DE2342885A1 - PROCESS FOR ISOMERIZATION OF LOW BUTADIENE POLYMERS - Google Patents

Description

Nippon Oil Co., Ltd., 3-12, Nishi-shimbashi 1-chome Minato-ku, Tokyo, Japan

Process for the isomerization of low butadiene polymers

The invention relates to a process for the isomerization of lower butadiene polymers, in which a low butadiene polymer or a low butadiene copolymer with a combination catalyst, which an organic alkali metal compound and a Has diamine compound, is treated, creating a non-conjugated double bond in the polymer a conjugated double bond is isomerized.

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The invention also relates to a process for producing isomerized lower butadiene polymers with conjugated double bonds, in which a, low polymerization and copolymerization of butadiene with an organic alkali metal catalyst or alkali metal, followed by a further reaction with addition of a diamine compound to the reaction mixture in situ to isomerize their non-conjugated Double bonds to conjugated double bonds.

It is known that a low butadiene polymer or copolymer can be prepared by polymerizing butadiene or copolymerizing butadiene with another monomer in the presence of a catalyst which is an alkali metal catalyst, an organic alkali metal catalyst or a combination catalyst of a compound belonging to Group VIII of the Periodic Table associated metal and an alkyl aluminum halide.

There is a large number of publications which allow the production of low polymers of butadiene and copolymers of butadiene with conjugated Diolefins or vinyl-substituted aromatic compounds when using organic alkali metals or alkali metal dispersions as a component of the catalyst. To the typical catalysts in the manufacture, for example, include a sodium metal dispersion-naphthalene complex JA-PSn 7051/65, 27432/68), a sodium metal-ether complex and an organolithium compound (JA-PS 26477/66, U.S. Patents 2,913 W, 3,097,108, 3,105,838, 3119 800 and 3 140 278: A Living Polymerization in tetrahydrofuran solvent) and a chain transfer

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Carrying polymerization process (JA-PS 7446/57), in which aromatic hydrocarbons such as tuluene, xylene as a chain transfer agent among Addition of dioxane and isopropyl alcohol etc. to metallic sodium dispersions are used.

Since a low butadiene polymer or copolymer produced by known processes has a large number of 1,2 double bonds and 1,4 double bonds in the molecule and has a comparatively high reactivity, the polymer is used in a wide variety of fields As a parb binder, thermosetting plastic, adhesive, rubber admixture, intermediate product for various synthesis reactions and prepolymer. However, since the double bonds of such a low butadiene polymer are non-conjugated it is still insufficient in terms of its reactivity compared to compounds with conjugated double bonds in the molecule, such as wood oil and dehydrated castor oil. It is therefore expected, if non-conjugated double bonds, that in a lower butadiene polymer or copolymer contained butadiene units by an economically advantageous process to conjugate double bonds can be isomerized and thereby the reactivity of the lower butadiene polymer can be improved, their field of application is further expanded.

As an example of such an isomerization process, there is known a process in which a low Butadiene polymer at a temperature between 110 and 25o ° C in the presence of a catalyst which-a compound a transition metal belonging to group VIII of the periodic table, brought to reaction

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becomes (JA-PS 5757/68). However, the method is disadvantageous in that the reaction takes place at a high temperature should continue while doing such undesirable phenomena as gelatinization and coloring of the polymer can easily occur. Furthermore, the one compound is one belonging to group VIII of the periodic table Metal-containing catalyst expensive, which is why this process is also from an economic point of view is fraught with disadvantages.

A method is also known in which a low butadiene polymer in the presence of a cobalt naphthenate catalyst is subjected to oxidation in air to improve the reactivity of the low polymer (JA-PSn H592 / 58 and 3865/71).

Furthermore, in order to use these low butadiene polymers and copolymers To make them marketable, it will be necessary that they are further isomerized in separate ways, leading to will result in higher production costs. In addition, in this method is the number of those formed in the reaction conjugated dienes are very small, and coloration and degradation are not uncommon.

In contrast, the invention provides a method of improving the reactivity of a low butadiene polymer or copolymer, in which as a result of the use of a combination catalyst, which one contains specific diamide compound, non-conjugated double bonds of the butadiene units of a such low polymer to conjugated double bonds with high conversion rate at low reaction temperature isomerized without the occurrence of coloration or gelatinization.

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It has also been shown that isomerization occurs Butadiene polymers can be obtained without the disadvantages of coloration and gelatinization when the polymerization of butadiene and copolymerization of butadiene with other monomers using organic Alkali metals or alkali metal dispersions as a catalyst, followed by further treatment of the polymerization reaction mixture under prescribed reaction conditions with the addition of certain diamine compounds, is carried out.

More particularly, the invention provides a process for isomerizing lower polymers of butadiene and lower copolymers of butadiene with at least one monomer selected from the group consisting of conjugated diolefins other than butadiene and vinyl-substituted aromatic compounds in which such a low polymer is at a temperature between O and 20O ⁰ C is reacted in the presence of a catalyst comprising an organic alkali metal compound and a diamine compound represented by the following general formula

►N- (C) -

^R 6 ^R 4

wherein η is 2 or 3, and R ·, R _{2 , R 1} , R 1, R ^, Rc and Rg represent hydrogen or an organic radical having 1-20 carbon atoms, with two optional elements of R _{1, R 2} , R_ and R ₁ J can be connected to one another in such a way that they have a cyclic structure

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form. The invention alternatively provides a second process for isomerizing lower polymers of butadiene and copolymers of butadiene with other monomers to convert their non-conjugated double bonds into conjugated double bonds, in which diamine compounds of the general formula above, the reaction system normally before the inactivation of the catalyst after the polymerization reaction, independently of the presence or absence of any monomers are added and the isomerization reaction is carried out at a temperature between 0 C and 200 C, preferably at a temperature between 30 ⁰ C and 150 ° C.

In other words, the invention is characterized by the isomerized lower butadiene polymer can be produced economically and at low production costs by using the polymer with a combination of organic alkali metal compounds or alkali metal dispersions, which catalysts for low polymerization and copolymerization of butadiene, and diamine compounds are treated, and by adding the polymerization catalyst for both the polymerization and isomerization reactions is used effectively.

When using alkali metal dispersions as polymerization catalyst and when the polymerization reaction is set in motion and propagates, it appears that the alkali metal is in the form of an organic alkali metal As a result, you get even when using an alkali metal dispersion as a polymerization catalyst in the subsequent isomerization reaction

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same results as using an organic Alkali metals.

Conjugated dienes containing lower butadiene polymers and copolymers, which according to the process of the invention are produced, are weakly colored compounds with high reactivity and are particularly suitable as quick-drying color binders, moldings and intermediates for a wide variety of synthesis reactions.

As the low butadiene polymer or copolymer, polymers prepared according to conventional methods can be used use, such as polymers with 1,2 double bonds in large numbers, polymers with 1 ^ double bonds in large numbers Number and polymers with both 1,2 double bonds and 1, M double bonds.

A low polymer of butadiene or a low copolymer of butadiene with another monomer, which are prepared by a process in which butadiene alone or butadiene with another monomer in the presence an alkali metal or an organic alkali metal compound being polymerized as a catalyst is a typical example of the low polymer like it is to be used within the scope of the invention. To control the molecular weight and a faintly colored low To effectively obtain lower gel fraction polymer, one typically uses a method of in this case living polymerization with tetrahydrofuran as solvent and a chain transfer polymerization process, in which an ether such as dioxane or an alcohol such as isopropyl alcohol is added to the polymerization system, and in which an aromatic hydrocarbon such as tuluene and xylene, as a chain transfer agent or solvent

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is applied. According to this polymerization process The low polymers produced can be used well within the scope of the invention. Furthermore, similarly use low polymers rich in!, ^ double bonds in the butadiene units and by polymerizing butadiene or copolymerizing butadiene with another monomer in the presence a catalyst consisting of a compound of a metal belonging to group VIII of the periodic table and an alkyl aluminum halide.

The lower copolymers referred to in the specification and claims include copolymers of butadiene with another conjugated diolefin such as isoprene, 2,3-dimethyl butadiene and piperylene, and copolymers of butadiene with a vinyl substituted aromatic compound such as Styrene, α-methyl styrene, vinyl toluene and divinyl benzene. When using such a low butadiene copolymer, the content of comonomer units should not exceed 50 mol #.

It is desirable that this be within the scope of the invention the low butadiene polymer or copolymer used is liquid or semi-solid at room temperature and its molecular weight is between 300 and 10,000.

In the context of the invention, either the 1,2 double bond or the 1, ¹ I-DOpPeI bond in the butadiene

¹ ^ τ th are isomerized to a conjugated diene bond.

The catalyst to be used in the invention comprises (1) an organic alkali metal compound and (2) a diamine compound.

/ ♦ 0 9 8 1 2 / Q 8 6 3

The organic alkali metal compound to be used as component (1) is a compound represented by the following general formula

R-Me

where Me is an alkali metal selected from the group consisting of lithium, sodium and potassium, and R for an alkyl group such as methyl, ethyl, propyl, butyl and pentyl, an alkenyl group such as allyl and methallyl, a cycloalkyl group such as cyclopentyl and cyclohexyl, or an aryl or aralkyl group such as phenyl and Benzyl, preferably having 1-20 carbon atoms.

Furthermore, complexes of an aromatic ■ polynuclear Use compounds such as naphthalene and anthracene with sodium or potassium as component (1). The foregoing Compounds can be used singly or in the form of mixtures of two or more of them.

As component (2) of the catalyst according to the invention The diamine compound to be used is a compound represented by the following general formula

where η is 2 or 3 and R ₁ , Rp, R 1, Rj., R ₁ - and R / - are a hydrogen atom or an organic radical having 1-20 carbon atoms and wherein two optional elements from R ₁ , R ₂ , R, and R ₁ ^ to

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- Io -

Formation of a cyclical structure can be linked.

Preferred examples of the elements R ₁ to Rg are hydrogen, hydrocarbon radicals such as alkyl, cycloalkyl and aryl, and nitrogen-containing organic radicals which have primary secondary or tertiary amino groups. When the above diamine compound contains a functional group such as carboxyl, hydroxyl or thiol, the effect of the organic alkali metal compound as component (1) is lowered by the presence of the functional group.

Typical examples of such a diamine compound are ethylenediamines and propylenediamines, such as ethylenediamine, Tetramethylethylenediamine, tetraäthy läthylenediamine, propylenediamine, Dimethyl propylenediamine and tetramethyl propylenediamine; Polyethylene polyamines of the following general formula

CH ^ -CH ₉ -N-) R%

* r m

^d R '

wherein m is an integer greater than or equal to 2 and R ^, R ^f ₂ , R ¹ , and R ₁₁ for a hydrogen atom or a hydrocarbon radical with 1-20 carbon atoms, such as diethylenetriamine, pentamethyldiethylenetriamine and hexamethyltriethylenetetramine; and cyclic diamines such as piperidine and triethylenediamine.

If an organic alkali metal compound is reacted with such a diamine compound, it occurs color changes violently, and the organic alkali metal compound which is insoluble in hydrocarbons

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is solubilized by this reaction. One takes hence suggests that a complex is formed with -N-C-CjN- or -N-C-C-C-N- as an effective group.

The amount of the diamine compound to be combined with the organic alkali metal compound is not especially critical, however, the diainine compound is preferred in an amount between 0.1 and 100 molar equivalents to the organic alkali metal compound (0.1 to 100 moles of the -N-C-C-N- or -N-C-C-C-N- unit of the diamine per mole of organic alkali metal compound) admitted. Particularly high isomerization effects are obtained when the diamine compound is in an amount between 0.5 and Io molar equivalents of the organic alkali metal compound is added.

If the amount of the diamine compound is too small, a complex having isomerization activity will be formed prevented, while on the other hand, too large an amount of diamine compound also does not result in an outstanding Leads to an increase in the catalytic activity and only makes the process uneconomical.

The amount of the organic alkali metal compound used is not particularly in the context of the invention critical, but preferably the organic alkali metal compound is used in an amount between 1 mmol and 1 Moles, especially 10 mmoles to 100 mmoles, are used per 100 g of the polymer.

The ·· 'isomerization using the invention Catalyst can be carried out in the absence of a solvent if the viscosity of the polymer is low,

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If this is high, however, a solvent that can dissolve the starting polymer is preferred, and not none has an adverse effect on the isomerization reaction, such as aliphatic and aromatic Hydrocarbons.

The isomerization when using the invention

Catalyst is at a temperature between

0 and 200 ⁰ C, preferably 30 and 150 ° C carried out.

The isomerization reaction of the present invention is not limited so far as it is substantial is carried out in a solvent. Preferably, however, a solvent should be used that has no adverse effects, but does dissolve the polymer. For example, are aliphatic or aromatic Hydrocarbons are particularly suitable.

In the following, the invention will now be explained in detail by means of examples.

example 1

100 g of polybutadiene having a molecular weight of 1,000, a 1,2-double bond content of 86 $ and a trans double bond content of 1R% were dissolved in 50 cc of benzene, with 20 mmol benzylsodium and UO mmol tetramethylethylenediamine were added to the solution. The mixture was reacted in a nitrogen stream at 60 ° C. for three hours. 6 cc of methanol was added to the reaction mixture to deactivate the catalyst, and the reaction mixture was treated with active clay and filtered to remove the sodium compound. This was followed by the solvent and the remainder

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Diamine distilled off under reduced pressure and a weakly colored alkali metal-free polymer obtained.

The diene value of the resulting polymer was 2390. Became a mass consisting of 100 parts by weight of the polymer thus formed and 1 part by weight of cobalt naphthenate (in the form of a 6S solution) applied in a layer of 30μ and dried at room temperature, see above the tack-free state was achieved in four hours and the complete hardening process took eight hours.

The starting polybutadiene with a diene value of 0.3 was made in a proportion of 1 part by weight to 100 parts by weight of the polymer, the cobalt naphthenate (in the form of a 6% solution) and the resulting The mass was applied in a layer 30u thick. When the coating was dried at room temperature, the tack-free state was achieved in 25 hours, and the Curing was complete after 50 hours. From the above results, it is immediately apparent that the reactivity the exit polybutadiene through which he fir. according to isomerization carried out was considerably improved.

Examples 2 to 6 and Comparative Examples 1 to 4

100 g of polybutadiene with a molecular weight of 1100, a 1,2 double bond content of 89? and a trans double bond fraction of 11? were dissolved in 100 ecm of toluene, 20 mmol of benzyl sodium and a tertiary amine as indicated in Table 1 being added to the solution . The mixture thus obtained was in a nitrogen stream

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reacted at 8O ⁰ C. for three hours for reaction, and the following post-treatments were as described in the same manner in Example 1 were carried out, with gave the results summarized in Table 1

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Table 1

m σ

Complexing agent O lot t. Properties of the polymer Drying rate of the coating
^J Itunp; at Raumterno. (H) Vinyl * -An Service KieDlΓβΐ complete Art mmol 4o Trans * -An- part in % value 25th Srtunp · - part in % 74 0.8 5o Comparison
example 1 Starting polymer HO Q CH, CH, k Example 2 4o 54 18th 9 CE ^ ^{2 2} CHj 11 5 Example 3 CH " β Η 4o 56 ' 16 Io C2H ⁵ > ^N '" ^CH 2" ^CH 2 " ^{N <} i ₂ H ⁵ 11 6th game 4 CH, CH, CH, 59 14th 12th UD 3v Jl / Io 30th
_i ^CH 3 ² " ^H " ^{N CH} 3 -O 3 Example 5 ptl CH, ΛΤΤ 4o 5o 21st 7th CO ¹ ^ SN-CH CH ^- N "~ PH PH ~ N 12th or> 6th Partial example 6 ^ CH ₂ CH _2v ^ 4o 58 14th 25th 12th N-CH ₃ CH ₀ -N O Io 71 0.8 5o Comparative
example 2 not added 2h Comparison 74 1.0 50 K> example 3 NEt, 9 25th Comparative 73 0.9 »: Example 4 9

cn

*: The double bond fraction was determined by infrared spectrophotometry using the extinction coefficient determined to Morero.

It is believed that this is why the sum of Transund Vinyl content does not make up 100 #, is that the terminal double bonds are not counted and some of the double bonds are lost during cycling.

From the results of Table 1 it can be seen that in the context of the method according to the invention, the conjugated Diene units are formed with a high conversion rate and a useful product results, while a monofunctional tertiary amine, such as triethylamine and pyridine, does not cause isomerization of the polymer. It is believed that this is due to the fact that such amines do not form a complex with benzyl sodium.

Examples 7 and 8 and Comparative Examples 5 to 7

A polybutadiene with a molecular weight of 1000 was dissolved in 100 ecm of benzene, with 2o ftiMol of phenyl sodium were added to the solution in an amine according to Table 2 below. The reaction was carried out in the same way as in Example 2 carried out, the results of Table 2 showed.

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Tabel

Complexing agent lenge
iMol Properties of the polymer Drying rate of loading,
^{& J} stratification at Räumterpp.
(H) Vinyl * -An
part in % Service
value Qeb free complete
■ i &'rtunß; Art MO Tr ans "* - An
part in% 7M
56 0.8
15th 25th
6th 50
12th Comparative
example 1
Example 7 Starting polymer
HgN-CHg-CHg-NHg ι ^3o 9
10 •
57 IN THE 7th 13th Example 8 HgN-CHg-CHg-NH-CHg-CHg-NH Mon Io 7M 1.5 2M 5o Comparative
example 5 NEt gH Mon 9 75 1.0 "25 50 Comparative
example 6 HgN- (CH) ₆ -NHg Mon Io 75 o.9 25th 50 Comparative
example 7 HpN-O-NH ₉
Cm % '·' W Io

Table 2 shows that when using an inventive Diamine compound the isomerization process extremely is effective. No isomerization activity is obtained even when using a primary or secondary amine, if it is a monoamine. Furthermore, in the case of a diamine without complexing property, such as hexamethylene diamine or p-phenylenediamine, the isomerization does not progress.

Example 9

800 g of butadiene copolymer with a molecular weight of 1350, a 1,2 double bond portion of 89JS, a Trans double bond content of 11% and a styrene content from Io Mol? were dissolved in 2200 parts of benzene, 200 mmol of benzyl sodium and 900 mmol of ethylenediamine were added to the solution. The mixture was stirred in a stream of nitrogen at 70 ° C. for eight hours Brought reaction and the resulting reaction liquid washed with water until in the washing liquid no more alkali metal was detected. The benzene was made from the reaction product by distillation removed and an isomerized butadiene copolymer was obtained.

The copolymer thus obtained had a molecular weight of 1370, a Gardner color number of 5, and a Dieh value of Was a mass of 100 parts by weight of the copolymer thus obtained and 1 part by weight of cobalt naphthenate (in the form a 6iigen solution) applied in a thickness of 30m and dried at room temperature, the tack-free state was achieved in four hours and the perfect one It took eight hours to cure.

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Example Io

100 g of cis-polybutadiene with a molecular weight of 1750, a proportion of cis double bonds of 75? » a trans double bond fraction of 19? and a 1,2-double bond content of 6? were dissolved in 100 cc of toluene to obtain 20 mmol of benzyl sodium and HO mmol tetramethylethylenediamine were added to the solution .. The mixture was reacted at a temperature of 7o ° C in a nitrogen stream over three hours to the reaction. Methanol was added to the reaction mixture to deactivate the catalyst, then the reaction mixture was mixed with 20 g of active clay and stirred vigorously. The mixture was then filtered off and the solvent and the remaining tetramethylethylenediamine were distilled off.

The resulting polymer had a molecular weight of 1800 and the diene value of the polymer was 32. As a result the infrared absorption spectrum analysis showed that the polymer had a cis double bond content of 53? » a trans double bond fraction of 12? and a vinyl double bond portion from 7? exhibited.

From the results of this example it is immediately apparent that the 1, ^ - double bond according to the invention Process is isomerized.

Examples 11 to 13 and Comparative Examples 8 to 11

100 g polybutadiene with a molecular weight of 750, a 1,2 double bond content of 85? and a trans-double. 15? were dissolved in 200 ecm of benzene, 40 mmol of tetramethylethylenediamine and 20 mmol

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- 2ο -

an organic alkali metal compound as specified in Table 3 was added to the solution. The mixture was reacted at 50 ° C. for five hours. Results analysis of the resulting polymer are shown in Table 3, as are the results for Comparative examples without the addition of tetramethylethylenediamine.

Table 3

Organic rAlkali
Metal connection Tetramethyl
ethylenediamine Service
value Comparative Example 8 (Starting polymer) - oil Comparative
example 9 Butyl lithium not added
adds 1.5 Example 11 dito added 15th Comparative
Example 10 Amyl sodium not added
joined 0.8 Example 12 dito added IH Comparative
example 11 Phenyl potassium not added
adds 1.0 Example 13 dito added 18th

The results of Table 3 as well as the results of the preceding examples show that the inventive Process with regard to the isomerization of non-conjugated Double bonds in conjugated double bonds

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Butadiene polymer works extremely effectively, example lfr

In a stainless steel autoclave with a capacity of 2 liters, 1000 ecm of benzene as a solvent, 50 ecm of tuluene as a chain transfer agent and 100 mmol of benzene / sodium were added, followed by 500 ecm of butadiene. The reaction was carried out at a temperature of 30 ^° C. over a period of 2.5 hours in such a way that almost all of the butadiene reacted. After the completion of the reaction, part of the reaction liquid, namely 100 cc, was taken out. 200 mmol of tetramethylethylenediamine were then added to the remaining reaction liquid. The reaction liquid thus obtained was subjected to isomerization reaction at 70 ° C. for eight hours. After the catalyst had been inactivated by adding 60 ecm of methanol to the reaction liquid, it was treated with 100 g of active clay and filtered to remove the sodium compounds. The resulting filtrate was vacuum distilled to evaporate the solvent and residual amine to give a pale colored polymer devoid of sodium. The amount of the polymer obtained was 300 g.

The polymer had a molecular weight of 1000, a diene value of 19, a 1,2 double bond content of 55% and a trans-ljli double bond content of 12 #. A mass consisting of 100.Teilen of the polymer and 1 part of cobalt naphthenate (? In the form of a 6 solution) was added to check in a thickness of 3Ou ¹ ^ applied to the drying rate at room temperature "The result was as indicated below:. Berührhärtung 4.5 hours

full hardness 9 hours.

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For comparison, the reaction liquid which had been taken out before the addition of the diamine was treated ± n in the same way, only without the diamine. The pale colored polymer produced in this way had a molecular weight of 950, a 1,2 double bond content of ! &%> A trans 1,4 double bond content of 12? and a diene value of 0.2. A dope composed of one part of cobalt naphthenate (in an oily solution) and 100 parts of the polymer was prepared for checking the drying speed of the coating film at ordinary temperature. The drying rate of a 3Ou thick coating film was as follows:

Touch hardening 25 hours, full hardness 50 hours.

From the above result, it is clearly seen that a low one formed by the polymerization of butadiene Butadiene polymer through the interaction of the polymerization catalyst and the amine compounds due to the addition of the Amine compounds into an isomerized low butadiene polymer is converted, and that the reactivity of the isomerized Polymer is significantly increased by the isomerization.

Examples 15-21 and Comparative Examples 12-16

In the same manner as in Example 14, the polymerization reaction was carried out performed using 100 mmol of benzyl sodium, followed by the various amine compounds, on an isomerization reaction

C was carried out for three hours. The results

are summarized in Table 4.

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Table 4

Numbers of the examples and comparative examples

Amine compound

Structure formula

Amount (mmol)

Property of the polymer

Trans * share in*

Vinyl ** share in *

Dien value

Dry speed

of the Eeschichtunfs film

when cleared

Bertihrhärtunp (h)

full hardness (h)

15 16

17 18

19 20 21

CH

C ₂ HC ₂ H ₅

CH, '

N-CH ₂ -CH ₂ -N

CH

CH

₀ 2

CH

CH

H ₂ N-CH ₂ -CH ₂ -NH ₂

H ₂ N-CH ₂ -CH ₂ -NH-CH ₂ -CH ₂ -Nh ₂

₂ -CH ₂

CH ₂ -CH ₂

₂ -CH ₂

12th

50

53

-58 '

56

52

59

60

Continued on page

21st

18th

16

20th

12th

11

4 7

■ 12

10

8 13

O «D CD- j PO

00 cn

12 * NEt ₃ 400 0 12th 74 0.5 25th 50 13t NEt ₂ H 400 11 74 0.6 25th 50 14 ⁺ H ₂ NC-CH ₂ -Mm ₂ 400 13th 75 1.0 24 48 15 ⁺ . O- 400 13th 74 0.7 24 "49 16 ⁺ 12th 75 0.2 25th 30th

Double bond fraction was determined by infrared spectrophotometri'e Use of the extinction coefficient according to Morero determined ι

JS-

N> U)

J> N) OO

00

cn

Example 22

¹ 100 cc of tetrahydrofuran was placed in a stainless steel autoclave having a passability of 2 liters, and 2 g of o-terphenyl was dissolved therein. After purifying the inside of the system with nitrogen gas, a mixture solution containing an o-terphenyl sodium complex was prepared by adding a dispersion containing 23 g of metallic sodium having an average particle diameter of 8μ in the form of a 50% concentration of metallic sodium using Containing kerosene as a dispersion medium. The mixture solution was cooled to -70 ° C., whereupon 1000 ecm of liquid butadiene was added to it over a period of four hours at a constant temperature with stirring. After adding the predetermined amount of butadiene, the polymerization reaction mixture solution was warmed to room temperature to remove the unreacted butadiene. Part of the reaction solution, namely 100 ecm, was removed at this temperature. 116 g of tetramethylethylenediamine were added to the remaining solution and the resulting solution was heated to 70 ° and kept at this temperature for a period of five hours. To inactivate the catalyst, 50 ecm of methanol were added to the heated solution, after which it was treated with 100 g of active clay to remove the sodium compounds. The pale colored polymer was obtained after the methanol, the tetrahydrofuran and the amine compounds had been distilled off in vacuo. The polymer had a molecular weight of 1,800, a diene value of 18, a 1,2 double bond fraction of 55 pounds, and a trans 1,4 double bond fraction of 10μ.

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On the other hand, the reaction solution sampled before the addition of the amine compound was used treated in the same way as described above. The polymer thus obtained had a molecular weight of 1900, a diene value of 0.4, a 1,2 double bond fraction of 902 and a trans 1,4 double bond fraction from £ 10.

Example 23

After the inside of the system was completely purged with nitrogen gas, 1500 ecm of tuluene was placed in a 2 liter stainless steel autoclave. A dispersion consisting of 2.3 g of metallic sodium with an average particle diameter of 9.5 µm in a sodium concentration of 20? Using Tuluol as a dispersion medium, and 4.4 g of dioxane was added. After 180 ecm of butadiene had been fed in at a temperature of 80 ° C. and over a period of one hour, a further 700 ecm of butadiene were fed in at a constant rate over a period of 90 hours. After adding the predetermined amount of butadiene, the reaction solution was allowed to stand for ten minutes, and then the unreacted butadiene was removed from the system. 100 ecm of the reaction solution were taken as a sample, and 46.4 g of tetramethylethylenediamine were added to the remaining solution to bring about an isomerization reaction. After carrying out the isomerization reaction at a temperature of 80 ⁰ C over a period of five hours it was added to inactivate the catalyst, 60 cc of methanol, and separated the sodium compounds with 100 g of activated clay. The filtrate thus obtained

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was used to distill off tuluene, methanol, dioxane and tetramethylethylenediamine by vacuum distillation subject. The resulting polymer was pale and viscous.

The polymer had a molecular weight of 1500, one Diene value of 21, a 1,2 double bond fraction of and a trans 1,4 double bond fraction of 8jf.

For comparison, the reaction solution sampled before the addition of the diamine compound became the same Procedure as stated above. The resulting polymer had a molecular weight of 1500, a diene value of 0.3, a 1,2 double bond share of 78% and a trans double bond share of 13 *.

Example 2fr

The inside of the system with a 2 liter stainless steel autoclave was completely purged with nitrogen gas, whereupon 985 ecm of tuluene, 13 ecm of tetrahydrofuran, 135 ecm of styrene, 900 ecm of butadiene and 10 ecm of a butyllithium solution were added to the autoclave. The mixture solution thus formed was taken three hours at 70 ⁰ C for reaction. After taking 100 ecm of the reaction mixture solution as a sample, 25 g of ethylenediamine were added to the remaining solution to carry out a further isomerization reaction. The isomerization reaction was continued for an additional six hours at this temperature. After completion of the reaction were

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² JO ecm of methanol was added to inactivate the catalyst, followed by washing with water. The washing was repeated until the solution was not alkaline. Distilling off the solvent gave a butadiene-styrene copolymer with a pale color.

The low copolymer had a molecular weight of 1800, a diene value of 19, a bonded styrene content of 10) S, a 1,2 double bond content of $ k% and a trans 1,4 double bond content of 10%. A coating composition was prepared by adding 1 part of cobalt naphthenate (in a 6 strength solution) to 100 parts of the copolymer. The 30μ thick coating film had a drying speed at room temperature as follows:

Touch hardening four hours, full hardening eight hours.

In contrast, a copolymer obtained by adding the prior to adding the diamine compound withdrawn solution subjected to the same procedure as indicated above, a molecular weight of 178O, one Diene value of 0.4, a bonded styrene fraction of £ lo, a 1,2 double bond fraction of $ 78, a Trans-l, J | -double bond portion of 10 ?.

A second dope was prepared by mixing; 100 parts of the latter copolymer and 1 part of cobalt naphthenate (in 6% solution) to check the drying speed a 3Ou thick coating film at room temperature manufactured. The result was as follows:

0 9 812/0863

Touch hardening 24 hours full hardness 50 hours.

In summary can the invention say, is a low polymer of butadiene or a low copolymer of butadiene with a different butadiene-conjugated diolefin or a vinyl-substituted aromatic comonomer at a temperature between 0 and 200 ⁰ C in the presence of a combination catalyst performed which an organic alkali metal compound and contains a specific diamine compound, the non-conjugated double bonds are isomerized to conjugated diene double bonds with extremely high conversion, whereby a polymer with high reactivity is obtained, which can be used as a color binder, as a thermosetting material, as an adhesive, as a material in connection with rubber and is suitable as an intermediate for various synthetic reactions.

- Patent claims 4098 12/086 3

Claims (1)

Claims Process for isomerization of low polymers of butadiene and low copolymers of butadiene with at least one monomer from the group consisting of conjugated diolefins other than butadiene and vinyl-substituted aromatic compounds, characterized in that such a low polymer at a temperature between 0 and 20O ⁰ C in Presence of a catalyst consisting of (1) an organic alkali metal compound and (2) a diamine compound represented by the following general formula / N-f C 4- n [ 'ι ^R 2 ^R 6 wherein η is 2 or 3, and R ₁ ; R ₂ , R 1, R ₂₁ , R _5, and Rg represent hydrogen or an organic radical having 1 to 20 carbon atoms and two optional elements of R ₁ , Rg, R, and R ₂ ^ are joined together to form a cyclic structure can, is made to react. 2. The method according to claim 1, characterized in that the low butadiene polymer is liquid or semi-solid at room temperature and has a molecular weight between 300 and 10,000. 409812/0883 3. The method according to claim 1, characterized in that the low butadiene copolymer is a low one Copolymer of butadiene with a comonomer from the Group consisting of isoprene, 2,3-dimethylbutadiene, Piperylene, styrene, α-methyl! Styrene, vinyltulol and Divinylbenzene, where the comonomer fraction is 50 mol? does not exceed. ¹ I. The method according to claim 1, characterized in that the reaction is carried out in a solvent of aliphatic or aromatic hydrocarbons. 5. The method according to claim 1, characterized in that the organic alkali metal compound (1) is a Compound of the general formula R-Me, where Me is an alkali metal selected from the group consisting of lithium, sodium and potassium, and R is one Alkyl, alkenyl, cycloalkyl, aryl or aralkyl group with 1-20 carbon atoms is. 6. The method according to claim 1, characterized in that that the organic alkali metal compound (1) is a complex of naphthalene or anthracene with sodium or potassium. 7. The method according to claim 1, characterized in that the diamine compound; a di- · ..in from the group, consisting of ÄtHyiehöiämin, tetramethylethylenediamine, Tetraethylethylenediamine, propylenediamine, dimethylpropylenediamine and tetramethylpropylenediamine. 40 98 12/0863 ORIGINAL BATHROOM 8. The method according to claim 1, characterized in that the diamine compound is a Polyäthylenpoly ^ amine of the general formula Nf CH ₀ -CH ₀ -N ^dd 'm ^RI 3 where m is an integer greater than or equal to 2, and R ^, R ' ₂ , R' and R '^ for a hydrogen atom or a hydrocarbon radical with 1 - 2o carbon atoms is. 9. The method according to claim 8, characterized in that the polyethylene polyamine is an element selected from the group consisting from diethylenetriamine, pentamethyldiäthylenetriamine and hexamethyltriethylenetetraamine is. 10 10. The method according to claim 1, characterized in that the diamine compound (2) is a cyclical diamine from the Group consisting of piperidine and triethylenediamine is. 11. The method according to claim 1, characterized in that the organic alkali metal! Compound in an amount between 1 mmole and 1 mole per 100 g of butadiene polymer is used. 12. The method according to claim 11, characterized in that the organic alkali metal compound in an amount between 10 and 100 mmoles per 100 g of butadiene polymer is used. 40981 2/0863 ' .13. Method according to claim 1, characterized in that that the diamine compound (2) in an amount between 0.1 and 100 Moläuqivalenten, based on the organic Alkali metal compound (1) is used. 1 ^. Method according to claim 13, characterized in that that the diamine compound (2) in an amount between 0.5 and 10 molar equivalents based on the organic alkali metal compound (1) is used. 15 · Process for isomerization of lower butadiene polymers and butadiene copolymers, characterized in that a low polymerization of butadiene or a low copolymerization of butadiene with a monomer from the group consisting of conjugated diolefins other than butadiene and vinyl-substituted ones aromatic compounds, with a compound selected from the group consisting of organic alkali metal compounds and alkali metals, is carried out as a catalyst, and that a diamine compound of the general formula Xn is 2 or 3, and R ₁ , R ₂ , R ,, R _1. , R ₁ - and Rg represent a hydrogen atom or an organic radical having 1-20 carbon atoms, where any two of the elements R ₁ , R ₂ , R ,, and R ₁₁ can be linked to form a cyclic structure) added to the polymerization and copolymerization reaction mixture in the presence or absence of butadiene and any other monomers and thus at a temperature between ⁰ ° C. and 200 ° C. for isomerization of non-conjugated double bonds of the lower butadiene polymers or copolymers 4098 12/0 8 63 is made to react. 16. The method according to claim 15, characterized in that the monomer consists of an element selected from the group from isoprene, 2,3-dimethylbutadiene, piperylene, styrene, ά-methylstyrene, vinyltulol and divenylbenzene. 17. The method according to claim 15, characterized in that the diamine compound is an element from the group consisting of. Ethylenediamine, propylenediamine, tetramethylethylenediamine, Tetraethylethylenediamine, dimethylpropylenediamine, tetramethylpropylenediamine and polyethylene polyamine the general formula —Ί- CH ₂ -CH ₂ -N - ^ - R ¹ ], R » ₂ where m is an integer greater than or equal to 2 and R ', R'o » ^R ' ^ ^unc * R'ji stand for a hydrogen atom or a hydrocarbon radical. l§.R method according to claim 17, characterized in that that the polyethylene polyamine is an element of the Group consisting of diethylenetriamine, pentamethyldiäthylenetriamine and hexamethyltriethylenetetramine. 19 · The method according to claim 15, characterized in that that the diamine compound is a cyclic diamine from the group consisting of piperidine and triethylenediamine, is. August 24, 1973/955 409812/0 86 3