CS233409B1 - Process for preparing homopolymers of dienes 1,3 and copolymers of butadiene 1,3 with isoprene and copolymers of diolefines-1,3 with vinyl monomers - Google Patents

Description

SUMMARY OF THE INVENTION The present invention relates to a process for the preparation of 1,3-diolefins and 1,3-bitadiene-1-olefin copolymers, as well as diilefin-1,3-copolymers and vinyl monomers, particularly styrene and styrene.

allyl diethylenate to live polymers of low and medium molarocular hooltnitts which, upon addition of the appropriate reagents, to the polymer, especially ethylene oxide, carbon dioxide, ethylenediamine and ethylenediufide at the chain ends of the functional groups of the group, especially -OH, -COOH, -MHg, -MHg, The electrolyte of the polymer of -1,3 naatavitnene is spun at values ranging from 75% to 1.4% to 90% of structure 1.2, wherein the polymerization is carried out in a homogeneous liquid phase in non-polar paraffinic, definitions and / or aromatic solvents in the presence of multifunctional alkali metal initiators. , optionally with the addition of polar substances, which consists in polymerization in the presence of new type initiators.

It is known that the polymerization of bioreactive reactions by compounds in stoichiologically crosslinkable reactions is well known. to prepare, for example, from polymers such as tertiary butyl, such as, for example, pure butadiene as the mondoers, polymers with a narrow molecular weight distribution. (JeterforKhiung und TextiltechnLk 25- / 1974/5, etr. 191; NSR-DOS 2,425,924, USSR-296,775). Most of these cell-initiated mutants and mutant potentiators are insoluble in hydrocarbons, also in gasoline fractions, or only slightly soluble.

Therefore, they cannot be used to move dimer polymers by relatively low. molar mass, e.g. in the range of - 1000 to 6,000 g / mol, with a narrow molecular weight distribution e. . at the same time and a high content of structure 1.4. Fleece! the addition of a small amount of initially, which is intended to affect the initiator growth under the oligo-organic conditions, the formation of a living pligpoir is very problematic and results in a broad molecular weight distribution, often associated with lower initiator efficiency.

Most of the bifunctional and ontLfUnkkϊϊ na na na na na na na b na na na na na na na na na na na na na na na na na na na na na na na na na na na na na na na na na na na na na na b na na b na b b na b b dá dá přip přip dá dá přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip jen přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip přip jen jen jen jen jen přip jen jen jen jen jen jen jen jen v v v v jen . If such initiator solutions, such as, in particular, ether, undergo polymerization at room temperature and at a higher temperature, reactions such as chain disruption, chain transfer, ether cleavage, and the like. This is associated with a decrease in the content of active Li-C species in the polymeric ssOsS. leading to losses. in the functionality, as well as to crosslink the content of the 1.2 palm polymer structure.

It is known to synthesize and copolymerize in pure form by the dropping of biocoupling and mutation alkali metal initiators, which are thermally stable, using only non-polar solutions, and these are well initiators, and these are well initiators. soluble (non-GDR 137 804, US 3,193,596).

These drawbacks are eliminated in the process for the preparation of homopolymer 1-1,3 and copolymers of butadiene-1,3 and isoprene, as well as of copolymers of diolefins-1,3 with ion-copolymerizable monomers, in particular styrene and styrene, alcohols, alkylene oxide (n or niethyl tertiarycrylate to living polymers of low to medium molecular weight) (the motif of the diene-1,3 'polymer is not capable of melting the spin at values between 75 * structure 1.4 and 90 * structure 1.2, wherein the polymerization is carried out in the hot liquid phase in non-polar parental definitions and / or epoelectric solvents, optionally in their relatively polar polar abrasives, in the presence of decomposable alkali metal initiators, wherein the didefins-1, 3 and vinyl polymers of polymers in the form of an etichioetric polymerization initiator are based on the mutations of the RR'R (CH <) &gt;

R, R,. R ", - R" 'are. CHg CH- or

If

R, R * and R "are CH ₂

CH- and R '' is

If

R '' -CH ₂ -CH (11bCH ₂ -, wherein R '' is io-alkyl, n-alkyl, cycloalkyl, aryl or arylalkyl of 2 to 8 carbon atoms, or

R and R 'are

and

R 'and R "are · R'', -CH ₂ -CH (Li) -CH _2, where R ^a' is as defined above, or R is allyl and R ', R" and R'"are CH ^ * ^Or CH

If

R 1 is -CH ₂ -CH (Li) -CH ₂ -, wherein R 1 is as defined above, or

R and R 'are allyl and R' * as are

or R '' -CH ₂ -CH (Li) -CH ₂ -, wherein R '' is as defined above and n is 2 to 6.

For the preparation of polymers 8 with a microstructure of 1,3-polybutadiene predominantly 1,4, polymerization is carried out in the absence of polar solvents, while polar solvents are present in the preparation of polymers with a microstructure of 1.2. The polymerization is preferably carried out in a temperature range of 263 to 373 K.

Butadiene-1,3 and isoprene are preferably used as conjugated dienes, in particular vinyl aromatic compounds such as styrene or acrylonitrile, alkylene oxide or methyl methacrylate are suitable for the random copolymerization. Comonomers are useful in the preparation of block copolymers of type A-B-A, wherein V is a polybutadiene block.

Since it is a stoichiometric polymerization, the initiator concentration is determined by the desired molecular weight of the polymer. By functionalizing living polymers, functionalized homopolymers and copolymers of low molecular weight, e.g., 1,000, as well as average molecular weight, e.g., 20,000 to 50,000, can be prepared.

The advantage of the process according to the invention is that it eliminates the disadvantages of known processes such as the insolubility of the initiator and the low efficiency of the initiators in non-polar solvents, can also be prepared in an ethereal environment, a narrow molecular weight distribution and higher functionality of living polymer.

The process according to the invention makes it possible to control polybutediene microstructure microstructure modifiers in the range of 75% 1.4 to 90% 1.2 by adding solvating agents of various types and amounts and thus to prepare functionalized polymers for various special applications. Polymerization in the absence of ether suppresses unwanted terminal reactions, so that functionality 2-4 can be obtained.

The process according to the invention is further elucidated by means of embodiments using a water-free solvent of a high degree of purity and the purest argon atmosphere.

Example 1

In 35 mmol of initiator RR'N (CH ₂ > ₂ NR 'R''(I) (R is CH ₂ = CH-CH ₂ -; R * e R''is CH 2

If

R * 'is R' ·· '- CH ₂ - CH (Li) - CH ₂ - (R "' is iso -C ^)), dissolved in 200 ml of bensene at 313 K polymers of 980 molar butadiene · Polymerization and · 150 ml of ethylene oxide, started to boil immediately to solid white gel · This was hydrolyzed with 30 ml of water · Benuunn fáue and centrifugation from the lthKi compounds continued by centrifugation after use in a non-rotary evaporator, a liquid polymer having a mean molecular weight of 2,700 permits well, adding a calculated value of 1,510.

The calculation of the polymer solubility of the polymer and that in all the examples was performed with respect to the build-up of the dianin into the polymer, but also with respect to the increase in the mole- lous molecular weight of the functionalizing agent.

The tulle polymer functionality 3.4. The infrared spectroscopy was melted with the structure 47, 1.4 of the caliper, 26% of the 1.4 duty at 27% of the 1.2. The yield was 95 »·

He said id 2

12 12.5 mool WNCC initiator ^ gNB ´ ^ ”´ (II) (B at B 'at B” is CH.J · * CH-;

. If

B 1 is iui-Cpg-CH ₂ -CH (Li) -CH ₂ -), started in 200 µl of benzene and at 1.93 K add 1.96 molar butediene-1.3 µ after 2.5 hours and the polymerization is complete · Boa flow cools down to 268 Kc and adds 110 aiool of ethyleneixide · Stirring is solidified to a solid white gel · After processing and yields a medium molecular weight viscosity of - 9620, the calculation is based on 8,467 · - Calculation is 3 9 · Polymer micristructure 48% 1.4 trans, 26% 1.4 cis at 26% 1.2 PB · The yield was 95% of theoretical ·

K 50 mool of initiator RH'N (CH2) ₂ NB ”R *” (III) (B at B * are CH ₂ = CH - CH ₂ -; B 'is CH ₂ '

B * "is the iun - C 4 H-CH ₂ - CH (Li) - CH ₂ -), dissolved in 250 mi Bensen ue added at - 313 980 К Mool - batudienu-1,3 in the polyoemije

2.5 hours, not reading temperature, dropping 268K, 220 molar ethylene oxide was added. A liquid polymer and a medium molecular weight of 3,200 were added to the hydration treatment gel, resulting in a calculation of 1,056 · ^ βιΟ ^ οι ^ · ^ · tulle 2,9 · - The polymer had a similar oicrostructure as in examples 1 and 2 · tulle yield 95% of theory ·

Ex a d 4

К 50 mool of initiator III, dissolved in 250 ml of bensene, were added at -3.3K 980 mool butudiene-1.3 u were polymerized for 2.5 hours · Pit but brought grubby no 268K u added 220 molar gamma-bilaylactin · Non-reddened viscous gel, in which the liquid polymer n of the middle molecular ЬтоПпши was leaked during processing. 3,000, whereby by calculating 1 058 · tulle 3.2 for an oicrostructure analogous to that in Examples 1 to 3 · Tulle yield 96% of theory

Example - 5 u '

For 35 moles of initiator I dissolved in 150 ml of banthene, 200 µl of tetretydrifuran was added to dry.

Example 5

Mol 35 moles of initiator I dissolved in 150 ml of benzene were added from cooling with 200 µl of tetrihydride urine. At 253 K. 980 mol of butediene-1,3 was added, and then polymerized. 3 hours at 283 K. 220 ml of ethylene oxide were then added with stirring to give a white gel. Mon. its processing yielded an easily flowing polymer having an average molecular weight of 2,950 with a calculated value of 1,058 and a function of 3.1. Product microstructure wasle.87%

1.2 and 13% 1.4 trans. The yield was 95% of theory.

Example 6

35 g of butediene-1,3 or 15 g of styrene were added to 2.5 ссП of initiator II dissolved in 200 ml of benzene at 323 K. The homogeneous solution was polymerized for 5 hours and then cooled to 288 K, after which 25 οοοΙ ethylene oxide was added from the stirring. A solid white gel was formed. After processing, an average molecular copolymer with an average molecular weight of 23,900 was obtained, with a calculated value of 22,871. The footaota was 3.8 and the yield of tulle was 98% of theory.

Example 7

To 5 mm> 1 initiator II in 300 n benzene was added 35 g of butadiene-1,3 at 323 K and polymerized for 2.5 h. Then 15 g of styrene were added and polymerized for a further 150 minutes. The solution was stirred at 288 [deg.] C. while stirring, 45 [mu] l of ethylene oxide was added. A white solid gel was formed. After treatment, a block copolymer with a styrene content of 35% was obtained. The mean molecular weight of the tulle was 11,900, which calculated 11,333. Fuukciit.aaite was 3.9 and the yield of tulle was 98% of theory.

EXAMPLE 8 n-Butyllithium in 50 ml of benzene and 25 ml of N, N ^, -dittyl-N, N ^, -dlyl ethylethylenediamine v. ¹⁰⁰ ml of benzene was treated with a non-bilting initiator. ^P by cooling to 4 ° C and adding 1,000 mol, 3. the mixture was polymerized for 2 h, then cooled to -5 ° C and 110 etyсП ethylene oxide was added with stirring. The solution solidified to a light solid gel. After the tulle has been worked up, the capillary polymer is obtained having a similar property. as the polymer of Example 2. The content of structure 1.4 was about 10% greater than that of the product of Example 2.

Example 9

105 mm &lt; -1 &gt; of lithium in 100 ml of benzene and 50 ml of N, N & apos ^; -II-n-hexyl-N, N ^, N-beta-ethylethylenediamine were processed to the boron initiator. ^P 4 on cooling to ⁰ ° C and ^{980 p} moles of isoprene řídavku the mixture was polymerized for 2 hours. Then the '-5 ° C and added under stirring

200 moles of ethylene oxide, after which the solution solidified on gel. After tydrolysis, an easily flowable polymer having an average molecular weight of 150 was obtained with a calculated molecular weight of .33.3-tylene polymer of 1.93.

EXAMPLE 10

The procedure of Example 2 was repeated, using only the initiator of the same structural formula, β except that B, R ', B "' and B '' tyl ^y CH ^ ⁷ · * ** · '> ^CH " anyl 3 ·

If

A polymer having a molecular weight Mn of 9600 was obtained with a calculated value of

467. FuncCotsalta Polymer Tulle 3.9, microstructure unmatched233409

They did

The pottup of Example 1 was repeated, and the difference was that the initiator used was the same structural formula where

R and R ^z are СН ^^ '^ СН-, · and R ^"and R"' being '

If

C ^ HH -C -CC ^--CHCl! an occiput 6 «was eískán polymer having a molecular haooiwoti 3200, which reads the value you ^ or ^ LA 1 51 ⁰ íWkcionnlitě about 3,6 ^M ikroatruktura Te podatatl changed.

Example · 12

The procedure of Example 1 was repeated with the difference that the initiator of the same etxuctural sample was the same, but I did not distinguish between R and R ' allyl, nyl 4 and cr &apos;.

R ”» R ”tulle CHg ......‘ ^ НИ-.

. LL

The polymer obtained has a molecular weight of 2,600 and a functionality of 2.0.

Example 13

Examples 12, 10 and 11 were repeated using thiaoprene, whereby the polymerization temperature of the tulle was increased by ЮK and the polymerization time was reduced by the molecular weight and fudtcioinity of the obtained tulle polymer at the same or better theoretically the same as butadiene-13. ‘

Example

Example 11 tulle repeated with the difference that R '' tulle CgO, or phtha!

Claims (1)

Pi DM ÉT VTMÁLBZU Process for preparing diene-1,3 homopolymers and butadiene-1,3 and isuprene copolymers as well as diolefin-1,3 polymers of diolefin-1,3 tons with an unreadable monomer, in particular with tetrate, alpha-methylatylemeam, but triethylamine. , tlkylene oxide, or methyl methacrylate for living polymers of low to medium molecular weight diene-1,3 polymer adjustable in spheres at values ranging from 75% attribute to 1.4% to 90% tucture · 12, whereby the polymerization is carried out in a homogeneous liquid phase in the most preferred pariarin, olefinic and / or aromatic solvents, optionally in their monks and flame solvents, in the presence of the mercury-containing alkali metal initiators, apparent that the diolefins-13 and the vinyl monommry polymeric in the presence of a mismtium mltilihiiwiditeecdiaminú types №'N (CB ^) _n MR '* R ”·, where