DE1620974C3 - Practically linear dicationically reactive homo- or copolymers with recurring ether units and processes for the production of linear dicationically reactive polymers or copolymers of tetrahydrofuran - Google Patents

Description

The invention relates to practically linear, dicationically reactive homo- or copolymers with recurring ether units and processes for the production of linear, dicationically reactive ones Polymer or copolymer of tetrahydrofuran. The new polymers show a high reactivity as alkylating or acylating agents. They are actionable e.g. B. block copolymers, polymeric diamines, polymeric dithiols, polymeric diisocyanates, bisphenols that form a polymeric bridge and other polymeric derivatives.

Polymers with high reactivity are used to modify physical and chemical Properties highly desirable, e.g. B. the adhesive strength of the polymer to metals and glass improve and polymer-analogous chemical reactions such as simple substitution reactions, crosslinking reactions, To carry out chain extension reactions, graft and block interpolymerizations, etc. Over the production of reactive polymers with anionic character was reported by M. S ζ w a r c et al., Journ. Amer. Chem. Soc. 78, 2656 (1956), and coined the term "living polymers". Polymers with such a living character behave as no chain termination reaction would have taken place.

In the article "Polymerisation des Tetrahydrofurans", Ang. Chem. 72, 927-1006 (1960), described Meerwein, Delfs and Mοrsche 1 the production of polymers of tetrahydrofuran in which one (1) of the end groups is cationically active or "living" is. Of course, such polymers only react at this one cationically reactive end.

According to the invention, "living polymers" of a dicationic nature are proposed, while those in contrast to the anionic "living polymers" that attach oxygen in the presence of air and thereby lose their "living" character, are quite stable in the presence of oxygen. Another The important difference between cationic and anionic "living polymers" is that Ability of the former to further increase in the presence of certain cationically polymerizable monomers polymerize. The cationic and anionic "living polymers" differ significantly in their reaction of compounds containing active (i.e., reacting in the Zerewitinoff reaction) hydrogen atoms exhibit. "Living polymers" of an anionic nature attack such compounds in a nucleophilic manner Way, d. H. a proton is applied to the polymer with the formation of an inactive, not a functional group transferring more containing polymer, while the cationic "living polymers" these compounds in an electrophilic manner to form macromolecules containing functional substituents, and attack a free proton. This significant difference can be seen e.g. B. in the reaction of the two types of "living polymers" with ammonia. When "living polymers" of anionic If the character reacts with ammonia at all, the protonated, non-functional polymer is formed as well as the free amide ion, while the cationic "living polymers" form with ammonia of the functional polymeric amine or amide and a free proton react. The reaction of the "Living polymers" with ammonia (or amines) is a remarkably easy one Reaction which is quantitative conversion at temperatures usually below 25 ° C and at atmospheric pressure supplies in the alkylated or acylated amines. The dicationically active polymers are therefore at their to recognize bifunctional alkylating and acylating capacity.

The object of the invention is to produce novel and useful polymers which have a high Have levels of polycationic activity, creating polymeric alkylating and acylating agents and the development of a process for the production of tetrahydrofuran polymers with "Living" properties from cationically polymerizable monomers and for the production of derivatives these polymers are based on.

According to the method proposed according to the invention, practically linear polycationically active ones

Polymers available. These polycationically active polymers are due to their reactivity towards Ammonia characterized, which - if at least a two-fold molar excess of ammonia and a temperature of 25 ° C or below is applied - rapidly with formation polymeric poly-primary diamines or diamides in which the functional groups mentioned are in the end positions of the polymer chain. These terminally dicationically active polymers can continue to be characterized by their ability to polymerize monomeric tetrahydrofuran initiate at 25 ° C, which is reflected in an increase in the molecular weight of the polymer as a result of attachment of repeating oxytetramethylene groups at the ends of the originally polycationically active Polymer shows.

The practically linear dicationically active polymers of the invention are produced by direct conversion of monomers in dicationically active polymers using certain catalysts that are defined below. According to a further process which is not the subject of Invention is, pre-formed polymers in the molecular weight range of 400-100,000, the specific have functional groups, converted into dicationically active polymers. Under »practical linear polymers "are relatively long-chain polymers to understand that on the Main polymer chain may have substituents, but these substituents are generally of a much shorter chain length than the main chain. Usually the chain length is of these substituents less than half the chain length of the main chain.

Direct manufacture of
dicationically active polymers

Certain acid polymerizable (i.e., cationically polymerizable) monomers can be used directly in practical linear, dicationically active polymers are converted. Tetrahydrofuran and sym-trioxane are preferred monomers in this regard. Tetrahydrofuran provides a dicationically active polyether with repeating oxytetramethylene groups and is particularly preferred.

Dicationically active polyether copolymers can, for. B. from tetrahydrofuran or sym-trioxane and little (i.e., less than 50 mole percent) of another acid polymerizable or interpolymerizable cyclic ether (or cyclic thioether), such as. B. propylene oxide, ethylene oxide, glycidyl methacrylate, Styrene oxide, ethylene sulfide, propylene sulfide or epichlorohydrin can be produced. The usage another cyclic ether as a comonomer in the tetrahydrofuran system is often desirable, to lower the melting point of the dicationically active polyethers and the low temperature flexibility the derivatives produced therefrom, such as. B. of products made by hardening from the polyethers manufactured polyether diamines with epoxy resins which have more than one epoxy group per molecule, be obtained to improve.

The polymerization of tetrahydrofuran - alone or in a mixture with other acid-polymerizable monomeric cyclic ethers - must be carried out in the presence of certain catalysts. These catalyst molecules may be viewed as consisting of two components for the sake of convenience will. Although some of these catalyst molecules are dissociable, it should be noted that they are not any useful catalysts will necessarily dissociate to a discernible extent. For example it was found that 1 mole

CF ₃ SO ₂ -OO ₂ SCF ₃ -

a non-conductive compound suitable as a catalyst - when added to about 10 moles Tetrahydrofuran (which is also non-conductive) is a solution with high electrical power at room temperature Conductivity supplies. Accordingly, it can be assumed that the polymerization of tetrahydrofuran - with or without an additional cyclic ether monomer - by heterolytic cleavage of the catalyst molecule to form a first component that quickly attaches to the oxygen atom of the Tetrahydrofuran attaches to form a complex cation, and a second component or anion is introduced. Although the specific mechanism of the reaction is not fully understood, one would Hypothesis that the catalysts must have ionic constituents, consistent with the well known cationic mechanism of tetrahydrofuran polymerization. With both of them Components of the catalyst molecule are meant here those parts of the molecule that during the Initiation of the tetrahydrofuran polymerization act as cation or anion donors.

A first class of useful catalysts can be represented by the general formula DQ will. Q corresponds to a radical which, in anionic form, is an anion that is associated with the Polymerization of tetrahydrofuran does not stop the growth of the polytetramethylene oxide chain. The rest of D corresponds to the remainder that occurs after a hydroxyl group has been detached from a monobasic acid (im Connection to this referred to as "catalyst base acid"), which is stronger than 100% sulfuric acid and which able to effect cationic polymerization of tetrahydrofuran remains. The ability of one strong acid to polymerize tetrahydrofuran can be easily determined. The strong acid can with Tetrahydrofuran (0.02 mol of acid to 1 mol of tetrahydrofuran) mixed and the whole react at 25 ° C be left. A polytetrahydrofuran yield of more than 50% after 1 week indicates that the strong Acid is a suitable catalyst base acid.

The cationic polymerization of tetrahydrofuran using acid catalysts has been reported in the literature, so that there is no need to discuss in detail the testing of the various monobasic acids for their usefulness for this polymerization. Acids that are effective tetrahydrofuran _{polymerization catalysts include FSO 3} H, ClSO ₃ H, HClO ₄ , HJO ₃ , CF ₃ SO ₃ H, and C ₄ F ₉ SO ₃ H, and the corresponding D radicals derived from these acids are FSO ₂ -, ClSO ₂ -, ClO ₃ -, JO ₂ -, CF ₃ SO ₂ - and C ₄ F ₉ SO ₂ -. In addition, the catalyst acid must be an acid which has virtually no chain transfer activity in the polymerization of tetrahydrofuran. Accordingly, chlorosulfonic acid is not a suitable catalyst parent acid because it has the ability to transfer chloride ions to growing polytetrahydrofuran chains under normal conditions and to act as chlorine substituents

to add chain-terminating substituents (cf. J. Furakawa and T. Saegusa, "Polymerization of Aldehydes and Oxides", p. 232, Interscience Publishers, New York, 1963). As a result, provides ClSO ₂ - D no useful component of the catalyst molecule is when polymerization temperatures above - be applied 1O ⁰ C. At lower temperatures, the chain transfer activity of catalysts containing ClSO2 groups is suppressed to a point at which these catalysts are quite useful for the production of practically linear dicationically active polyethers. Residues that are preferred as D components include FSO2-, CIO3- and RfSO ₂ -, where Rf is a polyfluoroaliphatic radical according to the definition given below, such as, for. B. a radical CF3-, means.

The Q component of this class of catalysts which are used in the production of dicationically active polymers corresponds to a radical which, in anionic form, is an anion which does not cause chain termination during the polymerization of tetrahydrofuran. It has been proven that the previously known polymerization of tetrahydrofuran always takes place according to a cationic mechanism, ie that the growing polymer chain contains a single cationically active end group, and that the ability of the polymer to add further monomer molecules and to increase the molecular weight of the maintenance of a single one cationically active site depends. Many anions react with this electrically charged site to produce a chain termination through a charge neutralization reaction, which either consists of a coupling reaction in which the anion (such as Cl-, Br-, NO ₃ -, CN-, CH ₃ CO ₂ - and CH ₃ SO ₃ -) combined directly with the polyether cation to form an electrically neutral compound, or from a transfer reaction in which part of the compound anion - usually as a halide ion - to form both a neutral polyether molecule and either a neutral compound, which is derived from the original anion, or a new anion with a lower electrical charge than the original anion. Examples of the latter type are ClSO ₃ - and the complex anions, which are derived from relatively weak Lewis acids such as TiCU, ZnJ ₂ , SiF ₄ and SeBr ₄ . A distinguishing feature of the process according to the invention, as far as the direct conversion of monomers into dicationically active polymers is concerned, is the fact that the polymerization takes place simultaneously at the opposite ends of the practically linear growing polymer chain.

A particularly useful class of anions or Q radicals that do not lead to a chain termination reaction are those that are derived from extremely strong protonic acids, such as FSO ₃ -, ClO ₄ ^- and RfSO ₃ -, where Rf is a polyfluoroaliphatic radical (which means polyfluorocycloaliphatic Radicals are included) with 1-18 carbon atoms and at least one fluorine atom on the «carbon atom. Rf can also be hydrogen atoms and other halogen atoms, such as. B. chlorine atoms, except for the fluorine atoms and interrupted by oxygen or amine nitrogen atoms, provided that these oxygen or nitrogen atoms are next to a fluorine-substituted carbon atom. Rf is preferably at least half fluorinated, ie preferably at least half of the monovalent atoms on the carbon atoms of the Rf group are fluorine atoms. Rf can e.g. B. a perfluoroalkyl radical (cf. US Pat. No. 2,732,398), a perfluorocycloaliphatic radical, a 3-hydroperfluoroalkyl radical (cf. US Pat. No. 2,4 03,207), an ω-chloroperfluoroalkyl radical (cf. US Pat. No. 2,877,267) The radical H (CX ₂ CX ₂ ) / j-, in which two substituents X, which are connected to a carbon atom, are fluorine atoms and the remaining substituents X are either hydrogen atoms or halogen atoms (such as, for example, chlorine, fluorine). Examples of specific Rf groups include
the trifluoromethyl,

the pentafluoroethyl,

the heptadecafluorooctyl,
the undecafluorcyclohexyl,
the 1,1,2,2-tetrafluoroethyl,
the 2-hydrohexafluoropropyl,

the 1,1-difluoroethyl,

the l, l-difluoro-2,2-dichloroethyl and
the 8-chloroperfluorooctyl group.
Another class of usable anions or. B. BF ₃ , SBF ₅ , SbCl ₅ , AsF ₅ and PF ₅ , derive. Examples of such anions which do not cause chain termination are BF ₄ -, SbFo ^- , SbF ₅ (O ₃ SF) -, SbCl ₆ -, AsF ₆ - and PF ₆ .

A general method that can be used to determine whether a particular anion causes chain termination or not is to carry out the cationic polymerization of tetrahydrofuran in the usual way using a known acid catalyst, but with the addition of a soluble salt containing this anion, to the polymerization system so that the effect this anion has on the polymerization reaction can be examined. For example, monomeric tetrahydrofuran and a small amount (such as, for example, 1 mol% of the total monomer mixture) ethylene oxide using 2 mol% (based on the total monomer mixture) boron trifluoride as the polymerization initiator can be polymerized under temperature conditions which result in at least 50% conversion of the monomers into polymer lead such. B. at 20 ^° C. If the same reaction is carried out with the addition of 2 mol% of a dissolved salt containing the anion in question, any significant decrease in the degree of conversion and / or in the molecular weight of the product formed indicates that the anion belongs to the group of chain-breaking anions. For example, lithium bromide, lithium nitrate, silver trifluoroacetate and silver cyanide cause reductions in the degree of conversion, so that no more than 10% polymer is formed, which shows that Br, NO ₃ , CF ₃ CO ₂ and CN chain-terminating anions. On the other hand, if identical reactions are carried out in the presence of silver perchlorate, silver trifluoromethanesulfonate, lithium hexafluorophosphate and silver hexafluoroantimonate, no significant influence on the amount of polyether formed or on its molecular weight can be determined, which shows that ClO ₄ -, CF ₃ SO ₃ -, PF ₆ - and SbF ₆ - do not cause chain termination.
Anhydrides, which are effective catalysts of the formula DQ, include pyrosulfuryl fluoride, ie (FSO ₂ J ₂ O (where FSO ₂ - D and FSO ₃ - Q), (CF ₃ SO ₂ I ₂ O (CF ₃ SO ₂ - and CF ₃ SO ₃ -) and Cl ₂ O ₇ (ClO ₃ -

and CIO4-), as well as the corresponding mixed anhydrides, such as FSO ₂ -OO ₂ SCF ₃ . Salts which are effective catalysts for preparing the dicationically active polyethers of the invention include

FSO ₂ F- PF ₅₁ CF ₃ SO ₂ F- SbF ₅ ,

SF ₃ SO ₂ Cl SbCl ₅ and ClO ₃ F BF ₃ ,

as

FSO ₂ + PF ⁶ -, CF ₃ SO ₂ + SbF ₆ -,

CF ₃ SO ₂ ⁺ SbCl ₆ - or CIO ₃ ⁺ BF ₄ - can be understood.

A second class of catalyst which can be effectively used for the preparation of the dicationically active polyethers of the invention by direct conversion of monomers are certain diesters of the abovementioned catalyst base acids, ie fluorosulphonic acid, the polyfluoroaliphatic sulphonic acids (ie of the formula RfSO ₃ H) and perchloric acid, and a diprimary glycol. This class can be given by the general formula

DZCH ₂ (A) _n CH ₂ ZD

are reproduced, where D has the meaning defined above and preferably a fluorosulfonate, a polyfluoroaliphatic sulfonate (such as, for example, RfSO ₃ -) or a perchlorate radical, A a difunctional organic radical which is free from acetylenic and olefinic bonds and free from alkylatable groups which contain Zerewitinoff hydrogen atoms (such as, for example, hydroxyl, amino, thiol and carboxyl groups) and preferably an alkylene or oxyalkylene radical or a radical consisting of repeating oxyalkylene units, Z is oxygen or sulfur and η O or 1 is. Particularly preferred catalysts of this class are 1,4-butane bis (fluorosulfonate), 1,4-butane bis (trifluoromethanesulfonate) and the corresponding esters of poly (tetramethylene) glycol. These compounds are conveniently prepared by a direct method in which pyrosulfuryl fluoride (fluorosulfonic anhydride) or trifluoromethanesulfonic anhydride is reacted with tetrahydrofuran. If stoichiometric amounts of these anhydrides and tetrahydrofuran are reacted at ⁰ C to -3O ⁰ C O, the 1,4-Butandiester is obtained in good yield. If excess tetrahydrofuran is used in this reaction, the resulting diester will contain oxytetramethylene repeating groups and the average molecular weight of the product will vary almost directly with the molar excess of tetrahydrofuran used.

Regarding the reaction conditions in the direct polymerization reaction are considerable Variations possible. It is important, however, that these reactions are carried out in a system that is relatively free of chain terminators. Under "chain termination" there is a chemical one To understand reaction during polymerization in which a cationically charged end of a polymer chain neutralized and one end group that practically no further under the polymerization conditions Has alkylatability, is attached to the previously cationically charged end part of the polymer chain. The polymerization according to the invention gives a product in which practically all chain ends are cationically active. The presence of chain terminators (i.e., compounds listed under the selected reaction conditions are only monoalkylatable, such as. B. soluble halide salts, Acyl halides, alcohols, acids and anhydrides, which are much weaker than fluorosulfonic acid), the are alkylated by the cationically active ends of the polymer chain, leads to the formation of a substantial one Number of inert end groups that prevent further chain growth. Some substances that normally viewed as a chain terminator for polymerization reactions other than those described herein are, lead in the process according to the invention under certain polymerization conditions no disadvantages. In particular, polyalkylatable compounds, such as. B. Connections, the two or have more active hydrogen atoms, such as water, alkylene or polyalkylene ether glycol, with two cationically charged polymer chain ends react and in this way act as chain extenders serve. Water can be combined with a dicationically active polymer to form a monocationic one active polymer react with a hydroxyl group, and the hydroxyl group of this product can easily be replaced by another dicationically active polymer to form a new dicationic active polymer of increased chain length alkylated will. The fact that the polymerization system according to the invention may contain water, is very advantageous from an economic point of view. Accordingly need polyalkylatable Compounds in amounts up to that stoichiometrically equivalent to the catalyst concentration is not necessarily to be excluded in the preparation of the dicationically active polymers.

While the use of a solvent is often not essential, an inert solvent may be desirable to moderate the rate of the reaction or to allow easier handling of the reaction mixture. Suitable solvents include methylene chloride, the fluorohalocarbon solvents, the cycloalkanes (such as, for example, cyclohexane). The temperature in this reaction is generally -40 ° C to + 7O ⁰ C when tetrahydrofuran is used, although the use of other monomers such as of sym-trioxane, temperatures can be used up to 100 ⁰ C. When solvents are used, it is normally desirable to carry out the reactions at lower temperatures such as, for example, hold at -2O ⁰ C to + 4O ⁰ C, and the solvent concentration below 40 wt ° / o.

The molecular weight of the polymers obtained can vary within a wide range; H. from 400 to 1,000,000. An effective method of controlling molecular weight is to use suitable choice of the molar concentration ratio of catalyst to monomer. If higher If molecular weights are desired, this molar ratio is preferably between 0.001 and 0.01 while the lower molecular weights are generally chosen at a molar ratio of from 0.01 to 0.5 can be obtained.

Indirect production of
terminally polycationically active polymers

Although the direct process for the preparation of the dicationically active polymers of the invention is extremely is useful, it is generally specific

609 539/437

cationically polymerizable monomers are limited, as explained above. Very versatile is an indirect process for the production of terminally polycationically active polymers where a preformed polymer (i.e. a prepolymer) is used as the starting material, which is used in has its end positions and only there certain functional substituents and otherwise of alkylatable groups (such as, for example, olefin, amine, hydroxyl, thiol or carboxyl groups) is free. The at The prepolymers that can be used in this process can be divided into two categories:

I. Polymers, the terminal —OH or —SH (or the alkali salts of these groups), —COOH or —SO3H groups, can be terminated in Polycationically active polymers can be converted by mixing them with either one to none Chain termination reaction leading catalyst base acid or with certain, defined below Reacts derivatives of such acids, the catalyst acid being capable of being cationic as such Initiate polymerization of tetrahydrofuran. More precisely, the terminal polycationic active polymers are prepared by mixing the above-mentioned prepolymers with catalyst base acids, their anhydrides, their acyl halides or an alkylenebisester of the structure

DZ-CH ₂ - (A) _n -CH ₂ -ZD

converts, wherein D, Z and A have the meaning defined above. Examples of such parent catalyst acids and their derivatives are

FSO ₃ H, (FSO ₂ ) ₂ O, FSO ₃ -C ₄ H ₈ -O ₃ SF,

SF ₃ SO ₃ H, (CF ₃ SO ₂ ) ₂ O, CF ₃ SO ₂ Cl,

CF ₃ SO ₃ (C ₄ H ₈ O) ₂ O ₂ SCF ₃ , HClO ₄ ,

Cl ₂ O ₇ and ClO ₄ -C ₄ H ₈ -O ₄ Cl.

These conversion reactions which lead to the terminally polycationically active polymers are Condensation reactions in which as a by-product either a salt, water, a hydrogen halide or an acid (i.e. the catalyst parent acid or the derivative) are formed, depending on the nature of the derivative, which is used to convert the prepolymer to its cationically active state. Such Condensation reactions can be carried out in a way that is evident from the polymer modification is well known. It is often desirable to use a dehydrating agent or a Acid acceptor to use, usually in stoichiometric amount, or as a solid heterogeneous phase, to the Inactivate by-product. In the terminally polycationically active polymers obtained, can they are polyesters, polythioesters or mixed polyanhydrides. They are by their ability characterized to initiate the tetrahydrofuran polymerization with the formation of block copolymers, as well as their remarkable ability to alkylate or acylate. Those terminally polycationic active polymeric products that differ from polymeric polyols and polythiols (or their equivalent Alkali salts) are excellent alkylating agents; as are the products that are part of the Reaction of the above-mentioned alkylenebisesters with polymeric polycarboxylic acids or polysulfonic acids are formed. In the terminally polycationically active polymers that are used in the implementation of polymeric polycarboxylic acids and anhydrides or the corresponding acyl halides, it is mixed anhydrides, which are remarkably effective as acylating agents.

II. Polymers containing terminal acyl halide groups (i.e. carbonyl or sulfonyl halide groups), preferably acyl chloride or acyl bromide end groups, can be converted into polymeric mixed anhydrides by treating them with a non-chain terminating acid (i.e. a catalyst base acid), which is capable of the

ίο initiate the polymerization of tetrahydrofuran, or a salt of such an acid, preferably a silver salt, is reacted. Examples of reactants which are suitable for the production of terminally polycationically active polymers from the above-mentioned prepolymers include FSO ₃ Ag, CF ₃ SO ₃ H, CF ₃ SO ₃ Ag, HClO ₄ , and AgClO ₄ .

Prepolymers with two or more terminal reactive groups, which are used for the production of cationically active polymeric compounds are suitable by the indirect method, can can be made in different ways. Polymers containing terminal hydroxyl groups are well known. Several polyethers containing two terminal hydroxyl groups are readily available on the market available substances such. B. Polyethers of various molecular weights, which differ from the ethylene oxide, Derive propylene oxide and tetrahydrofuran. Polyoxymethylene polymers that contain hydroxyl end groups, are also obtained in the ionic polymerization of formaldehyde or sym-trioxane. Branched chain Polyethers which contain more than two terminal hydroxyl groups can be polymerized of ethylene oxide in the presence of a basic catalyst and a polyol that has more than two Contains hydroxyl groups are produced. The use of trimethylolpropane or pentaerythritol as a reactant in the polymerization of ethylene oxide thus leads to the formation of a branched one Polyethers with three or four terminal hydroxyl groups. When such branched substances as Prepolymers are used, the products obtained have a terminal cationic Activity of more than 2.

Polyesters that contain hydroxyl end groups are improved by the use of excess polyol in the Condensation has been made with a dicarboxylic acid. The molecular weights of these polyesters are achieved through a suitable choice of the degree of conversion of the "monomers" (i.e. the polyol and the dicarbon

acid) and the excess of polyol used.

Vinyl polymers that differ from ethylenically unsaturated. Derived saturated monomers and terminal hydroxyl groups are included using suitable free radical initiators such as z. B. hydrogen peroxide.

Processes for the preparation of polymers with terminal thiol groups are also known. Polymers with terminal thiol groups can be obtained by adding a small excess of hydrogen sulfide or from alkylenedithiols to alkylenebisesters of acrylic and methacrylic acid as described in US Pat. No. 3,397,189. A second process for the production of polymers with two terminal thiol groups consists in the condensation of certain organic dihalides with a slight excess of sodium sulfide or polysulfide. In another method for

The production of polymers with terminal thiol groups are polymers with terminal thiol groups Carboxyl groups reacted with mercaptoethanol.

Polyester or poly-N-alkylamides, the terminal ones Containing carboxyl or sulfonic acid groups, by condensation of a small excess of one suitable dicarboxylic acid (or disulfonic acid) with a polyol or an amine with two or more secondary amino groups are produced. Monomers that when treated with an organic Polymerize dilithium compound (such as styrene, which when using 1,2-diphenyl-1,2-dilithiumethane polymerized as a catalyst), deliver when treated with carbon dioxide or with sulfur dioxide and an oxidizing agent, polymeric dicarboxylic acids and difulsonic acids, respectively.

Terminal acyl halide groups (i.e., carbonyl and sulfonyl halide groups) can be added to polymers can be produced by various methods. For example, polymers containing free acid groups can be used contain, by reaction with phosphorus pentachloride or thionyl chloride or bromide in the desired Prepolymer derivatives are converted. The use of a small excess of an alkylene or arylene diacyl chloride (such as adipyl chloride, terephthaloyl chloride or ρ, ρ'-diphenyldisulfonyl chloride) offers the possibility of producing polyesters or polyamides with terminal acyl halide groups, such as B. sulfonyl halide groups. Implementation of excess phosgene with Polymers containing alcohol groups is another way of introducing terminal Acyl halide groups - in this case chloroformate groups - in the prepolymer.

With respect to the reaction conditions to be used in the indirect process for the preparation of the cationically active polymers, considerable variation is normally possible. If uncrosslinked, soluble, terminally polycationically active polymers are desired, such as. B. as reactive intermediates for subsequent chemical modification reactions, it is usually desirable to use a prepolymer which has a molecular weight of 400-20,000 and contains the required functional groups in the end positions of a linear or branched chain. The use of about five times the stoichiometric amount of catalyst base acid or its derivative, based on the number of functional groups to be converted, is normally preferred for the production of an uncrosslinked product. If an acid acceptor is desired, the prepolymer can first with a tertiary amine, such as. B. triethylamine, are mixed in an amount that is just sufficient to neutralize the acid formed by the reaction. (If a prepolymer with terminal alkali alkoxide or alkali mercaptide groups is used, the use of additional acid acceptor is usually not necessary.) The selection of the reaction temperature is normally not of decisive importance. It can be applied, a preferred range of from -80 ⁰ C to 100 ⁰ C, although the reaction rate at lower temperatures may be undesirably low. Inert, anhydrous solvents are often used in the indirect process; suitable solvents have already been mentioned. The prepolymer used as starting material can contain various other groups along its chain apart from those mentioned above, provided that these are inert to the action of the derivative of the catalyst master acid used in the reaction and to the alkylating or acylating capacity of the polycationically active polymer obtained. For example, ester, ether, nitro and halogen substituents can be present in the polymer without the

ίο Production of polycationically active polymers to disturb after the indirect method.

From the above description it can be seen that for the preparation of the cationically active polymers the invention a large number of prepolymers can be used, the appropriate terminal functionally contain groups, such as. B. Polymers based on styrene, vinyl chloride, vinyl alkyl ethers, Esters of acrylic and methacrylic acid and / or vinyl esters, and polymeric compounds such as polyesters and polyether.

Reactions from
polycationically active polymers

As already mentioned above, the polycationically active polymers prepared according to the invention are more remarkable Alkylating or acylating agents and can actually be alkylated or Acylating ability can be characterized. Furthermore, they provide effective polymeric initiators for the further polymerization of acid-polymerizable monomers, the products being block copolymers can be obtained. Many other useful products can be polycationic using this active polymers are produced as intermediates if one uses the highly electrophilic Exploiting the nature of these macromolecules.

Inorganic or organic compounds (including polymeric substances) which contain active hydrogen atoms, in particular compounds with -OH, -COOH, -SH, -SO ₃ H and -NHR 'groups (where R' denotes a hydrogen atom, an alkyl radical or an aryl radical ), react easily with the polycationically active polymers of the invention, these reactions being essentially alkylation or acylation reactions in which the polymer chain alkylates or acylates the electronegative group to which the active hydrogen atom is attached. Suitable compounds that contain active hydrogen atoms include water, hydrogen sulfide, ammonia, urea, hydrazine, aniline, methylamine, mercaptoethanol, glycolic acid, polymers of acrylic acid, vinyl alcohol polymers, succinic acid, glycine, proteins, piperazine, triethylene.

tetramine and ethylene glycol. The products of these alkylation or acylation reactions are therefore the corresponding polymeric derivative and the catalyst master acid obtained. In many cases it is a Acid acceptor is desirable in order to convert the strong catalyst acid formed as a reaction product neutralize. This neutralization is often necessary in order to avoid undesirable side reactions. In the alkylation or acylation of amino compounds, such as. B. of amines and ammonia, can be used for

To neutralize the acid product, an excess of the amino compound can be used. In cases where the Reaction proceeds rapidly, e.g. B. in the alkylation of an alkyl mercaptan, an acid ac-

septor, like ζ. Β. Pyridine, can be used, preferably in stoichiometric amounts.

The reaction temperatures are generally not of critical importance. It has a range of -8O ⁰ C to 150 ⁰ C were found to be suitable, although the low temperatures have (such. As below 25 ° C) to moderate the reaction rate generally preferred proved. The use of an inert solvent is not always necessary and in some cases even undesirable. Suitable inert solvents have been mentioned above. The regulation of the concentrations of the reactants is important in alkylation and acylation reactions using the cationically active polymers. In determining the optimal proportions of the reactants, the functionality of the reactants, whether or not an acid acceptor is required, and the desired end product should be taken into account, as is well known to those skilled in the art. The functionality of the compound to be alkylated or acylated corresponds to the number of alkylatable or acylatable groups present in the molecule, multiplied by the number of times the group in question can react with the cationically active sites on the polymers prepared according to the invention. Water z. B. has a functionality of 2, since each water molecule can react with two cationically active sites on the polymer. If water reacts with a cationically active site on the polycationic polymer, a polymeric polyol is obtained as the product; if the water reacts with two cationically active sites, the product obtained is a polymeric polyether. Similarly, ammonia having a functionality of 4 can react with the polycationically active polymeric alkylating agents to form a polymeric primary, secondary, or tertiary amine or quaternary ammonium salt. If the polymeric primary amine is desired, therefore, one uses a large excess of ammonia, such as. B. at least a 5-fold stoichiometric excess.

The following explanations serve to further explain the effects, functionality and concentration of the reactants exert an influence on the nature of the reaction products. When connected to two active hydrogen atoms are reacted with a polymer with two cationically active groups, the product obtained is a chain-extended linear polymer if the molar concentration ratio the reactant is kept close to 1: 1. When containing two active hydrogen atoms Compound is used in excess, preferably at least 2 times the stoichiometric Excess, the disubstituted polymeric product with remaining functional groups is favored. This process provides a possibility for the production of low molecular weight polymeric dithiols or dicarboxylic acids by using alkylenedithiols (or H2S) or dicarboxylic acids in excess. When a compound with 3 or more active hydrogen atoms with the dicationically active polymer with two cationically active groups is implemented in an approximately stoichiometric quantitative ratio is called The main product obtained is a crosslinked polymer whose properties are determined by a suitable choice of Reactants can be varied.

In the case of a polycationically active polymer with more than two cationically active groups in the; End positions of a branched chain is the product that, when implemented with a connection with a j single active hydrogen atom is obtained, an i

simple substitution product, while the conversion j

A crosslinked polymer is obtained with a compound having two or more active hydrogen atoms;

can be. I.

The polycationically active polymers of the invention

manure continue to react with numerous metal salts j (such as, for example, potassium cyanate or sodium phenolate) according to ', the principle of double conversion, where j products are the polymer formed during the alkylation of the anion of the salt with the cationically active polymer, and the salt of the common catalyst acid can be obtained. ^Such: salts of alkali metals. Example, lithium iodide, sodium cyanide, potassium cyanate, <sodium bisulfite, sodium bisulfite, sodium hydroxide, Mo j nonatriumadipinat, disodium succinate, potassium hydrogen phthalate and sodium are preferred, particularly when they are very soluble in the reaction medium, although salts such as calcium and silver cyanide can also be used. These reactions can be carried out either in homogeneous solutions or in heterogeneous dispersions. These reactions represent a preferred process for the preparation of the desired derivative of the cationically active polymers, since up to now the catalyst acid has not been released and an acid acceptor is not required.

The above reaction of the polycationically active polymers of the invention with metal salts is similar to the above-discussed alkylation of compounds containing active hydrogen atoms in that the functionalities and concentrations of the reaction; participants here also have an effect on the structure; of the product. Various processes are often possible for the production of the desired terminally polyfunctional polymers. So you can polytetramethylene oxide, the primary amino groups as; Contains end groups, by any of the following ^: Process: (A) reaction of the dicationically active tetrahydrofuran polymer with ammonia in the manner described above, (B) reaction with lithium azide and subsequent reduction of the azide groups obtained into primary amino groups, (C) reaction with lithium cyanide and subsequent Hy-; dration of the terminal nitrile groups to primary amino groups, (D) reaction with sodium p-nitrophenolate and subsequent hydrogenation of the nitro groups to primary amino groups, (E) reaction with lithium phthalimide and subsequent reaction of the imide groups obtained with hydrazine to give the desired primary amino groups. Certain of these reactions can occasionally be used to great advantage when side reactions are to be avoided, such as e.g. B. polyalkylations that occur in the reaction of the polycationically active polymer with a compound having several active hydrogen atoms, such as. B. ammonia, normally occur to a minor extent. So if you want a polymer which contains amino groups only in the form of terminal primary amino groups, the reactions with lithium azide or phthalimide described above under (B) or (E) generally give better results than the reaction of the polycationically active polymer with ammonia .
The polycationically active polymers of the invention

fertilization continue to react with such aromatic compounds, which lead to a Friedel-Crafts reaction are capable of forming the ring-alkylated or ring-acylated derivative. Benzene and many of its derivatives enter into this reaction. Ring alkylation of benzene is practical in about 4 hours at 78 ° C completely finished. If electron donor groups or electron repelling groups (such as Alkyl, alkoxy or hydroxyl groups) are present, the reaction is greatly accelerated, and the alkylation occurs mainly in the o- and p-ring positions. On the other hand, if the ring is electron-attracting Groups (such as halogen, nitro or trifluoromethyl substituents) are present, the reaction will noticeably slowed down. In fact, p-dichlorobenzene, nitrobenzene and benzotrifluoride have one sufficient poor reactivity to be used as an inert solvent in these reactions to be able to.

The alkylation and acylation of aromatic compounds with these polycationically active Polymers are capable of entering into a Friedel-Crafts reaction, leads to extremely valuable Products and intermediates for chemical synthesis. Such reactive aromatic Connections include Benzene, toluene, mesitylene, ethylbenzene, phenol, anisole, naphthalene, fluorene, Acenaphthene, diphenyl, diphenyl ether, anthracene and dibenzofuran. The introduction of aromatic groups on the polymer chain offers the possibility of subsequent chemical modification of the polymer, such as B. by chlorination, nitration, sulfonylation, polyetherification and polyesterification. In the Alkylation of phenol should also be noted that the phenolic hydroxyl group of the alkylation is much less subject to acidic conditions than the p-ring position created by the phenolic hydroxyl group is activated.

Masses based on aromatic compounds, especially phenolic compounds, which have been alkylated or acylated with the cationically active polymers of the invention can for the production of flexible resins, such as. B. phenolic resins, epoxy resins, polycarbonate resins and amino-aldehyde resins be used. Such alkylated or acylated phenolic substances can also as intermediates in the synthesis of dyes, drugs and other chemical compounds be used.

The polycationically active polymeric alkylating agents of the invention are further suitable for alkylation in that enables them to attach to compounds with localized electron-rich sites. A An example of such an alkylation by addition is the reaction with tertiary amines, where the quaternary ammonium salt of the catalyst common acid is formed.

What matters is that most of the reactions described above do not it is necessary to prepare and isolate the polycationically active polymers in special stages. The polycationically active polymers of the invention are often intermediates in the production of high molecular weight polymers, which are of value as such, as is the case in the manufacture of polytetramethylene oxide from tetrahydrofuran is the case. The use of the proposed according to the invention Catalysts offers a very simple and economical way to manufacture this extremely usable polymers from the monomers. The cationically active polymers, however, find their own greatest application as intermediates in graft or block copolymerizations or in alkylation or acylation reactions of the type described above. When this is the case, it is frequent desirable to produce the polycationically active polymer in situ and the desired alkylation or acylation reactions either simultaneously with their formation or following their formation perform.

The novel products obtainable by the processes described provide useful substances the production of molding compounds for plastic moldings, protective coating compounds, elastomers, polymers surface-active agents, impregnation agents, binders, embedding compounds, adhesives, fibers, Supports or supports for tapes, such as adhesive tapes, foams and films.

example 1

This example presents two extremely useful methods of making high molecular weight Polytetramethylene oxide described.

A. 444 grams of anhydrous tetrahydrofuran were added to a round bottom flask equipped with a stirrer, and a dry ice bath to - 30 ⁰ C cooled before 0.9 g (CF ₃ SO ₂ ^ O was added The mixture was under stirring. Allowed to warm to room temperature, and a constant increase in viscosity was observed at this temperature. After several hours the solution had become so viscous that it could no longer be stirred. The reaction mixture was left to stand at room temperature for 72 hours was a non-flowable rubber-like mass, was cut into small pieces, which were quenched overnight in dilute aqueous NaOH. After washing with water, the polymer was dissolved in tetrahydrofuran and reprecipitated with water. The yield of dried, gray-white polymer was 336 g, which corresponds to a conversion of nearly 76%. The molecular weight is about 300,000 as estimated by Gru nd the intrinsic viscosity of 2.48 in benzene at 25 ° C. In the unvulcanized state, the polymer has a tensile strength of 385 kg / cm ² and an elongation at break of 650%. The low-temperature properties are excellent: The brittleness temperature is below - 80 ° C. The polyether was vulcanized with a normal peroxide-sulfur formulation as well as with a peroxide-divinylbenzene formulation to form very tough, resilient elastomers with excellent water resistance. The unvulcanized product can be used in protective coatings, paints or paint formulations.

B. 1 liter of tetrahydrofuran was from L1AIH4 in a 2 liter flask equipped with a stirrer was distilled off. 0.5 ecm of pyrosulfuryl fluoride were used at room temperature admitted. After brief stirring to homogenize the reaction mixture, the Stirring stopped and the material allowed to stand overnight. At the end of this time there was a non-flowable, colorless mass which - apart from a slight increase in rigidity - no visible within 5 more days

609 539/437

Changes received. The polymer was then cut into pieces, quenched in dilute aqueous ammonia solution, dissolved in tetrahydrofuran, reprecipitated by pouring into water and dried. The polymer obtained was a hard, white leather-like substance having an intrinsic viscosity, measured in benzene at 31.5 ⁰ C, of 5.11. The yield of product was 75% and the calculated molecular weight was about 700,000. Coatings made from this high molecular weight polymer were very tough and abrasion-resistant.

Example 2

In this example, several reactions are described in which dicationically active polymers used to alkylate ammonia and various primary amines.

A. 275 cc anhydrous tetrahydrofuran was placed in a 500 cc round bottom flask equipped with a stirrer. The flask was cooled to 40 ⁰ C, and there were 3 cc of trifluoromethanesulfonic anhydride was added. An increase in viscosity was observed on warming to room temperature, indicating that polymerization was occurring. When the solution was quite viscous, ammonia gas was slowly bubbled through the dicationically active polyether solution at such a rate that a relatively low concentration of ammonia was maintained. When the ammonia addition began, an immediate reaction could be determined from a very rapid and abrupt increase in viscosity of the solution. The addition of ammonia was stopped when the reaction mixture could no longer be stirred satisfactorily. The product was poured into dilute aqueous sodium hydroxide solution and heated on a steam bath with stirring. It was then washed with water and dried in a vacuum oven at 50 ° C.

The product (150 g) was not completely soluble in benzene, whereas a normal tetramethylene oxide polymer was is completely soluble in benzene. It was soluble in methyl ethyl ketone and showed in this solvent an intrinsic viscosity of 0.402, which corresponds to an average molecular weight of 28,000. Elemental analysis showed a nitrogen content of 2.22%, which is about 44 nitrogen atoms each Average molecule, calculated on the basis of the molecular weight determined from the intrinsic viscosity, is equivalent to. This branched chain polyether polyamine product was made into a very tough rubber with good adhesion to aluminum, hardenable when heated with 1% by weight diglycidyl ether of bisphenol A. would.

B. 417 grams of tetrahydrofuran and 83 grams of propylene oxide were placed in a 1 liter flask fitted with a stirrer and drying tube. The mixture was heated - cooled to -20 ⁰ C and mixed with 26 cc (CF ₃ SO ₂ ^ O as a catalyst with the cooling was stopped and the reaction mixture stirred for 20 minutes After this time, a viscous solution was obtained of the dicationic active polymer... The polymerization was terminated by pouring the reaction mixture into a mixture of 300 ecm of liquid NH ₃ and 250 ecm of tetrahydrofuran, which was kept at -7O ⁰ C. The volatile substances were then removed, and the polymer was washed with dilute aqueous KOH- The resulting diprimary ω, ω'-copolyether diamine (200 g yield) was a liquid at room temperature. Analysis of this substance gave the following results: molecular weight = 2637, nitrogen content = 1.16% (corresponds to 2.18 nitrogen atoms / molecule), total content of amino groups per molecule, determined by perchloric acid titration = 2.24.
This copolyether diamine diprimary was cured.

by reacting it with the diglycidyl ether of bisphenol A. It became a rubbery one Vulcanizate obtained, which became stiffer with decreasing temperature much more slowly than a comparable one Material made from a diprimary diamine of the homopolymer of tetrahydrofuran had been.

C. 550 ecm of tetrahydrofuran were placed in a 1 liter flask equipped with a stirrer and drying tube. 25 ecm of trifluoromethanesulfonic anhydride were added at room temperature with vigorous stirring and cooling with cold water. Approximately 4 minutes after the start of the catalyst addition was stopped the cooling and poured the somewhat viscous solution of the dicationic active polymer while stirring in a mixture of about 500 cc of liquid ammonia and 500 cc of tetrahydrofuran at - 70 ⁰ C. The addition took about 2 minutes. At this point the overall reaction mixture was a cloudy, white liquid.

It was stirred for a short time at -70 ° C. and then allowed to warm to room temperature overnight. The diprimary Polyätherdiamin formed was precipitated by pouring into water and washed repeatedly with aqueous base and water and then dried in vacuo at 6O ⁰ C. the

. The yield was 199.8 g. The analysis showed a nitrogen content of 0.904% and a numerical average the molecular weight of 3350. There are thus about 2.16 amino groups per molecule.

D. 125 ecm tetrahydrofuran and 6 ecm trifluoromethanesulphonic anhydride were placed in a 250 cc flask equipped with a stirrer and drying tube. An exothermic reaction had taken place 4 minutes after the addition of the catalyst, as a result of which the reaction mixture had become somewhat viscous. 100 cc of isobutylamine was rapidly added to the dicationically active product at this point and the reaction mixture was stirred overnight. The product was then poured into water and washed with hot aqueous potassium hydroxide solution and then with hot water until the washing water reacted neutrally. The material was then dried for several days in a vacuum oven at 6O ⁰ C. Yield = 55 g. The analysis showed a nitrogen content of 1.23% and a number average molecular weight of 2180. There are therefore 1.91 nitrogen atoms per molecule in the form of secondary amino groups.

Such polymeric diamines are useful for block copolymerizations, such as. B. for condensation with a polyester or polyamide with terminal carboxyl groups. When treated with diisocyanates, Epoxy resins, diaziridine compounds and various aminoplast resins (such as tetramethylolurea), they continue to enter into chain-lengthening and cross-linking reactions. Products that differ from derive from these polyether diamines, have excellent water resistance, toughness and abrasion resistance.

and are very useful for making protective coatings.

E. 2500 cc of tetrahydrofuran was distilled and condensed through a column filled with molecular sieve material into a 5 liter flask. The flask was fitted with a stirrer and a drying tube. The tetrahydrofuran was cooled to -62 ° C. and _{treated with 425 g of (CF 3} SO ₂ I ₂ O. The reaction mixture was allowed to warm to 0 ° C. and kept at this temperature for 15 minutes. The viscous solution of the dicationically active polymer was stirred Quickly added to a mixture of 858 g of allylamine and 500 ecm of methylene chloride, which was kept at -70 ° C. The combined solutions were warmed to room temperature and the volatile constituents were then removed

CF ₃ SO ₃ Q ⁹ NH ₃ CH ₂ CH = Ch ₂

away. The deposit was filtered off and was able to recover the catalyst originally used be used. The benzene solution was then made with a strong base ion exchange resin treated to remove the remaining traces of catalyst. After removing the solvent the polymer was analyzed and the following results were obtained: numerical average the molecular weight = 2800, amino group equivalent weight (for the secondary amino groups) = 1390 (which corresponds to 2.01 secondary amino groups per molecule), 1.27% N (which corresponds to 2.58 nitrogen atoms per molecule corresponds).

F. 500 cc of anhydrous tetrahydrofuran was placed in a 1 liter flask fitted with a stirrer and drying tube. It was cooled to -70 ⁰ C and mixed with 20 cc pyrosulfuryl. The mixture was allowed to ^{warm to 0} ° C. and kept at this temperature for 10-12 minutes. The viscous solution of the dicationic active polyether was added rapidly with stirring into a flask containing 300 cc ethylamine of -70 ⁰ C. After allowing to warm to room temperature overnight with stirring, the unreacted volatiles were removed. The catalyst residues were removed by treatment with potassium hydroxide in methanol, followed by treatment in benzene solution with a strongly basic ion exchange resin. After drying, 165 g of a polyether with terminal amino groups were present, which was identified as N, N'-diethyl poly (tetramethylene oxide) diamine. The numerical average of the molecular weight was 1550. Analysis values: 1.77% N (which corresponds to 1.96 nitrogen atoms per molecule) and 1.32 milliequivalents / g of amino groups (which corresponds to 2.05 amino groups per molecule).

G. 400 ecm of anhydrous tetrahydrofuran were placed in a 1 liter flask and 16 ecm of pyrosulfuryl fluoride were added at -57 ° C. The mixture was ^{heated to 0} ° C. with stirring and kept at this temperature for 15 minutes. The temperature was then rapidly to - 10 ⁰ C and decreased the polymerization by the addition of 250 cc ethylamine at a temperature of - 70 ° C aborted. The catalyst residues were then removed by filtration and treatment with a basic ion exchange resin. The yield of the purified disecondary polyether diamine was 110 g. The numerical mean value of the molecular weight was 2700. Analysis values: 1.09% N (which corresponds to 2.1 nitrogen atoms per molecule), amino group equivalent weight = 1410 (which corresponds to 1.9 amino groups per molecule). This diamine product can be used to harden epoxy resins, giving hard, very impact-resistant products.

The following substances were placed in a 500 cc flask equipped with a stirrer: 15.5 g of the disecondary polyether diamine obtained as above, 1.14 g of trans-2,5-dimethylpiperazine and 207 g of dimethylformamide. A solution of 4.8 g of methylene bis (4-phenyl isocyanate) in a mixture of 33 g of dimethylformamide and 66 g of xylene was added dropwise to the amine solution at room temperature with stirring. A significant increase in viscosity was observed. After the chain extension reaction had ended, films were cast from this solution. The elastomer obtained had a tensile strength of 286 kg / cm ² and an elongation at break of 525%. By wet spinning a 15% solution of this product in dimethylformamide, elastic fibers with good properties could be obtained.

Example 3

This example illustrates the preparation of a dicationically active polyether and its use in the manufacture of the corresponding polyetherithiol and the products derived from it.

20 cc of purified tetrahydrofuran was placed in a 250 cc round bottom flask equipped with a stirrer. In -4o C ⁰ 3 cc of trifluoromethanesulfonic anhydride were added, and the mixture was stirred and allowed to warm to room temperature and allowed to polymerize. A thick paste had formed in about an hour. 100 ecm of anhydrous pyridine saturated with hydrogen sulfide were added to this dicationically active polymer, and further hydrogen sulfide was introduced from time to time using a glass filter tube with constant stirring until the polymer had dissolved in the pyridine, which was the case after several days . The product obtained was precipitated by pouring the solution into water, washed with water and dried in a vacuum oven at 50 ° C overnight.

The yield of tough, light-colored, solid polymer was 9.7 g. The infrared spectrum showed an absorption in the area of the C-S bond (14.6 μ). The product showed a when measured in benzene at 25 ° C intrinsic viscosity of 1.19, which is an approximate Molecular weight of 100,000 corresponds. The elemental analysis showed a sulfur content of 0.46% S, which corresponds to 14 sulfur atoms per molecule. About the formation of thioether bonds had a certain Chain extension occurred and the terminal groups were thiol groups. The chain extension and thus the increase in molecular weight can be achieved by quenching the tetrahydrofuran polymer in liquid hydrogen sulfide can be reduced to a minimum.

These polymeric dithiols, such as. B. Polysulfidthiol, can easily by reacting with ethylenically diunsaturated Compounds (such as ethylene dimethacrylate), active polyhalides (such as ethylene dibromide, 1,2,3-tribromopropane), polyisocyanates and certain oxidizing agents, such as. B. barium peroxide, hardened. Through the free radical polymerization of ethylenically unsaturated Monomers in the presence of the polymeric dithiols

9.5 g Styrene 0.5 g Polyetherithiol 20 g benzene 30 mg Azobisisobutyronitrile 7.5 g Styrene 2.5 g Polyetherithiol 20 g benzene 30 mg Azobisisobutyronitrile 5g Styrene 5g Polyetherithiol 30 g benzene 30 mg Azobisisobutyronitrile 10g Styrene 20 g benzene 30 mg Azobisisobutyronitrile

block copolymers can be obtained. The latter implementation is explained below.

Using the polyetherithiol prepared as above, the following approaches were carried out in Ampoules filled:

These ampoules were kept in motion ^{at 50 ° C. for 5 days.} The block copolymers obtained and the homopolymer used as a control sample were precipitated by pouring into heptane and dried. Yields: (1) 6.2 g, (2) 4.8 g, (3) 6.7 g, and (4) 4.6 g. The infrared spectra showed the presence of both polystyrene and polyether units in the products of ampoules 1, 2 and 3, the proportion of polyether units increasing in the order given. If the homopolymer was mixed with benzene in an amount of 10% by weight, two clearly separate liquid phases are formed when the mixture is left to stand for several hours. In the case of 10% strength solutions of the block copolymer products 1, 2 and 3, no such phase separation was found even after standing for much longer. The flexibility and impact resistance of the block copolymers increase considerably with increasing polyether content. Such block copolymers are used in coatings, binders, adhesives and in the production of plastic parts.

Example 4

This example describes the preparation of a dicationically active polyether and its use explained for the production of a polyether dicarboxylic acid.

100 ecm anhydrous tetrahydrofuran and 10 ecm freshly distilled trifluoromethanesulphonic anhydride were placed at room temperature in a 250 cc flask equipped with a stirrer and a drying tube. The reaction was exothermic and was moderated with the aid of a cold water bath. After a few minutes, the reaction mixture had become quite viscous, whereupon a suspension of 20 g of succinic acid in 100 ecm of tetrahydrofuran was added to the dicationically active polymer. The solution was stirred for several hours at room temperature and then poured into dilute aqueous ammonium hydroxide solution, a cloudy solution but no coagulation being obtained. The polymer precipitated when a small amount of concentrated HCl was added. The polymer was then washed with water and reprecipitated twice from tetrahydrofuran in water. The product was washed 4 times with hot Waser and dried in a vacuum oven at 5O ⁰ C. Yield 49g. Analysis values: number average molecular weight = 3300; Carboxyl group neutralization equivalent weight = 1640. These data show that 2.01 COOH groups are present per molecule of the polymer, the terminal carboxyl groups being linked to the polyether chain via ester bonds. The brittle, waxy product was quite surface-active in aqueous alkaline solutions.

ίο It can be used to produce block copolymers by condensation with polyethers or polyesters with terminal hydroxyl groups or with polyamides with terminal amino groups can be used. It can also be achieved by reacting with polyepoxides or polyaziridines are cured to a rubbery state.

Example 5

In this example, the use of dicationically active polymers, which according to the direct processes have been prepared for initiating a subsequent polymerization in which Block copolymers are obtained, explained.

A. 10 cc tetrahydrofuran and 0.5 cc trifluoromethanesulfonic anhydride were melted in a glass ampoule. After overnight at room temperature had been kept moving, the product became a non-flowable dicationically active Tetrahydrofuran polymer obtained. The ampoule was opened, the contents cooled in liquid air 10 ecm of ethylene oxide were added and the ampoule was closed again. After shaking vigorously overnight at A homogeneous, clear solution was obtained at room temperature. Then it went on for several days continued to stir gently, an increase in viscosity being observed. Stirring was continued until the Reaction mixture suddenly turned black. The product was then immediately diluted in a aqueous sodium hydroxide solution quenched 70 hours and then washed with water, which is something Contained sodium bromide to prevent dissolution of the polymer.

After drying at 50 ° C overnight in a vacuum oven there were 7 g of a viscous liquid, dark red polymer. The fact that it is a block copolymer can be seen Hand of the infrared spectrum as well as the surface activity of the product as well as recognize that the product shows a cloud point in water. By shaking benzene with 1% aqueous Solutions of the product enabled stable emulsions of benzene in water to be obtained.

B. 10 ecm tetrahydrofuran and 0.5 ecm trifluoromethanesulfonic anhydride were allowed to react in a glass ampoule at 25 ° C. After 24 hours the Ampoule opened and 10 cc of distilled styrene was added to the solid reaction product. the The ampoule was resealed and shaken vigorously for 72 hours. At this point there was a clear homogeneous, viscous solution. The material was then dissolved in dilute ammonium hydroxide solution Quenched for 24 hours.

The dried polymer (9 g) was a low-melting solid. The infrared spectrum showed the presence of units from both monomers and no OH absorption. From a solution this Block copolymer product could be cast clear films.

Example 6

This example explains the use of dicationically active polymers in the alkylation of anions of suitable salts.

A. 330 g of anhydrous tetrahydrofuran was placed in a three-necked flask equipped with a stirrer given. The flask and charge were cooled in an ice bath to give 47.4 grams of trifluoromethanesulfonic anhydride admitted. After the initially released amount of heat has been dissipated, the ice bath was removed. After about 45 minutes the reaction mixture had become noticeably more viscous. to At this point a solution of 70 g of sodium phenolate in 500 ecm of tetrahydrofuran was added.

The polymer obtained was coagulated by pouring it into water and washed several times with hot ammonium hydroxide solution and then with hot water. The polymer was dried in a vacuum oven for 24 hours at 8O ⁰ C. The number average molecular weight of the polyether was 974. Yield = 223 g. Infrared analysis confirmed the presence of phenoxy groups and showed no absorption of free phenol or -OH. When heated to 310 ° C. in air at a constant rate of 10 ° per minute, a weight loss of only 10% by weight was found, which shows the excellent heat resistance of the two-terminal phenoxy group-containing polytetramethylene oxide.

B. 100 ecm anhydrous tetrahydrofuran were in into a 250 cc round bottom flask equipped with a stirrer and drying tube. 10 ecm Trifluoromethanesulfonic anhydride was added at room temperature. It left an exothermic Notice a reaction and an increase in viscosity. A few minutes after adding the anhydride 26 g of potassium cyanate were added to the dicationically active polymer. Over the weekend it was further stirred vigorously at room temperature. However, the reaction mixture gelled in the process. The product was then shaken with benzene, a soluble and an insoluble portion being found. Both Fractions showed rather strong alkyl isocyanate absorption bands in the infrared spectrum (at 4.4 μ; potassium cyanate absorbed at 4.6 μ). The soluble material became upon almost instantaneous reaction with hexamethylenediamine insoluble at 25 ° C. The obtained insoluble substance showed none in the infrared spectrum Isocyanate absorption, indicating complete formation of the urea compound.

Example 7

This example illustrates the use of a diester catalyst in the manufacture of dicationically active polymers is effective.

8 ml of trifluoromethanesulfonic anhydride were placed in a test tube and cooled to -60 ° C. 4 ecm of tetrahydrofuran were then added dropwise over the course of 5 minutes, a solid immediately forming. The temperature was allowed to ^{rise to 0} ° C., after which 25 ecm of cold carbon tetrachloride was added. After thorough mixing, the liquid was decanted and discarded. The remaining solid was dissolved in 150 ecm boiling carbon tetrachloride and crystallized by cooling with ice. The crystals were washed thoroughly with 60 ecm cold water and again recrystallized from hot carbon tetrachloride. Yield = 8.4 g of white crystals with a melting point of 36 ° C. The NMR and IR spectra show that this is the compound

CF ₃ SO ₂ - O - (CH ₂ ) 4 - O - SO ₂ CF ₃

acts. Elemental analysis showed 32.5% F, 20.1% C and 2.7% H. The calculated values are 32.2% F, 20.3% C and 2.3% H.
72 grams of tetrahydrofuran distilled from L1AIH4 was placed in a 125 cc, 3 neck, round bottom flask equipped with a stirrer and in an ice bath. 5.30 g of tetramethylene bis (trifluoromethanesulfonate) were then added, and polymerization was carried out ^{at 0 ° C. for 60 minutes.} The piston

20. Was completely sealed off from the atmosphere. The dicationically active polyether formed was added to a solution of 40 ml of ethylamine in 250 ml of tetrahydrofuran at -60 ° C. with stirring. After stirring for 5 minutes, the excess amine was removed by stripping off in vacuo. 30 g of a copolymer of styrene and divinylbenzene were added, and the mixture was ^{stirred at 25 °} C. for 18 hours. The ion exchange resin was then filtered off and the solvent removed by vacuum stripping at 75 ⁰ C. The yield of disecondary polyether diamine was about 20%. Number average molecular weight = 5760; Amino group equivalent weight = 1960. So there are 2.9 amino groups per molecule.

Example 8

This example explains the examination of a number of anions to determine whether they can terminate the chain generate or not.

The following standard polymerization conditions were observed in the test experiments: 115 cc anhydrous tetrahydrofuran, which contained a soluble salt, were placed in a 250 cc flask equipped with a thermometer, stirrer and drying tube. The temperature was lowered to ⁰ -5o C, and 5 cc of redistilled (CF3SO _{2) 2} O was added. The amount of salt was equimolar to the amount of (CF ₃ SO ₂ ) ₂ O, ie it was sufficient to reduce the functionality of the poly (tetramethylene oxide) obtained to only 1 and to reduce the molecular weight of the polymer, if it was a Anion acted, which causes a chain termination. The temperature of the tetrahydrofuran solution was allowed to ^{rise to 0} ° C., which required 7 minutes, and held at this value for 10 minutes. The chain termination of the polymerization was carried out by adding a solution of excess LiBr in tetrahydrofuran. In this chain termination reaction, a Br atom is attached to each cationic site that is still present in the polymer solution. A determination of the molecular weight and the percentage bromine content of the polymer obtained therefore enables the functionality of the polymer to be calculated. The results obtained for the purified polymeric products are summarized in the following table:

009 539/437

table

Yield of polymer

Molecular weight of the polymer % Br

Functionality of the
Polymer

1885
1510
2300
1314
1282
1800
1022

854

433

*) The functionality could not be determined directly. From the known chain termination ability of the Br ion and the however, the greatly reduced molecular weight and the greatly reduced yield can be concluded with certainty that the polymer is monofunctional.

AgO3SCF3 31% AgC104 33% AgSbFe 41% AgBF4 33% LiPFe 43% L1CIO4 32% LiMnCM 9% LiNOa 11% LiBr 2%

9.69 difunctional 11.24 difunctional 7.52 difunctional 12.58 difunctional 11.90 difunctional 10.50 difunctional 7.43 monofunctional 11.80 monofunctional - *)

The data in the table above show that of the tested ions CF ₃ SO ₃ ⁹ , ClO ₄ ⁹ , SbCl ₆ ^9, BF ₄ ⁹ and PF ₆ ⁹ do not cause chain termination and that MnO ₄ ⁹ , ΝΟ ₃ ^Θ and Br ⁹ to one Chain termination. The present example thus shows that in the catalysts of the formula DQ which can be used for the preparation of dicationically active polymers, Q is any of the radicals CF ₃ SO ₃ -, ClO ₄ -, SbCl ₆ -, BF ₄ - or PF ₆ - can. However, Q must not be any of the radicals MnO ₄ -, NO ₃ - or Br-, since the radicals have been shown to cause chain termination in tetrahydrofuran polymerization when they are in their anionic form.

Example 9

This example illustrates the preparation of a complex salt and its use in the conversion of tetrahydrofuran in a dicationically active polymer.

4.6 g CF ₃ SO2F and 1.3 ecm SbFs were reacted in a sealed glass ampoule at room temperature. The CF ₃ SO2p was used in excess to serve as both a reactant and a solvent. A crystalline, light amber colored product was obtained in the reaction. The excess of CF ₃ SO ₂ F was removed under vacuum. The obtained salt that with the formula

CF ₃ SO ₂ ⁺ SbF ₆ -

can then be used to polymerize tetrahydrofuran in the following manner used:

100 ecm of tetrahydrofuran are _{distilled off from LiAlH 4} in a 200 cc flask equipped with a stirrer and thermometer. 3.7 g of the above salt are added to the tetrahydrofuran at 22 ° C. After 4.7 minutes the temperature had risen to 44 ° C and was still rising. The solution had become viscous. The reaction was terminated by adding 13 g of LiBr, as a result of which Br atoms were attached to all cationically active sites in the polymer solution. After the unreacted tetrahydrofuran had been removed, the polymer was purified by extraction with cyclohexane. The yield of purified polymer was. 27%. Its molecular weight was 9570. The bromine analysis (2.07%) showed that a bromine atom is present at each end of the polyether chain, which clearly shows the ability of this complex salt to convert tetrahydrofuran into a dicationically active polymer.

The following Examples 10-12 illustrate the indirect Process for the preparation of dicationically active polymers from suitable prepolymers.

Example 10

This example illustrates the conversion of a ω, ω'-polyether glycol into a dicationically active polymer and the subsequent conversion of this product to a disecondary ω, ω'-polyether diamine.

200 g of poly (tetramethylene oxide) glyco) (molecular weight = 2700) and 600 ecm of methylene chloride were placed in a 1 liter flask equipped with a stirrer and a drying tube. The solution was cooled to -40 ° C. and 50 ecm (CF ₃ SO ₂ ) ₂ O were added. The reaction mixture was left for 2.5 hours at a temperature from -30 ° C to

- 40 ° C stirred. During this period the glycol was converted to a dicationically active product. The solution was then quickly poured into a mixture of 300 ecm ethylamine and 300 ecm toluene, which at

- 70 ° C was kept. The mixture was over Allowed to warm to room temperature overnight with stirring. The volatile substances have been removed, and the polymer was taken up in benzene, filtered, with a strongly basic ion exchange resin treated to remove the catalyst residues and dried. Analysis of the polymer obtained gave the following results: number average molecular weight = 2000, amino group equivalent weight = 981 (which corresponds to 2.04 secondary amino groups per molecule); 1.59% N (which is 2.27 Corresponds to nitrogen atoms per molecule).

Example 11

1314 g adipic acid, 874 g 1,4-butanediol and Ig Tetrabutyltin was heated to 200-210 ° C. for 7 hours while stirring. The result of the reaction Water was removed by azeotropic distillation with the aid of heptane. During the 7 hour Reaction time 339 g of water were collected. The solvent and the unreacted 1,4-butanediol were removed by vacuum peeling. Analysis of the polyester obtained gave an acid number less than 1 and a hydroxyl equivalent weight of 1970.

4.9 ecm (CF ₃ SO ₂ J ₂ O, which had been freshly _{distilled from P 2} O ₅ , and 100 ecm anhydrous dichloromethane were placed in a 250 cc three-necked round bottom flask equipped with a stirrer, thermometer and dropping funnel The temperature of the solution was on

-2O ⁰ C and a solution of 39.4 g of the butanediol adipate polyester prepared as above and 2.4 ecm pyridine in 100 ecm dichloromethane at -20 ° C was added within 2 hours. The temperature of the mixture was then reduced to -50 ° C and the solid pyridinium trifluoromethanesulfonate salt removed by filtration. The filtrate, which contained the dicationically active polyester, was poured into a solution of 25 g of LiBr in 500 ecm of tetrahydrofuran with stirring, and the mixture was stirred at room temperature for 1 hour. After washing the solution with 750 cc of 5% KOH solution and 200 cc of water and drying with MGSC> 4, the solvent was removed by evaporation in vacuo at 7O ⁰ C. The polymer was then extracted with boiling cyclohexane and the clear cyclohexane layer discarded. The residue was dissolved in 150 ecm toluene, dried with anhydrous MgSO4 and centrifuged. The solvent was then removed by evaporation under vacuum at 8O ⁰ C. The infrared spectrum of the polymer (yield 20 g) showed no hydroxyl group absorption maximum. The analysis showed a bromine content of 4.09%. The bromine content calculated on the assumption that there are two terminal bromine atoms per molecule is 3.94%.

Example 12

3.5 ecm (CF ₃ SO ₂ ) _{2 O freshly distilled over P 2} O ₅ and 100 ecm dichloromethane were placed in a 250 cc three-necked round bottom flask equipped with a stirrer, dropping funnel and thermometer. The temperature of the stirred solution was lowered to -2O ⁰ C and a solution of 39.4 g at the Butandioladipinat-polyester prepared according to Example 11 and 1.7 cc of pyridine and 100 cc of dichloromethane was added dropwise - 20 ⁰ C over 2 hours was added. The temperature of the mixture was adjusted to - decreased 60 ⁰ C and filtered, the solid Pyridiniumtrifluormethansulfonatsalz. The filtrate, which contained the dicationically active polyester, was added to 130 g of freshly distilled tetrahydrofuran in a 500 cc two-necked round bottom flask equipped with a stirrer and a vacuum tube. The temperature was allowed to rise to 25 ° C and a vacuum was applied until the dichloromethane was removed. The polymerization was continued for 3 hours at 25 ° C. and then terminated by pouring the contents of the flask into a solution of 10 g of LiBr in 500 ecm of tetrahydrofuran. After washing this solution with 400 ecm of 5% KOH and then with 200 ecm of water and drying over anhydrous MgSU4, the solvent was removed by stripping off in vacuo at 70 ° C. The polymer, which was obtained in a yield of 50 g, was at 70 ⁰ C a viscous liquid and was completely soluble at 25 ° C in cyclohexane, a nonsolvent for the polyester itself. The infrared spectrum showed that

ίο Presence of both ester and Ether bonds and the absence of hydroxyl groups. All indications were that the product was a Block copolymer containing polyester sections with sections of polyether at their ends have terminal bromine substituents.

Example 13

This example illustrates the preparation of another diester catalyst that is used in the preparation of dicationically active polymers is effective.

56.4 g (0.2 mol) of trifluoromethanesulfonic anhydride were added together with 100 ecm of methylene chloride in added to a 500 cc flask and the mixture was cooled to 0 ° C. A mixture of 6.2 g (0.1 mol) ethylene glycol and 15.8 g (0.2 mol) pyridine in 150 ecm methylene chloride was added slowly with stirring added from a separatory funnel over the course of 2.5 hours. The mixture was then at for 30 minutes Stirred at 20 ° C. The precipitated pyridine acid salt was quickly filtered off and the filtrate in a The stoppered bottle is placed in a dry ice bath for 24 hours. The precipitate that formed was filtered off and discarded. A 200 cc portion of the filtrate was placed in a rotary flask evaporator and the solvent is removed under vacuum at a temperature slightly below 30 ° C. the The residue was distilled, with 6.1 g of a water-white fraction being collected at 30-32 ° C. and 0.001 mm Hg became. A second fraction with a light brown color (0.8 g) was at a higher one Temperature captured. The water-white fraction was identified as the desired diester product, which arose after the following reaction:

2 (CF ₃ SO ₂ ) ₂ O + HIGH ₂ CH ₂ OH + 2 C ₅ H ₅ N ₊

- CF ₃ SO ₂ OCh ₂ CH ₂ OSO ₂ CF ₃ + 2 CF ₃ SO ₃ HNC ₅ H ₅

Claims (3)

Patent claims: 1. Practically linear, dicationically reactive homo- or copolymers, the recurring Have ether units, with molecular weights in the range from 400 to 1,000,000, consisting of repeating units of the formulas [- (CHz) ₄ -O-] or [- (CH ₂ O) ₃ -] (A) IO or recurring units of the formula (A) with less than 50 mol% of other ether units which are derived from polymerizable cyclic ethers, each end of the polymer being an anion radical of the formula FSO ₃ -, ClO ₄ -, BF ₄ -, SbF ₆ -, SbF ₅ (O ₃ SF) -, SbCl ₆ -, AsF ₆ -, PF ₆ - or RfSO ₃ - and Rf denotes a polyfluoroaliphatic or polyfluorocycloaliphatic radical with 1 to 18 carbon atoms and at least one fluorine atom on the carbon atom. 2. Process for the production of practically linear, dicationically reactive polymers and copolymers of tetrahydrofuran with less than 50 mole percent of another acid polymerizable or copolymerizable cyclic ether or thioether, characterized in that one polymerizes the monomers in a medium which is free from chain terminators and a) a compound of the formula DQ, in which Q is an anion radical of the formula FSO ₃ , CIO4, RfSO ₃ , BF ₄ , SbF ₆ , SbF ₅ (O ₃ SF), SbCl ₆ , AsF ₆ , or PF ₆ , D is a radical FSO ₂ , ClO ₃ or RfSO ₂ and R _f denotes a polyfluoroaliphatic or polyfluorocycloaliphatic radical with 1-18 carbon atoms and at least one fluorine atom on the carbon atom or b) a compound of the formula DZCH ₂ (A) / jCH ₂ ZD, in which A is an alkylene, oxyalkylene or a radical consisting of repeating oxyalkylene units, Z is an oxygen or sulfur atom, η is a number equal to 0 or 1 and D is the Has the meaning given above, in a molar ratio of 0.001 to 0.5, based on the total monomers. 3. Use of the practically linear, dicationically reactive homo- and copolymers according to claim 1 as polymeric alkylating or acylating agents. 50