DE1645152A1 - Process for the production of terminally active, liquid polymers - Google Patents

Description

Priority: Canada No. 937,644 of August 9, 1965 and Canada Mr. 957,645 dated August 9, 1965

! The invention relates to a process for preparing ve endstHndig-active, liquid diolefin iPülymerer of "see hydrocarbon monomers.:

In this specification, "liquid" polymers pII fremein are defined as polymers whose Intriiisio-vialcosität m toluene ⁰ C is at 3O about 0.04 to 1.0, and "Yulkrni π η te" are di e / Re ^ ktioiisproclukte the liquid polymers mxb compounds, white or, more sparks-ionelle Gru open oiled ζ s and diesel.?-molecules of f.lü- £ 3Rigen Pol ^ Moron mifceinf'nder connect can.

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BATH ORIGINAL

Polymers which are permanently active have hitherto been used, according to yerschier · -, _r ,, _; ., _{: for} which processes such as (a) by condensation ■ of monomers containing active end groups, with the formation of · *, Δ-difunctional polymeric molecules, Cb) anionic polymerization of unsaturated monomers with organic alkali initiators such as lithium

organic compounds with the formation of. Polymers containing alkali metal atoms in the chain and subsequent replacement of the alkali metal by reactive groups, and Cc) degradation of a previously built-up polymer under conditions in which the ends of the polymer fragments are provided with chemically reactive groups at the chain breaking points. These products and processes have been used with varying Erfolg.als basis for the production of sealants Kalfatermitteln binders for solid rocket propellants, etc., but they were looking for other, simpler w products and processes in order to obtain products with better. Properties and to reduce the high cost of the previous process chi> arskteri.

The invention is characterized by one according to the method emulsion polymerization in an aqueous medium

obtained 'mixture' of a; 'Not found, oils finer-tie: - Unsaturated liquid polymers, the molecules of which polymerized

fp / -Tif <h ■ ■ '"■ γ ΛτηρπηΊ t' on - ^ the" n ", · r ^

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'-' ■ ■ '' - '. - BAPORiQINAL

Diolefinic hydrocarbons containing 4 to 8 carbon atoms, the majority of these molecules being characterized by the "presence of two separate (-C = CCX) structures in the molecular skeleton, in which. X is a halogen atom such as chlorine, bromine or iodine," and the '© mixture of from about 0.04 intrinsic viscosity liquid polymers ine - 1.0 as measured in toluene at 30 ⁰ C, having ■■ ■■ .- _..;.

The inventive polymers can with multifunctional Connections are vulcanized. Such vulcanizates are relatively inexpensive, can be obtained at room temperature and have high tensile strength. .

The mixtures of the liquid polymer can be prepared by a process which consists in forming a monomeric system of diolefinic hydrocarbons with 4 to 8 carbon atoms under the conditions of emulsion polymerization in an aqueous medium in a value of at least about 0.15 moles (per 100 moles of Monomers ") of a compound of the type Z (Y") Z used for polymerization? Cn ⁴ : in which X is Br, J or Cl, Z -CBr ₅ ,, -CJ ,,, -CCi ₇ . or } C J_ and T a Rcdiksl with a structure like

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-) or (Jg

represents where R is a hydrocarbon or substituted hydrocarbon radical of molecular weight

to is from 14 to / about 1000, and a latex of the polymer

is obtained from which the polymer is then isolated.

The consistency of the blends of the liquid polymers is at room temperature in the range from pourable liquids to highly viscous or va se 1 ine similar ₌ substances. The Intrinsicviscosität 'measured in üoluol at 3Q ⁰ O, is 0.04 to 1.0 and vorzugwsweise 0.05 to 0.6. Even if the ideal polymer mixtures are characterized by the presence of an allyl-like bonded halogen atom at or near each chain end of each polymer molecule, this ideal can be practically unattainable in production on an economic scale because not all molecules of the polymer have this structure. It has been found that excellent properties can be achieved in mixtures in which only the main part of the molecules has the structure indicated above, while the remaining molecules are monofunctional, ie only one terminal group with one

I3S / 14

like bonded halogen atom, and also include the possibility that a smaller part of the molecules on the terminal groups does not contain any halogen at all.

The presence of the allyl-like bonded halogen atoms on or near the terminal carbon atoms of the polymer chains gives the polymers considerable vulcanization activity when they come into contact with multifunctional compounds. These are compounds that contain two or more functional groups in the molecule, such as multifunctional amines, which react with the halogen atoms and can bring about a linkage of the molecules of the polymer, which leads to a conversion of the liquid polymers to elastomeric end products. The halogen content of the uncured polymer is usually in the range from 1 to 15 weight percent based on the total weight of the polymer mixture and preferably is about 1.5 to 10 weight percent.

Jen ⁿ ch the molecular weight of the polymers and raw - the Λτ'-t in which it - was mixed ouf that Mi can wrap the SM "nBefore vulcanization a -Kaltf lie KISSING" ■ / uni'.er Walked, for some Application purposes can turn out to be undesirable "."

30983S / 1404 "" '"" "

BATH

It can be eliminated by adding 5–20 parts by weight of substances that give the polymer mixtures thixotropic properties. Substances such as polyethylene, polypropylene and trans-polyisoprene have proven to be suitable for this purpose. For example, adding about 10 parts of polyethylene to 100 parts by weight of a polymer that is intrinsic-; .i _Sk os _lta t of about Ο, Λ, aas cold food wi, -kungsvoll switched off, and the mixture still retains its softness and easy processing. These substances can be added to the liquid polymer directly or as a solution or as a mixture with a solvent that is compatible with the liquid polymer, such as a suitable oil.

As stated previously, contains a part of the molecular structure of the liquid polymers overbased a polymerized W-, diene-type hydrocarbon having 4 to 8 carbon atoms. Preferably, the polymerized diene forms the bulk of the polymer, Bs can, more than one diene hydrocarbon can be used to form the diene part of the liquid polymers, and if the polymer is a copolymer of a diolefin and a monoolefin, more than one monolefinic can be used Monomer can be used to form the rii chtdienartipen part of the polymer. As a serving with 4 to 6 coal

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- - "BAD ORiGiNAL

Material atoms are conjugated dienes such as butadiene-1,3 »2-methylbiitadiene-i, 3 _T pentadiene-1,3, hexadiene-i: ^, 2,3-hexadiene-1, 3, 2-chlorobutadiene-1, 3 and 2,3-Pimethylbutadiene-1,3 ', with butadiene-1,3 being used with preference. Compounds such as styrene, acrylonitrile and methyl methacrylate can be used as raoncd-definition monomers. Among the various liquid homopolymers and copolymers which can be prepared by the process according to the invention, those are preferred which contain "mainly polymerized 1,3-butadiene. ■■■" --.-. ■■ · ■ "■. ■ f -

For the production of halogen-containing liquid polymers the polymerizable monomeric system is emulsified in water and brought to polymerization in the presence of a compound of the type X (Y) Z, in which X is Br, J or 01, Z

-OBr- ,, -GCl- ,, -CJ ^ or> CJ "and Y is a radical with a - 1> ■ yj c

Structure. Like (- | -G = 0-), (-4-G-), (- (Jj - ^ - R-) or (-0-0-R-)

Indicates where R is hydrocarbon or substituted Hydrocarbon radical with a molecular weight from 14 to about 1000. Compounds of the type X (Y) Z Although they decompose thermally with the formation of free radicals, which initiate the polymerization of the monomers can, but the polymerization is preferably initiated

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by the decomposition of free radical forming compounds the conventional kind such as oxygen per compounds, used in aqueous emulsion polymerizations.

The required amount of the compound of the type X (Y) Z depends on the type of compound used and on the viscosity which is desired in the halogen-containing liquid polymer to be produced. The amount should be at least 0.15 moles of the compound per 100 moles of each monomer. A larger amount can also be used, but in general it should not exceed about -6.5 moles per -100 moles of the monomer. As stated earlier, the nature of the compound, ie the degree of its activity, is a determining factor with regard to the amount used, since not all compounds are equally active, for example if the halogen compound X (T) Z is of the Br ₃ C- (polybutadiene-1,5 ^ radical) -Br, where the Polybutadiene-1 _V 3-radicals have a length of 2-10 butadiene units and the butadiene is polymerized via carbon atoms 1 and 4, at least 0.5 mol and preferably 0.8-> 6.5 mol should be used if the monomeric system to be polymerized consists only of 1,3-butadiene. If the compound X (Y) Z is of the type HJ ₂ C- (polybutadiene-1, J radical) -J, where -

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Radical and monomeric system both the previous one Example should be at least 0.15 moles of the compound and preferably 0.25-2 ', .0 mol is used because this "connection is more active. The compounds mentioned lead to the formation of excellent liquid polymers. The required proportion of halogen compound and polymerizable, monomeric system can easily be explained by a simple preceding Test attempt to be determined. '*

If in the polymerization reaction anionic emulsifiers are used, it may be desirable to add a buffer compound to adjust the pH of the Keep the system in the alkaline range. If required, a small amount of a CL 2 "^ g-Me rc apt ans can also be present be. Examples of suitable conventional polymerization initiators are cumene hydroperoxide,

Diisopropylbenzene hydroperoxide, azo-bis-isobutyronitrile, I.

Potassium persulfate and sodium persulfate. The amount in which the compounds mentioned are used is variable within a wide range, which is about 0.1 to 5.0 percent by weight of the monomers. The presence of the compound of type X (T) Z during polymer! Sationsreaktion int'wesentlich fo-af ¹ · the formation of the novel halogen-containing, liquid ^ polymers.

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The polymerization reaction can generally feel anyone. Any temperature from about 5 ° C to about 8O ⁰ C or performed later. The use of redox (reduction-oxidation) reactions to initiate polymerization is conducted at temperatures of about 5 - 4-5 ° C, and preferably about 5-20 ⁰ C. - ·.

9P When the polymerization of potassium persulfate to be initiated by thermal decomposition of initiators such as are temperatures in the range of 4-5 - 8O ⁰ C particularly favorable, and preferably in a temperature range of 50 - 70 ^O worked C. Surprisingly, it has also been found that when redox systems are used at 5-4-5 ° C., practically no polymerization is achieved before that in the case of aqueous emulsion polymer. ₌ Sate ions usually used ratio of 1.5-2 / 1

^ for water / monomer increased to about 3-4 / 1 or more

is. The properties of the product such as tensile strength and sol-gel behavior of the vulcanizates are made with increasing conversion in the polymerization of the monomer continuously better. The best features seem to have reached 100% conversion when 1,3-butadiene is the only monomer.

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It has also been found that, by reheating a material with low conversion, an increase in the strength properties of the vulcanized product can be achieved if the heating is carried out after the unconverted monomer has been removed. Temperatures of about 4-5 - 60 ⁰ C appear to be useful in Nächerwärmen.

The by Bg ^ eic ^ ung. The compounds described by the symbols X (Y) Z can be produced by any known methods. A very satisfactory process consists in .der. Production of a mixture of an acyclic diolefinic hydrocarbon with A to carbon atoms, preferably 1,3-butadiene, a tri or tet / tr.ahalogen-substituted methane in which the halogen is chlorine, bromine or iodine, preferably tetrabromomethane , and seek an oil oil, free radical forming compound such as benzoyl peroxide, cumene hydroperoxide or azo-bis-isobutylronitrile and heating the mixture to a temperature at which free radicals form, whereby the desired compound is obtained. For example, a suitable compound with the structure Br ₇ O- (polybutadiene-1,3-radical) -Br is obtained if a mixture of clay contains 100 parts by weight of butadiene-1,3, AO parts of tetrabromomethene and 0.5 parts of benzoyl-

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; ■■ .- ■■■■ ■■.-..- - 12 - ■. '■ - ■

peroxide Λ hour is heated to 60 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 1,3-butadiene and extracting with acetone or alcohol or by removing unreacted tetrabromomethane by steam distillation another method is to

W e-ee - that to polymer sierende monomeric system, the b-forming compound and the diolefin, carbon tetrabromide and the oil- or water-soluble, free radicals other desirable materials such as buffering compounds, and an activator for the formation of the free Hadikale ±±! contains-, simply emulsified in water and the emulsion is then stirred, the formation of the compound in situ before and during the polymerization reaction to form the liquid

^ Polymers takes place. Both methods will be excellent obtained liquid polymers.

After completion of the polymerization reaction, the halogen-containing, liquid polymer becomes by coagulation obtained from the latex in which it is obtained. The usual method for obtaining solid, chewy-chewy Polymers made from their latices is what makes the latex

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first a stripping process to remove the is subjected to unreacted monomers, whereupon the polymers by blending the latex with one aqueous solution of an ionizable salt and / or an acid are coagulated and the coagulated Polymers are finally filtered off, washed with water and dried. This procedure is common to the liquid polymers in the present lalle not very satisfactory since it is not for the removal of the monofunctional Low molecular weight molecules, which are also formed, and which in the subsequent vulcanization processes to which the liquid polymers are subjected have a disruptive effect » Therefore, the properties of the liquid polymers, which are possible per se, cannot be fully developed will. It has been found to be a very satisfactory one Product is obtained when the coagulated, liquid polymer is washed with a before drying Substance such as acetone or a low molecular weight alcohol such as ethanol, in which the monofunctional, Vulcanization-interfering fraction with the low molecular weight is soluble, but the difunctional 11e 'liquid polymer' with higher molecular weight is insoluble. Another good, but more expensive, method the cleaning consists in that the polymer one or

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■. ■ '.. ■ - 1.4 -

several precipitations with acetone or alcohol from one Solution in a solvent such as benzene or Tduol is subjected.

The liquid polymers according to the invention can easily be "cold" vulcanized with multifunctional compounds which can react with the allyl-like bonded halogen atoms to form solid, rubber-like products, that is to say at normal temperatures of 15-35 ° C · Mit multifunctional amines that form the preferred vulcanizing agents, vulcanization within a very short time of a few minutes or even within a few hours or even legends can be done, _what's the amount and type of applied by the activity of the amine and the polymer, the temperature used amine usi "abhängte the amount of the amine employed normally in the range ψ of about 0.5 - 15 weight percent to 100 (part of the polymer and preferably at about 1 -» 10 percent by weight Aliphatic ^, cycloaliphatic and aromatic amines having primary, secondary or tertiary

F / W

Amino groups can cause the 'vulcanizates' amines,

which contain only one nitrogen atom are usable, when the nitrogen atom is attached to one or more hydrogen atoms is bound, but in general are amines

P 'vulcanization of liquid polymers zn fe ^ tf-n rubber

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"preferred which contain two or more nitrogen atonies" Suitable amines are hexamethylenediamine, diethylene triamine, triethylenetetramine,! petraethyl enp ent amine, H-aminoethyl-piperazine and the like. and their partial or fully alkylated derivatives such as methyl and ethyl derivatives. The multifunctional amines are preferably aliphatic polyamines and most preferably liquid aliphatic Polyamines with low vapor pressure and little Odor that are easy to handle »For liquid horses Lower molecular weight amines with four or more functional groups as vulcanizing agents particularly useful because they contain a certain amount of the monofunctional which interferes with vulcanization Can bind polymer chains and still extend the chain of the difunctional polymer allow, leading to the development of good physical properties how tensile strength leads to elongation. Natural loan can also be mixtures of amines with different Number of functional groups used to make the desired properties in the end vulcanizates obtain. Rubber with a tensile strength of more than

2 2

than 7 kg / cm and even 14-28 kg / cm and above can be obtained. When fillers and other known. Mixing additives before the "vulcanization" s <^ carefully with mixed with the liquid polymer! can be

Vulcanizates with a tensile strength of 35 - * 70 kg / cm or

get higher.

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Suitable fillers are carbon black, finely divided metals, Metal oxides, silica, silicates, carbonates, clays etc. Particularly good results are achieved with high abrasion furnace soot low structure achieved. Other mixing additives such as plasticizers, waxes, drying oils, solid or, liquid rubber-like and resin-like polymers, asphalt-like and bitumen-like substances, chlorinated polyphenyl resins, Antioxidants, Antiozonants, Tritraviolet Absorbents, Color Pigments, etc. can also be used.

In this application, the terms "multifunctional" and "polyfunctional" used alternately and have the same meaning «

The following examples serve to provide a more detailed explanation the invention. Bi these examples are, if not otherwise indicated, all parts are parts by weight.

example 1 \

100 parts of 1,3-butadiene, 10 parts of tetrabromomethane, 160 parts Water, 5 parts of sodium dodecylbenzene sulfonate, 3rd parts Tripotassium phosphate and 0.5 part potassium persulfate were placed in a heating vessel and kept for one hour

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Stirred for 60 ⁰ O "The contents of the reaction vessel was washed with a saturated aqueous solution of barium chloride: - Analysis" Meithanol and extracted to give the desired product was isolated as an oil precipitated ^v, then the water was fil ^r -and trated with acetone to remove. This product showed that it was a compound with 44 weight percent bromine, which had the structure Br-, C ~ (polymerized butadiene-1 \ 3-Rs-dical) -Br with an average value of 7.3 for η . ■

If 20 parts of this compound together with 100 parts; 1,3-butadiene, 5 parts of sodium dodecylbenzenesulfonate, 3 parts of tripotassium phosphate -and 3 parts of potassium persulfate in a polymerization for 19 hours at 60 ⁰ G '. were stirred, all of the 1,3-butadiene had been polymerized to a latex. An easily pourable, viscous, liquid polymer with terminal , aUyI-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

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Example 2

When the process according to Example 1 was repeated, but using 40 parts of tetrabromomethane in the preparation of the oily. Initial product, this product contained 69 »9 percent by weight of bromine and η had an average value of 2.3 °. 1.3 was used as in Example 1, a more easily pourable, amine-vulcanizable, liquid polymer could be obtained. The polymer had an intrinsic viscosity of 0.13 "and a bromine content of 7> 7 percent by weight. When samples of the polymer were mixed with 3> 5 and. Parts N, N ₁ F ¹ , IJ'-tetramethylhexamethylenediamine, it was found that all Samples were vulcanized to dry, elastic masses after one hour at room temperature Tear strength of 1D ₉ 2, 12 or 14.8 kg / cm vulcanized.

Example 3

80 parts 1,3-butadiene, 10 parts tetrabromomethane and

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1 * 0 part of benzene peroxide was placed in a leak-tight container and ^{stirred at 60 0} G for 24 hours. After degassing and stripping off steam for one hour, an oily product was obtained. 20 parts of this oily product together with 100 parts of 1,3-butadiene, 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 carried out at 60 ° 0 I.

carried out within 21 hours. Analysis of the obtained latex showed that 70% of the 1,3-butadiene was converted to the liquid polymer. The Lat # x was made to coagulate by freezing out and the liquid polymer obtained was purified by washing with acetone, dissolving in benzene and precipitating with acetone and then dried in vacuo at 50 ° C. 1.25 parts methylene-bis (2-nonyl-4-methylphenol) was added as an antioxidant prior to vacuum drying. "The content of the liquid polymer bound bromine was 2.74%, and the intrinsic viscosity in toluene at 30 ⁰ C was 0.49.

When adding 1, 2, 3 »4 and 5 parts of a difunctional amine, namely the H, Ii, K" ¹ , ΪΓ'-tetramethylhexamethylenediamine obtained by complete methylation of hexamethylenediamine to 100 parts of the liquid

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I64 & f52 ■

Polymers hardened the polymer mixtures within: ^ "To toughen, dry, for two hours at room temperature, elastic masses. '".:; .- ■■ -.

The intrinsic viscosity of each ebb in toluene

the/

was 0.82, 0.76, 0.67, 0.74 and 0.70 and / percent; entuale in toluene / ■ '... ■■■ * ■ -.' ■

Solubility / was 98, 98, 98, 97 and 97, the increase; g the intrinsic viscosity shows that a chain extension has occurred and therefore active bromine atoms are present in the liquid polymers. The development of rubbery Properties after vulcanization together with the observed properties in terms of solubility and the intrinsic viscosity is characteristic of the im essential difunctional character of the liquid Polymers.

When samples of the liquid polymer were mixed with -the polyfunctional tetraethylene-pentamine in amounts of 1 ^ 2, 3 and M- parts of amine per 100 parts of the polymer, the samples were vulcanized to solid dry, elastic masses at room temperature.

The solubility in toluene was for the samples mentioned at 16, 9 * 11 and 16, what a chain extension and indicates a high degree of crosslinking. Die-Zerreissfestig-

was 11, 12 _V 7th, 11.6 and 6.7 kg / cm ² and the. ^ 'percentage elongation at break 220, 210, 320 and 130, which proves the favorable properties of the vulcanized polymers. ''. "'

Example 4

100 parts of 1,3-butadiene were emulsified in 180 parts of water, the 5 parts of sodium dodecylbenzene sulfonate as λ

Emulsifier, '5 parts of tripotassium phosphate as a buffer and 10 parts of tetrabromomethane contained. After "was increased, the temperature in the reaction system at 60 ⁰ O, 0.6 parts were EaIiumpersulfat. Added. The system was stirred for 65 hours at this temperature, after which time 95% warsn of 1,3-butadiene is converted into the polymer. this was isolated by coagulation with methanol from the latex, then purified dirch dissolving in benzene and precipitating with acetone and then at ⁰ C 7Q: in

Vacuum dried. 1.25 parts methylene-bis (2-nonyl ~ 4- '

-m'ethyl-phenol) were added as an antioxidant before vacuum drying. The dried polymer formed a wasserklere, viscous liquid with "a. Intrinsic viscosity of 0.4-1, as measured in toluene at 50 ⁰ G, and the content of bromine bound was 2.5 per cent by weight". ·

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'■ "' ■ .. '■■ ^ - ²² - -: ■■■■■■.

When adding 2.0 parts of the difunctional methylated hexamethylenediamine to 100 parts of the liquid * polymer got this within two Vulcanized to a solid, dry, elastic mass at room temperature for hours. But the product was completely soluble in benzene, and the determination of the Intrinsic viscosity showed a substantial increase the molecular weight.

When mixing the liquid polymer with 3 * 0 parts of the multifunctional tetraethylene pentamine = on 100 Parts by weight of the polymer hardened the liquid polymer at room temperature to a solid, dry, -. elastic mass, but this time the product was too

91% insoluble in benzene and had a tensile strength

• 2 speed of 9.5 kg / cm.

example 5 '-. ~.

100 parts of 1,3-butadiene and 10 parts of tetrabromomethane were emulsified in 160 parts of water, the 5 parts Fctrium dodecylbenzene sulfonate as an emulsifier and 5 parts Tripotassium phosphate dissolved as a buffer contained. After that the temperature in the polymerization vessel was increased to 60 ° C, 0.6 parts of potassium persulfate were added, and the emulsion was 21 hours at this ®apera; fcur;

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touched. Thereafter, the butadiene was converted to the polymer, which was obtained in the form of an "aqueous latex." 1,3-Butadiene-1,3 was removed from the latex and this was then removed with a further 60 (Beile water diluted and divided into two parts ”One part was heated to 60 ° C for a further 1 ½ hours, while the second part was not heated any further. Both parts of the latex were then eoagulated by freezing out, and the separated polymer durcn loosening "in benzene and precipitating was cleaned with acetone and then dried in vacuo at 5O ⁰ C" before drying were 1.25 parts methylene-bis (2-nonyl-4 ^ methyl-phenol) as the Antioxydationsmittei to both Sroben Polymers were added. Both samples were obtained as Tfiskose, pourable liquids of similar appearance and viscosity. The bromine content of both samples was determined and one part Λ of each sample was mixed with 3 parts of completely methylated hecametylenediamine (MHMi) A) ". ,

mixed and at room temperature before vulcanization subject. Tensile strength, elongation - ^^ and modulus of vulcanized samples were measured ". ■ ·:," · ■ ".

Warmed up Not warmed up

Table T

Brojngelialt - weight percent ^> 70 2.66

Tensile Strength - kg / cm 26.7 8.1

Bruclidelmung - % '■■' '.. ".? 00 ·; 515.

Module at 100% - kg / cm ² ■ 9.1 ': .6.0

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ö ■% ϋ

The results show the verbe β soap strength properties, obtained when reheating liquid polymers with low conversion. ,.-.-.

Example 6 _s -

A number of polymerizations were carried out in which 100 parts of 1,3-butadiene in 180 parts of water ■; Were emulsified containing 5 parts of sodium dodecylbenzene sulfonate and 3 parts of tripotassium phosphate dissolved. The polymerization was carried out within 17 hours at 60 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

Experiment Ήτβ Tetrabromomethane Intrinsic bromine content Comments

Part viscosity Qew.%

- solid polymer

1,4, vulcanizable liquid.

3.3 -

1 2.5 1.5 2 5.0 0.77 5 8.0 0.51 4th 10.0 0.37 LfN -15.0 ■ Ov26

II . H It ff H ■ ■ It

The results show (that with increasing amounts of Te tr a-

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Bromomethane The intrinsic viscosity and 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 Runs 2-5 were. 'Converted into tough, elastic products by mixing with small amounts of methylated hexamethylenediamine and standing for a few hours at room temperature. When the polymer from Experiment 2 was mixed with 4-0 parts of high abrasion furnace carbon and 2 parts of tetraethylene-pentamine, formed into a film and left to stand overnight at room temperature, the determination of the physical properties gave a tensile strength of 76 kg / cm, an elongation at break of 360% and a modulus of 56.5 "with an elongation of 30QP / 0.

Example 7 t

A number of polymerizations have been carried out with different polymerizable monomers, different ones Ratio of components and carried out under different polymerization conditions «The results are given in Table III.

9 O 9 8 3 5/1 A O A

. . ⁼ - 26 ~; ■ '": ■■

All polymers were liquid and with polyfunctional Amines vulcanizable. Table IV gives "some of the with Tetraethylene pentamine as a vulcanizing agent again obtained results. Triethyltrimethylene triamine was the vulcanizing agent for sample 9ν and in this one Trap, no numerical values for tensile strength and elongation were determined - the vulcanized Sample was only checked and proven by hand after 25 minutes air drying at 144- ° C "as elastic and very elastic.

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90U '/ 9 € 8606

Table III

No monomer

Water Emulsifier Buffer Initiator Halogen Reaction Reaction Intrin Halogen

connection time <§td. ) tem. · (C) sicvis thread ',. kosity

1 butadiene-1,3 (100) 180

. (a) E ₅ PO ₄ E ₂ ^S 2 ° 8 ° ^Br 4

• 5 '

34 «c c 4, 0.20

65,

60

0.4-0 · 2.7

2 butadiene-1 , 3 (100) 180 (b)
. . ''5 ■ K ₅ PO ₄
■ 4 ^K 2 ^S 2 ° 8
0.40 ^CBr 4
10. ■ 65. ' ^: .
I. 60 .-. O. ■ 2. 17th · '· _: Barbel dien-1 , 3 (100) .180 . ■■ ■ '5; ■■ K ₅ PO ₄ K ₂ S ₂ O ₈
3.0 20th • v '1.7 ·'. :. ■. ■ ': 60
ι. O. ⁵⁴ ■: '»"' Butödien-1 , 3 (100) 180 ν (a) K ₅ PO ₄ K ₂ S ₂ O ₈
1.0 ' CBr ₄ -IO
ni>DM> 0.2 '. 25 "'' ■ '.. ■ 50 ■■; ■ '■■ - ■ 01 ₅ .., 3utadiene-i (loo) 160 Ca) K ₅ PO ₄
..3. '■■■' DIP.
.1.0 CBr ₄ ;
10 \ 47- ■ ν · '■. ;; 60 0 « 7 « - ΓΟ. M. ^: ■ 24 '.; ■ • 32

.6 1,3-butadiene (100) '360

(a) K ₅ PO ₄ DIP

65

13: Ö.5O 1.5 ·

10

1.0 '(c)

-cn cn

ο>

9J3

I »'

Cs

CN

I *

I, -rf

vT '"

,1-

I® '

egg

v OI iA Pl ^

4 pp

co- Fh

K \

te

r-

I IA

Cl ^ O)

rid ρ

Q Q

■ ir

co

Iu

m Q

■ ©

J *

Si! A

'tA

P ■>'. H m ry

.ar

Kr. Monomer

Water Emulsifier Buffer Initiator Halogen Reaction Reaction Intrin Halogen

verb in time (hrs.) temp. ( ⁰ C) s'icvis grounding. ' kosity

Isoprene

(100) 180 (a)

CBr,

CO O CD CX> U>

DIP'-jDi'isopropylbenzene-liydroperoxide, ...

η-DDM - n-Dodecy! mercaptan

IBIW - azo-bis-isobutyronitrile

(a) - Itodium dodecylbenzene sulfonate

(b) - potassium stearate.,. _: ·

Cc) - activated with Na ₅ PO ₄ - 0.48 parts; FeSO ₄ ^ H ₂ O - 0.12 parts;

Sodium formaldehyde sulfoxylate - 0.48 parts; Ethylenediamine tetrasodium acetate - 0.15 parts,

0.19 3.15

Butadiene-1, 3 (100) 180 (a) 4th K ₂ S
■ 3. 0 10 V 60 0.16 8th. 04 14th Isoprene " (100) 180 Ca)
"-5 '■'' V ° 4
. 3 K ₂ S
10. 2 ° 8
0 CHI ₃
10 41 60 - 3 « 9 15th K ₃ PO ₄
','"5' 2 ° 8
0 CBr ₄
10

- - j.0 ..- J Table IV

Sample Vulcanization Vulcanization Tear Elongation medium (parts) permanent strength ', [

(kg / cm).

1 2 over night - 10.2 240 ■ 3 4th It 11.6 215 5 2 ti 8.8 '820 . 6th 2 Il 7> 7 760 ft ⁷ ; 3 η 10.2 160 • 9 ■ 7.5 25 min at 144 ° C not measured 10 3 7 days 7.7 295 11th 3 6 hours 10.5 480 12th 3 over night 9.1 145 14th 3 2 hours 10.9 220 Example 8

A liquid homopolymer was prepared as in Example 4, but 15 parts of tetrabromomethane were used here. The polymer had a bulk viscosity of 335 poise, an intrinsic viscosity of 0.29 and one Bromine content of 3.4-5 percent by weight. ";

Samples of the polymer were made with various fillers mixed up and at room temperature for vulcanization brought. After one hour, all mixtures were sufficiently cured to be tack-free; After 7 days tensile strength and elongation were determined for aliteji samples

^: - ί ■ & Ϊ ■ ;! i: ■ ··: - ■ . \ -. ■. ■

it's correct. The results are given in Table V. 909835 / UOi

- - O ;. " XQ
CO ■ Γ LfN O OQ IfN ■ "f "r · CQ ο pj OJ OJ OJ OJ ' O, CO OJ sr -. ■ P- LfN ■ *> Q - - OJ I. ο "·" "4" LfN Q. '; - «■ Ο α OJ O ΙΑ. Ö .- "' ω. ψ LfN GQ . - W. Q- CD OJ W; Oi LfN LfN Ψ Oj LfN m 'Φ. Gi OJ LfN S ^ Q Ψ- KN §§ ■■ Q C3 Φ
Φ Q Q KN KN ' O ai Q KN OJ 1 a B. "r .. Φ OJ rf ä) .P (Tt ₁ Il : ^ ^: pt-) I. £ S. pH rf I. ^ s CQ ' r φ- cö -fj IQ J ' § rÖ ? ri 'S Ä crt I. Ί & ■ ι: (H
Jp to
ά) I. I. W. Ί ro ■ t? (9 ■ M. φ Γ M. H m ic S. fa* EQ ! ■■■ J ⁵ . Hf '' #, ■ ft Φ
: # - O ä ' ti

θ fe

ill 1

Example 9 '■'". · '■ ■"'"^;'"

100 parts of 1,3-butadiene and 10 parts of teJbrabromomethane were emulsified in 160 parts of water which contained 5 parts of sodium dodecylbenzenesulfonate as an emulsifier and 3 parts of tripotassium phosphate as a buffer. 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 a conversion of more than 95% of the monomer into the liquid polymer, which was obtained in the form of an aqueous latex. The resulting isolated polymer ¹ had a viscosity of 4600 poise at 25 ⁰ Cf an intrinsic viscosity of 0.38 and a bromine content of 3 »72 Gewiclfcsprozent. Samples of the separated polymer were mixed with various materials on- and ■: · ■ -. Vulcanized.-The vulcanizates were tested as shown in Table VI.

ν "- ';;■■:' vo ■ ^:. '■ ■■ ^; - ■■■' ■■ ^.: ^ -

In the case of sample 1, a Paraffin oil and polyethylene are used. that it was a low density product with a melt index of 25, at 150 ° G in. dem. . ·. Paraffin oil, dissolved. This, along with the filler, became the. Added to polymers and that. Mixture-again-: picks up sent through a 3-roller paint mill until one

909835/1404

thorough mossing was achieved. Toluene and amine used for vulcanization (Ν, ΙΤ, Ν ¹ , N'-tetramethyl- hexamethylenediamine) were added as a solution. The compositions obtained before vulcanization were soft, thixotropic, slightly extensible mixtures suitable for use as sealants or caulking agents.

Table VI Sample no. 1 2 -> 3 Polymer 100 100 100 Hydrocarbon oil 40 - " _ Chlorinated polyphenyl (liquid) - 40 40 Polyethylene - 10 10. 10 Russ (SEI ¹ ). 40 - - - Titanium dioxide - 20th - Aluminum powder _i ■ ■ 10 toluene • 10 10 10 Amine 2.5 2.5 2.5

Vulcanization temperature room temperature

Duration of vulcanization 7 days 7 days 7 days.

Tensile strength (kg / cm ² ) 28 20.4 16.2

Elongation (%) 630 900 790

Modulus at 100% (kg / cm ² ) 9.8 8.4 9.5

Example 10

A liquid homopolymer was prepared as in Example 9, but in this case there were 200 parts of water

909835 / 140.4

'. ■ - 34 -

used. The polymer had an intrinsic viscosity of 0.24 · and a bromine content of 5 »7 percent by weight.

Mixtures with a smaller amount of a vulcanizing agent and = a larger amount of a difunctional, Chain extenders were added to the polymer. Two mixes were made. Mixture 1 consisted of 0.5 parts of 2,4,6-Tr! (Dimethylaminomethyl) phenol, 2.0 parts of 1,3-di-4-pyridylpropane and 100 parts of the liquid polymer. Mixture 2 corresponded Mixture 1, instead of the 2,4,6-tri (dimethylaminoamethylphenol but became N, IT, N ', 1 ", 1'", I "'-hexamethyltriethylenetetramine used as a vulcanizing agent. The ones used for vulcanization and chain extension Substances were used as 50% solutions in Toluene added to achieve better dispersion in the polymer.

The "usage time ^11" , that is to say the time it takes a mixture to thicken to a no longer workable state, was determined for all samples. The tensile elongation properties were measured after a vulcanization time of 7 days at 25 ° C.

if

The properties of the mixture and the vulcanizates are in, Table VII reproduced.

09835/1404

Table TII ^;

characteristic

Usage time (hours) Tear strength (kg / cm ² )

Mixture Λ Mxschung 2 5 '_ Ί "i9,3 ~ 26.4 680 " 730

strain

Module at 100% elongation

·. - ■ - (kg / cm ² ) - ■: ⁶ ^ ■■ · - ■ '^ -7 _: -,, - ■, .. ^ j

Modulus at 300% elongation. . ".; i.

■■ '/ s'' 2v ■ 10.9 -10.9 (kg / cm) -. ,:. . ; _: . .

The results show that these mixtures "and especially Mixture 1" should be suitable for use as a sealant in the construction industry, since there a usage time of at least one hour is required. This can be achieved, as in this example, by using a mixture which contains a smaller amount of a polyfunctional vulcanizing agent and a larger amount of a difunctional chain extender. A usage time of 10-15 minutes, which is achieved if the vulcanization system is based only on a larger amount of a polyfunctional vulcanizing agent, would be suitable for this special purpose. not acceptable;'^;''

9 0 9835 / U 04

Claims (2)

Claims 1. Process for the polymerization of a diolefinic Hydrocarbons having 4 to 8 carbon atoms containing monomeric system under the conditions of Emulsion polymerization in an aqueous medium and using a polymerization initiator which forms free radicals, characterized in that during the polymerization to 100 moles of the monomer at least 0.15 mol of a compound of the type X (T) Z are added, in which X Br, J or Cl, Z -CBr ,, · -CCl ^, -CJ, or ^ .CJp and Y is a radical with a Structure like (- (J-C = C-), (C-C-), (- (Lc = C-R-) or (-C-C-R) is -C-. where ~ R is a hydrocarbon or substituted hydrocarbon radical with a molecular weight of 14 up to about 100, whereby a latex of a liquid polymer with an intrinsic viscosity 'at 30 ⁰ C in toluene of 0.04-1.0 is obtained and a Major part of the molecules of the liquid polymer contains two separate -Q "CCX structures, and that the liquid polymer thus obtained is subjected at will to a further treatment, in particular a compound of the molecules of the liquid polymer serves with each other by means of multifunctional compounds, previously using other polymers or known ones Mixing additives may or may not be admixed. 909835/14 04 2. The method according to claim 1, characterized in that that a major part of the molecules of the polymer has a -C = G-C-X structure & αχεχ Id «at each end. 9098 3S / 1404