) of KOH in tablets and 24.4 g (0.2 mol) of 2,6-dimethylphenol. The reaction of lead in the atmosphere of nitrogen, allowing it to pass through the aperture and out through the fridge in the form of bubbles containing mineral oil. By injection through the aperture and add 5-norbornene-2-carboxaldehyde (9,8 g, 0.08 mol). The reacting mixture is heated at the temperature of reflux distilled for 16 h under stirring. After cooling the 100 ml dichloromethane. Then carry out a triple rinse in a separating funnel portions of fresh water and 30 ml. of the Solution is dried with magnesium sulfate. After filtration to remove the drying agent, the solution is evaporated to obtain 27.5 g of the solid residue. The residue is purified by chromatographic column (silica gel, 1/1 hexanchiformes) and obtain 16.5 g of the product, the yield is 59% of theoretical value. Re-crystallization from toluene gives colorless crystals which have a melting point 176-178aboutC. This product is similar to bisphenol N, with phenolic rings instead of groups, tert-butyl their alternates methyl group.

P R I m e R 9B. Polymerization ternary ethylene-propylene-diene copolymer with an alpha, alpha-bis(2,6-dimethylphenol)-5-methylene-2-norbornene.

In the dispenser Sutherland load 900 ml of dehydrated hexane, purged with nitrogen and propylene, to remove traces of oxygen, and raise the pressure to 0.17 MPa, conducting compression with propylene. To bring the total pressure in the dispenser to 0.31 MPa, add an additional amount of a mixture containing 60% ethylene and 40% propylene.

Thereafter, the dispenser add to 4.8 mmol of sackvil is and N, added in the form of a solution in toluene, and 0.05 mmol of trichloride vanadyl. The reaction temperature 40aboutWith the pressure in the dispenser is supported at the level of 0.31 MPa during the whole time of passage of the reaction, the pressure is maintained by adding a raw material containing 60% ethylene. The reaction is interrupted after 20 min after the start by adding 1.0 ml of isopropanol. The polymer is coagulated in isopropanol and dehydrated in a vacuum oven.

Just got 5.8 g of polymer. He had the viscosity of the solution decreased to 2.08. The polymer was 65,1% by weight of ethylene and 0.79% by weight of alpha, alpha-bis(2,6-dimethylphenol)-5-methylene-2-norbornene, as determined by IR analysis.

P R I m e R 10. Polymerization of polypropylene with bisphenol N c by using a titanium catalyst.

In the dispenser Sutherland load 500 ml of dehydrated hexane and purge it with nitrogen and then with propylene to remove traces of oxygen. After the dispenser has added 5.4 mmol chloride diethylamine in hexane, the temperature is increased to 60aboutC. Then loaded into the dispenser 0.18 g of bisphenol N in hexane and 2.7 mmol of catalyst trichloride titanium. Using propylene pressure in the dispenser immediately increases to 0.31 MPa. Support him n istoricheskogo polypropylene recovered by filtration after as a hexane slurry was extracted twice using 400 ml of water. IR analysis of kiln dried polypropylene showed the presence of bisphenol N in the amount of 0.3% by weight.

P R I m e R s 11 A-E. the Copolymerization of bisphenol a IX with ethylene and propylene.

The polymers are given as in example 3, except that ethylidenenorbornene was not used. The presence of bisphenol N in solution upon completion of the polymerization reaction is not observed. Polymers restore through coagulation with isopropanol, dehydrated at room temperature in vacuum and used as samples in the analysis based on the absorption band of the infrared spectrum at a frequency 3610 cm-1. The results are shown in table. 4.

P R I m e R 12 and 13. The following examples 12 a and 13 a-E compared polymerization of ethylene, propylene and bisphenol N in toluene and ethylidenenorbornene as solvents.

P R I m e R 12 A-E. receive Polymers in accordance with the method described in example 2, except that using 0.2 mmol of vanadium chloride and 0.1 mmol of butylperoxybenzoate. Bisphenol N added in the form of a solution of 0.6 g of bisphenol N in 25 ml of toluene. The results are shown in table.5.

PQS is a torus, where the polymerization, in the form of a solution in an inert solvent. Although toluene is a good solvent to bisphenol N, it is possible to use other solvents. Generally speaking, you can apply any solvent which does not contain polar groups, poison the catalyst. In particular, an acceptable solvent for the introduction of bisphenol N in D reactors is ethylidenenorbornene because it is already added as comonomer.

P R I m e R s 13 A-that is, the Polymers produced by the method described in example 2, except that the addition of bisphenol N is in the form of a solution of 1 g of bisphenol N in 25 ml of ethylidenenorbornene. In addition, adding an additional number of ethylidenenorbornene, so that its total amount was 1.0, the Results are shown in table.6.

P R I m e R 14. A copolymer of polyethylene with bisphenol N, obtained with the use of vanadium catalysts.

In the dispenser Sutherland load 900 ml of dehydrated hexane and 0.16 g of bisphenol N, then rinsed several times to get rid of traces of oxygen, and use of ethylene increase the pressure to 0.28 MPa. To control molecular weight, add hydrogen under a pressure of 0.03 MPa. The dispenser is heated to 40<'s the MINIA, 0.12 mmol of butylmethacrylate and 0.02 mmol of trichloride vanadyl. Ethylene during the reaction is added continuously to maintain the dispenser pressure of 0.31 MPa. After 20 min after start of the reaction, add 1.0 ml of isopropanol, to stop the reaction. The obtained polymer (7.6 g) restore, and then double-diluted with trichlorobenzene and re-precipitated before subjected to analysis by the methods of IR-spectroscopy in the presence of the corresponding phenolic groups. IR analysis showed that the polyethylene contains bisphenol N in number 0,64% by weight.

P R I m e R 15. Polyethylene with an associated antioxidant, obtained by using a titanium catalyst.

P R I m e R 15A (polyethylene). The polyethylene can be obtained by using titanium catalysts. In the dispenser Sutherland load 900 ml of dehydrated hexane, rinsed several times to remove traces of oxygen, and using ethylene raise the pressure to 0.31 MPa. The dispenser is heated to 40aboutAnd add it to 6.0 mmol chloride diethylamine and 1.8 mmol of trichloride beta-titanium. Ethylene is added during the reaction continuously to maintain the pressure response at the level of 0.31 MPa. After 20 min after the start add 1.0 ml of isopropanol, so that the OS is="ptx2">

P R I m e R 15V (bisphenol N). Polyethylene is produced in the same manner as in example 15A, except that add 0,096 g of bisphenol N. the Obtained polymer (9.3 g) restore and re-precipitated before studied by IR-spectroscopy in the presence of the corresponding phenolic groups. IR analysis showed that the polyethylene contains bisphenol N in the amount of 0.33% by weight.

P R I m e R s 16-21. The study of thermal ageing of polymers containing bisphenol n

The following examples illustrate thermal aging of the EPM copolymers containing bisphenol n

Samples of Hermas and D containing either mixed or copolymerizing bisphenol N, and get tested for resistance to thermal aging at a temperature of 100aboutWith in an oven with forced air supply. Samples containing industrially produced mixed antioxidant "Irganox 1076" company "Ciba-Geigy", and samples containing no antioxidant, used as a control. The compositions of the samples EPM regulate the viscosity of the recovered solution. The compositions D regulate the measurement of gelation. The research results of thermal aging are listed in table.7 and 8.

aboutUsing the mixture, which consists of 60% ethylene and 40% propylene. Then in the dispenser add sesquichloride ethylaluminum (4.8 mmol), pyridine (0.3 mmol), butylmethacrylate (0.2 mmol) and chloride vanadyl (0.1 mmol). The reaction is stopped after 20 min by adding 1.0 ml of isopropanol, and the polymer is isolated and dried. The reaction product is a copolymer of ethylene and propylene, having a viscosity of recovered solution of 1.9 and an ethylene content of 57 mol.

C o n t R o l b n m s p R I m e R 16B. The polymer obtained in reference example 16 was dissolved in hexane. To the solution was added bisphenol N (0,35 hours 100 hours of rubber). Rubber produce coagulation in acetone.

C o n t R o l b n m s p R I m e R 16C. The polymer obtained in reference example 16 was dissolved in hexane. To the solution was added bisphenol N (0,35 hours 100 hours of rubber). Rubber allocate evaporation of the hexane.

C o n t R o l b n m s p R I m e R 16D. The polymer obtained in reference example 16 was dissolved in hexane. To the solution add "Irganox 1076" (0,35 hours 100 hours of rubber). Rubber allocate vcto in example 16 And, only add in the dispenser another 1.0 g of ethylidenenorbornene. The reaction product is an ethylene (propylene)ethylidenenorbornene the trimer with the viscosity of the recovered solution of 2.1, the molar ratio of ethylene and propylene, equal to 65:35, and the content of ethylidenenorbornene, equal to 4.6% by weight.

C o n t R o l b n m s p R I m e R 17C. The polymer obtained in reference example 17A, dissolved in hexane. To the solution was added bisphenol N (0,2 hours 100 hours of rubber). Rubber produce coagulation in acetone.

C o n t R o l b n m s p R I m e R 17C. The polymer obtained in reference example 17A, dissolved in hexane. To the solution add biphenol N (0,2 hours 100 hours of rubber). Rubber allocate evaporation of the hexane.

C o n t R o l b n m s p R I m e R 17D. The polymer obtained in reference example 17A, dissolved in hexane. To the solution add "Irganox 1076" (0,2 hours 100 hours of rubber). Rubber allocate evaporation of the hexane.

P R I m e R s 17 and 18. These polymers receive the same manner as in example 16, but the bisphenol N added in the form of a solution of 0.6 g of bisphenol N in 25 ml of toluene. Different amounts of this solution was added to reaction mixture to obtain the content of the bisphenol N, equal to 0.2% by weight in example 18, and Rav is istwa are listed in table.7 along with the properties of the products, obtained in reference examples 16A D. Before test thermal ageing the samples dissolved in hexane, and then carry out their coagulation with acetone.

P R I m e R s 20 and 21. These polymers receive the same manner as in example 17, but bisphenol N added in the form of a solution of bisphenol N in ethanobotany. Order to get the content of the bisphenol N is equal to 0.1% by weight in example 20, and 0.2% by weight in example 21, in the solution add different amounts of bisphenol n In each sample solution add such number of ethylidenenorbornene to its total each time was 1.0, the Products of the reaction are trimers of the ethylene (propylene) bisphenol N, their properties are listed in table.8 along with the properties of the products obtained in reference examples 17 A-D. Before test thermal ageing the samples dissolved in hexane, and then carry out their coagulation with acetone.

Listed in the table. 7 and 8 the results show that the curable antioxidant bisphenol N in the form of a copolymer behaves the same as blended with antioxidants (comparison of copolymers of bisphenol N with control samples C and D), and after 10 weeks has additional advantages of the mi and In). Comparison of the control samples a and b shows that coagulation in acetone removes unbound antioxidant. Copolymerizing bisphenol N is not removed by coagulation in acetone.

P R I m e R s 22-23. The influence of variable reactions to the introduction of bisphenol n

Bisphenol N does not manifest itself as a poisoner of the catalyst. This can be seen from the previous examples 4-8, where the bisphenol N in number 0,78 of 5.4% by weight, copolymerizable part D, had little effect on the number of developed polymer. However, all these examples were carried out under similar conditions, were therefore performed further experiments to see whether you can make the same conclusions at different levels of the activator and/or at different levels of concentrations of the monomers.

P R I m e R s 22 A-d Polymers receive the same manner as in examples 16 and 17, except that the levels of activator butylperoxybenzoate (butyl-PVA) were different. Also use large quantities of bisphenol N at two different levels. The results are shown in table.9.

Data show a decrease in molesti catalyst at high levels of bisphenol N. This slightly-D.

Polymers receive the same manner as in examples 18-19, except that they use 0.6 mmol activator butylperoxybenzoate and feed dispenser spend a mixture consisting of 80% ethylene and 20% of propylene. To regulate the molecular weight of conduct and recharge of hydrogen, while maintaining its pressure at normal levels. The results are shown in table.10.

The influence of hydrogen appears to be typical for systems of catalysis, in which the amount of bisphenol N slightly. There is also a small effect of hydrogen on the chemical properties of the polymers, as shown by measurements of BBP and penetrating chromatography gel. The results are shown in table.11.

P R I m e R 24. Continuous polymerization bisphenol n

The reaction is carried out in a glass reactor with a capacity of 4 l, in the top steel cover which made the openings for the additive components, the cover is equipped with a dip tube for removing liquid at the polymerization, a blade mixer for mixing and internal coil for cooling. Continuous polymerization is carried out at a temperature of 33aboutC and a pressure of 0.33 MPa, temperature control is carried out by circulating cold market and other components are continuously added to the reactor during the whole of that time, while from the reactor flows a continuous stream of liquid during polymerization to maintain the level of the liquid in the reactor was constant.

The speed of feeding of the reactor are: hexane 4,72 l/h, propylene -3,2 standard liters per minute, ethylene 1,90 standard liters per minute hydrogen 17 cm3/min (93,5 mol. in terms) and ammonia 1,12 cm3/min (0.50 mmol/l). Diluted solutions of sesquichloride ethylamine, oxytrichloride vanadium and butylferrocene add separate flows with the speed of feeding, respectively, 10,0, 0.50 to 0.60 mmol/h of Ethylidenenorbornene add with the speed of feeding of 11.2 g/h dissolved in hexane. Bisphenol N feed speed from zero (experience) to 3.2 g/h (experience) and 6.1 g/h (experience With). Bisphenol N added in the form of a solution of bisphenol N in ethylidenenorbornene (EN).

A continuous flow of air ventilation (air flow is 450 cm3/min) is removed from the reactor evaporation to provide samples for gas chromatography and avoid contact with the inert gas in the reactor.

Unloading solution of polymer from the reactor to carry out continuous deactivation and washing the solution with water in the second tank with mixer. The exit velocity of the polymer is thanki ferry and the resulting polymer is dehydrated by hot air in an oven at a temperature of 50-60aboutWith over 40 minutes of the Antioxidant type "make up 1076" add to the experience And the solution washed in the reactor to the distillation with steam. In experiments b and C Supplement "make up 1076" do not produce. The results are shown in table.12.

P R I m e R 25. Polymerization D with alpha-(2,6-di-tri-butylphenol)-5-methylene-2-norbornene.

Using the same General procedure described in example 9B, alpha-(2,6-di-tri-butylphenol)-5-methylene-2-norbornene lightly copolymerized with ethylene and propylene. The resulting polymer may contain curable antioxidant in the amount of 0,84% by weight.

The amount of antioxidant for each example are given in table.13.

Thus, these data clearly show the amount of oxidant introduced into the process and chemically linked (co)polymer.

1. Spatial employed phenols with antioxidant properties, formulas

< / BR>
< / BR>
where n 0 3;

R1and R2the following deputies

R3hydrogen or lower alkyl; or

WHILE (R1R2)

where R1and R2spatial employed the de X and X1divalent oxygen;

R4, R5, R6and R7WITH1WITH8-alkyl;

R4and R6hydrogen;

R8hydrogen or methyl or ethyl, the same or different.

2. Connection on p. 1, wherein R4, R5, R6and R7selected from the group: methyl, isopropyl or tert-butyl.

3. Connection PP.1 and 2, characterized in that X and X1each oxygen.

4. Connection PP.1 to 3, characterized in that R1and R2- each group of the formula

< / BR>
5. Connection PP.1 to 5, characterized in that R3hydrogen, R1and R2have the formula

< / BR>
and connected with norbornene skeleton in o - or p-positions to the phenolic group.

6. A method of obtaining a spatial difficult phenols with antioxidant properties, the General formula

< / BR>
where n=0 to 3;

R1and R2spatial employed substituents, and R1has a General formula

< / BR>
R2=R1or has the General formula

< / BR>
where R3hydrogen or lower alkyl;

X and X1divalent oxygen;

R4, R5, R6and R7each1- C8-alkyl;
the tives such as those what does the interaction between disubstituted phenol and 2-norbornenedicarboxylic with base catalysis in an environment of lower alcohol as solvent.

7. A method of obtaining a spatial difficult phenols with antioxidant properties, the General formula

< / BR>
where R1has a General formula

< / BR>
R2=R1or has the General formula

< / BR>
X and X1divalent oxygen;

R4, R5, R6and R7each1- C8-alkyl;

R4and R6hydrogen;

R8hydrogen, or methyl, or ethyl, same or different,

characterized in that the connection is produced by interaction between the disubstituted phenol and a-or g-unsaturated norbornene with base catalysis in an environment of lower alcohol as solvent.

8. The method of producing polyolefins by polymerization of a-olefins or copolymerization of them with each other and/or with denami in the presence of a catalyst of the Ziegler type and phenolic antioxidant, characterized in that as a phenolic antioxidant use spatial hindered bisphenol General formula

< / BR>
< / BR>
where n=0 to 3;

R1and R2the following semesternoten employed deputies, and R1has a General formula

< / BR>
where R2=R1or has the General formula

< / BR>
X and X1divalent oxygen;

R4, R5, R6and R7each1- C8-alkyl;

R4and R6hydrogen;

R8hydrogen, or methyl, or ethyl, same or different,

moreover, the process is carried out at a mass ratio of phenolic antioxidant: monomer (0,1 40) 100 and (co)polymerization is carried out before the content of phenolic antioxidant, chemically linked (co)polymer, of 0.05 to 20 wt. on 100 wt. (co)polymer.

Priority points:

10.07.90 on PP. 1,2,3,4,5 and 7;

02.11.90 on PP.6 and 8.

 

Same patents:

The invention relates to the field of production of low molecular weight rubbers used in the production of binders for solid rocket fuels and combustible materials, sealants, chemical resistant coatings, paint coats and t

The invention relates to the chemistry of polymers and can be used to obtain a low viscosity of polystyrene, which finds wide application in the manufacture of electrophotographic developing compositions (toners)

The invention relates to a method of gas-phase polymerization of alpha-olefins in a reactor with a fluidized bed

The invention relates to organic chemistry, particularly the chemistry of high molecular compounds

The invention relates to organic chemistry, particularly the chemistry of high molecular compounds

The invention relates to the petrochemical industry, in particular to the process of inhibiting polymerization vinylaromatic compounds in the process of receiving, storage and transportation

The invention relates to the petrochemical industry, in particular to the process of inhibiting polymerization vinylaromatic and diene compounds in the process of receiving, storage and transportation

The invention relates to a technology for chromatographic materials used for the selection of chemical compounds in biological systems, chemical, pharmaceutical and food industry
The invention relates to the control of chemical engineering processes, in particular to methods for control of batch polymerization

The invention relates to chemical technology, and specifically to a method for producing 2,2-methylene-bis-(4-methyl-6-tert-butylphenol) highly effective antioxidant used to stabilize rubbers, synthetic rubbers, plastics, polymeric substances, food products, lubricants

The invention relates to an improved method for producing 2,2-bis-(3,5-dibromo-4-hydroxyphenyl) propane (tetrabromdifenilolpropan, tetrabromobisphenol, TRIP), which can be used as a flame retardant to obtain epoxy resins with low Flammability, used in electrical products with improved dielectric properties and other polymeric materials

The invention relates to chemical technology and can be used in the production of pyrocatechin and hydroquinone, which are widely used as intermediates for the production of antioxidants, pharmaceuticals, dyes, etc

The invention relates to the production of additives to polymeric materials, and in particular to a method for producing 3,5-di-tert-butyl-4 - hydroxyphenylacetate (formula I), which is the initial product in the synthesis of valuable phenolic stabilizer 2,4,6-tri-(3,5-di-tert-butyl-4-hydroxybenzyl) mesitylene (see

The invention relates to petrochemical synthesis, namely to obtain 2,6-di-tert-butylphenol (2,6-DTBP) emitted from the products of alkylation of phenol with isobutylene by rectification method

FIELD: chemical technology.

SUBSTANCE: invention relates to preparing antioxidants of phenolic type. Method involves using alkylation products of mixture of para- and ortho-isomers of isononylphenol with isobutylene as an antioxidant. Alkylation reaction is carried out at 40-120°C and 0.02-0.4 MPa in the presence of acid catalyst in batch and continuous feeding isobutylene to reactor unit providing maintaining isobutylene concentration in reaction mass 0.8 mole/l, not above, and the total amount of isobutylene feeding to alkylation 1.82-2.0 mole per 1 mole parent alkylphenols. Method provides preparing antioxidant showing good technological properties and high effectiveness of protective effect for rubbers of emulsion polymerization and rubbers based on thereof, and simple method for its synthesis also.

EFFECT: improved method for preparing.

6 cl, 3 tbl, 7 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of phenols alkylated at ortho-position as parent substances used in preparing organic compounds. Method for preparing o-alkylphenols is carried out by interaction of phenol with alkanol at increased temperature in gaseous phase in the presence of metal oxide as a catalyst. Process is carried out for at least two stages in the molar ratio alkanol : phenol about ≤0.4, preferably, from 0.2 to 0.4 at each stage. Methanol is used as alkanol usually using aluminum gamma-oxide as a catalyst and process is carried out at temperature 300-400°C. Reaction products are separated by distillation. Invention provides increasing yield the end product due to enhancing selectivity with respect to o-alkylphenol.

EFFECT: improved method for preparing.

9 cl, 4 tbl, 2 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to phenolic compounds, derivatives of dialkoxyethanals that are intermediate substances in organic synthesis and can be used as cross-linking agents of phenolic type no evolving formaldehyde also. Phenolic compounds are described of the general formula (I):

wherein: R means (C3-C17)-dialkoxymethyl, 1,3-dioxolan-2-yl substituted possibly at positions 4 and/or 5 with one or some (C1-C8)-alkyls, or 1,3-dioxane-2-yl substituted possibly at positions 4 and/or 5, and/or 6 with one or some (C1-C8)-alkyls; n = 1, 2 or 3, and group or groups of the formula: -CH(OH)-R are at ortho-position and/or at para-position with respect to OH in the cycle group; m = from 0 to 4-n; X means the functional group, such as OH or Hal, or (C1-C8)-alkyl, or (C1-C8)-alkoxyl, or (C5-C12)-aryl comprising in the known cases 1 or 2 heteroatoms, such as nitrogen or oxygen, or carboxy-group, or the group -CO-Y wherein Y means (C1-C8)-alkyl or (C1-C8)-alkoxyl, or amido-group, or amino-group, or thiol-group under condition that at least on of ortho- or para-positions in phenol cycle must be substituted with hydrogen atom, and their salts with alkaline metals, earth-alkaline metals and amines also. Method for preparing indicated phenolic compounds involves interaction of the corresponding substituted phenol wherein at least one ortho- or para-position in phenol cycle must be substituted with hydrogen atom with substituted aldehyde in the presence of a base. Invention provides preparing new compounds that can be used as cross-linking agents no evolving formaldehyde and as intermediate compounds used in organic synthesis.

EFFECT: improved method for preparing.

13 cl, 1 dwg, 10 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing hydroxyaromatic compounds by oxidation of aromatic compounds with nitrous oxide in gaseous phase in the presence of zeolites. Method is realized by interaction of aromatic compounds of the formula (I): Ar-Rn wherein Ar means benzene or naphthalene; R means bromine, chlorine, fluorine atom, -NO2, -CN, -NH2, hydroxy-group, alkyl with 1-6 carbon atoms or phenyl; n = 0, 1 or 2 with nitrous oxide in gaseous phase in the presence of zeolites taken among the following order: pentasil, ferrierite and zeolite-β. Zeolite crystallites size is less 100 nm that is calcined before using at temperature from 500°C to 1350°C for 0.5-18 h. Before the calcination process zeolite is modified preferably by precipitation of silane or borane. Method provides realization of the process for a single step with high yield of the end compound and minimal formation of by-side substances.

EFFECT: improved preparing method.

11 cl, 3 tbl, 13 ex

Up!