SU533326A3 - Catalyst system for producing unsaturated hydrocarbon polymers - Google Patents

Description

the phosphoric compound used is organic phosphines of the general formula R R R where R and R mean an apical group and R is an alkyl or aryl group. The special phosphines used are very expensive. Conduct polymerization in the presence of known catalysis-t. system does not allow to get polymers. whose molecular weight is below 5,000 and which are particularly interesting from the point of view of the production of varnishes.

To increase the selectivity of the catalyst system, the proposed system as an organic phosphorus compound contains phosphites of the general formula

/ Oe,

OB

where R, R and R alkyl, alkenyl, diarnyl, naphtha or unsubstituted or substituted with halogen aryl,

with the following quantitative ratio of the components, mol: phosphig - 1O -

-5-10; cobalt compound - 10 -

-ten ; halogen-containing alyumiypiyuyori weighty compound - 10 - 2, per 1 mole of polymerized monomer,

Using the present catalyst system, low molecular weight iolibutadienes containing up to 85%, preferably 10 to 75% vinyl groups and polyisoprenes containing up to 5O%, preferably 1O to 45%, of isoprenyl groups can be obtained, and in each case there is the highest content 1,4-trans double bonds. So it is possible to polymerise and other conjugated dienes, such as, for example, pentadiene-1,3, hexadiene - 1,3, heptadiene 1, 3, okgadiene 1,3, n-octatriene 1,3, e n-octatriene-1 , 3,7, 4-methylpentadienyl, 3, 3-methylpentadien-1,3, 3-megylhexadien-1, 3, 4-methylhexadien-1,3, 3,7-dimethyloctadien-1, 3 and 5-methylheptatriene- 1,3,6.

Typical examples of the phosphites used are trimethyl-, triethyl-, tripropyl-, tributyl, tricyclohexyl-, triallyl, triphenyl-, diphenylethyl-, diphenyllyl-, dif-enbutyl, diethylphenyl- and dibutylphenylphosphine, tris-, tp-, unproduced, diethylphenyl- and dibutylphenylphenylphenyl, tris-, disphenylbutyl, diethylphenyl- and dibutylphenylphenylphenyl, tris-, butyphenylphenylphenylphenylphenyl, triphenylphenylphenylphenyl, triphenylphenylphenyl, triphenylphenylphenyl, triphenylphenylphenylphenylphenol , tris- (1-nafgil) -, tris- (2-nafgil) -, tris- (2-chlorophenyl) -, tris- (2,4,6-trichlorfeiil) -, tris- (2 bromophenyl) - and tris - (2,4,6 tribromophenyl) phosphites.

In the implementation of the proposed method is used preferably Tris - (o-phenylphenyl) phosphite and tris- (nafgil) -phosphites, and also gris- (2-chlorophenyl) 4 phosphite

Preferred alkyl groups are straight-chained, branched or cyclic alkyl groups with 1-8 carbon atoms, such as, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl; octyl and diclohexyl. Preferred alkenyl groups are vinyl, vinyl, allyl and crotyl. Phenyl, tolyl and benzyl are preferred as aryl groups.

The present catalyst system may contain an H-acidic compound, for example, water, alcohol, or an organic acid. Water is preferably used. Other components are a cobalt compound and an organoaluminum compound.

Suitable cobalt compounds are salts of inorganic or organic acids and complex cobalt compounds such as cobalt chloride, cobalt bromide, iodide, cobalt sul (1zat cobalt sulfide, cobalt, cobalt nitrate, cobalt carbonate, kobaltga phosphate, cyanate cobalt cobalt hydroxide, acetate kobal1, .ta, cobalt oxalate, valeri- en-atoms of cobalt, cobalt okgoag (shftenat cobalt sgearat cobalt bis-atsetigdatsetona g of cobalt and cobalt bis atsetoatsegat Dietz klopentadienilkobalg ,, I redpochtite. 11c about 1: zuyut soluble organic chesk1-Lq rastvorite.tah cobalt compound, for example cobalt octoate and cobalt atsegilatsetonag,

The halogenides of dialkylaluminium, for example, dimethylaluminium chloride, diethyl chloride, aluminum: diisobutylaluminium chloride} 1i, are particularly suitable as halogen-containing aluminum organoaluminum compounds.

Cobalt is added in an amount of C, 001 - 1 mmo. ,. preferably 0, O1. Oj5 mmol, per 1 mole of polymerization monomer.

Equivalent to the number of catalysts of the back of the torrent mixture can be, if necessary, arbitrarily in the cooler, with a view of the components, conditions of polymorphism, CI AND the properties of the polymer to be obtained, with the egalMonomic ratio of the cobalt to sharpened; aluminum is 1: 1-1; 2000; prodopochigelno 1: 10-1:: 100,

The content of the organic phosphorus compound is 0.1 - 50 moles, preferably O, .2: - 20 moles, for 1 mole of the cobalt compound and the molar ratio H of the acidic compound: aluminum cmr is 0.001 - 1.5,

A particular advantage of the proposed catalysis of the 1O system is that there is no need to treat it against aging before use. Unsaturated hydrocarbon polymers can be obtained continuously or intermittently by contacting conjugated dienes with the proposed catalyst in a hydrocarbon solvent or a halogenated hydrocarbon solvent, or without a solvent. The monomer concentration is limited by the viscosity of the solution. Suitable solvents are commonly used for polymerization using Ziegler-Natta catalysts. From the group of aliphatic, alidiklicheskih, aro matic and halogenated uglevodoro rows frequently as used are pentane, hexane, heptane, n- and isooctane, isononane (hydrogenated trimeric propene), n-decane, isododecane (hydrogenated propene tetramer) diklopentan, cyclohexane, IU Ti Cyclopane nant, methylcyclohexane, ethylpiklohexane, isopropylpiclohexane, dicloctane, decahydronaphthalene, hydrogenated terpenes like pinan and campan, diclohexane and its substitution products, benzene, toluene O-, m-, p-xylene, ethylbenzene, o -, m-, p-di ethylbenvol, n-p opylbenzene, isopropylbenzene and other mono- and polyalkylbenzenes, tetrahydronaphthalene, cichlorine, methane, chloroform, carbon tetrachloride, 1,2-dichloroethylene, trichlorethylene, tetrachlorotylene, chlorobenzene, o-dichlorobenzene, trichlorobenzene (a mixture of isomers, a mixture of isomers, a mixture of isomers, a mixture of isomers, a mixture of isomers, a mixture of isomers, a mixture of isomers, a mixture of isomers, a mixture of isomers, a mixture of isomers, a mixture of isomers, chloroform, chloroform, chloroform, chloroform, chloroform, chloroform, chloroform 2-dichloroethane. To increase the polymerization activity, an aromatic hydrocarbon, such as benzene, is used as a solvent. The process is carried out at temperatures from -20 to + 1OO C, preferably from 0 to 80 ° C. The termination of the polymerization at the end of the reaction is carried out by pouring the polymer solution into a mixture of isopropanol and stabilizer solution. For example, phenylnaphthylamine in benzene solution is used as a stabilizer. The processing of the deactivated stabilized polymer solution thus obtained is carried out by precipitation in isopropanol, the polymer solution is poured into an intensively placed excess precipitant, or by distillation of the solvents with water vapor. Then the polymer is in vacuum. Hydrocarbon polymers obtained using the proposed catalyst system are characterized by a higher content of vinyl or substituted vinyl groups. So, for example, polybutyadienes are obtained, containing up to 70%, preferably 10 to 60%, of vinyl groups and polyisoprenes, containing up to 50%, preferably 10 to 45%, of isopropenyl groups, each with a low content of 1 , 4-trans-double bonds. In this case, the content of vinyl or substituted vinyl groups can be controlled by the concentration of an organic phosphorus compound or the molar ratio of phosphorus and cobalt compounds. The products obtained, mainly polybutadienes, have the following distribution of double bonds; vpnilnye double bonds - Yu-85%; 1,4-cis double bonds 15 to 90%; 1,4-trans double O bonds — 10%. Molecular weight is temperature dependent and increases as it rises. The products obtained according to the invention are suitable for many technical purposes, for example for obtaining air-dried and kiln-coated coatings, as rubbers, for the manufacture of running tires for vehicle tires. They have good pg and slide properties. Thus, it is possible to dispense with combinations of emulsion rubber based on styrene p butadiene and cx-1,4-butadiene, which are commonly used in the tire industry. The use of the proposed butadiene homopolymers makes it possible to avoid the use of the increasingly rare and expensive styrene as a monomeric component. Replacing 1,4-bonds with 1,2-bonds, for example, it is possible to regulate the gas permeability or diffusion ability of low-molecular substances in similar vulcanizates of the proposed polymers. (For example, swelling of oil). By changing the structure of the molecules, it is possible to co-ordinate properties during cold (glass transition temperature ranges from -20 to -100 ° C depending on the content of 1,2-bonds). In the examples, the indicated specific viscosity (RV) is specified in toluene at 25 C. The distribution of double bonds in polymers is determined by the absorption spectrum of infrared, Example 1. 1675 ml of benzene and 0.75 mmol of cobalt octoate in the form of a benzene solution, 0.2 Water (11D mmol) and varying amounts of benzene solution of triphenylphosphite in the specified sequence are fed into an autoclave made of 5 l steel, then 250 g of butadium 1-br-1.3 are added. The autoclave is closed and heated to 2: 5 Co. At this temperature, 20 mmoles of dithyl aluminum chloride are added. The reactor is heated to 50 ° C. For 5 hours while stirring the osuestB-Molar transformation, j RUV,% dl / g ratio R: Co

79.3

1.7 O

ten

86 L5} 1 elkmerization. At the end of the polymerization, with a / g solution, isopropanol and 1% phenyl- | 2t-naphtylamine are added as a stabilizer. The green solution is incubated under vacuum. The results are given as follows: a microstructure,% dis -, - I vinyl

85

Comparative. Experience L) O

EXAMPLE 2 “The process is conducted ii.; K:.,; It is natural to Example 1, but with not |; Zmon; we have the ratio P; With equal to 2; 1. Zagrjut amount of various H-acidic compounds. The results are givivodena in TAS ;;, 2,

Example o, Grootse Vedut a.11.d; logical example 1. zamai okgoat iuioa /:;,.-.

: The process is carried out anamo vary KOHUej-j-Sol KoGa n mg;., 1 n: C ratio, Rose ;; /: effect:; 1 1EG: don Tab., 4,

l;: nil

10 11 12 13

9 Determined by osmosis under vapor pressure

A. cetiladegonon cobalt

533326

ten

Continued table. 2

Table 3

44,40,0925О6

67.20.11 26520 molecular weight of polymer 1080;

About 1Yar11OS

Co ,, mm oh

R: Co ratio

one

0.2

65.4 0.3 0.5

0.5

0.75

1.0

1.0

1.0 1.5 1.5 2.0

example 5, repeat olisc; - ::

in example 1, experience, and prvpav: 1I1og m Number in higher kokdo.chtraii ha i- results are given in gabl, 5.

Exercise and {The Process and the Senate a ;;. Gichpo example 1, pmesg .: 0: ;; 1; ash iic ;; aue other solvents; Psluchoyuchi and

Bekzod, s

Experience

(mole

1280

1290

834

427

ABOUT

four

.7: -le13

533326

14 Table 6

Table 7

15

Aeitce. When added, iC, i. 15 cyclizations are observed, caused by stronger Friedel-Crafts activity of highly halogenated organoaluminum compounds. The content of trans-1,4 bonds in the polymer is significantly increased.

When using triethylaluminum in normal concentrations only reach

Triethyl Phosphite: Cobalt

ETFB: With

620,5

631

642

Diphenylallylphosphite; cobalt

0.5

60.4 1 81.0

533326

16 Continued table. 7

of wearing

And Parame 8, the process is carried out analogously to example 1, but other organophosphorus compounds are added. The results of these polymerization processes are given in ta bl, 8 o

Table 8

eleven

6

eight

18 3

0.95 0.62 very little interest. Even with the addition of acids, such as salt, a substantial amount is not reached.

Trialilylofofig: cobalg

ETFB - 1-egil-3.5,8-griox-4-phospha-2.2,2-bi1 xyclooi.

Example 9, at 0.75 mmol cobalt octoate, 0.2 ml water, 1.5 mmol of griphenyl phosphite, 1675 ml of benzene, 25 O g butadiene-1, 3, 2 O, O mmol of diethyl chloride 533326

18 Continuation of table 8

aluminum (otherwise unchanged) investigates the effect of temperature on polymerization. The test was carried out for 5 hours. The results are shown in Table. 9.

JU

For example;: example t. poly small and :: oo ° a re

PRA polymerin example 1

P r and 0.2 mm o L pogo ras ra rio- (yu in uka; clave from C li. .JioO I cover:; 1Yes

JB CO

; .. h tkBn-:;.

.J, y;. D TO ... -, J,., „

-, oh, day

leggings; ai-j-i; fooloba l

™:; ao. Blaz.

533326

21

37.2

20

30 45.6

35 47.2

45 69.9

60 66.1

120 68.3

180 70.6

300 75.6

0.5

47.2 1 2 5

70,8

67.6

8.2 Polymerization with Modified Hydrated (TZNPt) Cobalt

22 Continued table. ten

3

47

48

2 2 2 50

45

42 53 48 51

46

2

45

2

43 54

2

46 49

2 S3

43

Table 11

Microstructure,%

Gel,

3.4

1.4

L

20

732

61 60 47

2

1644

2

11,441,6

6 1ablitsa 12 gris- (2-yafgil) -phosphite catalyst 23 Polymerization with the aid of

113

60,8

11 p and mep 14, the process is carried out analogously to example 12, but instead of gris (2-naphthyl) phosphite, tris- (2 chlorophenyl) phosphite is used. Results are given in gabl, 14,

Polymerization with modified cobalt trpc- (2-chlorophenyl) phosphite catalyst

sixteen

82 69 48 28

50

56

42

3

2

Example 15. The process is carried out analogously to example 12, but instead of tris- (2-naphgyl) phosphite, add tris {o-fe- 1-: ylphenyl) phosphorus (ToPPi). Results from Table 1, 15.

Table 14 I-qualified griss- (1-naphthyl) phosphorus cobalt 533326 24 Tabl and a 13 catalysis

25

Example 16. The Vedoug process is analogous to Examples 12 and 15, but instead of cobalt octoate, other cobalt compounds are used, partly in different quantities than specified in Example 12. The results are shown in Table. sixteen.

Example 17. The process is carried out analogously to Examples 12 and 15 with the difference that, with an unchanged amount of phosphite, the concentration of cobalt octoate varies. The results are shown in Table. 17

Example 18. The process is carried out similarly to examples 12 and 15 with the difference that varying the concentration of monomer. Investigated in two directions: if not. Change the component of the cobalt catalyst.

Bisacceta tocobal127

0.2

40

Cobalt bisacetate 128 0.6 DCPA

533326

26 Continued table. 15

the concentration of the catalyst and with the concentration of the catalyst reduced by half using half the monomer concentration (4.63 mol of butadiene (25O g) 100%). The results are shown in Table. 18.

Example 19. The process is carried out analogously to examples 12 and 15 with the difference that, with a constant molar ratio of P: Co 1.5: 1, the number of different H-acidic compounds varies. (O-Phenyl (|) enyl) phosphite (0.3 mmol) was added as the phosphorus compound and cobalt octoate (O, 2 mmol) was added as the cobalt compound. The results are shown in Table. nineteen.

Table 16

0.321.6 1.2 2559 36 0.3 0.3 12.0 0.48 11 9 48 DA, 4 1.5 2 2 87 11 51

27

533326

28

Continued table. sixteen

29

533326

30 Table 18

31

Trifhoruksuona acid

32.2

1.38 2.77 39.4

Example 2O, With the above uelo-ena (1,3), 15.0 mmol diethyl lavium chloride (0.2 mmol cobalt octoate, 0.2 ml min), the effect of temperature on the

 , 0.3 mmol Tris- (o-phenylphenyl) - dolimerization. The reaction proceeds (with the claim of β-phosphlut and 0.6 mmol of the trio- (o-phenylphenyl) -lution of experience 164 - 3 hours) for 5 hours,

-phosphite, 1675 ml of benzene, 250 g of bugadk-Results are given in B table. 20,

Transformation

30.0 65j5 55.2 92.5 78.0

p-1 o. ,and

56,8

R: With 3: 1 (0.0 mmol ToPPx)

533326

32

Continued table. nineteen

2 2

37

55 74

8 6 20

Gel,

RUV,

.c l / g

2.9 2.0 1.7 1.5 1.3 1D.

71 69 61 62

39 59 47 50 53 50 44

2 47

Example 21, under the same conditions, given in gabl, 12. As a phosphite

x, as in Example 20, tris (o phenylphenyl) phosphite is used to examine the time.

polymerization course. Temperature 50 ° С. The results are shown in Table. 21.

Example 22, the process is conducted ana-B table. 23 shows the results, logically to examples 12 and 15, except for Example 24. The process is conducted by anaopyts 200-202, see column 2, tab., 22; similarly to examples 12 and 15 with the difference

test 200 - 0.75 (at 0.4 mmol octoate at (other conditions are unchanged)

cobalt); run 201 to 1.0 (polymerization of JQToPPi: Co 1.5: 1 and 0.2 mmol octoprotein for 4 minutes); 202-cobalt experience varying the amount of chloride

1.5 (within 2 hours), but instead of benzene diethyl aluminum. In tab. 24 shows added solvents. The results are the results.

Polymerization in various solvents

533326

Example 23 Instead of butadiene (1,3), the same amounts of isoprene will be polymerized by analogy with Examples 12 and 15,

Table 21

a b and c a 22

35

533326

36 Continued table. 2

37

38 Table 23

Table 24