KR101553917B1 - Method for removing weakly soluble deposits of a high-molecular-weight polymer from polymerization equipment(variant embodiments) - Google Patents

Abstract

The present invention relates to a process for removing high molecular weight polymeric deposits from a polymerization apparatus comprising reacting a reaction apparatus comprising sediments of a high molecular weight polymer and a hydrocarbon solvent with a ligand selected from the group consisting of 1,3- Comprising treating a benzylidene ligand with an amino substituted methyl group, and the amino substituent is a dimethylamino group, di < RTI ID = 0.0 > Ethylamino group, methylethylamino group, methylphenylamino group and ethylphenylamino group, and also cyclic amino groups, especially pyrrolidinyl, piperidinyl and morpholinyl are used; Or a ligand, with a ruthenium compound having l, 3-bis (2,6-dimethylphenyl) -2-imidazolidinylidene, two chlorine atoms and an ortho-substituted benzylidene, Wherein the substituent of the benzylidene ligand is an amino-substituted methyl group, and as the amino substituent, a dialkylamino group, a methylphenylamino group and an ethylphenylamino group, and also a cyclic amino group, especially piperidinyl, pyrrolidinyl and morpholinyl are used do. The present invention makes it possible to remove sediments of high molecular weight polymer from the polymerization apparatus at low cost by reducing the consumption rate of the complex ruthenium compound wherein the products which can be produced as a result of the partial destruction of the weakly soluble high molecular weight polymer, Liquid plasticizers, oligomers and commercial rubbers.

Description

Methods for removing weakly soluble deposits of high molecular weight polymer from polymerisation apparatus (various embodiments) {Methods for removing weakly soluble deposits of a high-molecular-weight polymer from polymerization equipment (variant embodiments)

The present invention relates to a process comprising removing a weakly soluble deposit which is a high molecular weight polymer from a reaction apparatus and converting the polymer into a commercial product.

For example, when preparing polymers or copolymers from unsaturated hydrocarbons such as SBR (synthetic butadiene rubber), SIR (synthetic isoprene rubber), and SDSR (synthetic divinyl-styrene rubber), a weakly soluble high molecular weight polymer is incorporated into the polymerization apparatus, Especially in the reactor and / or in the transport line. Such polymers must be removed for effective subsequent use of the device. Polymers are typically removed by methods including steaming, treating with water at high pressure to strip the polymer from the device surface, and physically removing the polymer. This process can take several weeks, and the polymer residue after the cleaning process is solid production waste.

There is a need for a new method of removing weakly soluble high molecular weight polymers from reactors, which is time consuming and economically ineffective, labor-consuming, power-consuming and ecologically hazardous.

The polymer removal process can be highly promoted using a metathesis catalyst as a solubilizer which reduces the molecular weight of the high molecular weight polymer and further removes the polymer from which the molecular weight has been reduced from the device. Molecular weight is reduced due to cross-metathesis reactions involving double bonds in the high molecular weight polymer structure.

As the closest prior art, a polymerisation apparatus cleaning method is contemplated (U.S. Patent No. 7,133,503 issued on Nov. 7, 2006), wherein an apparatus comprising a weakly soluble high molecular weight polymer swollen in a hydrocarbon solvent is prepared by a Grubbs generation or second generation catalyst solution of the same solvent Treated and heated to a temperature of 40 to 45 캜, wherein the catalyst / polymer ratio is 0.1 mmol of catalyst in 100 g of high molecular weight polymer. The patent does not disclose further utilization of the removed polymer.

A disadvantage of the process is the rapid rate of consumption of the catalyst and waste formation, which requires additional utilization.

It is an object of the present invention to provide a method for reducing the rate of consumption of the catalyst and for removing the waste formed after cleaning the polymerization apparatus.

This specific object is solved by adding a solution of a agent capable of dissolving a high molecular weight polymer, especially a ruthenium complex solution, to a reaction apparatus comprising a high molecular weight polymer deposit and a hydrocarbon solvent. The reactor-unit contents are then maintained at a temperature of 45 to 85 占 폚. In contrast to the closest prior art, the ruthenium complex is added in an amount of 0.03 to 0.07 g per kg of dry high molecular weight polymer. The high molecular weight polymer is dissolved due to its partial destruction. The average molecular weight (Mn) of the product obtained after such destruction can vary from 630 to 350,000 depending on the conditions under which the removal process is carried out. The products can also be used as plasticizers, oligomers, and commercial rubbers which are viscous and liquid.

The term "weakly soluble high molecular weight polymer" refers to polymers having an average molecular weight of more than 1,000,000, especially high molecular weight polymers formed by diene hydrocarbon polymerization, such as synthetic butadiene rubber, synthetic isoprene rubber, and synthetic divinyl- .

Examples of the hydrocarbon solvent include aliphatic hydrocarbons such as toluene, xylene, benzene and the like, aliphatic hydrocarbons such as heptane, hexane and the like or solvents produced from petroleum refining such as some aromatic hydrocarbons as well as gasoline and kerosene fractions fractions of nefrases can be used [Khimicheskaya entsyklopediya (Chemical Encyclopedia), IL Knunyants, vol.3, p.237, col.466].

Also, the ruthenium complex is a ruthenium compound having, as a ligand, 1,3-dimethyimethylimidazolidinylidene, two chlorine atoms as ligands and orthosubstituted benzylidene, wherein the substituent in the benzylidene ligand Is an amino-substituted methyl group, and the dimethylamino group, diethylamino group, methylethylamino group, methylphenylamino group, and ethylphenylamino group can be used as an amino substituent, and as the cyclic amino group, in particular, pyrrolidinyl, piperidinyl, Nil wherein the ruthenium compound has the general formula:

Where X is _{(CH 3) 2 N-, (} C 2 H 5) 2 N-, (CH 3) (C 2 H 5) N-, CH 3 PhN-, C 2 H 5 PhN-, (CH 2) ₄ N-, (CH ₂ ) ₅ N-, or O (CH ₂ ) ₄ N-.

The ruthenium compound of the above formula, 1,3-bis- (2,4,6-trimethylphenyl) -2-imidazolidinylidene] dichloro (2- (N, N- dimethylaminomethyl) benzylidene) , As a dicyclopentadiene polymerization catalyst, RU Patent 2374269 (2009.11.27). The use of the catalyst as a solubilizer in the method for removing weakly soluble high molecular weight polymers according to the present invention is demonstrated in Examples 1, 2 and 3 below. X is _{(C 2 H 5) 2 N-} , (CH 3) (C 2 H 5) N-, (CH 2) 4 N-, or O (CH ₂₎ a ruthenium compound of formula ₄ N- are the above-described PCT / RU2008 / 000794 filed as dicyclopentadiene polymerization catalyst (published as WO 2009/142535 (November 26, 2009)).

Another embodiment of the process according to the invention is a process for the preparation of ruthenium (R < 1 >) with ligand having 1,3-bis- Wherein the substituent in the benzylidene ligand is an amino substituted methyl group and the dialkylamino group, the methylphenylamino group, and the ethylphenylamino group can be used as the amino substituent and also the cyclic amino group, especially pyrrolidinyl, piperidinyl, and The morpholinyl may be used, wherein the ruthenium compound has the general formula:

Where X is _{(Alk) 2 N-, CH 3} PhN-, C 2 H 5 PhN-, CH 3 PhN-, C 2 H 5 PhN-, (CH 2) 4 N-, (CH 2) 5 N-, or O (CH _{2) 4} N- gt; And

Alk is CH ₃ or C ₂ H _5.

In the disclosed ruthenium compound structure, the N-heterocyclic ligand is coordinated to ruthenium via a donor-acceptor bond, which is generally referred to as "↓" [E.Tzur, A. Szadkovska, A Ben-Asuly, A. Makal, I. Goldberg,. Wozniak,. Grela, N.G. Lemcoff. Chem. Eur. J., 16, 8726-8737.] Or "| ". H. Grubbs, Handbook of Metathesis, Volume 1 - Catalyst Development Wiley-VCH, Weinheim, 2003 pp. 72, 73, 113; R. H. Grubbs / Tetrahedron 60 (2004), 7117-7140]. These combined notations are equivalent.

The consumption ratio and the cleaning duration of the ruthenium complex can be adjusted by adding to the system an olefin, in particular a single substituted alkene, such as styrene, hexene, octene, decene, etc., in an amount of 7 to 30 g per kg of dry high molecular weight polymer Lt; / RTI > This enables the production of polymers with a narrow molecular weight distribution, wherein the molecular weight of the resulting polymer is close to the molecular weight of a commercial rubber.

The achieved technical results lie in an additional end product that can be produced from a weakly soluble high molecular weight polymer without reducing the consumption of catalyst and forming sediments.

The proposed invention is illustrated in the following specific embodiments.

Example  One

 Conversion of weakly soluble high molecular weight polymers into commercial rubber during polymerizer cleaning.

 A destruction was performed in a 5 liter reactor. The reactor was loaded with 350.0 grams of nefrase-swollen, high molecular weight DSR-ND (a divinyl synthetic rubber produced on a neodymium-containing catalyst system) from a commercial polymerization reactor wherein the swollen polymer contained a solvent ) Was 157.1 g, which corresponds to 44.89 wt.% Of solvent and 55.11 wt.% (192.3 g) of the polymer. Next, to the reactor were sequentially added 4400 ml of a dried Neffrase solvent, [1,3-bis- (2,4,6-trimethylphenyl) -2 -Imidazolidinylidene] dichloro (2- (N, N-dimethylaminomethyl) benzylidene) ruthenium was stirred at 25-40 ° C under stirring. The reaction mass was then heated to 75 < 0 > C and held at this temperature for 3 hours.

After 3 hours, the high molecular weight polymer was completely dissolved and the resulting solution was cooled and released from the reactor, and the molecular weight characteristics of the resulting polymer were determined: Mn = 265000 Da, Mw = 647000, and polydispersity index D = 2.44. Further, the polymer solution was subjected to steam degassification, and the resulting rubber crumb was dried in a 110 ° C vacuum drying cabinet, and the weight of the obtained product was 189.3 g.

Example  2

 Conversion of weakly soluble high molecular weight polymers into low molecular weight rubbers during polymerizer cleaning to obtain viscous plasticizers

Disruption was performed in a 5 liter reactor. The reactor was loaded with 450.0 grams of a nephrasse swollen high molecular weight DSR-ND from a commercial polymerization reactor where the amount of nephrase in the swollen gel was 193.8 grams, which was 43.07 wt.% Solvent and 56.93 wt.% (256.2 g). Next, to the reactor were added 4300 ml of dried Nephrase solvent, [1,3-bis- (2,4,6-trimethylphenyl) -2-imidazole used as catalyst in 20 ml of dry nephrase and 8 g of hexene- (N, N-dimethylaminomethyl) benzylidene) ruthenium in 10 ml of tetrahydrofuran was successively loaded under stirring at 25 to 40 占 폚. The reaction mass was then heated to 75 < 0 > C and held at this temperature for 4 hours.

After 4 hours the high molecular weight polymer was completely dissolved; The resulting solution was cooled and released from the reactor; The molecular weight characteristics of the obtained polymer were measured: Mn = 42600 Da, Mw = 115800, and polydispersity index D = 2.72. In addition, the polymer solution was steam degassed and the resulting viscous oil was dried in a 110 [deg.] C vacuum drying cabinet and the weight of the product obtained was 249.4 g.

Example  3

Conversion of weakly soluble high molecular weight polymers into low molecular weight rubbers during washing of the polymerization apparatus to obtain liquid plasticizers

Disruption was performed in a 5 liter reactor. The reactor was loaded with 550.0 grams of a nephrase swollen, high molecular weight DSR-ND from a commercial polymerization reactor wherein the amount of the nephrasase solvent in the swollen polymer was 243.8 grams, which was 44.33 wt.% Solvent and 55.67 wt.% Polymer. (306.2 g). Next, the reactor was charged with 4200 ml of dry toluene, 9.2 g of hexene-1, and 20 ml of dry toluene. The catalyst used as the catalyst was 1,3-bis- (2,4,6-trimethylphenyl) -2-imidazolidi Nylidene] dichloro (2- (N, N-dimethylaminomethyl) benzylidene) ruthenium in 20 ml of tetrahydrofuran was successively loaded under stirring at 25 to 40 ° C. The reaction mass was heated to 75 < 0 > C and held at this temperature for 4 hours.

After 4 hours the high molecular weight polymer was completely dissolved; The resulting solution was cooled and released from the reactor; The measured molecular weight characteristics of the obtained polymer are as follows: Mn = 5300 Da, Mw = 13600, and polydispersity index D = 2.56. Further, the polymer solution was steam degassed, and the obtained oil was dried in a 110 DEG C vacuum drying cabinet, and the weight of the obtained product was 307.9 g.

Example 4

Conversion of weakly soluble high molecular weight polymers into low molecular weight rubbers in polymerizer cleaning to obtain low molecular weight oligomers.

Disruption was performed in a 5 liter reactor. The reactor was charged with 550.0 grams of a nephrasse swollen high molecular weight DSR-ND from a commercial polymerization reactor wherein the amount of neplacease in the swollen polymer was 234.7 grams, which contained 42.67 wt.% Solvent and 57.33 wt.% 315.3 g). The reactor was then charged with 4200 ml of dry nephrase, 12.6 g of hexene-1, and 20 ml of dry nephrase, [1,3-bis- (2,4,6-trimethylphenyl) (N, N-dimethylaminomethyl) benzylidene) ruthenium in 20 ml of tetrahydrofuran was successively loaded under stirring at 25 to 40 占 폚. The reaction mass was heated to 80 < 0 > C and held at this temperature for 5 hours.

After 5 hours the high molecular weight polymer was completely dissolved; The resulting solution was cooled and released from the reactor; And the molecular weight characteristics of the obtained polymer were measured: Mn = 630 Da. The polymer solution was also subjected to anhydrous degassification in a rotary evaporator under a gradual depressurization from a bath temperature of 60 DEG C and atmospheric pressure to 10 mmHg. The obtained oil was 376.9 g.

Example  5

Conversion of weakly soluble high molecular weight polymers into low molecular weight rubbers during washing of the polymerization apparatus to obtain liquid plasticizers

Disruption was performed in a 5 liter reactor. The reactor was charged with 550 g of a nephrase swollen high molecular weight DSR-ND from a commercial polymerization reactor wherein the amount of Neflazse solvent in the swollen polymer was 249.21 g, which was 45.31 wt.% Of solvent and 54.69 wt.% Of polymer. (300.80 g). Next, to the reactor was added 4200 ml of dry toluene, 7.5 g of [1,3-bis- (2,4,6-trimethylphenyl) -2-imidazolidine Nylidene] dichloro (2- (piperid-1-ylmethyl) benzylidene) ruthenium in 50 ml of tetrahydrofuran was sequentially charged under stirring at 25 to 40 ° C. The reaction mass was then heated to 75 < 0 > C and held at this temperature for 4 hours.

After 4 hours the high molecular weight polymer was completely dissolved; The resulting solution was cooled and released from the reactor; The molecular weight characteristics of the obtained polymer were measured: Mn = 7500 Da, Mw = 15900, and polydispersity index D = 2.12. Further, the polymer solution was steam degassed, and the obtained oil was dried in a 110 캜 vacuum drying cabinet, and the weight of the obtained product was 297.9 g.

Example  6

Conversion of weakly soluble high molecular weight polymers into low molecular weight rubbers during polymerizer cleaning to obtain viscous plasticizers

Disruption was performed in a 5 liter reactor. The reactor was charged with 450 g of heptane-swollen, high molecular weight DSR-ND from a commercial polymerization reactor wherein the amount of heptane in the swollen polymer was 202.86 g, which contained 45.08 wt% solvent and 54.92 wt.% (247.14 g ). Next, the reactor was charged with 2300 ml of dry toluene solvent, 2000 ml of dry benzene, 7.4 g of styrene, and 1, 3-bis- (2,4,6-trimethylphenyl) -2- (N-phenyl, N-methylbenzylidene) ruthenium were sequentially charged with stirring at a temperature of 25 to 40 占 폚. The reaction mass was then heated to 75 < 0 > C and held at this temperature for 4 hours.

After 4 hours the high molecular weight polymer was completely dissolved; The resulting solution was cooled and released from the reactor; The molecular weight characteristics of the obtained polymer were measured: Mn = 65800 Da, Mw = 15,700, and polydispersity index D = 2.39. In addition, the polymer solution was steam degassed and the resulting viscous oil was dried in a 110 < 0 > C vacuum drying cabinet and the weight of product obtained was 245.2 g.

Example  7

Conversion of weakly soluble high molecular weight polymers into low molecular weight rubbers during polymerizer cleaning to obtain viscous plasticizers

Disruption was performed in a 5 liter reactor. The reactor was charged with 400 g of heptane-swollen, high molecular weight SIR-3 (synthetic isoprene rubber) from a commercial polymerization reactor wherein the amount of heptane in the swollen polymer was 162.48 g, which was 40.62 wt% solvent and 59.38 wt .% (237.52 g). Next, the reactor was charged with 2350 ml of dry toluene, 2000 ml of dry benzene, 7.0 g of octene-1, and 20 g of [1,3-bis- (2,4,6-trimethylphenyl) -Imidazolidinylidene] dichloro (N-phenyl, N-ethylbenzylidene) ruthenium were sequentially charged under stirring at 25 to 40 ° C. The reaction mass was then heated to 75 < 0 > C and held at this temperature for 4 hours.

After 4 hours the high molecular weight polymer was completely dissolved; The resulting solution was cooled and released from the reactor; The molecular weight characteristics of the obtained polymer were measured: Mn = 58400 Da, Mw = 139500, and polydispersity index D = 2.39. Further, the polymer solution was steam degassed and the resulting viscous oil was dried in a 110 [deg.] C vacuum drying cabinet and the weight of the product obtained was 235.6 g.

Example  8

Conversion of weakly soluble high molecular weight polymers into low molecular weight rubbers during washing of the polymerization apparatus to obtain liquid plasticizers

Disruption was performed in a 5 liter reactor. The reactor was charged with 400 g of heptane-swollen, high molecular weight DSR-ND from a commercial polymerization reactor wherein the amount of heptane in the swollen polymer was 163.2 g, which contained 40.80 wt% solvent and 59.20 wt.% Polymer (236.80 g ). The reactor was then charged with 4350 ml of dry nephrase, [1,3-bis- (2,6-dimethylphenyl) -2-imidazolidinyl] quinolinecarboxylic acid used as catalyst in 20 ml of dry nephrase and 8.3 g of octene- D] dichloro (N, N-dimethylbenzylidene) ruthenium was sequentially charged under stirring at a temperature of 25 to 40 ° C. The reaction mass was then heated to 75 < 0 > C and held at this temperature for 4 hours.

After 4 hours the high molecular weight polymer was completely dissolved; The resulting solution was cooled and released from the reactor; The molecular weight characteristics of the obtained polymer were measured: Mn = 8650 Da, Mw = 18700, and polydispersity index D = 2.16. Further, the polymer solution was steam degassed, and the obtained oil was dried in a 110 캜 vacuum drying cabinet, and the weight of the obtained product was 235.3 g.

Example  9

Conversion of weakly soluble high molecular weight polymers into low molecular weight rubbers in polymerizer cleaning to obtain low molecular weight oligomers.

Disruption was performed in a 5 liter reactor. The reactor was charged with 450 g of heptane-swollen, high molecular weight DSR-ND from a commercial polymerization reactor wherein the amount of heptane in the swollen polymer was 199.44 g, which contained 44.32 wt% solvent and 55.68 wt.% (250.56 g ). Next, to the reactor was added [1,3-bis- (2,6-dimethylphenyl) -2-imidazolidinylidene] dichloro used as a catalyst in 4300 ml of dried Nephrase, 9.0 g of styrene and 20 ml of dried nephrase (N, N-diethylbenzylidene) ruthenium (17 mg) were successively loaded under stirring at a temperature of 25 to 40 占 폚. The reaction mass was then heated to 75 < 0 > C and held at this temperature for 5 hours.

After 5 hours the high molecular weight polymer was completely dissolved; The resulting solution was cooled and released from the reactor; The molecular weight characteristics of the obtained polymer were measured: Mn = 870 Da. Further, the polymer solution was subjected to anhydrous degassing in a rotary evaporator under a gradual depressurization from a bath temperature of 60 DEG C and an atmospheric pressure to 10 mmHg, and the obtained oil was 248.9 g.

Example  10

Conversion of weakly soluble high molecular weight polymers into low molecular weight rubbers during washing of the polymerization apparatus to obtain liquid plasticizers

Disruption was performed in a 5 liter reactor. 500 g of a heptane-swollen high molecular weight DSR-ND from a commercial polymerization reactor was loaded into the reactor, where the amount of heptane in the swollen polymer was 228.10 g, which was 45.62 wt% solvent and 54.38 wt.% (271.90 g ). Next, to the reactor was added [1,4-bis- (2,6-dimethylphenyl) -2-imidazolidinylidene] dichloro used as a catalyst in 4200 ml of dry nephrase, 8.1 g of styrene and 20 ml of dried nephrase (N-methyl, N-ethylbenzylidene) ruthenium (15 mg) were sequentially charged under stirring at 25 to 40 ° C. The reaction mass was then heated to 75 < 0 > C and held at this temperature for 4 hours.

After 4 hours the high molecular weight polymer was completely dissolved; The resulting solution was cooled and released from the reactor; The molecular weight characteristics of the obtained polymer were measured: Mn = 8100 Da, Mw = 21000, and polydispersity index D = 2.59. Further, the polymer solution was steam degassed, and the obtained oil was dried in a 110 캜 vacuum drying cabinet, and the weight of the obtained product was 270.2 g.

Example  11

Conversion of weakly soluble high molecular weight polymers into commercial rubber during polymerizer cleaning.

Disruption was performed in a 5 liter reactor. The reactor was charged with 350 g of a nephra-swollen, high molecular weight DSR-ND from a commercial polymerization reactor, where the amount of nephrase in the swollen polymer was 148.37 g, which was 42.39 wt.% Solvent and 57.61 wt.% 201.64 g). Next, to the reactor was added [1,4-bis- (2,6-dimethylphenyl) -2-imidazolidinylidene] dichloro used as a catalyst in 4200 ml of dry toluene, 4.0 g of styrene and 20 ml of dried nephrase (2- (piperid-1-ylmethyl) benzylidene) ruthenium were sequentially loaded under stirring at 25 to 40 ° C. The reaction mass was then heated to 75 < 0 > C and held at this temperature for 3 hours.

After 3 hours the high molecular weight polymer was completely dissolved; The resulting solution was cooled and released from the reactor; The molecular weight characteristics of the obtained polymer were measured: Mn = 210000 Da, Mw = 485100, and polydispersity index D = 2.31. Further, the polymer solution was steam degassed, and the obtained rubber crumb was dried in a 110 캜 vacuum drying cabinet, and the weight of the obtained product was 201.2 g.

Example  12

Conversion of weakly soluble high molecular weight polymers into commercial rubber during polymerizer cleaning.

Disruption was performed in a 5 liter reactor. The reactor was charged with 400 grams of a nephrasse swollen high molecular weight DSR-2545 (divinyl-styrene rubber) from a commercial polymerization reactor, wherein the amount of nephrase in the swollen polymer was 174.04 g, which was 43.51 wt% And 56.49 wt.% (225.96 g) of polymer. Next, to the reactor was added [1,3-bis- (2,6-dimethylphenyl) -2-imidazolidinylidene] dichloro used as a catalyst in 4300 ml of dry toluene, 4.5 g of styrene and 20 ml of dried nephrase (2- (pyrrolidin-1-ylmethyl) benzylidene) ruthenium were sequentially loaded under stirring at a temperature of 25 to 40 ° C. The reaction mass was then heated to 75 < 0 > C and held at this temperature for 3 hours.

After 3 hours the high molecular weight polymer was completely dissolved; The resulting solution was cooled and released from the reactor; The molecular weight characteristics of the obtained polymer were measured: Mn = 180000 Da, Mw = 464400, and polydispersity index D = 2.58. Further, the polymer solution was steam degassed, and the obtained rubber crumb was dried in a 110 占 폚 vacuum drying cabinet, and the weight of the obtained product was 224.8 g.

Example  13

Conversion of weakly soluble high molecular weight polymers into low molecular weight rubbers during polymerizer cleaning to obtain viscous plasticizers

Disruption was performed in a 5 liter reactor. The reactor was loaded with 550 g of a nephrase swollen high molecular weight DSR-ND from a commercial polymerization reactor, where the amount of neplacease in the swollen polymer was 278.36 g, which was 50.61 wt% solvent and 59.39 wt% 271.64 g). Next, to the reactor was added [1,4-bis- (2,6-dimethylphenyl) -2-imidazolidinylidene] dichloro used as a catalyst in 4200 ml of dry toluene, 9.0 g of styrene and 20 ml of dried nephrase (2-morpholinomethylbenzylidene) ruthenium (13 mg) were sequentially charged under stirring at a temperature of 25 to 40 占 폚. The reaction mass was then heated to 75 < 0 > C and held at this temperature for 4 hours,

After 4 hours the high molecular weight polymer was completely dissolved; The resulting solution was cooled and released from the reactor; The molecular weight characteristics of the obtained polymer were measured: Mn = 86900 Da, Mw = 199800, and polydispersity index D = 2.29. Further, the polymer solution was steam degassed and the resulting viscous oil was dried in a 110 [deg.] C vacuum drying cabinet, and the weight of the product obtained was 271.1 g.

Example  14

Conversion of weakly soluble high molecular weight polymers into low molecular weight rubbers during washing of the polymerization apparatus to obtain liquid plasticizers

Disruption was performed in a 5 liter reactor. The reactor was charged with 500 g of a nephrase swollen high molecular weight DSR-ND from a commercial polymerization reactor, where the amount of neplacease in the swollen polymer was 210.35 g, which contained 42.07 wt.% Of solvent and 57.93 wt.% 289.65 g). Next, to the reactor was added [1,3-bis- (2,6-dimethylphenyl) -2-imidazolidinyl] diol as a catalyst in 4200 ml of dry toluene, 10.0 g of octene- D] dichloro (N-phenyl, N-methylbenzylidene) ruthenium were sequentially charged under stirring at 25 to 40 ° C. The reaction mass was then heated to 75 < 0 > C and held at this temperature for 4 hours.

After 4 hours the high molecular weight polymer was completely dissolved; The resulting solution was cooled and released from the reactor; The molecular weight characteristics of the obtained polymer were measured: Mn = 9900 Da, Mw = 21200, and polydispersity index D = 2.14. Further, the polymer solution was steam degassed, and the obtained oil was dried in a 110 占 폚 vacuum drying cabinet, and the weight of the obtained product was 288.6 g.

Example  15

Conversion of weakly soluble high molecular weight polymers into low molecular weight rubbers in polymerizer cleaning to obtain low molecular weight oligomers.

Disruption was performed in a 5 liter reactor. The reactor was charged with 500 g of a nephrasse swollen high molecular weight DSR-ND from a commercial polymerization reactor, where the amount of nephrase in the swollen polymer was 230.1 g, which contained 46.02 wt.% Solvent and 53.98 wt.% 269.9 g). Next, the reactor was charged with 4200 ml of dry toluene, 10.7 g of octene-1, and 20 g of [1,3-bis- (2,6-dimethylphenyl) -2-imidazolidinyl] D] dichloro (N-phenyl, N-ethylbenzylidene) ruthenium was sequentially loaded under stirring at 25 to 40 ° C. The reaction mass was then heated to 75 < 0 > C and held at this temperature for 5 hours.

After 5 hours the high molecular weight polymer was completely dissolved; The resulting solution was cooled and released from the reactor; The molecular weight characteristics of the obtained polymer were measured: Mn = 910 Da. In addition, the polymer solution was dehydrogenated anhydrous in a rotary evaporator under a gradual depressurization from a bath temperature of 60 占 폚 and atmospheric pressure to 10 mmHg. The obtained oil was 268.7 g.

Example  16

Conversion of weakly soluble high molecular weight polymers into commercial rubber during polymerizer cleaning.

Disruption was performed in a 5 liter reactor. The reactor was charged with 400.0 grams of a nephrasse swollen high molecular weight DSR-ND from a commercial polymerization reactor wherein the amount of neplace in the swollen polymer was 164.40 grams, which contained 41.10 wt.% Solvent and 58.90 wt.% 235.60 g). Next, to the reactor was added [1,3-bis- (2,4,6-trimethylphenyl) -2-imidazolidinylidene] dichloro (2, - (N, N-dimethylaminomethyl) benzylidene) ruthenium were sequentially loaded under stirring at 25 to 40 占 폚. The reaction mass was then heated to 75 < 0 > C and held at this temperature for 6 hours.

After 6 hours the high molecular weight polymer was completely dissolved; The resulting solution was cooled and released from the reactor; The molecular weight characteristics of the obtained polymer were measured: Mn = 350000 Da, Mw = 795000, and polydispersity index D = 2.27. Further, the polymer solution was steam degassed, and the obtained rubber crumb was dried in a 110 ° C vacuum drying cabinet, and the weight of the obtained product was 234.5 g.

Example  17

Conversion of weakly soluble high molecular weight polymers into low molecular weight rubbers during polymerizer cleaning to obtain viscous plasticizers

Disruption was performed in a 5 liter reactor. The reactor was loaded with 400.0 grams of a nephrasse swollen high molecular weight DSR-ND from a commercial polymerization reactor, where the amount of nephrase in the swollen gel was 190.44 grams, which included 47.61 wt.% Of solvent and 52.39 wt.% Of polymer (209.56 g). Next, to the reactor was added [1,3-bis- (2,4,6-trimethylphenyl) -2-imidazolidinylidene] dichloro (2, - (N, N-dimethylaminomethyl) benzylidene) ruthenium were sequentially loaded under stirring at 25 to 40 占 폚. The reaction mass was then heated to 75 DEG C and held at this temperature for 7 hours.

After 7 hours the high molecular weight polymer was completely dissolved; The resulting solution was cooled and released from the reactor; The molecular weight characteristics of the obtained polymer were measured: Mn = 98600 Da, Mw = 255300, and polydispersity index D = 2.59. Further, the polymer solution was subjected to steam degassification, and the obtained viscous oil was dried in a 110 ° C vacuum drying cabinet, and the weight of the obtained product was 207.9 g.

Example  18

Pilot scale cleaning of polymerization reactor without device open

Slightly Soluble and containing 1.3 ton DSR ND-polymer of molecular weight, four vertical filled plastic 17 m ³ [1,3- used as a catalyst for the (process-flowsheet-excluded) polymerization reactor having a volume excluded from the process flow diagram bis Solution of 70 g of ruthenium (R) - (2,4,6-trimethylphenyl) -2-imidazolidinylidene] dichloro (2- (N, N- dimethylaminomethyl) benzylidene) And a tube fitted to the head of the reactor, and then the reactor was heated to 70-75 DEG C, the mixture was stirred, and the specified temperature was maintained with the steam periodically supplied to the reactor jacket. The reactor was heated and the mixture was stirred for 6 hours (until the dry residue in the solvent ceased to increase), where the dry residue was monitored every 2 hours. The steam supply was then stopped and the rubber solution was discharged from the reactor to the balance reservoir. The polymerization reactor was washed with the solvent until the amount of dry residue was 0.2%, which was then connected to a battery and used for polymerization.

The rubber solution of the residue reservoir was fed to the steam degassing to separate the commercial product. The polymer analysis showed that the amount of 1,4-cis-butadiene units was 79.9%, the amount of 1,4-trans-units was 19%, the amount of 1,2-units was 1.1%, and the Mn was 8,000.

When the reactor was opened and irradiated, the high molecular weight polymer was completely dissolved and the internal reactor elements were cleaned.

Example  19

Conversion of weakly soluble high molecular weight polymers into commercial rubber during polymerizer cleaning.

Disruption was performed in a 5 liter reactor. The reactor was charged with 450.0 grams of a nephrasse swollen high molecular weight DSR-ND from a commercial polymerization reactor, where the amount of neplacease in the swollen polymer was 189.63 g, which was 42.14 wt.% Solvent and 57.86 wt.% 260.37 g). Next, to the reactor were added 4300 ml of dried Nephrase, 5.5 g of styrene and 20 g of [1,3-bis- (2,4,6-trimethylphenyl) -2-imidazolidinylidene ] Dichloro (2- (N, N-diethylaminomethyl) benzylidene) ruthenium was sequentially loaded under stirring at 25 to 40 ° C. The reaction mass was then heated to 75 < 0 > C and held at this temperature for 3 hours.

After 3 hours the high molecular weight polymer was completely dissolved; The resulting solution was cooled and released from the reactor; The molecular weight characteristics of the obtained polymer were measured: Mn = 241500 Da, Mw = 591600, and polydispersity index D = 2.45. Further, the polymer solution was steam degassed, and the obtained rubber crumb was dried in a 110 占 폚 vacuum drying cabinet, and the weight of the obtained product was 258.6 g.

Example  20

Conversion of weakly soluble high molecular weight polymers to low molecular weight rubbers during polymerizer washing to obtain liquid plasticizers.

Disruption was performed in a 5 liter reactor. The reactor was loaded with 400.0 grams of a nephrasse swollen high molecular weight DSR-ND from a commercial polymerization reactor, wherein the amount of nepraese in the swollen polymer was 190.60 grams, which included 47.65 wt.% Solvent and 52.35 wt.% 209.40 g). Next, in the reactor, 4350 ml of dry toluene, 7.3 g of styrene and [1,3-bis- (2,4,6-trimethylphenyl) -2-imidazolidinylidene] dichloro (2- (N, N-diethylaminomethyl) benzylidene) ruthenium were sequentially loaded under stirring at 25 to 40 占 폚. The reaction mass was then heated to 75 < 0 > C and held at this temperature for 4 hours.

After 4 hours the high molecular weight polymer was completely dissolved; The resulting solution was cooled and released from the reactor; The molecular weight characteristics of the obtained polymer were measured: Mn = 5150 Da, Mw = 12500, and polydispersity index D = 2.43. Further, the polymer solution was steam degassed, and the obtained oil was dried in a 110 DEG C vacuum drying cabinet, and the weight of the obtained product was 208.4 g.

Example  21

Conversion of weakly soluble high molecular weight polymers into low molecular weight rubbers during polymerizer cleaning to obtain viscous plasticizers

Disruption was performed in a 5 liter reactor. 500.0 g of a heptane swollen, high molecular weight DSR-ND from a commercial polymerization reactor was loaded into the reactor, where the amount of heptane in the swollen polymer was 217.9 g, which was 43.58 wt.% Solvent and 56.22 wt.% (282.1 g ). Next, to the reactor was added a solution of [1,3-bis- (2,4,6-trimethylphenyl) -2-imidazolidinylidene] dicarboxylate used as a catalyst in 4250 ml of dry heptane, 12.5 g of styrene and 20 ml of dry heptane solvent. A solution of dichloro (2- (N-methyl, N-ethylaminomethyl) benzylidene) ruthenium in 21 mg was successively loaded under stirring at 25-40 캜. The reaction mass was then heated to 75 < 0 > C and held at this temperature for 4 hours.

After 4 hours the high molecular weight polymer was completely dissolved; The resulting solution was cooled and released from the reactor; The molecular weight characteristics of the obtained polymer were measured: Mn = 38900 Da, Mw = 110476, and polydispersity index D = 2.84. Further, the polymer solution was steam degassed, and the resulting viscous oil was dried in a 110 deg. C vacuum drying cabinet, and the weight of the obtained product was 281.7 g.

Example  22

Conversion of weakly soluble high molecular weight polymers to low molecular weight rubbers during polymerizer washing to obtain liquid plasticizers.

Disruption was performed in a 5 liter reactor. The reactor was loaded with 350.0 grams of a nephrasse swollen high molecular weight DSR-2545 from a commercial polymerization reactor wherein the amount of nephrase in the swollen polymer was 161.28 grams, which contained 46.08 wt.% Solvent and 53.92 wt.% 188.72 g). Next, to the reactor was added [1,3-bis- (2,4,6-trimethylphenyl) -2-imide as catalyst in 2400 ml of dry toluene, 2000 ml of dry benzene, 5.7 g of styrene, and 20 ml of dry toluene (N-methyl, N-ethylaminomethyl) benzylidene) ruthenium was sequentially loaded under stirring at 25 to 40 占 폚. The reaction mass was then heated to 75 < 0 > C and held at this temperature for 4 hours.

After 4 hours the high molecular weight polymer was completely dissolved; The resulting solution was cooled and released from the reactor; The molecular weight characteristics of the obtained polymer were measured: Mn = 6200 Da, Mw = 16750, and polydispersity index D = 2.70. Further, the polymer solution was steam degassed, and the obtained oil was dried in a 110 캜 vacuum drying cabinet, and the weight of the obtained product was 187.2 g.

Example  23

Conversion of weakly soluble high molecular weight polymers into low molecular weight rubbers during polymerizer cleaning to obtain viscous plasticizers

Disruption was performed in a 5 liter reactor. The reactor was charged with 400 g of a nephrasse swollen high molecular weight DSR-ND from a commercial polymerization reactor, where the amount of nephrase in the swollen polymer was 165.44 g, which was 41.36 wt% solvent and 58.64 wt% 234.56 g). Next, to the reactor was added [1,3-bis- (2,4,6-trimethylphenyl) -2-imidazolidinylidene] benzene as catalyst in 4350 ml of dry toluene, 9.3 g of styrene, and 20 ml of dry toluene. A solution of 11 mg of dichloro (2- (pyrrolidin-1-ylmethyl) benzylidene) ruthenium was sequentially charged under stirring at 25 to 40 ° C. The reaction mass was then heated to 75 < 0 > C and held at this temperature for 4 hours.

After 4 hours the high molecular weight polymer was completely dissolved; The resulting solution was cooled and released from the reactor; The molecular weight characteristics of the obtained polymer were measured: Mn = 37200 Da, Mw = 105600, and polydispersity index D = 2.83. Further, the polymer solution was steam degassed, and the resulting viscous oil was dried in a 110 占 폚 vacuum drying cabinet, and the weight of the obtained product was 233.1 g.

Example  24

Conversion of weakly soluble high molecular weight polymers to low molecular weight rubbers during polymerizer washing to obtain liquid plasticizers.

Disruption was performed in a 5 liter reactor. The reactor was charged with 550 g of a nephrasse swollen high molecular weight DSR-ND from a commercial polymerization reactor, wherein the amount of neplacease in the swollen polymer was 267.96 g, which was 48.72 wt% solvent and 51.28 wt% 282.04 g). The reactor was then charged with 2200 ml of dry toluene, 2000 ml of dry benzene, 5.6 g of octene-1, and [1,3-bis- (2,4,6-trimethylphenyl) -Imidazolidinylidene] dichloro (2-morpholinomethylbenzylidene) ruthenium in 20 ml of tetrahydrofuran was sequentially charged with stirring at a temperature of 25 to 40 占 폚. The reaction mass was then heated to 75 < 0 > C and held at this temperature for 4 hours.

After 4 hours the high molecular weight polymer was completely dissolved; The resulting solution was cooled and released from the reactor; The molecular weight characteristics of the obtained polymer were measured: Mn = 9600 Da, Mw = 22750, and polydispersity index D = 2.37. Further, the polymer solution was steam degassed, and the obtained oil was dried in a 110 캜 vacuum drying cabinet, and the weight of the obtained product was 281.2 g.

Claims (8)

A method of cleaning a polymerization apparatus comprising treating a device comprising a swollen polymer in a hydrocarbon solvent with a solution of a ruthenium complex in a hydrocarbon solvent at a temperature of from 45 to 85 DEG C,
As the ruthenium complex, there is used a ruthenium compound having as a ligand 1,3-dimethymethyl-imidazolidinylidene, two chlorine atoms, and ortho-substituted benzylidene, wherein the substituent in the benzylidene ligand is An amino-substituted methyl group, and as the amino substituent, at least one selected from a dimethylamino group, a diethylamino group, a methylethylamino group, a methylphenylamino group, and an ethylphenylamino group and a cyclic amino group is used, wherein the ruthenium compound has the following general formula ≪ / RTI >

Where X is _{(CH 3) 2 N-, (} C 2 H 5) 2 N-, (CH 3) (C 2 H 5) N-, CH 3 PhN-, C 2 H 5 PhN-, (CH 2) ₄ N-, (CH ₂ ) ₅ N-, or O (CH ₂ ) ₄ N-;
Wherein the ruthenium complex compound is used in an amount of 0.03 to 0.07 g per kg of dry polymer. Treating a device comprising a swollen polymer in a hydrocarbon solvent with a ruthenium complex solution in a hydrocarbon solvent at a temperature of from 45 to 85 DEG C, wherein the ruthenium complex comprises 1,3-bis- ( 2,6-dimethylphenyl) -2-imidazolidinylidene, two chlorine atoms, and an ortho-substituted benzylidene are used, wherein the substituent in the benzylidene ligand is an amino-substituted methyl group , And at least one selected from a dialkylamino group, a methylphenylamino group, and an ethylphenylamino group and a cyclic amino group is used as an amino substituent, wherein the ruthenium compound has the following general formula:

Wherein X is (Alk) ₂ N-, CH ₃ PhN-, C ₂ H ₅ PhN-, (CH ₂ ) ₄ N-, (CH ₂ ) ₅ N- or O (CH ₂ ) ₄ N-;
Alk is CH ₃ or C ₂ H _5, and;
Wherein the ruthenium complex compound is used in an amount of 0.03 to 0.07 g per kg of dry polymer. A method of cleaning a polymerization apparatus comprising treating a device comprising a swollen polymer in a hydrocarbon solvent with a solution of a ruthenium complex in a hydrocarbon solvent at a temperature of from 45 to 85 DEG C,
The rinsing is carried out in the presence of an olefin, and as the ruthenium complex, a ruthenium compound having 1,3-dimethyimethyl-imidazolidinylidene, two chlorine atoms, and ortho-substituted benzylidene is used as a ligand , Wherein the substituent in the benzylidene ligand is an amino-substituted methyl group, and at least one selected from a dimethylamino group, a diethylamino group, a methylethylamino group, a methylphenylamino group, and an ethylphenylamino group and a cyclic amino group is used as an amino substituent group Wherein the ruthenium compound has the following general formula:

Where X is _{(CH 3) 2 N-, (} C 2 H 5) 2 N-, (CH 3) (C 2 H 5) N-, CH 3 PhN-, C 2 H 5 PhN-, (CH 2) ₄ N-, (CH ₂ ) ₅ N-, or O (CH ₂ ) ₄ N-;
Wherein the ruthenium complex compound is used in an amount of 0.03 to 0.07 g per kg of dry polymer. The method of claim 3,
Characterized in that mono-substituted alkenes are used as said olefins. The method of claim 3,
Characterized in that the olefin is used in an amount of 7 to 30 g per kg of dry polymer. A method of cleaning a polymerization apparatus comprising treating a device comprising a swollen polymer in a hydrocarbon solvent with a solution of a ruthenium complex in a hydrocarbon solvent at a temperature of from 45 to 85 DEG C,
Wherein the washing is carried out in the presence of an olefin and wherein as the ruthenium complex there is used 1,3-bis- (2,6-dimethylphenyl) -2-imidazolidinylidene as the ligand, two chlorine atoms, Wherein a substituent in the benzylidene ligand is an amino-substituted methyl group, and at least one selected from a dialkylamino group, a methylphenylamino group, and an ethylphenylamino group and a cyclic amino group is used as an amino substituent group , Wherein the ruthenium compound has the following general formula:

Wherein X is (Alk) ₂ N-, CH ₃ PhN-, C ₂ H ₅ PhN-, (CH ₂ ) ₄ N-, (CH ₂ ) ₅ N- or O (CH ₂ ) ₄ N-;
Alk is CH ₃ or C ₂ H _5, and;
Wherein the ruthenium complex compound is used in an amount of 0.03 to 0.07 g per kg of dry polymer. The method according to claim 6,
Characterized in that mono-substituted alkenes are used as said olefins. The method according to claim 6,
Characterized in that the olefin is used in an amount of 7 to 30 g per kg of dry polymer.