The method of obtaining elastomeric copolymers of ethylene and propylene

 

(57) Abstract:

The method of obtaining elastomeric copolymers of ethylene with propylene in the suspension of liquid monomer in the presence of a catalyst chosen from titanium salt deposited on a salt of magnesium, and soluble in hydrocarbon solvents, vanadium compounds, or deposited on an inert material, or pre-polymerized, and socializaton, essentially consisting of an organic aluminum compounds, and possibly chlorinated activator carried out at a constant temperature. At the exit of the reactor for polymerization to the reaction mixture a solid material, insoluble in the reaction medium, suspended in a liquid monomer, while the solid material is at least of 0.05 wt.% with respect to the obtained polymer, usually 0.5-8 wt.% with respect to the polymer. Unreacted monomers are removed by evaporation and extracted freely flowable polymer in the form of particles. In addition to allowing the polymers in free flowing form of the method according to the present invention provides economically less expensive process of dry final processing compared to conventional subsequent processing water and steam. 2 C.p. of receipt of an ethylene-propylene elastomers (EP) and ternary ethylene-propylene-diene elastomers (EPDM).

More specifically the present invention relates to a method of obtaining the above elastomers freely in this powdered form.

Ways to get EP(D)M in suspension include phase evaporation of the solvent is carried out in a Stripping apparatus containing water as a dispersing medium. The polymer particles are in fact not free flowing and therefore cannot be processed (in the direction of flow) of the reaction apparatus without dispersing medium.

In 1T-A-M1 94 And 02528 (15/12/94) of the same applicant describes heterogeneous catalysts, able to give EP(D)M, which, while retaining the same characteristics as a conventional EP(D)M is in the form of particles. However, during the evaporation of the reaction medium, these particles tend to re-form agglomerates, which, however, can easily be destroyed.

The method described in the patent application 1T-A-M1 95 01403 (30/6/95), filed by this same applicant, which describes a method, implemented using a pre-polymerized catalysts, has the same drawback.

In US-A-5.086.132 describes a method for not agglomerated polymers in suspension, which includes the use (during Polimeri, silicon dioxide, metal oxides, clays.

But the method described in US-A-5.086.132, has various disadvantages.

First of all, since the catalytic system is the system of the Ziegler-Natta, the materials used must be of high purity.

In addition, the above method has a serious drawback, due to a decrease in catalytic output (see experimental examples US-And-5.086.132) more than 50% when moving from comparative tests to that at which the free flowing polymer is produced by adding 4% carbon black. This disadvantage occurs despite preventive treatment of carbon black with 100oWith under vacuum over night.

Now found a method which eliminates the above drawbacks.

Thus, in accordance with the present invention features a method of producing copolymers of ethylene with propylene and, optionally, a diene in a suspension of liquid monomer in the presence of a catalyst selected from (a) titanium salt deposited on a salt of magnesium and (b) soluble in hydrocarbon solvents, vanadium compounds, or deposited on an inert material, or the pre-polimerizovannaja activator, characterized in that:

1) when the polymerization is almost complete, to the reaction mixture a solid material, insoluble in the reaction medium and having an average particle diameter of 0.001-200 microns, preferably from 0.005 to 5 microns.

2) suspension of the polymer and the solid material is kept in contact for a sufficient time to obtain a totally free flowing polymer particles.

3) obtain totally free flowing polymer particles obtained in stage (2).

Probably, but without any experimental evidence, the solid material is adsorbed on the polymer particles, and therefore the duration of stage (2), probably connected with the necessity of adsorption is carried solid material on the surface of the polymer.

Material added to the polymer dispersion may be of organic nature (for example, carbon black and the polymer products of nature) or inorganic (for example, silicon dioxide, aluminum oxide and other oxides, carbonates, sulfates and silicates).

In a preferred embodiment, the added material has, in addition to the required average diameter, surface area above 10 m2/g, and more preferably above 40 m2/g and g

In a preferred embodiment, the material added to the end of the polymerization reaction or, in the case of continuing the polymerization, at the exit of the reactor for polymerization, selected from carbon black and silica.

Silicon dioxide preferably has an average particle size from 0.01 to 0.025 μm, the surface area of 130-200 m2/g and a porosity of 200-300 ml/100 g

As for the carbon black, it preferably has an average particle size of 0.015 to 0.04 μm, the surface area of 50-100 m2/g and a porosity of 80-120 ml/100 g

The amount of material added to the polymer dispersion is at least 0.05% of the formed polymer, usually 0.5-8% by weight relative to the polymer. Can be used in large quantities, obviously depending on the final application of elastomeric copolymers.

With regard to stage (2), if the following conditions polymerization she takes 1-50 minutes. After 30 minutes usually is almost a complete dispersion of the solid material.

The use of a salt of titanium deposited on a salt of magnesium, in particular magnesium chloride and magnesium carboxylate, and of vanadium compounds, soluble in hydrocarbon solvents, in particular acetylate the hay on inert material, and pre-polymerized canadawork catalyst described in two patent applications filed by this same applicant (EP-A-717050 and EP-96 107090, respectively). The latter document describes, in particular, the method of polymerization of ethylene with alpha-olefins, C3-C10, preferably propylene, and optionally, also with conjugated diene double bonds, in a suspension of liquid monomer in the presence of a catalyst containing vanadium, and socializaton, essentially consisting of an organic aluminum compounds, and, optionally, in the presence of halogenated activator, characterized in that the containing vanadium catalyst insoluble in the reaction medium, is the residue that is obtained by mixing in the atmosphere of ethylene or alpha-olefins:

a) compounds of vanadium in the oxidation state 3 to 5, preferably the solution or suspension of the above compounds of vanadium, and

b) essentially hydrocarbon solution of compounds selected from compounds having the General formula (1) Rnlmwhere R represents a C1-C20alkyl radical, X is halogen, m+n=3, m represents an integer from 0 to 2.

Polymerization can batalinii 5-100 bar (0.5 to 10 MPa), preferably 8-30 bar (0,8-3 MPa), with a ratio between partial pressure of the ethylene partial pressure of hydrogen greater than 4, preferably more than 20. But as regulators of molecular weight can be used and other compounds.

The polymerization temperature is usually maintained within the range from -5 to 65oC, preferably from 25 to 50oC. the contact Time ranges from 10 minutes to 6 hours, preferably from 15 minutes to 1 hour.

Elastomeric copolymers of ethylene and propylene (EP) obtained by the method according to the present invention contain from 35 to 85% of ethylene, preferably from 45 to 75% by weight, and have a characteristic viscosity (measured at 135oWith in-dichlorobenzene) of 0.5-6 DL/g, preferably 1-3 DL/g in Addition to ethylene and propylene elastomeric copolymers EP can contain other alpha-olefins having from 4 to 10 carbon atoms, in an amount not exceeding 10% by weight. Typical examples of these higher alpha-olefins are butene-1 and penten-1.

As the EP copolymers, the method in accordance with the present invention can be obtained elastomeric terpolymer (EPDM). In addition to ethylene and propylene EPDM contain a third monomer selected as WPI is a new branched chain, such as 5-methyl-1,4-hexadiene, 3,6-dimethyl-1,6-octadiene, 3,7-dimethyl-1,7-octadien,

- alicyclic dienes with one ring, such as 1,4-cyclohexadiene, 1, 5cyclooctadiene, 1,5-cyclododecatriene,

- dienes having condensed and has an internal bridge alicyclic ring, such as methyltetrahydrofuran, Dicyclopentadiene, bicyclo [2.2.1] hepta-2,5-2,5-diene; alkenyl, alkylidene-, cycloalkenyl and cycloalkylcarbonyl, such as 5-methylene-2-norbornene, 5-ethylidene-2-norbornene (ENB, ENB), 5-propenyl-2-norbornene.

Among the dienes with non-conjugate double bonds, usually used for obtaining the copolymers are preferred diene containing at least a double bond in a tight ring, and most preferred is 5-ethylidene-2-norbornene (ENB).

At the end of the polymerization after addition of the solid material according to the method of the present invention, the polymer suspension is subjected to the process of obezvozhivanija (removal of volatile products) of the solvent by lowering the pressure, increasing temperature and inert gas purge may hot. The polymer in the form of free flowing grains gradually freed from unreacted monome, balls for pressing.

In addition to allowing the polymers in free flowing (in the form of separate particles) (high temperature) the method according to the present invention provides economically less expensive process of dry final processing compared to conventional subsequent processing water and steam.

The following examples better illustrate the present invention.

EXAMPLES

All reagents are commercial products; solvents used in the polymerization, and the activators were deaerated under nitrogen and anhydrous aluminum oxide and molecular sieves.

Organic aluminum compounds used in dilute solution in hexane.

The obtained copolymers were characterized as follows.

A) Composition: it is defined by the method of infrared spectroscopy of polymer in the form of a film having a thickness of 0.2 mm, using FT-IR (flame infrared) spectrophotometer Perkin-Elmer model 1760.

The content of propylene is determined by determining the ratio between the spectral absorption ability of the strips in 4390 cm-1and 4255 cm-1using calibre elali at 125oIn accordance with S 1646-87.

COMPARATIVE EXAMPLE 1 Copolymerization of ethylene and propylene

In waterless resistant cylindrical pressure reactor with a capacity of 2.8 DM3equipped with a propeller stirrer, placed 1675 ml of liquid propylene. Regulate the temperature of the reactor at 40oAnd then saturate the contents of the reactor with ethylene until then, until you reach excess pressure 6.0 bar (600 kPa), and then add 0.2 bar (20 kPa) overpressure of hydrogen. The total pressure in the upper part of the reactor is 21.7 bar (2.17 MPa).

Then add small portions (10) 4.7 mmol JAH (diethylaluminium), dissolved in hexane, and the amount of 0.118 mmol of vanadium acetylacetonate, abbreviated V (ASAS)3dissolved in toluene, containing 0.47 mmol of ethyltrichlorosilane.

The reaction is carried out at a constant temperature with a continuous flow of ethylene to maintain a constant total pressure.

After 60 minutes, when the reaction has ceased, evaporated monomers, resulting in 130 grams of copolymer, which, as it turned out, was completely agglomerated.

EXAMPLE 2 Copolymerization of ethylene and propylene

In the stand the temperature of the reactor at 40oAnd then saturate the contents of the reactor with ethylene until then, until you reach excess pressure 6.0 bar (600 kPa), and then add 0.2 bar (20 kPa) overpressure of hydrogen. The total pressure in the upper part of the reactor is 21.7 bar (2.17 MPa).

Then add small portions (10) 4.7 mmol DEAH, dissolved in hexane, and the amount of 0.118 mmol V (ASAS)3dissolved in toluene, containing 0.47 mmol of ethyltrichlorosilane.

The reaction is carried out at a constant temperature with a continuous flow of ethylene to maintain a constant total pressure.

After 60 minutes, when the reaction has ceased, was added 2 grams of carbon black of the type HAF ASTM T 330, particles which have a surface area of 80 m2/g, porosity 102 ml/100 g and a particle size of 0,027 microns, suspended in ethanol, and then evaporated monomers, resulting in 140 grams of copolymer, which, as it turned out, was quite free flowing.

The research data presented in table 1.

EXAMPLE 3 Copolymerization of ethylene and propylene

In resistant pressure reactor described in comparative example 1, load 792 grams of liquid propylene. Regulate the temperature of the reactor is offered by a pressure of 5.0 bar (500 kPa), then add 0.2 bar (20 kPa) overpressure of hydrogen. The total pressure in the upper part of the reactor is 20.7 bar (2,07 MPa).

Then charged to the reactor in small portions (10) 4.7 mmol DEAH, dissolved in hexane, and the amount of 0.118 mmol V (ASAS)3dissolved in toluene, containing 0.47 mmol of ethyltrichlorosilane.

The reaction is carried out at a constant temperature with a continuous flow of ethylene to maintain a constant total pressure.

After 60 minutes, when the reaction has ceased, was added 2 grams of carbon black of the type HAF ASTM N 330, suspended in ethanol and then evaporated monomers, resulting in 110 grams of copolymer, which, as it turned out, was quite free flowing.

The research data presented in table 1.

EXAMPLES 4 and 5

Examples 4 and 5 was carried out with a catalyst belonging to the group of catalysts based on titanium deposited on magnesium chloride.

For example, the used catalyst prepared by the method described in EP-A-523785, and he had the following mass composition: Ti=12,1%, MD=6,5%, CL= 46%, Al=1.4 percent, the organic residue = 34%.

COMPARATIVE EXAMPLE 4 Copolymerization of ethylene and propylene

In the shape of the temperature of the reactor at 40oAnd then saturate the contents of the reactor with ethylene until then, until you reach excess hydrogen pressure of 3 bar (50 kPa), and then add another 0.5 bar excess pressure of hydrogen. The total pressure in the upper part of the reactor is 19,0 bar (1.9 MPa).

Then, the reactor was loaded 4.0 mmol CHIBA (triisobutylaluminum) and an aliquot of catalyst containing 0,077 mmol of titanium, suspended in hexane.

The reaction is carried out at a constant temperature with a continuous flow of ethylene to maintain a constant total pressure.

After 60 minutes, evaporated monomers, resulting in 93 grams of a copolymer, which, as it turned out, was completely agglomerated. The research data presented in table 1.

EXAMPLE 5 Copolymerization of ethylene and propylene

In resistant pressure reactor described in comparative example 1, load 827 grams of liquid propylene. Regulate the temperature of the reactor at 40oAnd then saturate the contents of the reactor with ethylene until then, until it reaches the overpressure of 3 bar (300 kPa), and then add another 0.5 bar (50 kPa) overpressure of hydrogen. The total pressure in the upper part of the reactor soderzhaschego of 0.013 mmol of titanium, suspended in hexane.

The reaction is carried out at a constant temperature with a continuous flow of ethylene to maintain a constant total pressure.

After 60 minutes was added 2 grams of silicon dioxide type Ultrasil VN, suspended in ethanol, and evaporated monomers, resulting in 160 grams of copolymer, which, as it turned out, was quite free flowing.

The research data presented in table 1. In this table, the molar percent of ethylene applies to the content of ethylene in the liquid phase, column "Sod." refers to the content of propylene in the polymer, the output refers to the kilograms of polymer per gram of catalyst (vanadium or titanium).

You can see that only the method according to the present invention provides the possibility of obtaining absolutely free flowing polymer particles in contrast to what happens in the implementation methods of the prior art.

COMPARATIVE EXAMPLE 6

A) obtaining a pre-polymerized catalyst.

In a glass flask is charged under nitrogen with mechanical stirring 17.2 grams of the suspension acetylacetonate, vanadium (III) at a concentration of 1.18% (mastora 0,984 grams of EACH (ethylaminoethanol) in 10 ml isopar-G and 5 ml of hexane (Al/V=2).

The mixture is left in an atmosphere of ethylene for 20 minutes, during which there is a flow of ethylene.

Catalytic slurry was poured into a test tube and diluted with isopara-G with 100 ml of suspension with a vanadium content of 0.2% (weight/volume).

C) Copolymerization of ethylene and propylene

In waterless resistant cylindrical pressure reactor with a capacity of 2.8 DM3equipped with a propeller stirrer, download 740 grams of liquid propylene. Regulate the temperature of the reactor at 40oAnd then saturate the contents of the reactor with ethylene until then, until it reaches the overpressure 8.2 bar (820 kPa), and then add 0.1 bar (10 kPa) overpressure of hydrogen. The total pressure in the upper part of the reactor is 23.8 bar (2.38 MPa).

After that add to 2.74 mmol DEAH (diethylaluminium) and then an aliquot of the previously prepared catalyst, equal 0,018 g of vanadium suspended in hexane, and containing 0.14 mmol of ethyltrichlorosilane.

The reaction is carried out at a constant temperature with a continuous flow of ethylene to maintain a constant total pressure (molar ratio Al/V=78).

After 60 minutes is evaporated moncoutie, with the release of 54 kg of polymer per gram of vanadium. The results of studies of the copolymer are shown in table 2.

EXAMPLE 7 Copolymerization of ethylene and propylene

In resistant pressure reactor described in comparative example 6, download 740 grams of liquid propylene, regulate the temperature of the reactor at 40oC and saturate the contents of the reactor with ethylene until then, until it reaches the overpressure 8.2 bar (820 kPa), and then add 0.1 bar (10 kPa) overpressure of hydrogen. The total pressure in the upper part of the reactor is 23.8 bar (2.38 MPa).

After that add to 2.74 mmol TEACH and then an aliquot of the catalyst of comparative example 6, equal 0,028 g of vanadium suspended in hexane, and containing 0.22 mmol of ethyltrichlorosilane. The reaction is carried out at a constant temperature with a continuous flow of ethylene to maintain a constant total pressure (molar ratio Al/V=50).

After 60 minutes the reaction mixture is added 2.5 grams of carbon black of the type HAF AS TM N 330, suspended in methanol. Evaporated monomers and open the reactor. Extract 151 grams of polymer, which has the form of individual particles and is freely flowing, the EP 8 - The copolymerization of ethylene and propylene

In the same resistant to the pressure of the reactor, as used in comparative example 6, download 740 grams of liquid propylene and saturate the contents of the reactor with ethylene until then, until it reaches the overpressure 8.2 bar (820 kPa), and then add 0.1 bar (10 kPa) overpressure of hydrogen. The total pressure in the upper part of the reactor is 23.8 bar (2.38 MPa).

Add to 2.74 mmol TEACH and then an aliquot of the catalyst used in comparative example 6, equal 0,018 g of vanadium suspended in hexane, and containing 0.14 mmol of ethyltrichlorosilane. The reaction is carried out at a constant temperature with a continuous flow of ethylene to maintain a constant total pressure (molar ratio Al/V=78).

After 60 minutes the reaction mixture is poured 5 grams of silicon dioxide type Ultrasil VN, suspended in methanol. Evaporated monomers and open the reactor. Extract 98 grams of polymer, which has the form of individual particles and is completely free flowing, with a yield of 54 kg of polymer per gram of vanadium. The results of studies of the copolymer are shown in table 2.

COMPARATIVE EXAMPLE 9 - Copolymerize is remov liquid propylene. Regulate the temperature of the reactor at 40oC and saturate the contents of the reactor with ethylene until then, until it reaches the pressure of the hydrogen 8.2 bar (20 kPa), and then add 0.2 bar overpressure of hydrogen until the total pressure in the upper part of the reactor will not be 24 bars (2,4 MPa).

After that add to 2.74 mmol TEACH and then an aliquot of the catalyst of comparative example 6, equal 0,028 g of vanadium suspended in hexane, and containing 0.22 mmol of ethyltrichlorosilane.

The reaction is carried out at a constant temperature with a continuous flow of ethylene to maintain a constant total pressure (molar ratio Al/V=50).

After 60 minutes the reaction mixture is poured 5 ml Pluronic PE 6200 (copolymer of ethylene oxide and propylene oxide) dissolved in methanol. Evaporated monomers and open the reactor. Extract 128 grams of polymer, which has the form of individual particles and is not quite free flowing (there are some agglomerates), with the release of 45.7 kg of polymer per gram of vanadium. The results of studies of the copolymer are shown in table 2.

COMPARATIVE EXAMPLE 10 Copolymerization of ethylene and propylene

In the stand is in propane as a diluent. Regulate the temperature of the reactor at 40oAnd then saturate the contents of the reactor with ethylene until then, until you reach excess hydrogen pressure of 5.5 bar (10 kPa), and then add 0.1 bar overpressure of hydrogen. The total pressure in the upper part of the reactor is 20.3 bar (2,03 MPa).

Add hexane solution containing 4,55 mmol DEAH (diethylaluminium) and then an aliquot of the catalyst of comparative example 6, corresponding to 0.03 grams of vanadium suspended in hexane, and containing 0.23 mmol of ethyltrichlorosilane. The reaction is carried out at a constant temperature with a continuous flow of ethylene to maintain a constant total pressure (molar ratio Al/V=78).

After 60 minutes is evaporated monomers and opening the reactor, remove 93 grams of the polymer in the form of individual agglomerates, which corresponds to the output 31 kg of polymer per gram of vanadium. The results of studies of the copolymer are shown in table 2.

EXAMPLE 11 Copolymerization of ethylene and propylene

In resistant pressure reactor described in comparative example 6, downloads 507 grams of liquid propylene in 270 grams of propane as a diluent. Regulate temperature excessive pressure 5.5 bar (550 kPa), then add 0.1 bar (10 kPa) overpressure of hydrogen. The total pressure in the upper part of the reactor is 20.3 bar (2,03 MPa).

After that add hexane solution containing 4,55 mmol TEACH and then an aliquot of the catalyst of comparative example 6, 0.03 gram of vanadium suspended in hexane, and containing 0.23 mmol of ethyltrichlorosilane. The reaction is carried out at a constant temperature with a continuous flow of ethylene to maintain a constant total pressure (molar ratio Al/V=78).

After 60 minutes the reaction mixture pour 1 gram of carbon black of the type HAF ASTM N 330, suspended in methanol. Then evaporated monomers and opening the reactor, remove the 90 grams of polymer, which has the form of individual particles and is completely free flowing, with a yield of 30 kg of polymer per gram of vanadium. The results of studies of the copolymer are shown in table 2.

COMPARATIVE EXAMPLE 12

A) Receiving the deposited catalyst

Slowly impregnated with pumping nitrogen and mechanical stirring of 5.15 grams of silicon dioxide, digidratirovannogo at 650oC for 6 hours, the solution containing 2,39 mmol acetylacetonate, vanadium (III) talization dried.

It is then saturated with ethylene and quickly add 4.3 mmol DEAH 50 cm3hexane. The mixture is left to react at room temperature for about 60 minutes and then left for decantation. The liquid is completely colorless. The fluid is drained and the solid is dried under vacuum obtaining of 7.93 grams of powder containing 1.5% vanadium.

C) Copolymerization of ethylene and propylene

In resistant pressure reactor described in comparative example 6, downloads 744 grams of liquid propylene, regulate the temperature of the reactor at 40oWith and enrich the contents of the reactor with ethylene until then, until it reaches the overpressure 6 bar (600 kPa), and then add 0.1 bar (10 kPa) overpressure of hydrogen. The total pressure in the upper part of the reactor is 21.6 bar (2,16 MPa).

Then add hexane solution containing 6,03 mmol TEACH and then an aliquot of the previously obtained catalyst, equal 0,061 gram of vanadium suspended in hexane, and containing 0.95 mmol of ethyltrichlorosilane. The reaction is carried out at a constant temperature with a continuous flow of ethylene to maintain a constant total pressure (molar ratio Al/V=50).

Aglomerated and is not freely flowing, with the release of 19.7 kg of polymer per gram of vanadium. The results of studies of the copolymer are shown in table 2.

EXAMPLE 13 Copolymerization of ethylene and propylene

In the same resistant to the pressure of the reactor, as described above, load 744 grams of liquid propylene, regulate the temperature of the reactor at 40oWith and enrich the contents of the reactor with ethylene until then, until it reaches the overpressure 6 bar (600 kPa), and then add 0.1 bar (10 kPa) overpressure of hydrogen. The total pressure in the upper part of the reactor is 21.6 bar (2,16 MPa).

After that add hexane solution containing 6,03 mmol TEACH, and then an aliquot of the catalyst used in example 12, equal 0,061 g of vanadium suspended in hexane, and containing 0.95 mmol of ethyltrichlorosilane. The reaction is carried out at a constant temperature with a continuous flow of ethylene to maintain a constant total pressure (molar ratio Al/V=50).

After 60 minutes the reaction mixture is poured 5 grams of silicon dioxide type Ultrasil VN, suspended in methanol. Evaporated monomers and opening the reactor, remove the 110 grams of polymer, which has the form of individual particles and is sowewhere in table 2.

With regard to examples 7 and 11, it was impossible to determine the content of the linked propylene as the polymers could not be subjected to analysis by infrared spectroscopy method on the films.

1. The method of obtaining elastomeric copolymers of ethylene with propylene in the suspension of liquid monomer in the presence of a catalyst chosen from titanium salt deposited on a salt of magnesium, and soluble in hydrocarbon solvents, vanadium compounds, or deposited on an inert material, or pre-polymerized, and socializaton, essentially consisting of an organic aluminum compounds, and possibly chlorinated activator carried out at a constant temperature, characterized in that 1) at the outlet of the reactor for polymerization to the reaction mixture a solid material, insoluble in the reaction medium and having an average particle diameter of 0.005 to 5 μm, the surface area above 10 m2/g and a porosity higher than 20 ml/100 g, suspended in a liquid monomer, while the solid material is at least 0,05 wt. % with respect to the obtained polymer, usually, 0.5 to 8 wt. % relative to the polymer; 2) unreacted monomers are removed by evaporation and remove freely the silicon dioxide and carbon black.

3. The method according to p. 1, characterized in that the solid material has a surface area greater than 40 m2/g and a porosity higher than 80 ml/100 g

 

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