SU423305A3 - METHOD OF OBTAINING STATISTICAL COPOLYMERS - Google Patents

Description

one

This invention relates to the production of conjugated dienes random copolymers with ethylenically unsaturated monomers.

Known is a method for preparing random copolymers of conjugated dienes by copolymerization with ethylenically unsaturated monomers capable of anionic polymerization, in an organic solvent medium in the presence of anionic initiators iatsrimer litiyorgaincheskih and as modifiers capable of preparing statistical copolymers microstructure, esters tretichpyh amines, thioesters.

The invention provides for the use of qualitatively excellent compounds as modifiers - soluble in the reaction medium, having the oxidizing properties of the compounds of elements 1B, 2B, 3A, 5,6, 7A and 8 groups, with the exception of titanium and vanadium compounds in the amount of 0.01-1 mol per 1 mol of initiator, better than 0.05-0.16 mol. This makes it possible to obtain copolymers with an improved statistical distribution of the monomer units, which therefore have improved properties.

Conjugated dienes used according to the invention are dienes, which themselves can be polymerized into homo-polymers using an anionic initiator. These include dienes containing

4-12 carbon atoms, in particular 4-8, for each molecule. Examples of such dienes are 1,3-butadiene, isoprene, 2,3-dimethyl-1, 3-butadiene, 1,3-petadiene (iperylene), 2-methyl-3-ethyl-1,3-butadiene, 3-methyl- 1,3-pentadiene, 2-methyl-3-ethyl-1,3-yentadiene, 2ethyl-1, 3-pentadiene, 1,3-hexadien, 2-methyl1, 3-hexadiene, 1,3-heptadien, 3-methyl- 1,3-heptadiene, 1,3-octadiene, 3-buty l-1,3-butadiene, 3,4-dimethyl-1,3-hexadiene, 2-fecil-1,3-butadiene, 2,3-di -n-propyl-1,3-butadiene and 2-methyl3-isopropyl-1, 3-butadiene.

Conjugated dienes containing pl-alkoxy halides can also be used. Examples of such dienes include 2-methoxy-1,3-butadiene and 2-ethoxy-3-methyl-1, 3-hexadiene. You can also use a mixture of dienes. Isoprene, butadiene and 2,3-dimethyl1, 3-butadiene are preferably used.

According to the invention, ethylenically unsaturated (unsaturated monoalkene) compounds utilize compounds suitable for anionic polymerization, for example styrene, styrene derivatives substituted in a ring, such as ortho- and metamethylstyrene, parachlorostyrene and vinyl toluene, acrylic esters and esters and esters of acrylic acid and polymethylmethylstyrene, parachlorostirol and vinyl toluene, acrylic esters and esters of acrylic acid and polymethylmethylstyrene; such as methyl methacrylate, ethyl acrylate, methyl acrylate, ethyl methacrylate,

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methyl propane, propyl acrylate, phenyl methacrylate;

The amounts of conjugated diopes and unsaturated monoalkene compounds in the monomer mixture that can be polymerized, according to the invention, can be varied within wide limits.

Driven monomer mixtures usually contain from 5 to 95% by weight of unsaturated monoalkene compounds and from 95 to 5% by weight of conjugated dienes. XopouiHx results are achieved if monomeric mixtures are used, containing from 10 to 50% by weight, often from 20 to 40% by weight, of unsaturated monoalkene compounds and from 90 to 50% by weight, and rarely from 80 to 60% by weight. % of dyne dyons.

Aromatic monovinyl compounds with 8-20, especially 8-12, carbon atoms per molecule, especially styrene, are preferred. As a compound or complex with oxidizing properties, it is possible to replace such a compound or complex that does not erode protons under polymerization conditions. Such compounds are metallic or non-metallic compounds in which the formal positive charge of a metal or non-metal atom is higher than the minimum formal positive charge of such an atom. The form of a small charge implies a charge characteristic of an atom if the structure of the compound or complex used is fully ionizable. Examples of such compounds (including complex ones) used as modifiers are compounds n complexes in which is present) from pyvalent molybdenum, tetravalent zirconium, chromium with a valence greater than 2, tetravalent cerium and tin, prolific uranium, divalent copper and mercury, pivalent phosphorus, antimony and trivalent manganese, iron, lanthanum, and bismuth.

The modifiers (cocatalysts) used in accordance with the invention must be soluble in solvents suitable for polymerization. Such soluble compounds include iron (P1) acetylacetonate, iron (III) -3,5-diisopropyl salicylate, uranyl acetate, copper (11) -diisopropyl salicylate, cerium (IV) -3,5-diisopropyl salicylate, cerium (IV) -atsetilatsetonat, chromium (III) -3,5-diisopropyl salicylate, tridecanol m lanthanum, molybdenum pentachloride, potassium permanganate, potassium dichromate, zirconium acetylacetonate (iIV), pentahloristy phosphorus pentahloristy mysch k pentaiodid antimony, tin tetrachloride, and also, mercury3,5-dysopropyl salicylate. Besides.

Other solvents used in the polymerization process, such as metal naphthenates and metals containing fatty acid residues, can also be used.

As cocatalysts, it is preferred to use compounds (including complex ones) in which metal or non-metal from group 1B, 3A, 4A, 5, b, 7A and 8 is present,

-in features of the 1B, 3A, 7A, 7A, and 8 soils of the periodic table of the Ele.mentov Mendeleev. Preferably, copper, silver, cerium, lanthanum, antimony, mouse, m, molybdenum, tungsten, iron, manganese, ruthenium are used.

and uranium. Best results are achieved when a cocatalyst is used, in which ferric iron, tetravalent cerium, trivalent lanthanum and divalent copper are present, as this results in large changes in the distribution of monomers in the polymer chains. Similar results are obtained using mixtures of cocatalysts. Compounds and complexes, which are preferably used as a cocatalyst according to the invention, if they are mixed in a 1: 2 molar ratio with an anionic initiator with a usual catalytic concentration, for example, 10 mg eq / l, temperature 20 ° C, give the reaction product

which is mainly soluble in

solvents suitable for copolymerisation.

As modifiers can not be

compounds and complexes that are capable of initiating radical polymerization, such as peroxides and diazo compounds, are employed. Such compounds, together with the anionic initiator, cause mixed radical and anionic -polymerization, which produces the formation of mixtures of products of conventional annon and radical polymerization. In contrast to this, cocatalysts used according to the invention are used.

cause only anionic polymerization.

The cocatalyst according to the invention is added in an amount of 0.01-1 mol per 1 mol of an anionic initiator, preferably 0.01-0.5, in particular 0.016-0.25. If you add more

1 times the molar amount of the cocatalyst, then the solid phase and the yield of the copolymer per unit time is reduced.

The amount used in my invention to the cocatalyst depends on that used for

sonolymerization solvent. If a polar solvent is used, a larger amount of cocatalyst is usually required to achieve the static microstructure of the copolymer than the amount of cocatalyst in the copolymer.

the case of copolymerization in a nonpolar solvent medium.

For the polymerization according to the invention, any anionic initiator can be used. As a rule, compounds containing one or more silk atom atoms are used.

metal or alkaline earth metal atom. Examples of anionic initiators are hydrocarbon compounds of lithium, such as methyl lithium, ethyllithium, butyl lithium, pentyl lithium, hexyl lithium, 2-ethyl hexyl lithium, n-hexadecyl lithium, 2-ethylhexyl lithium, n-hexadecyl lithium; unsaturated hydrocarbon compounds of lithium, such as alli lithium, metal lithium; dilithium compounds such as dilithium methane, 1,4-dilithium butane, 1,10-dilithium decane, 1,4-dilithium cyclohexane, 1,4-dilithium butyl, 1,4-diLithium benzene, 1,5-dilithium naphthalene, 1,2-dilithium-1 , 2-diphenyl ethane; trilithium compounds, such as 1,3,5-trilithium pentane, 1,5,15 trilithium dicano, 1,3,5-trilithium cyclohexane, 1,2,5-trilithium naphthalene, 1,3,5-trilithium anthracene, as well as other poly lithium compounds, such as 1,2,3,5-tepralithium-4-hexylanthraien.

These compounds can also be used if lithium is replaced by one or more atoms of an alkali or alkaline earth metal. You can also use such initiators in which a metal atom is bound by a non-carbon atom. Examples include lithium hydride, sodium ethanolate, rubidium amide, sodium caprolactam, potassium lauryl lactam, potassium phthalimide, lithium thiolate, and potassium allyl sulfide.

Organic compounds of lithium are preferred to be used, since with the help of the latter polymers are obtained from conjugated lienes with a relatively high content of c * 1,4 structure. In addition, it is desirable to use organic compounds of lithium, the hydrocarbon group of which is branched, since such lithium minates have a short induction period.

The copolymerization according to the invention can be carried out in any solvent which is inert with respect to the anionic initiator. Can be used as a polar. and non-polar solvent. The solvents include hexane, heptane, pentane, nicholic hydrocarbons, such as cyclohexane, benzene, toluene; tetrahydrofuran, dimethylsulfoxyl are used as polar solvents. Pyridine, triamide hexamethylphosphorus, as well as dimethylformamide. It is also possible to use mixtures of solvents, for example polar with non-polar solvents, as well as mixtures of incomplete solvents. In the case of the preparation of copolymers from conjugated dienes, such as isoprene and butadiene, in particular, copolymers of these conjugated dienes with monovinyl flavors, such as. in particular, styrene, it is preferred to use non-polar solvents, since the latter produce copolymers containing conjugated diene units with cis structure.

The copolymerization according to the invention can be carried out at any temperature, preferably from f-60 ° C to the decomposition temperature of the polymer.

In the copolymerization according to the invention, the pressure is not critical, it can be either increased or decreased. However, it is preferred that the pressure at which the monomers used are liquid. The required pressure can be easily determined by a specialist.

According to the invention, an anionic initiator with a co0 catalyst can be pre-biased, a cocatalyst and monomers can be added simultaneously to the anionic initiator. In both cases, the same results are obtained.

Copolymerisadia can be carried out as

5 continuously and periodically.

The copolymers obtained in the examples below are examined in relation to the nature of the incorporation of styrene into the copolymer, the content of styrene, and also in relation to the character

0 inclusion of isoprene.

Example 1. 50 ml of dry cyclohexane, 9 g of styrene and 21 g of isoprene, with the exception of moisture and in a nitrogen atmosphere, are successively fed into a 250 ml glass reaction vessel. equipped with a cooler, a baffle, a thermometer and a pipeline for supplying nitrogen. Then a certain amount of 3.5-diisopropyl salicylate containing trivalent iron is introduced into the vessel.

0 Fe (IIT) DTPS (see Table 1) and. stirring, the mixture is heated to a temperature of 50 ° C. In order to initiate polymerization, 0.3 recycled butyl lithium is added. After 2 hours, the polymerization is stopped, the reaction mixture is poured into 250 ml of acetone, in which 0.1 g of a stabilizer, which is known under the trade name Plastonox 2246, is dissolved. The results of the experiments are given in Table. one.

0

Example 2. Example 1 is repeated, using mmol of secondary butyl lithium and NpoM (PT) -3.5-thi-isopropyl salicylate fCr (TTT) DIPS (see Table 2) as cocatalyst. After the same period of polymerization and in the same reaction CONDITIONS as R, Example 1.

Teach the results. are given in table. 2

Example 2 is repeated, but the anionic initiator is first attenuated with cocatalyst. After 1 hour, it is served in a mixture of monomers to be copolymerized with a mixture of monomers. Get similar results.

Similar results are achieved if the mixture of anionic innator with cocatalyst is added after 48 hours after the displacement

Example 3. Example 2 is repeated, USING as a cocatalyst (PPP) 3, 5-diochopropyl salicylate GT.a (TP) G) 1P5 (see Table 3).

Get results. in tabt 3

Example 3 is repeated. Using instead of 5 lanthanum (TTI) -3,5-di-11-propyl salicylate

Table 1

table 2

Table 3

Table 4

Table 5

Table 6

Taalnza 7

Table 8

Table 9

II

Calculator, mmol

0.03

0.045

0.06

lanthanum (III) acetylacetoate. Get similar results.

Example 4. Example 2 is repeated. Different numbers of different cocatalysts are repeated, especially molybdenum pentachloride (Mods) and cerium (IV) -3,5-diisopronyl Ce (IV) DIPS salicylate (see Table 4).

Get the results shown in the table. four.

Example 5. Example 4 was repeated, using different amounts of the following cocatalysts: copper (11) -3,5-diisopropyl GSi (P) DIPS salicylate and phosphorus pentachloride (PClj).

Get the results given in ta-bl. five.

Comparative Example 1a Example 2 is repeated, using vanadium oxychloride (VoCl) and titanium tetrabutylate as the cocatalyst.

Get the results shown in the table. 6

It can be seen from the above comparative example that it is impossible to obtain copolymers with an improved statistical distribution of monomer units by the addition of vanadium and / or a titanium compound with oxidizing properties.

Example 6. Example 4 is repeated, using different amounts of different cocatalysts, in particular manganese (P1) HMP (1P) acac, acetylacetonate cyoconich (IV) rZr (IV) acac. iron acetylacetonate SP) Fe (III) acac, and also chromium acetylacetonate (P1) Cr (III) -acac.

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Table 10

Table 11

Get the results shown in the table. 7

Example 7. Example 4 was repeated, using uranyl-3,5-diiso-propyl salicylate U02 (DIPS) 2 as well as co-catalyst and Rutenyl-3,5-diisopropyl RuO salicylate (DIPS) 2 as cocatalyst.

Get the results shown in the table. eight.

Example 8. Example 2 is repeated using mercury (II) -3.5 diisopronyl salicylate Hg (II) DIPS, tin tetrachloride (SnCl4), and also tetraethyl lead (PbEt) as a cocatalyst.

Get the results shown in the table. 9.

Table 12

Comparative example 2a. Example 2 is repeated, using divalent zinc stearate as a co-catalyst.

Get the results shown in the table. ten.

Comparative example For. Example 2 is repeated, using 13

and dibutyl maglisers triethylaluminium neither.

Get the results shown in the table. eleven.

Example 9. Example 2 is repeated using bismuth (111) 3, 5-diisopropyl salicylate as a cocatalyst.

Get the results shown in the table. 12.

Example 10. Example 2 is repeated using butadiene instead of isoprene. 22.6 g of polymer of a completely statistical structure are obtained.

Subject invention

Method of obtaining statistical copolymers by copolymerization of conjugated dienes

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with ethylenically unsaturated monomers capable of anionic polymerization, for example, with styrene, methyl methacrylate or acrylonitrile, in an inert organic medium

solvent in the presence of anionic initiators, such as organolithium, and modifiers, which provide for obtaining the statistical microstructure of copolymers, characterized in that, in order to improve the statistical distribution of monomer units in the copolymer and improve its properties, oxidizing properties compounds of elements 1B, 2B, 3A, 4, 5, 6, 7A, and 8 groups soluble in the reaction medium, with the exception of titanium and vanadium compounds, in an amount of 0.01-1 mol by 1 m Pa 1 m l initiator.