DE2333307A1 - PROCESS FOR MANUFACTURING A FUNCTIONAL POLYMER - Google Patents

Description

1A-524

MC-41 June 29, 1973

MITSUBISHI CHEMICAL INDUSTRIES LTD., Tokyo ", Japan

Process for the production of a functional polymer

The invention relates to a method for producing a functional polymer dux'ch living polymerisation of a conjugated diolefin and / or a vinyl compound of the formula

.R ₁
OH ₂ = C ^

"^ ^R 2

where R _{1 is} a hydrogen atom or an alkyl group and R _? represent an aryl group or pyridyl group and by reacting the resulting living polymer with an epoxy compound.

It is known to use a living polymer with a monoepoxy compound, how to implement ethylene oxide and then to implement the reaction product obtained with a protic acid, whereby a polyhydroxyl polymer is obtained. It is further known to hydrogenate the polyhydroxyl polymer. The polymers produced in this way only have hydroxyl groups at both ends of the polymer chains. You cannot use conventional crosslinking agents or hardeners how toluene diisocyanate are crosslinked.

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It is also known to have an excess (molar ratio 1 - 40) of polyepoxide, epoxy aldehyde, epoxy ketone or epoxy ester with to react the living polymer to produce a polymer having epoxy groups and hydroxyl groups. The polymers produced by such a process have a structure which depends on the extent of the excess of the polyepoxide, of the epoxy aldehyde, the epoxy ketone or the epoxy ester. The hardened ones made from this product However, bodies are extremely fragile.

It is also known to be a saturated polyhydroxy hydrocarbon polymer thereby to prepare, that a polymer of the polyhydroxydiene type by radical polymerization of a Conjugated diene type monomers polymerized and then hydrogenated. The polyhydroxy hydrocarbon polymer, which according to This process is produced has a main chain of the polyethylene type, since the polymerization takes place radically. Therefore the polymer is in the form of a wax or in the form of a solid. Accordingly, the application of such Polymers such as B. the crosslinking or curing or the like. Difficulties with it. In addition, such polymers have the functional groups do not appear at selected locations, but rather unreasonably throughout the polymer. distributed.

It is also known to carbon dioxide with a living polymer to implement a polycarbonate polymer. The polymer produced by this process has carboxyl groups only on both ends of the polymer, and the number of functional groups is limited to less than two. Accordingly, it is difficult to obtain such a polymer without using special curing agents or crosslinking agents network.

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It is also known to prepare a polymer having carboxyl groups by using a monomer of the type conjugated diene with a radical polymerization initiator (e.g. peroxide or azobis compound), which Has carboxyl groups, polymerized. Here, too, the crosslinking reaction is subject to the aforementioned considerable conditions regrets.

It is therefore an object of the present invention to provide a method for producing a functional polymer which is easily crosslinkable to a product with excellent mechanical strength, the functional groups in defined Positions and excellent weather resistance, Heat resistance and excellent electrical properties has to create.

According to the invention, this object is achieved in that the living polymer is mixed with haloalkylene oxide and / or polyepoxide in a molar ratio of less than 1.0 and the obtained Reacts product with a monoepoxide.

The functional polymer according to the invention is at normal temperature in liquid form so that it can be easily processed and hardened. Because of these properties, the functional polymer is known as liquid rubber. Through cross-linking, various cross-linked polymers can be combined with the respective desired properties dush application of various Crosslinking methods are produced. The method according to the invention differs fundamentally from all previous ones known procedures. The polymer produced according to the invention is a polyhydroxyl polymer or a polycarboxylic polymer or an unsaturated polymer. The process according to the invention also leads to a hydrogenated polyhydroxyl polymer. The term "functional polymer" denotes a polymer with a multiplicity of functional groups, which with one Crosslinking agents to produce a crosslinked product

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reacted. The functional polymer can be a variety of Have hydroxyl groups. In this case it is called a polyhydroxyl polymer ". Furthermore, the polymer may have a variety of carboxyl groups. In this case, it is referred to as Polycarböxylpolymeres. Or the polymer can have a large number of unsaturated groups. In in this case it is called an unsaturated polymer. As a starting material for the process according to the invention living polymers used has alkali metal at both ends of the polymer chain and it has an average Molecular weight of 500-10,000. Such living polymers can easily be produced by reaction of alkali metal or organic alkali compounds with the conjugated diene and / or the vinyl compound of the above formula according to conventional ones Process are produced.

The conjugated diene, which is used as the starting material for the living Used for polymers, it can be 1,3-butadiene or 2-methylbutadiene-1 , 3, pentadiene-1, 3, 2,3-dimethylbutadiene-1,3, 1-phenylbutadiene-1,3 or the like. The vinyl compounds of the formula mentioned include vinyl aromatic compounds such as styrene, α-methylstyrene, tertiary-butylstyrene, para-methoxystyrene, Vinyltoluene and vinylpyridines, such as 2-vinylpyridine and 4-vinylpyridine.

In the production of the living polymer, the monomers mentioned can be used in a mixture. It is preferred use more than 25 percent by weight and preferably more than 50 percent by weight of the conjugated diene, since in this case, the crosslinking of the functional polymer can be easily carried out. The ones used for the production of the Alkali metals used in living polymers include lithium, sodium, potassium, rubidium, cesium or the like.

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The alkali metal organic compounds include organic complexes of alkali metals such as naphthalene complex, Anthracene complex, biphenyl complex, diene complex, styrene complex or dialkali metal hydrocarbons, such as 1,4-dialkali metal butane, 1,5-dialkali metal pentane, 1,10-dialkali metal decane, 1,2-dialkali metal-1,2-diphenylethane, 1,4-dialkali metal-1 »1,4,4-tetraphenylbutane or the like

In making the living polymer, one usually uses a hydrocarbon solvent such as hexane, heptane, benzene, toluene, xylene, cyclohexane, methylcaclohexane or the like. to carry out a smooth reaction. It is preferred to use a mixed solvent of the hydrocarbon and a Lewis base so that the reaction proceeds uniformly. Oxygenated Lewis bases can be used as Lewis bases, such as dirnethyl ether, diethyl ether, diisopropyl ether, üfetrahydrofuran, dioxane, ethylene glycol dimethyl ether, anisole, Ethylphenyl ether or the like. As well as nitrogen-containing Lewis bases such as trimethylamine, triethylmain, dimethylaniline or the like.

In the first stage of the inventive reaction, the living polymer produced is mixed with the haloalkylene oxide and / or polyepoxy compound implemented. The halogen alkylene oxides used have the following general formula:

"X - (CH _{2 m} - OH-CH ₂

where X is a halogen atom, m is 1 or a number greater than 1. These haloalkylene oxides include e.g. B. epichlorohydrin, epibromohydrin, epifluorohydrin, chlorobutylene oxide, Bromobutylene oxide or the like.

The polyepoxy compounds associated with the living polymer implemented include two or more than two

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Epoxy groups in one molecule. Come as polyepoxy compounds Diglycidyl ethers of disphenols in question, as well as diglycidyl ethers of phenol derivatives, diglycidyl ethers of glycol, ζ, - Β. of ethylene glycol or diethylene ether glycol; Diepoxides of service, such as of butadiene or 1,4-hexadiene; Dicyclopentadiene diepoxides, such as vinyl cyclohexene diepoxide, lime diepoxide. It is necessary a molar ratio of the polyfunctional epoxy compound (haloalkylene oxide and / or polyepoxy compound) to choose the living polymer of less than 1. This is because of the following reasons. In the first stage of the reaction Polymers formed by reacting the living polymer in the polyfunctional epoxy compound. In this polymer two or more living polymer chains are chain-extended via a polyfunctional epoxy compound. It is necessary that unreacted at both ends of the polymer Alkali metal remains. When the molar ratio is larger than 1, both ends of the obtained polymer cannot be alkali metal and accordingly it is difficult in this case, in the second stage, the obtained product with the monoepoxy compound to implement.

The amount of the polyfunctional epoxy compound can be selected within a wide range. The exact amount depends on the molecular weight of the living polymer, on the properties of the desired crosslinked product of the functional Polymers (tensile strength, elongation at break, hardness or the like), on the workability and on the processability during crosslinking away. As the amount of the polyfunctional epoxy compound is increased, the molecular weight of the functional component also becomes Polymers increased and the number of functional groups in the polymer is also increased, so that the crosslinked Product has excellent tensile strength and hardness or the like. However, there is a deterioration in terms of this the stretching and the processing to carry out the crosslinking it's not always easy. On the other hand, when the amount of the polyfunctional epoxy compound is very small, so can

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it happens in some cases that the number of functional Groups in the polymer obtained is too few, so that perfect crosslinking or curing is not possible. It is generally possible to crosslink the polymer even if the amount of the polyfunctional epoxy compound is about 0.05 mol per 1 Hol of the living polymer is. However, it is preferred that the amount be above 0.1 mole and especially above 0.2-0.5 mol based on 1 mol of the living polymer.

In this reaction of the living polymer with the polyfunctional epoxy compound in the first stage, the polyfunctional epoxy compound is added to a solution of the living polymer in a hydrocarbon and the reaction easily takes place at -78 ⁰ G - + 100 ⁰ G and in particular from 0-80 ⁰ G instead. It is assumed that a polymer is obtained in the first stage in which a large number of the chains of the living polymer are connected to one another via haloalkylene oxide and / or polyepoxide and where at the. alkali metal is present at both ends of the polymer.

In this case, the ring cleavage of the haloalkylene oxide and / or the polyepoxy compound causes the formation of -OM groups (M = alkali metal) and the -0M group obtained connects to a secondary or tertiary carbon atom. Treatment with a proton donor (third stage) converts the -OM groups into hydroxyl groups. Accordingly, the molecular weight and the number of functional groups of the polymer can be controlled by the amount of haloalkylene oxide and / or polyepoxide selects in a certain way during the first reaction stage. The monoepoxy compounds have only one epoxy group and they have no halogen in the molecule. Thus, the monoepoxy compound is clearly different from the polyepoxy or the haloalkylene oxide.

3 0 9 8 8? / 12 2 1

-R-

In the second stage, the Monoepoxyver "bond with the Reacted polymers obtained in the first stage. Preferably, low molecular weight mono-epoxy compounds are earthed and low viscosity are used. Such monoepoxy compounds are ethylene oxide, propylene oxide, butylene oxide, Cyclohexene oxide and monooxides of dienes. Ethylene oxide is preferably used. If ethylene oxide is used, can a polymer having primary hydroxyl groups at both ends is obtained by treating the polymer with a proton donor treated in a subsequent stage (third stage). The primary hydroxyl groups are for the crosslinking reaction more reactive.

However, those hydroxyl groups of the polymer which are obtained when using other monoepoxide compounds, such as propylene oxide, also have a sufficiently high reactivity. In the second reaction stage, preferably more than 1 mole and in particular more than 2 moles of the monoepoxide compound, based on the polymer obtained in the first stage, are reacted. In the second reaction stage, the monoepoxy compound reacts with at least one carbon-alkali metal bond at the ends of the polymer chain, which is obtained in the first stage. It is possible to use an excess of the monoepoxy compound based on the carbon-alkali metal bonds. The, the second stage reaction is preferably carried out at -78 - 100 ⁰ C, particularly at 0 - from 80 ⁰ C, the same as in the first reaction stage. It is believed that the monoepoxy compound reacts with ring cleavage with the carbon-alkali metal bond at the ends of the polymer chain and is bonded here, so that -OM groups are formed. If 0.5 moles of epichlorohydrin are reacted with 1 mol of the living polymer, and if 2 moles of ethylene oxide are reacted with the reaction product, a polymer according to the following schematic formula is obtained:

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-s-

Cl - CH ₀ - CH - CH ₀

ν ²

OM + MCl

V7 ^H

ρττ ___ fill

^CH 2 - / ^GH 2

YiOGS ^ S & g ** ·· ^^ - * ^ * ^^^ CH ₂ CH-CH ₂

OM

In this formula, M - ^^^ - ^^^^ M means a living polymer; M means an alkali metal and ^ v ^ -v ^ - 'x ^^ - "means a hydrocarbon chain. The functional -QM group in the functional polymer obtained can by 'treatment with a Proton donor (third stage) easily converted into the hydroxyl group " will. This is done according to the following reaction scheme:

MOCH ₂ CH ₂ / ^^^^^ V ^^^^ CHgCHCH,

OM

Proton donor t

HIGH ₀ CH ₀ <X / -N- ^ V - ^ - v ^ -CH ₀ CHCH ₀ ^ ν ^^^^ νχν, -ν ^^ τCH ₀ CH ₀ OH

ά ά ά ι ά CC-

OH

An inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid or an organic acid such as acetic acid can be used as the proton donor. The proton donor can be used in aqueous solution or in solution in a lower aliphatic alcohol or in a mixture thereof .

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- ίο -

You can also use gaseous acid. A water-alcohol solution and one of the proton acids mentioned can be used as proton donors. The amount of proton donor should be sufficient to neutralize the alkali metal groups in the polymer. All functional groups (-0M) in the polymer are converted into hydroxyl groups by this treatment. The reaction temperature of the reaction with the proton donor "is usually less than 100 ⁰ C and preferably 0-25

G. In the treatment with the proton donor, an alkali metal salt is formed, such as. B. sodium chloride, lithium sulfate, Sodium hydroxide, lithium hydroxide or the like. The separated compounds are water-soluble, so that an impurity the polymer can be prevented by washing out the functional polymer.

In the treatment with the proton donor, this is the case with the second stage obtained polymers converted into a polymer, which at each connection atelle of two living polymers has at least one hydroxyl group (in the case of using haloalkylene oxide 1 group and in the case of using from a diepoxy compound 2 groups). Further, at each end of the polymer obtained, there are preferably at least 1 2 hydroxyl groups. Accordingly, the obtained polymer is an unsaturated hydrocarbon polymer having more as 2 hydroxyl groups if a conjugated diene is used as a monomer in the production of the living polymer will. If only a vinyl monomer is used, such as styrene or vinylpyridine, the resultant has functionalities Polymers have a saturated main chain.

According to the invention, the polymer obtained with unsaturated hydrocarbon chains and with more than 2 hydroxyl groups can be catalytically active are hydrogenated with molecular hydrogen (fourth stage). The hydrogenation can be carried out completely or partially will. However, it is preferred to hydrogenate

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make up to nearly 100 ° / o, so that at least more than hydrogenated f> of the unsaturated bonds. This is preferred from the practical point of view and from the point of view of the physical properties of the crosslinked product. In particular, a hydrogenation 80-100 ° / o preferably the double bonds. In this case, the properties of the crosslinked product are particularly favorable. The catalytic hydrogenation can be carried out in a conventional manner. Molecular hydrogen or a gas containing molecular hydrogen can be used as the starting material for the hydrogenation. However, the gas must not contain any significant amounts of impurities which would poison the catalyst and thus reduce the activity of the catalyst. Various known catalysts such as nickel, Kolbalt, platinum, palladium, rhodium or mixed only catalysts or alloy catalysts can be used for the catalytic hydrogenation. These catalysts can be used per se as solids or in the form of a soluble complex or on a support material such as carbon, silica gel, diatomaceous earth or the like.

A metal complex obtained by reducing a nickel compound, a cobalt compound, a titanium compound or the like with an organometallic compound such as trialkylaluminum, alkyl lithium or the like can be used as a catalyst for the analytical hydrogenation. In the. Hydrogenation, the hydrogen pressure may be one atmosphere or it may be higher, and the temperature may be ⁰ to 150 G in the range from room temperature to 200 ⁰ C and preferably in the range of room temperature. The polymer can be used with or without a solvent. Suitable solvents are aliphatic hydrocarbons, acyclic hydrocarbons, aromatic hydrocarbons, alcohols, aliphatic hydrocarbons or mixtures thereof.

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The polymer obtained in the process according to the invention has a molecular weight which is an integral multiple of the molecular weight of the living polymer.

The polymer has a primary or secondary hydroxyl group at the end of the polymer chain and also has a secondary or tertiary hydroxyl groups at each junction of two living polymer chains (pendant hydroxyl group). That Polymers is a saturated or unsaturated or partially unsaturated hydrocarbon with more than two hydroxyl groups per polymer molecule. The polymer can be easily crosslinked or cured by a curing or crosslinking agent will. It is Z. B. possible using polyisocyanate, polybasic acids, anhydrides of polybasic Acids and epoxy compounds as crosslinking agents the polymer to crosslink to a plastic which is excellent in hydrogenation resistance, heat resistance and excellent electrical properties. Have the hardened products various properties ranging from those of rubbery elastomers to those of rigid resins are sufficient.

In the process according to the invention, a polymer, its molecular weight, its hydroxyl group content and its The degree of unsaturation can be regulated as desired, so that the polymer obtained is tailored precisely to the particular application can be. In addition, the polymer according to the invention is in liquid form at room temperature, see above that it can be conveniently used and crosslinked (simply mixing it with the crosslinking agent, filler or Like. And shapes of the mixtures). The above has been the method of treating the functional obtained in the second stage Polymers with a proton donor and the process for hydrogenating the product is explained. The invention is but not limited to these embodiments.

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The functional polymer which is obtained in the second stage can be with an acid halide or an ester Carboxylic acid are reacted, which are polymerizable unsaturated Have double bonds (third stage). The functional groups (-OM) of the functional polymer can thus be converted into a polymerizable unsaturated group are converted. As a carboxylic acid with polymerizable unsaturated bonds Acrylic acid, methacrylic acid, cinnamic acid, kaleic acid, fumaric acid or the like are suitable.

Acid halides of carboxylic acids which are substituted by halogen, such as chlorine, bromine or iodine, or esters of carboxylic acids with alcohol, methanol, ethanol or the like can be used. The amount of the halide or the ester of the carboxylic acid having a polymerizable unsaturated bond is preferably more than 1 equivalent based on the alkali metal atoms in the functional polymer obtained in the second stage. The reaction is usually carried out at 0-100 ^° C. and preferably at 30-80 ^° C. in the solvent which is also used for the living polymerization. In the reaction, it is preferred to add a radical polymerization inhibiting substance, such as hydroquinone, benzoquinone, 2,6-di-tert-butyl-p -] ^ resol or the like. The following is a chemical reaction scheme for the reaction with a Molecular equivalent of acrylic acid chloride stated:

MOCH ₀ CH ₀ S ^^^ s QE ₀ GECE ₀ - ^ - v ^^ _v ^^^ CH _o CH _o 2 2 c ι 2 2 2

3 CH ₂ = CH-COCl

CH ₀ = CH-CO-CH ₀ CH _{0 o}

C. it CC C ,

■ 0 0-C-CH = CH ₀ 0

+ 3MCl 3 0 9 8 8 2/1221

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The reaction product is a polymer having a molecular weight equal to the integral multiple of the molecular weight of the living polymer with more than two functional groups (polymerizable double bonds) per mole of the polymer. The functional polymer can be cured or crosslinked Product with excellent properties can be converted by mixing the polymer with a radical polymerization initiator such as benzoyl peroxide, azobisisobutyronitrile or the like. Heated. If a polymerizable compound, like Styrene, methyl methacrylate, acrylonitrile, diyinylbenzene, ethylene glycol dimethacrylate, Diallyl phthalate or the like is added to the functional polymer during the crosslinking process is, various crosslinked products can be easily obtained whose properties are different from those of one rubbery elastomers range to that of a rigid synthetic resin. The functional obtained in the second stage Polymers can be made with an organic polyearboxylic acid anhydride (third stage) are implemented so that the functional Ie Group (-0M) of the functional polymer is converted into a carboxyl group. The organic polycarboxylic anhydride can be an aliphatic carboxylic acid anhydride such as maleic anhydride or succinic anhydride, as well as an aromatic polycarboxylic anhydride, such as phthalic anhydride, Pyromellitic anhydride, trimellitic anhydride or an acyclic polycarboxylic anhydride such as hexahydrophthalic anhydride and tetrahydtophthalic anhydride.

The amount of the polycarboxylic acid anhydride is preferably more than 1 molar equivalent based on the alkali metal atoms of the functional polymer obtained in the second stage. The reaction is usually carried out at 0-100 ^° C. and preferably at 30-80 ^° C. in a solvent which is also used for the living polymerization.

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The reaction product contains a. Polymer with a molecular weight which is an integral multiple of the molecular weight of the living polymer and it is more than two functional groups (carboxyl groups) per polymer molecule. The functional groups (-0M) of the functional polymer form ester groups with the organic polyearboxylic acid anhydride. The alkali metal ions which are released during the action react with unreacted carboxyl groups and convert them to alkali metal salt. This reaction follows the following general reaction scheme, one molar equivalent of phthalic anhydride being used as the polyearboxylic anhydride will.

MOCH ₂ CH ₂ ~ wwww ^ w CH ₂ CHCH ₂

OM

CO.

CH ₂ CH ₂ OM

CH ₂ CH ₂ O

C = O

MO-C

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The functional polymer obtained after the above reaction can be separated from the reaction mixture, if necessary, with removal of the solvent. After separation, the product is purified, if necessary, and a suitable crosslinking agent is added and the mixture is heated to produce a crosslinked product. Usually, the reaction mixture is treated with a proton donor at 0 - 100 ⁰ G and treated preferably at room temperature to convert it into a polymer having free carboxyl groups in the molecule (fourth stage).

The polycarbocyl polymer, its schematic formula below can be generated by treatment with the proton donor.

C =

I HOOC

The functional polymer having free carboxyl groups can be reacted with a crosslinking agent such as e.g. B. with a polyisocyanate, polyamine, polyepoxide, with a polyhydroxyl compound or the like, whereby a cured product having specific properties is obtained. Yfenn maleic anhydride is used as the polycarboxylic anhydride, the functional polymer contains both carboxylic acid groups as well as polymerizable unsaturated groups.

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OCH ₂ CH ₂ / \ - ^ v- "v ^ _. _V _- ■ ^ .- v .-. Vv CH ₂ CHCH ₂

C = O. 0 C = O

f 1 y

CH C = O CH

H -B

CH CH CH

Ii

COOH. CH COOH

COOH

Accordingly, the functional polymer can be added by adding a Vinyl monomers such as styrene, methyl methacrylate, acrylonitrile, Divinylbenzene, ethylene glycol dimethaerylate as hardening agent and by heating the mixture in the presence of a free radical polymerization initiator be networked. A wide variety of crosslinked products can be obtained, which from rubbery elastomers to rigid resins.

The process of treating the functional polymer to convert the groups (-0M) into hydroxyl groups, polymerizable unsaturated groups or carboxyl groups and for the subsequent crosslinking of the product with a crosslinking agent has been explained. Such further processing is from the standpoint of the physical properties of the crosslinked Product and processability. However, the invention is not limited to these embodiments.

In some cases the functional polymer used in the second stage of the process according to the invention is obtained, schott reacted with a crosslinking agent and crosslinked will. For example, this can be obtained in the second stage functional polymers by reaction with a polyisocyanate, a polycarboxylic acid anhydride, a polycarboxylic acid or an acid halide or the like. Are crosslinked.

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Cross-linked products with different physical properties can be produced by crosslinking the functional polymer with a crosslinking agent. It is possible, a filler material such as carbon black, silica, titanium dioxide, clay, zinc oxide, calcium carbonate, calcium silicate, lime, aluminum oxide, magnesium oxide or the like. It is also possible to use other additives, such as plasticizers, emollients, sulfur or the like. It is particularly preferred to distribute carbon black in the functional polymer and then to crosslink the mixture. The distribution of RuS in the functional polymer can be done by mechanical kneading with a roller mill. It is also preferred to treat the functional polymer of the invention with an aqueous dispersion of carbon black, so that the carbon black is uniformly dispersed in the functional Polymers is transferred. According to the invention, a wide variety of functional polymers with a wide variety of functions can be obtained will. The polymers produced according to the invention can cannot be obtained by any of the previously known methods.

In the following the invention is illustrated by means of embodiments explained in more detail.

example 1

0.02 moles of naphthalene, 0.3 g atom of metallic lithium and 0.2 mol of isoprene are mixed and poured into 100 ml of diethyl ether implemented under an argon atmosphere, using a dilithium starter is obtained. A small amount of butadiene is polymerized using 40 mmol of the dilithium starter, whereupon 500 ml of cyclohexane are added to the polymerized product to dissolve it. 50 g of butadiene are then initiated and the polymerization is carried out at room temperature for 3 h, with a living polymer with a molecular weight of 1250 is obtained.

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A tetrahydrofuran solution of 3.0 g of vinyl cyclohexene diepoxide becomes to the üä) terminated polymer in a molar ratio of about 0.5 based on the living polymer and the reaction of this mixture is carried out at room temperature 1 h carried out. A solution of 10 g of ethylene oxide in tetrahydrofuran is then added to the reaction product and the reaction is carried out with stirring for 10 Ii. To the reaction is a mixture of methanol / hydrochloric acid, which contains 0.5 g of 2,6-di-t-butyl-p-cresol (antioxidants) to the Product is added and the product is purified by conventional precipitation methods and dried in vacuo, leaving 55 g of a polymer with a molecular weight of 2800 (measured by vapor pressure osmosis). The infrared spectrum has a broad absorption band of the hydroxyl group at about 3500 cm "". 100 parts of the polymer obtained are with 30 parts of carbon black HAP, with 13 parts of 2,4-toluene diisocyanate and 0.3 parts of dibutyltin dilaurate are mixed and the mixture is heated to 120 G for 2 hours. The received cross-linked product is a rubber-like elastomer with no tackiness and with a tensile strength of 152 kg / cm.

Comparative example 1

A solution of 8.4 g of vinylcyclohexene diepoxide in tetrahydrofuran becomes the living polymer which, according to Example 1 is obtained, and a molar ratio of 1.5 based on the living polymer is selected. After that, that will Process according to Example 1 using this reaction mixture carried out, wherein 50 g of a polymer with a Molecular weight of 2900 and having an absorption band of hydroxyl group in infrared spectrum is obtained. 100 parts of the polymer are mixed with 30 parts of carbon black HAF and 20.8 g of 2,4-toluene diisocyanate and 0.3 parts of dibutyltin dilaurate are mixed and the mixture is crosslinked according to the method of Example 1.

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The crosslinked product obtained has. a tensile strength of

ο
70 kg / cm and an elongation of 75 ^c / °.

Example 2

The procedure of Example 1 is carried out using a solution of 10 g of propylene oxide in tetrahydrofuran in place of the Solution of 10 g of ethylene oxide repeated, with 55 g of a polymer with a molecular weight of 3000 and with a broad Absorption band in the infrared spectrum assigned to the hydroxyl group is obtained. The polymer is according to example 1 cross-linked and a cross-linked product is obtained with

a tensile strength of 120 kg / cm.
Example 3

The procedure of Example 1 is repeated, using a solution of 1.9 g (0.5 molar ratio) of epichlorohydrin instead the 3.0 g of vinylcyclohexene diepoxide in tetrahydrofuran is used. 53 g of a polymer are obtained with a Molecular weight of 2700 and with a broad absorption band in the infrared spectrum, which is assigned to the hydroxyl group will. The polymer is crosslinked according to Example 1 and jnan receives a cross-linked product with a tensile strength of

131 kg / cm and with an elongation of 420 fo. Example 4

The process of Example 1 is repeated using 100 g of butadiene, a living polymer with a Molecular weight of 2500 is obtained. A solution of 1.9 g of epichlorohydrin in tetrahydrofuran becomes the living polymer given. A molar ratio of about 0.5 is chosen.

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Then the implementation takes place. A solution of 10 g of ethylene oxide in tetrahydrofuran is added to the reaction product. After the reaction, the product is further treated as in Example 1, 83 g of a polymer having a molecular weight of 5700 and having a broad absorption band in the infrared spectrum, which is assigned to the hydroxyl group, is obtained. 100 parts of the polymer are mixed with 30 parts of KiiT carbon black, 5.1 parts of 2,4-toluene diisocyanate and 0.1 part of dibutyltin dilaurate, and the mixture is ^{heated to 10C 0} G for 2 hours and crosslinked, a crosslinked product having a tensile strength of 103 kg / cm and with an elongation of 409 / ^u .

Example 5

The process according to Example 1 is repeated, 20 mmol of dilithium starter being used to polymerize 50 g of butadiene, so that a living polymer with a molecular weight of 2500 and 39 ° 1.4 units is obtained. A solution of 0.48 g of epichlorohydrin in tetrahydrofuran becomes the living polymer in a molar ratio of about. 0.25 and the reaction is carried out. One. Solution of 10 g of propylene oxide in tetrahydrofuran is added to the reaction mixture. After the reaction, the reaction mixture is treated further as in Example 1 and 43 g of a polymer with a molecular weight of 3900 and with a broad absorption band in the infrared spectrum, which is assigned to the hydroxyl group, are obtained. 100 parts of the polymer are mixed with 30 parts of carbon black HAP, 5.5 parts of 2,4-toluene diisocyanate and 0.1 parts of dibutyltin dilaurate and the mixture is heated for 2 h to 100 ⁰ G and cured. The cured product has a tensile strength of 122 kg / cm and an elongation of 670 · ^.

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Comparison example 2

A solution of 2.9 g of epichlorohydrin in tetrahydrofuran is added to the living polymer according to Example 5 and reacted. After the reaction, the reaction mixture is further treated according to Example 1 and 50 g of a polymer with a molecular weight of 6300 * 100 parts of ■ polymers overcame with 30 parts of carbon black mixed HAi ¹ ,, and, G is with 5.2 parts of 2,4-toluene diisocyanate and 0.1 parts of dibutyltin dilaurate and the mixture was heated for 2 hours at 100 ^0th Las networked

Product shows a tensile strength of 69 kg / cm and an elongation from $ 307

Example 6

30 ml of a solution of 10 mmol vinylcyclohexene diepoxide in cyclohexane are added to the living polymer according to Example 1. 30 ml of a solution of 100 mmol of ethylene epoxide in tetrahydrofuran are then added to the reaction mixture with vigorous stirring. The whole is left to stand overnight and the reaction product is decomposed with hydrochloric acid and washed with water and dried, whereby 50 g of a polyhydroxyl polymer with a molecular weight of 1800 (vapor pressure osmosis measurement) and with 2.1 hydroxyl groups per molecule and with 32 ^ Trans-1,4 units is obtained with 6 ° / o cis-1,4-units, and 62 ^c / o 1,2 units in the microstructure (IR method).

50 g of the polymer are dissolved in 200 ml of cyclohexane and ^{hydrogenated at 150 °} C. under a hydrogen pressure of 30-4G kg / cm for 1 hour. I & ei v / ground 5 g of catalyst in the form of nickel-diatomaceous earth (40 ^a / ° ITi) is used, which has been heated under a hydrogen atmosphere for 3 at 180 ⁰ C.

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The polymer obtained does not show any absorption Double bonds can be traced back (absorption bands at 970, 910, 740 cm ") in the infrared spectrum, but it shows

■ —1

Absorption bands of the methyl groups at 1380 cm and absorption

· -1

tion bands of the methylene group at 1470 cm

The molecular weight of the polymer is the same as that of the unhydrogenated polymer. 100 parts of the hydrogenated polymer are mixed with 30 parts of carbon black HAF, 13 parts of 2,4-toluene diisocyanate and 0.3 part of dibutyltin dilaurate and the mixture is heated ^{to 120 ° C. for 2 h for crosslinking.} The crosslinked polymer is a rubber-like elastomer,

ο which is not sticky and has a tensile strength of 102 kg / cm

and has an elongation of 380 fo .
Example 7

0.02 mole of naphthalene, 0.4 g atom of lithium metal, 0.3 mole of isoprene are added to 100 ml of diethyl ether under dried argon and reacted. 40 mmol of the dilithium starter obtained added to 500 ml of cyclohexane in a 1 1 flask and 50 g of butadiene are polymerized in the presence of this starter, wherein a living polybutadiene polymer ui '; a molecular weight from about 1250 is obtained.

30 ml of a solution of cyclohexane containing 20 mmol of epichlorohydrin are added to the solution of the living polymer and reacted. An excess of ethylene oxide is then added and reacted. The reaction product is left to stand overnight. The reaction product is then decomposed with hydrochloric acid, washed with water and dried, a polymer with a molecular weight of 2300 and about three hydroxyl groups in the molecule being obtained. 50 g of the polymer are dissolved in 200 ml of cyclohexane and at 80 ^° C. under a hydrogen pressure of 20-30 kg / cm

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for 10 h in the presence of a toluene solution of 0.8 mg atom Hydrogenated (nickel metal) of a soluble nickel catalyst. The nickel catalyst is made by reducing nickel naphthenate made by triethylaluminum.

The polymer obtained shows no absorption which can be attributed to double bonds in the infrared spectrum and it shows an absorption of the methyl group at 1330 cm "*" and an absorption of the methylene group at 1470 cm and a molecular weight of 2400, which is the same as that of the non-hydrogenated polymer . 100 parts of the obtained hydrogenated polymer v / ground with 30 parts of carbon black HAi ^1, 11 parts of 2,4-toluene diisocyanate and 0.3 parts Dibutylζinndilaurat mixed and the mixture is used for crosslinking for 2 hours at 120 ⁰ C heated. ' This gives a cross-linked product in the form of a _r gummia, rtigen elastomers, v / hich is not sticky and has a tensile strength of 110 kg / cm and an elongation of 430 ^u / i> has.

Example 8

A small amount of butadiene is polymerized using 40 mmoles of dilithium starter. The initiator is prepared by reacting γόη 0.02 mole of naphthalene, 0.4 g of metallic lithium atom and 0.3 mol Isopren'in Hiäthyläther 100 ml under an argon atmosphere obtained. The polymer is dissolved in 500 ml of cyclohexane and 50 g of butadiene are introduced and polymerized at room temperature for 3 hours, a living polybutadiene with a molecular weight of 1,250 being obtained. 20 mmoles of vinylcyclohexene diepoxide are added to the living polymer solution in a molar ratio of 0.5 with stirring. After 1 hour, 80 mmol of propylene epoxide are added. The reaction system is in the form of a gel. Therefore it cannot be stirred. The whole thing is left to stand overnight. Thereafter, 100 ml of methacrylic acid chloride were added and the reaction was carried out at room temperature for 5 hours.

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After the reaction niiBfflij the meag ^> of the gel product from. and the whole thing can be stirred. You get a milky, low-viscosity solution. ^ ö-JOi-tert-butyl-p-eresol are added as a stick ilisatotf and the polymer is through; Failures, off. To-luo! '- ^ methanol cleaned, and! ^{Dried 50 0} G in a vacuum. The polymer obtained has a molecular weight of -2600 and es. shows an absorption band at

-1
1? 20 cm "", which is ascribed to the carboxylic acid ester, in the infrared spectrum. An absorption band, which corresponds to the hydroxyl group and lies at 5500 cm, is not observed, 10 g of the polymer (functional polymer with polymerizable unsaturated groups) is dissolved in 5 g of styrene and 0.2 g of bensoyl peroxide is added and the mixture is added for 2 h crosslinked at 90 ⁰ C, with a guiBiBiartiges elastomer is obtained which is non-sticky,

Example 9

20 ibMoI epichiorhydrin. are added to 50 g of the living polymer according to Example 8, which has a molecular weight of 1,250. A molar ratio of 0.5 is chosen. 80 mmol of ethylene oxide are added after 1 h and the mixture is left to stand over Haoht in order to complete the reaction. 120 mmol of methyl methacrylate are added to the resulting gel polymers, and reacted for 30 minutes at mertemperatur and for 5 h at 70 ⁰ C. After the reaction, the product is purified and dried according to Example 8. A polymer is obtained with a molecular weight of 2700, which has the same infrared spectrum as that according to Example 8. The "" product is crosslinked according to Example 8 "and a rubber-like elastomer which is not sticky is obtained.

233330

Example 10

20 mMoi. Epiehlorhydrin in cyclohexane. are added to 50 g of the living polybutadiene having a molecular weight of 1250 according to Example 3. Compartment for 1 hour, 80 ml of propylene oxide in tetrahydrofuran are added to the reaction mixture and. the whole is monitored to "completion, allowed to stand the reaction of phthalic anhydride are furan mHol 80 in · tetrahydro -gegeben to the Gelreaktionsprodukt ■■ ', - to this at ZIM mertemperatur implement min and then at-7G ⁰ for 30... G. for 3 hours to give a uniform viscous solution, the egg product disappears ... 2,6-di-tert-butyl-p-cres oil is used as a stabilizer and a small amount of hydrochloride is added to the reaction mixture and the product is purified by precipitation from a mixture of toluene and methanol, a polymer having a molecular weight being obtained

—T

of 2800, which has no absorption at 3500 em, polygons would indicate hydroxyl groups. The Infrarat ^ - spektrura shows an absorption at 3500 - 3100 cm ~ which indicates associated carboxyl groups and an absorption at 1720 cm, which ^on: indicates an ester of a carboxylic acid, 10 g of the polymer (functional polymer having carboxyl groups) are mixed with 2 g Diglyei.dyl.äther of bisphenol A and 0.1 g ii, 17-j} imethylanil.in mixed and the mixture is during. 1Ch crosslinked at 120 ⁰ C, whereby a guminiartiges elastomer is obtained which is not sticky.

Example 11

10 ml-iol vinylcyclohexene diepoxide in tetrahydrofuran to 50 g of the living polybutadiene having a molecular weight of 1250 given according to Example 8 and it becomes. a. Mon 1-

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Ratio of O £ 5 chosen. After 30 min, 120 mmol propylene oxide are added to the reaction mixture and this is left to stand overnight to complete the reaction * ■ 80. mmoles of maleic anhydride in tetrahydrofuran are added to the gel reaction product. The reaction product is treated further according to Example 10, a purified “polymer” having a molecular weight of 1900, the infrared spectrum of which is identical to that according to Example 10, being obtained. 10 g of .des polymer (functional polymer with both carboxyl groups and polymerizable unsaturated groups) were dissolved in 5 g of styrene and 0.2 g of benzoyl peroxide are added and the mixture is ^{crosslinked for 2 h at 100 °} C., a rubber-like elastomer being obtained , which is not sticky.

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Claims (1)

PATENT CLAIMS 1. Process for the production of a functional polymer by living polymerization of a conjugated diolefin and / or a vinyl compound of the formula CH ₂ = C where R. is a hydrogen atom or an alkyl group and R "is a Means aryl group or a pyridyl group, whereupon the obtained living polymer is reacted with an epoxy compound is characterized in that the living polymer with haloalkylene oxide and / or polyepoxide in a molar ratio Clay is reacted less than 1.0, whereupon the polymer obtained is reacted with a honey epoxide. 2. The method according to claim 1, characterized in that " that in the first stage a molar ratio of the haloalkylene oxide and / or the polyepoxide to the living polymer of 0, ü5 - 1.0 is selected. 5. The method according to any one of claims 1 or 2, characterized in that a molar ratio in the first reaction stage of the haloalkylene oxide and / or the polyepoxide for the living polymer of 0.2-0.5 is selected. 4. The method according to any one of claims 1 to 3, characterized characterized in that the monoepoxide is ethylene oxide. 5. The method according to any one of claims 1 to 4, characterized in that the molar ratio of monoepoxide to Polymerem in the second reaction stage is more than 2. 309882/12 ?! 6. The method according to any one of claims 1 to 5, characterized in that the product of the second reaction stage is implemented with a proton donator. 7. The method according to any one of claims 1 to 6, characterized characterized in that the product of the second reaction stage is reacted with an acid halide or an ester of a carboxylic acid having polymerizable unsaturated bonds. 8. The method according to any one of claims 1 to 7, characterized characterized in that the product of the second reaction stage is reacted with an organic polycarboxylic acid anhydride. 9. The method according to claim 8, characterized in that the polymer obtained with garboxylate groups with a Proton donor is implemented. 10. The method according to any one of claims 1 to 9 »thereby characterized in that the product is hydrogenated. 309882/1221