DE1165863B - Process for the production of polybutadiene - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Boarding school Class: C08d

Number:
File number:
Registration date:
Display day:

German class: 39 c - 25/05

F 36497 IVd / 39 c
April 7, 1962
March 19, 1964

The invention relates to a process for the production of polymers of butadiesn with the aid of organometallic catalysts with the formation of rubber-like polymers.

Numerous processes for the polymerization of 1,3-butadiene with the aid of organometallic catalysts are already known in the literature. Depending on the catalyst used, the polymers obtained differ in their steric structure, ie in the type of linkage of the monomer units. Are obtained with Lithium catalysts butadiene polymers, trans- 1,4-monomer units whose about ⁰ to 50 J in 1,4-cis, 40% in, and are linked to lO ° / o in the 1,2-position. Butadiene polymers with over 90% cis-1,4 linkages are obtained with titanium tetraiodide-containing mixed catalysts and with cobalt-containing mixed catalysts. Regardless of the great differences in the steric structure, the technological behavior of these polymers is in part very similar. All butadiene polymers described so far show a low film strength as a raw material. As a result of the low inherent tackiness of the raw materials, the polymers tend to form crumbs on rolling within wide temperature ranges, so that the mixtures produced from them have a poor filler distribution or the preparation of the mixture causes great difficulties under technical conditions.

Due to the processing difficulties mentioned, it is not possible to use mixtures based on Manufacture polybutadiene on an industrial scale. The types of polybutadiene described so far are only in a blend with natural rubber or styrene-butadiene copolymers as well as synthetic cis-1,4-polyisoprene processable, thereby the properties characteristic of polybutadiene become Part again worsened. An increase in the cis-1,4 content The processing technology appears to be over 95% through the use of cobalt-containing mixed catalysts Deficiency of such polymers can only be remedied to a small extent.

It has now been found that polybutadienes which can be processed on their own can be obtained without cutting Products with good technological properties can be processed using catalysts used by reacting a) a titanium compound of the general formula

Ti (OR) "X ₄ - _w

obtained with b) iodine monochloride or iodine monobromide and / or iodine and c) an alkyl aluminum compound have been. The proportions of the above processes for the preparation of polybutadiene

Applicant:

Paint factories Bayer Aktiengesellschaft,

Leverkusen

Named as inventor:

Dr. Nikolaus Schön,

Dr. Gottfried Pampus, Leverkusen,

Dr. Josef Witte, Cologne-Stammheim

Components are to be chosen so that for 1 mole of titanium compound 0.5 to 10 moles of iodine monohalide or iodine and 1 to 20 moles of alkylaluminum compound can be used.

In the above general formula, η - 1, 2, 3 or 4, X = chlorine or bromine, OR = an anion of an aliphatic branched or unbranched, saturated or unsaturated or a cycloaliphatic or aromatic carboxylic acid with 1 to 20 carbon atoms, such as acetic acid Propionic acid, lauric acid, stearic acid, oleic acid, chloroacetic acid, diethyl acetic acid, benzoic acid, salicylic acid, naphthoic acid, an anion of a vinyl carboxylic acid with 1 to 20 carbon atoms, such as the enolate ions of ß-ketocarboxylic acid esters or / S-diketones, for example acetoacetate, benzoyl acetic ester , Benzoylacetone, as well as anions of aromatic oxaldehydes, such as 2-hydroxy-benzaldehyde, which can also be addressed as vinylogous carboxylic acids.

Instead of two OR radicals, the dianion of a dicarboxylic acid can also be used, e.g. B. adipic acid.

Titanium compounds particularly suitable for the process according to the invention are:

CH ₃

¹ VCH ₃ - C - CH = CO - / Ji;

CH ₈

VCH ₃ -C-CH = CO- / sTiCl;
(O CH ₃ \

VCH ₃ - C - CH = CO - Z ₈ TiCl ₂ ;

409 539/592

/ O CH ₃

VCH ₃ - C - CH = CO - / TiCl ₃ ;
(CH ₃ CH ₂ COO) ₃ TiCl;

(CH ₃ COO) ₂ TiCl ₂ ;
/ CH ₃

Ti 1 - O - C = CH - COOC ₂ HsZ _{2 Cl 2} ;
(η-C ₁₁ H ₂₃ COO) ₂ TiCl ₂ ;
(11-C _n H ₂₃ COO) TiCl ₃ ;
(η-C ₁₁ H ₂₃ COO) ₃ TiCl;

(C ₆ H ₅ COO) ₂ TiCl ₂ ;
(C ₈ H ₁₇ CH = CH (CH ₂ ) ₇ COO) ₂ TiCl ₂ :
(C ₈ H ₁₇ CH = CH (CH ₂ ) ₇ COO) TiCl ₃ ;
(C ₈ H ₁₇ CH = CH (CH ₂ ) ₇ COO) ₃ TiCl;

TiCl;

(C ₂ H ₅ ) ₂ CHCOO _{2 TiCl 2} ;
(η - C ₁₁ H ₃₃ COO) ₂ TiBr ₂ .

As iodine monohalide components come for the representation of the mixed catalyst to be used according to the invention on the one hand iodine monochloride and iodine monobromide or mixtures of these iodine monohalides. Instead of these iodine monohalides or iodine can be used in a mixture with them.

Alkylaluminum compounds are understood to mean compounds of the general formula A1R'R "R", in the R'R "R" aliphatic or cycloaliphatic hydrocarbon radicals having 1 to 12 carbon atoms mean, and in which R 'and R "can also be hydrogen.

It is thus possible to use aluminum trialkyls as well as mono- or dialkylaluminum hydrides. Alkylaluminum compounds with alkyl radicals containing 2 to 4 carbon atoms are preferred into consideration.

As alkyl aluminum compounds suitable for the preparation of the catalyst combinations to be used according to the invention are for example:

Al (C ₂ Hg) ₃ , Al (iso-C ₄ H ₉ ) ₃ , Al (nC ₃ H ₇ ) ₃ , Al (iso-C ₈ H ₁₇ ) ₃ , Al (nC ₁₂ H ₂₃ ) ₃ , Al ( iso-C ₄ H ₉ ) H ", AlH (iso-C ₄ H ₉ ) ₂ .

Particularly suitable catalysts for the present process are obtained when 1 mol Titanium compound of the formula

Ti (OR) "Cl ₄ -"

1 to 8 mol of iodine monohalide or iodine and 3 to 15 mol of alkylaluminum compound are used, with it is advantageous to use the alkyl aluminum - ■ iodine monohalide or iodine ratio should not be lower than 2: 1 to 3: 1.

A reduction in the ratio of alkyl aluminum compound to iodine monohalide or iodine in the preparation of the catalyst causes the butadiene polymers obtained with these catalysts have lower film strengths and are less easy to process. The properties of the polymers then approach those of the previously known polybutadiene types, but show in contrast to this one markedly diminished cold river.

The butadiene polymers produced according to the invention show in the raw state in contrast to previously known polybutadienes behave similarly to natural rubber. You have one at the hitherto known types of polybutadiene do not have a high inherent tack and in the raw state have a film strength similar to that of natural rubber. The process polymers according to the invention very well; they show a over a wide temperature range excellent rolled skin formation, while the previously known polybutadiene types have a poor or only have good fur formation at temperatures below 40 to 50 ° C.

The high film strength is also evident in the unvulcanized ones made from the raw material Mixtures. Show mixtures produced from the polymers according to the invention excellent filler absorption in all technically occurring temperature ranges, Distribution of fillers and high level of tack. The excellent properties of the after Polybutadienes produced in the present process come into their own in particular because this polybutadiene does not have to be blended with other elastomers.

The monomeric butadiene used should not be more than 0.01% 1,2-butadiene and not more than 0.01% Contains 0.015% acetylenes.

It is known that small amounts of water are used in polymerization with titanium-containing mixed catalysts advantageous. Larger amounts of such substances that react with the catalyst and make it ineffective make, such as water, oxygen, carbon dioxide as well as 1,2-butadiene and acetylenes, must be used Process according to the invention can be eliminated before the polymerization or by increased addition Alkylaluminum compound are destroyed so that the composition of the catalysts according to the invention remains unchanged.

As a solvent for the preparation of the catalysts and for carrying out the polymerization come aliphatic and cycloaliphatic hydrocarbons, as well as aromatic hydrocarbons or mixtures thereof, e.g. B. butane, hexane, octane, petroleum ether, ligroin, Cyclohexane, methylcyclohexane, benzene, toluene or xylene. The following apply to the solvents used same purity conditions as for the monomeric butadiene.

The catalysts are prepared in aliphatic and / or aromatic solvents, as they come into consideration for carrying out the polymerization, with the exclusion of air and Moisture by mixing the alkyl aluminum compound with the halogen compound or the halogen

5 6

or the halogen mixture reacts and then the acids and bases are achieved. The

Titanium compound adds or by adding the amount of titanium of these substances so that still

compound with the alkylaluminum compound no precipitation of the polymer occurs and the

sets and then the halogen compound or the precipitation only through subsequent addition of a larger one Halogen or the halogen mixture adds. After 5 amount of a lower aliphatic alcohol like

In a preferred mode of operation, however, methanol, ethanol, isopropanol, etc. is first effected,

the titanium compound with the halogen compound or furthermore, in the course of the work-up, stabilizers

the halogen or with the halogen mixture converters and antioxidants, such as phenyl - /? - naphthyl-

set and then the alkylaluminum compound amine, N, N'-diphenyl-p-phenylenediamine, di-tert-

manure added. At -5 to 50 ⁰ C one obtains the io-butyl-p-cresol, di-tert-butyl-hydroquinone, tris- (nonyl-

Catalyst in the form of a black-brown colored phenyl) phosphite, furthermore substances with a buffering effect,

Solution or suspension. such as calcium stearate, can be added.

In the representation of the catalysts, it is also not necessary to use the pure titanium compound niche mineral oils and phenolaldehyde resins, but also titanium tetrachloride 15 alkyd resins and low molecular weight Butadienpolybzw. Titanium tetrabromide and the OR in the merisate are added in the course of the work-up. Formula The parts Ti (OR) X - ^s ' ^nc * parts by weight given in the following examples.

corresponding carboxylic acid or the vinylogous carbon 2 ° B e i s ρ i e 1 1 acid in the intended for catalyst preparation

Solvents are implemented. Since an elimination in a stirred vessel was in 1000 parts of toluene, The small amounts produced during the reaction, which had been purified by distillation, caused difficulties under AusShydrochloric acid, there is a type of catalyst with this exclusion of air and moisture the catalyst preparation a slightly higher 25 solution by adding 0.57 parts Consumption of alkyl aluminum compound.

When using aromatic solvents

it proves to be advantageous to use the catalysts at / CH ₃ C CH = CO - \ TiCl

To produce temperatures of -5 to 20 ° C. So I I! )

Catalysts prepared possess a high poly 3 ° \ O _CH3 J ₃ merisationsgeschwindigkeit. Brief heating of the
prepared catalyst solutions to 30 to 50 ° C

increase the activity of the catalysts. 2.5 parts of iodine monochloride and 3.3 parts of aluminum

Paraffin oil or hydrogenated diesel oil as well as triisobutyl in the order mentioned at 0 ° C

higher-boiling aromatic hydrocarbons are produced. It had become a black-brown solution

turn out to be appropriate solvents for the formed; 125 parts of butadiene were incorporated into this

Alkyl aluminum compounds because it is conductive when used. The polymerization started immediately when the

such solvent reaction increased the alkyl viscosity of the solution. The temperature

aluminum compounds with air and moisture were kept at 5 to 10 ° C. After 6 hours

is largely prevented. 4 ° the polymerization was started by adding 2 parts

The polymerization can take place at temperatures in the range of a phenolic stabilizer and 2 parts of abietin

Range from -40 to + 80 ° C. acid, dissolved in a little methanol, stopped. That

A temperature range from 0 to 50 ° C. is preferred. The polymer was then replaced by increased methanol

The polymerization can be precipitated with normal, reduced additives and with methanol, which is 5%

or increased pressure. Furthermore, 45 phenolic stabilizer contained, kneaded. To

the polymerization in the presence of an inert- subsequent drying at 50 ° C in a vacuum

gases such as nitrogen, helium or argon, or 120 parts of polybutadiene with good film strength

possibly under the autogenous pressure of the steam and get stickiness. The polymer showed

each solvent used are carried out. a roller at 100 ° C very good rolled head

The catalysts are in such a concentration 5 ° education.

tions used that to 1 mole of butadiene 0.05 to The structure showed the following additions in the IR spectrum

15 millimoles, preferably 0.1 to 5Millimol, titanium composition: cis-1,4 69.4 ° / _0; trans-1.4: 18.0;

connection are available. 1.2: 12.6. The intrinsic viscosity was 2.2.

With the catalysts to be used according to the invention, the butadiene polymerization can be carried out in both examples 2 to 15 operated discontinuously and continuously

will. Particularly suitable for discontinuous under the same conditions as in Example 1

The working method is stirred autoclaves, some of which were working using another

Allow in the absence of air and moisture. Titanium acetylacetone compounds a number of others

The continuous polymerization process can carry out 60 polymerizations (Table I). The cata-

In a screw, the further polymerization vessels were lysers in 1000 parts of toluene at

can be connected upstream, also produced at a suitable temperature between 0 and 10 ° C. In

Pipe system to be carried out. Examples 2, 3 and 10 was used as a titanium compound

The work-up of the polymers, the deactivation bond
The removal and possible removal of the catalyst can 65

z. B. by treatment with alcohols, water, acetone / ^CH s - C - CH = C - O - \ Ti

or mixtures of these substances, optionally I II I

organic addition and / or inorganic \ O CH _3/4

η in Examples 4, 5, 6, 11 and 15

/ CH ₃ - C - CH = C - O - \ TiCl

\ O CH _3/3

in Examples 7, 12, 13 and 14

/ CH, -C -CH = C-O- \ TiCL and in Examples 8 and 9

/ CH ₃ - C - CH = CO- \ TiCl ₃

CH _S

CH, used. The polymerization times were generally 4 to 8 hours when the polymerization was carried out at 5 to 10 ° C. The polymers had very good film strengths and ίο also showed satisfactory stickiness. The rolling behavior at 80 to 100 ° C, natural rubber was similar.

Table I.

example Ti compound
Teüe JCl
Parts AKi-C ₄ H ₈ ) S.
Teüe Butadiene
Dear yield η ice cream structure 1.2 % 71.7 trans 20th 2 0.66 2.42 3.0 130 70 2.2 75.5 8.3 - 2 0.34 0.32 1.58 120 86 3.0 72.9 12.6 4th 0.28 0.33 1.60 100 100 2.8 84.6 14.5 10.9 5 0.28 0.33 2.20 100 100 3.2 .— 4.5 - 6th 0.55 0.32 2.3 100 71 3.4 83.0 -. 10.5 7th 0.32 0.65 2.1 100 100 2.9 83.9 6.5 10.3 8th 0.19 0.35 1.61 100 90 2.2 77.6 5.8 19.1 9 0.19 0.35 1.9 100 98 2.4 3.3 iodine Dear 81.9 10.9 10 0.7 1.9 3.1 100 100 3.1 78.3 7.2 - · 11 0.38 1.0 2.3 120 100 2.7 A1 (C _S H ₅ ) ₃ Dear 83.5 12th 0.32 0.51 1.1 150 85 2.7 - - - 13th 0.32 0.51 0.9 140 100 2.7 - ■ JBr Al (iC _ä H ₈ ) ₃ Dear Dear 76.7 14.5 14th 0.24 0.41 1.65 100 80 3.2 80.0 8.8 18.0 15th 0.27 0.40 1.73 100 90 2.8 2.0

Examples ₂ , 1 part of aluminum triisobutyi and 0.33 part of iodine

As in B e i s ρ i e 1 5, a catalyst solution was prepared in monochloride in the order mentioned.

950 parts of toluene were prepared, but the addition of 45 100 parts of butadiene provided 68 parts of polybutadiene

0.32 parts iodine monochloride, 2.2 parts aluminum tri-good film strength and tack. cis-1,4-content:

isobutyl and 0.28 parts 76%. ?? - value: 3.5.

/ CH ₃ -C-CH = CO-XTiCl Example 18

CH.

in that order. 100 parts of butadiene were passed into the black-brown catalyst solution. The polymerization temperature was 10 to 15 ° C. After 10 hours, the polymerization was stopped stopped by adding 2 parts of abietic acid. After precipitation with methanol and drying in In vacuo, 48.5 parts of polybutadiene with good film strength were obtained. cis-1,4-content: 76.5% j? value: 3.4.

Example 17

As in Example 16, a catalyst solution was made by adding 0.28 parts

With one out of 0.24 parts

/ CH ₃ -C -CH = CO

\ O CH ₃

TiCL

/ CH, -C -CH = C-O-

TiCl

CH ₃ 0.73 part of iodine monochloride and 1.62 parts of aluminum triisobutyl catalyst solution prepared analogously to Example 1, 100 parts of butadiene were polymerized. The polybutadiene obtained in a yield of 80% showed poor film strength. Intrinsic viscosity: 2.8. Structure: 88.3% cis, 4.1% trans, 7.6% 1.2.

Example 19

The advantages of the polybutadiene according to the invention over the known polybutadienes are on best from a comparison of the raw material properties and the vulcanizate properties of running

to see surface mixtures. According to Examples 1 and 12, two polymer samples were produced (Part I and Part II). Type I is a _{polybutadiene produced with TiJ 4} : A1R ₃ catalysts, while Type II is obtained with lithium butyl. Type II was not produced as a mixture for reasons of poor processability.

a) Raw material properties

plasticity
(Mooney ML 4 ',
100 ° C)

Rolling behavior
at 20 ° C ...

at 8O ⁰ C ...
at 100 ° C ...
at 12O ⁰ C ...

Lot I. II Tj I. 35 45 42 smooth fur smooth fur smooth fur Crumbs smooth fur Crumbs smooth fur Crumbs

II

31

Crumbs

Crumbs Crumbs Crumbs

b) Production of a tread compound

Mix recipe parts

Polybutadiene 100

Stearic acid 1.5

Zinc oxide 5

Highly abrasion-resistant furnace black 48

35

Plasticizers (aromatic mineral oil) ... 10

Tackifier (rosin) 5

Anti-fatigue agents

(p-phenylenediamine derivative) 0.75

Anti-aging agents

(Phenyl-tt-naphthylamine) 0.75

Paraffin 0.6

Sulfur 1.8

Vulcanization accelerator

(N-mercaptobenzothiazole sulfenamide) .. 0.9

Game I. Game II very good Polybutadiene
Type I. Roller temp temperature, ⁰ C, 60 to 70 20 to 25 Mixing behavior .. very good mixture Well crumbles, Soot pick-up difficult Filler distribution Well moderate Ready-made stickiness 2 to 3 (1 = very small rest, 5 = not smooth sticky) 2 Appearance of the Fells smooth dull, uneven

Continuation of the table

IO

Game I. Game II Polybutadiene
Type I. Vulcanization speed (optical vulcanization at 40 atm [= 151 ° C] Volcanic meter Measurement), Minutes 20th 20th 30th

c) Properties of the vulcanizates:

Game I. Game II Polybutadiene
Type I. Tensile strength,
kg / cm ² 145 152 130 Strain, % 630 640 540 Hardness (Shore) ... 56 57 58 Rebound
elasticity 48 48 49 Notch toughness
(kg abs. 4 mm) 22nd 24 18th Dynamic
Warming ... 53 54 55 Goodrich Flexo
meter, ° C to
25 minutes
Abrasion
resistance
DIN, mm ³ 13th 15th 36

55

6o example 20 to 29

In Examples 20 to 29, a number of further titanium compounds, in particular those with carboxylic acids, were used to prepare the catalysts according to the invention. The preparation was carried out according to the procedure of Example 1 at temperatures from 0 to 10 ⁰ C. In the case of polymerization of 5 to 15 ° C were the polymerization times an average of 3 to 8 hours. Polymers with considerable film strength and good tack were obtained. The polymers showed no cold flow on storage, and at 80 ^° C. on a roller they also had good skin and bulge formation. Table II shows the catalyst compositions and the physical properties of the butadiene polymers obtained.

Example 30

In a stirred vessel with the exclusion of air and moisture, 0.19 part of titanium tetrachloride and 0.2 part of acetylacetone were dissolved in 900 parts of toluene. The reddish solution was stirred for 10 minutes. Then 1.0 part of iodine and 1.4 parts of aluminum triethyl were added at a temperature of 20 ^{° C.} 130 parts of butadiene were passed into the black-brown catalyst solution. The polymerization was terminated after 5 hours. In a yield of 95%, a polybutadiene obtained with good film strength, which could be rolling good at 9O ⁰ C. Structure: 81.3% cis content. π value: 2.7.

409 539/592

Table II

example

Titanium compound

TeUe JCl
Parts

AKi-C ₄ H,),
Parts

Butadiene
Dear

yield
Parts

structure

eis j trans I 1,2

(CH ₃ COO) ₂ TiCl ₂
On-C ₁₁ H ₂₃ COO) ₂ TiCl ₂
(C ₆ H ₅ COO) ₂ TiCl ₂
(C ₈ H ₁₇ CH = CH (OHQ ₇ COO) ₃ TiCl 'CH _3x O

Ti

^N -CHO ^
, - Ο— ι

C = CH-C ^

Cl ₂

OC ₂ H

₂ H _5/2

^TiCl2

h ¹

((C ₂ H ₅ ) ₂ CHCOO) ₂ TiCl ₂
(CH ₃ CH ₂ COO) ₃ TiCl

(C ₈ H ₁₇ CH = CH (CHj) ₇ COO) ₈ TiCl ₁

0.24 0.39 0.25 0.93

0.28

0.4

0.47

0.35 0.22

0.51

2.1
1.7
2.1
2.0

2.1
2.4
2.6

AI (C ₃ Hb) ₃
Dear

1.2
0.9

AKi-C ₄ H ₉ ),
Parts

2.0

100
110
100
100

100
100
100

100
120

120

100
80
45
86

100

100
100

3.0 2.8 2.8 3.0

2.0

2.3

2.4

2.9 2.7

2.8

78.5 8.5 j 13.5 82.0 - I - 75.0 j -

79.6 7.4

82.3 j 6.6

89.0 2.8 8.2

87.5 i 3.5

84.6 79.0

84.2 3.8 12.0

Example 31

0.6 part of (^ C ₁₁ H ₂₃ COO) ₂ TiBr ₂ , 0.6 part of iodine and 1.95 part of aluminum triisobutyl were added to 900 parts of toluene at 20 ° C. with stirring in the order given. At 15 to 18 ^° C., 120 parts of butadiene were polymerized in 6 hours. There were obtained 110 parts of polymer, had good film strength and good rolled sheet formation at 90 ⁰ C. η value: 2.4. Structure: 75.6% cis, 9.3% trans, 15.1% 1.2.

5o example 32

a) In a stirred autoclave, a catalyst solution was prepared in 1000 parts of toluene at 15 ° C. by adding 1.2 parts of aluminum triisobutyl, 0.32 parts of titanium (IV) trichloro-mono-oleate and 0.47 parts of iodine. In the catalyst solution, 100 parts of butadiene were introduced .. In a polymerization temperature of 40 to 50 ⁰ C the yield after 5 to 6 hours 100% · After the usual On ararbeitung a polymer was obtained, which had good rolling at 100 ° C and next good film strength had the following properties: i? value: 3.4; Mooney plasticity (ML 4 '100 ^° C.): 40; Content of cis-1,4 linkages: 76%

b) Using 0.48 parts of iodine monochloride in place .of iodine, a catalyst was obtained comprising 100 parts of butadiene at 50 ⁰ C in 6 hours and polymerised completely to a polymer having the following properties: Film strength and rolled sheet formation at 8O ⁰ C good. jy value: 2.6; Mooney Plastitität (ML4 '100 ⁰ C): 33; Structure: 70.9% cis, 16.5% trans, 12.6% 1.2.

Claims (1)

Claim: Process for the preparation of polymers of butadiene by polymerizing butadiene in the presence of iodine-containing mixed catalysts, characterized in that one such mixed catalysts are used, which are produced by reacting (1) alkylaluminum compounds, (2) iodine monochloride or iodine monobromide and / or iodine and (3) titanium compounds of the formula Ti (OR) "V" have been obtained, in which formula: n- 1, 2, 3 or 4, X is chlorine or bromine, OR is the anion of an aliphatic, cycloaliphatic, aromatic or vinylogous carboxylic acid containing 1 to 20 carbon atoms, with 0.5 per mole of titanium compound up to 10 moles of iodine monohalide or iodine and 1 to 20 moles of alkylaluminum compound were used. Documents considered: German Auslegeschrift No. 1 113 311.