DE1645152C3 - Vulcanizable liquid butadiene polymers - Google Patents

Description

in an amount of 0.8-6.5 moles per 100 moles of the monomeric butadiene- (1,3) has been prepared, the compound

Br ₃ C- (CH ₂ -CH = CH-CH ₂ ) ₂ riöBr

either in situ by using the for production this compound required amounts of carbon tetrabromide and additional butadiene (1,3) or via a separate process by heating a mixture of butadiene- (1,3), carbon tetrabromide and an oil-soluble free radical forming compound or in an aqueous emulsion of 1,3-butadiene and carbon tetrabromide means Potassium persulfate has been obtained as an initiator

to

Terminal active polymers have so far been produced by various processes such as (a) by condensation of monomers containing active end groups, with the formation of oc / u-difunctional polymeric molecules, (b) anionic polymerization of r> unsaturated monomers with organic alkali initiators, such as . B. organolithium compounds with the formation of polymers that contain terminal alkali metal atoms and subsequent replacement of the alkali metal by reactive groups, and (c) -in degradation of a previously built polymer under conditions in which the ends of the polymer fragments at the chain breakpoints provided with chemically reactive groups will. These products and processes have been used with varying degrees of success as the basis for the production of sealants, caulking agents, and binders for rocket propellants, but other and simpler products and processes have been sought to obtain products with better properties and to reduce those used previously Process characteristic high cost.

In the past, liquid polymers were produced by polymerizing conjugated diolefins in a solvent, using an oil-soluble γ, chen catalyst and a modifying agent such as diisopropylxanthogen disulfide or carbon tetrachloride. This process is described in US Pat. No. 2,586,594.

It is also known from US _{Pat. No. 2,463,225 to produce b} o polymers with increased plasticity and improved processability in the presence of a polyiodine compound such as CHJi, CJ4 or RCb.

The liquid polymers obtained by this known process or polymers with increased (, <, However, plasticity does not show any terminal reactivity necessary for curing liquid polymers in one rubber-like condition is important.

The invention relates to vulcanizable liquid butadiene polymers having terminal allyl bromide * and having an intrinsic viscosity of 0.05 to 0.6 dl / g as measured in toluene at 30 ⁰ C, prepared by polymerization of butadiene (l ^) in aqueous Emulsion using a catalyst which forms free radicals and a compound of the formula

BnC- (CH ₂ -CH = CH -CH ₂ ) ^ Br,

in an amount of 0.8 to 6.5 moles per 100 moles of the monomeric butadiene (1,3), has been prepared, being the connection

Br ₃ C- (CH ₂ -CH = CH-CH ₂ ) ₂ riöBr

either in situ by using the amounts of carbon tetrabromide required to produce this compound and additional butadiene (1,3) or via a separate procedure by means of formatting a mixture of butadiene- (1,3), carbon tetrabromide and an oil-soluble, free radical-forming one Compound or in an aqueous emulsion of butadiene (1,3) and carbon tetrabromide by means of potassium persulfate has been obtained as an initiator

If anionic emulsifiers are used in the polymerization reaction, it may be desirable to add a buffer compound to reduce the Keep the pH of the system in the alkaline range. It can also take a small amount of one off as needed 12 to 16 carbon atoms built up mercaptans be present. Examples of suitable conventional ones Polymerization initiators are cumene hydroperoxide, diisopropylbenzene hydroperoxide, azobisisobutyrolnitrile, potassium persulphate and sodium persulphate. in which the compounds mentioned are used is variable within a wide range, which is approximately at 0.1 to 5.0 percent by weight based on the monomers

The polymerization reaction can generally be carried out at temperatures from about 5 up to about 80 ° C or higher be performed. When using redox catalysts to initiate the polymerization usually a temperature of about 5 to 45 ° C, preferably from about 5 to 20 ° C, maintained.

When the polymerization is to be initiated by thermal decomposition of initiators such as potassium persulfate, temperatures in the range of 45 to 8O ⁰ C are particularly favorable, is preferably carried out in a temperature range of 50 to 70 ⁰ C. Surprisingly, it has also been found that when using redox systems at 5 to 45 ° C. practically no polymerization is achieved before the ratio of 13 to 2/1 for water / monomer usually used in aqueous emulsion polymerizations to about 3 to 4/1 or is increased more.

The properties of the subsequently vulcanized products, such as tensile strength and sol-gel behavior of the vulcanizates, improve continuously with increasing conversion during the polymerization of the monomer. The best properties appear to be obtained at 100% conversion. Further, it has been found that, by heating a material having a low conversion, an increase in the strength properties of the vulcanized product can be achieved if the heating is carried out after the removal of the unreacted monomer. Temperatures of about 45 to 6O ⁰ Cscheinen

be suitable when m Nacherwftrmen. A compound of the formula

B ^ C- (CH ₂ -CH = CH-CH ₂ ) JRaBr

For example, erbalten when a mixture of 100 Gewientsteilen butadiene (LSS), 40 parts of carbon tetrabromide and 0.5 parts benzoyl peroxide is heated for 1 hour at 6O ⁰ C. The unpurified product can be used as it is for the polymerization of the liquid polymers, but it can also be used prior to addition to the polymerization system by stripping off the unreacted butadiene (1,3) and extracting with acetone or alcohol or by. Removal of unreacted tetrabromomethane can be cleaned by steam distillation.

Another method is that the monomer system to be polymerized, the butadiene (1,3), tetrabromomethane and the oil- or water-soluble, free radical-forming compound and other x desired substances, such as buffer compounds and an activator for the Formation of the free radicals contains, simply emulsified in water and the emulsion is then stirred, the formation of the compound taking place in situ before and during the polymerization reaction to form the liquid polymer

After the polymerization reaction has ended, the vulcanizable liquid butadiene polymers are obtained by coagulation from the latex in which they arise. The usual method for obtaining solid rubber-like polymers from their latexes consists in first distilling off the unreacted monomer from the latex under vacuum, whereupon the polymer is prepared by mixing the J5 latex with an aqueous solution, an ionizable salt and / or a Acid is coagulated and the coagulated polymer is filtered off, washed with water and dried. This process is not very satisfactory in the production of the butadiene polymer according to the invention, since the monofunctional molecules with a low molecular weight, which are also formed, are not removed when it is carried out. These molecules interfere with the subsequent vulcanization process to which the liquid polymers are subjected. According to the invention, therefore, the procedure is in such a way that, before drying, the coagulated liquid polymer is washed with acetone or an alcohol with a low molecular weight, such as ethanol, the monofunctional, the vulcanization interfering with low molecular weight fractions are removed due to their solubility, while the difunctional liquid polymer having higher molecular weight due to its insolubility remains another, but slightly for costly v> geres purifying methods is the polymer one or more times with acetone or alcohol from a solution in a solvent such as benzene or toluene to precipitate.

The liquid butadiene polymers according to the invention Sates with terminal allyl bromide groups can be linked with multifunctional compounds that are allyl-like bound Bformatömen can react, easily cold vulcanized to form solid rubbery products, d. H. at temperatures of 15 tn up to 35 ° C. With multifunctional amines, which are preferred vulcanizing agents, the Vulcanization takes place within a very short time, for example during a period of a few minutes. The vulcanization time can also be a few hours or days, depending on the activity of the amine and the polymer, the temperature maintained and the amount of amine used. The amount of amine used is normally in the range from about 0.5 to 35 percent by weight, based on 100 parts of the polymer, and preferably about 1 to 10 percent by weight. Aliphatic, cycloaliphatic and aromatic amines with primary, secondary or tertiary amino groups could cause the vulcanization of the cause liquid polymers to solid rubber-like vulcanizates. Amines containing only one nitrogen atom are useful when the nitrogen atom is bonded to one or more hydrogen atoms. In general, amines containing two or more nitrogen atoms are preferred. Suitable amines are e.g. B. hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylene pentamine and N-aminoethylpiperazine and their partially or fully alkylated derivatives, such as methyl or ethyl derivatives. The multifunctional amines are preferably liquid aliphatic polyamines which have a low vapor pressure and develop little odor and, moreover, are easy to handle. For liquid polymers with low molecular weight, amines with four or more functional groups are particularly useful as vulcanizing agents, since they can bind a certain amount of the monofunctional polymer chains which interfere with vulcanization and yet still allow the chain extension of the bifunctional polymer, which leads to the development of good physical properties, such as Tensile strength and elongation, leads Of course, mixtures of amines with different numbers of functional groups can also be used in order to obtain the desired properties in the final vulcanizates. A rubber with a tensile strength of more than 7 kg / cm ² and even 14 to 28 kg / cm ² and. about it can be obtained. If fillers and other known mixing additives are carefully mixed with the liquid polymer before vulcanization, vulcanizates with a tensile strength of 35 to 70 kg / cm ² or higher can be obtained.

Suitable fillers are carbon blacks, finely divided metals, Metal oxides, silicas, silicates, carbonates and clays. Particularly good results are achieved with high-abrasion furnace blacks with a low structure. Other mixing additives, such as plasticizers, waxes, drying oils, solid or liquid rubbery and resinous Polymers, asphalt-like and bituminous materials, chlorinated polyphenyl resins, antioxidants, antiozonants, ultraviolet absorbers and Color pigments can also be used.

You can add 5 to 20 parts by weight to the polymeric mixtures Give additives thixotropic properties. Such additives are polyethylene, and polypropylene Suitable for transpolyisoprene. For example, adding about 10 parts of polyethylene makes 100 Parts by weight of a polymer that has an intrinsic viscosity of about 0.4 is effective in eliminating cold flow, and the mixture still retains their softness and ease of processing. These substances can be used directly or as a liquid polymer Solution or mixed with a solvent that is mixed with the liquid polymer is compatible, such as. 3. a suitable oil.

In the following examples are, if not different indicated, all parts listed as parts by weight,

example 1

100 parts of butadiene ^ j β), 10 parts of tetrabromomethane, 160 parts of water, 5 parts of sodium dodecylbenzene sulfonate, 3 parts of tripotassium phosphate and 0.5 part of potassium persulfate were introduced into a reaction vessel and ^{stirred at 60 °} C. for 1 hour a saturated aqueous barium chloride solution, then filtered to remove the water and extracted with acetone and methanol, the desired product being isolated as an oil. Analysis of this product indicated that it was a 44 weight percent bromine compound which had the structure Br3C- (polymerized butadiene t3 radical) ii-Br with an average of 7.3 for π .

When 20 parts of this compound were stirred together with 100 parts of butadiene (1,3), 5 parts of sodium dodecylbenzene sulfonate, 3 parts of tripotassium phosphate and 3 parts of potassium persulfate in a polymerization vessel at 60 ^° C. for 19 hours, all butadiene was An easily pourable, viscous, liquid polymer with terminal, allyl-like bound bromine in the molecular structure could be isolated from the latex when mixed with a small amount of a polyfunctional amine and left to stand overnight at room temperature the polymer was vulcanized into an elastic product with good strength properties

Example 2

When the procedure of Example 1 was repeated, but using 40 parts of tetrabromomethane in the preparation of the oily intermediate, this product contained 693 weight percent bromine and π had an average value of 2.3. When this intermediate product was used in the polymerization of butadiene-ο (13) as described in Example 1, a more easily pourable, amine-vulcanizable, liquid polymer could be obtained. The polymer had an intrinsic viscosity of 0.13 dl / g and a bromine content of 7.7 percent by weight. When 100 g samples of the polymer were mixed with 3.5 and 7 parts of Ν, Ν, Ν ', Ν'-tetramethylhexamethylenediamine, it was found that all samples had vulcanized to dry, elastic masses after one hour at room temperature. When the 100 g samples of the polymer that was so liquid were mixed with 3.5 or 7 parts of tetraethylene pentaryine and left to stand at room temperature overnight, all samples were elastic products with a tensile strength of 10, 2, 12 and 14, respectively. 8 kg / cm * vulcanized.

Example 3

80 parts of butadiene (LSS), 10 parts of carbon tetrabromide, and 1.0 part of benzoyl peroxide were eingebfacht in a leak-tight container and stirred for 24 hours at 6O ⁰ C. After one hour of degassing and vacuum treatment, an oily product was obtained. 20 parts of this oily product together with 100 parts of butadiene (1,3), 180 parts of water, 5 parts of sodium dodecylbenzene sulfonate, 5 parts of tripotassium phosphate and 1.0 part of potassium persulfate were placed in a polymerization vessel, and the polymerization was started at 60 ° C carried out within 21 hours. The analysis d? S The latex obtained showed that 70% of the butadiene (U) was converted to the liquid polymer. The latex was made by freezing for coagulation and the recovered liquid polymers by washing with acetone, dissolving in benzene and precipitating cleaned with acetone and then vacuum dried at ⁵⁰ C 1.25 parts methylene-bis (2-methyl-4-nonyI phenol) were added as an antioxidant before vacuum drying. The bound bromine content of the liquid polymer was 2.74%, and the intrinsic viscosity in toluene at 30 ° C. was 0.49 dl / g.

When mixing 1, 2, 3, 4 and 5 parts of a difunctional amine, namely the complete Methylation of hexamethylenediamine obtained Ν, Ν, Ν ', Ν'-tetramethylhexamethylenediamine to 100 Parts of the liquid polymer hardened the polymer mixtures within 2 hours at room temperature to form tough, dry, elastic masses.

The intrinsic viscosity of the individual samples in toluene was 0.82, 0.76, 0.67, 0.74 and 0.70 dl / g and the Percent solubility in toluene was 98, 98, 98, 97 and 97. The increase in intrinsic viscosity shows that Celtic elongation has occurred and therefore active bromine atoms are present in the liquid polymers. The development of rubber-like properties after vulcanization together with the observed behavior in terms of solubility and intrinsic viscosity is essentially characteristic of the difunctional character of liquid polymers.

When samples of the liquid polymer with the polyfunctional tetraethylene-peutamine in quantities of 1, 2, 3 and 4 parts of amine to 100 parts of the polymer were mixed, the samples were at Vulcanized to solid, dry, elastic masses at room temperature

The solubility in toluene for the samples mentioned was 16, 9, 11 and 16, which indicates a chain extension and a high degree of crosslinking. The tensile strength was 11, 12, 7, 11.6 and 6.7 kg / cm ² and the percentage elongation at break 220, 210, 320 'and 130, with which the favorable properties of the vulcanized polymers are proven.

Lead game 4

100 parts of butadiene lf1,3) were emulsified in 180 parts water containing 5 parts of sodium dodecylbenzenesulfonate as an emulsifying agent, 5 parts Trikafiumphosphat as a buffer, and 10 parts carbon tetrabromide containing After the temperature was increased in the reaction system at 60 ⁰ C, 0 6 parts of ralium sulfate were added. The system was stirred at this temperature for 65 hours, after which time 95% of the butadiene (l _r 3) had been converted to the polymer. This wound was isolated from the latex by coagulation with methanol, then by dissolving in benzene and precipitating with acetone cleaned and then dried in a vacuum at 70 ° C. 1.25 parts of methylene-bis (2'fic> nyl-4-methylphenol) were added as an antioxidant before the vacuum drying. The dried polymer formed a water clear, viscous liquid with eitier Intrinsicviskosiiät of 0.41 dl / g, measured in toluene at 3O ⁰ C, and the content of bound bromine was 23 weight percent.

When adding 2.0 parts of the difunctional methylated hexamethylenediamine to 100 parts of the liquid polymer, this became a solid, dry, elastic mass vulcanized. The product

but was completely soluble in benzene, and the determination of the intrinsic viscosity showed a considerable Increase in molecular weight.

When the liquid polymer was mixed with 3.0 parts of the multifunctional tetraethylene pentamine for 100 parts by weight of the polymer, the liquid polymer set to a solid, dry, resilient mass at room temperature, but this time the product was 91% insoluble in benzene and had one Tensile strength of 9.5 kg / cm ² .

Example 5

100 parts of butadiene (1.3) and 10 parts of tetrabromomethane were emulsified in 160 parts of water which contained 5 parts of sodium dodecylbenzene sulfonate as an emulsifier and 5 parts of tripotassium phosphate as a buffer. After the temperature in the polymerization vessel was raised to 60 ° C., 0.6 part of potassium persulfate was added and the emulsion was stirred at this temperature for 21 hours. Then 28% of the butadiene (1,3) is converted into the polymer, which was obtained in the form of an aqueous latex. Unreacted 1,3-butadiene was removed from the latex, which was then diluted with an additional 60 parts of water and divided into two parts. One part was ^{heated to 60 °} C. for a further 17 hours, while the second part was not heated any further. Both approaches of the latex were then taken by freezing for coagulation, and the separated polymer was purified by dissolving in benzene and precipitating with acetone, followed by C ^c in vacuo at 50 dried. Before drying, 1.25 parts of methylene-bis (2-nonyl-4-methyl-phenol) had been added as an antioxidant to both samples of the polymer. Both samples were obtained as viscous, pourable liquids of similar appearance and viscosity. The bromine content of both samples was determined and one part of each sample was mixed with 3 parts of completely methylated hexamethylenediamine and subjected to vulcanization at room temperature. The tensile strength, elongation and modulus of the vulcanized samples were measured.

Table I.

Bromine content [weight percent]
¹ 'tensile strength [kg / cm-]
Elongation at break [%]
Module at 100% [kg / cm- ']

warmed up not warmed up ent] 4.70 2.66 26.7 8.1 700 515 9.1 6.0

The results ζ £! ^σ

the hot flexibility properties obtained when reheating liquid polymers with low conversion.

Example 6

A number of polymerizations were carried out in which 100 parts of butadiene (U) were emulsified in 180 parts of water which contained 5 parts of sodium dodecylbenzene sulfonate and 3 parts of tripotassium phosphate in solution. The polymerization was carried out within 17 hours at 6O ⁰ C in the presence of 3 parts of potassium persulfate, and various amounts of carbon tetrabromide. The results are given in Table II.

Table II Tetra
bromine
methane
[Parts] Intrinsic
viscosity
[dl / g] bromine
salary
[% By weight] Remarks Comparison test or
Attempt no. 2.5
8.0
10.0
15.0 1.3
0.51
0.37
0.26 1.9
3.3
3.9 solid polymer
vulcanizable liquid
the same
the same Comparative experiment A
1
2
3

The results show that with increasing amounts of tetrabromomethane, the intrinsic viscosity and the molecular weight of the polymers decreased and the bromine content increased. They also show that 2.5 parts of tetrabromomethane are insufficient to form a liquid polymer. The polymers obtained in Experiments 1 to 3 were converted into tough, elastic products by mixing them with small amounts of methylated hexamethylene diamine and allowing them to stand for a few hours at room temperature

Example 7

A number of polymerizations of butadiene- (1,3) have been made with varying proportions of components and carried out under different polymerization conditions. The results are in Table III reproduced.

All polymers were liquid and vulcanizable with polyfunctional amines. Table IV gives some of the results obtained with tetraethylene pentamine as the vulcanizing agent.

Tabel III water Emulsifier buffer initiator CBm Reak React Intrinsic bromine Ver lot lot Kind and system Kind and as well as possibly tion time functional viscosity salary search to Bu lot lot lot other temp. No. tadien
(U) ^ 1153 tZC [Hours] PC] [dl / g] [% By weight] 100 180 (a) K3PO4 K2S2O8 65 60 0.40 Z7 1 5 4th 0.20 10 100 180 0>) K3PO4 K2S2O8 65 60 031 2.17 2 5 4th 0.40 10

DIP lot 9 water Kinulsifier sobutvronitri 1 buffer 6 45 1 52 Renk 10 Inlrinsic Hioin n-DDM to Bu lot Kind and System ions / .eil viscosity lulled ABIN tadien lot lot Rciik- (I.J) initiator CBr. [S.d.] ttons- [dl / g] [(ic ».-» / continuation 100 180 (a) K1PO4 Ail and as well as possibly 17th tcmp. 0.24 5.54 Ver 5 3 lot other rci search 100 180 (a) K.3PO4 25th 60 - 2.01 No. 5 3 K2S2O8 3.0 20th 50 3 100 160 (a) K3PO4 K2S2OS 10 47 0.32 7.2 5 3 1.0 n-DDM 4th 100 360 (a) K.3PO4 0.2 65 60 0.50 1.5 10 3 DIP 1.0 10 13th 5 100 360 (a) K3PO4 DIP 76 0.13 7.7 5 7 "; 1.0 10 6th 100 160 (a) K3PO4 (C) 21 60 _ 5 3 K2S2O8 = Diisopropylbenzene hydroperoxy IIS 40 60 7th = n-dodecyl mercaptan ABIN = Azobisi 2.0 10 8th

Sodium Dodecylbenzenesulfonate Potassium Stearate

activated with NajPOi - 0.48 parts; FeSOi. 7 H2O Ethylenediamine tetra sodium acetate - 0.15 part

- 0.12 part: sodium formaldehyde sulfoxylate - 0.48 part:

Tabel IV Vulkani
station
duration Tear
strength strain sample Vulkani
sations
middle [kg / cm '] [%] [Parts] over night
the same
the same
the same
the same 10.2
11.6
8.8
7.7
10.2 240
215
820
760
160 1
3
5
6th
7th 2
4th
2
2
3

Example 8

A liquid homopolymer was prepared as described in Example 4, but here it was 15 parts Tetrabromomethane used. The polymer had a viscosity of 335 poise, an intrinsic viscosity of 0.29 dl / g and a bromine content of 3.45 percent by weight

Table V

Samples of the polymer were mixed up with various fillers and taken at room temperature Vulcanization brought. All mixtures were sufficiently cured to be tack-free after 1 hour to be. After 7 days, the tensile strength and elongation of all samples were determined. The results are given in Table V.

Sample No. 1 2

Polymer
soot

SRF

LS-HAF

HAF
kaolin

Powdered aluminum
Vulcanizing agent (1)

100

100

100 40

100

30th

100

25th

100

100

100

60

8th
0.25

Il

continuation

Sample no. 2 i 4th 5 I. 3
32.9
1130 2.5
40.8
960 2.5
65.8
750 2.5
71.8
810 14.4
710 structure - fine Ί soot
- semi-reinforcing furnace soot
- Highly abrasion furnace soot lower
- High abrasion furnace soot Vulcanizing agent (2)
Tensile strength (kg / cm ² )
Strain(%) FT -
SRF -
LS-HAF -
HAF -

NNN'.N'-tetramethylhexamethyleneduimine
NNN ', N ", N'", N '"- hexamethyl-triethyl-tetramine 2.5

60.0

630

2.5

45.4

1000

22.1
1085

Example 9

100 parts of butadiene (U) and 10 parts of tetrabromomethane were emulsified in 160 parts of water, the 5 parts Sodium dodecylbenzenesulfonate as an emulsifier and 5 parts of TnkäliUiVipnüSpnäi as Püffci 'dissolved

After the temperature in the polymerization vessel had increased to 60 ^° C., 0.6 part of potassium persulfate was added and the polymerization reaction was started. It was possible to achieve more than 95% conversion of the monomer into the liquid polymer, which was obtained in the form of an aqueous latex. The polymer isolated therefrom had a viscosity of 4600 poise at 25 ° C., an intrinsic viscosity of 0.38 dl / g and a bromine content of 3.72 percent by weight. Samples of the separated polymer were mixed up with various materials and vulcanized. The vulcanizates were tested as shown in Table VI.

In the case of the sample 1, a paraffin oil was used as the hydrocarbon, and the polyethylene, which is acted to a product having low density and a melt index of 25, was dissolved at 150 ⁰ C in the paraffin oil. This was added to the polymer along with the filler and the mixture repeatedly passed through a 3-roll paint mill until thorough mixing was achieved. Toluene and vulcanizing amine (N, N, N ', N'-tetramethylhexamethylenediamate) were added as a solution. The compositions obtained before vulcanization were soft, thixotropic, easily extensible mixtures suitable for use as sealants or caulking agents.

Example 10

A liquid homopolymer was prepared as in Example 9, but in this case it was 200 parts Water used. The polymer had an intrinsic

ciUilicli. viscosity vüi'i 0.24 üi / 'g uiiu a Biumgcnäii VOm j, 7

Weight percent.

Mixtures with a minor amount of a vulcanizing agent and a major amount of one difunctional chain extending agents were added to the polymer. There were two mixes manufactured. Mixture 1 consisted of 0.5 parts of 2,4,6-tri (dimethylaminomethyl) phenol, 2.0 parts of 1,3-di-4-pyridylpropane and 100 parts of the liquid polymer. Mixture 2 corresponded to mixture 1, but instead of the 2,4,6-tri (dimethylaminomethyl) phenol, was N, N, N ', N ", N"', N "'- Hexamethyltriethylenetetramine used as a vulcanizing agent. The one used for vulcanization and substances used for chain extension were added as 50% solutions in toluene to achieve better dispersion in the polymer.

The "usage time", that is, the time that a mixture needs to become something that can no longer be processed The state of thickening was determined for all samples measured with a vulcanization time of 7 days at 25 ° C.

The properties of the mix and the vuü> inisate are shown in Table VII.

Table VII

Table VI sample No. 511 3 20.4 7 days ₆₅ 1 2 100 ₅₅ 900 16.2 100 100 8.4 790 Polymer 40 - 40 95 Hydrocarbon oil - 40 10 Chlorinated polyphenyl (liquid) 10 10 - Polyethylene 40 - - 60 soot - 20th 10 Titanium dioxide - - 10 Aluminum powder 10 10 23 toluene 23 23 Room temperature Amine 7 days 7 days Vulcanization temperature 28 Vulcanization time 630 Tensile strength (kg / cm ² ) 9.8 Strain (%) Module at 100% (kg / cm ² )

characteristic Mixture I. Mixture 2 Usage time (hours) 3 1 Tensile strength (kg / cm ² ) 19.3 26.4 Strain(%) 680 730 Module at 100% elongation 6.7 6.7 (kg / cm ² ) Modulus at 300% elongation 10.9 103 (kg / cm ² )

The results show that these mixtures, and especially Mixture 1, are suitable for use as sealants would be useful in the construction industry, since there a usage time of at least one Hour is required This can be achieved by using a mixture as in this example, that is, a lesser amount of a polyfunctional vulcanizing agent and a greater amount of one contains difunctional chain extender A usage time of 10 to 15 minutes that achieves

will if the vulcanization system is only on one Larger amount of a polyfunctional vulcanizing agent would not be acceptable for this particular use.

Vulcanization of liquid polybutadiene
with various amines

A liquid polybutadiene was used in an emulsion polymerization system prepared according to the procedure of Example 9 and then with various

Amines vulcanized. The liquid polymer has a viscosity of 615 poise at 25 ° C., an intrinsic viscosity of 0.26 dl / g and a bromine content of 3.35 percent by weight. 5 parts basic lead carbonate and 3 Parts of any of the amine compounds listed below were added to each 100 parts of the given above liquid polymer. D'e mixes were examined for service life. The properties of the vulcanizate were measured after the mixture had been subjected to the vulcanization conditions described below.

Table VIII

Λπιίη niclhvlierlcs 1,3- Di- 2,4, b-tri- Äthvlen- Diethvlen- 4-pipericlyl- (dimethyl- cluimin triathlete propiin aminomethyl
phenol i0 'vim. 4 Siu. 6 rviin. wcui'aüCnSuaüüi ' ^ * r f. -i 10 min. 10 min. 21 hours Vulcanization conditions 30 min. at 122 ^° C at 122 ° C at 66 ° C at 122 ° C 42.2 17.6 25.3 Tensile strength (kg / cm ² ) 10.5 1100 440 810 Strain(%) 260 9.8 7th 6.3 100% module (kg / cm?) 7th 14.1 12th 9.14 300% module (kg / cm *) -

The results show that the liquid polymer has a longer useful life. if it is with primary or secondary amines is mixed than when mixed with tertiary amines. The vulcanizate properties show that the liquid polymer is satisfactory with primary, secondary and tertiary amines can be vulcanized.

In further experiments, proportions of 100 parts of the liquid polymer were in each case with 5 parts basic lead carbonate and varying amounts of the heterocyclic amines listed below mixed.

After vulcanization, the vulcanizates were examined for permanent elongation and resistance to aging. The test for permanent elongation consisted of heating a sample to 100 ^° C., stretching to 100% elongation, cooling to 25 ° C., relaxing and measuring the length after one minute. "Permanent elongation" is the percentage increase in the length of the sample after this The resistance to aging was determined by measuring the solubility of the vulcanizate in toluene at room temperature before and after heating to 150 ^° C. under nitrogen for three hours.

Table IX

Amine Piperazine Triethylene methylated Hexa diamine Diethylene methylene triamine tetramine 2.0 1.5 2.25 Quantity (parts) 4.6 20 min. 40 min. 20 min. Vulcanization time (min.) 5 min. at 122 C. 10.5 22.5 57 Tensile strength (kg / cm ² ) 16.2 890 400 1170 Strain (%) 320 2.11 12th 9.14 100% module (kg / cm ² ) 7th 3.52 19.7 14.1 300% module (kg / cm *) 14.8 1Z5 373 56.2 Deformation (%) 9.4 41.4 283 12 ^ Solubility Before Heating (%) 10.5 15.6 18.8 223 Solubility after heating (%) 10.2

The results show that heterocyclic secondary and tertiary amines are one of the liquid polymer less permanent deformation and a higher resistance to aging than tertiary amines.

Claims (1)

Claim; A vulcanizable flössige butadiene polymers having terminal Ally Ibromidgruppen and a [ntrinsicviskosität of 0.05 to 0.6 dl / g as measured in toluene at 30 ⁰ C, the forming by polymerization of butadiene (13) in an aqueous emulsion using a free radical Catalyst and a compound of the formula Br ₃ C- (CH ₂ -CH = CH - 10