DE2226370A1 - Prepolymers and cured products made therefrom - Google Patents

Description

PATENT LAWYERS

DR. W. SCHALK DIPL.-ING. P.WlRTH · DIPL.-I NG. G. DAN N EN BERG DR. V. SCHMIED-KOWARZIK · DR. P. WEl N HOLD · DR. D. GUDEL

6 FRANKFURT AM MAIN

CR. ESCHENHEIMER STRASSE S?

Case C-8689-G- Wd / Seh

TJNIOIf CARBIDE CORPORATIOiT 270 Park Avenue
New York, Έ.Ύ. 10017 USA

Prepolymers and cured products made therefrom.

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The invention relates to unsaturated prepolymers which are exclusively reactive functional at the end of each polymer molecule. Carry groups that can react with polyfunctional compounds and thereby hardened, crosslinked products and linear products high molecular weight. The invention also relates to liquid aliphatically unsaturated derivatives of these prepolymers, which are themselves still prepolymers and can be further converted to hardened, crosslinked products.

The production of essentially difunctional polymers from butadiene or isoprene by what is known as "living, anionic polymerization" is known from the literature. Living anionic polymerization means that the resulting polymer chains have a high proportion of branched structural units, which is due to the fact that predominantly 3-k and 1-2 polymerization takes place. Unsaturated prepolymers of this type are generally unsuitable for the production of cured, crosslinked products because they are usually destroyed at the double bond with age by attack by chemical oxidizing agents and by atmospheric ozone. Their applicability is therefore very limited. The hydrogenated derivatives of such prepolymers are usually solids or very viscous rubbers at room temperature and, as such, are not generally suitable for the manufacture of elastomeric, crosslinked products. This characteristic of such prepolymers can be attributed to their greater bulkiness and the resulting steroid inhibition of the bond rotation, which arises from the highly twisted jl \ and t-2 structures formed during living anionic polymerization. As expected, these materials have a high

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Inlet impurities and higher viscosities at a given temperature above that the glass transition temperature is desirable.

In accordance with this, saturated and unsaturated are essentially divergent. Lon oll e prepolymers produced that are free flowing liquid cuJLon. This property is due to the predominance of the 1-4-polyinol nation, which is obtained according to the invention by polymerizing ion with free radicals. It has been found that the prepolymers according to the invention normally have more than 90% 1 / j-polymerization addition. For example, a saturated prepolymer according to the invention which was produced by hydrogenating 1, / + - polymerized prepolymer with an isoprene skeleton is | ^{substantially} an alternating copolymer, it ¹ and j of ethylene "
. (Propylene This chemical structure is also reflected in the physical characteristics of the hj ^r drierten prepolymer again 01, 'u;. (U.) he gangs temper a door of the fully hydrogenated only from isoprene existing prepolymer is -65 ⁰ C, d It lies between polyethylene and polypropylene. Because of the static arrangement of the methyl groups on the polymer core, crystallinity is complete.

Dio (^ rf I tulungo-like saturated hydrocarbon prepolymers bonll.tfon a carbon / hydrogen ratio of essentially 1 Mn 2 without considering the reactive functions Enc groups. NiQ prepolymers according to the invention have a charaktor.i:; l.l.-u'hoü Number average molecular weight (determined by

from about 500 to about 6000. The molecular G is relatively tight. Hindostens 60 weight pi-üi - '. (! Iit , K-n prepolymers have a holocular weight within

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-Zf-

+ _ 33% of the average molecular weight of the prepolymer. The poly _: mers are essentially difunctional and only have reactive, functional end groups. In most cases, the average functionality is between 1.8 and 2.0.

The prepolymers of the invention comprise essentially amorphous, normally liquid, mainly random, through free Radically initiated copolymers from one or more diene monomers the following formula

R ₁ R ₂ R ^ R ^

(III

H-C = C-C = C-H

in which: R ₁ , R 2, R * and R, each hydrogen, lower alkyl radicals, lower alkoxy radicals, halogen or lower alkoxysilyl groups; R ₁ and R ~, taken together, can represent a 1,3-butadienylene group and R ₁ and R, taken together, represent a methylene, ethylene or propylene group; with the proviso that no more than two of the groups R in any monomer should be other than hydrogen; where the polymer should not be produced exclusively from a monomer in which R ₁ , Rp, R ^ and R, all denote hydrogen or R ₁ and Rp taken together denote a 1,3-butadienyl group. The prepolymers according to the invention have essentially no other reactive functional groups than an average of 1 to 2 functional end groups such as hydroxy, carboxyl, lower carboalkoxyl, metal carboxylic acid salt, lower alkanoyl, formyl, amino, halogen, nitrile, Isocyanate / oaor A :: iridinyl groups. The compounds preferred according to the invention have an average of 1.8 to 2.0 functional end groups.

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2 / U

The term "reactive functional group" as used according to the invention used refers to fertilizers other than unsaturated compounds that react with a polyfunctional crosslinking agent and three-dimensional cured products give and / or with a difunctional agent high molecular weight linear polymeric products result. Suitable crosslinking agents and difunctional agents and the products formed thereby are described herein.

Suitable according to the invention for the production of prepolymers Monomers correspond to the above formula. Suitable for example according to the invention as monomers: butadiene, isoprene, piperylene, 1,3-hexadiene, 2-ethyl-1,3-butadiene, 1,2-dimethyl-1,3-butadiene, 1,3-dimethyl-1,3-butadiene, 1,4-dimethyl-i, 3-butadiene, 1-methoxy-1,3-butadiene, 2-methoxy-1,3-butadiene, chloroprene, 1-chloro-1,3-butadiene, 1,2-dichloro-1,3-butadiene, i-chloro-2-methyl-1,3-butadiene, 1, / f-dibromo-1,3-butadiene, trimethoxy- (butadienylsilane), trimethoxy- (3-methylbutadienylsilane), Triethoxy (3-iaethylbutadienylsilane), Styrene, cyclopentadiene, cyclohexadiene and cyclopentadiene.

According to the invention, isoprene and mixtures are preferred as monomers of isoprene with other monomers within the range of the above general formula, at least 20 percent by weight

^ w ith safety / isoprene are contained in the mixture, so that normally liquid, non-crystalline prepolymers are formed after de-hydrogenation. It is further preferred that in the case of butadiene as a constituent part of the mixture of the monomers, the butadiene content is less than 20 percent by weight, since hydrogenated prepolymers with a higher butadiene content tend to be more resinous and crystalline.

The prepolymers according to the invention are generally by

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Initiation of the monomers or mixture of monomers by free radicals manufactured. As described herein, in the presence of a free radical azo initiator or organic peroxide polymerized, which are present in an amount to initiate the polymerization and allow the polymer chain to grow and ' complete or stop the chain when the desired molecular weight is reached. The preferred free radical formers Initiators are azoesters. The initiator asserts itself at the beginning of the Free radical-excited polymerization puts one reactive functional group at the beginning of the polymer chain and puts a second reactive

my besti ned parts Sj functional group at the other EndeVHieser Polyinerkette when the desired molecular weight is reached, thereby ending the polymerization. To obtain these end groups, the initiator is mainly used in amounts which far exceed the amounts usually used (from 0.01 to 0.1 percent by weight) and from 0.5 to about 30 percent by weight, based on the weight of the monomers be. If desired, the amount of initiator required can be reduced by using a chain transfer agent. It is preferred, however, not to use a chain transfer agent since the presence of such an agent tends to reduce the amount of purely difunctional polymer. From about 1 to 30 weight percent, preferably from about 1 to 10 weight percent, based on the weight of the monomers, a chain transfer agent can be used to stop the polymerization and add a reactive functional group to the terminal carbon atom. To put polymer chain.

Suitable chain transfer agents are, for example: ßC-broricobutyric acid, udder of the I-bromoisobutyric acid _/ \ yie methyl- ^ -bromiSwbutyrat, mono-, di- and jericiloroacetic acid and similar compounds,

the
/ are fähigt to halogen transfer reactions with polymer chain radicals be _T. Further chain transfer agents which can be used are isobutyric acid and its esters, thioglycolic acid, diethyl hydrogen phosphite and similar compounds which are capable of hydrogen transfer reactions with polymer chain radicals. .

The polymerization can be either bulk or solution polymerization be undertaken, the initiator usually being added as a solution in a suitable solvent. Suitable Solvents for the solution polymerization are solvents for the monomer, are compatible with the copolymer formed and inert with regard to the reaction components and the initiator. Aliphatic, aromatic and heterocyclic solvents are also suitable, provided they meet the abovementioned conditions Oxygen-containing solvents, such as t-butyl alcohol,

Dioxane and Tetrahydrofuran especially made for use together with peroxide initiators are suitable.

Suitable temperatures for the polymerization reaction are in the range of 25 ° C to 15O ⁰ C. The pressure (up to 50 000. 50 psig), preferably between 7 atm 3 atm _f 5-3500 to 1400th (100 to.

20,000 psig). Since the molecular weight depends on the pressure,

increasingj
can prepare prepolymers with / higher molecular weight

can be obtained at increasingly higher pressure.

The choice of the azo or organic peroxide initiator and the Kotten transfer agents, if their use is desired, is based on the reactive function of the group, which is aimed at the At the end of the polywoi-kotte is too solion, Boicpiclswoiso can be a polymer with oiji- ^ r Knrbo ^ ylondgruppc using dicarbon-

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Acid peroxides _f such as oxalic acid peroxide, sebacic acid peroxide, glutaric acid peroxide, succinic acid peroxide, cyclopropane-1,2-dicarboxylic acid peroxide and alkyl-substituted glutaric and succinic acid peroxides, for example methylglutaric acid peroxide and the like. These dicarboxylic acid peroxides can be prepared by reacting the dicarboxylic acid anhydrides with about 10 % aqueous hydrogen peroxide at temperatures below 30 ° C. in a time of 2 hours or less. Other initiators that give carboalkoxy end group polymers include azobisalkane carboxylic acids, e.g., dimethylazobisisobutyrate, diethylazobisisobutyric, esters of azobis-if-cyanopentanoic acid, and the like. The resulting ester end groups can, if desired, be hydrolyzed to carboxylic acid end groups. A suitable chain transfer agent for the introduction of the carboxylic acid end group is alpha-bromoisobutyric acid. The alkyl esters of alpha-bromoisobutyric acid and similar compounds introduce carboalkoxy end groups.

By neutralizing the carboxyl end group polymers with a suitable one Metal base, metal carboxylate end groups can be obtained. Suitable bases are sodium hydroxide, potassium hydroxide, zinc hydroxide, Tin hydroxide and the like.

Nitrile end groups can be introduced using azobisisobutyronitrile as an initiator. This initiator also makes it possible to introduce other functional groups at the end of the polymer chains. For example, the cyano group can be hydrolyzed to the carboxyl group in an acidic or basic medium. It can also be reduced to the amino group with sodium bis (methoxyethoxy) aluminum hydride or lithium aluminum hydride or converted to an alkoxycarbonyl group by alcoholysis. ⁽ . '

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Isocyanate end groups can be converted by reacting one amino end group bearing polymers can be obtained with phosgene or by the known Curtius reaction. ■.

Carboalkoxy end groups can be obtained by using diethyl 2,2-azobisisobutyrate (described in U.S. Patent 2,877,212) was introduced as an initiator. These groups can then become carboxyl groups hydrolyzed or reduced to hydroxyl groups.

Formyl end groups can be introduced by oxidation of a prepolymer bearing hydroxyl end groups with potassium dichromate.

Aziridinyl end groups can be introduced in such a way that in a prepolymer bearing hydroxyl end groups, the end group 'is replaced by chlorine and then the chlorine atoms with ethyleneimine implemented.

Halogen end groups can be introduced using halogen-containing chain transfer agents (as described above). Halogen end groups and carboxyl end groups can be introduced at the same time when a halogen-containing carboxylic acid chain transfer agent as described above) is used. The halogen atom can then be converted by dehydrobromination and the resulting double bond through subsequent oxidation to the carboxyl group being transformed"

The saturated and unsaturated prepolymers of the invention can be beneficial as pour point reducers in lubricants '' or fuel oils can be used. The mono-lithium and mono-sodium salts The carboxyl end group prepolymers are used as high-performance lubricants usable. Fully neutralized metal salts

'■ * ^M pour point depressaj ^' g gg q / γ

ORfGINAL

difunctional prepolymers can be used as thermoplastic elastomers. Cured or cross-linked prepolymers are flexible or elastomeric materials which are used as binders _/ for potting and encapsulation purposes. They can also be used as sound absorbing agents, electrical insulation or sealing agents. They can also be shaped into seals, for example window seals. The linear reaction products of the prepolymers can be formed into fibers or films, or made into a variety of useful articles.

The unsaturated prepolymers can, for example, by reaction halogenated with chlorine, hydrogen bromide, chlorine or bromine. The partially halogenated prepolymers can become saturated Prepolymers are hydrogenated. The properties and purposes of use these materials essentially correspond to those of the non-halogenated prepolymers, but also have high Flame resistance on.

In general, the prepolymers of the invention are made polyfunctional by mixing with about the stoichiometric amount of a. Crosslinking agent that has reactive groups associated with the functional End groups of the prepolymer to three-dimensionally cured Products can react, hardened. This is either heated, to achieve cure or to add a catalyst to cure at room temperature. On the other hand, it makes linear products obtained that you see the prepolymer with about dor stoichiofnotri Amount of a difunctional compound; the reactive group: possesses that with the functional end group of the prepolymer too high molecular weight linear products react, mixed and the

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Triggers a reaction by heating or adds a catalyst that allows curing at room temperature.

Polyfunctional crosslinking agents which contain groups which are linked with Carboxyl end groups react include, for example, polyepoxides

such as iriglycidyl ether of p-aminophenol, 2,4-epoxy-6-methyl-cyclohexylmethyl-3,4-epoxy-6-methylcyclohexane-carboxylate, diglycidyl ether of H, 2 ~ ßis (/ f-hydroxyphenyl) propane and the like; Polyisocyanates such as toluene triisocyanate, polyphenylmethylene triisocyanate and the like; Polyaziridines _χ such as tris (N-methylethyleneimine) phosphorus oxide, tris (N-methylethyleneimine) phosphorus sulfide * and the like; polyamines such as diethylenetriamine, triethylenetetraamine, tetraethylene pentamine, triaminobenzene, triaminonaphthalene and the like; polyols such as propylene triol, hexane polyols and polyols such as propylene triol, hexane polyols and the like; Similar crosslinking agents that contain groups that can react with hydroxyl end groups are, for example, polyisocyanates and polycarboxylic acids such as 1, 2, if-hexane tricarboxylic acid, 2-propyl-1,2, if-pentane-tricarboxylic acid, 5-octane-3 _} 3 , 6-tricarboxylic acid, 1,2,3-propane-tricarboxylic acid, 3-hexane-2,2,3, A - tetracarboxylic acid, 1 ^^, ^ - benzene tetracarboxylic acid, acid chlorides of these acids and the like Amino end groups can react, for example: polyisocyanates, polyepoxides and polycarboxylic acids _/ as described above, and the like t formyl end groups are, for example, polymethylolated phenols _; such as 2, ^, 6-trimethylolphenol, trimethylolated bisphenolsulfone, trinethylöl-p-tert-butylphenol, dimethy Γ-p-iaothylphenol, pyrocatechin, resorcinol _f hydroquinone, pyrogallol, hydroxyhydroquinone, phloroglucin and

phosphorous or sulfide " _t

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like that. Crosslinking agents and difunctional compounds, the Contain groups that can react with cyano end groups are, for example, 1,3-dipole-generating compounds such as p-phenylenebistrazole, Terephthalonitrile dioxide, isophthalonitrile dioxide and the like. Crosslinking agents and difunctional compounds,. which contain groups that can react with alkoxycarbonyl end groups are, for example, compounds that are used for transesterification with Alkoxycarbonyl groups are capable, for example diols and polyols v / ie described above. Crosslinking agents and difunctional compounds containing groups that react with aziridil end groups are, for example, di- and polycarboxylic acids as described above, diols and polyols as described above and the like.

Difunctional compounds that contain reactive groups that can react with carboxyl end groups are, for example, diols and diisocyanates, which form polyesters and polyamides, respectively; suitable diols are, for example, ethylene glycol, diethylene glycol, propylene glycol, Dipropylene glycol, glycerin and the like; suitable diisocyanates are, for example, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, bis (4-isocyanatophenyl) methane, polyphenylmethylene diisocyanate and the same. Difunctional compounds containing groups that react with hydroxyl end groups are for example Diisocyanates which, as described above, form polyurethanes and dicarboxylic acids that form polyesters, for example malonic acid, Succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, glutaoonic acid, muconic acid and similar prepolymer3, The amino end groups can be mixed with adipic acid to form polyamides implemented.

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The prepolymers according to the invention can contain fillers and / or additives for plasticizing, stretching, lubricating, preventing Oxidation or for coloring included. Such fillers and additives are generally "known and can be incorporated, without thereby departing from the scope of protection of the invention.

The prepolymers according to the invention are produced as described by free radical catalysis. This procedure is essential for the practice of the invention as it ensures that the reactive functional groups are at the ends of each Polymer chain are located. However, it can also be reactive fractional Groups are introduced into the prepolymer chain in such a way that the monomers described copolymerize with a monomer containing the desired end group. For example, a prepolymer containing carboxyl groups can be prepared if you have one of the monomers described and sufficient amounts of an alpha-unsaturated mono- or dicarboxylic acid brings about the reaction that 2 to / {. Carboxyl groups in each Polymer molecule are included.

The following examples are intended to explain the invention in more detail, but in no way restrict it. Unless otherwise stated, all percentages and parts are based on weight. In the examples, molecular weight is understood to mean the number average molecular weight = Pt ^ _1.

For β ρ ie 1 1

Production of an unsaturated prepolymer with ester end groups.

In a stirred autoclave reactor, 530 g of isoprene (dectil-

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liert to remove the inhibitor), 88 g of benzene and 1.72 g of dimethylazobisisobutyrate added under an inert atmosphere of nitrogen. The reactor was then heated to 89 ° C. under its own pressure (2.8 kg / cm 2 initially). Then a solution of 15.5 μl of dimethylazobisisobutyrate in 2 ^ 2 g of benzene was pumped into the well-stirred reactor over the course of 3.25 hours. During this loading time, the reactor was kept at a temperature of 89-9A- ⁰ C and a pressure of 2.8-5.6 kg / cm. After this time the reactor was cooled and the discharged contents evaporated in vacuo to remove unreacted monomer and benzene solvent. 5k g of a liquid polymer were obtained. The Brookfield viscosity was 9.6 poise at 23 ° C.

The determination of the polymer structure by nuclear magnetic resonance spectroscopy showed that more than 90% of the isoprene residues had a 1, / f polymer structure. The infrared spectroscopic analysis showed using DinethyltetramethylsbernstoinsäuroeGter as a comparison substance

-weight;
an ester equivalent of 1112. The molecular weight determination in chlorobenzene at y / C by vapor pressure osmometry gave a value of 2225. The analysis shows an average functionality of 2 ester groups per molecule.

Example

Production of a saturated prepolymer with an ester end group.

75 liquid polyisoprene, which was obtained according to Example 1, 150 g of methylcyclohexane solvent and 11.3 g of active Raney-Nickcl-Ilydrierungskatalysator were oinge in a shake bomb pressure vessel. The mixture was under pressure under pressure

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shaken from 70 - 280 kg / cm ² at 12 ^ to 135 ° C for 16.25 hours. After separating off the catalyst by filtration and vacuum evaporation to separate off the solvent, the saturated polymer was obtained as a clear, colorless oil. The Brookfield viscosity was 2100 poise at 25 ° C.

The infrared spectroscopic analysis confirmed the absence of double bonds by complete lack of double bond absorption near 6.1 microns wavelength. The equivalent weight, based on methyl ester end groups, was 1147 using dimethyltetramethylsuccinic acid ester as a comparative substance. As from the structure of a hydrogenated predominantly 1, Zf-polymerized Polyisoprene was to be expected "is. The nuclear magnetic resonance spectrum of the product practically not different from that of a 1: 1 ethylene / To distinguish between propylene copolymers.

Example 3

Preparation of an unsaturated polymer with potassium carboxylate end groups.

A. 10.3 g of the product obtained in Example 2 was heated with stirring and under nitrogen atmosphere to 19O ⁰ C. Then, while stirring and purging with nitrogen to remove the water vapor, 5.1 ml of 5j8b η-aqueous potassium hydroxide solution were added dropwise. 15 minutes after the solution had been added and all the water seemed to have been removed, the reaction mixture at first became very liquid. suddenly foot (at 190 ° C) and gave a white putty-like similar Fes Lkörjier, which assumed a rubbery character on cooling to room temperature. The product is completely insoluble

determined by infrared spectroscopy

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in heptane. The polymer was shown to have potassium carboxylate end groups by infrared spectroscopy.

Production of an unsaturated prepolymer with carboxyl end groups,

B. To the ionomeric rubber-like product described above, 10 ml of glacial acetic acid and 50 nil of heptane were added; After standing over During the night the solid had dissolved in the heptane phase and a crystalline precipitate had formed on the bottom of the reaction vessel Formed potassium acetate. After washing the heptane phase with additional acetic acid and then washing twice with water the heptane was distilled off. 7.8 g of a colorless liquid remained, which according to infrared spectroscopy

_t neutralized
Product was mTEjiiäFboxylendgruppen. The molecular weight determined by vapor pressure osmometry in tetrahydrofuran at 37 ° C. was 2434. The neutralization equivalent determined by titration with tetrabutylammonium hydroxide was 1253, which showed that the average functionality was 1.9% of carboxyl groups per molecule.

Example 4

Production of a saturated prepolymer with hydroxyl end / rruppon.

A. To a stirred suspension of 6.34 g of lithium aluminum hydride a solution became dropwise in 150 ml of anhydrous diethyl ether of 20 g of the product obtained according to Example 2 with ester end groups given in 50 ml · anhydrous diethyl ether. After completion After the addition, the stirred reaction was allowed to continue for another hour held at reflux and then the excess hydride through Hydrolysis destroyed. Hach distilling off the solvent from the

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18.7 g of colorless oil remained on the upper ether layer. By infrared spectral analysis, which showed the complete absence of ester absorption and the presence of intense hydroxyl absorptions, it was found that the chemical reduction of the ester end groups to hydroxyl groups was complete. The equivalent weight based on hydroxyl end groups by infrared spectral analysis was 1254 · The molecular weight determined by vapor pressure osmometry in chlorobenzene at 3 ° 0 was 2440 · The average hydroxyl functionality of the product was therefore 1.95 hydroxyl groups per molecule.

Production of a saturated, crosslinked, cured polymer.

B. The following components were combined and mixed under vacuum: 4> 9856 g of the saturated hydrocarbon described above diols, 0.1 / f29 g trimethylolpropane and 0.3406 g hexamethylene diisocyanate. The mixture was introduced into a Teflon-coated mold in which there were end pieces made of steel and there by standing at room temperature within 45 hours hardened. After removing the cured rubber sample from the mold, leaving the steel end pieces on the sample, the product had an elongation modulus of 6.68 kg / cm, an elongation strength of 0.98kg / cm and an elongation at break of 1300%. Excellent adhesion to the steel end pieces was observed.

Example 5

Production of an unsaturated prepolymer with polyester end groups.

208S60 / 11 40- ^; " ^: ■ ■

Λ. According to the method described in Example 1, 1374 G Isoprene polymerized, v / obei 51 g diethylazobisisobufcyrat in

10 % ± ger benzene solution within 2 1/2 hours

_o 2 were j

96 - 101 G and a pressure of 4 »78 - 5.62 kg / cm / i The product was obtained by valuium distillation of unreacted · Isoprene and benzene separated and then initiator residues removed by countercurrent extraction between heptane and methanol. ! laugh Distilling off the heptane were 389 S of a liquid polyisoprene obtained with ester end groups. The molecular weight was 2699 (vapor pressure osmometry in chlorobenzene at 37 ° C); the ester equivalent weight was 1320 (by infrared spectroscopy), indicating that the product was difunctional.

Manufacture of unsaturated potassium carboxylate prepolymers.

B. S 50.1 g of the above-described polyisoprenes with ester end was heated under stirring and under nitrogen to a temperature just above 100 G ^0. Then 31.7 ml of 5.89% aqueous potassium hydroxide solution were added dropwise with stirring and the V / ascor was distilled off by heating, the solution was added for 30 minutes and the water was distilled off. It was further heated up to 17.5 ° ^C. Fifteen minutes later, the originally liquid reaction mixture began to thicken and solidified into a rubbery mass on further heating. The spectral investigation of the mass showed that the ester groups had completely changed into the potassium salt groups, etc.

Hersi.öl.! Original of the unsaturated prepolymer r :: it

G, IVio described in Example 3. arde the solid chews.; - »cL ^: _; i: arl.ige product in ^ 6,92 Γ, d ^ s liquid Poiyiaopreus with XarLo- ^ leadg

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pen, whose neutralization equivalent was 1510. The molecular weight was 30AfO.

Example "6

Production of an unsaturated prepolymer with ester end groups.

stirred andj

An autoclave reactor was used which could be operated continuously, that is to say that reaction components could be fed in and the reaction product withdrawn at the same time. Were fed a blend of 60.75% isoprene, ₅ 37 71% benzene and 1.72% Diäthylazobisisobutyrat at a rate of 3.72 kg / hour at 131 ° C and a pressure of 63j3 kg / cm '. During the reaction time, the reactor was filled hydraulically and the contents removed continuously. After uniform "reaction conditions" had been achieved, the reaction components were fed in until 3.1 kg of product had been removed. The solvent was distilled off from this. 37 g of a polyisoprene "containing two ethyl ester end groups" per molecule and an ester equivalent weight were obtained from 1225.

Production of a saturated prepolymer with hydroxyl end groups.

B. 301 g of the product described above and 30.1 g of a Horshav / CuOAfOI-P copper chromite hydrogenolysis catalyst were placed in a shaking autoclave and heated to 1 / | 0 ° C. ^{under a V / acserctoff pressure of 2 / f6 to 313 kg / cm 2} . While the reactor was heated to -60 ° C, hydrogen was introduced while maintaining this pressure. After a total reaction time of 5 3/4 hours, the autoclave was cooled and the catalyst was filtered off. Kn.

* steady state oonult ^ _{ß Q}

were 2 f g of a clear colorless oil with a Brookfield visco-sity of 6 * f1 poise at 23 ⁰ C obtained. The glass transition temperature of this saturated hydroxyl group-terminated liquid polymer was determined by thermal penetration measurement. It was -59 ° C. The molecular weight of the product was 2433 (determined by vapor pressure osmometry in chlorobenzene at 37 ^° C.). When using neopentyl alcohol as a comparison substance, infrared spectroscopy showed a hydroxyl equivalent weight of 1226 and thus an average hydroxyl group functionality of 1.99 per molecule. It was also determined by infrared spectroscopy that there were no ester groups or double bonds left in the product.

Production of a saturated, hardened, crosslinked polymer.

C · The following "components were combined and mixed under vacuum: 4-0 g -des -obenbescliriebenen -diisocyanate, ~ 0.7S6 -g toluene diisocyanate and 0.0192 g toluene triisocyanate. The mixture was poured into a Teflon entered coated mold, in which there were end pieces made of steel and cured there for 72 hours at 80 ^° C. After this "" time, the rubber-like test piece together with the "steel end pieces" was removed from the mold and fixed in an "Instron" testing device The sample was elongated to breakage, found to have an initial modulus of 11.8 kg / cm, a yield strength of 2 _t 7 kg / cra, an ultimate elongation of 85%, an ultimate tensile strength of 5.3 kg / cm and an elongation at break of

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Example?

Production of an unsaturated prepolymer with hydroxyl end groups.

A. The boiling flask of a Soxhlet extraction device was filled with 10.6 g of the ester group-terminated polyisoprene obtained according to Example β , dissolved in 80 ml of anhydrous ethyl ether. The extraction thimble was charged with 0.3 g of lithium aluminum hydride which had been ground into small grains (^ Zf mm) and powder. The work was carried out under nitrogen with a water-cooled condenser. The ether condensate ran through the lithium aluminum hydride before it flowed back into the boiling flask. After: 5 minutes, sufficient hydride had been extracted to cause partial gelling of the reaction mixture in the boiling flask. However, when the extraction was continued, the gel dissolved again. After a total reflux time of 23 / k hours, the excess hydride was destroyed by hydrolysis and the prepolymer containing hydroxyl end groups was isolated from the ether layer. 10 g of a clear, colorless oil with an equivalent weight of 1,100 were obtained.

Manufacture of an unsaturated, hardened, crosslinked polymer.

B. The following ingredients were combined and mixed under vacuum: 5.2if23 g of the polyisoprene diol described above and O, Jf373 S toluene diisocyanate. The mixture was introduced into a mold and ^{cured at 80 °} C. for 72 hours, as described in Example 5. The resulting rubber-like test specimens had an initial modulus of 7.52. kg / cr: ² , a tensile strength of 3.98 kg / cm ~ and an elongation at break of 510 ^.

'>. 0 9 H Κ 0/1 I 4 0

Example 8

Production of an unsaturated prepolymer with ester end groups. A. 6860 g of freshly distilled isoprene were introduced into a stirred 19 l autoclave. After thorough purging with nitrogen, the reactor was sealed, heated to 10O ⁰ C. The intrinsic pressure was 562 kg / cm. Then a solution of 250 g diethylazobisisobutyrate initiator in 1980 g benzene at a Ge. pumped into the reactor at a rate of 7 g per minute. During the addition of the initiator, the temperature was maintained at 98 to 100 ⁰ C, while the pressure gradually to 7, k5 kg / cm increased. It took 5 hours to add the initiator. When all of the initiator had been added, a cooling coil located in the reactor was used in order to lower the temperature more quickly and to enable the reactor to be opened and the contents to be removed. Unreacted isoprene and the benzene solvent were then distilled off and the polymer recovered as a residue. 2912 g of the ester group-terminated polyisoprene were obtained. The product was a liquid with a Brookfield viscosity of 97 poise at 25 ° C.

Production of a saturated prepolymer with hydroxyl end groups. B. 1025 g of the above product together with 103.2 g of Harshaw Cu-1106-P copper chromite catalyst were introduced into a 2.8 liter shaking autoclave. The autoclave was first flushed with nitrogen and then pressed. 2 1/2 stumion was heated to 250 (', while Y / as ^ orstoff was scooped up to a pressure of 70, -5 I) Lf; ') öC l -' / cin '' au cheeky t'jujrhaL ton. Λη dl υ ί :; or Stolle vorlLof

2 0 Π 8 S 0/1 U 0

the reaction was exothermic, the temperature rising to 3O3 ° C and hydrogen being absorbed very quickly. After the exothermic course, a pressure of 267-306 kg / cm ^{2 was} maintained for 3 1/2 hours. The mixture was cooled to room temperature overnight, then the pressure was released, the reactor contents were removed, dissolved in 10 l of heptane and filtered to remove the catalyst. After distilling off the solvent, were charged 969 g of a crystal clear, colorless, liquid product obtained, the Brookfield viscosity 11ZfO poise "was at 28 ⁰ C and 28 poise at 83 ° C by infrared spectroscopy, it was confirmed that the ester end were completely reduced to hydroxyl groups and Polymer chain was saturated. The molecular weight of the liquid, hydroxyl-terminated product was ± 030 ± 160 (determined by vapor pressure osmometry in toluene at 37 ° C.). The hydroxyl equivalent was +15 in 1985 (determined by acetylation). Based on these results, the hydroxyl functionality is calculated to be 2.16 +0.18. If the error limit is taken into account, the polymer contains exactly 2 hydroxyl groups per molecule.

Example9

Preparation of an unsaturated ester group terminated prepolymer. A. Following the procedure described in Example 1, 1,374 grams of a C-5 fraction was obtained from a petroleum cracking process (containing 21% isoprene, M \% trans-piperylon, 9% cis-piperylene, and 11% cyclopentadiene; the remainder of 45% consisted of a mixture of relatively non-reactive monoolefins) at 95-10O ⁰ C using 51 g of diethylazobisisobutyrate, which within 1 1A hours in the

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Reactor was fed, polymerized. 121 g of pale colored oil were obtained. The molecular weight was 736 (determined by vapor pressure osmometry in toluene at 37 ° C). The ester equivalent weight was 374 (determined by nuclear magnetic resonance spectroscopy). The values show an ester functionality of 1.97.

Preparation of a saturated hydroxyl group terminated prepolymer.

B. By hydrogenolysis of 57 g of the product described above according to the method described in Example 6, 45 g of saturated liquid diol H = 905 (determined by vapor pressure osmometry in

ο received;
Toluene at 37 ° C./7 The OH equivalent weight was 450 (determined by nuclear magnetic resonance spectroscopy). A hydroxyl functionality of 2.01 was calculated.

Example 10

Preparation of an unsaturated ester group terminated prepolymer.

A. Following the procedure described in Example 1, there was 681 grams

Piperylene concentrate. (contained 42.84% trans-piperylene, 30.28% cis-piperylene, 1.82% isoprene; the remainder of 25% was a mixture of non-reactive monoolefins), the 2.02 g of diethyl azodiisobutyrate

₀ where

contained, polymerized at 88-91 ° C., a further 18.2 g of diethyl azodiisobutyrate initiator were fed into the reactor within 3 1/4 hours. 50 g of slightly amber-colored oil were obtained, the Brookfield viscosity of which at 26 ^° C. was 10 poise.

Preparation ^{1 of} a saturated hydroxyl-terminated prepolymer. >

B. As described in Example 6, this Polypiperylcn was with Diesterendgruppun hydrogenolyzed. Receive v.oirde thereby a ge; -

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saturated liquid diol with a hydroxyl equivalent weight of / f71 £ 21 (determined by acetylation). The molecular weight was 1097 + 50. A hydroxyl functionality is calculated from these values of 2.3 + 0.2.

Examples 11-19

Production of various unsaturated halogen-substituted ones Prepolymer "and polymers obtained therefrom»

According to the method described in Example 1, 789 S chloroprene was _{polymerized using a total of 15 S} 79 S diethylazobisisobutyrate, which was introduced into the reactor as a solution in 239> 6 g of benzene within 3 1A hours. 287 S of a polychloroprene with ester end groups (cf. Example 11 in the table below) were obtained as a dark amber-colored, very viscous one

Copolymers of chloroprene with butadiene (Examples 12 ~ 1ij.) With isoprene (Examples 15-17) and made with styrene (Examples 18 and 19). From the following The table shows the composition of the starting mixtures and the properties of the chloroprene-containing polymers.

A solution of 12 g of chloroprene hormone polymer (Example 11) in / y 0 ml Ether was tropfomveiso with stirring to 2.3 g of LiAlH. in 180 ml A'thcr given. After 1 1/2 hours of reaction there was then excess Hydride hydrolyzes and the reduced © Polychloroprene obtained as 10.1 g of a "dark amber-colored, very viscous oil", infrared spectroscopy showed the complete absence of the original

2O3SS0 / 1HQ-

lichen 1730 cm "'ester absorption and the presence of a strong

OH band at 3420 cm. A hydroxyl equivalent weight of 33 Ik was obtained by infrared spectroscopy using neopentyl alcohol as a comparative substance.

The reaction of this liquid polychloroprene with hydroxyl end groups Mi "c of the stoichiome trioch amount of toluene diisocyanate gave one hardened rubber with the characteristics of a vulcanized polychloroprene «

The butadiene-chloropron copolyester was used in a similar manner Esterond groups of Example 12 using lithium aluminum hydride in diethyl ether to give a product with hydroxyl end groups and an equivalent weight of ζΠΟ reduced (determined by Azotylioron). Thin layer chromatography of this product showed the presence of a single product, i.e. the diol.

By reacting the above product with the stoichiometric Amount of toluene diisocyanate results in a cured rubber with greater solvent resistance than a cured pcly: utadiene rubber.

The induction dos according to Example 1Ü hergostollen P .. "dakl :: ·: .. it Liliiiumaüu.-iiniiunhydrid in 'iOtrahyarcfuranlucungs ;; ::. ttel '.-:' gave a hydroxyl group en thai te rides styrene chloropr en-Co j lyr .. ::! · .... ri t an err. llydroirylaquivalontgov / ichl from 30uS. The product ϊ; λγ b, rl:. 'Aiimtc: .-.} /: · - ratur eLn -ohr vicko ^ or Our; ::. Ii and \? · Π · δ.ο unt -orhalL before. '' ■ '.. "C fostund onröde. Di ·' ¹ Kettehvorlängorung the product with u .orzilJ.l --sigo:;: Dii'3; oyanar- ν / Le ToJ.iioldiiaocyanat, iiap] ithrilindii3oc-y: u ! i; ': - - ^; r Paraph'ji:;,'! j: i: U ! .soeyan :; '; gives soluble, vhermoplasti ciu;: 1 · ... ^% ζο, the

2 0 3 8 5 0/1 U a

calibrated as air-drying coatings. Coatings made from this resin cure further due to the terminal isocyanate groups when they come into contact with moist air, and are thereby crosslinked and have excellent solvent resistance and etching resistance.

In the table:

* Λθ% initially ^mi "b eggs monomers added Diäthylazodiiso-

butyrate ** in methylcyclohexane, 8O ⁰ C

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Chloroprene polymers with ester end groups

example 11 12th 13th 14th 15th 16 17th 18th 19th Comonomer (g)
Chloroprene (g) 789.3 Butadiene
509
27.3 Isoprene
543.6
47.2 Stvrol Mole fraction
Chloroprene 1, 00 0.03 499
80 450
198.5 0.06 518
100.2 466.7
245.7 237.3
457.9 141.9
654.7 DSAB entered
feeds Cg) ** .15.79 20.98 '. 0.09 0.21 22.47 0.13 0.29 0.69 0.84 reaction time 21.32 22.05 22.73 23.40 18.65 18.75 ro
ο Yield Co
polymer (g) 287 129 147 · Ϊ8 50 / Specific
Viscosity** 0.074 0.057 145 192 0.061 176 220 276 t
302 ^ ro
- “OO
-P- I Saponification
number (M.equ / g) 1.146 0.934 0.055 0.065 0.787 0.059 0.077 0.069 0.069 O Weight%
chlorine 37.5 3.7 1.091 0.908 4.4 0.971 0.744 1.103 * 1,132 iodine number 19.2 367 11.2 14.7 299 8.4. 15.7 25.3 ^{32) 5} ro Brookfield
Viscosity
(Poice)
Solidification
point ( ⁰ C) -20 ° 23/23 ⁰ C.
<-70 ° 330 265 59/22 ⁰ C
-60 ° 306 224 21.8 ro.
23.7 ro 'Density (g / cm) 1.229 /
25 ⁰ C 0.919 /
17 ⁰ C 40/20 ⁰ C
<-70 ° ' 85/21 ⁰ C
-65 ° 0.921 /
23 ⁰ C 96/21 ⁰ C
-65 ° 19/22 ⁰ C
-56 ° 20 ° ro
05
CO
-J
σ
ο, ς 0.928 / 0.980 /
19 ⁰ C 0.944 /
15 ⁰ C 0.922 /
25 ⁰ C 1.138 /
24 ⁰ C. , 1ΓΓ41 /
25 ⁰ C

Example 20

Production of polymers from unsaturated, hydroxyl end groups bearing prepolymers.

A. Using the polymerization procedure described in Example 18 and the lithium aluminum hydride reduction described in Example Zf a hydroxyl-terminated polyisoprene with an equivalent weight of 1870 was prepared. Under anhydrous Conditions were 18.70 g (10.0 milliequivalents (meq.) Hydroxyl) of the diol combined with 1.848 g (21.23 meq. isocyanate) of toluene diisocyanate in 50 ml of dry pentane solvent. To this solution 0.05 ml of dibutyltin dilaurate were added and the reaction mixture was heated for 2 / f hours with stirring and reflux. Then the Mix for a further 22 hours at room temperature under dry nitrogen left atmosphere. Then a part was taken out and analyzed. The isocyanate content was determined by reaction with excess di-n-butylamine and subsequent potentiometric Titration of the excess amine with aqueous hydrochloric acid. The result shows that the pentane solution with toluene diisocyanate converted polyisoprene diol 0.1 ^ 2-n to unreacted isocyanate end groups v / ar.

30 ml of the above-described pentane solution were poured into a 6 × 25 cm glass dish and the solvent was allowed to evaporate overnight at room temperature. A sticky, soft, rubber-like film with a thickness of 25 mil was formed. After a further 2½ hours under ambient conditions, "the film was no longer sticky and could be removed from the glass shell as a coherent film

* 0.625 mm 209850 / 1UO

subtracted from. It had a tensile modulus (1%) of 28.8 kg / cm, a yield strength of

ρ ρ

10.5 kg / cm at 63% elongation and a tensile strength of 38.7 kg / cm break occurred at 500% elongation with the specimen regaining its original dimensions.

A faster curing rubber that vulcanizes at room temperature was obtained by adding 0.63 g (2.95 meq. amine) ^ -aminopropyltriethoxysilane to 20 ml (2.84 meq. isocyanate) of the solution of the diol extended with toluene diisocyanate. ¥ / enn that Pentane was removed by vacuum evaporation, a viscous resin remained which quickly formed a surface skin in moist air formed. Spreading the resin on a glass pad gave a v / cal but non-sticky overnight at ambient conditions Rubber. The resulting rubber adhered well to the glass surface.

The following mixtures were made from the above-described saturated, liquid hydrocarbon diol prepolymers, toluene diisocyanate (TDI) and trimethylo.lpropane (TMP).

Composition AB C DE

100 100 100

0.1Hf 0.023 0.1 Η;

4,678 4,2Zf.8 if, 505

1.015 0.966 0.977

O, O / + 81 0.0105 £ 0.04 l

After 70 hours of curing the above-mentioned mixtures at 80 ⁰ C in 9.5 x 9.5 x 50.8 mm Teflon becchichtoten forms with 9.5 x 9 x 19 ^ '- "r. Steel end pieces for attachment in the Instron tester were made

Parts prepolymer 100 , 026 100 , OZf 2 Parts TMP 0 , 491 0 , 551 Parts TDI k , 012 Zf , 020 NCO / OH ratio 1 1 Triol OH / total OH .0115 .018 relationship 0 0

steel end taps 209850 / TUO

9.14 ' 10.8 11 , 7 8.2 8th, 2.67 3.1 3 , 4 2.2 2, 150 125 110 150 13C 4.0 4.6 '5 , 7 2.9 4, 1400 990 875 1400 , 51 , 6 ) ,1 1260

the cured rubber samples are taken, the end pieces in the testing device attached and uniaxially tested at room temperature.

Composition AB C_DE initial module, kg / cm ² 9,

Yield strength, kg / cm Ultimate elongation, %

Tensile strength kg / cm

Elongation at break %

After the stretching, the test specimens were pulled back to their original position Dimension together. The test specimens B, C and E were due to a small bubble near the joint to the steel end piece, faulty .. The test specimens A and D showed within Instron tester travel limit is not an error. All test specimens adhered excellently to the steel end pieces to which they were vulcanized.

The cured rubber test specimens showed the influence of the crosslink density on the elongation properties. The test specimens A, B and C have a greater crosslink density than the triol content would result, since allophanates are formed from the excess isocyanate and the NH groups of the urethane bond. In the test specimens, the crosslinking density increases in the following direction: C>B> E > Λ>D; in the same direction the modulus and the tensile strength decrease and the elongation increases.

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Example 21

Preparation of a prepolymer with methoxy substituents and ester end groups. ·

A solution of 50 g of 2-methoxy-l, 3-butadiene, 10 g of benzene and 0.11? G Diäthylazobisisobutyrat (DEAB) was heated at atmospheric pressure under nitrogen to 76 · ⁰ C. A solution of 1.07 g DEAB in 25.83 benzene was pumped in within a reaction time of 7 hours. During this time the temperature of the reaction vessel was kept at 76-79 ° C. After distilling off the solvent and unreacted monomer in vacuo, 9 S of a slightly browned, semi-solid polymer were obtained which had a specific viscosity of 0.0Zf6 at 80 ° C. in methylcyclohexane. An ester content of 1.12 / f meq / g was determined by saponification.

Example 22

Following the procedure described in Example 21, 51 g of 1-methoxy-1,3-butadiene were prepared by adding a total of 1.197 g of DEAB within 3 hours and ^ minutes at 86 - polymerised> 88 C. The resulting prepolymer with ester end groups was a pale yellow oil with a specific viscosity of 0.026 (in methylcyclohexane) and an ester content of 2.92 meq / g (determined by saponification).

Example 23

Production of an unsaturated prepolymer with silyl end groups ..;

According to the method described in Example 5 a, a mini

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made up of ] 37k S freshly distilled isoprene and 68.7 S trimethoxy- (3-methyl-1,3-butadienyl) -silane

oil, - U

CH ₃ - O Si - CH = CH - C = CH

CH ₇ - O

polymerized 101 ⁰ C - using 5X DEAB g initiator in 11 g of benzene Jf within 1 1 / Zf hours at 97th After distilling off the solvent and the unreacted monomers, 3 ^ 3 S of a liquid polymer were obtained. The presence of silyl groups in the polymer was confirmed by infrared spectroscopy (by the absorption at 1573 cm, which is characteristic of CC double bonds in vinylsilanes). The ester equivalent weight of the product was 1201.

If. Glass pads with aqueous emulsions of the above Copolymers treated, there was better adhesion when a rubber such as styrene-butadiene rubber on the treated Glass pads was vulcanized.

Example 2 / f

Production of an unsaturated prepolymer with ester end groups.

A. After the continuous polymerization described in Example 6 was a mixture of 30.29% isoprene, 30.29? o butadiene, 37.71% benzene and 1.71% DEAB at a rate of 3, ^ 6 kg / Stcl is pumped into the continuously stirred reactor. The reactor

209850 / 1UQ

- 3k -

was kept at a temperature of 130-131 C and a pressure of 63.3-73 »8 kg / cm. Under continuous conditions, 1.34 kg of monomer and initiator were pumped into the reactor. The product removed during this time was worked up by distilling off the solvent and the unreacted monomer. 287 g of a liquid polymer with a Brookfield viscosity of 21.2 poise at 2Zf ⁰ C. were obtained. This product had a saponification equivalent weight of 985 and a molecular weight of 1962 (determined by vapor pressure osmometry in chlorobenzene at 37 ° C.). From the ester content and the "Wij's" iodine number of 351, a corrected iodine number for the end groups of 379 is calculated. The correspondingly corrected iodine number for an isoprene homopolymer is 350 and for a butadiene homopolymer is kk5 Obtained copolymers of 0.33.

Production of a saturated prepolymer with hydroxyl end groups.

B. Hydrogenolysis of the above polymer according to the procedure described in Example 6 using a copper chromite catalyst gave a fully saturated liquid product. This saturated polymer had a Brookfield viscosity of W33 poise at 25 ° C. The molecular weight was 2179 (by vapor pressure osmometry in chlorobenzene at 37 ° C). The hydroxyl equivalent weight was 1070 (by infrared spectroscopy with lioopentyl alcohol as comparison substance). This gave a calculated hydroxyl group functionality of 2.0 / f. per molecule. ^r Le glass transition temperature dos saturated liquid diol was -64 ⁰ C (as determined by thermal penetration measurement).

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100 601 100 100 100 0 0.044 0.228 0.496 8th, 058 8,643 8,983 9.467 0 0.0104 0.0518 0.1062 1, 1.052 1.048 1.040

Production of hardened, saturated, cross-linked polymers.

C. From the above liquid diol, trimethylol propane (TMP) and Toluene Diisocyanate (TDI) the following mixtures were prepared:

Composition AB C_ D

Parts diol

Parts TMP

Parts TDI

Triol OH / total OH NCO / OH

After thorough mixing in vacuo, these mixtures were placed in 9.5 x 9.5 x 50.8 mm Teflon-coated strain specimen molds with 9.5 x 9.5 x 19 mm steel end pieces that were bonded to the test specimen as it cured . The 'forms were stored in an oven at 80 ^° C. for 2 days and then removed. They then contained well cured rubbery test samples. These were tested in an Instron tester and showed the following values:

Composition AB £ D

Initial module, kg / cm

Yield strength, kg / cm "extreme elongation, $ tensile strength, kg / cm elongation at break %

11 , 3 10 , 5 17th 50 19 4th 2 , 95 3 , 51 k, VJl 77 90 100 15th 3 80 4th , 51 4th , 6 8th, 8th, 12th 760 620 525 3.15

Examples 25 and 26

Comparison of prepolymers with a high butadiene content.

After the procedure described in Example 1, isoprene, butadiene, Benzene and DEAB in one under a nitrogen atmosphere

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stirred autoclave. ■ After heating to the polymerization temperature a solution of DEAB in Benzene is pumped into the reactor. The table below shows the quantities introduced into the reactor, the reaction conditions, the ' Yield and a product description can be found.

The ester-terminated copolymers were then in the presence of a Copper chromite catalyst, as described in Example 6, hydrogenolyzed. In contrast to the results of Examples 6, 24 and 25 were the saturated hydrogenolyzed copolymers with higher butadiene content not completely flowable at room temperature. The product of Example 25 was partially crystalline and possessed the Consistency of a thick fat with a melting point of 40 to

Example . 25 26

Initial charge (g)

Butadiene. . 470.6 344.0

Isoprene 52.3 186.1

Benzene "90.5 92.0

DSAB 1.17 1.19

Feed during the reaction (g)

Benzene 2 / _f 5.6 249.8

DEAii 10.3B 11.57

Reaction condition ;; un ;; en

Temperature, ⁰ C 88-91 88-91

Pressure (kg / cra ^) 12.7-13 4.2-12

Response time (3 days) 3 3/4 3 I / 4

Yield (g) -86 91

20985PMU3

• - 37 -

example

Properties before hydrogenolysis Product description kl £

Brookfield viscosity determined, .25 ° C Specific viscosity, 8O ⁰ C solidifying point ⁰ C Estergehalt by saponification

V / i j's iodine number corrected iodine number butadiene mole fraction

Properties after hydrogenolysis Product description fe

Brookfield viscosity Specific viscosity solidification ^{temperature, 0} C molecular weight * hydroxyl equivalent weight

* "By vapor pressure osmometry in toluene at 37 ^{C 1} C.

26th

s colorless' clear colorless oil oil 45.7 poise 34.21 poise 0.076 0.069 <-70 ° <-70 ° 0.689 meq / g 0.725 meq / g 403 379 438 413 0.93 0.66 OC
1 ·
it's gray fat cloudy straw color benes oil —- · 1340 poise 0.092 - 0.082. + z _f 0-45 ° -58 ° 3290 2446 1586 1264

Examples 27 and

Comparison of styrene / butadiene »and styrene / isoprene prepolymers.

According to the method described in Example 1, mixtures of styrene and isoprene or butadiene were polymerized under autogenous pressure at 89-91 using DEAB initiator which forms free radicals. Details of the two polymerizations and the
Product analyzes can be found in the table below.

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The ester-terminated liquid styrene copolymers were then used hydrogenolyzed by the method described in Example 6 in the presence of a copper chromite catalyst.

In the case of the butadiene / styrene copolymer, the product was the Hydrogenolysis of a white fat with a specific viscosity of 0.081 in methylcyclohexane at 80 ° C. The product had a Molecular weight of 2900 and an equivalent weight of 1376 (determined by acetylation).

Example 2? 28

Initial charge (g)

Styrene 157.5

Isoprene

Butadiene

Benzene 92.2

DSAB 2.1

Feed during the reaction (g) benzene
DEAB

Reaction conditions temperature, ⁰ G pressure (kg / cm ^) reaction time (hrs.) Yield (g) (Koptan soluble) specific viscosity Brookfield viscosity, poise eater content (Mäqu. / G) Wij's iodine value % styrene (corrected by

Iodine number) 31.2 22.8

429 5 167 0 97 9 2, 22nd

250.3 265.9 20, if 21.6 89-91 89-91 10-14.3 4.6-9.1 3 1/4 3/4 149- 154 0.0626 ^ 0.0648 * 80 at 23.5 ° C 169 at 24.3 ⁰ O 0.815 0.795 323 288

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Example 27 28

Set point, ⁰ C -65. -42

N _d 3O 1.5222 1.5210

Density. 0.926 0.930

H- in methylcyclohexane at 80 ^° C

The isoprene-styrene copolymers was after the hydrogenolysis a cloudy, slightly colored oil having a Brookfield viscosity of 2080 poise at 24.5 ° C and a specific viscosity in Methylcyklohexan of 0.079 at 80 ⁰ C. This product had a hydroxyl equivalent weight of saturated I46O (determined by acetylation) and a molecular weight of 2840 · This gives a hydroxyl group functionality of 1.95 <ie molecule.

The two styrene copolymers were converted into unsaturated diols by reduction with lithium aluminum hydride.

Example 29

Mr. division of an unsaturated prepolymar with nitrile end ;; group.

Λ. T-Tach d :::: in the Beioirir ;! 8 processes described were 6.86 kr lijoju-on ut ^ r Vcrv; -.: - j ₄ ; huir: from 2 / + 7.5 G A-obisiGcbutyronitril (AIBN) air; Initiator which was dissolved in 2.64 kg benzene, under GJnern egg _t ', oi; pressure from 4.57 to 7.38 k ^r / cn durcli gleichihoßigeo Einspeißor: innerhaib of 6 3/4 hours of reaction time polynori-'

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sated. After vacuum evaporation for removing benzene and non polymerized isoprene of the crude residue was (2.47 kg) dissolved in 5-times its volume of pentane, cooled to -50 ⁰ C, to remove unreacted AIBN and its principal decomposition product Tetramethylbernsteinsäuredinitril deposit. The cold solution was filtered and pentane was distilled off from the clear filtrate. 2.5 kg of a prepolymer with nitrile end groups and a molecular weight of 3615 were obtained.

Production of a saturated prepolymer with amine end groups.

B. Following the procedure described in Example 7, 102.67g of the above-described polyisoprene with nitrile end groups dissolved in 400 ml of absolute ether and a Soxhlet extraction apparatus filled. 2.817 g of lithium aluminum hydride were placed in the extraction thimble and refluxed and heated under a dry nitrogen atmosphere. To After three hours of extraction, a portion was removed from the boiling flask and worked up by hydrolysis. By doing no nitrile absorption could be determined by infrared spectral analysis. After a total reaction time of 4 1/2 hours, the reaction mixture was allowed to cool to room temperature and then excess LiAlH ^

209880/1 UO

destroyed by adding water. The ether layer was dried by filtering over anhydrous Na-SO, and that Solvent distilled off. 91 »4 g of a clear, slightly amber-colored oil were obtained. In the absence of the CdN absorption at 2200 cm in the infrared spectrum is confirmed, that the nitrile group from the AIBN initiator is complete is reduced. Amine groups were detected by absorption at 3300 and 3500 cm ". Hydrobromic acid in acetic acid was then used to titrate the amine groups to the blue-green end point of the crystal violet indicator is used. The titration gave an amine equivalent weight of 1652. Vapor pressure osmometry in chlorobenzene at 37 ° C gave a molecular weight of 3300. The calculated amine functionality was 2.0 amine groups per molecule.

Manufacture of a cured, crosslinked polymer.

C. The reaction of this liquid polyisoprene diamine with the stoichiometric amount of a diepoxide or a diisocyanate gives a cured rubber.

Example 30

Production of an unsaturated prepolymer with carbpxyl end groups.

Following the procedure described in Example 29, the weight was 1.2 kg Isoprene using i + 5 g of azobiscyanovaleric acid as a slurry in 719 g of a 4: 1 t-butyl alcohol / benzene

209850 / 1H0

Mixture was pumped over 3 1/2 hours, at 96 - 10O ⁰ C polymerized. 376 g of a prepolymer with carboxyl end groups and having a neutralization equivalent of 1327 were obtained. This product was cured by reaction with the stoichiometric amount of a di- or tri-functional epoxide or aziridine.

Example 31

Production of a saturated, brominated prepolymer with ester end groups.

A polyisoprene with ester end groups and a molecular weight of 2838 was prepared by the method described in Example 8. 5.32. g of this product were dissolved in 100 ml of CCl and treated with 10 ml of a 0.5 M solution of bromine in CCl, the bromine being added to all vinyl groups attached to the 1,2-polymerized isoprene residues. While JBrom was instantly absorbed and decolorized by the polyisoprene solution, no evolution of HBr was observed. However, after 9 ml was added, HBr smoke began to develop. The brominated product was obtained by first washing the CCl ^ solution with (0.1-n) v / aq NaOH and then distilling off the solvent.

The brominated polyisoprene obtained in this way contained 12 percent by weight Bromine and is an effective flame retardant.

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Example 32

Preparation of a low molecular weight prepolymer.

According to the method described in Example 6, a poly * isoprene with ester end groups and a molecular weight of 803 manufactured. The lower molecular weight was due to a higher concentration of feed to the reactor DEAB (7.4%) achieved. By hydrogenolysis of the product in the presence a saturated liquid diol having a molecular weight of 760 was obtained from copper chromite.

Example 33 "

Preparation of a high molecular weight prepolymer.

A polyisoprene with ester end groups and a molecular weight of 5030 was prepared by the method described in Example 6. The higher molecular weight was obtained by using a lower concentration of DEAB fed to the reactor (1.03%). After hydrogenolysis with copper chromite, a saturated liquid diol with a molecular weight of k790 was obtained.

209850 / 1U0

Claims (1)

Claims lower alkyl groups, lower alkoxy groups, halogen or lower alkoxysilyl groups; R and R _{p taken} together can mean a {l3utadienylene group and R 1 and R p, taken together, mean a methylene, ethylene or propylene group, with the proviso that not more than '. zv / ei of the groups R in any monomer can be radicals other than hydrogen; where the polymer * cannot be produced exclusively from a monomer in which R ₁ , Rp, R ^, and R ^ all denote hydrogen or R. and Rp taken together denote a 1,3-butadienylene group; wherein the prepolymer has essentially no other reactive, functional groups than an average of about 1 to 2 of the functional end groups: hydroxy, carboxyl, lower carboalkoxyl, metal carboxylic acid salt, lower alkanoyl, formyl, amino, halogen, Contains nitrile, isocyanate and / or aziridinyl groups. 209850 / 1U0 2, prepolymer according to Claim 1, characterized in that each polymer molecule has an average of about twelve 1.8 to 2 reactive, functional groups on the end Jiohlenstoff carrying atoms. 3. prepolymer according to claim i ^ - characterized by that the polymer is made from one or more of the following monomers: isoprene, piperylon, cyclopentadiene, Chloroprene, butadiene, styrene, 2-mothoxy-1,3-butadiene, 1-methoxy-1,3-butadiene and trimethyl-1,3-butadienyl-silane. l \, prepolymer according to claim! / ^ characterized in that the polymer is made from isoprene or a mixture of isoprene and one or more of the following monomers: piperylene, cyclopentadiene, chloroprene, 'butadiene, styrene, 2-methoxy-1,3 -butadiene, 1-methoxy ^ 1,3-butadiene and trimethyl-1,3-butadienyl-silane. 5. A substantially amorphous, normally liquid aliphatically saturated prepolymer that is derived from a random prepolymer initiated by free radicals from one or more diene monomers of the formula ₃ ^ I Il I H-C = C-C = C-H in which: R., R-, Rz and R, in each case hydrogen, lower alkyl radicals, lower alkoxy radicals, .halogen or ■■■■> 0 98SOArUO- lower alkoxysilyl groups; R ₁ and R taken together can mean a butadienylene group and R and R taken together can mean a methylene, ethylene or propylene group with the proviso that not more than two of the groups R in any monomer can be radicals other than hydrogen; wherein the polymer cannot be made exclusively from a monomer in which R., R ₂ , R * and R ^ all denote hydrogen or R. and R "taken together denote a 1,3-butadienylene group; the prepolymer having essentially no other reactive, functional of the groups than about 1 to 2 functional on average End groups: hydroxy, carboxyl, lower carboalkoxyl, Metal carboxylic acid salt, lower alkanoyl, formyl, amino, halogen, nitrile, isocyanate and / or aziridinyl groups contains. 6. prepolymer according to claim 5, characterized in that that there are an average of 1.8 to 2.0 reactive, functional groups on the end carbon atom of each polymer molecule wearing. .5-6, 7. prepolymer according to claims, characterized in that the polymer is made from one or more of the following monomers: isoprene, piperylon, cyclopentadiene, Chloroprene, butadiene, styrene, 2-methoxy-1,3-butadiene, i-methoxy-1,3-butadiene and trimethyl-1,3-butadienyl-silane. 209850 / 1U0 222637Ü -7 8. prepolymer according to claim 5> characterized in that the polymer is made from isoprene or a mixture of isoprene and one or more of the following monomers is: piperylene, cyclopentadiene, chloroprene, butadiene, styrene, 2-methoxy-1,3-butadiene, 1-methoxy-1,3-butadiene and Trimethyl-1,3-butadienyl-silane. 9. Curable composition, characterized in that it is a substantially amorphous, normally liquid prepolymer according to claims 1-4 or 5-8 and a polyfunctional crosslinking agent, which has reactive groups which react with the reactive functional groups of the prepolymer can contains. . 10. Composition according to claim 9, characterized in that the Monomers consists of at least about 20 percent by weight isoprene. 11. Hardened mass according to claim 9. 12. High molecular weight linear reaction product from an im essentially amorphous, normally liquid, aliphatically saturated prepolymer made from a free radical initiated random polymers from claims 1-4 or 5-8 and a difunctional agent, the reactive groups possesses, which can react with the reactive, functional groups of the prepolymer, has been produced. 209850/1 UO